CN114464889A - Non-aqueous electrolyte for high-voltage lithium ion battery and lithium ion battery thereof - Google Patents
Non-aqueous electrolyte for high-voltage lithium ion battery and lithium ion battery thereof Download PDFInfo
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- CN114464889A CN114464889A CN202210122666.9A CN202210122666A CN114464889A CN 114464889 A CN114464889 A CN 114464889A CN 202210122666 A CN202210122666 A CN 202210122666A CN 114464889 A CN114464889 A CN 114464889A
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- Prior art keywords
- lithium
- ion battery
- lithium ion
- electrolyte
- voltage
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 116
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 75
- 239000003792 electrolyte Substances 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims abstract description 9
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 40
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 28
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims description 18
- 159000000002 lithium salts Chemical class 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 15
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 14
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 14
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 13
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 12
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 229920005554 polynitrile Polymers 0.000 claims description 6
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 4
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- MMPXAACYTDXBFA-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] MMPXAACYTDXBFA-UHFFFAOYSA-M 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 description 42
- 239000000203 mixture Substances 0.000 description 16
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 12
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010405 anode material Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- LNLFLMCWDHZINJ-UHFFFAOYSA-N hexane-1,3,6-tricarbonitrile Chemical compound N#CCCCC(C#N)CCC#N LNLFLMCWDHZINJ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009517 secondary packaging Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
Abstract
The invention discloses a non-aqueous electrolyte for a high-voltage lithium ion battery and the lithium ion battery. The non-aqueous electrolyte for the high-voltage lithium ion battery comprises an electrolyte, a non-aqueous solvent and an additive, wherein the additive comprises a compound shown in a structural formula (I). The high-voltage lithium ion battery electrolyte provided by the invention can effectively establish a positive electrode protection interface, protect a positive electrode material, prevent the structural damage caused by deep delithiation of the positive electrode material, and inhibit the side reaction of the electrolyte and the positive electrode interface at high voltage, thereby improving the stability of the lithium ion battery at high voltage.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a non-aqueous electrolyte for a high-voltage lithium ion battery and the lithium ion battery containing the same.
Background
Since Sony corporation introduced the first commercial lithium ion battery in 1991, the lithium ion battery has been widely used in the fields of notebook computers, smart phones, electric vehicles, and the like due to its advantages of high energy density, long cycle life, wide operating temperature range, and the like. Particularly in the 3C digital neighborhood, the lithium ion battery technology becomes an almost irreplaceable technical solution. Nowadays, due to the large-scale popularization of portable charging devices such as smart phones, wireless earphones and smart watches, consumers expect that lithium ion batteries can be lighter and have longer endurance, which means that the lithium ion batteries need higher energy density.
The high-voltage lithium cobalt oxide anode material is an important development direction for improving the energy density of the lithium ion battery, the high-voltage anode means that the output voltage of the lithium ion battery is higher, and the capacity exertion of the anode material under the high voltage is also improved, so that the whole lithium ion battery can be effectively improved in both the voltage and the capacity, and further the energy density is obviously improved. However, the lithium ions extracted from the cathode material at high voltage become more, which causes more vacancies to occur in the original crystal structure, which easily causes the original crystal structure to collapse to form a new structure without charge-discharge capability, resulting in the attenuation of the battery capacity; on the other hand, the high-voltage electrolyte is also easy to generate side reaction with the positive electrode, consume lithium ions, damage the positive electrode material and further cause irreversible attenuation of the lithium ion battery. Therefore, it is necessary to develop a new electrolyte additive capable of forming an effective interface on the surface of the positive electrode, protecting the positive electrode, and inhibiting the occurrence of side reactions of the electrolyte, thereby solving the problem of rapid decay of the lithium ion battery under high voltage.
Disclosure of Invention
In order to solve the problems, the invention provides a non-aqueous electrolyte for a high-voltage lithium ion battery and the lithium ion battery containing the same, which can well solve the structural damage of a positive electrode material under high voltage, reduce the side reaction of the electrolyte and the positive electrode material and further improve the stability of the battery.
A non-aqueous electrolyte for a high-voltage lithium ion battery, comprising an electrolyte, a non-aqueous solvent and an additive, wherein the additive comprises a compound represented by the structural formula (I):
wherein R is1And R2Each independently selected from the group consisting of a hydrogen atom, an alkyl group and a fluoroalkyl group, the alkyl group or fluoroalkyl group having less than 3 carbon atoms.
The compound of the structural formula (I) is selected from one or more of a compound (1), a compound (2) and a compound (3);
the content of the compound of the structural formula (I) accounts for 0.3-3% of the total mass of the electrolyte.
The additive comprises a polynitrile compound selected from one or more of succinonitrile, adiponitrile, 1, 2-bis (2-cyanoethoxy) ethane, 1,3, 6-hexanetrinitrile;
the content of the polynitrile compound accounts for 2-7% of the total mass of the electrolyte.
The additive comprises 1, 3-propane sultone, fluoroethylene carbonate or ethylene sulfate;
the content of the 1, 3-propane sultone accounts for 3-6% of the total mass of the electrolyte;
the content of the fluoroethylene carbonate accounts for 3-8% of the total mass of the electrolyte;
the content of the ethylene sulfate accounts for 0.5-3% of the total mass of the electrolyte.
The electrolyte is lithium salt; the lithium salt is selected from one or the combination of at least two of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium difluorophosphate, lithium tetrafluoroborate, lithium difluorooxalate borate or lithium bis (oxalate) phosphate;
the content of the lithium hexafluorophosphate accounts for 10-16% of the total mass of the electrolyte; the content of the lithium bis (fluorosulfonyl) imide, lithium difluorophosphate, lithium tetrafluoroborate, lithium difluorooxalato borate or lithium bis (oxalato) phosphate accounts for 0.5-3% of the total mass of the electrolyte.
The non-aqueous solvent comprises a carbonate solvent and a carboxylate solvent;
the carbonate solvent comprises any one or combination of Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC);
the carboxylic ester solvent comprises one or more of propyl acetate, butyl acetate, Methyl Propionate (MP), Ethyl Propionate (EP), Propyl Propionate (PP), butyl propionate;
the content of the carbonate solvent accounts for 15-25% of the total mass of the electrolyte;
the content of the carboxylate solvent accounts for 40-60% of the total mass of the electrolyte.
A lithium ion battery comprises the high-voltage lithium ion battery non-aqueous electrolyte.
The positive electrode material of the lithium ion battery is lithium cobaltate, and the negative electrode is artificial graphite or a silicon-carbon composite negative electrode.
The charge cut-off voltage of the lithium ion battery is more than 4.45V.
The invention has the beneficial effects that: according to the invention, a good anode protective interface (CEI) can be effectively formed on the surface of the anode by introducing the novel additive (I), the structure damage of the lithium cobaltate anode is prevented, the side reaction of the electrolyte under high voltage is inhibited, and meanwhile, the polynitrile compound and other additives are introduced, so that the cobalt ions overflowing from the anode material are effectively chelated, and the decomposition of the metal ions in the cathode interface catalytic electrolyte is avoided. Through the action mechanism, the problem of attenuation of the high-voltage lithium cobalt oxide battery is effectively solved, and the service life of the battery is prolonged.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example 1
The embodiment provides a lithium ion battery nonaqueous electrolyte, wherein the lithium ion nonaqueous electrolyte comprises 5 mass percent of fluoroethylene carbonate, 4 mass percent of 1, 3-propane sultone, 1 mass percent of vinyl sulfate, 1 mass percent of succinonitrile, 2 mass percent of adiponitrile, 1 mass percent of 1,3, 6-hexane trinitrile, 0.3 mass percent of compound (1), lithium salt comprises 1 mass percent of lithium bis-fluorosulfonylimide and 14 mass percent of lithium hexafluorophosphate, and the balance is a nonaqueous solvent, and the composition and mass ratio of each solvent in the nonaqueous solvent are EC: PC: EP: PP 10: 15: 35: 30.
the preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte is prepared in a glove box, wherein the argon content in the glove box is 99.999%, the actual oxygen content is less than 0.1ppm, and the moisture content is less than 0.1 ppm. And uniformly mixing the non-aqueous solvent, the additive and the lithium salt according to the proportion to prepare the non-aqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps:
preparing a positive plate: the method comprises the following steps of mixing a positive electrode active material high-voltage material lithium cobaltate, a conductive agent carbon black (Super-P), a carbon nano tube and a binder polyvinylidene fluoride according to a mass ratio of 96: 1.5: 1: 1.5 dissolving in N-methyl pyrrolidone solvent, and mixing to obtain the anode slurry. And then uniformly coating the positive electrode slurry on a current collector aluminum foil, drying at 80 ℃, cold pressing, trimming, cutting into pieces, slitting, drying at 80 ℃ for 10 hours in vacuum, and welding tabs to prepare the positive electrode plate of the lithium ion battery.
Preparing a negative plate: preparing a negative electrode active material artificial graphite, a conductive agent carbon black (Super-P), a thickening agent sodium carboxymethyl cellulose and a binder styrene butadiene rubber according to a mass ratio of 96: 0.5: 1.5: 2, dissolving in solvent deionized water, and uniformly mixing to prepare cathode slurry. And then uniformly coating the negative electrode slurry on the front and back surfaces of the current collector copper foil, drying at 70 ℃, cold pressing, trimming, cutting into pieces, slitting, drying at 80 ℃ for 10 hours in vacuum, and welding tabs to prepare the negative electrode piece of the lithium ion battery.
Stacking the positive plate, the lithium battery isolation film and the negative plate in sequence to enable the lithium battery isolation film to be positioned between the positive plate and the negative plate to play an isolation role, and then winding to obtain a bare cell; and placing the bare cell in an aluminum-plastic film shell, injecting the prepared electrolyte into the dried battery, and performing vacuum packaging, standing, formation, aging, secondary packaging, capacity grading and other processes to obtain the high-voltage lithium cobalt oxide soft package lithium ion battery, wherein the nominal capacity of a single battery is 300 mAh.
Example 2
The embodiment provides a lithium ion battery nonaqueous electrolyte, wherein the lithium ion nonaqueous electrolyte comprises, by mass, 5% of fluoroethylene carbonate, 4% of 1, 3-propane sultone, 1% of vinyl sulfate, 1% of succinonitrile, 2% of adiponitrile, 1% of 1,3, 6-hexanetricarbonitrile, 1% of a compound (1), a lithium salt containing 1% of lithium bis (fluorosulfonyl) imide and 14% of lithium hexafluorophosphate, and the balance of a nonaqueous solvent, wherein the nonaqueous solvent comprises the following components in mass ratio, and the EC: PC: EP: PP 10: 15: 35: 30.
the preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion nonaqueous electrolyte solution in this example was the same as that of example 1, and the respective compositions and proportions of the nonaqueous electrolyte solution were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 3
The embodiment provides a lithium ion battery nonaqueous electrolyte, wherein the lithium ion nonaqueous electrolyte comprises, by mass, 5% of fluoroethylene carbonate, 4% of 1, 3-propane sultone, 1% of vinyl sulfate, 1% of succinonitrile, 2% of adiponitrile, 1% of 1,3, 6-hexanetrinitrile, 1.5% of a compound (1), a lithium salt comprising 1% of lithium bis (fluorosulfonyl) imide and 14% of lithium hexafluorophosphate, and the balance being a nonaqueous solvent, wherein the nonaqueous solvent comprises the following components in mass ratio, based on 100% of the total mass of the nonaqueous electrolyte, and the EC: PC: EP: PP 10: 15: 35: 30.
the preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion nonaqueous electrolyte solution in this example was the same as that of example 1, and the respective compositions and proportions of the nonaqueous electrolyte solution were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 4
The embodiment provides a lithium ion battery nonaqueous electrolyte, wherein the lithium ion nonaqueous electrolyte comprises, by mass, 5% of fluoroethylene carbonate, 4% of 1, 3-propane sultone, 1% of vinyl sulfate, 1% of succinonitrile, 2% of adiponitrile, 1% of 1,3, 6-hexanetricarbonitrile, 2% of a compound (1), a lithium salt containing 1% of lithium bis (fluorosulfonyl) imide and 14% of lithium hexafluorophosphate, and the balance of a nonaqueous solvent, wherein the nonaqueous solvent comprises the following components in mass ratio, and the EC: PC: EP: PP 10: 15: 35: 30.
the preparation method of the lithium ion battery non-aqueous electrolyte comprises the following steps:
the preparation method of the lithium ion nonaqueous electrolyte solution in this example was the same as that of example 1, and the respective compositions and proportions of the nonaqueous electrolyte solution were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 5
The embodiment provides a lithium ion battery nonaqueous electrolyte, wherein the lithium ion nonaqueous electrolyte comprises, by mass, 5% of fluoroethylene carbonate, 4% of 1, 3-propane sultone, 1% of vinyl sulfate, 1% of succinonitrile, 2% of adiponitrile, 1% of 1,3, 6-hexanetrinitrile, 1.5% of a compound (2), a lithium salt comprising 1% of lithium bis (fluorosulfonyl) imide and 14% of lithium hexafluorophosphate, and the balance being a nonaqueous solvent, wherein the nonaqueous solvent comprises the following components in mass ratio, based on 100% of the total mass of the nonaqueous electrolyte, and the EC: PC: EP: PP 10: 15: 35: 30.
the preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion nonaqueous electrolyte solution in this example was the same as that of example 1, and the respective compositions and proportions of the nonaqueous electrolyte solution were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 6
The embodiment provides a lithium ion battery nonaqueous electrolyte, wherein the lithium ion nonaqueous electrolyte comprises, by mass, 5% of fluoroethylene carbonate, 4% of 1, 3-propane sultone, 1% of vinyl sulfate, 1% of succinonitrile, 2% of adiponitrile, 1% of 1,3, 6-hexanetricarbonitrile, 1% of compound (1), 1% of compound (2), lithium salt comprising 1% of lithium bis (fluorosulfonyl) imide and 14% of lithium hexafluorophosphate, and the balance of a nonaqueous solvent, wherein the total mass of the nonaqueous electrolyte is 100%, and the compositions and mass ratios of the solvents in the nonaqueous solvent are EC: PC: EP: PP 10: 15: 35: 30.
the preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion nonaqueous electrolyte solution in this example was the same as that of example 1, and the respective compositions and proportions of the nonaqueous electrolyte solution were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 7
The embodiment provides a lithium ion battery nonaqueous electrolyte, wherein the lithium ion nonaqueous electrolyte comprises, by mass, 3% of fluoroethylene carbonate, 6% of 1, 3-propane sultone, 3% of vinyl sulfate, 1% of adiponitrile, 1% of 1,3, 6-hexanetricarbonitrile, and 1.5% of compound (1), the lithium salt comprises 1% of lithium difluorooxalato borate, 2% of lithium difluorosulfonimide and 10% of lithium hexafluorophosphate, and the balance is a nonaqueous solvent, and the compositions and mass ratios of the solvents in the nonaqueous solvent are EC: PC: EP: PP 10: 15: 35: 30.
the preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion nonaqueous electrolyte solution in this example was the same as that of example 1, and the respective compositions and proportions of the nonaqueous electrolyte solution were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 8
The embodiment provides a lithium ion battery non-aqueous electrolyte, wherein the total mass of the non-aqueous electrolyte is 100%, the lithium ion non-aqueous electrolyte comprises 8% of fluoroethylene carbonate, 4% of 1, 3-propane sultone, 1% of vinyl sulfate, 2% of succinonitrile, 2% of adiponitrile, 1.5% of 1,3, 6-hexane trinitrile, 1% of compound (1), lithium salt comprises 1% of lithium bis (fluorosulfonyl) imide and 14% of lithium hexafluorophosphate, and the balance is a non-aqueous solvent, the composition of each solvent in the non-aqueous solvent and the mass ratio are EC: PC: EP: PP 10: 15: 35: 30.
the preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion nonaqueous electrolyte solution in this example was the same as that of example 1, and the respective compositions and proportions of the nonaqueous electrolyte solution were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 8
The embodiment provides a lithium ion battery nonaqueous electrolyte, wherein the lithium ion nonaqueous electrolyte comprises, by mass, 8% of fluoroethylene carbonate, 4% of 1, 3-propane sultone, 1% of vinyl sulfate, 2% of succinonitrile, 2% of adiponitrile, 1.5% of 1,3, 6-hexanetrinitrile, 1% of a compound (1), a lithium salt comprising 1% of lithium bis (fluorosulfonyl) imide and 14% of lithium hexafluorophosphate, and the balance being a nonaqueous solvent, wherein the nonaqueous solvent comprises the following components in mass ratio, based on 100% of the total mass of the nonaqueous electrolyte, and the EC: PC: EP: PP 10: 15: 35: 30.
the preparation method of the lithium ion battery non-aqueous electrolyte comprises the following steps:
the preparation method of the lithium ion nonaqueous electrolyte solution in this example was the same as that of example 1, and the respective compositions and proportions of the nonaqueous electrolyte solution were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 9
The embodiment provides a lithium ion battery nonaqueous electrolyte, wherein the lithium ion nonaqueous electrolyte comprises, by mass, 3% of fluoroethylene carbonate, 3% of 1, 3-propane sultone, 0.5% of vinyl sulfate, 2% of succinonitrile, 2% of adiponitrile, 2% of 1, 2-bis (2-cyanoethoxy) ethane, 1% of 1,3, 6-hexane trinitrile, 0.3% of a compound (1), a lithium salt containing 0.5% of lithium bis (fluorosulfonyl imide) and 16% of lithium hexafluorophosphate, and the balance of a nonaqueous solvent, wherein the total mass of the nonaqueous electrolyte is 100%, the EC: PC: EP: PP 10: 15: 35: 30.
the preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion nonaqueous electrolyte solution in this example was the same as that of example 1, and the respective compositions and proportions of the nonaqueous electrolyte solution were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Example 10
The embodiment provides a lithium ion battery nonaqueous electrolyte, wherein the lithium ion nonaqueous electrolyte comprises, by mass, 5% of fluoroethylene carbonate, 4% of 1, 3-propane sultone, 1% of vinyl sulfate, 1% of succinonitrile, 2% of adiponitrile, 1% of 1,3, 6-hexanetrinitrile, 3% of a compound (1), lithium salt containing 0.5% of lithium difluorooxalato borate, 1% of lithium difluorosulfonimide and 14% of lithium hexafluorophosphate, and the balance of a nonaqueous solvent, wherein the total mass of the nonaqueous electrolyte is 100%, and the compositions and mass ratios of the solvents in the nonaqueous solvent are EC: PC: EP: PP 10: 15: 35: 30.
the preparation method of the non-aqueous electrolyte of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion nonaqueous electrolyte solution in this example was the same as that of example 1, and the respective compositions and proportions of the nonaqueous electrolyte solution were as described in this example.
The preparation method of the lithium ion battery comprises the following steps:
the preparation method of the lithium ion battery of the present example is the same as that of example 1.
Comparative example 1
The comparative example is different from example 1 in that all additives are not added, the lithium salt contains only lithium hexafluorophosphate, and the amount of the nonaqueous solvent is adjusted adaptively so that the total amount of the electrolyte is 100% based on 100% by mass of the total mass of the nonaqueous electrolyte, and the other raw materials, the compounding ratio, and the mass percentage of each component are the same as those of example 1.
Comparative example 2
The comparative example is different from example 1 in that the compound of the structural formula (I) is not added and the polynitrile compound is not added based on 100% of the total mass of the nonaqueous electrolytic solution, the lithium salt only contains lithium hexafluorophosphate, and other raw materials, mixture ratios and mass percentages of the components are the same as those of example 1.
Comparative example 3
The comparative example is different from example 1 in that the compound of the structural formula (I) is not contained based on 100% of the total mass of the nonaqueous electrolytic solution, and other raw materials, compounding ratios and mass percentages of the components are the same as those of example 1.
The performance test method comprises the following steps:
the lithium ion batteries prepared in examples 1 to 10 and comparative examples 1 to 3 were respectively tested for high temperature performance and cycle performance by the following methods:
(1) and (3) testing the cycle performance: charging the batteries at a rate of 0.5C (150mA) in a thermostatic chamber at 25 ℃, and then discharging the batteries at a rate of 1C (300mA) in a reciprocating manner; the capacity retention rate was calculated according to the following formula:
capacity retention ratio (discharge capacity after end of cycle/discharge capacity of first cycle)
(2) And (3) high-temperature storage test: charging the battery to 4.48V at constant current and constant voltage with 0.5C multiplying power and 15mA cutoff current at normal temperature, discharging the battery to 3V at constant current with 1C multiplying power, and recording the discharge capacity as C0(ii) a Charging the battery to 4.48V at constant current and constant voltage at 1C rate and cutoff current of 15mA at normal temperature, placing the battery in a 55 deg.C incubator for 7 days, taking out, cooling to normal temperature, observing the gas expansion condition of the battery, discharging the battery to 3V at constant current at 1C rate and measuring the discharge capacity as C1(ii) a And the capacity retention rate was calculated according to the following formula:
capacity retention rate ═ C1/C0)×100％
The results of the test are shown in table 1:
table 1:
from table 1, it can be found that the lithium ion batteries prepared in examples 1 to 10 provided by the present invention have more superior performance than those in comparative examples 1 to 3: the flatulence phenomenon is not generated after the storage for 7 days at the high temperature of 55 ℃, and the capacity retention rate is over 88 percent; in the aspect of cycle life, after the electrolyte provided by the invention is circulated for 400 weeks, the capacity rate is more than 83%, which shows that the technical scheme provided by the invention can effectively improve the performance of the high-voltage cobalt acid lithium battery and prolong the service life of the high-voltage lithium ion battery.
Comparing the properties of comparative column 3 with examples 1, 5, 6, it can be seen that: the compound with the structural formula (I) provided by the invention can well solve the problem of high-temperature air expansion of the high-voltage lithium ion battery, and can also prolong the cycle life of the high-voltage lithium ion battery. The compound with the structural formula (I) can form a good anode protection interface (CEI) on the surface of an anode in a formation stage, so that the anode material is protected, and the stability of the anode material is improved; on the other hand, the side reaction between the electrolyte and the high-voltage positive electrode material can be effectively inhibited, the service life of the electrolyte is prolonged, and the high-voltage lithium ion battery can still exert good performance at the voltage of 4.48V.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The non-aqueous electrolyte for the high-voltage lithium ion battery is characterized by comprising an electrolyte, a non-aqueous solvent and an additive, wherein the additive comprises a compound represented by a structural formula (I):
wherein R is1And R2Each independently selected from the group consisting of a hydrogen atom, an alkyl group and a fluoroalkyl group, the alkyl group or fluoroalkyl group having less than 3 carbon atoms.
2. The nonaqueous electrolytic solution for a high-voltage lithium-ion battery according to claim 1, wherein the compound of the formula (i) is one or more selected from a compound (1), a compound (2) and a compound (3);
the content of the compound of the structural formula (I) accounts for 0.3-3% of the total mass of the electrolyte.
3. The nonaqueous electrolyte solution for a high-voltage lithium-ion battery according to claim 1, wherein the additive comprises a polynitrile compound selected from one or more of succinonitrile, adiponitrile, 1, 2-bis (2-cyanoethoxy) ethane, and 1,3, 6-hexanetrinitrile;
the content of the polynitrile compound accounts for 2-7% of the total mass of the electrolyte.
4. The nonaqueous electrolytic solution for a high-voltage lithium ion battery according to claim 1, wherein the additive comprises 1, 3-propane sultone, fluoroethylene carbonate, or ethylene sulfate;
the content of the 1, 3-propane sultone accounts for 3-6% of the total mass of the electrolyte;
the content of the fluoroethylene carbonate accounts for 3-8% of the total mass of the electrolyte;
the content of the ethylene sulfate accounts for 0.5-3% of the total mass of the electrolyte.
5. The nonaqueous electrolyte solution for a high-voltage lithium ion battery according to claim 1, wherein the electrolyte is a lithium salt; the lithium salt is selected from one or the combination of at least two of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium difluorophosphate, lithium tetrafluoroborate, lithium difluorooxalate borate or lithium bis (oxalate) phosphate;
the content of the lithium hexafluorophosphate accounts for 10-16% of the total mass of the electrolyte; the content of the lithium bis (fluorosulfonyl) imide, lithium difluorophosphate, lithium tetrafluoroborate, lithium difluorooxalato borate or lithium bis (oxalato) phosphate accounts for 0.5-3% of the total mass of the electrolyte.
6. The nonaqueous electrolyte solution for a high-voltage lithium ion battery according to claim 1, wherein the nonaqueous solvent contains a carbonate solvent and a carboxylate solvent;
the carbonate solvent comprises any one or a combination of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate;
the carboxylic ester solvent comprises one or more of propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate and butyl propionate;
the content of the carbonate solvent accounts for 15-25% of the total mass of the electrolyte;
the content of the carboxylate solvent accounts for 40-60% of the total mass of the electrolyte.
7. A lithium ion battery comprising the high-voltage lithium ion battery nonaqueous electrolyte solution according to any one of claims 1 to 6.
8. The lithium ion battery of claim 7, wherein the positive electrode material of the lithium ion battery is lithium cobaltate, and the negative electrode is artificial graphite or silicon carbon composite negative electrode.
9. The lithium ion battery of claim 7, wherein the charge cutoff voltage of the lithium ion battery is greater than 4.45V.
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