CN1862871A - Electrolytic solution and battery - Google Patents

Electrolytic solution and battery Download PDF

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Publication number
CN1862871A
CN1862871A CNA200610092715XA CN200610092715A CN1862871A CN 1862871 A CN1862871 A CN 1862871A CN A200610092715X A CNA200610092715X A CN A200610092715XA CN 200610092715 A CN200610092715 A CN 200610092715A CN 1862871 A CN1862871 A CN 1862871A
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electrolyte
lithium
battery
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CN100486030C (en
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川岛敦道
井原将之
山口裕之
堀内博志
窪田忠彦
山口晃
高木久美子
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Murata Northeast China
Murata Manufacturing Co Ltd
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Sony Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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

An electrolytic solution and a battery capable of improving cycle characteristics are provided. A separator is impregnated with an electrolytic solution. The electrolytic solution includes a cyclic carbonate derivative having a halogen atom such as 4-fluoro-1,3-dioxolane-2-one or 4-chloro-1,3-dioxolane-2-one and a cyclic imide salt such as 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide lithium. Thereby, the decomposition reaction of the electrolytic solution can be inhibited, and the cycle characteristics can be improved.

Description

Electrolyte and battery
The cross reference of related application
The present invention comprises the theme of the Japanese patent application JP2006-37698 that submits to Japan Patent office in Japanese patent application JP2005-116187 that the Japanese patent application JP2005-112052 that submits to Japan Patent office that relates on April 8th, 2005, on April 13rd, 2005 submit to Japan Patent office and on February 15th, 2006, and its full content here is incorporated herein by reference.
Technical field
The present invention relates to the battery that comprises the electrolyte of electrolytic salt and use this electrolyte.
Background technology
In recent years, a large amount of portable electric appts has appearred, for example camcorder, digital camera, cell phone, personal digital assistant and kneetop computer, and reduced the trial of their size and weight.Actively promoted target to be to improve the research and development of the energy density of battery (particularly secondary cell) as the compact power of electronic equipment.In these batteries, the composite material that uses material with carbon element to be used for negative pole, lithium (Li) and transition metal is used for positive pole and compares with nickel-cadmium cell with lead-acid battery of the prior art with the lithium rechargeable battery that carbonic ester is used for electrolyte, can obtain high energy density, so lithium rechargeable battery practical application widely.
And, recently, expected further to improve capacity along with the enhancing of the performance of portable electric appts, and after deliberation use tin (Sn) or silicon (Si) as negative active core-shell material to replace material with carbon element.This is because the theoretical capacity of tin and silicon is respectively 994mAh/g and 4199mAh/g, and it is than big many of the theoretical capacity of the graphite of 372mAh/g, and therefore, but anticipated capability improves.Particularly, it is reported by in the negative pole that forms by the film that on collector body, forms tin or silicon, negative active core-shell material can and not take off embedding and pulverize owing to the embedding of lithium, and can keep big relatively discharge capacity (for example, referring to international publication number WO01/031724 content).
In addition, as the secondary cell that can obtain high-energy-density, there is the lithium of use metal to be used for negative pole and only to use the deposition of lithium metal and the lithium metal secondary batteries that solubilizing reaction is used for negative reaction.The lithium metal has 2054mAh/cm 3The theoretical electrochemistry equivalent, its theoretical electrochemistry equivalent than graphite is big 2.5 times, so the lithium metal secondary batteries is hopeful the improvement capacity.Many researchers have carried out target and have been lithium metal secondary batteries Research on Practical Application and exploitation (for example, referring to " Lithium Batteries ", being edited Academic Press, 1983, London, New York by Jean-Paul Gabano).
In addition, developed a kind of secondary cell recently, wherein capacity of negative plates comprises by lithium and embeds and take off the capacity part of embedding and the capacity part of separating out and dissolving by lithium, and represents (for example, referring to international publication number WO01/22519 content) with their sums.In secondary cell, can embed with the material with carbon element of removal lithium embedded as negative pole, and in charging process, lithium is deposited on the surface of material with carbon element.As the situation of lithium metal secondary batteries, this secondary cell is hopeful to obtain high-energy-density.
Summary of the invention
Yet, using tin, silicon or lithium metal to be used for the battery of negative pole by this way, use material with carbon element to be used for the active height of the battery of negative pole in its specific activity prior art, therefore such problem is arranged: when using the carbonic ester that is used for electrolyte in the prior art, lithium hexafluoro phosphate or the like, electrolyte will decompose, and the lithium passivation.Therefore, when recharge and discharge, efficiency for charge-discharge descends, and therefore is difficult to obtain enough cycle characteristicss.
As everyone knows, even be used as under the situation of negative active core-shell material at material with carbon element, when cell voltage increased, discharge capacity also improved; Yet in this case, such problem is arranged: electrolyte decomposes easily, so efficiency for charge-discharge decline, and cycle characteristics descends.
Consider the above, be desirable to provide a kind of electrolyte that can improve cycle characteristics, and the battery that uses this electrolyte.
According to the embodiment of the present invention, provide a kind of electrolyte, comprise: cyclic imide salt; With cyclic carbonate derivative with halogen atom.
First embodiment of the invention, a kind of battery is provided, comprise: positive pole, negative pole and electrolyte, wherein this negative pole comprises the material that can embed and take off embedding electrode reaction thing, and comprise at least a conduct that is selected from metallic element and metalloid element and constitute element, and this electrolyte comprises cyclic imide salt.
Second embodiment of the invention, provide a kind of battery, comprise: anodal, negative pole and electrolyte, wherein the every pair of positive pole and the open circuit voltage of negative pole under the state of charging fully are 4.25V or higher, and this electrolyte comprises cyclic imide salt.
According to the 3rd execution mode of the present invention, a kind of battery is provided, comprise: positive pole, negative pole and electrolyte, wherein the lithium metal is used as negative active core-shell material, and this electrolyte comprises cyclic imide salt and the cyclic carbonate derivative with halogen atom.
According to the 4th execution mode of the present invention, a kind of battery is provided, comprise: positive pole, negative pole and electrolyte, wherein the capacity of this negative pole comprises the embedding by light metal and takes off the capacity part of embedding and the capacity part of separating out and dissolving by light metal, and the summation with them is represented, and this electrolyte comprises cyclic imide salt and the cyclic carbonate derivative with halogen atom.
In electrode solution according to the embodiment of the present invention, comprise cyclic imide salt, therefore can suppress the decomposition reaction of electrolyte, and further comprise cyclic carbonate derivative with halogen atom, therefore can obtain higher effect.
In battery according to first and second execution modes of the present invention, comprise cyclic imide salt, therefore the decomposition reaction of electrolyte can be suppressed, and cycle characteristics can be improved.And, when further comprising cyclic carbonate derivative, the decomposition reaction of electrolyte can be further suppressed, and cycle characteristics can be further improved with halogen atom.
In battery according to third and fourth execution mode of the present invention, comprise cyclic imide salt and cyclic carbonate derivative with halogen atom, therefore the decomposition reaction of electrolyte can be suppressed, and cycle characteristics can be improved.
Especially, in the scope of 0.1 weight % to 31 weight %, when (comprising end points), can obtain higher effect when the content of the imide salts in the electrolyte.
And, when electrolyte comprises when being selected from cyclic carbonate with unsaturated bond and sultone at least a, can improve the cycle characteristics under hot conditions.
Of the present invention other will embody from following description more fully with further purpose, feature and advantage.
Description of drawings
Fig. 1 is to use the sectional view according to first kind of secondary cell of the electrolyte of embodiment of the present invention;
Fig. 2 is the amplification sectional view of the part of the spiral winding electrode in the secondary cell shown in Figure 1;
Fig. 3 is to use the decomposition diagram according to the 5th kind of secondary cell of embodiment of the present invention electrolyte;
Fig. 4 is the sectional view along the spiral winding electrode of the line I-I of Fig. 3;
Fig. 5 is the sectional view of the secondary cell that forms in the example;
Fig. 6 is the figure of the example at the peak that obtains by X-ray photoelectron spectroscopy about the material that contains CoSnC that forms in the example;
Fig. 7 is for showing the curve chart of the relation between maximum charging voltage and the discharge capacitance.
Embodiment
Describe preferred implementation below with reference to accompanying drawings in detail.
Electrolyte according to embodiment of the present invention comprises for example solvent and the electrolytic salt that is dissolved in this solvent.
Solvent comprises that relative dielectric constant is 30 or bigger high dielectric constant solvent, because can increase the quantity of lithium ion by high dielectric constant solvent.
The example of high-k comprises ethylene carbonate, propylene carbonate, butylene carbonate, cyclic carbonate for example 1,3-dioxole (dioxol)-2-ketone and 4-vinyl-1,3-dioxolanes-2-ketone, the carbonic acid ester derivative that replaced by halogen of the part hydrogen in the cyclic carbonate, lactone gamma-butyrolacton and gamma-valerolactone, lactams N-N-methyl-2-2-pyrrolidone N-, cyclic carbamate for example tetramethylene sulfone and sultone of 3-methyl-2-oxazolidinedione, sulphones for example for example for example wherein.Be selected from above-mentioned a kind of or comprise that the mixture that is selected from above-mentioned two or more can be used as high dielectric constant solvent.
Wherein, preferably has the cyclic carbonate derivative of halogen atom, because can suppress the decomposition reaction of solvent.As this carbonic acid ester derivative, for example enumerate the carbonic acid ester derivative of representing in the Chemical formula 1, and more particularly, be set forth in the Chemical formula 2 (1) quoted to the carbonic acid ester derivative shown in 2 (26).Wherein, the 4-fluoro-1 of preferred Chemical formula 2 (1) expression, the 4-chloro-1 of 3-dioxolanes-2-ketone or Chemical formula 2 (2) expression, 3-dioxolanes-2-ketone, and especially, expectation 4-fluoro-1,3-dioxolanes-2-ketone is because can obtain higher effect.
(Chemical formula 1)
Figure A20061009271500101
Wherein R11, R12, R13 and R14 represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl or group that wherein part hydrogen is replaced by fluorine, chlorine and bromine in methyl or the ethyl separately, and at least one among R11, R12, R13 and the R14 is the group with halogen, and they can be same to each other or different to each other.
(Chemical formula 2)
And, the cyclic carbonate that preferably has a unsaturated bond is for example in the chemical formula 3 (1) 1 of expression, the 4-vinyl-1 of expression in 3-dioxole-2-ketone or the chemical formula 3 (2), 3-dioxolanes-2-ketone, or show in sultone such as the chemical formula 4 (1) 1, the 3-propylene sultone that show in 3-propane sultone or the chemical formula 4 (2) because can suppress the decomposition reaction of solvent, and can obtain high effect under hot conditions.Comprise in electrolyte under the situation of the cyclic carbonate with unsaturated bond, the content of cyclic carbonate is preferably in the scope of 0.05 weight % to 20 weight % (comprising end points).And, in electrolyte, containing under the situation of sultone, the content of sultone is preferably in the scope of 0.01 weight % to 5 weight % (comprising end points).This is because can obtain high effect in these scopes.
(chemical formula 3)
Figure A20061009271500121
(chemical formula 4)
And, preferably be that 1mPas or littler low viscosity solvent mix with high dielectric constant solvent and use, because by using low viscosity solvent can obtain higher ionic conductance with viscosity.The example of low viscosity solvent comprises for example dimethyl carbonate of linear carbonate, diethyl carbonate, methyl ethyl carbonate and carbonic acid first propyl ester, the chain carboxylate is methyl acetate for example, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethylacetate and tri-methyl ethyl acetate, ketone is pinacoline for example, ether for example 1, the 2-dimethoxy-ethane, oxolane, the 2-methyltetrahydrofuran, oxinane, 1, the 3-dioxolanes, the 4-methyl isophthalic acid, the 3-dioxolanes, 1,3-two  alkane and 1,4-two  alkane, the chain acid amides is N for example, N-dimethylacetylamide and N, dinethylformamide, and chain carbamate methyl-N for example, the N-dimethylcarbamate, methyl-N, N-diethylamino formic acid esters and ethyl-N, N-diethylamino formic acid esters.Be selected from above-mentioned a kind of or comprise the mixture that is selected from above-mentioned two or more and can be used as low viscosity solvent.
As electrolytic salt, comprise cyclic imide salt, because cyclic imide salt not only plays electrolytic salt but also works to suppress the decomposition reaction of electrolyte.The example of cyclic imide salt comprises the compound of expression in the chemical formula 5 (1) to 5 (6).In chemical formula 5 (1) to 5 (6), show alkali metal salt; Yet, also can use alkali salt or aluminum metal salt with similar characteristic.
(chemical formula 5)
Wherein M1, M2, M3, M4, M5 and M6 represent alkalinous metal separately, R1, R2 and R3 represent straight or branched alkylidene with 2 to 5 carbon atoms or group that wherein part hydrogen is replaced by fluorine in this alkylidene separately, R41, R42, R43, R44, R51, R52, R53, R54, R61, R62, R63 and R64 represent hydrogen separately, have alkyl itself or the group that wherein part hydrogen is replaced by fluorine in this alkyl of 1 to 4 carbon atom, and R41, R42, R43, R44, R51, R52, R53, R54, R61, R62, R63 and R64 can be same to each other or different to each other.
More particularly, the embodiment of cyclic imide salt comprise chemical formula 6 (1) represented 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium, chemical formula 6 (2) represented 2,2,3,3,4,4-hexafluoro glutarimide lithium, the adjacent sulfo group benzimide lithium (lithium ortho-sulphobenzimide) that chemical formula 6 (3) is represented, 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines sodium, 2,2,3,3,4,4-hexafluoro glutarimide sodium, adjacent sulfo group benzimide sodium, 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines potassium, 2,2,3,3,4,4-hexafluoro glutarimide potassium, adjacent sulfo group benzimide potassium, 1,1 of chemical formula 6 (4) expressions, 2,2-HFC-134a-1,3-disulfonyl imines lithium, the 1-Trifluoromethyl-1 that chemical formula 6 (5) is represented, 2,2,3,3-pentafluoropropane-1,3-disulfonyl imines lithium, with chemical formula 6 (6) represented 1,1,2,2,3,3,4,4-octafluoro butyl-1,3-disulfonyl imines lithium.Wherein, preferably use 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium, 2,2,3,3,4,4-hexafluoro glutarimide lithium, adjacent sulfo group benzimide lithium, 1,1,2,2-HFC-134a-1,3-disulfonyl imines lithium or 1,1,2,2,3,3,4,4-octafluoro butyl-1,3-disulfonyl imines lithium is because can obtain higher effect.
(chemical formula 6)
Figure A20061009271500141
The content of cyclic imide salt is preferably between 0.1 weight % to 31 weight % (comprising end points), because can obtain higher effect in this scope in whole electrolyte.Be selected from a kind of of them or comprise two or more the mixture that is selected from them and can be used as cyclic imide salt.
Electrolyte can only comprise cyclic imide salt, maybe can comprise the mixture of cyclic imide salt and one or both or multiple other salt.The example of other salt comprises lithium hexafluoro phosphate (LiPF 6), LiBF4 (LiBF 4), hexafluoroarsenate lithium (LiAsF 6), hexafluoro-antimonic acid lithium (LiSbF 6), hexafluorosilicic acid lithium (LiSiF 6), lithium perchlorate (LiClO 4), tetrachloro-lithium aluminate (LiAlCl 4), lithium chloride (LiCl), lithium bromide (LiBr), two (oxalate closes) boron lithium lithium (LiB (C 2O 4) 2), tetraphenyl lithium borate (LiB (C 6H 5) 4), four (trifluoroacetic acid base) lithium borate (LiB (OCOCF 3) 4), four (five fluorine propionyloxies) boron lithium (LiB (OCOCF 5) 4), methanesulfonic acid lithium (LiCH 3SO 3), trifluoromethanesulfonic acid lithium (LiCF 3SO 3), for example two (fluoroform sulfone) imines lithium (LiN (CF of lithium salts of chemical formula 7 (1) expression 3SO 2) 2), two (pentafluoroethane sulfone) imines lithium (LiN (C 2F 5SO 2) 2) or (nine fluorine butane sulfones) (fluoroform sulfone) imines lithium (LiN (C 4F 9SO 2) (CF 3SO 2)) and the lithium salts of chemical formula 7 (2) expression as three (fluoroform sulfone) lithium methide ((CF 3SO 2) 3CLi).
(chemical formula 7)
LiN(C mF 2m+1SO 2)(C nF 2n+1SO 2) ………(1)
LiC(C pF 2p+1SO 2)(C qF 2q+1SO 2)(C rF 2r+1SO 2) ………(2)
Wherein m, n, p, q and r respectively do for oneself 1 or bigger integer.
Particularly, preferably will be selected from lithium hexafluoro phosphate, LiBF4, two (oxalate closes) lithium borate, LiB (OCOCF 3) 4, LiB (OCOC 2F 5) 4, lithium perchlorate, hexafluoroarsenate lithium and chemical formula 7 expressions at least a and cyclic imide salt of lithium salts mix and use because can obtain higher effect, and can obtain high conductivity.Wherein, more preferably mix with cyclic imide salt and use to major general's lithium hexafluoro phosphate.
The following secondary cell that is used for of electrolyte.
(first kind of secondary cell)
Fig. 1 shows the sectional view that has used according to first kind of secondary cell of the electrolyte of execution mode.This secondary cell is so-called lithium rechargeable battery, and wherein the capacity of negative pole is by by partly representing as the embedding of the lithium of electrode reaction thing and the capacity that takes off embedding.This secondary cell is so-called cylindrical battery, and comprises that spiral winding electrode 20, this spiral winding electrode are included in positive pole 21 and the negative pole 22 and the barrier film therebetween 23 of the screw winding in the cylindrical battery shell 11 of hollow basically.Battery case 11 is made by the iron (Fe) of for example nickel plating (Ni).One end of battery case 11 seals, and the other end opens wide.In battery case 11, a pair of insulation board 12 and 13 is set makes spiral winding electrode 20 be clipped in therebetween with direction perpendicular to outside twisting surface.
At the open end of battery case 11, by liner 17 calking assemble lid 14 be arranged on the relief valve mechanism 15 and the positive temperature coefficient device (PTC device) 16 of battery cover 14 inside, and the inside of sealed cell shell 11.Battery cover 14 is by for example making with battery case 11 identical materials.Relief valve mechanism 15 is electrically connected to battery cover 14 by PTC device 16, and when owing to internal short-circuit or external heat cell internal pressure being increased to be higher than to a certain degree, disk 15A returns and scratches (flip), thereby disconnects the electrical connection between battery cover 14 and the spiral winding electrode 20.When temperature raise, PTC device 16 was by increasing the unusual heat of resistance limits electric current to prevent to produce owing to big electric current.Liner 17 is made by for example insulating material, and its surface-coated has pitch.
Centrepin 24 is inserted in the center of spiral winding electrode 20.The positive wire of being made by aluminium (Al) etc. 25 is connected on the positive pole 21 of spiral winding electrode 20, and the negative wire of being made by nickel etc. 26 is connected on the negative pole 22.Positive wire 25 is soldered to relief valve mechanism 15 and makes and be electrically connected to battery cover 14, and negative wire 26 welding and be electrically connected to battery case 11.
Fig. 2 has shown the enlarged drawing of the part of spiral winding electrode 20.Anodal 21 comprise the anode active material layer 21B on positive electrode collector 21A with a pair of apparent surface and the two sides that is arranged on positive electrode collector 21A.Positive electrode collector 21A is made by for example metal material such as aluminium, nickel or stainless steel.Anode active material layer 21B comprises one or both or multiplely can embed and take off the positive electrode of embedding as the lithium of electrode reaction thing, and if necessary, can comprise electric conductor for example material with carbon element and adhesive such as polyvinylidene fluoride.
As the positive electrode that can embed with removal lithium embedded, for example, preferred lithium cobalt/cobalt oxide, lithium nickel oxide, comprise the solid solution (Li (Ni of lithium and cobalt oxides and lithium nickel oxide xCo yMn z) O 2)) (value of x, y and z is 0＜x＜1,0＜y＜1,0＜z＜1, x+y+z=1), lithium composite xoide for example have the lithium manganese oxide (LiMn of spinel structure 2O 4) or its solid solution (Li (Mn 2-vNi v) O 4(value of v is v＜2) or phosphate compounds with olivine structural be LiFePO4 (LiFePO for example 4), because can obtain high energy density.And the example that can embed with the positive electrode of removal lithium embedded comprises oxide for example titanium oxide, vanadium oxide and manganese dioxide, and disulphide is ferrous disulfide, titanium disulfide and molybdenum sulfide for example, sulphur, and the big molecule of conductivity for example polyaniline and polythiophene.
Negative pole 22 has such structure, and wherein anode active material layer 22B is arranged on the two sides of the negative electrode collector 22A with a pair of apparent surface.Negative electrode collector 22A is made by for example metal material such as copper (Cu), nickel or stainless steel.
Anode active material layer 22B comprises one or both or the multiple negative material that can embed with removal lithium embedded, and if necessary, can comprise electric conductor, binding agent or the like.As the negative material that can embed with removal lithium embedded, for example, enumerating can embedding and removal lithium embedded and comprise and be selected from least a as the material that constitutes element of metallic element and metalloid element.Because can obtain high-energy-density, preferably use this negative material.Negative material can be made by simple substance, alloy or the compound of metallic element and metalloid element, and is selected from above-mentioned one or both or multiplely can be included at least in the part of negative material mutually.In the present invention, except the alloy that comprises two or more metallic elements, alloy also comprises the alloy that comprises one or more metallic elements and one or more metalloid elements.In addition, alloy can comprise nonmetalloid.As the structure of alloy, enumerate solid solution, eutectic (eutectic mixture), intermetallic compound or be selected from wherein two or more coexistence.
Be included in the metallic element in the negative material and the example of metalloid element and comprise the metallic element and the metalloid element that can form alloy with lithium.More particularly, comprise magnesium (Mg), boron (B), aluminium (Al), gallium (Ga), indium (In), silicon, germanium (Ge), tin, lead (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd), platinum (Pt) or the like.Wherein, especially preferably use silicon or tin,, thereby can obtain high-energy-density because silicon and tin have the high embedding and the ability of removal lithium embedded.
As this negative material, for example preferably comprise the negative material that constitutes element and the 3rd formation element as first tin, second that constitutes element.Second constitutes element comprises and is selected from least a of cobalt (Co), iron, magnesium, titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), nickel, copper, zinc, gallium, zirconium, niobium (Nb), molybdenum (Mo), silver, indium, cerium (Ce), hafnium, tantalum (Ta), tungsten (W), bismuth and silicon.The 3rd constitutes element comprises and is selected from least a of boron, carbon (C), aluminium and phosphorus (P).When comprising the second formation element and the 3rd formation element, can improve cycle characteristics.
Wherein, as negative material, the material that preferably contains CoSnC, wherein comprise tin, cobalt and carbon as constituting element and carbon content in the scope of 9.9 weight % to 29.7 weight % (comprising end points), cobalt to the ratio Co/ (Sn+Co) of the total amount of tin and cobalt in the scope of 30 weight % to 70 weight % (comprising end points), because in such compositing range, can obtain high-energy-density and good cycle characteristics.
If desired, the material that contains CoSnC can comprise other element.As this element, for example preferred silicon, iron, nickel, chromium, indium, niobium, germanium, titanium, molybdenum, aluminium, phosphorus, gallium or bismuth, and can comprise above-mentioned two or more.This is because can further improve capacity and cycle characteristics.
The material that contains CoSnC comprises and comprises tin, cobalt and carbon mutually, and this preferably has low crystalline texture or impalpable structure mutually.And, in containing the material of CoSnC, as constituting preferably with as another metallic element or metalloid element that constitutes element combining to small part carbon of element.The decay that it is believed that cycle characteristics is caused by the cohesion or the crystallization of tin etc., and when carbon and another constitute element and combine, can suppress this cohesion or crystallization.
As the method for measurement of the bonding state of measuring element, for example use X-ray photoelectron spectroscopy (XPS).In XPS, under the situation of graphite, in equipment, observe the peak of the 1s track (C1s) of carbon at the 284.5eV place, in this equipment, carry out energy calibration and make the peak of the 4f track (Au4f) of observing gold atom at the 84.0eV place.On the other hand, under the situation that carbon charge density increases, for example under carbon and situation that metallic element or metalloid element combine, in being lower than the scope of 284.5eV, observe the peak of C1s.In other words, in being lower than the scope of 284.5eV, observe under the situation at peak of the complex wave that is containing the C1s that obtains in the CoSnC material, contain comprise in the material of CoSnC to small part carbon with combine as another metallic element or metalloid element that constitutes element.
And, in XPS measuring, for example, use the energy axes of the peak calibration spectrum of C1s.Usually, surface contamination carbon is present on the material surface, so the peak of the C1s of surface contamination carbon is fixed as 284.8eV, and uses this peak as the energy reference.In XPS measuring, the waveform at the peak of the C1s that obtains as comprise the peak of surface contamination carbon and in containing the material of CoSnC the form at the peak of carbon, for example be purchased this waveform of software analysis the peak of the peak of surface contamination carbon with carbon in containing the material of CoSnC separated by using.In the analysis of waveform, the position of using the main peak on minimum binding energy side is as energy reference (284.8eV).
Negative material as embedding with removal lithium embedded for example, but can use material with carbon element such as graphite, ungraphitised carbon or graphitized carbon, and material with carbon element also can use with above-mentioned negative material.In material with carbon element, according to the embedding of lithium with to take off the changes of crystal of embedding very little, so material with carbon element preferably uses with above-mentioned negative material, because can obtain high-energy-density and good cycle characteristics, and material with carbon element also plays the effect of electric conductor.
In secondary cell, regulate positive electrode active materials and charging capacity that the amount with the negative material of removal lithium embedded of can embedding makes it possible to embed with the negative material of removal lithium embedded becomes bigger than the charging capacity of positive electrode active materials, though therefore when charging fully the lithium metal do not separate out on negative pole 22 yet.
Barrier film 23 separate anodal 21 and negative pole 22 make and allow lithium ion pass through, prevent simultaneously because anodal 21 and negative pole 22 between the short circuit current of contact.Barrier film 23 is by for example synthetic resin such as polytetrafluoroethylene, polypropylene or poly perforated membrane, and perhaps ceramic porous membrane is made, and barrier film 23 also can have the wherein structure of two or more perforated membrane laminations.
Barrier film 23 is impregnated with the electrolyte according to embodiment of the present invention.
For example, secondary cell can be made by following steps.
At first, for example, positive electrode active materials 21B is formed on positive electrode collector 21A and goes up to form anodal 21.Anode active material layer 21B forms by following steps.Positive electrode active material powder, electric conductor and binding agent are being mixed with after forming cathode mix, cathode mix is distributed in the solvent of N-N-methyl-2-2-pyrrolidone N-for example to form pasty state cathode mix slurry, and this cathode mix slurry is coated on the positive electrode collector 21A, and, therefore form anode active material layer 21B with cathode mix slurry drying and compression molded.And for example, as anodal 21, anode active material layer 22B is formed on negative electrode collector 22A to form negative pole 22.
Next, wait positive wire 25 attached on the positive electrode collector 21A, wait negative wire 26 attached on the negative electrode collector 22A by welding by welding.Then, with anodal 21 and negative pole 22 with its in the middle of barrier film 23 screw windings, and the fore-end of positive wire 25 is welded on the relief valve mechanism 15, and the fore-end of negative wire 26 is welded on the battery case 11.Next, the positive pole 21 and the negative pole 22 of screw winding is clipped between a pair of insulation board 12 and 13, and they are included in the battery case 11.After positive pole 21 and negative pole 22 be included in battery case 11, inject the electrolyte into battery case 11 with electrolyte dipping barrier film 23.Afterwards, by liner 17 calkings battery cover 14, relief valve mechanism 15 and PTC device 16 are fixed on the open end portion of battery case 11.Thus, finish the secondary cell shown in Fig. 1 and 2.
When secondary cell charge, lithium ion takes off embedding from positive pole 21, and embeds negative pole 22 by electrolyte.On the other hand, when secondary cell discharged, lithium ion took off embedding and embeds anodal 21 by electrolyte from negative pole 22.At this moment, owing to comprise cyclic imide salt in the electrolyte, can suppress the decomposition reaction of electrolyte.
Therefore, in secondary cell, comprise cyclic imide salt, therefore can suppress the decomposition reaction of electrolyte, and can improve cycle characteristics.And, when comprising cyclic carbonate derivative, the decomposition reaction of electrolyte can be further suppressed, and cycle characteristics can be further improved with halogen atom.
Particularly, in that use can embedding and removal lithium embedded and comprising under at least a situation as the material that constitutes element that is selected from metallic element and metalloid element, negative pole 22 active high, and electrolyte decomposes easily, thus can obtain higher effect.
And, when the content of cyclic imide salt in electrolyte solution when (comprising end points), can obtain higher effect in the scope of 0.1 weight %-31 weight %.
In addition, when electrolyte comprises when being selected from by cyclic carbonate with unsaturated bond and sultone at least a, can improve cycle characteristics at high temperature.
(second kind of secondary cell)
Except that the structure difference of negative pole, second kind of secondary cell has identical structure, function and effect with first kind of secondary cell, and second kind of secondary cell can form by identical method.Therefore, second kind of secondary cell described with reference to Fig. 1 and 2, and same assembly with first kind of numeral that secondary cell is identical, and will no longer describe.
Negative pole 22 has such structure, wherein as first kind of secondary cell, anode active material layer 22B is arranged on the two sides of negative electrode collector 22A.Anode active material layer 22B comprises and for example comprises tin or silicon as the negative active core-shell material that constitutes element.More particularly, for example, negative active core-shell material comprises simple substance, alloy or the compound of tin, the perhaps simple substance of silicon, alloy or compound, and negative active core-shell material can comprise two or more that are selected from them.
And, anode active material layer 22B forms by for example vapor phase method, liquid phase method, spray-on process or sintering method or the combination that is selected from above-mentioned two or more, and anode active material layer 22B and negative electrode collector 22A are preferably in the alloying to the small part at its interface.More particularly, on the interface, the element preferred diffusion of negative electrode collector 22A is advanced among the anode active material layer 22B, perhaps the element preferred diffusion of negative active core-shell material is advanced among the negative electrode collector 22A, perhaps their preferred phase counterdiffusion, because can suppress, and can improve conductivity between anode active material layer 22B and the negative electrode collector 22A by breaking of causing according to the expansion of anode active material layer 22B of charging and discharge and contraction.
As vapor phase method, for example, can use physical deposition method or chemical deposition, and more particularly, can use vacuum deposition method, sputtering method, ion plating method, laser ablation method, hot CVD (chemical vapour deposition (CVD)) method, plasma chemical vapor deposition etc.As liquid phase method, can use known technology for example to electroplate or electroless plating.In sintering method, for example, granular negative active core-shell material and binding agent etc. are mixed to form mixture, mixture is dispersed in the solvent, and coating, under than the high temperature of fusing points such as binding agent, add hot mixt then.As sintering method, can use known technology such as atmosphere sintering method, reaction sintering method or hot pressing sintering method.
(the third secondary cell)
The third secondary cell is so-called lithium metal secondary batteries, and wherein the capacity of negative pole 22 is partly represented by the capacity of separating out and dissolving of lithium.Except that anode active material layer 22B was made by the lithium metal, this secondary cell had and first kind of structure that secondary cell is identical, and this secondary cell can be by identical method manufacturing.Therefore, describe the third secondary cell, and same assembly uses and first kind of numeral that secondary cell is identical, and will no longer describe with reference to Fig. 1 and 2.
In other words, this secondary cell uses the lithium metal as negative active core-shell material, thereby can obtain high energy density.Anode active material layer 22B the time can exist in assembling, perhaps can not exist when assembling, forms and separate out the lithium metal during by charging.And anode active material layer 22B also can be used as collector body, and can remove negative electrode collector 22A.
In secondary cell, electrolyte preferably comprises cyclic imide salt and has the cyclic carbonate derivative of halogen atom, and can further comprise above-mentioned other component, because when electrolyte comprises them, only comprise situation any in them with electrolyte and compare, can improve the effect that suppresses solvolysis reaction significantly.In this case, have the content 50 volume % or still less preferably of the cyclic carbonate derivative of halogen atom in the solvent, because can obtain higher effect.
When secondary cell charge, lithium ion takes off embedding from positive pole 21, and lithium ion is deposited as the lithium metal by electrolyte on the surface of negative electrode collector 22A.When secondary cell discharged, the lithium metal was dissolved as lithium ion from anode active material layer 22B, and lithium ion embeds anodal 21 by electrolyte.Therefore, in negative pole 22, repeat separating out of lithium metal and dissolve according to charging and discharge, and the activity of negative pole 22 becomes very high.Yet in secondary cell, electrolyte comprises cyclic imide salt and has the cyclic carbonate derivative of halogen atom, therefore can be suppressed at the decomposition reaction of electrolyte in the negative pole 22.Therefore, can improve the efficiency for charge-discharge of lithium in the negative pole 22.
Therefore, in secondary cell, electrolyte comprises cyclic imide salt and has the cyclic carbonate derivative of halogen atom, therefore can be suppressed at the decomposition reaction of electrolyte in the negative pole 22.Thereby, can improve the efficiency for charge-discharge in the negative pole 22, and can improve cycle characteristics.
(the 4th kind of secondary cell)
In the 4th kind of secondary cell, the capacity of negative pole comprises by as the embedding of the lithium of electrode reaction thing with take off the capacity part of embedding and the capacity part of separating out and dissolving by lithium, and with their expression of summation.Except that the structure difference of anode active material layer 22B, this secondary cell has identical structure with first kind of secondary cell, and this secondary cell can be by identical method manufacturing.Therefore, describe the 4th kind of secondary cell, and same part uses and first kind of numeral that secondary cell is identical, and will no longer describe with reference to Fig. 1 and 2.
Anode active material layer 22B comprises one or both or the multiple negative material that can embed with removal lithium embedded as negative active core-shell material, and also comprises binding agent if desired.The example of this negative material comprises the material with carbon element of describing among first embodiment and comprises and can form the metallic element of alloy or the material of metalloid element with lithium.In them, preferably use material with carbon element, because can obtain good cycle characteristics.
Regulate and to embed and the amount of the negative material of removal lithium embedded makes the charging capacity of negative material become littler than the charging capacity of positive pole 21.Thus, in secondary cell, in charging process, when open circuit voltage (that is, cell voltage) than overcharging when forcing down, the lithium metal begins to be deposited on the negative pole 22.
Overcharged voltage is meant the open circuit voltage when battery becomes overcharge condition, and expression is for example than describing in " Guideline for safety assessment of lithium secondary batteries " (SBA G1101) (it is the criterion that Japanese The Storage Battery Industry in China association (Japan Storage Battery industries Incorporated) (Japanese battery association (BatteryAssociation of Japan)) formulates) and the high voltage of open circuit voltage of " charging fully " battery of definition.In other words, overcharged voltage is represented than the high voltage of open circuit voltage after charging by the charging method of using charging method, standard charging method or the recommendation used when determining each battery nominal capacity.More particularly, for example secondary cell charges fully under the open circuit voltage of 4.2V, in the part scope of open circuit voltage 0V to 4.2V, the lithium metal separate out can embed and the surface of the negative material of removal lithium embedded on.Therefore, in secondary cell, can embed and the negative material of removal lithium embedded and the effect that the lithium metal plays negative active core-shell material, and can embed and the negative material of removal lithium embedded is the basis of lithium metal when separating out.Therefore, in secondary cell, can obtain high-energy-density, and can improve cycle characteristics and rapid charge characteristic.
And, the same with the third secondary cell in secondary cell, the cyclic carbonate derivative that in electrolyte, preferably comprises cyclic imide salt and have halogen atom, and comprise above-mentioned other component.With comprise them in any situation compare, can improve the effect of acquisition significantly.In this case, have the content 50 volume % or still less preferably of the cyclic carbonate derivative of halogen atom in the solvent, because can obtain higher effect.
When secondary cell charge, lithium ion takes off embedding from anodal 21, and embeds by electrolyte and into to be included in can embed in the negative material with removal lithium embedded in the negative pole 22.When secondary cell further charges, when open circuit voltage wherein than the state that forces down that overcharges under, the lithium metal begin to be deposited on can embed and the surface of the negative material of removal lithium embedded on.Later, finish up to charging, the lithium metal continues to be deposited on the negative pole 22.Next, when secondary cell discharged, the lithium people dissolving metal that is deposited on the negative pole 22 was a lithium ion, and lithium ion embeds in anodal 21 by electrolyte.When secondary cell further discharges, lithium ion from negative pole 22, can embed and the negative material of removal lithium embedded in take off embedding, and embed anodal 21 by electrolyte.Therefore, in secondary cell, in negative pole 22, repeat separating out and dissolving of lithium metal, so the activity of negative pole 22 becomes very high.Yet in secondary cell, electrolyte comprises cyclic imide salt and has the cyclic carbonate derivative of halogen atom, therefore can suppress the decomposition reaction of electrolyte in the negative pole 22.Therefore, can improve the efficiency for charge-discharge of lithium in the negative pole 22.
Therefore, in secondary cell, electrolyte comprises cyclic imide salt and has the cyclic carbonate derivative of halogen atom, thereby can suppress the decomposition reaction of the electrolyte in the negative pole 22.Therefore, the efficiency for charge-discharge of negative pole 22 can be improved, and cycle characteristics can be improved.
(the 5th kind of secondary cell)
Fig. 3 has shown the structure of the 5th kind of secondary cell.This secondary cell is so-called lamination membranous type, and in this secondary cell, the spiral winding electrode 30 that is attached with positive wire 31 and negative wire 32 is included in the film shape package component 40.
Positive wire 31 is for example guided the outside with identical direction into from the inside of package component 40 with negative wire 32.Positive wire 31 and negative wire 32 are made by for example sheet or netted metal material such as aluminium, copper, nickel or stainless steel.
Package component 40 is made by the rectangular aluminum laminated film of nylon membrane, aluminium foil and polyethylene film that for example comprises with this order combination.Package component 40 is set so that the polyethylene film of each package component 40 is faced spiral winding electrode 30, and the marginal portion of package component 40 is adhering to each other by melting welding or binding agent.Adhesive film 41 inserts between package component 40 and positive wire 31 and the negative wire 32 to prevent that extraneous air from entering.Adhesive film 41 is made by for example having the material that positive wire 31 and negative wire 32 are had a bonding force, for example vistanex such as polyethylene, polypropylene, modified poly ethylene or modified polypropene.
In addition, package component 40 can replace above-mentioned aluminium lamination press mold to make by the laminated film with any other structure, high molecular weight membrane such as polypropylene or metal film.
Fig. 4 has shown along the sectional view of the spiral winding electrode 30 of the line I-I of Fig. 3.This spiral winding electrode 30 is the screw winding sandwichs that comprise positive pole 33 and negative pole 34 and barrier film therebetween 35 and dielectric substrate 36, and the outermost portion of spiral winding electrode 30 adopts boundary belt 37 to protect.
Anodal 33 have anode active material layer 33B wherein is arranged on structure on the two sides of positive electrode collector 33A.Negative pole 34 has anode active material layer 34B wherein and is arranged on structure on the two sides of negative electrode collector 34A, and negative pole 34 is set so that anode active material layer 34B in the face of anode active material layer 33B.The structure of positive electrode collector 33A, anode active material layer 33B, negative electrode collector 34A, anode active material layer 34B and barrier film 35 is identical with above-mentioned first, second, third and the structure of positive electrode collector 21A, anode active material layer 21B, negative electrode collector 22A, anode active material layer 22B and the barrier film 23 of the 4th kind of secondary cell respectively.
Dielectric substrate 36 comprises according to the electrolyte of execution mode and conduct and keeps the high-molecular weight compounds of the maintenance body of electrolyte, and is so-called gel electrolyte.Preferred gel electrolyte because gel electrolyte can obtain high ionic conductance, and can prevent battery drain.As high-molecular weight compounds, for example use based on the high-molecular weight compounds such as the poly(ethylene oxide) of ether or comprise poly(ethylene oxide) crosslinked, based on the high-molecular weight compounds of ester such as polymethacrylates or based on the polymer of the high-molecular weight compounds of acrylate or polyvinylidene fluoride or the vinylidene fluoride copolymer of vinylidene fluoride and hexafluoropropylene for example, and can use be selected from above-mentioned a kind of or use and comprise the mixture that is selected from above two or more.More particularly, according to OR stability, be preferably based on the high-molecular weight compounds of fluorine.
For example, secondary cell can be by the following steps manufacturing.
At first, be coated on positive pole 33 and the negative pole 34 by the precursor solution that will comprise electrolyte, high-molecular weight compounds and mixed solvent and evaporate mixed solvent and form dielectric substrate 36.Next, positive wire 31 is attached on the positive electrode collector 33A, and negative wire 32 is attached on the negative electrode collector 34A.Then; form the positive pole 33 of dielectric substrate 36 and form the negative pole 34 of dielectric substrate 36 stacked with after forming sandwich thereon thereon with barrier film 35 therebetween; with this sandwich screw winding in the vertical, thereby and the outermost end that boundary belt 37 is attached at this sandwich form spiral winding electrode 30.Afterwards, for example spiral winding electrode 30 is clipped between the package component 40, and the marginal portion of package component 40 mutually combines so that spiral winding electrode 30 is sealed in the package component 40 by thermofussion welding etc.At this moment, adhesive film 41 is inserted between positive wire 31, negative wire 32 and the package component 40.Thus, finish the secondary cell shown in Fig. 3 and Fig. 4.
And, can make battery by following steps.At first, as mentioned above, form positive pole 33 and negative pole 34, and positive wire 31 and negative wire 32 are attached to respectively on positive pole 33 and the negative pole 34.Then, positive pole 33 and negative pole 34 is stacked with the formation sandwich with barrier film 35 therebetween, and with the sandwich screw winding.To such an extent as to boundary belt 37 is attached to the screw winding body of the outermost end formation of screw winding sandwich as the precursor of spiral winding electrode 30.Next, this screw winding body is clipped between the package component 40, will packs except that other marginal portion the side of package component 40 adheres to form bag shape by thermofussion welding, thereby this screw winding body is included in the package component 40.To be used for electrolytical component injects in the package component 40, and pack the opening portion of assembly 40 then by thermofussion welding, this component comprises electrolyte, as monomer and polymerization initiator and if necessary any other material such as the polymerization inhibitor of the material of high-molecular weight compounds.After this, thereby come polymerization single polymerization monomer to form high-molecular weight compounds, thereby form gel electrolyte layer 36 with installation diagram 3 and secondary cell shown in Figure 4 by applying heat.
The function of this secondary cell is identical with the 4th kind of secondary cell with above-mentioned first, second, third with effect.
(the 6th kind of secondary cell)
The 6th kind of secondary cell has and first to the 5th kind of identical structure of secondary cell, the amount of remove regulating positive electrode active materials and negative active core-shell material make every pair of positive pole and negative pole when charging fully open circuit voltage (, cell voltage) between 4.25V to 6.00V, (comprise end points) in addition, and the 6th kind of secondary cell can form with identical method.
In this secondary cell, although use identical positive electrode active materials, but the amount of per unit mass removal lithium embedded compares the amount height of the battery per unit mass institute removal lithium embedded when open circuit voltage is 4.20V when charging fully, therefore according to these, regulate the amount of positive electrode active materials and negative active core-shell material, thereby can obtain high energy density.
As negative active core-shell material, the preferred lithium metal maybe can embed the material with carbon element with removal lithium embedded, because lithium metal and material with carbon element have low charging-discharge voltage, therefore can easily improve the energy density of battery.
When secondary cell charge, for example, lithium ion takes off embedding from positive pole 21, and embeds negative pole 22 by electrolyte.On the other hand, when secondary cell discharged, for example, lithium ion took off embedding from negative pole 22, and embedded anodal 21 by electrolyte.In this case, cell voltage is 4.25V or bigger during charging, so electrolyte decomposes easily.Yet, comprise cyclic imide salt as mentioned above, therefore can suppress the decomposition reaction of electrolyte.
This secondary cell has identical effect with first to the 5th kind of secondary cell.
(embodiment)
Specific embodiments of the invention will be in following detailed description.
(embodiment 1-1 to 1-5)
Form the Coin shape secondary cell shown in Fig. 5.This secondary cell forms by following steps.Positive pole 51 and negative pole 52 are stacked with the barrier film that is impregnated with electrolyte 53 in the middle of it, and they are clipped between pack case 54 and the packing cap 55.Then, adopt 56 pairs of pack case of liner 54 and 55 calkings of packing cap to form secondary cell.At first, will be as 94 weight portion lithium cobalt composite oxide (LiCoO of positive electrode active materials 2), mix forming mixture as 3 weight portion graphite of electric conductor with as 3 weight portion polyvinylidene fluoride of binding agent, and will add this mixture as the N-N-methyl-2-2-pyrrolidone N-of solvent to form anodal mixed slurry.Next, the anodal mixed slurry that obtains is applied on the positive electrode collector 51A that the aluminium foil of 20 μ m thickness makes equably, and dry to form the thick anode active material layer 51B of 70 μ m.Then, the positive electrode collector 51A that forms anode active material layer 51B on it is struck out to have diameter be that the circle of 15mm is to form anodal 51.
And, use silicon as negative active core-shell material, and the thick anode active material layer 52B of the 5 μ m that made by silicon is formed on the thick negative electrode collector 52A of the 15 μ m that made by Copper Foil by sputter.Then, the negative electrode collector 52A that forms negative active core-shell material 52B layer on it being struck out diameter is that the circle of 16mm is to form negative pole 52.Simultaneously, regulate the loading of positive electrode active materials and negative active core-shell material so that the open circuit voltage when charging fully (, cell voltage) becomes 4.20V, and prevent that the lithium metal is separated out on negative pole 52 in charging process, the capacity of negative pole 52 is partly represented by embedding by lithium and the capacity that takes off embedding thus.
Next, with anodal 51 and the thick barrier film 53 of negative pole 52 and the 25 μ m that make by many microporous polypropylene membranes stacked, the electrolyte of 0.1g is injected barrier film 53.Then, they are included in the packing cap of being made by stainless steel 55 and pack case 54, and to packing cap 55 and pack case 54 calkings to obtain the secondary cell shown in Fig. 5.In embodiment 1-1, by will as the ethylene carbonate (EC) of solvent and dimethyl carbonate (DMC) and as the lithium hexafluoro phosphate of electrolytic salt with ethylene carbonate: dimethyl carbonate: the weight ratio of lithium hexafluoro phosphate=mix at 42: 42: 15, and add the cyclic imide salt of 1 weight % and form electrolyte.In embodiment 1-2, by will be as the 4-chloro-1 of solvent, 3-dioxolanes-2-ketone (CIEC) (it is the cyclic carbonate derivative with halogen atom) and dimethyl carbonate and as the lithium hexafluoro phosphate of electrolytic salt with 4-chloro-1,3-dioxolanes-2-ketone: dimethyl carbonate: the weight ratio of lithium hexafluoro phosphate=42: 42: 15 is mixed, and the cyclic imide salt that adds 1 weight % is to form electrolyte.In embodiment 1-3 and 1-5, by will be as the 4-fluoro-1 of solvent, 3-dioxolanes-2-ketone (FEC) (it is the cyclic carbonate derivative with halogen atom) and dimethyl carbonate (DMC) and as the lithium hexafluoro phosphate of electrolytic salt with 4-fluoro-1,3-dioxolanes-2-ketone: dimethyl carbonate: the weight ratio of lithium hexafluoro phosphate=42: 42: 15 is mixed, and the cyclic imide salt that adds 1 weight % is to form electrolyte.Cyclic imide salt is 1,1,2 of chemical formula 6 (1) expressions in embodiment 1-1 to 1-3,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium, in embodiment 1-4 2,2,3 of chemical formula 6 (2) expressions, 3,4,4-hexafluoro glutarimide lithium is the adjacent sulfo group benzimide lithium of chemical formula 6 (3) expressions in embodiment 1-5.
As Comparative Examples 1-1 to 1-3, except that not adding cyclic imide salt, as embodiment 1-1 to 1-5, prepare secondary cell with respect to embodiment 1-1 to 1-5.More particularly, in Comparative Examples 1-1, electrolyte is to comprise ethylene carbonate, the mixture of dimethyl carbonate and lithium hexafluoro phosphate, ethylene carbonate wherein: dimethyl carbonate: the weight ratio of lithium hexafluoro phosphate=42: 42: 15, in Comparative Examples 1-2, electrolyte is to comprise 4-chloro-1,3-dioxolanes-2-ketone, the mixture of dimethyl carbonate and lithium hexafluoro phosphate, wherein the 4-chloro-1,3-dioxolanes-2-ketone: dimethyl carbonate: the weight ratio of lithium hexafluoro phosphate=42: 42: 15, in Comparative Examples 1-3, electrolyte is to comprise 4-fluoro-1,3-dioxolanes-2-ketone, the mixture of dimethyl carbonate and lithium hexafluoro phosphate, wherein the 4-fluoro-1,3-dioxolanes-2-ketone: dimethyl carbonate: the weight ratio of lithium hexafluoro phosphate=42: 42: 15.
For charge and discharge cycles, the secondary cell that embodiment 1-1 to 1-5 and Comparative Examples 1-1 to 1-3 are obtained is charging 12 hours under the condition of 4.2V at maximum voltage under 1.77mA, 25 ℃, then after at interval 10 minutes, secondary cell discharges up to 2.5V under 1.77mA, and repeats charge and discharge cycles to be determined at the discharge capacitance of 50 circulations.Calculate discharge capacitance by (discharge capacity/initial capacity in 50 circulations) * 100% 50 circulations.This result is presented in the table 1.
(table 1)
Cell shapes: coin shape
Maximum charging voltage: 4.20V
Negative active core-shell material Solvent Cyclic imide salt Discharge capacitance (%)
Embodiment 1-1 Si EC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 60.5
Embodiment 1-2 CIEC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 79.4
Embodiment 1-3 FEC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 87.8
Embodiment 1-4 2,2,3,3,4,4-hexafluoro glutarimide lithium 88.6
Embodiment 1-5 Adjacent sulfo group benzimide lithium 87.2
Comparative Examples 1-1 Si EC+DMC Do not comprise 47.0
Comparative Examples 1-2 CIEC+DMC 68.4
Comparative Examples 1-3 FEC+DMC 75.6
EC: ethylene carbonate DMC: dimethyl carbonate
CIEC:4-chloro-1,3-dioxolanes-2-ketone
FEC:4-fluoro-1,3-dioxolanes-2-ketone
Can obviously find out from table 1, wherein use the embodiment 1-1 to 1-5 of cyclic imide salt to compare, obtain higher discharge capacitance with the Comparative Examples 1-1 to 1-3 that does not use cyclic imide salt.And, using 4-chloro-1 therein, 3-dioxolanes-2-ketone or 4-fluoro-1 among the embodiment 1-2 to 1-5 of 3-dioxolanes-2-ketone, are more in particular in and wherein use 4-fluoro-1, among the embodiment 1-3 to 1-5 of 3-dioxolanes-2-ketone, observe high effect.
In other words, find when electrolyte comprises cyclic imide salt, can improve cycle characteristics, and more preferably in electrolyte, comprise cyclic carbonate derivative with halogen atom.
(embodiment 2-1 to 2-5,3-1 to 3-5)
As embodiment 2-1 to 2-5, remove and use tin as negative active core-shell material, and the thick anode active material layer 52B of the 5 μ m that made by tin is formed on beyond the thick negative electrode collector 52A of 15 μ m that is made by Copper Foil goes up by vapour deposition, forms the Coin shape secondary cell as embodiment 1-1 to 1-5.Simultaneously, the loading of regulating positive electrode active materials and negative active core-shell material makes that open circuit voltage becomes 4.20V when charging fully, and prevent that the lithium metal is separated out on negative pole 52 in charging process, thereby the capacity of negative pole 52 is represented partly by embedding by lithium and the capacity that takes off embedding.
As embodiment 3-1 to 3-5, remove to use comprise indium and titanium contain the CoSnC material powder as negative active core-shell material, and 94 weight portions are contained the CoSnC material powder, as the graphite of 3 weight portions of electric conductor and as the polyvinylidene fluoride of 3 weight portions of binding agent be dispersed in as in the N-N-methyl-2-2-pyrrolidone N-of solvent to form mixture, mixture is applied on the thick negative electrode collector 52A of the 15 μ m that made by Copper Foil equably, dry then to form beyond the thick anode active material layer 52B of 70 μ m, as embodiment 1-1 to 1-5, form coin shape secondary cell.Simultaneously, regulate the loading of positive electrode active materials and negative active core-shell material so that the open circuit voltage when charging fully becomes 4.20V, and prevent that the lithium metal is separated out on negative pole 52 in charging process, thereby the capacity of negative pole 52 is represented partly by embedding by lithium and the capacity that takes off embedding.
Contain the CoSnC material powder and mix, and induce the mechanico-chemical reaction between them to synthesize by mixing tin-cobalt-indium-titanium alloy powder and carbon dust.When analyze obtained contain the composition of CoSnC material the time, the content of tin is 48.0 weight %, the content of cobalt is 23.0 weight %, the content of indium is 5.0 weight %, the content of titanium is 2.0 weight %, the content of carbon is 20.0 weight %, and cobalt is 32 weight % to the ratio Co/ (Sn+Co) of the total amount of tin and cobalt.Measure carbon content by carbon/sulphur analyzer, measure the content of tin, cobalt, indium and titanium by IPC (induction coupling gas ions) emission spectrometric method.And, when to obtain contain the CoSnC material and carry out X-ray diffraction the time, in the scope of the angle of diffraction 2 θ=20 ° to 50 °, observe and have the diffraction maximum that the angle of diffraction 2 θ are 1.0 ° or bigger wide half width.In addition, when to obtain contain the CoSnC material and carry out XPS measuring the time, the peak P1 that can obtain to represent among Fig. 6.When analyzing peak P1, can obtain the peak P2 of surface contamination carbon and the peak P3 that contains C1s in the CoSnC material on the energy side lower than peak P2.In being lower than the scope of 284.5eV, obtain peak P3.In other words, confirm that being included in the carbon that contains in the CoSnC material combines with another element.
As Comparative Examples 2-1 to 2-3 and 3-1 to 3-3 with respect to these embodiment, except not adding cyclic imide salt, as the same secondary cell that forms of embodiment 2-1 to 2-5, more particularly, use and the identical electrolyte of electrolyte that uses at Comparative Examples 1-1 to 1-3 with 3-1 to 3-5.
As among the embodiment 1-1 to 1-5, measure the discharge capacitance of the secondary cell of embodiment 2-1 to 2-5 and 3-1 to 3-5 and Comparative Examples 2-1 to 2-3 and 3-1 to 3-3 acquisition at the 50th circulation time.Simultaneously, be to secondary cell charge under the situation of 4.2V at maximum voltage.The results are shown in table 2 and the table 3.The numeral of separating with oblique line in bracket in negative active core-shell material is docile and obedient the content (weight %) that preface is represented the element that occurred.
(table 2)
Cell shapes: coin shape
Maximum charging voltage: 4.20V
Negative active core-shell material Solvent Cyclic imide salt Discharge capacitance (%)
Embodiment 2-1 Sn EC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 72.2
Embodiment 2-2 CIEC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 81.5
Embodiment 2-3 FEC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 90.1
Embodiment 2-4 2,2,3,3,4,4-hexafluoro glutarimide lithium 90.9
Embodiment 2-5 Adjacent sulfo group benzimide lithium 89.5
Comparative Examples 2-1 Sn EC+DMC Do not comprise 53.3
Comparative Examples 2-2 CIEC+DMC 69.8
Comparative Examples 2-3 FEC+DMC 77.1
EC: ethylene carbonate DMC: dimethyl carbonate
CIEC:4-chloro-1,3-dioxolanes-2-ketone
FEC:4-fluoro-1,3-dioxolanes-2-ketone
(table 3)
Cell shapes: coin shape
Maximum charging voltage: 4.20V
Negative active core-shell material Solvent Cyclic imide salt Discharge capacitance (%)
Embodiment 3-1 Sn-Co-In -Ti-C (48/23/5/ 2/20) EC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 77.8
Embodiment 3-2 CIEC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 85.7
Embodiment 3-3 FEC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 94.7
Embodiment 3-4 2,2,3,3,4,4-hexafluoro glutarimide lithium 95.5
Embodiment 3-5 Adjacent sulfo group benzimide lithium 94.1
Comparative Examples 3-1 Sn-Co-In -Ti-C (48/23/5/ 2/20) EC+DMC Do not comprise 57.5
Comparative Examples 3-2 CIEC+DMC 71.9
Comparative Examples 3-3 FEC+DMC 79.5
EC: the inferior second DMC of carbonic acid: dimethyl carbonate
CIEC:4-chloro-1,3-dioxolanes-2-ketone
FEC:4-fluoro-1,3-dioxolanes-2-ketone
From table 2 and table 3, can find out, as among the embodiment 1-1 to 1-5, use cyclic imide salt embodiment 2-1 and 3-1, embodiment 2-2 and 3-2 therein, embodiment 2-3 to 2-5 and 3-3 in 3-5, compare with 3-3 with 3-2 and Comparative Examples 2-3 with 3-1, Comparative Examples 2-2 with the Comparative Examples 2-1 that does not use cyclic imide salt, obtain higher discharge capacitance.And, use 4-chloro-1 therein, 3-dioxolanes-2-ketone or 4-fluoro-1, among the embodiment 2-2 to 2-5 and 3-2 to 3-5 of 3-dioxolanes-2-ketone, particularly, use 4-fluoro-1 therein, among the embodiment 2-3 to 2-5 and 3-3 to 3-5 of 3-dioxolanes-2-ketone, observe higher effect.
In other words, when comprising cyclic imide salt in the electrolyte, still can improve cycle characteristics, and more preferably comprise cyclic carbonate derivative under the situation of using other negative active core-shell material even find with halogen atom.
(embodiment 4-1 to 4-4)
Remove and adopt graphite as negative active core-shell material, and mix to form mixture with 97 weight portion graphite with as 3 weight portion polyvinylidene fluoride of binding agent, and the N-N-methyl-2-2-pyrrolidone N-is joined in this mixture, and this mixture is applied on the thick negative electrode collector 52A of the 15 μ m that made by Copper Foil equably, dry then to form beyond the thick anode active material layer 52B of 70 μ m, as embodiment 1-1, form the Coin shape secondary cell.Simultaneously, positive electrode active materials is lithium-manganese-cobalt-ni compound oxide (LiMn 0.3Co 0.2Ni 0.5O 2).And, the loading of regulating positive electrode active materials and negative active core-shell material makes that open circuit voltage becomes 4.60V in embodiment 4-1 when charging fully, in embodiment 4-2, become 4.50V, in embodiment 4-3, become 4.35V and in embodiment 4-4, become 4.25V.In addition, preventing that in charging process lithium metal from separating out makes the capacity of negative pole 52 partly be represented by embedding by lithium and the capacity that takes off embedding on negative pole 52.
As Comparative Examples 4-1 to 4-4 with respect to embodiment 4-1 to 4-4.Except that not adding cyclic imide salt, as embodiment 4-1 to 4-4, form secondary cell.When charging fully, open circuit voltage is 4.60V in Comparative Examples 4-1, and open circuit voltage is 4.50V in Comparative Examples 4-2, and open circuit voltage is 4.35V in Comparative Examples 4-3, and open circuit voltage is 4.25V in Comparative Examples 4-4.
And 4-5 and 4-6 except that the loading of regulating positive electrode active materials and negative active core-shell material makes that open circuit voltage becomes the 4.20V when charging fully, form secondary cell as embodiment 4-1 to 4-4 as a comparison case.Simultaneously, in Comparative Examples 4-6, cyclic imide salt is joined in the electrolyte, in Comparative Examples 4-5, do not add cyclic imide salt.
As embodiment 1-1 to 1-5, measure the discharge capacitance of the secondary cell of embodiment 4-1 to 4-4 and Comparative Examples 4-1 to 4-6 acquisition at the 50th circulation time.Simultaneously, under the following conditions to secondary cell charge: maximum charging voltage is 4.60V in embodiment 4-1 and Comparative Examples 4-1, in embodiment 4-2 and Comparative Examples 4-2 is 4.50V, in embodiment 4-3 and Comparative Examples 4-3 is 4.35V, in embodiment 4-4 and Comparative Examples 4-4 is 4.25V, is 4.20V in Comparative Examples 4-5 and 4-6.This results are shown among table 4 and Fig. 7.
(table 4)
Cell shapes: coin shape
Negative active core-shell material Maximum charging voltage (V) Solvent Cyclic imide salt Discharge capacitance (%)
Embodiment 4-1 Graphite 4.60 EC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 81.8
Embodiment 4-2 4.50 92.8
Embodiment 4-3 4.35 95.4
Embodiment 4-4 4.25 97.0
Comparative Examples 4-1 Graphite 4.60 EC+DMC Do not comprise 77.8
Comparative Examples 4-2 4.50 88.2
Comparative Examples 4-3 4.35 93.3
Comparative Examples 4-4 4.25 96.6
Comparative Examples 4-5 4.20 97.3
Comparative Examples 4-6 4.20 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 97.5
EC: ethylene carbonate DMC: dimethyl carbonate
From table 4 and Fig. 7 as seen, electrolyte comprises among the embodiment 4-1 to 4-4 of cyclic imide salt therein, compares with the Comparative Examples 4-1 to 4-4 that does not wherein comprise cyclic imide salt, obtains higher discharge capacitance.And in Comparative Examples 4-5 and 4-6, the effect that adds cyclic imide salt is low; Yet charging voltage is among 4.25V or the bigger embodiment 4-1 to 4-4 therein, obtains high effect.
In other words, even under the discovery situation that open circuit voltage is high when charging fully, when electrolyte comprises cyclic imide, still can improve cycle characteristics.
(embodiment 5-1 to 5-4)
Remove and adopt graphite as negative active core-shell material, and mix to form mixture with 97 weight portion graphite with as 3 weight portion polyvinylidene fluoride of binding agent, and the N-N-methyl-2-2-pyrrolidone N-is joined in the mixture, and this mixture is applied on the thick negative electrode collector 52A of the 15 μ m that made by Copper Foil equably, dry then to form beyond the thick anode active material layer 52B of 70 μ m, as embodiment 1-2 to 1-5, form the Coin shape lithium rechargeable battery.Simultaneously, positive electrode active materials is lithium-manganese-cobalt-ni compound oxide (LiMn 0.3Co 0.2Ni 0.5O 2).And the loading of regulating positive electrode active materials and negative active core-shell material makes that open circuit voltage becomes 4.50V when charging fully.In addition, preventing that in charging process lithium metal from separating out makes the capacity of negative pole 52 partly be represented by embedding by lithium and the capacity that takes off embedding on negative pole 52.
As Comparative Examples 5-1 to 5-2 with respect to embodiment 5-1 to 5-4, except that not adding cyclic imide salt, as embodiment 5-1 to 5-4, form secondary cell, promptly use the electrolyte identical with the electrolyte that in Comparative Examples 1-2 and 1-3, uses.
As embodiment 1-1 to 1-5, measure the discharge capacitance of the secondary cell of embodiment 5-1 to 5-4 and Comparative Examples 5-1 to 5-2 acquisition at the 50th circulation time.Simultaneously, be to charge under the condition of 4.50V secondary cell at maximum charging voltage.This result is shown in Table 5 with the result of embodiment 4-2 and Comparative Examples 4-2.
(table 5)
Cell shapes: coin shape
Maximum charging voltage: 4.50V
Negative active core-shell material Solvent Cyclic imide salt Discharge capacitance (%)
Embodiment 4-2 Graphite EC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 92.8
Embodiment 5-1 CIEC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 93.2
Embodiment 5-2 FEC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 97.1
Embodiment 5-3 2,2,3,3,4,4-hexafluoro glutarimide lithium 97.9
Embodiment 5-4 Adjacent sulfo group benzimide lithium 96.1
Comparative Examples 4-2 Graphite EC+DMC Do not comprise 88.2
Comparative Examples 5-1 CIEC+DMC 90.5
Comparative Examples 5-2 FEC+DMC 92.3
EC: ethylene carbonate DMC: dimethyl carbonate
CIEC:4-chloro-1,3-dioxolanes-2-ketone
FEC:4-fluoro-1,3-dioxolanes-2-ketone
As seen from Table 5, use therein among the embodiment 5-1 and 5-2 to 5-4 of cyclic imide salt, compare, obtain higher discharge capacitance with the embodiment 5-1 to 5-2 that does not wherein use cyclic imide salt.And, use 4-chloro-1 therein, 3-dioxolanes-2-ketone or 4-fluoro-1, among the embodiment 5-1 to 5-4 of 3-dioxolanes-2-ketone, do not compare, obtain higher discharge capacitance with wherein not using the two embodiment 4-2, particularly, use 4-fluoro-1 therein, among the embodiment 5-2 to 5-4 of 3-dioxolanes-2-ketone, obtain high effect.
In other words, even find under open circuit voltage is high when charging fully the situation, also preferably except that the ring-type imide salts, also comprise cyclic carbonate derivative with halogen atom.
(embodiment 6-1,6-2,7-1,7-2,8-1,8-2,9-1,9-2)
Remove 1,1,2,2,3,3-HFC-236fa-1, the content of 3-disulfonyl imines lithium in electrolyte is outside 10 weight % or the 0.1 weight %, as the same secondary cell that forms of embodiment 1-3,2-3,3-3 and 4-2.
As embodiment 1-1 to 1-5, measure the discharge capacitance of secondary cell at the 50th circulation time.Simultaneously, in embodiment 9-1 and 9-2, be to charge under the condition of 4.50V secondary cell at maximum charging voltage, be 4.20V in other embodiments.This result is shown in table 6 to 9 with the result of Comparative Examples 1-3,2-3,3-3 and 4-2.
(table 6)
Cell shapes: coin shape
Maximum charging voltage: 4.20V
Negative active core-shell material Solvent Cyclic imide salt Discharge capacitance (%)
Kind Content (weight %)
Embodiment 6-1 Si FEC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 10 76.3
Embodiment 1-3 1.0 87.8
Embodiment 6-2 0.1 75.9
Comparative Examples 1-3 Si FEC+DMC Do not comprise 0 75.6
DMC: dimethyl carbonate FEC:4-fluoro-1,3-dioxolanes-2-ketone
(table 7)
Cell shapes: coin shape
Maximum charging voltage: 4.20V
Negative active core-shell material Solvent Cyclic imide salt Discharge capacitance (%)
Kind Content (weight %)
Embodiment 7-1 Sn FEC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 10 77.8
Embodiment 2-3 1.0 90.1
Embodiment 7-2 0.1 77.2
Comparative Examples 2-3 Sn FEC+DMC Do not comprise 0 77.1
DMC: dimethyl carbonate FEC:4-fluoro-1,3-dioxolanes-2-ketone
(table 8)
Cell shapes: coin shape
Maximum charging voltage: 4.20V
Negative active core-shell material Solvent Cyclic imide salt Discharge capacitance (%)
Kind Content (weight %)
Embodiment 8-1 Sn-Co-In- Ti-C (48/23/5/ 2/20) FEC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 10 80.2
Embodiment 3-3 1.0 94.7
Embodiment 8-2 0.1 79.8
Comparative Examples 3-3 Sn-Co-In- Ti-C (48/23/5/ 2/20) FEC+DMC Do not comprise 0 79.5
DMC: dimethyl carbonate FEC:4-fluoro-1,3-dioxolanes-2-ketone
(table 9)
Cell shapes: coin shape
Maximum charging voltage: 4.50V
Negative active core-shell material Solvent Cyclic imide salt Discharge capacitance (%)
Kind Content (weight %)
Embodiment 9-1 Graphite EC+ DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 10 89.1
Embodiment 4-2 1.0 92.8
Embodiment 9-2 0.1 88.7
Comparative Examples 4-2 Graphite EC+DMC Do not comprise 0 88.2
EC: ethylene carbonate DMC: dimethyl carbonate
From table 6 to 9 as can be seen, such trend is arranged: along with 1,1,2,2,3,3-HFC-236fa-1, the content of 3-disulfonyl imines lithium in electrolyte increases, discharge capacitance increases to maximum, reduces then.
In other words, find that the content of cyclic imide salt in electrolyte is preferably in the scope of 0.1 weight % to 10 weight % (comprising end points).
(embodiment 10-1 to 10-8,11-1 to 11-8)
As embodiment 10-1 to 10-4, as embodiment 1-1, form secondary cell, except as solvent, except that carbonic acid ethyl and dimethyl carbonate, also use 1 of chemical formula 3 (1) expressions, the 4-vinyl-1 of 3-dioxole-2-ketone (VC), chemical formula 3 (2) expressions, 1 of 3-dioxolanes-2-ketone (VEC), chemical formula 4 (1) expressions, 1 of 3-propane sultone (PS) or chemical formula 4 (2) expressions are outside the 3-propylene sultone.The concrete composition of solvent is ethylene carbonate in embodiment 10-1: dimethyl carbonate: 1,3-dioxole-2-ketone=40: 42: 2 (weight ratio), it in embodiment 10-2 ethylene carbonate: dimethyl carbonate: 4-vinyl-1,3-dioxolanes-2-ketone=40: 42: 2 (weight ratio), it in embodiment 10-3 ethylene carbonate: dimethyl carbonate: 1,3-propane sultone=40: 42: 2 (weight ratio), and be ethylene carbonate in embodiment 10-4: dimethyl carbonate: 1,3-propylene sultone=40: 42: 2 (weight ratio).
As embodiment 10-5 to 10-8, as embodiment 1-3, form secondary cell, except as solvent, remove 4-fluoro-1, beyond 3-dioxolanes-2-ketone and the dimethyl carbonate, also use 1,3-dioxole-2-ketone, 4-vinyl-1,3-dioxolanes-2-ketone, 1,3-propane sultone or 1 is outside the 3-propylene sultone.The concrete composition of solvent is 4-fluoro-1 in embodiment 10-5,3-dioxolanes-2-ketone: dimethyl carbonate: 1,3-dioxole-2-ketone=41: 42: 1 (weight ratio), it in embodiment 10-6 4-fluoro-1,3-dioxolanes-2-ketone: dimethyl carbonate: 4-vinyl-1,3-dioxolanes-2-ketone=41: 42: 1 (weight ratio), it in embodiment 10-7 4-fluoro-1,3-dioxolanes-2-ketone: dimethyl carbonate: 1,3-propane sultone=41: 42: 1 (weight ratio), in embodiment 10-8 4-fluoro-1,3-dioxolanes-2-ketone: dimethyl carbonate: 1,3-propylene sultone=41: 42: 1 (weight ratio).
As embodiment 11-1 to 11-4, as embodiment 3-1, form secondary cell, except as solvent, except that carbonic acid ethyl and dimethyl carbonate, also use 1,3-dioxole-2-ketone, 4-vinyl-1,3-dioxolanes-2-ketone, 1,3-propane sultone or 1 is outside the 3-propylene sultone.The concrete composition of solvent is ethylene carbonate in embodiment 11-1: dimethyl carbonate: 1,3-dioxole-2-ketone=40: 42: 2 (weight ratio), it in embodiment 11-2 ethylene carbonate: dimethyl carbonate: 4-vinyl-1,3-dioxolanes-2-ketone=40: 42: 2 (weight ratio), it in embodiment 11-3 ethylene carbonate: dimethyl carbonate: 1,3-propane sultone=40: 42: 2 (weight ratio), be ethylene carbonate in embodiment 11-4: dimethyl carbonate: 1,3-propylene sultone=40: 42: 2 (weight ratio).
As embodiment 11-5 to 11-8, as embodiment 3-3, form secondary cell, except as solvent, remove 4-fluoro-1, beyond 3-dioxolanes-2-ketone and the dimethyl carbonate, also use 1,3-dioxole-2-ketone, 4-vinyl-1,3-dioxolanes-2-ketone, 1,3-propane sultone or 1 is outside the 3-propylene sultone.The concrete composition of solvent is 4-fluoro-1 in embodiment 11-5,3-dioxolanes-2-ketone: dimethyl carbonate: 1,3-dioxole-2-ketone=41: 42: 1 (weight ratio), it in embodiment 11-6 4-fluoro-1,3-dioxolanes-2-ketone: dimethyl carbonate: 4-vinyl-1,3-dioxolanes-2-ketone=41: 42: 1 (weight ratio), it in embodiment 11-7 4-fluoro-1,3-dioxolanes-2-ketone: dimethyl carbonate: 1,3-propane sultone=41: 42: 1 (weight ratio), in embodiment 11-8 4-fluoro-1,3-dioxolanes-2-ketone: dimethyl carbonate: 1,3-propylene sultone=41: 42: 1 (weight ratio).
As Comparative Examples 10-1 to 10-8 and 11-1 to 11-8, except that not adding cyclic imide salt, as the same secondary cell that forms among embodiment 10-1 to 10-8 and the 11-1 to 11-8 with respect to embodiment 10-1 to 10-8 and 11-1 to 11-8.
As embodiment 1-1 to 1-5, measure the discharge capacitance of the 50th circulation time of secondary cell of acquisition.Simultaneously, be to charge under the condition of 4.20V secondary cell at maximum voltage.The result of this result in embodiment 1-1,1-3,3-1 and 3-3 and Comparative Examples 1-1,1-3,3-1 and 3-3 is shown in table 10 and table 11.
(table 10)
Cell shapes: coin shape
Maximum charging voltage: 4.20V
Negative active core-shell material Solvent Cyclic imide salt Discharge capacitance (%)
Embodiment 1-1 Si EC+DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 60.5
Embodiment 10-1 EC+DMC+VC 67.2
Embodiment 10-2 EC+DMC+VEC 67.8
Embodiment 10-3 EC+DMC+PS 63.2
Embodiment 10-4 EC+DMC+PRS 65.3
Embodiment 1-3 Si FEC+DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 87.8
Embodiment 10-5 FEC+DMC+VC 90.1
Embodiment 10-6 FEC+DMC+VEC 90.3
Embodiment 10-7 FEC+DMC+PS 88.7
Embodiment 10-8 FEC+DMC+PRS 89.1
Comparative Examples 1-1 Si EC+DMC Do not comprise 47.0
Comparative Examples 10-1 EC+DMC+VC 48.0
Comparative Examples 10-2 EC+DMC+VEC 48.8
Comparative Examples 10-3 EC+DMC+PS 47.6
Comparative Examples 10-4 EC+DMC+PRS 47.9
Comparative Examples 1-3 Si FEC+DMC Do not comprise 75.6
Comparative Examples 10-5 FEC+DMC+VC 76.6
Comparative Examples 10-6 FEC+DMC+VEC 76.9
Comparative Examples 10-7 FEC+DMC+PS 75.9
Comparative Examples 10-8 FEC+DMC+PRS 76.4
EC: ethylene carbonate DMC: dimethyl carbonate
FEC:4-fluoro-1,3-dioxolanes-2-ketone VC:1,3-dioxole-2-ketone
VEC:4-vinyl-1,3-dioxolanes-2-ketone PS:1,3-propane sultone
PRS:1,3-propylene sultone
(table 11)
Cell shapes: coin shape
Maximum charging voltage: 4.20V
Negative active core-shell material (weight) Solvent Cyclic imide salt Discharge capacitance (%)
Embodiment 3-1 Sn-Co-In -Ti-C (48/23/5/ 2/20) EC+DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 77.8
Embodiment 11-1 EC+DMC+VC 79.8
Embodiment 11-2 EC+DMC+VEC 80.0
Embodiment 11-3 EC+DMC+PS 78.0
Embodiment 11-4 EC+DMC+PRS 78.3
Embodiment 3-3 Sn-Co-In -Ti-C (48/23/5/ 2/20) EC+DMC 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium 94.7
Embodiment 11-5 EC+DMC+VC 96.0
Embodiment 11-6 EC+DMC+VEC 96.1
EC+DMC+PS 95.2
Embodiment 11-7
Embodiment 11-8 EC+DMC+PRS 95.7
Comparative Examples 3-1 Sn-Co-In -Ti-C (48/23/5/ 2/20) EC+DMC Do not comprise 57.5
Comparative Examples 11-1 EC+DMC+VC 59.6
Comparative Examples 11-2 EC+DMC+VEC 60.0
Comparative Examples 11-3 EC+DMC+PS 58.0
Comparative Examples 11-4 EC+DMC+PRS 58.4
Comparative Examples 3-3 Sn-Co-In -Ti-C (48/23/5/ 2/20) FEC+DMC Do not comprise 79.5
Comparative Examples 11-5 FEC+DMC+VC 83.0
Comparative Examples 11-6 FEC+DMC+VE C 83.7
Comparative Examples 11-7 FEC+DMC+PS 80.0
Comparative Examples 10-8 FEC+DMC+PR S 80.8
EC: ethylene carbonate DMC: dimethyl carbonate
FEC:4-fluoro-1,3-dioxolanes-2-ketone VC:1,3-dioxole-2-ketone
VEC:4-vinyl-1,3-dioxolanes-2-ketone PS:1,3-propane sultone
PRS:1,3-propylene sultone
From table 10 and 11 as seen, the same in embodiment 1-1,1-3,3-1 and 3-3, use therein among the embodiment 10-1 to 10-8 and 11-1 to 11-8 of cyclic imide salt, compare with 11-1 to 11-8 with the Comparative Examples 10-1 to 10-8 that does not wherein use cyclic imide salt, obtain higher capability retention.And, use 1 therein, 3-dioxole-2-ketone, 4-vinyl-1,3-dioxolanes-2-ketone, 1,3-propane sultone or 1, among embodiment 10-1 to 10-4,10-5 to 10-8,11-1 to 11-4 and the 11-5 to 11-8 of 3-propylene sultone, compare, obtain higher discharge capacitance with embodiment 1-1, the 1-3,3-1 and the 3-3 that do not use these compounds.
In other words, find when use has the cyclic carbonate of unsaturated bond or sultone, can further to improve cycle characteristics.
(embodiment 12-1-1 and 12-1-2 to 12-27-1 and 12-27-2)
Form cylinder type secondary battery as illustrated in fig. 1 and 2.At first, with lithium carbonate (Li 2CO 3) and cobalt carbonate (CoCO 3) mix with 0.5: 1 molar ratio, and mixture is fired 5 hours to obtain lithium cobalt composite oxide (LiCoO in air under 890 ℃ 2).When carrying out X-ray diffraction on the lithium cobalt composite oxide to acquisition, the LiCoO of acquisition 2The LiCoO that lists in diffraction pattern and JCPDS (the Joint Committee of Powder DiffractionStandard) file 2The peak approximate match.Then, the lithium cobalt composite oxide is ground into the powder type that average grain diameter is 10 μ m, thereby forms positive electrode active materials.
Next, with the LiCoO of 95 weight portions 2Li with 5 weight portions 2CO 3Mixing is to form mixture, with this mixtures of 91 weight portions, as the Delanium (KS-15 of 6 weight portions of electric conductor, Lonza) and the polyvinylidene fluoride of 3 weight portions mix with the preparation mixture, then this mixture is dispersed in as in the N-N-methyl-2-2-pyrrolidone N-of solvent to form the cathode mix slurry.Next, just the cathode mix slurry is coated on two faces of the thick positive electrode collector 21A of the 20 μ m that made by banded aluminium foil and after the drying equably, forms anodal 21 thereby form positive-electrode mixture layer 21B by compression molding.Afterwards, positive wire made of aluminum 25 is attached to the end of positive electrode collector 21A.
By using the synthetic tin that comprises of mechanico-chemical reaction, and in embodiment 12-1-1 and 12-1-2 to 12-27-1 and 12-27-2 as first negative active core-shell material that constitutes element, the composition of negative active core-shell material as table 12 to the change shown in 17.More particularly, in embodiment 12-1-1 and 12-1-2 to 12-21-1 and 12-21-2, second element becomes cobalt, iron, magnesium, titanium, vanadium, chromium, manganese, nickel, copper, zinc, gallium, zirconium, niobium, molybdenum, silver, indium, cerium, hafnium, tantalum, tungsten or bismuth, and element is a carbon.In embodiment 12-22-1 and 12-22-2 to 12-24-1 and 12-24-2, second element is a cobalt, and element becomes boron, aluminium or phosphorus.In embodiment 12-25-1 and 12-25-2 to 12-27-1 and 12-27-2, second element is a cobalt, and element is carbon, and except that them, also adds another element.
The composition that obtains the negative active core-shell material powder is analyzed.Measure carbon content by carbon/sulphur analyzer, and pass through the content of other element of IPC diverging light spectrometry.In the bracket that the results are shown in the negative active core-shell material part of table 12 in 17 that obtains.The numeral of being separated by oblique line in bracket is docile and obedient the content (weight %) that preface is represented the element that wherein occurs.
At the negative active core-shell material powder that 80 weight portions are obtained, as the Delanium (KS-15 of 14 weight portions of electric conductor, Lonza) and the acetylene black of 1 weight portion and mix to form mixture as 5 weight portion polyvinylidene fluoride of adhesive, and with this mixture be dispersed in as in the N-N-methyl-2-2-pyrrolidone N-of solvent to form the negative pole mixture paste, this negative pole mixture paste is coated onto on the negative electrode collector 22A, and dry, thereby form negative pole 22 with formation anode active material layer 22B.Simultaneously, the loading of regulating positive electrode active materials and negative active core-shell material makes that open circuit voltage becomes 4.20V when charging fully, and prevent that the lithium metal is separated out on negative pole 22 in charging process, the capacity of negative pole 22 is partly represented by embedding by lithium and the capacity that takes off embedding thus.Next, will be attached to the end of negative electrode collector 22A by the negative wire 26 that nickel is made.
After forming positive pole 21 and negative pole 22; the barrier film 23 of the 25 μ m that preparation is made by polyethylene; and negative pole 22, barrier film 23, positive pole 21 and barrier film 23 are formed sandwich with this sequential cascade; and several times with this sandwich screw winding; and the outermost portion of screw winding sandwich protected with adhesive tape, thereby form spiral winding electrode 20.
After forming spiral winding electrode 20, spiral winding electrode 20 is clipped between a pair of insulation board 12 and 13, negative wire 26 is welded on the battery case 11, and positive wire 25 is welded on the relief valve mechanism 15, then spiral winding electrode 20 is included in the battery case of being made by the iron of nickel plating 11.Afterwards, electrolyte is injected in the battery case 11 by the decompression method, thereby the formation diameter is 18mm, highly is the cylinder type secondary battery of 65mm.As electrolyte, use to comprise as the ethylene carbonate of solvent and dimethyl carbonate and as the LiPF of electrolytic salt 6With by 1,1,2,2,3 of chemical formula 6 (1) expression, 3-HFC-236fa-1, the mixture of 3-disulfonyl imines lithium (it is a cyclic imide salt), wherein ethylene carbonate: dimethyl carbonate: LiPF 6: 1,1,2,2,3,3-HFC-236fa-1, the weight ratio of 3-disulfonyl imines lithium=40: 37.4: 7.6: 15, or use the 4-fluoro-1 comprise as solvent, 3-dioxolanes-2-ketone, ethylene carbonate and dimethyl carbonate and as the LiPF of electrolytic salt 6With 1,1,2,2,3,3-HFC-236fa-1, the mixture of 3-disulfonyl imines lithium (it is a cyclic imide salt), wherein the 4-fluoro-1,3-dioxolanes-2-ketone: ethylene carbonate: dimethyl carbonate: LiPF 6: 1,1,2,2,3,3-HFC-236fa-1, the weight ratio of 3-disulfonyl imines lithium=20: 20: 37.4: 7.6: 15.
As Comparative Examples with respect to embodiment, to remove and do not use 1,1,2,2,3,3-HFC-236fa-1 outside the 3-disulfonyl imines lithium, forms secondary cell as embodiment.More particularly, in the Comparative Examples composition of electrolyte as table 12 to shown in 17.
Measure the cycle characteristics of secondary cell under 25 ℃ and 50 ℃ that embodiment and Comparative Examples obtain.The results are shown in table 12 in 17.As charge and discharge cycles, under 25 ℃ or 50 ℃, secondary cell charging under the constant current of 2500mA and constant voltage is discharged secondary cell up to final voltage 2.6V under the constant current of 2000mA then up to reaching maximum voltage 4.2V.Repeat 150 times charge and discharge cycles, and the first time cyclic discharge capacity be to measure the discharge capacitance (%) of the 150th circulation time under 100 the situation as cycle characteristics.
(table 12)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material The composition of electrolyte (weight %) Discharge capacitance (%)
FEC EC DMC LiPF 6 Chemical formula 6 (1) 25℃ 50℃
Embodiment 12-1-1 Sn-Co-C (50/29.4/ 19.6) - 40 37.4 7.6 15 61 55
Embodiment 12-1-2 20 20 37.4 7.6 15 90 88
Comparative Examples 12-1-1 - 40 52.4 7.6 - 60 52
Comparative Examples 12-1-2 20 20 52.4 7.6 - 90 84
Embodiment 12-2-1 Sn-Fe-C (50/29.4/ 19.6) - 40 37.4 7.6 15 58 54
Embodiment 12-2-2 20 20 37.4 7.6 15 80 78
Comparative Examples 12-2-1 - 40 52.4 7.6 - 50 42
Comparative Examples 12-2-2 20 20 52.4 7.6 - 78 71
Embodiment 12-3-1 Sn-Mg-C (50/29.4/ 19.6) - 40 37.4 7.6 15 52 47
Embodiment 12-3-2 20 20 37.4 7.6 15 82 79
Comparative Examples 12-3-1 - 40 52.4 7.6 - 51 43
Comparative Examples 12-3-2 20 20 52.4 7.6 - 80 74
Embodiment 12-4-1 Sn-Ti-C (50/29.4/ 19.6) - 40 37.4 7.6 15 65 56
Embodiment 12-4-2 - 20 20 37.4 7.6 15 90 87
Comparative Examples 12-4-1 - 40 52.4 7.6 - 60 52
Comparative Examples 12-4-2 20 20 52.4 7.6 - 90 84
Embodiment 12-5-1 Sn-V-C (50/29.4/ 19.6) - 40 37.4 7.6 15 54 46
Embodiment 12-5-2 20 20 37.4 7.6 15 79 75
Comparative Examples 12-5-1 - 40 52.4 7.6 - 50 42
Comparative Examples 12-5-2 20 20 52.4 7.6 - 78 72
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
(table 13)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) The composition of electrolyte (weight %) Discharge capacitance (%)
FEC EC DMC LiPF 6 Chemical formula 6 (1) 25℃ 50℃
Embodiment 12-6-1 Sn-Cr-C (50/29.4/ 19.6) - 40 37.4 7.6 15 56 46
Embodiment 12-6-2 20 20 37.4 7.6 15 80 78
Comparative Examples 12-6-1 - 40 52.4 7.6 - 52 44
Comparative Examples 12-6-2 20 20 52.4 7.6 - 78 71
Embodiment 12-7-1 Sn-Mn-C (50/29.4/ 19.6) - 40 37.4 7.6 15 51 47
Embodiment 12-7-2 20 20 37.4 7.6 15 76 74
Comparative Examples 12-7-1 - 40 52.4 7.6 - 49 42
Comparative Examples 12-7-2 20 20 52.4 7.6 - 75 69
Embodiment 12-8-1 Sn-Ni-C (50/29.4/ 19.6) - 40 37.4 7.6 15 54 46
Embodiment 12-8-2 20 20 37.4 7.6 15 80 77
Comparative Examples 12-8-1 - 40 52.4 7.6 - 52 43
Comparative Examples 12-8-2 20 20 52.4 7.6 - 79 73
Embodiment 12-9-1 Sn-Cu-C (50/29.4/ 19.6) - 40 37.4 7.6 15 56 49
Embodiment 12-9-2 20 20 37.4 7.6 15 85 81
Comparative Examples 12-9-1 - 40 52.4 7.6 - 54 46
Comparative Examples 12-9-2 20 20 52.4 7.6 - 84 78
Embodiment 12-10-1 Sn-Zn-C (50/29.4/ 19.6) - 40 37.4 7.6 15 53 49
Embodiment 12-10-2 20 20 37.4 7.6 15 78 75
Comparative Examples 12-10-1 - 40 52.4 7.6 - 51 43
Comparative Examples 12-10-2 20 20 52.4 7.6 - 77 71
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
(table 14)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) The composition of electrolyte (weight %) Discharge capacitance (%)
FEC EC DMC LiPF 6 Chemical formula 6 (1) 25℃ 50℃
Embodiment 12-11-1 Sn-Ga-C (50/29.4/ 19.6) - 40 37.4 7.6 15 52 48
Embodiment 12-11-2 20 20 37.4 7.6 15 78 74
Comparative Examples 12-1 1-1 - 40 52.4 7.6 - 50 42
Comparative Examples 12-11-2 20 20 52.4 7.6 - 77 71
Embodiment 12-12-1 Sn-Zr-C (50/29.4/ 19.6) - 40 37.4 7.6 15 53 48
Embodiment 12-12-2 20 20 37.4 7.6 15 80 78
Comparative Examples 12-12-1 - 40 52.4 7.6 - 52 43
Comparative Examples 12-12-2 20 20 52.4 7.6 - 78 72
Embodiment 12-13-1 Sn-Nb-C (50/29.4/ 19.6) - 40 37.4 7.6 15 54 49
Embodiment 12-13-2 20 20 37.4 7.6 15 80 78
Comparative Examples 12-13-1 - 40 52.4 7.6 - 52 44
Comparative Examples 12-13-2 20 20 52.4 7.6 - 78 71
Embodiment 12-14-1 Sn-Mo-C (50/29.4/ 19.6) - 40 37.4 7.6 15 53 48
Embodiment 12-14-2 20 20 37.4 7.6 15 79 76
Comparative Examples 12-14-1 - 40 52.4 7.6 - 50 42
Comparative Examples 12-14-2 20 20 52.4 7.6 - 77 72
Embodiment 12-15-1 Sn-Ag-C (50/29.4/ 19.6) - 40 37.4 7.6 15 54 49
Embodiment 12-15-2 20 20 37.4 7.6 15 79 76
Comparative Examples 12-15-1 - 40 52.4 7.6 - 52 43
Comparative Examples 12-15-2 20 20 52.4 7.6 - 78 72
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
(table 15)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) The composition of electrolyte (weight %) Discharge capacitance (%)
FEC EC DMC LiPF 6 Chemical formula 6 (1) 25℃ 50℃
Embodiment 12-16-1 Sn-In-C (50/29.4/ 19.6) - 40 37.4 7.6 15 55 51
Embodiment 12-16-2 20 20 37.4 7.6 15 87 85
Comparative Examples 12-16-1 - 40 52.4 7.6 - 55 46
Comparative Examples 12-16-2 20 20 52.4 7.6 - 85 79
Embodiment 12-17-1 Sn-Ce-C (50/29.4/ 19.6) - 40 37.4 7.6 15 52 48
Embodiment 12-17-2 20 20 37.4 7.6 15 79 75
Comparative Examples 12-17-1 - 40 52.4 7.6 - 49 42
Comparative Examples 12-17-2 20 20 52.4 7.6 - 77 71
Embodiment 12-18-1 Sn-Hf-C (50/29.4/ 19.6) - 40 37.4 7.6 15 51 47
Embodiment 12-18-2 20 20 37.4 7.6 15 78 74
Comparative Examples 12-18-1 - 40 52.4 7.6 - 50 42
Comparative Examples 12-18-2 20 20 52.4 7.6 - 76 70
Embodiment 12-19-1 Sn-Ta-C (50/29.4/ 19.6) - 40 37.4 7.6 15 50 45
Embodiment 12-19-2 20 20 37.4 7.6 15 77 73
Comparative Examples 12-19-1 - 40 52.4 7.6 - 48 41
Comparative Examples 12-19-2 20 20 52.4 7.6 - 76 70
Embodiment 12-20-1 Sn-W-C (50/29.4/ 19.6) - 40 37.4 7.6 15 50 44
Embodiment 12-20-2 20 20 37.4 7.6 15 77 73
Comparative Examples 12-20-1 - 40 52.4 7.6 - 48 40
Comparative Examples 12-20-2 20 20 52.4 7.6 - 75 70
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
(table 16)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) The composition of electrolyte (weight %) Discharge capacitance (%)
FEC EC DMC LiPF 6 Chemical formula 6 (1) 25℃ 50℃
Embodiment 12-21-1 Sn-Bi-C (50/29.4/ 19.6) - 40 37.4 7.6 15 51 46
Embodiment 12-21-2 20 20 37.4 7.6 15 77 74
Comparative Examples 12-21-1 - 40 52.4 7.6 - 49 41
Comparative Examples 12-21-2 20 20 52.4 7.6 - 76 71
Embodiment 12-22-1 Sn-Co-B (50/29.4/ 19.6) 20 20 37.4 7.6 15 72 67
Comparative Examples 12-22-1 20 20 52.4 7.6 - 71 64
Embodiment 12-23-1 Sn-Co-Al (50/29.4/ 19.6) 20 20 37.4 7.6 15 75 73
Comparative Examples 12-23-1 20 20 52.4 7.6 - 73 67
Embodiment 12-24-1 Sn-Co-P (50/29.4/ 19.6) 20 20 37.4 7.6 15 75 75
Comparative Examples 12-24-1 20 20 52.4 7.6 - 74 68
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
(table 17)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) The composition of electrolyte (weight %) Discharge capacitance (%)
FEC EC DMC LiPF 6 Chemical formula 6 (1) 25℃ 50℃
Embodiment 12-25-1 Sn-Co-In -C (50/24.4/ 5/19.6) - 40 37.4 7.6 15 67 61
Embodiment 12-25-2 20 20 37.4 7.6 15 94 91
Comparative Examples 12-25-1 - 40 52.4 7.6 - 64 56
Comparative Examples 12-25-2 20 20 52.4 7.6 - 92 86
Embodiment 12-26-1 Sn-Co-In -Ti-C (49/23.4/ 5/2/19.6) - 40 37.4 7.6 15 74 73
Embodiment 12-26-2 20 20 37.4 7.6 15 95 92
Comparative Examples 12-26-1 - 40 52.4 7.6 - 70 62
Comparative Examples 12-26-2 20 20 52.4 7.6 - 94 88
Embodiment 12-27-1 Sn-Si-Co -C (48/3.9/2 7.5/19.6) - 40 37.4 7.6 15 60 55
Embodiment 12-27-2 20 20 37.4 7.6 15 86 83
Comparative Examples 12-27-1 - 40 52.4 7.6 - 55 46
Comparative Examples 12-27-2 20 20 52.4 7.6 - 85 79
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
17 as seen,, in each embodiment do not compare to from table 12, can improve discharge capacitance, and particularly, under 50 ℃, observe higher effect with wherein not using the Comparative Examples of cyclic imide salt.In addition, when using 4-fluoro-1,3-dioxolanes-2-ketone can obtain higher performance during as solvent.In other words, find when comprising cyclic imide salt in the electrolyte, even comprise in use under the situation of negative material as negative active core-shell material of tin, still can improve cycle characteristics, and particularly, can effectively improve the cycle characteristics under hot conditions.In addition, find when using 4-fluoro-1 that 3-dioxolanes-2-ketone can obtain higher effect during as solvent.
(embodiment 13-1 to 13-6)
Except that change contains the composition of SnCoC material, as embodiment 12-1-2, form secondary cell.As embodiment 5-1-2, analyze the composition that contains the SnCoC material that forms among the embodiment 13-1 to 13-6.The results are shown in table 18 and 19.And, when to the containing the SnCoC material and carry out X-ray diffraction of embodiment 13-1 to 13-6, in the scope of the angle of diffraction 2 θ=20 ° to 50 °, observe and have the diffraction maximum that the angle of diffraction 2 θ are 1 ° or bigger wide half width.In addition, when when containing the SnCoC material and carry out XPS measuring, obtain peak P1 shown in Figure 6.When peak P1 is analyzed, obtain the peak P2 of surface contamination carbon and the peak P3 that contains C1s in the SnCoC material on the energy side lower than peak P2.In being lower than the scope of 284.5eV, obtain peak P3.In other words, confirm that containing the carbon that comprises in the SnCoC material combines with another element.
As embodiment 12-1-2, measure the cycle characteristics of the secondary cell of embodiment 13-1 to 13-6.This result is shown in table 18 and 19 together with the result of embodiment 12-1-2.In table 19, also be illustrated in 25 ℃ of discharge capacities that circulate for the first time down.
(table 18)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material Discharge capacitance (%)
Form (weight %) Co/ (Sn+Co) (weight %)
Sn Co C 25℃ 50℃
Embodiment 13-1 56.1 33.0 9.9 37 79 81
Embodiment 12-1-2 50.0 29.4 19.6 90 88
Embodiment 13-1 43.7 25.6 29.7 81 81
(table 19)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material Discharge capacity (mAh) Discharge capacitance (%)
Component (weight %) Co/ (Sn+Co) (weight %)
Sn Co C 25℃ 50℃
Embodiment 13-3 55.4 23.8 19.8 30 3480 82 81
Embodiment 13-4 53.1 26.1 19.8 33 3420 85 84
Embodiment 12-1-2 50.0 29.4 19.6 37 3350 90 88
Embodiment 13-5 31.7 47.5 19.8 60 2990 92 91
Embodiment 13-6 23.8 55.4 19.8 70 2860 93 92
Shown in table 18, such trend is arranged: along with the increase of carbon content, discharge capacitance increases to maximum, reduces then.And shown in table 19, such trend is arranged: the ratio Co/ (Sn+Co) to the total amount of tin and cobalt increases along with cobalt, and discharge capacitance improves, but discharge capacity reduces.In other words, find preferably to use wherein carbon content in the scope of 9.9 weight % to 29.7 weight % (comprising end points), and cobalt is to the ratio Co/ (Sn+Co) of the total amount of tin and the cobalt material that contains SnCoC of (comprising end points) in the scope of 30 weight % to 70 weight %, because can obtain high power capacity, and can obtain superior cycle characteristics.
(embodiment 14-1 to 14-7)
Remove in the change electrolyte shown in table 20 1,1,2,2,3,3-HFC-236fa-1 outside the content of 3-disulfonyl imines lithium, forms secondary cell as embodiment 12-1-2.The composition of each electrolyte is shown in table 20.
(table 20)
Cell shapes: cylindric
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) Electrolyte is formed (weight %) Discharge capacitance (%)
FEC EC DMC LiPF 6 Chemical formula 6 (1) 25℃ 50℃
Embodiment 14-1 Sn-Co- C (50/29.4/ 19.6) 20 20 29.6 0 30.4 90 85
Embodiment 14-2 20 20 44.8 0 15.2 90 85
Embodiment 14-3 20 20 40.4 9.0 10.6 91 87
Embodiment 14-4 20 20 40.4 10.6 9.0 91 92
Embodiment 14-5 20 20 37.4 15.0 7.6 91 90
Embodiment 14-6 20 20 44.7 15.0 0.3 91 88
Embodiment 14-7 20 20 44.8 15.1 0.1 90 87
Comparative Examples 14-1 Sn-Co-C (50/29.4/ 19.6) 20 20 44.8 15.2 - 90 84
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
As the Comparative Examples 14-1 with respect to embodiment 14-1 to 14-7, except that not adding 1,1,2,2,3 in electrolyte, 3-HFC-236fa-1 outside the 3-disulfonyl imines lithium, forms secondary cell as embodiment 14-1 to 14-7.The composition of electrolyte is shown in table 20.
As embodiment 12-1-2, measure the cycle characteristics of the secondary cell of embodiment 14-1 to 14-7 and Comparative Examples 14-1 acquisition.The results are shown in table 20.
As seen from Table 20, such trend is arranged: along with in the electrolyte 1,1,2,2,3,3-HFC-236fa-1, the increase of 3-disulfonyl imines lithium content, discharge capacitance increases to maximum, reduces then.And, except that the ring-type imide salts, also mix LiPF therein 6Embodiment 14-3 to 14-7 in, its with do not mix LiPF 6Comparative Examples 14-1 compare, discharge capacitance has higher value.
In other words, find that the content of cyclic imide salt in the electrolyte is preferably in the scope of 0.1 weight % to 31 weight % (comprising end points), particularly preferably in the scope of 0.2 weight % to 15 weight % (comprising end points).And, find the also preferred LiPF of mixing except that the ring-type imide salts 6
(embodiment 15-1-1,15-1-2,15-1-3 and 15-1-4 to 15-27-1,15-27-2,15-27-3 and 15-27-4)
Remove as solvent, except 4-fluoro-1, outside 3-dioxolanes-2-ketone, ethylene carbonate and the dimethyl carbonate, also use 1 of chemical formula 3 (1) expressions, the 4-vinyl-1 of 3-dioxole-2-ketone, chemical formula 3 (2) expressions, 1 of 3-dioxolanes-2-ketone, chemical formula 4 (1) expressions, 1 of 3-propane sultone or chemical formula 4 (2) expressions, beyond the 3-propylene sultone, as embodiment 12-1-2 to 12-27-2, form secondary cell.The composition of each electrolyte is shown among the table 21-25.
As embodiment 12-1-2 to 12-27-2, measure the cycle characteristics of the secondary cell of embodiment acquisition.The results are shown in table 21 in 25.
(table 21)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) Electrolyte is formed (weight %) Discharge capacitance (%)
FE C EC VC VE C PS PR S DM C LiP F 6 Chemical formula 6 (1) 25 ℃ 50 ℃
Embodiment 12-1-2 Sn-Co- C (50/29.4 /19.6) 20 20 - - - - 37.4 7.6 15 90 88
Embodiment 15-1-1 20 18 2 - - - 37.4 7.6 15 92 93
Embodiment 15-1-2 20 18 - 2 - - 37.4 7.6 15 92 95
Embodiment 15-1-3 20 18 - - 2 - 37.4 7.6 15 90 90
Embodiment 15-1-4 20 18 - - - 2 37.4 7.6 15 90 91
Embodiment 12-2-2 Sn-Fe-C (50/29.4 /19.6) 20 20 - - - - 37.4 7.6 15 80 78
Embodiment 15-2-1 20 18 2 - - - 37.4 7.6 15 87 90
Embodiment 15-2-2 20 18 - 2 - - 37.4 7.6 15 86 90
Embodiment 15-2-3 20 18 - - 2 - 37. 7.6 15 86 86
Embodiment 15-2-4 20 18 - - - 2 37.4 7.6 15 86 87
Embodiment 12-3-2 Sn-Mg- C (50/29.4 /19.6) 20 20 - - - - 37.4 7.6 15 82 79
Embodiment 15-3-1 20 18 2 - - - 37.4 7.6 15 83 86
Embodiment 15-3-2 20 18 - 2 - - 37.4 7.6 15 83 86
Embodiment 15-3-3 20 18 - - 2 - 37.4 7.6 15 82 83
Embodiment 15-3-4 20 18 - - - 2 37.4 7.6 15 82 85
Embodiment 12-4-2 Sn-Ti-C (50/29.4 /19.6) 20 20 - - - - 37.4 7.6 15 90 87
Embodiment 15-4-1 20 18 2 - - - 37.4 7.6 15 90 92
Embodiment 15-4-2 20 18 - 2 - - 37.4 7.6 15 90 91
Embodiment 15-4-3 20 18 - - 2 - 37.4 7.6 15 90 90
Embodiment 15-4-4 20 18 - - - 2 37.4 7.6 15 90 90
Embodiment 12-5-2 Sn-V-C (50/29.4 /19.6) 20 20 - - - - 37.4 7.6 15 79 75
Embodiment 15-5-1 20 18 2 - - - 37.4 7.6 15 80 82
Embodiment 15-5-2 20 18 - 2 - - 37.4 7.6 15 80 82
Embodiment 15-5-3 20 18 - - 2 - 37.4 7.6 15 79 77
Embodiment 15-5-4 20 18 - - - 2 37.4 7.6 15 79 79
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate VC:1,3-dioxole-2-ketone
VEC:4-vinyl-1,3-dioxolanes-2-ketone PS:1,3-propane sultone
PRS:1,3-propylene sultone
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
(table 22)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) Electrolyte is formed (weight %) Discharge capacitance (%)
FE C EC VC VE C PS PR S DM C LiP F 6 Chemical formula 6 (1) 25 ℃ 50 ℃
Embodiment 12-6-2 Sn-Cr-C (50/29.4 /19.6) 20 20 - - - - 37.4 7.6 15 80 78
Embodiment 15-6-1 20 18 2 - - - 37.4 7.6 15 82 90
Embodiment 15-6-2 20 18 - 2 - - 37.4 7.6 15 82 91
Embodiment 15-6-3 20 18 - - 2 - 37.4 7.6 15 80 88
Embodiment 15-6-4 20 18 - - - 2 37.4 7.6 15 80 87
Embodiment 12-7-2 Sn-Mn- C (50/29.4 /19.6) 20 20 - - - - 37.4 7.6 15 76 74
Embodiment 15-7-1 20 18 2 - - - 37.4 7.6 15 77 80
Embodiment 15-7-2 20 18 - 2 - - 37.4 7.6 15 77 80
Embodiment 15-7-3 20 18 - - 2 - 37.4 7.6 15 76 77
Embodiment 15-7-4 20 18 - - - 2 37.4 7.6 15 76 77
Embodiment 12-8-2 Sn-Ni-C (50/29.4 /19.6) 20 20 - - - - 37.4 7.6 15 80 77
Embodiment 15-8-1 20 18 2 - - - 37.4 7.6 15 81 84
Embodiment 15-8-2 20 18 - 2 - - 37.4 7.6 15 81 84
Embodiment 15-8-3 20 18 - - 2 - 37.4 7.6 15 80 79
Embodiment 15-8-4 20 18 - - - 2 37.4 7.6 15 80 81
Embodiment 12-9-2 Sn-Cu-C (50/29.4 /19.6) 20 20 - - - - 37.4 7.6 15 85 81
Embodiment 15-9-1 20 18 2 - - - 37.4 7.6 15 86 88
Embodiment 15-9-2 20 18 - 2 - - 37.4 7.6 15 86 88
Embodiment 15-9-3 20 18 - - 2 - 37.4 7.6 15 85 83
Embodiment 15-9-4 20 18 - - - 2 37.4 7.6 15 85 85
Embodiment 12-10-2 Sn-Zn-C (50/29.4 /19.6) 20 20 - - - - 37.4 7.6 15 78 75
Embodiment 15-10-1 20 18 2 - - - 37.4 7.6 15 80 83
Embodiment 15-10-2 20 18 - 2 - - 37.4 7.6 15 80 83
Embodiment 15-10-3 20 18 - - 2 - 37.4 7.6 15 78 77
Embodiment 15-104 20 18 - - - 2 37.4 7.6 15 78 79
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate VC:1,3-dioxole-2-ketone
VEC:4-vinyl-1,3-dioxolanes-2-ketone PS:1,3-propane sultone
PRS:1,3-propylene sultone
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
(table 23)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) Electrolyte is formed (weight %) Discharge capacitance (%)
FE C EC VC VE C PS PR S DM C LiP F 6 Chemical formula 6 (1) 25 ℃ 50 ℃
Embodiment 12-11-2 Sn-Ga-C (50/29.4/ 19.6) 20 20 - - - - 37.4 7.6 15 78 74
Embodiment 15-11-1 20 18 2 - - - 37.4 7.6 15 79 80
Embodiment 15-11-2 20 18 - 2 - - 37.4 7.6 15 80 80
Embodiment 15-11-3 20 18 - - 2 - 37.4 7.6 15 78 76
Embodiment 15-11-4 20 18 - - - 2 37.4 7.6 15 78 78
Embodiment 12-12-2 Sn-Zr-C (50/29.4/ 19.6) 20 20 - - - - 37.4 7.6 15 80 78
Embodiment 15-12-1 20 18 2 - - - 37.4 7.6 15 82 90
Embodiment 15-12-2 20 18 - 2 - - 37.4 7.6 15 82 90
Embodiment 15-12-3 20 18 - - 2 - 37.4 7.6 15 80 88
Embodiment 15-12-4 20 18 - - - 2 37.4 7.6 15 80 87
Embodiment 12-13-2 Sn-Nb-C (50/29.4/ 19.6) 20 20 - - - - 37.4 7.6 15 80 78
Embodiment 15-13-1 20 18 2 - - - 37.4 7.6 15 81 84
Embodiment 15-13-2 20 18 - 2 - - 37.4 7.6 15 81 84
Embodiment 15-13-3 20 18 - - 2 - 37.4 7.6 15 80 80
Embodiment 15-13-4 20 18 - - - 2 37.4 7.6 15 80 81
Embodiment 12-14-2 Sn-Mo- C (50/29.4/ 19.6 ) 20 20 - - - - 37.4 7.6 15 79 76
Embodiment 15-14-1 20 18 2 - - - 37.4 7.6 15 80 82
Embodiment 15-14-2 20 18 - 2 - - 37.4 7.6 15 80 82
Embodiment 15-14-3 20 18 - - 2 - 37.4 7.6 15 79 78
Embodiment 15-14-4 20 18 - - - 2 37.4 7.6 15 79 79
Embodiment 12-15-2 Sn-Ag-C (50/29.4/ 19.6) 20 20 - - - - 37.4 7.6 15 79 76
Embodiment 15-15-1 20 18 2 - - - 37.4 7.6 15 80 82
Embodiment 15-15-2 20 18 - 2 - - 37.4 7.6 15 80 82
Embodiment 15-15-3 20 18 - - 2 - 37.4 7.6 15 79 78
Embodiment 15-15-4 20 18 - - - 2 37.4 7.6 15 79 79
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate VC:1,3-dioxole-2-ketone
VEC:4-vinyl-1,3-dioxolanes-2-ketone PS:1,3-propane sultone
PRS:1,3-propylene sultone
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
(table 24)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) Electrolyte is formed (weight %) Discharge capacitance (%)
FE C EC VC VE C PS PR S DM C LiP F 6 Chemical formula 6 (1) 25 ℃ 50 ℃
Embodiment 12-16-2 Sn-In-C (50/29.4/ 19.6) 20 20 - - - - 37.4 7.6 15 87 85
Embodiment 15-16-1 20 18 2 - - - 37.4 7.6 15 88 90
Embodiment 15-16-2 20 18 - 2 - - 37.4 7.6 15 88 90
Embodiment 15-16-3 20 18 - - 2 - 37.4 7.6 15 87 87
Embodiment 15-16-4 20 18 - - - 2 37.4 7.6 15 87 88
Embodiment 12-17-2 Sn-Ce-C (50/29.4/ 19.6) 20 20 - - - - 37.4 7.6 15 79 75
Embodiment 15-17-1 20 18 2 - - - 37.4 7.6 15 80 80
Embodiment 15-17-2 20 18 - 2 - - 37.4 7.6 15 80 80
Embodiment 15-17-3 20 18 - - 2 - 37.4 7.6 15 79 77
Embodiment 15-17-4 20 18 - - - 2 37.4 7.6 15 79 78
Embodiment 12-18-2 Sn-Hf-C (50/29.4/ 19.6) 20 20 - - - - 37.4 7.6 15 78 74
Embodiment 15-18-1 20 18 2 - - - 37.4 7.6 15 79 80
Embodiment 15-18-2 20 18 - 2 - - 37.4 7.6 15 79 80
Embodiment 15-18-3 20 18 - - 2 - 37.4 7.6 15 78 76
Embodiment 15-18-4 20 18 - - - 2 37.4 7.6 15 78 78
Embodiment 12-19-2 Sn-Ta-C (50/29.4/ 19.6) 20 20 - - - - 37.4 7.6 15 77 73
Embodiment 15-19-1 20 18 2 - - - 37.4 7.6 15 78 79
Embodiment 15-19-2 20 18 - 2 - - 37.4 7.6 15 78 79
Embodiment 15-19-3 20 18 - - 2 - 37.4 7.6 15 77 78
Embodiment 15-19-4 20 18 - - - 2 37.4 7.6 15 77 76
Embodiment 12-20-2 Sn-W-C (50/29.4/ 19.6) 20 20 - - - - 37.4 7.6 15 77 73
Embodiment 15-20-1 20 18 2 - - - 37.4 7.6 15 78 79
Embodiment 15-20-2 20 18 - 2 - - 37.4 7.6 15 78 79
Embodiment 15-20-3 20 18 - - 2 - 37.4 7.6 15 77 75
Embodiment 15-20-4 20 18 - - - 2 37.4 7.6 15 77 76
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate VC:1,3-dioxole-2-ketone
VEC:4-vinyl-1,3-dioxolanes-2-ketone PS:1,3-propane sultone
PRS:1,3-propylene sultone
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
(table 25)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) Electrolyte is formed (weight %) Discharge capacitance (%)
FE C EC VC - VE C PS PR S DM C LiP F 6 Chemical formula 6 (1) 25 ℃ 50 ℃
Embodiment 12-21-2 Sn-Bi-C (50/29.4/ 19.6) 20 20 - - - - 37.4 7.6 15 77 74
Embodiment 15-21-1 20 18 2 - - - 37.4 7.6 15 78 80
Embodiment 15-21-2 20 18 - 2 - - 37.4 7.6 15 78 80
Embodiment 15-21-3 20 18 - - 2 - 37.4 7.6 15 77 76
Embodiment 15-21-4 20 18 - - - 2 37.4 7.6 15 77 77
Embodiment 12-25-2 Sn-Co-In -C (50/24.4/ 5/19.6) 20 20 - - - - 37.4 7.6 15 94 91
Embodiment 15-25-1 20 18 2 - - - 37.4 7.6 15 95 96
Embodiment 15-25-2 20 18 - 2 - - 37.4 7.6 15 94 96
Embodiment 15-25-3 20 18 - - 2 - 37.4 7.6 15 94 93
Embodiment 15-25-4 20 18 - - - 2 37.4 7.6 15 94 93
Embodiment 12-26-2 Sn-Co-In -Ti-C (49/23.4/ 5/2/19.6) 20 20 - - - - 37.4 7.6 15 95 92
Embodiment 15-26-1 20 18 2 - - - 37.4 7.6 15 96 96
Embodiment 15-26-2 20 18 - 2 - - 37.4 7.6 15 96 96
Embodiment 15-26-3 20 18 - - 2 - 37.4 7.6 15 95 95
Embodiment 15-26-4 20 18 - - - 2 37.4 7.6 15 95 95
Embodiment 12-27-2 Sn-Si-Co -C (48/3.9/ 27.5/19.6) 20 20 - - - - 37.4 7.6 15 86 83
Embodiment 15-27-1 20 18 2 - - - 37.4 7.6 15 87 89
Embodiment 15-27-2 20 18 - 2 - - 37.4 7.6 15 87 89
Embodiment 15-27-3 20 18 - - 2 - 37.4 7.6 15 86 85
Embodiment 15-27-4 20 18 - - - 2 37.4 7.6 15 86 85
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate VC:1,3-dioxole-2-ketone
VEC:4-vinyl-1,3-dioxolanes-2-ketone PS:1,3-propane sultone
PRS:1,3-propylene sultone
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
From table 21 25 as seen to, when mixing 1,3-dioxole-2-ketone, 4-vinyl-1,3-dioxolanes-2-ketone, 1,3-propane sultone or 1 is during 3-propylene sultone, improve discharge capacitance, and particularly, under 50 ℃, observe higher effect.
In other words, find when use has the cyclic carbonate of unsaturated bond or sultone as solvent, can further to improve cycle characteristics, and particularly, can effectively improve the cycle characteristics under hot conditions.
(embodiment 16-1-1 to 16-1-8,16-2-1 to 16-2-8,17-1-1 to 17-1-8,17-2-1 to 17-2-7)
In embodiment 16-1-1 to 16-1-8, remove in the electrolyte 1, the content of 3-dioxole-2-ketone forms secondary cell outside changing as embodiment 15-1-1 in the scope of 0.05 weight % to 20 weight %.In embodiment 16-2-1 to 16-2-8, remove 4-vinyl-1 in the electrolyte, the content of 3-dioxolanes-2-ketone forms secondary cell outside changing as embodiment 15-1-2 in the scope of 0.05 weight % to 20 weight %.In embodiment 17-1-1 to 17-1-8, remove in the electrolyte 1, the content of 3-propane sultone forms secondary cell outside changing as embodiment 15-1-3 in the scope of 0.01 weight % to 5 weight %.In embodiment 17-2-1 to 17-2-7, remove in the electrolyte 1, the content of 3-propylene sultone forms secondary cell outside changing as embodiment 15-1-4 in the scope of 0.05 weight % to 5 weight %.The composition of each electrolyte is shown in table 26 and 27.
As among the embodiment 15-1-1 to 15-1-4, measure the cycle characteristics of the secondary cell of embodiment acquisition.The result is shown in table 26 and 27 with the result of embodiment 12-1-2.
(table 26)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) Discharge capacitance (%) Discharge capacitance (%)
FE C EC VC VEC DMC LiPF 6 Chemical formula 6 (1) 25℃ 50℃
Embodiment 16-1-1 Sn-Co-C (50/29.4/ 19.6) 20 - 20 - 37.4 7.6 15 92 86
Embodiment 16-1-2 20 10 10 - 37.4 7.6 15 92 93
Embodiment 16-1-3 20 12 8 - 37.4 7.6 15 93 94
Embodiment 16-1-4 20 15 5 - 37.4 7.6 15 93 96
Embodiment 15-1-1 20 18 2 - 37.4 7.6 15 92 93
Embodiment 16-1-5 20 19 1 - 37.4 7.6 15 92 93
Embodiment 16-1-6 20 19.5 0.5 - 37.4 7.6 15 92 92
Embodiment 16-1-7 20 19.9 0.1 - 37.4 7.6 15 91 91
Embodiment 16-1-8 20 19.95 0.05 - 37.4 7.6 15 90 90
Embodiment 16-2-1 Sn-Co-C (50/29.4/ 19.6) 20 - - 20 37.4 7.6 15 92 87
Embodiment 16-2-2 20 10 - 10 37.4 7.6 15 92 94
Embodiment 16-2-3 20 12 - 8 37.4 7.6 15 93 95
Embodiment 16-2-4 20 15 - 5 37.4 7.6 15 93 97
Embodiment 15-1-2 20 18 - 2 34.7 7.6 15 92 95
Embodiment 16-2-5 20 19 - 1 37.4 7.6 15 92 94
Embodiment 16-2-6 20 19.5 - 0.5 37.4 7.6 15 92 93
Embodiment 16-2-7 20 19.9 - 0.1 37.4 7.6 15 92 91
Embodiment 16-2-8 20 19.95 - 0.05 37.4 7.6 15 90 90
Embodiment 12-1-2 20 20 - - 37.4 7.6 15 90 88
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate VC:1,3-dioxole-2-ketone
VEC:4-vinyl-1,3-dioxolanes-2-ketone
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
(table 27)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) Discharge capacitance (%) Discharge capacitance (%)
FEC EC PS PRS DM C LiP F 6 Chemical formula 6 (1) 25℃ 50℃
Embodiment 17-1-1 Sn-Co-C (50/29.4/ 19.6) 20 15 5 - 37.4 7.6 15 90 89
Embodiment 17-1-2 20 17 3 - 37.4 7.6 15 90 90
Embodiment 15-1-3 20 18 2 - 37.4 7.6 15 90 90
Embodiment 17-1-3 20 19 1 - 37.4 7.6 15 91 91
Embodiment 17-1-4 20 19.5 0.5 - 37.4 7.6 15 91 91
Embodiment 17-1-5 20 19.7 0.3 - 37.4 7.6 15 91 91
Embodiment 17-1-6 20 19.9 0.1 - 37.4 7.6 15 91 91
Embodiment 17-1-7 20 19.95 0.05 - 37.4 7.6 15 90 91
Embodiment 17-1-8 20 19.99 0.01 - 37.4 7.6 15 90 89
Embodiment 17-2-1 Sn-Co-C (50/29.4/ 19.6) 20 15 - 5 37.4 7.6 15 90 89
Embodiment 17-2-2 20 17 - 3 37.4 7.6 15 90 90
Embodiment 15-1-4 20 18 - 2 37.4 7.6 15 90 91
Embodiment 17-2-3 20 19 - 1 37.4 7.6 15 92 92
Embodiment 17-2-4 20 19.5 - 0.5 37.4 7.6 15 91 91
Embodiment 17-2-5 20 19.7 - 0.3 37.4 7.6 15 91 91
Embodiment 17-2-6 20 19.9 - 0.1 37.4 7.6 15 90 90
Embodiment 17-2-7 20 19.99 - 0.05 37.4 7.6 15 90 89
Embodiment 12-1-2 Sn-Co-C (50/29.4/ 19.6) 20 20 - - 37.4 7.6 15 90 88
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate PS:1,3-propane sultone
PRS:1,3-propylene sultone
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
From table 26 and 27, as seen, such trend is arranged: along with in electrolyte 1,3-dioxole-2-ketone, 4-vinyl-1,3-dioxolanes-2-ketone, 1,3-propane sultone or 1, the content of 3-propylene sultone increases, discharge capacitance increases to maximum, reduces then.
In other words, find in electrolyte, to have the cyclic carbonate of unsaturated bond preferably in the scope of 0.05 weight % to 20 weight % (comprising end points).And the content of sultone is preferably in the scope of 0.01 weight % to 5 weight % (comprising end points) in electrolyte.
(embodiment 18-1)
Form the secondary cell shown in Fig. 3 and 4.At first, as embodiment 12-1-1, form positive pole 33 and negative pole 34, and adhere to positive wire 31 and negative wire 32.As negative active core-shell material, use the employed identical SnCoC material that contains with embodiment 12-1-1.
Next, as high-molecular weight compounds, the preparation mean molecule quantity be 700,000 vinylidene fluoride and the copolymer (A) of hexafluoropropylene and mean molecule quantity be 310,000 vinylidene fluoride and the copolymer (B) of hexafluoropropylene with (A): the mixture of weight ratio (B)=9: 1.The ratio of hexafluoropropylene is 7 weight % in the copolymer.Afterwards, high-molecular weight compounds and electrolyte are mixed with mixed solvent to form precursor solution.As electrolyte, use by will be the mixture of 3-dioxolanes-2-ketone and ethylene carbonate and as the LiPF of electrolytic salt as the 4-fluoro-1 of solvent 6With 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium (it is a cyclic imide salt) mixes the electrolyte that forms.The composition of electrolyte is shown in table 28.
Next, by after using metering bar coater to be coated in the precursor solution that forms on positive pole 33 and the negative pole 34, mixed solvent is volatilized to form gel electrolyte layer 36.Afterwards, with positive pole 33 and negative pole 34 and the thick barrier film 35 stacked formation sandwichs of the 16 μ m that make by polyethylene (E16MMS, Tonen Chemical) therebetween, sandwich level (flatly) coiling is formed spiral winding electrode 30.Next, with spiral winding electrode 30 vacuum seals in the package component of making by laminated film 40, thereby make secondary cell.
As Comparative Examples 18-1,, as embodiment 18-1, form secondary cell except that not using cyclic imide salt to do the electrolytic salt with respect to embodiment 18-1.
Measurement is at the cycle characteristics of the secondary cell of 25 ℃ and 50 ℃ of following embodiment 18-1 and Comparative Examples 18-1.The results are shown in table 18.As charge and discharge cycles, under the environment of 25 ℃ or 50 ℃, secondary cell charges under constant current 830mA and constant voltage up to maximum voltage 4.2V, and discharging up to final voltage secondary cell under the constant current of 660mA then is 2.6V.Repeat 150 times charge and discharge cycles, and the discharge capacitance (%) that is determined at the 150th circulation time under 100 the situation of circulation time discharge capacity for the first time is as cycle characteristics.
(table 28)
Cell shapes: lamination membranous type
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) Electrolyte is formed (weight %) Discharge capacitance (%)
FEC EC LiPF 6 Chemical formula 6 (1) 25℃ 50℃
Embodiment 18-1 Sn-Co-C (50/29.4/19.6) 43.2 43.2 4.6 9.0 92 91
Comparative Examples 18-1 45.45 45.45 9.1 92 86
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
Shown in table 28, in an embodiment, as above-mentioned embodiment, compare with Comparative Examples, under 50 ℃, can improve discharge capacitance.In other words, keep electrolyte, also can obtain same effect even find high-molecular weight compounds.
(embodiment 19-1)
Except that using hollow prism shape battery case made of aluminum, as embodiment 12-1-2, form secondary cell.Simultaneously, as electrolyte, use by will be as the LiPF of electrolytic salt 6With 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium (it is a cyclic imide salt) with comprise 4-fluoro-1, the electrolyte that the mixture of 3-dioxolanes-2-ketone, ethylene carbonate and dimethyl carbonate forms as the solvent of solvent.The composition of electrolyte is shown in table 29.As negative active core-shell material, use with embodiment 12-1-1 in the identical SnCoC material that contains.
(table 29)
Cell shapes: hollow prism shape
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) Electrolyte is formed (weight %) Discharge capacitance (%)
FE C EC DM C LiPF 6 Chemical formula 6 (1) 25℃ 50℃
Embodiment 19-1 Sn-Co-C (50/29.4/19.6) 20 20 37.4 7.6 15 90 88
Comparative Examples 19-1 20 20 44.8 15.2 - 90 84
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
As Comparative Examples 19-1,, as embodiment 19-1, form secondary cell except that not using cyclic imide salt as the electrolytic salt with respect to embodiment 19-1.The composition of electrolyte is shown in the table 29.
As embodiment 12-1-1, measure the cycle characteristics of the secondary cell of embodiment 19-1 and Comparative Examples 19-1.The results are shown in table 29.
Shown in table 29, in embodiment 19-1, obtain the result the same with embodiment 12-1-1.In other words, even find the alteration of form of battery case, also can obtain identical effect.
(embodiment 20-1 to 20-9)
The capacity that forms negative pole 22 wherein is by the battery of partly representing by the capacity of separating out and dissolving of lithium, that is, and and so-called lithium metal secondary batteries.At this moment, form battery shown in Figure 1.
At first, with lithium carbonate (Li 2CO 3) and cobalt carbonate (CoCO 3) with Li 2CO 3: CoCO 3Be the mixed of 0.5: 1 (mol ratio), and with this mixture under 900 ℃ in air sintering 5 hours to obtain lithium cobalt composite oxide (LiCoO 2).Next, with the lithium cobalt composite oxide of 91 weight portions, mix with the preparation cathode mix as the graphite of 6 weight portions of electric conductor with as the polyvinylidene fluoride of 3 weight portions of binding agent.Then, cathode mix is dispersed in as in the N-N-methyl-2-2-pyrrolidone N-of solvent to form the cathode mix slurry.Next, on the two sides that the cathode mix slurry is coated in equably the thick positive electrode collector 21A of the 20 μ m that make by banded aluminium foil and after the drying, form positive-electrode mixture layer 21B to form anodal 21 by the roller press compression molding.Then, positive wire made of aluminum 25 is attached to the end of positive electrode collector 21A.
And, the thick lithium metal foil of 30 μ m being attached to the thick negative electrode collector 22A of 10 μ m that is made by banded Copper Foil going up to form anode active material layer 22B, the shape negative pole 22 thus.
After forming positive pole 21 and negative pole 22, prepare the thick barrier film of making by the microporous polyethylene film 23 of 25 μ m, and with negative pole 22, barrier film 23, anodal 21 and barrier film 23 with this to form sandwich, with the sandwich screw winding for several times to form spiral winding electrode 20.
After forming spiral winding electrode 20, spiral winding electrode 20 is clipped between a pair of insulation board 12 and 13, and negative wire 26 is welded on the battery case 11, positive wire 25 is welded on the relief valve mechanism 15, then spiral winding electrode 20 is included in the battery case of being made by the iron of nickel plating 11.Then, inject the electrolyte in the battery case 11 by the decompression method.
As electrolyte, use is by being dissolved in the electrolyte that forms in the solvent with electrolytic salt with the concentration of 1.0mol/kg, this solvent comprise cyclic carbonate derivative with halogen atom and dimethyl carbonate with cyclic carbonate derivative: the mixture of the volume ratio of dimethyl carbonate=30: 70.Simultaneously, cyclic carbonate derivative is 4-fluoro-1 in embodiment 20-1 to 20-5,3-dioxolanes-2-ketone, be 4-chloro-1 in embodiment 20-6,3-dioxolanes-2-ketone is 4-bromo-1 in embodiment 20-7,3-dioxolanes-2-ketone (BrEC), in embodiment 20-8 4-fluoro-4-methyl isophthalic acid, 3-dioxolanes-2-ketone (FPC) and be 4-chloro-4-methyl isophthalic acid in embodiment 20-9,3-dioxolanes-2-ketone (CIPC).As electrolytic salt, embodiment 20-1 use represent in the chemical formula 6 (4) 1,1,2,2-HFC-134a-1,3-disulfonyl imines lithium [1,2-hexafluoroethane disulfonyl imines lithium].In embodiment 20-2, use LiPF 6With 1,1,2 of expression in the chemical formula 6 (4), 2-HFC-134a-1,3-disulfonyl imines lithium, and in electrolyte LiPF 6With 1,1,2,2-HFC-134a-1, the concentration of 3-disulfonyl imines lithium is respectively 0.8mol/kg and 0.2mol/kg.In embodiment 20-3 and 20-6 to 20-9, use LiPF 6With 1,1,2,2,3 of chemical formula 6 (1) expression, 3-HFC-236fa-1,3-disulfonyl imines lithium [1,3-perfluoropropane disulfonyl imines lithium], and in electrolyte LiPF 6With 1,1,2,2,3,3-HFC-236fa-1, the concentration of 3-disulfonyl imines lithium is respectively 0.8mol/kg and 0.2mol/kg.In embodiment 20-4, use LiPF 6With 1,1,2,2,3,3,4 of chemical formula 6 (6) expression, 4-octafluoro butyl-1,3-disulfonyl imines lithium [1,4-perfluorinated butane disulfonyl imines lithium], and in electrolyte LiPF 6With 1,1,2,2,3,3,4,4-octafluoro butyl-1, the concentration of 3-disulfonyl imines lithium is respectively 0.8mol/kg and 0.2mol/kg.In embodiment 20-5, use LiPF 6With 2,2,3,3,4 of chemical formula 6 (2) expression, 4-hexafluoro glutarimide lithium (PF 5070 diacid imide li), and in electrolyte LiPF 6With 2,2,3,3,4, the concentration of 4-hexafluoro glutarimide lithium is respectively 0.8mol/kg and 0.2mol/kg.
After electrolyte charges into battery case 11, the liner 17 that scribbles pitch by the surface with battery cover 14 calkings to battery case 11, thereby obtain the high 65mm of embodiment 20-1 to 20-9, the cylinder type secondary battery of diameter 14mm.
As Comparative Examples 20-1 and the 20-2 with respect to embodiment 20-1 to 20-9, remove to use by comprising ethylene carbonate and dimethyl carbonate with ethylene carbonate: dissolving is as the LiPF of the concentration of the 0.8mol/kg of electrolytic salt in the solvent of the mixture of the volume ratio of dimethyl carbonate=30: 70 6With 1 of chemical formula 6 (4) expression of 0.2mol/kg, 1,2,2-HFC-134a-1,3-disulfonyl imines lithium and the electrolyte that forms, perhaps use by comprising 4-fluoro-1,3-dioxolanes-2-ketone and dimethyl carbonate be with 4-fluoro-1,3-dioxolanes-2-ketone: dissolving is as the LiPF of the concentration of the 1.0mol/kg of electrolytic salt in the solvent of the mixture of the volume ratio of dimethyl carbonate=30: 70 6And outside the electrolyte that forms, as embodiment 20-1 to 20-9, form secondary cell.
And 20-3 to 20-6 except that the composition that uses Delanium as negative material and change electrolyte, forms secondary cell as embodiment 20-1 to 20-9 as a comparison case.Simultaneously, negative pole forms by following steps.Mix to form mixture with the Delanium powder of 90 weight portions with as the polyvinylidene fluoride of 10 weight portions of binding agent, will add in the mixture as the N-N-methyl-2-2-pyrrolidone N-of solvent.Next, mixture is coated on the thick negative electrode collector 22A of the 15 μ m that made by banded Copper Foil equably, and dry, form negative pole 22 thereby form anode active material layer 22B by the roller press compression molding then.In addition, as electrolyte, use by comprising ethylene carbonate and dimethyl carbonate with ethylene carbonate: dissolving is as the LiPF of the concentration of the 1.0mol/kg of electrolytic salt in the solvent of the mixture of the volume ratio of dimethyl carbonate=30: 70 6And the electrolyte that forms, by comprising ethylene carbonate and dimethyl carbonate with ethylene carbonate: dissolving is as the LiPF of the concentration of the 0.8mol/kg of electrolytic salt in the solvent of the mixture of the volume ratio of dimethyl carbonate=30: 70 6With 1 of chemical formula 6 (4) expression of 0.2mol/kg, 1,2,2-HFC-134a-1,3-disulfonyl imines lithium and the electrolyte that forms, by comprising 4-fluoro-1,3-dioxolanes-2-ketone and dimethyl carbonate be with 4-fluoro-1,3-dioxolanes-2-ketone: dissolving is as the LiPF of the concentration of the 1.0mol/kg of electrolytic salt in the solvent of the mixture of the volume ratio of dimethyl carbonate=30: 70 6And electrolyte that forms or use are by comprising 4-fluoro-1,3-dioxolanes-2-ketone and dimethyl carbonate be with 4-fluoro-1,3-dioxolanes-2-ketone: dissolving is as the LiPF of the concentration of the 0.8mol/kg of electrolytic salt in the solvent of the mixture of the volume ratio of dimethyl carbonate=30: 70 6With 1,1,2 of chemical formula 6 (4) expression of 0.2mol/kg, 2-HFC-134a-1,3-disulfonyl imines lithium and the electrolyte that forms.Set anodal 21 and negative pole 22 between surface density than making the capacity of negative pole 22 partly represent by embedding by lithium and the capacity that takes off embedding.
Measure the cycle characteristics of the secondary cell of embodiment 20-1 to 20-9 and Comparative Examples 20-1 to 20-6 acquisition by following steps.
As charge and discharge cycles, secondary cell is charged after cell voltage reaches 4.2V under constant current 100mA, secondary cell charged under constant voltage 4.2V reaches 1mA up to electric current, and secondary cell is discharged under constant current 300mA reaches 3.0V up to cell voltage then.Repeat charge and discharge cycles, and the capability retention of initial discharge capacity (discharge capacity of circulation for the first time) is determined cycle characteristics with the 100th circulation, that is, and (discharge capacity/initial discharge capacity of the 100th circulation) * 100 (%).The results are shown in table 30.
(table 30)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material Solvent Electrolytic salt Discharge capacitance (%)
Embodiment 20-1 The lithium metal FEC+DMC Chemical formula 6 (4) 60
Embodiment 20-2 FEC+DMC LiPF 6+ chemical formula 6 (4) 65
Embodiment 20-3 FEC+DMC LiPF 6+ chemical formula 6 (1) 68
Embodiment 20-4 FEC+DMC LiPF 6+ chemical formula 6 (6) 62
Embodiment 20-5 FEC+DMC LiPF 6+ chemical formula 6 (2) 60
Embodiment 20-6 CIEC+DMC LiPF 6+ chemical formula 6 (1) 64
Embodiment 20-7 BrEC+DMC LiPF 6+ chemical formula 6 (1) 60
Embodiment 20-8 FPC+DMC LiPF 6+ chemical formula 6 (1) 62
Embodiment 20-9 CIPC+DMC LiPF 6+ chemical formula 6 (1) 60
Comparative Examples 20-1 The lithium metal EC+DMC LiPF 6+ chemical formula 6 (4) 40
Comparative Examples 20-2 FEC+DMC LiPF 6 53
Comparative Examples 20-3 Carbon EC+DMC LiPF 6 91
Comparative Examples 20-4 EC+DMC LiPF 6+ chemical formula 6 (4) 94
Comparative Examples 20-5 FEC+DMC LiPF 6+ 89
Comparative Examples 20-6 FEC+DMC LiPF 6+ chemical formula 6 (4) 92
FEC:4-fluoro-1,3-dioxolanes-2-ketone CIEC:4-chloro-dioxolanes-2-ketone
BrEC:4-bromo-1,3-dioxolanes-2-ketone
FPC:4-fluoro-4-methyl isophthalic acid, 3-dioxolanes-2-ketone
CIPC:4-chloro-4-methyl isophthalic acid, 3-dioxolanes-2-ketone
EC: ethylene carbonate DMC: dimethyl carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
Chemical formula 6 (2): 2,2,3,3,4,4-hexafluoro glutarimide lithium
Chemical formula 6 (4): 1,1,2,2-HFC-134a-1,3-disulfonyl imines lithium
Chemical formula 6 (6): 1,1,2,2,3,3,4,4-octafluoro butyl-1,3-disulfonyl imines lithium
As can be seen from Table 30, use 4-fluoro-1 therein, 3-dioxolanes-2-ketone and 1,1,2,2-HFC-134a-1, among the embodiment 20-2 of 3-disulfonyl imines lithium, with do not use 4-fluoro-1, the Comparative Examples 20-1 of 3-dioxolanes-2-ketone or do not use 1,1,2,2-HFC-134a-1, the Comparative Examples 20-2 of 3-disulfonyl imines lithium compares, and discharge capacitance significantly improves.And, use another cyclic carbonate derivative to replace 4-fluoro-1 therein with halogen atom, 3-dioxolanes-2-ketone and another cyclic imide salt replace 1,1,2,2-HFC-134a-1, among the embodiment 20-3 to 20-9 of 3-disulfonyl imines lithium, obtain high discharge capacitance equally.And, adding therein among the embodiment 20-2 of another slaine, discharge capacitance improves more than the embodiment 20-1 that only adds cyclic imide salt.In addition, use therein among the Comparative Examples 20-3 to 20-6 of electrographite as negative material, even mix cyclic carbonate derivative and the cyclic imide salt with halogen atom, discharge capacitance does not improve yet.
In other words, discovery is being used under the situation of lithium metal as negative active core-shell material, when use has the cyclic carbonate derivative of halogen atom and cyclic imide salt, can improve cycle characteristics, and except that the ring-type imide salts, preferably mix another light metal salt.
(embodiment 21-1 to 21-4)
4-fluoro-1 in desolventizing, the content of 3-dioxolanes-2-ketone is outside 1 volume %, 5 volume %, 20 volume %, the 50 volume %, forms secondary cell as embodiment 20-3.Simultaneously, in embodiment 21-1, by with 4-fluoro-1,3-dioxolanes-2-ketone and dimethyl carbonate be with 4-fluoro-1,3-dioxolanes-2-ketone: the volume ratio of dimethyl carbonate=50: 50 is mixed and is formed solvent.In embodiment 21-2,21-3 and 21-4, by with 4-fluoro-1,3-dioxolanes-2-ketone, ethylene carbonate and dimethyl carbonate be respectively with 4-fluoro-1,3-dioxolanes-2-ketone: ethylene carbonate: the volume ratio of dimethyl carbonate=20: 10: 70, mixed in 5: 25: 70 and 1: 29: 70 and form solvent.
As embodiment 20-1 to 20-9, measure the cycle characteristics of the secondary cell of embodiment 21-1 to 21-4 acquisition.The result is shown in table 31 with the result of embodiment 20-3.
(table 31)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material Solvent Electrolytic salt Discharge capacitance (%)
FEC EC DMC
Embodiment 21-1 The lithium metal 50 0 50 LiPF 6+ chemical formula 6 (1) 62
Embodiment 20-3 30 0 70 68
Embodiment 21-2 20 10 70 65
Embodiment 21-3 5 25 70 60
Embodiment 21-4 1 29 70 57
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
From table 31 as can be seen, such trend is arranged: along with 4-fluoro-1, the content of 3-dioxolanes-2-ketone increases, and discharge capacitance increases to maximum, reduces then.
In other words, the content of cyclic carbonate derivative in solvent of finding to have halogen atom 50 volume % or still less preferably.
(embodiment 22-1 to 22-4)
Remove and use by further being the LiBF of 0.2mol/kg dissolving as electrolytic salt with concentration 4Or LiB (OCOCF 3) 4And outside the electrolyte that forms, as embodiment 20-2, form secondary cell.Simultaneously, the cyclic carbonate derivative with halogen atom is 4-fluoro-1 in embodiment 22-1 and 22-2, and 3-dioxolanes-2-ketone is 4-chloro-1 in embodiment 22-3 and 22-4,3-dioxolanes-2-ketone.
As embodiment 20-1 to 20-9, measure the cycle characteristics of the secondary cell of embodiment 22-1 to 22-4.The result is shown in table 32 with the result of embodiment 20-2.
(table 32)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material Solvent Electrolytic salt Discharge capacitance (%)
Embodiment 20-2 The lithium metal FEC+ DMC LiPF 6+ chemical formula 6 (4) 65
Embodiment 22-1 LiPF 6+ chemical formula 6 (4)+LiPF 4 72
Embodiment 22-2 LiPF 6+ chemical formula 6 (4)+LiB (OCOCF3) 4 74
Embodiment 22-3 CIEC+ DMC LiPF 6+ chemical formula 6 (4)+LiPF 4 71
Embodiment 22-4 LiPF 6+ chemical formula 6 (4)+LiB (OCOCF 3) 4 70
FEC:4-fluoro-1,3-dioxolanes-2-ketone CIEC:4-chloro-dioxolanes-2-ketone
DMC: dimethyl carbonate
Chemical formula 6 (4): 1,1,2,2-HFC-134a-1,3-disulfonyl imines lithium
From table 32, as can be seen, also mix LiBF therein 4Or LiB (OCOCF 3) 4Embodiment 22-1 to 22-4 in, compare with not mixing above-mentioned any one embodiment 20-2, discharge capacitance improves.
In other words, find except that the ring-type imide salts, preferably to mix LiPF 6With other light metal salt.
(embodiment 23-1 to 23-20)
Except as solvent, remove 4-fluoro-1, outside 3-dioxolanes-2-ketone and the dimethyl carbonate, also use 1 of chemical formula 3 (1) expressions, the 4-ethene-1 of 3-dioxole-2-ketone, chemical formula 3 (2) expressions, 1 of 3-dioxolanes-2-ketone, chemical formula 4 (1) expressions, 1 of 3-propane sultone or chemical formula 4 (2) expressions, beyond the 3-propylene sultone, as embodiment 20-3, form secondary cell.The variation shown in table 33 of the composition of solvent.
The secondary cell that embodiment is obtained charges down and discharge at 25 ℃ and 50 ℃ under as the identical condition that discharges and recharges of embodiment 20-3, and measures the cycle characteristics of secondary cell at the 100th circulation time.The results are shown in table 33.
(table 33)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material Solvent (weight %) Electrolytic salt Discharge capacitance (%)
FEC DMC VC VE C PS PRS 25 ℃ 50℃
Embodiment 20-3 The lithium metal 30 70 - - - - LiPF 6+ chemical formula 6 (1) 68 65
Embodiment 23-1 30 69.95 0.05 - - - 68 66
Embodiment 23-2 30 69.9 0.1 - - - 69 69
Embodiment 23-3 30 68 2 - - - 70 72
Embodiment 23-4 30 60 10 - - - 70 70
Embodiment 23-5 30 50 20 - - - 68 68
Embodiment 23-6 30 69.95 - 0.05 - - 68 67
Embodiment 23-7 30 69.9 - 0.1 - - 69 70
Embodiment 23-8 30 68 - 2 - - 70 73
Embodiment 23-9 30 60 - 10 - - 70 71
Embodiment 23-10 30 50 - 20 - - 68 69
Embodiment 23-11 30 69.99 - - 0.01 - 68 66
Embodiment 23-12 30 69.95 - - 0.05 - 68 68
Embodiment 23-13 30 69 - - 1 - 69 70
Embodiment 23-14 30 67 - - 3 - 69 68
Embodiment 23-15 30 65 - - 5 - 68 66
Embodiment 23-16 30 69.99 - - - 0.01 68 67
Embodiment 23-17 30 69.95 - - - 0.05 68 69
Embodiment 23-18 30 69 - - - 1 70 71
Embodiment 23-19 30 67 - - - 3 69 69
Embodiment 23-20 30 65 - - - 5 68 67
FEC:4-fluoro-1,3-dioxolanes-2-ketone DMC: dimethyl carbonate
VC:1,3-dioxole-2-ketone VEC:4-vinyl-1,3-dioxolanes-2-ketone
PS:1,3-propane sultone PRS:1,3-propylene sultone
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
From table 33 as can be seen, when mixing 1,3-dioxole-2-ketone, 4-ethene-1,3-dioxolanes-2-ketone, 1,3-propane sultone or 1, during 3-propylene sultone, discharge capacitance improves, particularly, under 50 ℃, observe higher effect.
In other words, find when use has the cyclic carbonate of unsaturated bond or sultone as solvent, can further to improve cycle characteristics, particularly, can effectively improve the cycle characteristics under hot conditions.
(embodiment 24-1 to 24-5)
Form the capacity part wherein comprise the embedding by lithium and to take off embedding and the capacity part of separating out and dissolving by the lithium metal, and by they with the secondary cell of expression.Simultaneously, remove and use Delanium, and as Comparative Examples 20-3 to 20-6, form outside the negative pole 22, as embodiment 20-1 to 20-9, form secondary cell as negative material.And the loading of setting positive electrode and negative material makes the capacity of negative pole 22 comprise the embedding by lithium and takes off the capacity part of embedding and the capacity part of separating out and dissolving by lithium, and with they and expression.In addition,, use by concentration of ordinary dissolution in solvent to be 1,1,2,2,3 of chemical formula 6 (1) expression of 0.2mol/kg as electrolyte, 3-HFC-236fa-1,3-disulfonyl imines lithium and concentration are the LiPF of 0.8mol/kg 6And the electrolyte that forms, this solvent comprises the 4-fluoro-1 of ratio shown in table 34, the mixture of 3-dioxolanes-2-ketone, ethylene carbonate and dimethyl carbonate.
(table 34)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material (weight %) Solvent (VOL%) Electrolytic salt Discharge capacitance (%)
FEC EC DMC
Embodiment 24-1 Lithium metal+carbon 50 0 50 LiPF6+ chemical formula 6 (1) 80
Embodiment 24-2 30 0 70 84
Embodiment 24-3 20 10 70 82
Embodiment 24-4 5 25 70 81
Embodiment 24-5 1 29 70 77
Comparative Examples 24-1 Lithium metal+carbon 0 30 70 LiPF6+ chemical formula 6 (1) 68
Comparative Examples 24-2 30 0 70 LiPF6 74
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
As Comparative Examples 24-1 with respect to embodiment 24-1 to 24-5, remove and to use by comprising ethylene carbonate and dimethyl carbonate with ethylene carbonate: in the solvent of the mixture of dimethyl carbonate volume ratio=30: 70 concentration of ordinary dissolution as the chemical formula 6 (1) of 0.2mol/kg represent 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium and concentration are the LiPF of 0.8mol/kg 6And outside the electrolyte that forms, as embodiment 24-1 to 24-5, form secondary cell.And, 24-2 as a comparison case, remove to use by comprising 4-fluoro-1,3-dioxolanes-2-ketone and dimethyl carbonate be with 4-fluoro-1,3-dioxolanes-2-ketone: concentration of ordinary dissolution is the LiPF as electrolytic salt of 1.0mol/kg in the solvent of the mixture of dimethyl carbonate volume ratio=30: 70 6And outside the electrolyte that forms, as embodiment 24-1 to 24-5, form secondary cell.
As embodiment 20-1 to 20-9, measure the cycle characteristics of the secondary cell of embodiment 24-1 to 24-5 and Comparative Examples 24-1 and 24-2 acquisition.The results are shown in table 34.
And, in the secondary cell of embodiment 24-1 to 24-5 and Comparative Examples 24-1 and 24-2, by the range estimation and 7The Li nuclear magnetic resonance spectrometry is checked lithium metal and the existence of lithium ion on negative pole 22.
As 7The result of Li nuclear magnetic resonance spectrometry, in the secondary cell of embodiment 24-1 to 24-5 and Comparative Examples 24-1 and 24-2, under complete charged state, near 265ppm, observe peak, and near 44ppm, observe peak owing to lithium ion owing to the lithium metal.These peak positions are the values with respect to the external perimysium reference lithium chloride.On the other hand, under complete discharge condition, do not observe peak owing to the lithium metal.And, only observing the lithium metal under the charged state fully by range estimation.In other words, the capacity that proves negative pole 22 comprises by the embedding of lithium and takes off the capacity part of embedding and the capacity part of separating out and dissolving by lithium, and represents with their summation.
From table 34 as seen, as embodiment 20-1 to 20-9, use therein among the embodiment 24-1 to 24-5 of cyclic carbonate derivative with halogen atom and cyclic imide salt, compare with the Comparative Examples 24-2 that does not use cyclic imide salt with the Comparative Examples 24-1 that does not use the cyclic carbonate derivative with halogen atom, discharge capacitance improves.And such trend is arranged: along with the content increase of the cyclic carbonate derivative with halogen atom, discharge capacitance is increased to maximum, reduces then.
In other words, the capacity of negative pole 22 therein found comprise by lithium embed and take off the capacity part of embedding and the capacity of separating out and the dissolving part by lithium and the secondary cell represented with their summation in, when use has the cyclic carbonate derivative of halogen atom and cyclic imide salt, can improve cycle characteristics, and have the content 50 volume % or still less preferably of the cyclic carbonate derivative of halogen atom in the solvent.
(embodiment 25-1 to 25-20)
Except the conduct dissolving, remove 4-fluoro-1, outside 3-dioxolanes-2-ketone and the dimethyl carbonate, also use 1 of chemical formula 3 (1) expressions, the 4-vinyl-1 of 3-dioxole-2-ketone, chemical formula 3 (2) expressions, 1 of 3-dioxolanes-2-ketone, chemical formula 4 (1) expressions, 1 of 3-propane sultone or chemical formula 4 (2) expressions, beyond the 3-propylene sultone, as embodiment 24-2, form secondary cell.The composition of solvent changes as shown in table 35.
The secondary cell that embodiment is obtained as with embodiment 24-2 under the identical condition that discharges and recharges 25 ℃ and 50 ℃ of charging and discharges down, and the measurement secondary cell is at the cycle characteristics of the 100th circulation time.The results are shown in table 35.
(table 35)
Cell shapes: cylindrical
Maximum charging voltage: 4.20V
Negative active core-shell material Solvent (weight %) Electrolytic salt Discharge capacitance (%)
FEC DMC VC VEC PS PRS 25℃ 50℃
Embodiment 24-3 Lithium metal+carbon 30 70 - - - - LiPF 6+ chemical formula 6 (1) 84 82
Embodiment 25-1 30 69.95 0.05 - - - 84 83
Embodiment 25-2 30 69.9 0.1 - - - 86 85
Embodiment 25-3 30 68 2 - - - 87 88
Embodiment 25-4 30 60 10 - - - 86 85
Embodiment 25-5 30 50 20 - - - 84 84
Embodiment 25-6 30 69.95 - 0.05 - - 85 83
Embodiment 25-7 30 69.9 - 0.1 - - 87 86
Embodiment 25-8 30 68 - 2 - - 88 90
Embodiment 25-9 30 60 - 10 - - 86 87
Embodiment 2510 30 50 - 20 - - 84 85
Embodiment 25-11 30 69.99 - - 0.01 - 84 83
Embodiment 25-12 30 69.95 - - 0.05 - 85 84
Embodiment 25-13 30 69 - - 1 - 86 86
Embodiment 25-14 30 67 - - 3 - 85 84
Embodiment 25-15 30 65 - - 5 - 84 83
Embodiment 25-16 30 69.99 - - - 0.01 85 84
Embodiment 25-17 30 69.95 - - - 0.05 86 86
Embodiment 25-18 30 69 - - - 1 87 88
Embodiment 25-19 30 67 - - - 3 85 86
Embodiment 25-20 30 65 - - - 5 84 85
FEC:4-fluoro-1,3-dioxolanes-2-ketone DMC: dimethyl carbonate
VC:1,3-dioxole-2-ketone VEC:4-vinyl-1,3-dioxolanes-2-ketone
PS:1,3-propane sultone PRS:1,3-propylene sultone
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
From table 35 as seen, when mixing 1,3-dioxole-2-ketone, 4-vinyl-1,3-dioxolanes-2-ketone, 1,3-propane sultone or 1 is during 3-propylene sultone, discharge capacitance improves, and particularly, observes higher efficacy under 50 ℃.
In other words, when find using cyclic carbonate with unsaturated bond or sultone, can further improve cycle characteristics, and particularly, can effectively improve the cycle characteristics under hot conditions as solvent.
(embodiment 26-1 to 26-4,27-1 to 27-4)
Form the battery of separating out and dissolve expression of the capacity of negative pole 22 wherein, i.e. the lithium metal secondary batteries by lithium.
In embodiment 26-1 to 26-4, secondary cell forms by following steps.At first, positive wire 31 and negative wire 32 are attached on the positive pole 33 and negative pole 34 that forms as embodiment 20-1 to 20-9, with positive pole 33 and negative pole 34 and barrier film 35 stacked formation sandwichs therebetween.Next,, and be clipped between the package component of making by laminated film 40, inject electrolyte and sealing, form secondary cell thus the sandwich screw winding.This laminated film comprises the thick nylon of 30 μ m, aluminium and the thick cast polypropylene of 30 μ m that 40 μ m are thick from the outside with this, makes that the gross thickness of laminated film is 100 μ m.Positive electrode collector 33A is made by the thick banded aluminium foil of 12um.
And, in embodiment 27-1 to 27-4, except that use 30mm wide * hollow prism that 48mm height * 5mm is thick describes the device, forms secondary cell as embodiment 20-1 to 20-9.Positive electrode collector 33A is made by the thick banded aluminium foil of 12 μ m.
In an embodiment, use is by comprising as the 4-fluoro-1 with cyclic carbonate derivative of halogen atom, 3-dioxolanes-2-ketone and dimethyl carbonate are with 4-fluoro-1,3-dioxolanes-2-ketone: in the solvent of the mixture of the volume ratio of dimethyl carbonate=30: 70, or comprising 4-chloro-1,3-dioxolanes-2-ketone and dimethyl carbonate are with 4-chloro-1,3-dioxolanes-2-ketone: in the solvent of the mixture of the volume ratio of dimethyl carbonate=50: 50, concentration of ordinary dissolution be 0.2mol/kg chemical formula 6 (4) expression 1,1,2,2-HFC-134a-1,1,1,2 of 3-disulfonyl imines lithium or chemical formula 6 (1) expressions, 2,3,3-HFC-236fa-1,3-disulfonyl imines lithium and concentration are the LiPF of 0.8mol/kg 6And the electrolyte that forms.
As Comparative Examples 26-1,26-2,27-1 and 27-2 with respect to embodiment, as the same secondary cell that forms of embodiment 26-1 to 26-4, remove and to use: dissolve in the solvent of the mixture of the volume ratio of dimethyl carbonate=30: 70 as the concentration of electrolytic salt LiPF as 0.8mol/kg by comprising ethylene carbonate and dimethyl carbonate with ethylene carbonate with 27-1 to 27-4 6With concentration be 0.2mol/kg chemical formula 6 (4) expression 1,1,2,2-HFC-134a-1,3-disulfonyl imines lithium and form electrolyte, perhaps use by comprising 4-fluoro-1,3-dioxolanes-2-ketone and dimethyl carbonate be with 4-fluoro-1,3-dioxolanes-2-ketone: dissolving is the LiPF of 1.0mol/kg as the concentration of electrolytic salt in the solvent of the mixture of the volume ratio of dimethyl carbonate=30: 70 6Outward.
As embodiment 20-1 to 20-9, measure the cycle characteristics of the secondary cell of embodiment 26-1 to 26-4 and 27-1 to 27-4 and Comparative Examples 26-1,26-2,27-1 and 27-2 acquisition.The results are shown in table 36 and 37.
(table 36)
Cell shapes: laminated-type
Negative active core-shell material Solvent Electrolytic salt Discharge capacitance (%)
Embodiment 26-1 The lithium metal FEC+DMC LiPF 6+ chemical formula 6 (4) 64
Embodiment 26-2 CIEC+DMC 60
Embodiment 26-3 FEC+DMC LiPF 6+ chemical formula 6 (1) 68
Embodiment 26-4 CIEC+DMC 63
Comparative Examples 26-1 The lithium metal EC+DMC LiPF 6+ chemical formula 6 (4) 38
Comparative Examples 26-2 FEC+DMC LiPF 6 45
FEC:4-fluoro-1,3-dioxolanes-2-ketone CIEC:4-chloro-dioxolanes-2-ketone
EC: ethylene carbonate DMC: dimethyl carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
Chemical formula 6 (4): 1,1,2,2-HFC-134a-1,3-disulfonyl imines lithium
(table 37)
Cell shapes: hollow is prismatic
Negative active core-shell material Solvent Electrolytic salt Discharge capacitance (%)
Embodiment 27-1 The lithium metal FEC+DMC LiPF 6+ chemical formula 6 (4) 62
Embodiment 27-2 CIEC+DMC 58
Embodiment 27-3 FEC+DMC LiPF 6+ chemical formula 6 (1) 67
Embodiment 27-4 CIEC+DMC 64
Comparative Examples 27-1 The lithium metal EC+DMC LiPF 6+ chemical formula 6 (4) 42
Comparative Examples 27-2 FEC+DMC LiPF 6 48
FEC:4-fluoro-1,3-dioxolanes-2-ketone CIEC:4-chloro-dioxolanes-2-ketone
EC: ethylene carbonate DMC: dimethyl carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
Chemical formula 6 (4): 1,1,2,2-HFC-134a-1,3-disulfonyl imines lithium
From table 36 and 37 as seen, as embodiment 20-1 to 20-9, use therein among the embodiment 26-1 to 26-4 and 27-1 to 27-4 of cyclic carbonate derivative with halogen atom and cyclic imide salt, compare with 27-2 with the Comparative Examples 26-2 that does not use cyclic imide salt with 27-1 with the Comparative Examples 26-1 that does not use cyclic carbonate derivative, obtain higher capability retention with halogen atom.
In other words, find,, when use has the cyclic carbonate derivative of halogen atom and cyclic imide salt, still can improve cycle characteristics even have in use under the situation of package component of any other shape.
(embodiment 28-1 to 28-4,29-1 to 29-4)
4-fluoro-1 in desolventizing, the content of 3-dioxolanes-2-ketone becomes 1 volume %, 5 volume %, 20 volume % or 50 volume %, promptly uses as outside the electrolyte among the embodiment 21-1 to 21-4, as the same secondary cell that forms with 27-3 of embodiment 26-3.
As embodiment 20-1 to 20-9, measure the cycle characteristics of the secondary cell that embodiment 28-1 to 28-4 and 29-1 to 29-4 make.The result is shown in table 38 and 39 with embodiment 26-3 and 27-3.
(table 38)
Cell shapes: laminated-type
Negative active core-shell material Solvent (volume %) Electrolytic salt Discharge capacitance (%)
FEC EC DMC
Embodiment 28-1 The lithium metal 50 0 50 LiPF 6+ chemical formula 6 (1) 65
Embodiment 26-3 30 0 70 68
Embodiment 28-2 20 10 70 67
Embodiment 28-3 5 25 70 62
Embodiment 28-4 1 29 70 61
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
(table 39)
Cell shapes: hollow is prismatic
Negative active core-shell material Solvent (volume %) Electrolytic salt Discharge capacitance (%)
FEC EC DMC
Embodiment 29-1 The lithium metal 50 0 50 LiPF 6+ chemical formula 6 (1) 64
Embodiment 27-3 30 0 70 67
Embodiment 29-2 20 10 70 66
Embodiment 29-3 5 25 70 60
Embodiment 29-4 1 29 70 59
FEC:4-fluoro-1,3-dioxolanes-2-ketone EC: ethylene carbonate
DMC: dimethyl carbonate
Chemical formula 6 (1): 1,1,2,2,3,3-HFC-236fa-1,3-disulfonyl imines lithium
From table 38 and 39 as seen, as embodiment 21-1 to 21-4, such trend is arranged: along with 4-fluoro-1, the content of 3-dioxolanes-2-ketone increases, and discharge capacitance is increased to maximum, reduces then.
In other words, even find under the situation of using another package component, in solvent, have the also 50 volume % or still less preferably of content of the cyclic carbonate derivative of halogen atom.
(embodiment 30-1 to 30-4,31-1 to 31-4)
Remove to use and pass through further with the LiBF of concentration 0.2mol/kg dissolving as electrolytic salt 4Or LiB (OCOCF 3) 4And the electrolyte that forms promptly uses as outside the electrolyte identical among the embodiment 22-1 to 22-4, as the same secondary cell that forms with 27-1 of embodiment 26-1.
As embodiment 20-1 to 20-9, measure the cycle characteristics of the secondary cell of embodiment 30-1 to 30-4 and 31-1 to 31-4 acquisition.The result is shown in table 40 and 41 with embodiment 26-1 and 27-1.
(table 40)
Cell shapes: laminated-type
Negative active core-shell material Solvent Electrolytic salt Discharge capacitance (%)
Embodiment 26-1 The lithium metal FEC+D MC LiPF 6+ chemical formula 6 (4) 64
Embodiment 30-1 LiPF 6+ chemical formula 6 (4)+LiPF 4 68
Embodiment 30-2 LiPF 6+ chemical formula 6 (4)+LiB (OCOCF 3) 4 70
Embodiment 30-3 CIEC+ DMC LiPF 6+ chemical formula 6 (4)+LiPF 4 65
Embodiment 30-4 LiPF 6+ chemical formula 6 (4)+LiB (OCOCF 3) 4 68
FEC:4-fluoro-1,3-dioxolanes-2-ketone CIEC:4-chloro-dioxolanes-2-ketone
DMC: dimethyl carbonate
Chemical formula 6 (4): 1,1,2,2-HFC-134a-1,3-disulfonyl imines lithium
(table 41)
Cell shapes: hollow is prismatic
Negative active core-shell material Solvent Electrolytic salt Discharge capacitance (%)
Embodiment 27-1 The lithium metal FEC+D MC LiPF 6+ chemical formula 6 (4) 62
Embodiment 31-1 LiPF 6+ chemical formula 6 (4)+LiPF 4 69
Embodiment 31-2 LiPF 6+ chemical formula 6 (4) LiB (OCOCF 3) 4 75
Embodiment 31-3 CIEC+ DMC LiPF 6+ chemical formula 6 (4)+LiPF 4 66
Embodiment 31-4 LiPF 6+ chemical formula 6 (4)+LiB (OCOCF 3) 4 72
FEC:4-fluoro-1,3-dioxolanes-2-ketone CIEC:4-chloro-dioxolanes-2-ketone
DMC: dimethyl carbonate
Chemical formula 6 (4): 1,1,2,2-tetrafluoroethene-1,3-disulfonyl imines lithium
From table 40 and 41, as seen, as embodiment 22-1 to 22-4, further mix LiBF therein 4Or LiB (OCOCF 3) 4Embodiment 30-1 to 30-4 and 31-1 to 31-4 in, compare with 27-1 with mixed both any one embodiment 26-1, discharge capacitance improves.
In other words, under the situation of using another package component, except cyclic imide salt, more preferably mix LiPF even find 6With another light metal salt.
Although described the present invention with reference to execution mode and embodiment, the present invention is not particularly limited to this, and can carry out multiple improvement.For example, in execution mode and the embodiment, described use electrolyte or wherein high-molecular weight compounds keep the situation of the gel electrolyte of electrolyte; Yet, can use any other electrolyte.Electrolytical example comprises as the ionic conduction inorganic compound of ionic conductivity ceramics, ionic conducting glass or ionic crystals and the mixture of electrolyte, the mixture of the mixture of another inorganic compound and electrolyte and inorganic compound and gel electrolyte.
And, in execution mode and embodiment, described and used the battery of lithium as the electrode reaction thing; Yet, the present invention also be suitable for using any other alkali metal such as the situation of sodium or potassium, alkaline-earth metal such as magnesium or calcium (Ca) or any other light metal such as aluminium.Simultaneously, in negative pole, the negative active core-shell material of describing in the foregoing description be can use in the same way, tin or silicon for example comprised as the material that constitutes element etc.
In addition, in execution mode and embodiment, cylinder type secondary battery, lamination membranous type secondary cell, prismatic secondary cell and Coin shape secondary cell have been described; Yet the present invention can be suitable for having for example secondary cell of button type of any other shape, the secondary cell of perhaps any other structure example such as laminar structure.In addition, the present invention not only is suitable for secondary cell and also is suitable for primary cell.
It will be appreciated by those skilled in the art that in the scope of claims or its equivalent, according to design requirement and other factors, can improve separately, combination, recombinant and replacement.

Claims (22)

1. electrolyte comprises:
Cyclic imide salt; With
Cyclic carbonate derivative with halogen atom.
2. according to the electrolyte of claim 1, wherein
As imide salts, comprise being selected from least a to the compound shown in 1 (6) of Chemical formula 1 (1):
(Chemical formula 1)
Wherein M1, M2, M3, M4, M5 and M6 represent alkali metal separately, on behalf of part hydrogen in the alkylidene of the straight or branched with 2-5 carbon atom or the wherein above-mentioned alkylidene, R1, R2 and R3 separately represented hydrogen separately, have the alkyl of 1 to 4 carbon atom or group that wherein part hydrogen is replaced by fluorine in the abovementioned alkyl by group and R41, R42, R43, R44, R51, R52, R53, R54, R61, R62, R63 and the R64 that fluorine replaces.
3. according to the electrolyte of claim 1, wherein
The content of imide salts comprises end points in the scope of 0.1 weight % to 31 weight %.
4. according to the electrolyte of claim 1, wherein
As carbonic acid ester derivative, comprise 4-fluoro-1,3-dioxolanes-2-ketone and 4-chloro-1, at least a in 3-dioxolanes-2-ketone.
5. according to the electrolyte of claim 1, also comprise:
Be selected from least a of cyclic carbonate with unsaturated bond and sultone.
6. according to the electrolyte of claim 5, wherein
The content of cyclic carbonate with unsaturated bond comprises end points in the scope of 0.05 weight % to 20 weight %.
7. according to the electrolyte of claim 5, wherein
The content of sultone comprises end points in the scope of 0.01 weight % to 5 weight %.
8. battery comprises:
Anodal;
Negative pole; With
Electrolyte,
Wherein this negative pole comprises and can embed and take off the material of embedding electrode reaction thing, and comprises be selected from metallic element and metalloid element at least a as constituting element, and
This electrolyte comprises cyclic imide salt.
9. battery according to Claim 8, wherein
As imide salts, comprise being selected from least a to the compound shown in 2 (6) of Chemical formula 2 (1):
(Chemical formula 2)
Figure A2006100927150003C1
Wherein M1, M2, M3, M4, M5 and M6 represent alkali metal separately, on behalf of part hydrogen in the alkylidene of the straight or branched with 2-5 carbon atom or the wherein above-mentioned alkylidene, R1, R2 and R3 separately represented hydrogen separately, have the alkyl of 1 to 4 carbon atom or group that wherein part hydrogen is replaced by fluorine in the abovementioned alkyl by group and R41, R42, R43, R44, R51, R52, R53, R54, R61, R62, R63 and the R64 that fluorine replaces.
10. battery according to Claim 8, wherein
This electrolyte also comprises the cyclic carbonate derivative with halogen atom.
11. battery according to Claim 8, wherein
This electrolyte also comprises and is selected from least a of cyclic carbonate with unsaturated bond and sultone.
12. battery according to Claim 8, wherein this negative pole comprises at least a negative material as the formation element that comprises in tin (Sn) and the silicon (Si).
13. a battery comprises:
Anodal;
Negative pole; With
Electrolyte,
Wherein the every pair of positive pole and the negative pole open circuit voltage under charged state fully is 4.25V or higher, and this electrolyte comprises cyclic imide salt.
14. according to the battery of claim 13, wherein
As imide salts, comprise being selected from least a of the compound shown in the chemical formula 3 (1) to 3 (6):
(chemical formula 3)
Wherein M1, M2, M3, M4, M5 and M6 represent alkali metal separately, on behalf of part hydrogen in the alkylidene of the straight or branched with 2-5 carbon atom or the wherein above-mentioned alkylidene, R1, R2 and R3 separately represented hydrogen separately, have the alkyl of 1 to 4 carbon atom or group that wherein part hydrogen is replaced by fluorine in the abovementioned alkyl by group and R41, R42, R43, R44, R51, R52, R53, R54, R61, R62, R63 and the R64 that fluorine replaces.
15. according to the battery of claim 13, wherein
This electrolyte also comprises the cyclic carbonate derivative with halogen atom.
16. according to the battery of claim 13, wherein
This electrolyte also comprises and is selected from least a of cyclic carbonate with unsaturated bond and sultone.
17. a battery comprises:
Anodal;
Negative pole; With
Electrolyte,
Wherein the lithium metal is used as negative active core-shell material, and
This electrolyte comprises cyclic imide salt and has the cyclic carbonate derivative of halogen atom.
18. according to the battery of claim 17, wherein
As imide salts, comprise being selected from least a of the compound shown in the chemical formula 4 (1) to 4 (6):
(chemical formula 4)
Wherein M1, M2, M3, M4, M5 and M6 represent alkali metal separately, on behalf of part hydrogen in the alkylidene of the straight or branched with 2-5 carbon atom or the wherein above-mentioned alkylidene, R1, R2 and R3 separately represented hydrogen separately, have the alkyl of 1 to 4 carbon atom or group that wherein part hydrogen is replaced by fluorine in the abovementioned alkyl by group and R41, R42, R43, R44, R51, R52, R53, R54, R61, R62, R63 and the R64 that fluorine replaces.
19. according to the battery of claim 17, wherein
This electrolyte also comprises and is selected from least a of cyclic carbonate with unsaturated bond and sultone.
20. a battery comprises
Anodal;
Negative pole;
Electrolyte,
Wherein the capacity of this negative pole comprises the embedding by light metal and takes off the capacity part of embedding and the capacity part of separating out and dissolving by light metal, and represents with their summation, and
This electrolyte comprises cyclic imide salt and has the cyclic carbonate derivative of halogen atom.
21. according to the battery of claim 20,
As imide salts, comprise being selected from least a of the compound shown in the chemical formula 5 (1) to 5 (6):
(chemical formula 5)
Figure A2006100927150006C1
Wherein M1, M2, M3, M4, M5 and M6 represent alkali metal separately, on behalf of part hydrogen in the alkylidene of the straight or branched with 2-5 carbon atom or the wherein above-mentioned alkylidene, R1, R2 and R3 separately represented hydrogen separately, have the alkyl of 1 to 4 carbon atom or group that wherein part hydrogen is replaced by fluorine in the abovementioned alkyl by group and R41, R42, R43, R44, R51, R52, R53, R54, R61, R62, R63 and the R64 that fluorine replaces.
22. according to the battery of claim 20, wherein
This electrolyte also comprises and is selected from least a of cyclic carbonate with unsaturated bond and sultone.
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CN102017270A (en) * 2008-04-25 2011-04-13 株式会社Lg化学 Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery having the same
CN102017270B (en) * 2008-04-25 2014-07-16 株式会社Lg化学 Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery having the same
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