CN110474088A - A kind of ternary high-voltage lithium-ion battery electrolyte - Google Patents
A kind of ternary high-voltage lithium-ion battery electrolyte Download PDFInfo
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- CN110474088A CN110474088A CN201910751245.0A CN201910751245A CN110474088A CN 110474088 A CN110474088 A CN 110474088A CN 201910751245 A CN201910751245 A CN 201910751245A CN 110474088 A CN110474088 A CN 110474088A
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- lithium
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- silicon substrate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 88
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 77
- -1 esters compounds Chemical class 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000004665 trialkylsilyl group Chemical group 0.000 claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 31
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 11
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 150000001721 carbon Chemical group 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 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
- 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 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims description 4
- LKSCJMIATJONBS-UHFFFAOYSA-K trilithium oxalic acid phosphate Chemical class P(=O)([O-])([O-])[O-].[Li+].C(C(=O)O)(=O)O.[Li+].[Li+] LKSCJMIATJONBS-UHFFFAOYSA-K 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 229960002645 boric acid Drugs 0.000 claims description 3
- 235000010338 boric acid Nutrition 0.000 claims description 3
- DGTVXEHQMSJRPE-UHFFFAOYSA-M difluorophosphinate Chemical compound [O-]P(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-M 0.000 claims description 3
- 150000002690 malonic acid derivatives Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 2
- 229910013172 LiNixCoy Inorganic materials 0.000 claims description 2
- MWQJGSUQGMJVCS-UHFFFAOYSA-N N=[S+]C(F)(F)F.[Li] Chemical compound N=[S+]C(F)(F)F.[Li] MWQJGSUQGMJVCS-UHFFFAOYSA-N 0.000 claims description 2
- GTTGLTZAOFBCRM-UHFFFAOYSA-N P(O)(O)(O)=O.C[SiH](C)C Chemical class P(O)(O)(O)=O.C[SiH](C)C GTTGLTZAOFBCRM-UHFFFAOYSA-N 0.000 claims description 2
- QRMHDYCPNIVCBO-UHFFFAOYSA-N [SH2]=N.[F] Chemical compound [SH2]=N.[F] QRMHDYCPNIVCBO-UHFFFAOYSA-N 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007770 graphite material Substances 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 3
- 229910052710 silicon Inorganic materials 0.000 claims 3
- 239000010703 silicon Substances 0.000 claims 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims 1
- WPDHZZSAAAREHB-UHFFFAOYSA-N B([O-])([O-])[O-].C[SiH](C)C.[Li+].[Li+].[Li+] Chemical class B([O-])([O-])[O-].C[SiH](C)C.[Li+].[Li+].[Li+] WPDHZZSAAAREHB-UHFFFAOYSA-N 0.000 claims 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims 1
- JWEKKXWDUIFOQQ-UHFFFAOYSA-N [Li].P(O)(O)(O)=O.C(C(=O)O)(=O)O Chemical compound [Li].P(O)(O)(O)=O.C(C(=O)O)(=O)O JWEKKXWDUIFOQQ-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- OPUAWDUYWRUIIL-UHFFFAOYSA-N methanedisulfonic acid Chemical compound OS(=O)(=O)CS(O)(=O)=O OPUAWDUYWRUIIL-UHFFFAOYSA-N 0.000 claims 1
- 150000003890 succinate salts Chemical class 0.000 claims 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical class C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 15
- 239000000654 additive Substances 0.000 abstract description 9
- 230000000996 additive effect Effects 0.000 abstract description 9
- 230000007774 longterm Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 230000001815 facial effect Effects 0.000 abstract description 3
- 238000010410 dusting Methods 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 4
- 239000008187 granular material Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 229910001290 LiPF6 Inorganic materials 0.000 description 10
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 10
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 10
- MOLYXOOGDFTUJT-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O.[Co] Chemical compound [Li].[Mn](=O)(=O)(O)O.[Co] MOLYXOOGDFTUJT-UHFFFAOYSA-L 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000005538 encapsulation Methods 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 238000003475 lamination Methods 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 238000004080 punching Methods 0.000 description 10
- 238000003466 welding Methods 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
- 241001269238 Data Species 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 description 1
- AOANMOLKQQXRCC-UHFFFAOYSA-N C(C)(=O)OC=C.C(O)(=O)F Chemical compound C(C)(=O)OC=C.C(O)(=O)F AOANMOLKQQXRCC-UHFFFAOYSA-N 0.000 description 1
- HMWVNKJRYWXJGS-UHFFFAOYSA-N C(C)(=O)OC=C.[C] Chemical group C(C)(=O)OC=C.[C] HMWVNKJRYWXJGS-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 229910012265 LiPO2F2 Inorganic materials 0.000 description 1
- UOIZEJXVVUGVNB-UHFFFAOYSA-N P(O)(O)O.C[SiH](C)C Chemical class P(O)(O)O.C[SiH](C)C UOIZEJXVVUGVNB-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development 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
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- MGNVWUDMMXZUDI-UHFFFAOYSA-N propane-1,3-disulfonic acid Chemical compound OS(=O)(=O)CCCS(O)(=O)=O MGNVWUDMMXZUDI-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of ternary high-voltage lithium-ion battery electrolyte, which includes bis- (trialkyl silyl) two acid esters compounds；Wherein, R1The alkyl for being 1-4 for carbon atom number, R2The alkyl for being 1-20 for carbon atom number；Wherein, R3One of the alkyl for being 1-4 for hydrogen atom, halogen or carbon atom number, R4One of the alkyl for being 1-4 for hydrogen atom, halogen or carbon atom number.Ternary high-voltage lithium-ion battery electrolyte of the present invention forms Stability Bound facial mask in positive electrode surface using additive, with good film forming characteristics, it can effectively inhibit electrolyte in the oxygenolysis on positive electrode surface, and it reduces the dusting of material granule and is crushed, guarantee the interface stability of positive and negative electrode under high voltages, which can be improved the long-term cycle performance and high-temperature storage performance of ternary high-voltage lithium ion power battery.
Description
Technical field
The invention belongs to technical field of lithium ion, are electrolysed more particularly, to a kind of ternary high-voltage lithium ion batteries
Liquid.
Background technique
The continuous improvement that the fast development of new-energy automobile and its course continuation mileage require, to high-energy density power lithium
The demand of ion battery constantly expands.
There are mainly two types of modes for the method for realization high-energy density: one is the nickelic ternary materials of selection high capacity, separately
One is use high voltage ternary material.But whether being nickelic or high voltage ternary material, as charging progresses, stablize
Property be deteriorated, oxidisability enhancing, one side oxidation electrolyte, after the digestion of metallic ion in another aspect positive electrode cathode also
Original destroys cathode SEI membrane structure, increases the internal resistance of cell, deteriorates the chemical properties such as circulation, the storage of battery.
Electrolyte is that the key factor for promoting battery comprehensive performance, the especially additive in electrolyte are each to battery is improved
Item performance plays a key effect.Therefore guarantee the performance of high-energy density ternary lithium-ion-power cell, the matching of electrolyte is
It is crucial.Current lithium-ion battery electrolytes mostly use traditional film for additive such as vinylene carbonate (VC) or fluoro carbonic acid second
Enester (FEC), but the oxidative resistance of VC is poor, and be easy to decompose under FEC is although anti-oxidant but high temperature and generate hydrofluoric acid (HF), meeting
The digestion of metallic ion being further exacerbated by tertiary cathode material, deterioration.
Summary of the invention
In view of this, the present invention is directed to propose a kind of ternary high-voltage lithium-ion battery electrolyte, used additive tool
There is good film forming characteristics, guarantee the interface stability of positive and negative electrode under high voltages, which can be improved ternary high voltage lithium
The long-term cycle performance and high-temperature storage performance of ion battery.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of ternary high-voltage lithium-ion battery electrolyte, the electrolyte include bis- (trialkyl silyls) two esters of gallic acid chemical combination
The structural formula of object, bis- (trialkyl silyl) two acid esters compounds is as follows:
Wherein, R1The alkyl for being 1-4 for carbon atom number, R2The alkyl for being 1-20 for carbon atom number；
The R2Structural formula it is as follows:
Wherein, R3One of the alkyl for being 1-4 for hydrogen atom, halogen or carbon atom number, R4For hydrogen atom, halogen or carbon
Atomicity is one of the alkyl of 1-4.
Further, bis- (trialkyl silyl) two acid esters compounds are bis- (trimethyl silicon substrate) malonates, double
It is (trimethyl silicon substrate) succinate, bis- (trimethyl silicon substrate) glutarates, bis- (trimethyl silicon substrate) 2- difluoro malonates, double
(trimethyl silicon substrate) 2- dimethyl malonic ester, bis- (trimethyl silicon substrate) 2- diethylmalonates, bis- (trimethyl silicon substrate) 2-
Dipropyl phenyl malonic ester, bis- (trimethyl silicon substrate) 2- dibutyl malonates, bis- (trimethyl silicon substrate) 2- methyl -2- fluorine malonic acid
Ester, bis- (trimethyl silicon substrate) 2- ethyl -2- fluorine malonates, bis- (trimethyl silicon substrate) 2- propyl -2- fluorine malonates or bis- (three
At least one of methylsilyl) 2- butyl -2- fluorine malonate compound.
Further, the quality of bis- (trialkyl silyl) two acid esters compounds is the 0.1- of electrolyte total weight
10%；Preferably, the quality of bis- (trialkyl silyl) two acid esters compounds is the 0.1-3% of electrolyte total weight.
It further, further include lithium salts in the electrolyte, the quality of the lithium salts is the 10- of electrolyte total weight
20%；The lithium salts is lithium hexafluoro phosphate.
It further, further include organic solvent in the electrolyte, the quality of the organic solvent is electrolyte gross weight
The 50-90% of amount；The organic solvent is ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid
Two or more in methyl ethyl ester, ethyl propionate or propyl propionate.
It further, further include auxiliary agent in the electrolyte, the quality of the auxiliary agent is the 0.1- of electrolyte total weight
20%；The auxiliary agent is vinylene carbonate, in vinyl ethylene carbonate, fluorinated ethylene carbonate, 1,3- propane sulfonic acid
Ester, propylene -1,3- sultones, methane-disulfonic acid methylene ester, difluorophosphate, difluorine oxalic acid boracic acid lithium, di-oxalate lithium borate,
The double oxalic acid lithium phosphates of difluoro, tetrafluoro oxalic acid lithium phosphate, double fluorine sulfimide lithiums, bis trifluoromethyl sulfimide lithium, three (trimethyls
At least one of silane) lithium borate, three (trimethyl silane) phosphite esters or three (trimethyl silane) phosphates.
A kind of ternary high-voltage lithium ion batteries, including anode, cathode and the electrolyte.
Further, the active material of the anode is ternary nickle cobalt lithium manganate LiNixCoyMn1-x-y, wherein 0 < x <
1,0 < y < 1.
Further, the active material of the anode is at least one in NCM523, NCM622, NCM712 or NCM811
Kind.
Further, the active material of the cathode is at least one of graphite or Si-C composite material.
Compared with the existing technology, ternary high-voltage lithium-ion battery electrolyte of the present invention has the advantage that
(1) ternary high-voltage lithium-ion battery electrolyte of the present invention forms stabilization in positive electrode surface using additive
Interfacial film has good film forming characteristics, can effectively inhibit electrolyte in the oxygenolysis on positive electrode surface, and reduce material
Expect the dusting of particle and be crushed, guarantee the interface stability of positive and negative electrode under high voltages, which can be improved ternary high voltage
The long-term cycle performance and high-temperature storage performance of lithium-ion-power cell.
(2) bis- (trialkyl silyls) of the present invention two acid esters compound additive has good in positive and negative electrode
Film forming characteristics improves the stability of tertiary cathode under high voltages, it is suppressed that destruction of the HF to sector electrode facial mask reduces anode gold
Belong to Ion release, two acid esters of fluorination of generation is deposited on positive and negative electrode surface, improves the stability of positive and negative electrode interfacial film, effectively mentions
The long-term cycle performance and high-temperature storage performance of high ternary high-voltage lithium ion power battery.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
Below with reference to embodiment, the present invention will be described in detail.
Embodiment 1
A kind of ternary high-voltage lithium-ion battery electrolyte, the electrolyte include 14%LiPF6, 84% organic solvent,
2% bis- (trimethyl silicon substrate) malonates；Wherein, organic solvent is ethylene carbonate and methyl ethyl carbonate, mass ratio 3:7.
A kind of ternary high-voltage lithium ion batteries, including ternary nickle cobalt lithium manganate NCM523 anode, graphite cathode with it is described
Electrolyte.
A kind of preparation method of ternary high-voltage lithium ion batteries, just extremely nickel ternary cobalt manganic acid lithium NCM523, cathode are
Graphite, battery obtain battery core to be injected by homogenate, coating, roll-in, punching, lamination, welding, encapsulation, inject electrolyte, that is, make
Obtain the ternary high-voltage lithium ion batteries.
Embodiment 2
A kind of ternary high-voltage lithium-ion battery electrolyte, the electrolyte include 13%LiPF6, 85% organic solvent,
1% vinylene carbonate (VC), 1% bis- (trimethyl silicon substrate) 2- difluoro malonates；Wherein, organic solvent is ethylene carbonate
Ester, methyl ethyl carbonate and diethyl carbonate, mass ratio 3:6:1.
A kind of ternary high-voltage lithium ion batteries, including ternary nickle cobalt lithium manganate NCM622 anode, graphite cathode with it is described
Electrolyte.
A kind of preparation method of ternary high-voltage lithium ion batteries, just extremely nickel ternary cobalt manganic acid lithium NCM622, cathode are
Graphite, battery obtain battery core to be injected by homogenate, coating, roll-in, punching, lamination, welding, encapsulation, inject electrolyte, that is, make
Obtain the ternary high-voltage lithium ion batteries.
Embodiment 3
A kind of ternary high-voltage lithium-ion battery electrolyte, the electrolyte include 14%LiPF6, 83.5% it is organic molten
Agent, 1% fluorinated ethylene carbonate (FEC), 1.5% bis- (trimethyl silicon substrate) 2- methyl -2- fluorine malonates；Wherein, You Jirong
Agent is ethylene carbonate, methyl ethyl carbonate and diethyl carbonate, mass ratio 3:6:1.
A kind of ternary high-voltage lithium ion batteries, including ternary nickle cobalt lithium manganate NCM622 anode, silicon-carbon cathode with it is described
Electrolyte.
A kind of preparation method of ternary high-voltage lithium ion batteries, just extremely nickel ternary cobalt manganic acid lithium NCM622, cathode are
Silicon-carbon, battery obtain battery core to be injected by homogenate, coating, roll-in, punching, lamination, welding, encapsulation, inject electrolyte, that is, make
Obtain the ternary high-voltage lithium ion batteries.
Embodiment 4
A kind of ternary high-voltage lithium-ion battery electrolyte, the electrolyte include 13%LiPF6, 85% organic solvent,
The double oxalic acid lithium phosphates (LiDFOP) of 1% difluoro, 1% bis- (trimethyl silicon substrate) 2- ethyl -2- fluorine malonates；Wherein, You Jirong
Agent is ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, mass ratio 3:6:1.
A kind of ternary high-voltage lithium ion batteries, including ternary nickle cobalt lithium manganate NCM811 anode, graphite cathode with it is described
Electrolyte.
A kind of preparation method of ternary high-voltage lithium ion batteries, just extremely nickel ternary cobalt manganic acid lithium NCM811, cathode are
Graphite, battery obtain battery core to be injected by homogenate, coating, roll-in, punching, lamination, welding, encapsulation, inject electrolyte, that is, make
Obtain the ternary high-voltage lithium ion batteries.
Embodiment 5
A kind of ternary high-voltage lithium-ion battery electrolyte, the electrolyte include 14%LiPF6, 82% organic solvent,
1% difluorine oxalic acid boracic acid lithium (LiDFOB), 3% bis- (trimethyl silicon substrate) 2- diethylmalonates；Wherein, organic solvent is carbon
Vinyl acetate, methyl ethyl carbonate and propyl propionate, mass ratio 3:6:1.
A kind of ternary high-voltage lithium ion batteries, including ternary nickle cobalt lithium manganate NCM811 anode, silicon-carbon cathode with it is described
Electrolyte.
A kind of preparation method of ternary high-voltage lithium ion batteries, just extremely nickel ternary cobalt manganic acid lithium NCM811, cathode are
Silicon-carbon, battery obtain battery core to be injected by homogenate, coating, roll-in, punching, lamination, welding, encapsulation, inject electrolyte, that is, make
Obtain the ternary high-voltage lithium ion batteries.
Embodiment 6
A kind of ternary high-voltage lithium-ion battery electrolyte, the electrolyte include 15%LiPF6, 82% organic solvent,
1% difluorophosphate (LiPO2F2), 2% bis- (trimethyl silicon substrate) 2- difluoro malonates；Wherein, organic solvent is ethylene carbonate
Ester, methyl ethyl carbonate and diethyl carbonate, mass ratio 3:5:2.
A kind of ternary high-voltage lithium ion batteries, including ternary nickle cobalt lithium manganate NCM811 anode, silicon-carbon cathode with it is described
Electrolyte.
A kind of preparation method of ternary high-voltage lithium ion batteries, just extremely nickel ternary cobalt manganic acid lithium NCM811, cathode are
Silicon-carbon, battery obtain battery core to be injected by homogenate, coating, roll-in, punching, lamination, welding, encapsulation, inject electrolyte, that is, make
Obtain the ternary high-voltage lithium ion batteries.
Comparative example 1
A kind of lithium-ion battery electrolytes, the electrolyte include 14%LiPF6, 86% organic solvent；Wherein, You Jirong
Agent is ethylene carbonate and methyl ethyl carbonate, mass ratio 3:7.
A kind of lithium ion battery, including ternary nickle cobalt lithium manganate NCM523 anode, graphite cathode and the electrolyte.
A kind of preparation method of lithium ion battery, just extremely nickel ternary cobalt manganic acid lithium NCM523, cathode are graphite, and battery is logical
Cross homogenate, coating, roll-in, punching, lamination, welding, encapsulation obtain battery core to be injected, inject electrolyte, obtain the lithium
Ion battery.
Comparative example 2
A kind of lithium-ion battery electrolytes, the electrolyte include 14%LiPF6, 85% organic solvent, 1% fluoro carbonic acid
Vinyl acetate (FEC)；Wherein, organic solvent is ethylene carbonate, methyl ethyl carbonate and diethyl carbonate, mass ratio 3:6:1.
A kind of lithium ion battery, including ternary nickle cobalt lithium manganate NCM622 anode, silicon-carbon cathode and the electrolyte.
A kind of preparation method of lithium ion battery, just extremely nickel ternary cobalt manganic acid lithium NCM622, cathode are silicon-carbon, and battery is logical
Cross homogenate, coating, roll-in, punching, lamination, welding, encapsulation obtain battery core to be injected, inject electrolyte, obtain the lithium
Ion battery.
Comparative example 3
A kind of lithium-ion battery electrolytes, the electrolyte include 13%LiPF6, 86% organic solvent, the double grass of 1% difluoro
Acid phosphoric acid lithium (LiDFOP)；Wherein, organic solvent be ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, mass ratio 3:
6:1。
A kind of lithium ion battery, including ternary nickle cobalt lithium manganate NCM811 anode, graphite cathode and the electrolyte.
A kind of preparation method of lithium ion battery, just extremely nickel ternary cobalt manganic acid lithium NCM811, cathode are graphite, and battery is logical
Cross homogenate, coating, roll-in, punching, lamination, welding, encapsulation obtain battery core to be injected, inject electrolyte, obtain the lithium
Ion battery.
Comparative example 4
A kind of lithium-ion battery electrolytes, the electrolyte include 14%LiPF6, 85% organic solvent, 1% difluoro oxalate
Lithium borate (LiDFOB)；Wherein, organic solvent is ethylene carbonate, methyl ethyl carbonate and propyl propionate, mass ratio 3:6:1.
A kind of lithium ion battery, including ternary nickle cobalt lithium manganate NCM811 anode, silicon-carbon cathode and the electrolyte.
A kind of preparation method of lithium ion battery, just extremely nickel ternary cobalt manganic acid lithium NCM811, cathode are silicon-carbon, and battery is logical
Cross homogenate, coating, roll-in, punching, lamination, welding, encapsulation obtain battery core to be injected, inject electrolyte, obtain the lithium
Ion battery.
The performance test of the electrolyte and lithium ion battery of embodiment 1-6 and comparative example 1-4:
1,55 DEG C of storage performance tests of high temperature
The lithium ion battery that above-described embodiment 1-6 and comparative example 1-4 is made, 25 DEG C, 1C constant-current constant-voltage charging to the upper limit
Voltage (4.35V or 4.4V), cut-off current 0.05C；1C constant-current discharge obtains storing preceding discharge capacity to 2.75V again；1C is used again
Constant-current constant-voltage charging is to upper limit voltage (4.35V or 4.4V), cut-off current 0.05C.Then battery is placed in 55 DEG C of environment
Storage is taken out after 7 days, and after normal temperature shelf 5h, 1C constant-current discharge to 2.75V keeps capacity after being stored；It is permanent with 1C constant current again
Pressure charges to upper limit voltage (4.35V or 4.4V), cut-off current 0.05C；Again with 1C constant-current discharge to 2.75V, after obtaining storage
Restore capacity.The calculation formula of capacity retention ratio, capacity restoration rate and internal resistance increase rate is as follows:
Capacity × 100% before capacity retention ratio (%)=holding capacity/storage；
Capacity × 100% before capacity restoration rate (%)=recovery capacity/storage；
55 DEG C of storage test results of high temperature of the lithium ion battery 4.35V and 4.4V of embodiment 1-6 and comparative example 1-4 production
Shown in following Tables 1 and 2.
55 DEG C of storage test datas of lithium ion battery 4.35V high temperature of table 1 embodiment 1-6 and comparative example 1-4
55 DEG C of storage test datas of lithium ion battery 4.4V high temperature of table 2 embodiment 1-6 and comparative example 1-4
The comparative example that compares it can be seen from data in Tables 1 and 2 1-4 electrolyte adds in embodiment 1-6 electrolyte
After bis- (trialkyl silyls) two acid esters compound additive of the invention, ternary high-voltage lithium ion batteries are effectively improved
High-temperature storage performance.
2, cycle performance is tested
The lithium ion battery that above-described embodiment 1-6 and comparative example 1-4 is made, 25 DEG C or 45 DEG C, 1C constant-current constant-voltage charging
To upper limit voltage (4.35V or 4.4V), cut-off current 0.05C, then 1C constant-current discharge to 2.75V so fill, put circulation 300 times,
Circulation volume is calculated to keep.The calculation formula of circulation volume conservation rate is as follows:
The cyclic discharge capacity average value of circulation volume conservation rate (%)=last time cyclic discharge capacity/3 times ×
100%.
The loop test result of embodiment 1-6 and comparative example 1-4 lithium ion battery is as shown in the following table 3 and the following table 4.
The lithium ion battery 4.35V of table 3 embodiment 1-6 and comparative example 1-4 recycles 300 data
The lithium ion battery 4.4V of table 4 embodiment 1-6 and comparative example 1-4 recycles 300 data
Compare comparative example 1-4 electrolyte it can be seen from table 3 and data in table 4, adds in embodiment 1-6 electrolyte
After bis- (trialkyl silyls) two acid esters compound additive of the invention, ternary high-voltage lithium ion batteries are effectively improved
Cycle performance.
Therefore, a kind of ternary high-voltage lithium-ion battery electrolyte provided by the invention adds bis- (trialkyl silyls) two
After acid esters compound additive, the stability of positive and negative electrode interfacial film is improved, oxygen of the anode to electrolyte under inhibition high voltage
Change, reduce the dissolution of metal ion, inhibits destruction of the HF to sector electrode facial mask, effectively increase ternary high-voltage lithium ion power
The long-term cycle performance of battery, high-temperature storage performance.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of ternary high-voltage lithium-ion battery electrolyte, it is characterised in that: the electrolyte includes bis- (trialkyl silyls) two
The structural formula of acid esters compound, bis- (trialkyl silyl) two acid esters compounds is as follows:
Wherein, R1The alkyl for being 1-4 for carbon atom number, R2The alkyl for being 1-20 for carbon atom number；
The R2Structural formula it is as follows:
Wherein, R3One of the alkyl for being 1-4 for hydrogen atom, halogen or carbon atom number, R4For hydrogen atom, halogen or carbon atom
Number is one of the alkyl of 1-4.
2. ternary high-voltage lithium-ion battery electrolyte according to claim 1, it is characterised in that: bis- (three alkane
Base silicon substrate) two acid esters compounds be bis- (trimethyl silicon substrate) malonates, bis- (trimethyl silicon substrate) succinates, bis- (front threes
Base silicon substrate) glutarate, bis- (trimethyl silicon substrate) 2- difluoro malonates, bis- (trimethyl silicon substrate) 2- dimethyl malonic esters,
Bis- (trimethyl silicon substrate) 2- diethylmalonates, bis- (trimethyl silicon substrate) 2- dipropyl phenyl malonic esters, bis- (trimethyl silicon substrates)
2- dibutyl malonate, bis- (trimethyl silicon substrate) 2- methyl -2- fluorine malonates, bis- (trimethyl silicon substrate) 2- ethyl -2- fluorine
Malonate, bis- (trimethyl silicon substrate) 2- propyl -2- fluorine malonates or bis- (trimethyl silicon substrate) 2- butyl -2- fluorine malonates
At least one of compound.
3. ternary high-voltage lithium-ion battery electrolyte according to claim 2, it is characterised in that: bis- (three alkane
Base silicon substrate) two acid esters compounds quality be electrolyte total weight 0.1-10%；Preferably, bis- (trialkyl silicas
Base) two acid esters compounds quality be electrolyte total weight 0.1-3%.
4. ternary high-voltage lithium-ion battery electrolyte according to claim 2, it is characterised in that: in the electrolyte
It further include lithium salts, the quality of the lithium salts is the 10-20% of electrolyte total weight；The lithium salts is lithium hexafluoro phosphate.
5. ternary high-voltage lithium-ion battery electrolyte according to claim 2, it is characterised in that: in the electrolyte
It further include organic solvent, the quality of the organic solvent is the 50-90% of electrolyte total weight；The organic solvent is carbon
Two in vinyl acetate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethyl propionate or propyl propionate
Kind is two or more.
6. ternary high-voltage lithium-ion battery electrolyte according to claim 2, it is characterised in that: in the electrolyte
It further include auxiliary agent, the quality of the auxiliary agent is the 0.1-20% of electrolyte total weight；The auxiliary agent be vinylene carbonate,
Vinyl ethylene carbonate, fluorinated ethylene carbonate, 1,3- propane sultone, propylene -1,3- sultones, methane-disulfonic acid
The double oxalic acid lithium phosphates of methylene ester, difluorophosphate, difluorine oxalic acid boracic acid lithium, di-oxalate lithium borate, difluoro, tetrafluoro oxalic acid phosphoric acid
Lithium, double fluorine sulfimide lithiums, bis trifluoromethyl sulfimide lithium, three (trimethyl silane) lithium borates, three (trimethyl silanes) are sub-
At least one of phosphate or three (trimethyl silane) phosphates.
7. a kind of ternary high-voltage lithium ion batteries, it is characterised in that: including any one of anode, cathode and claim 1-6
The electrolyte.
8. ternary high-voltage lithium ion batteries according to claim 7, it is characterised in that: the active material of the anode
For ternary nickle cobalt lithium manganate LiNixCoyMn1-x-y, wherein 0 < x <, 1,0 < y < 1.
9. ternary high-voltage lithium ion batteries according to claim 7, it is characterised in that: the active material of the anode
For at least one of NCM523, NCM622, NCM712 or NCM811.
10. ternary high-voltage lithium ion batteries according to claim 7, it is characterised in that: the active material of the cathode
Material is at least one of graphite or Si-C composite material.
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| CN111769328A (en) * | 2020-07-10 | 2020-10-13 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device and electronic device |
| CN112713309A (en) * | 2021-01-11 | 2021-04-27 | 天津市捷威动力工业有限公司 | Safety lithium ion battery electrolyte and lithium ion battery thereof |
| CN113451646A (en) * | 2020-03-25 | 2021-09-28 | 深圳格林德能源集团有限公司 | Ternary lithium manganese oxide doped secondary battery electrolyte |
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| JP2015156372A (en) * | 2014-01-15 | 2015-08-27 | 旭化成株式会社 | Electrolyte for nonaqueous power storage device and lithium ion secondary battery |
| CN105655640A (en) * | 2016-03-28 | 2016-06-08 | 宁德新能源科技有限公司 | Non-aqueous electrolyte and lithium-ion battery containing same |
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| JP2015156372A (en) * | 2014-01-15 | 2015-08-27 | 旭化成株式会社 | Electrolyte for nonaqueous power storage device and lithium ion secondary battery |
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| CN113451646A (en) * | 2020-03-25 | 2021-09-28 | 深圳格林德能源集团有限公司 | Ternary lithium manganese oxide doped secondary battery electrolyte |
| CN111769328A (en) * | 2020-07-10 | 2020-10-13 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device and electronic device |
| CN111769328B (en) * | 2020-07-10 | 2022-02-08 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device and electronic device |
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