WO2022199163A1 - Non-aqueous electrolyte additive, non-aqueous electrolyte and lithium ion battery - Google Patents
Non-aqueous electrolyte additive, non-aqueous electrolyte and lithium ion battery Download PDFInfo
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- WO2022199163A1 WO2022199163A1 PCT/CN2021/140300 CN2021140300W WO2022199163A1 WO 2022199163 A1 WO2022199163 A1 WO 2022199163A1 CN 2021140300 W CN2021140300 W CN 2021140300W WO 2022199163 A1 WO2022199163 A1 WO 2022199163A1
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- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- aqueous electrolyte
- carbonate
- electrolyte solution
- phosphate
- Prior art date
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 49
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 239000000654 additive Substances 0.000 title claims abstract description 26
- 230000000996 additive effect Effects 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000011701 zinc Chemical group 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 12
- 239000011777 magnesium Substances 0.000 claims abstract description 12
- 229910052725 zinc Chemical group 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 7
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 11
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 11
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical group [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 5
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- XNENYPKLNXFICU-UHFFFAOYSA-N P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C XNENYPKLNXFICU-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 3
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 3
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 3
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 claims description 3
- FCTINJHSYHFASK-UHFFFAOYSA-N tris(prop-2-ynyl) phosphate Chemical compound C#CCOP(=O)(OCC#C)OCC#C FCTINJHSYHFASK-UHFFFAOYSA-N 0.000 claims description 3
- DPDMZACOTSJMOY-UHFFFAOYSA-N 1,1,1-trifluoropentan-3-yl hydrogen carbonate Chemical compound FC(F)(F)CC(CC)OC(O)=O DPDMZACOTSJMOY-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
- AUBNQVSSTJZVMY-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] AUBNQVSSTJZVMY-UHFFFAOYSA-M 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
- FFYPMLJYZAEMQB-UHFFFAOYSA-N diethyl pyrocarbonate Chemical compound CCOC(=O)OC(=O)OCC FFYPMLJYZAEMQB-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 150000008282 halocarbons Chemical group 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-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
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- WOPQEKPPPBCAEG-UHFFFAOYSA-N 3-[1-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOC(C)OCCC#N WOPQEKPPPBCAEG-UHFFFAOYSA-N 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 17
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 14
- 102100028667 C-type lectin domain family 4 member A Human genes 0.000 description 12
- 101000766908 Homo sapiens C-type lectin domain family 4 member A Proteins 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 8
- PXQPEWDEAKTCGB-UHFFFAOYSA-N orotic acid Chemical group OC(=O)C1=CC(=O)NC(=O)N1 PXQPEWDEAKTCGB-UHFFFAOYSA-N 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 229940125773 compound 10 Drugs 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000000879 imine group Chemical group 0.000 description 3
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZWGIZHOZSXFSNW-UHFFFAOYSA-N 4-(2-oxo-1,3-dioxolan-4-yl)-1,3-dioxolan-2-one Chemical compound O1C(=O)OCC1C1OC(=O)OC1 ZWGIZHOZSXFSNW-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 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 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- OQPHEVHDBFEJRQ-UHFFFAOYSA-N [Li].P(O)(O)(O)=O Chemical compound [Li].P(O)(O)(O)=O OQPHEVHDBFEJRQ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 239000007789 gas Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- DMFBPGIDUUNBRU-UHFFFAOYSA-N magnesium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Mg+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F DMFBPGIDUUNBRU-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
Definitions
- the present application belongs to the technical field of lithium ion batteries, and particularly relates to electrolyte additives, non-aqueous electrolytes and lithium ion batteries.
- Lithium-ion batteries are widely used because of their high energy density, high charge-discharge efficiency, small self-discharge, long service life, and environmental friendliness. At present, it has been applied to the fields of consumer electronics, aerospace, military, power tools and electric vehicles. With the development of technology, whether it is in the field of consumption or power batteries, people have higher and higher requirements for the endurance of lithium-ion batteries, and the development of high-energy density (mass energy density and volume energy density) lithium batteries has become the key.
- the development of high-energy-density lithium batteries can be done in two ways. One is to develop new positive and negative electrode materials with high gram capacity; the other is to improve the charging and discharging voltage of lithium batteries. Increasing the charge-discharge voltage of lithium batteries can simultaneously improve the mass energy density and volumetric energy density of lithium batteries, and can also reduce the cost of lithium batteries, which has become a research hotspot.
- the purpose of the present application is to provide a non-aqueous electrolyte additive, which can improve the cycle performance and high-temperature storage performance of a lithium ion battery under a high voltage system.
- Another object of the present application is to provide a non-aqueous electrolyte solution, the non-aqueous electrolyte solution containing the above-mentioned non-aqueous electrolyte solution additive can improve the cycle performance and high-temperature storage performance of a lithium ion battery under a high voltage system.
- Another object of the present application is to provide a lithium ion battery, the lithium ion battery containing the above non-aqueous electrolyte has better cycle performance and high temperature storage performance in a high-voltage system.
- non-aqueous electrolyte additive including the compound shown in structural formula 1:
- R 1 , R 2 , R 3 , and R 4 are each independently selected from an oxygen atom or a sulfur atom
- R 5 , R 6 , R 7 , and R 8 are each independently selected from a hydrogen atom or a C1-C5 hydrocarbon group
- R 10 is each independently selected from a hydrogen atom, a halogen atom, a C1-C5 hydrocarbon group or a C1-C5 halogenated hydrocarbon group
- R 11 is selected from magnesium or zinc.
- the present application provides a non-aqueous electrolyte additive with a special structure, which exists in the form of ion pairs in the electrolyte due to its weak ionization ability.
- the orotic acid group in the additive will bring special metal (Mg, Zn) ions into the surface of the positive electrode while participating in the formation of nitrogen-containing CEI film, so as to participate in the formation of special metal (Mg, Zn) ions.
- the coating layer is coated on the positive electrode surface so that the positive electrode material can withstand higher temperature and higher voltage, so the non-aqueous electrolyte additive can significantly improve the lithium ion battery in high voltage system
- the imine group on the orotic acid group has the function of complexing with fluoride ions in the electrolyte, which can significantly remove hydrofluoric acid and further improve the lithium ion battery in high voltage system. cycle performance and high temperature storage performance.
- R 5 , R 6 , R 7 and R 8 are each independently selected from a hydrogen atom, a C1-C5 straight-chain alkyl group or a C1-C5 branched-chain alkyl group.
- R 9 and R 10 are each independently selected from hydrogen atom, halogen atom, C1-C5 chain alkyl, C2-C5 chain alkenyl, C2-C5 chain alkynyl or C1-C5 chain
- the C1-C5 chain alkyl group refers to a straight-chain alkyl group or a branched chain alkyl group with 1 to 5 carbon atoms
- the C2-C5 chain alkenyl group refers to a carbon atom number of 1 to 5.
- C2-C5 chain alkynyl refers to straight-chain or branched alkynyl having 2 to 5 carbon atoms.
- the compound represented by the structural formula 1 of the present application is selected from at least one of compounds 1 to 6:
- the present application also provides a non-aqueous electrolyte solution, including a lithium salt, a non-aqueous organic solvent, and the above-mentioned non-aqueous electrolyte solution additive.
- the non-aqueous electrolyte solution of the present application includes the above-mentioned non-aqueous electrolyte solution additive, and the non-aqueous electrolyte solution is applied to a lithium ion battery.
- the orotic acid group in the non-aqueous electrolyte additive will take special metal (Mg, Zn) ions into the surface of the positive electrode while participating in the formation of nitrogen-containing CEI film to make it participate.
- a coating layer containing special metal (Mg, Zn) ions is formed, and the coating layer is coated on the surface of the positive electrode so that the positive electrode material can withstand higher temperatures and higher voltages, so the non-aqueous electrolyte additive can significantly improve lithium The cycle performance and high temperature storage performance of the ion battery under high voltage system; at the same time, the imine group on the orotic acid group has the function of complexing with fluoride ions in the electrolyte, which can significantly remove hydrofluoric acid and further improve lithium Cycling performance and high temperature storage performance of ion batteries in high voltage systems.
- special metal Mg, Zn
- the mass percentage of the non-aqueous electrolyte additive of the present application in the non-aqueous electrolyte is 0.1-1%; specifically, it can be 0.1%, 0.2%, 0.5%, 0.8%, 1%, but not limited to the above. Recited values apply equally well to other non-recited values within that range.
- the lithium salt of the present application is selected from lithium hexafluorophosphate (LiPF 6 ), lithium difluorophosphate (LiPO 2 F 2 ), lithium bis-oxalate borate (LiBOB), lithium difluorooxalate borate (LiODFB), difluorobisoxalate phosphoric acid Lithium (LiPF 2 (C 2 O 4 ) 2 ), Lithium Tetrafluoroborate (LiBF 4 ), Lithium Tetrafluorooxalate Phosphate (LiPF 4 (C 2 O 4 )), Lithium Bistrifluoromethanesulfonimide (LiN (SO 2 CF 3 ) 2 ), at least one of lithium bisfluorosulfonimide (Li[N(SO 2 F) 2 ), and lithium tetrafluoromalonate phosphate.
- LiPF 6 lithium hexafluorophosphate
- LiPO 2 F 2 lithium bis-oxa
- the mass percentage of the lithium salt of the present application in the non-aqueous electrolyte is 10-20%; specifically, it can be 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17% , 18%, 19%, 20%, but are not limited to the listed values, and other unlisted values within the numerical range are also applicable.
- the non-aqueous organic solvent of the present application is selected from ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), propylene carbonate (PC) , at least one of butyl acetate (n-BA), ⁇ -butyrolactone ( ⁇ -GBL), propyl propionate (n-PP), ethyl propionate (EP) and ethyl butyrate (EB) kind.
- the non-aqueous organic solvent is preferably ethylene carbonate (EC), diethyl carbonate (DEC) and ethyl methyl carbonate (EMC).
- the mass percentage of the non-aqueous organic solvent of the present application in the non-aqueous electrolyte is 60-80%, specifically 60%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 80%, but not limited to the recited values, and other non-recited values within the numerical range are also applicable.
- the non-aqueous electrolyte solution of the present application further includes an auxiliary agent, and the mass percentage of the auxiliary agent in the non-aqueous electrolyte solution is 0.1-10.5%;
- the auxiliary agent is selected from 2,2,2-trifluoroethyl methyl carbonate , 2,2,2-trifluorodiethyl carbonate, 2,2,2-trifluoroethylpropyl carbonate, vinylene carbonate (VC), fluoroethylene carbonate (FEC), diethyl pyrocarbonate Esters (DEPC), 1,3-Propane Sultone (PS), Vinyl Sulfate (DTD), 1,2-Difluoroethylene Carbonate (DFEC), Tris(trimethylsilane) Phosphate (TMSP) ), tris(trimethylsilane) phosphite (TMSPi), 4,4'-bi-1,3-dioxolane-2,2'-dione (BDC), 3,3-bisulfuric acid Vinyl Este
- the additive can form a stable passivation film on the surface of the positive electrode, prevent the oxidative decomposition of the electrolyte on the surface of the positive electrode, inhibit the dissolution of transition metal ions from the positive electrode, improve the stability of the structure and interface of the positive electrode material, and significantly improve the high temperature of the lithium ion battery. Storage performance and cycle performance.
- the auxiliary agent is selected from vinylene carbonate (VC), fluoroethylene carbonate (FEC), 1,3-propane sultone (PS), vinyl sulfate (DTD), tris(trimethylsilane) ) Phosphate (TMSP), Tris(trimethylsilane) phosphite (TMSPi), 4,4'-bi-1,3-dioxolane-2,2'-dione (BDC), 3, Vinyl 3-bisulfate (BDTD) or 1,2-difluoroethylene carbonate (DFEC), and the content is 0.1-2%, 0.2-6%, 0.2-2%, 0.2-2%, 0.1%, respectively ⁇ 1.5%, 0.1 to 1.5%, 0.1 to 1.5%, 0.1 to 1.5%, 0.1 to 1.5%.5%.
- VC vinylene carbonate
- FEC fluoroethylene carbonate
- PS 1,3-propane sultone
- DTD vinyl sulfate
- TMSP tris(trimethyls
- vinyl sulfate (DTD) is added to the electrolyte as an auxiliary agent, which can modify the SEI film components on the negative electrode surface of lithium ion batteries and increase the relative content of sulfur atoms and oxygen atoms, which contain lone pair electrons. , which can attract lithium ions, accelerate the shuttle of lithium ions in the SEI film, and reduce the battery interface impedance, thereby effectively improving the charge and discharge performance of lithium ion batteries.
- 1,3-Propane sultone (PS) has good film-forming properties as an auxiliary agent, which can form a large number of CEI films containing sulfonic acid groups at the positive interface, inhibit the decomposition and gas production of FEC at high temperature, and improve lithium-ion batteries.
- Tris(trimethylsilane) phosphate (TMSP) and tris(trimethylsilane) phosphite (TMSPi) can absorb moisture and free acid to improve the cycling performance of lithium-ion batteries.
- the present application also provides a lithium ion battery, which includes a positive electrode and a negative electrode, and also includes the above-mentioned non-aqueous electrolyte, and the highest charging voltage is 4.53V.
- the non-aqueous electrolyte of the lithium ion battery of the present application includes a non-aqueous electrolyte additive, and the non-aqueous electrolyte additive is a compound shown in structural formula 1.
- the structural formula While participating in the formation of nitrogen-containing CEI film, the orotate group in 1 will bring special metal (Mg, Zn) ions into the surface of the positive electrode to participate in the formation of a coating layer containing special metal (Mg, Zn) ions.
- the coating layer is coated on the surface of the positive electrode so that the positive electrode material can withstand higher temperature and higher voltage, so the non-aqueous electrolyte additive can significantly improve the cycle performance and high temperature storage performance of lithium ion batteries under high voltage systems
- the imine group on the orotic acid group has the function of complexing with fluoride ions in the electrolyte, which can significantly remove hydrofluoric acid and further improve the cycle performance and high temperature storage performance of lithium ion batteries under high voltage systems.
- the active material of the positive electrode of the present application is lithium cobalt oxide.
- the active material of the negative electrode of the present application is natural graphite.
- ethylene carbonate, diethyl carbonate and ethyl methyl carbonate were uniformly mixed in a mass ratio of 1:1:2 to obtain 79.8 g of water organic solvent, and then 0.2 g of compound 1 was added as an additive to obtain a mixed solution.
- the mixed solution was sealed and packaged and placed in the freezing room (-4°C) for 2 hours and then taken out.
- a nitrogen-filled glove box O 2 ⁇ 1ppm, H 2 O ⁇ 1ppm
- Capacity retention rate discharge capacity of the last cycle / discharge capacity of the first cycle ⁇ 100%
- DCIR boost rate DCIR of the last 50 laps / DCIR of the first lap ⁇ 100%
- Capacity retention rate discharge capacity of the last cycle / discharge capacity of the first cycle ⁇ 100%
- DCIR boost rate DCIR of the last 50 laps / DCIR of the first lap ⁇ 100%
- the formed lithium-ion battery was charged to 4.53V at 1C constant current and constant voltage at room temperature, and the initial discharge capacity and thickness of the battery were measured, and then stored at 85°C for 8 hours, and then discharged to 3.0V at 1C, and the capacity retention of the battery was measured. and recovery capacity and battery thickness after storage. Calculated as follows:
- Battery capacity retention rate (%) retained capacity / initial capacity ⁇ 100%;
- Thickness swelling ratio (%) (battery thickness after storage ⁇ initial battery thickness)/initial battery thickness ⁇ 100%.
- the coating layer of special metal (Mg, Zn) ions is coated on the surface of the positive electrode, so that the positive electrode material can withstand higher temperature and higher voltage, so the non-aqueous electrolyte additive can significantly improve the lithium ion battery. Cycling performance and high temperature storage performance under high voltage system.
Abstract
A non-aqueous electrolyte additive, a non-aqueous electrolyte, and a lithium ion battery, the non-aqueous electrolyte additive comprising a compound as represented by structural formula 1, wherein R1, R2, R3 and R4 are each independently selected from an oxygen atom or a sulfur atom; R5, R6, R7 and R8 are each independently selected from a hydrogen atom or a C1-C5 hydrocarbyl group; R9 and R10 are each independently selected from a hydrogen atom, a halogen atom, a C1-C5 hydrocarbyl group or a C1-C5 halogenated hydrocarbyl group; and R11 is selected from magnesium or zinc. The non-aqueous electrolyte additive can improve the cycling performance and high-temperature storage performance of the lithium ion battery in a high-voltage system.
Description
本申请属于锂离子电池技术领域，尤其涉及电解液添加剂、非水电解液和锂离子电池。The present application belongs to the technical field of lithium ion batteries, and particularly relates to electrolyte additives, non-aqueous electrolytes and lithium ion batteries.
锂离子电池因为其能量密度高、充放电效率高、自放电小、使用寿命长和对环境友好等优点，被人们广泛应用。目前已经应用到消费电子、航天航空、军事、电动工具及电动汽车等领域。随着技术的发展，不论是消费领域还是动力电池领域，人们对锂离子电池的续航能力要求越来越高，发展高能量密度(质量能量密度和体积能量密度)锂电池成为关键。发展高能量密度锂电池可以充两个方面入手，一是发展新的高克容量的正负极材料；二是提高锂电池的充放电电压。提高锂电池的充放电电压，可以同时提高锂电池的质量能量密度和体积能量密度，还可以降低锂电池的成本，成为人们研究的热点。Lithium-ion batteries are widely used because of their high energy density, high charge-discharge efficiency, small self-discharge, long service life, and environmental friendliness. At present, it has been applied to the fields of consumer electronics, aerospace, military, power tools and electric vehicles. With the development of technology, whether it is in the field of consumption or power batteries, people have higher and higher requirements for the endurance of lithium-ion batteries, and the development of high-energy density (mass energy density and volume energy density) lithium batteries has become the key. The development of high-energy-density lithium batteries can be done in two ways. One is to develop new positive and negative electrode materials with high gram capacity; the other is to improve the charging and discharging voltage of lithium batteries. Increasing the charge-discharge voltage of lithium batteries can simultaneously improve the mass energy density and volumetric energy density of lithium batteries, and can also reduce the cost of lithium batteries, which has become a research hotspot.
但是在研究高电压锂电池时，人们发现随着锂电池电压的升高，电池的性能劣化明显。比如高电压(≥4.5V)钴酸锂(LCO)，当LCO充电至4.45V以上电压时，它会经历从O3六方相到杂化O1-O3相的有害相变，此过程伴随着晶格层间的滑动和O3晶格结构的部分塌陷。伴随着LCO的内部应力增加，进一步导致LCO裂纹形成和颗粒破碎。另外，由于O
2-:2p共振带的顶部与低自旋Co
3+/4+:t
2g共振带重叠，所以氧在高电压下开始发生氧化还原反应。由于过氧根离子O
1-的离子迁移率高于O
2-，在LCO表面的O
-容易转化为O
2并脱离LCO颗粒，这会破坏正极-电解质界面，从而导致界面不稳定。所以减缓LCO材料在高电压下的界面活性及减缓电解液的分解将能提高锂离子电池于高压体系下的循环性能及存储性能。
However, when studying high-voltage lithium batteries, it was found that with the increase of lithium battery voltage, the performance of the battery deteriorated significantly. Such as high voltage (≥4.5V) lithium cobalt oxide (LCO), when the LCO is charged to a voltage above 4.45V, it will undergo a detrimental phase transition from the O3 hexagonal phase to the hybrid O1-O3 phase, which is accompanied by a lattice Sliding between layers and partial collapse of the O3 lattice structure. The concomitant increase in the internal stress of the LCO further leads to LCO crack formation and particle breakage. In addition, since the top of the O 2− :2p resonance band overlaps with the low-spin Co 3+/4+ :t 2g resonance band, the oxygen redox reaction starts to occur at high voltages. Due to the higher ionic mobility of peroxide ions O 1- than O 2- , O on the LCO surface is easily converted into O 2 and detached from the LCO particles, which would destroy the cathode-electrolyte interface, resulting in interfacial instability. Therefore, slowing down the interfacial activity of LCO materials under high voltage and slowing down the decomposition of electrolyte will improve the cycle performance and storage performance of lithium-ion batteries under high voltage systems.
因此，亟需一种非水电解液添加剂、非水电解液及锂离子电池，以解决现有技术问题的不足。Therefore, a non-aqueous electrolyte additive, a non-aqueous electrolyte and a lithium ion battery are urgently needed to solve the deficiencies of the prior art.
申请内容Application content
本申请的目的是提供一种非水电解液添加剂，该非水电解液添加剂能够提高锂离子电池于高电压体系下的循环性能与高温存储性能。The purpose of the present application is to provide a non-aqueous electrolyte additive, which can improve the cycle performance and high-temperature storage performance of a lithium ion battery under a high voltage system.
本申请的另一目的是提供一种非水电解液，含有上述非水电解液添加剂的非水电解液能够提高锂离子电池于高电压体系下的循环性能与高温存储性能。Another object of the present application is to provide a non-aqueous electrolyte solution, the non-aqueous electrolyte solution containing the above-mentioned non-aqueous electrolyte solution additive can improve the cycle performance and high-temperature storage performance of a lithium ion battery under a high voltage system.
本申请的又一目的是提供一种锂离子电池，含有上述非水电解液的锂离子电池于高压体系下具有较佳的循环性能与高温存储性能。Another object of the present application is to provide a lithium ion battery, the lithium ion battery containing the above non-aqueous electrolyte has better cycle performance and high temperature storage performance in a high-voltage system.
为实现以上目的，本申请提供了一种非水电解液添加剂，包括结构式1所示的化合物：To achieve the above purpose, the application provides a non-aqueous electrolyte additive, including the compound shown in structural formula 1:
其中，R
1、R
2、R
3、R
4各自独立地选自氧原子或硫原子，R
5、R
6、R
7、R
8各自独立地选自氢原子或C1-C5的烃基，R
9、R
10各自独立地选自氢原子、卤素原子、C1-C5的烃基或C1-C5的卤代烃基，R
11选自镁或锌。
Wherein, R 1 , R 2 , R 3 , and R 4 are each independently selected from an oxygen atom or a sulfur atom, R 5 , R 6 , R 7 , and R 8 are each independently selected from a hydrogen atom or a C1-C5 hydrocarbon group, and R 9. R 10 is each independently selected from a hydrogen atom, a halogen atom, a C1-C5 hydrocarbon group or a C1-C5 halogenated hydrocarbon group, and R 11 is selected from magnesium or zinc.
与现有技术相比，本申请提供了一种特殊结构的非水电解液添加剂，由于该添加剂的电离能力较弱，故在电解液中以离子对形式存在。在首次充放电过程中，该添加剂中的乳清酸基团在参与形成含氮CEI膜的同时，会将特殊金属(Mg、Zn)离子带入正极表面进而使其参与形成含特殊金属(Mg、Zn)离子的包覆层，该包覆层包覆在正极表面从而使得正极材料能耐更高温度以及能耐更高的电压，故该非水电解液添加剂能显著提高锂离子电池于高电压体系下的循环性能和高温存储性能；同时，乳清酸基团上的亚胺基在电解液中具有与氟 离子络合的作用，能够显著除去氢氟酸，进一步提高锂离子电池于高电压体系下的循环性能和高温存储性能。Compared with the prior art, the present application provides a non-aqueous electrolyte additive with a special structure, which exists in the form of ion pairs in the electrolyte due to its weak ionization ability. During the first charge and discharge process, the orotic acid group in the additive will bring special metal (Mg, Zn) ions into the surface of the positive electrode while participating in the formation of nitrogen-containing CEI film, so as to participate in the formation of special metal (Mg, Zn) ions. , Zn) ion coating layer, the coating layer is coated on the positive electrode surface so that the positive electrode material can withstand higher temperature and higher voltage, so the non-aqueous electrolyte additive can significantly improve the lithium ion battery in high voltage system At the same time, the imine group on the orotic acid group has the function of complexing with fluoride ions in the electrolyte, which can significantly remove hydrofluoric acid and further improve the lithium ion battery in high voltage system. cycle performance and high temperature storage performance.
较佳地，R
5、R
6、R
7、R
8各自独立地选自氢原子、C1-C5的直链烷基或C1-C5的支链烷基。
Preferably, R 5 , R 6 , R 7 and R 8 are each independently selected from a hydrogen atom, a C1-C5 straight-chain alkyl group or a C1-C5 branched-chain alkyl group.
较佳地，R
9、R
10各自独立地选自氢原子、卤素原子、C1-C5的链状烷基、C2-C5的链状烯基、C2-C5的链状炔基或C1-C5的卤代烃基；具体地，C1-C5的链状烷基是指碳原子数目为1～5的直链烷基或者支链烷基，C2-C5的链状烯基是指碳原子数目为2～5的直链烯基或者支链烯基，C2-C5的链状炔基是指碳原子数目为2～5的直链炔基或者支链炔基。
Preferably, R 9 and R 10 are each independently selected from hydrogen atom, halogen atom, C1-C5 chain alkyl, C2-C5 chain alkenyl, C2-C5 chain alkynyl or C1-C5 chain Specifically, the C1-C5 chain alkyl group refers to a straight-chain alkyl group or a branched chain alkyl group with 1 to 5 carbon atoms, and the C2-C5 chain alkenyl group refers to a carbon atom number of 1 to 5. 2-5 straight-chain alkenyl or branched alkenyl, and C2-C5 chain alkynyl refers to straight-chain or branched alkynyl having 2 to 5 carbon atoms.
较佳地，本申请的结构式1所示的化合物选自化合物1～化合物6中的至少一种：Preferably, the compound represented by the structural formula 1 of the present application is selected from at least one of compounds 1 to 6:
其中，化合物3、化合物4、化合物5、化合物6的合成方法如下所示：Among them, the synthetic methods of compound 3, compound 4, compound 5 and compound 6 are as follows:
为实现以上目的，本申请还提供了一种非水电解液，包括锂盐、非水有机溶剂，还包括上述的非水电解液添加剂。To achieve the above purpose, the present application also provides a non-aqueous electrolyte solution, including a lithium salt, a non-aqueous organic solvent, and the above-mentioned non-aqueous electrolyte solution additive.
与现有技术相比，本申请的非水电解液包括上述非水电解液添加剂，将该非水电解液应用于锂离子电池。锂离子电池在首次充放电过程中，非水电解液添加剂中的乳清酸基团在参与形成含氮CEI膜的同时，会将特殊金属(Mg、Zn)离子带入正极表面进而使其参与形成含特殊金属(Mg、Zn)离子的包覆层，该包覆层包覆在正极表面从而使得正极材料能耐更高温度以及能耐更高的电压，故该非水电解液添加剂能显著提高锂离子电池于高电压体系下的循环性能和高温存储性能；同时，乳清酸基团上的亚胺基在电解液中具有与氟离子络合的作用，能够显著除去氢氟酸，进一步提高锂离子电池于高电压体系下的循环性能和高温存储性能。Compared with the prior art, the non-aqueous electrolyte solution of the present application includes the above-mentioned non-aqueous electrolyte solution additive, and the non-aqueous electrolyte solution is applied to a lithium ion battery. During the first charge and discharge process of lithium-ion batteries, the orotic acid group in the non-aqueous electrolyte additive will take special metal (Mg, Zn) ions into the surface of the positive electrode while participating in the formation of nitrogen-containing CEI film to make it participate. A coating layer containing special metal (Mg, Zn) ions is formed, and the coating layer is coated on the surface of the positive electrode so that the positive electrode material can withstand higher temperatures and higher voltages, so the non-aqueous electrolyte additive can significantly improve lithium The cycle performance and high temperature storage performance of the ion battery under high voltage system; at the same time, the imine group on the orotic acid group has the function of complexing with fluoride ions in the electrolyte, which can significantly remove hydrofluoric acid and further improve lithium Cycling performance and high temperature storage performance of ion batteries in high voltage systems.
较佳地，本申请的非水电解液添加剂于非水电解液中的质量百分比为0.1～1％；具体可为0.1％、0.2％、0.5％、0.8％、1％，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。Preferably, the mass percentage of the non-aqueous electrolyte additive of the present application in the non-aqueous electrolyte is 0.1-1%; specifically, it can be 0.1%, 0.2%, 0.5%, 0.8%, 1%, but not limited to the above. Recited values apply equally well to other non-recited values within that range.
较佳地，本申请的锂盐选自六氟磷酸锂(LiPF
6)、二氟磷酸锂(LiPO
2F
2)、双草酸硼酸锂(LiBOB)、二氟草酸硼酸锂(LiODFB)、二氟二草酸磷酸锂(LiPF
2(C
2O
4)
2)、四氟硼酸锂(LiBF
4)、四氟草酸磷酸锂(LiPF
4(C
2O
4))、双三 氟甲基磺酰亚胺锂(LiN(SO
2CF
3)
2)、双氟代磺酰亚胺锂(Li[N(SO
2F)
2)和四氟丙二酸磷酸锂中的至少一种。
Preferably, the lithium salt of the present application is selected from lithium hexafluorophosphate (LiPF 6 ), lithium difluorophosphate (LiPO 2 F 2 ), lithium bis-oxalate borate (LiBOB), lithium difluorooxalate borate (LiODFB), difluorobisoxalate phosphoric acid Lithium (LiPF 2 (C 2 O 4 ) 2 ), Lithium Tetrafluoroborate (LiBF 4 ), Lithium Tetrafluorooxalate Phosphate (LiPF 4 (C 2 O 4 )), Lithium Bistrifluoromethanesulfonimide (LiN (SO 2 CF 3 ) 2 ), at least one of lithium bisfluorosulfonimide (Li[N(SO 2 F) 2 ), and lithium tetrafluoromalonate phosphate.
较佳地，本申请的锂盐于非水电解液中的质量百分比为10～20％；具体可为10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、20％，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。Preferably, the mass percentage of the lithium salt of the present application in the non-aqueous electrolyte is 10-20%; specifically, it can be 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17% , 18%, 19%, 20%, but are not limited to the listed values, and other unlisted values within the numerical range are also applicable.
较佳地，本申请的非水有机溶剂选自碳酸乙烯酯(EC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸丙烯酯(PC)、乙酸丁酯(n-BA)、γ-丁内酯(γ-GBL)、丙酸丙酯(n-PP)、丙酸乙酯(EP)和丁酸乙酯(EB)中的至少一种。非水有机溶剂优选为碳酸乙烯酯(EC)、碳酸二乙酯(DEC)和碳酸甲乙酯(EMC)。Preferably, the non-aqueous organic solvent of the present application is selected from ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), propylene carbonate (PC) , at least one of butyl acetate (n-BA), γ-butyrolactone (γ-GBL), propyl propionate (n-PP), ethyl propionate (EP) and ethyl butyrate (EB) kind. The non-aqueous organic solvent is preferably ethylene carbonate (EC), diethyl carbonate (DEC) and ethyl methyl carbonate (EMC).
较佳地，本申请的非水有机溶剂于非水电解液中的质量百分比为60～80％，具体可为60％、65％、66％、67％、68％、69％、70％、71％、72％、73％、74％、75％、80％，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。Preferably, the mass percentage of the non-aqueous organic solvent of the present application in the non-aqueous electrolyte is 60-80%, specifically 60%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 80%, but not limited to the recited values, and other non-recited values within the numerical range are also applicable.
较佳地，本申请的非水电解液还包括助剂，助剂于非水电解液中的质量百分比为0.1-10.5％；助剂选自2,2,2-三氟代碳酸甲乙酯、2,2,2-三氟代碳酸二乙酯、2,2,2-三氟代碳酸乙丙酯、碳酸亚乙烯酯(VC)、氟代碳酸乙烯酯(FEC)、焦碳酸二乙酯(DEPC)、1,3-丙烷磺酸内酯(PS)、硫酸乙烯酯(DTD)、1,2-二氟代碳酸乙烯酯(DFEC)、三(三甲基硅烷)磷酸酯(TMSP)、三(三甲基硅烷)亚磷酸酯(TMSPi)、4,4'-联-1,3-二氧戊环-2,2'-二酮(BDC)、3,3-联二硫酸乙烯酯(BDTD)、磷酸三烯丙酯(TAP)、磷酸三炔丙酯(TPP)、丁二腈(SN)、己二腈(ADN)、1,3,6-己烷三腈(HTCN)和1,2-双(氰乙氧基)乙烷(DENE)中的至少一种。助剂能够在正极表面形成稳定的钝化膜，阻止电解液在正极表面的氧化分解，抑制过渡金属离子从正极中溶出，提高正极材料结构和界面的稳定性，进而显著提高锂离子电池的高温存储性能和循环性能。优选地，助剂选自碳酸亚乙烯酯(VC)、氟代碳酸乙烯酯(FEC)、1,3-丙烷磺酸内酯(PS)、硫酸乙烯酯(DTD)、三(三甲基硅烷)磷酸酯(TMSP)、三(三甲基硅烷)亚磷酸酯(TMSPi)、4,4'-联-1,3-二氧戊环-2,2'-二酮(BDC)、3,3-联二硫酸乙烯酯(BDTD)或1,2-二氟代碳酸乙 烯酯(DFEC)，且含量各自为0.1～2％、0.2～6％、0.2～2％、0.2～2％、0.1～1.5％、0.1～1.5％、0.1～1.5％、0.1～1.5％、0.1～1.5％。其中，硫酸乙烯酯(DTD)作为助剂加入到电解液中，可对锂离子电池负极表面SEI膜组分进行修饰，提高硫原子和氧原子的相对含量，硫原子和氧原子含有孤对电子，可以吸引锂离子，加快锂离子在SEI膜中穿梭，降低电池界面阻抗，从而有效提升锂离子电池的充放电性能。1,3-丙烷磺酸内酯(PS)作为助剂具有良好的成膜性能，可在正极界面形成大量含磺酸基团的CEI膜，抑制高温下FEC的分解产气，提高锂离子电池首次充放电的容量损失，从而有利于提升锂离子电池的可逆容量，进而改善了锂离子电池的高温性能以及长期循环性能。三(三甲基硅烷)磷酸酯(TMSP)、三(三甲基硅烷)亚磷酸酯(TMSPi)能够吸收水分和游离酸，提高锂离子电池的循环性能。Preferably, the non-aqueous electrolyte solution of the present application further includes an auxiliary agent, and the mass percentage of the auxiliary agent in the non-aqueous electrolyte solution is 0.1-10.5%; the auxiliary agent is selected from 2,2,2-trifluoroethyl methyl carbonate , 2,2,2-trifluorodiethyl carbonate, 2,2,2-trifluoroethylpropyl carbonate, vinylene carbonate (VC), fluoroethylene carbonate (FEC), diethyl pyrocarbonate Esters (DEPC), 1,3-Propane Sultone (PS), Vinyl Sulfate (DTD), 1,2-Difluoroethylene Carbonate (DFEC), Tris(trimethylsilane) Phosphate (TMSP) ), tris(trimethylsilane) phosphite (TMSPi), 4,4'-bi-1,3-dioxolane-2,2'-dione (BDC), 3,3-bisulfuric acid Vinyl Ester (BDTD), Triallyl Phosphate (TAP), Tripropargyl Phosphate (TPP), Succinonitrile (SN), Adiponitrile (ADN), 1,3,6-Hexanetrinitrile (HTCN) ) and at least one of 1,2-bis(cyanoethoxy)ethane (DENE). The additive can form a stable passivation film on the surface of the positive electrode, prevent the oxidative decomposition of the electrolyte on the surface of the positive electrode, inhibit the dissolution of transition metal ions from the positive electrode, improve the stability of the structure and interface of the positive electrode material, and significantly improve the high temperature of the lithium ion battery. Storage performance and cycle performance. Preferably, the auxiliary agent is selected from vinylene carbonate (VC), fluoroethylene carbonate (FEC), 1,3-propane sultone (PS), vinyl sulfate (DTD), tris(trimethylsilane) ) Phosphate (TMSP), Tris(trimethylsilane) phosphite (TMSPi), 4,4'-bi-1,3-dioxolane-2,2'-dione (BDC), 3, Vinyl 3-bisulfate (BDTD) or 1,2-difluoroethylene carbonate (DFEC), and the content is 0.1-2%, 0.2-6%, 0.2-2%, 0.2-2%, 0.1%, respectively ~1.5%, 0.1 to 1.5%, 0.1 to 1.5%, 0.1 to 1.5%, 0.1 to 1.5%. Among them, vinyl sulfate (DTD) is added to the electrolyte as an auxiliary agent, which can modify the SEI film components on the negative electrode surface of lithium ion batteries and increase the relative content of sulfur atoms and oxygen atoms, which contain lone pair electrons. , which can attract lithium ions, accelerate the shuttle of lithium ions in the SEI film, and reduce the battery interface impedance, thereby effectively improving the charge and discharge performance of lithium ion batteries. 1,3-Propane sultone (PS) has good film-forming properties as an auxiliary agent, which can form a large number of CEI films containing sulfonic acid groups at the positive interface, inhibit the decomposition and gas production of FEC at high temperature, and improve lithium-ion batteries. The capacity loss of the first charge and discharge is beneficial to improve the reversible capacity of the lithium-ion battery, thereby improving the high-temperature performance and long-term cycle performance of the lithium-ion battery. Tris(trimethylsilane) phosphate (TMSP) and tris(trimethylsilane) phosphite (TMSPi) can absorb moisture and free acid to improve the cycling performance of lithium-ion batteries.
为实现以上目的，本申请还提供了一种锂离子电池，包括正极和负极，还包括上述提及的非水电解液，且最高充电电压为4.53V。In order to achieve the above purpose, the present application also provides a lithium ion battery, which includes a positive electrode and a negative electrode, and also includes the above-mentioned non-aqueous electrolyte, and the highest charging voltage is 4.53V.
与现有技术相比，本申请的锂离子电池的非水电解液中包括非水电解液添加剂，非水电解液添加剂为结构式1所示的化合物，锂离子电池在首次充放电过程中，结构式1中的乳清酸基团在参与形成含氮CEI膜的同时，会将特殊金属(Mg、Zn)离子带入正极表面进而使其参与形成含特殊金属(Mg、Zn)离子的包覆层，该包覆层包覆在正极表面从而使得正极材料能耐更高温度以及能耐更高的电压，故该非水电解液添加剂能显著提高锂离子电池于高电压体系下的循环性能和高温存储性能；同时，乳清酸基团上的亚胺基在电解液中具有与氟离子络合的作用，能够显著除去氢氟酸，进一步提高锂离子电池于高电压体系下的循环性能和高温存储性能。Compared with the prior art, the non-aqueous electrolyte of the lithium ion battery of the present application includes a non-aqueous electrolyte additive, and the non-aqueous electrolyte additive is a compound shown in structural formula 1. During the first charge and discharge process of the lithium ion battery, the structural formula While participating in the formation of nitrogen-containing CEI film, the orotate group in 1 will bring special metal (Mg, Zn) ions into the surface of the positive electrode to participate in the formation of a coating layer containing special metal (Mg, Zn) ions. , the coating layer is coated on the surface of the positive electrode so that the positive electrode material can withstand higher temperature and higher voltage, so the non-aqueous electrolyte additive can significantly improve the cycle performance and high temperature storage performance of lithium ion batteries under high voltage systems At the same time, the imine group on the orotic acid group has the function of complexing with fluoride ions in the electrolyte, which can significantly remove hydrofluoric acid and further improve the cycle performance and high temperature storage performance of lithium ion batteries under high voltage systems. .
较佳地，本申请的正极的活性物质为钴酸锂。Preferably, the active material of the positive electrode of the present application is lithium cobalt oxide.
较佳地，本申请的负极的活性物质为天然石墨。Preferably, the active material of the negative electrode of the present application is natural graphite.
为更好地说明本申请的目的、技术方案和有益效果，下面将结合具体实施例对本申请作进一步说明。需说明的是，下述实施所述方法是对本申请做的进 一步解释说明，不应当作为对本申请的限制。In order to better illustrate the purpose, technical solutions and beneficial effects of the present application, the present application will be further described below with reference to specific embodiments. It should be noted that the following implementation of the method is a further explanation for the application, and should not be used as a limitation to the application.
实施例1Example 1
在充满氮气的手套箱(O
2＜1ppm，H
2O＜1ppm)中，将碳酸乙烯酯、碳酸二乙酯和碳酸甲乙酯按照质量比1:1:2混合均匀，制得79.8g非水有机溶剂，再加入0.2g化合物1作为添加剂并得到混合溶液。将混合溶液密封打包放置急冻间(-4℃)冷冻2h之后取出，在充满氮气的手套箱(O
2＜1ppm，H
2O＜1ppm)中，向混合溶液中缓慢加入20g六氟磷酸锂，混合均匀后即制成电解液。
In a nitrogen-filled glove box (O 2 <1 ppm, H 2 O < 1 ppm), ethylene carbonate, diethyl carbonate and ethyl methyl carbonate were uniformly mixed in a mass ratio of 1:1:2 to obtain 79.8 g of water organic solvent, and then 0.2 g of compound 1 was added as an additive to obtain a mixed solution. The mixed solution was sealed and packaged and placed in the freezing room (-4°C) for 2 hours and then taken out. In a nitrogen-filled glove box (O 2 <1ppm, H 2 O <1ppm), slowly add 20g lithium hexafluorophosphate to the mixed solution, and mix well. Then the electrolyte is made.
实施例2～19和对比例1～6的电解液配方如表1所示，配制电解液的步骤同实施例1。The electrolyte formulations of Examples 2 to 19 and Comparative Examples 1 to 6 are shown in Table 1, and the steps for preparing electrolytes are the same as those of Example 1.
表1电解液配方Table 1 Electrolyte formula
其中化合物7、化合物8、化合物9、化合物10的结构式如下所示：The structural formulas of compound 7, compound 8, compound 9, and compound 10 are as follows:
以最高充电电压为4.53V的钴酸锂为正极材料，天然石墨为负极材料，以实施例1～19和对比例1～6的电解液参照常规锂电池制备方法制成锂离子电池，并分别进行常温循环性能、高温循环性能、高温存储性能测试，测试条件如下，测试结果如表2所示：Taking lithium cobalt oxide with a maximum charging voltage of 4.53V as the positive electrode material and natural graphite as the negative electrode material, the electrolytes of Examples 1 to 19 and Comparative Examples 1 to 6 were used to prepare lithium ion batteries with reference to the conventional lithium battery preparation method, and respectively. The normal temperature cycle performance, high temperature cycle performance, and high temperature storage performance tests were carried out. The test conditions are as follows, and the test results are shown in Table 2:
常温循环性能测试：Normal temperature cycle performance test:
将锂离子电池置于25℃的环境中，以1C的电流恒流充电至4.53V，然后恒压充电至电流下至0.05C，然后以1C的电流恒流放电至3.0V，如此循环，然后每隔50圈测一次DCIR。记录第一圈的放电容量和最后一圈的放电容量，以及每隔50圈的DCIR。按下式计算高温循环的容量保持率以及DCIR提升率。Place the lithium-ion battery in an environment of 25°C, charge it to 4.53V with a constant current of 1C, then charge it with a constant voltage until the current drops to 0.05C, and then discharge it to 3.0V with a constant current of 1C. DCIR is measured every 50 laps. Record the discharge capacity of the first lap and the discharge capacity of the last lap, as well as the DCIR every 50 laps. The capacity retention rate and DCIR improvement rate of the high temperature cycle were calculated by the following formulas.
容量保持率＝最后一圈的放电容量/第一圈的放电容量×100％Capacity retention rate = discharge capacity of the last cycle / discharge capacity of the first cycle × 100%
DCIR提升率＝最后50圈的DCIR/第一圈的DCIR×100％DCIR boost rate = DCIR of the last 50 laps / DCIR of the first lap × 100%
高温循环性能测试：High temperature cycle performance test:
将锂离子电池置于恒温45℃的烘箱中，以1C的电流恒流充电至4.53V，然后恒压充电至电流下至0.05C，然后以1C的电流恒流放电至3.0V，如此循环，然后每隔50圈测一次DCIR。记录第一圈的放电容量和最后一圈的放电容量，以及每隔50圈的DCIR。按下式计算高温循环的容量保持率以及DCIR提升率。Place the lithium-ion battery in an oven with a constant temperature of 45°C, charge it to 4.53V with a constant current of 1C, then charge it with a constant voltage until the current drops to 0.05C, and then discharge it to 3.0V with a constant current of 1C. Then measure the DCIR every 50 laps. Record the discharge capacity of the first lap and the discharge capacity of the last lap, as well as the DCIR every 50 laps. The capacity retention rate and DCIR improvement rate of the high temperature cycle were calculated by the following formulas.
容量保持率＝最后一圈的放电容量/第一圈的放电容量×100％Capacity retention rate = discharge capacity of the last cycle / discharge capacity of the first cycle × 100%
DCIR提升率＝最后50圈的DCIR/第一圈的DCIR×100％DCIR boost rate = DCIR of the last 50 laps / DCIR of the first lap × 100%
高温存储测试：High temperature storage test:
将化成后的锂离子电池在常温下1C恒流恒压充电至4.53V，测量电池初始放电容量及初始电池厚度，然后再85℃存储8h后再以1C放电至3.0V，测量电池的容量保持和恢复容量及存储后电池厚度。计算公式如下：The formed lithium-ion battery was charged to 4.53V at 1C constant current and constant voltage at room temperature, and the initial discharge capacity and thickness of the battery were measured, and then stored at 85℃ for 8 hours, and then discharged to 3.0V at 1C, and the capacity retention of the battery was measured. and recovery capacity and battery thickness after storage. Calculated as follows:
电池容量保持率(％)＝保持容量/初始容量×100％；Battery capacity retention rate (%) = retained capacity / initial capacity × 100%;
电池容量恢复率(％)＝恢复容量/初始容量×100％；Battery capacity recovery rate (%)=recovered capacity/initial capacity×100%;
厚度膨胀率(％)＝(存储后电池厚度-初始电池厚度)/初始电池厚度×100％。Thickness swelling ratio (%)=(battery thickness after storage−initial battery thickness)/initial battery thickness×100%.
表2锂离子电池的性能测试结果Table 2 Performance test results of lithium-ion batteries
从表2可知，实施例1、实施例4-8的锂离子电池的性能皆优于对比例3-5，这表明与本申请结构式1相近的化合物7、化合物8、化合物9，虽然在一定程度上能提高锂离子电池的循环以及高温存储性能，但是由于化合物7、化合物8、化合物9不是金属盐类化合物，故其热稳定性以及高电压下的稳定性并不好，且没有特殊金属(Mg、Zn)离子对正极CEI膜的修饰，因此化合物7、化合物8、化合物9在提高锂离子电池的循环性能和高温存储性能方面没有结构式1所示的化合物好。It can be seen from Table 2 that the performances of the lithium ion batteries of Example 1 and Examples 4-8 are all better than those of Comparative Examples 3-5, which shows that Compound 7, Compound 8, and Compound 9, which are similar to the structural formula 1 of the present application, although under certain conditions It can improve the cycle and high temperature storage performance of lithium-ion batteries to a certain extent, but because compound 7, compound 8 and compound 9 are not metal salt compounds, their thermal stability and stability under high voltage are not good, and there is no special metal (Mg, Zn) ions modify the positive electrode CEI film, so compound 7, compound 8 and compound 9 are not as good as compounds shown in structural formula 1 in improving the cycle performance and high temperature storage performance of lithium ion batteries.
实施例1、实施例4-8的锂离子电池的性能皆优于对比例6，这表明虽然化合物10(双(三氟甲基磺酰基)酰亚胺镁)中也含有镁离子，但化合物10在电解液中的电离能力太强，使得镁离子大部分游离在电解液中而不会随着双(三氟甲基磺酰基)酰亚胺根离子参与成膜反应，故镁离子不但不会修饰正极CEI膜，反而会引起镁离子参与放电，影响锂离子电池的性能；而本申请结构式1所示的化合物的电离能力较弱，故在电解液中以离子对形式存在，锂离子电池在首次充放电过程中，结构式1所示的化合物中的乳清酸基团在参与形成含氮CEI膜的同时，会将特殊金属(Mg、Zn)离子带入正极表面进而使其参与形成含特殊金属(Mg、Zn)离子的包覆层，该包覆层包覆在正极表面从而使得正极材料能耐更高温度以及能耐更高的电压，故该非水电解液添加剂能显著提高锂离子电池于高电压体系下的循环性能和高温存储性能。The performances of the lithium-ion batteries of Example 1 and Examples 4-8 are all better than those of Comparative Example 6, which shows that although compound 10 (bis(trifluoromethylsulfonyl)imide magnesium) also contains magnesium ions, the compound 10 The ionization ability in the electrolyte is too strong, so that most of the magnesium ions are free in the electrolyte and will not participate in the film-forming reaction with the bis(trifluoromethylsulfonyl)imide ions, so the magnesium ions not only do not It will modify the positive electrode CEI film, but will cause magnesium ions to participate in the discharge, which will affect the performance of the lithium ion battery; and the compound shown in the structural formula 1 of the present application has a weak ionization ability, so it exists in the electrolyte in the form of ion pairs, and the lithium ion battery During the first charge-discharge process, the orotic acid group in the compound represented by structural formula 1 will bring special metal (Mg, Zn) ions into the surface of the positive electrode while participating in the formation of the nitrogen-containing CEI film, so that it will participate in the formation of a nitrogen-containing CEI film. The coating layer of special metal (Mg, Zn) ions, the coating layer is coated on the surface of the positive electrode, so that the positive electrode material can withstand higher temperature and higher voltage, so the non-aqueous electrolyte additive can significantly improve the lithium ion battery. Cycling performance and high temperature storage performance under high voltage system.
最后应当说明的是，以上实施例仅用以说明本申请的技术方案而非对本申请保护范围的限制，尽管参照较佳实施例对本申请作了详细说明，本领域的普 通技术人员应当理解，可以对本申请的技术方案进行修改或者等同替换，而不脱离本申请技术方案的实质和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should The technical solutions of the present application may be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present application.
Claims (10)
- 一种非水电解液添加剂，其特征在于，包括结构式1所示的化合物：A non-aqueous electrolyte additive is characterized in that, comprises the compound shown in structural formula 1:
其中，R 1、R 2、R 3、R 4各自独立地选自氧原子或硫原子，R 5、R 6、R 7、R 8各自独立地选自氢原子或C1-C5的烃基，R 9、R 10各自独立地选自氢原子、卤素原子、C1-C5的烃基或C1-C5的卤代烃基，R 11选自镁或锌。 Wherein, R 1 , R 2 , R 3 , and R 4 are each independently selected from an oxygen atom or a sulfur atom, R 5 , R 6 , R 7 , and R 8 are each independently selected from a hydrogen atom or a C1-C5 hydrocarbon group, and R 9. R 10 is each independently selected from a hydrogen atom, a halogen atom, a C1-C5 hydrocarbon group or a C1-C5 halogenated hydrocarbon group, and R 11 is selected from magnesium or zinc. - 如权利要求1所述的非水电解液添加剂，其特征在于，所述结构式1所示的化合物选自化合物1～化合物6中的至少一种：The non-aqueous electrolyte additive according to claim 1, wherein the compound represented by the structural formula 1 is selected from at least one of compounds 1 to 6:
- 一种非水电解液，包括锂盐和非水有机溶剂，其特征在于，还包括如权利要求1～2任一项所述的非水电解液添加剂。A non-aqueous electrolyte solution comprising a lithium salt and a non-aqueous organic solvent is characterized in that, further comprising the non-aqueous electrolyte solution additive according to any one of claims 1-2.
- 如权利要求3所述的非水电解液，其特征在于，所述非水电解液添加剂于所述非水电解液中的质量百分比为0.1～1％。The non-aqueous electrolyte solution according to claim 3, wherein the mass percentage of the non-aqueous electrolyte solution additive in the non-aqueous electrolyte solution is 0.1-1%.
- 如权利要求3所述的非水电解液，其特征在于，所述锂盐选自六氟磷酸锂、二氟磷酸锂、双草酸硼酸锂、二氟草酸硼酸锂、二氟二草酸磷酸锂、四氟硼酸锂、四氟草酸磷酸锂、双三氟甲基磺酰亚胺锂、双氟代磺酰亚胺锂和四氟丙二酸磷酸锂中的至少一种。The non-aqueous electrolyte according to claim 3, wherein the lithium salt is selected from the group consisting of lithium hexafluorophosphate, lithium difluorophosphate, lithium bis-oxalate borate, lithium difluorooxalate borate, lithium difluorobisoxalate phosphate, tetrafluoroborate At least one of lithium, lithium tetrafluorooxalate phosphate, lithium bistrifluoromethanesulfonimide, lithium bisfluorosulfonimide, and lithium tetrafluoromalonate phosphate.
- 如权利要求3所述的非水电解液，其特征在于，所述锂盐于所述非水电解液中的质量百分比为10～20％。The non-aqueous electrolyte solution according to claim 3, wherein the mass percentage of the lithium salt in the non-aqueous electrolyte solution is 10-20%.
- 如权利要求3所述的非水电解液，其特征在于，所述非水有机溶剂选自碳酸乙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸丙烯酯、乙酸丁酯、γ-丁内酯、丙酸丙酯、丙酸乙酯和丁酸乙酯中的至少一种。The non-aqueous electrolyte solution according to claim 3, wherein the non-aqueous organic solvent is selected from ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, butyl acetate , at least one of γ-butyrolactone, propyl propionate, ethyl propionate and ethyl butyrate.
- 如权利要求3所述的非水电解液，其特征在于，还包括助剂，所述助剂选自2,2,2-三氟代碳酸甲乙酯、2,2,2-三氟代碳酸二乙酯、2,2,2-三氟代碳酸乙丙酯、碳酸亚乙烯酯、氟代碳酸乙烯酯、焦碳酸二乙酯、1,3-丙烷磺酸内酯、硫酸乙烯酯、1,2-二氟代碳酸乙烯酯、三(三甲基硅烷)磷酸酯、三(三甲基硅烷)亚磷酸酯、4,4'-联-1,3-二氧戊环-2,2'-二酮、3,3-联二硫酸乙烯酯、磷酸三烯丙酯、磷酸三炔丙酯、丁二腈、己二腈、1,3,6-己烷三腈和1,2-双(氰乙氧基)乙烷中的至少一种。The non-aqueous electrolyte solution according to claim 3, further comprising an auxiliary agent selected from the group consisting of 2,2,2-trifluoroethyl methyl carbonate, 2,2,2-trifluorocarbonate Diethyl carbonate, 2,2,2-trifluoroethylpropyl carbonate, vinylene carbonate, fluoroethylene carbonate, diethyl pyrocarbonate, 1,3-propane sultone, vinyl sulfate, 1,2-difluoroethylene carbonate, tris(trimethylsilane) phosphate, tris(trimethylsilane) phosphite, 4,4'-bi-1,3-dioxolane-2, 2'-diketone, vinyl 3,3-disulfate, triallyl phosphate, tripropargyl phosphate, succinonitrile, adiponitrile, 1,3,6-hexanetrinitrile and 1,2 - at least one of bis(cyanoethoxy)ethane.
- 一种锂离子电池，包括正极和负极，其特征在于，还包括如权利要求3～8任一项所述的非水电解液，且最高充电电压为4.53V。A lithium ion battery, comprising a positive electrode and a negative electrode, is characterized in that, further comprising the non-aqueous electrolyte according to any one of claims 3 to 8, and the highest charging voltage is 4.53V.
- 如权利要求9所述的锂离子电池，其特征在于，所述正极的活性物质为钴酸锂。The lithium ion battery according to claim 9, wherein the active material of the positive electrode is lithium cobalt oxide.
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