CN101663790A - Nonaqueous electrolyte, and rechargeable battery with the nonaqueous electrolyte - Google Patents

Nonaqueous electrolyte, and rechargeable battery with the nonaqueous electrolyte Download PDF

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Publication number
CN101663790A
CN101663790A CN200880012840A CN200880012840A CN101663790A CN 101663790 A CN101663790 A CN 101663790A CN 200880012840 A CN200880012840 A CN 200880012840A CN 200880012840 A CN200880012840 A CN 200880012840A CN 101663790 A CN101663790 A CN 101663790A
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nonaqueous electrolytic
electrolytic solution
atom
weight
battery
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加藤竜一
德田浩之
藤井隆
古田土稔
竹原雅裕
大贯正道
大桥洋一
木下信一
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Mitsubishi Chemical Corp
Mitsubishi Kasei Corp
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Mitsubishi Kasei Corp
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Priority to CN202310092102.XA priority Critical patent/CN116014240A/en
Priority to CN201510395046.2A priority patent/CN104966849B/en
Priority to CN201910392658.4A priority patent/CN110233290B/en
Publication of CN101663790A publication Critical patent/CN101663790A/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A subject is to provide a nonaqueous electrolyte excellent in cycle performances such as capacity retention after cycling, output after cycling, discharge capacity after cycling, and cycle discharge capacity ratio, output characteristics, high-temperature storability, low-temperature discharge characteristics, heavy-current discharge characteristics, high-temperature storability, safety, high capacity, high output, high-current-density cycle performances, compatibility of these performances, etc. Another subject is to provide a nonaqueous-electrolyte secondary battery employing the nonaqueouselectrolyte. The subjects have been accomplished with a nonaqueous electrolyte which contains a monofluorophosphate and/or a difluorophosphate and further contains a compound having a specific chemical structure or specific properties.

Description

Nonaqueous electrolytic solution and the rechargeable nonaqueous electrolytic battery that uses this nonaqueous electrolytic solution
Technical field
The present invention relates to secondary cell with nonaqueous electrolytic solution and the rechargeable nonaqueous electrolytic battery that uses this nonaqueous electrolytic solution, more specifically, the present invention relates to the rechargeable nonaqueous electrolytic battery that contains the nonaqueous electrolytic solution of special component and use this nonaqueous electrolytic solution.
Background technology
In recent years, be accompanied by the miniaturization of electronic equipment, the requirement of the high capacity of secondary cell is improved constantly, the lithium secondary battery that energy density is higher than nickel-cadmium cell and Ni-MH battery receives publicity.
As the electrolyte of lithium secondary battery, adopted is to make LiPF 6, LiBF 4, LiClO 4, LiCF 3SO 3, LiAsF 6, LiN (CF 3SO 2) 2, LiCF 3(CF 2) 3SO 3Deng electrolyte dissolution at cyclic carbonates such as ethylene carbonate, propylene carbonates, linear carbonate such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate; Cyclic ester such as gamma-butyrolacton, gamma-valerolactone class; In the nonaqueous solventss such as chain such as methyl acetate, methyl propionate ester class and the nonaqueous electrolytic solution that obtains
＜nonaqueous electrolytic solution 1, rechargeable nonaqueous electrolytic battery 1〉be equivalent to claim 1～4,23～29
At first, described rechargeable nonaqueous electrolytic battery has the energy density height and is difficult for producing the advantage of self discharge.Therefore, in recent years, be widely used in the power supply that civilian portable equipments such as mobile phone, notebook computer, PDA are used.The electrolyte that rechargeable nonaqueous electrolytic battery is used is by constituting as the lithium salts of supporting electrolyte and the organic solvent of non-water system.For the organic solvent of non-water system, require it to have the high-k that is used for lithium salts is dissociated, show high ionic conductivity and stable in battery in wide temperature province.Owing to be difficult to realize these requirements, therefore, common propylene carbonate, ethylene carbonate etc. are used in combination for the high boiling solvent of representative and low boiling point solvents such as dimethyl carbonate, diethyl carbonate with a kind of solvent.
In addition, reported a large amount of in electrolyte, add various additives with improve initial capacity, speed characteristic, cycle characteristics, high temperature preservation characteristics, trickle charge characteristic, self-discharge characteristics, overcharging prevents the method for characteristic etc.For example, as the method that suppresses self discharge at high temperature, reported the method (with reference to patent documentation 1) of adding the lithium fluophosphate class.
＜nonaqueous electrolytic solution 2, rechargeable nonaqueous electrolytic battery 2〉be equivalent to claim 5～9,23～29
Secondly, for battery behaviors such as the output characteristic of improving above-mentioned lithium secondary battery, cycle characteristics, preservation characteristics, nonaqueous solvents and electrolyte various researchs have been carried out.For example, in patent documentation 2, put down in writing and contain with respect to the gross activity material layer area on the positive electrode collector by use to be the electrolyte of a certain amount of tetrafluoroborate, to make the battery of low temperature output characteristic excellence.
But, in the method, though have the effect that improves output characteristic to a certain extent, and high-temperature cycle is reduced, the degree that its output improves is limited, can not tackle the requirement of higher output.
＜nonaqueous electrolytic solution 3, rechargeable nonaqueous electrolytic battery 3〉be equivalent to claim 10～15,23～29
The 3rd, for battery behaviors such as the load characteristic of improving above-mentioned lithium secondary battery, cycle characteristics, preservation characteristics, low-temperature characteristicss, nonaqueous solvents and electrolyte have been carried out various researchs.For example, in patent documentation 3, contain the electrolyte of vinylethylene carbonate compound, the decomposition of electrolyte can be suppressed at Min., thereby can make the battery of preservation characteristics, cycle characteristics excellence by use; In patent documentation 4, contain the electrolyte of propane sultone by use, the recovery capacity after the preservation is increased.
But, when in making electrolyte, containing above-claimed cpd, improve the effect of preservation characteristics and cycle characteristics though obtained to a certain extent, owing to can form the higher epithelium of resistance in negative side, thereby especially exist the problem that the discharge load characteristic reduces.
＜nonaqueous electrolytic solution 4, rechargeable nonaqueous electrolytic battery 4〉be equivalent to claim 16～29
The 4th, for battery behaviors such as the load characteristic of improving above-mentioned lithium secondary battery, cycle characteristics, preservation characteristics, low-temperature characteristicss, nonaqueous solvents and electrolyte have been carried out various researchs.For example, in patent documentation 5, contain the electrolyte of vinylethylene carbonate compound, the decomposition of electrolyte can be controlled at bottom line, thereby can make the battery of preservation characteristics, cycle characteristics excellence by use.In addition, in patent documentation 6, contain the electrolyte of propane sultone, the recovery capacity after the preservation is increased by use.
, when in making electrolyte, containing above-claimed cpd, improve the effect of preservation characteristics and cycle characteristics though obtained to a certain extent, owing to can form the higher epithelium of resistance in negative side, thereby especially exist the problem that the discharge load characteristic reduces.
On the other hand, in patent documentation 5, reported by adding the represented compound of formula (1) of patent documentation 5, the technology that cycle characteristics and current characteristics are improved simultaneously.In addition, in patent documentation 6, reported by adding the technology that specific compound improves cryogenic discharging characteristic.
But battery behaviors such as load characteristic, cycle characteristics, preservation characteristics, low-temperature characteristics are also insufficient, still have room for improvement.
＜nonaqueous electrolytic solution 5, rechargeable nonaqueous electrolytic battery 5〉be equivalent to claim 30～34
The 5th, from mobile phone, notebook computer etc. so-called civilian power supply use to automobile etc. and to drive with the purposes widely of vehicle power, nonaqueous electrolyte batteries such as lithium secondary battery are practical gradually.But, in recent years, the requirement of the high performance of nonaqueous electrolyte battery is improved constantly, when improving battery behavior, also wish the improvement of battery security strongly.
The electrolyte that is used for nonaqueous electrolyte battery mainly is made of electrolyte and nonaqueous solvents usually.As the main component of nonaqueous solvents, can use cyclic carbonates such as ethylene carbonate, propylene carbonate; Linear carbonate such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate; Cyclic carboxylic esters such as gamma-butyrolacton, gamma-valerolactone etc.
But, above-mentioned organic solvent has volatility, and catch fire easily, therefore, for the nonaqueous electrolyte battery that has used the electrolyte that contains a large amount of above-mentioned organic solvents, when when heating, internal short-circuit of battery, during external short-circuit of battery, when when overcharging or overdischarge etc., under the situation of misuse, abuse or during, exist and catch fire and potential danger such as blast in accident, particularly, seeking to be applicable to that its danger is high in the large-sized battery in automobile electrical source.
From above viewpoint, the nonaqueous electrolytic solution of use normal temperature fuse salt (being also referred to as room temperature fuse salt or ionic liquid) has been proposed.Known this normal temperature fuse salt is a liquid, and its volatility is low to moderate the degree that can't detect, and in addition, because this normal temperature fuse salt is non-volatile, thereby does not fire.In patent documentation 7, disclose by using this normal temperature fuse salt as electrolyte for lithium secondary batteries, obtained the nonaqueous electrolyte battery of excellent in safety.
In addition; following technology is disclosed in patent documentation 8: except the normal temperature fuse salt dissolving with quaternary ammonium cation that makes the reduction excellent in stability; also be dissolved with the such compound of comparing reduction decomposition under high potential with above-mentioned normal temperature fuse salt of ethylene carbonate or vinylene carbonate in the electrolyte; so; compare the compound that the reduction decomposition takes place with the normal temperature fuse salt under high potential and carry out electrochemical reaction in the charge and discharge process in the early stage; on electrode active material; particularly on negative electrode active material, form the electrode protection tunicle, thereby improve efficiency for charge-discharge.
Patent documentation 1: No. 3439085 communique of Japan Patent
Patent documentation 2: TOHKEMY 2004-273152 communique
Patent documentation 3: TOHKEMY 2001-006729 communique
Patent documentation 4: Japanese kokai publication hei 10-050342 communique
Patent documentation 5: Japanese kokai publication hei 08-078053 communique
Patent documentation 6: Japanese kokai publication hei 11-185804 communique
Patent documentation 7: Japanese kokai publication hei 4-349365 communique
Patent documentation 8: TOHKEMY 2004-146346 communique
Summary of the invention
The problem that invention will solve
＜nonaqueous electrolytic solution 1, rechargeable nonaqueous electrolytic battery 1 〉
, along with improving constantly that the rechargeable nonaqueous electrolytic battery high performance is required, require to realize having simultaneously various characteristicses such as high power capacity, high temperature preservation characteristics, trickle charge characteristic, cycle characteristics with higher level.In the prior art that only is patent documentation 1 that the high temperature preservation characteristics is told on, shown in the comparative example of back, there is the especially such problem of cycle characteristics difference under high voltage condition.Therefore, the present invention 1 finishes in view of the aforementioned technical background, and its purpose is to provide the nonaqueous electrolytic solution 1 of cycle characteristics excellence.
＜nonaqueous electrolytic solution 2, rechargeable nonaqueous electrolytic battery 2 〉
The present invention 2 finishes in view of the aforementioned technical background, and its purpose is to provide the also secondary cell nonaqueous electrolytic solution 2 (nonaqueous electrolytic solution 2) of excellence of output characteristic excellence, high temperature preservation characteristics and cycle characteristics.
＜nonaqueous electrolytic solution 3, rechargeable nonaqueous electrolytic battery 3 〉
The present invention 3 finishes in view of the aforementioned technical background, and its purpose is to provide the secondary cell nonaqueous electrolytic solution 3 (nonaqueous electrolytic solution 3) of cycle characteristics excellence.
＜nonaqueous electrolytic solution 4, rechargeable nonaqueous electrolytic battery 4 〉
The present invention 4 finishes in view of above-mentioned problem.That is, the present invention 4 problem is, cryogenic discharging characteristic and heavy-current discharge excellent are provided, and high temperature preservation characteristics and cycle characteristics are also excellent, also no problem nonaqueous electrolytic solution 4 in fail safe.
＜nonaqueous electrolytic solution 5, rechargeable nonaqueous electrolytic battery 5 〉
,, require to realize high power capacity, high output, high temperature preservation characteristics, cycle characteristics etc. and high security to improving constantly that the battery high performance requires along with in recent years with higher level.
With regard to the nonaqueous electrolyte battery that has used the electrolyte that patent documentation 7 put down in writing, since its when discharging and recharging the invertibity of electrode reaction insufficient, so the such battery performance of charge/discharge capacity, efficiency for charge-discharge and cycle characteristics can not satisfactory (with reference to the present invention 5 comparative example 1～3).In addition; for the nonaqueous electrolyte battery of the electrolyte that forms being dissolved with ethylene carbonate or vinylene carbonate in the normal temperature fuse salt put down in writing among the embodiment that has used patent documentation 8; when keeping rechargeable battery more than 80 ℃; the electrode protection tunicle that decomposition by ethylene carbonate or vinylene carbonate forms can not suppress the decomposition of normal temperature fuse salt, thereby produces a large amount of decomposition gases in battery.When in battery, producing decomposition gas, press in the battery and rise and cause safety valve work, in addition, in not having the battery of safety valve,, cause battery itself not use sometimes because the pressure of the gas of generation causes cell expansion.In addition, when the gas of generation is imflammable gas,, but also there is the danger of catching fire or exploding even used the nonaqueous electrolytic solution of normal temperature fuse salt not have flammability.
Therefore, under the situation of having used the nonaqueous electrolytic solution that adopts the normal temperature fuse salt that patent documentation 7 or patent documentation 8 put down in writing, from possessing battery behavior and fail safe aspect simultaneously, still can not be satisfactory.
Therefore, the present invention 5 purpose is, under the situation of using the nonaqueous electrolytic solution 5 that adopts the normal temperature fuse salt, can improve efficiency for charge-discharge, keeps high security simultaneously.
The method of dealing with problems
＜nonaqueous electrolytic solution 1, rechargeable nonaqueous electrolytic battery 1〉claim 1～4,23～29
The present inventor furthers investigate in view of above-mentioned problem, found that, contain fluorophosphate in the nonaqueous electrolytic solution by making, and contain the iron family element of specific concentrations, when keeping high power capacity, particularly can improve the cycle characteristics under high voltage condition, thereby finish the present invention 1.
Promptly, the present invention 1 relates to nonaqueous electrolytic solution 1, this nonaqueous electrolytic solution contains electrolyte and this electrolytical nonaqueous solvents of dissolving, and described nonaqueous electrolytic solution contains mono-fluor phosphate and/or difluorophosphoric acid salt, and also containing with respect to the nonaqueous electrolytic solution total amount is the iron family element of 1～2000ppm.
In addition, the present invention 1 also relates to rechargeable nonaqueous electrolytic battery 1, and this rechargeable nonaqueous electrolytic battery 1 has used above-mentioned nonaqueous electrolytic solution 1.
＜nonaqueous electrolytic solution 2, rechargeable nonaqueous electrolytic battery 2〉claim 5～9,23～29
The present inventor furthers investigate in view of above-mentioned problem, found that, when containing certain organic compound and specific inorganic compound in the nonaqueous electrolytic solution, the output characteristic excellence, and can make high temperature preservation characteristics and cycle characteristics keep good, thereby finish the present invention 2.
Promptly, the present invention 2 relates to nonaqueous electrolytic solution 2, this nonaqueous electrolytic solution 2 mainly is made of electrolyte and this electrolytical nonaqueous solvents of dissolving, described nonaqueous electrolytic solution contains and is selected from chain saturated hydrocarbons, cyclic saturated hydrocarbons, has the aromatic compound class of halogen atom and has at least a kind of compound in the ethers of fluorine atom, also contains mono-fluor phosphate and/or difluorophosphoric acid salt.
In addition, the present invention 2 also relates to rechargeable nonaqueous electrolytic battery 2, and this rechargeable nonaqueous electrolytic battery contains nonaqueous electrolytic solution and can occlusion and emit the negative pole and the positive pole of lithium ion, and wherein, described nonaqueous electrolytic solution is above-mentioned nonaqueous electrolytic solution.
＜nonaqueous electrolytic solution 3, rechargeable nonaqueous electrolytic battery 3〉claim 10～15,23～29
The present inventor furthers investigate in view of above-mentioned problem, found that, when adding specific compound and " mono-fluor phosphate and/or difluorophosphoric acid salt " in nonaqueous electrolytic solution, can make cycle characteristics keep good, thereby finish the present invention 3.
Promptly, the present invention 3 main points are secondary cell nonaqueous electrolytic solution 3, it is used for rechargeable nonaqueous electrolytic battery, described rechargeable nonaqueous electrolytic battery has nonaqueous electrolytic solution and can occlusion and emit the negative pole and the positive pole of ion, wherein, described nonaqueous electrolytic solution contains electrolyte and nonaqueous solvents, also contain mono-fluor phosphate and/or difluorophosphoric acid salt, and with respect to this nonaqueous electrolytic solution total amount to be the compound that the ratio of 0.001 weight %～10 weight % contains following general formula (1) and/or following general formula (2) expression
[Chemical formula 1]
Figure A20088001284000121
[R 1, R 2, R 3, R 4Independent separately, be organic group or halogen atom, R 1, R 2, R 3, R 4In at least one group be that atom with the X Direct Bonding is heteroatomic group, R 1, R 2, R 3, R 4Identical or different.X is the atom beyond the carbon atom.]
[Chemical formula 2]
Figure A20088001284000122
[R 5, R 6, R 7Independent separately, be organic group or halogen atom, R 5, R 6, R 7In at least one group be that atom with the Y Direct Bonding is heteroatomic group, R 5, R 6, R 7Identical or different.Y is the atom beyond the carbon atom.]
In addition, the present invention 3 main points are secondary cell nonaqueous electrolytic solution 3, it is used for rechargeable nonaqueous electrolytic battery, described rechargeable nonaqueous electrolytic battery has nonaqueous electrolytic solution and can occlusion and emit the negative pole and the positive pole of ion, wherein, described nonaqueous electrolytic solution contains mono-fluor phosphate and/or difluorophosphoric acid salt, and this nonaqueous electrolytic solution is used for the rechargeable nonaqueous electrolytic battery that adopts following general formula (1) and/or the represented compound of following general formula (2) that negative or positive electrode is handled.
[chemical formula 3]
Figure A20088001284000131
[R 1, R 2, R 3, R 4Independent separately, be organic group or halogen atom, R 1, R 2, R 3, R 4In at least one group in, with the atom of X Direct Bonding be hetero-atom, R 1, R 2, R 3, R 4Identical or different.X is the atom beyond the carbon atom.]
[chemical formula 4]
[R 5, R 6, R 7Independent separately, be organic group or halogen atom, R 5, R 6, R 7In at least one group in, with the atom of Y Direct Bonding be hetero-atom, R 5, R 6, R 7Identical or different.Y is the atom beyond the carbon atom.]
In addition, the present invention 3 main points are rechargeable nonaqueous electrolytic battery 3, and this rechargeable nonaqueous electrolytic battery 3 has nonaqueous electrolytic solution and can occlusion and emit the negative pole and the positive pole of ion at least, and wherein, described nonaqueous electrolytic solution is above-mentioned nonaqueous electrolytic solution 3.
＜nonaqueous electrolytic solution 4, rechargeable nonaqueous electrolytic battery 4〉claim 16～29
The present inventor furthers investigate in view of above-mentioned problem, found that, when in nonaqueous electrolytic solution, adding specific compound, can produce cryogenic discharging characteristic and heavy-current discharge excellent, and the battery that high temperature preservation characteristics and cycle characteristics are also excellent, thereby finished the present invention 4.
That is, the present invention 4 relates to nonaqueous electrolytic solution 4, and this nonaqueous electrolytic solution 4 contains the nonaqueous solvents of lithium salts and this lithium salts of dissolving, and described nonaqueous electrolytic solution contains the represented compound of following general formula (1), and contains mono-fluor phosphate and/or difluorophosphoric acid salt.Below, this invention is abbreviated as " execution mode 4-1 ".
[chemical formula 5]
Figure A20088001284000133
[in the general formula (1), A and B represent various substituting groups, and wherein at least one is a fluorine, and n represents the natural number more than 3.]
In addition, the present invention 4 relates to nonaqueous electrolytic solution 4, this nonaqueous electrolytic solution 4 contains the nonaqueous solvents of lithium salts and this lithium salts of dissolving, described nonaqueous electrolytic solution is being that the ratio of 0.001 weight %～5 weight % contains the represented compound of above-mentioned general formula (1) with respect to the nonaqueous electrolytic solution total amount, and, being that the ratio of 0.001 weight %～5 weight % contains carbonic ester with respect to the nonaqueous electrolytic solution total amount, described carbonic ester have in unsaturated bond and the halogen atom one of at least.Below, this invention is abbreviated as " execution mode 4-2 ".
In addition, the present invention 4 main points are rechargeable nonaqueous electrolytic battery 4, and this rechargeable nonaqueous electrolytic battery 4 comprises nonaqueous electrolytic solution and can occlusion and emit the negative pole and the positive pole of lithium ion, and wherein, described nonaqueous electrolytic solution is above-mentioned nonaqueous electrolytic solution.
＜nonaqueous electrolytic solution 5, rechargeable nonaqueous electrolytic battery 5〉claim 30～34
To achieve these goals, the present inventor etc. further investigate repeatedly, found that, by containing the compound with ad hoc structure in the nonaqueous electrolytic solution that has used the normal temperature fuse salt, can solve above-mentioned problem, thereby have finished the present invention 5.
That is, the present invention 5 main points are nonaqueous electrolytic solution 5, and this nonaqueous electrolytic solution 5 contains lithium salts and normal temperature fuse salt, wherein, contain mono-fluor phosphate and/or difluorophosphoric acid salt in nonaqueous electrolytic solution.
In addition, the present invention 5 main points are nonaqueous electrolyte battery 5, and this nonaqueous electrolyte battery 5 has nonaqueous electrolytic solution and can occlusion and emit the negative pole and the positive pole of lithium ion, and wherein, described nonaqueous electrolytic solution is above-mentioned nonaqueous electrolytic solution.
The effect of invention
＜nonaqueous electrolytic solution 1, rechargeable nonaqueous electrolytic battery 1 〉
According to the present invention 1, can provide the nonaqueous electrolytic solution 1 and the rechargeable nonaqueous electrolytic battery 1 of high power capacity and cycle characteristics excellence.
＜nonaqueous electrolytic solution 2, rechargeable nonaqueous electrolytic battery 2 〉
According to the present invention 2, the output characteristic excellence can be provided, and high temperature preservation characteristics and also excellent nonaqueous electrolytic solution that is used for secondary cell 2 and the rechargeable nonaqueous electrolytic battery 2 of cycle characteristics.
＜nonaqueous electrolytic solution 3, rechargeable nonaqueous electrolytic battery 3 〉
According to the present invention 3, can provide the nonaqueous electrolytic solution that is used for secondary cell 3 and the rechargeable nonaqueous electrolytic battery 3 of cycle characteristics excellence.
＜nonaqueous electrolytic solution 4, rechargeable nonaqueous electrolytic battery 4 〉
4 the nonaqueous electrolytic solution according to the present invention, cryogenic discharging characteristic and heavy-current discharge excellent can be provided, and also excellent rechargeable nonaqueous electrolytic battery 4 of high temperature preservation characteristics and cycle characteristics and the nonaqueous electrolytic solution 4 in this rechargeable nonaqueous electrolytic battery 4.
＜nonaqueous electrolytic solution 5, rechargeable nonaqueous electrolytic battery 5 〉
According to the present invention 5, can keep high security as the great advantage of the nonaqueous electrolytic solution that uses the normal temperature fuse salt, and can realize high charge-discharge capacity and the high charge-discharge efficient that the nonaqueous electrolytic solution with the non-water system organic solvent of normally used employing compares favourably, and can realize the maximization of nonaqueous electrolyte battery and further high performance.
Embodiment
Below, be elaborated to the present invention's 5 (sometimes they being abbreviated as " the present invention ") execution mode at the present invention 1, but the example (typical example) that is illustrated as embodiments of the present invention to inscape of following record, the present invention is not subjected to the restriction of these particular contents, can carry out various distortion in the scope that does not exceed main points of the present invention and implement the present invention.
＜nonaqueous electrolytic solution 1, rechargeable nonaqueous electrolytic battery 1 〉
[1. nonaqueous electrolytic solution 1]
The nonaqueous electrolytic solution that uses in the present invention 1 the rechargeable nonaqueous electrolytic battery (below, suitably be called " nonaqueous electrolytic solution among the present invention 1 ") be the nonaqueous electrolytic solution that contains electrolyte and this electrolytical nonaqueous solvents of dissolving, this nonaqueous electrolytic solution contains mono-fluor phosphate and/or difluorophosphoric acid salt, and also containing with respect to the nonaqueous electrolytic solution total amount is the iron family element of 1～2000ppm.
＜1-1. electrolyte 〉
The electrolyte that is used for the present invention 1 nonaqueous electrolytic solution does not have particular restriction, can contain the known electrolyte that uses as electrolyte in the target rechargeable nonaqueous electrolytic battery arbitrarily.When the present invention 1 nonaqueous electrolytic solution was used for rechargeable nonaqueous electrolytic battery, electrolyte was preferably lithium salts.
As electrolytical object lesson, for example can enumerate:
LiClO 4, LiAsF 6, LiPF 6, Li 2CO 3, LiBF 4Deng inorganic lithium salt;
LiCF 3SO 3, LiN (CF 3SO 2) 2, LiN (C 2F 5SO 2) 2, LiN (CF 3SO 2) (C 4F 9SO 2), LiC (CF 3SO 2) 3, LiPF 4(CF 3) 2, LiPF 4(C 2F 5) 2, LiPF 4(CF 3SO 2) 2, LiPF 4(C 2F 5SO 2) 2, LiBF 3(CF 3), LiBF 3(C 2F 5), LiBF 2(CF 3) 2, LiBF 2(C 2F 5) 2, LiBF 2(CF 3SO 2) 2, LiBF 2(C 2F 5SO 2) 2Etc. fluorine-containing organic lithium salt;
Two (oxalate closes) lithium borate, three (oxalate closes) lithium phosphate, difluoro oxalate root close the lithium salts that lithium borate etc. contains the dicarboxylic acids complex compound;
KPF 6, NaPF 6, NaBF 4, CF 3SO 3Sodium salts such as Na or sylvite etc.
In the above-mentioned electrolyte, preferred LiPF 6, LiBF 4, LiCF 3SO 3, LiN (CF 3SO 2) 2, LiN (C 2F 5SO 2) 2, two (oxalate closes) lithium borate, preferred especially LiPF 6Or LiBF 4
Lithium salts can use a kind separately, also can use more than 2 kinds with combination in any and ratio.Wherein,, produce gas in the time of can being suppressed at trickle charge or be suppressed at high temperature and preserve the back deterioration takes place when being used in combination 2 kinds of specific inorganic lithium salts or being used in combination inorganic lithium salt and during fluorine-containing organic lithium salt, therefore preferred.
Especially preferred compositions is used LiPF 6And LiBF 4, or with LiPF 6, LiBF 4Deng inorganic lithium salt and LiCF 3SO 3, LiN (CF 3SO 2) 2, LiN (C 2F 5SO 2) 2Be used in combination etc. fluorine-containing organic lithium salt.
In addition, when being used in combination LiPF 6And LiBF 4The time, contained LiBF 4Shared ratio is preferably 0.01 weight %～20 weight % usually in the electrolyte total amount.Work as LiBF 4Degree of dissociation low excessively, when ratio is too high, may cause the resistance of nonaqueous electrolytic solution to raise.
On the other hand, with LiPF 6, LiBF 4Deng inorganic lithium salt and LiCF 3SO 3, LiN (CF 3SO 2) 2, LiN (C 2F 5SO 2) 2When being used in combination etc. fluorine-containing organic lithium salt, inorganic lithium salt shared ratio in the lithium salts total amount is preferably the scope of 70 weight %～99 weight % usually.Usually, when fluorine-containing organic lithium salt compare with inorganic lithium salt molecular weight excessive, when ratio is too high, causes nonaqueous solvents shared ratio in the nonaqueous electrolytic solution total amount to reduce sometimes, thereby the resistance of nonaqueous electrolytic solution raise.
In addition, in the scope of not obvious destruction the present invention's 1 effect, the concentration of lithium salts in the final composition of the present invention 1 nonaqueous electrolytic solution can be arbitrarily, but usually more than the 0.5mol/L, preferably more than the 0.6mol/L, more preferably more than 0.8mol/L, in addition, usually below the 3mol/L, preferably below the 2mol/L, the more preferably scope below 1.5mol/L.Cross when low when this concentration, may cause the conductance deficiency of nonaqueous electrolytic solution; When excessive concentration, because viscosity raises, conductance descends, and the performance of rechargeable nonaqueous electrolytic battery that causes using the present invention 1 nonaqueous electrolytic solution sometimes reduces.
Particularly, when the nonaqueous solvents of nonaqueous electrolytic solution when being main, can use LiPF separately with carbonate products such as alkylene carbonates or dialkyl carbonates 6, but preferably with LiPF 6With LiBF 4Be used in combination, because can suppress the capacity deterioration that causes because of trickle charge like this.When being used in combination LiPF 6And LiBF 4The time, LiBF 4With LiPF 6Mol ratio usually more than 0.005,, and usually below 0.4, preferably below 0.2 preferably more than 0.01, especially preferably more than 0.05.When this mol ratio was excessive, the tendency that has the battery behavior after causing high temperature to be preserved to reduce on the contrary, when mol ratio is too small, was difficult to obtain to suppress that gas produces and the effect of capacity deterioration when trickle charge.
In addition, when containing cyclic carboxylic acids ester compounds such as the above gamma-butyrolacton of 50 volume %, gamma-valerolactone in the nonaqueous solvents of nonaqueous electrolytic solution, preferred LiBF 4Account for more than the 50mol% of the 1st lithium salts (using maximum lithium salts) total amount.
＜1-2. nonaqueous solvents 〉
The present invention 1 the nonaqueous solvents that nonaqueous electrolytic solution contained is not particularly limited so long as can not bring dysgenic solvent to get final product to battery behavior when making battery, but in the solvent that uses in the nonaqueous electrolytic solution of enumerating below preferred more than a kind.
As normally used examples of non-aqueous, can enumerate: chain and cyclic carbonate, chain and cyclic carboxylic esters, chain and cyclic ether, phosphorous organic solvent, sulfur-bearing organic solvent etc.
In addition, the kind of linear carbonate without limits, the example as normally used linear carbonate is preferably dialkyl carbonate, the carbon number that constitutes the alkyl of dialkyl carbonate is preferably 1～5 respectively, especially is preferably 1～4.Particularly, can enumerate: dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, carbonic acid methyl n-pro-pyl ester, carbonic acid ethyl n-pro-pyl ester, carbonic acid di-n-propyl ester etc.
In above-mentioned linear carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate are because industry property obtained and the various characteristics in rechargeable nonaqueous electrolytic battery are good, and be therefore preferred.
Kind for cyclic carbonate is also unrestricted, and as normally used cyclic carbonate, the carbon number that preferably constitutes the alkylidene of cyclic carbonate is 2～6, especially is preferably 2～4.Particularly, can enumerate: ethylene carbonate, propylene carbonate, butylene carbonate (2-ethyl carbonate ethyl, cis and trans 2,3-dimethyl ethylene carbonate) etc.
In above-mentioned cyclic carbonate, ethylene carbonate or the propylene carbonate various characteristics in rechargeable nonaqueous electrolytic battery is good, and is therefore preferred.
In addition, for the kind of chain carboxylate also without limits, as the example of normally used chain carboxylate, can enumerate: methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, propionic acid n-propyl, isopropyl propionate, n-butyl propionate, isobutyl propionate, the propionic acid tert-butyl ester etc.
In above-mentioned chain carboxylate, ethyl acetate, methyl propionate, ethyl propionate are because industry property obtained and the various characteristics in rechargeable nonaqueous electrolytic battery are good, and be therefore preferred.
In addition, for the kind of cyclic carboxylic esters also without limits,, can enumerate gamma-butyrolacton, gamma-valerolactone, δ-Wu Neizhi etc. as the example of normally used cyclic carboxylic esters.
In above-mentioned cyclic carboxylic esters, gamma-butyrolacton is because industry property obtained and the various characteristics in rechargeable nonaqueous electrolytic battery are good, and is therefore preferred.
In addition, the kind of chain ether as the example of normally used chain ether, can be enumerated also without limits: dimethoxymethane, dimethoxy-ethane, diethoxymethane, diethoxyethane, ethyoxyl methoxy methylmethane, ethyoxyl methoxy base ethane etc.
In above-mentioned chain ether, dimethoxy-ethane, diethoxyethane are because industry property obtained and the various characteristics in rechargeable nonaqueous electrolytic battery are good, and be therefore preferred.
In addition, the kind of cyclic ether as the example of normally used cyclic ether, can be enumerated also without limits: oxolane, 2-methyltetrahydrofuran, oxinane etc.
In addition, do not have particular restriction yet, as the example of normally used phosphorous organic solvent, can enumerate: phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate for the kind of phosphorous organic solvent; Phosphorous acid esters such as Trimethyl phosphite, triethyl phosphite, triphenyl phosphite; Phosphinoxides such as trimethyl phosphine oxide, triethyl group phosphine oxide, triphenylphosphine oxide etc.
In addition, kind for the sulfur-bearing organic solvent does not have particular restriction yet, example as common use sulfur-bearing organic solvent, can enumerate: sulfurous acid glycol ester, 1,3-N-morpholinopropanesulfonic acid lactone, 1,4-butyl sultone, methyl mesylate, 1,4-dimethane sulfonoxybutane, sulfolane, cyclobufene sultone, dimethyl sulfone, diphenyl sulfone, methyl phenyl sulfone, dibutyl disulfide, dicyclohexyldisulfide, tetramethylthiuram monosulfide, N, N-dimethyl methyl sulfonamide, N, N-diethyl Methanesulfomide etc.
In above-mentioned nonaqueous solvents, chain and cyclic carbonate or chain and the cyclic carboxylic esters various characteristics in rechargeable nonaqueous electrolytic battery is good, therefore preferred, wherein, more preferably ethylene carbonate, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethyl acetate, methyl propionate, ethyl propionate, gamma-butyrolacton, further preferred ethylene carbonate, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethyl acetate, methyl propionate, gamma-butyrolacton.
Above-mentioned nonaqueous solvents can use separately, also can make up more than 2 kinds and use, and preferred compositions is used the compound more than 2 kinds.For example, preferably low viscosity solvents such as cyclic carbonates high dielectric constant solvent and linear carbonate class or chain ester class are used in combination.
One of preferred combination of nonaqueous solvents is the combination based on cyclic carbonates and linear carbonate class.Wherein, the total amount of cyclic carbonates and linear carbonate class shared ratio in the nonaqueous solvents total amount is more than the 80 volume %, be preferably more than the 85 volume %, more preferably more than the 90 volume %, and, the volume of cyclic carbonates with respect to cyclic carbonates and linear carbonate class total amount be more than 5%, be preferably more than the 10 volume %, more preferably more than the 15 volume %, and be generally 50 volume % following, be preferably 35 volume % following, more preferably below the 30 volume %.When adopting the combination of such nonaqueous solvents, the battery that uses this combination to make can be obtained the well balanced of cycle characteristics and high temperature preservation characteristics (remaining capacity and high capacity discharge capacity after particularly high temperature is preserved), thereby preferred.
As the object lesson of the preferred compositions of cyclic carbonates and linear carbonate class, can enumerate: ethylene carbonate and dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and diethyl carbonate and methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate and methyl ethyl carbonate etc.
In the combination of above-mentioned ethylene carbonate and linear carbonate class,, can also enumerate the combination of further interpolation propylene carbonate as preferred combination.When containing propylene carbonate, the volume ratio of ethylene carbonate and propylene carbonate is preferably 99: 1～and 40: 60, especially be preferably 95: 5～50: 50.In addition, be more than the 0.1 volume % when making propylene carbonate shared ratio in the nonaqueous solvents total amount, be preferably 1 volume %, more preferably more than the 2 volume %, and be generally below the 10 volume %, be preferably below the 8 volume %, when more preferably 5 volume % are following, the combined characteristic that can keep ethylene carbonate and linear carbonate class, and further obtain more excellent discharge load characteristic, therefore preferred.
In combinations thereof, more preferably contain the combination of asymmetric linear carbonate class, particularly, the combination that contains ethylene carbonate and symmetrical linear carbonate class and asymmetric linear carbonate class that ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and diethyl carbonate and methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate and methyl ethyl carbonate are such or further contain the combination of propylene carbonate, these combinations can obtain the well balanced of cycle characteristics and discharge load characteristic, and are therefore preferred.Wherein, the combination that preferred asymmetric linear carbonate class is a methyl ethyl carbonate, in addition, the alkyl carbon atoms number that constitutes dialkyl carbonate is preferably 1～2.
Other example of preferred mixed solvent is the mixed solvent that contains the chain ester.Particularly, consider, preferably in above-mentioned cyclic carbonates and linear carbonate class mixed solvent, contain the mixed solvent of chain ester from the angle of the discharge load characteristic that improves battery, as the chain ester, especially ethyl acetate, methyl propionate.The volume of chain ester accounts for more than 5% in nonaqueous solvents usually, preferably accounts for more than 8%, more preferably accounts for more than 15%, and accounts for below 50% usually, preferably accounts for below 35%, more preferably accounts for below 30%, further preferably accounts for below 25%.
As other preferred examples of non-aqueous, can be account for total amount 60 volume % above be selected from a kind of organic solvent in the following solvents or by the mixed solvent that organic solvent is formed more than 2 kinds that is selected from the following solvents, described solvent comprises: ethylene carbonate, propylene carbonate and butylene carbonate, gamma-butyrolacton and gamma-valerolactone.The flash-point of preferred this class mixed solvent is more than 50 ℃, wherein, especially is preferably more than 70 ℃.Even use the nonaqueous electrolytic solution of this solvent at high temperature to use evaporation or the leak of liquid that also is difficult for taking place solvent.Wherein, when total amount shared ratio in nonaqueous solvents of using ethylene carbonate and gamma-butyrolacton is more than the 80 volume %, be preferably more than the 90 volume %, and when the volume ratio of ethylene carbonate and gamma-butyrolacton is 5: 95～45: 55 a solvent, perhaps the total amount shared ratio in nonaqueous solvents when use ethylene carbonate and propylene carbonate is more than the 80 volume %, be preferably more than the 90 volume %, and when the volume ratio of ethylene carbonate and propylene carbonate is 30: 70～80: 20 a solvent, can obtain the well balanced of cycle characteristics and discharge load characteristic etc. usually.
＜1-3. mono-fluor phosphate, difluorophosphoric acid salt 〉
The present invention 1 nonaqueous electrolytic solution contains mono-fluor phosphate and/or difluorophosphoric acid salt must composition as it." mono-fluor phosphate and/or the difluorophosphoric acid salt " that in the present invention 1, uses if by single fluorophosphoric acid radical ion and/or difluorophosphoric acid radical ion, and cation form, its kind there is not particular restriction, because the nonaqueous electrolytic solution of finally making must be the electrolyte that can be used as rechargeable nonaqueous electrolytic battery, thereby need select in view of the above.
Thus, mono-fluor phosphate among the present invention 1, difluorophosphoric acid salt are preferably single fluorophosphoric acid radical ion, the difluorophosphoric acid radical ion more than 1 and are selected from salt that metal ion more than a kind in the 1st family in the periodic table of elements, the 2nd family and the 13rd family (below, suitably abbreviate " special metal ion " as) forms or and the salt that forms in season.Mono-fluor phosphate and/or difluorophosphoric acid salt can use a kind, also can be used in combination any more than 2 kinds.
The single fluorophosphoric acid slaine of＜1-3-1., difluorophosphoric acid slaine 〉
At first, at the mono-fluor phosphate among the present invention 1, difluorophosphoric acid salt be the salt that forms of single fluorophosphoric acid radical ion, difluorophosphoric acid radical ion and special metal ion (below, also divide another name they be " single fluorophosphoric acid slaine ", " difluorophosphoric acid slaine ") situation describe.
Be used for single fluorophosphoric acid slaine of the present invention 1, the special metal of difluorophosphoric acid slaine,, can enumerating lithium, sodium, potassium, caesium etc. as the object lesson of the 1st family's metal of the periodic table of elements.Wherein, preferred lithium or sodium, especially preferred lithium.
As the object lesson of group II metal in the periodic table of elements, can enumerate magnesium, calcium, strontium, barium etc.Wherein, preferably magnesium or calcium, especially preferably magnesium.
As the object lesson of the 13rd family's metal in the periodic table of elements, can enumerate aluminium, gallium, indium, thallium etc.Wherein, preferred aluminium or gallium, especially preferred aluminium.
For the atomicity of these special metals that had in single fluorophosphoric acid slaine of per 1 molecule the present invention 1, the difluorophosphoric acid slaine without limits, can only be 1 atom, also can be for more than 2 atoms.
When containing the above special metal of 2 atoms in single fluorophosphoric acid slaine of per 1 molecule the present invention 1, the difluorophosphoric acid slaine, the kind of these special metal atoms can be mutually the same, also can be different.Can also have the metallic atom except special metal more than 1 or 2 in addition.
As the object lesson of single fluorophosphoric acid slaine, difluorophosphoric acid slaine, can enumerate Li 2PO 3F, Na 2PO 3F, MgPO 3F, CaPO 3F, Al 2(PO 3F) 3, Ga 2(PO 3F) 3, LiPO 2F 2, NaPO 2F 2, Mg (PO 2F 2) 2, Ca (PO 2F 2) 2, Al (PO 2F 2) 3, Ga (PO 2F 2) 3Deng.Wherein, preferred Li 2PO 3F, LiPO 2F 2, NaPO 2F 2, Mg (PO 2F 2) 2Deng.
The single fluorophosphoric acid quaternary salt of＜1-3-2., difluorophosphoric acid quaternary salt 〉
Then, at the mono-fluor phosphate among the present invention 1, difluorophosphoric acid salt be the salt that forms in single fluorophosphoric acid radical ion, difluorophosphoric acid radical ion and season (below, also divide another name they be " single fluorophosphoric acid quaternary salt ", " difluorophosphoric acid quaternary salt ") situation describe.
Be used for the present invention 1 single fluorophosphoric acid quaternary salt, difluorophosphoric acid quaternary salt season be generally cation, particularly, can enumerate cation with following general formula (1) expression.
[chemical formula 6]
Figure A20088001284000211
In the above-mentioned general formula (1), R 1m～R 4mRepresentation hydrocarbyl independently of one another.For the kind of alkyl without limits.That is, can be aliphatic alkyl, also can be aromatic hydrocarbyl, can also be the alkyl that aliphatic alkyl and aromatic hydrocarbyl bonding form.When it is aliphatic alkyl, can be chain, also can be ring-type, can also be the structure that chain and ring-type bonding form.When it is the chain alkyl, can be the straight chain shape, also can be a chain.In addition, can be saturated hydrocarbyl, also can have unsaturated bond.
As R 1m～R 4mThe object lesson of alkyl, can enumerate alkyl, cycloalkyl, aryl, aralkyl etc.
As the object lesson of alkyl, for example can enumerate: methyl, ethyl, 1-propyl group, 1-Methylethyl, 1-butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl ethyl etc.
Wherein, preferable methyl, ethyl, 1-propyl group, 1-butyl etc.
Object lesson as cycloalkyl, for example can enumerate: cyclopenta, the 2-methylcyclopentyl, the 3-methylcyclopentyl, 2, the 2-dimethylcyclopentyl, 2, the 3-dimethylcyclopentyl, 2, the 4-dimethylcyclopentyl, 2, the 5-dimethylcyclopentyl, 3, the 3-dimethylcyclopentyl, 3, the 4-dimethylcyclopentyl, 2-ethyl cyclopenta, 3-ethyl cyclopenta, cyclohexyl, the 2-methylcyclohexyl, the 3-methylcyclohexyl, the 4-methylcyclohexyl, 2, the 2-Dimethylcyclohexyl, 2, the 3-Dimethylcyclohexyl, 2, the 4-Dimethylcyclohexyl, 2, the 5-Dimethylcyclohexyl, 2, the 6-Dimethylcyclohexyl, 3, the 4-Dimethylcyclohexyl, 3, the 5-Dimethylcyclohexyl, 2-ethyl cyclohexyl, 3-ethyl cyclohexyl, 4-ethyl cyclohexyl, dicyclo [3,2,1] suffering-1-base, dicyclo [3,2,1] suffering-2-base etc.
Wherein, preferred cyclopenta, 2-methylcyclopentyl, 3-methylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl etc.
As the object lesson of aryl, for example can enumerate: phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2,3-3,5-dimethylphenyl etc.
Wherein, preferred phenyl.
As the object lesson of aralkyl, for example can enumerate: phenyl methyl, 1-phenylethyl, 2-phenylethyl, diphenyl methyl, trityl group etc.
Wherein, preferred phenyl methyl, 2-phenylethyl.
R 1m～R 4mAlkyl can also be replaced by the substituting group more than 1 or 2.For substituent kind, if in the scope of not obvious destruction the present invention's 1 effect without limits, as substituent example, can enumerate halogen atom, hydroxyl, amino, nitro, cyano group, carboxyl, ether, aldehyde radical etc.Need to prove, work as R 1m～R 4mAlkyl when having substituting group more than 2, these substituting groups can be mutually the same, also can be different.
To any plural R 1m～R 4mWhen alkyl compared, they can be mutually the same, also can be different.Work as R 1m～R 4mAlkyl when having substituting group, comprise that the substituted hydrocarbon radical of these substituting groups can be mutually the same, also can be different.In addition, R 1m～R 4mAlkyl in any bonding and form circulus mutually more than 2.
R 1m～R 4mThe carbon number of alkyl usually more than 1, and its upper limit is usually below 20, preferably below 10, more preferably below 5.When carbon number was too much, the molal quantity of Unit Weight reduced, and the tendency that causes various effects to reduce is arranged.Need to prove, work as R 1m～R 4mAlkyl when having substituting group, comprise that the carbon number of the substituted hydrocarbon radical of these substituting groups satisfies above-mentioned scope.
In addition, in above-mentioned general formula (1), the atom under in Q representative element periodic table the 15th family.Wherein, preferred nitrogen atom or phosphorus atoms.
So, as above-mentioned general formula (1) preferred embodiment in represented season, can enumerate aliphat chain quaternary salt class, aliphat ring-type ammonium, aliphat ring shape Phosphonium, nitrogen heterocyclic ring aromatic series cation etc.
As aliphat chain quaternary salt class, especially preferred tetra-allkylammonium, four alkane base Phosphonium etc.
As the object lesson of tetra-allkylammonium, for example can enumerate: tetramethyl-ammonium, ethyl trimethyl ammonium, diethyl-dimethyl ammonium, triethyl group ammonium methyl, tetraethyl ammonium, tetra-n-butyl ammonium etc.
As the object lesson of Si Wan Ji Phosphonium, for example can enumerate: tetramethyl phosphonium, Yi base San Jia Ji Phosphonium, diethyl Er Jia Ji Phosphonium, triethyl group Jia Ji Phosphonium, Si Yi Ji Phosphonium, Si Zheng Ding Ji Phosphonium etc.
As aliphat ring-type ammonium, especially preferred pyrrolidines, morpholine class, imidazoles, tetrahydropyrimidine class, piperazines, piperidines etc.
As the object lesson of pyrrolidines, for example can enumerate: N, N-dimethyl pyrrolidine, N-ethyl-N-crassitude, N, N-diethyl pyrrolidines etc.
As the object lesson of morpholine class, for example can enumerate: N, N-thebaine, N-ethyl-N-methylmorpholine, N, N-diethyl morpholine etc.
As the object lesson of imidazoles, for example can enumerate: N, N '-methylimidazole, N-ethyl-N '-methylimidazole, N, N '-diethyl imidazoles, 1,2,3-tri-methylimidazolium etc.
As the object lesson of tetrahydropyrimidine class, for example can enumerate: N, N '-dimethyl tetrahydro pyrimidine, N-ethyl-N '-methyl tetrahydropyrimidine, N, N '-diethyl tetrahydropyrimidine, 1,2,3-trimethyl tetrahydropyrimidine etc.
As the object lesson of piperazines, for example can enumerate: N, N, N ', N '-tetramethyl piperazine, N-ethyl-N, N ', N '-tri methyl piperazine, N, N-diethyl-N ', N '-lupetazin, N, N, N '-triethyl group-N '-methyl piperazine, N, N, N ', N '-tetraethyl piperazine etc.
As the object lesson of piperidines, for example can enumerate: N, N-lupetidine, N-ethyl-N-methyl piperidine, N, N-diethyl piperidines etc.
As nitrogen heterocyclic ring aromatic series cation, especially preferred pyridines, imidazoles etc.
As the object lesson of pyridines, for example can enumerate: N-picoline, N-ethylpyridine, 1,2-dimethyl pyrimidine, 1,3-dimethyl pyrimidine, 1,4-dimethyl pyrimidine, 1-ethyl-2-methylpyrimidine etc.
As the object lesson of imidazoles, for example can enumerate: N, N '-methylimidazole, N-ethyl-N '-methylimidazole, N, N '-diethyl imidazoles, 1,2,3-tri-methylimidazolium etc.
That is, the salt of above-mentioned Ji Yudan fluorophosphoric acid radical ion of enumerating and/or difluorophosphoric acid radical ion formation is the single fluorophosphoric acid quaternary salt among the present invention 1, the preferred object lesson of difluorophosphoric acid quaternary salt.
＜1-3-3. content, detection (source of containing), technical scope etc. 〉
In the present invention 1 nonaqueous electrolytic solution, can only use a kind of mono-fluor phosphate or difluorophosphoric acid salt, also can be used in combination mono-fluor phosphate and/or difluorophosphoric acid salt more than 2 kinds with combination in any and ratio, but, preferably use a kind of mono-fluor phosphate or difluorophosphoric acid salt from the angle that rechargeable nonaqueous electrolytic battery can effectively be worked.
In addition, for the molecular weight of mono-fluor phosphate, difluorophosphoric acid salt and unrestricted, in the scope of not obvious destruction the present invention's 1 effect, can be any molecular weight, but usually more than 100.In addition, the molecular weight upper limit is not had particular restriction, but in view of the reactivity of this reaction, usually below 1000, more preferred from point of view of practicability when following when reaching 500.
In addition, the preparation method of mono-fluor phosphate, difluorophosphoric acid salt also is not particularly limited, and can select known method to prepare arbitrarily.
In nonaqueous electrolytic solution, the total amount of mono-fluor phosphate and difluorophosphoric acid salt shared ratio in the nonaqueous electrolytic solution total amount is preferably (more than the 0.001 weight %) more than the 10ppm, more preferably 0.01 weight % above, especially be preferably 0.05 weight % above, more preferably more than the 0.1 weight %.In addition, the upper limit of its total amount be preferably 5 weight % following, more preferably 4 weight % following, more preferably below the 3 weight %.Cross when low when the concentration of mono-fluor phosphate or difluorophosphoric acid salt, be difficult to obtain the effect of improving of discharge load characteristic sometimes, on the other hand, when excessive concentration, cause efficiency for charge-discharge to reduce sometimes.
When mono-fluor phosphate and difluorophosphoric acid salt are actually used in the making of rechargeable nonaqueous electrolytic battery as nonaqueous electrolytic solution, even take this battery apart and extract nonaqueous electrolytic solution again, remarkable reduction can take place in the content of mono-fluor phosphate wherein and difluorophosphoric acid salt as a rule.Therefore, even only detect in a spot of mono-fluor phosphate and/or the difluorophosphoric acid salt at least a kind in the nonaqueous electrolytic solution that extracts from battery, this situation still is regarded as belonging to the present invention 1.In addition, when mono-fluor phosphate and difluorophosphoric acid salt are actually used in the making of rechargeable nonaqueous electrolytic battery as nonaqueous electrolytic solution, even do not contain in the nonaqueous electrolytic solution that after taking this battery apart, extracts again under the situation of mono-fluor phosphate and/or difluorophosphoric acid salt, mostly also can on positive pole, negative pole or dividing plate, detect the existence of mono-fluor phosphate and/or difluorophosphoric acid salt as other building block of rechargeable nonaqueous electrolytic battery.Therefore, even detect in mono-fluor phosphate and/or the difluorophosphoric acid salt at least a kind at least in a kind of building block in positive pole, negative pole, dividing plate, this situation still is regarded as belonging to the present invention 1.
In addition, for making mono-fluor phosphate and/or difluorophosphoric acid salt not only be contained in the nonaqueous electrolytic solution, also being contained in positive pole, negative pole, the dividing plate situation at least a kind of building block simultaneously, also be regarded as belonging to the present invention 1.
On the other hand, can also make the anodal interior or anodal surface of the rechargeable nonaqueous electrolytic battery of making contain mono-fluor phosphate and/or difluorophosphoric acid salt in advance.At this moment, can expect partly or entirely being dissolved in the nonaqueous electrolytic solution and the performance function of the mono-fluor phosphate that contains in advance and/or difluorophosphoric acid salt, this situation also is regarded as belonging to the present invention 1.
Contain the method for mono-fluor phosphate and/or difluorophosphoric acid salt in advance for making anodal interior or anodal surface, there is no particular restriction, as object lesson, can enumerate as described later, making the method that makes when anodal in the slurry that mono-fluor phosphate and/or difluorophosphoric acid salt is dissolved in preparation described later; Or mono-fluor phosphate and/or difluorophosphoric acid salt are dissolved in arbitrarily in the nonaqueous solvents, after utilizing the solution make that the positive pole of having made is coated with again or soaking into, dry, remove employed solvent, thereby make anodal in or anodal surface contain the method etc. of mono-fluor phosphate and/or difluorophosphoric acid salt.
In addition, when the actual fabrication rechargeable nonaqueous electrolytic battery, also can by the nonaqueous electrolytic solution that comprises at least a kind of mono-fluor phosphate and/or difluorophosphoric acid salt make anodal in or anodal surface contain mono-fluor phosphate and/or difluorophosphoric acid salt.When making rechargeable nonaqueous electrolytic battery because nonaqueous electrolytic solution is impregnated in the positive pole, therefore as a rule in anodal or anodal surface can contain mono-fluor phosphate and difluorophosphoric acid salt.Thereby the situation for can detect mono-fluor phosphate and/or difluorophosphoric acid salt from the positive pole that is recovered at least when taking this battery apart is regarded as belonging to the present invention 1.
In addition, can also make in the negative pole of the rechargeable nonaqueous electrolytic battery of making or negative terminal surface contains mono-fluor phosphate and difluorophosphoric acid salt in advance.At this moment, can expect partly or entirely being dissolved in the nonaqueous electrolytic solution and the performance function of the mono-fluor phosphate that contains in advance and/or difluorophosphoric acid salt, this situation is regarded as belonging to the present invention 1.For making in the negative pole or negative terminal surface contains the method for mono-fluor phosphate and difluorophosphoric acid salt in advance, there is no particular restriction, as object lesson, can enumerate as described later, when making negative pole, make mono-fluor phosphate and difluorophosphoric acid salt be dissolved in method in the slurry of preparation; Or mono-fluor phosphate and difluorophosphoric acid salt are dissolved in arbitrarily in the nonaqueous solvents, after utilizing the solution make that the negative pole of having made is coated with again or soaking into, dry, remove employed solvent, thereby make in the negative pole or negative terminal surface contains the method etc. of mono-fluor phosphate and difluorophosphoric acid salt.
In addition, when the actual fabrication rechargeable nonaqueous electrolytic battery, also can make in the negative pole or negative terminal surface contains mono-fluor phosphate and difluorophosphoric acid salt from the nonaqueous electrolytic solution that comprises at least a kind of mono-fluor phosphate and difluorophosphoric acid salt.When making secondary cell because nonaqueous electrolytic solution is impregnated in the negative pole, therefore as a rule in negative pole or negative terminal surface can contain mono-fluor phosphate and difluorophosphoric acid salt.Thereby the situation for can detect mono-fluor phosphate and difluorophosphoric acid salt from the negative pole that is recovered at least when taking this battery apart is regarded as belonging to the present invention 1.
In addition, can also make in the dividing plate of the rechargeable nonaqueous electrolytic battery of making or baffle surface contains mono-fluor phosphate and/or difluorophosphoric acid salt in advance.At this moment, can expect partly or entirely being dissolved in the nonaqueous electrolytic solution and the performance function of the mono-fluor phosphate that contains in advance and difluorophosphoric acid salt, this situation is regarded as belonging to the present invention 1.For making in the dividing plate or baffle surface contains the method for mono-fluor phosphate and/or difluorophosphoric acid salt in advance, there is no particular restriction, as object lesson, can enumerate: the method that mono-fluor phosphate and difluorophosphoric acid salt are mixed, or mono-fluor phosphate and difluorophosphoric acid salt are dissolved in arbitrarily in the nonaqueous solvents, and after before making rechargeable nonaqueous electrolytic battery, utilizing the solution that makes that dividing plate is coated with or soaking into, dry, remove and desolvate, thereby make in the dividing plate or baffle surface contains the method for mono-fluor phosphate and/or difluorophosphoric acid salt.
In addition, when the actual fabrication rechargeable nonaqueous electrolytic battery, also can make in the dividing plate or baffle surface contains mono-fluor phosphate and/or difluorophosphoric acid salt from the nonaqueous electrolytic solution that comprises mono-fluor phosphate and/or difluorophosphoric acid salt.When making rechargeable nonaqueous electrolytic battery because nonaqueous electrolytic solution is impregnated in the dividing plate, therefore as a rule in dividing plate or baffle surface can contain mono-fluor phosphate and difluorophosphoric acid salt.Therefore, the situation for can detect mono-fluor phosphate and difluorophosphoric acid salt from the dividing plate that reclaims at least when taking this battery apart is regarded as belonging to the present invention 1.
＜1-4. iron family element 〉
In the present invention 1 the nonaqueous electrolytic solution, except above-mentioned mono-fluor phosphate and/or difluorophosphoric acid salt, also contain the iron family element of specific concentrations.The mono-fluor phosphate by making the present invention 1 and/or the iron family element of difluorophosphoric acid salt and specific concentrations exist simultaneously, can show synergy, particularly, can obviously improve and surpassing as the cycle characteristics under the high voltage condition of the 4.2V of the upper limit working voltage of common rechargeable nonaqueous electrolytic battery.
For the principal element that shows such synergy, its details is still indeterminate, and the present invention 1 scope is not subjected to the restriction of this factor, but can think that it has following mechanism.Promptly; in reduction reaction product as " mono-fluor phosphate and/or the difluorophosphoric acid salt " of the necessary composition of the present invention 1 nonaqueous electrolytic solution; the cation of iron family element enters into reaction product; for example; form the P-O-M-O-P key (here; M represents iron family element) such ionomer, thus form more stable protection tunicle.In order to form such protection tunicle, can think to make in the charging stage at initial stage that forms tunicle that to contain iron family element in the nonaqueous electrolytic solution be effective.
The kind of＜1-4-1. iron family element 〉
The present invention 1 " iron family element " that nonaqueous electrolytic solution contained particularly, is ferro element, cobalt element, nickel element.In these iron family elements, consider preferred cobalt element, nickel element from the viewpoint that forms more stable tunicle.
In the present invention 1,, preferably make the iron group compound be dissolved in method in the nonaqueous electrolytic solution as making the method that contains iron family element in the nonaqueous electrolytic solution.Here, as " the iron group compound " among the present invention 1, the usually preferred oxidation number that uses iron family element be+2 or+3 ionic compound.
As the object lesson of " iron group compound ", for example can enumerate: hexafluorophosphoric acid iron (II), hexafluorophosphoric acid iron (III), hexafluorophosphoric acid cobalt (II), hexafluorophosphoric acid nickel hexafluorophosphates such as (II);
Tetrafluoro boric acid iron (II), tetrafluoro boric acid iron (III), cobalt (II), tetrafluoro boric acid nickel tetrafluoroborates such as (II);
Ferric perchlorate (II), ferric perchlorate (III), cobaltous perchlorate (II), nickelous perchlorate perchlorate such as (II);
Ferric sulfate (II), ferric sulfate (III), cobaltous sulfate (II), nickelous sulfate sulfate such as (II);
Ferric nitrate (II), ferric nitrate (III), cobalt nitrate (II), nickel nitrate nitrate such as (II);
Ferric acetate (II), ferric acetate (III), cobalt acetate (II), nickel acetate acetates such as (II);
Ferric carbonate (II), ferric carbonate (III), cobalt carbonate (II), nickelous carbonate carbonate such as (II);
Ferric oxalate (II), ferric oxalate (III), cobalt oxalate (II), nickel oxalate oxalates such as (II);
Ironic citrate (II), ironic citrate (III), citric acid cobalt (II), citric acid nickel citrates such as (II);
Benzoic acid iron (II), benzoic acid iron (III), cobalt benzoate (II), nickel benzoate benzoates such as (II);
Ferric phosphate (II), ferric phosphate (III), cobalt phosphate (II), nickel phosphate phosphate such as (II);
Ferric flouride (II), ferric flouride (III), cobaltous fluoride (II), nickel fluoride fluorides such as (II);
Acetyl acetone iron (II), acetyl acetone iron (III), acetyl acetone cobalt (II), acetyl acetone cobalt (III), nickel acetylacetonate iron family element acetylacetonates such as (II); Or the like.
In these iron group compounds, preferably in battery, be difficult for the anion and the salt of cobalt or nickel formation, for example hexafluorophosphoric acid cobalt (II), the hexafluorophosphoric acid nickel hexafluorophosphates such as (II) that react; Cobalt (II), tetrafluoro boric acid nickel tetrafluoroborates such as (II); Cobaltous perchlorate (II), nickelous perchlorate perchlorate such as (II); Cobalt phosphate (II), nickel phosphate phosphate such as (II); Cobaltous fluoride (II), nickel fluoride fluorides such as (II).
Wherein, from battery, stablizing this respect, more preferably hexafluorophosphoric acid cobalt (II), hexafluorophosphoric acid nickel hexafluorophosphates such as (II); Cobaltous fluoride (II), nickel fluoride fluorides such as (II).These iron group compounds can use a kind, also can combination in any use more than 2 kinds.In addition, the preferred anhydride of these iron group compounds, but also can use hydrate, as long as it has carried out dehydration described later as required.
＜1-4-2. content and detection method thereof 〉
The content of the iron family element among the present invention 1 with respect to the nonaqueous electrolytic solution total amount be generally more than the 1ppm, be preferably more than the 2ppm, more preferably more than the 3ppm, be preferably more than the 5ppm especially, most preferably be more than the 8ppm, and be generally 2000ppm following, be preferably 600ppm following, more preferably 100ppm following, especially be preferably 50ppm following, most preferably be below the 30ppm.If be lower than the lower limit of this scope, then can show above-mentioned effect of the present invention 1 sometimes hardly.In addition, surpass last prescribing a time limit, iron family element is reduced and separates out on negative pole with the form of metal at negative pole easily sometimes.In addition, also cause the decomposition of electrolyte, the result makes cycle characteristics reduce sometimes.Need to prove that when being used in combination the iron family element of the present invention 1 more than 2 kinds, the total concentration of employed iron family element is in the above-mentioned scope.
With regard to the present invention 1, can add iron family element, also can in electrolyte, generate iron family element.When in electrolyte, generating, as the method that detects the iron family element content that is contained in the nonaqueous electrolytic solution, be common metallic element analysis method, for example, can be undertaken quantitatively by atomic absorption analysis (AAS), inductively coupled plasma luminescence analysis (ICP), fluorescent x-ray analyzer (XRF) etc.ICP luminescence analysis particularly, its pre-treatment is easy, and precision is also high, also is not subject to the influence of other element, therefore preferred the use.
＜1-5. additive 〉
In the scope of not obvious destruction the present invention's 1 effect, the present invention 1 nonaqueous electrolytic solution can also contain various additives.Prepare when handling adding additive, can use known in the past additive arbitrarily.Need to prove that additive can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
As the example of additive, can enumerate overcharges prevents agent, be used for improving the capacity retention performance after high temperature is preserved and the auxiliary agent of cycle characteristics etc.In these additives, as being used for improving the capacity retention performance after high temperature is preserved and the auxiliary agent of cycle characteristics, the preferred carbonic ester (following abbreviate as sometimes " particular carbon acid esters ") that one of has in unsaturated bond and the halogen atom at least that adds.Below, respectively particular carbon acid esters and other additives are described.
＜1-5-1. particular carbon acid esters 〉
The particular carbon acid esters is the carbonic ester that one of has in unsaturated bond and the halogen atom at least, and the particular carbon acid esters can only have unsaturated bond, also can only have halogen atom, can also have unsaturated bond and halogen atom simultaneously.
Molecular weight for the particular carbon acid esters there is no particular restriction, can be any molecular weight in the scope of not obvious destruction the present invention's 1 effect, but is generally more than 50, is preferably more than 80, and be generally below 250, be preferably below 150.When molecular weight was excessive, the dissolubility of particular carbon acid esters in nonaqueous electrolytic solution reduced, and may cause being difficult to demonstrate effect of sufficient.
In addition, do not have particular restriction yet, can select known method manufacturing arbitrarily for the preparation method of particular carbon acid esters.
In addition, can make in the present invention 1 the nonaqueous electrolytic solution and contain any a kind of particular carbon acid esters separately, also can with combination in any and and ratio contain simultaneously more than 2 kinds.
In addition, for the particular carbon acid esters without limits with respect to the combined amount of the present invention 1 nonaqueous electrolytic solution, in the scope of not obvious destruction the present invention's 1 effect can be any combined amount, but nonaqueous electrolytic solution with respect to the present invention 1, the ideal concentration of contained particular carbon acid esters be generally 0.01 weight % above, be preferably 0.1 weight % above, more preferably more than the 0.3 weight %, and be generally 70 weight % following, be preferably 50 weight % following, more preferably below the 40 weight %.
If be lower than the lower limit of this scope, then when the nonaqueous electrolytic solution with the present invention 1 is used for rechargeable nonaqueous electrolytic battery, may causes this rechargeable nonaqueous electrolytic battery to be difficult to demonstrate sufficient cycle characteristics and improve effect.In addition, when the ratio of particular carbon acid esters was excessive, when the present invention 1 nonaqueous electrolytic solution was used for rechargeable nonaqueous electrolytic battery, the high temperature preservation characteristics of this rechargeable nonaqueous electrolytic battery and trickle charge characteristic had the trend of reduction, especially gas generated increasing, capability retention descends.
(1-5-1-1. unsaturated carbon acid esters)
In the present invention 1 particular carbon acid esters, as the carbonic ester with unsaturated bond (below, sometimes abbreviate " unsaturated carbon acid esters " as), then there is not other restriction so long as have the carbonic ester of carbon-to-carbon unsaturated bonds such as carbon-to-carbon double bond, carbon-to-carbon triple bond, can use unsaturated carbon acid esters arbitrarily.It is pointed out that the carbonic ester with aromatic rings also belongs to the carbonic ester with unsaturated bond.
As the example of unsaturated carbon acid esters, can enumerate the vinylene carbonate derivatives class, had ethylene carbonate derivative class that the substituting group of aromatic rings or carbon-to-carbon unsaturated bond replaces, carbonic acid phenyl ester class, ethylene carbonate class, allyl carbonate class etc.
As the object lesson of vinylene carbonate derivatives class, can enumerate vinylene carbonate, methyl carbonic acid vinylene, 4,5-dimethyl vinylene carbonate, phenyl-carbonic acid vinylene, 4,5-diphenyl vinylene carbonate, catechol carbonic ester etc.
The object lesson of the ethylene carbonate derivative class that replaces as substituting group with aromatic rings or carbon-to-carbon unsaturated bond, can enumerate vinylethylene carbonate, 4,5-divinyl ethylene carbonate, phenyl-carbonic acid ethyl, 4,5-diphenyl ethylene carbonate etc.
As the object lesson of carbonic acid phenyl ester class, can enumerate diphenyl carbonate, carbonic acid ethyl phenyl ester, carbonic acid aminomethyl phenyl ester, carbonic acid tert-butyl-phenyl ester etc.
As the object lesson of ethylene carbonate class, can enumerate divinyl carbonate, carbonic acid methyl ethylene ester etc.
As the object lesson of allyl carbonate class, can enumerate carbonic acid diallyl, carbonic acid methacrylic ester etc.
In these unsaturated carbon acid esters; as the particular carbon acid esters; preferred vinylene carbonate derivatives class, had the ethylene carbonate derivative class of the substituting group replacement of aromatic rings or carbon-to-carbon unsaturated bond; vinylene carbonate, 4 particularly; 5-diphenyl vinylene carbonate, 4; 5-dimethyl vinylene carbonate, vinylethylene carbonate, owing to can form stable interface protection tunicle, thereby be more preferably use.
(1-5-1-2. halo carbonic ester)
On the other hand, in the related particular carbon acid esters of the present invention 1, as the carbonic ester with halogen atom (below, abbreviate " halo carbonic ester " sometimes as), then there is no other particular restriction so long as have the carbonic ester of halogen atom, can use halo carbonic ester arbitrarily.
As the object lesson of halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom.Wherein, preferred fluorine atom or chlorine atom, especially preferred fluorine atom.In addition, the halogen atom number that the halo carbonic ester is had needs only is not then having particular restriction more than 1, but is generally below 6, is preferably below 4.When the halo carbonic ester had a plurality of halogen atom, these halogen atoms can be mutually the same, also can be different.
As the example of halo carbonic ester, can enumerate ethylene carbonate derivative class, dimethyl carbonate derivatives class, methyl ethyl carbonate derivatives class, diethyl carbonate derivatives class etc.
Object lesson as the ethylene carbonate derivative class, can enumerate: the fluorine ethylene carbonate, vinylene carbonate, 4,4-difluoro ethylene carbonate, 4,5-difluoro ethylene carbonate, 4,4-two vinylene carbonates, 4,5-two vinylene carbonates, 4-fluoro-4-methyl carbonic acid ethyl, 4-chloro-4-methyl carbonic acid ethyl, 4,5-two fluoro-4-methyl carbonic acid ethyls, 4,5-two chloro-4-methyl carbonic acid ethyls, 4-fluoro-5-methyl carbonic acid ethyl, 4-chloro-5-methyl carbonic acid ethyl, 4,4-two fluoro-5-methyl carbonic acid ethyls, 4,4-two chloro-5-methyl carbonic acid ethyls, 4-(methyl fluoride) ethylene carbonate, 4-(chloromethyl) ethylene carbonate, 4-(difluoromethyl) ethylene carbonate, 4-(dichloromethyl) ethylene carbonate, 4-(trifluoromethyl) ethylene carbonate, 4-(trichloromethyl) ethylene carbonate, 4-(methyl fluoride)-4-fluorine ethylene carbonate, 4-(chloromethyl)-4-vinylene carbonate, 4-(methyl fluoride)-5-fluorine ethylene carbonate, 4-(chloromethyl)-5-vinylene carbonate, 4-fluoro-4,5-dimethyl ethylene carbonate, 4-chloro-4,5-dimethyl ethylene carbonate, 4,5-two fluoro-4,5-dimethyl ethylene carbonate, 4,5-two chloro-4,5-dimethyl ethylene carbonate, 4,4-two fluoro-5,5-dimethyl ethylene carbonate, 4,4-two chloro-5,5-dimethyl ethylene carbonate etc.
As the object lesson of dimethyl carbonate derivatives class, can enumerate: carbonic acid fluoromethane methyl ester, carbonic acid methyl difluoromethyl ester, carbonic acid methyl trifluoro methyl ester, carbonic acid two (methyl fluoride) ester, carbonic acid two (difluoromethyl) ester, carbonic acid two (trifluoromethyl) ester, carbonic acid methyl chloride methyl ester, carbonic acid methyl dichloro methyl ester, carbonic acid methyl trichloromethyl ester, carbonic acid two (chloromethyl) ester, carbonic acid two (dichloromethyl) ester, carbonic acid two (trichloromethyl) ester etc.
Object lesson as the methyl ethyl carbonate derivatives class, can enumerate: carbonic acid methyl 2-fluoro ethyl ester, carbonic acid ethyl methyl fluoride ester, carbonic acid methyl 2,2-difluoro ethyl ester, carbonic acid methyl fluoride 2-fluoro ethyl ester, carbonic acid ethyl difluoro methyl ester, carbonic acid methyl 2,2,2-trifluoroethyl ester, carbonic acid methyl fluoride 2,2-difluoro ethyl ester, carbonic acid difluoromethyl 2-fluoro ethyl ester, carbonic acid ethyl methyl ester trifluoroacetate, carbonic acid methyl 2-chloro-ethyl ester, carbonic acid ethyl chloromethyl ester, carbonic acid methyl 2,2-Dichloroethyl ester, carbonic acid chloromethyl 2-chloro-ethyl ester, carbonic acid ethyl dichloromethyl ester, carbonic acid methyl 2,2,2-three chloro-ethyl esters, carbonic acid chloromethyl 2,2-Dichloroethyl ester, carbonic acid dichloromethyl 2-chloro-ethyl ester, carbonic acid ethyl trichloromethyl ester etc.
Object lesson as the diethyl carbonate derivatives class, can enumerate: carbonic acid ethyl (2-fluoro ethyl) ester, carbonic acid ethyl (2,2-two fluoro ethyls) ester, carbonic acid two (2-fluoro ethyl) ester, carbonic acid ethyl (2,2, the 2-trifluoroethyl) ester, carbonic acid 2,2-two fluoro ethyls-2 '-fluoro ethyl ester, carbonic acid two (2,2-two fluoro ethyls) ester, carbonic acid 2,2,2-trifluoroethyl-2 '-fluoro ethyl ester, carbonic acid 2,2,2-trifluoroethyl-2 ', 2 '-difluoro ethyl ester, carbonic acid two (2,2, the 2-trifluoroethyl) ester, carbonic acid ethyl (2-chloroethyl) ester, carbonic acid ethyl (2, the 2-Dichloroethyl) ester, carbonic acid two (2-chloroethyl) ester, carbonic acid ethyl (2,2,2-three chloroethyls) ester, carbonic acid 2,2-Dichloroethyl-2 '-chloro-ethyl ester, carbonic acid two (2, the 2-Dichloroethyl) ester, carbonic acid 2,2,2-three chloroethyls-2 '-chloro-ethyl ester, carbonic acid 2,2,2-three chloroethyls-2 ', 2 '-Dichloroethyl ester, carbonic acid two (2,2,2-three chloroethyls) ester etc.
In above-mentioned halo carbonic ester; the carbonic ester that preferably has fluorine atom; the ethylene carbonate derivative class that more preferably has fluorine atom; particularly; because when using fluorine ethylene carbonate, 4-(methyl fluoride) ethylene carbonate, 4; 4-difluoro ethylene carbonate, 4 can form interface protection tunicle during 5-difluoro ethylene carbonate, thereby more preferred.
(1-5-1-3. halo unsaturated carbon acid esters)
In addition, as the particular carbon acid esters, can also use the carbonic ester (it suitably being abbreviated as " halo unsaturated carbon acid esters ") that has unsaturated bond and halogen atom simultaneously.As halo unsaturated carbon acid esters, there is no particular restriction, in the scope of the effect of significantly not destroying the present invention 1, can use halo unsaturated carbon acid esters arbitrarily.
As the example of halo unsaturated carbon acid esters, can enumerate the vinylene carbonate derivatives class, had ethylene carbonate derivative class that the substituting group of aromatic rings or carbon-to-carbon unsaturated bond replaces, allyl carbonate class etc.
As the object lesson of vinylene carbonate derivatives class, can enumerate: fluorine vinylene carbonate, 4-fluoro-5-methyl carbonic acid vinylene, 4-fluoro-5-phenyl-carbonic acid vinylene, 4-(trifluoromethyl) vinylene carbonate, chlorine vinylene carbonate, 4-chloro-5-methyl carbonic acid vinylene, 4-chloro-5-phenyl-carbonic acid vinylene, 4-(trichloromethyl) vinylene carbonate etc.
The object lesson of the ethylene carbonate derivative class that replaces as substituting group with aromatic rings or carbon-to-carbon unsaturated bond, can enumerate: 4-fluoro-4-vinylethylene carbonate, 4-fluoro-5-vinylethylene carbonate, 4,4-two fluoro-4-vinylethylene carbonates, 4,5-two fluoro-4-vinylethylene carbonates, 4-chloro-5-vinylethylene carbonate, 4,4-two chloro-4-vinylethylene carbonates, 4,5-two chloro-4-vinylethylene carbonates, 4-fluoro-4,5-divinyl ethylene carbonate, 4,5-two fluoro-4,5-divinyl ethylene carbonate, 4-chloro-4,5-divinyl ethylene carbonate, 4,5-two chloro-4,5-divinyl ethylene carbonate, 4-fluoro-4-phenyl-carbonic acid ethyl, 4-fluoro-5-phenyl-carbonic acid ethyl, 4,4-two fluoro-5-phenyl-carbonic acid ethyls, 4,5-two fluoro-4-phenyl-carbonic acid ethyls, 4-chloro-4-phenyl-carbonic acid ethyl, 4-chloro-5-phenyl-carbonic acid ethyl, 4,4-two chloro-5-phenyl-carbonic acid ethyls, 4,5-two chloro-4-phenyl-carbonic acid ethyls, 4,5-two fluoro-4,5-diphenyl ethylene carbonate, 4,5-two chloro-4,5-diphenyl ethylene carbonate etc.
Object lesson as carbonic acid phenylester class, can enumerate: carbonic acid methyl fluoride phenylester, carbonic acid 2-fluoro ethyl phenylester, carbonic acid 2,2-difluoro ethyl phenyl ester, carbonic acid 2,2,2-trifluoroethyl phenylester, carbonic acid chloromethyl phenyl ester, carbonic acid 2-chloroethyl phenylester, carbonic acid 2,2-Dichloroethyl phenyl ester, carbonic acid 2,2,2-trichlorine ethyl phenyl ester etc.
Object lesson as the ethylene carbonate class, can enumerate: carbonic acid methyl fluoride vinyl esters, carbonic acid 2-fluoro ethyl vinyl esters, carbonic acid 2,2-difluoro cyclic olefin copolymers, ethylvinyl, carbonic acid 2,2,2-trifluoroethyl vinyl esters, carbonic acid chloromethyl vinyl esters, carbonic acid 2-chloroethyl vinyl esters, carbonic acid 2,2-Dichloroethyl vinyl esters, carbonic acid 2,2,2-trichlorine cyclic olefin copolymers, ethylvinyl etc.
Object lesson as the allyl carbonate class, can enumerate: carbonic acid methyl fluoride allyl ester, carbonic acid 2-fluoro ethyl allyl ester, carbonic acid 2,2-difluoro allyl ethyl ester, carbonic acid 2,2,2-trifluoroethyl allyl ester, carbonic acid chloromethyl allyl ester, carbonic acid 2-chloroethyl allyl ester, carbonic acid 2,2-Dichloroethyl allyl ester, carbonic acid 2,2,2-trichlorine allyl ethyl ester etc.
In the example of above-mentioned halo unsaturated carbon acid esters, as the particular carbon acid esters, especially preferred vinylene carbonate, vinylethylene carbonate, the fluorine ethylene carbonate and 4 that uses the better effects if when being selected from independent the use, the compound more than a kind in 5-difluoro ethylene carbonate and their derivative.
Other additive of＜1-5-2. 〉
Below, describe at the additive beyond the particular carbon acid esters.As the additive beyond the particular carbon acid esters, can enumerate overcharges prevents agent, be used for improving the capacity retention performance after high temperature is preserved and the auxiliary agent of cycle characteristics etc.
＜1-5-2-1. overcharges and prevents agent 〉
Prevent the object lesson of agent as overcharging, can enumerate:
Toluene derivative such as toluene, dimethylbenzene;
Non-replacements such as biphenyl, 2-methyl biphenyl, 3-methyl biphenyl, 4-methyl biphenyl or the biphenyl derivatives that is replaced by alkyl;
Non-replacements such as ortho-terphenyl, meta-terphenyl, para-terpheny or the terphenyl derivative that is replaced by alkyl;
The partial hydrogenation thing of non-replacement or the terphenyl derivative that replaced by alkyl;
Cycloalkyl benzene derivatives such as cyclopenta benzene, cyclohexyl benzene;
Isopropylbenzene, 1,3-diisopropyl benzene, 1,4-diisopropyl benzene etc. has the benzene derivative of the tertiary carbon of Direct Bonding on phenyl ring;
Tert-butyl benzene, tert-amyl benzene, uncle's hexyl benzene etc. have the benzene derivative of the quaternary carbon of Direct Bonding on phenyl ring;
Diphenyl ether, dibenzofurans etc. have the aromatic compounds such as aromatic compound of oxygen atom; In aromatic compound.
In addition, prevent the object lesson of agent, can also enumerate: fluorobenzene, toluene fluoride, benzotrifluoride, 2-fluorine biphenyl, adjacent cyclohexyl fluorobenzene, the partially fluorinated thing of above-mentioned aromatic compounds such as cyclohexyl fluorobenzene as overcharging of other; 2,4-difluoroanisole, 2,5-difluoroanisole, 1, fluorine-containing benzyl ether compounds such as 6-difluoroanisole etc.
Need to prove that these overcharge and prevent that agent from can use a kind separately, also can use simultaneously more than 2 kinds with combination in any.In addition, when using simultaneously, belong to the compound of same classification in the above-mentioned example of use capable of being combined, also can be used in combination different classes of compound with combination in any.
Object lesson when being used in combination different classes of compound, can enumerate:
Toluene derivative and biphenyl derivatives;
Toluene derivative and terphenyl derivative;
The partial hydrogenation thing of toluene derivative and terphenyl derivative;
Toluene derivative and cycloalkyl benzene derivative;
Toluene derivative and benzene derivative with Direct Bonding tertiary carbon on phenyl ring;
Toluene derivative and benzene derivative with Direct Bonding quaternary carbon on phenyl ring;
Toluene derivative and aromatic compound with oxygen atom;
The partially fluorinated thing of toluene derivative and aromatic compound;
Toluene derivative and fluorine-containing benzyl ether compounds;
Biphenyl derivatives and terphenyl derivative;
The partial hydrogenation thing of biphenyl derivatives and terphenyl derivative;
Biphenyl derivatives and cycloalkyl benzene derivative;
Biphenyl derivatives and benzene derivative with Direct Bonding tertiary carbon on phenyl ring;
Biphenyl derivatives and benzene derivative with Direct Bonding quaternary carbon on phenyl ring;
Biphenyl derivatives and aromatic compound with oxygen atom;
The partially fluorinated thing of biphenyl derivatives and aromatic compound;
Biphenyl derivatives and fluorine-containing benzyl ether compounds;
The partial hydrogenation thing of terphenyl derivative and terphenyl derivative;
Terphenyl derivative and cycloalkyl benzene derivative;
Terphenyl derivative and benzene derivative with Direct Bonding tertiary carbon on phenyl ring;
Terphenyl derivative and benzene derivative with Direct Bonding quaternary carbon on phenyl ring;
Terphenyl derivative and aromatic compound with oxygen atom;
The partially fluorinated thing of terphenyl derivative and aromatic compound;
Terphenyl derivative and fluorine-containing benzyl ether compounds;
The partial hydrogenation thing of terphenyl derivative and cycloalkyl benzene derivative;
The partial hydrogenation thing of terphenyl derivative and benzene derivative with Direct Bonding tertiary carbon on phenyl ring;
The partial hydrogenation thing of terphenyl derivative and benzene derivative with Direct Bonding quaternary carbon on phenyl ring;
The partial hydrogenation thing of terphenyl derivative and aromatic compound with oxygen atom;
The partial hydrogenation thing of terphenyl derivative and the partially fluorinated thing of aromatic compound;
The partial hydrogenation thing of terphenyl derivative and fluorine-containing benzyl ether compounds;
Cycloalkyl benzene derivative and benzene derivative with Direct Bonding tertiary carbon on phenyl ring;
Cycloalkyl benzene derivative and benzene derivative with Direct Bonding quaternary carbon on phenyl ring;
Cycloalkyl benzene derivative and aromatic compound with oxygen atom;
The partially fluorinated thing of cycloalkyl benzene derivative and aromatic compound;
Cycloalkyl benzene derivative and fluorine-containing benzyl ether compounds;
Have the benzene derivative and benzene derivative with Direct Bonding quaternary carbon on phenyl ring of Direct Bonding at the tertiary carbon on the phenyl ring;
Benzene derivative and aromatic compound with Direct Bonding tertiary carbon on phenyl ring with oxygen atom;
Have the benzene derivative of the tertiary carbon of Direct Bonding on phenyl ring and the partially fluorinated thing of aromatic compound;
Benzene derivative and fluorine-containing benzyl ether compounds with Direct Bonding tertiary carbon on phenyl ring;
Benzene derivative and aromatic compound with Direct Bonding quaternary carbon on phenyl ring with oxygen atom;
Have the benzene derivative of the quaternary carbon of Direct Bonding on phenyl ring and the partially fluorinated thing of aromatic compound;
Benzene derivative and fluorine-containing benzyl ether compounds with Direct Bonding quaternary carbon on phenyl ring;
Have the aromatic compound of oxygen atom and the partially fluorinated thing of aromatic compound;
Aromatic compound and fluorine-containing benzyl ether compounds with oxygen atom;
The partially fluorinated thing of aromatic compound and fluorine-containing benzyl ether compounds.
Object lesson as combinations thereof, can be listed below: the combination of biphenyl and ortho-terphenyl, the combination of biphenyl and meta-terphenyl, the combination of the partial hydrogenation thing of biphenyl and terphenyl derivative, the combination of biphenyl and isopropylbenzene, the combination of biphenyl and cyclopenta benzene, the combination of biphenyl and cyclohexyl benzene, the combination of biphenyl and tert-butyl benzene, the combination of biphenyl and tert-amyl benzene, the combination of biphenyl and diphenyl ether, the combination of biphenyl and dibenzofurans, the combination of biphenyl and fluorobenzene, the combination of biphenyl and benzotrifluoride, the combination of biphenyl and 2-fluorine biphenyl, the combination of biphenyl and adjacent fluorine cyclohexyl benzene, biphenyl and to the combination of fluorine cyclohexyl benzene, biphenyl and 2, the combination of 4-difluoroanisole;
The combination of the partial hydrogenation thing of ortho-terphenyl and terphenyl derivative, the combination of ortho-terphenyl and isopropylbenzene, the combination of ortho-terphenyl and cyclopenta benzene, the combination of ortho-terphenyl and cyclohexyl benzene, the combination of ortho-terphenyl and tert-butyl benzene, the combination of ortho-terphenyl and tert-amyl benzene, the combination of ortho-terphenyl and diphenyl ether, the combination of ortho-terphenyl and dibenzofurans, the combination of ortho-terphenyl and fluorobenzene, the combination of ortho-terphenyl and benzotrifluoride, the combination of ortho-terphenyl and 2-fluorine biphenyl, the combination of ortho-terphenyl and adjacent fluorine cyclohexyl benzene, ortho-terphenyl and to the combination of fluorine cyclohexyl benzene, ortho-terphenyl and 2, the combination of 4-difluoroanisole;
The combination of the partial hydrogenation thing of meta-terphenyl and terphenyl derivative, the combination of meta-terphenyl and isopropylbenzene, the combination of meta-terphenyl and cyclopenta benzene, the combination of meta-terphenyl and cyclohexyl benzene, the combination of meta-terphenyl and tert-butyl benzene, the combination of meta-terphenyl and tert-amyl benzene, the combination of meta-terphenyl and diphenyl ether, the combination of meta-terphenyl and dibenzofurans, the combination of meta-terphenyl and fluorobenzene, the combination of meta-terphenyl and benzotrifluoride, the combination of meta-terphenyl and 2-fluorine biphenyl, the combination of meta-terphenyl and adjacent fluorine cyclohexyl benzene, meta-terphenyl and to the combination of fluorine cyclohexyl benzene, meta-terphenyl and 2, the combination of 4-difluoroanisole;
The partial hydrogenation thing of terphenyl derivative and the combination of isopropylbenzene, the partial hydrogenation thing of terphenyl derivative and the combination of cyclopenta benzene, the partial hydrogenation thing of terphenyl derivative and the combination of cyclohexyl benzene, the partial hydrogenation thing of terphenyl derivative and the combination of tert-butyl benzene, the partial hydrogenation thing of terphenyl derivative and the combination of tert-amyl benzene, the partial hydrogenation thing of terphenyl derivative and the combination of diphenyl ether, the partial hydrogenation thing of terphenyl derivative and the combination of dibenzofurans, the partial hydrogenation thing of terphenyl derivative and the combination of fluorobenzene, the partial hydrogenation thing of terphenyl derivative and the combination of benzotrifluoride, the combination of the partial hydrogenation thing of terphenyl derivative and 2-fluorine biphenyl, the partial hydrogenation thing of terphenyl derivative and the combination of adjacent fluorine cyclohexyl benzene, the partial hydrogenation thing of terphenyl derivative and to the combination of fluorine cyclohexyl benzene, the partial hydrogenation thing and 2 of terphenyl derivative, the combination of 4-difluoroanisole;
The combination of combination, isopropylbenzene and the adjacent fluorine cyclohexyl benzene of the combination of the combination of the combination of the combination of the combination of the combination of the combination of the combination of isopropylbenzene and cyclopenta benzene, isopropylbenzene and cyclohexyl benzene, isopropylbenzene and tert-butyl benzene, isopropylbenzene and tert-amyl benzene, isopropylbenzene and diphenyl ether, isopropylbenzene and dibenzofurans, isopropylbenzene and fluorobenzene, isopropylbenzene and benzotrifluoride, isopropylbenzene and 2-fluorine biphenyl, isopropylbenzene and to combination, the isopropylbenzene and 2 of fluorine cyclohexyl benzene, the combination of 4-difluoroanisole;
The combination of combination, cyclohexyl benzene and the adjacent fluorine cyclohexyl benzene of the combination of the combination of the combination of the combination of the combination of the combination of cyclohexyl benzene and tert-butyl benzene, cyclohexyl benzene and tert-amyl benzene, cyclohexyl benzene and diphenyl ether, cyclohexyl benzene and dibenzofurans, cyclohexyl benzene and fluorobenzene, cyclohexyl benzene and benzotrifluoride, cyclohexyl benzene and 2-fluorine biphenyl, cyclohexyl benzene and to combination, the cyclohexyl benzene and 2 of fluorine cyclohexyl benzene, the combination of 4-difluoroanisole;
The combination of combination, tert-butyl benzene and the adjacent fluorine cyclohexyl benzene of the combination of the combination of the combination of the combination of the combination of tert-butyl benzene and tert-amyl benzene, tert-butyl benzene and diphenyl ether, tert-butyl benzene and dibenzofurans, tert-butyl benzene and fluorobenzene, tert-butyl benzene and benzotrifluoride, tert-butyl benzene and 2-fluorine biphenyl, tert-butyl benzene and to combination, the tert-butyl benzene and 2 of fluorine cyclohexyl benzene, the combination of 4-difluoroanisole;
The combination of combination, tert-amyl benzene and the adjacent fluorine cyclohexyl benzene of the combination of the combination of the combination of the combination of tert-amyl benzene and diphenyl ether, tert-amyl benzene and dibenzofurans, tert-amyl benzene and fluorobenzene, tert-amyl benzene and benzotrifluoride, tert-amyl benzene and 2-fluorine biphenyl, tert-amyl benzene and to combination, the tert-amyl benzene and 2 of fluorine cyclohexyl benzene, the combination of 4-difluoroanisole;
The combination of diphenyl ether and dibenzofurans, the combination of diphenyl ether and fluorobenzene, the combination of diphenyl ether and benzotrifluoride, the combination of diphenyl ether and 2-fluorine biphenyl, the combination of diphenyl ether and adjacent fluorine cyclohexyl benzene, diphenyl ether and to the combination of fluorine cyclohexyl benzene, diphenyl ether and 2, the combination of 4-difluoroanisole, the combination of dibenzofurans and fluorobenzene, the combination of dibenzofurans and benzotrifluoride, the combination of dibenzofurans and 2-fluorine biphenyl, the combination of dibenzofurans and adjacent fluorine cyclohexyl benzene, dibenzofurans and to the combination of fluorine cyclohexyl benzene, dibenzofurans and 2, the combination of 4-difluoroanisole;
The combination of combination, fluorobenzene and the adjacent fluorine cyclohexyl benzene of the combination of fluorobenzene and benzotrifluoride, fluorobenzene and 2-fluorine biphenyl, fluorobenzene and to combination, the fluorobenzene and 2 of fluorine cyclohexyl benzene, the combination of 4-difluoroanisole;
The combination of the combination of benzotrifluoride and 2-fluorine biphenyl, benzotrifluoride and adjacent fluorine cyclohexyl benzene, benzotrifluoride and to combination, the benzotrifluoride and 2 of fluorine cyclohexyl benzene, the combination of 4-difluoroanisole;
The combination of 2-fluorine biphenyl and adjacent fluorine cyclohexyl benzene, 2-fluorine biphenyl and to combination, the 2-fluorine biphenyl and 2 of fluorine cyclohexyl benzene, the combination of 4-difluoroanisole;
Adjacent fluorine cyclohexyl benzene and to combination, the adjacent fluorine cyclohexyl benzene and 2 of fluorine cyclohexyl benzene, the combination of 4-difluoroanisole, to fluorine cyclohexyl benzene and 2, the combination of 4-difluoroanisole, or the like.
When containing, the present invention 1 nonaqueous electrolytic solution overcharges when preventing agent, in the scope of not obvious destruction the present invention's 1 effect, its concentration can be any concentration, but with respect to the nonaqueous electrolytic solution total amount, its ideal concentration is generally the scope of 0.1 weight %～5 weight %.
In the scope of not obvious destruction the present invention's 1 effect, make to contain to overcharge in the present invention 1 the nonaqueous electrolytic solution and prevent agent; even can just in case take place using method mistake or charging device unusual etc. at additives for overcharge protection circuit non-normal working situation and when causing overcharging; also can improve the fail safe of rechargeable nonaqueous electrolytic battery, therefore preferred.
＜1-5-2-2. auxiliary agent 〉
On the other hand, as the object lesson of the auxiliary agent that is used to improve capacity retention performance after high temperature is preserved and cycle characteristics, can enumerate: the acid anhydrides of dicarboxylic acids such as butanedioic acid, maleic acid, phthalic acid; Carbonic acid erythrite ester (エ リ ス リ タ Application カ one ボ ネ one ト), the carbonic acid spiral shell-two-dimethylene ester carbonate products except the carbonic ester that is equivalent to the particular carbon acid esters such as (ス ピ ロ-PVC ス-ジ メ チ レ Application カ one ボ ネ one ト);
Sulfurous acid glycol ester, 1,3-N-morpholinopropanesulfonic acid lactone, 1,4-butyl sultone, methyl mesylate, 1,4-dimethane sulfonoxybutane, sulfolane, cyclobufene sultone, dimethyl sulfone, diphenyl sulfone, methyl phenyl sulfone, dibutyl disulfide, dicyclohexyldisulfide, tetramethylthiuram monosulfide, N, N-dimethyl methyl sulfonamide, N, sulfur-containing compounds such as N-diethyl Methanesulfomide;
1-Methyl-2-Pyrrolidone, 1-methyl-2-piperidones, 3-methyl-2-oxazolidone, 1, nitrogen-containing compounds such as 3-dimethyl-2-imidazolidinone, N-methyl succimide;
Hydrocarbon compounds such as heptane, octane, cycloheptane;
Aromatic fluorine compounds such as fluorobenzene, two fluorobenzene, benzotrifluoride etc.
The preparation method of＜1-6. nonaqueous electrolytic solution 〉
The present invention 1 nonaqueous electrolytic solution can prepare by " mono-fluor phosphate and/or difluorophosphoric acid salt ", " the iron group compound " that dissolves electrolyte, the present invention 1 in nonaqueous solvents, " other auxiliary agent " that uses as required.
When the preparation nonaqueous electrolytic solution, preferably to the various raw materials of nonaqueous electrolytic solution, promptly lithium salts, the present invention's 1 mono-fluor phosphate and/or difluorophosphoric acid salt, iron group compound, nonaqueous solvents and other auxiliary agent dewater in advance.As the degree of dehydration, wish usually to dewater to 50ppm, preferably dewater to 30ppm.Need to prove that said in this manual ppm is meant the ratio based on weight basis.
If there is water in the nonaqueous electrolytic solution, the reaction of electrolysis, water and the lithium metal of water, the hydrolysis of lithium salts etc. then may take place, not preferred.Dehydration method is not particularly limited, and for example, when the dehydration object is liquid such as nonaqueous solvents, can use molecular sieve etc.In addition, when the dehydration object is solid such as electrolyte, can take place to carry out drying below the temperature of decomposing.When the iron group compound is hydrate, the iron group compound can be dissolved in the nonaqueous solvents, and then use molecular sieve etc. to dewater.
[2. rechargeable nonaqueous electrolytic battery]
The present invention 1 rechargeable nonaqueous electrolytic battery have the invention described above 1 nonaqueous electrolytic solution and can occlusion and emit the positive pole and the negative pole of ion.
＜2-1. battery structure 〉
For other structure except negative pole and nonaqueous electrolytic solution in the present invention 1 the rechargeable nonaqueous electrolytic battery, with known rechargeable nonaqueous electrolytic battery was identical in the past, has usually and clip the perforated membrane (dividing plate) that soaks into the nonaqueous electrolytic solution that the present invention 1 is arranged and be accommodated in form in the shell (packaging body) with anodal and negative pole lamination and with them.Thereby, there is not particular restriction for the shape of the present invention 1 rechargeable nonaqueous electrolytic battery, can be cylindrical shape, square, stacked shape, coin shape, arbitrary shape such as large-scale.
＜2-2. nonaqueous electrolytic solution 〉
As nonaqueous electrolytic solution, can use the nonaqueous electrolytic solution of the invention described above 1.Need to prove, in the scope of the main points that do not depart from the present invention 1, can also in the present invention 1 nonaqueous electrolytic solution, mix other nonaqueous electrolytic solution.
＜2-3. negative pole 〉
Below, describe at the negative electrode active material that is used for negative pole.As negative electrode active material, so long as electrochemically occlusion/emit the negative electrode active material of lithium ion, then there is not particular restriction.As its object lesson, can enumerate carbonaceous material, alloy type material, contain the metallic composite oxides material of lithium etc.
＜2-3-1. carbonaceous material 〉
As carbonaceous material as negative electrode active material, because the carbonaceous material that is selected from following (1)～(4) can obtain the well balanced of initial stage irreversible capacity, high current density charge-discharge characteristic, thereby preferred.In addition, the carbonaceous material of (1)～(4) can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.The carbonaceous material of described (1)～(4) is: (1) native graphite; (2) in 400～3200 ℃ scope, artificial carbon's metallic substance and Delanium material carried out heat treatment more than 1 time and the carbonaceous material that obtains; (3) negative electrode active material layer is by having more than at least 2 kinds that different crystalline carbonaceous constitute and/or its different crystalline carbonaceous have the carbonaceous material at contacted interface; (4) negative electrode active material layer is made of the carbonaceous that has different orientation more than at least 2 kinds and/or the carbonaceous of its different orientation has the carbonaceous material at contacted interface.
As the artificial carbon's metallic substance of above-mentioned (2) and the object lesson of Delanium material, can enumerate native graphite, coal class coke, petroleum-type coke, coal class pitch, petroleum-type pitch or these pitches are carried out oxidation processes and material, needle coke, pitch coke that obtains and the material with carbon element that their part graphitizations are obtained; But the organic substance of organic thermal decomposition product carbonizations such as furnace black, acetylene black, pitch-based carbon fiber, and they carbide or but the organic substance of charing is dissolved in the small molecular organic solvents such as benzene,toluene,xylene, quinoline, n-hexane and solution that obtains and their carbide etc.
Wherein, but as the organic object lesson of described charing, can enumerate coal class heavy oil such as coal tar asphalt from the maltha to the pitch or dry distillation liquid carburetion; Direct current such as atmospheric resids, decompression residual oil class heavy oil, the ethylene bottom oil of by-product etc. decomposes the class black petroleum products during thermal decompositions such as crude oil, naphtha; And aromatic hydrocarbon such as acenaphthylene, decacyclene, anthracene, phenanthrene; Azophenlyene or acridine etc. contain the heterocyclic compound of nitrogen-atoms; Thiophene, di-thiophene etc. contain the heterocyclic compound of sulphur atom; Polyphenyl such as biphenyl, terphenyl; Organic polymers such as polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral resin, their insoluble handled thing, nitrogenous polyacrylonitrile, polypyrrole; Organic polymers such as the polythiophene of sulfur-bearing, polystyrene; With cellulose, lignin, mannocarolose, polygalacturonic acid, shitosan, sucrose is the natural polymers such as polysaccharide of representative; Thermoplastic resin such as polyphenylene sulfide, polyphenylene oxide; Thermosetting resins such as furfuryl alcohol resin, phenolic resins, imide resin etc.
Structure, rerum natura, the preparation method of＜2-3-2. carbonaceous negative pole 〉
About the character of carbonaceous material, the negative electrode that contains carbonaceous material and electric polarization method, collector body, rechargeable nonaqueous electrolytic battery, preferably satisfy wantonly 1 or multinomial in (1) as follows～(18) simultaneously.
(1) X ray parameter
By adopt learning the method for shaking the d value (interfloor distance) that carbonaceous material carries out the lattice plane (002 face) that X-ray diffraction obtains is generally 0.335～0.340nm, is preferably 0.335～0.338nm, especially is preferably 0.335～0.337nm.In addition, the crystallite size of obtaining by X-ray diffraction that adopt to learn the method for shaking (Lc) be generally 1.0nm above, be preferably 1.5nm above, especially be preferably more than the 2nm.
As the carbonaceous material that obtains with amorphous carbon coated graphite surface, preferably the d value of the lattice plane of obtaining with X-ray diffraction (002 face) is that the graphite of 0.335～0.338nm is as nuclear material, and the d value of the lattice plane of being obtained by X-ray diffraction in its surface attachment (002 face) is greater than the carbonaceous material of this nuclear material, and the d value of nuclear material and the lattice plane (002 face) obtained by X-ray diffraction is counted 99/1～80/20 carbonaceous material greater than the ratio of the carbonaceous material of this nuclear material with weight ratio.When using this carbonaceous material, can produce the negative pole that has high power capacity and be difficult for reacting with electrolyte.
(2) ash content
With respect to the total weight of carbonaceous material, contained ash content is below the 1 weight %, wherein is preferably below the 0.5 weight %, especially is preferably below the 0.1 weight % in the carbonaceous material, and its lower limit is preferably more than 1ppm.If the part by weight of ash content surpasses above-mentioned scope, when discharging and recharging, can cause that the deterioration that can't ignore appears in battery performance because of reacting with nonaqueous electrolytic solution.On the other hand, when being lower than above-mentioned scope, then being necessary for and making cost plenty of time, energy and be used for antipollution equipment, further cause cost to increase.
(3) volume reference average grain diameter
The volume reference average grain diameter of carbonaceous material is to utilize the average grain diameter (median particle diameter) of the volume reference that laser diffraction/scattering method obtains, it typically is 1 μ m above, be preferably 3 μ m above, more preferably 5 μ m above, especially be preferably more than the 7 μ m, and be generally 100 μ m following, be preferably 50 μ m following, more preferably 40 μ m following, more preferably 30 μ m following, especially be preferably below the 25 μ m.If the volume reference average grain diameter is lower than above-mentioned scope, irreversible capacity is increased and causes initial stage battery capacity loss.In addition, when surpassing above-mentioned scope, when utilizing coating to prepare electrode, forming uneven coated face easily, is not preferred sometimes on the battery production process.
The volume reference average grain diameter adopts following method to measure: carbon dust is dispersed in the 0.2 weight % aqueous solution (about 10mL) of polyoxyethylene (20) Span-20 as surfactant, and utilizes laser diffraction/diffuse transmission type particle size distribution meter (the hole field makes the LA-700 that company of institute makes) to measure.To be defined as the volume reference average grain diameter of the present invention 1 carbonaceous material by the median particle diameter that this mensuration is obtained.
(4) Raman R value, Raman half breadth
The value that the Raman R value of carbonaceous material is to use the argon laser Raman spectroscopy to measure, it typically is more than 0.01, be preferably more than 0.03, more preferably more than 0.1, and be generally below 1.5, be preferably below 1.2, more preferably below 1, especially be preferably below 0.5.
When Raman R value was lower than above-mentioned scope, the crystallinity of particle surface was too high, followed to discharge and recharge the site (サ イ ト) that may cause Li to enter interlayer and tail off.That is, the acceptance that may cause charging reduces.In addition, after the coating, when carrying out densification by the compacting anticathode, crystallization along the direction orientation parallel with battery lead plate, may cause load characteristic to reduce easily on collector body.On the other hand, when surpassing above-mentioned scope, the crystallinity of particle surface reduces, and causing increases with the reactivity of nonaqueous electrolytic solution, may cause that efficient reduces or the gas that produces increases.
In addition, for carbonaceous material at 1580cm -1Near Raman half breadth does not have particular restriction, is generally 10cm -1More than, be preferably 15cm -1More than, and be generally 100cm -1Below, be preferably 80cm -1Below, 60cm more preferably -1Below, especially be preferably 40cm -1Below.
When the Raman half breadth was lower than above-mentioned scope, the crystallinity of particle surface was too high, followed to discharge and recharge the site that may cause Li to enter interlayer and tail off.That is, the acceptance that may cause charging reduces.In addition, after the coating, when carrying out densification by the compacting anticathode, crystallization along the direction orientation parallel with battery lead plate, may cause load characteristic to reduce easily on collector body.On the other hand, when surpassing above-mentioned scope, the crystallinity of particle surface reduces, and causing increases with the reactivity of nonaqueous electrolytic solution, may cause that efficient reduces or the gas that produces increases.
The mensuration of Raman spectrum is as described below: use raman spectroscopy device (the raman spectroscopy device that Japanese beam split company makes), sample is fallen naturally and be filled in the cell (cell), surface irradiation argon laser to sample in the pond, make simultaneously cell with the face of laser vertical in rotate, measure thus.Raman spectrum at obtaining is determined at 1580cm -1Near peak P AIntensity I A, with at 1360cm -1Near peak P BIntensity I B, and calculate both strength ratio R (R=I B/ I A).With the Raman R value defined that utilizes this mensuration to obtain Raman R value for carbonaceous material among the present invention 1.In addition, measure resulting Raman spectrum at 1580cm -1Near peak P AHalf breadth, it is defined as the Raman half breadth of carbonaceous material among the present invention 1.
In addition, the condition of above-mentioned Raman mensuration is as follows.
Argon laser wavelength: 514.5nm
Laser power on the sample: 15～25mW
Resolution: 10～20cm -1
Measurement range: 1100cm -1～1730cm -1
Raman R value, Raman half breadth are analyzed: background (background) is handled
Smoothly (smoothing) handles: simple average, convolution 5 points (convolution 5 point)
(5) BET specific area
The value of the BET specific area of the carbonaceous material that employing BET method is measured is generally 0.1m 2G -1More than, be preferably 0.7m 2G -1More than, 1.0m more preferably 2G -1More than, especially be preferably 1.5m 2G -1More than, and be generally 100m 2G -1Below, be preferably 25m 2G -1Below, 15m more preferably 2G -1Below, especially be preferably 10m 2G -1Below.
When the value of BET specific area was lower than this scope, acceptance variation, the lithium of lithium were separated out easily to electrode surface when causing charging easily used as negative material the time, and then may cause that stability reduces.On the other hand, when surpassing this scope, used as negative material the time, cause increasing, being easy to produce more gas, and then may be difficult to obtain desirable battery with the reactivity of nonaqueous electrolytic solution.
Carry out according to following method when adopting BET method measurement the specific area: use surface area meter (the full automatic watch area estimation device that the reason development of big storehouse is made), under nitrogen current, under 350 ℃, sample is carried out 15 minutes predrying backs, uses nitrogen accurately to be adjusted to 0.3 nitrogen helium gas mixture body with respect to atmospheric relative pressure value, measure by 1 method of nitrogen absorption BET that adopts the gas flow method.The specific area of utilizing this mensuration to obtain is defined as the BET specific area of carbonaceous material among the present invention 1.
(6) micropore diameter distributes
The micropore diameter of carbonaceous material distributes and obtains by measuring the mercury amount of being pressed into.Measure as can be known by adopting mercury porosimeter (mercury penetration method), in carbonaceous material, by the particle internal pore of carbonaceous material, because of the particle surface micropore that the concavo-convex and interparticle contact-making surface that causes etc. causes that is uneven is equivalent to the micropore that diameter is 0.01 μ m～1 μ m, preferably have following micropore diameter in the carbonaceous material and distribute: be generally 0.01cm 3G -1More than, be preferably 0.05cm 3G -1More than, 0.1cm more preferably 3G -1More than, and be generally 0.6cm 3G -1Below, be preferably 0.4cm 3G -1Below, 0.3cm more preferably 3G -1Below.
When micropore diameter distributes above above-mentioned scope, when carrying out pole plate, may need a large amount of adhesives.On the other hand, if be lower than above-mentioned scope, then may cause the reduction of high current density charge-discharge characteristic and when discharging and recharging, can't obtain the alleviation effects that electrode expands and shrinks.
In addition, adopt micropore total measurement (volume) that mercury porosimeter (mercury penetration method) is obtained, that diameter is equivalent to the micropore of 0.01 μ m～100 μ m to be generally 0.1cm 3G -1More than, be preferably 0.25cm 3G -1More than, 0.4cm more preferably 3G -1More than, and be generally 10cm 3G -1Below, be preferably 5cm 3G -1Below, 2cm more preferably 3G -1Below.When the micropore total measurement (volume) surpasses above-mentioned scope, when carrying out pole plate, may need a large amount of adhesives.On the other hand, if be lower than above-mentioned scope, then may cause when carrying out pole plate, can't reaching the dispersion effect of thickener or binding agent.
In addition, average micropore diameter be generally 0.05 μ m above, be preferably 0.1 μ m above, more preferably more than the 0.5 μ m, and be generally 50 μ m following, be preferably 20 μ m following, more preferably below the 10 μ m.When average micropore diameter surpasses above-mentioned scope, may need a large amount of adhesives.On the other hand, if be lower than above-mentioned scope, then may cause the high current density charge-discharge characteristic to reduce.
The mercury amount of being pressed into utilizes following method to measure: use mercury void determination instrument (AutoPore9520, Micrometritics company makes) as the device as the mercury porosimeter.As pre-treatment, about 0.2g sample is enclosed powder with in the container, carry out the degassing in 10 minutes at (below the 50 μ mHg) under room temperature, the vacuum.Then, be decompressed to 4psia (about 28kPa), and import mercury, make pressure behind the stage 40000psia of rising to of 4psia (about 28kPa) (about 280MPa), reduce to 25psia (about 170kPa) again.Number of stages in the process of boosting is arranged on more than 80 grades, in each stage, after through the equilibration time in 10 seconds, measures the mercury amount of being pressed into.
Utilize the Washburn formula to be pressed into opisometer and calculate the micropore diameter distribution by the mercury that in said determination, obtains.Here, the surface tension of mercury (γ) is set at 485dynecm -1(1dyne=10 μ N), contact angle (φ) are 140 °.What average micropore diameter used is that the accumulation micro pore volume reaches 50% o'clock micropore diameter.
(7) circularity
When the mensuration circularity was estimated the spherical degree of carbonaceous material, the circular degree was in following ranges.Need to prove that circularity defines with following formula: circularity=(having girth)/(perimeter of particle projection of shape) with the equivalent circular of particle projection of shape area identical.When circularity is 1, become theoretical proper sphere.
Particle diameter is that the circularity of the particle of 3～40 mu m ranges approaches 1 more and unreasonablely thinks in the carbonaceous material, and its circularity is preferably more than 0.1, wherein is preferably more than 0.5, more preferably more than 0.8, more preferably more than 0.85, especially be preferably more than 0.9.
When circularity was big more, the high current density charge-discharge characteristic was excellent more.Thereby when circularity was lower than above-mentioned scope, resistance increased between the reduction of the fillibility of negative electrode active material, particle, may cause short time high current density charge-discharge characteristic to reduce.
Circularity adopts flow-type particle picture analytical equipment (FPIA that Sysmex company makes) to measure.About 0.2g sample is dispersed in the 0.2 weight % aqueous solution (about 50mL) of polyoxyethylene (20) Span-20 as surfactant, and with the ultrasonic wave of 28kHz with the power output irradiation of 60W after 1 minute, specifying 0.6～400 μ m is detection range, and particle diameter is measured at the particle of 3～40 mu m ranges.The circularity of utilizing this mensuration to obtain is defined as the circularity of carbonaceous material among the present invention 1.
There is no particular restriction for the method that improves circularity, but handle particle is converted into and can realize that the shape of inter-particle voids is neatly unified when being applied to electrode body after the sphere by implementing spheroidization, therefore preferred.As the example that spheroidization is handled, can enumerate by applying shearing force, compression stress and come the method for subglobular mechanically, utilize adhesive or adhesive force that particle itself had to carry out the machinery/physical treatment method etc. of the granulation of a plurality of particulates.
(8) real density
The real density of carbonaceous material is generally 1.4gcm -3More than, be preferably 1.6gcm -3More than, 1.8gcm more preferably -3More than, especially be preferably 2.0gcm -3More than, and be generally 2.26gcm -3Below.When real density was lower than above-mentioned scope, the crystallinity of carbon was low excessively, may cause the initial stage irreversible capacity to increase.Need to prove, be limited to the limit value in theory of graphite real density on the above-mentioned scope.
The real density of carbonaceous material is measured by the liquid phase displacement method (hydrometer method) of using butanols.With the value defined that utilizes this mensuration to obtain real density for carbonaceous material among the present invention 1.
(9) tap density
The tap density of carbonaceous material is generally 0.1gcm -3More than, be preferably 0.5gcm -3More than, 0.7gcm more preferably -3More than, especially be preferably 1gcm -3More than, and be preferably 2gcm -3Below, 1.8gcm more preferably -3Below, especially be preferably 1.6gcm -3Below.
If tap density is lower than above-mentioned scope, be difficult to improve packed density during then as negative pole, may cause obtaining the battery of high power capacity.In addition, when surpassing above-mentioned scope, the inter-particle voids in the electrode becomes very few, is difficult to guarantee interparticle conductivity, may cause obtaining desirable battery behavior.
Tap density is measured by following method: make sample drop into 20cm behind the sieve that by mesh is 300 μ m 3The jolt ramming container in, after sample is filled to the upper surface of container, utilize powder density analyzer (for example, the Tap densor that Seishin enterprise-like corporation makes) to carry out the vibration that 1000 times length of stroke is 10mm, volume in the time of thus and sample weight are asked the calculation tap density.The tap density of utilizing this mensuration to calculate is defined as the tap density of carbonaceous material among the present invention 1.
(10) orientation ratio
The orientation ratio of carbonaceous material is generally more than 0.005, is preferably more than 0.01, more preferably more than 0.015, and be generally below 0.67.If orientation ratio is lower than above-mentioned scope, then may cause the high density charge-discharge characteristic to reduce.Need to prove that the upper limit of above-mentioned scope is the limit value in theory of carbonaceous material orientation ratio.
Orientation ratio is to utilize X-ray diffraction to measure after sample is carried out extrusion forming.Be that the 0.47g sample is filled in the make-up machine that diameter is 17mm, at 58.8MNm -2Lower compression obtains formed body, fixes this formed body with clay again, and making itself and the face of measuring with specimen mounting is same, measures thereby carry out X-ray diffraction.Calculate ratio by the peak intensity of (110) diffraction of resulting carbon and (004) diffraction so that (110) diffraction peak intensity/(004) diffraction peak intensity is represented.The orientation ratio that utilizes this mensuration to obtain is defined as the orientation ratio of carbonaceous material among the present invention 1.
The condition determination of X-ray diffraction is as described below.Wherein, " 2 θ " represents the angle of diffraction.
The monochromatic photometer of target: Cu (K alpha ray) graphite
Slit:
Divergent slit=0.5 degree
Be subjected to optical slits=0.15mm
Scatter slit=0.5 degree
Measurement range and step angle/minute:
(110) face: 75 degree≤2 θ≤80 degree 1 are spent/60 seconds
(004) face: 52 degree≤2 θ≤57 degree 1 are spent/60 seconds
(11) draw ratio (powder)
The draw ratio of carbonaceous material is generally more than 1, and be generally below 10, be preferably below 8, more preferably below 5.If draw ratio surpasses above-mentioned scope, may produce striped when then carrying out pole plate, can't obtain uniform coated face, the high current density charge-discharge characteristic reduces.Need to prove the following theory lower bound value that is limited to the carbonaceous material draw ratio of above-mentioned scope.
The mensuration of draw ratio is undertaken by utilizing ESEM that the particle of carbonaceous material is amplified to observe.Selection is fixed on any 50 graphite particles on the thick metal end face below 50 microns, rotation, inclination are fixed with the objective table of these samples, be determined at the major diameter A that carries out 3 dimensions observed carbonaceous material particle when observing and perpendicular minor axis B respectively, and obtain the mean value of A/B.The draw ratio (A/B) of utilizing this mensuration to obtain is defined as the draw ratio of carbonaceous material among the present invention 1.
(12) auxiliary material mixes
So-called auxiliary material mixes, and is meant in negative electrode and/or contains the carbonaceous material of different in kind more than 2 kinds in the negative electrode active material.Described character wherein is meant: be selected from more than one characteristics in X-ray diffraction parameter, median particle diameter, draw ratio, BET specific area, orientation ratio, Raman R value, tap density, real density, micropore distribution, circularity, the ash amount.
As the particularly preferred example that above-mentioned auxiliary material mixes, can enumerate: the volume reference particle size distribution is asymmetric about when being the center with the median particle diameter, it is not equal to contain Raman R value is different more than 2 kinds carbonaceous material and X ray parameter.
One of example of the effect of mixing as auxiliary material can be enumerated: by containing carbonaceous materials such as amorphous carbon such as carbon black, needle coke such as graphite such as native graphite, Delanium (graphite), acetylene black as electric conducting material, resistance is minimized.
When the hybrid conductive material mixes as auxiliary material, can mix a kind separately, also can be more than 2 kinds with combination in any and mixed.In addition, the mixing ratio of electric conducting material and carbonaceous material be generally 0.1 weight % above, be preferably 0.5 weight % above, more preferably more than the 0.6 weight %, and be generally 45 weight % following, be preferably below the 40 weight %.If mixing ratio is lower than above-mentioned scope, then may cause being difficult to obtain to improve the effect of conductivity.In addition, if surpass above-mentioned scope, then may cause the initial stage irreversible capacity to increase.
(13) electrode is made
In the scope of the effect that does not significantly limit the present invention 1, can adopt the method for any known to prepare electrode.For example, can make slurry, and it is coated on the collector body, suppresses after dry and form electrode by in negative electrode active material, adding adhesive, solvent, the thickener that adds as required, electric conducting material, packing material etc.
In the stage before the nonaqueous electrolytic solution injection process of closing on of battery, on the battery on each face the thickness of negative electrode active material layer be generally 15 μ m above, be preferably 20 μ m above, more preferably more than the 30 μ m, and be generally 150 μ m following, be preferably 120 μ m following, more preferably below the 100 μ m.If the thickness of negative electrode active material surpasses this scope,, therefore may cause the high current density charge-discharge characteristic to reduce then because nonaqueous electrolytic solution is difficult to be impregnated into the collector body near interface.On the other hand, if be lower than this scope, then may cause the volume ratio of collector body and negative electrode active material to increase, battery capacity reduces.In addition, negative electrode active material can be carried out the roller moulding and make pellet electrode, or make mosaic electrode by compression forming.
(14) collector body
As the collector body that negative electrode active material is kept, can use known collector body arbitrarily.As the collector body of negative pole, can enumerate for example metal materials such as copper, nickel, stainless steel, nickel-plated steel, consider from processing simplification and cost aspect, especially preferably copper.
In addition, as the shape of collector body, when collector body is metal material, can enumerate for example metal forming, metal cylinder, wire coil, metallic plate, metallic film, expansion alloy, perforated metal, foaming metal etc.Wherein, preferable alloy film, more preferably Copper Foil further preferably utilize rolled copper foil that rolling process obtains and the electrolytic copper foil that utilizes electrolysis to obtain, and any all can be used as collector body and uses in above-mentioned.
In addition, when copper thickness during, can working strength be higher than the copper alloy (phosphor bronze, titanium copper, Corson alloy, Cu-Cr-Zr alloy etc.) of fine copper less than 25 μ m.
In the collector body that constitutes by the Copper Foil that utilizes rolling process to make,,, still be difficult for breaking, applicable to small cylinder shape battery even therefore negative pole is closely curled or be curled into acute angle because the copper crystallization arranges along rolling direction.
Electrolytic copper foil obtains by following method: for example: metal drum is immersed in the nonaqueous electrolytic solution that is dissolved with copper ion, and galvanization when rotating this drum so that copper separates out on the drum surface, obtains electrolytic copper foil thereby it is peeled off.Can also utilize electrolysis that copper is separated out on above-mentioned rolled copper foil surface.Also can carry out roughened or surface treatment (base treatment such as for example, the chromate processing of thickness about number nm～1 μ m, Ti etc.) to the one or both sides of Copper Foil.
The collector body substrate also preferably has following rerum natura.
(14-1) average surface roughness (Ra)
The average surface roughness (Ra) that the negative electrode active material film of the collector body substrate of stipulating in the method for the JISB0601-1994 record forms face does not have particular restriction, be generally 0.05 μ m above, be preferably 0.1 μ m above, more preferably more than the 0.15 μ m, and be generally 1.5 μ m following, be preferably 1.3 μ m following, more preferably below the 1.0 μ m.This be because: when the average surface roughness (Ra) of collector body substrate is in above-mentioned scope, can expect the favorable charge-discharge cycle characteristics; And, big with the interfacial area change of negative electrode active material film, with the adhesiveness raising of negative electrode active material film.Need to prove, higher limit for average surface roughness (Ra) there is no particular restriction, when average surface roughness (Ra) surpasses 1.5 μ m, be difficult to obtain the paper tinsel of thickness practicality when using usually as battery, therefore adopt the average surface roughness (Ra) below the 1.5 μ m usually.
(14-2) hot strength
So-called hot strength is meant the value that needed maximum pull obtained divided by the sectional area of test film when fracture took place test film.Hot strength among the present invention 1 adopts the device and method identical with the record of JISZ2241 (metal material tensile test method) to measure.
Hot strength for the collector body substrate does not have particular restriction, is generally 100Nmm -2More than, be preferably 250Nmm -2More than, 400Nmm more preferably -2More than, especially be preferably 500Nmm -2More than.The value of hot strength is high more then to be preferred more, considers the industry property obtained, and is generally 1000Nmm -2Below.If the high collector body substrate of hot strength then can be suppressed at the be full of cracks of the collector body substrate that is caused by negative electrode active material film expansion in the charge/discharge process, thereby can obtain good cycle characteristics.
(14-3) 0.2% yield strength
So-called 0.2% yield strength is meant to produce 0.2% the necessary load size of plasticity (forever) strain, apply this size loads after, even, still keep 0.2% deformation except that unloading.The 0.2% yield strength utilization device and method identical with measuring hot strength measured.
0.2% yield strength for the collector body substrate there is no particular restriction, is generally 30Nmm -2More than, be preferably 150Nmm -2More than, especially be preferably 300Nmm -2More than.The value of 0.2% yield strength is high more then to be preferred more, from the angle of the industry property obtained, is preferably 900Nmm usually -2Below.If the high collector body substrate of 0.2% yield strength then can be suppressed at the plastic deformation of the collector body substrate that is caused by negative electrode active material film expansion in the charge/discharge process, thereby can obtain good cycle characteristics.
(14-4) thickness of collector body
Collector body can be an any thickness, but be generally 1 μ m above, be preferably 3 μ m above, more preferably more than the 5 μ m, and be generally 1mm following, be preferably 100 μ m following, more preferably below the 50 μ m.When the thickness of metal epithelium during, because intensity decreases, thereby may cause the coating difficulty that becomes less than 1 μ m.In addition, when thickness during greater than 100 μ m, the electrode shape that then may cause reeling etc. deforms.Need to prove that collector body can be netted.
(15) the thickness ratio of collector body and negative electrode active material layer
Thickness ratio for collector body and negative electrode active material layer there is no particular restriction, but the value of " (at the thickness that closes on the negative electrode active material layer on nonaqueous electrolytic solution single before injecting)/(thickness of collector body) " is preferably below 150, more preferably below 20, especially be preferably below 10, and be preferably more than 0.1, more preferably more than 0.4, especially be preferably more than 1.
If collector body surpasses above-mentioned scope with the thickness ratio of negative electrode active material layer, then when high current density discharged and recharged, collector body may cause heat release because of Joule heat.In addition, when the thickness ratio was lower than above-mentioned scope, collector body increased with respect to the volume ratio of negative electrode active material, may cause battery capacity to reduce.
(16) electrode density
Electrode structure when negative electrode active material is made electrode does not have particular restriction, and the density that is present in the negative electrode active material on the collector body is preferably 1gcm -3More than, 1.2gcm more preferably -3More than, especially be preferably 1.3gcm -3More than, and be preferably 2gcm -3Below, 1.9gcm more preferably -3Below, 1.8gcm more preferably -3Below, especially be preferably 1.7gcm -3Below.When the density of the negative electrode active material on being present in collector body surpasses above-mentioned scope, the negative electrode active material particle can be damaged, cause initial stage irreversible capacity increase, nonaqueous electrolytic solution to reduce in the impregnability of collector body/negative electrode active material near interface, and then cause high current density charge-discharge characteristic generation deterioration.In addition, if be lower than above-mentioned scope, then may cause the conductivity between negative electrode active material to reduce, cell resistance increases, and the capacity of unit volume reduces.
(17) adhesive
As the adhesive of bonding negative electrode active material, so long as the material of the solvent-stable that uses when making with respect to nonaqueous electrolytic solution and electrode does not then have particular restriction.
As object lesson, can enumerate resinae macromolecules such as polyethylene, polypropylene, PETG, polymethyl methacrylate, aromatic polyamide, cellulose, NC Nitroncellulose; Rubber-like macromolecules such as SBR (butadiene-styrene rubber), isoprene rubber, butadiene rubber, fluorubber, NBR (acrylonitrile-butadiene rubber), ethylene-propylene rubber; SBS or its hydride; Thermoplastic elastomer (TPE) shape macromolecules such as EPDM (ethylene-propylene-diene terpolymers), SIS/SEBS, SIS or its hydride; Syndiotactic 1, soft resinous macromolecules such as 2-polybutadiene, polyvinyl acetate, vinyl-vinyl acetate copolymer, propylene-alpha-olefin copolymers; Kynoar, polytetrafluoroethylene, fluoridize fluorine family macromolecules such as Kynoar, polytetrafluoroethylene-ethylene copolymer; The polymeric composition with ionic conductivity of alkali metal containing ion (particularly lithium ion) etc.Above-mentioned material can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
As the solvent that is used to form slurry, so long as can dissolve or disperse negative electrode active material, adhesive and as required and the thickener that uses and the solvent of electric conducting material get final product, its kind is not had particular restriction, can use in aqueous solvent or the organic kind solvent any.
As the example of aqueous solvent, can enumerate water, alcohol etc.; Example as organic kind solvent, can enumerate N-methyl pyrrolidone (NMP), dimethyl formamide, dimethylacetylamide, methylethylketone, cyclohexanone, methyl acetate, methyl acrylate, diethyl triamine, N, N-dimethylamino propylamine, oxolane (THF), toluene, acetone, ether, hexamethyl phosphoramide, methyl-sulfoxide, benzene, dimethylbenzene, quinoline, pyridine, methyl naphthalene, hexane etc.
Particularly, when using aqueous solvent, preferably when using thickener, make and wherein contain dispersant etc., and adopt latex such as SBR carry out slurryization.In addition, above-mentioned solvent can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
Adhesive is preferably more than the 0.1 weight %, more preferably more than the 0.5 weight %, especially be preferably more than the 0.6 weight % with respect to the ratio of negative electrode active material, and be preferably 20 weight % following, more preferably 15 weight % following, more preferably 10 weight % following, especially be preferably below the 8 weight %.If adhesive surpasses above-mentioned scope with respect to the ratio of negative electrode active material, then there is not the ratio of the adhesive of contribution to increase to battery capacity in the amount of binder, may cause battery capacity to reduce.In addition, when being lower than above-mentioned scope, may cause the intensity of negative electrode to reduce.
Particularly, when containing in the main component with SBR when being the rubber-like macromolecule of representative, adhesive with respect to the ratio of negative electrode active material be generally more than the 0.1 weight %, be preferably more than the 0.5 weight %, more preferably more than the 0.6 weight %, and be generally 5 weight % following, be preferably 3 weight % following, more preferably below the 2 weight %.
In addition, when containing in the main component with the Kynoar when being the fluorine family macromolecule of representative, its ratio with respect to negative electrode active material is generally more than the 1 weight %, is preferably more than the 2 weight %, more preferably more than the 3 weight %, and be generally 15 weight % following, be preferably 10 weight % following, more preferably below the 8 weight %.
Thickener is generally used for regulating the viscosity of slurry.As thickener, there is no particular restriction, specifically can enumerate: carboxymethyl cellulose, methylcellulose, CMC, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, zymoprotein and their salt etc.Above-mentioned thickener can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
In addition, when using thickener, thickener with respect to the ratio of negative electrode active material be generally more than the 0.1 weight %, be preferably more than the 0.5 weight %, more preferably more than the 0.6 weight %, and be generally 5 weight % following, be preferably 3 weight % following, more preferably below the 2 weight %.If thickener is lower than above-mentioned scope with respect to the ratio of negative electrode active material, then may cause the remarkable reduction of coating.On the other hand, when surpassing above-mentioned scope, the shared ratio of negative electrode active material descends in the negative electrode active material layer, may cause problem and the increase of the resistance between negative electrode active material that battery capacity reduces.
(18) pole plate orientation ratio
The pole plate orientation ratio is generally more than 0.001, is preferably more than 0.005, more preferably more than 0.01, and be generally below 0.67.If the pole plate orientation ratio is lower than above-mentioned scope, then may cause the high density charge-discharge characteristic to reduce.Need to prove, be limited to the limit value in theory of carbonaceous material pole plate orientation ratio on the above-mentioned scope.
The mensuration of pole plate orientation ratio is carried out according to following method: negative electrode is suppressed to target density, utilized X-ray diffraction to measure the negative electrode active material orientation ratio of the electrode of this moment.There is not particular restriction for concrete grammar, as standard method, adopt asymmetric Pearson (ピ ア ソ Application) VII as (profile) function that distributes, (110) diffraction maximum and (004) diffraction maximum to the carbon that obtained by X-ray diffraction are carried out match, and carry out the peak separation thus, thereby calculate the integrated intensity of (110) diffraction maximum and (004) diffraction maximum respectively.Calculate ratio by the integrated intensity of gained so that (110) diffraction integral intensity/(004) diffraction integral intensity is represented.The negative electrode active material orientation ratio of the electrode that utilizes this mensuration to obtain is defined as the pole plate orientation ratio of the electrode that forms by carbonaceous material among the present invention 1.
The X-ray diffraction condition determination is as described below.Wherein, " 2 θ " represents the angle of diffraction.
The monochromatic photometer of target: Cu (K alpha ray) graphite
Slit:
Divergent slit=1 degree
Be subjected to optical slits=0.1mm
Scatter slit=1 degree
Measurement range, and step angle/minute:
(110) face: 76.5 degree≤2 θ≤78.5 degree 0.01 are spent/3 seconds
(004) face: 53.5 degree≤2 θ≤56.0 degree 0.01 are spent/3 seconds
Specimen preparation: the two-sided tape thick with 0.1mm is fixed on electrode on the glass plate
＜2-3-3. metal compound composition material and used structure, rerum natura, the preparation method of the negative pole of metal compound composition material
As metal compound composition material as negative electrode active material, as long as can occlusion/emit lithium, then can be any materials that forms in the compounds such as the metal simple-substance of lithium alloy or alloy or their oxide, carbide, nitride, silicide, sulfide, phosphide, there is no particular restriction.As described metallic compound, can enumerate the compound of metals such as containing Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn, Sr, Zn.Wherein, be preferably formed the metal simple-substance or the alloy of lithium alloy, preferably contain the 13rd family and the 14th family's metal/metalloid element (promptly, except carbon) material, the more preferably metal simple-substance of silicon (Si), tin (Sn) or plumbous (Pb) (below, sometimes these 3 kinds of elements are called " special metal element ") or comprise the alloy of these atoms or the compound of these metals (special metal element).Above-mentioned material can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
As the example of negative electrode active material with the atom that is selected from the special metal element at least a kind, the alloy that can enumerate the metal simple-substance of any a kind of special metal element, constitute by special metal element more than 2 kinds, by special metal element more than a kind or 2 kinds and other alloy that metallic element constitutes more than a kind or 2 kinds and contain the compound of special metal element more than a kind or 2 kinds or the complex chemical compound of oxide of described compound, carbide, nitride, silicide, sulfide, phosphide etc.As negative electrode active material, can realize the high capacity of battery by using these metal simple-substances, alloy or metallic compound.
In addition, as the example of above-mentioned complex chemical compound, can also enumerate compound with multiple element complex combination such as metal simple-substance, alloy or nonmetalloids.More specifically, for example silicon or tin can use the alloy of these elements and the metal that can't play a role as negative pole.In addition, tin for example can use by combination tin and can be used as metal that negative pole plays a role and the complex compound that contains 5～6 kinds of elements that the metal that can't play a role as negative pole and nonmetalloid obtain except silicon.
In above-mentioned negative electrode active material, the metal simple-substance of preferred wantonly a kind of special metal element, the alloy, oxide, carbide or the nitride etc. of special metal element of special metal element more than 2 kinds, this is because their capacity of per unit weight when making battery are bigger, and consider the capacity of per unit weight and the load that environment is caused, metal simple-substance, alloy, oxide, carbide or the nitride etc. of especially preferred silicon and/or tin.
In addition, when using metal simple-substance or alloy, though the capacity variation of per unit weight because the cycle characteristics excellence, thereby still preferably contains the following compound of silicon and/or tin.
" oxide of silicon and/or tin ", wherein, silicon and/or tin is generally more than 0.5 with the element ratio of oxygen, is preferably more than 0.7, more preferably more than 0.9, and be generally below 1.5, be preferably below 1.3, more preferably below 1.1.
" nitride of silicon and/or tin ", wherein, silicon and/or tin is generally more than 0.5 with the element ratio of nitrogen, is preferably more than 0.7, more preferably more than 0.9, and be generally below 1.5, be preferably below 1.3, more preferably below 1.1.
" carbide of silicon and/or tin ", wherein, silicon and/or tin is generally more than 0.5 with the element ratio of carbon, is preferably more than 0.7, more preferably more than 0.9, and be generally below 1.5, be preferably below 1.3, more preferably below 1.1.
Need to prove that above-mentioned negative electrode active material can use wantonly a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
Negative pole in the present invention 1 the rechargeable nonaqueous electrolytic battery can adopt known any means preparation.Particularly,, for example can enumerate: in above-mentioned negative electrode active material, add binding agent and electric conducting material etc., more resulting material is directly carried out the method that pellet electrode is made in the roller moulding as the manufacture method of negative pole; Make the method for mosaic electrode by compression forming.But what usually adopt is to utilize methods such as rubbing method, vapour deposition method, sputtering method, plating method to go up the method that forms the thin layer (negative electrode active material layer) that contains above-mentioned negative electrode active material at negative pole with collector body (below, also be called " negative electrode collector ").At this moment, in above-mentioned negative electrode active material, add binding agent, thickener, electric conducting material, solvent etc., make pulp-like, again it is coated on the negative electrode collector and drying, suppress then so that its densification, thereby on negative electrode collector, form negative electrode active material layer.
As the material of negative electrode collector, can enumerate steel, copper alloy, nickel, nickel alloy, stainless steel etc.In these materials, consider to be easy to be processed into film and cost aspect preferred Copper Foil.
The thickness of negative electrode collector be generally 1 μ m above, be preferably more than the 5 μ m, and be generally 100 μ m following, be preferably below the 50 μ m.If the thickness of negative electrode collector is blocked up, then the capacity of entire cell may become low, otherwise, if thin excessively, then may cause operating difficulties.
It is pointed out that the bond effect in order to make the surperficial negative electrode active material layer that forms is improved, and preferably carries out roughened to the surface of above-mentioned negative electrode collector in advance.Method as surface roughening, can enumerate following method: blasting treatment, adopt the matsurface roller to roll, with the abrasive cloth paper, sandstone, the Carborundum wheel that are fixed with abrasive particle, have mechanical milling method that the wire brush etc. of steel wire etc. grinds the collector body surface, electrolytic polishing method, a chemical grinding method etc.
In addition, for the weight that reduces negative electrode collector to improve the energy density of battery per unit weight, can also use the negative electrode collector of perforatings such as expansion alloy or perforated metal.Such negative electrode collector can also change weight arbitrarily by changing its aperture opening ratio.In addition, when on the two sides of such negative electrode collector, forming negative electrode active material layer, owing to there is the anchoring effect that runs through this hole, can make that negative electrode active material layer is more difficult to be peeled off.But, if aperture opening ratio is too high, then can cause the contact area between negative electrode active material layer and the negative electrode collector to diminish, may cause adhesion strength to reduce on the contrary.
The slurry that is used to form negative electrode active material layer is made by add binding agent, thickener etc. in negative material usually.Need to prove that said in this specification " negative material " is meant the material that comprises negative electrode active material and electric conducting material.
The content of negative electrode active material in negative material is generally more than the 70 weight %, especially is preferably more than the 75 weight %, and be generally 97 weight % following, especially be preferably below the 95 weight %.When the content of negative electrode active material is very few, may cause having used the capacity of the secondary cell of the negative pole that is obtained to be tending towards not enough; If content is too much, then, may cause the intensity of resulting negative pole to be tending towards not enough owing to can cause the content relative deficiency of binding agent etc.Need to prove, when being used in combination more than 2 kinds negative electrode active material, as long as make the total amount of negative electrode active material satisfy above-mentioned scope.
As the electric conducting material that is used for negative pole, can enumerate metal materials such as copper, nickel; Material with carbon element such as graphite, carbon black etc.These electric conducting materials can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.Particularly, when using material with carbon element,, therefore preferred because material with carbon element can also be brought into play the effect of active material as electric conducting material.The content of the electric conducting material in the negative material be generally 3 weight % above, be preferably more than the 5 weight % especially, and be generally 30 weight % following, be preferably below the 25 weight % especially.If electric conducting material content is very few, then may cause conductivity to be tending towards not enough, in the time of too much, owing to can make the content relative deficiency of negative electrode active material etc., thereby may cause battery capacity and intensity to have a declining tendency.Need to prove, when the electric conducting material that is used in combination more than 2 kinds, as long as make the total amount of electric conducting material satisfy above-mentioned scope.
As the binding agent that is used for negative pole,, can use binding agent arbitrarily when making electrode so long as solvent and the electrolyte safe material of using got final product.For example can enumerate: Kynoar, polytetrafluoroethylene, polyethylene, polypropylene, butadiene-styrene rubber, isoprene rubber, butadiene rubber, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer etc.Above-mentioned binding agent can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.With respect to negative material 100 weight portions, the content of binding agent be generally 0.5 weight portion above, be preferably more than 1 weight portion especially, and be generally 10 weight portions following, be preferably below 8 weight portions especially.If the content of binding agent is very few, then may cause the intensity of resulting negative pole to be tending towards not enough, in the time of too much, because the content relative deficiency of negative electrode active material etc. may cause battery capacity and conductivity to be tending towards not enough.Need to prove, when being used in combination more than 2 kinds binding agent, as long as make the total amount of binding agent satisfy above-mentioned scope.
As the thickener that is used for negative pole, can enumerate carboxymethyl cellulose, methylcellulose, CMC, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, zymoprotein etc.These thickeners can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.Thickener can use as required, and when using thickener, the content of thickener in negative electrode active material layer is preferably the scope of 0.5 weight %～5 weight % usually.
The slurry that is used to form negative electrode active material layer can be by mixing required electric conducting material and binding agent, thickener in above-mentioned negative electrode active material, and formulated as decentralized medium with aqueous solvent or organic solvent.As aqueous solvent, make water usually, but also can be being that ratio about below the 30 weight % is used in combination other solvent beyond dewatering such as cyclic amides such as alcohols such as ethanol or N-methyl pyrrolidone with respect to water.In addition, as organic solvent, can enumerate cyclic amides such as N-methyl pyrrolidone usually; N, dinethylformamide, N, straight chain shape amide-types such as N-dimethylacetylamide; Arenes such as methyl phenyl ethers anisole, toluene, dimethylbenzene; Alcohols such as butanols, cyclohexanol.Wherein, cyclic amide such as preferred N-methyl pyrrolidone; N, dinethylformamide, N, straight chain shape amide-types such as N-dimethylacetylamide etc.Wherein, above-mentioned solvent can use any separately, also can be used in combination more than 2 kinds with combination in any and ratio.
As long as the viscosity of slurry is able to coat the viscosity on the collector body, there is no particular restriction.As the viscosity that can be coated with, can wait suitably by change solvent load when preparing slurry and adjust.
Resulting slurry is coated on the above-mentioned negative electrode collector and drying after, form negative electrode active material layer by suppressing.Method for coating there is no particular restriction, can use itself known method.Method for drying does not have particular restriction yet, can adopt known methods such as air dry, heat drying, drying under reduced pressure.
Electrode structure when by said method negative electrode active material being made electrode does not have particular restriction, but the density that is present in the active material on the collector body is preferably 1gcm -3More than, 1.2gcm more preferably -3More than, especially be preferably 1.3gcm -3More than, and be preferably 2gcm -3Below, 1.9gcm more preferably -3Below, 1.8gcm more preferably -3Below, especially be preferably 1.7gcm -3Below.
Surpass above-mentioned scope if be present in the density of the active material on the collector body, then active material particle can be damaged, may cause the initial stage irreversible capacity to increase and near the impregnability reduction of nonaqueous electrolytic solution collector body/reactive species interface, and then cause high current density charge-discharge characteristic deterioration.On the other hand, if be lower than above-mentioned scope, may cause conductivity reduction, cell resistance between active material to increase, the capacity of unit volume reduces.
＜2-3-4. contains the lithium-metal composite oxides material, reaches the structure, rerum natura, the preparation method that use the negative pole that contains the lithium-metal composite oxides material 〉
As containing the lithium-metal composite oxides material as negative electrode active material, as long as can occlusion/emit lithium, then do not have particular restriction, but preferably comprise the lithium-contained composite metal oxide material of titanium, the composite oxides (being designated hereinafter simply as " lithium-titanium composite oxide ") of special preferred lithium and titanium.That is, when containing the lithium-titanium composite oxide with spinel structure in making the anode for nonaqueous electrolyte secondary battery active material, output resistance can decline to a great extent, thereby preferred especially.
In addition, the composite oxides that obtain and lithium in the preferred lithium titanium composite oxide or titanium, for example are selected from least a kind of element replacement among Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and the Nb by other metallic element.
Above-mentioned metal oxide is the lithium-titanium composite oxide with general formula (2) expression, when satisfying 0.7≤x≤1.5,1.5≤y≤2.3,0≤z≤1.6 in the general formula (2), and the Stability Analysis of Structures of lithium ion when dopings/dedoping, therefore preferably.
Li xTi yM zO 4(2)
[in general formula (2), the M representative is selected from least a kind of element among Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and the Nb.]
In the represented composition of above-mentioned general formula (2), the battery performance of following (a) and (b), (c) structure can obtain well balanced, and is therefore preferred especially.
(a)1.2≤x≤1.4、1.5≤y≤1.7、z＝0
(b)0.9≤x≤1.1、1.9≤y≤2.1、z＝0
(c)0.7≤x≤0.9、2.1≤y≤2.3、z＝0
As particularly preferred typical composition in the above-claimed cpd, can be listed below: be Li (a) 4/3Ti 5/3O 4, be Li in (b) 1Ti 2O 4, be Li in (c) 4/5Ti 11/5O 4In addition, for the structure of Z ≠ 0, can enumerate for example Li 4/3Ti 4/3Al 1/3O 4As preferred composition.
The lithium-titanium composite oxide that is used as negative electrode active material among the present invention 1 also preferably further satisfies at least a kind in the features such as described rerum natura in following (1)～(13) and shape except will satisfying above-mentioned requirements, especially preferably satisfy more than 2 kinds simultaneously.
(1) BET specific area
Adopt the value of the BET specific area of that the BET method is measured, as to be used as negative electrode active material lithium-titanium composite oxide to be preferably 0.5m 2G -1More than, 0.7m more preferably 2G -1More than, 1.0m more preferably 2G -1More than, especially be preferably 1.5m 2G -1More than, and be preferably 200m 2G -1Below, 100m more preferably 2G -1Below, 50m more preferably 2G -1Below, especially be preferably 25m 2G -1Below.
If the BET specific area is lower than above-mentioned scope, then reduce with the contacted response area of nonaqueous electrolytic solution when the negative material, may cause the output resistance increase.On the other hand, when surpassing above-mentioned scope, can cause that the plane of crystal of titanium-containing metal oxide and end face part increase, and cause crystal defect (askew) thus, and then can cause irreversible capacity to become very important, thereby can't obtain desirable battery.
Carry out as follows when utilizing BET method measurement the specific area: use surface area meter (the full automatic watch area estimation device that the reason development of big storehouse is made), under nitrogen current, 350 ℃, sample carried out 15 minutes predrying after, use nitrogen accurately to be adjusted to 0.3 nitrogen helium gas mixture body, measure by 1 method of nitrogen absorption BET that adopts the gas flow method with respect to atmospheric relative pressure value.The specific area of utilizing this mensuration to obtain is defined as the BET specific area of lithium-titanium composite oxide among the present invention 1.
(2) volume reference average grain diameter
The average grain diameter (median particle diameter) of the volume reference of utilizing laser diffraction/scattering method to record is defined as the volume reference average grain diameter (assemble the situation that forms secondary for primary particle, be secondary particle diameter) of lithium-titanium composite oxide.
The volume reference average grain diameter of lithium-titanium composite oxide be generally 0.1 μ m above, be preferably 0.5 μ m above, more preferably more than the 0.7 μ m, and be generally 50 μ m following, be preferably 40 μ m following, more preferably 30 μ m following, especially be preferably below the 25 μ m.
The volume reference average grain diameter adopts following method to measure: carbon dust is dispersed in the 0.2 weight % aqueous solution (about 10mL) of polyoxyethylene (20) Span-20 as surfactant, and utilizes laser diffraction/diffuse transmission type particle size distribution meter (the hole field makes the LA-700 that company of institute makes) to measure.To be defined as the volume reference average grain diameter of carbonaceous material among the present invention 1 by the median particle diameter that this mensuration is obtained.
If the volume average particle size of lithium-titanium composite oxide is lower than above-mentioned scope, then when the preparation electrode, need a large amount of binding agents, its result may cause battery capacity to reduce.On the other hand, when surpassing above-mentioned scope, when the preparation electrode pad, form uneven applicator surface easily, not preferred on the cell preparation operation.
(3) primary particle average grain diameter
Assemble under the situation that forms secondary at primary particle, the primary particle average grain diameter of lithium-titanium composite oxide be generally 0.01 μ m above, be preferably 0.05 μ m above, more preferably 0.1 μ m above, especially be preferably more than the 0.2 μ m, and be generally 2 μ m following, be preferably 1.6 μ m following, more preferably 1.3 μ m following, especially be preferably below the 1 μ m.If volume reference primary particle average grain diameter surpasses above-mentioned scope, then be difficult to form spherical secondary, the powder fillibility is brought harmful effect, or the specific area reduction, may cause battery performance reductions such as output characteristic thus.In addition, if volume reference primary particle average grain diameter is lower than above-mentioned scope,, thereby may cause the problem of the secondary cell decreased performance such as invertibity difference that discharge and recharge then because usually crystallization is incomplete.
Need to prove that primary particle diameter is measured by utilizing ESEM (SEM) to observe.Particularly, under the multiplying power that can confirm particle, for example multiplying power is in 10000～100000 times the photo, at 50 primary particles arbitrarily, obtain the greatest length of the boundary line, the left and right sides of primary particle, average again and obtain the primary particle average grain diameter with respect to the straight line gained intercept of horizontal direction.
(4) shape
The shape of particle of lithium-titanium composite oxide can adopt in the past the bulk that adopts, polyhedral, spherical, oval spherical, tabular, needle-like, column etc., wherein, preferred primary particle is assembled the formation secondary, and the shape of secondary is preferably spherical or oval spherical.
Usually, electrochemical element is followed charge and discharge process, and the active material in its electrode can expand contraction, therefore, and the easy deterioration of the destruction of initiating activity material and conduction break-make etc. in the presence of this stress.Thus, compare with the single particle active material that only has primary particle, preferred primary particle is assembled the situation that forms secondary, this be because, when forming secondary, its expansion shrinkage stress is relaxed, and can prevent deterioration.
In addition, compare with axle orientation particle such as tabular, the situation of more preferably spherical or oval spherical particle, this be because, the orientation of spherical or oval spherical particle when electrode moulding a little less than, the expansion of electrode is shunk also lessly when discharging and recharging, and also realizes easily evenly mixing when carrying out with the mixing of electric conducting material when the preparation electrode.
(5) tap density
The tap density of lithium-titanium composite oxide is preferably 0.05gcm -3More than, 0.1gcm more preferably -3More than, 0.2gcm more preferably -3More than, especially be preferably 0.4gcm -3More than, and be preferably 2.8gcm -3Below, 2.4gcm more preferably -3Below, especially be preferably 2gcm -3Below.If tap density is lower than above-mentioned scope, during then used as negative pole, packed density is difficult to improve, and the minimizing of interparticle contact area, thereby may cause interparticle resistance to increase, and output resistance increases.In addition, when surpassing above-mentioned scope, interparticle space is very few in the electrode, and the stream of nonaqueous electrolytic solution reduces, and may cause output resistance to increase thus.
Tap density can be measured by following method: make sample drop into 20cm behind the sieve that by mesh is 300 μ m 3The jolt ramming container in, be filled to the upper surface of container up to sample, utilize powder density analyzer (for example, the Tap densor that Seishin enterprise-like corporation makes) to carry out the vibration that 1000 times length of stroke is 10mm then, the volume in the time of thus and the weight of sample are obtained density.The tap density of utilizing this mensuration to calculate is defined as the tap density of lithium-titanium composite oxide among the present invention 1.
(6) circularity
When measuring circularity as the spherical degree of lithium-titanium composite oxide, the circular degree is within following ranges.Circularity defines with following formula: circularity=(having the girth with particle projection of shape equivalent circular of the same area)/(perimeter of particle projection of shape).When circularity is 1, become theoretical proper sphere.
The circularity of lithium-titanium composite oxide is preferred near 1 more more, is generally more than 0.10, is preferably more than 0.80, more preferably more than 0.85, especially be preferably more than 0.90.The big more then high current density of circularity charge-discharge characteristic is high more.Thereby when circularity was lower than above-mentioned scope, the fillibility of negative electrode active material descended, interparticle resistance increases, and may cause short time high current density charge-discharge characteristic to reduce.
Circularity is measured by using flow-type particle picture analytical equipment (for example, the FPIA of Sysmex Industrial company manufacturing).About 0.2g sample is dispersed in the 0.2 weight % aqueous solution (about 50mL) of polyoxyethylene (20) Span-20 as surfactant, and with the ultrasonic wave of 28kHz with the power output irradiation of 60W after 1 minute, specifying 0.6～400 μ m is detection range, and particle diameter is measured at the particle of 3～40 mu m ranges.The circularity of utilizing this mensuration to obtain is defined as the circularity of lithium-titanium composite oxide among the present invention 1.
(7) draw ratio
The draw ratio of lithium-titanium composite oxide is generally more than 1, and is generally below 5, is preferably below 4, more preferably below 3, especially be preferably below 2.When draw ratio surpasses above-mentioned scope, when making pole plate, may produce striped, can't obtain uniform coated face, cause short time high current density charge-discharge characteristic to reduce.Need to prove the following theory lower bound value that is limited to the draw ratio of lithium-titanium composite oxide of above-mentioned scope.
Draw ratio is measured by using ESEM that the lithium-titanium composite oxide particle is amplified to observe.Selection is fixed on any 50 particles on the following metal end face of thick 50 μ m, rotation, tilts to be fixed with the objective table of sample, the major diameter A of particle and perpendicular minor axis B when being determined at 3 dimensions respectively and observing, and obtain the mean value of A/B.The draw ratio (A/B) of utilizing this mensuration to obtain is defined as the draw ratio of lithium-titanium composite oxide among the present invention 1.
(8) preparation method of negative electrode active material
As the preparation method of lithium-titanium composite oxide,, can enumerate several method as long as in the scope of the main points that do not exceed the present invention 1, there is no particular restriction.As the manufacture method of inorganic compound, can adopt usual way.
For example, can enumerate raw material and LiOH, Li with titanium material materials such as titanium oxide, other element of using as required 2CO 3, LiNO 3Deng the Li source evenly mix, and at high temperature sintering obtain the method for active material.
Particularly, can consider that the whole bag of tricks prepares spherical or oval spherical active material.As an example wherein, can enumerate following method: with titanium material material such as titanium oxide and as required and dissolving of the raw material of other element that uses or grinding dispersion in the water equal solvent, when stirring, regulate the pH value, make and collect spherical precursor, be dried as required, add LiOH, Li then 2CO 3, LiNO 3In the Li source, and sintering at high temperature, thereby obtain the method for active material.
In addition, as another example, can enumerate following method: with titanium material material such as titanium oxide and as required and dissolving of the raw material of other element that uses or grinding dispersion in the water equal solvent, utilize spray dryer etc. to be dried moulding, make spherical or oval spherical precursor, to wherein adding LiOH, Li 2CO 3, LiNO 3In the Li source, and sintering at high temperature, thereby obtain the method for active material.
As another method, can also enumerate following method: with titanium material material, LiOH, Li such as titanium oxide 2CO 3, LiNO 3Deng the raw material dissolving of Li source and other element of using as required or grinding dispersion in the water equal solvent, utilize spray dryer etc. to be dried moulding, make spherical or oval spherical precursor,, thereby obtain the method for active material its sintering at high temperature.
In addition, in above-mentioned operation, can also be in the metal oxide structures of titaniferous and/or have other element except Ti with the contacted form of the oxide of titaniferous, for example: Al, Mn, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, C, Si, Sn, Ag.By containing above-mentioned element, can realize the operating voltage to battery, the control of capacity.
(9) making of electrode
Can adopt the method for any known to make electrode.For example, can form electrode by following method: in negative electrode active material, add adhesive, solvent, the thickener that adds as required, electric conducting material, packing material etc., make slurry, be coated on the collector body it and drying, form electrode by compacting then.
In the stage before the nonaqueous electrolytic solution injection process of closing on of battery, the ideal thickness of the negative electrode active material layer on each face be generally 15 μ m above, be preferably 20 μ m above, more preferably more than the 30 μ m, on be limited to 150 μ m following, be preferably 120 μ m following, more preferably below the 100 μ m.
When surpassing this scope,, may cause the high current density charge-discharge characteristic to reduce because nonaqueous electrolytic solution is difficult to infiltrate into the collector body near interface.In addition, if be lower than this scope, then may cause collector body to increase with respect to the volume ratio of negative electrode active material, battery capacity reduces.In addition, negative electrode active material can be carried out the roller moulding and make pellet electrode, or make mosaic electrode by compression forming.
(10) collector body
As the collector body that negative electrode active material is kept, can use the collector body of any known.As the collector body of negative pole, can enumerate metal materials such as copper, nickel, stainless steel, nickel-plated steel, wherein, consider from processing simplification and cost aspect, especially preferably copper.
In addition, as the shape of collector body, when collector body is metal material, can enumerate for example metal forming, metal cylinder, wire coil, metallic plate, metallic film, expansion alloy, perforated metal, foaming metal etc.Wherein, preferably contain the metal foil film of copper (Cu) and/or aluminium (Al), more preferably Copper Foil, aluminium foil further preferably utilize rolled copper foil that rolling process obtains and the electrolytic copper foil that utilizes electrolysis to obtain, and any in above-mentioned all can be used as collector body and use.
In addition, when the thickness of Copper Foil during, can working strength be higher than the copper alloy (phosphor bronze, titanium copper, Corson alloy, Cu-Cr-Zr alloy etc.) of fine copper less than 25 μ m.In addition, because the proportion of aluminium foil is lighter, when it is used as collector body, the weight of battery is reduced, thereby can preferably use.
In the collector body that constitutes by the Copper Foil that utilizes rolling process preparation,,, still be difficult for breaking, applicable to small cylinder shape battery even therefore negative pole is closely curled or be curled into acute angle because the copper crystallization arranges along rolling direction.
Electrolytic copper foil can obtain by following method: for example, metal drum is immersed in the nonaqueous electrolytic solution that is dissolved with copper ion, galvanization when rotating this drum so that copper separates out on the drum surface, thereby is peeled off the acquisition electrolytic copper foil with it.Can also utilize electrolysis that copper is separated out on above-mentioned rolled copper foil surface.Also can carry out roughened or surface treatment (base treatment such as for example, the chromate processing of thickness about number nm～1 μ m, Ti etc.) to the one or both sides of Copper Foil.
In addition, the collector body substrate also preferably has following rerum natura.
(10-1) average surface roughness (Ra)
The average surface roughness (Ra) that the negative electrode active material film of the collector body substrate of stipulating in the method for the JISB0601-1994 record forms face does not have particular restriction, be generally 0.01 μ m above, be preferably more than the 0.03 μ m, and be generally 1.5 μ m following, be preferably 1.3 μ m following, more preferably below the 1.0 μ m.
This be because, when the average surface roughness (Ra) of collector body substrate is in above-mentioned scope, can expect the favorable charge-discharge cycle characteristics.In addition, with the interfacial area increase of active material film, with the adhesiveness raising of negative electrode active material film.Wherein, higher limit for average surface roughness (Ra) there is no particular restriction, but when average surface roughness (Ra) surpassed 1.5 μ m, therefore the paper tinsel of thickness practicality when very difficult acquisition is used as battery adopted the average surface roughness (Ra) below the 1.5 μ m usually.
(10-2) hot strength
So-called hot strength is meant the value that needed maximum pull obtained divided by the sectional area of test film when fracture took place test film.Hot strength among the present invention 1 adopts the device and method identical with the record of JISZ2241 (metal material tensile test method) to measure.
Hot strength for the collector body substrate does not have particular restriction, is generally 50Nmm -2More than, be preferably 100Nmm -2More than, 150Nmm more preferably -2More than.Tensile strength values is high more then to be preferred more, considers the industry property obtained, and is generally 1000Nmm -2Below.
If the high collector body substrate of hot strength then can be suppressed at the be full of cracks of the collector body substrate that is caused by active material film expansion in the charge/discharge process, can obtain good cycle characteristics.
(10-3) 0.2% yield strength
So-called 0.2% yield strength is meant to produce 0.2% the necessary load size of plasticity (forever) strain, apply this load after, even, still keep 0.2% deformation except that unloading.The 0.2% yield strength utilization device and method identical with measuring hot strength measured.
0.2% yield strength for the collector body substrate there is no particular restriction, is generally 30Nmm -2More than, be preferably 100Nmm -2More than, especially be preferably 150Nmm -2More than.The value of 0.2% yield strength is high more then to be preferred more, from the angle of the industry property obtained, is preferably 900Nmm usually -2Below.
If the high collector body substrate of 0.2% yield strength then can be suppressed at the plastic deformation of the collector body substrate that is caused by active material film expansion in the charge/discharge process, can obtain good cycle characteristics.
(10-4) thickness of collector body
Collector body can be an any thickness, but be generally 1 μ m above, be preferably 3 μ m above, more preferably more than the 5 μ m, and be generally 1mm following, be preferably 100 μ m following, more preferably below the 50 μ m.
When the thickness of collector body during,, thereby may cause the coating difficulty that becomes because intensity can descend less than 1 μ m.In addition, when thickness during greater than 100 μ m, the electrode shape that then may cause reeling etc. deforms.Need to prove that collector body can be netted.
(11) the thickness ratio of collector body and active material layer
Thickness ratio for collector body and active material layer there is no particular restriction, but the value of " (at the thickness that closes on the active material layer on nonaqueous electrolytic solution single before injecting)/(thickness of collector body) " is generally below 150, is preferably below 20, more preferably below 10, and be generally more than 0.1, be preferably more than 0.4, more preferably more than 1.
If collector body surpasses above-mentioned scope with the thickness ratio of negative electrode active material layer, when then high current density discharged and recharged, collector body may cause heat release because of Joule heat.In addition, when the thickness ratio was lower than above-mentioned scope, collector body increased with respect to the volume ratio of negative electrode active material, may cause battery capacity to reduce.
(12) electrode density
Electrode structure when negative electrode active material is made electrode does not have particular restriction, and the density that is present in the negative electrode active material on the collector body is preferably 1gcm -3More than, 1.2gcm more preferably -3More than, 1.3gcm more preferably -3More than, especially be preferably 1.5gcm -3More than, and be preferably 3gcm -3Below, 2.5gcm more preferably -3Below, 2.2gcm more preferably -3Below, especially be preferably 2gcm -3Below.
When the density of the active material on being present in collector body surpassed above-mentioned scope, the bonding of collector body and negative electrode active material died down, and may cause electrode and active material to be separated.In addition, if be lower than above-mentioned scope, then may cause the conductivity between negative electrode active material to reduce, cell resistance increases.
(13) adhesive
As the adhesive of bonding negative electrode active material, so long as the material of the solvent-stable that uses when making with respect to nonaqueous electrolytic solution and electrode does not then have particular restriction.
As object lesson, can enumerate resinae macromolecules such as polyethylene, polypropylene, PETG, polymethyl methacrylate, polyimides, aromatic polyamide, cellulose, NC Nitroncellulose; Rubber-like macromolecules such as SBR (butadiene-styrene rubber), isoprene rubber, butadiene rubber, fluorubber, NBR (acrylonitrile-butadiene rubber), ethylene-propylene rubber; SBS and hydride thereof; Thermoplastic elastomer (TPE) shape macromolecules such as EPDM (ethylene-propylene-diene terpolymers), SIS/SEBS, SIS and hydride thereof; Syndiotactic 1, soft resinous macromolecules such as 2-polybutadiene, polyvinyl acetate, vinyl-vinyl acetate copolymer, propylene-alpha-olefin copolymers; Kynoar, polytetrafluoroethylene, fluoridize fluorine family macromolecules such as Kynoar, polytetrafluoroethylene-ethylene copolymer; The polymeric composition with ionic conductivity of alkali metal containing ion (particularly lithium ion) etc.Above-mentioned material can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
As the solvent that is used to form slurry, so long as can dissolve or disperse negative electrode active material, adhesive and as required and the thickener that uses and the solvent of electric conducting material get final product, its kind is not had particular restriction, can use in aqueous solvent or the organic kind solvent any.
As the example of aqueous solvent, can enumerate water, alcohol etc.; Example as organic kind solvent, can enumerate N-methyl pyrrolidone (NMP), dimethyl formamide, dimethylacetylamide, methylethylketone, cyclohexanone, methyl acetate, methyl acrylate, diethyl triamine, N, N-dimethylamino propylamine, oxolane (THF), toluene, acetone, dimethyl ether, hexamethyl phosphoramide, methyl-sulfoxide, benzene, dimethylbenzene, quinoline, pyridine, methyl naphthalene, hexane etc.Particularly, when using aqueous solvent, preferably when using thickener, add dispersant etc., and adopt latex such as SBR carry out slurryization.In addition, above-mentioned solvent can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
Adhesive with respect to the ratio of negative electrode active material be generally more than the 0.1 weight %, be preferably more than the 0.5 weight %, more preferably more than the 0.6 weight %, and be generally 20 weight % following, be preferably 15 weight % following, more preferably 10 weight % following, especially be preferably below the 8 weight %.
If adhesive surpasses above-mentioned scope with respect to the ratio of negative electrode active material, then there is not the ratio of the adhesive of contribution to increase to battery capacity in the amount of binder, may cause battery capacity to reduce.In addition, when being lower than above-mentioned scope, may cause the intensity of negative electrode to reduce, consider from the cell production process aspect, not preferred.
Particularly, when containing in the main component with SBR when being the rubber-like macromolecule of representative, adhesive with respect to the ratio of active material be generally more than the 0.1 weight %, be preferably more than the 0.5 weight %, more preferably more than the 0.6 weight %, and be generally 5 weight % following, be preferably 3 weight % following, more preferably below the 2 weight %.
In addition, when containing in the main component with the Kynoar when being the fluorine family macromolecule of representative, its ratio with respect to active material is more than the 1 weight %, be preferably more than the 2 weight %, more preferably more than the 3 weight %, be generally 15 weight % following, be preferably 10 weight % following, more preferably below the 8 weight %.
Thickener is generally used for regulating the viscosity of slurry.As thickener, there is no particular restriction, specifically can enumerate carboxymethyl cellulose, methylcellulose, CMC, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, zymoprotein and their salt etc.Above-mentioned thickener can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
In addition, when using thickener, thickener with respect to the ratio of negative electrode active material be more than the 0.1 weight %, be preferably more than the 0.5 weight %, more preferably more than the 0.6 weight %, and be generally 5 weight % following, be preferably 3 weight % following, more preferably below the 2 weight %.If thickener is lower than above-mentioned scope with respect to the ratio of negative electrode active material, then may cause the remarkable reduction of coating.On the other hand, when surpassing above-mentioned scope, the shared ratio of active material reduces in the negative electrode active material layer, may cause that resistance increases between problem that battery capacity reduces and negative electrode active material.
＜2-4. positive pole 〉
Below describe at the positive pole that in the present invention 1 rechargeable nonaqueous electrolytic battery, uses.
＜2-4-1. positive active material 〉
Below describe at being used for anodal positive active material.
(1) forms
As positive active material,, for example, preferably contain the material of lithium and at least a kind of transition metal as long as electrochemically occlusion/emit lithium ion does not then have particular restriction.As object lesson, can enumerate lithium-compound transition metal oxide, contain the transition metal phosphate cpd of lithium.
As the transition metal in lithium-compound transition metal oxide, preferred V, Ti, Cr, Mn, Fe, Co, Ni, Cu etc. as the object lesson of lithium-compound transition metal oxide, can enumerate LiCoO 2Deng lithium-cobalt composite oxide, LiNiO 2Deng lithium-ni compound oxide, LiMnO 2, LiMn 2O 4, Li 2MnO 4Deng lithium-manganese composite oxide, with composite oxides that obtain as the part in the transition metal atoms of main body in the above-mentioned lithium-compound transition metal oxide of other metal substitute such as Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Si etc.
The object lesson of the composite oxides that obtain can be enumerated for example LiNi as an alternative 0.5Mn 0.5O 2, LiNi 0.85Co 0.10Al 0.05O 2, LiNi 0.33Co 0.33Mn 0.33O 2, LiMn 1.8Al 0.2O 4, LiMn 1.5Ni 0.5O 4Deng.
As the transition metal in the transition metal phosphate cpd that contains lithium, preferred V, Ti, Cr, Mn, Fe, Co, Ni, Cu etc. as the object lesson of the transition metal phosphate cpd that contains lithium, can enumerate for example LiFePO 4, Li 3Fe 2(PO 4) 3, LiFeP 2O 7Deng the ferric phosphate class, LiCoPO 4Deng the cobalt phosphate class, with compound that obtains as the part in the transition metal atoms of main body in the above-mentioned lithium of other metal substitute such as Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Si-transition metal phosphate cpd etc.
(2) surface coats
Can also use in above-mentioned positive active material surface attachment by forming different material (below, suitably abbreviate " surface attachment material " as) with the material that constitutes positive active material as main body.Example as the surface attachment material, can enumerate oxides such as aluminium oxide, silica, titanium oxide, zirconia, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, sulfate such as lithium sulfate, sodium sulphate, potassium sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, carbonate such as lithium carbonate, calcium carbonate, magnesium carbonate etc.
Can make these surface attachment materials be attached to the positive active material surface by following method, for example, the surface attachment material is dissolved or suspended in the solvent, and its impregnation is added in the positive active material, and then carry out dry method; Surface attachment material precursor is dissolved or suspended in the solvent, and its impregnation is added in the positive active material, wait the method that makes its reaction by heating then; The surface attachment material is added in the positive active material precursor, carry out the method for sintering etc. simultaneously.
Weight with respect to positive active material, the weight that is attached to the surface attachment material on positive active material surface be generally 0.1ppm above, be preferably 1ppm above, more preferably more than the 10ppm, and be generally below 20%, be preferably below 10%, more preferably below 5%.
Can suppress nonaqueous electrolytic solution by the surface attachment material and oxidation reaction take place, and then improve battery life on the positive active material surface., if adhesion amount is lower than above-mentioned scope, then its effect can't demonstrate fully; And when surpassing above-mentioned scope, can cause obstruction to the discrepancy of lithium ion, may cause resistance to increase, therefore preferred above-mentioned scope.
(3) shape
Shape as the positive active material particle, the shape that can use bulk, polyhedral, spherical, oval spherical, tabular, needle-like, column etc. in the past to be adopted, wherein, preferred primary particle is assembled the formation secondary, and the shape of described secondary is preferably spherical or oval spherical.
Therefore easily usually, electrochemical element is followed and is discharged and recharged, and the active material in its electrode can expand contraction, the deterioration of the destruction of initiating activity material and conduction break-make etc. under this stress.Thus, compare with the single particle active material that only has primary particle, preferred primary particle is assembled the situation that forms secondary, this be because, assemble when forming secondary, its expansion shrinkage stress is relaxed, and can prevent deterioration.
In addition, compare with axle orientation particle such as tabular, the situation of more preferably spherical or oval spherical particle, this be because, the orientation of spherical or oval spherical particle when electrode moulding a little less than, the expansion of electrode is shunk also lessly when discharging and recharging, and also realizes easily evenly mixing when carrying out with the mixing of electric conducting material when the preparation electrode.
(4) tap density
The tap density of positive active material is generally 1.3gcm -3More than, be preferably 1.5gcm -3More than, 1.6gcm more preferably -3More than, especially be preferably 1.7gcm -3More than, and be generally 2.5gcm -3Below, be preferably 2.4gcm -3Below.
By using the high composite oxide of metal powder of tap density, can form highdensity positive electrode active material layer.Thereby, if the tap density of positive active material is lower than above-mentioned scope, then the amount of necessary decentralized medium increases when forming positive electrode active material layer, the necessary amount of electric conducting material and binding agent increases simultaneously, the filling rate of positive active material in positive electrode active material layer is restricted, and may cause battery capacity to be restricted.In addition, tap density is big more usually to be preferred more, does not have the special upper limit, if but be lower than above-mentioned scope, then in the positive electrode active material layer be the factor that the diffusion of the lithium ion of medium becomes decision speed with the nonaqueous electrolytic solution, may cause load characteristic to reduce.
Tap density is measured as follows: make sample drop into 20cm behind the sieve that by mesh is 300 μ m 3The jolt ramming container in, be full of the volume of container up to sample, utilize powder density analyzer (for example, the Tap densor that Seishin enterprise-like corporation makes) to carry out the vibration that 1000 times length of stroke is 10mm then, volume and sample weight in the time of are thus obtained tap density.The tap density of utilizing this mensuration to calculate is defined as the tap density of positive active material among the present invention 1.
(5) median particle diameter d50
The median particle diameter d50 of the particle of positive active material (primary particle is assembled when forming secondary, is secondary particle diameter) can utilize laser diffraction/diffuse transmission type particle size distribution device to measure.
Median particle diameter d50 be generally 0.1 μ m above, be preferably 0.5 μ m above, more preferably 1 μ m above, especially be preferably more than the 3 μ m, and be generally 20 μ m following, be preferably 18 μ m following, more preferably 16 μ m following, especially be preferably below the 15 μ m.If median particle diameter d50 is lower than above-mentioned scope, then possibly can't obtain the high product of volume density, and when surpassing above-mentioned scope, then because the diffusion of the interior lithium of particle needs the time, may cause battery behavior to reduce, perhaps making anode, when promptly adopting solvent that active material is carried out slurryization and then is coated with into film like with electric conducting material or adhesive etc., producing the situation of striped etc.
Need to prove, can also mix the fillibility that improves when making positive pole with arbitrary proportion by the positive active material that will have different median particle diameter d50 more than 2 kinds.
Median particle diameter d50 can measure by following method: the sodium hexametaphosphate solution with 0.1 weight % is a decentralized medium, use the hole field to make the LA-920 of company of institute manufacturing as the particle size distribution meter, after the ultrasonic wave that carried out 5 minutes disperseed, setting and measuring refractive index was 1.24 to measure.
(6) primary particle average grain diameter
When elementary particle accumulation forms secondary, the primary particle average grain diameter of positive active material be generally 0.01 μ m above, be preferably 0.05 μ m above, more preferably 0.08 μ m above, especially be preferably more than the 0.1 μ m, and be generally 3 μ m following, be preferably 2 μ m following, more preferably 1 μ m following, especially be preferably below the 0.6 μ m.If the primary particle average grain diameter surpasses above-mentioned scope, then be difficult to form spherical secondary, can cause harmful effect to the powder fillibility, perhaps can cause specific area significantly to reduce, may cause battery performance reductions such as output characteristic thus; In addition,, then can cause crystallization incomplete usually, and then may cause the performance reduction of the secondary cells such as invertibity difference that discharge and recharge if the primary particle average grain diameter is lower than above-mentioned scope.
In addition, the primary particle average grain diameter can be measured by utilizing ESEM (SEM) to observe.Particularly, in multiplying power is 10000 times photo,, obtain the greatest length of the boundary line, the left and right sides of primary particle, average again and obtain the primary particle average grain diameter with respect to the straight line gained intercept of horizontal direction at 50 primary particles arbitrarily.
(7) BET specific area
The value of the BET specific area of the positive active material that employing BET method is measured is generally 0.2m 2G -1More than, be preferably 0.3m 2G -1More than, 0.4m more preferably 2G -1More than, and be generally 4.0m 2G -1Below, be preferably 2.5m 2G -1Below, 1.5m more preferably 2G -1Below.If the value of BET specific area is lower than above-mentioned scope, then battery performance reduces easily.On the other hand, if surpass above-mentioned scope, then tap density is difficult for improving, and may cause the coating when forming positive active material to reduce.
The BET specific area uses surface area meter (the full automatic watch area estimation device that the reason development of big storehouse is made) to measure.Under nitrogen current, 150 ℃ to sample carry out 30 minutes predrying, use then nitrogen accurately is adjusted to 0.3 nitrogen helium gas mixture body with respect to atmospheric relative pressure value, measure by 1 method of nitrogen absorption BET that adopts the gas flow method to carry out.The specific area of utilizing this mensuration to obtain is defined as the BET specific area of positive active material among the present invention 1.
(8) preparation method of positive active material
As the preparation method of positive active material, only otherwise the scope that exceeds the present invention 1 main points does not then have particular restriction, can enumerate several method, but, can adopt usual way as the manufacture method of inorganic compound.
Particularly, can consider that the whole bag of tricks prepares spherical or oval spherical active material.For example, as one of method, can enumerate following method: with the raw material dissolving of transition metal raw materials such as transition metal nitrate, sulfate and other element that uses as required or grinding dispersion in the water equal solvent, when stirring, regulate pH, preparation is also collected spherical precursor, as required this precursor is carried out drying, add LiOH, Li then 2CO 3, LiNO 3In the Li source, and sintering at high temperature, thereby obtain the method for active material.
In addition, example as other method, can enumerate following method: with transition metal raw material such as transition metal nitrate, sulfate, hydroxide, oxide and as required and dissolving of the raw material of other element that uses or grinding dispersion in the water equal solvent, utilize spray dryer etc. to its drying and moulding, make spherical or oval spherical precursor, again to wherein adding LiOH, Li 2CO 3, LiNO 3In the Li source, at high temperature carry out sintering, thereby obtain the method for active material.
As another method, can also enumerate following method: with transition metal raw material and LiOH, Li such as transition metal nitrate, sulfate, hydroxide, oxides 2CO 3, LiNO 3Deng the Li source, and the raw material dissolving of other element of using as required or grinding dispersion in the water equal solvent, utilize spray dryer etc. that it is carried out drying and moulding, make spherical or oval spherical precursor, it is at high temperature carried out sintering, thereby obtain the method for active material.
＜2-4-2. electrode structure and manufacture method 〉
Below, describe at structure of the positive pole that in the present invention 1, uses and preparation method thereof.
(1) Zheng Ji manufacture method
Positive pole makes by form the positive electrode active material layer that contains positive active material particle and binding agent on collector body.Use the manufacturing of the positive pole of positive active material can utilize known any means to prepare.Promptly, can be with positive active material and binding agent and as required and electric conducting material that uses and thickener etc. carry out dry type and mix and make sheet, again this flaky material is attached on the positive electrode collector, or with these material dissolves or be dispersed in and make slurry in the liquid medium, and be coated on this slurry on the positive electrode collector and carry out drying, thereby on collector body, form positive electrode active material layer, and then obtain anodal.
The content of positive active material in positive electrode active material layer is generally more than the 10 weight %, is preferably more than the 30 weight %, especially is preferably more than the 50 weight %, and be generally 99.9 weight % following, be preferably below the 99 weight %.This be because, when the positive active material content in the positive electrode active material layer is lower than above-mentioned scope, may cause electric capacity to become insufficient; And when content surpasses above-mentioned scope, may cause anodal undercapacity.Need to prove that the positive electrode active material powder among the present invention 1 can use a kind separately, also can be used in combination the positive electrode active material powder that has different compositions or different powder properties more than 2 kinds with combination in any and ratio.
(2) electric conducting material
As electric conducting material, can use the electric conducting material of any known.As object lesson, can enumerate metal materials such as copper, nickel; Graphite such as native graphite, Delanium (graphite); Carbon blacks such as acetylene black; Carbonaceous materials such as amorphous carbon such as needle coke etc.Wherein, above-mentioned electric conducting material can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
In the positive electrode active material layer contained electric conducting material be generally 0.01 weight % above, be preferably 0.1 weight % above, more preferably more than the 1 weight %, and be generally 50 weight % following, be preferably 30 weight % following, more preferably below the 15 weight %.When content is lower than above-mentioned scope, may cause the conductivity deficiency.And when surpassing above-mentioned scope, may cause battery capacity to reduce.
(3) binding agent
The binding agent that uses when making positive electrode active material layer is not so long as with respect to the binding agent of employed solvent-stable when making nonaqueous electrolytic solution or electrode, then have particular restriction.
When adopting rubbing method, so long as solubilized or the material that is dispersed in the liquid medium that uses when making electrode get final product, as object lesson, can enumerate resinae macromolecules such as polyethylene, polypropylene, PETG, polymethyl methacrylate, aromatic polyamide, cellulose, NC Nitroncellulose; Rubber-like macromolecules such as SBR (butadiene-styrene rubber), NBR (acrylonitrile-butadiene rubber), fluorubber, isoprene rubber, butadiene rubber, ethylene-propylene rubber; Thermoplastic elastomer (TPE) shape macromolecules such as SBS or its hydride, EPDM (ethylene-propylene-diene terpolymers), styrene-ethylene-butadiene vinyl copolymer, SIS or its hydride; Syndiotactic 1, soft resinous macromolecules such as 2-polybutadiene, polyvinyl acetate, vinyl-vinyl acetate copolymer, propylene-alpha-olefin copolymers; Kynoar (PVdF), polytetrafluoroethylene, fluoridize fluorine family macromolecules such as Kynoar, polytetrafluoroethylene-ethylene copolymer; Polymeric composition etc. with ionic conductivity of alkali metal ion (particularly lithium ion).Above-mentioned substance can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
In the positive electrode active material layer the shared ratio of binding agent be generally 0.1 weight % above, be preferably 1 weight % above, more preferably more than the 3 weight %, and be generally 80 weight % following, be preferably 60 weight % following, more preferably 40 weight % following, especially be preferably below the 10 weight %.If the ratio of binding agent is lower than above-mentioned scope, then positive active material can't be able to abundant maintenance, may cause degradation of cell performance such as anodal mechanical strength deficiency, cycle characteristics.In addition, when surpassing above-mentioned scope, then may cause battery capacity or conductivity and reduce.
(4) liquid medium
As the liquid medium that is used to form slurry, so long as can dissolve or disperse positive active material, electric conducting material, binding agent and as required and the solvent of the thickener that uses gets final product, its kind is not had particular restriction, can use in aqueous solvent and the organic solvent any.
The example of aqueous medium can be enumerated the blending agent of water for example, alcohol and water etc.As the example of organic class medium, can enumerate: fat hydrocarbons such as hexane; Arene such as benzene,toluene,xylene, methyl naphthalene; Heterocyclic compound such as quinoline, pyridine; Ketones such as acetone, methylethylketone, cyclohexanone; Ester such as methyl acetate, methyl acrylate class; Diethylenetriamines, N, amines such as N-dimethylamino propylamine; Ether, oxolane ethers such as (THF); Amide-types such as N-methyl pyrrolidone (NMP), dimethyl formamide, dimethylacetylamide; Non-proton property such as hexamethyl phosphoramide, methyl-sulfoxide polar solvent etc.Need to prove that above-mentioned medium can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
(5) thickener
When using the aqueous medium conduct to be used to form the liquid medium of slurry, preferably use the latex of thickener and butadiene-styrene rubber (SBR) etc. carry out slurryization.Thickener can be used to regulate the viscosity of slurry usually.
As thickener, in the scope of the effect that does not significantly limit the present invention 1, there is no the system limit, specifically can enumerate carboxymethyl cellulose, methylcellulose, CMC, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, zymoprotein and their salt etc.Above-mentioned thickener can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
In addition, when using thickener, thickener with respect to the ratio of active material be generally more than the 0.1 weight %, be preferably more than the 0.5 weight %, more preferably more than the 0.6 weight %, and be generally 5 weight % following, be preferably 3 weight % following, more preferably below the 2 weight %.If be lower than above-mentioned scope, then may cause the remarkable reduction of coating, and when surpassing above-mentioned scope, active material shared ratio in positive electrode active material layer descends, and may cause the problem that resistance increases between problem that battery capacity reduces or positive active material.
(6) compacting
In order to improve the packed density of positive active material, preferably the positive electrode active material layer that obtains through coating, drying is carried out compacting by hand press, roll squeezer etc.The density of positive electrode active material layer is preferably 1gcm -3More than, 1.5gcm more preferably -3More than, especially be preferably 2gcm -3More than, and be preferably 4gcm -3Below, more preferably at 3.5gcm -3Below, especially preferably at 3gcm -3Below.
If the density of positive electrode active material layer surpasses above-mentioned scope, then near the impregnability of nonaqueous electrolytic solution collector body/reactive species interface reduces, and particularly, may cause the charge-discharge characteristic under high current density to reduce.And when the density of positive electrode active material layer is lower than above-mentioned scope, may cause the conductivity between active material to reduce, cell resistance increases.
(7) collector body
Material as positive electrode collector does not have particular restriction, can use known material arbitrarily.As object lesson, can enumerate metal materials such as aluminium, stainless steel, nickel plating, titanium, tantalum; Carbonaceous material such as carbon cloth, carbon paper.Wherein, preferred metal materials, especially preferred aluminium.
As the shape of collector body, when material is metal material, can enumerate metal forming, metal cylinder, wire coil, metallic plate, metallic film, expansion alloy, perforated metal, foaming metal etc.; When material is carbonaceous material, can enumerate carbon plate, carbon film, carbon cylinder etc.In these materials, the preferable alloy film.Need to prove that film can suitably form netted.
Collector body can be any thickness, but be generally 1 μ m above, be preferably 3 μ m above, more preferably more than the 5 μ m, and be generally 1mm following, be preferably 100 μ m following, more preferably below the 50 μ m.If film thickness less than above-mentioned scope, then may cause the necessary undercapacity as collector body.And, may destroy operability when film thickness during greater than above-mentioned scope.
＜2-5. dividing plate 〉
In order to prevent short circuit, between positive pole and negative pole, sandwich dividing plate usually.At this moment, the present invention 1 nonaqueous electrolytic solution is soaked in this dividing plate and uses.
Material and shape for dividing plate do not have particular restriction, as long as in the scope of the effect of significantly not destroying the present invention 1, can adopt material known and shape arbitrarily.Wherein, can use with resin that the stable material of nonaqueous electrolytic solution of the present invention is formed, glass fibre, inorganic matter etc., the preferred use has the excellent porousness sheet material of fluidity or the material of nonwoven fabrics shape form etc. protected.
As the separator material of resin, glass fibre, can use for example polyolefin such as polyethylene, polypropylene, polytetrafluoroethylene, polyether sulfone, glass filter etc.Wherein, preferred glass filter, polyolefin, especially preferred polyolefm.These materials can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
Aforementioned barriers can be an any thickness, but be generally 1 μ m above, be preferably 5 μ m above, more preferably more than the 10 μ m, and be generally 50 μ m following, be preferably 40 μ m following, more preferably below the 30 μ m.If block board thickness less than above-mentioned scope, then may cause insulating properties or mechanical strength to reduce.In addition, when block board thickness surpasses above-mentioned scope, then not only may cause battery performance reductions such as speed characteristics, the energy density that also may cause rechargeable nonaqueous electrolytic battery integral body descends.
In addition, when using porous materials such as porousness sheet material or nonwoven fabrics as dividing plate, the voidage of dividing plate is arbitrarily, but be generally more than 20%, be preferably more than 35%, more preferably more than 45%, and be generally below 90%, be preferably below 85%, more preferably below 75%.If voidage is less than above-mentioned scope, then film resistance increases, and may cause the speed characteristics variation.And compare with above-mentioned scope when excessive when voidage, may cause the mechanical strength of dividing plate to reduce, insulating properties descends.
In addition, the average pore size of dividing plate also is arbitrarily, but be generally 0.5 μ m following, be preferably below the 0.2 μ m, and be generally more than the 0.05 μ m.If average pore size surpasses above-mentioned scope, then be short-circuited easily.On the other hand, if average pore size is lower than above-mentioned scope, then may cause film resistance increase, speed characteristics to reduce.
On the other hand, as inorganic material, can use that for example aluminium oxide or silicon dioxide etc. are oxide-based, Sulfates such as aluminium nitride or silicon nitride etc. are nitride-based, barium sulfate or calcium sulfate, can use the inorganic material of shape of particle or fiber shape.
As form, can adopt nonwoven fabrics, weave cotton cloth, film shape such as micro-porous film.As film shape, being fit to use the aperture is that 0.01～1 μ m, thickness are the film of 5～50 μ m.Except above-mentioned independently film shape, can also use following dividing plate: use resinous binding agent on the top layer of positive pole and/or negative pole, to form the dividing plate that contains the composite porous layer of above-mentioned inorganic particles and obtain.For example, can use fluororesin, make the aluminium oxide particles of 90% particle diameter less than, 1 μ m on the two sides of positive pole, form porous layer as binding agent.
＜2-6. battery design 〉
[electrode group]
The electrode group can be to clip the above-mentioned positive plate of aforementioned barriers lamination and negative plate and the laminar structure that obtains and clip aforementioned barriers above-mentioned positive plate and negative plate are wound in the spiral helicine structure any one.The volume of electrode group shared ratio (hereinafter referred to as electrode group occupation rate) in internal cell volume is generally more than 40%, is preferably more than 50%, and is generally below 90%, is preferably below 80%.If electrode group occupation rate is lower than above-mentioned scope, then can cause battery capacity to reduce.And when electrode group occupation rate surpasses above-mentioned scope, void space is little, when battery is in high temperature, can cause that parts expand, or the vapour pressure that causes electrolytical liquid component raises, internal pressure rises, and reduces as all characteristics such as the repeated charge performance of battery and high temperature preservations, and then may need gas release valve to carry out work to be released into the outside to help internal pressure.
[current collection structure]
Do not have particular restriction for the current collection structure, but the structure that reduces distribution part and bonding part resistance is preferably made in the raising of the flash-over characteristic that causes for the nonaqueous electrolytic solution of more effectively realizing by the present invention 1.So, when internal resistance is reduced, use the effect of the present invention 1 nonaqueous electrolytic solution to be brought into play especially excellently.
In the electrode group is under the situation of above-mentioned laminar structure, preferably adopts following structure: the metal-cored part of each electrode layer is tied together and welding on terminal and the structure that forms.Because when increasing the area of 1 cube electrode, internal resistance increases, thereby also preferably adopts the method that a plurality of terminals reduce resistance that is provided with in electrode thereupon.In the electrode group is under the situation of above-mentioned winding-structure, can on anodal and negative pole a plurality of pin configurations be set respectively, and is bundled in and reduces internal resistance on the terminal.
[battery case (adorning ケ one ス outward)]
As the material of battery case,, there is no particular restriction so long as the stable material of nonaqueous electrolyte that uses is got final product.Particularly, can adopt metal species such as nickel-clad steel plate, stainless steel, aluminum or aluminum alloy, magnesium alloy, or the stack membrane of resin and aluminium foil (stacked film).Consider from the lightweight aspect, preferably use metal, the stacked film of aluminum or aluminum alloy.
State in the use in the battery case of metal species, can enumerate shell with following structure: by laser welding, resistance welded, ultrasonic bonding with the sealing closed structure that forms of welding mutually between the metal; Or use above-mentioned metal species and the riveted structure that forms through resin system packing ring.State in the use in the battery case of stacked film, can enumerate by with the mutual sealing closed structure made of heat fused etc. between the resin bed.In order to improve sealing, can also between above-mentioned resin bed, sandwich the resin different with the resin that is used for stacked film.Particularly, when resin bed being carried out the incompatible formation closed structure of hot melt by current-collecting terminals, because bonding mutually between metal and the resin, thereby the preferred modified resin that has the resin of polar group or imported polar group that uses is as the resin that is clamped between the resin bed.
[protection component]
As above-mentioned protection component; the PTC (Positive Temperature Coefficient, positive temperature coefficient) that resistance increases in the time of can being set forth in unusual heat release or super-high-current and flowing through, temperature fuse, thermistor, when unusual heat release, sharply raise and flow through the valve (current blocking valve) etc. of electric current in the blocking circuit by cell internal pressure or internal temperature.The element of idle condition when the routine that above-mentioned protection component preferably is chosen in high electric current is used, the angle from height output does not exist protection component to be unlikely to take place the design of unusual heat release or thermal runaway even more preferably make yet.
[shell (exterior body)]
The present invention 1 rechargeable nonaqueous electrolytic battery normally is accommodated in above-mentioned nonaqueous electrolytic solution, negative pole, positive pole, dividing plate etc. in the shell and constitutes.For this shell without limits, in the scope of the effect of significantly not destroying the present invention 1, can adopt known shell arbitrarily.
Particularly, shell can be any material, but usually iron, stainless steel, aluminium or its alloy, nickel, the titanium etc. of nickel plating have for example been implemented in use.
In addition, the shape of shell also is arbitrarily, can be for example cylinder type, square, cascade type, Coin shape, the arbitrary shape in large-scale etc.
＜nonaqueous electrolytic solution 2, rechargeable nonaqueous electrolytic battery 2 〉
[1. secondary cell nonaqueous electrolytic solution]
The present invention 2 secondary cell nonaqueous electrolytic solution is to be the main nonaqueous electrolytic solution that constitutes by electrolyte and this electrolytical nonaqueous solvents of dissolving, described nonaqueous electrolytic solution contain be selected from chain saturated hydrocarbons, cyclic saturated hydrocarbons, have the aromatic compound class of halogen atom and have at least a kind of compound in the ethers of fluorine atom (below, abbreviate " the present invention 2 compound group " as), also contain mono-fluor phosphate and/or difluorophosphoric acid salt
＜1-1. electrolyte 〉
Electrolyte for the nonaqueous electrolytic solution that is used for the present invention 2 is also unrestricted, wherein can adopt arbitrarily and contain to can be used as the known electrolyte that electrolyte uses in the target rechargeable nonaqueous electrolytic battery.In addition, when the present invention 2 nonaqueous electrolytic solution was used for rechargeable nonaqueous electrolytic battery, electrolyte was preferably lithium salts.
As electrolytical object lesson, for example can enumerate: be documented in the present invention 1 in identical electrolyte.
Wherein, preferred LiPF 6, LiBF 4, LiCF 3SO 3, LiN (CF 3SO 2) 2, LiN (C 2F 5SO 2) 2, two (oxalate closes) lithium borate, especially preferred LiPF 6Or LiBF 4
Electrolytical kind, the electrolytical ratio when being used in combination when being used in combination electrolyte are identical with situation in being documented in the present invention 1.
In addition, the lithium salt in the final composition of the present invention 2 nonaqueous electrolytic solution, preferred concentration etc. are identical with situation in being documented in the present invention 1.In addition, the phenomenon that when departing from number range, takes place also be documented in the present invention 1 in situation identical.
Particularly, for the nonaqueous solvents of nonaqueous electrolytic solution situation based on the such carbonate products of alkylene carbonates or dialkyl carbonate, also be documented in the present invention 1 in situation identical.The phenomenon that takes place when in addition, departing from number range also be documented in the present invention 1 in situation identical.
In addition, during cyclic carboxylic acids ester compounds such as the gamma-butyrolacton more than containing 50 volume % in the nonaqueous solvents in the nonaqueous electrolytic solution, gamma-valerolactone, also be documented in the present invention 1 in situation identical.
＜1-2. nonaqueous solvents 〉
The present invention 2 the nonaqueous solvents that nonaqueous electrolytic solution contained is identical with situation in the nonaqueous solvents that nonaqueous electrolytic solution contained that is documented in the present invention 1.
＜1-3. the present invention 2 compound group 〉
" the present invention 2 compound group " is to be selected from chain saturated hydrocarbons, cyclic saturated hydrocarbons, to have the aromatic compound class of halogen atom and to have at least a kind of compound in the ethers of fluorine atom, in these compounds, from the high angle of the climbing of output characteristic, preferred cyclic saturated hydrocarbons or have the ethers of fluorine atom.The compound of selecting from the present invention 2 compound group can use a kind, also can combination in any use more than 2 kinds.Below, each compound that constitutes " the present invention 2 compound group " among the present invention 2 is more specifically described.
＜1-3-1. chain saturated hydrocarbons 〉
As the chain saturated hydrocarbons, be not particularly limited, but consider from the viewpoint of operation, be the low chain saturated hydrocarbons of liquid and toxicity at normal temperatures preferably; Consider the chain saturated hydrocarbons that preferred molecular weight is smaller from the viewpoint of battery behavior.More specifically, the chain saturated hydrocarbons of preferred carbon number 5～20, the chain saturated hydrocarbons of preferred especially carbon number 7～16.
Particularly, preference such as pentane, hexane, heptane, octane, nonane, decane, hendecane, 12 carbon alkane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane or icosane, preferred especially heptane, octane, nonane, decane, hendecane, 12 carbon alkane, tridecane, tetradecane, pentadecane or hexadecane.These chain saturated hydrocarbons can be the straight chain shapes, also can be chains.In addition, these chain saturated hydrocarbons can use a kind, also can combination in any use more than 2 kinds.
＜1-3-2. cyclic saturated hydrocarbons 〉
As cyclic saturated hydrocarbons, be not particularly limited, but the cyclic saturated hydrocarbons of preferred carbon number 3～20, the cyclic saturated hydrocarbons of preferred especially carbon number 5～16.
Particularly, preferred cyclopropane, cyclobutane, pentamethylene, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, ring hendecane, ring 12 carbon alkane, ring tridecane, ring tetradecane, ring pentadecane, ring hexadecane, ring heptadecane, ring octadecane, ring nonadecane or ring icosane, special optimization cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, ring hendecane, ring 12 carbon alkane, ring tridecane, ring tetradecane, ring pentadecane or ring hexadecane.
In addition, these cyclic saturated hydrocarbons can also have straight chained alkyl in molecule, described straight chained alkyl without limits, the alkyl of preferred carbon number 1～8.Particularly, for example can enumerate: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or octyl group.The most preferred example of cyclic saturated hydrocarbon is a cyclohexane.These cyclic saturated hydrocarbons can be used a kind, also can combination in any use more than 2 kinds.
＜1-3-3. has the aromatic compound class of halogen atom 〉
Aromatic compound class as having halogen atom is not particularly limited, as halogen atom, and preferred fluorine atom or chlorine atom, preferred especially fluorine atom.In addition, but the halogen atom Direct Bonding also can contain halogen atom in substituting group on aromatic rings.
Object lesson as aromatic compound class with halogen atom, for example can enumerate: fluorobenzene, chlorobenzene, 1,2-two fluorobenzene, 1,3-two fluorobenzene, 1,4-two fluorobenzene, 1,2-dichloro-benzenes, 1,3-dichloro-benzenes, 1,4-dichloro-benzenes, 1,2,4-trifluoro-benzene, 1,3,5-trifluoro-benzene, 1,2,4,6-phenyl tetrafluoride, phenyl-hexafluoride, 2-toluene fluoride, 3-toluene fluoride, 4-toluene fluoride, methyl fluoride benzene, benzal fluoride, trifluoromethylbenzene, 2-fluoro-1-trifluoromethylbenzene, 4-fluoro-1-trifluoromethylbenzene, 2-fluorine biphenyl, adjacent cyclohexyl fluorobenzene, to cyclohexyl fluorobenzene etc.Preferred fluorobenzene, 2-toluene fluoride, 4-toluene fluoride or trifluoromethylbenzene.These " the aromatic compound classes with halogen atom " can use a kind, also can combination in any use more than 2 kinds.
＜1-3-4. has the ethers of fluorine atom 〉
Ethers as having fluorine atom is not particularly limited, if with general formula ethers is expressed as " R 5-O-R 6", then " ethers with fluorine atom " is at R 5Or R 6At least one group in contain fluorine atom.Wherein, if R 5Be the group that contains fluorine atom, then R 5Be preferably the alkyl of the carbon number 1～20 that is replaced by 1～30 fluorine atom.
Wherein, as preferred object lesson, for example can enumerate:
Methyl fluoride, difluoromethyl, trifluoromethyl;
1-fluoro ethyl, 2-fluoro ethyl, 1,1-two fluoro ethyls, 1,2-two fluoro ethyls, 2,2-two fluoro ethyls, 1,1,2-trifluoroethyl, 1,2,2-trifluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoro ethyl, 1,2,2,2-tetrafluoro ethyl, pentafluoroethyl group;
3-fluoropropyl, 3,3-two fluoropropyls, 3,3,3-trifluoro propyl, 2,2,3,3,3-five fluoropropyls, seven fluoropropyls;
4-fluorine butyl, 4,4-difluoro butyl, 4,4,4-trifluoro butyl, 3,3,4,4,4-five fluorine butyl, 2,2,3,3,4,4,4-seven fluorine butyl, nine fluorine butyl;
5-fluorine amyl group, 5,5-difluoro amyl group, 5,5,5-trifluoro amyl group, 4,4,5,5,5-five fluorine amyl groups, 3,3,4,4,5,5,5-seven fluorine amyl groups, 2,2,3,3,4,4,5,5,5-nine fluorine amyl groups, 11 fluorine amyl groups;
6-fluorine hexyl, 6,6-difluoro hexyl, 6,6,6-trifluoro hexyl, ten trifluoro hexyls etc.
In addition, R 6Be preferably the alkyl of choosing the carbon number 1～20 that is replaced by substituting groups such as halogen atoms wantonly, particularly, except R 5In cited containing beyond the fluoroalkyl, also can list: common chain-like alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl (a straight chain shape or a chain); And contain cycloalkyl such as alkylhalide group, cyclohexyl etc. beyond the fluorine.
Instantiation as fluorine-containing ethers, can enumerate: ethyl 2-fluoro ethyl ether, two (2-fluoro ethyl) ether, ethyl 2,2,2-trifluoroethyl ether, two (2,2, the 2-trifluoroethyl) ether, two (pentafluoroethyl group) ether, methyl 3-fluoropropyl ether, 3-fluoropropyl fluoromethyl ether, 3-fluoropropyl trifluoromethyl ethers, 3-fluoropropyl ethylether, 3-fluoropropyl 2-fluoro ethyl ether, methyl 3,3,3-trifluoro propyl ether, ethyl 3,3,3-trifluoro propyl ether, 3,3,3-trifluoro propyl 2-fluoro ethyl ether, 3,3,3-trifluoro propyl 2,2,2-trifluoroethyl ether, methyl seven fluoropropyl ethers, ethyl seven fluoropropyl ethers, seven fluoropropyls 2,2,2-trifluoroethyl ether, seven fluoropropyl pentafluoroethyl group ethers, methyl 4-fluorine butyl ether, ethyl 4-fluorine butyl ether, 4-fluorine butyl 2-fluoro ethyl ether, ethyl 4,4,4-trifluoro butyl ether, 4,4,4-trifluoro butyl 2-fluoro ethyl ether, 4,4,4-trifluoro butyl 2,2,2-trifluoroethyl ether, 4,4,4-trifluoro butyl pentafluoroethyl group ether, methyl nine fluorine butyl ethers, ethyl nine fluorine butyl ethers, nine fluorine butyl 2-fluoro ethyl ethers, nine fluorine butyl 2,2,2-trifluoroethyl ether, nine fluorine butyl pentafluoroethyl group ethers etc.
Wherein, preferred ethyl 2-fluoro ethyl ether, two (2-fluoro ethyl) ether, ethyl 2,2,2-trifluoroethyl ether, two (2,2, the 2-trifluoroethyl) ether, ethyl seven fluoropropyl ethers or ethyl nine fluorine butyl ethers.These fluorine-containing ethers can use a kind, also can combination in any use more than 2 kinds.
＜1-3-5. content 〉
As " the present invention 2 compound group " content with respect to the nonaqueous electrolytic solution total amount, be not particularly limited, but viewpoint from battery behavior, be preferably 0.01 weight % above, more preferably 0.1 weight % above, be preferably more than the 0.3 weight % especially, on the other hand, its upper limit be preferably 15 weight % following, more preferably 12 weight % following, be preferably below the 10 weight % especially.When the content of " the present invention 2 compound group " is very few, might not can help " mono-fluor phosphate and/or difluorophosphoric acid salt " described later to have the excellent effect of " output " and " output of circulation back ".
＜1-4. mono-fluor phosphate, difluorophosphoric acid salt 〉
" mono-fluor phosphate and/or the difluorophosphoric acid salt " that uses among the present invention 2 is identical with the present invention 1.Preferred range is also identical with invention 1.
The single fluorophosphoric acid slaine of＜1-4-1., difluorophosphoric acid slaine 〉
At first, be the situation of the salt that forms of single fluorophosphoric acid radical ion, difluorophosphoric acid radical ion and special metal ion for the mono-fluor phosphate among the present invention 2, difluorophosphoric acid salt, its object lesson can be enumerated the example identical with the present invention 1.
The single fluorophosphoric acid quaternary salt of＜1-4-2., difluorophosphoric acid quaternary salt 〉
Secondly, be single fluorophosphoric acid radical ion, difluorophosphoric acid radical ion and the situation of the salt of season formation for the mono-fluor phosphate among the present invention 2, difluorophosphoric acid salt, its object lesson can be enumerated the example identical with the present invention 1.
＜1-4-3. content, detection (source of containing), technical scope etc. 〉
In the present invention 2 nonaqueous electrolytic solution, can only use a kind of mono-fluor phosphate or difluorophosphoric acid salt, also can be so that combination and ratio are used mono-fluor phosphate and/or difluorophosphoric acid salt more than 2 kinds simultaneously arbitrarily, but, preferably use a kind of mono-fluor phosphate or difluorophosphoric acid salt from making the effectively viewpoint consideration of work of rechargeable nonaqueous electrolytic battery.
In addition, the molecular weight of mono-fluor phosphate and difluorophosphoric acid salt, preparation method, the ratio in nonaqueous electrolytic solution etc. are with illustrated identical among the present invention 1.
In addition, the detection period of mono-fluor phosphate or difluorophosphoric acid salt (period of containing), the place (source of containing), the method that contains that at first contain at first, be regarded as in nonaqueous electrolytic solution, containing the detection place of (or having contained) etc., with illustrated identical among the present invention 1.
＜1-5. additive 〉
In the scope of the effect of significantly not destroying the present invention 2, can also contain various additives in the present invention 2 the nonaqueous electrolytic solution.Prepare when handling adding additive, can use known in the past additive arbitrarily.Need to prove that additive can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
As the example of additive, the capacity retention performance that can enumerate overcharges after preventing from agent or be used to improve high temperature to preserve and the auxiliary agent of cycle characteristics etc.Wherein, as being used to improve the capacity retention performance after high temperature is preserved and the auxiliary agent of cycle characteristics, the preferred carbonic ester one of at least that has in unsaturated bond and the halogen atom (below, abbreviate " particular carbon acid esters " sometimes as) that adds.
＜1-5-1. particular carbon acid esters 〉
The object lesson of particular carbon acid esters, can enumerate with the present invention 1 in same particular carbon acid esters.
Other additive of＜1-5-2. 〉
Below, describe at other additive beyond the particular carbon acid esters.As the additive beyond the particular carbon acid esters, can enumerate overcharges prevents agent, be used for improving the capacity retention performance after high temperature is preserved and the auxiliary agent of cycle characteristics etc.
＜1-5-2-1. overcharges and prevents agent 〉
Prevent the object lesson of agent as overcharging, can enumerate following aromatic compound:
Toluene derivative such as toluene, dimethylbenzene;
Non-replacements such as biphenyl, 2-methyl biphenyl, 3-methyl biphenyl, 4-methyl biphenyl or the biphenyl derivatives that is replaced by alkyl;
Non-replacements such as ortho-terphenyl, meta-terphenyl, para-terpheny or the terphenyl derivative that is replaced by alkyl;
The partial hydrogenation thing of non-replacement or the terphenyl derivative that replaced by alkyl;
Cycloalkyl benzene derivatives such as cyclopenta benzene, cyclohexyl benzene;
Isopropylbenzene, 1,3-diisopropyl benzene, 1,4-diisopropyl benzene etc. has the benzene derivative of the tertiary carbon of Direct Bonding on phenyl ring;
Tert-butyl benzene, tert-amyl benzene, uncle's hexyl benzene etc. have the benzene derivative of the quaternary carbon of Direct Bonding on phenyl ring;
Diphenyl ether, dibenzofurans etc. have the aromatic compound of oxygen atom etc.
Need to prove that these overcharge and prevent that agent from can use a kind separately, also can use simultaneously more than 2 kinds with combination in any.In addition, when using simultaneously, belong to the compound of same classification in the above-mentioned example of use capable of being combined, also can be used in combination different classes of compound with combination in any.
Instantiation when being used in combination different classes of compound is identical with the present invention 1.
The present invention 2 nonaqueous electrolytic solution contains and overcharges when preventing agent, and its concentration, its effect are identical with the present invention 1.
＜1-5-2-2. auxiliary agent 〉
Object lesson as the auxiliary agent that is used to improve capacity retention performance after high temperature is preserved and cycle characteristics can be listed below:
The acid anhydrides of dicarboxylic acids such as butanedioic acid, maleic acid, phthalic acid;
Carbonic acid erythrite ester, the carbonic acid spiral shell-two-carbonate products except the carbonic ester that is equivalent to the particular carbon acid esters such as dimethylene ester;
Sulfurous acid glycol ester, 1,3-N-morpholinopropanesulfonic acid lactone, 1,4-butyl sultone, methyl mesylate, 1,4-dimethane sulfonoxybutane, sulfolane, cyclobufene sultone, dimethyl sulfone, diphenyl sulfone, methyl phenyl sulfone, dibutyl disulfide, dicyclohexyldisulfide, tetramethylthiuram monosulfide, N, N-dimethyl methyl sulfonamide, N, sulfur-containing compounds such as N-diethyl Methanesulfomide;
1-Methyl-2-Pyrrolidone, 1-methyl-2-piperidones, 3-methyl-2-oxazolidone, 1, nitrogen-containing compounds such as 3-dimethyl-2-imidazolidinone, N-methyl succimide;
Hydrocarbon compounds such as heptane, octane, cycloheptane etc.
The preparation method of＜1-6. nonaqueous electrolytic solution 〉
The preparation method of nonaqueous electrolytic solution 2 is identical with the present invention 1.
[2. rechargeable nonaqueous electrolytic battery]
The present invention 2 rechargeable nonaqueous electrolytic battery have the invention described above 2 nonaqueous electrolytic solution and can occlusion and emit the negative pole and the positive pole of ion.
Battery structure; Negative pole; Carbonaceous material; The structure of carbonaceous negative pole, rerum natura, preparation method; The metal compound composition material, and use structure, rerum natura, the preparation method of the negative pole of metal compound composition material; Anodal; Dividing plate; Battery design etc. are identical with the present invention's 1 record.
＜effect 〉
Be selected from the present invention's 2 by using to contain simultaneously " the present invention 2 compound group " though compound and the nonaqueous electrolytic solution of mono-fluor phosphate and/or difluorophosphoric acid salt make rechargeable nonaqueous electrolytic battery show that effect, the principle of high output characteristic are also indeterminate, can think following mechanism.But the present invention 2 is not limited to following effect, principle.Promptly, " the present invention 2 comparative example 6 " is such as described later, also can obtain to a certain degree height output even only contain difluorophosphoric acid salt, and as " the present invention 2 comparative example 2～5 ", only be that the compound that is selected from " the present invention 2 compound group " does not then show clear and definite effect, therefore, can think that the compound of " the present invention 2 the compound group " that be selected from the present invention 2 has booster action to the effect of mono-fluor phosphate and difluorophosphoric acid salt.Particularly, can think that the interaction of compound by being selected from " the present invention 2 compound group " and electrode makes output is had mono-fluor phosphate that improves effect or the more depths that difluorophosphoric acid salt is induced to electrode active material layer, thereby improve the interaction with electrode.
＜nonaqueous electrolytic solution 3, rechargeable nonaqueous electrolytic battery 3 〉
[1. nonaqueous electrolytic solution]
The present invention 3 nonaqueous electrolytic solution is identical with nonaqueous electrolytic solution commonly used, contains electrolyte and this electrolytical nonaqueous solvents of dissolving.
＜1-1. electrolyte 〉
The electrolyte that is contained in the nonaqueous electrolytic solution for the present invention 3 there is no the system limit, and can adopt arbitrarily and contain can be as the known electrolyte of electrolyte use in the target rechargeable nonaqueous electrolytic battery.Need to prove that when the present invention 3 nonaqueous electrolytic solution was used for lithium rechargeable battery, electrolyte preferably used lithium salts.
As electrolytical object lesson, for example can enumerate be documented in the present invention 1 in identical electrolyte.
Wherein, preferred LiPF 6, LiBF 4, LiCF 3SO 3, LiN (CF 3SO 2) 2, LiN (C 2F 5SO 2) 2, two (oxalate closes) lithium borate, especially preferred LiPF 6Or LiBF 4
Electrolytical kind, the electrolytical ratio when being used in combination when being used in combination electrolyte are identical with situation in the nonaqueous electrolytic solution that is documented in the present invention 1.
In addition, the lithium salt in the final composition of the present invention 3 nonaqueous electrolytic solution, preferred concentration etc. are identical with situation in being documented in nonaqueous electrolytic solution 1.In addition, the phenomenon that when departing from number range, takes place also be documented in nonaqueous electrolytic solution 1 in situation identical.
Particularly, for the nonaqueous solvents of nonaqueous electrolytic solution situation, also identical with situation in the nonaqueous electrolytic solution that is documented in the present invention 1 based on the such carbonate products of alkylene carbonates or dialkyl carbonate.The phenomenon that takes place when in addition, departing from number range is also identical with situation in the nonaqueous electrolytic solution that is documented in the present invention 1.
In addition, during cyclic carboxylic acids ester compounds such as the gamma-butyrolacton more than containing 50 volume % in the nonaqueous solvents in the nonaqueous electrolytic solution, gamma-valerolactone, also be documented in the present invention 1 in situation identical.
The represented compound of＜1-2. general formula (1) 〉
In the present invention 3, the represented compound of general formula (1) is following compound.
[chemical formula 7]
Figure A20088001284000821
[R 1, R 2, R 3, R 4Independent separately, be organic group or halogen atom, R 1, R 2, R 3, R 4In at least one be that atom with the X Direct Bonding is heteroatomic group, R 1, R 2, R 3, R 4Identical or different, X is the atom beyond the carbon atom.]
In the present invention 3 the general formula (1),,, be not particularly limited, but in view of the stability in nonaqueous electrolytic solution etc., preferably silicon atom or titanium atom so long as the atom beyond the carbon atom get final product for X.
R 1, R 2, R 3, R 4Represent organic group or halogen atom independently of one another.Described organic group is not particularly limited, and in " described organic group ", is the group of carbon atom as the atom with the X bonding, can enumerate optional have substituent alkyl, alkenyl, alkynyl etc.The carbon number of these organic groups more preferably 1～10.
Particularly, as alkyl, can enumerate: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, isopropyl, isobutyl group, 2-methyl-propyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1,2-dimethyl propyl, neopentyl etc.; As alkenyl, can enumerate: vinyl, pi-allyl, isopropenyl, 1-acrylic, cyclobutenyl, butadienyl, pentenyl etc.; As alkynyl, can enumerate: acetenyl, 1-propinyl, 1-butynyl, 1-pentynyl, 2-propynyl, 2-butynyl, 3-butynyl etc.
The substituting group of these groups is not particularly limited, and can enumerate: fluorine atom, chlorine atom, methacryloxy, sulfydryl, alkyl amino, arylamino, glycidoxy, benzoyloxy group, acetoxyl group etc.
As halogen atom, can enumerate: fluorine atom, chlorine atom, bromine atoms, iodine atom, preferred especially chlorine atom or fluorine atom.
In addition, R 1, R 2, R 3, R 4In at least one be that become the atom of direct key with X-shaped be heteroatomic group.Hetero-atom is not particularly limited so long as the atom beyond the carbon atom gets final product, but because the reactive height of B, N, O, P, S or halogen atom, the result can obtain excellent cycle characteristics, and is therefore preferred.Wherein, preferred especially halogen atom, oxygen atom or nitrogen-atoms.
" with the atom of X Direct Bonding be heteroatomic group " in, when hetero-atom is oxygen atom, particularly, for example can enumerate: alkoxyls such as methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, isopropoxy, 1-methyl propoxyl group, 2-methyl propoxyl group, tert-butoxy; Benzoyloxy group, acetoxyl group etc.In addition, when hetero-atom is nitrogen-atoms, particularly, for example can enumerate: dimethylamino, diethylamino, ethylmethylamino etc.Wherein, because reason same as described above, more preferably alkoxyls such as methoxyl group, ethyoxyl, propoxyl group, butoxy.
" with the atom of X Direct Bonding be heteroatomic group " can be halogen atom.The halogen atom of this moment is preferably fluorine atom, chlorine atom, bromine atoms or iodine atom, because reason same as described above, more preferably chlorine atom.
" with the atom of X Direct Bonding be heteroatomic group " optional have substituting group, but because reason same as described above does not more preferably have substituent alkoxyl or chlorine atom.
With regard to the represented compound of the general formula among the present invention 3 (1), R 1, R 2, R 3, R 4In at least 1 be that atom with the X Direct Bonding is heteroatomic group, preferred R 1, R 2, R 3, R 4In at least 2 be that atom with the X Direct Bonding is heteroatomic group, preferred especially R 1, R 2, R 3, R 4In 2 or 3 for " with the atom of X Direct Bonding be heteroatomic group ".At this moment, can obtain the secondary cell nonaqueous electrolytic solution of cycle characteristics excellence.
As its reason, electrode with " with the atom of X Direct Bonding be heteroatomic group " when take place interacting, if " with the atom of X Direct Bonding be heteroatomic group " very few, then the interaction between these groups is sometimes very little, in addition, R particularly 1, R 2, R 3, R 4These 4 groups be " with the atom of X Direct Bonding be heteroatomic group " time disappear owing to interactional group takes place with nonaqueous electrolytic solution, therefore, can not carry out the stabilisation of electrode sometimes fully.
In general formula (1), R 1, R 2, R 3, R 4Can be the same or different.
As the object lesson of the represented compound of the present invention's 3 formula ofs (1), for example can enumerate: vinyl trichlorosilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, the 3-methyl allyl acyloxypropyl trimethoxysilane, the 2-methyl allyl acyloxypropyl trimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-mercaptopropyl trimethoxysilane, N-(2-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(2-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-(2-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, the 3-aminopropyl trimethoxysilane, the 3-aminopropyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, the 3-glycidoxy-propyltrimethoxy silane, 3-epoxypropoxy triethoxysilane, (the positive butoxy carbonyl benzoyloxy group of 2-) three titanium butoxide, diisopropoxy titanium diisostearate (ジ イ ソ プ ロ Port キ シ チ タ Application ジ イ ソ ス テ ア レ one ト), stearic acid titanium etc.Above-claimed cpd can be used singly or in combination of two or more.
When X was titanium, preferred acetylacetone,2,4-pentanedione, Acetacetic acid alkyl ester isochela combination compound carried out coordination to titanium and the organic titanium chelate compound that forms etc.Above-claimed cpd can be used singly or in combination of two or more.
The represented compound of＜1-3. general formula (2) 〉
In the present invention 3, the represented compound of general formula (2) is following compound.
[chemical formula 8]
[R 5, R 6, R 7Independent separately, be organic group or halogen atom, R 5, R 6, R 7In at least one be that atom with the Y Direct Bonding is the hetero-atom group of (comprising halogen atom), R 5, R 6, R 7Identical or different, Y is the atom beyond the carbon atom.]
In the present invention 3 general formula (2), R 5, R 6, R 7Independent separately, be organic group or halogen atom, here, for organic group or halogen atom, organic group or the halogen atom put down in writing in the general formula (1) are all applicable.In addition, R 5, R 6, R 7In at least one be that atom with the Y Direct Bonding is heteroatomic group, here, for " hetero-atom " and " with the atom of Y Direct Bonding be heteroatomic group ", hetero-atom of being put down in writing in the general formula (1) and corresponding group are all applicable.
For the Y in the present invention 3 the general formula (2), if the stability of consideration in electrolyte etc., preferred aluminium atom.
R 5, R 6, R 7In at least one be " with the atom of Y Direct Bonding be heteroatomic group ", but preferred R 5, R 6, R 7Any 2 be that the atom that forms direct key with Y is heteroatomic group.At this moment, can obtain the secondary cell nonaqueous electrolytic solution of cycle characteristics excellence.
As its reason, electrode with " with the atom of Y Direct Bonding be heteroatomic group " when take place interacting, at R 5, R 6, R 7In " with the atom of Y Direct Bonding be heteroatomic group " under the very few situation, the interaction between these groups is too small sometimes, in addition, R 1, R 2, R 3These 3 groups be " with the atom of Y Direct Bonding be heteroatomic group " time disappear owing to interactional group takes place with nonaqueous electrolytic solution, therefore, can not carry out the stabilisation of electrode sometimes fully.
In general formula (2), R 5, R 6, R 7Can be the same or different.
As the represented compound of the present invention's 3 formula ofs (2), particularly, can enumerate acetylacetone,2,4-pentanedione diisopropyl aluminium etc.These compounds can be used singly, or in combination of two or more kinds separately.
For aluminium, except the acetylacetone,2,4-pentanedione of above-mentioned concrete example, can also enumerate coordination has organo-aluminium chelate compound of other chelate compounds such as alkyl acetylacetonate etc.These compounds can be used singly, or in combination of two or more kinds separately.
The content of the compound that compound that＜1-4. general formula (1) is represented and general formula (2) are represented 〉
Total amount shared ratio in the nonaqueous electrolytic solution total amount of the compound that represented compound, the present invention's 3 formula ofs (2) of the present invention's 3 formula ofs (1) are represented is preferably 0.001 weight %～10 weight %, is preferably the ratio of 0.01 weight %～5 weight % especially.With respect to the nonaqueous electrolytic solution total amount, when the total content of the compound that represented compound, the present invention's 3 formula ofs (2) of the present invention's 3 formula ofs (1) are represented is very few, its effect can not be given full play to, the secondary cell nonaqueous electrolytic solution of cycle characteristics excellence might be able to not obtained; On the other hand, when the total content of the compound that represented compound, the present invention's 3 formula ofs (2) of the present invention's 3 formula ofs (1) are represented was too much, because the reaction of himself, the capacity of battery might be impaired.
Be preferably as follows the preparation nonaqueous electrolytic solution, that is, with respect to the nonaqueous electrolytic solution total amount, the total amount of the compound that the present invention's 3 formula ofs (1) of interpolation or general formula (2) are represented is 0.001 weight %～10 weight %; The total amount of the compound that preferred especially the present invention's 3 formula ofs (1) that add or general formula (2) are represented is 0.01 weight %～5 weight %.
＜1-5. nonaqueous solvents 〉
The present invention 3 the nonaqueous solvents that nonaqueous electrolytic solution contained is identical with the present invention 1 the nonaqueous solvents that nonaqueous electrolytic solution contained.
＜1-6. mono-fluor phosphate, difluorophosphoric acid salt 〉
The present invention 3 nonaqueous electrolytic solution contains mono-fluor phosphate and/or the conduct of difluorophosphoric acid salt must composition." mono-fluor phosphate and/or the difluorophosphoric acid salt " that uses among the present invention 3 is identical with " mono-fluor phosphate and/or the difluorophosphoric acid salt " of use among the present invention 1.
The single fluorophosphoric acid slaine of＜1-6-1., difluorophosphoric acid slaine 〉
Mono-fluor phosphate among the present invention 3, difluorophosphoric acid salt be single fluorophosphoric acid radical ion, difluorophosphoric acid radical ion and special metal ion form salt (note is made " single fluorophosphoric acid slaine ", " difluorophosphoric acid slaine " respectively) time, identical with situation among the present invention 1.
The single fluorophosphoric acid quaternary salt of＜1-6-2., difluorophosphoric acid quaternary salt 〉
When the mono-fluor phosphate among the present invention 3, difluorophosphoric acid salt were the salt (note is made " single fluorophosphoric acid quaternary salt ", " difluorophosphoric acid quaternary salt " respectively) that forms in single fluorophosphoric acid radical ion, difluorophosphoric acid radical ion and season, also the situation with the present invention 1 was identical.
＜1-6-3. content, detection (source of containing), technical scope etc. 〉
In the present invention 3 the nonaqueous electrolytic solution, can only use a kind of mono-fluor phosphate or difluorophosphoric acid salt, also can be so that combination and ratio are used in combination mono-fluor phosphate and/or difluorophosphoric acid salt more than 2 kinds arbitrarily, but, preferably use a kind of mono-fluor phosphate or difluorophosphoric acid salt from making the effectively viewpoint consideration of work of rechargeable nonaqueous electrolytic battery.
In addition, the molecular weight of mono-fluor phosphate and difluorophosphoric acid salt, preparation method, the ratio in nonaqueous electrolytic solution etc. are with illustrated identical among the present invention 1.
In addition, the detection period of mono-fluor phosphate or difluorophosphoric acid salt (period of containing), the place (source of containing), the method that contains that at first contain at first, be regarded as in nonaqueous electrolytic solution, containing the detection place of (or having contained) etc., also with the present invention 1 in illustrated identical.
＜1-7. additive 〉
In the scope of the effect of significantly not destroying the present invention 3, can also contain various additives in the present invention 3 the nonaqueous electrolytic solution.Prepare when handling adding additive, can use known in the past additive arbitrarily.Need to prove that additive can use a kind separately, also can be used in combination more than 2 kinds with combination in any and ratio.
As the example of additive, can enumerate overcharges prevents agent, be used to improve the capacity retention performance after high temperature is preserved and the auxiliary agent of cycle characteristics etc.Wherein, as being used to improve the capacity retention performance after high temperature is preserved and the auxiliary agent of cycle characteristics, the preferred carbonic ester one of at least that has in unsaturated bond and the halogen atom (below, also can abbreviate " particular carbon acid esters " as) that adds.
＜1-7-1. particular carbon acid esters 〉
The object lesson of particular carbon acid esters is identical with the present invention 1.
Other additive of＜1-7-2. 〉
As the additive beyond the particular carbon acid esters, can enumerate overcharges prevents agent, be used to improve the capacity retention performance after high temperature is preserved and the auxiliary agent of cycle characteristics etc.The overcharge object lesson that prevents agent and the object lesson of concentration, its effect and auxiliary agent thereof, with put down in writing among the present invention 1 identical.
The preparation method of＜1-6. nonaqueous electrolytic solution 〉
The preparation method of nonaqueous electrolytic solution 3 is identical with the present invention 1.
[2. rechargeable nonaqueous electrolytic battery]
The present invention 3 rechargeable nonaqueous electrolytic battery have the invention described above 3 nonaqueous electrolytic solution and can occlusion and emit the positive pole of ion and negative pole and constitute.In addition, the present invention 3 rechargeable nonaqueous electrolytic battery can also have other structure.
Battery structure; Negative pole; Carbonaceous material; The structure of carbonaceous negative pole, rerum natura, preparation method; The metal compound composition material, and use structure, rerum natura, the preparation method of the negative pole of metal compound composition material; Anodal; Dividing plate; Battery design etc., situation about being put down in writing with the present invention 1 is identical.As negative electrode active material,, be not particularly limited so long as electrochemically occlusion and the material of emitting lithium ion get final product.As its object lesson, can enumerate carbonaceous material, alloy type material, contain the metallic composite oxides material of lithium etc.Carbonaceous material, alloy type material, metal compound composition material, contain the object lesson separately of the metallic composite oxides material of lithium; Use structure, rerum natura, the preparation method of the negative pole of various materials also identical with the situation that the present invention 1 is put down in writing.
The processing of＜electrode 〉
In addition, from the battery that can obtain the cycle characteristics excellence and be suppressed at aspects such as electrode surface reacts and consider, preferably the nonaqueous electrolytic solution with the present invention 3 is used for following rechargeable nonaqueous electrolytic battery, and described rechargeable nonaqueous electrolytic battery has the negative or positive electrode of being crossed by the present invention 3 above-mentioned general formula (1) and/or the represented compound treatment of general formula (2).
Employing is selected from the method that at least a kind of compound in the represented compound of the represented compound of the present invention 3 general formula (1) and general formula (2) handles negative or positive electrode and is not particularly limited, but compound that the general formula (1) that preferably makes the present invention 3 is represented and/or the represented compound of general formula (2) are evenly distributed on the method for electrode surface, particularly, the represented compound of preferred that the present invention 3 general formula (1) is represented especially compound and/or general formula (2) dissolves or is dispersed in solvent or the decentralized medium, re-uses the method that resulting liquid floods or is coated with this electrode.
In addition, can also handle positive active material or negative electrode active material, this situation is also contained among the present invention 3 the notion of " processing of negative or positive electrode ".At this moment, can followingly handle: the represented compound of compound that the present invention 3 general formula (1) is represented or general formula (2) dissolves or is dispersed in solvent or the decentralized medium, the liquid that obtains is mixed with positive active material or negative electrode active material, handle thus; Can also use the active material after the processing to make negative or positive electrode.In addition, more firm for compound and the interaction between electrode or the electrode active material that the represented compound of the general formula (1) that makes the present invention 3 and/or general formula (2) are represented, preferably the electrode after handling is carried out Overheating Treatment.Overtemperature is preferably 45 ℃～300 ℃, more preferably 60 ℃～200 ℃.
＜nonaqueous electrolytic solution 4, rechargeable nonaqueous electrolytic battery 4 〉
[1. nonaqueous electrolytic solution]
The present invention 4 nonaqueous electrolytic solution is identical with nonaqueous electrolytic solution commonly used, contains electrolyte and this electrolytical nonaqueous solvents of dissolving.
＜1-1〉lithium salts
The lithium salts that contains in the present invention 4 the nonaqueous electrolytic solution is not particularly limited, and can use the known lithium salts that uses as electrolyte in the target rechargeable nonaqueous electrolytic battery arbitrarily.As the object lesson of lithium salts, for example can enumerate with the present invention 1 in the identical lithium salts of lithium salts put down in writing as electrolyte.
Electrolytical kind, the ratio of lithium salts when being used in combination are identical with the lithium salts of putting down in writing as electrolyte among the present invention 1 when being used in combination electrolyte.
In addition, the lithium salt in the final composition of the present invention 4 nonaqueous electrolytic solution 4, preferred concentration etc. are identical with situation in being documented in nonaqueous electrolytic solution 1.In addition, the phenomenon that when departing from number range, takes place also be documented in nonaqueous electrolytic solution 1 in situation identical.
Particularly, for the nonaqueous solvents of nonaqueous electrolytic solution situation based on the such carbonate products of alkylene carbonates or dialkyl carbonate, also be documented in nonaqueous electrolytic solution 1 in situation identical.The phenomenon that takes place when in addition, departing from number range also be documented in nonaqueous electrolytic solution 1 in situation identical.
＜1-2. nonaqueous solvents 〉
The present invention 4 the nonaqueous solvents that nonaqueous electrolytic solution contained is identical with solvent described in the nonaqueous solvents that the present invention 1 nonaqueous electrolytic solution contains.
＜1-3〉additive
The present invention 4 nonaqueous electrolytic solution must contain the represented compound of following general formula (1), preferably further contains mono-fluor phosphate and/or difluorophosphoric acid salt, in addition, also preferably contains the carbonic ester that one of has in unsaturated bond and the halogen atom at least.That is to say, in the present invention 4 execution mode 4-1, contain the represented compound of following general formula (1) and " mono-fluor phosphate and/or difluorophosphoric acid salt " as additive.In addition, in the present invention 4 execution mode 4-2, containing with respect to the nonaqueous electrolytic solution total amount is the represented compound of general formula (1) of 0.001 weight %～5 weight %, and to contain with respect to the nonaqueous electrolytic solution total amount be 0.001 weight %～5 weight % one of " have in unsaturated bond and the halogen atom at least carbonic ester ".
＜1-3-1〉the represented compound of general formula (1)
About the present invention 4 nonaqueous electrolytic solution, be the represented necessary composition of compound conduct of general formula (1) that execution mode 4-1 or execution mode 4-2 contain following the present invention 4.
[chemical formula 9]
[in general formula (1), A and B represent various substituting groups, and wherein at least 1 is fluorine, and n represents the natural number more than 3.]
In the present invention 4 above-mentioned general formula (1), A and B represent various substituting groups, and wherein at least 1 is a fluorine.Substituting group beyond the defluorination is not particularly limited, but considers its reactivity, preferred not replacement or the alkyl or aryl that is replaced by fluorine.In addition, between preferred described alkyl or aryl and the P by oxygen atom with ehter bond and P bonding.That is to say, also preferred on described alkyl or aryl bonding the group of oxygen atom is arranged.
The carbon number of abovementioned alkyl, aryl is not particularly limited, but when substituting group when shared structure/part by weight increases in the represented basic framework of general formula (1), the addition of the compound represented with respect to general formula (1), its effect weakens, also has side effect in addition, therefore preferred carbon number below 10, the more preferably alkyl or aryl of carbon number below 6, only with regard to alkyl, more preferably carbon number is below 3.
As the concrete example of these alkyl, can enumerate: methyl, methyl fluoride, difluoromethyl, trifluoromethyl, ethyl, the 1-fluoro ethyl, the 2-fluoro ethyl, 1,1-two fluoro ethyls, 1,2-two fluoro ethyls, 2,2-two fluoro ethyls, 1,1, the 2-trifluoroethyl, 1,2, the 2-trifluoroethyl, 2,2, the 2-trifluoroethyl, 1,1,2,2-tetrafluoro ethyl, 1,2,2,2-tetrafluoro ethyl, pentafluoroethyl group, propyl group (n-pro-pyl), the 1-fluoropropyl, the 2-fluoropropyl, the 3-fluoropropyl, 1,1-two fluoropropyls, 1,2-two fluoropropyls, 1,3-two fluoropropyls, 2,2-two fluoropropyls, 2,3-two fluoropropyls, 3,3-two fluoropropyls, 1,1, the 2-trifluoro propyl, 1,2, the 2-trifluoro propyl, 1,1, the 3-trifluoro propyl, 1,2, the 3-trifluoro propyl, 1,3, the 3-trifluoro propyl, 2,2, the 3-trifluoro propyl, 2,3, the 3-trifluoro propyl, 3,3, the 3-trifluoro propyl, 1,1,2,2-tetrafluoro propyl group, 1,1,2,3-tetrafluoro propyl group, 1,1,3,3-tetrafluoro propyl group, 1,2,2,3-tetrafluoro propyl group, 1,2,3,3-tetrafluoro propyl group, 2,2,3,3-tetrafluoro propyl group, 2,3,3,3-tetrafluoro propyl group, 1,1,2,2,3-five fluoropropyls, 1,2,2,3,3-five fluoropropyls, 1,1,3,3,3-five fluoropropyls, 1,2,3,3,3-five fluoropropyls, 2,2,3,3,3-five fluoropropyls, 1,1,2,2,3,3-hexafluoro propyl group, 1,1,2,3,3,3-hexafluoro propyl group, 1,2,2,3,3,3-hexafluoro propyl group, seven fluoropropyls, 1-Methylethyl (isopropyl), 1-fluoro-1-Methylethyl, 2-fluoro-1-Methylethyl, 1,2-two fluoro-1-Methylethyls, 1,2-two fluoro-1-(methyl fluoride) ethyls, 1,2,2-three fluoro-1-Methylethyls, 2,2,2-three fluoro-1-Methylethyls, 2,2,-two fluoro-1-(methyl fluoride) ethyls, 1,2,2,2-tetrafluoro-1-Methylethyl, 1,2,2-three fluoro-1-(methyl fluoride) ethyls, 2,2,2-three fluoro-1-(methyl fluoride) ethyls, 2,2-two fluoro-1-(difluoromethyl) ethyls, 1,2,2,2-tetrafluoro-1-(methyl fluoride) ethyl, 1,2,2-three fluoro-1-(difluoromethyl) ethyls, 2,2,2-three fluoro-1-(difluoromethyl) ethyls, 1,2,2,2-tetrafluoro-1-(difluoromethyl) ethyl, 2,2,2-three fluoro-1-(trifluoromethyl) ethyls, 1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl etc.
Wherein, consider from the angle of easy manufacturing, more preferably methyl, methyl fluoride, trifluoromethyl, ethyl, 2-fluoro ethyl, 2,2,2-trifluoroethyl, pentafluoroethyl group, propyl group, 3-fluoropropyl, 3,3,3-trifluoro propyl, seven fluoropropyls, 1-Methylethyl, 1-fluoro-1-Methylethyl, 2-fluoro-1-Methylethyl, 2-fluoro-1-(methyl fluoride) ethyl, 2,2,2-three fluoro-1-(trifluoromethyl) ethyls, 1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl, special preferable methyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, propyl group, 1-Methylethyl.
As aryl, preferred replace or, particularly, can enumerate: phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2 by the phenyl that fluorine replaces, 3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4,5-tetrafluoro phenyl, 2,3,4,6-tetrafluoro phenyl, 2,3,5,6-tetrafluoro phenyl, pentafluorophenyl group etc.
Wherein, more preferably phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, preferred especially phenyl.
In n repetitive, A can be the same or different, but preferably identical.In addition, in n the repetitive, B can be the same or different, but preferably identical.
A or B are that the ratio of fluorine atom is not particularly limited, consider from the angle of the above-mentioned effect of easy performance, preferred A or B are the high person of ratio of fluorine atom, and preferably its ratio is more than 1/3, more preferably more than 1/2, be preferably more than 2/3 especially, most preferably is the situation of fluorine entirely.
On structural stability, n is necessary for more than 3, but higher limit is not particularly limited.
As the present invention 4 the represented compound of general formula (1), particularly, can enumerate for example following compound.
[Chemical formula 1 0]
(the ring three phosphonitrile classes that hydrogen atom is all replaced by fluorine atom)
Figure A20088001284000911
(ring three phosphonitrile classes) with the methyl that connects by oxygen
Figure A20088001284000912
(ring three phosphonitrile classes) with the ethyl that connects by oxygen
Figure A20088001284000913
(ring three phosphonitrile classes) with the propyl group that connects by oxygen
Figure A20088001284000914
(ring three phosphonitrile classes) with the isopropyl that connects by oxygen
Figure A20088001284000915
(ring three phosphonitrile classes) with the phenyl that connects by oxygen
Figure A20088001284000916
[Chemical formula 1 1]
(ring three phosphonitrile classes) with the trifluoromethyl that connects by oxygen
Figure A20088001284000921
(ring three phosphonitrile classes) with the trifluoroethyl that connects by oxygen
Figure A20088001284000922
(the ring four phosphonitrile classes that hydrogen atom is all replaced by fluorine atom)
Figure A20088001284000923
(ring four phosphonitrile classes) with the methyl that connects by oxygen
Figure A20088001284000924
(ring four phosphonitrile classes) with the ethyl that connects by oxygen
Figure A20088001284000925
[Chemical formula 1 2]
(ring four phosphonitrile classes) with the propyl group that connects by oxygen
Figure A20088001284000931
(ring four phosphonitrile classes) with the isopropyl that connects by oxygen
Figure A20088001284000932
(ring four phosphonitrile classes) with the phenyl that connects by oxygen
Figure A20088001284000933
(ring four phosphonitrile classes) with the trifluorophenyl that connects by oxygen
Figure A20088001284000934
(ring four phosphonitrile classes) with the trifluoroethyl that connects by oxygen
Figure A20088001284000935
[Chemical formula 1 3]
(the ring five phosphonitrile classes that hydrogen atom is all replaced by fluorine atom)
Figure A20088001284000941
(ring five phosphonitrile classes) with the methyl that connects by oxygen
Figure A20088001284000942
(ring five phosphonitrile classes) with the ethyl that connects by oxygen
Figure A20088001284000943
[Chemical formula 1 4]
(ring five phosphonitrile classes) with the propyl group that connects by oxygen
Figure A20088001284000951
(ring five phosphonitrile classes) with the isopropyl that connects by oxygen
(ring five phosphonitrile classes) with the phenyl that connects by oxygen
Figure A20088001284000953
[Chemical formula 1 5]
(ring five phosphonitrile classes) with the trifluoromethyl that connects by oxygen
Figure A20088001284000961
(ring five phosphonitrile classes) with the trifluoroethyl that connects by oxygen
Figure A20088001284000962
(the ring six phosphonitrile classes that hydrogen atom is all replaced by fluorine atom)
Figure A20088001284000963
[Chemical formula 1 6]
(ring six phosphonitrile classes) with the methyl that connects by oxygen
Figure A20088001284000971
(ring six phosphonitrile classes) with the ethyl that connects by oxygen
Figure A20088001284000972
[Chemical formula 1 7]
(ring six phosphonitrile classes) with the propyl group that connects by oxygen
Figure A20088001284000981
(ring six phosphonitrile classes) with the isopropyl that connects by oxygen
Figure A20088001284000982
[Chemical formula 1 8]
(ring six phosphonitrile classes) with the phenyl that connects by oxygen
(ring six phosphonitrile classes) with the trifluorophenyl that connects by oxygen
Figure A20088001284000992
[Chemical formula 1 9]
(ring six phosphonitrile classes) with the trifluoroethyl that connects by oxygen
Figure A20088001284001001
In execution mode 4-1, these that contain in the nonaqueous electrolytic solution are not particularly limited with the ratio of the represented compound of the present invention 4 general formula (1), but the scope of preferred 0.001 weight %～2 weight %, more preferably scope, the further scope of preferred 0.1 weight %～1 weight % of scope, the preferred especially 0.05 weight %～1.3 weight % of 0.01 weight %～1.7 weight %.In addition, the scope of preferred 0.001 volume %～1 volume %, more preferably scope, the further scope of preferred 0.1 volume %～0.5 volume % of scope, the preferred especially 0.05 volume %～0.7 volume % of 0.01 volume %～0.8 volume %.
In addition, in execution mode 4-2, these that contain in the nonaqueous electrolytic solution are necessary for the scope of 0.001 weight %～5 weight %, more preferably scope, the further scope of preferred 0.1 weight %～1 weight % of scope, the preferred especially 0.05 weight %～2 weight % of 0.01 weight %～3 weight % with the ratio of the represented compound of the present invention 4 general formula (1).In addition, the scope of preferred 0.001 volume %～3 volume %, more preferably scope, the further scope of preferred 0.1 volume %～0.5 volume % of scope, the preferred especially 0.05 volume %～1 volume % of 0.01 volume %～2 volume %.
Above-mentioned " volume % " 4 the represented compound of general formula (1) calculates in the density of room temperature according to the present invention.
No matter in execution mode 4-1 or in execution mode 4-2, it is above and 0.001 volume % is above, more preferably 0.01 weight % is above and 0.01 volume % is above, preferred especially 0.05 weight % is above and 0.05 volume % is above, further preferred 0.1 weight % is above and more than the 0.1 volume % that these that contain in the nonaqueous electrolytic solution all are preferably 0.001 weight % with the ratio of the represented compound of the present invention 4 general formula (1).In addition, preferred upper limit is below the 2 weight % and below the 1 volume %.The compound concentrations represented as if the present invention 4 general formula (1) is low excessively, then is difficult to obtain the effect of improving of discharge load characteristic sometimes, and be opposite if excessive concentration then causes efficiency for charge-discharge to reduce sometimes.Need to prove that when containing the represented compound of the general formula (1) of the present invention 4 more than 2 kinds, above-mentioned content is meant its total amount.
＜1-4. mono-fluor phosphate, difluorophosphoric acid salt 〉
" mono-fluor phosphate and/or the difluorophosphoric acid salt " that uses among the present invention 4 is identical with the present invention 1.Preferred range is also identical with invention 1.
The single fluorophosphoric acid slaine of＜1-4-1., difluorophosphoric acid slaine 〉
At first, be the situation of the salt that forms of single fluorophosphoric acid radical ion, difluorophosphoric acid radical ion and special metal ion for the present invention 4 mono-fluor phosphate, difluorophosphoric acid salt, its concrete example can be enumerated the example identical with the present invention 1.
The single fluorophosphoric acid quaternary salt of＜1-4-2., difluorophosphoric acid quaternary salt 〉
Then, be under the situation of the salt that forms in single fluorophosphoric acid radical ion, difluorophosphoric acid radical ion and season for the present invention 4 mono-fluor phosphate, difluorophosphoric acid salt, its concrete example can be enumerated the example identical with the present invention 1.
＜1-4-3. content, detection (source of containing), technical scope etc. 〉
In the present invention 4 nonaqueous electrolytic solution, can only use a kind of mono-fluor phosphate or difluorophosphoric acid salt, also can be used in combination mono-fluor phosphate and/or difluorophosphoric acid salt more than 2 kinds with combination in any and ratio, consider from the viewpoint that makes the rechargeable nonaqueous electrolytic battery efficient operation, preferably use a kind of mono-fluor phosphate or difluorophosphoric acid salt.
In addition, the molecular weight of mono-fluor phosphate, difluorophosphoric acid salt, manufacture method, the ratio in nonaqueous electrolytic solution etc. all with the present invention 1 in illustrated identical.
In addition, the detection period of mono-fluor phosphate or difluorophosphoric acid salt (period of containing), the place (source of containing), the method that contains that at first contain at first, be regarded as in nonaqueous electrolytic solution, containing the detection place of (or having contained) etc., also with the present invention 1 in illustrated identical.
＜1-5-1〉the particular carbon acid esters
In execution mode 4-1, preferred add the carbonic ester that one of has in unsaturated bond and the halogen atom at least (below, sometimes abbreviate " particular carbon acid esters " as) as the additive except that the represented compound of the present invention 4 general formula (1), mono-fluor phosphate or difluorophosphoric acid salt, in execution mode 4-2, then must add the carbonic ester that one of has in unsaturated bond and the halogen atom at least (below, abbreviate " particular carbon acid esters " sometimes as) as the additive except that the represented compound of the present invention 4 general formula (1), mono-fluor phosphate or difluorophosphoric acid salt.When containing the particular carbon acid esters, have and prevent the effect of overcharging, but also can improve capacity retention performance after high temperature is preserved, cycle characteristics etc.
The particular carbon acid esters can only contain unsaturated bond, also can only contain halogen atom, can also contain unsaturated bond and halogen atom.
The particular carbon acid esters is identical with particular carbon acid esters described in the present invention 1.
＜1-5-2〉other additive
In the scope of the effect that does not influence the present invention 4, the present invention 4 nonaqueous electrolytic solution also can further contain to overcharge and prevents agent, is used to improve the capacity retention performance after high temperature is preserved and " other additives " such as auxiliary agents of cycle characteristics.As other additive, can use known in the past additive arbitrarily.The concrete example that prevents agent and concentration, its effect etc. of overcharging all with the present invention 1 in put down in writing identical.
In addition, these overcharge and prevent that agent from can use a kind separately, also can be used in combination more than 2 kinds with combination in any.In addition, be used in combination with combination in any and overcharge more than 2 kinds when preventing agent, can be used in combination the compound of the above-mentioned same category of enumerating, also can be used in combination the compounds of different classification.
As the concrete example of the situation of the compounds that are used in combination different classification, can enumerate the example identical with the present invention 1.
In addition, as the object lesson of the auxiliary agent that is used to improve capacity retention performance after high temperature is preserved and cycle characteristics, except that the cited auxiliary agent of the present invention 1, can also enumerate: phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate; Phosphorous acid esters such as Trimethyl phosphite, triethyl phosphite, triphenyl phosphite; Phosphorus-containing compounds such as phosphinoxides such as trimethyl phosphine oxide, triethyl group phosphine oxide, triphenylphosphine oxide etc.
These " other additives " are not particularly limited with respect to the addition of the present invention 4 nonaqueous electrolytic solution, only otherwise appreciable impact the present invention 4 effect gets final product, can be addition arbitrarily, nonaqueous electrolytic solution with respect to the present invention 4, usually wish to contain the above concentration of 0.01 weight %, preferably contain the above concentration of 0.1 weight %, more preferably contain the above concentration of 0.3 weight %, and wish to contain the following concentration of 10 weight % usually, preferably contain the following concentration of 5 weight %, more preferably contain the following concentration of 3 weight %, further preferably contain the following concentration of 2 weight %.
The preparation method of＜1-6. nonaqueous electrolytic solution 〉
The preparation method of the present invention 4 nonaqueous electrolytic solution is identical with the present invention 1.
[2. rechargeable nonaqueous electrolytic battery]
The present invention 4 rechargeable nonaqueous electrolytic battery have the invention described above 4 nonaqueous electrolytic solution and can occlusion and emit the negative pole and the positive pole of ion.
Battery structure; Negative pole; Carbonaceous material; The structure of carbonaceous negative pole, rerum natura, preparation method; The metal compound composition material, and use structure, rerum natura, the preparation method of the negative pole of metal compound composition material; Anodal; Dividing plate; Battery design etc. all with the present invention 1 put down in writing identical.
By with the said structure optimization, can reduce internal resistance as far as possible.In the battery that uses with big electric current, the preferably impedance of measuring with the 10kHz alternating current method (below, abbreviate " DC resistance component " as) be below 10 milliohms (m Ω), more preferably DC resistance component is below 5 milliohms (m Ω).
When DC resistance component is 0.1 milliohm when following, high output characteristic improves, but the shared ratio of employed sometimes current collection structural material increases, and battery capacity reduces.
The present invention 4 nonaqueous electrolytic solution has effect for reducing because of lithium breaks away from and inserts aspect the reaction resistance that (taking off Inserted goes into) produce in electrode active material, this is the major reason that can realize good cryogenic discharging characteristic.But in the battery of common D.C. resistance greater than 10 milliohms (m Ω), be subjected to the influence of D.C. resistance sometimes, the effect that reaction resistance reduces can not 100% be reflected on the cryogenic discharging characteristic.Therefore, by using the few battery of DC resistance component, can improve this situation, thereby can give full play to the effect of the present invention 4 nonaqueous electrolytic solution.
In addition, consider from the effect of giving full play to nonaqueous electrolytic solution, the viewpoint of making the battery with high cryogenic discharging characteristic, especially preferably satisfy above-mentioned condition and following condition simultaneously: being accommodated in the electric capacity (electric capacity when battery is discharged to discharge condition by fully charged state) that the cell device (important document) in 1 battery case (adorning) of above-mentioned secondary cell had outward is more than 3 ampere-hours (Ah).
＜nonaqueous electrolytic solution 5, rechargeable nonaqueous electrolytic battery 5 〉
[1. nonaqueous electrolytic solution]
The present invention 5 nonaqueous electrolytic solution is identical with nonaqueous electrolytic solution commonly used, contains lithium salts and dissolves the normal temperature fuse salt of this lithium salts, and be main component with them usually.
＜1-1〉lithium salts
The lithium salts that is contained in the nonaqueous electrolytic solution for the present invention 5 is not particularly limited, and can use the known lithium salts that uses as electrolyte in the target rechargeable nonaqueous electrolytic battery arbitrarily.As the object lesson of lithium salts, for example can enumerate the lithium salts of putting down in writing as electrolyte among the present invention 1.
The ratio of the lithium salts of the electrolytical kind when lithium salts is used in combination, this moment, with in the nonaqueous electrolytic solution 1 as electrolyte put down in writing identical.
Concentration for lithium salts in the nonaqueous electrolytic solution is not particularly limited, and is generally more than the 0.1mol/L, is preferably more than the 0.2mol/L, more preferably more than the 0.3mol/L.In addition, its upper limit be generally 3mol/L following, be preferably 2mol/L following, more preferably 1.8mol/L following, be preferably below the 1.5mol/L especially.If the concentration of lithium salts is low excessively, then the conductivity of nonaqueous electrolytic solution is insufficient sometimes, and on the other hand, if the excessive concentration of lithium salts, then because viscosity increases, and conductivity reduces, battery performance might reduce.
The present invention 5 nonaqueous electrolytic solution contains lithium salts and normal temperature fuse salt.And, in described nonaqueous electrolytic solution, contain " being selected from least a compound in mono-fluor phosphate and the difluorophosphoric acid salt ".
＜1-2. normal temperature fuse salt 〉
Said among the present invention 5 " normal temperature fuse salt " is meant the ionic substance (salt) that 1 molecular structure is made of 1 or 1 above cation and anion, and 45 ℃ down these salt be the material of liquid partly or entirely.In addition,, keep supercooled state steadily in the long term and exist, also can include the scope of the present invention 5 normal temperature fuse salt in liquid form as long as it operates in 45 ℃ by quenching etc. even the fusing point that records by the heat analysis is the compound more than 45 ℃.In addition, even at 45 ℃ of salt that are solid state, when described salt can become liquid condition by mixing with other ionic substances such as lithium salts, mono-fluor phosphate class or difluorophosphoric acid salts under 45 ℃, this salt also can be included the scope of the present invention 5 normal temperature fuse salt in.
As the normal temperature fuse salt that uses among the present invention 5, as long as satisfy above-mentioned condition, be not particularly limited, wherein, preferably be the normal temperature fuse salt of liquid condition down at 25 ℃, more preferably be the normal temperature fuse salt of liquid condition down, be the normal temperature fuse salt of liquid condition down particularly preferably in 10 ℃ at 15 ℃.
The cationic structural that forms the normal temperature fuse salt is not particularly limited, and the cationic structural that is formed by organic substance easily becomes liquid condition at 45 ℃, and is therefore preferred.Contain in this nonaqueous electrolytic solution be selected from uncle's sulfonium salt with structure shown in the following general formula (1), when having the quaternary ammonium salt of structure shown in the following general formula (2) and having at least a kind of normal temperature fuse salt in the structure De quaternary alkylphosphonium salt shown in the following general formula (3), viscosity is low, therefore more preferably.
[Chemical formula 2 0]
Figure A20088001284001041
[in general formula (1), R 1r, R 2rAnd R 3rThe organic group of representing carbon number 1～12 independently of one another.R 1r, R 2rAnd R 3rIn the optional mutual bonding of 2 organic groups and form ring structure.]
[Chemical formula 2 1]
Figure A20088001284001051
[in general formula (2), R 4r, R 5r, R 6rAnd R 7rThe organic group of representing carbon number 1～12 independently of one another.R 4r, R 5r, R 6rAnd R 7rIn the optional mutual bonding of 2～4 organic groups and form ring structure, perhaps R 4r, R 5r, R 6rAnd R 7rIn 2 organic groups be actually 1 organic group, described 1 organic group and " N +" connect with two keys between the atom.]
[Chemical formula 2 2]
Figure A20088001284001052
[in general formula (3), R 8r, R 9r, R 10rAnd R 11rThe organic group of representing carbon number 1～12 independently of one another.R 8r, R 9r, R 10rAnd R 11rIn the optional mutual bonding of 2～4 organic groups and form ring structure, perhaps R 8r, R 9r, R 10rAnd R 11rIn 2 organic groups be actually 1 organic group, this 1 organic group and " P +" connect with two keys between the atom.]
[the represented compound of general formula (1)]
R in the represented sulfonium cation structure of the present invention 5 above-mentioned general formula (1) 1r, R 2rAnd R 3rFor the organic group of identical or different carbon number 1～12, as R 1r, R 2rAnd R 3r, can enumerate: chain-like alkyls such as methyl, ethyl, n-pro-pyl, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group; Cyclic alkyl such as cyclohexyl, norborny; Alkenyls such as vinyl, 1-acrylic, pi-allyl, cyclobutenyl, 1,3-butadiene base; Alkynyls such as acetenyl, propinyl, butynyl; Haloalkyls such as trifluoromethyl, trifluoroethyl, hexafluoro propyl group; Choose aryl such as substituent phenyl such as having alkyl substituent wantonly; Aralkyl such as benzyl, phenylethyl; Trialkylsilkls such as trimethyl silyl; Ethoxycarbonyl-ethyls etc. contain the alkyl of carbonyl; Methoxy ethyl, phenoxymethyl, ethoxyethyl group, allyloxy ethyl, methoxyethoxyethyl, ethoxy ethoxy ethyl etc. contain the alkyl of ether; Sulfonyl methyl etc. contains the alkyl of sulfonyl etc.
R in this sulfonium cation structure 1r, R 2rAnd R 3rChoose mutual bonding wantonly and form ring structure, R 1r, R 2rAnd R 3rSaturated or the unsaturated bond that can also form by assorted unit such as oxygen, nitrogen, sulphur, P elements on above-mentioned substituting group is combined with substituting group.
At R 1r, R 2rAnd R 3rIn, the alkyl of carbon number 1～6, haloalkyl, pi-allyl, contain ether alkyl by reducing the intermolecular interaction of this sulfonium salt, form low-melting salt easily, therefore preferred.
Wherein, because viscosity reduces easily, therefore preferred especially trimethylsulfonium, the triethyl group sulfonium, the dimethyl ethyl sulfonium, methyl diethyl sulfonium, the tripropyl sulfonium, the dimethyl propyl sulfonium, methyl dipropyl sulfonium, diethyl propyl group sulfonium, ethyl dipropyl sulfonium, Methylethyl propyl group sulfonium, the tributyl sulfonium, the dimethylbutyl sulfonium, methyl dibutyl sulfonium, diethyl butyl sulfonium, ethyl dibutyl sulfonium, dipropyl butyl sulfonium, propyl group dibutyl sulfonium, Methylethyl butyl sulfonium, methyl-propyl butyl sulfonium, ethyl propyl butyl sulfonium, or 1 above hydrogen atom in these alkyl is replaced by fluorine atom and the compound that forms; Dimethyl vinyl sulfonium, the dimethyl-allyl sulfonium, dimethyl butyrate thiazolinyl sulfonium, diethyl vinyl sulfonium, diethyl pi-allyl sulfonium, diethyl cyclobutenyl sulfonium, Methylethyl vinyl sulfonium, Methylethyl pi-allyl sulfonium, Methylethyl cyclobutenyl sulfonium, dimethyl methoxy ylmethyl sulfonium, dimethyl methoxy base ethyl sulfonium, dimethyl ethoxyl methyl sulfonium, dimethyl ethoxyethyl group sulfonium, dimethyl methoxy base oxethyl ethyl sulfonium, dimethyl ethoxy ethoxy ethyl sulfonium, diethyl methoxy sulfonium, diethyl methoxy ethyl sulfonium, diethyl ethoxyethyl group sulfonium, diethyl methoxyethoxyethyl sulfonium, diethyl ethoxy ethoxy ethyl sulfonium etc.
Anion as uncle's sulfonium salt of the represented structure of the above-mentioned general formula (1) with the present invention 5 is not particularly limited, and anionic van der Waals radius is
Figure A20088001284001061
Above uncle's sulfonium salt is becoming liquid condition easily below 45 ℃, therefore preferred.Wherein, the element that in form has a negative electrical charge combines with electron-attracting substituent and the anion structure that forms at room temperature becomes liquid condition easily, therefore more preferably.
Wherein, consider that from thermal endurance and the good angle of oxidative resistance preferred especially electron-attracting substituent is a fluorine atom; Cyano group; Contain fluorine, cyano group, alkyl, fluoro-alkyl, cyaniding alkyl, phenyl, fluoro phenyl, have the carbonyl of cyaniding phenyl, and carboxyl, sulfonic group, sulfonyl; Phenyl, fluoro phenyl, the phenyl that contains fluoro-alkyl, cyano-phenyl; Phenoxy group, fluorinated phenoxy, the phenyl that contains fluoro-alkyl, cyaniding phenoxy group; Sulfo-phenoxy group, fluoro sulfo-phenoxy group, the sulfo-phenoxy group that contains fluoro-alkyl, cyaniding sulfo-phenoxy group; Fluoroalkyl, cyaniding alkoxyl; Fluoro thio alkoxy, cyaniding thio alkoxy.
In addition, BF 3Or AlF 3, PF 3, PF 5, SbF 5, AsF 5Deng the lewis acidity compound, by with anion structure in the negative electrical charge position interact and to form the strong anion of oxidative resistance, so identical with above-mentioned electron-attracting substituent group, also can be used as particularly preferred substituting group.
[the represented compound of general formula (2)]
R in the represented quaternary ammonium salt cationic structure of the present invention 5 above-mentioned general formula (2) 4r, R 5r, R 6rAnd R 7rBe the organic group of identical or different carbon number 1～12, as R 4r, R 5r, R 6rAnd R 7r, can enumerate with general formula (1) in " R 1r, R 2rAnd R 3r" identical chain-like alkyl; Cyclic alkyl; Alkenyl; Alkynyl; Haloalkyl; Optional aryl such as phenyl with alkyl substituent; Aralkyl; Trialkylsilkl; The alkyl that contains carbonyl; The alkyl that contains ether; Contain the alkyl of sulfonyl etc.In addition, preferred concrete group also with above-mentioned general formula (1) in " R 1r, R 2rAnd R 3" identical.
R 4r, R 5r, R 6rAnd R 7rIn 2～4 optional mutual bondings and form ring structure, R 4r, R 5r, R 6rAnd R 7rSaturated or the unsaturated bond that can also form by assorted element such as oxygen, nitrogen, sulphur, P elements on above-mentioned substituting group is combined with substituting group.
Shown in above-mentioned in the quaternary ammonium salt cationic structure of general formula (2), in the chain ammonium cation, as R 4r, R 5r, R 6rAnd R 7r, alkyl, haloalkyl, the pi-allyl of preferred carbon number 1～6, contain the alkyl of ether, because they form low-melting salt easily by the intermolecular interaction that reduces this ammonium salt.
Wherein, consider from the angle that viscosity is easy to reduce, more preferably the trimethyl propyl ammonium, trimethyl butyl ammonium, the tri-methyl-amyl ammonium, trimethyl hexyl ammonium, the dimethyl ethyl propyl ammonium, dimethyl ethyl butyl ammonium, dimethyl ethyl amyl group ammonium, dimethyl ethyl hexyl ammonium, the dimethyl dipropylammonium, dimethyl propyl butyl ammonium, dimethyl propyl amyl group ammonium, dimethyl propyl hexyl ammonium, dimethyl dibutyl ammonium, dimethylbutyl amyl group ammonium, dimethylbutyl hexyl ammonium, dimethyl diamyl ammonium, dimethyl amyl group hexyl ammonium, dimethyl dihexyl ammonium, methyl diethyl propyl ammonium, methyl diethyl butyl ammonium, methyl diethyl amyl group ammonium, methyl diethylhexyl ammonium, the Methylethyl dipropylammonium, Methylethyl propyl group butyl ammonium, Methylethyl propyl group amyl group ammonium, Methylethyl propyl group hexyl ammonium, Methylethyl dibutyl ammonium, Methylethyl butyl amyl group ammonium, Methylethyl butyl hexyl ammonium, Methylethyl diamyl ammonium, Methylethyl amyl group hexyl ammonium, Methylethyl dihexyl ammonium, methyl tripropyl ammonium, methyl dipropyl butyl ammonium, methyl dipropyl amyl group ammonium, methyl dipropyl hexyl ammonium, methyl-propyl dibutyl ammonium, methyl-propyl butyl amyl group ammonium, methyl-propyl butyl hexyl ammonium, methyl-propyl diamyl ammonium, methyl-propyl amyl group hexyl ammonium, methyl-propyl dihexyl ammonium, methyltributylammoni,m, methyl dibutyl amyl group ammonium, methyl dibutyl hexyl ammonium, methyl butyl diamyl ammonium, methyl butyl amyl group hexyl ammonium, methyl butyl dihexyl ammonium, methyl three amyl group ammoniums, methyl diamyl hexyl ammonium, methyl amyl dihexyl ammonium, methyl three hexyl ammoniums, the triethyl group propyl ammonium, triethyl group butyl ammonium, triethyl group amyl group ammonium, triethyl group hexyl ammonium etc., or the hydrogen atom in these alkyl is replaced and the compound of formation by 1 above fluorine atom, the trimethyl allyl-ammonium, trimethyl cyclobutenyl ammonium, trimethyl methoxy ammonium, trimethyl methoxy ethyl ammonium, trimethyl methoxyethoxyethyl ammonium etc.
Wherein, can not become excessive from cation size, the number of ions of unit volume (being ion concentration) is not for influencing the suitable size of normal temperature fuse salt feature, and with fusing point, the good angle of the balance of viscosity is considered, preferred especially trimethyl propyl ammonium, trimethyl butyl ammonium, the tri-methyl-amyl ammonium, trimethyl hexyl ammonium, the dimethyl ethyl propyl ammonium, dimethyl ethyl butyl ammonium, dimethyl ethyl amyl group ammonium, dimethyl ethyl hexyl ammonium, dimethyl propyl butyl ammonium, dimethyl propyl amyl group ammonium, dimethyl propyl hexyl ammonium, the triethyl group propyl ammonium, triethyl group butyl ammonium, triethyl group amyl group ammonium, triethyl group hexyl ammonium etc., and the hydrogen atom in these alkyl is replaced and the compound of formation by 1 above fluorine atom, the trimethyl allyl-ammonium, trimethyl cyclobutenyl ammonium, trimethyl methoxy ammonium, trimethyl methoxy ethyl ammonium etc.
In the quaternary ammonium cation structure of above-mentioned general formula (2), R 4r, R 5r, R 6rAnd R 7rIn 2～4 optional mutual bondings and form ring structure, wherein, following general formula (4), general formula (5), the represented saturated heterocyclic structure of general formula (6) form low-melting salt easily, and be therefore preferred.In following general formula (4), general formula (5) and general formula (6), R 12a, R 13a, R 12b, R 13b, R 12c, R 13cWith in the general formula (2) " can different mutually R 4r, R 5r, R 6rAnd R 7r" identical.
[Chemical formula 2 3]
Figure A20088001284001091
[Chemical formula 2 4]
Figure A20088001284001092
[Chemical formula 2 5]
Figure A20088001284001093
In pyrrolidines cation shown in the above-mentioned general formula (4), consider from the angle of easy formation normal temperature fuse salt, more preferably dimethyl pyrrolidine, eryptopyrrole alkane, the diethyl pyrrolidines, the methyl-propyl pyrrolidines, the ethyl propyl pyrrolidines, the dipropyl pyrrolidines, the methyl butyl pyrrolidines, the ethyl-butyl pyrrolidines, the propyl group butyl pyrrolidine, the dibutyl pyrrolidines, or the hydrogen atom in these alkyl is replaced and the compound of formation by 1 above fluorine atom, the methyl ethylene pyrrolidines, the ethyl vinyl pyrrolidines, propyl ethylene base pyrrolidines, the butyl vinyl pyrrolidines, the methacrylic pyrrolidines, the allyl ethyl pyrrolidines, propyl group pi-allyl pyrrolidines, butyl pi-allyl pyrrolidines, the diallyl pyrrolidines, methyl butene base pyrrolidines, ethyl cyclobutenyl pyrrolidines, propyl group cyclobutenyl pyrrolidines, butyl cyclobutenyl pyrrolidines, dibutene base pyrrolidines, methyl methoxy ylmethyl pyrrolidines, methyl methoxy base ethyl pyrrolidine, the methyl ethoxy ethyl pyrrolidine, methyl methoxy base oxethyl ethyl pyrrolidine, methyl ethoxy ethoxyethyl group pyrrolidines, ethyl methoxy pyrrolidines, ethyl methoxy ethyl pyrrolidines, ethyl ethoxyethyl group pyrrolidines, ethyl methoxyethoxyethyl pyrrolidines, ethyl ethoxy ethoxy ethyl pyrrolidine, propyl group methoxy pyrrolidines, propyl group methoxy ethyl pyrrolidines, propyl group ethoxyethyl group pyrrolidines, propyl group methoxyethoxyethyl pyrrolidines, propyl group ethoxy ethoxy ethyl pyrrolidine, butyl methoxy pyrrolidines, butyl methoxy ethyl pyrrolidines, butyl ethoxyethyl group pyrrolidines, butyl methoxyethoxyethyl pyrrolidines, butyl ethoxy ethoxy ethyl pyrrolidine etc.
Wherein, consider special preferable methyl ethyl pyrrolidine from the angle that viscosity reduces easily, the methyl-propyl pyrrolidines, the ethyl propyl pyrrolidines, the methyl butyl pyrrolidines, the ethyl-butyl pyrrolidines, or the hydrogen atom in these alkyl is replaced and the compound of formation by 1 above fluorine atom, the methacrylic pyrrolidines, the allyl ethyl pyrrolidines, propyl group pi-allyl pyrrolidines, butyl pi-allyl pyrrolidines, methyl butene base pyrrolidines, ethyl cyclobutenyl pyrrolidines, propyl group cyclobutenyl pyrrolidines, butyl cyclobutenyl pyrrolidines, methyl methoxy ylmethyl pyrrolidines, methyl methoxy base ethyl pyrrolidine, ethyl methoxy pyrrolidines, ethyl methoxy ethyl pyrrolidines etc.
In the represented piperidines cation of above-mentioned general formula (5), consider from the angle of easy formation normal temperature fuse salt, more preferably lupetidine, the Methylethyl piperidines, the diethyl piperidines, the methyl-propyl piperidines, the ethyl propyl piperidines, the dipropyl piperidines, the methyl butyl piperidines, the ethyl-butyl piperidines, the propyl group butyl piperidine, the dibutyl piperidines, or the hydrogen atom in these alkyl is replaced and the compound of formation by 1 above fluorine atom, the ethylene methacrylic phenylpiperidines, the ethylethylene phenylpiperidines, the propyl ethylene phenylpiperidines, the butylethylene phenylpiperidines, the methacrylic piperidines, the allyl ethyl piperidines, propyl group pi-allyl piperidines, butyl pi-allyl piperidines, the diallyl piperidines, the methyl butene phenylpiperidines, ethyl cyclobutenyl piperidines, propyl group cyclobutenyl piperidines, butyl cyclobutenyl piperidines, the dibutene phenylpiperidines, methyl methoxy ylmethyl piperidines, methyl methoxy base ethyl piperidine, the methyl ethoxy ethyl piperidine, methyl methoxy base oxethyl ethyl piperidine is defeated, methyl ethoxy ethoxyethyl group piperidines, ethyl methoxy methyl phenylpiperidines, ethyl methoxy ethyl piperidines, ethyl ethoxyethyl group piperidines, ethyl methoxyethoxyethyl piperidines, ethyl ethoxy ethoxy ethyl piperidine, propyl group methoxy methyl phenylpiperidines, propyl group methoxy ethyl piperidines, propyl group ethoxyethyl group piperidines, propyl group methoxyethoxyethyl piperidines, propyl group ethoxy ethoxy ethyl piperidine, butyl methoxy methyl phenylpiperidines, butyl methoxy ethyl piperidines, butyl ethoxyethyl group piperidines, butyl methoxyethoxyethyl piperidines, butyl ethoxy ethoxy ethyl piperidine etc.
Wherein, consider special preferable methyl ethyl piperidine from the angle that viscosity reduces easily, the methyl-propyl piperidines, the ethyl propyl piperidines, the methyl butyl piperidines, the ethyl-butyl piperidines, or the hydrogen atom in these alkyl is replaced and the compound of formation by 1 above fluorine atom, the methacrylic piperidines, the allyl ethyl piperidines, propyl group pi-allyl piperidines, butyl pi-allyl piperidines, the methyl butene phenylpiperidines, ethyl cyclobutenyl piperidines, propyl group cyclobutenyl piperidines, butyl cyclobutenyl piperidines, methyl methoxy ylmethyl piperidines, methyl methoxy base ethyl piperidine, ethyl methoxy methyl phenylpiperidines, ethyl methoxy ethyl piperidines etc.
In the represented morpholine of above-mentioned general formula (6) (モ Le ホ リ ニ ウ system) cation, consider from the angle of easy formation normal temperature fuse salt, more preferably thebaine, the Methylethyl morpholine, the diethyl morpholine, the methyl-propyl morpholine, the ethyl propyl morpholine, the dipropyl morpholine, the methyl butyl morpholine, the ethyl-butyl morpholine, propyl group butyl morpholine, the dibutyl morpholine, or the hydrogen atom in these alkyl is replaced and the compound of formation by 1 above fluorine atom, the methyl ethylene morpholine, the ethyl vinyl morpholine, propyl ethylene base morpholine, the butyl vinyl morpholine, the methacrylic morpholine, the allyl ethyl morpholine, propyl group pi-allyl morpholine, butyl pi-allyl morpholine, the diallyl morpholine, methyl butene base morpholine, ethyl cyclobutenyl morpholine, propyl group cyclobutenyl morpholine, butyl cyclobutenyl morpholine, dibutene base morpholine, methyl methoxy ylmethyl morpholine, methyl methoxy base ethyl morpholine, the methyl ethoxy ethyl morpholine, methyl methoxy base oxethyl ethyl morpholine, methyl ethoxy ethoxyethyl group morpholine, ethyl methoxy morpholine, ethyl methoxy ethyl morpholine, ethyl ethoxyethyl group morpholine, ethyl methoxyethoxyethyl morpholine, ethyl ethoxy ethoxy ethyl morpholine, propyl group methoxy morpholine, propyl group methoxy ethyl morpholine, propyl group ethoxyethyl group morpholine, propyl group methoxyethoxyethyl morpholine, propyl group ethoxy ethoxy ethyl morpholine, butyl methoxy morpholine, butyl methoxy ethyl morpholine, butyl ethoxyethyl group morpholine, butyl methoxyethoxyethyl morpholine, butyl ethoxy ethoxy ethyl morpholine etc.
Wherein the angle that reduces easily from viscosity is considered, special preferable methyl ethyl morpholine, the methyl-propyl morpholine, the ethyl propyl morpholine, the methyl butyl morpholine, the ethyl-butyl morpholine, or the hydrogen atom in these alkyl is replaced and the compound of formation by 1 above fluorine atom, the methacrylic morpholine, the allyl ethyl morpholine, propyl group pi-allyl morpholine, butyl pi-allyl morpholine, methyl butene base morpholine, ethyl cyclobutenyl morpholine, propyl group cyclobutenyl morpholine, butyl cyclobutenyl morpholine, methyl methoxy ylmethyl morpholine, methyl methoxy base ethyl morpholine, ethyl methoxy morpholine, ethyl methoxy ethyl morpholine etc.
The present invention 5 general formula (2) also comprises following structure: in the quaternary ammonium cation structure of above-mentioned general formula (2), and R 4r, R 5r, R 6rAnd R 7rIn 2 organic groups be actually 1 organic group, this 1 organic group and " N +" connect by two keys between the atom.That is to say that general formula (2) also comprises R 4r, R 5r, R 6rAnd R 7rIn 2 situations of merging into alkylidene.In addition, also preferred this alkylidene forms ring structure.In described structure, unsaturated heterocycle structure shown below forms low-melting salt easily, and is therefore preferred.
[Chemical formula 2 6]
[Chemical formula 2 7]
Figure A20088001284001122
[Chemical formula 2 8]
Figure A20088001284001123
[Chemical formula 2 9]
Figure A20088001284001124
[chemical formula 30]
[chemical formula 31]
Figure A20088001284001131
[chemical formula 32]
Figure A20088001284001132
[chemical formula 33]
Figure A20088001284001133
[chemical formula 34]
Figure A20088001284001134
In the represented pyridylium of above-mentioned general formula (7), consider preferred R from the angle of easy formation normal temperature fuse salt 14For ethyl, propyl group, butyl, amyl group, hexyl, and these alkyl in hydrogen atom replaced the compound that forms, pi-allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxy ethoxy ethyl etc. by 1 above fluorine atom, and R 15～R 19Be hydrogen atom or methyl.
Wherein, consider preferred especially 1-ethylpyridine, 1-propyl group pyridine, 1-butyl-pyridinium, 1-pentyl pyridine, 1-hexyl pyridine, 1-allyl pyridine, 1-cyclobutenyl pyridine, 1-methoxy methyl yl pyridines, 1-methoxy ethyl pyridine etc. from the angle that viscosity reduces easily.
In the represented pyridazine cation of above-mentioned general formula (8), consider preferred R from the angle of easy formation normal temperature fuse salt 20For ethyl, propyl group, butyl, amyl group, hexyl, and these alkyl in hydrogen atom replaced the compound that forms, pi-allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxy ethoxy ethyl etc. by 1 above fluorine atom, and R 21～R 24Be hydrogen atom or methyl.
Wherein, consider preferred especially 1-ethyl pyridazine, 1-propyl group pyridazine, 1-butyl pyridazine, 1-amyl group pyridazine, 1-hexyl pyridazine, 1-pi-allyl pyridazine, 1-cyclobutenyl pyridazine, 1-methoxy methyl radical pyridazine, 1-methoxy ethyl pyridazine etc. from the angle that viscosity reduces easily.
In the represented pyrimidine cation of above-mentioned general formula (9), consider preferred R from the angle of easy formation normal temperature fuse salt 25For ethyl, propyl group, butyl, amyl group, hexyl, and these alkyl in hydrogen atom replaced the compound that forms, pi-allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxy ethoxy ethyl etc. by 1 above fluorine atom, and R 26～R 29Be hydrogen atom or methyl.
Wherein, consider preferred especially 1-ethyl-pyrimidine, 1-propyl group pyrimidine, 1-butyl pyrimidine, 1-amyl group pyrimidine, 1-hexyl pyrimidine, 1-pi-allyl pyrimidine, 1-cyclobutenyl pyrimidine, 1-methoxy methyl yl pyrimidines, 1-methoxy ethyl pyrimidine etc. from the angle that viscosity reduces easily.
In the represented pyrazine cation of above-mentioned general formula (10), consider preferred R from the angle of easy formation normal temperature fuse salt 30For ethyl, propyl group, butyl, amyl group, hexyl, and these alkyl in hydrogen atom replaced the compound that forms, pi-allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxy ethoxy ethyl etc. by 1 above fluorine atom, and R 31～R 34Be hydrogen atom or methyl.
Wherein, consider preferred especially 1-ethyl pyrazine, 1-propyl group pyrazine, 1-butyl pyrazine, 1-amyl group pyrazine, 1-hexyl pyrazine, 1-pi-allyl pyrazine, 1-cyclobutenyl pyrazine, 1-methoxy pyrazine, 1-methoxy ethyl pyrazine etc. from the angle that viscosity reduces easily.
In the represented glyoxaline cation of above-mentioned general formula (11), consider preferred R from the angle of easy formation normal temperature fuse salt 36And R 39For ethyl, propyl group, butyl, amyl group, hexyl, and these alkyl in hydrogen atom replaced the compound that forms, vinyl, pi-allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxy ethoxy ethyl etc. by 1 above fluorine atom, and R 35, R 37, R 38Be hydrogen atom or methyl.
Wherein, consider from the angle that viscosity reduces easily, preferred especially 1, the 3-methylimidazole, 1-ethyl-3-methylimidazole, 1-propyl group-3-methylimidazole, 1-butyl-3-methylimidazole, 1-amyl group-3-methylimidazole, 1-hexyl-3-methylimidazole, 1,3-diethyl imidazoles, 1-ethyl-3-propyl imidazole, 1-ethyl-3-butyl imidazole, 1-ethyl-3-amyl group imidazoles, 1-ethyl-3-hexyl imidazoles, 1,3-dipropyl imidazoles, 1-propyl group-3-butyl imidazole, 1-propyl group-3-amyl group imidazoles, 1-hexyl-3-butyl imidazole, 1,2, the 3-tri-methylimidazolium, 1-ethyl-2, the 3-methylimidazole, 1-propyl group-2, the 3-methylimidazole, 1-butyl-2, the 3-methylimidazole, 1-amyl group-2, the 3-methylimidazole, 1-hexyl-2, the 3-methylimidazole, 1,3-diethyl-glyoxal ethyline, 1-propyl group-2-methyl-3-ethyl imidazol(e), 1-butyl-2-methyl-3-ethyl imidazol(e), 1-amyl group-2-methyl-3-ethyl imidazol(e), 1-hexyl-2-methyl-3-ethyl imidazol(e), 1,2,3,4,5-pentamethyl imidazoles, 1-ethyl-2,3,4,5-tetramethyl imidazoles, 1-propyl group-2,3,4,5-tetramethyl imidazoles, 1-butyl-2,3,4,5-tetramethyl imidazoles, 1-amyl group-2,3,4,5-tetramethyl imidazoles, 1-hexyl-2,3,4,5-tetramethyl imidazoles, and the hydrogen atom in these alkyl is replaced and the compound of formation by 1 above fluorine atom, 1-pi-allyl-3-methylimidazole, 1-pi-allyl-3-ethyl imidazol(e), 1-pi-allyl-3-propyl imidazole, 1-pi-allyl-3-butyl imidazole, 1-pi-allyl-2, the 3-methylimidazole, 1-pi-allyl-2,3,4,5-tetramethyl imidazoles, 1-cyclobutenyl-3-methylimidazole, 1-cyclobutenyl-3-ethyl imidazol(e), 1-cyclobutenyl-3-propyl imidazole, 1-cyclobutenyl-3-butyl imidazole, 1-cyclobutenyl-2, the 3-methylimidazole, 1-cyclobutenyl-2,3,4,5-tetramethyl imidazoles, 1-methoxy-3-methylimidazole, 1-methoxy-3-ethyl imidazol(e), 1-methoxy-3-propyl imidazole, 1-methoxy-3-butyl imidazole, 1-methoxy-2, the 3-methylimidazole, 1-methoxy-2,3,4,5-tetramethyl imidazoles, 1-methoxy ethyl-3-methylimidazole, 1-methoxy ethyl-3-ethyl imidazol(e), 1-methoxy ethyl-3-propyl imidazole, 1-methoxy ethyl-3-butyl imidazole, 1-methoxy ethyl-2, the 3-methylimidazole, 1-methoxy ethyl-2,3,4,5-tetramethyl imidazoles etc.
In the represented oxazole cation of above-mentioned general formula (12), consider preferred R from the angle of easy formation normal temperature fuse salt 41For ethyl, propyl group, butyl, amyl group, hexyl, and these alkyl in hydrogen atom replaced the compound that forms, vinyl, pi-allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxy ethoxy ethyl etc. by 1 above fluorine atom, and R 40, R 42, R 43Be hydrogen atom or methyl.
Wherein, consider from the angle that viscosity reduces easily, preferred especially 1-Yi Ji oxazole, 1-Bing Ji oxazole, 1-Ding Ji oxazole, 1-Wu Ji oxazole, 1-Ji Ji oxazole, 1-Xi Bing Ji oxazole, 1-Ding Xi Ji oxazole, 1-methoxy ylmethyl oxazole, 1-methoxyl group Yi Ji oxazole, 1-ethyl-2,4,5-San Jia Ji oxazole, 1-propyl group-2,4,5-San Jia Ji oxazole, 1-butyl-2,4,5-San Jia Ji oxazole, 1-amyl group-2,4,5-San Jia Ji oxazole, 1-hexyl-2,4,5-San Jia Ji oxazole, 1-pi-allyl-2,4,5-San Jia Ji oxazole, 1-cyclobutenyl-2,4,5-San Jia Ji oxazole, 1-methoxy-2,4,5-San Jia Ji oxazole, 1-methoxy ethyl-2,4,5-San Jia Ji oxazole etc.
In the represented thiazole of above-mentioned general formula (13) (チ ア ゾ リ ウ system) cation, consider preferred R from the angle of easy formation normal temperature fuse salt 45For ethyl, propyl group, butyl, amyl group, hexyl, and these alkyl in hydrogen atom replaced the compound that forms, vinyl, pi-allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxy ethoxy ethyl etc. by 1 above fluorine atom, and R 44, R 46, R 47Be hydrogen atom or methyl.
Wherein, consider from the angle that viscosity reduces easily, preferred especially 1-ethyl thiazole, 1-propyl group thiazole, 1-butyl thiazole, 1-amyl group thiazole, 1-hexyl thiazole, 1-pi-allyl thiazole, 1-cyclobutenyl thiazole, 1-methoxy thiazole, 1-methoxy ethyl thiazole, 1-ethyl-2,4, the 5-trimethylthiazole, 1-propyl group-2,4, the 5-trimethylthiazole, 1-butyl-2,4, the 5-trimethylthiazole, 1-amyl group-2,4, the 5-trimethylthiazole, 1-hexyl-2,4, the 5-trimethylthiazole, 1-pi-allyl-2,4, the 5-trimethylthiazole, 1-cyclobutenyl-2,4, the 5-trimethylthiazole, 1-methoxy-2,4, the 5-trimethylthiazole, 1-methoxy ethyl-2,4,5-trimethylthiazole etc.
In the represented pyrazoles cation of above-mentioned general formula (14), consider preferred R from the angle of easy formation normal temperature fuse salt 49For ethyl, propyl group, butyl, amyl group, hexyl, and these alkyl in hydrogen atom replaced the compound that forms, vinyl, pi-allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxy ethoxy ethyl etc. by 1 above fluorine atom, and R 48, R 50～R 52Be hydrogen atom or methyl.
Wherein, consider preferred especially 1-ethyl pyrazoles from the angle that viscosity reduces easily, 1-propyl group pyrazoles, 1-butyl pyrazoles, 1-amyl group pyrazoles, 1-hexyl pyrazoles, 1-pi-allyl pyrazoles, 1-cyclobutenyl pyrazoles, 1-methoxy pyrazoles, 1-methoxy ethyl pyrazoles, 1-ethyl-2,3,4,5-tetramethyl pyrazoles, 1-propyl group-2,3,4,5-tetramethyl pyrazoles, 1-butyl-2,3,4,5-tetramethyl pyrazoles, 1-amyl group-2,3,4,5-tetramethyl pyrazoles, 1-hexyl-2,3,4,5-tetramethyl pyrazoles, 1-pi-allyl-2,3,4,5-tetramethyl pyrazoles, 1-cyclobutenyl-2,3,4,5-tetramethyl pyrazoles, 1-methoxy-2,3,4,5-tetramethyl pyrazoles, 1-methoxy ethyl-2,3,4,5-tetramethyl pyrazoles etc.
In the represented triazole of above-mentioned general formula (15) (ト リ ア ゾ リ ウ system) cation, consider preferred R from the angle of easy formation normal temperature fuse salt 54For ethyl, propyl group, butyl, amyl group, hexyl, and these alkyl in hydrogen atom replaced the compound that forms, vinyl, pi-allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxy ethoxy ethyl etc. by 1 above fluorine atom, and R 53, R 55, R 56Be hydrogen atom or methyl.
Wherein, consider preferred especially 1-ethyl triazole from the angle that viscosity reduces easily, 1-propyl group triazole, the 1-triazbutil, 1-amyl group triazole, 1-hexyl triazole, 1-pi-allyl triazole, 1-cyclobutenyl triazole, 1-methoxy triazole, 1-methoxy ethyl triazole, 1-ethyl-2,3,4,5-tetramethyl triazole, 1-propyl group-2,3,4,5-tetramethyl triazole, 1-butyl-2,3,4,5-tetramethyl triazole, 1-amyl group-2,3,4,5-tetramethyl triazole, 1-hexyl-2,3,4,5-tetramethyl triazole, 1-pi-allyl-2,3,4,5-tetramethyl triazole, 1-cyclobutenyl-2,3,4,5-tetramethyl triazole, 1-methoxy-2,3,4,5-tetramethyl triazole, 1-methoxy ethyl-2,3,4,5-tetramethyl triazole etc.
Anion for the quaternary ammonium salt with the represented structure of above-mentioned general formula (2) among the present invention 5 is not particularly limited, and can enumerate with the anion of above-mentioned lithium salts or has the identical anion of the anion of uncle's sulfonium salt of the represented structure of above-mentioned general formula (1) as preferred example.
[the represented compound of general formula (3)]
R in the present invention 5 the represented De quaternary phosphine of above-mentioned general formula (3) cationic structural 8r, R 9r, R 10rAnd R 11rBe the organic group of identical or different carbon number 1～12, as R 8r, R 9r, R 10rAnd R 11r, can enumerate " the R in the general formula (1) with the present invention 5 1r, R 2rAnd R 3r" identical chain-like alkyl; Cyclic alkyl; Alkenyl; Alkynyl; Haloalkyl; Optional aryl such as phenyl with alkyl substituent; Aralkyl; Trialkylsilkl; The alkyl that contains carbonyl; The alkyl that contains ether; Contain the alkyl of sulfonyl etc.In addition, preferred concrete group also with above-mentioned general formula (1) in " R 1r, R 2rAnd R 3" identical.
R 8r, R 9r, R 10rAnd R 11rIn 2～4 optional mutual bondings and form ring structure, R 8r, R 9r, R 10rAnd R 11rCan also on above-mentioned substituting group, be combined with substituting group by the saturated or unsaturated bond that forms by assorted elements such as oxygen, nitrogen, sulphur, P elements.
In addition, the above-mentioned general formula (3) among the present invention 5 also comprises following structure: above-mentioned general formula of the present invention 5 (in the 3) De quaternary phosphine cationic structurals, R 8r, R 9r, R 10rAnd R 11rIn 2 organic groups be actually 1 organic group, this 1 organic group and " P +" connect with two keys between the atom.That is to say that the above-mentioned general formula (3) among the present invention 5 also comprises R 8r, R 9r, R 10rAnd R 11rIn 2 groups merge into the situation of alkylidene.
At R 8r～R 10rIn, alkyl, haloalkyl, the pi-allyl of preferred carbon number 1～10, contain the alkyl of ether, because form low-melting salt easily by the intermolecular interaction that reduces Gai phosphonium salt.
Wherein, consider from the angle of easy reduction viscosity, more preferably triethyl group fourth base Phosphonium, triethyl group Wu Ji Phosphonium, triethyl group Ji Ji Phosphonium, triethyl group Geng Ji Phosphonium, triethyl group Xin Ji Phosphonium, diethyl propyl group Ding Ji Phosphonium, diethyl propyl group Wu Ji Phosphonium, diethyl propyl group Ji Ji Phosphonium, diethyl propyl group Geng Ji Phosphonium, diethyl propyl group Xin Ji Phosphonium, diethyl butyl Wu Ji Phosphonium, diethyl butyl Ji Ji Phosphonium, diethyl butyl Geng Ji Phosphonium, diethyl butyl Xin Ji Phosphonium, diethyl amyl group Ji Ji Phosphonium, diethyl amyl group Geng Ji Phosphonium, diethyl amyl group Xin Ji Phosphonium, diethylhexyl Geng Ji Phosphonium, diethylhexyl Xin Ji Phosphonium, diethyl heptyl Xin Ji Phosphonium, diethyl Er Xin Ji Phosphonium, ethyl dipropyl Ding Ji Phosphonium, ethyl dipropyl Wu Ji Phosphonium, ethyl dipropyl Ji Ji Phosphonium, ethyl dipropyl Geng Ji Phosphonium, ethyl dipropyl Xin Ji Phosphonium, ethyl propyl Er Ding Ji Phosphonium, ethyl propyl butyl Wu Ji Phosphonium, ethyl propyl butyl Ji Ji Phosphonium, ethyl propyl butyl Geng Ji Phosphonium, ethyl propyl butyl Xin Ji Phosphonium, ethyl propyl Er Wu Ji Phosphonium, ethyl propyl amyl group Ji Ji Phosphonium, ethyl propyl amyl group Geng Ji Phosphonium, ethyl propyl amyl group Xin Ji Phosphonium, ethyl propyl Er Ji Ji Phosphonium, ethyl propyl hexyl Geng Ji Phosphonium, the own Ji Xinji Phosphonium of ethyl propyl, ethyl propyl Er Geng Ji Phosphonium, ethyl propyl heptyl Xin Ji Phosphonium, ethyl propyl Er Xin Ji Phosphonium, ethyl San Ding Ji Phosphonium, ethyl dibutyl Wu Ji Phosphonium, ethyl dibutyl Ji Ji Phosphonium, ethyl dibutyl Geng Ji Phosphonium, ethyl dibutyl Xin Ji Phosphonium, ethyl-butyl Er Wu Ji Phosphonium, ethyl-butyl amyl group Ji Ji Phosphonium, ethyl-butyl amyl group Geng Ji Phosphonium, ethyl-butyl amyl group Xin Ji Phosphonium, ethyl-butyl Er Ji Ji Phosphonium, ethyl-butyl hexyl Geng Ji Phosphonium, the own Ji Xinji Phosphonium of ethyl-butyl, ethyl-butyl heptyl Xin Ji Phosphonium, ethyl-butyl Er Xin Ji Phosphonium, ethyl San Wu Ji Phosphonium, ethyl diamyl Ji Ji Phosphonium, ethyl diamyl Geng Ji Phosphonium, ethyl diamyl Xin Ji Phosphonium, ethyl pentyl group Er Ji Ji Phosphonium, ethyl pentyl group hexyl Geng Ji Phosphonium, the own Ji Xinji Phosphonium of ethyl pentyl group, ethyl pentyl group Er Geng Ji Phosphonium, ethyl pentyl group heptyl Xin Ji Phosphonium, ethyl pentyl group Er Xin Ji Phosphonium, ethyl three Ji Ji Phosphonium, ethyl dihexyl Geng Ji Phosphonium, ethyl dihexyl Xin Ji Phosphonium, ethylhexyl Er Geng Ji Phosphonium, ethylhexyl heptyl Xin Ji Phosphonium, ethylhexyl Er Xin Ji Phosphonium, ethyl three Geng Ji Phosphonium, ethyl diheptyl Xin Ji Phosphonium, ethyl heptyl Er Xin Ji Phosphonium, ethyl San Xin Ji Phosphonium, tripropyl Ding Ji Phosphonium, tripropyl Wu Ji Phosphonium, tripropyl Ji Ji Phosphonium, tripropyl Geng Ji Phosphonium, tripropyl Xin Ji Phosphonium, dipropyl Er Ding Ji Phosphonium, dipropyl butyl Wu Ji Phosphonium, dipropyl butyl Ji Ji Phosphonium, dipropyl butyl Geng Ji Phosphonium, dipropyl butyl Xin Ji Phosphonium, dipropyl Er Wu Ji Phosphonium, dipropyl amyl group Ji Ji Phosphonium, dipropyl amyl group Geng Ji Phosphonium, dipropyl amyl group Xin Ji Phosphonium, dipropyl Er Ji Ji Phosphonium, dipropyl hexyl Geng Ji Phosphonium, the own Ji Xinji Phosphonium of dipropyl, dipropyl Er Geng Ji Phosphonium, dipropyl heptyl Xin Ji Phosphonium, dipropyl Er Xin Ji Phosphonium, propyl group San Ding Ji Phosphonium, propyl group dibutyl Wu Ji Phosphonium, propyl group dibutyl Ji Ji Phosphonium, propyl group dibutyl Geng Ji Phosphonium, propyl group dibutyl Xin Ji Phosphonium, propyl group butyl Er Wu Ji Phosphonium, propyl group butyl amyl group Ji Ji Phosphonium, propyl group butyl amyl group Geng Ji Phosphonium, propyl group butyl amyl group Xin Ji Phosphonium, propyl group butyl Er Geng Ji Phosphonium, propyl group butyl heptyl Xin Ji Phosphonium, propyl group butyl Er Xin Ji Phosphonium, propyl group San Wu Ji Phosphonium, propyl group diamyl Ji Ji Phosphonium, propyl group diamyl Geng Ji Phosphonium, propyl group diamyl Xin Ji Phosphonium, propyl group amyl group hexyl Geng Ji Phosphonium, the own Ji Xinji Phosphonium of propyl group amyl group, propyl group amyl group Er Geng Ji Phosphonium, propyl group amyl group heptyl Xin Ji Phosphonium, propyl group amyl group Er Xin Ji Phosphonium, propyl group three Ji Ji Phosphonium, propyl group dihexyl Geng Ji Phosphonium, propyl group dihexyl Xin Ji Phosphonium, propyl group hexyl Er Geng Ji Phosphonium, propyl group hexyl heptyl Xin Ji Phosphonium, propyl group hexyl Er Xin Ji Phosphonium, propyl group three Geng Ji Phosphonium, propyl group diheptyl Xin Ji Phosphonium, propylheptyl Er Xin Ji Phosphonium, propyl group San Xin Ji Phosphonium, 4-butyl-phosphonium, tributyl Wu Ji Phosphonium, tributyl Ji Ji Phosphonium, tributyl Geng Ji Phosphonium, tributyl Xin Ji Phosphonium, Si Wu Ji Phosphonium, three amyl group Ji Ji Phosphonium, three amyl group Geng Ji Phosphonium, three amyl group Xin Ji Phosphonium, Si Ji Ji Phosphonium, three hexyl Geng Ji Phosphonium, three own Ji Xinji Phosphonium, Si Geng Ji Phosphonium, three heptyl Xin Ji Phosphonium, Si Xin Ji Phosphonium etc., or the hydrogen atom in these alkyl is replaced and the compound triethyl group Xi Bing Ji Phosphonium of formation by 1 above fluorine atom, triethyl group Ding Xi Ji Phosphonium, tripropyl Xi Bing Ji Phosphonium, tripropyl Ding Xi Ji Phosphonium, San butyl Xi Bing Ji Phosphonium, tributyl Ding Xi Ji Phosphonium, triethyl group methoxyl group Yi Ji Phosphonium, triethyl group methoxy ethoxy Yi Ji Phosphonium, tripropyl methoxyl group Yi Ji Phosphonium, tripropyl methoxy ethoxy Yi Ji Phosphonium, tributyl methoxyl group Yi Ji Phosphonium, tributyl methoxy ethoxy Yi Ji Phosphonium etc.
Wherein, number of ions (being ion concentration) in unit volume is a suitable size of not damaging normal temperature fuse salt feature, and with fusing point, the good angle of the balance of viscosity is considered, preferred especially triethyl group Ding Ji Phosphonium, triethyl group Wu Ji Phosphonium, triethyl group Ji Ji Phosphonium, triethyl group Geng Ji Phosphonium, triethyl group Xin Ji Phosphonium, tripropyl Ding Ji Phosphonium, tripropyl Wu Ji Phosphonium, tripropyl Ji Ji Phosphonium, tripropyl Geng Ji Phosphonium, tripropyl Xin Ji Phosphonium, 4-butyl-phosphonium, tributyl Wu Ji Phosphonium, tributyl Ji Ji Phosphonium, tributyl Geng Ji Phosphonium, tributyl Xin Ji Phosphonium, Si Wu Ji Phosphonium, three amyl group Ji Ji Phosphonium, three amyl group Geng Ji Phosphonium, three amyl group Xin Ji Phosphonium, Si Ji Ji Phosphonium, three hexyl Geng Ji Phosphonium, three own Ji Xinji Phosphonium, Si Geng Ji Phosphonium, three heptyl Xin Ji Phosphonium, Si Xin Ji Phosphonium etc., and the hydrogen atom in these alkyl is replaced and the compound of formation by 1 above fluorine atom, triethyl group Xi Bing Ji Phosphonium, triethyl group Ding Xi Ji Phosphonium, tripropyl Xi Bing Ji Phosphonium, tripropyl Ding Xi Ji Phosphonium, San butyl Xi Bing Ji Phosphonium, tributyl Ding Xi Ji Phosphonium, triethyl group methoxyl group Yi Ji Phosphonium, triethyl group methoxy ethoxy Yi Ji Phosphonium, tripropyl methoxyl group Yi Ji Phosphonium, tripropyl methoxy ethoxy Yi Ji Phosphonium, tributyl methoxyl group Yi Ji Phosphonium, tributyl methoxy ethoxy Yi Ji Phosphonium etc.
The anion that has the represented structure De quaternary alkylphosphonium salt of general formula (3) among the present invention 5 is not particularly limited, as preference, can enumerate with the anion of above-mentioned lithium salts, have the represented structure of above-mentioned general formula (1) uncle's sulfonium salt anion or have the identical anion of anion of the quaternary ammonium salt of the represented structure of above-mentioned general formula (2).
In the scope of the effect of not damaging the present invention 5, the nonaqueous solvents in the present invention 5 the nonaqueous electrolytic solution can also contain in the past as the known solvent of the solvent of nonaqueous electrolytic solution.At this moment, can from the solvent of known nonaqueous electrolytic solution, suitably select to use.As preferred example, for example can enumerate combination: polysiloxane-based, the normal temperature fuse salt of normal temperature fuse salt and linear carbonate class, normal temperature fuse salt and cyclic carbonates, normal temperature fuse salt and cyclic ester class, normal temperature fuse salt and cyclic sulfones class, normal temperature fuse salt and fluoro chain ethers, normal temperature fuse salt and fluoro linear carbonate class, normal temperature fuse salt and molecular weight about 500～3000 and polyethers, normal temperature fuse salt and the phosphoric acid ester etc. of molecular weight 700～3000 degree based on following solvents.
With respect to the nonaqueous electrolytic solution composition except lithium salts and " mono-fluor phosphate, difluorophosphoric acid salt " described later, preferably contain the normal temperature fuse salt of 0.01 weight %～100 weight %.About described " except that the nonaqueous electrolytic solution composition lithium salts and ' mono-fluor phosphate, the difluorophosphoric acid salt ' ", for example can enumerate: " high boiling solvent or noninflammability solvents " such as the fluoride class of chain or cyclic carbonates, chain or cyclic ester class, chain or cyclic sulfones class, chain or ring-type ethers, these compounds, polysiloxane-based, polyethers etc.Can also enumerate nonaqueous solvents described later.
With respect to the total amount of mentioned component, more preferably the content of normal temperature fuse salt is 50 weight %～100 weight %, is preferably 60 weight %～95 weight %, 70 weight %～90 weight % more preferably especially.Under the very few situation of normal temperature fuse salt, for nonaqueous electrolytic solution, sometimes can't obtain fail safe effects such as noninflammability, high thermal stability, on the other hand, under the too much situation of normal temperature fuse salt, the structure of normal temperature fuse salt causes viscosity too high, and ionic conductivity reduction sometimes, this nonaqueous electrolytic solution become and be difficult to infiltrate through in dividing plate or the positive pole/negative pole.
In the present invention 5, one of the preferred compositions that contains the nonaqueous solvents of normal temperature fuse salt is the combination based on normal temperature fuse salt and cyclic carbonates.Wherein, in the nonaqueous solvents the shared ratio of normal temperature fuse salt be 50 weight % above, be preferably 60 weight % above, more preferably more than the 70 weight %, and be generally 95 weight % following, be preferably 90 weight % following, more preferably below the 85 weight %.When using the combination of this nonaqueous solvents, compare when only using the normal temperature fuse salt as the nonaqueous electrolytic solution solvent, the viscosity of nonaqueous electrolytic solution reduces, and because cyclic carbonate has the effect of the good tunicle of on negative terminal surface formation, use charge/discharge capacity and the cycle characteristics excellence of battery under high current density of the combination making of this nonaqueous solvents, therefore preferred.
As the object lesson of normal temperature fuse salt, for example can enumerate: normal temperature fuse salt and ethylene carbonate, normal temperature fuse salt and propylene carbonate, normal temperature fuse salt and fluorine ethylene carbonate, normal temperature fuse salt and butylene carbonate, normal temperature fuse salt and gamma-butyrolacton, normal temperature fuse salt and gamma-valerolactone, normal temperature fuse salt and sulfolane, normal temperature fuse salt and fluoro sulfolane etc. with the preferred compositions of " cyclic carbonates or cyclic ester class, cyclic sulfones class ".
In addition, one of other preferred compositions is the combination based on normal temperature fuse salt and fluoro chain ethers.Wherein, in the nonaqueous solvents the shared ratio of normal temperature fuse salt be 50 weight % above, be preferably 60 weight % above, more preferably more than the 70 weight %, and be generally 95 weight % following, be preferably 90 weight % following, more preferably below the 85 weight %.Because when using the combination of this nonaqueous solvents, can not damage the noninflammability that the normal temperature fuse salt is had, compare when only using the normal temperature fuse salt as the solvent of nonaqueous electrolytic solution, the viscosity of nonaqueous electrolytic solution reduces, and nonaqueous electrolytic solution infiltrates through in the pore of negative or positive electrode easily, use the charge/discharge capacity of battery under high current density of the combination making of this nonaqueous solvents to improve, therefore preferred.
As the object lesson of the preferred compositions of normal temperature fuse salt and fluoro chain ethers, for example can enumerate: normal temperature fuse salt and nine fluorine butyl methyl ethers, normal temperature fuse salt and nine fluorine butyl ethyl ethers, normal temperature fuse salt and trifluoro ethoxy ethoxy methane, normal temperature fuse salt and trifluoro ethoxy Ethoxyethane, normal temperature fuse salt and hexafluoro ethoxy ethoxy methane, normal temperature fuse salt and hexafluoro ethoxy ethoxy ethane etc.
As the object lesson of the preferred compositions of normal temperature fuse salt and phosphoric acid ester, for example can enumerate: normal temperature fuse salt and trimethyl phosphate, normal temperature fuse salt and triethyl phosphate, normal temperature fuse salt and di(2-ethylhexyl)phosphate Methylethyl ester, normal temperature fuse salt and phosphoric acid methyl diethyl ester, normal temperature fuse salt and tricresyl phosphate (trifluoroethyl) ester, normal temperature fuse salt and methylethylene phosphate, normal temperature fuse salt and ethyl ethylidene phosphate, normal temperature fuse salt and tri hexyl phosphate, normal temperature fuse salt and trioctyl phosphate etc.
＜1-3. mono-fluor phosphate, difluorophosphoric acid salt 〉
Except that above-mentioned lithium salts and normal temperature fuse salt, the present invention 5 nonaqueous electrolytic solution also contains " mono-fluor phosphate and/or difluorophosphoric acid salt ".
The counter cation of mono-fluor phosphate and difluorophosphoric acid salt is not particularly limited, except that metallic elements such as Li, Na, K, Mg, Ca, Fe, Cu, can also enumerate the represented uncle's sulfonium of general formula (1), represented quaternary ammonium, the represented De quaternary phosphine of general formula (3) of general formula (2).Wherein, the represented counter cation in general formula (1)～(3) is identical with employed counter cation structure in the above-mentioned normal temperature fuse salt.
In these counter cations, the characteristic aspect of battery is considered when being used for nonaqueous electrolyte battery, preferred lithium, sodium, potassium, magnesium, calcium or uncle's sulfonium, quaternary ammonium, quaternary phosphine, special preferred lithium.
In addition, in mono-fluor phosphate, difluorophosphoric acid salt, consider preferred difluorophosphoric acid salt, preferred especially difluorophosphate from aspects such as the cycle characteristics of battery, high temperature preservation characteristics.In addition, these compounds can directly use in nonaqueous solvents synthetic in fact, also can with in addition synthetic and separate in fact after compound add in the nonaqueous solvents or in the nonaqueous electrolytic solution.
Nonaqueous electrolytic solution total amount with respect to the present invention 5, the addition of " mono-fluor phosphate and/or difluorophosphoric acid salt " without limits, only otherwise appreciable impact the present invention 5 effect gets final product, can be any amount, nonaqueous electrolytic solution total amount with respect to the present invention 5, its always contain concentration be generally 0.001 weight % above, be preferably 0.01 weight % above, more preferably more than the 0.1 weight %, and be generally 20 weight % following, be preferably 10 weight % following, more preferably below the 5 weight %.When too high levels, mono-fluor phosphate and/or difluorophosphoric acid salt are separated out at low temperature, cause battery behavior to reduce sometimes, and cross when hanging down when mono-fluor phosphate and/or difluorophosphoric acid salt content, and the raising effect of cycle characteristics, high temperature preservation characteristics etc. obviously reduces sometimes.Under the situation of mono-fluor phosphate and/or difluorophosphoric acid salt double as normal temperature fuse salt, the concentration of contained mono-fluor phosphate and/or difluorophosphoric acid salt be generally 0.001 weight % above, be preferably 0.01 weight % above, more preferably more than the 0.1 weight %, and be generally 100 weight % following, be preferably 95 weight % following, more preferably 90 weight % following, be preferably below the 85 weight % especially.When the too high levels of mono-fluor phosphate and/or difluorophosphoric acid salt, the viscosity of nonaqueous electrolytic solution increases, and ionic conductivity reduces, is difficult for infiltrating through in dividing plate or the positive pole/negative pole sometimes.On the other hand, cross when low when mono-fluor phosphate and/or difluorophosphoric acid salt content, same as described above, the raising effect of low-temperature characteristics, cycle characteristics, high temperature preservation characteristics etc. obviously reduces sometimes.
In addition, about the molecular weight of mono-fluor phosphate or difluorophosphoric acid salt, preparation method etc., also with the present invention 1 in illustrated identical.
In addition, the detection period of mono-fluor phosphate or difluorophosphoric acid salt (period of containing), the place (source of containing), the method that contains that at first contain at first, be regarded as in nonaqueous electrolytic solution, containing the detection place of (or having contained) etc., also with the present invention 1 in illustrated identical.
Other compound of＜1-4. 〉
In the scope of the effect of not damaging the present invention 5, the present invention 5 nonaqueous electrolytic solution can contain " other compound ".As described " other compound ", can enumerate that known in the past negative pole tunicle forms agent, anodal protective agent, all cpds such as preventing agent, auxiliary agent overcharges.
＜1-4-1. negative pole tunicle forms agent 〉
Form agent by containing the negative pole tunicle, can improve the reaction invertibity of the lithium ion of negative pole, thereby can improve charge/discharge capacity, efficiency for charge-discharge, cycle characteristics.Form agent, preference such as vinylene carbonate, vinylethylene carbonate, fluorine ethylene carbonate etc. as the negative pole tunicle.These negative pole tunicles form agent can use a kind separately, also can will be used in combination with combination in any and ratio more than 2 kinds.
These negative pole tunicles in the nonaqueous electrolytic solution form proportional being not particularly limited that contain of agent, with respect to the nonaqueous electrolytic solution total amount, be respectively 0.01 weight % above, be preferably 0.1 weight % above, more preferably more than the 0.2 weight %, be limited on it 12 weight % following, be preferably 10 weight % following, more preferably below the 8 weight %.
The anodal protective agent of＜1-4-2. 〉
By containing anodal protective agent, the capacity that can improve after high temperature is preserved keeps and cycle characteristics.As anodal protective agent, preferred glycol sulfite, the inferior propyl ester of sulfurous acid, propane sultone, butyl sultone, methyl mesylate, 1,4-dimethane sulfonoxybutane etc.These anodal protective agents more than 2 kinds can be used in combination.
Anodal protectant proportional being not particularly limited that contain of in the nonaqueous electrolytic solution these; with respect to the nonaqueous electrolytic solution total amount; be respectively 0.01 weight % above, be preferably 0.1 weight % above, more preferably more than the 0.2 weight %, on be limited to 5 weight % following, be preferably 3 weight % following, more preferably below the 2 weight %.
＜1-4-3. overcharges and prevents agent 〉
Prevent agent by containing to overcharge, battery breaks, catches fire under the situation such as can suppress to overcharge.
Prevent the object lesson of agent as overcharging, for example can enumerate overcharging of being put down in writing among the present invention 1 and prevent agent.Overcharging in the nonaqueous electrolytic solution prevents that the ratio of agent is generally more than the 0.1 weight %, is preferably more than the 0.2 weight %, is preferably more than the 0.3 weight % especially, most preferably is more than the 0.5 weight % with respect to the nonaqueous electrolytic solution total amount, and the upper limit is generally below the 5 weight %, is preferably below the 3 weight %, is preferably below the 2 weight % especially.Concentration is lower than this time in limited time, and can not bringing into play substantially overcharges prevents the effect of agent.Otherwise if excessive concentration, then battery behavior such as high temperature preservation characteristics has the tendency of reduction.
＜1-4-4. auxiliary agent 〉
As the object lesson of auxiliary agent, for example can enumerate auxiliary agent cited among the present invention 1.These auxiliary agents more than 2 kinds can be used in combination.Wherein, as being used to improve the capacity retention performance after high temperature is preserved and the auxiliary agent of cycle characteristics, the preferred carbonic ester one of at least that contains in unsaturated bond and the halogen atom (below, abbreviate " particular carbon acid esters " sometimes as) that adds.The object lesson of particular carbon acid esters is identical with the present invention 1.
The ratio of these auxiliary agents is generally more than the 0.01 weight %, is preferably more than the 0.1 weight %, is preferably especially more than the 0.2 weight % with respect to the nonaqueous electrolytic solution total amount in the nonaqueous electrolytic solution, and the upper limit is generally below the 5 weight %, is preferably below the 3 weight %, is preferably below the 1 weight % especially.By adding these auxiliary agents, can improve capacity retention performance and cycle characteristics after high temperature is preserved.Concentration is lower than this time in limited time, can not bring into play the effect of auxiliary agent substantially.Otherwise if excessive concentration, battery behaviors such as then high capacity flash-over characteristic have the tendency of reduction.
The preparation of＜1-5. nonaqueous electrolytic solution 〉
The present invention 5 nonaqueous electrolytic solution can prepare by following method: with lithium salts, normal temperature fuse salt, mono-fluor phosphate class or difluorophosphoric acid salt and " other compound " dissolving mutually of use as required.During the preparation nonaqueous electrolytic solution, the moisture when making nonaqueous electrolytic solution in order to reduce preferably dewaters each raw material in advance.Usually can dewater raw material to 50ppm, preferably dewater to 30ppm, especially preferably dewater to 10ppm.In addition, also can dewater behind the nonaqueous electrolytic solution in preparation, depickling processing etc.
The present invention 5 nonaqueous electrolytic solution preferably uses with (for example secondary lithium batteries) electrolyte as the secondary cell in the nonaqueous electrolyte battery.Below, just use the nonaqueous electrolyte battery of the present invention 5 nonaqueous electrolytic solution to describe.
The preparation method of＜1-6. nonaqueous electrolytic solution 〉
The preparation method of the present invention 5 nonaqueous electrolytic solution is identical with the present invention 1.
[2. rechargeable nonaqueous electrolytic battery]
The present invention 5 rechargeable nonaqueous electrolytic battery have the invention described above 5 nonaqueous electrolytic solution and can occlusion and emit the negative pole and the positive pole of ion.
Battery structure; Negative pole; Carbonaceous material; The structure of carbonaceous negative pole, rerum natura, preparation method; The metal compound composition material, and use structure, rerum natura, the preparation method of the negative pole of metal compound composition material; Anodal; Dividing plate; Battery design etc. all with illustrated identical of the present invention 1.
[current collection structure]
The current collection structure is not particularly limited, and realizes the raising of charge-discharge characteristic of the present invention 5 the high current density that nonaqueous electrolytic solution brought for better effects if ground, preferably makes the structure of the resistance that reduces wiring portion and bonding part.Under the situation of such reduction internal resistance, especially can give full play to the effect of the nonaqueous electrolytic solution that uses the present invention 5.
In the electrode group is under the situation of above-mentioned laminar structure, preferably adopts following structure: the metal-cored part of each electrode layer is tied together and welding on terminal and the structure that forms.Because when increasing the area of 1 cube electrode, internal resistance increases, thereby also preferably adopts the method that a plurality of terminals reduce resistance that is provided with in electrode thereupon.In the electrode group is under the situation of above-mentioned winding-structure, can on anodal and negative pole a plurality of pin configurations be set respectively, and is bundled in and reduces internal resistance on the terminal.
By with the said structure optimization, can reduce internal resistance as far as possible.In the battery that uses with big electric current, the preferably impedance of measuring with the 10kHz alternating current method (below, abbreviate " DC resistance component " as) be that more preferably DC resistance component is below the 5m Ω below 10 milliohms (m Ω).DC resistance component is 0.1m Ω when following, though output characteristic strengthens, the shared ratio of the current collection structural material of Shi Yonging increases sometimes, the battery capacity minimizing.
[effect]
With regard to the present invention 5, contain " mono-fluor phosphate class or difluorophosphoric acid salt " in the nonaqueous electrolytic solution of use normal temperature fuse salt, reduction effect, charge and discharge cycles that described " mono-fluor phosphate class or difluorophosphoric acid salt " has interface resistance improve effect etc.The present invention 5 plays the action principle of above-mentioned effect and unclear, think that its action principle is as follows, but the present invention 5 is not subjected to the restriction of following effects principle.That is, in the compound that constitutes nonaqueous electrolytic solution, mono-fluor phosphate class or difluorophosphoric acid salt act preferentially on electrode, take place to concentrate or surface adsorption at electrode interface.Can realize following function like this: prevent the stripping of positive active material in nonaqueous electrolytic solution, suppress to follow the shortcoming of the electrical conductivity path that the electrode active material that discharges and recharges causes because of change in volume, or under the situation of single lithium fluophosphate or difluorophosphate, improve the lithium concentration of electrode surface, inferred these function endowings just and reduced interface resistance, improved the effect of charge and discharge cycles.In addition, mono-fluor phosphate class, difluorophosphoric acid salt are inorganic matter, can not produce imflammable gas because of its decomposition.
In addition, single lithium fluophosphate or the difluorophosphate dissolubility in the widely used nonaqueous electrolytic solution that with linear carbonate such as cyclic carbonate such as ethylene carbonate and dimethyl carbonates is the main composition composition is very low, with in above-mentioned organic solvent electrolyte, compare, single lithium fluophosphate or difluorophosphate can dissolve in the normal temperature fuse salt in a large number.And single fluorophosphoric acid root anion or difluorophosphoric acid root anion can also be as the counter anion of normal temperature fuse salt.Like this, by with mono-fluor phosphate or difluorophosphoric acid salt and the combination of normal temperature fuse salt, can bring into play the effect that reduces interface resistance, improves charge more remarkable and synergistically.
Embodiment
Below, enumerate embodiment and comparative example the present invention is carried out more specific description, but only otherwise exceed its purport, the present invention is not subjected to the restriction of these embodiment.
[about the present invention 1]
[anodal manufacturing]
With 92 weight portion cobalts acid lithium (LiCoO 2), 4 weight portion Kynoar (below, abbreviate " PVdF " as) and 4 weight portion acetylene blacks mix, and make slurry to wherein adding the N-methyl pyrrolidone, and this slurry is coated on the two sides of aluminum collector body, and are and dry, obtain positive pole.
[manufacturing of negative pole]
92 weight portion powdered graphites and 8 weight portion PVdF are mixed, and make slurry, this slurry is coated on the face of copper collector body to wherein adding the N-methyl pyrrolidone, and dry, obtain negative pole.
[manufacturing of rechargeable nonaqueous electrolytic battery]
Above-mentioned positive pole, negative pole and polyethylene system dividing plate are carried out lamination according to the order of negative pole, dividing plate, positive pole, dividing plate, negative pole.The cell device that obtains is thus wrapped up with tubular aluminium stack membrane, behind the injection aftermentioned electrolyte, carry out vacuum seal, make the rechargeable nonaqueous electrolytic battery of sheet.In addition, in order to improve interelectrode adaptation, clip this sheet battery with glass plate and pressurize.
[capacity evaluation]
In 25 ℃ thermostat, the sheet rechargeable nonaqueous electrolytic battery is carried out constant current-constant-potential charge (following suitably be called " CCCV charging ") with 0.2C, discharge until 3.0V with 0.2C then until 4.4V.Repeat this circulation 3 times, regulate.Subsequently, carry out the CCCV charging until 4.4V, discharge once more until 3.0V, obtain the initial stage discharge capacity with 1C with 0.7C.Cut-off current during charging is 0.05C.Need to prove, 1C be meant can be in 1 hour current value during with the total capacity discharge of battery.
[cycle characteristics evaluation]
To put into 25 ℃ thermostat through the battery after the overcapacity evaluation test, carry out following charge and discharge cycles repeatedly 50 times: carry out the CCCV charging until 4.4V with 0.7C, carry out the constant current discharge until 3V with 1C.Obtain the capability retention of circulation after 50 times by following calculating formula, in the hope of value carry out the evaluation of cycle characteristics.This numerical value is big more, shows that the circulation deterioration of battery is low more.
Capability retention (%) after 50 times circulates
=[the 50th time discharge capacity (mAh/g)/1st time discharge capacity (mAh/g)] * 100
The present invention 1 embodiment 1
To in the mixed solvent (mixed volume was than 2: 8) of ethylene carbonate (EC) and methyl ethyl carbonate (EMC), the ratio with 1mol/L be dissolved with electrolyte LiPF 6Electrolyte as basic electrolyte (I), in this basic electrolyte (I), add difluorophosphate (LiPO 2F 2) and as hexafluorophosphoric acid nickel (II) (Ni (PF of iron group compound 6) 2), make them be respectively 0.5 weight % and 20ppm (densimeter with the Ni element is equivalent to 3.4ppm) with respect to the concentration of nonaqueous electrolytic solution, make nonaqueous electrolytic solution.The nonaqueous electrolytic solution that use obtains is made rechargeable nonaqueous electrolytic battery according to the method described above, and carries out capacity evaluation and cycle characteristics evaluation.The result is as shown in table 1.
The present invention 1 embodiment 2
In basic electrolyte (I), add difluorophosphate (LiPO 2F 2) and as hexafluorophosphoric acid nickel (II) (Ni (PF of iron group compound 6) 2), make them be respectively 0.5 weight % and 50ppm (with the densimeter of Ni element with respect to the concentration of nonaqueous electrolytic solution, be equivalent to 8.4ppm), make nonaqueous electrolytic solution, use this nonaqueous electrolytic solution to make rechargeable nonaqueous electrolytic battery according to the method described above, and carry out capacity evaluation and cycle characteristics evaluation.The result is as shown in table 1.
The present invention 1 embodiment 3
In basic electrolyte (I), add difluorophosphate (LiPO 2F 2) and as hexafluorophosphoric acid nickel (II) (Ni (PF of iron group compound 6) 2), make them be respectively 0.5 weight % and 100ppm (with the densimeter of Ni element with respect to the concentration of nonaqueous electrolytic solution, be equivalent to 16.8ppm), make nonaqueous electrolytic solution, use this nonaqueous electrolytic solution to make rechargeable nonaqueous electrolytic battery according to the method described above, and carry out capacity evaluation and cycle characteristics evaluation.The result is as shown in table 1.
The present invention 1 embodiment 4
In basic electrolyte (I), add difluorophosphate (LiPO 2F 2) and as hexafluorophosphoric acid nickel (II) (Ni (PF of iron group compound 6) 2), make them be respectively 0.5 weight % and 200ppm (with the densimeter of Ni element with respect to the concentration of nonaqueous electrolytic solution, be equivalent to 33.7ppm), make nonaqueous electrolytic solution, use this nonaqueous electrolytic solution to make rechargeable nonaqueous electrolytic battery according to the method described above, and carry out capacity evaluation and cycle characteristics evaluation.The result is as shown in table 1.
The present invention 1 embodiment 5
In basic electrolyte (I), add difluorophosphate (LiPO 2F 2) and as hexafluorophosphoric acid nickel (II) (Ni (PF of iron group compound 6) 2), make them be respectively 0.5 weight % and 300ppm (with the densimeter of Ni element with respect to the concentration of nonaqueous electrolytic solution, be equivalent to 50.5ppm), make nonaqueous electrolytic solution, use this nonaqueous electrolytic solution to make rechargeable nonaqueous electrolytic battery according to the method described above, and carry out capacity evaluation and cycle characteristics evaluation.The result is as shown in table 1.
The present invention 1 embodiment 6
In basic electrolyte (I), add difluorophosphate (LiPO 2F 2) and as hexafluorophosphoric acid nickel (II) (Ni (PF of iron group compound 6) 2), make them be respectively 0.5 weight % and 1000ppm (with the densimeter of Ni element with respect to the concentration of nonaqueous electrolytic solution, be equivalent to 168ppm), make nonaqueous electrolytic solution, use this nonaqueous electrolytic solution to make rechargeable nonaqueous electrolytic battery according to the method described above, and carry out capacity evaluation and cycle characteristics evaluation.The result is as shown in table 1.
The present invention 1 embodiment 7
In basic electrolyte (I), add difluorophosphate (LiPO 2F 2) and as hexafluorophosphoric acid nickel (II) (Ni (PF of iron group compound 6) 2), make them be respectively 0.5 weight % and 3500ppm (with the densimeter of Ni element with respect to the concentration of nonaqueous electrolytic solution, be equivalent to 589ppm), make nonaqueous electrolytic solution, use this nonaqueous electrolytic solution to make rechargeable nonaqueous electrolytic battery according to the method described above, and carry out capacity evaluation and cycle characteristics evaluation.The result is as shown in table 1.
The present invention 1 embodiment 8
In basic electrolyte (I), add difluorophosphate (LiPO 2F 2) and as hexafluorophosphoric acid nickel (II) (Ni (PF of iron group compound 6) 2), make them be respectively 0.5 weight % and 10000ppm (with the densimeter of Ni element with respect to the concentration of nonaqueous electrolytic solution, be equivalent to 1684ppm), make nonaqueous electrolytic solution, use this nonaqueous electrolytic solution to make rechargeable nonaqueous electrolytic battery according to the method described above, and carry out capacity evaluation and cycle characteristics evaluation.The result is as shown in table 1.
The present invention 1 embodiment 9
In basic electrolyte (I), add difluorophosphate (LiPO 2F 2) and as hexafluorophosphoric acid cobalt (II) (Co (PF of iron group compound 6) 2), make them be respectively 0.5 weight % and 50ppm (with the densimeter of Co element with respect to the concentration of nonaqueous electrolytic solution, be equivalent to 8.4ppm), make nonaqueous electrolytic solution, use this nonaqueous electrolytic solution to make rechargeable nonaqueous electrolytic battery according to the method described above, and carry out capacity evaluation and cycle characteristics evaluation.The result is as shown in table 1.
The present invention 1 embodiment 10
In basic electrolyte (I), add difluorophosphate (LiPO 2F 2) and as hexafluorophosphoric acid cobalt (II) (Co (PF of iron group compound 6) 2), make them be respectively 0.5 weight % and 100ppm (with the densimeter of Co element with respect to the concentration of nonaqueous electrolytic solution, be equivalent to 16.9ppm), make nonaqueous electrolytic solution, use this nonaqueous electrolytic solution to make rechargeable nonaqueous electrolytic battery according to the method described above, and carry out capacity evaluation and cycle characteristics evaluation.The result is as shown in table 1.
The present invention 1 comparative example 1
In basic electrolyte (I), only add difluorophosphate (LiPO 2F 2), making its concentration with respect to nonaqueous electrolytic solution is 0.5 weight %, makes nonaqueous electrolytic solution, uses this nonaqueous electrolytic solution to make rechargeable nonaqueous electrolytic battery according to the method described above, and carries out capacity evaluation and cycle characteristics evaluation.The result is as shown in table 1.
The present invention 1 comparative example 2
In basic electrolyte (I), only add hexafluorophosphoric acid nickel (II) (Ni (PF as the iron group compound 6) 2), making its concentration with respect to nonaqueous electrolytic solution is 100ppm (densimeter with the Ni element is equivalent to 16.8ppm), makes nonaqueous electrolytic solution, use this nonaqueous electrolytic solution to make rechargeable nonaqueous electrolytic battery according to the method described above, and carry out capacity evaluation and cycle characteristics evaluation.The result is as shown in table 1.
[table 1]
As shown in Table 1, with regard to the rechargeable nonaqueous electrolytic battery of embodiment 1～embodiment 10 of the present invention 1 of the nonaqueous electrolytic solution that contains iron family element and " mono-fluor phosphate and/or difluorophosphoric acid salt " that used the present invention 1, compare with the rechargeable nonaqueous electrolytic battery that only contains difluorophosphoric acid salt (the present invention 1 comparative example 1) or only contain iron family element (the present invention 1 comparative example 2), cycle characteristics (capability retention after the circulation) improves.
[about the present invention 2]
The present invention 2 embodiment 1
The making of＜rechargeable nonaqueous electrolytic battery 〉
[making of positive active material]
Use composition formula LiMn 0.33Ni 0.33Co 0.33O 2Represented lithium-transition metal composite oxide is as positive active material.Described positive active material is synthetic according to following method.Weighing is as the Mn of manganese raw material 3O 4, as the NiO of nickel raw material, as the Co (OH) of cobalt raw material 2, make their mol ratio Mn: Ni: Co=1: 1: 1, make slurry to wherein adding pure water, with circulating medium-stirring wet-type ball mill the solid constituent in the slurry is carried out case of wet attrition while stirring, making its median particle diameter is 0.2 μ m.
Slurry is carried out spray drying with spray dryer, the about 5 μ m of particle diameter that obtain only making, granulation particle spherical in shape roughly by manganese raw material, nickel raw material, cobalt raw material.Adding median particle diameter in the granulation particle that obtains is the LiOH powder of 3 μ m, the molal quantity that makes Li is 1.05 times with respect to the ratio of the total mole number of Mn, Ni and Co, mix with super mixer, obtain the granulation particle of nickel raw material, cobalt raw material, manganese raw material and the mixed-powder of lithium raw material.This mixed-powder under circulation of air, 950 ℃ of calcinings (5 ℃/minute of warming and cooling rates) 12 hours, is pulverized subsequently, and the sieve by width of mesh 45 μ m obtains positive active material.
[anodal making]
In N-crassitude ketone solvent, mix 90 weight % above-mentioned positive active material, 5 weight % as the acetylene black of electric conducting material and 5 weight % as the Kynoar (PVdF) of binding agent, make slurry.The slurry that obtains is coated on the face of aluminium foil of thickness 15 μ m, and carries out drying, roll into thickness 80 μ m with press after, the aluminium foil after handling is like this struck out the discoid of diameter 12.5mm with pierce punch, make anodal.By this anodal part, conduct lithium metallic plate, the use of electrode are dissolved with LiPF with 1mol/L concentration in the solvent of EC (ethylene carbonate): DMC (dimethyl carbonate): EMC (methyl ethyl carbonate)=3: 3: 4 (volume ratio) 6Electrolyte and as the porous polyethylene membrane assembling Coin-shaped battery of the thickness 25 μ m of dividing plate.
The Coin-shaped battery that obtains is carried out 0.2mA/cm 2Constant-current constant-voltage charging, promptly under upper voltage limit is the condition of 4.2V, carry out emitting the reaction of lithium ion by positive pole.Under being the condition of 3.0V, lower voltage limit carries out 0.2mA/cm then 2Constant current discharge, when just making the reaction of lithium ion occlusion on positive pole, at this moment, the initial stage charging capacity of per unit weight positive active material is set at Qs (C) [mAh/g], the initial stage discharge capacity is set at Qs (D) [mAh/g].
[making of negative pole]
(Timcal (テ イ system カ Le) company makes at 98 weight portion Delanium powder KS-44, trade name) adds the aqueous liquid dispersion (concentration of sodium carboxymethylcellulose be 1 weight %) of 100 weight portions in as the sodium carboxymethylcellulose of thickener, 2 weight portions are as the aqueous liquid dispersion (concentration of styrene butadiene rubbers is 50 weight %) of the styrene butadiene rubbers of adhesive, mix with disperser, make slurry.The slurry that makes is coated on the two sides of the Copper Foil of thickness 10 μ m, and carries out drying, roll into thickness 75 μ m with press after, the Copper Foil after handling is like this struck out the discoid of diameter 12.5mm with pierce punch, make negative pole.
In addition, as the test utmost point, as to electrode, 0.2mA/cm is used in the assembled battery unit with the lithium metal with the part of this negative pole 2Constant current-constant voltage process of-3mV (cut-off current 0.05mA) is to make the test of lithium ion occlusion on negative pole under the condition of 0V in lower voltage limit, at this moment, the initial stage occlusion capacity of per unit weight negative electrode active material is set at Qf[mAh/g].
[nonaqueous electrolytic solution]
Under the argon atmospher of drying, in the mixture (volume ratio 3: 3: 4) of ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate with the mixed of 1mol/L LiPF through intensive drying 6Make that to contain in this mixed solution with respect to the nonaqueous electrolytic solution total amount be the heptane (being selected from the compound of the present invention 2 compound group) of 2 weight % ratios, dissolve difluorophosphate more therein, making its concentration with respect to the nonaqueous electrolytic solution total amount is 0.2 weight %, makes desired electrolyte.
[assembling of battery]
Make up positive pole, the negative pole of above-mentioned making, use Coin-shaped battery (コ イ Application セ Le) assembling testing battery, its battery performance is estimated.That is to say, anodal jar of (Zheng Very narrow-necked earthen jar at Coin-shaped battery) go up and place the above-mentioned positive pole of making, be provided as the porous polyethylene membrane of the thickness 25 μ m of dividing plate more thereon, after compressing with polypropylene system packing ring, in above-mentioned nonaqueous electrolytic solution added jar, make nonaqueous electrolytic solution fully penetrate into dividing plate after, place above-mentioned negative pole, put the negative pole jar again and seal, make the Coin shape lithium secondary battery thus.Need to prove that set the balance of positive active material weight and negative electrode active material weight this moment, makes it satisfy following formula substantially.
(negative electrode active material weight [g] * Qf[mAh/g])/(positive active material weight [g] * Qs (C) [mAh/g])=1.2
＜battery behavior test 〉
For the low temperature load characteristic of the battery of measuring such acquisition, 1 hour rate (the 1 Time Inter leads) current value of setting battery according to following formula is 1C, carries out following test.
1C[mA]=Qs (D) * positive active material weight [g]/h
At first, the constant current 0.2C that carries out 1 circulation in room temperature discharges and recharges, and carries out 2 following circulations then: carry out carrying out constant current 1/3C discharge after constant current decides voltage 1/3C charging.Need to prove, be limited to 4.1V in the charging wherein, lower voltage limit is 3.0V.
(output test)
Then, under 25 ℃ environment, export determination test to depth of charge being adjusted into 50% Coin-shaped battery by the 1/3C constant current charge.Carry out discharge in 10 seconds (ended 15 minutes the discharge back, charges with the pairing capacitance of each time discharge then, ended 15 minutes, and then carry out ensuing discharge test) with 0.3C, 1.0C, 3.0C, 10.0C, measure the voltage in the 10th second respectively.The area of 3 dihedrals that surrounded with current-voltage straight line and lower voltage limit (3V) is as initial stage power output (W), and the result is as shown in table 2.
(cyclic test)
Under 60 ℃ hot environment of the actual SC service ceiling temperature that is considered to lithium secondary battery, carry out cyclic test.With following charge and discharge cycles as 1 circulation, carry out this circulation 100 times repeatedly, described charge and discharge cycles is: charging until the charging upper voltage limit with the constant-current constant-voltage method of 2C is 4.1V, and discharging until final discharging voltage with the constant current of 2C then is 3.0V.Battery after under 25 ℃ of environment cyclic test being finished carries out the discharging and recharging of 1/3C of 3 circulations, carry out and preliminary phase with output test.With the value the measured power output after as circulation, the result is as shown in table 2.
The present invention 2 embodiment 2
In the preparation of nonaqueous electrolytic solution, the amount of heptane is changed to 0.5 weight % by 2 weight %, in addition, make rechargeable nonaqueous electrolytic battery according to the method identical with the present invention 2 embodiment 1, carry out the battery behavior test.The result is as shown in table 2.
The present invention 2 embodiment 3
In the preparation of nonaqueous electrolytic solution, use the cyclohexane of 2 weight % to replace the heptane of 2 weight %, in addition, make rechargeable nonaqueous electrolytic battery according to the method identical with the present invention 2 embodiment 1, carry out the battery behavior test.The result is as shown in table 2.
The present invention 2 embodiment 4
In the preparation of nonaqueous electrolytic solution, the amount of cyclohexane is changed to 0.5 weight % by 2 weight %, in addition, make rechargeable nonaqueous electrolytic battery according to the method identical with the present invention 2 embodiment 3, carry out the battery behavior test.The result is as shown in table 2.
The present invention 2 embodiment 5
In the preparation of nonaqueous electrolytic solution, use the fluorobenzene of 2 weight % to replace the heptane of 2 weight %, in addition, make rechargeable nonaqueous electrolytic battery according to the method identical with the present invention 2 embodiment 1, carry out the battery behavior test.The result is as shown in table 2.
The present invention 2 embodiment 6
In the preparation of nonaqueous electrolytic solution, the amount of fluorobenzene is changed to 0.5 weight % by 2 weight %, in addition, make rechargeable nonaqueous electrolytic battery according to the method identical with the present invention 2 embodiment 5, carry out the battery behavior test.The result is as shown in table 2.
The present invention 2 embodiment 7
In the preparation of nonaqueous electrolytic solution, use the nine fluorine butyl ethyl ethers of 2 weight % to replace the heptane of 2 weight %, in addition, make rechargeable nonaqueous electrolytic battery according to the method identical with the present invention 2 embodiment 1, carry out the battery behavior test.The result is as shown in table 2.
The present invention 2 embodiment 8
In the preparation of nonaqueous electrolytic solution, the amount of nine fluorine butyl ethyl ethers is changed to 0.5 weight % by 2 weight %, in addition, make rechargeable nonaqueous electrolytic battery according to the method identical with the present invention 2 embodiment 7, carry out the battery behavior test.The result is as shown in table 2.
The present invention 2 embodiment 9
In the preparation of nonaqueous electrolytic solution, use the difluorophosphoric acid sodium of 0.2 weight % to replace the difluorophosphate of 0.2 weight %, in addition, make rechargeable nonaqueous electrolytic battery according to the method identical with the present invention 2 embodiment 3, carry out the battery behavior test.The result is as shown in table 2.
The present invention 2 comparative example 1
In the preparation of nonaqueous electrolytic solution, do not use the compound and the difluorophosphate of the present invention 2 compound group, in addition, make rechargeable nonaqueous electrolytic battery according to the method identical with the present invention 2 embodiment 1, carry out the battery behavior test.The result is as shown in table 2.
The present invention 2 comparative example 2
In the preparation of nonaqueous electrolytic solution, do not use difluorophosphate, in addition, make rechargeable nonaqueous electrolytic battery according to the method identical with the present invention 2 embodiment 1, carry out the battery behavior test.The result is as shown in table 2.
The present invention 2 comparative example 3
In the preparation of nonaqueous electrolytic solution, do not use difluorophosphate, in addition, make rechargeable nonaqueous electrolytic battery according to the method identical with the present invention 2 embodiment 3, carry out the battery behavior test.The result is as shown in table 2.
The present invention 2 comparative example 4
In the preparation of nonaqueous electrolytic solution, do not use difluorophosphate, in addition, make rechargeable nonaqueous electrolytic battery according to the method identical with the present invention 2 embodiment 5, carry out the battery behavior test.The result is as shown in table 2.
The present invention 2 comparative example 5
In the preparation of nonaqueous electrolytic solution, do not use difluorophosphate, in addition, make rechargeable nonaqueous electrolytic battery according to the method identical with the present invention 2 embodiment 7, carry out the battery behavior test.The result is as shown in table 2.
The present invention 2 comparative example 6
In the preparation of nonaqueous electrolytic solution, do not use the compound of the present invention 2 compound group, in addition, make rechargeable nonaqueous electrolytic battery according to the method identical with the present invention 2 embodiment 7, carry out the battery behavior test.The result is as shown in table 2.
It is the initial stage power output of 100% o'clock each battery and the ratio of circulation back power output that table 2 shows with the initial stage power output of the battery of the present invention 2 comparative example 1 and circulation back power output.
[table 2]
The compound of compound group of the present invention Mono-fluor phosphate and/or difluorophosphoric acid salt Initial stage power output (%) Circulation back institute's power output (%)
Embodiment 1 Heptane 2% Difluorophosphate 0.2% ??128 ??133
Embodiment 2 Heptane 0.5% Difluorophosphate 0.2% ??126 ??131
Embodiment 3 Cyclohexane 2% Difluorophosphate 0.2% ??132 ??138
Embodiment 4 Cyclohexane 0.5% Difluorophosphate 0.2% ??128 ??133
Embodiment 5 Fluorobenzene 2% Difluorophosphate 0.2% ??126 ??132
Embodiment 6 Fluorobenzene 0.5% Difluorophosphate 0.2 ??124 ??130
Embodiment 7 Nine fluorine butyl ethyl ethers 2% Difluorophosphate 0.2% ??130 ??135
Embodiment 8 Nine fluorine butyl ethyl ethers 0.5% Difluorophosphate 0.2% ??127 ??132
Embodiment 9 Cyclohexane 2% Difluorophosphoric acid sodium 0.2% ??127 ??133
Comparative example 1 Do not have Do not have ??100 ??100
Comparative example 2 Heptane 2% Do not have ??100 ??100
Comparative example 3 Cyclohexane 2% Do not have ??100 ??101
Comparative example 4 Fluorobenzene 2% Do not have ??99 ??100
Comparative example 5 Nine fluorine butyl ethyl ethers 2% Do not have ??100 ??101
Comparative example 6 Do not have Difluorophosphate 0.2% ??121 ??124
As shown in Table 2, the rechargeable nonaqueous electrolytic battery of embodiment 1～embodiment 9 of the present invention 2 has used the compound that contains the compound group that belongs to the present invention 2 simultaneously and the nonaqueous electrolytic solution of difluorophosphoric acid salt; The rechargeable nonaqueous electrolytic battery of the present invention 2 comparative example 1 does not contain any one in the nonaqueous electrolytic solution of the compound of the compound group that belongs to the present invention 2 and difluorophosphoric acid salt; The rechargeable nonaqueous electrolytic battery of the present invention 2 comparative example 6 only contains difluorophosphate, compare with the rechargeable nonaqueous electrolytic battery of the rechargeable nonaqueous electrolytic battery of the present invention 2 comparative example 1, the present invention's 2 comparative example 6, the rechargeable nonaqueous electrolytic battery of embodiment 1～embodiment 9 of the present invention 2 demonstrates high output characteristic.And even relatively pass through power output after the high temperature circulation, the battery of embodiment 1～embodiment 9 of the present invention 2 is also bigger with respect to the climbing of the power output of the present invention 2 comparative example 1.
On the other hand, the rechargeable nonaqueous electrolytic battery of the rechargeable nonaqueous electrolytic battery of comparative example 2～comparative example 5 of the present invention 2 (contain the compound of the compound group that belongs to the present invention 2 but do not contain difluorophosphoric acid salt) and the present invention 2 comparative example 1 (not containing any one in the nonaqueous electrolytic solution of the compound of the compound group that belongs to the present invention 2 and difluorophosphoric acid salt) is compared as can be known, we can say that power output does not change fully.The result can confirm the present invention 2 serviceability thus, promptly by being used in combination the compound and the difluorophosphate of the compound group that belongs to the present invention 2, has improved output characteristic.
[about the present invention 3]
The present invention 3 embodiment 1
The making of＜secondary cell 〉
[anodal making]
In N-crassitude ketone solvent, mix the cobalt acid lithium (LiCoO of 94 weight % as positive active material 2), 3 weight % as the Kynoar (PVdF) of adhesive, make slurry as the acetylene black of electric conducting material and 3 weight %.The slurry that obtains is coated on the two sides of the aluminium foil of thickness 14 μ m, and carries out drying, roll into thickness 85 μ m with press, the aluminium foil after will handling so again strikes out diameter 12.5mm circle, as positive pole.
[making of negative pole]
With the electrolytic copper foil of thickness 18 μ m as the collector body substrate, with Si as the target electrode material, with dc sputtering device (" HSM-52 " that company of Shimadzu Seisakusho Ltd. makes), with power density 4.7W/cm 2, the about 1.8nm/sec of stackeding speed (film forming speed) carries out the film forming of Si film, obtains the Si film cathode.
[nonaqueous electrolytic solution]
Under the argon atmospher of drying, dissolving is respectively through the LiPF of intensive drying in the mixture (volume ratio 3: 7) of ethylene carbonate and diethyl carbonate 6With difluorophosphoric acid salt, make LiPF 6Be respectively 1mol/L, 1 weight % with the concentration of difluorophosphoric acid salt, make desired nonaqueous electrolytic solution.
[processing of electrode]
According to following method the above-mentioned negative pole that obtains is handled.Dissolving 3-methacryl propyl-triethoxysilicane in diethyl carbonate (DEC), making its concentration with respect to diethyl carbonate (DEC) is 1 weight %, preparation negative pole treatment fluid.Described electrode is immersed in this negative pole treatment fluid, under 110 ℃, carries out 1 hour heat treated then.Use after 11 hours at 60 ℃ of following drying under reduced pressure then.In addition, positive pole does not carry out above-mentioned processing, uses after 11 hours at 80 ℃ of following drying under reduced pressure.
[making of rechargeable nonaqueous electrolytic battery]
Positive pole is encased in the stainless steel tank of double as cathode conductor, places negative pole by soaking into the polyethylene system dividing plate that electrolyte is arranged thereon.The hush panel of this tank body and double as negative pole electric conductor is sealed with packing ring etc. by insulation, make Coin-shaped battery.
The evaluation of＜battery 〉
Above-mentioned battery is carried out 5 following circulations, make battery operated stablely, described circulation is: 25 ℃ with the constant current charge that is equivalent to 0.2C to end of charge voltage 4.2V, be discharged to final discharging voltage 2.5V again; The 6th circulation is: with the current charges that is equivalent to 0.2C to end of charge voltage 4.2V, after charging to charging current value again and be 4.2V-constant-current constant-voltage charging (CCCV charging) (0.02C cut-out) of the current value that is equivalent to 0.02C, carry out 2.5V with the constant current value that is equivalent to 0.5C and discharge; The 7th circulation is: after carrying out 4.2V-constant-current constant-voltage charging (CCCV charging) (0.02C cut-out) with the electric current that is equivalent to 0.2C, carry out the 2.5V discharge with the constant current value that is equivalent to 1.0C.Then, circulate under the following conditions 92 times, described condition is: carry out 4.2V-constant-current constant-voltage charging (CCCV charging) (0.05C cut-out) with the electric current that is equivalent to 0.5C, carry out the 2.5V discharge with the constant current value that is equivalent to 0.5C then; The 100th circulation is: carry out 4.2V-constant-current constant-voltage charging (CCCV charging) (0.02C cut-out) with the electric current that is equivalent to 0.2C, carry out the 2.5V discharge with the constant current value that is equivalent to 0.2C then.Here said 1C represents to reach the current value of full charging in 1 hour.
Embodiment 2～the present invention's 3 of the present invention 3 embodiment 4
According to making anodal, negative pole and prepare nonaqueous electrolytic solution with the same method of the present invention 3 embodiment 1.Carry out the processing of electrode then respectively.That is to say, described according to table 3, use diethyl carbonate (DEC) or pure water respectively, dissolve therein respectively or dispersion 3-methacryl propyl-triethoxysilicane or 3-aminopropyl triethoxysilane, making 3-methacryl propyl-triethoxysilicane or 3-aminopropyl triethoxysilane is 1 weight % with respect to the concentration of diethyl carbonate (DEC) or pure water, preparation negative pole treatment fluid is according to handling with the same method anticathode of the present invention 3 embodiment 1.Identical with the present invention 3 embodiment 1, do not carry out anodal processing yet.Make rechargeable nonaqueous electrolytic battery according to the method identical, carry out the evaluation of battery according to the method identical then with the present invention 3 embodiment 1 with the present invention 3 embodiment 1.The result is shown in table 3 in the lump.
The present invention 3 comparative example 1
Except not using difluorophosphate, according to preparing nonaqueous electrolytic solution according to the method identical with the present invention 3 embodiment 1.In addition, make positive pole and negative pole according to the method identical with the present invention 3 embodiment 1.Then, only carry out 11 hours drying under reduced pressure at 60 ℃ of following anticathodes.Anodal processing is also carried out equally with the present invention 3 embodiment 1.After making rechargeable nonaqueous electrolytic battery according to the method identical, carry out the evaluation of battery according to the method identical with the present invention 3 embodiment 1 with the present invention 3 embodiment 1.The result is shown in table 3 in the lump.
Comparative example 2～comparative example 5 of the present invention 3
Except not using difluorophosphate, prepare nonaqueous electrolytic solution according to the method identical with the present invention 3 embodiment 1.In addition, make positive pole and negative pole according to the method identical with the present invention 3 embodiment 1.Then, do not carry out the processing of electrode.That is to say, as described in Table 3, use diethyl carbonate (DEC) or pure water respectively, dissolve therein respectively or dispersion 3-methacryl propyl-triethoxysilicane or 3-aminopropyl triethoxysilane, making 3-methacryl propyl-triethoxysilicane or 3-aminopropyl triethoxysilane is 1 weight % with respect to the concentration of diethyl carbonate (DEC) or pure water, preparation negative pole treatment fluid is according to handling with the same method anticathode of the present invention 3 embodiment 1.Anodal processing is also carried out equally with the present invention 3 embodiment 1.Make rechargeable nonaqueous electrolytic battery according to the method identical, carry out the evaluation of battery according to the method identical then with the present invention 3 embodiment 1 with the present invention 3 embodiment 1.The result is shown in table 3 in the lump.
The present invention 3 comparative example 6
According to the method same, make anodal, negative pole and also prepare nonaqueous electrolytic solution with the present invention 3 embodiment 1.Then, only carry out 11 hours drying under reduced pressure at 60 ℃ of following anticathodes.Carry out anodal processing according to the method identical with the present invention 3 embodiment 1.Make rechargeable nonaqueous electrolytic battery according to the method identical, carry out the evaluation of battery according to the method identical then with the present invention 3 embodiment 1 with the present invention 3 embodiment 1.The result is shown in table 3 in the lump.
Confirm by gas chromatograph, in the nonaqueous electrolytic solution after the rechargeable nonaqueous electrolytic battery of the present invention 3 embodiment 1, the present invention's 3 embodiment 2, the present invention's 3 comparative example 2 and comparative example 3 is made, containing with respect to this nonaqueous electrolytic solution total amount is the 3-methacryl propyl-triethoxysilicane of 0.06 weight %.In addition, confirm by gas chromatograph, in the nonaqueous electrolytic solution after the rechargeable nonaqueous electrolytic battery of the present invention 3 embodiment 3, the present invention's 3 embodiment 4, the present invention's 3 comparative example 4 and comparative example 5 is made, containing with respect to this nonaqueous electrolytic solution total amount is the 3-aminopropyl triethoxysilane of 0.13 weight %.
As a result of, the likening to " 50 times cyclic discharge capacity compares " of discharge capacity with 50 circulations of the comparative example 1 (do not carry out negative pole and handle, do not use difluorophosphoric acid salt) of discharge capacity and the present invention 3 of 50 circulations in each example is shown in Table 3.That is to say that described " 50 cyclic discharge capacity ratios " is expressed as: (50 cyclic discharge capacity ratios)=(discharge capacities of 50 circulations)/(discharge capacity of the present invention's 3 of 50 circulations comparative example 1).
[table 3]
The negative pole treatment fluid Difluorophosphoric acid salt (weight %) The discharge capacity ratio of 50 circulations
Embodiment 1 3-methacryl propyl-triethoxysilicane (1%DEC solution) Difluorophosphate (1) ??1.24
Embodiment 2 3-methacryl propyl-triethoxysilicane (1%H 2O solution) Difluorophosphate (1) ??1.24
Embodiment 3 3-aminopropyl triethoxysilane (1%DEC solution) Difluorophosphate (1) ??1.22
Embodiment 4 3-aminopropyl triethoxysilane (1%H 2O solution) Difluorophosphate (1) ??1.27
Comparative example 1 Do not have Do not have ??1
Comparative example 2 3-methacryl propyl-triethoxysilicane (1%DEC solution) Do not have ??1.15
Comparative example 3 3-methacryl propyl-triethoxysilicane (1%H 2O solution) Do not have ??1.06
Comparative example 4 3-aminopropyl triethoxysilane (1%DEC solution) Do not have ??1.17
Comparative example 5 3-aminopropyl triethoxysilane (1%H 2O solution) Do not have ??1.08
Comparative example 6 Do not have Difluorophosphate (1) ??1.19
As shown in Table 3, satisfy condition 1 and the rechargeable nonaqueous electrolytic battery made of use the present invention's 3 of condition 2 nonaqueous electrolytic solution with only satisfy condition 1 or condition 2 in one, or 1 also do not satisfy condition 2 the rechargeable nonaqueous electrolytic battery that neither satisfies condition is compared, discharge capacity after 50 circulations demonstrates bigger value, in the deterioration that suppresses to follow battery charging and discharging, succeed in the extending battery life aspect, described condition 1 is for to handle with compound anticathode shown in general formula (1) or the general formula (2), and described condition 2 is for containing the difluorophosphate as " mono-fluor phosphate and/or difluorophosphoric acid salt " in nonaqueous electrolytic solution.
Particularly, satisfy condition 1 simultaneously, embodiment 1～embodiment 4 of the present invention 3 of condition 2 suppressed to follow the deterioration of the battery behavior that discharges and recharges.In contrast, the present invention 3 the discharge capacitance of comparative example 1 that does not satisfy any one condition as can be known is little, and deterioration of battery is remarkable.And, only satisfy condition 1 or condition 2 in comparative example 2～comparative example 6 of the present invention 3 of one compare with the present invention 3 comparative example 1, all demonstrate bigger discharge capacity, determine to have the effect that suppresses deterioration of battery, but compare with the present invention 3 rechargeable nonaqueous electrolytic battery (embodiment 1～embodiment 4 of the present invention 3), it has little effect.Need to prove,,, be not defined as the content of the present invention 3 embodiment as long as be the described content of claim though carried out the record of condition 1, condition 2.
[about the present invention 4]
[preparation of electrolyte]
To mix according to the amount of 381.6g/310.0g/391.5g (about 290mL/290mL/385mL) respectively by the ethylene carbonate/dimethyl carbonate/carbonic acid ethyl methyl esters of purifying under the dry argon gas atmosphere, dissolving 151.9g is through the lithium hexafluoro phosphate (LiPF of intensive drying in the solvent that obtains in mixing 6).The proportion of this solution is 1.22.In above-mentioned solution, add additive, and make it dissolving according to the amount shown in the table 4.
[table 4]
Figure A20088001284001391
In table 4, " execution mode 1 " expression " execution mode 4-1 ", " execution mode 2 " expression " execution mode 4-2 "." the represented compound of general formula (1) " expression " the represented compound of the present invention's 4 formula ofs (1) ".
[chemical formula 35]
Compd A platform thing B
Figure A20088001284001401
Change platform thing C
[making of secondary cell]
The making of＜" secondary cell 1 " 〉
(anodal making)
In N-crassitude ketone solvent, mix the cobalt acid lithium (LiCoO of 90 weight % as positive active material 2), 5 weight % as the acetylene black of electric conducting material, 5 weight % as the Kynoar of binding agent (below, abbreviate " PVDF " as), preparation slurry.The slurry that obtains is coated on the two sides of the aluminium foil of 15 μ m, and carry out drying, and roll into thickness 80 μ m with press, the size that the aluminium foil after handling like this is cut into active material layer is wide 100mm, long 100mm, and have the shape of the uncoated part of wide 30mm, as positive pole.
(making of negative pole)
(Timcal company makes at 98 weight portion Delanium powder KS-44, trade name) adds the aqueous liquid dispersion (concentration of sodium carboxymethylcellulose be 1 weight %) of 100 weight portions in as the sodium carboxymethylcellulose of thickener, 2 weight portions are as the aqueous liquid dispersion (concentration of styrene butadiene rubbers is 50 weight %) of the styrene butadiene rubbers of adhesive, mix with disperser, make slurry.
The slurry that obtains is coated on the two sides of the thick Copper Foil of 10 μ m, and carry out drying, and roll into 75 μ m with press, the size that the Copper Foil after handling like this is cut into active material layer is wide 104mm, long 104mm, and have the shape of the uncoated part of wide 30mm, as negative pole.
(assembling of battery)
Do not make under positive pole and the condition that negative pole directly contacts anodal, negative pole and polyethylene system dividing plate overlapping curling, making electrode body.It is encased in the battery can, makes the terminal of anodal and negative pole be exposed to the outside.Then,, carry out ca(u)lk moulding (か め shaping), make 18650 type cylinder batteries to wherein injecting 5mL electrolyte described later, with it as " secondary cell 1 ".
The making of＜" secondary cell 2 " 〉
With nickel manganese cobalt acid lithium (LiNi 1/3Mn 1/3Co 1/3O 2) replace cobalt acid lithium as positive active material, charging voltage is 4.25V, in addition, makes battery according to the method identical with secondary cell 1, with it as " secondary cell 2 ".
The making of＜" secondary cell 3 " 〉
With LiFePO4 (LiFePO 4) replace cobalt acid lithium as positive active material, charging voltage is 4.25V, in addition, makes battery according to the method identical with secondary cell 1, with it as " secondary cell 3 ".
The making of＜" secondary cell 4 " 〉
Use 73.2 weight portions as non-material with carbon element silicon, 8.1 weight portion copper and 12.2 weight portion Delanium powder (Timcal corporate system trade name " KS-6 ") as negative electrode active material, to wherein adding N-methyl pyrrolidone solution 54.2 weight portions and the 50 weight portion N-methyl pyrrolidones that contain 12 weight %PVDF, mix with disperser, make slurry.
The slurry that obtains is uniformly coated on the Copper Foil as the thickness 18 μ m of negative electrode collector, after the air dry, finally at 85 ℃ of following drying under reduced pressure diels.Suppressing then and making electrode density is 1.5gcm -3About, strike out the discoid of diameter 12.5mm, as negative pole (silicon alloy negative pole), in addition, make battery according to the method identical with secondary cell 1, with it as " secondary cell 4 ".
The making of＜" secondary cell 5 " 〉
In N-crassitude ketone solvent, mix 90 weight % negative electrode active material (Li 4/3Ti 5/3O 4), 5 weight % are as the acetylene black of electric conducting material, the 5 weight % Kynoar (PVdF) as adhesive, make slurry.
The slurry that obtains is coated on the face of the thick rolled copper foil of 10 μ m, and carry out drying, roll into 90 μ m with press, the size that Copper Foil after handling like this is cut into active material layer is wide 104mm, long 104mm, and have the shape of the uncoated part of wide 30mm, as negative pole, in addition, make battery according to the method identical with secondary cell 1, with it as " secondary cell 5 ".
The present invention 4 embodiment 1～14 and the present invention 4 comparative example 1～8
As the present invention 4 embodiment 1～14 and the present invention 4 comparative example 1～8, the combination of the experimental condition that each the present invention's 4 embodiment, each the present invention's 4 comparative example is all put down in writing according to following table 5, table 6 (kind of electrolyte and secondary cell) is tested, and obtains the result at following assessment item.Its result is shown in following table 5, table 6.
[evaluation of secondary cell]
The evaluation of secondary cell is estimated each battery according to following condition.
The evaluation of＜secondary cell 1 〉
(initial capacity)
Constant-current constant-voltage mise-a-la-masse method with 0.2C under 25 ℃ charges to 4.2V, and the constant current with 0.2C is discharged to 3.0V then.This circulation is carried out 5 times, made battery stable.Discharge capacity with the 5th circulation at this moment is " initial capacity ".Need to prove, can make current value that rated capacity discharged in 1 hour as 1C.
(circulation conservation rate)
Carry out following charge and discharge cycles 500 times, described discharging and recharging to: the battery after the initial stage of will having implemented discharges and recharges charges to 4.2V with the constant-current constant-voltage methods of 1C down at 60 ℃, the constant current with 1C is discharged to 3.0V then.The 500th cyclic discharge capacity of this moment accounted for the ratio of the 1st cyclic discharge capacity as " circulation conservation rate ".
(initial stage low temperature discharge rate)
Battery after the initial stage of having implemented discharged and recharged charges to 4.2V with the constant-current constant-voltage methods of 0.2C down at 25 ℃, then-30 ℃ of constant-current discharges of enforcement 0.2C down.As initial stage low temperature capacity, the ratio that initial stage low temperature capacity is accounted for initial capacity is as " initial stage low temperature discharge rate " with discharge capacity at this moment.
(circulation back low temperature discharge rate)
Battery after cyclic test constant-current constant-voltage mise-a-la-masse method with 0.2C under 25 ℃ is charged to 4.2V, and the constant current with 0.2C is discharged to 3.0V then.This circulation is carried out 3 times, with the discharge capacity of the 3rd circulation as circulation back capacity.Then, same battery constant-current constant-voltage mise-a-la-masse method with 0.2C under 25 ℃ is charged to 4.2V, then-30 ℃ of constant currents discharges of implementing 0.2C down.As circulation back low temperature capacity, the ratio that circulation back low temperature capacity is accounted for the back capacity that circulates is as " circulation back low temperature discharge rate " with discharge capacity at this moment.
The evaluation of＜secondary cell 2 〉
The charging voltage of each test is changed to 4.25V by 4.2V, in addition,, similarly estimate for the project identical with the evaluation of secondary cell 1.
The evaluation of＜secondary cell 3 〉
The charging voltage of each test is changed to 3.8V and discharge voltage is changed to 2.5V by 3.0V by 4.2V, in addition,, similarly estimate for the project identical with the evaluation of secondary cell 1.
The evaluation of＜secondary cell 4 〉
The discharge voltage of each test is changed to 2.5V by 3.0V, in addition,, similarly estimate for the project identical with the evaluation of secondary cell 1.
The evaluation of＜secondary cell 5 〉
The charging voltage of each test is changed to 2.7V and discharge voltage is changed to 1.9V by 3.0V by 4.2V, in addition,, similarly estimate for the project identical with the evaluation of secondary cell 1.
The initial capacity of the present invention's 4 of use electrolyte 1～12 embodiment 1～16, circulation conservation rate, initial stage low temperature discharge rate and circulation back low temperature discharge rate are all good, and the present invention's 4 of use electrolyte A～D then at least one of comparative example 1～8 is very poor.
[table 5]
??No. Electrolyte Battery Initial capacity [mA] Circulation conservation rate [%] Initial stage low temperature discharge rate [%] Circulation back low temperature discharge rate [%]
Embodiment 1 ??1 Secondary cell 1 ??700 ??74 ??65 ??63
Embodiment 2 ??2 Secondary cell 1 ??700 ??75 ??66 ??65
Embodiment 3 ??3 Secondary cell 1 ??703 ??78 ??63 ??63
Embodiment 4 ??4 Secondary cell 1 ??701 ??76 ??68 ??66
Embodiment 5 ??5 Secondary cell 1 ??700 ??68 ??71 ??69
Embodiment 6 ??6 Secondary cell 1 ??700 ??70 ??73 ??72
Embodiment 7 ??7 Secondary cell 1 ??700 ??70 ??72 ??71
Embodiment 8 ??8 Secondary cell 1 ??700 ??71 ??75 ??73
Embodiment 9 ??9 Secondary cell 1 ??700 ??68 ??68 ??67
Embodiment 10 ??10 Secondary cell 1 ??700 ??77 ??75 ??74
Embodiment 11 ??11 Secondary cell 1 ??700 ??78 ??56 ??54
Embodiment 12 ??12 Secondary cell 1 ??680 ??78 ??65 ??63
Comparative example 1 ??A Secondary cell 1 ??700 ??64 ??61 ??54
Comparative example 2 ??B Secondary cell 1 ??701 ??74 ??59 ??56
Comparative example 3 ??C Secondary cell 1 ??700 ??66 ??68 ??65
Comparative example 4 ??D Secondary cell 1 ??690 ??60 ??50 ??48
[table 6]
??No. Electrolyte Battery Initial capacity [mA] Circulation conservation rate [%] Initial stage low temperature discharge rate [%] Circulation back low temperature discharge rate [%]
Embodiment 13 ??1 Secondary cell 2 ??755 ??70 ??65 ??64
Comparative example 5 ??A Secondary cell 2 ??750 ??60 ??62 ??56
Embodiment 14 ??1 Secondary cell 3 ??727 ??65 ??60 ??55
Comparative example 6 ??A Secondary cell 3 ??725 ??57 ??55 ??49
Embodiment 15 ??1 Secondary cell 4 ??701 ??58 ??70 ??65
Comparative example 7 ??A Secondary cell 4 ??700 ??50 ??65 ??58
Embodiment 16 ??1 Secondary cell 5 ??725 ??89 ??96 ??92
Comparative example 8 ??A Secondary cell 5 ??725 ??85 ??92 ??88
[about the present invention 5]
Each evaluation method of the battery that obtains in following embodiment and the comparative example is as described below.
[discharge capacity evaluation]
With nonaqueous electrolyte battery under 60 ℃ with the constant current charge that is equivalent to 0.1C to 4.2V, the constant current with 0.1C is discharged to 3V then.This circulation is carried out 20 times, and obtaining with the initial stage discharge capacity is 100 o'clock discharge capacities (%) after 20 circulations, as " circulation back discharge capacity (%) ".Here said 1C represent can be in 1 hour with the current value of the reference capacity discharge of battery, 0.1C represents its current value of 1/10.
The present invention 5 embodiment 1
[manufacturing of nonaqueous electrolytic solution]
Under the dry argon gas atmosphere, N-butyl-N-crassitude two (fluoroform sulphonyl) imines (below, abbreviate " BMPTFSI " as) in dissolving through two (fluoroform sulphonyl) imidization lithium of intensive drying (below, abbreviate " LiTFSI " as), making its ratio is 0.4mol/L.Again to wherein dissolve with respect to the mixture of 98 weight portion BMPTFSI and LiTFSI be 2 weight portions the difluorophosphate through intensive drying (below, abbreviate " LiPO sometimes as 2F 2"), make nonaqueous electrolytic solution.
[manufacturing of nonaqueous electrolyte battery]
In N-crassitude ketone solvent, mix the cobalt acid lithium (LiCoO of 90 weight % as positive active material 2), 5 weight % as the Kynoar (PVdF) of adhesive, make slurry as the acetylene black of electric conducting material and 5 weight %.The slurry that obtains is coated on the face of aluminium foil of thickness 15 μ m, and carry out drying, roll into thickness 80 μ m with press, it is the discoid of diameter 12.5mm that aluminium foil after handling is like this struck out the active material layer size, make electrode, as work electrode (Zuo Very), across soaking into dummy plate that nonaqueous electrolytic solution is arranged nonaqueous electrolyte battery as the Coin shape lithium secondary battery, this battery, and is estimated as to electrode with the lithium paper tinsel.The composition of nonaqueous electrolytic solution is as shown in table 7, and evaluation result is as shown in table 8.
The present invention 5 embodiment 2
In the nonaqueous electrolytic solution of the present invention 5 embodiment 1, use N-butyl-N, N, N-trimethyl ammonium two (fluoroform sulphonyl) imines (below, abbreviate " BTMATFSI " as) replacement BMPTFSI, in addition, make the Coin shape lithium secondary battery according to the method identical, and estimate with the present invention 5 embodiment 1.The composition of nonaqueous electrolytic solution is as shown in table 7, and evaluation result is as shown in table 8.
The present invention 5 embodiment 3
In the nonaqueous electrolytic solution of the present invention 5 embodiment 1, use N, N-dimethyl-N-methyl-N-methoxy ethyl ammonium two (fluoroform sulphonyl) imines (below, abbreviate " DEMETFSI " as) replacement BMPTFSI, in addition, make the Coin shape lithium secondary battery according to the method identical, and estimate with the present invention 5 embodiment 1.The composition of nonaqueous electrolytic solution is as shown in table 7, and evaluation result is as shown in table 8.
The present invention 5 comparative example 1
Dissolving is through the LiTFSI of intensive drying in BMPTFSI, and making its ratio is 0.4mol/L, the preparation nonaqueous electrolytic solution, and use this nonaqueous electrolytic solution, in addition, make the Coin shape lithium secondary battery according to the method identical, and estimate with the present invention 5 embodiment 1.The composition of nonaqueous electrolytic solution is as shown in table 7, and evaluation result is as shown in table 8.
The present invention 5 comparative example 2
Dissolving is through the LiTFSI of intensive drying in BTMATFSI, and making its ratio is 0.4mol/L, the preparation nonaqueous electrolytic solution, and use this nonaqueous electrolytic solution, in addition, make the Coin shape lithium secondary battery according to the method identical, and estimate with the present invention 5 embodiment 1.The composition of nonaqueous electrolytic solution is as shown in table 7, and evaluation result is as shown in table 8.
The present invention 5 comparative example 3
Dissolving is through the LiTFSI of intensive drying in DEMETFSI, and making its ratio is 0.4mol/L, the preparation nonaqueous electrolytic solution, and use this nonaqueous electrolytic solution, in addition, make the Coin shape lithium secondary battery according to the method identical, and estimate with the present invention 5 embodiment 1.The composition of nonaqueous electrolytic solution is as shown in table 7, and evaluation result is as shown in table 8.
[table 7]
??No. Lithium salts The normal temperature fuse salt ??LiPO 2F 2
Embodiment 1 ??LiTFSI ??BMPTFSI 2 weight %
Embodiment 2 ??LiTFSI ??BTMATFSI 2 weight %
Embodiment 3 ??LiTFSI ??DEMETFSI 2 weight %
Comparative example 1 ??LiTFSI ??BMPTFSI ??-
Comparative example 2 ??LiTFSI ??BTMATFSI ??-
Comparative example 3 ??LiTFSI ??DEMETFSI ??-
[table 8]
?No. The discharge of circulation back
Embodiment 1 ??91.2
Embodiment 2 ??90.8
Embodiment 3 ??92.5
Comparative example 1 ??32.4
Comparative example 2 ??65.9
Comparative example 3 ??69.5
As shown in Table 8, use the battery (the present invention 5 embodiment 1～3) of the present invention 5 nonaqueous electrolytic solution, its charge-discharge characteristic height.By contrast, do not use the charge-discharge characteristic of battery (the present invention 5 comparative example 1～3) of the present invention 5 nonaqueous electrolytic solution poor.
Industrial applicibility
Adopt the present invention 1 nonaqueous electrolytic solution can make the rechargeable nonaqueous electrolytic battery of capacity height, cycle characteristics excellence, therefore can be preferred for using any field of the electronic equipment etc. of rechargeable nonaqueous electrolytic battery.
The present invention 1 nonaqueous electrolytic solution and the purposes of rechargeable nonaqueous electrolytic battery are not particularly limited, and can be used for known various uses. As concrete example, can enumerate notebook computer, a control type PC, pocket pc, e-book player, mobile phone, portable facsimile printer, portable copier, portable printer, stereophone, video camera, LCD TV, portable type cleaner, portable CD, minidisk, portable wireless walkie-talkie, electronic notebook, calculator, storage card, portable recorder, radio, stand-by power supply, motor, automobile, motorcycle, electric bicycle, bicycle, ligthing paraphernalia, toy, game machine, table, lathe, flash lamp, camera etc.
Adopt that the present invention 2 nonaqueous electrolytic solution can make that output characteristics is good, also excellent rechargeable nonaqueous electrolytic battery of High temperature storage characteristic and cycle characteristics, therefore can be preferred for using any field of the electronic equipment etc. of rechargeable nonaqueous electrolytic battery.
The present invention 2 nonaqueous electrolytic solution and the purposes of rechargeable nonaqueous electrolytic battery are not particularly limited, and can be used for known various uses. As concrete purposes, can enumerate purposes described in the present invention 1.
Adopt the present invention 3 nonaqueous electrolytic solution, the good nonaqueous electrolytic solution of cycle characteristics and rechargeable nonaqueous electrolytic battery can be provided. Therefore can be preferred for using any field of the electronic equipment etc. of rechargeable nonaqueous electrolytic battery.
The present invention 3 non-aqueous electrolyte for secondary battery and the purposes of rechargeable nonaqueous electrolytic battery are not particularly limited, and can be used for known various uses. As concrete purposes, can enumerate purposes described in the present invention 1.
Adopt the present invention 4 lithium secondary battery cryogenic discharging characteristic, the heavy-current discharge characteristic of nonaqueous electrolytic solution good, and High temperature storage characteristic, cycle characteristics are excellent, therefore can be preferred for using any field of the electronic equipment etc. of secondary cell. As concrete purposes, can enumerate purposes described in the present invention 1.
Use the nonaqueous electrolyte battery of the present invention 5 nonaqueous electrolytic solution can keep high capacity and security etc. good, can be used for known various uses. As concrete purposes, can enumerate the purposes described in the present invention 1.
The application quotes the full content of following application based on following Japanese patent application at this, and it is incorporated in the content of specification of the present invention.
The present invention 1: the Japanese Patent Application 2007-111918 (applying date: on April 20th, 2007)
The present invention 2: the Japanese Patent Application 2007-111976 (applying date: on April 20th, 2007)
The present invention 3: the Japanese Patent Application 2007-116448 (applying date: on April 26th, 2007)
The present invention 4: the Japanese Patent Application 2007-272163 (applying date: on October 19th, 2007)
The present invention 5: the Japanese Patent Application 2007-116444 (applying date: on April 26th, 2007)

Claims (34)

1. nonaqueous electrolytic solution, this nonaqueous electrolytic solution contains electrolyte and this electrolytical nonaqueous solvents of dissolving, wherein, described nonaqueous electrolytic solution contains mono-fluor phosphate and/or difluorophosphoric acid salt, and also containing with respect to the nonaqueous electrolytic solution total amount is the iron family element of 1～2000ppm.
2. nonaqueous electrolytic solution according to claim 1, wherein, iron family element is cobalt element and/or nickel element.
3. nonaqueous electrolytic solution according to claim 1 and 2, wherein, mono-fluor phosphate and/or difluorophosphoric acid salt are difluorophosphoric acid salt.
4. according to each described nonaqueous electrolytic solution in the claim 1～3, wherein, the total amount of mono-fluor phosphate that contains and/or difluorophosphoric acid salt is the 0.001 weight %～5 weight % of nonaqueous electrolytic solution total amount.
5. nonaqueous electrolytic solution, this nonaqueous electrolytic solution mainly is made of electrolyte and this electrolytical nonaqueous solvents of dissolving, wherein, described nonaqueous electrolytic solution contains and is selected from chain saturated hydrocarbons, cyclic saturated hydrocarbons, has the aromatic compound class of halogen atom and has at least a kind of compound in the ethers of fluorine atom, also contains mono-fluor phosphate and/or difluorophosphoric acid salt.
6. nonaqueous electrolytic solution according to claim 5 wherein, is selected from chain saturated hydrocarbons, cyclic saturated hydrocarbons, has the aromatic compound class of halogen atom and at least a kind of compound having in the ethers of fluorine atom is a cyclic saturated hydrocarbons.
7. nonaqueous electrolytic solution according to claim 5 wherein, is selected from chain saturated hydrocarbons, cyclic saturated hydrocarbons, has the aromatic compound class of halogen atom and at least a kind of compound having in the ethers of fluorine atom is the ethers with fluorine atom.
8. according to each described nonaqueous electrolytic solution in the claim 5～7, wherein, the content that be selected from chain saturated hydrocarbons, cyclic saturated hydrocarbons, has the aromatic compound class of halogen atom and have at least a kind of compound in the ethers of fluorine atom is 0.01～15 weight % of nonaqueous electrolytic solution total amount.
9. according to each described nonaqueous electrolytic solution in the claim 5～8, wherein, the total amount of mono-fluor phosphate that contains and/or difluorophosphoric acid salt is the 0.001 weight %～5 weight % of nonaqueous electrolytic solution total amount.
10. secondary cell nonaqueous electrolytic solution, this nonaqueous electrolytic solution is used for rechargeable nonaqueous electrolytic battery, described rechargeable nonaqueous electrolytic battery has nonaqueous electrolytic solution and can occlusion and emit the negative pole and the positive pole of ion, wherein, described nonaqueous electrolytic solution contains electrolyte and nonaqueous solvents, also contain mono-fluor phosphate and/or difluorophosphoric acid salt, and contain following general formula (1) and/or the represented compound of following general formula (2), the compound that following general formula (1) and/or following general formula (2) are represented contain proportional 0.001 weight % of the described nonaqueous electrolytic solution total amount～10 weight % that are
In the formula, R 1, R 2, R 3, R 4Independent separately, be organic group or halogen atom, R 1, R 2, R 3, R 4In at least one group in, with the atom of X Direct Bonding be hetero-atom, R 1, R 2, R 3, R 4Identical or different, X is the atom beyond the carbon atom;
Figure A2008800128400003C2
In the formula, R 5, R 6, R 7Independent separately, be organic group or halogen atom, R 5, R 6, R 7In at least one group in, with the atom of Y Direct Bonding be hetero-atom, R 5, R 6, R 7Identical or different, Y is the atom beyond the carbon atom.
11. secondary cell nonaqueous electrolytic solution, this nonaqueous electrolytic solution is used for rechargeable nonaqueous electrolytic battery, described rechargeable nonaqueous electrolytic battery has nonaqueous electrolytic solution and can occlusion and emit the negative pole and the positive pole of ion, wherein, described nonaqueous electrolytic solution contains mono-fluor phosphate and/or difluorophosphoric acid salt, and, anodal and negative pole are handled with following general formula (1) and/or the represented compound of following general formula (2)
Figure A2008800128400003C3
In the formula, R 1, R 2, R 3, R 4Independent separately, be organic group or halogen atom, R 1, R 2, R 3, R 4In at least one group in, with the atom of X Direct Bonding be hetero-atom, R 1, R 2, R 3, R 4Identical or different, X is the atom beyond the carbon atom;
Figure A2008800128400003C4
In the formula, R 5, R 6, R 7Independent separately, be organic group or halogen atom, R 5, R 6, R 7In at least one group in, with the atom of Y Direct Bonding be hetero-atom, R 5, R 6, R 7Identical or different, Y is the atom beyond the carbon atom.
12. according to claim 10 or 11 described secondary cell nonaqueous electrolytic solutions, wherein, the X in the represented compound of above-mentioned general formula (1) is Si or Ti.
13. according to claim 10 or 11 described secondary cell nonaqueous electrolytic solutions, wherein, the Y in the represented compound of above-mentioned general formula (2) is Al.
14. according to each described secondary cell nonaqueous electrolytic solution in the claim 10～13, wherein, the hetero-atom with X or Y Direct Bonding in the represented compound of above-mentioned general formula (1) or above-mentioned general formula (2) is B, N, O, P, S or halogen atom.
15. according to each described secondary cell nonaqueous electrolytic solution in the claim 10～14, wherein, the total amount of mono-fluor phosphate that contains and/or difluorophosphoric acid salt is the 0.001 weight %～5 weight % of nonaqueous electrolytic solution total amount.
16. a nonaqueous electrolytic solution, this nonaqueous electrolytic solution contain the nonaqueous solvents of lithium salts and this lithium salts of dissolving, wherein, described nonaqueous electrolytic solution contains the represented compound of following general formula (1), and contains mono-fluor phosphate and/or difluorophosphoric acid salt,
In general formula (1), A and B represent various substituting groups, and wherein at least 1 is fluorine, and n represents the natural number more than 3.
17. nonaqueous electrolytic solution according to claim 16 wherein, also contains the carbonic ester one of at least that has in unsaturated bond and the halogen atom.
18. according to claim 16 or 17 described nonaqueous electrolytic solutions, wherein, the content of the compound that above-mentioned general formula (1) is represented is the 0.001 volume %～1 volume % of nonaqueous electrolytic solution total amount.
19. according to each described nonaqueous electrolytic solution in the claim 16～18, wherein, the content of mono-fluor phosphate and/or difluorophosphoric acid salt is the 0.001 weight %～5 weight % of nonaqueous electrolytic solution total amount.
20. according to each described nonaqueous electrolytic solution in the claim 16～19, wherein, the content with the carbonic ester one of at least in unsaturated bond and the halogen atom is the 0.001 weight %～5 weight % of nonaqueous electrolytic solution total amount.
21. nonaqueous electrolytic solution, this nonaqueous electrolytic solution contains the nonaqueous solvents of lithium salts and this lithium salts of dissolving, wherein, it is the represented compound of following general formula (1) of 0.001 weight %～5 weight % that described nonaqueous electrolytic solution contains with respect to the nonaqueous electrolytic solution total amount, and contain with respect to the nonaqueous electrolytic solution total amount is the carbonic ester one of at least in unsaturated bond and the halogen atom of having of 0.001 weight %～5 weight %
Figure A2008800128400004C2
In general formula (1), A and B represent various substituting groups, and wherein at least 1 is fluorine, and n represents the natural number more than 3.
22. nonaqueous electrolytic solution according to claim 21, wherein, the content of the compound that above-mentioned general formula (1) is represented is the 0.001 volume %～1 volume % of nonaqueous electrolytic solution total amount.
23. according to each described nonaqueous electrolytic solution in the claim 1～22, this nonaqueous electrolytic solution is used for rechargeable nonaqueous electrolytic battery, described rechargeable nonaqueous electrolytic battery has used active material in negative pole, and described active material comprises carbonaceous material.
24. according to each described nonaqueous electrolytic solution in the claim 1～22, this nonaqueous electrolytic solution is used for rechargeable nonaqueous electrolytic battery, described rechargeable nonaqueous electrolytic battery has used active material in negative pole, described active material has at least a kind of atom that is selected from Al atom, Si atom, Sn atom, Pb atom and the Ti atom.
25. a rechargeable nonaqueous electrolytic battery wherein, has used each described nonaqueous electrolytic solution in the claim 1～22.
26. a rechargeable nonaqueous electrolytic battery, this rechargeable nonaqueous electrolytic battery comprise nonaqueous electrolytic solution and can occlusion and emit the negative pole and the positive pole of lithium ion, wherein, described nonaqueous electrolytic solution is each described nonaqueous electrolytic solution in the claim 1～22.
27. rechargeable nonaqueous electrolytic battery according to claim 26, wherein, negative pole contains carbonaceous material.
28. rechargeable nonaqueous electrolytic battery according to claim 26 wherein, contains negative electrode active material in the negative pole, described negative electrode active material has at least a kind of atom that is selected from Al atom, Si atom, Sn atom, Pb atom and the Ti atom.
29. according to each described rechargeable nonaqueous electrolytic battery in the claim 25～28, wherein, the structure of positive pole and/or negative pole contains at least a kind of mono-fluor phosphate and/or difluorophosphoric acid salt.
30. a nonaqueous electrolytic solution, this nonaqueous electrolytic solution contain lithium salts and normal temperature fuse salt, wherein, contain mono-fluor phosphate and/or difluorophosphoric acid salt in the described nonaqueous electrolytic solution.
31. nonaqueous electrolytic solution according to claim 30, wherein, the normal temperature fuse salt is uncle's sulfonium salt with the represented structure of following general formula (1), has the quaternary ammonium salt of the represented structure of following general formula (2) or have the represented structure De quaternary alkylphosphonium salt of following general formula (3)
Figure A2008800128400005C1
In general formula (1), R 1r, R 2rAnd R 3rThe organic group of representing carbon number 1～12 independently of one another, R 1r, R 2rAnd R 3rIn the optional mutual bonding of 2 organic groups and form ring structure;
Figure A2008800128400006C1
In general formula (2), R 4r, R 5r, R 6rAnd R 7rThe organic group of representing carbon number 1～12 independently of one another, R 4r, R 5r, R 6rAnd R 7rIn the optional mutual bonding of 2～4 organic groups and form ring structure, perhaps R 4r, R 5r, R 6rAnd R 7rIn 2 organic groups be actually 1 organic group, described 1 organic group and " N +" connect with two keys between the atom;
Figure A2008800128400006C2
In general formula (3), R 8r, R 9r, R 10rAnd R 11rThe organic group of representing carbon number 1～12 independently of one another, R 8r, R 9r, R 10rAnd R 11rIn the optional mutual bonding of 2～4 organic groups and form ring structure, perhaps R 8r, R 9r, R 10rAnd R 11rIn 2 organic groups be actually 1 organic group, described 1 organic group and " P +" connect with two keys between the atom.
32. according to claim 30 or 31 described nonaqueous electrolytic solutions, wherein, the total content of mono-fluor phosphate and/or difluorophosphoric acid salt is the 0.001 weight %～100 weight % of nonaqueous electrolytic solution total amount.
33. according to each described nonaqueous electrolytic solution in the claim 30～32, wherein, the content of normal temperature fuse salt is the 0.01 weight %～100 weight % of the nonaqueous electrolytic solution composition beyond lithium salts, mono-fluor phosphate, the difluorophosphoric acid salt.
34. a nonaqueous electrolyte battery, this nonaqueous electrolyte battery have nonaqueous electrolytic solution and can occlusion and emit the negative pole and the positive pole of lithium ion at least, wherein, described nonaqueous electrolytic solution is each described nonaqueous electrolytic solution in the claim 30～33.
CN200880012840A 2007-04-20 2008-04-18 Nonaqueous electrolyte, and rechargeable battery with the nonaqueous electrolyte Pending CN101663790A (en)

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