CN111934017A - Non-aqueous electrolyte for lithium ion battery and lithium ion battery containing same - Google Patents
Non-aqueous electrolyte for lithium ion battery and lithium ion battery containing same Download PDFInfo
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- CN111934017A CN111934017A CN202010893084.1A CN202010893084A CN111934017A CN 111934017 A CN111934017 A CN 111934017A CN 202010893084 A CN202010893084 A CN 202010893084A CN 111934017 A CN111934017 A CN 111934017A
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- Prior art keywords
- lithium ion
- lithium
- ion battery
- phosphate
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 80
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 32
- -1 unsaturated phosphate compound Chemical class 0.000 claims abstract description 41
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 229920001774 Perfluoroether Polymers 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical class 0.000 claims abstract 2
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 229910013172 LiNixCoy Inorganic materials 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- FCTINJHSYHFASK-UHFFFAOYSA-N tris(prop-2-ynyl) phosphate Chemical compound C#CCOP(=O)(OCC#C)OCC#C FCTINJHSYHFASK-UHFFFAOYSA-N 0.000 claims description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- XSMRUVQSORWBJY-UHFFFAOYSA-N bis(prop-2-ynyl) hydrogen phosphate Chemical compound C#CCOP(=O)(O)OCC#C XSMRUVQSORWBJY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- FFYPMLJYZAEMQB-UHFFFAOYSA-N diethyl pyrocarbonate Chemical compound CCOC(=O)OC(=O)OCC FFYPMLJYZAEMQB-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- AYHKRRVXHIUOIY-UHFFFAOYSA-N dipropyl prop-2-ynyl phosphate Chemical compound CCCOP(=O)(OCCC)OCC#C AYHKRRVXHIUOIY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- QWOVEJBDMKHZQK-UHFFFAOYSA-N 1,3,5-tris(3-trimethoxysilylpropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CO[Si](OC)(OC)CCCN1C(=O)N(CCC[Si](OC)(OC)OC)C(=O)N(CCC[Si](OC)(OC)OC)C1=O QWOVEJBDMKHZQK-UHFFFAOYSA-N 0.000 claims description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 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 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 2
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 11
- 238000001556 precipitation Methods 0.000 abstract description 9
- 238000009736 wetting Methods 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 229910020784 Co0.2O2 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- AJYQMCHCOGIXMR-IDTAVKCVSA-N [(2r,3s,4r,5r)-5-[6-(4-bromo-2,3-dioxobutyl)sulfanylpurin-9-yl]-3,4-dihydroxyoxolan-2-yl]methyl phosphono hydrogen phosphate Chemical compound O[C@@H]1[C@H](O)[C@@H](COP(O)(=O)OP(O)(O)=O)O[C@H]1N1C2=NC=NC(SCC(=O)C(=O)CBr)=C2N=C1 AJYQMCHCOGIXMR-IDTAVKCVSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 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
- 239000011230 binding agent Substances 0.000 description 1
- CBMFIMRGALBISQ-UHFFFAOYSA-N bis(ethenyl) sulfate Chemical compound C=COS(=O)(=O)OC=C CBMFIMRGALBISQ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- WNDPCPCMZSEBON-UHFFFAOYSA-N ethyl 1,1,1-trifluoropropan-2-yl carbonate Chemical compound C(OCC)(OC(C)C(F)(F)F)=O WNDPCPCMZSEBON-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000011701 zinc Substances 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
- H01M10/056—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
- H01M10/052—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
- H01M10/42—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a lithium ion battery non-aqueous electrolyte and a lithium ion battery containing the same, wherein the lithium ion battery non-aqueous electrolyte comprises a lithium salt, a non-aqueous organic solvent and an additive, the additive comprises a fluoroether compound with a structural formula 1, an unsaturated phosphate compound with a structural formula 2 and a cyclic sulfate compound with a structural formula 3 or 4, wherein R is1、R2、R3、R4、R5、R6Each independently selected from fluorine atom, C1-C4 fluoroalkyl; r7、R8、R9Each independently selected from unsaturated hydrocarbon or fluorinated hydrocarbon groups of C1-C4; r10Is hydrogen or C1-C5 alkyl, and n is an integer of 1-5. Lithium ion battery tool prepared by adopting non-aqueous electrolyte of lithium ion batteryThe lithium ion battery has better wetting performance, low-temperature charge and discharge performance, high-temperature storage performance, high-temperature cycle performance and normal-temperature cycle performance, and can effectively avoid low-temperature lithium precipitation.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery non-aqueous electrolyte and a lithium ion battery containing the same.
Background
The lithium ion battery is a secondary battery and has the obvious advantages of high specific energy, large specific power, long cycle life, small self-discharge and the like. With the application field of the lithium ion battery becoming more and more extensive, the requirements for high voltage and high energy density of the lithium ion battery are also becoming higher and higher. In a lithium ion battery, a high-voltage ternary cathode material (NCM or NCA) is widely applied to electric equipment due to the advantages of high energy density, environmental friendliness, long cycle life and the like, but the market has higher and higher requirements on the energy density of the lithium ion battery, so that the commercial ternary cathode material lithium ion battery cannot meet the use requirements.
At present, research shows that one of effective ways for improving the energy density of the ternary electrode material is to improve the working voltage of the battery, which is a trend of battery development and is also an inevitable requirement for new energy automobile development. However, after the working voltage of the ternary power battery is increased, the performances of the battery, such as charge and discharge cycles, are reduced. Among them, the electrolyte, which is an important component of a lithium ion battery, has a significant influence on performance degradation such as charge and discharge cycles of the battery. The electrolyte determines lithium ions (Li)+) The migration rate in a liquid phase and the matching property of the migration rate and an electrode also influence the wetting performance of the battery, simultaneously participate in the formation of a Solid Electrolyte Interface (SEI) film and play a critical role in the performance of the SEI film, so that the electrolyte can cause poor high-temperature storage performance and high-temperature cycle of the lithium ion batteryThe ring performance is poor, and the normal-temperature cycle performance is poor; meanwhile, the viscosity of the electrolyte is increased at low temperature, the conductivity is reduced, and the SEI film impedance is increased, so that the electrolyte can cause poor low-temperature discharge performance of the lithium ion battery, and even risk of low-temperature lithium precipitation is caused.
Therefore, the development of a lithium ion battery nonaqueous electrolyte suitable for a high-voltage ternary material system is urgently needed.
Disclosure of Invention
The invention aims to provide a lithium ion battery non-aqueous electrolyte, wherein a fluoroether compound, an unsaturated phosphate compound and a cyclic sulfate compound are used as additives of the electrolyte, so that the lithium ion battery has better wetting performance, high-temperature storage performance, high-temperature cycle performance and normal-temperature cycle performance, has better low-temperature discharge performance and can effectively avoid low-temperature lithium precipitation.
The invention also aims to provide a lithium ion battery containing the electrolyte, which has better wetting performance, low-temperature charge and discharge performance, high-temperature storage performance, high-temperature cycle performance and normal-temperature cycle performance, and can effectively avoid low-temperature lithium precipitation.
In order to achieve the above purpose, the invention provides a lithium ion battery non-aqueous electrolyte, comprising lithium salt, non-aqueous organic solvent and additive, wherein the additive comprises fluoroether compound with structural formula 1, unsaturated phosphate compound with structural formula 2, and cyclic sulfate compound with structural formula 3 or 4,
wherein R is1、R2、R3、R4、R5、R6Each independently selected from fluorine atom, C1-C4 fluoroalkyl; r7、R8、R9Each independently selected from unsaturated hydrocarbon or fluorinated hydrocarbon groups of C1-C4; r10Is hydrogen or C1-C5 alkyl, and n is an integer of 1-5.
Compared with the prior art, the lithium of the inventionThe additive of the non-aqueous electrolyte of the ion battery comprises a fluoroether compound, an unsaturated phosphate compound and a cyclic sulfate compound. The high-temperature storage performance, the high-temperature cycle performance and the normal-temperature cycle performance of the lithium ion battery can be remarkably improved by a phosphorus-containing SEI film formed by the unsaturated phosphate compound in the formation process of the lithium ion battery, but the wettability of the unsaturated phosphate compound in the negative electrode active material graphite is poor, so that the wettability of the lithium ion battery is poor, and the phosphorus-containing SEI film formed at low temperature has poor conductivity and high impedance, so that the Li is poor in wettability+The migration rate in a liquid phase is slow, so that the low-temperature discharge performance is poor, lithium ions cannot be timely inserted into a negative electrode during low-temperature circulation, metal lithium is separated out, the film forming speed of the unsaturated phosphate ester compound is high, the formed SEI film containing phosphorus is generally thick, and even the SEI film can reach the excessive thickness of the initiation risk. Based on the above, the problem can be overcome by adding the fluoroether compound into the electrolyte, the fluoroether compound has better wettability so as to improve the wettability of the lithium ion battery, and an SEI film containing a large amount of LiF can be formed in the formation process of the lithium ion battery, and the SEI film containing a large amount of LiF can obviously reduce the impedance of the SEI film containing phosphorus, so that the impedance of the SEI film containing phosphorus is improved, and the Li battery can be further improved+The migration rate in the liquid phase further obviously improves the low-temperature discharge performance of the lithium ion battery, reduces the phenomenon of low-temperature lithium precipitation, and LiF covers the surface of a phosphorus-containing high-carbon SEI film formed by the unsaturated phosphate compounds, so that the film forming speed of the unsaturated phosphate compounds is reduced, and the risk caused by the excessively thick phosphorus-containing SEI film is avoided. In addition, the cyclic sulfate compound can form a large amount of LiSO in the formation process of the lithium ion battery3、ROSO2SEI film of Li containing a large amount of LiSO3、ROSO2The Li SEI film has higher conductivity at low temperature, and can modify thicker phosphorus-containing high-carbon components formed by unsaturated phosphate in surface SEI film components to improve the relative contents of sulfur atoms and oxygen atoms, and the sulfur atoms and the oxygen atoms both contain lone-pair electrons and can attract Li+Thereby accelerating Li+Shuttling in SEI film to proceedThe low-temperature discharge performance of the lithium ion battery is improved and the low-temperature lithium precipitation phenomenon is further reduced. Three additives, namely a fluoroether compound, an unsaturated phosphate compound and a cyclic sulfate compound, added into the non-aqueous electrolyte of the lithium ion battery can enhance the wettability, the high-temperature storage performance, the high-temperature cycle performance, the normal-temperature cycle performance and the low-temperature discharge performance of the lithium ion battery.
Preferably, the mass percentages of the fluoroether compound, the unsaturated phosphate compound and the cyclic sulfate compound in the non-aqueous electrolyte of the lithium ion battery are respectively 0.1-3%. Specifically, the mass percentages of the fluoroether compound, the unsaturated phosphate compound and the cyclic sulfate compound in the nonaqueous electrolyte solution of the lithium ion battery are independently, but not limited to, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5% and 3%.
Preferably, the structural formula 1 of the present invention is selected from any one of the following compounds 1 to 4:
preferably, the structural formula 2 of the present invention is at least one selected from the group consisting of tripropargyl phosphate, dipropargyl phosphate, propargyl dipropyl phosphate, triallyl phosphate, diallyl propyl phosphate and allyl dipropyl phosphate. Wherein the tripropargyl phosphate, the dipropargyl phosphate, the propargyl dipropyl phosphate, the diallyl propyl phosphate and the allyl dipropyl phosphate can be respectively prepared by the following preparation methods:
preferably, the structural formula 3 of the present invention is selected from any one of vinyl sulfate (DTD) and divinyl sulfate (BDTD).
Preferably, the lithium salt of the present invention is selected from at least one of lithium hexafluorophosphate, lithium difluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) phosphate, lithium tetrafluoroborate, lithium tetrafluorooxalato phosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide and lithium difluoro (malonato) phosphate.
Preferably, the non-aqueous organic solvent of the present invention is selected from at least one of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, butyl acetate, γ -butyrolactone, propyl propionate, ethyl 2,2, 2-trifluoro-methyl-ethyl carbonate, diethyl 2,2, 2-trifluoro-ethyl carbonate, ethyl propyl 2,2, 2-trifluoro-carbonate and ethyl butyrate.
Preferably, the lithium ion battery non-aqueous electrolyte further comprises an auxiliary agent, the mass percentage of the auxiliary agent in the lithium ion battery non-aqueous electrolyte is 0.1% -13.5%, and the mass percentage of the auxiliary agent in the lithium ion battery non-aqueous electrolyte can be selected from but not limited to 0.1%, 5%, 8%, 10%, 12% and 13.5%; the auxiliary agent is at least one selected from ethylene carbonate (VC), Diethylpyrocarbonate (DEPC), 1, 3-propane sultone (1,3-PS), fluoroethylene carbonate (FEC), 4 '-bi-1, 3-dioxolane-2, 2' -dione (BDC), tris (trimethylsilane) phosphate (TMSP) and 1,3, 5-tris [3- (trimethoxysilyl) propyl ] -1,3, 5-triazine-2, 4, 6-trione (TTMSPi).
The invention also provides a lithium ion battery which comprises a positive electrode, a negative electrode, a diaphragm for separating the positive electrode and the negative electrode and the lithium ion battery non-aqueous electrolyte.
Compared with the prior art, the lithium ion battery non-aqueous electrolyte comprises three additives, namely a fluoroether compound, an unsaturated phosphate compound and a cyclic sulfate compound, and the three additives can enable the lithium ion battery to have good wetting performance, high-temperature storage performance, high-temperature cycle performance, normal-temperature cycle performance and low-temperature discharge performance and can effectively avoid low-temperature lithium precipitation.
Preferably, the active material of the positive electrode of the present invention is LiNixCoyMnzM(1-x-y-z)O2Or LiNixCoyAlzM(1-x-y-z)O2Which isIn the formula, M is any one of Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti, and x is more than or equal to 0 and less than or equal to x<1，0≤y≤1，0≤z≤1，x+y+z≤1。
Preferably, the active material of the negative electrode of the present invention is selected from any one of artificial graphite, natural graphite, lithium titanate, a silicon-carbon composite material, and silicon monoxide.
Detailed Description
The purpose, technical solution and advantages of the present invention will be further described by the following embodiments, but the present invention is not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
(1) Preparing a lithium ion battery nonaqueous electrolyte: in a nitrogen-filled glove box (O)2＜2ppm，H2O < 3ppm), dimethyl carbonate (DMC), diethyl carbonate (DEC), and Ethyl Methyl Carbonate (EMC) were mixed uniformly in a mass ratio of 3:5:2 to prepare 83.9g of a nonaqueous organic solvent, and 0.3g of Compound 1, 0.3g of Tripropargyl phosphate, and 0.5g of DTD were added to obtain a mixed solution. The solution was sealed, packed, and frozen in a freezing chamber (-4 ℃) for 2 hours, and then taken out of the chamber and placed in a nitrogen-filled glove box (O)2＜2ppm，H2O is less than 3ppm), 15g of lithium hexafluorophosphate is slowly added into the mixed solution, and the lithium ion battery non-aqueous electrolyte is prepared after uniform mixing.
(2) Preparation of the positive electrode: LiNi prepared from nickel cobalt lithium manganate ternary material0.5Mn0.3Co0.2O2Uniformly mixing PVDF (polyvinylidene fluoride) as an adhesive and SuperP (super P) as a conductive agent according to the mass ratio of 95:1:4 to prepare a lithium ion battery anode slurry with a certain viscosity, coating the mixed slurry on two sides of an aluminum foil, drying and rolling to obtain an anode sheet.
(3) Preparation of a negative electrode: preparing artificial graphite, a conductive agent SuperP, a thickening agent CMC and a binding agent SBR (styrene butadiene rubber emulsion) into slurry according to the mass ratio of 95:1.5:1.0:2.5, uniformly mixing, coating the mixed slurry on two sides of a copper foil, drying and rolling to obtain the negative plate.
(4) Preparing a lithium ion battery: and preparing the positive electrode, the diaphragm and the negative electrode into a square battery cell in a lamination mode, packaging by adopting a polymer, filling the prepared non-aqueous electrolyte of the lithium ion battery, and preparing the lithium ion battery with the capacity of 2300mAh after working procedures of formation, capacity grading and the like.
The formulations of the lithium ion battery nonaqueous electrolytic solutions of examples 2 to 5 and comparative examples 1 to 7 are shown in Table 1, and the procedure for preparing the lithium ion battery nonaqueous electrolytic solution was the same as that of example 1.
TABLE 1 composition of nonaqueous electrolyte for lithium ion batteries of examples and comparative examples
The lithium ion batteries prepared in examples 1 to 5 and comparative examples 1 to 7 were subjected to normal temperature cycle performance, high temperature storage test, low temperature discharge test, and negative electrode soaking time test, respectively, under the following specific test conditions, and the results of the lithium ion battery performance test are shown in table 2.
(1) And (3) testing the normal-temperature cycle performance:
and (3) placing the lithium ion battery in an environment with the temperature of 25 ℃, charging to 4.5V at a constant current of 1C, then charging at a constant voltage until the current is reduced to 0.05C, then discharging to 3.0V at a constant current of 1C, and repeating the steps to record the discharge capacity of the first circle and the discharge capacity of the last circle. The calculation formula is as follows:
capacity retention rate is the discharge capacity of the last cycle/discharge capacity of the first cycle × 100%.
(2) And (3) testing high-temperature cycle performance:
and (3) placing the battery in an oven with a constant temperature of 45 ℃, charging the battery to 4.5V at a constant current of 1C, then charging the battery at a constant voltage until the current is reduced to 0.05C, then discharging the battery to 3.0V at a constant current of 1C, and repeating the steps to record the discharge capacity of the first circle and the discharge capacity of the last circle. The calculation formula is as follows:
capacity retention rate is the discharge capacity of the last cycle/discharge capacity of the first cycle × 100%.
(3) And (3) high-temperature storage test:
and (3) charging the formed battery to 4.5V at a constant current and a constant voltage at 1C under normal temperature, measuring the initial discharge capacity and the initial battery thickness of the battery, then storing the battery for 30 days at 60 ℃, discharging the battery to 3.0V at 1C, and measuring the capacity retention and recovery capacity of the battery and the thickness of the battery after storage. The calculation formula is as follows:
battery capacity retention (%) — retention capacity/initial capacity × 100%;
battery capacity recovery (%) — recovery capacity/initial capacity × 100%;
thickness swell (%) (cell thickness after storage-initial cell thickness)/initial cell thickness x 100%.
(4) And (3) low-temperature discharge test:
and (3) charging the formed battery to 4.5V at a constant current and a constant voltage of 1C at normal temperature, placing the battery in a low-temperature environment of 20 ℃ below zero for 4 hours, discharging the battery to 3.0V at 0.5C, and measuring the capacity retention rate of the battery. The calculation formula is as follows:
battery capacity retention (%) — retention capacity/initial capacity × 100%.
(5) Testing the cathode infiltration time:
accurately dropping 20 μ L of the electrolyte solution with a pipette to obtain a solution with a diameter d of 12mm and a compacted density of 1.65g/cm3And (4) recording the absorption time until the electrolyte is completely absorbed by the graphite pole piece, and dropping for three times to obtain an average value. The calculation formula is as follows:
the absorption time(s) is (first absorption time + second absorption time + third absorption time)/3.
(6) Low-temperature lithium extraction test:
and (3) placing the lithium ion battery in an oven with constant temperature of-10 ℃, charging to 4.5V at a constant current of 0.5C, then charging at a constant voltage until the current is reduced to 0.05C, then discharging to 3.0V at a constant current of 0.5C, circulating for 20 weeks, disassembling the battery, and observing the lithium precipitation condition on the surface of the negative electrode of the lithium ion battery.
Table 2 lithium ion battery performance test results
As can be seen from table 2, the lithium ion batteries of all the embodiments have better wetting performance, high-temperature storage performance, high-temperature cycle performance, normal-temperature cycle performance, and low-temperature discharge performance, and can also effectively avoid low-temperature lithium precipitation, which indicates that the introduction of the fluoroether compound, the unsaturated phosphate compound, and the cyclic sulfate compound into the electrolyte can jointly enhance the performance of the lithium ion batteries.
Finally, it should be noted that the above embodiments are only for technical solution of the present invention and not for limitation of the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, the present invention is not limited to the above disclosed embodiments, but should cover various modifications, equivalent combinations, made according to the essence of the present invention.
Claims (10)
1. A lithium ion battery non-aqueous electrolyte comprises lithium salt, a non-aqueous organic solvent and an additive, and is characterized in that the additive comprises a fluoroether compound with a structural formula 1, an unsaturated phosphate compound with a structural formula 2, and a cyclic sulfate compound with a structural formula 3 or 4,
wherein R is1、R2、R3、R4、R5、R6Each independently selected from fluorine atom, C1-C4 fluoroalkyl; r7、R8、R9Each independently selected from unsaturated hydrocarbon or fluorinated hydrocarbon groups of C1-C4; r10Is hydrogen or C1-C5 alkyl, and n is an integer of 1-5.
2. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein the mass percentages of the fluoroether compound, the unsaturated phosphate compound and the cyclic sulfate compound in the nonaqueous electrolyte solution for lithium ion batteries are each independently 0.1% to 3%.
3. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein the structural formula 1 is selected from any one of the following compounds 1 to 4:
4. the nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein the structural formula 2 is at least one selected from the group consisting of tripropargyl phosphate, dipropargyl phosphate, propargyl dipropyl phosphate, triallyl phosphate, diallyl propyl phosphate and allyl dipropyl phosphate.
5. The nonaqueous electrolyte for lithium ion batteries according to claim 1, wherein the lithium salt is at least one selected from the group consisting of lithium hexafluorophosphate, lithium difluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) phosphate, lithium tetrafluoroborate, lithium tetrafluorooxalato phosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide and lithium difluoro (malonato) phosphate.
6. The nonaqueous electrolyte for lithium ion batteries according to claim 1, wherein the nonaqueous organic solvent is at least one selected from the group consisting of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, butyl acetate, γ -butyrolactone, propyl propionate, ethyl 2,2, 2-trifluoroethyl methyl carbonate, diethyl 2,2, 2-trifluorocarbonate, ethyl propyl 2,2, 2-trifluorocarbonate, and ethyl butyrate.
7. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, further comprising an auxiliary agent, wherein the auxiliary agent is present in the nonaqueous electrolyte solution for lithium ion batteries in an amount of 0.1 to 13.5% by mass, and the auxiliary agent is at least one selected from the group consisting of ethylene carbonate, diethyl pyrocarbonate, 1, 3-propanesultone, fluoroethylene carbonate, 4 '-bi-1, 3-dioxolane-2, 2' -dione, tris (trimethylsilane) phosphate and 1,3, 5-tris [3- (trimethoxysilyl) propyl ] -1,3, 5-triazine-2, 4, 6-trione.
8. A lithium ion battery comprising a positive electrode, a negative electrode, and a separator for separating the positive electrode and the negative electrode, characterized by further comprising the lithium ion battery nonaqueous electrolyte according to any one of claims 1 to 7.
9. The lithium ion battery of claim 8, wherein the active material of the positive electrode is LiNixCoyMnzM(1-x-y-z)O2Or LiNixCoyAlzN(1-x-y-z)O2Wherein M is any one of Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti, N is any one of Mn, Mg, Cu, Zn, Sn, B, Ga, Cr, Sr, V and Ti, and 0<x<1，0<y≤1，0<z≤1，x+y+z≤1。
10. The lithium ion battery according to claim 8, wherein the active material of the negative electrode is selected from any one of artificial graphite, natural graphite, lithium titanate, silicon-carbon composite material, and silicon oxide.
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