CN101609911B - Nonaqueous electrolyte solution and lithium secondary battery using same - Google Patents

Nonaqueous electrolyte solution and lithium secondary battery using same Download PDF

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CN101609911B
CN101609911B CN2009101614705A CN200910161470A CN101609911B CN 101609911 B CN101609911 B CN 101609911B CN 2009101614705 A CN2009101614705 A CN 2009101614705A CN 200910161470 A CN200910161470 A CN 200910161470A CN 101609911 B CN101609911 B CN 101609911B
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ester
carbonic acid
nonaqueous electrolyte
ethyl
compound
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CN101609911A (en
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古田土稔
岛邦久
木下信一
小湊麻绪
藤井隆
山田铁兵
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Mu Electrolyte Co ltd
Mitsubishi Chemical Corp
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Mitsubishi Kasei Corp
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Priority claimed from JP2004229188A external-priority patent/JP4655536B2/en
Priority claimed from JP2004229757A external-priority patent/JP4655537B2/en
Priority claimed from JP2004301751A external-priority patent/JP4670305B2/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

The invention provides a non-aqueous electrolyte solution and a lithium secondary battery using the same. The non-aqueous electrolyte solution is provided that realizes a large capacity, exhibits high storage characteristics and cycle characteristics, and is capable of inhibiting gas generation. The non-aqueous electrolyte solution comprises a lithium salt and a non-aqueous solvent, and further comprises: a cyclic carbonate compound having an unsaturated bond in a concentration of 0.01 weight % or higher and 8 weight % or lower; and a compound expressed by general formula (Ib) in a concentration of 0.01 weight % or higher and 5 weight % or lower. (in the formula (Ib), R<21> represents the alkyl having 1-12 carbon atoms and containing the fluorine atom substituent; and the alkenyl having 2-12 carbon atoms and containing the fluorine atom substituent, wherein the chain in the group has ether bond).

Description

The lithium secondary battery of nonaqueous electrolyte and this nonaqueous electrolyte of use
The application divides an application, the international application no of its original application is PCT/JP2005/007455, the China national application number is 200580011823.3, and the applying date is on 04 19th, 2005, and denomination of invention is " lithium secondary battery of nonaqueous electrolyte and this nonaqueous electrolyte of use ".
Technical field
The present invention relates to the lithium secondary battery of nonaqueous electrolyte and this nonaqueous electrolyte of use.
Background technology
In many applications, from so-called civilian power supplys such as portable phone, notebook computers to the vehicle power that is used for driving automobile, non aqueous electrolysis solution batteries such as lithium secondary battery have dropped into practical application.Yet, in recent years, the requirement of the high performance of non aqueous electrolysis solution battery is increased day by day, except that demanding capacity and good high-temperature preservation characteristics, also require to have excellent cycle characteristics.
So, in order to obtain the non aqueous electrolysis solution battery of high power capacity, present method for designing attempts to fill active material as much as possible usually in limited battery volume, for example, in described method, exert pressure with increase density for the active material layer of electrode, and reduce the space that electrode interior keeps.Yet the space in the battery is reduced the problem of being brought and is, produces when electrolyte decomposition even during a small amount of gas, the internal pressure of battery also can significantly increase.
In addition, when the non aqueous electrolysis solution battery when having a power failure stand-by power supply or during the power supply of portable equipment, for the self-discharge of balancing battery,, make it be in charged state for this battery sustainable supply weak current always.Under this trickle charge state, the active material in the electrode remains on the high activity level, and simultaneously, because the heat production of equipment, the capacity of this battery can descend rapidly, or electrolyte can decompose and causes the generation of gas.Particularly increase unusually in the battery that starts safety valve in the interior pressure that can perception causes owing to abnormal conditions such as overcharge, the generation of a large amount of gases also can start safety valve.On the other hand, in not having the battery of safety valve, the pressure of the gas that is produced can make cell expansion, and battery itself can not be used.
In order to be met the desired various performances of the non aqueous electrolysis solution battery non aqueous electrolysis solution battery of (comprising the above-mentioned generation that prevents gas), the someone has studied to nonaqueous electrolyte and has added all cpds.
For example, patent documentation 1 open road, when the nonaqueous electrolyte that adopts asymmetric linear carbonate compound as non-aqueous solvent, simultaneously, to wherein adding when containing two strong cyclic carbonate compound, preferential and the negative reaction of described double bond containing cyclic carbonate compound, form the coverlay of high-quality in negative terminal surface, thereby suppress forming by non-electrical conductance coverlay on the caused negative terminal surface of described asymmetric linear carbonate compound, so the secondary cell of gained shows the improvement of preservation characteristics and cycle characteristics.
Patent documentation 2 open roads, by in nonaqueous electrolyte, adding carbonate products with ehter bond, this compound covers the active site on anodal surface, can suppress the oxidation Decomposition of non-aqueous solvent contained in the electrolyte, thus the improvement that makes the secondary cell of gained show the storage stability under the high temperature high voltage.
Patent documentation 3 open roads when adding benzene sulfonyl fluorine or toluenesulfonyl fluoride in nonaqueous electrolyte, can improve the flash-over characteristic under the low temperature, thereby obtain having the battery of excellent cycle characteristics.
The runaway reaction that causes because of overheated when comprising the ether compound of the ad hoc structure with contain fluorine atoms in the electrolyte, can not take place in the open roads of patent documentation 4, thus the fail safe that improves electrolyte.
Patent documentation 5 open roads, when comprising one or more aromatic compounds with fluorine-containing ad hoc structure, ester, carbonic ester and monoether in the electrolyte, can suppress the generation of the hydrogen that causes owing to electrolyte decomposition on the interface between positive pole and the dividing plate, thereby, even under hot environment, also can suppress the expansion of battery.
The open roads of patent documentation 6, when the mixture that adopts cyclic carbonate and linear carbonate added the cyclic ether compound in as the nonaqueous electrolyte of non-aqueous solvent, the battery of gained had high capacity and excellent cycle characteristics.
Patent documentation 7 report when containing the compound monomer of acylamino-or polymer forming the negative pole coverlay in adopting molecule, can improve the heat-resistant stability of this negative pole coverlay.
[patent documentation 1] spy opens flat 11-185806
[patent documentation 2] spy opens 2002-237328
[patent documentation 3] spy opens 2002-359001
[patent documentation 4] international brochure of 00/16427 that discloses
[patent documentation 5] spy opens 2002-343424
[patent documentation 6] spy opens flat 10-116631
[patent documentation 7] spy opens 2003-31260
Problem solved by the invention
Yet, about disclosed secondary cell in the patent documentation 1, this secondary cell adopts the nonaqueous electrolyte of the cyclic carbonate compound that contains the two keys of band, although its cycle characteristics at room temperature improves, but the problem that exists is, because cycle characteristics is impaired under the low temperature, can increase gas generated under the trickle charge state.
About the disclosed nonaqueous electrolyte that contains benzene sulfonyl fluorine or toluenesulfonyl fluoride in the patent documentation 3, existing problem is that trickle charge characteristic and high temperature preservation characteristics under the high temperature can suffer damage.
About patent documentation 4, the amount that it has only provided fluorine-containing ether compound is the embodiment of 60 weight %～70 weight %, and does not mention battery behavior, so the problem that exists is that when it was actually used in battery, battery behaviors such as trickle charge characteristic can descend.
About patent documentation 5, the document is not mentioned the cyclic carbonate that has unsaturated bond, does not mention the trickle charge characteristic under the high voltage yet.So the problem of existence is that in fact the trickle charge characteristic can descend.
In addition, as mentioned below, when using patent documentation 4 and patent documentation 5 disclosed electrolyte under high voltage, the problem of existence is, described battery can deterioration, and battery behavior can descend.Specifically, although can make battery obtain having more small size and more highdensity battery with high-voltage charge and discharge, when in fact using battery under high voltage, the electrode of high potential can react with electrolyte, cause deterioration of battery, and shorten the life-span of battery.
About 1 described in the patent documentation 6, monocycle cyclic ether compounds such as 3-dioxolanes, oxolane, oxinane or dioxane, the inventor studies by it is added nonaqueous electrolyte, the result who obtains is that trickle charge characteristic (the particularly residual capacity after the trickle charge) and high temperature preservation characteristics do not improve.
In addition, 7 of patent documentations are mentioned the compound widely of the specific portion structure with nitrogenous and oxygen, and most important battery behavior, the degradation characteristic in the particularly preservation process and the generation of gas when not mentioning actual use.
In recent years, purposes such as portable phone require the battery of reduced size, yet along with the increase of capacity, prevent that cell expansion from becoming prior problem.The one of the main reasons of this expansion is, except the expansion of electrode etc. and shrinking, also has the generation of the gas that decomposition caused of electrolyte etc.Just can develop the battery of reduced size owing to prevent this expansion, so, still need and further to improve in order under the situation that does not weaken other characteristics, to prevent the generation of gas.During the battery of trickle charge state, the problem of existence is that the electrode of high potential and electrolyte reaction cause gas generation increase, deterioration of battery and shorter battery life under adopting high voltage.
Summary of the invention
Consider the problems referred to above and made the present invention.
The purpose of this invention is to provide a kind of nonaqueous electrolyte, described nonaqueous electrolyte can suppress the generation of gas when keeping high cycle characteristics, and can improve trickle charge characteristic and high temperature preservation characteristics; The present invention also provides the lithium secondary battery that adopts this nonaqueous electrolyte.
Another object of the present invention provides a kind of nonaqueous electrolyte of the deterioration of battery can suppress high voltage and use the time, and the lithium secondary battery that adopts this nonaqueous electrolyte.
Another purpose of the present invention provides a kind of nonaqueous electrolyte, the deterioration of battery when described nonaqueous electrolyte can suppress under the discharge condition to preserve, and can suppress the generation of gas; The present invention also provides the lithium secondary battery that adopts this nonaqueous electrolyte.
The method of dealing with problems
The inventor is by concentrating on studies, found that, when the nonaqueous electrolyte that contains lithium salts and non-aqueous solvent further contains the cyclic carbonate compound (A composition) with unsaturated bond and has the combination of the compound of ad hoc structure (I) (B composition) hereinafter described, or contain when having hereinafter described the compound of ad hoc structure (II) (C composition), can overcome the above problems effectively, finish the present invention thus.
According to a first aspect of the invention, the invention provides a kind of nonaqueous electrolyte (claim 1), described nonaqueous electrolyte comprises: lithium salts; Non-aqueous solvent; Concentration is the cyclic carbonate compound with unsaturated bond of 0.01 weight %～8 weight %; With concentration be the represented compound of following general formula (Ia) of 0.01 weight %～5 weight %.
[Chemical formula 1]
Figure G2009101614705D00051
(in general formula (Ia), R 11And R 12Represent the organic group of being made up of one or more carbon atoms and hydrogen atom independently of one another, described organic group can contain one or more oxygen atoms, but does not contain unsaturated bond.At least R 11Or R 12One of contain ehter bond.R 11And R 12In the total number of carbon atoms be 3～18, and R 11And R 12In contained oxygen atom sum be 1～6.)
According to a second aspect of the invention, the invention provides a kind of nonaqueous electrolyte (claim 2), described nonaqueous electrolyte comprises: lithium salts; Non-aqueous solvent; Cyclic carbonate compound with unsaturated bond; With the represented compound of following general formula (Ib).
[Chemical formula 2]
Figure G2009101614705D00052
(in general formula (Ib), R 21Representative can have the substituent alkyl with 1～12 carbon atom of fluorine atom, maybe can have the substituent thiazolinyl with 2～12 carbon atoms of fluorine atom, can have ehter bond in the chain of wherein said group.)
In general formula (Ib), preferred R 21Be to have the substituent alkyl (claim 3) of fluorine atom with 1～3 carbon atom.
Also the represented compound of preferred formula (Ib) is 0.001 weight %～5 weight % (claim 4) with respect to the concentration of described nonaqueous electrolyte.
The cyclic carbonate compound that also preferably has a unsaturated bond is 0.01 weight %～8 weight % (claim 5) with respect to the concentration of described nonaqueous electrolyte.
According to a third aspect of the present invention, the invention provides a kind of nonaqueous electrolyte (claim 6), described nonaqueous electrolyte comprises: lithium salts; Non-aqueous solvent; Concentration is the cyclic carbonate compound with unsaturated bond of 0.01 weight %～8 weight %; With concentration be the represented compound of following general formula (Ic) of 0.01 weight %～5 weight %.
[chemical formula 3]
CF nH (3-n)CH 2X 3 (Ic)
(in general formula (Ic), n represents 1～3 integer, X 3Representative is selected from by with the represented group of following formula (Ic-1)～(Ic-4).
[chemical formula 4]
-O-R 31 (Ic-1)
-O-Y 3-O-R 32 (Ic-2)
Figure G2009101614705D00061
(in formula (Ic-1)～(Ic-4), R 31～R 34Representative independently of one another can have the substituent alkyl with 1～20 carbon atom of halogen atom, Y 3Representative can have the substituent bivalent hydrocarbon radical with 1～10 carbon atom of halogen atom.)
In general formula (Ic), preferred X 3By formula (Ic-2) expression, in formula (Ic-2), Y 3Be to have the substituent divalent alkyl (claim 7) of halogen atom with 1～10 carbon atom.
In general formula (Ic), also preferred X 3With formula (Ic-3) expression (claim 8).
In general formula (Ic), also preferred X 3With formula (Ic-4) expression (claim 9).
In general formula (Ic-1)～(Ic-4), also preferred R 31～R 34Each has 1～3 substituent alkyl (claim 10) with 1～20 carbon atom of fluorine atom naturally.
According to a fourth aspect of the present invention, the invention provides a kind of nonaqueous electrolyte (claim 11), described nonaqueous electrolyte comprises: lithium salts; Non-aqueous solvent; With with the represented compound of following formula (IIa).
[chemical formula 5]
Figure G2009101614705D00071
Preferred described compound by following formula (IIa) expression is the compound of representing with following general formula (IIa ') (claim 12).
[chemical formula 6]
Figure G2009101614705D00072
(in general formula (IIa '), R 41～R 44Represent hydrogen atom independently of one another, can have the substituent alkyl with 1～12 carbon atom of fluorine atom, can have the substituent thiazolinyl with 2～12 carbon atoms of fluorine atom, can have that fluorine atom is substituent to have 6～12 carbon atom aryl and maybe can have the substituent aralkyl with 7～12 carbon atoms of fluorine atom.Can have ehter bond in the chain of these groups.R 41Can with R 42Link to each other R 43Can with R 44Link to each other, thereby form the ring that can have oxygen atom.)
The compound that also preferably has the represented structure of general formula (IIa) is 0.001 weight %～5 weight % (claim 13) with respect to the concentration of described nonaqueous electrolyte.
According to a fifth aspect of the present invention, the invention provides a kind of nonaqueous electrolyte (claim 14), described nonaqueous electrolyte comprises: lithium salts; Non-aqueous solvent; With the represented compound of following general formula (IIb).
[chemical formula 7]
(in formula (IIb), Z 5Represent the integer more than 2, X 5Representative is by being selected from the Z that is made of the one or more atomic buildings in the group carbon atom, hydrogen atom, fluorine atom and oxygen atom 5The valency linking group, fluorosulfonyl combines with the carbon atom of this linking group.)
The represented compound of preferred formula (IIb) is 0.001 weight %～5 weight % (claim 15) with respect to the concentration of described nonaqueous electrolyte.
Aspect above-mentioned the present invention the 4th and the 5th, preferably the concentration that also comprises with respect to described nonaqueous electrolyte is the cyclic carbonate compound (claim 16) with unsaturated bond of 0.01 weight %～8 weight %.
According to a sixth aspect of the invention, the invention provides a kind of nonaqueous electrolyte (claim 17), described nonaqueous electrolyte comprises: lithium salts; Non-aqueous solvent; With the represented compound of following general formula (IIc), with respect to described nonaqueous electrolyte, the represented compound concentrations of described general formula (IIc) is 0.01 weight %～4 weight %.
[chemical formula 8]
Figure G2009101614705D00081
(in formula (IIc), Z 6Represent the integer more than 2, X 6Representative has the Z of 1～6 carbon atom 6The valency alkyl, R 61Representative independently of one another has the alkyl of 1～6 carbon atom, R 62Representative independently of one another has the substituent alkyl with 1～6 carbon atom of one or more halogen atoms.Any two or more R 61And/or R 62Can be interconnected to ring.)
The preferred concentration that also contains with respect to described nonaqueous electrolyte is the cyclic carbonate compound (claim 18) with unsaturated bond of 0.01 weight %～5 weight %.
Aspect the 6th, preferred described cyclic carbonate compound with unsaturated bond is one or more compounds (claim 19) that are selected from vinylene carbonate, ethylene thiazolinyl ethyl, carbonic acid divinyl ethyl, ethylene thiazolinyl vinylene and carbonic acid methylene ester in above-mentioned the present invention first.
The 7th aspect the invention provides a kind of lithium secondary battery (claim 20) according to the present invention, and described lithium secondary battery comprises: nonaqueous electrolyte; With the positive pole and the negative pole that can absorb and discharge lithium ion; Wherein, described nonaqueous electrolyte is as above-mentioned of the present invention first to the 6th described nonaqueous electrolyte in aspect.
The advantageous effects of invention
Adopt the described nonaqueous electrolyte in first aspect of the present invention, can provide a kind of jumbo, have the good preservation characteristics and the battery of cycle characteristics, and can realize the miniaturization and the high performance of lithium secondary battery.
Adopt second described nonaqueous electrolyte in aspect of the present invention, a kind of like this battery can be provided, this battery has big capacity, and have good preservation characteristics, part throttle characteristics and a cycle characteristics, and when trickle charge, suppressed the decline of capacity and the generation of gas, and can realize the miniaturization and the high performance of lithium secondary battery.
Adopt the described nonaqueous electrolyte of third aspect of the present invention, can obtain good nonaqueous electrolyte, described nonaqueous electrolyte can suppress the deterioration of the battery of use under the high voltage.Adopt described nonaqueous electrolyte can obtain a kind of so good lithium secondary battery, this lithium secondary battery can carry out high-voltage charge and discharge, thereby can realize miniaturization and densification.
Adopt the 4th described nonaqueous electrolyte in aspect of the present invention, a kind of like this battery can be provided, this battery has big capacity, and have good preservation characteristics, part throttle characteristics and cycle characteristics, and suppressed the decline of capacity and the generation of gas in that trickle charge is out-of-date, and can realize the miniaturization and the high performance of non aqueous electrolysis solution battery.
Adopt the 5th described nonaqueous electrolyte in aspect of the present invention, a kind of like this battery can be provided, this battery has big capacity, and have good preservation characteristics, part throttle characteristics and cycle characteristics, and suppressed the decline of capacity and the generation of gas in that trickle charge is out-of-date, and can realize the miniaturization and the high performance of non aqueous electrolysis solution battery.
Adopt the 6th described nonaqueous electrolyte in aspect of the present invention, can obtain good nonaqueous electrolyte, described nonaqueous electrolyte can be suppressed at the deterioration when preserving under the discharge condition, suppresses the generation of gas simultaneously.Adopt described nonaqueous electrolyte, also can obtain a kind of good lithium secondary battery.
Embodiment
Hereinafter, will describe embodiments of the present invention in detail, but the present invention never is limited to following execution mode, only otherwise depart from main idea of the present invention, can implements with any version.
First kind of nonaqueous electrolyte of the present invention comprises lithium salts and non-aqueous solvent, the feature of this nonaqueous electrolyte is, also comprises the compound (I) (below be also referred to as " B composition ") of cyclic carbonate compound with unsaturated bond (below be also referred to as " A composition ") and the following stated.
Second kind of nonaqueous electrolyte of the present invention comprises lithium salts and non-aqueous solvent, and the feature of this nonaqueous electrolyte is, also comprises the compound (II) (below be also referred to as " C composition ") of the following stated.In addition, preferably also comprise cyclic carbonate compound with unsaturated bond (below be also referred to as " D composition ").
Lithium secondary battery of the present invention is to contain nonaqueous electrolyte and can absorb and discharge the positive pole of lithium ion and the lithium secondary battery of negative pole, the feature of this lithium secondary battery is that described nonaqueous electrolyte is first kind of nonaqueous electrolyte of the present invention or second kind of nonaqueous electrolyte.
In the following description, first kind of nonaqueous electrolyte of the present invention and second kind of nonaqueous electrolyte will be described at first successively, the lithium secondary battery of the present invention of these nonaqueous electrolytes is adopted in explanation then.Mention in passing, when explaining first kind of nonaqueous electrolyte of the present invention and second kind of nonaqueous electrolyte discriminatively, first kind of nonaqueous electrolyte and second kind of nonaqueous electrolyte are called " nonaqueous electrolyte (I) " and " nonaqueous electrolyte (II) ", when not needing to distinguish especially, they will be referred to as " nonaqueous electrolyte of the present invention ".
[1: nonaqueous electrolyte (I)]
Described nonaqueous electrolyte (I) comprises lithium salts, non-aqueous solvent, has cyclic carbonate compound of unsaturated bond (A composition) and compound hereinafter described (I) (B composition).
[electrolyte]
The used electrolyte of nonaqueous electrolyte (I) is not particularly limited, but can select the known electrolytical compound that can be used as the target secondary cell arbitrarily.For being used for lithium secondary battery, adopt lithium salts usually as electrolyte.
The example of lithium salts is: LiClO 4, LiAsF 6, LiPF 6, Li 2CO 3And LiBF 4Deng inorganic lithium salt; LiCF 3SO 3, LiN (CF 3SO 2) 2, LiN (C 2F 5SO 2) 2, ring-type 1,3-perfluoropropane disulfonyl imines lithium, 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 2(CF 3) 2, LiBF 2(C 2F 5) 2, LiBF 2(CF 3SO 2) 2And LiBF 2(C 2F 5SO 2) 2Etc. fluorine-containing organic lithium salt; Oxalates borates such as two (oxalic acid) lithium borate, difluorine oxalic acid boracic acid lithium; KPF 6, NaPF 6, NaBF 4And Na 2CF 3SO 3Deng sodium salt or sylvite.These salt can use or use the mixture of two or more salt separately.Wherein, preferred LiPF 6, LiBF 4, LiCF 3SO 3, LiN (CF 3SO 2) 2And LiN (C 2F 5SO 2) 2, preferred especially LiPF 6And LiBF 4
Can use above-mentioned lithium salts separately or be used in combination any two or more above-mentioned lithium salts with arbitrary proportion, but be fit to be used in combination two or more inorganic lithium salts, or be used in combination inorganic lithium salt and fluorine-containing organic lithium salt, because the generation of gas in the time of can suppressing trickle charge, or because of the deterioration that can prevent after high temperature from preserving.Particularly suitable is to be used in combination LiPF 6With LiBF 4, or be used in combination LiPF 6Or LiBF 4Deng inorganic lithium salt and LiCF 3SO 3, LiN (CF 3SO 2) 2Or LiN (C 2F 5SO 2) 2Etc. fluorine-containing organic lithium salt.Be used in combination LiPF 6And LiBF 4The time, with respect to whole lithium salts, preferred contained LiBF 4Ratio be generally 0.01 weight %～20 weight %.Be used in combination LiPF 6Or LiBF 4Deng inorganic lithium salt and LiCF 3SO 3, LiN (CF 3SO 2) 2Or LiN (C 2F 5SO 2) 2During etc. fluorine-containing organic lithium salt, it is desirable to, with respect to whole lithium salts, the ratio of described inorganic lithium salt is generally 70 weight %～99 weight %.
The concentration of lithium salts is generally more than the 0.5mol/l in the described nonaqueous electrolyte (I), more than the preferred 0.6mol/l, more preferably more than the 0.8mol/l, and is generally below the 3mol/l, below the preferred 2mol/l, more preferably below the 1.5mol/l.When described concentration was too low, the conductivity of described electrolyte can be not enough, and described concentration is when too high, because viscosity increases, conductivity can reduce, thereby causes the decline of battery performance.
[non-aqueous solvent]
As the non-aqueous solvent of described nonaqueous electrolyte (I), any compound as non-aqueous electrolyte solvent known to can adopting in the past adopts organic solvent usually.Representative examples of organic is linear carbonate and cyclic carbonate, chain carboxylate and cyclic carboxylic esters and chain ether and cyclic ethers.
The example of cyclic carbonate is the alkylene carbonate that alkylidene has 2～4 carbon atoms, for example ethylene carbonate, propylene carbonate, butylene carbonate and carbonic acid fluoro ethyl.Wherein, preferred ethylene carbonate and propylene carbonate.
The example of linear carbonate is the dialkyl carbonate that alkyl has 1～4 carbon atom, for example dimethyl carbonate, diethyl carbonate, carbonic acid di-n-propyl ester, ethylmethyl carbonate, carbonic acid methyl n-pro-pyl ester and carbonic acid ethyl n-pro-pyl ester.Wherein, preferred dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate.
The example of cyclic carboxylic esters is gamma-butyrolacton and gamma-valerolactone.
The example of chain carboxylate is methyl acetate, ethyl acetate, methyl propionate, ethyl propionate and methyl butyrate.
The example of cyclic ethers is oxolane and 2-methyltetrahydrofuran.
The example of chain ether is diethoxyethane, dimethoxy-ethane and dimethoxymethane.
Can use any described non-aqueous solvent separately, also can be used in combination any two or more described non-aqueous solvents by arbitrary proportion, but preferred compositions be used two or more compounds.For example, it is desirable to be used in combination for example solvent and low viscosity solvents such as for example linear carbonate or chain carboxylate of high-k such as cyclic carbonate or cyclic carboxylic esters.
When containing the chain carboxylate in the described non-aqueous solvent, with respect to this non-aqueous solvent, the ratio of described chain carboxylate is generally below the 50 weight %, below the preferred 30 weight %, more preferably below the 20 weight %.If described ratio surpasses this upper limit, conductivity will descend.Should be pointed out that the chain carboxylate is not the neccessary composition of non-aqueous solvent, this non-aqueous solvent can not contain the chain carboxylate.
When described non-aqueous solvent contained cyclic carboxylic esters, with respect to this non-aqueous solvent, the ratio of described cyclic carboxylic esters was generally below the 60 weight %, below the preferred 55 weight %, more preferably below the 50 weight %.If described ratio surpasses this upper limit, the decline or the output characteristic deterioration of liquid injection will appear at low temperatures.Should be pointed out that cyclic carboxylic esters is not the neccessary composition of non-aqueous solvent, this non-aqueous solvent can not contain cyclic carboxylic esters.
When containing chain ether in the described non-aqueous solvent, with respect to this non-aqueous solvent, the ratio of described chain ether is generally below the 60 weight %, below the preferred 40 weight %, more preferably below the 30 weight %.If described ratio surpasses this upper limit, the decline of conductivity will appear.Should be pointed out that chain ether is not the neccessary composition of non-aqueous solvent, this non-aqueous solvent can not contain chain ether.
When containing cyclic ethers in the described non-aqueous solvent, with respect to this non-aqueous solvent, the ratio of described cyclic ethers is generally below the 60 weight %, below the preferred 50 weight %, more preferably below the 40 weight %.If described ratio surpasses this upper limit, the decline of preservation characteristics will appear.Should be pointed out that cyclic ethers is not the neccessary composition of non-aqueous solvent, this non-aqueous solvent can not contain cyclic ethers.
One of non-aqueous solvent Ideal Match is the mixture of mainly being made up of cyclic carbonate and linear carbonate.The cyclic carbonate in the preferred especially described non-aqueous solvent and the toatl proportion of linear carbonate are generally more than the 85 volume %, more than the preferred 90 volume %, more preferably more than the 95 volume %, and the volume ratio between cyclic carbonate and the linear carbonate is generally more than 5: 95, preferred more than 10: 90, more preferably more than 15: 85, be generally below 45: 55, preferred below 40: 60.Preferred electrolyte, the cyclic carbonate compound (A composition) with unsaturated bond and the compounds (I) (B composition) such as above-mentioned mixed solvent and for example lithium salts of adopting prepare nonaqueous electrolyte (I), because the scalable balance between the characteristics such as cycle characteristics, heavy-current discharge characteristic and the generation of inhibition gas for example like this.
The preferred example of the combination of cyclic carbonate and linear carbonate is the combination of ethylene carbonate and dialkyl carbonate.Specifically, that can mention has, the combination of the combination of the combination of the combination of the combination of the combination of the combination of ethylene carbonate and dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and ethylmethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and ethylmethyl carbonate, ethylene carbonate and diethyl carbonate and ethylmethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate and ethylmethyl carbonate etc.
In these combinations of ethylene carbonate and dialkyl carbonate, add propylene carbonate, can obtain other preferred compositions.At this moment, the volume ratio of ethylene carbonate and propylene carbonate is generally below 99: 1, and is preferred below 95: 5, is generally more than 1: 99, preferred more than 20: 80.
The combination of also preferred propylene carbonate and above-mentioned dialkyl carbonate.
Other preferred examples of described non-aqueous solvent are that containing proportional is the non-aqueous solvent of the above following organic solvent of 60 volume %, and described organic solvent is selected from the group of being made up of ethylene carbonate, propylene carbonate, gamma-butyrolacton and gamma-valerolactone.The evaporation and the seepage of solvent when adopting the nonaqueous electrolyte (I) of electrolyte, cyclic carbonate compound (A composition) and compound (I) (B composition) gained such as one of these mixed solvents and for example lithium salts can suppress to use under the high temperature with unsaturated bond.Wherein preferred such non-aqueous solvent: with respect to described non-aqueous solvent, the cumulative volume of ethylene carbonate and gamma-butyrolacton is more than the 80 volume %, and more than the preferred 90 volume %, and the volume ratio of ethylene carbonate and gamma-butyrolacton is 5: 95～45: 55; With respect to described non-aqueous solvent, the cumulative volume of ethylene carbonate and propylene carbonate is more than the 80 volume %, and more than the preferred 90 volume %, and the volume ratio of ethylene carbonate and the inferior ester of carbonic acid is 30: 70～80: 20.Preferred electrolyte, the cyclic carbonate compound (A composition) with unsaturated bond and the compounds (I) (B composition) such as one of these mixed solvents and for example lithium salts of adopting prepare nonaqueous electrolyte (I), because can reach preservation characteristics like this and suppress well balanced between the gas generation.
Described non-aqueous solvent also preferably adopts phosphorous organic solvent.By being generally more than the 10 volume % to described non-aqueous solvent additional proportion, the phosphorous organic solvent of preferred 10 volume %～80 volume % can reduce the combustibility of described electrolyte.Especially preferably phosphorous organic solvent and the non-aqueous solvent that is selected from following group are used in combination, form by ethylene carbonate, propylene carbonate, gamma-butyrolacton, gamma-valerolactone and dialkyl carbonate for described group, because balance cycle characteristics and heavy-current discharge characteristic so well.
Mention in passing, in this manual, the volume of non-aqueous solvent is meant 25 ℃ of volumes of measuring down in principle, still, is solid-state solvent under 25 ℃ for for example ethylene carbonate etc., and volume then is meant the volume that records under fusing point.
[unsaturated cyclic carbonate products (A composition)]
Described nonaqueous electrolyte (I) contain have unsaturated bond cyclic carbonate compound (being abbreviated as in this manual, " unsaturated cyclic carbonate products " sometimes) as the A composition.Term " unsaturated cyclic carbonate products " is meant and contains at least one carbonic ester structure, at least one carbon-to-carbon double bond and at least one circulus in individual molecule.
The example of unsaturated cyclic carbonate products is vinylene carbonate compound, ethylene thiazolinyl ethyl compound and carbonic acid methylene ethyl compound, but can adopt any compound, as long as this compound drops in the above-mentioned definition.
The example of vinylene carbonate compound is vinylene carbonate (following be abbreviated as sometimes " VC "), carbonic acid methyl vinylene, carbonic acid ethyl vinylene, carbonic acid-4,5-dimethyl vinylene, carbonic acid-4,5-diethyl vinylene, carbonic acid fluoro vinylene, carbonic acid trifluoromethyl vinylene, carbonic acid-4-vinyl vinylene etc.
The example of ethylene thiazolinyl ethyl compound is ethylene thiazolinyl ethyl, carbonic acid-4-methyl-4-vinyl ethyl, carbonic acid-4-ethyl-4-vinyl ethyl, carbonic acid-4-n-pro-pyl-4-vinyl ethyl, carbonic acid-5-methyl-4-vinyl ethyl, carbonic acid-4,4-divinyl ethyl, carbonic acid-4,5-divinyl ethyl etc.
The example of carbonic acid methylene ethyl compound is carbonic acid methylene ethyl, carbonic acid-4,4-dimethyl-5-methylene ethyl, carbonic acid-4,4-diethyl-5-methylene ethyl etc.
Wherein, preferred unsaturated cyclic carbonate products is vinylene carbonate and ethylene thiazolinyl ethyl, preferred especially vinylene carbonate.
Can use any described unsaturated cyclic carbonate products separately, or be used in combination any two or more described unsaturated cyclic carbonate products with arbitrary proportion.
In described nonaqueous electrolyte (I), the ratio of described unsaturated cyclic carbonate products is generally more than the 0.01 weight %, more than the preferred 0.1 weight %, more than the preferred especially 0.5 weight %, most preferably more than the 1 weight %, be generally below the 8 weight %, below the preferred 6 weight %, below the preferred especially 4 weight %.If the amount of unsaturated cyclic carbonate products is lower than this lower limit, the negative pole coverlay of mentioning below then being difficult to form fully, thus can cause deterioration.On the other hand, if the amount of unsaturated cyclic carbonate products surpasses this upper limit, then the negative pole coverlay can excessive formation and stop the migration of lithium ion.When being used in combination two or more unsaturated cyclic carbonate products, the total amount of described unsaturated cyclic carbonate products should satisfy above-mentioned scope.
[compound (I) (B composition)]
Described nonaqueous electrolyte (I) contains at least a compound in compound (Ia), compound (Ib) and the compound (Ic) of the following stated as B composition (below be also referred to as " compound (I) ").Described nonaqueous electrolyte (I) can contain any compound in compound (Ia), compound (Ib) and the compound (Ic), or contains two or three combination wherein.In the following description, when additional symbols, the nonaqueous electrolyte (I) that contains compound (Ia), compound (Ib) and compound (Ic) respectively will be called " nonaqueous electrolyte (Ia) ", " nonaqueous electrolyte (Ib) " and " nonaqueous electrolyte (Ic) ", and when not needing to distinguish especially, they will be referred to as " nonaqueous electrolyte (I) ".
＜compound (Ia) 〉
Compound (Ia) is the represented compound of following general formula (Ia).
[chemical formula 9]
Figure G2009101614705D00151
In general formula (Ia), R 11And R 12Represent such organic group independently of one another, described organic group contains one or more carbon atoms and hydrogen atom, can also also have one or more oxygen atoms, but does not contain unsaturated bond, R at least 11Or R 12One of have an ehter bond.R 11And R 12Can be same to each other or different to each other.R 11And R 12The total number of carbon atoms be 3～18, R 11And R 12Contained oxygen atom adds up to 1～6.R 11And R 12The total number of carbon atoms be preferably 3～10, R 11And R 12Contained oxygen atom adds up to 1～4.
Preferred each R 11And R 12Be alkyl or alkyl with ehter bond.Preferred alkyl is methyl and ethyl, and the alkyl with ehter bond preferably methoxy alkyl and ethoxy alkyl.Also preferred R 11And R 12Different mutually, preferred especially R 11Or R 12One of be methyl.
As compound (Ia), can mention following material.
(a) have the carbonic ester of an ehter bond in each molecule:
The example that has the carbonic ester of an ehter bond in each molecule comprises: carbonic acid (methyl) (methoxy) ester, carbonic acid (methyl) (1-methoxy ethyl) ester, carbonic acid (methyl) (2-methoxy ethyl) ester, carbonic acid (methyl) (1-methoxy-propyl) ester, carbonic acid (methyl) (2-methoxy-propyl) ester, carbonic acid (methyl) (3-methoxy-propyl) ester, carbonic acid (methyl) (1-methyl isophthalic acid-methoxy ethyl) ester, carbonic acid (methyl) (1-methyl-2-methoxy ethyl) ester, carbonic acid (methyl) (1-methoxyl group butyl) ester, carbonic acid (methyl) (2-methoxyl group butyl) ester, carbonic acid (methyl) (3-methoxyl group butyl) ester, carbonic acid (methyl) (4-methoxyl group butyl) ester, carbonic acid (methyl) [1-(methoxy) propyl group] ester, carbonic acid (methyl) (1-methyl-2-methoxy-propyl) ester, carbonic acid (methyl) (ethoxyl methyl) ester, carbonic acid (methyl) (1-ethoxyethyl group) ester, carbonic acid (methyl) (2-ethoxyethyl group) ester, carbonic acid (methyl) (1-ethoxycarbonyl propyl) ester, carbonic acid (methyl) (2-ethoxycarbonyl propyl) ester, carbonic acid (methyl) (3-ethoxycarbonyl propyl) ester, carbonic acid (methyl) (1-methyl isophthalic acid-ethoxyethyl group) ester, carbonic acid (methyl) (1-methyl-2-ethoxyethyl group) ester, carbonic acid (methyl) (1-ethyoxyl butyl) ester, carbonic acid (methyl) (2-ethyoxyl butyl) ester, carbonic acid (methyl) (3-ethyoxyl butyl) ester, carbonic acid (methyl) (4-ethyoxyl butyl) ester, carbonic acid (methyl) [1-(ethoxyl methyl) propyl group] ester, carbonic acid (methyl) (1-methyl-2-ethoxycarbonyl propyl) ester, carbonic acid (methyl) (butoxymethyl) ester, carbonic acid (methyl) (1-butoxyethyl group) ester, carbonic acid (methyl) (2-butoxyethyl group) ester, carbonic acid (methyl) (1-butoxy propyl group) ester, carbonic acid (methyl) (2-butoxy propyl group) ester, carbonic acid (methyl) (3-butoxy propyl group) ester, carbonic acid (methyl) (1-methyl isophthalic acid-butoxyethyl group) ester, carbonic acid (methyl) (1-methyl-2-butoxyethyl group) ester, carbonic acid (methyl) (1-butoxy butyl) ester, carbonic acid (methyl) (2-butoxy butyl) ester, carbonic acid (methyl) (3-butoxy butyl) ester, carbonic acid (methyl) (4-butoxy butyl) ester, carbonic acid (methyl) [1-(butoxymethyl) propyl group] ester, carbonic acid (methyl) (1-methyl-2-butoxy propyl group) ester, carbonic acid (methyl) (tetrahydrofurfuryl) ester, carbonic acid (methyl) (oxinane ylmethyl) ester, carbonic acid (ethyl) (methoxy) ester, carbonic acid (ethyl) (1-methoxy ethyl) ester, carbonic acid (ethyl) (2-methoxy ethyl) ester, carbonic acid (ethyl) (1-methoxy-propyl) ester, carbonic acid (ethyl) (2-methoxy-propyl) ester, carbonic acid (ethyl) (3-methoxy-propyl) ester, carbonic acid (ethyl) (1-methyl isophthalic acid-methoxy ethyl) ester, carbonic acid (ethyl) (1-methyl-2-methoxy ethyl) ester, carbonic acid (ethyl) (1-methoxyl group butyl) ester, carbonic acid (ethyl) (2-methoxyl group butyl) ester, carbonic acid (ethyl) (3-methoxyl group butyl) ester, carbonic acid (ethyl) (4-methoxyl group butyl) ester, carbonic acid (ethyl) [1-(methoxy) propyl group] ester, carbonic acid (ethyl) (1-methyl-2-methoxy-propyl) ester, carbonic acid (ethyl) (ethoxyl methyl) ester, carbonic acid (ethyl) (1-ethoxyethyl group) ester, carbonic acid (ethyl) (2-ethoxyethyl group) ester, carbonic acid (ethyl) (1-ethoxycarbonyl propyl) ester, carbonic acid (ethyl) (2-ethoxycarbonyl propyl) ester, carbonic acid (ethyl) (3-ethoxycarbonyl propyl) ester, carbonic acid (ethyl) (1-methyl isophthalic acid-ethoxyethyl group) ester, carbonic acid (ethyl) (1-methyl-2-ethoxyethyl group) ester, carbonic acid (ethyl) (1-ethyoxyl butyl) ester, carbonic acid (ethyl) (2-ethyoxyl butyl) ester, carbonic acid (ethyl) (3-ethyoxyl butyl) ester, carbonic acid (ethyl) (4-ethyoxyl butyl) ester, carbonic acid (ethyl) [1-(ethoxyl methyl) propyl group] ester, carbonic acid (ethyl) (1-methyl-2-ethoxycarbonyl propyl) ester, carbonic acid (ethyl) (butoxymethyl) ester, carbonic acid (ethyl) (1-butoxyethyl group) ester, carbonic acid (ethyl) (2-butoxyethyl group) ester, carbonic acid (ethyl) (1-butoxy propyl group) ester, carbonic acid (ethyl) (2-butoxy propyl group) ester, carbonic acid (ethyl) (3-butoxy propyl group) ester, carbonic acid (ethyl) (1-methyl isophthalic acid-butoxyethyl group) ester, carbonic acid (ethyl) (1-methyl-2-butoxyethyl group) ester, carbonic acid (ethyl) (1-butoxy butyl) ester, carbonic acid (ethyl) (2-butoxy butyl) ester, carbonic acid (ethyl) (3-butoxy butyl) ester, carbonic acid (ethyl) (4-butoxy butyl) ester, carbonic acid (ethyl) [1-(butoxymethyl) propyl group] ester, carbonic acid (ethyl) (1-methyl-2-butoxy propyl group) ester, carbonic acid (ethyl) (tetrahydrofurfuryl) ester, carbonic acid (ethyl) (oxinane ylmethyl) ester, carbonic acid (butyl) (methoxy) ester, carbonic acid (butyl) (1-methoxy ethyl) ester, carbonic acid (butyl) (2-methoxy ethyl) ester, carbonic acid (butyl) (1-methoxy-propyl) ester, carbonic acid (butyl) (2-methoxy-propyl) ester, carbonic acid (butyl) (3-methoxy-propyl) ester, carbonic acid (butyl) (1-methyl isophthalic acid-methoxy ethyl) ester, carbonic acid (butyl) (1-methyl-2-methoxy ethyl) ester, carbonic acid (butyl) (1-methoxyl group butyl) ester, carbonic acid (butyl) (2-methoxyl group butyl) ester, carbonic acid (butyl) (3-methoxyl group butyl) ester, carbonic acid (butyl) (4-methoxyl group butyl) ester, carbonic acid (butyl) [1-(methoxy) propyl group] ester, carbonic acid (butyl) (1-methyl-2-methoxy-propyl) ester, carbonic acid (butyl) (ethoxyl methyl) ester, carbonic acid (butyl) (1-ethoxyethyl group) ester, carbonic acid (butyl) (2-ethoxyethyl group) ester, carbonic acid (butyl) (1-ethoxycarbonyl propyl) ester, carbonic acid (butyl) (2-ethoxycarbonyl propyl) ester, carbonic acid (butyl) (3-ethoxycarbonyl propyl) ester, carbonic acid (butyl) (1-methyl isophthalic acid-ethoxyethyl group) ester, carbonic acid (butyl) (1-methyl-2-ethoxyethyl group) ester, carbonic acid (butyl) (1-ethyoxyl butyl) ester, carbonic acid (butyl) (2-ethyoxyl butyl) ester, carbonic acid (butyl) (3-ethyoxyl butyl) ester, carbonic acid (butyl) (4-ethyoxyl butyl) ester, carbonic acid (butyl) [1-(ethoxyl methyl) propyl group] ester, carbonic acid (butyl) (1-methyl-2-ethoxycarbonyl propyl) ester, carbonic acid (butyl) (butoxymethyl) ester, carbonic acid (butyl) (1-butoxyethyl group) ester, carbonic acid (butyl) (2-butoxyethyl group) ester, carbonic acid (butyl) (1-butoxy propyl group) ester, carbonic acid (butyl) (2-butoxy propyl group) ester, carbonic acid (butyl) (3-butoxy propyl group) ester, carbonic acid (butyl) (1-methyl isophthalic acid-butoxyethyl group) ester, carbonic acid (butyl) (1-methyl-2-butoxyethyl group) ester, carbonic acid (butyl) (1-butoxy butyl) ester, carbonic acid (butyl) (2-butoxy butyl) ester, carbonic acid (butyl) (3-butoxy butyl) ester, carbonic acid (butyl) (4-butoxy butyl) ester, carbonic acid (butyl) [1-(butoxymethyl) propyl group] ester, carbonic acid (butyl) (1-methyl-2-butoxy propyl group) ester, carbonic acid (butyl) (tetrahydrofurfuryl) ester, carbonic acid (butyl) (oxinane ylmethyl) ester, carbonic acid (hexyl) (methoxy) ester, carbonic acid (hexyl) (1-methoxy ethyl) ester, carbonic acid (hexyl) (2-methoxy ethyl) ester, carbonic acid (hexyl) (1-methoxy-propyl) ester, carbonic acid (hexyl) (2-methoxy-propyl) ester, carbonic acid (hexyl) (3-methoxy-propyl) ester, carbonic acid (hexyl) (1-methyl isophthalic acid-methoxy ethyl) ester, carbonic acid (hexyl) (1-methyl-2-methoxy ethyl) ester, carbonic acid (hexyl) (1-methoxyl group butyl) ester, carbonic acid (hexyl) (2-methoxyl group butyl) ester, carbonic acid (hexyl) (3-methoxyl group butyl) ester, carbonic acid (hexyl) (4-methoxyl group butyl) ester, carbonic acid (hexyl) [1-(methoxy) propyl group] ester, carbonic acid (hexyl) (1-methyl-2-methoxy-propyl) ester, carbonic acid (hexyl) (ethoxyl methyl) ester, carbonic acid (hexyl) (1-ethoxyethyl group) ester, carbonic acid (hexyl) (2-ethoxyethyl group) ester, carbonic acid (hexyl) (1-ethoxycarbonyl propyl) ester, carbonic acid (hexyl) (2-ethoxycarbonyl propyl) ester, carbonic acid (hexyl) (3-ethoxycarbonyl propyl) ester, carbonic acid (hexyl) (1-methyl isophthalic acid-ethoxyethyl group) ester, carbonic acid (hexyl) (1-methyl-2-ethoxyethyl group) ester, carbonic acid (hexyl) (1-ethyoxyl butyl) ester, carbonic acid (hexyl) (2-ethyoxyl butyl) ester, carbonic acid (hexyl) (3-ethyoxyl butyl) ester, carbonic acid (hexyl) (4-ethyoxyl butyl) ester, carbonic acid (hexyl) [1-(ethoxyl methyl) propyl group] ester, carbonic acid (hexyl) (1-methyl-2-ethoxycarbonyl propyl) ester, carbonic acid (hexyl) (butoxymethyl) ester, carbonic acid (hexyl) (1-butoxyethyl group) ester, carbonic acid (hexyl) (2-butoxyethyl group) ester, carbonic acid (hexyl) (1-butoxy propyl group) ester, carbonic acid (hexyl) (2-butoxy propyl group) ester, carbonic acid (hexyl) (3-butoxy propyl group) ester, carbonic acid (hexyl) (1-methyl isophthalic acid-butoxyethyl group) ester, carbonic acid (hexyl) (1-methyl-2-butoxyethyl group) ester, carbonic acid (hexyl) (1-butoxy butyl) ester, carbonic acid (hexyl) (2-butoxy butyl) ester, carbonic acid (hexyl) (3-butoxy butyl) ester, carbonic acid (hexyl) (4-butoxy butyl) ester, carbonic acid (hexyl) [1-(butoxymethyl) propyl group] ester, carbonic acid (hexyl) (1-methyl-2-butoxy propyl group) ester, carbonic acid (hexyl) (tetrahydrofurfuryl) ester and carbonic acid (hexyl) (oxinane ylmethyl) ester.
Wherein, preferred carbonic acid (methyl) (2-methoxy ethyl) ester, carbonic acid (methyl) (3-methoxy-propyl) ester, carbonic acid (methyl) (4-methoxyl group butyl) ester, carbonic acid (methyl) (2-ethoxyethyl group) ester, carbonic acid (methyl) (3-ethoxycarbonyl propyl) ester, carbonic acid (methyl) (4-ethyoxyl butyl) ester, carbonic acid (methyl) (2-butoxyethyl group) ester, carbonic acid (methyl) (3-butoxy propyl group) ester, carbonic acid (methyl) (4-butoxy butyl) ester, carbonic acid (methyl) (tetrahydrofurfuryl) ester, carbonic acid (methyl) (oxinane ylmethyl) ester, carbonic acid (ethyl) (2-methoxy ethyl) ester, carbonic acid (ethyl) (3-methoxy-propyl) ester, carbonic acid (ethyl) (4-methoxyl group butyl) ester, carbonic acid (ethyl) (2-ethoxyethyl group) ester, carbonic acid (ethyl) (3-ethoxycarbonyl propyl) ester, carbonic acid (ethyl) (4-ethyoxyl butyl) ester, carbonic acid (ethyl) (2-butoxyethyl group) ester, carbonic acid (ethyl) (3-butoxy propyl group) ester, carbonic acid (ethyl) (4-butoxy butyl) ester, carbonic acid (ethyl) (tetrahydrofurfuryl) ester and carbonic acid (ethyl) (oxinane ylmethyl) ester.
Wherein, preferred especially carbonic acid (methyl) (2-methoxy ethyl) ester, carbonic acid (methyl) (3-methoxy-propyl) ester, carbonic acid (methyl) (4-methoxyl group butyl) ester, carbonic acid (methyl) (2-ethoxyethyl group) ester, carbonic acid (methyl) (3-ethoxycarbonyl propyl) ester, carbonic acid (methyl) (4-ethyoxyl butyl) ester, carbonic acid (ethyl) (2-methoxy ethyl) ester, carbonic acid (ethyl) (3-methoxy-propyl) ester, carbonic acid (ethyl) (4-methoxyl group butyl) ester, carbonic acid (ethyl) (2-ethoxyethyl group) ester, carbonic acid (ethyl) (3-ethoxycarbonyl propyl) ester and carbonic acid (ethyl) (4-ethyoxyl butyl) ester.
(b) have the carbonic ester of two ehter bonds in each molecule:
The example that has the carbonic ester of two ehter bonds in each molecule comprises: carbonic acid two (methoxy) ester, carbonic acid two (1-methoxy ethyl) ester, carbonic acid two (2-methoxy ethyl) ester, carbonic acid two (1-methoxy-propyl) ester, carbonic acid two (2-methoxy-propyl) ester, carbonic acid two (3-methoxy-propyl) ester, carbonic acid two (1-methyl isophthalic acid-methoxy ethyl) ester, carbonic acid two (1-methyl-2-methoxy ethyl) ester, carbonic acid two (1-methoxyl group butyl) ester, carbonic acid two (2-methoxyl group butyl) ester, carbonic acid two (3-methoxyl group butyl) ester, carbonic acid two (4-methoxyl group butyl) ester, carbonic acid two [1-(methoxy) propyl group] ester, carbonic acid two (1-methyl-2-methoxy-propyl) ester, carbonic acid two (ethoxyl methyl) ester, carbonic acid two (1-ethoxyethyl group) ester, carbonic acid two (2-ethoxyethyl group) ester, carbonic acid two (1-ethoxycarbonyl propyl) ester, carbonic acid two (2-ethoxycarbonyl propyl) ester, carbonic acid two (3-ethoxycarbonyl propyl) ester, carbonic acid two (1-methyl isophthalic acid-ethoxyethyl group) ester, carbonic acid two (1-methyl-2-ethoxyethyl group) ester, carbonic acid two (1-ethyoxyl butyl) ester, carbonic acid two (2-ethyoxyl butyl) ester, carbonic acid two (3-ethyoxyl butyl) ester, carbonic acid two (4-ethyoxyl butyl) ester, carbonic acid two [1-(ethoxyl methyl) propyl group] ester, carbonic acid two (1-methyl-2-ethoxycarbonyl propyl) ester, carbonic acid two (butoxymethyl) ester, carbonic acid two (1-butoxyethyl group) ester, carbonic acid two (2-butoxyethyl group) ester, carbonic acid two (1-butoxy propyl group) ester, carbonic acid two (2-butoxy propyl group) ester, carbonic acid two (3-butoxy propyl group) ester, carbonic acid two (1-methyl isophthalic acid-butoxyethyl group) ester, carbonic acid two (1-methyl-2-butoxyethyl group) ester, carbonic acid two (tetrahydrofurfuryl) ester, carbonic acid two (oxinane ylmethyl) ester, carbonic acid (methyl) [2-(2-methoxy ethoxy) ethyl] ester, carbonic acid (methyl) [2-(2-ethoxy ethoxy) ethyl] ester, carbonic acid (methyl) [2-(2-butoxy ethyoxyl) ethyl] ester, carbonic acid (methyl) [2-(2-methoxy ethoxy) propyl group] ester, carbonic acid (methyl) [2-(2-ethoxy ethoxy) propyl group] ester, carbonic acid (methyl) [2-(2-butoxy ethyoxyl) propyl group] ester, carbonic acid (methyl) [3-(2-methoxy ethoxy) propyl group] ester, carbonic acid (methyl) [3-(2-ethoxy ethoxy) propyl group] ester, carbonic acid (methyl) [3-(2-butoxy ethyoxyl) propyl group] ester, carbonic acid (methyl) [4-(2-methoxy ethoxy) butyl] ester, carbonic acid (methyl) [4-(2-ethoxy ethoxy) butyl] ester, carbonic acid (methyl) [4-(2-butoxy ethyoxyl) butyl] ester, carbonic acid (methyl) [2-(2-methoxyl group butoxy) ethyl] ester, carbonic acid (methyl) [2-(2-ethyoxyl butoxy) ethyl] ester, carbonic acid (methyl) [2-(2-butoxy butoxy) ethyl] ester, carbonic acid (methyl) [2-(2-methoxyl group butoxy) propyl group] ester, carbonic acid (methyl) [2-(2-ethyoxyl butoxy) propyl group] ester, carbonic acid (methyl) [2-(2-butoxy butoxy) propyl group] ester, carbonic acid (methyl) [3-(2-methoxyl group butoxy) propyl group] ester, carbonic acid (methyl) [3-(2-ethyoxyl butoxy) propyl group] ester, carbonic acid (methyl) [3-(2-butoxy butoxy) propyl group] ester, carbonic acid (methyl) [4-(2-methoxyl group butoxy) butyl] ester, carbonic acid (methyl) [4-(2-ethyoxyl butoxy) butyl] ester, carbonic acid (methyl) [4-(2-butoxy butoxy) butyl] ester, carbonic acid (ethyl) [2-(2-methoxy ethoxy) ethyl] ester, carbonic acid (ethyl) [2-(2-ethoxy ethoxy) ethyl] ester, carbonic acid (ethyl) [2-(2-butoxy ethyoxyl) ethyl] ester, carbonic acid (ethyl) [2-(2-methoxy ethoxy) propyl group] ester, carbonic acid (ethyl) [2-(2-ethoxy ethoxy) propyl group] ester, carbonic acid (ethyl) [2-(2-butoxy ethyoxyl) propyl group] ester, carbonic acid (ethyl) [3-(2-methoxy ethoxy) propyl group] ester, carbonic acid (ethyl) [3-(2-ethoxy ethoxy) propyl group] ester, carbonic acid (ethyl) [3-(2-butoxy ethyoxyl) propyl group] ester, carbonic acid (ethyl) [4-(2-methoxy ethoxy) butyl] ester, carbonic acid (ethyl) [4-(2-ethoxy ethoxy) butyl] ester, carbonic acid (ethyl) [4-(2-butoxy ethyoxyl) butyl] ester, carbonic acid (ethyl) [2-(2-methoxyl group butoxy) ethyl] ester, carbonic acid (ethyl) [2-(2-ethyoxyl butoxy) ethyl] ester, carbonic acid (ethyl) [2-(2-butoxy butoxy) ethyl] ester, carbonic acid (ethyl) [2-(2-methoxyl group butoxy) propyl group] ester, carbonic acid (ethyl) [2-(2-ethyoxyl butoxy) propyl group] ester, carbonic acid (ethyl) [2-(2-butoxy butoxy) propyl group] ester, carbonic acid (ethyl) [3-(2-methoxyl group butoxy) propyl group] ester, carbonic acid (ethyl) [3-(2-ethyoxyl butoxy) propyl group] ester, carbonic acid (ethyl) [3-(2-butoxy butoxy) propyl group] ester, carbonic acid (ethyl) [4-(2-methoxyl group butoxy) butyl] ester, carbonic acid (ethyl) [4-(2-ethyoxyl butoxy) butyl] ester, carbonic acid (ethyl) [4-(2-butoxy butoxy) butyl] ester, carbonic acid (butyl) [2-(2-methoxy ethoxy) ethyl] ester, carbonic acid (butyl) [2-(2-ethoxy ethoxy) ethyl] ester, carbonic acid (butyl) [2-(2-butoxy ethyoxyl) ethyl] ester, carbonic acid (butyl) [2-(2-methoxy ethoxy) propyl group] ester, carbonic acid (butyl) [2-(2-ethoxy ethoxy) propyl group] ester, carbonic acid (butyl) [2-(2-butoxy ethyoxyl) propyl group] ester, carbonic acid (butyl) [3-(2-methoxy ethoxy) propyl group] ester, carbonic acid (butyl) [3-(2-ethoxy ethoxy) propyl group] ester, carbonic acid (butyl) [3-(2-butoxy ethyoxyl) propyl group] ester, carbonic acid (butyl) [4-(2-methoxy ethoxy) butyl] ester, carbonic acid (butyl) [4-(2-ethoxy ethoxy) butyl] ester, carbonic acid (butyl) [4-(2-butoxy ethyoxyl) butyl] ester, carbonic acid (butyl) [2-(2-methoxyl group butoxy) ethyl] ester, carbonic acid (butyl) [2-(2-ethyoxyl butoxy) ethyl] ester, carbonic acid (butyl) [2-(2-butoxy butoxy) ethyl] ester, carbonic acid (butyl) [2-(2-methoxyl group butoxy) propyl group] ester, carbonic acid (butyl) [2-(2-ethyoxyl butoxy) propyl group] ester, carbonic acid (butyl) [3-(2-methoxyl group butoxy) propyl group] ester, carbonic acid (butyl) [3-(2-ethyoxyl butoxy) propyl group] ester, carbonic acid (hexyl) [2-(2-methoxy ethoxy) ethyl] ester, carbonic acid (hexyl) [2-(2-ethoxy ethoxy) ethyl] ester, carbonic acid (hexyl) [2-(2-butoxy ethyoxyl) ethyl] ester, carbonic acid (hexyl) [2-(2-methoxy ethoxy) propyl group] ester, carbonic acid (hexyl) [2-(2-ethoxy ethoxy) propyl group] ester, carbonic acid (hexyl) [3-(2-methoxy ethoxy) propyl group] ester, carbonic acid (hexyl) [3-(2-ethoxy ethoxy) propyl group] ester, carbonic acid (hexyl) [4-(2-methoxy ethoxy) butyl] ester, carbonic acid (hexyl) [4-(2-ethoxy ethoxy) butyl] ester, carbonic acid (hexyl) [2-(2-methoxyl group butoxy) ethyl] ester, carbonic acid (hexyl) [2-(2-ethyoxyl butoxy) ethyl] ester, carbonic acid (hexyl) [2-(2-methoxyl group butoxy) propyl group] ester and carbonic acid (hexyl) [3-(2-methoxyl group butoxy) propyl group] ester.
Wherein, preferred carbonic acid two (2-methoxy ethyl) ester, carbonic acid two (3-methoxy-propyl) ester, carbonic acid two (4-methoxyl group butyl) ester, carbonic acid two (2-ethoxyethyl group) ester, carbonic acid two (3-ethoxycarbonyl propyl) ester, carbonic acid two (4-ethyoxyl butyl) ester, carbonic acid two (2-butoxyethyl group) ester, carbonic acid two (3-butoxy propyl group) ester, carbonic acid two (4-butoxy butyl) ester, carbonic acid two (tetrahydrofurfuryl) ester, carbonic acid (methyl) [2-(2-methoxy ethoxy) ethyl] ester, carbonic acid (methyl) [2-(2-ethoxy ethoxy) ethyl] ester, carbonic acid (methyl) [2-(2-butoxy ethyoxyl) ethyl] ester, carbonic acid (ethyl) [2-(2-methoxy ethoxy) ethyl] ester, carbonic acid (ethyl) [2-(2-ethoxy ethoxy) ethyl] ester and carbonic acid (ethyl) [2-(2-butoxy ethyoxyl) ethyl] ester.
Wherein, preferred especially carbonic acid two (2-methoxy ethyl) ester, carbonic acid two (3-methoxy-propyl) ester, carbonic acid two (4-methoxyl group butyl) ester, carbonic acid two (2-ethoxyethyl group) ester, carbonic acid two (3-ethoxycarbonyl propyl) ester, carbonic acid two (4-ethyoxyl butyl) ester, carbonic acid (methyl) [2-(2-methoxy ethoxy) ethyl] ester, carbonic acid (methyl) [2-(2-ethoxy ethoxy) ethyl] ester, carbonic acid (ethyl) [2-(2-methoxy ethoxy) ethyl] ester and carbonic acid (ethyl) [2-(2-ethoxy ethoxy) ethyl] ester.
(c) have the carbonic ester of three ehter bonds in each molecule:
The example that has the carbonic ester of three ehter bonds in each molecule comprises: carbonic acid (methyl) [2-(2-(2-methoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (methyl) [2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (methyl) [2-(2-(2-butoxy ethyoxyl) ethyoxyl) ethyl] ester, carbonic acid (ethyl) [2-(2-(2-methoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (ethyl) [2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (ethyl) [2-(2-(2-butoxy ethyoxyl) ethyoxyl) ethyl] ester, carbonic acid (hexyl) [2-(2-(2-methoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (hexyl) [2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-methoxy ethoxy) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-ethoxy ethoxy) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-butoxy ethyoxyl) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-methoxy ethoxy) propyl group] ester, carbonic acid (2-methoxy ethyl) [2-(2-ethoxy ethoxy) propyl group] ester, carbonic acid (2-methoxy ethyl) [2-(2-butoxy ethyoxyl) propyl group] ester, carbonic acid (2-methoxy ethyl) [3-(2-methoxy ethoxy) propyl group] ester, carbonic acid (2-methoxy ethyl) [3-(2-ethoxy ethoxy) propyl group] ester, carbonic acid (2-methoxy ethyl) [3-(2-butoxy ethyoxyl) propyl group] ester, carbonic acid (2-methoxy ethyl) [4-(2-methoxy ethoxy) butyl] ester, carbonic acid (2-methoxy ethyl) [4-(2-ethoxy ethoxy) butyl] ester, carbonic acid (2-methoxy ethyl) [4-(2-butoxy ethyoxyl) butyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-methoxyl group butoxy) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-ethyoxyl butoxy) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-butoxy butoxy) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-methoxyl group butoxy) propyl group] ester, carbonic acid (2-methoxy ethyl) [2-(2-ethyoxyl butoxy) propyl group] ester, carbonic acid (2-methoxy ethyl) [2-(2-butoxy butoxy) propyl group] ester, carbonic acid (2-methoxy ethyl) [3-(2-methoxyl group butoxy) propyl group] ester, carbonic acid (2-methoxy ethyl) [3-(2-ethyoxyl butoxy) propyl group] ester, carbonic acid (2-methoxy ethyl) [3-(2-butoxy butoxy) propyl group] ester, carbonic acid (2-methoxy ethyl) [4-(2-methoxyl group butoxy) butyl] ester, carbonic acid (2-methoxy ethyl) [4-(2-ethyoxyl butoxy) butyl] ester, carbonic acid (2-ethoxyethyl group) [2-(2-methoxy ethoxy) ethyl] ester, carbonic acid (2-ethoxyethyl group) [2-(2-ethoxy ethoxy) ethyl] ester, carbonic acid (2-ethoxyethyl group) [2-(2-butoxy ethyoxyl) ethyl] ester, carbonic acid (2-ethoxyethyl group) [2-(2-methoxy ethoxy) propyl group] ester, carbonic acid (2-ethoxyethyl group) [2-(2-ethoxy ethoxy) propyl group] ester, carbonic acid (2-ethoxyethyl group) [2-(2-butoxy ethyoxyl) propyl group] ester, carbonic acid (2-ethoxyethyl group) [3-(2-methoxy ethoxy) propyl group] ester, carbonic acid (2-ethoxyethyl group) [3-(2-ethoxy ethoxy) propyl group] ester, carbonic acid (2-ethoxyethyl group) [3-(2-butoxy ethyoxyl) propyl group] ester, carbonic acid (2-ethoxyethyl group) [4-(2-methoxy ethoxy) butyl] ester, carbonic acid (2-ethoxyethyl group) [4-(2-ethoxy ethoxy) butyl] ester, carbonic acid (2-ethoxyethyl group) [4-(2-butoxy ethyoxyl) butyl] ester, carbonic acid (2-ethoxyethyl group) [2-(2-methoxyl group butoxy) ethyl] ester, carbonic acid (2-ethoxyethyl group) [2-(2-ethyoxyl butoxy) ethyl] ester, carbonic acid (2-ethoxyethyl group) [2-(2-butoxy butoxy) ethyl] ester, carbonic acid (2-ethoxyethyl group) [2-(2-methoxyl group butoxy) propyl group] ester, carbonic acid (2-ethoxyethyl group) [2-(2-ethyoxyl butoxy) propyl group] ester, carbonic acid (2-ethoxyethyl group) [3-(2-methoxyl group butoxy) propyl group] ester, carbonic acid (2-ethoxyethyl group) [3-(2-ethyoxyl butoxy) propyl group] ester, carbonic acid (2-ethoxyethyl group) [4-(2-methoxyl group butoxy) butyl] ester, carbonic acid (2-ethoxyethyl group) [4-(2-ethyoxyl butoxy) butyl] ester and carbonic acid (tetrahydrofurfuryl) [2-(2-methoxy ethoxy) ethyl] ester.
Wherein, preferred carbonic acid (methyl) [2-(2-(2-methoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (methyl) [2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (ethyl) [2-(2-(2-methoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (ethyl) [2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-methoxy ethoxy) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-ethoxy ethoxy) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-butoxy ethyoxyl) ethyl] ester, carbonic acid (2-ethoxyethyl group) [2-(2-methoxy ethoxy) ethyl] ester, carbonic acid (2-ethoxyethyl group) [2-(2-ethoxy ethoxy) ethyl] ester and carbonic acid (tetrahydrofurfuryl) [2-(2-methoxy ethoxy) ethyl] ester.
Wherein, preferred especially carbonic acid (methyl) [2-(2-(2-methoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (methyl) [2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (ethyl) [2-(2-(2-methoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (ethyl) [2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-methoxy ethoxy) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-ethoxy ethoxy) ethyl] ester, carbonic acid (2-ethoxyethyl group) [2-(2-methoxy ethoxy) ethyl] ester and carbonic acid (2-ethoxyethyl group) [2-(2-ethoxy ethoxy) ethyl] ester.
(d) have the carbonic ester of four ehter bonds in each molecule:
The example that has the carbonic ester of four ehter bonds in each molecule comprises: carbonic acid two [2-(2-methoxy ethoxy) ethyl] ester, carbonic acid two [2-(2-ethoxy ethoxy) ethyl] ester, carbonic acid two [2-(2-propoxyl group ethyoxyl) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-(2-methoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (2-ethoxyethyl group) [2-(2-(2-methoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (2-butoxyethyl group) [2-(2-(2-methoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-(2-butoxy ethyoxyl) ethyoxyl) ethyl] ester, carbonic acid (2-ethoxyethyl group) [2-(2-(2-butoxy ethyoxyl) ethyoxyl) ethyl] ester, carbonic acid (2-butoxyethyl group) [2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid (methyl) [2-(2-(2-methoxy ethoxy) ethyoxyl) ethyoxyl] ethyl] ester, carbonic acid (ethyl) [2-(2-(2-(2-methoxy ethoxy) ethyoxyl) ethyoxyl) ethyl] ester, carbonic acid (butyl) [2-(2-(2-(2-methoxy ethoxy) ethyoxyl) ethyoxyl) ethyl] ester, carbonic acid (butyl) [2-(2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyoxyl) ethyl] ester, carbonic acid (methyl) [2-(2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyoxyl) ethyl] ester, carbonic acid (methyl) [2-(2-(2-(2-butoxy ethyoxyl) ethyoxyl) ethyoxyl) ethyl] ester and carbonic acid (ethyl) [2-(2-(2-(2-butoxy ethyoxyl) ethyoxyl) ethyoxyl) ethyl] ester.
Wherein, preferred carbonic acid two [2-(2-methoxy ethoxy) ethyl] ester and carbonic acid (2-methoxy ethyl) [2-(2-(2-methoxy ethoxy) ethyoxyl) ethyl] ester.
(e) have the carbonic ester of five ehter bonds in each molecule:
The example that has the carbonic ester of five ehter bonds in each molecule comprises: carbonic acid (methyl) [2-(2-(2-(2-(2-methoxy ethoxy) ethyoxyl) ethyoxyl) ethyoxyl) ethyl] ester, carbonic acid (methyl) [2-(2-(2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyoxyl) ethyoxyl) ethyl] ester, carbonic acid (ethyl) [2-(2-(2-(2-(2-methoxy ethoxy) ethyoxyl) ethyoxyl) ethyoxyl) ethyl] ester, carbonic acid (ethyl) [2-(2-(2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyoxyl) ethyoxyl) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-(2-(2-methoxy ethoxy) ethyoxyl) ethyoxyl) ethyl] ester, carbonic acid (2-methoxy ethyl) [2-(2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyoxyl) ethyl] ester, carbonic acid (2-ethoxyethyl group) [2-(2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyoxyl) ethyl] ester, carbonic acid [2-(2-methoxy ethoxy) ethyl] [2-(2-(2-methoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid [2-(2-ethoxy ethoxy) ethyl] [2-(2-(2-methoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid [2-(2-methoxy ethoxy) ethyl] [2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyl] ester and carbonic acid [2-(2-ethoxy ethoxy) ethyl] [2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyl] ester.
(f) have the carbonic ester of six ehter bonds in each molecule:
The example that has the carbonic ester of six ehter bonds in each molecule comprises: carbonic acid two [2-(2-(2-methoxy ethoxy) ethyoxyl) ethyl] ester, carbonic acid two [2-(2-(2-ethoxy ethoxy) ethyoxyl) ethyl] ester and carbonic acid two [2-(2-(2-propoxyl group ethyoxyl) ethyoxyl) ethyl] ester.
Can use any described compound (Ia) separately, or be used in combination any two or more described compounds with arbitrary proportion.
With respect to nonaqueous electrolyte (Ia), the ratio of described compound (Ia) is generally more than the 0.01 weight %, more than the preferred 0.1 weight %, more than the preferred especially 0.3 weight %, be generally below the 5 weight %, below the preferred 4 weight %, below the preferred especially 3 weight %.If described ratio is too little, then can not improve the cycle characteristics under the low temperature.On the other hand, if described ratio is too big, the battery behavior meeting deterioration after then high temperature is preserved is so be not preferred.When being used in combination two or more these compounds (Ia), require the toatl proportion of compound (Ia) to satisfy above-mentioned scope.
In described nonaqueous electrolyte (Ia), weight ratio between unsaturated cyclic carbonate products and the compound (the Ia) (weight of unsaturated cyclic carbonate products: the weight of compound (Ia)) be generally more than 1: 0.01, preferred more than 1: 0.1, common below 1: 50, preferred below 1: 10.If the ratio of compound (Ia) is too big, the battery behavior after high temperature is preserved will worsen, and if described ratio is too little, the cycle characteristics low temperature under just can not improve.When being used in combination two or more unsaturated cyclic carbonate products and/or two or more compounds (Ia), require the toatl proportion of unsaturated cyclic carbonate products and/or compound (Ia) to satisfy above-mentioned scope.
The nonaqueous electrolyte (Ia) that contains unsaturated cyclic carbonate products and compound (Ia) can improve the cycle characteristics under the low temperature, and its reason it be unclear that, but infers that reason is as follows.
At first, in the charging process, for example unsaturated cyclic carbonate products such as vinylene carbonate is reduced, and forms stable coverlay in negative terminal surface, thereby improves the cycle characteristics under the room temperature in the early stage.Yet because the lithium ion permeability of the coverlay that forms on this negative terminal surface is big with the fluctuation of temperature, the infiltrative rapid decline of lithium ion can cause the cycle characteristics under the low temperature to descend under the low temperature.
On the contrary, when electrolyte contains compound (Ia), on negative terminal surface, form the compound coverlay that originates from described unsaturated cyclic carbonate products and compound (Ia).Because even this compound coverlay also has good lithium ion permeability at low temperatures, thus can keep cycle characteristics good under the room temperature, even also can obtain also good at low temperatures cycle characteristics.
＜compound (Ib) 〉
Described compound (Ib) is the compound of following general formula (Ib) representative.
[Chemical formula 1 0]
In general formula (Ib), R 21Representative has the alkyl of 1～12 carbon atom or has the thiazolinyl of 2～12 carbon atoms.Wherein, preferred alkyl.
The example of described alkyl is that its carbon atom number is 1～12, and is preferred 1～8, and preferred especially 1～3 alkyl comprises methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, cyclopenta and cyclohexyl.Described alkyl can be chain or ring-type, wherein chain preferably.
The example of described thiazolinyl is that its carbon atom number is 2～12, and is preferred 2～8, and preferred especially 2～4 thiazolinyl comprises vinyl and acrylic.Described thiazolinyl can be chain or ring-type, wherein chain preferably.
These alkyl and thiazolinyl can have the one or more fluorine atoms that replaced part or all of hydrogen atom, and, can have one or more ehter bonds in the chain of these alkyl and thiazolinyl.
The molecular weight of described compound (Ib) is generally 98～650, and is preferred below 350, more preferably below 250.If described molecular weight is too high, then the dissolubility in described electrolyte can significantly descend.
The example of described compound (Ib) is a Fumette, the second sulfuryl fluoride, third sulfuryl fluoride, 2-third sulfuryl fluoride, the butyl sulfuryl fluoride, 2-butyl sulfuryl fluoride, the hexyl sulfuryl fluoride, the octyl group sulfuryl fluoride, the decyl sulfuryl fluoride, the dodecyl sulfuryl fluoride, the cyclohexyl sulfuryl fluoride, the fluoroform sulfuryl fluoride, perfluor second sulfuryl fluoride, perfluor third sulfuryl fluoride, perfluoro butyl sulfonic acid fluoride, the vinyl sulfuryl fluoride, 1-acrylic-1-sulfuryl fluoride, 2-acrylic-1-sulfuryl fluoride, 2-methoxyl group-second sulfuryl fluoride and 2-ethyoxyl-second sulfuryl fluoride.
Wherein, preferred Fumette, second sulfuryl fluoride, third sulfuryl fluoride, 2-third sulfuryl fluoride, butyl sulfuryl fluoride and 2-butyl sulfuryl fluoride, preferred especially Fumette, second sulfuryl fluoride and third sulfuryl fluoride.
Can use any described compound (Ib) separately, or be used in combination any two or more described compounds (Ib) with arbitrary proportion.
With respect to described nonaqueous electrolyte (Ib), the ratio of described compound (Ib) is generally more than the 0.001 weight %, more than the preferred 0.05 weight %, more preferably more than the 0.1 weight %.If the concentration of compound (Ib) is too low, then almost without any effect.Yet on the other hand, if the concentration of compound (Ib) is too high, the preservation characteristics of described battery can descend.Be limited on it below 5 weight %, below the preferred 3 weight %, more preferably below the 1 weight %.When being used in combination two or more compounds (Ib), require the toatl proportion of compound (Ib) to satisfy above-mentioned scope.
In nonaqueous electrolyte (Ib), weight ratio (the weight of compound (Ib): the weight of unsaturated cyclic carbonate products) be generally more than 1: 1 of compound (Ib) and unsaturated cyclic carbonate products, preferred more than 1: 2, common below 1: 50, preferred below 1: 25.If the ratio of compound (Ib) is too high, the battery behavior after high temperature is preserved will descend, and if the ratio of compound (Ib) is too low, just can not suppress the generation of gas in the trickle charge process.When being used in combination two or more unsaturated cyclic carbonate products and/or two or more compounds (Ib), require the toatl proportion of described unsaturated cyclic carbonate products and/or compound (Ib) to satisfy above-mentioned scope.
The nonaqueous electrolyte (Ib) that contains unsaturated cyclic carbonate products and compound (Ib) can make the battery of gained keep high cycle characteristics, improve trickle charge characteristic and preservation characteristics under the high temperature high voltage condition simultaneously, its reason it be unclear that, but infers that reason is as follows.
In the initial stage charging process, on negative terminal surface, form compound coverlay, unite on anodal surface by compound (Ib) and other bath compositions and form compound coverlay by unsaturated cyclic carbonate products and compound (Ib).Described compound coverlay has good lithium ion permeability, simultaneously even at high temperature also be stable: by inference, even under the state of trickle charge state or higher temperature, described coverlay can prevent that also the high activity electrode from contacting with electrolyte, suppressing the contingent side reaction of inside battery, thereby improve trickle charge characteristic and preservation characteristics under the high temperature.
And because under charged state, the unsaturated cyclic carbonate products is easy to and the positive electrode reaction, the problem of existence is that when electrolyte contained the unsaturated cyclic carbonate products, the generation of gas increased in the trickle charge process.Yet, by inference, when with compound (Ib) when being used in combination, the coverlay that anodal surface forms can prevent that the unsaturated cyclic carbonate products from contacting with positive pole, suppressing gas generated increase, thereby realize the battery behavior under cycle characteristics and the high temperature simultaneously.
＜compound (Ic) 〉
Described compound (Ic) is the compound of following general formula (Ic) representative.
[Chemical formula 1 1]
CF nH (3-n)CH 2X 3 (Ic)
(in general formula (Ic), n represents 1～3 integer, X 3Representative is selected from the group with the group of following formula (Ic-1)～(Ic-4) representative.
[Chemical formula 1 2]
-O-R 31 (Ic-1)
-O-Y 3-O-R 32 (Ic-2)
Figure G2009101614705D00281
In formula (Ic-1)～(Ic-4), R 31～R 34Representative independently of one another can have the substituent alkyl with 1～20 carbon atom of halogen atom, Y 3Representative can have the substituent bivalent hydrocarbon radical with 1～10 carbon atom of halogen atom.)
In described formula, R 31～R 34Representative can have substituent straight chained alkyl, branched alkyl or the cycloalkyl with 1～20 carbon atom of halogen atom separately.The number of its carbon atom is generally more than 1, and is preferred more than 2, is generally below 20, preferred below 10, more preferably below 6.
R 31～R 34Object lesson be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, cyclopenta, hexyl, cyclohexyl, octyl group, decyl and dodecyl etc.
R 31～R 34Can have the halogen atom substituting group.The kind of halogen atom is not particularly limited, but with regard to electrochemical stability, preferred fluorine atom or chlorine atom, preferred especially fluorine atom.The substituent number of halogen atom is not particularly limited, but is generally below 20, and is preferred below 12.
Example with the substituent alkyl of halogen atom is:
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;
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, 1,1, the 3-trifluoro propyl, 1,2, the 2-trifluoro propyl, 1,2, the 3-trifluoro propyl, 1,3, the 3-trifluoro propyl, 2,2, the 2-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, 1,3,3,3-tetrafluoro propyl group, 2,3,3,3-tetrafluoro propyl group, 1,1,2,2,3-five fluoropropyls, 1,1,2,3,3-five fluoropropyls, 1,1,3,3,3-five fluoropropyls, 1,2,2,3,3-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-fluorine butyl, 2-fluorine butyl, 3-fluorine butyl, 4-fluorine butyl, 1,1-difluoro butyl, 1,2-difluoro butyl, 1,3-difluoro butyl, 1,4-difluoro butyl, 2,2-difluoro butyl, 2,3-difluoro butyl, 2,4-difluoro butyl, 3,3-difluoro butyl, 3,4-difluoro butyl, 4,4-difluoro butyl, 1,1,2-trifluoro butyl, 1,1,3-trifluoro butyl, 1,1,4-trifluoro butyl, 1,2,2-trifluoro butyl, 1,2,3-trifluoro butyl, 1,2,4-trifluoro butyl, 1,3,3-trifluoro butyl, 1,3,4-trifluoro butyl, 1,4,4-trifluoro butyl, 2,2,3-trifluoro butyl, 2,2,4-trifluoro butyl, 2,3,3-trifluoro butyl, 2,3,4-trifluoro butyl, 2,4,4-trifluoro butyl, 3,3,4-trifluoro butyl, 3,4,4-trifluoro butyl, 4,4,4-trifluoro butyl;
1-fluorine amyl group, 2-fluorine amyl group, 3-fluorine amyl group, 4-fluorine amyl group, 5-fluorine amyl group, 1,1-difluoro amyl group, 1,2-difluoro amyl group, 1,3-difluoro amyl group, 1,4-difluoro amyl group, 1,5-difluoro amyl group, 2,2-difluoro amyl group, 2,3-difluoro amyl group, 2,4-difluoro amyl group, 2,5-difluoro amyl group, 3,3-difluoro amyl group, 3,4-difluoro amyl group, 3,5-difluoro amyl group, 4,4-difluoro amyl group, 4,5-difluoro amyl group, 5,5-difluoro amyl group, 1,1,2-trifluoro amyl group, 1,1,3-trifluoro amyl group, 1,1,4-trifluoro amyl group, 1,1,5-trifluoro amyl group, 1,2,2-trifluoro amyl group, 1,2,3-trifluoro amyl group, 1,2,4-trifluoro amyl group, 1,2,5-trifluoro amyl group, 1,3,3-trifluoro amyl group, 1,3,4-trifluoro amyl group, 1,3,5-trifluoro amyl group, 1,4,4-trifluoro amyl group, 1,4,5-trifluoro amyl group, 1,5,5-trifluoro amyl group, 2,2,2-trifluoro amyl group, 2,2,3-trifluoro amyl group, 2,2,4-trifluoro amyl group, 2,2,5-trifluoro amyl group, 2,3,3-trifluoro amyl group, 2,3,4-trifluoro amyl group, 2,3,5-trifluoro amyl group, 2,4,4-trifluoro amyl group, 2,4,5-trifluoro amyl group, 2,5,5-trifluoro amyl group, 3,3,3-trifluoro amyl group, 3,3,4-trifluoro amyl group, 3,3,5-trifluoro amyl group, 3,4,4-trifluoro amyl group, 3,4,5-trifluoro amyl group, 3,5,5-trifluoro amyl group, 4,4,4-trifluoro amyl group, 4,4,5-trifluoro amyl group, 4,5,5-trifluoro amyl group, 5,5,5-trifluoro amyl group;
1-fluorine hexyl, 1,1-difluoro hexyl and 1,1,2-trifluoro hexyl.
In general formula (Ic-1)～(Ic-4), preferred especially each R 31～R 34Be to have 1～3 substituent alkyl of fluorine atom with 1～20 carbon atom.Specifically, described compound (Ic) preferably has fluorine atom at its two ends.
In general formula (Ic-2), Y 3Representative can have the halogen atom substituting group and the bivalent hydrocarbon radical that 1～10 carbon atom is arranged.The number of its carbon atom is generally more than 1, and is preferred more than 2, is generally below 6, preferred below 4.The example of described bivalent hydrocarbon radical comprises from alkane and aromatic hydrocarbons removes two hydrogen atoms and the bivalent hydrocarbon radical such as for example alkylidene and arlydene etc. that obtains, described alkane is for example methane, ethane, propane, normal butane, iso-butane, pentane, isopentane, neopentane etc., and described aromatic hydrocarbons is for example benzene,toluene,xylene etc.Preferred alkylidene.
These alkyl also can have the halogen atom substituting group.The kind of described halogen atom is not particularly limited, but with regard to electrochemical stability, preferred fluorine atom or chlorine atom, preferred fluorine atom among both.The substituent number of halogen atom is not particularly limited, but is generally below 20, and is preferred below 12.
The molecular weight of described compound (Ic) is generally more than 70, and is preferred more than 90, is generally below 1000, preferred below 500.In order to satisfy the structure of general formula (Ic), described molecular weight must be equal to or greater than above-mentioned lower limit.On the other hand, if molecular weight surpasses the described upper limit, this compound molecule can closely not assembled when negative terminal surface forms coverlay when as described below, therefore the characteristic that can not get expecting.
The example of described compound (Ic) is as described below, but the kind of described compound is not limited to following example, as long as without prejudice to purport of the present invention, can be any compound.
X wherein 3Compound (monoether compound) by general formula (Ic-1) expression is:
CFH 2CH 2OCH 2CH 3 (1)
CFH 2CH 2OCH 2CH 2F (2)
CF 2HCH 2OCH 2CH 3 (3)
CF 2HCH 2OCH 2CHF 2 (4)
CF 3CH 2OCH 2CH 3 (5)
CF 3CH 2OCH 2CF 3 (6)
X wherein 3Compound (diether compounds) by general formula (Ic-2) expression is:
CFH 2CH 2OCH 2CH 2OCH 2CH 3 (7)
CFH 2CH 2OCH 2CH 2OCH 2CH 2F (8)
CF 2HCH 2OCH 2CH 2OCH 2CH 3 (9)
CF 2HCH 2OCH 2CH 2OCH 2CHF 2 (10)
CF 3CH 2OCH 2CH 2OCH 2CH 3 (11)
CF 3CH 2OCH 2CH 2OCH 2CF 3 (12)
X wherein 3Compound (ester type compound) by general formula (Ic-3) expression is:
CFH 2CH 2OC(＝O)CH 3 (13)
CFH 2CH 2OC(＝O)CFH 2 (14)
CF 2HCH 2OC(＝O)CH 3 (15)
CF 2HCF 2OC(＝O)CF 2H (16)
CF 3CH 2OC(＝O)CH 3 (17)
CF 3CH 2OC(＝O)CF 3 (18)
X wherein 3Compound (carbonate products) by general formula (Ic-4) expression is:
CFH 2CH 2OC(＝O)OCH 2CH 3 (19)
CFH 2CH 2OC(＝O)OCH 2CH 2F (20)
CF 2HCH 2OC(＝O)OCH 2CH 3 (21)
CF 2HCH 2OC(＝O)OCH 2CHF 2 (22)
CF 3CH 2OC(＝O)OCH 2CH 3 (23)
CF 3CH 2OC(＝O)OCH 2CF 3 (24)
In described nonaqueous electrolyte (Ic), can use any described compound (Ic) separately, or be used in combination any two or more described compounds (Ic) with arbitrary proportion.
The concentration of compound (Ic) is generally more than the 0.01 weight % in the described nonaqueous electrolyte (Ic), more than the preferred 0.05 weight %, more than the preferred especially 0.1 weight %, be generally below the 5 weight %, below the preferred 4 weight %, more preferably below the 3 weight %, below the preferred especially 2 weight %.If the content of compound (Ic) is too low, then can not produce the inhibition effect of enough degree to the deterioration under the high voltage.On the other hand, if described ratio is too high, then for example large current characteristic of battery etc. will descend.When being used in combination two or more compounds (Ic), require the total amount of described compound (Ic) to satisfy above-mentioned scope.
In nonaqueous electrolyte (Ic), weight ratio between unsaturated cyclic carbonate products and the compound (Ic) (weight of the weight/compound of unsaturated cyclic carbonate products (Ic)) is generally more than 0.001, preferred more than 0.01, preferred especially more than 0.05, be generally below 1000, preferred below 100.If the ratio of compound (Ic) is too high, the battery behavior after high temperature is preserved will descend.If described ratio is too low, just can not suppress the generation of gas in the trickle charge process.When being used in combination two or more unsaturated cyclic carbonate products and/or two or more compounds (Ic), require the toatl proportion of described unsaturated cyclic carbonate products and/or compound (Ic) to satisfy above-mentioned scope.
In secondary cell (particularly lithium secondary battery), use when containing the nonaqueous electrolyte (Ic) of described unsaturated cyclic carbonate products and compound (Ic), deterioration in the time of can suppressing to use under the high voltage, its reason it be unclear that, but infers that reason is as follows.
In nonaqueous electrolyte (Ic), described unsaturated cyclic carbonate products forms good coverlay at negative pole.Yet, because the unsaturated cyclic carbonate products is easy to oxidation, so when under high voltage, using, can adverse effect be arranged to battery behavior.On the other hand, fluorochemical also forms coverlay, but produce excessive coverlay under high voltage battery behavior is worsened.Therefore, unsaturated cyclic carbonate products and fluorochemical have their merits and demerits separately.Yet, when being used in combination the unsaturated cyclic carbonate products with the time as the compound (Ic) of fluorochemical, by inference, the coverlay that described compound (Ic) forms can suppress the oxidation of described unsaturated cyclic carbonate products, and the coverlay that described unsaturated cyclic carbonate products forms can suppress the decomposition of compound (Ic).According to the present invention and since be used in combination described unsaturated cyclic carbonate products with as the compound (Ic) of fluorochemical, so these compounds can be complementary, thereby be created in the tolerance of use high voltage under.
From obtaining the angle of above-mentioned effect, if the concentration of the compound (Ic) in the described nonaqueous electrolyte (Ic) is too low, the coverlay of formation will be insufficient, thereby can not produce described effect.On the other hand, if described concentration is too high, described coverlay will excessively form, and the character of coverlay can change, thereby battery behavior is produced adverse effect.The concentration of the unsaturated cyclic carbonate products in the described nonaqueous electrolyte (Ic) also is like this: if this concentration is too high, the negative pole coverlay will excessively form and hinder the migration of lithium ion, if but this concentration is too low, the formation of negative pole coverlay will be insufficient, thereby cause deterioration.Owing to this reason, think that defined concentration range is optimum among the present invention.
＜other 〉
When described nonaqueous electrolyte (I) contains two or more compounds (Ia), compound (Ib) and compound (Ic), with respect to described nonaqueous electrolyte (I), the total concentration of compound (I) is generally more than the 0.01 weight %, more than the preferred 0.05 weight %, more than the preferred especially 0.1 weight %, and be generally below the 5 weight %, below the preferred 4 weight %, more preferably below the 3 weight %.If the content of described compound (I) is too low, just can not have enough inhibitory action to the deterioration under the high voltage.On the other hand, when this ratio was too high, the large current characteristic of battery etc. will descend.
When described nonaqueous electrolyte (I) contains two or more compounds (Ia), compound (Ib) and compound (Ic), weight ratio (total weight of the weight/compound of unsaturated cyclic carbonate products (I)) in this nonaqueous electrolyte (I) between the total amount of unsaturated cyclic carbonate products and compound (I) is generally more than 0.001, preferred more than 0.01, preferred especially more than 0.05, and be generally below 1000, preferred below 100.If the ratio of compound (I) is too high, the battery behavior after high temperature is preserved will worsen.If described ratio is too low, just can not improve the cycle characteristics under the low temperature, can not suppress the generation of gas in the trickle charge process.
[other compositions]
Except above-mentioned electrolyte, non-aqueous solvent, unsaturated cyclic carbonate products (A composition) and compound (I) (B composition), nonaqueous electrolyte of the present invention (I) also can contain one or more other compositions, and the amount of described other compositions is advisable not weaken effect of the present invention.The example of other compositions is known traditionally various auxiliary agents, for example overcharges to prevent agent, deacidification agent, dehydrating agent and fire retardant.
In these auxiliary agents, the example that prevents agent that overcharges is: aromatic compound, for example the partial hydrogenation product of biphenyl, alkyl biphenyl, terphenyl, terphenyl, cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene, diphenyl ether, dibenzofurans etc.; The partially fluorinated product of above-mentioned aromatic compound, for example 2-fluorine biphenyl, adjacent cyclohexyl fluorobenzene and to the cyclohexyl fluorobenzene; Fluorine-containing benzyl ether compounds, for example 2,4-difluoroanisole, 2,5-difluoroanisole and 2,6-difluoroanisole.Can use any described overcharging to prevent agent separately, also can be used in combination two or more described overcharging and prevent agent with arbitrary proportion.Prevent agent by containing the overcharging of concentration that is equal to or higher than following lower limit, can suppress battery and under the situation of overcharging, break or catch fire.If the described concentration that prevents agent of overcharging surpasses following higher limit, then in high temperature preservation process, they will react at the high activity position of electrode.Because the reaction of these compounds can make internal battery impedance obviously raise or cause the generation of gas, so the flash-over characteristic after flash-over characteristic after the trickle charge and high temperature are preserved can significantly descend.
The example of other auxiliary agents is: carbonate products, for example carbonic acid fluoroethylene, the inferior propyl ester of carbonic acid trifluoro, carbonic acid phenyl ethyl, carbonic acid pentaerythrite (erythritan) ester and carbonic acid spiral shell-two (dimethylene) ester; Carboxylic acid anhydrides, for example succinyl oxide, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, diethyl dicarboxylic anhydride, cyclohexane diacid acid anhydride, ring penta tetracarboxylic dianhydride and phenyl succinyl oxide; Sulfur-containing compound, glycol sulfite, 1 for example, 3-third sultone, 1,4-fourth sultone, methyl mesylate, 1,4-dimethane sulfonoxybutane, sulfolane, cyclobufene sultone (sulfolene), dimethyl sulfone, tetra methylthiuram monosulfide, N, N-dimethyl methyl sulfonamide and N, N-diethyl first sulfonamide; Nitrogen-containing compound, for example 1-Methyl-2-Pyrrolidone, 1-methyl-2-piperidones, 3-methyl-2-oxazolidone, 1,3-dimethyl-2-imidazolidinone and N methyl succinimide; Hydrocarbon compound, for example heptane, octane and cycloheptane; Fluorine-containing aromatic compound, for example fluorobenzene, difluoro-benzene, phenyl-hexafluoride and benzotrifluoride; With phosphorous compound, for example trimethyl phosphate, triethyl phosphate, di(2-ethylhexyl)phosphate Methylethyl ester, phosphoric acid methyl diethyl ester, phosphoric acid ethylidene methyl ester, phosphoric acid ethylidene ethyl ester and tricresyl phosphate (trifluoroethyl) ester.Can use any these materials separately, or be used in combination two or more these materials with arbitrary proportion.
When nonaqueous electrolyte of the present invention (I) contained these auxiliary agents, with respect to described nonaqueous electrolyte, their content was generally 0.01 weight %～5 weight %.The capacity that these contained auxiliary agents of nonaqueous electrolyte of the present invention can improve after high temperature is preserved is kept characteristic and cycle characteristics.
[preparation method of nonaqueous electrolyte (I)]
By above-mentioned electrolyte, unsaturated cyclic carbonate products (A composition) and compound (I) (B composition) and other used as required auxiliary agents are dissolved in above-mentioned non-aqueous solvent, thereby prepare nonaqueous electrolyte of the present invention (I).At the described nonaqueous electrolyte of preparation (I) before, it is desirable to, each compositions such as for example non-aqueous solvent are dewatered in advance.Specifically, it is desirable to, the moisture content of each composition of dehydration back is below the 50ppm, below the preferred 30ppm.Dehydration method can be selected arbitrarily, and the example of described method is the decompression heating or passes through molecular sieve.
Also can the gelation of gelling agent such as macromolecule prepares semi-solid nonaqueous electrolyte of the present invention (I) by for example adopting.In the described semisolid electrolyte, with respect to the electrolytical total weight of described semisolid, the ratio of nonaqueous electrolyte (I) is generally more than the 30 weight %, more than the preferred 50 weight %, more preferably more than the 75 weight %, and be generally below the 99.95 weight %, below the preferred 99 weight %, more preferably below the 98 weight %.If the ratio of described nonaqueous electrolyte (I) is too high, then this nonaqueous electrolyte (I) is difficult to keep, and is easy to occur seepage.On the other hand, if the ratio of described nonaqueous electrolyte (I) is too low, the efficiency for charge-discharge of battery and capacity will be not enough.
[2: nonaqueous electrolyte (II)]
Second described nonaqueous electrolyte in aspect of the present invention (below be also referred to as " nonaqueous electrolyte (II) ") contains lithium salts and non-aqueous solvent, it is characterized in that this nonaqueous electrolyte (II) also contains described subsequently compound (II) (below be also referred to as " C composition ").In addition, preferably contain cyclic carbonate compound with unsaturated bond (below be also referred to as " D composition ").
[electrolyte]
Used electrolyte is not particularly limited in the nonaqueous electrolyte (II), can be the electrolytical material as secondary cell of selecting oneself arbitrarily and knowing.When being used for lithium secondary battery, adopt lithium salts usually as electrolyte.For example the kind of described lithium salts is identical with above-mentioned explanation about nonaqueous electrolyte (I) with details such as consumptions.
[non-aqueous solvent]
As the non-aqueous solvent in the nonaqueous electrolyte (II), can adopt any material of the known traditionally solvent as nonaqueous electrolyte, but select organic solvent usually for use.For example the kind of described organic solvent is identical with above-mentioned explanation about nonaqueous electrolyte (I) with details such as consumptions.
[compound (II) (C composition)]
Nonaqueous electrolyte (II) contains at least a compound in compound (IIa), compound (IIb) and the compound (IIc) (below be also referred to as " compound (II) ") as the C composition.Nonaqueous electrolyte (II) can contain any compound in described compound (IIa), compound (IIb) and the compound (IIc) separately, or contains two or three combination of compounds in them.In the following description, when separately explaining, the nonaqueous electrolyte (II) that contains one of compound (IIa), compound (IIb), compound (IIc) respectively will be called " nonaqueous electrolyte (IIa) ", " nonaqueous electrolyte (IIb) ", " nonaqueous electrolyte (IIc) ", and when not needing to distinguish especially, they are commonly referred to as " nonaqueous electrolyte (II) ".
＜compound (IIa) 〉
Described compound (IIa) is the compound that has by the represented structure of following general formula (IIa).
[Chemical formula 1 3]
Figure G2009101614705D00361
In the described compound (IIa), preferably by the represented compound of following general formula (IIa ') (below be also referred to as " compound (IIa) ' ").
[Chemical formula 1 4]
(in general formula (IIa '), R 41～R 44Represent hydrogen atom independently of one another, can have the substituent alkyl with 1～12 carbon atom of fluorine atom, can have the substituent thiazolinyl with 2～12 carbon atoms of fluorine atom, can have the substituent aryl of fluorine atom, maybe can have the substituent aralkyl of fluorine atom with 7～12 carbon atoms with 6～12 carbon atoms.Can have ehter bond on the chain of described group.R 41Can with R 42Link to each other R 43Can with R 44Link to each other, thereby form ring with oxygen atom.)
In general formula (IIa '), R 41～R 44Represent hydrogen atom independently of one another, have 1～12 carbon atom alkyl, have 2～12 carbon atoms thiazolinyl, have the aryl of 6～12 carbon atoms, or have the aralkyl of 7～12 carbon atoms.
Described alkyl, thiazolinyl, aryl or aralkyl can have the one or more fluorine atoms that replaced part or all of hydrogen atom, also can have ehter bond on its chain.
The example of alkyl is the alkyl with 1～12 carbon atom, preferably has the alkyl of 1～8 carbon atom, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, cyclopenta, cyclohexyl etc.
The example of thiazolinyl is the thiazolinyl with 1～12 carbon atom, preferably has the thiazolinyl of 2～8 carbon atoms, especially preferably has the thiazolinyl of 2～4 carbon atoms, for example vinyl and acrylic.
The example of aryl comprises phenyl, tolyl and xylyl, wherein preferred phenyl.
The example of aralkyl comprises benzyl and phenethyl.
R 41Can with R 42Link to each other R 43Can with R 44Link to each other, thereby form the circulus that contains oxygen atom, for example have the cycloalkanes structure of 3～12 carbon atoms.
Wherein, preferred R 41～R 44Represent hydrogen atom independently of one another, can have the substituent alkyl of fluorine atom, maybe can have the substituent thiazolinyl of fluorine atom with 2～12 carbon atoms with 1～12 carbon atom.
The molecular weight of described compound (IIa ') is generally more than 160, is generally below 900, and is preferred below 650.If described molecular weight is too big, the dissolubility of described compound (IIa ') in electrolyte can significantly descend.
The example of described compound (IIa ') is as described below.
As each R 41～R 44Be the described compound of hydrogen atom, can mention 2,4,8,10-four oxygen spiral shell [5.5] hendecanes.
As R 41～R 44In any one is the compound of alkyl, can mention 3,9-dimethyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-diethyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-dipropyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-dioctyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-didecyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-two (undecyl)-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-two (dodecyl)-2,4,8,1 0-, four oxygen spiral shell [5.5] hendecanes, 3,3,9,9-tetramethyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,3,9,9-tetraethyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-diethyl-3,9-dimethyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-dicyclohexyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes etc.
As R 41～R 44In any one is the compound of thiazolinyl, can mention 3,9-divinyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-two-1-acrylic-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-two-2-acrylic-2,4,8,10-four oxygen spiral shell [5.5] hendecanes etc.
As R 41～R 44In any one is the compound of aryl, can mention 3,9-diphenyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-two (4-fluorophenyl)-2,4,8,10-four oxygen spiral shell [5.5] hendecanes etc.
As R 41With R 42Link to each other or R 43With R 44Be connected to the compound of circulus, can mention 7,11,18,21-four oxygen, three spiral shells [5.2.2.5.2.2] heneicosane, 6,10,16,19-four oxygen, three spiral shells [4.2.2.4.2.2] nonadecane etc.
As R 41～R 44In any one has the compound of ehter bond on its chain, can mention 3,9-dimethoxy-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-diethoxy-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-two (methoxy)-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-two (2-methoxy ethyl)-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-two (2-ethoxyethyl group)-2,4,8,10-four oxygen spiral shell [5.5] hendecanes etc.
Wherein, preferred 2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-dimethyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-diethyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-dipropyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-divinyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, 3,9-two-1-acrylic-2,4,8,10-four oxygen spiral shell [5.5] hendecanes and 3,9-two-2-acrylic-2,4,8,10-four oxygen spiral shell [5.5] hendecanes, preferred especially 2,4,8,10-four oxygen spiral shell [5.5] hendecanes and 3,9-divinyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes.
For described nonaqueous electrolyte (IIa), can use any described compound (IIa) separately, also can be used in combination any two or more described compounds (IIa) by arbitrary proportion.
The ratio of compound (IIa) is generally more than the 0.001 weight % in the described nonaqueous electrolyte (IIa).If its concentration is lower than described boundary, then almost without any effect.More than the preferred 0.05 weight % of described concentration, more than the preferred especially 0.1 weight %.On the other hand, if described concentration is too high, the preservation characteristics of battery will descend.The upper limit is generally below the 10 weight %, below the preferred 5 weight %, more preferably below the 4 weight %.In view of described concentration relevant with the multifrequency nature of electrolyte, below the preferred 3 weight % of this concentration, more preferably below the 2 weight %, also more preferably below the 1 weight %.When being used in combination two or more compounds (IIa), require the toatl proportion of described compound (IIa) to satisfy above-mentioned scope.
The nonaqueous electrolyte (IIa) that contains described compound (IIa) can improve the trickle charge characteristic, and its reason it be unclear that, but infers that reason is as follows.At first, in the early stage in the charging process, described compound (IIa) can cause the reaction on negative pole and anodal surface, forms compound coverlay with other compositions in the described electrolyte.Infer that from the represented structure of general formula (IIa) described compound coverlay contains a large amount of oxygen atoms, and oxygen atom is positioned on the suitable position, can forms excellent lithium ion permeability and high-temperature stability like this.By inference, even under trickle charge state or higher temperature state, described coverlay also can prevent contacting of high activity electrode and electrolyte, suppressing the side reaction of inside battery, thereby improves the trickle charge characteristic.
On the other hand, when the cyclic ether compounds that adopts its structure not belong to the defined structure of general formula (IIa) for example when dioxolane, oxolane, oxinane and dioxane, battery behavior will descend, and this is because the lithium ion poor permeability of the compound coverlay of gained and at high temperature due to the instability by inference.
＜compound (IIb) 〉
Described compound (IIb) is the represented compound of following general formula (IIb).
[Chemical formula 1 5]
In general formula (IIb), Z 5Represent the integer more than 2, be generally below 8, preferred below 4.Preferred especially Z 5=2.
X 5Representative is by the Z valency linking group that is selected from one or more atomic buildings of following group, is made up of carbon atom, hydrogen atom, fluorine atom and oxygen atom for described group, and fluorosulfonyl links to each other with the carbon atom of described linking group.The example of described linking group is alkyl and fluoro alkyl, and contains for example ehter bond or ester bond etc. in the chain of described alkyl.The example of described alkyl is aliphatic alkyls such as for example saturated aliphatic alkyl and undersaturated aliphatic alkyl, and aromatic hydrocarbyl.Wherein, preferred aliphat alkyl, preferred especially saturated aliphatic alkyl.Described aliphatic alkyl can be chain or ring-type, but preferred chain.These alkyl can contain the one or more fluorine atoms that replaced part or all of hydrogen atom.The carbon atom number of described linking group is generally 1～12, and preferred 2～8.
Z 5The example of=2 linking group is listed below.
[Chemical formula 1 6]
-CH 2-
Figure G2009101614705D00411
Figure G2009101614705D00412
Z 5The example of=3 linking group is listed below.
[Chemical formula 1 7]
Figure G2009101614705D00421
Z 5The example of=4 linking group is listed below.
[Chemical formula 1 8]
Figure G2009101614705D00422
The molecular weight of described compound (IIb) is generally more than 180, and is generally below 1000, and is preferred below 650, more preferably below 350.If this molecular weight is too big, then the dissolubility of compound (IIb) in electrolyte will significantly descend.
Z 5The example of=2 compound (IIb) is two (fluorosulfonyl) methane; 1,2-two (fluorosulfonyl) ethane; 1,3-two (fluorosulfonyl) propane; 1; 2-two (fluorosulfonyl) propane; 1,4-two (fluorosulfonyl) butane; 1,2-two (fluorosulfonyl) butane; 1; 3-two (fluorosulfonyl) butane; two (fluorosulfonyl) difluoromethane; 1,2-two (fluorosulfonyl)-1,1; 2, the 2-HFC-134a; 1,3-two (fluorosulfonyl)-1; 1,2,2; 3, the 3-HFC-236fa; 1,4-two (fluorosulfonyl)-1; 1,2,2; 3,3,4; the 4-octafluorobutane; 2,2 '-oxygen two (second sulfuryl fluoride); 2,2 '-oxygen two (1; 1,2,2-tetrafluoro second sulfuryl fluoride) etc.
Z 5The example of=3 compound (IIb) is 1,2,3-three (fluorosulfonyl) propane, 1,2,3-three (fluorosulfonyl) butane, 1,2,4-three (fluorosulfonyl) butane, 1,2,3-three (fluorosulfonyl)-1,1,2,3,3-pentafluoropropane etc.
Z 5The example of=4 compound (IIb) is 1,2,3,4-four (fluorosulfonyl) butane, 1,2,3,4-four (fluorosulfonyl)-1,1,2,3,4,4-hexafluoro butane etc.
Wherein, preferred two (fluorosulfonyl) methane, 1,2-two (fluorosulfonyl) ethane, 1,3-two (fluorosulfonyl) propane, 1,2-two (fluorosulfonyl) propane, 1; 4-two (fluorosulfonyl) butane, two (fluorosulfonyl) difluoromethane, 1,2-two (fluorosulfonyl)-1,1,2,2-HFC-134a, 1; 3-two (fluorosulfonyl)-1,1,2,2; 3,3-HFC-236fa, 1,4-two (fluorosulfonyl)-1,1; 2,2,3,3; 4,4-octafluorobutane and 1,2,3-three (fluorosulfonyl) propane.
More preferably, can mention 1,2-two (fluorosulfonyl) ethane, 1,3-two (fluorosulfonyl) propane, 1; 4-two (fluorosulfonyl) butane, 1,2-two (fluorosulfonyl)-1,1,2; 2-HFC-134a, 1,3-two (fluorosulfonyl)-1,1,2; 2,3,3-HFC-236fa and 1,4-two (fluorosulfonyl)-1; 1,2,2,3; 3,4, the 4-octafluorobutane.
In described nonaqueous electrolyte (IIb), can use any described compound (IIb) separately, or be used in combination any two or more compounds (IIb) with arbitrary proportion.
The ratio of compound (IIb) is generally more than the 0.001 weight % in the described nonaqueous electrolyte (IIb).If the concentration of compound (IIb) is lower than this boundary, it will be almost without any effect.More than the preferred 0.05 weight % of this concentration, more than the preferred especially 0.1 weight %.Yet if described concentration is too high, the preservation characteristics of battery will descend.Therefore, its upper limit is generally below the 5 weight %, below the preferred 3 weight %, more preferably below the 1 weight %.When being used in combination two or more compounds (IIb), require the toatl proportion of described compound (IIb) to satisfy above-mentioned scope.
The nonaqueous electrolyte that contains compound (IIb) can improve the battery behavior under the high temperature high voltage condition, for example trickle charge characteristic and preservation characteristics, and its reason it be unclear that, but infers that reason is as follows.
At first, in the early stage in the charging process, described compound (IIb) can cause the reaction on negative pole and anodal surface, forms compound coverlay with other compositions in the described electrolyte.Because described compound coverlay has excellent lithium ion permeability and high-temperature stability, by inference, even under trickle charge state or higher temperature state, described coverlay can prevent contacting of high activity electrode and electrolyte, to suppress the generation of inside battery side reaction.
On the other hand, for example compound with single fluorosulfonyl such as benzene sulfonyl fluorine and toluenesulfonyl fluoride can form compound coverlay, the lithium ion poor permeability of this compound coverlay and at high temperature unstable.By inference, this is because the internal driving increase of gained battery when preserving under hot conditions has worsened for example battery behavior such as high temperature preservation characteristics and trickle charge characteristic.
＜compound (IIc) 〉
Described compound (IIc) is the represented compound of following general formula (IIc).
[Chemical formula 1 9]
Figure G2009101614705D00441
In general formula (IIc), Z 6Represent the integer more than 2.Though without limits, its upper limit is preferred below 4, more preferably below 3.Preferred especially Z 6=2.If Z 6Less than 2, the discharge preservation characteristics can be impaired.
R 61Represent alkyl independently of one another.Its carbon atom number is generally more than 1, and is generally below 6, and is preferred below 4.R 61The example of alkyl is methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, cyclopenta and cyclohexyl.Can have other substituting groups on these alkyl.Described R 61The substituting group that alkyl can have is not particularly limited, as long as they do not break away from the purport of nonaqueous electrolyte of the present invention, but suitable be halogen atom, alkoxyl, hydroxyl and amino.Z 6Individual R 61Alkyl (substituting group that comprises them if any) can be mutually the same, also can be different mutually.
R 62Representative independently of one another contains the substituent alkyl of one or more halogen atoms.Its carbon atom number is generally more than 1, and is generally below 6, and is preferred below 3.The kind of described halogen atom is not particularly limited, but with regard to electrochemical stability, preferred fluorine atom.The substituent number of the halogen atom of described alkyl is generally more than 1, and is preferred more than 2.This upper limit depends on the carbon atom number of described alkyl, but is generally below 6, and is preferred below 4.R 62Example comprise methyl fluoride, difluoromethyl, trifluoromethyl, 1-fluoro ethyl, 2-fluoro ethyl, 2,2-two fluoro ethyls, 2,2,2-trifluoroethyl, pentafluoroethyl group, seven fluoropropyls etc.The fluoro-alkyl that wherein preferably has 1～6 carbon atom especially preferably has the fluoro-alkyl of 1～3 carbon atom.These alkyl can have one or more other substituting groups.Described R 62The substituting group that alkyl can have is not particularly limited, as long as they do not break away from the purport of nonaqueous electrolyte of the present invention, but suitable be alkoxyl, hydroxyl and amino.Z 6Individual R 62Can be mutually the same, also can be different mutually.
Any two or more R 61And/or R 62Can be interconnected to circulus, can reduce the hydrogen atom number in the described molecule like this, thereby suppress the generation of hydrogen.
The coupling part X that a plurality of functional groups are linked together 6Represent Z 6The valency alkyl.Its carbon atom number is generally more than 1, and is generally below 6, and is preferred below 3.X 6Example be from alkyl such as for example ethane, propane, normal butane, iso-butane, pentane, isopentane and neopentane or for example aryl such as benzene and toluene remove Z 6The Z of individual hydrogen atom gained 6The valency alkyl.These alkyl can have one or more other substituting groups.Described X 6The substituting group that alkyl can have is not particularly limited, as long as they do not break away from the purport of nonaqueous electrolyte of the present invention, but suitable be halogen atom, alkoxyl, hydroxyl and amino.
The molecular weight of described compound (IIc) is generally more than 150, and is preferred more than 180, and is generally below 1000, preferred below 500.In order to satisfy the structure of general formula (IIc), described molecular weight must equal or exceed this lower limit.On the other hand, if described molecular weight surpasses this upper limit, in the process that forms compound coverlay, described compound molecule just can closely not assembled, thereby when discharge condition is preserved deterioration takes place.
The example of described compound (IIc) is listed below, but its kind is not limited to following example.Can adopt any compound, as long as it is without prejudice to purport of the present invention.
Z 6＝2：
[Chemical formula 2 0]
Figure G2009101614705D00461
Z 6＝3：
[Chemical formula 2 1]
Figure G2009101614705D00462
Z 6＝4：
[Chemical formula 2 2]
Figure G2009101614705D00471
More than in the cited compound, preferred (A-1), (A-2), (A-3) and (B-1) compound as described compound (IIc), especially preferably (A-1), (A-2) and (A-3).
In described nonaqueous electrolyte (IIc), can use any described compound (IIc) separately, or be used in combination any two or more compounds (IIc) with arbitrary proportion.
The concentration of compound (IIc) is generally more than the 0.01 weight % in described nonaqueous electrolyte (IIc), more than the preferred 0.05 weight %, more than the preferred especially 0.1 weight %, and be generally below the 4 weight %, below the preferred 3 weight %, more preferably below the 2 weight %, below the preferred especially 1 weight %.If the ratio of compound (IIc) is too low, just can show sufficient gas and suppress effect.On the other hand, if described ratio is too high, the discharge preservation characteristics of battery will descend.When being used in combination two or more compounds (IIc), require the toatl proportion of described compound (IIc) to satisfy above-mentioned scope.
At secondary cell particularly in the lithium secondary battery, employing contains the nonaqueous electrolyte (IIc) of described compound (IIc) as electrolyte, can suppress the deterioration in the discharge condition preservation process, also can significantly reduce the generation of gas, its reason it be unclear that, but infers that reason is as follows.
In the charging process, described nonaqueous electrolyte (IIc) can cause the reaction of negative or positive electrode in the early stage, forms the organic polymer coverlay.Because the compound that adopted of patent documentation 7 has an acid amides position, i.e. independent reaction position is so it can have the effect that stops polymerization reaction.Therefore, the producing high-molecular degree will be insufficient, and the result who causes is, compares with the solution that does not contain described compound, when discharge condition is preserved, contains the poor stability of organic coverlay of solution in electrolyte of described compound.On the other hand, because contained compound (IIc) has a plurality of acid amides position in the described nonaqueous electrolyte (IIc), promptly a plurality of reactions position can not stop so can keep producing polymerization reaction.By inference, because described nonaqueous electrolyte (IIc) can form good coverlay, therefore can suppress the generation of gas and do not damage stability in the discharge condition preservation process.
If the concentration of compound (IIc) is too low in the described nonaqueous electrolyte (IIc),, just can not tell on owing to can not form the coverlay of capacity.On the other hand, if described concentration is too high, the amount of the coverlay that can form is bigger, and the character of coverlay changes, thereby other battery behaviors such as the preservation characteristics that for example discharges are produced ill effect.Therefore think that determined concentration range is appropriate among the present invention.
＜other 〉
During in containing compound (IIa), compound (IIb) and compound (IIc) in the described nonaqueous electrolyte (II) two or more, with respect to described nonaqueous electrolyte (II), the total concentration of compound (II) is generally more than the 0.01 weight %, more than the preferred 0.05 weight %, more than the preferred especially 0.1 weight %, and be generally below the 5 weight %, below the preferred 4 weight %, more preferably below the 3 weight %, below the preferred especially 2 weight %.If the content of described compound (II) is too low, then the deterioration under the high voltage is not just had enough inhibition effects.On the other hand, if described content is too high, the large current characteristic of battery etc. will descend.
[unsaturated cyclic carbonate products (D composition)]
Except above-mentioned C composition, described nonaqueous electrolyte (II) also preferably contains the unsaturated cyclic carbonate products as the D composition.As mentioned above, the unsaturated cyclic carbonate products is meant to have at least one carbonic ester structure and at least one carbon-to-carbon double bond in each molecule, and the compound that has at least one circulus in each molecule.
By in nonaqueous electrolyte, adding the unsaturated cyclic carbonate products, can improve the preservation characteristics of gained battery.Its reason it be unclear that, but by inference, this is owing to formed stable protectiveness coverlay in negative terminal surface.If its content is too low, preservation characteristics just can not be fully improved.The use of unsaturated cyclic carbonic ester normally produces the reason of gas in the high temperature preservation process in the electrolyte.Yet it is favourable that unsaturated cyclic carbonic ester and compound (II) are used in combination, because the battery that produces can suppress the generation of gas like this, and improves the shortcoming of unsaturated cyclic carbonic ester.
The example of unsaturated cyclic carbonate products is vinylene carbonate compound, ethylene thiazolinyl ethyl compound and carbonic acid methylene ethyl compound.
The example of vinylene carbonate compound comprises vinylene carbonate, carbonic acid methyl vinylene, carbonic acid ethyl vinylene, carbonic acid-4,5-dimethyl vinylene, carbonic acid-4,5-diethyl vinylene, carbonic acid fluoro vinylene and carbonic acid trifluoromethyl vinylene.
The example of ethylene thiazolinyl ethyl compound comprises ethylene thiazolinyl ethyl, carbonic acid-4-methyl-4-vinyl ethyl, carbonic acid-4-ethyl-4-vinyl ethyl, carbonic acid-4-n-pro-pyl-4-vinyl ethyl, carbonic acid-5-methyl-4-vinyl ethyl, carbonic acid-4,4-divinyl ethyl and carbonic acid-4,5-divinyl ethyl.
The example of carbonic acid methylene ethyl compound is carbonic acid methylene ethyl, carbonic acid-4,4-dimethyl-5-methylene ethyl and carbonic acid-4,4-diethyl-5-methylene ethyl.
Wherein, the preferred vinylene carbonate of unsaturated cyclic carbonate products, ethylene thiazolinyl ethyl, preferred especially vinylene carbonate.
Can use any described unsaturated cyclic carbonate products separately, or be used in combination two or more unsaturated cyclic carbonate products with arbitrary proportion.
When described nonaqueous electrolyte (II) contains unsaturated cyclic carbonate products and above-claimed cpd (IIa) or compound (IIb) simultaneously, the ratio of unsaturated cyclic carbonate products is generally more than the 0.01 weight % in this nonaqueous electrolyte (II), more than the preferred 0.1 weight %, more than the preferred especially 0.3 weight %, most preferably more than the 0.5 weight %, and be generally below the 8 weight %, below the preferred 4 weight %, below the preferred especially 3 weight %.When being used in combination two or more unsaturated cyclic carbonate products, require the toatl proportion of described unsaturated cyclic carbonate products to satisfy above-mentioned scope.
When nonaqueous electrolyte (II) contains unsaturated cyclic carbonate products and above-claimed cpd (IIc) simultaneously, the ratio of unsaturated cyclic carbonate products is generally more than the 0.01 weight % in this nonaqueous electrolyte (II), more than the preferred 0.1 weight %, more than the preferred especially 0.5 weight %, most preferably more than the 1 weight %, and be generally below the 10 weight %, below the preferred 5 weight %, below the preferred especially 2.5 weight %.When being used in combination two or more unsaturated cyclic carbonate products, require the toatl proportion of described unsaturated cyclic carbonate products to satisfy above-mentioned scope.
If the content of described unsaturated cyclic carbonate products is too low, just can not fully produce the effect of improving the battery cycle characteristics.Because the unsaturated cyclic carbonate products is easy to the reaction of the positive electrode of charged state, so when in described nonaqueous electrolyte, using the unsaturated cyclic carbonate products, usually can cause the problem that the generation of gas in the trickle charge process increases.Yet preferred compositions is used unsaturated cyclic carbonate products and compound (II), because can suppress gas generated increase like this, can improve cycle characteristics, and suppresses the generation of gas.On the other hand,, will tend to increase the generation of gas in the high temperature preservation process, the flash-over characteristic under the infringement low temperature if the content of unsaturated cyclic carbonate products is too high.
When nonaqueous electrolyte (II) contains unsaturated cyclic carbonate products and above-claimed cpd (II) simultaneously, in the stage of preparation nonaqueous electrolyte (II), the weight ratio between described compound (II) and the described unsaturated cyclic carbonate products is generally 1: 1～and 1: 50.When being used in combination two or more unsaturated cyclic carbonate products and/or compound (II), require the toatl proportion of described unsaturated cyclic carbonate products and/or compound (II) to satisfy above-mentioned scope.
[other compositions]
Except above-mentioned electrolyte, non-aqueous solvent and compound (II) (C composition) and the unsaturated cyclic carbonate products (D composition) that uses as required, described nonaqueous electrolyte (II) also can contain other compositions, as long as described other compositions do not damage effect of the present invention.The example of other compositions is known traditionally multiple auxiliary agents, for example overcharges to prevent agent, deacidification agent, dehydrating agent and fire retardant.The for example described kind that prevents agent and other auxiliary agents of overcharging is identical with above-mentioned explanation about nonaqueous electrolyte (I) with details such as consumptions.
[preparation method of nonaqueous electrolyte (II)]
By above-mentioned electrolyte, compound (II) (C composition) and other compositions such as used as required unsaturated cyclic carbonate products (D composition) and other auxiliary agents are dissolved in above-mentioned non-aqueous solvent, thereby prepare nonaqueous electrolyte of the present invention (II).At the described nonaqueous electrolyte of preparation (II) before, it is desirable to, in advance with each composition dehydrations such as for example described non-aqueous solvents.Specifically, it is desirable to, the water content of each composition of dehydration back is below the 50ppm, below the preferred 30ppm.Dehydration method can be selected arbitrarily, and the example of described method is the decompression heating or passes through molecular sieve.
Also can the gelation of gelling agent such as macromolecule prepares semi-solid nonaqueous electrolyte (II) by for example adopting.In the described semisolid electrolyte, with respect to described semisolid electrolyte, the ratio of nonaqueous electrolyte (II) is generally more than the 30 weight %, more than the preferred 50 weight %, more preferably more than the 75 weight %, and be generally below the 99.95 weight %, below the preferred 99 weight %, more preferably below the 98 weight %.If the ratio of described nonaqueous electrolyte (II) is too high, then this nonaqueous electrolyte (II) will be difficult to keep, and be easy to occur seepage.On the other hand, if the ratio of described nonaqueous electrolyte (II) is too low, then the efficiency for charge-discharge of battery and capacity will be not enough.
[3: lithium secondary battery]
Next, will explain lithium secondary battery of the present invention.
Lithium secondary battery of the present invention comprises negative pole and anodal and the above-mentioned nonaqueous electrolyte of the present invention that can absorb and discharge lithium ion at least.
Promptly, except described nonaqueous electrolyte, lithium secondary battery of the present invention is identical with known traditionally lithium secondary battery configuration: described lithium secondary battery normally, stacked positive pole and negative pole, be inserted with the perforated membrane (dividing plate) that is soaked with nonaqueous electrolyte of the present invention between described positive pole and the negative pole, in the shell of then these elements being packed into.The shape of lithium secondary battery of the present invention is not particularly limited, and can be Any shape such as cylinder type, square, cascade type, Coin shape, large scale type for example.
[positive active material]
The example of described positive active material is inorganic compound, lithium metal, lithium alloy and their complexs such as the composite oxides (lithium-transition metal composite oxide), transient metal sulfide, for example metal oxide of transition metal oxide, transition metal and lithium.Concrete example is: for example MnO, V 2O 5, V 6O 13And TiO 2Deng transition metal oxide; Basic composition is LiCoO 2The lithium cobalt composite oxide; By LiNiO 2The lithium nickel composite oxide of expression; By LiMn 2O 4Or LiMnO 2The complex Li-Mn-oxide of expression; Lithium-transition metal composite oxide such as lithium nickel manganese cobalt composite oxide and lithium nickel cobalt aluminum composite oxide for example; Transient metal sulfide such as TiS and FeS for example; SnO for example 2And SiO 2Deng metal oxide.Wherein, the preferred lithium-transition metal composite oxide that adopts, specifically, preferred lithium cobalt composite oxide, lithium nickel composite oxide, lithium cobalt ni compound oxide, lithium nickel manganese cobalt composite oxide and lithium nickel cobalt aluminum composite oxide are because they can obtain big capacity and high cycle characteristics.Can preferably replace part cobalt, nickel or the manganese of described lithium-transition metal composite oxide, because can stablize described structure like this with for example metals such as Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga and Zr.Can use any described positive active material separately, or be used in combination two or more described positive active materials with arbitrary ratio.
[negative electrode active material]
As negative electrode active material, can adopt the material that can absorb and discharge lithium, for example carbonaceous material, metallic compound, lithium metal and lithium alloy.Wherein preferred carbonaceous material, preferred especially graphite and surface coverage have the graphite than the more unbodied material with carbon element of graphite.Can use any described negative electrode active material separately, or be used in combination two or more described negative electrode active materials with arbitrary ratio.
Desirable graphite is as follows: be generally 0.335nm～0.340nm according to the method (Japanese Academy for the Advancement of Science formulate method) of shaking through the d value (interfloor distance) of the lattice plane (002 face) of X-ray diffraction gained, preferred 0.335nm～0.338nm, preferred especially 0.335nm～0.337nm.Be generally more than the 30nm according to the crystallite size (Lc) of method by the X-ray diffraction gained that shake, more than the preferred 50nm, more than the preferred especially 100nm.Ash content is generally below the 1 weight %, below the preferred 0.5 weight %, below the preferred especially 0.1 weight %.
Desirable surface coverage has the graphite of amorphous carbon as follows: employing is core material through the d value (interfloor distance) of the lattice plane (002 face) of X-ray diffraction gained for the graphite of 0.335nm～0.338nm, this graphite surface is coated with material with carbon element, and this material with carbon element is bigger than the d value of described core material through the d value (interfloor distance) of the lattice plane (002 face) of X-ray diffraction gained.In addition, described core material and be generally 99/1～80/20 through the weight ratio of the d value (interfloor distance) of the lattice plane (002 face) of the X-ray diffraction gained material with carbon element bigger than the d value of described core material.The employing above-mentioned material can make the negative pole that has high power capacity and be difficult to react with described electrolyte.
With regard to regard to the median diameter of laser diffraction/scattering method gained, the particle diameter of described carbonaceous material is generally more than the 1 μ m, more than the preferred 3 μ m, more preferably more than the 5 μ m, most preferably more than the 7 μ m, and be generally below the 100 μ m, below the preferred 50 μ m, more preferably below the 40 μ m, most preferably below the 30 μ m.
The specific area of the described carbonaceous material that records through the BET method is generally 0.3m 2More than/the g, preferred 0.5m 2More than/the g, more preferably 0.7m 2More than/the g, 0.8m most preferably 2More than/the g, and be generally 25m 2Below/the g, preferred 20m 2Below/the g, more preferably 15m 2Below/the g, 10m most preferably 2Below/the g.
When measuring described carbonaceous material, use I by the Raman spectrum analysis that adopts argon laser beam B/ I ARatio represent the R value, the R value is preferably 0.01～0.7, wherein I ARepresentative is at 1570cm -1～1620cm -1The peak P that measures in the scope AIntensity, I BRepresentative is at 1300cm -1～1400cm -1The peak P that measures in the scope BIntensity.In addition, 1570cm -1～1620cm -1The half breadth at desirable peak is generally 26cm in the scope -1Below, preferred 25cm -1Below.
The example that can absorb and discharge the metallic compound of lithium is to contain for example compound of metals such as Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn, Sr, Zn.Can use the described metal of any state, for example simple substance, oxide or lithium alloy.In the present invention, preferred use contains the compound of the element that is selected from Al, Ge, Si and Sn etc., is preferably selected from the oxide or the lithium alloy of the metal of Al, Si and Sn especially.
Compare with the material with carbon element that with graphite is representative, per unit weight described can absorb and discharge the metallic compound of lithium and their oxide and lithium alloy and usually have bigger capacity, so be applicable to and require to have the more lithium secondary battery of high-energy-density.
[preparation method of electrode]
Can prepare electrode according to method commonly used.According to a kind of method, negative electrode active material or positive active material and adhesive, tackifier, electric conducting material, solvent etc. are mixed make slurries, the slurries of gained are coated on the collector body, carry out drying, compacting then, thus form electrode.
As the adhesive of bonding described active material, can adopt any material, as long as this material is in preparation during electrode in the used solvent and all stable in the electrolyte.The example of described adhesive is a fluororesin such as polyvinylidene fluoride and polytetrafluoroethylene for example, polyolefin such as polyethylene and polypropylene for example, for example unsaturated polymer and their copolymers such as styrene butadiene rubbers, isoprene rubber, butadiene rubber, for example acrylate copolymer such as ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer and their copolymer.
In order to improve mechanical strength and conductivity, electrode can contain for example materials such as tackifier, electric conducting material and filler.
The example of tackifier is carboxymethyl cellulose, methylcellulose, CMC, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch and casein etc.
The example of electric conducting material is a metal material such as copper and mickel for example, and material with carbon element such as graphite and carbon black for example.
Described active material can mix with for example other materials such as adhesive and electric conducting material, can directly described mixture be rolled into plate electrode, is pressed into pellet electrode, or forms electrode material membrane by methods such as evaporation, sputter, plating on collector body.
When making negative electrode active material with graphite, the density of the negative electrode active material layer after the dry also extruding is generally 1.45g/cm 3More than, preferred 1.55g/cm 3More than, preferred especially 1.60g/cm 3More than.
The density of the positive electrode active material layer after the dry also extruding is generally 3.0g/cm 3More than.
Collector body is made by metal or alloy usually.Specifically, the example of negative electrode collector is copper and alloy, nickel and alloy, stainless steel etc., wherein preferably copper and alloy thereof.The example of positive electrode collector is aluminium, titanium, tantalum and their alloy, wherein preferred aluminium and alloy thereof.In order to improve collector body bonding effect surperficial and formed active material layer on it, preferably in advance roughened is carried out on this collector body surface.The example of surface roughening process is: blasting treatment; Roll with shaggy roller; Grind the mechanical milling method on collector body surface with the metal plug etc. that sticks emery cloth or sand paper, grinding stone, emery buff that abrasive particles is arranged, steel mesh etc. is housed; Electrolytic polishing method and chemical grinding method etc.
In addition, for the weight that alleviates collector body and improve energy density, also can use for example drawn metal or stamped metal diplodal collector body with respect to battery weight.Such collector body can freely be regulated its weight by regulating its porosity.In addition, when all forming active material layer on the two sides of such collector body, this active material layer by rivet clasp on these holes with slip-off preventing.Yet if porosity is too high, because the contact area of active material layer and collector body is too little, bond strength will descend.
The thickness of described collector body is generally more than the 1 μ m, more than the preferred 5 μ m, and is generally below the 100 μ m, below the preferred 50 μ m.If it is too thick, the capacity of entire cell will obviously descend.On the other hand, if it is too thin, will be difficult to operation.
[dividing plate]
In order to prevent short circuit, between positive pole and negative pole, insert dividing plate usually.Dividing plate is soaked with nonaqueous electrolyte of the present invention usually.
Though material and shape to dividing plate are not particularly limited, preferred porous plate or non-weaving cloth by the made guarantor's fluidity excellence of material stable in nonaqueous electrolyte of the present invention.The example of separator material is for example polyolefin such as polyethylene, polypropylene and polytetrafluoroethylene and polyether sulfone, wherein preferred polyolefm.
The thickness of described dividing plate is generally more than the 1 μ m, more than the preferred 5 μ m, more preferably more than the 10 μ m, and is generally below the 50 μ m, below the preferred 40 μ m, more preferably below the 30 μ m.If dividing plate is too thin, then insulation property and mechanical strength can worsen, and if dividing plate is too thick, then not only for example battery behavior such as speed characteristic can worsen, and the energy density of entire cell can descend.
The porosity of described dividing plate is generally more than 20%, and is preferred more than 35%, more preferably more than 45%, and is generally below 90%, preferred below 85%, more preferably below 75%.If this porosity is too low, then because membrane impedance increases, speed characteristic will worsen.If this porosity is too high, then because the mechanical strength of dividing plate reduces, insulation property can descend.
The average pore size of dividing plate is generally below the 0.5 μ m, below the preferred 0.2 μ m, and is generally more than the 0.05 μ m.Average pore size is crossed conference and is caused short circuit, and the too small meeting of average pore size worsens speed characteristic owing to membrane impedance increases.
[shell]
The used battery case of lithium secondary battery of the present invention can be made by any material, and examples of material comprises iron, stainless steel, aluminium and alloy thereof, nickel, titanium of nickel plating etc.
Embodiment
Be further explained in detail the present invention below with reference to embodiment, but following examples only are used at length explaining the present invention.Under the situation of purport of the present invention, the present invention is not limited to following examples.
[embodiment/comparative example group (Ia)]
Implement the program that following each embodiment and comparative example are narrated, thereby make nonaqueous electrolyte, adopt the gained nonaqueous electrolyte to prepare lithium secondary battery, and estimate the lithium secondary battery of gained.
In each embodiment and comparative example, the preparation of lithium secondary battery is identical with assessment process, explains these preparations and assessment process in advance.
[preparation of battery and assessment process]
The preparation of negative pole:
The native graphite powder of 94 weight portions is mixed with the polyvinylidene fluoride of 6 weight portions, under the situation that the N-N-methyl-2-2-pyrrolidone N-exists, make slurries.Described native graphite powder is 0.336nm through the d value of the lattice plane (002 face) of X-ray diffraction gained, crystallite size (Lc) is 652nm, ash content is 0.07 weight %, is 12 μ m according to the median diameter of laser diffraction/scattering method gained, is 7.5m according to the specific area of BET method gained 2/ g, R the value (=I of the Raman spectrum analysis gained of employing argon laser B/ I A) be 0.12, at 1570cm -1～1620cm -1The half breadth at the peak in the scope is 19.9cm -1The gained slurries are coated on the surface that thickness is the Copper Foil of 12 μ m equably, dry and extruding, the density that makes the negative electrode active layer is 1.6g/cm 3Thereby, make negative pole.
Anodal preparation:
LiCoO with 85 weight portions 2, the carbon black of 6 weight portions and 9 weight portions polyvinylidene fluoride (trade mark is " KF-1000 ", and society produces by the Wu Yu chemistry) mix, under the situation that the N-N-methyl-2-2-pyrrolidone N-exists, make slurries.The gained slurries are coated on two surfaces that thickness is the aluminium foil of 15 μ m equably, dry and extruding, the density that makes anodal active layer is 3.0g/cm 3Thereby, make positive pole.
The preparation of lithium secondary battery:
The positive pole that obtains like this is in the same place according to the sequential cascade of negative pole, dividing plate, positive pole, dividing plate and negative pole with negative pole and the dividing plate of being made by polyethylene, to make cell device.This cell device inserted by the two sides all be coated with in the stacked film formed bag of aluminium (thickness is 40 μ m) of resin bed, the end of described positive pole and negative pole stretches out this bag.In described bag, inject by following each embodiment and the prepared nonaqueous electrolyte of comparative example, vacuum seal then, thus make plate battery (lithium secondary battery of each embodiment and comparative example).
Capacity is estimated:
Each embodiment and the described lithium secondary battery of comparative example are clipped between the glass plate, described electrode more closely is in contact with one another, carry out following program then.At 25 ℃, give described battery charge with constant current corresponding to 0.2C, up to reaching 4.2V, the constant current with 0.2C discharges then, up to reaching 3V.Described step is carried out three circulations to stablize this battery.In the 4th circulation, give described battery charge with the constant current of 0.5C, up to reaching 4.2V, under the constant voltage of 4.2V, charge then, reach 0.05C up to current value, with the constant current discharge of 0.2C, up to reaching 3V.Thereby obtain the initial stage discharge capacity.
In this manual, the 1C representative made the current value of the reference capacity discharge of battery in 1 hour, and 0.2C represents 1/5 of described current value.
The evaluation of low temperature cycle characteristics:
After the capacity evaluation test, lithium secondary battery placed carry out cyclic test under 0 ℃, wherein, constant current with 0.5C is given described battery charge, up to reaching 4.2V, under the constant voltage of 4.2V, charge then, reach 0.05C up to current value, with the constant current discharge of 0.2C, up to reaching 3V.Determine the percentage of the 50th discharge capacity after the circulation with respect to the discharge capacity of the 1st circulation.
The evaluation of room temperature cycle characteristics:
After the capacity evaluation test, lithium secondary battery placed carry out cyclic test under 25 ℃, wherein, constant current with 0.5C is given described battery charge, up to reaching 4.2V, charges under the constant voltage of 4.2V then, reach 0.05C up to current value, with the constant current discharge of 1C, up to reaching 3V.Determine the percentage of the discharge capacity before the 300th discharge capacity after the circulation is with respect to circulation experiment.
The evaluation of trickle charge characteristic:
After the capacity evaluation test, lithium secondary battery is immersed in the ethanol bath, to measure its volume.This battery is placed under 60 ℃, give described battery charge,, then under constant voltage, charged for 1 week up to reaching 4.25V with the constant current of 0.5C.Then with in this battery cooling and the immersion ethanol bath, to measure volume of battery.Variable quantity with battery volume before and after the trickle charge is that the basis is determined gas generated.
Behind the measurement gas generation, battery is placed under 25 ℃, with the discharge of the constant current of 0.2C, up to reaching 3V, thereby obtain the residual capacity after the trickle charge test.Determine the percentage of the discharge capacity before residual capacity after the trickle charge is with respect to the trickle charge test.
[embodiment (Ia-1)]
In the argon gas atmosphere of drying, with the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 97 weight portions with mix as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products with as carbonic acid (methyl) (2-methoxy ethyl) ester of 1 weight portion of compound (Ia).In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (Ia-1)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (Ia-1)).
[comparative example (Ia-1)]
The mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 98 weight portions is mixed with vinylene carbonate as 2 weight portions of unsaturated cyclic carbonate products.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ia-1)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ia-1)).
[comparative example (Ia-2)]
The mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 99 weight portions is mixed with carbonic acid (methyl) (2-methoxy ethyl) ester of 1 weight portion.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ia-2)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ia-2)).
[comparative example (Ia-3)]
In the mixture of ethylene carbonate, ethylmethyl carbonate and dimethyl carbonate (volume ratio is 2: 4: 4), dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ia-3)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ia-3)).
[embodiment (Ia-2)]
With the mixture of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate (volume ratio was in 2: 4: 4) of 96 weight portions with mix as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products and as carbonic acid (methyl) (2-methoxy ethyl) ester of 2 weight portions of compound (Ia).In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (embodiment (Ia-2) nonaqueous electrolyte).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (Ia-2)).
[embodiment (Ia-3)]
The mixture of the ethylene carbonate of 97 weight portions, ethylmethyl carbonate and dimethyl carbonate (volume ratio is 2: 4: 4) with mix as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products and as carbonic acid two (2-methoxy ethyl) ester of 1 weight portion of compound (Ia).In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (Ia-3)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (Ia-3)).
[evaluation result of battery]
To carrying out the evaluation of low temperature and room temperature cycle characteristics and the evaluation of trickle charge characteristic according to the embodiment (Ia-1)～(Ia-3) of said procedure gained and the lithium secondary battery of comparative example (Ia-1)～(Ia-3).Evaluation result is shown in table (Ia-1)～(Ia-3).
[table 1]
Table (Ia-1)
Figure G2009101614705D00591
[table 2]
Table (Ia-2)
Low temperature cycle characteristics (%) Room temperature cycle characteristics (%)
Embodiment (Ia-1) 95 89
Comparative example (Ia-1) 87 88
Comparative example (Ia-2) 94 80
Comparative example (Ia-3) 94 79
Embodiment (Ia-2) 95 88
Embodiment (Ia-3) 94 88
[table 3]
Table (Ia-3)
Gas generated (ml) Residual capacity after the trickle charge (%)
Embodiment (Ia-1) 0.48 96
Comparative example (Ia-1) 0.76 89
Comparative example (Ia-3) 0.46 88
Can obviously find out from table (Ia-1), (Ia-2), compare with the lithium secondary battery of comparative example (Ia-1)～(Ia-3), embodiment (Ia-1) even～(Ia-3) lithium secondary battery still has higher cycle characteristics at low temperatures, at room temperature keeps high cycle characteristics simultaneously.
In addition, can obviously find out from table (Ia-3), compare with the lithium secondary battery of comparative example (Ia-1)～(Ia-3), the lithium secondary battery of embodiment (Ia-1)～(Ia-3) produces the gas of minute quantity in the trickle charge process, have good battery behavior after trickle charge.
Therefore, according to definition of the present invention, as the lithium secondary battery of embodiment (Ia-1)～(Ia-3), very clearly can make such battery, promptly under room temperature and low temperature, all have excellent cycle characteristics, under high temperature, high voltage condition, stablize, and have the battery of excellent preservation characteristics.
[embodiment/comparative example group (Ib)]
Implement the program that following each embodiment and comparative example are narrated, thereby make nonaqueous electrolyte, adopt the gained nonaqueous electrolyte to prepare lithium secondary battery, and estimate the lithium secondary battery of gained.
In each embodiment and comparative example, the preparation of lithium secondary battery is identical with assessment process, explains these preparations and assessment process in advance.
[preparation of battery and assessment process]
The preparation of negative pole:
The native graphite powder of 94 weight portions is mixed with the polyvinylidene fluoride of 6 weight portions, under the situation that the N-N-methyl-2-2-pyrrolidone N-exists, make slurries.Described native graphite powder is 0.336nm through the d value of the lattice plane (002 face) of X-ray diffraction gained, crystallite size (Lc) is 652nm, ash content is 0.07 weight %, is 12 μ m according to the median diameter of laser diffraction/scattering method gained, is 7.5m according to the specific area of BET method gained 2/ g, R the value (=I of the Raman spectrum analysis gained of employing argon laser B/ I A) be 0.12, at 1570cm -1～1620cm -1The half breadth at the peak in the scope is 19.9cm -1The gained slurries are coated on the surface that thickness is the Copper Foil of 12 μ m equably, dry and extruding, the density that makes negative electrode active material layer is 1.6g/cm 3Thereby, make negative pole.
Anodal preparation:
LiCoO with 85 weight portions 2, the carbon black of 6 weight portions and 9 weight portions polyvinylidene fluoride (trade mark is " KF-1000 ", and society produces by the Wu Yu chemistry) mix, under the situation that the N-N-methyl-2-2-pyrrolidone N-exists, make slurries.The gained slurries are coated on two surfaces that thickness is the aluminium foil of 15 μ m equably, dry and extruding, the density that makes positive electrode active material layer is 3.0g/cm 3Thereby, make positive pole.
The preparation of lithium secondary battery:
The positive pole that obtains like this is in the same place according to the sequential cascade of negative pole, dividing plate, positive pole, dividing plate and negative pole with negative pole and the dividing plate of being made by polyethylene, to make cell device.This cell device inserted by the two sides all be coated with in the stacked film formed bag of aluminium (thickness is 40 μ m) of resin bed, the end of described positive pole and negative pole stretches out this bag.In described bag, inject by following each embodiment and the prepared nonaqueous electrolyte of comparative example, vacuum seal then, thus make plate battery (lithium secondary battery of each embodiment and comparative example).
Capacity is estimated:
Each embodiment and the described lithium secondary battery of comparative example are clipped between the glass plate, described electrode more closely is in contact with one another, carry out following program then.At 25 ℃, give described battery charge with constant current corresponding to 0.2C, up to reaching 4.2V, the constant current with 0.2C discharges then, up to reaching 3V.Described step is carried out three circulations to stablize this battery.In the 4th circulation, give described battery charge with the constant current of 0.5C, up to reaching 4.2V, under the constant voltage of 4.2V, charge then, reach 0.05C up to current value, with the constant current discharge of 0.2C, up to reaching 3V.Thereby obtain the initial stage discharge capacity.
In this manual, the 1C representative made the current value of the reference capacity discharge of battery in 1 hour, and 0.2C represents 1/5 of described current value.
The evaluation of trickle charge characteristic:
After the capacity evaluation test, lithium secondary battery is immersed in the ethanol bath, to measure its volume.This battery is placed under 60 ℃, give described battery charge,, then under constant voltage, charge, continued for 1 week up to reaching 4.25V with the constant current of 0.5C.
Then with in this battery cooling and the immersion ethanol bath, to measure volume of battery.Variable quantity with battery volume before and after the trickle charge is that the basis is determined gas generated.
Behind the measurement gas generating capacity, battery is placed under 25 ℃, with the discharge of the constant current of 0.2C, up to reaching 3V, thereby obtain the residual capacity after the trickle charge test.The percentage of the discharge capacity of the residual capacity of determining trickle charge before with respect to the trickle charge test.
The evaluation of high temperature preservation characteristics:
After the capacity evaluation test, charge to lithium secondary battery with the constant current of 0.5C, up to reaching 4.2V, under the constant voltage of 4.2V, charge then, reach 0.05C up to current value, then preserved 3 days down at 85 ℃.Subsequently, after this battery fully cooled off,,, up to reaching 3V, thereby obtain preserving residual capacity after the test with the constant current discharge of 0.2C at 25 ℃.Definite residual capacity of preserving after testing is tested the percentage of preceding discharge capacity with respect to preservation.
The evaluation of cycle characteristics:
After the capacity evaluation test, lithium secondary battery placed carry out cyclic test under 25 ℃, wherein, constant current with 0.5C is given described battery charge, up to reaching 4.2V, charges under the constant voltage of 4.2V then, reach 0.05C up to current value, with the constant current discharge of 1C, up to reaching 3V.Determine the percentage of the discharge capacity before the 300th discharge capacity after the circulation is with respect to cyclic test.
[embodiment (Ib-1)]
In the argon gas atmosphere of drying, with the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 96 weight portions with mix as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products with as the Fumette of 2 weight portions of compound (Ib).In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (Ib-1)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (Ib-1)).
[embodiment (Ib-2)]
In the argon gas atmosphere of drying, with the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 97 weight portions with mix as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products with as the Fumette of 1 weight portion of compound (Ib).In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (Ib-2)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (Ib-2)).
[embodiment (Ib-3)]
In the argon gas atmosphere of drying, with the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 97 weight portions with mix as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products with as the second sulfuryl fluoride of 1 weight portion of compound (Ib).In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (Ib-3)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (Ib-3)).
[embodiment (Ib-4)]
In the argon gas atmosphere of drying, with the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 97 weight portions with mix as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products with as third sulfuryl fluoride of 1 weight portion of compound (Ib).In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (Ib-4)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (Ib-4)).
[embodiment (Ib-5)]
In the argon gas atmosphere of drying, with the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 97.5 weight portions with mix as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products with as the Fumette of 0.5 weight portion of compound (Ib).In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (Ib-5)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (Ib-5)).
[comparative example (Ib-1)]
The mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 98 weight portions is mixed with vinylene carbonate as 2 weight portions of unsaturated cyclic carbonate products.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ib-1)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ib-1)).
[comparative example (Ib-2)]
With the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 96 weight portions with mix as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products and as the benzene sulfonyl fluorine of 2 weight portions of additive.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ib-2)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ib-2)).
[comparative example (Ib-3)]
With the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 96 weight portions with mix as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products and as the toluenesulfonyl fluoride of 2 weight portions of additive.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ib-3)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ib-3)).
[comparative example (Ib-4)]
In the argon gas atmosphere of drying, the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 98 weight portions is mixed with Fumette as 2 weight portions of compound (Ib).In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ib-4)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ib-4)).
[evaluation result of battery]
To carrying out the evaluation of trickle charge characteristic, high temperature preservation characteristics and cycle characteristics according to the embodiment (Ib-1)～(Ib-5) of said procedure gained and the lithium secondary battery of comparative example (Ib-1)～(Ib-4).Evaluation result is as table (Ib-1) and table (Ib-2).
[table 4]
Table (Ib-1)
Figure G2009101614705D00651
[table 5]
Table (Ib-2)
Gas generated (ml) Residual capacity after the trickle charge (%) Residual capacity (%) after high temperature is preserved Cycle characteristics (%)
Embodiment (Ib-1) 0.59 96 80 88
Embodiment (Ib-2) 0.60 96 80 89
Embodiment (Ib-3) 0.57 95 81 89
Embodiment (Ib-4) 0.55 95 82 -
Embodiment (Ib-5) 0.60 95 79 -
Comparative example (Ib-1) 0.76 89 75 88
Comparative example (Ib-2) 0.73 88 67 -
Comparative example (Ib-3) 1.28 83 63 -
Comparative example (Ib-4) 0.52 90 73 79
Can obviously find out from table (Ib-1) and table (Ib-2), compare with the lithium secondary battery of comparative example (Ib-1)～(Ib-4), the lithium secondary battery of embodiment (Ib-1)～(Ib-5) gas generated little under the trickle charge state, and have battery behavior after the good trickle charge, high temperature is preserved back battery behavior and cycle characteristics.
[embodiment/comparative example group (Ic)]
Implement the program that following each embodiment and comparative example are narrated, thereby make nonaqueous electrolyte, adopt the gained nonaqueous electrolyte to prepare lithium secondary battery, and estimate the lithium secondary battery of gained.
In each embodiment and comparative example, the preparation of lithium secondary battery is identical with assessment process, explains these preparations and assessment process in advance.
[preparation of battery and assessment process]
Anodal preparation:
LiCoO with 85 weight portions 2, the carbon black of 6 weight portions and 9 weight portions polyvinylidene fluoride (trade mark is " KF-1000 ", and society produces by the Wu Yu chemistry) mix, under the situation that the N-N-methyl-2-2-pyrrolidone N-exists, make slurries.The gained slurries are coated on the two sides that thickness is the aluminium foil of 15 μ m equably, dry and extruding, the density that makes positive electrode active material layer is 3.0g/cm 3Thereby, make positive pole.
The preparation of negative pole:
The native graphite powder of 94 weight portions is mixed with the polyvinylidene fluoride of 6 weight portions, under the situation that the N-N-methyl-2-2-pyrrolidone N-exists, make slurries.Described native graphite powder is 0.336nm through the d value of the lattice plane (002 face) of X-ray diffraction gained, crystallite size (Lc) is 652nm, ash content is 0.07 weight %, is 12 μ m according to the median diameter of laser diffraction/scattering method gained, is 7.5m according to the specific area of BET method gained 2/ g, R the value (=I of the Raman spectrum analysis gained of employing argon laser B/ I A) be 0.12, at 1570cm -1～1620cm -1The half breadth at the peak in the scope is 19.9cm -1The gained slurries are coated on the one side that thickness is the Copper Foil of 12 μ m equably, dry and extruding, the density that makes negative electrode active material layer is 1.6g/cm 3Thereby, make negative pole.
The preparation of lithium secondary battery:
The dividing plate made from the positive pole that obtains like this and negative pole and by polyethylene forces together according to the sequential layer of negative pole, dividing plate, positive pole, dividing plate and negative pole, to make cell device.This cell device inserted by the two sides all be coated with in the stacked film formed bag of aluminium (thickness is 40 μ m) of resin bed, the end of described positive pole and negative pole stretches out this bag.In described bag, inject by following each embodiment and the prepared nonaqueous electrolyte of comparative example, vacuum seal then, thus make plate battery (lithium secondary battery of each embodiment and comparative example).
[initial stage evaluation]
Each embodiment and the described lithium secondary battery of comparative example are clipped between the glass plate, and it is closer that described electrode is in contact with one another, and carries out following program then.At 25 ℃, give described battery charge with the constant current of 0.2C, up to reaching 4.2V, the constant current with 0.2C discharges then, up to reaching 3V.Described step is carried out three circulations to stablize this battery.In this manual, the 1C representative made the current value of the reference capacity discharge of battery in 1 hour, and 0.2C represents 1/5 of described current value.Subsequently, measure this volume of battery according to Archimedes's method.
[evaluation of trickle charge characteristic]
Lithium secondary battery trickle charge after giving evaluation in the early stage under the constant voltage of 4.3V 7 days keeps 60 ℃ steady temperature simultaneously.Make the fully cooling naturally of this battery, according to volume of battery after Archimedes's method measurement trickle charge.The value of gained and initial stage estimate in the difference of battery volume be gas generated in the trickle charge process.Gas generated by reducing, can realize suppressing the battery design of the expansion in the trickle charge process.Then, give this battery discharge,, then,,, under the constant voltage of 4.2V, charge, reach 0.05C up to current value up to reaching 4.2V with the constant current charge of 0.5C up to reaching 3V with the constant current of 0.2C.Give this battery discharge with the constant current of 1C then, up to reaching 3V, the capacity when obtaining 1C discharge after the trickle charge.Capacity when increasing the 1C discharge can realize having suppressed the battery design of deterioration.
[embodiment (Ic-1)]
In the argon gas atmosphere of drying, to mix with vinylene carbonate (VC) as the mixture (volume ratio is 1: 2) of the ethylene carbonate of 975 weight portions of non-aqueous solvent and ethylmethyl carbonate, then with the making up of 5 weight portions by the represented compound of above-mentioned chemical formula (7) (additive B 1) as 20 weight portions of unsaturated cyclic carbonate products.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (Ic-1)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (Ic-1)).
[embodiment (Ic-2)]
In the argon gas atmosphere of drying, to mix with vinylene carbonate (VC) as the mixture (volume ratio is 1: 2) of the ethylene carbonate of 975 weight portions of non-aqueous solvent and ethylmethyl carbonate, then with the making up of 5 weight portions by the represented compound of above-mentioned chemical formula (8) (additive B 2) as 20 weight portions of unsaturated cyclic carbonate products.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (Ic-2)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (Ic-2)).
[embodiment (Ic-3)]
In the argon gas atmosphere of drying, to mix with vinylene carbonate (VC) as the mixture (volume ratio is 1: 2) of the ethylene carbonate of 975 weight portions of non-aqueous solvent and ethylmethyl carbonate, then with the making up of 5 weight portions by the represented compound of above-mentioned chemical formula (11) (additive B 3) as 20 weight portions of unsaturated cyclic carbonate products.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (Ic-3)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (Ic-3)).
[embodiment (Ic-4)]
In the argon gas atmosphere of drying, to mix with vinylene carbonate (VC) as the mixture of the ethylene carbonate of 975 weight portions of non-aqueous solvent and ethylmethyl carbonate (volume ratio is 1: 2), then with the making up of 5 weight portions by the represented compound of above-mentioned chemical formula (12) (additive B 4) as 20 weight portions of unsaturated cyclic carbonate products.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (Ic-4)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (Ic-4)).
[embodiment (Ic-5)]
In the argon gas atmosphere of drying, to mix with vinylene carbonate (VC) as the mixture (volume ratio is 1: 2) of the ethylene carbonate of 975 weight portions of non-aqueous solvent and ethylmethyl carbonate, then with the making up of 5 weight portions by the represented compound of above-mentioned chemical formula (13) (additive B 5) as 20 weight portions of unsaturated cyclic carbonate products.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (Ic-5)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (Ic-5)).
[embodiment (Ic-6)]
In the argon gas atmosphere of drying, to mix with vinylene carbonate (VC) as the mixture (volume ratio is 1: 2) of the ethylene carbonate of 975 weight portions of non-aqueous solvent and ethylmethyl carbonate, then with the making up of 5 weight portions by the represented compound of above-mentioned chemical formula (19) (additive B 6) as 20 weight portions of unsaturated cyclic carbonate products.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (Ic-6)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (Ic-6)).
[embodiment (Ic-7)]
In the argon gas atmosphere of drying, to mix with vinylene carbonate (VC) as the mixture (volume ratio is 1: 2) of the ethylene carbonate of 975 weight portions of non-aqueous solvent and ethylmethyl carbonate, then with the making up of 5 weight portions by the represented compound of above-mentioned chemical formula (20) (additive B 7) as 20 weight portions of unsaturated cyclic carbonate products.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (Ic-7)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (Ic-7)).
[comparative example (Ic-1)]
In the argon gas atmosphere of drying, will be as the ethylene carbonate of non-aqueous solvent and the mixture of ethylmethyl carbonate (volume ratio is 1: 2) and LiPF as electrolytical intensive drying 6Mix and dissolving described LiPF 6Ratio be 1.0mol/L.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ic-1)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ic-1)).
[comparative example (Ic-2)]
In the argon gas atmosphere of drying, will mix with vinylene carbonate (VC) as the mixture (volume ratio is 1: 2) of the ethylene carbonate of 980 weight portions of non-aqueous solvent and ethylmethyl carbonate as 20 weight portions of unsaturated cyclic carbonate products.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ic-2)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ic-2)).
[comparative example (Ic-3)]
In the argon gas atmosphere of drying, will be as ethylene carbonate and the mixture (volume ratio is 1: 2) of ethylmethyl carbonate and mixing of 5 weight portions of 995 weight portions of non-aqueous solvent by the represented compound of above-mentioned chemical formula (7) (additive B 1).In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ic-3)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ic-3)).
[comparative example (Ic-4)]
In the argon gas atmosphere of drying, will be as ethylene carbonate and the mixture (volume ratio is 1: 2) of ethylmethyl carbonate and mixing of 5 weight portions of 995 weight portions of non-aqueous solvent by the represented compound of above-mentioned chemical formula (8) (additive B 2).In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ic-4)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ic-4)).
[comparative example (Ic-5)]
In the argon gas atmosphere of drying, will be as ethylene carbonate and the mixture (volume ratio is 1: 2) of ethylmethyl carbonate and mixing of 5 weight portions of 995 weight portions of non-aqueous solvent by the represented compound of above-mentioned chemical formula (11) (additive B 3).In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ic-5)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ic-5)).
[comparative example (Ic-6)]
In the argon gas atmosphere of drying, will be as ethylene carbonate and the mixture (volume ratio is 1: 2) of ethylmethyl carbonate and mixing of 5 weight portions of 995 weight portions of non-aqueous solvent by the represented compound of above-mentioned chemical formula (12) (additive B 4).In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ic-6)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ic-6)).
[comparative example (Ic-7)]
In the argon gas atmosphere of drying, will be as ethylene carbonate and the mixture (volume ratio is 1: 2) of ethylmethyl carbonate and mixing of 5 weight portions of 995 weight portions of non-aqueous solvent by the represented compound of above-mentioned chemical formula (13) (additive B 5).In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ic-7)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ic-7)).
[comparative example (Ic-8)]
In the argon gas atmosphere of drying, will be as ethylene carbonate and the mixture (volume ratio is 1: 2) of ethylmethyl carbonate and mixing of 5 weight portions of 995 weight portions of non-aqueous solvent by the represented compound of above-mentioned chemical formula (19) (additive B 6).In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ic-8)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ic-8)).
[comparative example (Ic-9)]
In the argon gas atmosphere of drying, will be as ethylene carbonate and the mixture (volume ratio is 1: 2) of ethylmethyl carbonate and mixing of 5 weight portions of 995 weight portions of non-aqueous solvent by the represented compound of above-mentioned chemical formula (20) (additive B 7).In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (Ic-9)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (Ic-9)).
[evaluation result of battery]
To carrying out the evaluation of trickle charge characteristic according to the embodiment (Ic-1)～(Ic-7) of said procedure gained and the lithium secondary battery of comparative example (Ic-1)～(Ic-9).Evaluation result is as table (Ic-1)～(Ic-7).
[table 6]
Table (Ic-1)
(effect that VC and additive B 1 are used in combination)
Figure G2009101614705D00711
[table 7]
Table (Ic-2)
(effect that VC and additive B 2 are used in combination)
Figure G2009101614705D00712
Figure G2009101614705D00721
[table 8]
Table (Ic-3)
(effect that VC and additive B 3 are used in combination)
Figure G2009101614705D00731
[table 9]
Table (Ic-4)
(effect that VC and additive B 4 are used in combination)
Figure G2009101614705D00732
[table 10]
Table (Ic-5)
(effect that VC and additive B 5 are used in combination)
Figure G2009101614705D00733
[table 11]
Table (Ic-6)
(effect that VC and additive B 6 are used in combination)
Figure G2009101614705D00741
[table 12]
Table (Ic-7)
(effect that VC and additive B 7 are used in combination)
Figure G2009101614705D00742
Obtain to draw a conclusion from table (Ic-1).
(Ic-1) compares with the comparative example that does not use VC, and in comparative example (Ic-2), the use of VC has increased the gas flow after the trickle charge.This is because VC is easily oxidized by inference.As a result, the interpolation of VC has reduced the 1C capacity after the trickle charge.
And, compare with the comparative example (Ic-1) that does not use additive B 1 (the represented compound of chemical formula (7)), in comparative example (Ic-3), the use of additive B 1 has suppressed the gas flow after the trickle charge.This is because additive B 1 has suppressed the decomposition of electrolyte by inference.On the other hand, the 1C capacity after the trickle charge descends.This is because the impedance of formed coverlay has increased by inference.
Therefore, when using A composition or B composition separately, battery behavior can worsen.
In contrast, with comparative example (Ic-1)～(Ic-3) compare, in embodiment (Ic-1), use A composition and B composition obviously to improve the 1C capacity after the trickle charge simultaneously.This is because the B composition has suppressed the decomposition of A composition by inference, and the coverlay of A composition formation has simultaneously suppressed the formation of B composition coverlay, the result, even in the trickle charge process, battery also is stable.
Identical with table (Ic-1), also can obviously find out that from table use A composition or B to become branch to make characteristic degradation separately, these compositions is used in combination the 1C capacity that can obviously improve after the trickle charge simultaneously (Ic-2)～(Ic-7).
[embodiment/comparative example group (IIa)]
Implement the program that following each embodiment and comparative example are narrated, thereby make nonaqueous electrolyte, adopt the gained nonaqueous electrolyte to prepare lithium secondary battery, and estimate the lithium secondary battery of gained.
In each embodiment and comparative example, the preparation of lithium secondary battery is identical with assessment process, explains these preparations and assessment process in advance.
[preparation of battery and assessment process]
The preparation of negative pole:
The native graphite powder of 94 weight portions is mixed with the polyvinylidene fluoride of 6 weight portions, under the situation that the N-N-methyl-2-2-pyrrolidone N-exists, make slurries.Described native graphite powder is 0.336nm through the d value of the lattice plane (002 face) of X-ray diffraction gained, crystallite size (Lc) is 652nm, ash content is 0.07 weight %, is 12 μ m according to the median diameter of laser diffraction/scattering method gained, is 7.5m according to the specific area of BET method gained 2/ g, R the value (=I of the Raman spectrum analysis gained of employing argon laser B/ I A) be 0.12, at 1570cm -1～1620cm -1The half breadth at the peak in the scope is 19.9cm -1The gained slurries are coated on the surface that thickness is the Copper Foil of 12 μ m equably, dry and extruding, the density that makes negative electrode active material layer is 1.6g/cm 3Thereby, make negative pole.
Anodal preparation:
LiCoO with 85 weight portions 2, the carbon black of 6 weight portions and 9 weight portions polyvinylidene fluoride (trade mark is " KF-1000 ", and society produces by the Wu Yu chemistry) mix, under the situation that the N-N-methyl-2-2-pyrrolidone N-exists, make slurries.The gained slurries are coated on two surfaces that thickness is the aluminium foil of 15 μ m equably, dry and extruding, the density that makes positive electrode active material layer is 3.0g/cm 3Thereby, make positive pole.
The preparation of lithium secondary battery:
The positive pole that obtains like this is in the same place according to the sequential cascade of negative pole, dividing plate, positive pole, dividing plate and negative pole with negative pole and the dividing plate of being made by polyethylene, to make cell device.This cell device inserted by the two sides all be coated with in the stacked film formed bag of aluminium (thickness is 40 μ m) of resin bed, the end of described positive pole and negative pole stretches out this bag.In described bag, inject by following each embodiment and the prepared nonaqueous electrolyte of comparative example, vacuum seal then, thus make plate battery (lithium secondary battery of each embodiment and comparative example).
Capacity is estimated:
Each embodiment and the described lithium secondary battery of comparative example are clipped between the glass plate, described electrode more closely is in contact with one another, carry out following program then.At 25 ℃, give described battery charge with constant current corresponding to 0.2C, up to reaching 4.2V, the constant current with 0.2C discharges then, up to reaching 3V.Described step is carried out three circulations to stablize this battery.In the 4th circulation, give described battery charge with the constant current of 0.5C, up to reaching 4.2V, under the constant voltage of 4.2V, charge then, reach 0.05C up to current value, with the constant current discharge of 0.2C, up to reaching 3V.Thereby obtain the initial stage discharge capacity.
In this manual, the 1C representative made the current value of the reference capacity discharge of battery in 1 hour, and 0.2C represents 1/5 of described current value.
The evaluation of trickle charge characteristic:
After the capacity evaluation test, lithium secondary battery is immersed in the ethanol bath, to measure its volume.This battery is placed under 60 ℃, give described battery charge,, then under constant voltage, charged for 1 week up to reaching 4.25V with the constant current of 0.5C.
Then with in this battery cooling and the immersion ethanol bath, to measure volume of battery.Variable quantity with battery volume before and after the trickle charge is that the basis is determined gas generated.
Behind the measurement gas generation, battery is placed under 25 ℃, with the discharge of the constant current of 0.2C, up to reaching 3V, thereby obtain the residual capacity after the trickle charge test.Determine the percentage of the discharge capacity before residual capacity after the trickle charge is with respect to the trickle charge test.
The evaluation of high temperature preservation characteristics:
After the capacity evaluation test, charge to lithium secondary battery with the constant current of 0.5C, up to reaching 4.2V, under the constant voltage of 4.2V, charge then, reach 0.05C up to current value, then preserved 3 days down at 85 ℃.Subsequently, this battery is fully cooled off,,, up to reaching 3V, thereby obtain preserving residual capacity after the test with the discharge of the constant current of 0.2C at 25 ℃.Definite residual capacity of preserving after testing is tested the percentage of preceding discharge capacity with respect to preservation.
The evaluation of cycle characteristics:
After the capacity evaluation test, lithium secondary battery placed carry out cyclic test under 25 ℃, wherein, constant current with 0.5C is given described battery charge, up to reaching 4.2V, charges under the constant voltage of 4.2V then, reach 0.05C up to current value, with the constant current discharge of 1C, up to reaching 3V.Determine the percentage of the discharge capacity before the 300th discharge capacity after the circulation is with respect to cyclic test.
[embodiment (IIa-1)]
In the argon gas atmosphere of drying, with the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 97 weight portions with as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products with as 2 of 1 weight portion of compound (IIa), 4,8,10-four oxygen spiral shell [5.5] hendecanes mix.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (IIa-1)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (IIa-1)).
[embodiment (IIa-2)]
With the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 97 weight portions with as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products with as 3 of 1 weight portion of compound (IIa), 9-divinyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes mix.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (IIa-2)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (IIa-2)).
[embodiment (IIa-3)]
With the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 97.5 weight portions with as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products with as 3 of 0.5 weight portion of compound (IIa), 9-divinyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes mix.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (IIa-3)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (IIa-3)).
[embodiment (IIa-4)]
With the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 97.8 weight portions with as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products with as 3 of 0.2 weight portion of compound (IIa), 9-divinyl-2,4,8,10-four oxygen spiral shell [5.5] hendecanes mix.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (IIa-4)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (IIa-4)).
[comparative example (IIa-1)]
The mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 98 weight portions is mixed with vinylene carbonate as 2 weight portions of unsaturated cyclic carbonate products.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (IIa-1)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (IIa-1)).
[comparative example (IIa-2)]
With the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 97 weight portions with as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products and as 1 of 1 weight portion of additive, the 3-dioxane mixes.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (IIa-2)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (IIa-2)).
[evaluation result of battery]
Lithium secondary battery according to the embodiment (IIa-1)～(IIa-4) of said procedure gained and comparative example (IIa-1), (IIa-2) is carried out the evaluation of trickle charge characteristic, high temperature preservation characteristics and cycle characteristics.Evaluation result such as following table (IIa).
[table 13]
Table (IIa)
Gas generated (ml) Residual capacity after the trickle charge (%) Residual capacity (%) after high temperature is preserved Cycle characteristics (%)
Embodiment (IIa-1) 0.40 94 82 88
Embodiment (IIa-2) 0.45 96 81 92
Embodiment (IIa-3) 0.48 92 80 93
Embodiment (IIa-4) 0.49 92 81 91
Comparative example (IIa-1) 0.76 89 75 88
Comparative example (IIa-2) 0.65 88 72 87
Can obviously find out from table (IIa), compare with the lithium secondary battery of comparative example (IIa-1), (IIa-2), the lithium secondary battery of embodiment (IIa-1)～(IIa-4) produces the gas of minute quantity in the trickle charge process, and has the battery behavior after the good trickle charge, battery behavior and the cycle characteristics after the high temperature preservation.
[embodiment/comparative example group (IIb)]
Implement the program that following each embodiment and comparative example are narrated, thereby make nonaqueous electrolyte, adopt the gained nonaqueous electrolyte to prepare lithium secondary battery, and estimate the lithium secondary battery of gained.
In each embodiment and comparative example, the preparation of lithium secondary battery is identical with assessment process, explains these preparations and assessment process in advance.
[preparation of battery and assessment process]
The preparation of negative pole:
The native graphite powder of 94 weight portions is mixed with the polyvinylidene fluoride of 6 weight portions, under the situation that the N-N-methyl-2-2-pyrrolidone N-exists, make slurries.Described native graphite powder is 0.336nm through the d value of the lattice plane (002 face) of X-ray diffraction gained, crystallite size (Lc) is 652nm, ash content is 0.07 weight %, is 12 μ m according to the median diameter of laser diffraction/scattering method gained, is 7.5m according to the specific area of BET method gained 2/ g, R the value (=I of the Raman spectrum analysis gained of employing argon laser B/ I A) be 0.12, at 1570cm -1～1620cm -1The half breadth at the peak in the scope is 19.9cm -1The gained slurries are coated on the surface that thickness is the Copper Foil of 12 μ m equably, dry and extruding, the density that makes negative electrode active material layer is 1.6g/cm 3Thereby, make negative pole.
Anodal preparation:
LiCoO with 85 weight portions 2, the carbon black of 6 weight portions and 9 weight portions polyvinylidene fluoride (trade mark is " KF-1000 ", and society produces by the Wu Yu chemistry) mix, under the situation that the N-N-methyl-2-2-pyrrolidone N-exists, make slurries.The gained slurries are coated on two surfaces that thickness is the aluminium foil of 15 μ m equably, dry and extruding, the density that makes positive electrode active material layer is 3.0g/cm 3Thereby, make positive pole.
The preparation of lithium secondary battery:
The positive pole that obtains like this is in the same place according to the sequential cascade of negative pole, dividing plate, positive pole, dividing plate and negative pole with negative pole and the dividing plate of being made by polyethylene, to make cell device.This cell device inserted by the two sides all be coated with in the stacked film formed bag of aluminium (thickness is 40 μ m) of resin bed, the end of described positive pole and negative pole stretches out this bag.In described bag, inject by following each embodiment and the prepared nonaqueous electrolyte of comparative example, vacuum seal then, thus make plate battery (lithium secondary battery of each embodiment and comparative example).
Capacity is estimated:
Each embodiment and the described lithium secondary battery of comparative example are clipped between the glass plate, described electrode more closely is in contact with one another, carry out following program then.At 25 ℃, give described battery charge with constant current corresponding to 0.2C, up to reaching 4.2V, the constant current with 0.2C discharges then, up to reaching 3V.Described step is carried out three circulations to stablize this battery.In the 4th circulation, give described battery charge with the constant current of 0.5C, up to reaching 4.2V, under the constant voltage of 4.2V, charge then, reach 0.05C up to current value, with the constant current discharge of 0.2C, up to reaching 3V.Thereby obtain the initial stage discharge capacity.
In this manual, the 1C representative made the current value of the reference capacity discharge of battery in 1 hour, and 0.2C represents 1/5 of described current value.
The evaluation of trickle charge characteristic:
After the capacity evaluation test, lithium secondary battery is immersed in the ethanol bath, to measure its volume.This battery is placed under 60 ℃, give described battery charge,, then under constant voltage, charged for 1 week up to reaching 4.25V with the constant current of 0.5C.
Then with in this battery cooling and the immersion ethanol bath, to measure volume of battery.Variable quantity with battery volume before and after the trickle charge is that the basis is determined gas generated.
Behind the measurement gas generation, battery is placed under 25 ℃, with the discharge of the constant current of 0.2C, up to reaching 3V, thereby obtain the residual capacity after the trickle charge test.Determine the percentage of the discharge capacity before residual capacity after the trickle charge is with respect to the trickle charge test.
The evaluation of high temperature preservation characteristics:
After the capacity evaluation test, charge to lithium secondary battery with the constant current of 0.5C, up to reaching 4.2V, under the constant voltage of 4.2V, charge then, reach 0.05C up to current value, then preserved 3 days down at 85 ℃.Subsequently, this battery is fully cooled off,,, up to reaching 3V, thereby obtain preserving residual capacity after the test with the discharge of the constant current of 0.2C at 25 ℃.Definite residual capacity of preserving after testing is tested the percentage of preceding discharge capacity with respect to preservation.
[embodiment (IIb-1)]
In the argon gas atmosphere of drying; with the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 97 weight portions with as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products and as 1 of 1 weight portion of compound (IIb), 3-two (fluorosulfonyl) propane mixes.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (IIb-1)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (IIb-1)).
[embodiment (IIb-2)]
In the argon gas atmosphere of drying; with the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 97 weight portions with as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products and as 1 of 1 weight portion of compound (IIb); 3-two (fluorosulfonyl)-1; 1; 2; 2,3, the 3-HFC-236fa is mixed.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (IIb-2)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (IIb-2)).
[embodiment (IIb-3)]
In the argon gas atmosphere of drying; with the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 97.5 weight portions with as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products and as 1 of 0.5 weight portion of compound (IIb), 3-two (fluorosulfonyl) propane mixes.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (IIb-3)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (IIb-3)).
[comparative example (IIb-1)]
The mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 98 weight portions is mixed with vinylene carbonate as 2 weight portions of unsaturated cyclic carbonate products.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (IIb-1)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (IIb-1)).
[comparative example (IIb-2)]
With the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 96 weight portions with mix as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products and as the benzene sulfonyl fluorine of 2 weight portions of additive.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (IIb-2)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (IIb-2)).
[comparative example (IIb-3)]
With the mixture (volume ratio is 2: 4: 4) of ethylene carbonate, ethylmethyl carbonate and the dimethyl carbonate of 96 weight portions with mix as the vinylene carbonate of 2 weight portions of unsaturated cyclic carbonate products and as the toluenesulfonyl fluoride of 2 weight portions of additive.In the mixture of gained, dissolve the LiPF of intensive drying in the ratio of 1.0mol/L 6Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (IIb-3)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (IIb-3)).
[evaluation result of battery]
To carrying out the evaluation of trickle charge characteristic and high temperature preservation characteristics according to the embodiment (IIb-1)～(IIb-3) of said procedure gained and the lithium secondary battery of comparative example (IIb-1)～(IIb-3).Evaluation result such as following table (IIb).
[table 14]
Table (IIb)
Figure G2009101614705D00831
Can obviously find out from table (IIb), compare with the lithium secondary battery of comparative example (IIb-1)～(IIb-3), the lithium secondary battery of embodiment (IIb-1)～(IIb-3) produces the gas of minute quantity in the trickle charge process, and has the battery behavior after battery behavior after the good trickle charge and high temperature are preserved.
[embodiment/comparative example group (IIc)]
Implement the program that following each embodiment and comparative example are narrated, thereby make nonaqueous electrolyte, adopt the gained nonaqueous electrolyte to prepare lithium secondary battery, and estimate the lithium secondary battery of gained.
In each embodiment and comparative example, the preparation of lithium secondary battery is identical with assessment process, explains these preparations and assessment process in advance.
[preparation of battery and assessment process]
The preparation of negative pole:
The native graphite powder of 94 weight portions is mixed with the polyvinylidene fluoride of 6 weight portions, under the situation that the N-N-methyl-2-2-pyrrolidone N-exists, make slurries.Described native graphite powder is 0.336nm through the d value of the lattice plane (002 face) of X-ray diffraction gained, crystallite size (Lc) is 652nm, ash content is 0.07 weight %, is 12 μ m according to the median diameter of laser diffraction/scattering method gained, is 7.5m according to the specific area of BET method gained 2/ g, R the value (=I of the Raman spectrum analysis gained of employing argon laser B/ I A) be 0.12, at 1570cm -1～1620cm -1The half breadth at the peak in the scope is 19.9cm -1The gained slurries are coated on the surface that thickness is the Copper Foil of 12 μ m equably, dry and extruding, the density that makes the negative electrode active layer is 1.6g/cm 3The plate of gained is cut into the shape of 3.5cm * 2.5cm, thereby makes negative pole.
Anodal preparation:
LiCoO with 85 weight portions 2, the carbon black of 6 weight portions and 9 weight portions polyvinylidene fluoride (trade mark is " KF-1000 ", and society produces by the Wu Yu chemistry) mix, under the situation that the N-N-methyl-2-2-pyrrolidone N-exists, make slurries.The gained slurries are coated on two surfaces that thickness is the aluminium foil of 15 μ m equably, dry and extruding, the density that makes positive electrode active material layer is 3.0g/cm 3, the plate of gained is cut into the shape of 3.5cm * 2.5cm, thereby makes positive pole.
The preparation of lithium secondary battery:
The positive pole that obtains like this is in the same place according to the sequential cascade of negative pole, dividing plate, positive pole, dividing plate and negative pole with negative pole and the dividing plate of being made by polyethylene, to make cell device.This cell device inserted by the two sides all be coated with in the stacked film formed bag of aluminium (thickness is 40 μ m) of resin bed, the end of described positive pole and negative pole stretches out this bag.In described bag, inject by following each embodiment and the prepared nonaqueous electrolyte of comparative example, vacuum seal then, thus make plate battery (lithium secondary battery of each embodiment and comparative example).
Initial stage is estimated:
The described lithium secondary battery of each embodiment and comparative example is clipped between the glass plate, and it is closer that described electrode is in contact with one another, and carries out following program then.At 25 ℃, give described battery charge with constant current corresponding to 0.2C, up to reaching 4.2V, the constant current with 0.2C discharges then, up to reaching 3V.Described step is carried out three circulations to stablize this battery.In this manual, the 1C representative made the current value of the reference capacity discharge of battery in 1 hour, and 0.2C represents 1/5 of described current value.Subsequently, measure this volume of battery according to Archimedes's method.
The evaluation of trickle charge characteristic:
After estimating in the early stage, under the constant voltage of 4.3V, give described lithium secondary battery trickle charge 7 days, keep 60 ℃ steady temperature simultaneously.Make the fully cooling naturally of this battery, according to volume of battery after Archimedes's method measurement trickle charge.The volume of gained and initial stage estimate in the difference of battery volume be gas generated in the trickle charge process.Gas generated by reducing, can realize suppressing the battery design of the expansion in the trickle charge process.Then, give this battery discharge,, then,,, under the constant voltage of 4.2V, charge, reach 0.05C up to current value up to reaching 4.2V with the constant current charge of 0.5C up to reaching 3V with the constant current of 0.2C.Give this battery discharge with the constant current of 1C then, up to reaching 3V, the capacity when obtaining 1C discharge after the trickle charge.Capacity when increasing the 1C discharge can realize having suppressed the battery design of deterioration.
The evaluation of high temperature preservation characteristics:
After estimating in the early stage, charge to lithium secondary battery,, under the constant voltage of 4.2V, charge then, reach 0.05C, preserved 72 hours down at 85 ℃ afterwards up to current value up to reaching 4.2V with the constant current of 0.5C.Subsequently, with the fully cooling naturally of this battery, measure high temperature according to Archimedes's method and preserve the back volume of battery.The volume of gained is gas generated with the difference of preserving preceding volume.Gas generated by reducing, can realize suppressing the battery design of the expansion in the preservation process.Then, with the constant current charge of 0.5C, up to reaching 4.2V, then, with the constant-potential charge of 4.2V, up to the current value that reaches 0.05C.Then with the discharge of the constant current of 1.0C, up to reaching 3V, the capacity when obtaining the 1C discharge after high temperature is preserved.Capacity when increasing the 1C discharge can realize having suppressed the battery design of deterioration.
The evaluation of discharge preservation characteristics:
After estimating in the early stage, lithium secondary battery is preserved and is monitored the variations of residual voltage under 60 ℃.Residual voltage changes to the time that 1V experiences from 3V and is confirmed as the holding time of discharging.So battery less deterioration in discharge process that the discharge holding time is long is just more stable.
[embodiment (IIc-1)]
In the argon gas atmosphere of drying, will be as the mixture (volume ratio is 1: 2) of the ethylene carbonate of 998 weight portions of non-aqueous solvent and ethylmethyl carbonate and above-mentioned illustrative compound (A-3) N as 2 weight portions of compound (Ic), N '-two (trifluoroacetyl) piperazine mixes.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (IIc-1)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (IIc-1)).
[embodiment (IIc-2)]
Will be as the mixture (volume ratio is 1: 2) of the ethylene carbonate of 995 weight portions of non-aqueous solvent and ethylmethyl carbonate and N as 5 weight portions of compound (Ic), N '-two (trifluoroacetyl) piperazine mixes.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (IIc-2)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (IIc-2)).
[embodiment (IIc-3)]
Will be as the mixture (volume ratio is 1: 2) of the ethylene carbonate of 98 weight portions of non-aqueous solvent and ethylmethyl carbonate and N as 2 weight portions of compound (Ic), N '-two (trifluoroacetyl) piperazine mixes.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (IIc-3)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (IIc-3)).
[comparative example (IIc-1)]
In as the ethylene carbonate of non-aqueous solvent and the mixture of ethylmethyl carbonate (volume ratio is 1: 2), add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (IIc-1)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (IIc-1)).
[comparative example (IIc-2)]
Will be as the mixture (volume ratio is 1: 2) of the ethylene carbonate of 995 weight portions of non-aqueous solvent and ethylmethyl carbonate and N as 5 weight portions of additive, N-dimethyl trifluoroacetamide mixes.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (IIc-2)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (IIc-2)).
[embodiment (IIc-4)]
Will as the mixture (volume ratio is 1: 2) of the ethylene carbonate of 978 weight portions of non-aqueous solvent and ethylmethyl carbonate with as the vinylene carbonate of 20 weight portions of unsaturated cyclic carbonate products and as the N of 2 weight portions of compound (Ic), N '-two (trifluoroacetyl) piperazine mixes.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (IIc-4)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (IIc-4)).
[embodiment (IIc-5)]
Will as the mixture (volume ratio is 1: 2) of the ethylene carbonate of 975 weight portions of non-aqueous solvent and ethylmethyl carbonate with as the vinylene carbonate of 20 weight portions of unsaturated cyclic carbonate products and as the N of 5 weight portions of compound (Ic), N '-two (trifluoroacetyl) piperazine mixes.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of embodiment (IIc-5)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of embodiment (IIc-5)).
[comparative example (IIc-3)]
To mix with vinylene carbonate as the mixture (volume ratio is 1: 2) of the ethylene carbonate of 98 weight portions of non-aqueous solvent and ethylmethyl carbonate as 2 weight portions of unsaturated cyclic carbonate products.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (IIc-3)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (IIc-3)).
[comparative example (IIc-4)]
Will as the mixture (volume ratio is 1: 2) of the ethylene carbonate of 975 weight portions of non-aqueous solvent and ethylmethyl carbonate with as the vinylene carbonate of 20 weight portions of unsaturated cyclic carbonate products and as the N of 5 weight portions of additive, N-dimethyl trifluoroacetamide mixes.In the mixture of gained, add LiPF as electrolytical intensive drying in the ratio of 1.0mol/L 6And dissolving.Thereby make nonaqueous electrolyte (nonaqueous electrolyte of comparative example (IIc-4)).The nonaqueous electrolyte of gained is carried out said procedure, thereby make lithium secondary battery (lithium secondary battery of comparative example (IIc-4)).
[evaluation result of battery]
To carrying out the evaluation of initial stage evaluation, trickle charge characteristic, high temperature preservation characteristics and discharge preservation characteristics according to the embodiment (IIc-1)～(IIc-5) of said procedure gained and the lithium secondary battery of comparative example (IIc-1)～(IIc-4).Evaluation result is shown in following table (IIc-1) and table (IIc-2).In " additive " hurdle of each table, " additive 1 " represents N, N-dimethyl trifluoroacetamide, and " additive 2 " representative is as the N of one of compound (IIc), N '-two (trifluoroacetyl) piperazine.In addition, in " auxiliary agent " hurdle of each table, " VC " representative is as the vinylene carbonate of one of unsaturated cyclic carbonate products.
[table 15]
Table (IIc-1)
Figure G2009101614705D00881
[table 16]
Table (IIc-2)
Figure G2009101614705D00891
Can obviously find out from table (IIc-1), compare with the lithium secondary battery of the comparative example 1 that adopts the nonaqueous electrolyte do not contain any additives, contain the gas generated obvious minimizing of lithium secondary battery of the embodiment (IIc-1)～(IIc-3) of compound (IIc) in the nonaqueous electrolyte.In addition, can obviously find out from table (IIc-2), in nonaqueous electrolyte, add in the comparative example (IIc-2) of the compound that only has an acid amides position, the discharge holding time of lithium secondary battery obviously worsens, and in nonaqueous electrolyte, contain among the embodiment (IIc-2) of the compound (IIc) with two acid amides positions, lithium secondary battery is not almost observed this deterioration in the discharge preservation process.By inference, this is owing to use when only having the compound at an acid amides position, can not produce effective organic coverlay, thereby cause the deterioration of characteristic.
In addition, employing does not contain additive and contains the nonaqueous electrolyte of unsaturated cyclic carbonic ester vinylene carbonate in the comparative example (IIc-3), compare with the situation of comparative example (IIc-3), contain among each embodiment (IIc-4) and embodiment (IIc-5) of nonaqueous electrolyte of compound (IIc) in employing, lithium secondary battery demonstrates gas and suppresses effect.In addition, as comparative example (IIc-4), when having added in the nonaqueous electrolyte when compound at an acid amides position is only arranged, the discharge holding time worsens on the contrary.
[other]
More than, explained the present invention in detail with reference to embodiment, but it will be clear to one skilled in the art that and under the prerequisite of the intent of the present invention and scope, can carry out multiple variation.
The application is based on following specification: the Japanese patent application No.2004-124174 that on April 20th, 2004 submitted to; The Japanese patent application No.2004-156209 that on May 26th, 2004 submitted to; The Japanese patent application No.2004-214104 that on July 22nd, 2004 submitted to; Japanese patent application Nos.2004-229188 and 2004-229757 that on August 5th, 2004 submitted to; The Japanese patent application No.2004-301751 that on October 15th, 2004 submitted to; This with referring to mode introduce its full content.
Industrial applicibility
Detailed description as mentioned, the lithium secondary battery of the excellence that nonaqueous electrolyte of the present invention makes has big capacity, demonstrates high preservation characteristics and cycle characteristics, can also suppress the generation of gas. So the present invention is applicable to a plurality of fields of using lithium secondary battery, for example electronic device field. As the example of purposes, can mention notebook computer, handwriting input PC, removable computer, electronic book readers, portable phone, portable facsimile printer, portable copier, portable printer, stereophone, video machines, LCD TV, Portable cleaner, portable CD player, pocket disc machine, wireless set, electronic notebook, electronic calculator, storage card, portable recorder, radio, emergency power supply, engine, ligthing paraphernalia, toy, game machine, wrist-watch, stroboscope, camera etc.

Claims (6)

1. nonaqueous electrolyte, described nonaqueous electrolyte comprises:
Lithium salts;
Non-aqueous solvent;
Cyclic carbonate compound with unsaturated bond; With
The represented compound of following general formula (Ib),
[Chemical formula 1]
Figure FSB00000222546700011
In general formula (Ib), R 21Representative can contain the substituent alkyl with 1～12 carbon atom of fluorine atom, maybe can have the substituent thiazolinyl with 2～12 carbon atoms of fluorine atom, wherein can have ehter bond in the chain of described group.
2. nonaqueous electrolyte as claimed in claim 1, wherein, in general formula (Ib), R 21Representative can have the substituent alkyl with 1～3 carbon atom of fluorine atom.
3. as claim 1 or the described nonaqueous electrolyte of claim 2, wherein, the represented compound of general formula (Ib) is 0.001 weight %～5 weight % with respect to the concentration of described nonaqueous electrolyte.
4. as claim 1 or the described nonaqueous electrolyte of claim 2, wherein, described cyclic carbonate compound with unsaturated bond is 0.01 weight %～8 weight % with respect to the concentration of described nonaqueous electrolyte.
5. as claim 1 or the described nonaqueous electrolyte of claim 2, wherein, described cyclic carbonate compound with unsaturated bond is one or more compounds that are selected from vinylene carbonate, ethylene thiazolinyl ethyl, carbonic acid divinyl ethyl, ethylene thiazolinyl vinylene and carbonic acid methylene ester.
6. lithium secondary battery, described lithium secondary battery comprises:
Nonaqueous electrolyte; With
Can absorb and discharge the positive pole and the negative pole of lithium ion;
Wherein, described nonaqueous electrolyte is each described nonaqueous electrolyte of claim 1～5.
CN2009101614705A 2004-04-20 2005-04-19 Nonaqueous electrolyte solution and lithium secondary battery using same Active CN101609911B (en)

Applications Claiming Priority (18)

Application Number Priority Date Filing Date Title
JP2004124174 2004-04-20
JP2004-124174 2004-04-20
JP2004124174A JP4608932B2 (en) 2004-04-20 2004-04-20 Non-aqueous electrolyte and non-aqueous electrolyte secondary battery
JP2004-156209 2004-05-26
JP2004156209 2004-05-26
JP2004156209 2004-05-26
JP2004214104 2004-07-22
JP2004-214104 2004-07-22
JP2004214104 2004-07-22
JP2004229757 2004-08-05
JP2004229188 2004-08-05
JP2004-229757 2004-08-05
JP2004229188A JP4655536B2 (en) 2004-08-05 2004-08-05 Non-aqueous electrolyte and non-aqueous electrolyte battery
JP2004229757A JP4655537B2 (en) 2004-08-05 2004-08-05 Non-aqueous electrolyte and non-aqueous electrolyte battery
JP2004-229188 2004-08-05
JP2004-301751 2004-10-15
JP2004301751 2004-10-15
JP2004301751A JP4670305B2 (en) 2004-10-15 2004-10-15 Non-aqueous electrolyte and lithium secondary battery

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JP5655828B2 (en) * 2012-08-31 2015-01-21 Tdk株式会社 Non-aqueous electrolyte for lithium ion secondary battery and lithium ion secondary battery
JP5614433B2 (en) * 2012-08-31 2014-10-29 Tdk株式会社 Non-aqueous electrolyte for lithium ion secondary battery and lithium ion secondary battery
CN103682437A (en) * 2012-09-11 2014-03-26 中国科学院宁波材料技术与工程研究所 Novel electrolysis system applicable to lithium titanate battery
WO2014101609A1 (en) * 2012-12-26 2014-07-03 中国科学院宁波材料技术与工程研究所 New electrolyte system for lithium-titanate battery
CN103633368B (en) * 2013-10-28 2015-08-19 山东海容电源材料有限公司 Flame-retardant additive used for electrolyte and flame-retardant lithium ion battery electrolyte
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