CN117293397A - Electrolyte for lithium ion battery with improved low-temperature performance and ultra-fast lithium ion battery - Google Patents
Electrolyte for lithium ion battery with improved low-temperature performance and ultra-fast lithium ion battery Download PDFInfo
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- CN117293397A CN117293397A CN202311194920.7A CN202311194920A CN117293397A CN 117293397 A CN117293397 A CN 117293397A CN 202311194920 A CN202311194920 A CN 202311194920A CN 117293397 A CN117293397 A CN 117293397A
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- Prior art keywords
- electrolyte
- carbonate
- lithium
- ion battery
- lithium ion
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 26
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 24
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 10
- 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 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound 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 9
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 6
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- NEILRVQRJBVMSK-UHFFFAOYSA-N B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C NEILRVQRJBVMSK-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 4
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 2
- VRZVZOAFGFXPKI-UHFFFAOYSA-N 4-fluoro-1,3,2-dioxathiolane 2,2-dioxide Chemical compound FC1COS(=O)(=O)O1 VRZVZOAFGFXPKI-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- BAASCWKOCWNWKR-UHFFFAOYSA-N 1,3,2-dioxathiole 2-oxide Chemical compound O=S1OC=CO1 BAASCWKOCWNWKR-UHFFFAOYSA-N 0.000 claims 1
- 150000002596 lactones Chemical class 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 17
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 44
- 238000000034 method Methods 0.000 description 22
- 230000000694 effects Effects 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical group OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 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 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QABDZOZJWHITAN-UHFFFAOYSA-F [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O Chemical compound [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O QABDZOZJWHITAN-UHFFFAOYSA-F 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XPVRBHCXMWRJEY-UHFFFAOYSA-N difluoro(imino)-$l^{4}-sulfane Chemical compound FS(F)=N XPVRBHCXMWRJEY-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses an electrolyte for a lithium ion battery with improved low-temperature performance and an ultra-fast lithium ion battery, wherein the electrolyte for the lithium ion battery comprises lithium salt, a solvent and an additive; the lithium salt comprises at least one of lithium hexafluorophosphate and lithium difluorosulfonimide; the solvent is a combination of carbonate and carboxylate. The 5C quick charge performance of the lithium ion battery is improved, lithium is basically not separated out from a battery disassembly interface, and the discharge capacity retention rate of the battery at low temperature is improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to electrolyte for a lithium ion battery with improved low-temperature performance and an ultra-fast lithium ion battery.
Background
As new energy automobiles have increased in market share, new demands are also being placed on various aspects of performance of electric automobiles in the market. The ideal new energy automobile has the characteristics of high mileage, stable endurance, good high and low temperature tolerance, high charging speed, high safety, attractive price and the like.
In recent years, the rapid development of China is realized, and a plurality of highways are crisscrossed, so that a plurality of convenience is brought to the communication among various cities in China; in order to meet the needs of the public, new energy automobiles propose a series of strategies, such as high specific energy batteries with improved surface density and energy storage batteries with circulation optimization, which all have a common defect, namely, low charging speed;
in order to solve the problem, the ternary lithium ion battery with better dynamics is a main research object in the last few years due to high energy density, good multiplying power performance and excellent low-temperature performance, but the market share is slightly smaller due to high cost, poor structural stability of the positive electrode and short circulating endurance time for the lithium iron phosphate battery; in recent years, the market is not broken to develop new fields of lithium iron phosphate batteries, and under the condition of meeting the requirements of high endurance, good safety and the like of the market, the low-temperature charge and discharge capability of the lithium iron phosphate batteries and the ultra-fast battery charge technology are required to be further improved.
CN 113851725A discloses a lithium ion fast-charging electrolyte, which comprises a solvent, lithium salt and an additive, wherein the solvent is a combination of methyl formate and carbonic ester, the additive is allyloxy trimethyl silicon, and a lithium ion battery using the electrolyte forms a stable SEI film on a negative electrode, so that the migration steric hindrance of lithium ions is reduced, and the charging rate and the cycle performance of the battery are obviously improved; however, the electrolyte lithium salt used in the scheme has poor stability, which is not beneficial to the long-term safety of the battery.
Disclosure of Invention
The invention aims to provide electrolyte for a lithium ion battery, which is compatible with low temperature and ultra-fast charging.
The electrolyte for the lithium ion battery provided by the invention comprises lithium salt, a solvent and an additive; the lithium salt comprises at least one of lithium hexafluorophosphate and lithium difluorosulfonimide; the solvent is a combination of carbonate and carboxylate.
Another object of the present invention is to provide a lithium ion battery that allows for both low temperature and ultra-fast charging.
The lithium ion battery provided by the invention comprises a negative electrode, a positive electrode, a diaphragm and electrolyte, wherein the diaphragm separates the positive electrode from the negative electrode, and the electrolyte is the electrolyte for the lithium ion battery.
The electrolyte for the lithium ion battery has improved conductivity. The 5C quick charge performance of the lithium ion battery is improved, lithium is basically not separated out from a battery disassembly interface, and the discharge capacity retention rate of the battery at low temperature is improved. .
Detailed Description
An aspect of the present invention provides an electrolyte for a lithium ion battery, which includes a lithium salt, a solvent, and an additive; the lithium salt comprises at least one of lithium hexafluorophosphate and lithium difluorosulfonimide; the solvent is a combination of carbonate and carboxylate.
The low-temperature charge and discharge and ultra-fast charge performance have strong requirements on diffusion of lithium ions in an electrode and electrolyte system and charge transfer in an electrode-electrolyte interface film, and meanwhile, the lithium ion migration capability of the electrolyte at low temperature is required to be considered.
Lithium hexafluorophosphate is an electrolyte with good comprehensive properties, wherein the comprehensive properties comprise high ionic conductivity, good thermal stability, good safety performance, low cost, good high-voltage resistance and wide electrochemical stability window in an organic system. The lithium bis (fluorosulfonyl) imide has the advantages of high conductivity, excellent low-temperature performance, good hydrolytic stability, small film-forming impedance and good high-temperature thermal stability, and can effectively improve high-temperature circulation and rate capability. Compared with other lithium salts, the difluoro sulfimide is favorable for improving the ionic conductivity of the electrolyte, improving the thermal stability, and simultaneously, the inhibition effect of hydrofluoric acid (HF) is obvious, and the leaching amount of Fe is reduced.
Lithium salt is the main supply of electrolyte ionic conductivity, lower lithium salt content is insufficient to promote quick charge transfer of lithium ions, and meanwhile, the increase of lithium salt content can increase the viscosity of the electrolyte and reduce the transmission performance of lithium ions.
In one embodiment the lithium salt is present in the electrolyte in a mass ratio of 3wt% to 17wt%.
In one embodiment, the lithium salt is present in the electrolyte at a mass ratio of 13wt%.
In one embodiment, the lithium salt is two of lithium hexafluorophosphate and lithium difluorosulfonimide, and the mass ratio of the lithium hexafluorophosphate to the lithium difluorosulfonimide is (4-10): 3-9.
The carbonic ester has good stability and less side reaction with the cathode; the carboxylic ester has low solidifying point, high boiling point and wide temperature range, and is friendly to both high and low temperature; meanwhile, the viscosity of the carboxylate is lower, which is favorable for the rapid ion transmission and low-temperature charge and discharge performance of the electrolyte.
In one embodiment, the carbonates include cyclic carbonates and linear carbonates. Compared with the prior art, the stability of the solvent in the electrolyte is higher, and the upper limit use temperature is higher.
In one embodiment, the cyclic carbonate is selected from at least one of ethylene carbonate and propylene carbonate.
In one embodiment, the linear carbonate is selected from at least one of methyl ethyl carbonate, diethyl carbonate, fluoroethylene carbonate, dimethyl carbonate, methyl propyl carbonate, and dipropyl carbonate.
In one embodiment, the carboxylic acid ester is selected from at least one of methyl acetate, propyl acetate, ethyl acetate, and ethyl propionate.
In one embodiment, the solvent is present in the electrolyte at a mass ratio of 80wt% to 92.99wt%.
In one embodiment, the mass ratio of the cyclic carbonate, the linear carbonate, and the carboxylate is 3:4:3
The additive is used for meeting the low-temperature ultra-fast charge requirement, and the initial negative electrode film forming of the battery cell is optimized by adopting a mode of matching and combining various additives, so that SEI with high stability and high charge transfer is formed.
In one embodiment, the additive is selected from at least one of vinylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate, ethylene sulfate, ethylene sulfite, fluoroethylene sulfate, 4, 5-difluoroethylene sulfate, 1, 3-propane sultone, 1, 3-propenoic acid sultone, 1, 4-butane sultone, 1, 4-butene sultone, methylene methane disulfonate, hexamethyldisilazane, tris (trimethylsilane) borate, tripropylester phosphate, tris (trimethylsilane) phosphite, and tris (trimethylsilane) phosphate. In one embodiment, the additive is present in an amount of 0.1wt% to 5wt%.
In one embodiment, the additive is 0.5wt% to 3wt% ethylene carbonate, 0.1wt% to 3wt% fluoroethylene carbonate, and 0.1wt% to 3.0wt% of at least one selected from the group consisting of ethylene sulfate, methylene methane disulfonate, tris (trimethylsilane) borate, tris (trimethylsilane) phosphite, and tris (trimethylsilane) phosphate.
The combination of various additives is favorable for forming a low-impedance high-passivation SEI film, inhibiting the reduction reaction of solvents and the like on the surface of a negative electrode, effectively improving the transmission capacity of lithium ions in a battery system, reducing the charging time and greatly improving the transmission speed of the battery at low temperature.
Another aspect of the present invention provides a lithium ion battery that allows for both low temperature and ultra-fast charging.
In one embodiment, the lithium ion battery comprises a negative electrode, a positive electrode, a diaphragm and an electrolyte, wherein the diaphragm separates the positive electrode from the negative electrode, and the electrolyte is the electrolyte for the lithium ion battery.
In one embodiment, the negative electrode includes a negative electrode current collector including but not limited to copper foil, carbon coated copper foil, and a negative electrode material including but not limited to graphite, hard carbon; the positive electrode comprises a positive electrode current collector and a positive electrode material, wherein the positive electrode current collector comprises aluminum foil and carbon-coated aluminum foil but is not limited to the positive electrode current collector, and the positive electrode material comprises lithium iron phosphate and nickel cobalt manganese ternary material but is not limited to the positive electrode current collector; the separator includes, but is not limited to, polyethylene separators and polypropylene separators.
In one embodiment, the upper charge voltage of the lithium ion battery is no more than 3.75V.
The electrolyte for the lithium ion battery adopts high-conductivity lithium salt, so that the conductivity of lithium ions is improved; the carboxylate solvent with low viscosity and wide temperature range is adopted, so that the lithium solvation energy barrier is reduced, the migration rate of lithium is improved, the low viscosity is favorable for the transmission of lithium ions at low temperature, and the lithium ion conductivity is improved. In addition, the adoption of various additives optimizes the electrode-interface solid electrolyte membrane (SEI), has low impedance and is beneficial to the deintercalation of a lithium desolvation structure.
Examples
Example 1
(1) Preparation of electrolyte
In a glove box or a drying room, mixing ethylene carbonate, methyl ethyl carbonate and methyl acetate according to a mass ratio of 3:4:3, adding 13% lithium hexafluorophosphate, 2% vinylene carbonate, 1% fluoroethylene carbonate and 0.5% methylene methane disulfonate, and uniformly mixing to prepare an electrolyte.
(2) Preparation of positive plate
The anode material LiFePO 4 Mixing PVDF binder, acetylene black as a conductive agent according to a mass ratio of 94:3:3, adding N-methyl pyrrolidone solvent to the system to form a uniform transparent state, stirring by a vacuum stirrer to obtain positive electrode slurry, uniformly coating the positive electrode slurry on aluminum foil (with a thickness of 12 mu m) as a current collector, airing at room temperature, transferring to a 120 ℃ oven for drying for 1h, and cold pressing (with a compaction density of 2.5 g/cm) 3 ) And cutting to obtain the positive plate.
(3) Preparation of negative electrode sheet
Mixing negative electrode material graphite, thickener sodium carboxymethyl cellulose solution and binder styrene-butadiene rubber emulsion according to a mass ratio of 96:2:2, adding deionized water solvent, stirring by a vacuum stirrer to prepare negative electrode slurry, uniformly coating the negative electrode slurry on a current collector copper foil (with a thickness of 8 mu m), airing at room temperature, transferring to a 120 ℃ oven for drying for 1h, and cold pressing (compaction density is 1.6 g/cm) 3 ) And cutting to obtain the negative plate.
(4) Preparation of lithium ion batteries
And winding the positive plate, the negative plate and the polypropylene isolating film, wrapping an aluminum plastic film, baking to remove water, injecting the electrolyte, sealing, standing, hot-cold pressing, forming, clamping, capacity-dividing and the like to prepare the soft-package lithium ion battery.
Example 2
The remainder of the procedure was as in example 1, except that the solvent in example 1 was changed to ethylene carbonate, methylethyl carbonate, ethyl acetate=3:4:3.
Example 3
The remainder of the procedure was as in example 1, except that the solvent in example 1 was changed to ethylene carbonate, methylethyl carbonate, ethyl propionate=3:4:3.
Example 4
The remaining procedure was as in example 1, except that the lithium salt in example 3 was changed to lithium hexafluorophosphate: lithium bis-fluorosulfonyl imide=10:3.
Example 5
The remaining procedure was as in example 1, except that the lithium salt in example 3 was changed to lithium hexafluorophosphate: lithium bis-fluorosulfonyl imide=7:6.
Example 6
The remaining procedure was as in example 1, except that the lithium salt in example 3 was changed to lithium hexafluorophosphate: lithium bis-fluorosulfonyl imide=4:9.
Example 7
The procedure was as in example 1 except that the lithium salt in example 3 was changed to 13% lithium bis-fluorosulfonyl imide.
Example 8
0.5% tetrafluoroboric acid was added to example 5, and the rest of the procedure was the same as in example 1.
Example 9
To example 5, 0.5% lithium difluorophosphate was added, and the remaining steps were identical to example 1.
Example 10
To example 5 was added 0.5% lithium difluorooxalato borate, the remaining steps remaining in accordance with example 1.
Example 11
The procedure of example 5 was followed except that methylene methane disulfonate was replaced with vinyl sulfate.
Example 12
The procedure is as in example 1 except that methylene methane disulfonate in example 5 is replaced with tris (trimethylsilane) borate.
Example 13
The methylene methane disulfonate in example 5 was replaced with tris (trimethylsilane) phosphite and the remaining procedure was consistent with example 1.
Example 14
The procedure is as in example 1 except that methylene methane disulfonate in example 5 is replaced with tris (trimethylsilane) phosphate.
Comparative example 1
The procedure was as in example 1 except that the dissolution in example 1 was changed to ethylene carbonate, methylethyl carbonate=4:6.
Comparative example 2
The procedure remains as in example 1 except that the solvent in example 1 is changed to ethylene carbonate, methylethyl carbonate, dimethyl carbonate = 3:4:3.
Comparative example 3
The remainder of the procedure was as in example 1 except that the solvent in example 1 was changed to ethylene carbonate, methylethyl carbonate, dimethyl carbonate = 2:5:3.
Comparative example 4
The remainder of the procedure was as in example 1 except that the solvent in example 1 was changed to ethylene carbonate, methylethyl carbonate, diethyl carbonate=3:4:3.
Comparative example 5
The procedure is as in example 1 except that the lithium salt of comparative example 2 is changed to lithium hexafluorophosphate: lithium bis-fluorosulfonyl imide=7:6.
Comparative example 6
To comparative example 5 was added 0.5% lithium tetrafluoroborate, and the rest of the procedure was the same as in example 1.
Comparative example 7
To comparative example 5 was added 0.5% lithium tetrafluorophosphate, and the remaining steps were consistent with example 1.
Comparative example 8
To comparative example 5 was added 0.5% lithium difluorooxalato borate, the remaining steps remaining in accordance with example 1.
Comparative example 9
The procedure of comparative example 5 was followed except that methylene methane disulfonate was replaced with vinyl sulfate.
Comparative example 10
The methylene methane disulfonate in comparative example 5 was replaced with tris (trimethylsilane) borate, and the remaining procedure was consistent with example 1.
Comparative example 11
The methylene methane disulfonate in comparative example 5 was replaced with tris (trimethylsilane) phosphite and the remaining procedure was in accordance with example 1.
Comparative example 12
The remaining procedure was as in example 1 except that methylene methane disulfonate in comparative example 5 was replaced with tris (trimethylsilane) phosphate.
The performance of lithium ion batteries assembled using the electrolytes prepared in examples 1 to 14 and comparative examples 1 to 12 was tested as follows:
(1) Conductivity test of electrolyte
The electrolytes of examples 1 to 14 and comparative examples 1 to 12 were put in a constant temperature water bath at 25℃for 30 minutes, and then the conductivities were measured with a conductivity meter.
(2) Low temperature performance test of lithium ion battery
The lithium ion batteries of examples 1 to 14 and comparative examples 1 to 12 were discharged to 2.0V at 1C, then charged to 3.75V at a constant current of 1C, charged to a cutoff current of 0.05C at a constant voltage, and charged to a charge capacity of C1 at 25 ℃; then, the furnace temperature was adjusted to-20℃and discharged to 2.0V with a constant current of 1C, and the discharge capacity was recorded as C2. The discharge capacity to charge capacity ratio (C2/C1) is the discharge capacity retention rate at low temperature of-20 ℃.
(3) 5C fast lithium-charging test
The cells of examples 1-14 and comparative examples 1-12 were discharged to 2.0V at 25C, then charged to 3.75V at 5C constant current, charged to 3.75V at 1C constant current after 10 cycles of charging and discharging, charged to 0.05C at constant voltage, and then brought into a disassembly room to see the negative electrode interface lithium evolution condition.
(4) 25 ℃ cycle test
The lithium ion batteries of examples 1 to 14 and comparative examples 1 to 12 were subjected to a cycle test after discharging at 1C to 2.0V at 25 ℃. The test process is that 1C constant current is charged to 3.75V, constant voltage is charged to cut-off current of 0.05C, then 1C constant current is discharged to 2.0V, and the charge/discharge is circulated, so that the capacity retention rate of the lithium ion battery at 25 ℃ for 1000 times in 1C/1C circulation is calculated.
TABLE 1 Performance test results
In table 1, the comparative examples and comparative examples find that the introduction of the carboxylate solvent in the examples improves the conductivity of the electrolyte, improves the 5C fast charge performance of the lithium ion battery, does not substantially precipitate lithium at the battery disassembly interface, improves the discharge capacity retention rate of the battery at low temperature, and indicates that the carboxylate is favorable for both fast charge and low temperature performance.
The effect of the different carboxylic acid esters of comparative examples 1-3 is that methyl acetate ≡methyl propionate > ethyl acetate.
In comparative examples 3 to 7, as the content of lithium difluorosulfimide increases, the conductivity increases, the effect of 5C fast charge improves obviously, and the dynamic performance of the battery becomes better, because lithium difluorosulfimide not only generates a lower SEI film impedance, but also has fewer LiF components, can inhibit corrosion of HF on a negative electrode SEI film, and reduces the incidence rate of side reactions; similarly, comparative example 5 and comparative example 2 can be seen to be consistent in regularity.
Comparing example 8 with example 5, lithium tetrafluoroborate has undesirable performance because the boron-containing reactant formed by the formation of borate ions in the negative electrode film is unfavorable for the rapid transmission of lithium ions, increases the risk of lithium precipitation on the surface of the negative electrode, and deteriorates the performance; meanwhile, comparative example 6 and comparative example 5 have the same tendency of lithium tetrafluoroborate to deteriorate performance.
In comparison between example 9 and example 5, lithium difluorophosphate forms an inorganic SEI film more easily, and the components are more LiF, so that the impedance is larger, the lithium precipitation risk exists, but the cycle performance is not greatly different; at the same time, comparative example 7 and comparative example 5 were comparable in performance effect.
Comparative example 10 and example 5, lithium difluorooxalato borate forms an inorganic SEI film with components of Li 2 CO 3 And LiF is a majority, there is a risk of gas production, and circulation is slightly deteriorated; at the same time, comparative example 8 and comparative example 5 were comparable in performance.
Comparing example 11 with example 5, vinyl sulfate substituted for methylene methane disulfonate, although it is a co-sulfur additive, vinyl sulfate performs poorly, probably due to the more lithium ions that the additive consumes in forming the SEI; meanwhile, the effect is not very good in comparison with comparative example 9 and comparative example 5.
Comparing examples 12-14 with example 5, the trimethylsilane additive has low film forming resistance, equivalent full-charge interface, and equivalent performance improvement effect on low-temperature discharge and 5C fast charge; meanwhile, comparative examples 10 to 12 and comparative example 5 were comparable in effect.
In comparative examples 1 to 3, the content of the cyclic ethylene carbonate affects the viscosity and the conductivity of the electrolyte, the content thereof decreases, the conductivity decreases, and the low temperature and 5C quick charge properties are not completely positively correlated;
in comparative examples 2-4, the different carbonate solvent components have a slight effect on the performance of the cells; diethyl carbonate has far less performance than dimethyl carbonate at high magnification/low temperature because of higher viscosity and weaker ion conducting capacity of the electrolyte.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical solution of the present invention in any way. Any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention fall within the protection scope of the present invention.
Claims (11)
1. An electrolyte for a lithium ion battery comprises lithium salt, a solvent and an additive;
wherein the lithium salt comprises at least one of lithium hexafluorophosphate and lithium bis-fluorosulfonyl imide;
the solvent is a combination of carbonate and carboxylate.
2. The electrolyte of claim 1 wherein the carbonate comprises a cyclic carbonate and a linear carbonate.
3. The electrolyte of claim 2, wherein the cyclic carbonate is selected from at least one of ethylene carbonate and propylene carbonate.
4. The electrolyte according to claim 3, wherein the linear carbonate is at least one selected from the group consisting of methyl ethyl carbonate, diethyl carbonate, fluoroethylene carbonate, dimethyl carbonate, methylpropyl carbonate and dipropyl carbonate.
5. The electrolyte of claim 1, wherein the carboxylic acid ester is selected from at least one of methyl acetate, propyl acetate, ethyl acetate, and ethyl propionate.
6. The electrolyte of claim 4 wherein the mass ratio of the cyclic carbonate, the linear carbonate, and the carboxylate is 3:4:3.
7. The electrolyte according to claim 1, wherein the lithium salt accounts for 3-17 wt% of the electrolyte.
8. The electrolyte of claim 1, wherein the solvent is present in the electrolyte at a mass ratio of 80wt% to 92.99wt%.
9. The electrolyte according to claim 1, wherein the mass ratio of the additive in the electrolyte is 0.1wt% to 5wt%.
10. The electrolyte of claim 1 wherein the additive is selected from at least one of vinylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate, ethylene sulfate, vinylene sulfite, fluoroethylene sulfate, 4, 5-difluoroethylene sulfate, 1, 3-propane sultone, 1, 3-propenesulfonic acid lactone, 1, 4-butane sultone, 1, 4-butene sultone, methylene methane disulfonate, hexamethyldisilazane, tris (trimethylsilane) borate, tripropylenyl phosphate, tris (trimethylsilane) phosphite, and tris (trimethylsilane) phosphate.
11. A lithium ion battery comprising a negative electrode, a positive electrode, a separator, and an electrolyte, wherein the separator separates the positive electrode and the negative electrode, and the electrolyte is the electrolyte for a lithium ion battery according to any one of claims 1 to 10.
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