CN111916824A - 一种锂离子电池用非水电解液及使用该非水电解液的锂离子电池 - Google Patents
一种锂离子电池用非水电解液及使用该非水电解液的锂离子电池 Download PDFInfo
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- CN111916824A CN111916824A CN202010615105.3A CN202010615105A CN111916824A CN 111916824 A CN111916824 A CN 111916824A CN 202010615105 A CN202010615105 A CN 202010615105A CN 111916824 A CN111916824 A CN 111916824A
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- Prior art keywords
- lithium ion
- electrolytic solution
- nonaqueous electrolytic
- ion battery
- equal
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Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 239000011255 nonaqueous electrolyte Substances 0.000 title abstract description 12
- -1 nitrile compound Chemical class 0.000 claims abstract description 79
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 24
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 claims abstract description 15
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 13
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 13
- LNLFLMCWDHZINJ-UHFFFAOYSA-N hexane-1,3,6-tricarbonitrile Chemical compound N#CCCCC(C#N)CCC#N LNLFLMCWDHZINJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical group 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000002905 metal composite material Substances 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- 239000011366 tin-based material Substances 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 125000006730 (C2-C5) alkynyl group Chemical group 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 10
- 239000012528 membrane Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 14
- 230000008859 change Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
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- 238000000034 method Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 230000009471 action Effects 0.000 description 3
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- 238000007710 freezing Methods 0.000 description 3
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 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 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910052794 bromium Inorganic materials 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical group 0.000 description 1
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- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- QVXQYMZVJNYDNG-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane Chemical compound [Li+].FC(F)(F)S(=O)(=O)[C-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F QVXQYMZVJNYDNG-UHFFFAOYSA-N 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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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
- H01M10/0569—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
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Abstract
本发明提供了一种锂离子电池用非水电解液及使用该非水电解液的锂离子电池。所述非水电解液包括(a)锂盐、(b)非水有机溶剂、(c)至少一种式1所示的化合物;
Description
技术领域
本发明属于锂离子电池用电解液技术领域,具体涉及一种锂离子电池用非水电解液及使用该非水电解液的锂离子电池。
背景技术
锂离子电池自从商业化以来,由于它的轻便、比能量高、无记忆效应、循环性能好,被广泛用于数码、储能、动力、军用航天和通讯设备等领域。随着锂离子电池的广泛应用,消费者对锂离子电池的能量密度、循环寿命、高温性能、安全性等性能提出了更高的要求。
多数锂离子电池产品存在高温性能和低温性能不能兼顾的问题,为此通常在电解液中加入添加剂进行锂离子电池高低温性能的改善,但是,一般的添加剂具有较优的高温作用时,阻抗则较大,而低阻抗添加剂的高温效果又欠缺,故需要通过添加剂的组合优化,获得较优的高低温性能。
发明内容
为了改善现有技术的不足,本发明提供一种锂离子电池用非水电解液及使用该非水电解液的锂离子电池。所述非水电解液包括(a)锂盐、(b)非水有机溶剂、(c)至少一种式1所示的化合物;其中,所述非水电解液还包括下述组分(d)和(e)中的至少一种:(d)腈类化合物,和(e)硫酸乙烯酯。通过它们之间的协同作用,可以降低锂离子电池的阻抗,同时使得所述锂离子电池具有较优的高温存储性能、循环性能和低温充放电性能。
本发明通过如下技术方案实现的:
一种非水电解液,所述非水电解液包括(a)锂盐、(b)非水有机溶剂、(c)至少一种式1所示的化合物;其中,所述非水电解液还包括下述组分(d)和(e)中的至少一种:
(d)包括1,3,6-己烷三腈、甘油三腈、3-甲氧基丙腈中的至少一种的腈类化合物,和
(e)硫酸乙烯酯;
其中,R1、R2相同或不同,彼此独立地选自氢、卤素、卤素取代或未取代的C1-C6的烷基、卤素取代或未取代的C2-C5的烯基、或卤素取代或未取代的C2-C5的炔基。
根据本发明,R1、R2相同或不同,彼此独立地选自氢、卤素、卤素取代或未取代的C1-C5的烷基。
根据本发明,R1、R2相同或不同,彼此独立地选自氢、氟、甲基、乙基或丙基。
根据本发明,所述式1所示的化合物选自如下化合物A1~A5中的至少一种:
根据本发明,所述腈类化合物选自1,3,6-己烷三腈、甘油三腈、3-甲氧基丙腈中的至少一种,所述腈类化合物的选择可以使得本发明的非水电解液具有更好的高温存储性能,而且具有更好的循环性能。
根据本发明,所述式1所示的化合物的含量占所述非水电解液总质量的0.1-10wt%,例如为0.1wt%、0.2wt%、0.5wt%、1.0wt%、1.5wt%、2wt%、2.5wt%、3wt%、3.5wt%、4wt%、4.5wt%、5wt%、5.5wt%、6wt%、6.5wt%,7wt%、7.5wt%、8wt%、8.5wt%、9wt%、9.5wt%、10wt%。
根据本发明,所述腈类化合物的含量占所述非水电解液总质量的0-8wt%,优选为0.1-8wt%,例如为0.1wt%、0.2wt%、0.5wt%、1.0wt%、1.5wt%、2wt%、2.5wt%、3wt%、3.5wt%、4wt%、4.5wt%、5wt%、5.5wt%、6wt%、6.5wt%,7wt%、7.5wt%、8wt%。
根据本发明,所述硫酸乙烯酯的含量占所述非水电解液总质量的0-2wt%,优选为0.1-2wt%,例如为0.1wt%、0.2wt%、0.5wt%、1.0wt%、1.5wt%、2wt%。
根据本发明,所述锂盐选自六氟磷酸锂、二氟磷酸锂、二氟草酸硼酸锂、双氟磺酰亚胺锂、双三氟甲基磺酰亚胺锂、二氟双草酸磷酸锂、四氟硼酸锂、双草酸硼酸锂、六氟锑酸锂、六氟砷酸锂、二(三氟甲基磺酰)亚胺锂、二(五氟乙基磺酰)亚胺锂、三(三氟甲基磺酰)甲基锂或二(三氟甲基磺酰)亚胺锂中的一种或两种以上。
根据本发明,所述锂盐的含量占所述非水电解液总质量的12-18wt%,例如为12wt%、12.5wt%、13wt%、13.5wt%、14wt%、14.5wt%、15wt%、15.5wt%、16wt%、16.5wt%、17wt%、17.5wt%、18wt%。
根据本发明,所述非水有机溶剂选自碳酸酯和/或羧酸酯。
示例性地,所述碳酸酯选自氟代或未取代的下述溶剂中的一种或几种:碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯。
示例性地,所述羧酸酯选自氟代或未取代的下述溶剂中的一种或几种:乙酸丙酯、乙酸正丁酯、乙酸异丁酯、乙酸正戊酯、乙酸异戊酯、丙酸乙酯、丙酸正丙酯、丁酸甲酯、正丁酸乙酯。
本发明还提供上述非水电解液的制备方法,所述方法包括如下步骤:
将(a)锂盐、(b)非水有机溶剂、(c)至少一种式1所示的化合物、以及(d)包括1,3,6-己烷三腈、甘油三腈、3-甲氧基丙腈中的至少一种的腈类化合物混合;或者,
将(a)锂盐、(b)非水有机溶剂、(c)至少一种式1所示的化合物、以及(e)硫酸乙烯酯混合;或者,
将(a)锂盐、(b)非水有机溶剂、(c)至少一种式1所示的化合物、以及(d)包括1,3,6-己烷三腈、甘油三腈、3-甲氧基丙腈中的至少一种的腈类化合物和(e)硫酸乙烯酯混合;
制备得到所述非水电解液。
示例性地,所述方法包括如下步骤:
将(b)非水有机溶剂、(c)至少一种式1所示的化合物、(d)包括1,3,6-己烷三腈、甘油三腈、3-甲氧基丙腈中的至少一种的腈类化合物均匀混合,检测水分,水分合格后,然后在-10℃左右的低温下冷冻2-5小时,再快速加入(a)锂盐,水分、游离酸检测合格后,制备得到所述非水电解液。
示例性地,所述方法包括如下步骤:
将(b)非水有机溶剂、(c)至少一种式1所示的化合物、(e)硫酸乙烯酯均匀混合,检测水分,水分合格后,然后在-10℃左右的低温下冷冻2-5小时,再快速加入(a)锂盐,水分、游离酸检测合格后,制备得到所述非水电解液。
示例性地,所述方法包括如下步骤:
将(b)非水有机溶剂、(c)至少一种式1所示的化合物、(d)包括1,3,6-己烷三腈、甘油三腈、3-甲氧基丙腈中的至少一种的腈类化合物以及(e)硫酸乙烯酯均匀混合,检测水分,水分合格后,然后在-10℃左右的低温下冷冻2-5小时,再快速加入(a)锂盐,水分、游离酸检测合格后,制备得到所述非水电解液。
本发明还提供一种锂离子电池,所述锂离子电池包括上述的非水电解液。
根据本发明,所述锂离子电池还包括含有正极活性材料的正极片、含有负极活性材料的负极片和锂离子隔膜。
根据本发明,所述的正极活性材料选自层状锂过渡金属复合氧化物、锰酸锂、钴酸锂混三元材料中的一种或几种;所述的层状锂过渡金属复合氧化物的化学式为Li1+ xNiyCozM(1-y-z)Q2,其中,-0.1≤x≤1,0≤y≤1,0≤z≤1,且0≤y+z≤1;其中,M为Mg、Zn、Ga、Ba、Al、Fe、Cr、Sn、V、Mn、Sc、Ti、Nb、Mo、Zr中的一种或几种;Q为O、F、P、S中的一种或几种。
根据本发明,所述的负极活性材料选自碳素材料、硅基材料、锡基材料或它们对应的合金材料中的一种或几种。
根据本发明,所述的锂离子电池的工作电压范围为4.25V及以上电压。
根据本发明,所述的锂离子电池在5℃、按照0.3C/0.5C的充放电制度下循环300圈后电池的厚度变化率≤7.0%(例如≤6.9%);容量保持率≥98%(例如≥98.1%)。
根据本发明,所述的锂离子电池在25℃、按照1C充到4.2V,再0.7C充到4.4V,再4.4V恒压充到截止电流0.05C,再以0.5C放电到3V的充放电制度下循环500圈后电池的厚度变化率≤9%(例如≤8.5%);容量保持率≥82%(例如≥82.8%)。
根据本发明,所述的锂离子电池在45℃、按照0.7C恒流充到4.4V,在4.4V恒压充到截止电流0.05C,再以0.5C放电的充放电制度下循环400圈后电池的厚度变化率≤9.5%(例如≤9.1%);容量保持率≥79%(例如≥79.6%)。
根据本发明,所述的锂离子电池在60℃、按照0.7C充到4.4V,再4.4V恒压充到截止电流0.05C,然后用0.5C恒流放电至3.0V,然后0.7C充到4.4V,再4.4V恒压充到截止电流0.05C,搁置14天后电池的厚度变化率≤9.0%(例如≤8.9%)。
术语与解释:
术语“卤素”指F、Cl、Br和I。
术语“C1-C6的烷基”应理解为优选表示具有1~6个碳原子的直链或支链饱和一价烃基,优选为C1-C5的烷基。“C1-C6的烷基”应理解为优选表示具有1、2、3、4、5或6个碳原子的直链或支链饱和一价烃基。所述烷基是例如甲基、乙基、丙基、丁基、戊基、己基、异丙基、异丁基、仲丁基、叔丁基、异戊基、2-甲基丁基、1-甲基丁基、1-乙基丙基、1,2-二甲基丙基、新戊基、1,1-二甲基丙基、4-甲基戊基、3-甲基戊基、2-甲基戊基、1-甲基戊基、2-乙基丁基、1-乙基丁基、3,3-二甲基丁基、2,2-二甲基丁基、1,1-二甲基丁基、2,3-二甲基丁基、1,3-二甲基丁基或1,2-二甲基丁基等或它们的异构体。特别地,所述基团例如甲基、乙基、丙基、丁基、异丙基、异丁基、仲丁基、叔丁基,更特别地,所述基团具有1、2或3个碳原子(“C1-3的烷基”),例如甲基、乙基、正丙基或异丙基。
术语“C2-5的烯基”应理解为优选表示直链或支链的一价烃基,其包含一个或多个双键并且具有2、3、4或5个碳原子,特别是2或3个碳原子(“C2-3的烯基”),应理解,在所述烯基包含多于一个双键的情况下,所述双键可相互分离或者共轭。所述烯基是例如乙烯基、烯丙基、(E)-2-甲基乙烯基、(Z)-2-甲基乙烯基、(E)-丁-2-烯基、(Z)-丁-2-烯基、(E)-丁-1-烯基、(Z)-丁-1-烯基、戊-4-烯基、(E)-戊-3-烯基、(Z)-戊-3-烯基、(E)-戊-2-烯基、(Z)-戊-2-烯基、(E)-戊-1-烯基、(Z)-戊-1-烯基、己-5-烯基、(E)-己-4-烯基、(Z)-己-4-烯基、(E)-己-3-烯基、(Z)-己-3-烯基、(E)-己-2-烯基、(Z)-己-2-烯基、(E)-己-1-烯基、(Z)-己-1-烯基、异丙烯基、2-甲基丙-2-烯基、1-甲基丙-2-烯基、2-甲基丙-1-烯基、(E)-1-甲基丙-1-烯基、(Z)-1-甲基丙-1-烯基、3-甲基丁-3-烯基、2-甲基丁-3-烯基、1-甲基丁-3-烯基、3-甲基丁-2-烯基、(E)-2-甲基丁-2-烯基、(Z)-2-甲基丁-2-烯基、(E)-1-甲基丁-2-烯基、(Z)-1-甲基丁-2-烯基、(E)-3-甲基丁-1-烯基、(Z)-3-甲基丁-1-烯基、(E)-2-甲基丁-1-烯基、(Z)-2-甲基丁-1-烯基、(E)-1-甲基丁-1-烯基、(Z)-1-甲基丁-1-烯基、1,1-二甲基丙-2-烯基、1-乙基丙-1-烯基、1-丙基乙烯基、1-异丙基乙烯基。
术语“C2-C5的炔基”应理解为表示直链或支链的一价烃基,其包含一个或多个三键并且具有2~5个碳原子,特别是2或3个碳原子(“C2-C3的炔基”)。所述炔基是例如乙炔基、丙-1-炔基、丙-2-炔基、丁-1-炔基、丁-2-炔基、丁-3-炔基、戊-1-炔基、戊-2-炔基、戊-3-炔基、戊-4-炔基、己-1-炔基、己-2-炔基、己-3-炔基、己-4-炔基、己-5-炔基、1-甲基丙-2-炔基、2-甲基丁-3-炔基、1-甲基丁-3-炔基、1-甲基丁-2-炔基、3-甲基丁-1-炔基、1-乙基丙-2-炔基。特别地,所述炔基是乙炔基、丙-1-炔基或丙-2-炔基。
本发明的有益效果:
本发明提供了一种锂离子电池用非水电解液及使用该非水电解液的锂离子电池。本发明采用的非水电解液包括(a)锂盐、(b)非水有机溶剂、(c)至少一种式1所示的化合物;其中,所述非水电解液还包括下述组分(d)和(e)中的至少一种:(d)包括1,3,6-己烷三腈、甘油三腈、3-甲氧基丙腈中的至少一种的腈类化合物,和(e)硫酸乙烯酯。其中,(c)至少一种式1所示的化合物具有相对更低的反应电位,可以优先在正负极极片表面形成致密且阻抗降低的膜,同时(d)包括1,3,6-己烷三腈、甘油三腈、3-甲氧基丙腈中的至少一种的腈类化合物可以在式1所示的化合物形成的膜的部位通过络合作用进一步保护正极并提高膜的韧性,而(e)硫酸乙烯酯可以进一步弥补正极表面膜的致密性,同时还可以在负极形成低阻抗的SEI膜。本发明通过它们之间的协同作用,在保护正极的同时,负极也起到一定的保护作用,且膜阻抗较低,电池具有较优的高温存储性能、循环性能和低温充放电性能。
具体实施方式
下文将结合具体实施例对本发明做更进一步的详细说明。应当理解,下列实施例仅为示例性地说明和解释本发明,而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法;下述实施例中所用的试剂、材料等,如无特殊说明,均可从商业途径得到。
对比例1
(1)正极片制备
将正极活性材料4.4V钴酸锂(LCO)、粘结剂聚偏氟乙烯(PVDF)、导电剂乙炔黑按照重量比97:1.5:1.5进行混合,加入N-甲基吡咯烷酮(NMP),在真空搅拌机作用下搅拌,直至混合体系成均一流动性的正极浆料;将正极浆料均匀涂覆于厚度为12μm的铝箔上;将上述涂覆好的铝箔在5段不同温度梯度的烘箱烘烤后,再将其在120℃的烘箱干燥8h,然后经过辊压、分切得到所需的正极片。
(2)负极片制备
将负极活性材料石墨、增稠剂羧甲基纤维素钠(CMC-Na)、粘结剂丁苯橡胶、导电剂乙炔黑按照重量比97:1:1:1进行混合,加入去离子水,在真空搅拌机作用下获得负极浆料;将负极浆料均匀涂覆在厚度为8μm的铜箔上;将铜箔在室温晾干后转移至80℃烘箱干燥10h,然后经过冷压、分切得到负极片。
(3)电解液制备
在充满氩气水氧含量合格的手套箱中,将碳酸乙烯酯、碳酸丙烯酯、碳酸二乙酯、丙酸正丙酯、氟代碳酸乙烯酯,按照质量比13.5:13.5:13.5:51:8.5的比例混合均匀(溶剂和添加剂需一起进行归一化),然后往其中快速加入14.3wt%的充分干燥的六氟磷酸锂(LiPF6),溶解于有机溶剂中,搅拌均匀,经过水分和游离酸检测合格后,得到对比例1的电解液。
(4)隔离膜的制备
选用8μm厚的聚乙烯隔离膜(旭化成公司提供)。
(5)锂离子电池的制备
将上述准备的正极片、隔离膜、负极片按顺序叠放好,保证隔离膜处于正、负极片之间起到隔离的作用,然后通过卷绕得到未注液的裸电芯;将裸电芯置于外包装箔中,将上述制备好的电解液注入到干燥后的裸电芯中,经过真空封装、静置、化成、整形、分选等工序,获得所需的锂离子电池。
(6)5℃低温循环实验
测试前测试满电电芯的厚度D0,将电池置于(5±2)℃环境中,静置3小时,待电芯本体达到(5±2)℃时,电池按照0.3C充到4.4V,再4.4V恒压充到截止电流0.05C,再以0.5C放电到3V,记录初始容量Q0,当循环达到所需的次数或容量衰减率低于70%或厚度超过测试要求的厚度时,以前一次的放电容量作为电池的容量Q1,计算容量保持率(%),再把电池满电,电芯取出后,常温静置3小时,测试满电厚度D1,计算厚度变化率(%),记录结果如表2。其中用到的计算公式如下:
厚度变化率(%)=(D1-D0)/D0×100%;容量保持率(%)=Q1/Q0×100%。
(7)25℃常温循环实验
测试前测试满电电芯的厚度D0,将电池置于(25±3)℃环境中,静置3小时,待电芯本体达到(25±3)℃时,电池按照1C充到4.2V,再0.7C充到4.4V,再4.4V恒压充到截止电流0.05C,再以0.5C放电到3V,记录初始容量Q0,当循环达到所需的次数或容量衰减率低于70%或厚度超过测试要求的厚度时,以前一次的放电容量作为电池的容量Q2,计算容量保持率(%),再把电池满电,电芯取出后,常温静置3小时,测试满电厚度D2,计算厚度变化率(%),记录结果如表2。其中用到的计算公式如下:
厚度变化率(%)=(D2-D0)/D0×100%;容量保持率(%)=Q2/Q0×100%。
(8)45℃高温循环实验
测试前测试满电电芯的厚度D0,将电池置于(45±3)℃环境中,静置3小时,待电芯本体达到(45±3)℃时,电池按照0.7C恒流充到4.4V,在4.4V恒压充到截止电流0.05C,再以0.5C放电,记录初始容量Q0,如此循环,当循环达到所需的次数或容量衰减率低于70%或厚度超过测试要求的厚度时,以前一次的放电容量作为电池的容量Q3,计算容量保持率(%),再把电池满电,芯取出后,常温静置3小时,测试此时满电厚度D3,计算厚度变化率(%),记录结果如表2。其中用到的计算公式如下:
厚度变化率(%)=(D3-D0)/D0×100%;容量保持率(%)=Q3/Q0×100%。
(9)60℃高温存储实验
在25℃下,测试满电电芯的厚度D0,将分选后的电池按照0.7C充到4.4V,再4.4V恒压充到截止电流0.05C,然后用0.5C恒流放电至3.0V,然后0.7C充到4.4V,再4.4V恒压充到截止电流0.05C,置于60℃的环境中搁置14天后,测试满电厚度D4,计算厚度变化率(%),记录结果如表2。其中用到的计算公式如下:
厚度变化率(%)=(D4-D0)/D0×100%。
表1实施例1-13和对比例1-9的电解液的组成和含量
表2实施例1-13和对比例1-9的电池的实验结果对比
实施例1-13和对比例2-9
实施例1-13和对比例2-9的制备过程同对比例1,区别仅在于电解液的组分及含量不同,具体添加的组分及含量如表1所示。测试结果列于表2中。
从上述表2可以看出,本申请实施例制备得到的电池均取得了更好的电学性能,具体分析如下所述:
通过对比例1和对比例2-10对比可发现,在空白电解液基础上,添加剂式1所示化合物、腈类化合物和硫酸乙烯酯均可改善电池的循环性能、高温存储性能,但均会劣化低温循环性能。
通过对比例2-10和实施例1-6对比可发现,式1所示化合物和包括1,3,6-己烷三腈、甘油三腈、3-甲氧基丙腈中的至少一种的腈类化合物,或式1所示化合物和硫酸乙烯酯的组合,可改善电池的循环性能、高温存储性能,并兼顾低温循环性能。
通过对比例9和实施例1-2、4可发现,相比丁二腈,本发明中的1,3,6-己烷三腈、甘油三腈及3-甲氧基丙腈的腈类化合物具有更优的循环性能和高温存储性能。
通过实施例1和7、实施例2和8、实施例4和9、实施例3和10、实施例6和11对比可发现,式1所示化合物、包括1,3,6-己烷三腈、甘油三腈、3-甲氧基丙腈中的至少一种的腈类化合物以及硫酸乙烯酯的组合可进一步改善电池的循环性能和高温存储。
通过实施例12和实施例7、实施例13和实施例10对比可以发现,多种式1所示化合物或多种包括1,3,6-己烷三腈、甘油三腈、3-甲氧基丙腈中的至少一种的腈类化合物组合可以进一步改善电池的循环性能和高温存储性能。
以上,对本发明的实施方式进行了说明。但是,本发明不限定于上述实施方式。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
3.根据权利要求1或2所述的非水电解液,其中,所述腈类化合物选自1,3,6-己烷三腈、甘油三腈、3-甲氧基丙腈中的至少一种。
4.根据权利要求1-3任一项所述的非水电解液,其中,所述式1所示的化合物的含量占所述非水电解液总质量的0.1-10wt%。
5.根据权利要求1-4任一项所述的非水电解液,其中,所述腈类化合物的含量占所述非水电解液总质量的0-8wt%。
6.根据权利要求1-5任一项所述的非水电解液,其中,所述硫酸乙烯酯的含量占所述非水电解液总质量的0-2wt%。
7.一种锂离子电池,所述锂离子电池包括权利要求1-6任一项所述的非水电解液。
8.根据权利要求7所述的锂离子电池,其中,所述锂离子电池还包括含有正极活性材料的正极片、含有负极活性材料的负极片和锂离子隔膜。
9.根据权利要求8所述的锂离子电池,其中,所述的正极活性材料选自层状锂过渡金属复合氧化物、锰酸锂、钴酸锂混三元材料中的一种或几种;所述的层状锂过渡金属复合氧化物的化学式为Li1+xNiyCozM(1-y-z)Q2,其中,-0.1≤x≤1,0≤y≤1,0≤z≤1,且0≤y+z≤1;其中,M为Mg、Zn、Ga、Ba、Al、Fe、Cr、Sn、V、Mn、Sc、Ti、Nb、Mo、Zr中的一种或几种;Q为O、F、P、S中的一种或几种;所述的负极活性材料选自碳素材料、硅基材料、锡基材料或它们对应的合金材料中的一种或几种。
10.根据权利要求7-9任一项所述的锂离子电池,其中,所述锂离子电池的工作电压范围为4.25V及以上电压。
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CN112803070A (zh) * | 2020-12-30 | 2021-05-14 | 珠海冠宇电池股份有限公司 | 一种锂离子电池用非水电解液及包括该非水电解液的锂离子电池 |
CN114024033A (zh) * | 2020-12-30 | 2022-02-08 | 珠海冠宇电池股份有限公司 | 一种锂离子电池用非水电解液及包括该非水电解液的锂离子电池 |
CN114122521A (zh) * | 2020-12-30 | 2022-03-01 | 珠海冠宇电池股份有限公司 | 一种锂离子电池用非水电解液及包括该非水电解液的锂离子电池 |
CN114122521B (zh) * | 2020-12-30 | 2023-12-19 | 珠海冠宇电池股份有限公司 | 一种锂离子电池用非水电解液及包括该非水电解液的锂离子电池 |
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