CN117393856A - Lithium ion battery electrolyte and lithium ion battery comprising same - Google Patents
Lithium ion battery electrolyte and lithium ion battery comprising same Download PDFInfo
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- CN117393856A CN117393856A CN202311627380.7A CN202311627380A CN117393856A CN 117393856 A CN117393856 A CN 117393856A CN 202311627380 A CN202311627380 A CN 202311627380A CN 117393856 A CN117393856 A CN 117393856A
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- Prior art keywords
- lithium ion
- ion battery
- lithium
- battery electrolyte
- carbonate
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 157
- 239000003792 electrolyte Substances 0.000 title claims abstract description 93
- 239000000654 additive Substances 0.000 claims abstract description 33
- 230000000996 additive effect Effects 0.000 claims abstract description 33
- -1 tri (trimethylsilyl) fluorobenzene phosphate compound Chemical class 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 27
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 15
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 229910013716 LiNi Inorganic materials 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000319 transition metal phosphate Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910013733 LiCo Inorganic materials 0.000 claims description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 2
- 229910011281 LiCoPO 4 Inorganic materials 0.000 claims description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 2
- 229910015645 LiMn Inorganic materials 0.000 claims description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims description 2
- 229910014689 LiMnO Inorganic materials 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000979 O alloy Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims description 2
- 229940017219 methyl propionate Drugs 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
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910021483 silicon-carbon alloy Inorganic materials 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910011570 LiFe 1-x Inorganic materials 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 19
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000014759 maintenance of location Effects 0.000 description 21
- 239000000243 solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910012888 LiNi0.6Co0.1Mn0.3O2 Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 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
- 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 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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 provides lithium ion battery electrolyte and a lithium ion battery comprising the same, and belongs to the technical field of lithium ion batteries. The lithium ion battery electrolyte comprises lithium salt, an organic solvent and a first additive, wherein the first additive is a tri (trimethylsilyl) fluorobenzene phosphate compound or a tri (trimethylsilyl) fluorobenzene borate compound. According to the invention, the specific composition of the electrolyte is designed, and the electrolyte with excellent performance is obtained by using the first additive with a specific structure, so that the lithium ion battery with excellent electrical performance and excellent storage performance is prepared.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to lithium ion battery electrolyte and a lithium ion battery comprising the same.
Background
In recent years, with the continuous development of new energy industries, the performance requirements of the automobile industry on lithium ion power secondary batteries are higher and higher. In order to meet the requirements of new energy automobiles on ultra-long endurance mileage and wider temperature range, development of lithium ion secondary batteries with higher energy density, high-temperature cycle and better high-temperature storage is required. Lithium ion secondary batteries with high energy density generally use transition metal oxides (such as nickel cobalt lithium manganate) with higher nickel content, but these materials often have higher working voltage, and particle breakage and interface destruction easily occur at high voltage, so that electrolyte is oxidized, and life degradation at high temperature is caused, so that development of electrolyte additives capable of stabilizing positive electrode interfaces at high temperature and high voltage is required.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide lithium ion battery electrolyte and a lithium ion battery comprising the same. According to the invention, the specific composition of the electrolyte is designed, and the electrolyte with excellent performance is obtained by using the first additive with a specific structure, so that the lithium ion battery with excellent electrical performance and excellent storage performance is prepared.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a lithium ion battery electrolyte comprising a lithium salt, an organic solvent, and a first additive;
the first additive has a structure shown in the following formula I or formula II:
wherein R in the compound shown in the formula I or the compound shown in the formula II 1 -R 12 Each independently represents H or F, and R 1 -R 12 At least one of which is F.
According to the invention, the specific composition of the electrolyte is designed, and the tris (trimethylsilyl) fluorobenzene phosphate compound or the tris (trimethylsilyl) fluorobenzene borate compound is further used as an additive, so that a stable CEI film can be formed on the positive electrode of the lithium ion battery, and the lithium ion battery electrolyte capable of stabilizing the interface of the positive electrode under high temperature and high pressure is prepared, thereby improving the capacity retention rate of the lithium ion battery at 60 ℃, reducing the storage gas production of the lithium ion battery and improving the cycle capacity retention rate of the lithium ion battery.
The following is a preferred technical scheme of the present invention, but not a limitation of the technical scheme provided by the present invention, and the following preferred technical scheme can better achieve and achieve the objects and advantages of the present invention.
As a preferred embodiment of the present invention, the first additive comprises, for example, any one of the compounds I-1 to I-3, II-1 or a combination of at least two of them:
taking the compound shown in the formula I-1 and the compound shown in the formula II-1 as examples, the synthetic route is as follows:
wherein R is 1 、R 2 、R 4 And represents H.
The specific synthesis method is as follows:
(1) Compound a (0.39 mol) was dissolved in 750mL THF (tetrahydrofuran), cooled to-78 ℃, then n-butyllithium solution (solvent THF, volume of solution 47mL, concentration 2.5M) was added dropwise to the solution over 1h, the temperature was controlled to-60 ℃, stirring was continued for half an hour, trimethylchlorosilane (128 g,1.18 mol) dissolved in 150mL THF was further stirred for 30min at-60 ℃, then the solution was warmed to 0 ℃ for 40min, the solution was poured into 1M hydrochloric acid solution, the aqueous phase was extracted with diethyl ether, the organic phase was extracted with water, saturated brine, and then dried with anhydrous magnesium sulfate, the obtained organic solution was concentrated in vacuo to obtain a colorless liquid, the crude product containing compound B was directly put into the next step without further purification;
(2) Dissolving the crude product containing the compound B obtained in the above in 750mL of THF, adding TBAF solution (TBAF is tetrabutylammonium fluoride, the solvent is THF, the concentration is 1M), stirring for 5min, pouring the mixture into water, standing for delamination, extracting an inorganic phase with diethyl ether, extracting an organic phase with water and saturated saline respectively, drying the organic phase with anhydrous magnesium sulfate, concentrating the organic phase in vacuo to obtain a light yellow oily substance, dissolving the oily substance with 500mL of mixed solvent (the mixed solvent consists of DCM: cyclohexane according to the volume ratio of 1:1), filtering the solution with silica gel, rotationally evaporating the filtrate to obtain the compound C, standing and solidifying the solution;
(3) Dissolving the compound C obtained in the step (2) in 50mL of DCM (dichloromethane), and concentrating 1M BCl 3 Cooling to-78 ℃, standing for 20min, heating the reaction solution to room temperature, stirring for 12h, removing the solvent, recrystallizing with n-pentane at-35 ℃, and washing the product obtained by recrystallization with ice n-pentane to obtain a colorless solid compound shown in formula I-1;
alternatively, the resulting compound C (9.9 mmol) and Et 3 N (10.5 mmol) was slowly added to POCl 3 (3 mmol) toluene (solution 90 mL) at 0deg.C, then stirring the reaction solution at room temperature for 6h, pouring NaOH (15 g) in water (150 mL), extracting the inorganic phase with toluene (toluene amount 25mL, extraction 3 times), washing the extracted mixed organic phase with saturated saline, then drying with anhydrous sodium sulfate, removing the solvent under reduced pressure, and separating the crude product by column chromatography to obtain the compound represented by formula II-1.
It should be noted that the first additive with other structures in the present invention may be prepared by referring to the above method.
As a preferred embodiment of the present invention, the first additive may be 0.1 to 5% (for example, 0.1%, 0.5%, 0.8%, 1%, 2%, 3%, 4% or 5% by mass) and more preferably 0.5 to 1% by mass based on 100% by mass of the lithium ion battery electrolyte.
According to the invention, the stable CEI film can be formed on the anode of the lithium ion battery by controlling the dosage of the first additive within a specific range, so that the capacity retention rate of the lithium ion battery at 60 ℃ is improved, the gas production of the lithium ion battery is reduced, and the cycle capacity retention rate of the lithium ion battery is improved. If the dosage of the first additive is too small, the prepared electrolyte has poor performance; if the amount of the first additive is too large, the performance of the lithium ion battery electrolyte cannot be further improved, but the performance of the lithium ion battery electrolyte is deteriorated, and the waste of raw materials is caused.
As a preferred embodiment of the present invention, the lithium salt comprises LiPF 6 。
LiPF 6 The self-solubility is high, the conductivity is high, the electrochemical stability is good, the compatibility with graphite is good, and the aluminum foil can be effectively passivated, if LiBOB/LiPO is selected 2 F 2 And the lithium ion electrolyte with high concentration cannot be obtained, if LiFSI/LiTFSI and the like are selected, the current collector can be severely corroded under a high-voltage system when the concentration is too high.
In the invention, liPF is used 6 The lithium salt can provide an electrolyte having a high lithium ion concentration and excellent performance.
In a preferred embodiment of the present invention, the mass percentage of the lithium salt is 10 to 20% based on 100% of the mass percentage of the lithium ion battery electrolyte, and may be, for example, 10%, 11.1%, 12.5%, 13.2%, 14%, 15%, 16%, 17%, 18%, 19% or 20%.
As a preferable technical scheme of the invention, the organic solvent comprises a cyclic ester compound and a chain ester compound.
Preferably, the volume ratio of the cyclic ester compound to the chain ester compound is 10-40:60-90, for example, 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, or the like.
The invention selects the combination of the cyclic carbonate compound and the chain carbonate compound as the organic solvent of the electrolyte, can better avoid the damage of water to the electrolyte, and is beneficial to promoting the more sufficient dissolution of each component in the electrolyte, thereby improving the synergy among the components and obtaining the electrolyte with excellent electrical property.
Preferably, the cyclic ester compound is selected from any one or a combination of at least two of ethylene carbonate, propylene carbonate, butylene carbonate or gamma-butyrolactone.
Preferably, the chain ester compound is selected from any one or a combination of at least two of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate or ethyl butyrate.
As a preferable technical scheme of the invention, the lithium ion battery electrolyte also comprises a second additive.
Preferably, the second additive is selected from any one or a combination of at least two of vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, vinyl sulfate, 1, 3-propane sultone, tris (trimethylsilane) borate tris (trimethylsilane) phosphate or fluorobenzene.
According to the invention, through the use of the second additive, the service life and the high-temperature discharge capacity of the lithium ion battery can be further improved, and meanwhile, the low-temperature performance of the electrolyte can be improved.
Preferably, the second additive is 0.01 to 3% by mass (for example, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5% or 3% by mass, etc.), and more preferably 0.1 to 2% by mass, based on 100% by mass of the lithium ion battery electrolyte.
In the present invention, the preparation method of the electrolyte is not particularly limited, and the preparation methods commonly used in the art are applicable, and exemplary include, but are not limited to: and uniformly mixing all components of the electrolyte to obtain the electrolyte.
In a second aspect, the invention provides a lithium ion battery, which comprises a positive plate, a negative plate and the lithium ion battery electrolyte according to the first aspect.
As a preferred embodiment of the present invention, the positive electrode material of the positive electrode sheet includes a lithium-containing transition metal oxide and/or a lithium-containing transition metal phosphate compound.
Preferably, the lithium-containing transition metal oxide is selected from LiCoO 2 、LiNi x Co y Mn z O 2 、LiNi x Mn y O 2 、LiMn 2 O 4 、LiMnO 2 、Li 2 MnO 4 、Li 1+a Mn 1-x M x O 2 、LiCo 1-x M x O 2 、LiMn 1-x M x O 4 Or Li (lithium) 2 Mn 1-x O 4 Any one or a combination of at least two of the following;
wherein M is selected from any one of Ni, co, mn, al, cr, mg, zr, mo, V, ti, 0.ltoreq.a <0.2 (for example, 0, 0.02, 0.04, 0.06, 0.08, 0.1, 0.12, 0.14, 0.16 or 0.18, etc.), 0.ltoreq.x.ltoreq.1 (for example, 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, etc.), 0.ltoreq.y.ltoreq.1 (for example, 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, etc.), 0.ltoreq.z.ltoreq.1 (for example, 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, etc.).
Preferably, the lithium-containing transition metal phosphate compound is selected from LiFePO 4 、LiMnPO 4 、LiCoPO 4 、LiFe 1- x M x PO 4 Any one or a combination of at least two of the following;
wherein M is selected from any one of Ni, co, mn, al, cr, mg, zr, mo, V, ti, and 0.ltoreq.x.ltoreq.1 (for example, 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, etc.).
As a preferred embodiment of the present invention, the negative electrode material of the negative electrode sheet is selected from any one or a combination of at least two of a carbonaceous material, an alloy-based material, and a metal composite material containing lithium, and preferably is a combination of at least two of any one of natural graphite, artificial graphite, soft carbon, hard carbon, lithium titanate, silicon, a silicon-carbon alloy, and a silicon-oxygen alloy.
Compared with the prior art, the invention has the following beneficial effects:
the electrolyte is designed according to the specific composition of the electrolyte, and the electrolyte further takes the tri (trimethylsilyl) fluorobenzene phosphate compound or the tri (trimethylsilyl) fluorobenzene borate compound as an additive, so that a stable CEI film can be formed on the positive electrode of the lithium ion battery, and the lithium ion battery electrolyte capable of stabilizing the interface of the positive electrode at high temperature and high pressure is prepared, thereby improving the capacity retention rate of the lithium ion battery at 60 ℃, reducing the storage gas production of the lithium ion battery, improving the cycle capacity retention rate of the lithium ion battery, wherein the capacity retention rate of the lithium ion battery at 60 ℃ is more than 87.0%, particularly 87.3-93.2%, the capacity retention rate after 800 cycles is more than 87.5%, particularly 87.8-94.5%, and the gas production expansion is less than or equal to 30% and particularly 14-30% after 30% at 60 ℃.
Drawings
Fig. 1 is a graph showing the cycle capacity retention rate at 45 ℃ of a lithium ion battery prepared from the lithium ion battery electrolyte provided in example 1 and comparative example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a lithium ion battery electrolyte, which comprises the following components in percentage by mass as 100 percent:
LiPF 6 12.5 percent of compound shown in a formula I-1, 0.5 percent of vinylene carbonate and the balance of organic solvent;
the organic solvent consists of Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) according to the volume ratio of 30:50:20.
The preparation method of the lithium ion battery electrolyte comprises the following steps:
and uniformly mixing all components of the lithium ion battery electrolyte to obtain the lithium ion battery electrolyte.
Example 2
This example provides a lithium ion battery electrolyte, which differs from example 1 only in that:
the lithium ion battery electrolyte comprises the following components in percentage by mass as 100 percent:
LiPF 6 12.5 percent of compound 1 percent of formula I-1, 0.5 percent of vinylene carbonate and the balance of organic solvent;
other conditions were the same as in example 1.
Example 3
This example provides a lithium ion battery electrolyte, which differs from example 1 only in that:
the lithium ion battery electrolyte comprises the following components in percentage by mass as 100 percent:
LiPF 6 12.5 percent of compound shown in a formula I-1, 0.1 percent of vinylene carbonate and the balance of organic solvent;
other conditions were the same as in example 1.
Example 4
This example provides a lithium ion battery electrolyte, which differs from example 1 only in that:
the lithium ion battery electrolyte comprises the following components in percentage by mass as 100 percent:
LiPF 6 12.5 percent of compound shown in a formula I-1, 5 percent of vinylene carbonate, 0.5 percent of rest organic solvent;
other conditions were the same as in example 1.
Example 5
This example provides a lithium ion battery electrolyte, which differs from example 1 only in that:
the lithium ion battery electrolyte comprises the following components in percentage by mass as 100 percent:
LiPF 6 12.5%, 7% of the compound of formula I-1, 0.5% of vinylene carbonate andthe balance of organic solvent;
other conditions were the same as in example 1.
Example 6
This example provides a lithium ion battery electrolyte, which differs from example 1 only in that:
the lithium ion battery electrolyte comprises the following components in percentage by mass as 100 percent:
LiPF 6 12.5 percent of compound shown in a formula I-2, 0.5 percent of vinylene carbonate and the balance of organic solvent;
other conditions were the same as in example 1.
Example 7
This example provides a lithium ion battery electrolyte, which differs from example 1 only in that:
the lithium ion battery electrolyte comprises the following components in percentage by mass as 100 percent:
LiPF 6 12.5 percent of compound shown in a formula I-3, 0.5 percent of vinylene carbonate and the balance of organic solvent;
other conditions were the same as in example 1.
Example 8
This example provides a lithium ion battery electrolyte, which differs from example 1 only in that:
the lithium ion battery electrolyte comprises the following components in percentage by mass as 100 percent:
LiPF 6 12.5% of a compound shown in a formula II-1, 0.5% of vinylene carbonate and the balance of an organic solvent;
other conditions were the same as in example 1.
Example 9
This example provides a lithium ion battery electrolyte, which differs from example 1 only in that:
the lithium ion battery electrolyte comprises the following components in percentage by mass as 100 percent:
LiPF 6 12.5 percent of a compound shown in a formula I-1, 0.5 percent of vinylene carbonate, 0.5 percent of tris (trimethylsilane) borate and the balance of an organic solvent;
other conditions were the same as in example 1.
Example 10
This example provides a lithium ion battery electrolyte, which differs from example 1 only in that:
the lithium ion battery electrolyte comprises the following components in percentage by mass as 100 percent:
LiPF 6 12.5 percent of compound shown in a formula I-1, 0.5 percent of vinylene carbonate, 0.5 percent of tris (trimethylsilane) phosphate and the balance of organic solvent;
other conditions were the same as in example 1.
Example 11
This example provides a lithium ion battery electrolyte, which differs from example 1 only in that:
the lithium ion battery electrolyte comprises the following components in percentage by mass as 100 percent:
LiPF 6 12.5 percent of compound shown in a formula I-1, 0.5 percent of vinylene carbonate, 1 percent of fluorobenzene and the balance of organic solvent;
other conditions were the same as in example 1.
Comparative example 1
This comparative example provides a lithium ion battery electrolyte which differs from example 1 only in that:
the lithium ion battery electrolyte comprises the following components in percentage by mass as 100 percent:
LiPF 6 12.5 percent of vinylene carbonate 0.5 percent and the balance of organic solvent;
other conditions were the same as in example 1.
Lithium ion batteries were prepared from the electrolyte solutions of the lithium ion batteries of the above examples and comparative examples, and the preparation methods of the lithium ion batteries were as follows:
(1) Preparation of positive plate of lithium ion secondary battery
The positive electrode active material nickel cobalt lithium manganate (LiNi 0.6 Co 0.1 Mn 0.3 O 2 ) The conductive agent Super-P and the adhesive PVDF are dissolved in the solvent N-methyl pyrrolidone according to the mass ratio of 96:2.0:2.0 to be uniformly mixed to prepare anode slurry, and the anode slurry is uniformly coated on the aluminum foil of the current collector, wherein the coating amount is 19mg/cm 2 Drying at 85 ℃ for 4 hours under vacuum condition at 85 ℃ after cold pressing, trimming, cutting and splitting, and welding the tab to prepare the positive plate of the lithium ion secondary battery meeting the requirements;
(2) Preparation of negative plate of lithium ion secondary battery
Dissolving negative active materials of artificial graphite, a conductive agent Super-P, a thickening agent CMC and a bonding agent SBR in solvent deionized water according to a mass ratio of 96.5:1.0:1.0:1.5, uniformly mixing to prepare negative slurry, uniformly coating the negative slurry on a current collector copper foil with a coating weight of 11.5mg/cm < 2 >, drying at 85 ℃, then carrying out cold pressing, trimming, cutting pieces and slitting, drying for 4 hours at 110 ℃ under vacuum condition, and welding tabs to prepare a negative plate of the lithium ion secondary battery meeting the requirements;
(3) Preparation of lithium ion batteries
The positive electrode sheet, the negative electrode sheet and the separator (PE film) of the lithium ion secondary battery prepared according to the above process are manufactured into a battery with a thickness of 8mm, a width of 60mm and a length of 130mm through a lamination process, and are baked in vacuum at 85 ℃ for 10 hours, injected with electrolyte, and stood for 24 hours, then charged to 4.4V with a constant current of 0.1C (200 mA), then charged to a constant voltage of 4.4V until the current drops to 0.05C (100 mA), then discharged to 2.8V with a constant current of 0.1C (200 mA), and repeatedly charged and discharged for 2 times, and finally charged to 3.8V with a constant current of 0.1C (200 mA), thereby obtaining the lithium ion battery.
The performance of the lithium ion battery prepared from the lithium ion battery electrolyte provided in the above examples and comparative examples was tested as follows:
(1) High temperature storage performance test
At 25 ℃, the lithium ion battery prepared by the lithium ion battery electrolyte provided by the examples and the comparative examples is charged to 4.4V at a constant current of 1C, the lithium ion battery is charged to 0.05C at a constant voltage of 4.4V, then the lithium ion battery is discharged to 2.8V at a constant current of 1C, and the discharge capacity of the lithium ion battery is the discharge capacity before high-temperature storage; then charging the lithium ion battery to 4.4V with a constant current of 1C, storing the lithium ion battery at 60 ℃ for 30 days, after the storage is finished, placing the lithium ion battery at 25 ℃, then discharging the lithium ion battery to 2.8V with a constant current of 0.5C, then charging the lithium ion battery to 4.4V with a constant current of 1C, further charging the lithium ion battery to 1C with a constant voltage of 4.4V, then discharging the lithium ion battery to 2.8V with a constant current of 1C, wherein the discharge capacity of the last time is the discharge capacity of the lithium ion battery after high-temperature storage;
capacity retention (%) = [ discharge capacity after high-temperature storage of lithium ion battery.
(2) High temperature cycle performance test
The lithium ion battery electrolyte provided by the above examples and comparative examples was tested for high temperature cycle performance of the lithium ion battery, and the specific method was as follows: at 45 ℃, respectively charging the lithium ion battery to 4.4V by using a constant current of 1C, charging the lithium ion battery to 0.05C by using a constant voltage of 4.4V, and discharging the lithium ion battery to 2.8V by using a constant current of 1C, wherein the discharge capacity is the discharge capacity of the first cycle, and the lithium ion battery is subjected to a cycle charge-discharge test according to the mode, so that the discharge capacity of 800 th cycle is taken;
capacity retention (%) = [ 800 th cycle discharge capacity/first cycle discharge capacity ] ×100% after 800 cycles of lithium ion battery;
the cycle capacity retention rate of the lithium ion battery prepared by the lithium ion battery electrolyte provided by the embodiment 1 and the comparative example 1 of the invention at 45 ℃ is shown in fig. 1, and as can be seen from fig. 1, the electrical property of the lithium ion battery is further improved by using the first additive, and after 800 cycles, the capacity retention rate of the lithium ion battery prepared by the lithium ion battery electrolyte provided by the invention is more than 92%, specifically 92.5%.
(3) High temperature storage gas production performance test
At 25 ℃, respectively charging the lithium ion batteries prepared by the lithium ion battery electrolytes provided by the examples and the comparative examples to 4.4V at a constant current of 1C, further charging the lithium ion batteries to 0.05C at a constant voltage of 4.4V, and discharging the lithium ion batteries to 2.8V at a constant current of 1C, wherein the discharge capacity is the discharge capacity of the lithium ion batteries before high-temperature storage; then charging the lithium ion battery to 4.4V with a constant current of 1C, charging the lithium ion battery to 0.05C with a constant voltage of 4.4V, fully charging the lithium ion battery, testing the volume of the battery by adopting a drainage method, and measuring the thickness of the battery by using a micrometer; then placing the lithium ion battery at 60 ℃ for 30 days, placing the lithium ion battery at 25 ℃ after the storage is finished, testing the volume of the battery by adopting a drainage method, and measuring the thickness of the battery by using a micrometer; then discharging the lithium ion battery to 2.8V with a constant current of 0.5C, then charging the lithium ion battery to 4.4V with a constant current of 1C, further charging the lithium ion battery to 1C with a constant voltage of 4.4V, then discharging the lithium ion battery to 2.8V with a constant current of 1C, wherein the discharge capacity of the last time is the discharge capacity of the lithium ion secondary battery after high-temperature storage;
battery volume expansion rate= (volume after storage/(volume before storage-1) ×100%).
The results of the above performance tests are shown in table 1 below:
TABLE 1
As can be seen from the above, the electrolyte is designed according to the specific composition, and the electrolyte further comprises a tri (trimethylsilyl) fluorobenzene phosphate compound or a tri (trimethylsilyl) fluorobenzene borate compound as an additive, the dosage of the additive is controlled within a specific range, a stable CEI film can be formed on the positive electrode of the lithium ion battery, and the lithium ion battery electrolyte capable of stabilizing the positive electrode interface at high temperature and high pressure is prepared, so that the capacity retention rate of the lithium ion battery at 60 ℃ is improved, the gas production of the lithium ion battery is reduced, the cycle capacity retention rate of the lithium ion battery is improved, the capacity retention rate of the lithium ion battery at 60 ℃ is more than 87.0%, particularly 87.3-93.2%, the capacity retention rate after 800 cycles is more than 87.5%, particularly 87.8-94.5%, and the gas production expansion at 60 ℃ is less than or equal to 30%, particularly 14-30%.
As is apparent from the contents of examples 1 to 5 and comparative example 1, in the present invention, by controlling the amount of the first additive within a specific range, an electrolyte having excellent electrical properties can be prepared, thereby improving the electrical properties of the lithium ion battery. If the electrolyte does not contain the first additive (comparative example 1), the lithium ion battery prepared from the electrolyte has poor electrical performance, low storage capacity retention rate, low circulating capacity retention, and high storage gas expansion; if the amount of the first additive used in the electrolyte is too large (example 5), the performance of the lithium ion battery electrolyte cannot be further improved, but the performance of the lithium ion battery electrolyte is deteriorated, and the raw materials are wasted.
As is clear from the contents of examples 1-4 and examples 9-11, the invention can further improve the electrical property and storage property of the lithium ion battery by using the first additive and the second additive together, wherein the capacity retention rate of the lithium ion battery stored at 60 ℃ is more than 90%, specifically 92.9-93.2%, the capacity retention rate after 800 cycles is more than 94%, specifically 94.2-94.5%, and the gas expansion of the lithium ion battery stored at 60 ℃ for 30 days is less than or equal to 17%, specifically 14-17%.
In summary, the lithium ion battery electrolyte with excellent electrical properties is prepared by designing the specific composition of the electrolyte, and the electrical properties and the storage properties of the lithium ion battery are further improved.
The applicant states that the detailed process flow of the present invention is illustrated by the above examples, but the present invention is not limited to the above detailed process flow, i.e. it does not mean that the present invention must be implemented depending on the above detailed process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A lithium ion battery electrolyte, which is characterized by comprising lithium salt, an organic solvent and a first additive;
the first additive has a structure shown in the following formula I or formula II:
wherein R in the compound shown in the formula I or the compound shown in the formula II 1 -R 12 Each independently represents H or F, and R 1 -R 12 At least one of which is F.
2. The lithium ion battery electrolyte according to claim 1, wherein the first additive comprises any one of or a combination of at least two of compounds I-1 to I-3, II-1:
3. the lithium ion battery electrolyte according to claim 1 or 2, wherein the first additive is 0.1 to 5% by mass, and more preferably 0.5 to 1% by mass, based on 100% by mass of the lithium ion battery electrolyte.
4. The lithium ion battery electrolyte of any of claims 1-3, wherein the lithium salt comprises LiPF 6 。
5. The lithium ion battery electrolyte according to any one of claims 1 to 4, wherein the mass percentage of the lithium salt is 10 to 20% based on 100% of the mass percentage of the lithium ion battery electrolyte.
6. The lithium ion battery electrolyte according to any one of claims 1 to 5, wherein the organic solvent comprises a cyclic ester compound and a chain ester compound;
preferably, the volume ratio of the cyclic ester compound to the chain ester compound is 10-40:60-90;
preferably, the cyclic ester compound is selected from any one or a combination of at least two of ethylene carbonate, propylene carbonate, butylene carbonate or gamma-butyrolactone;
preferably, the chain ester compound is selected from any one or a combination of at least two of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate or ethyl butyrate.
7. The lithium ion battery electrolyte according to any one of claims 1-6, further comprising a second additive in the lithium ion battery electrolyte;
preferably, the second additive is selected from any one or a combination of at least two of vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, vinyl sulfate, 1, 3-propane sultone, tris (trimethylsilane) borate, tris (trimethylsilane) phosphate or fluorobenzene;
preferably, the mass percentage of the second additive is 0.01-3%, and more preferably 0.1-2%, based on 100% of the mass percentage of the lithium ion battery electrolyte.
8. A lithium ion battery, characterized in that the lithium ion battery comprises a positive plate, a negative plate and the lithium ion battery electrolyte as claimed in any one of claims 1-7.
9. The lithium ion battery of claim 8, wherein the positive electrode material of the positive electrode sheet comprises a lithium-containing transition metal oxide and/or a lithium-containing transition metal phosphate compound;
preferably, the lithium-containing transition metal oxide is selected from LiCoO 2 、LiNi x Co y Mn z O 2 、LiNi x Mn y O 2 、LiMn 2 O 4 、LiMnO 2 、Li 2 MnO 4 、Li 1+a Mn 1-x M x O 2 、LiCo 1-x M x O 2 、LiMn 1-x M x O 4 Or Li (lithium) 2 Mn 1-x O 4 Any one or a combination of at least two of the following;
wherein M is selected from any one of Ni, co, mn, al, cr, mg, zr, mo, V, ti, a is more than or equal to 0 and less than or equal to 0.2, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1;
preferably, the lithium-containing transition metal phosphate compound is selected from LiFePO 4 、LiMnPO 4 、LiCoPO 4 、LiFe 1-x M x PO 4 Any one or a combination of at least two of the following;
wherein M is selected from any one of Ni, co, mn, al, cr, mg, zr, mo, V, ti, and x is more than or equal to 0 and less than or equal to 1.
10. The lithium ion battery according to claim 8, wherein the negative electrode material of the negative electrode sheet is selected from any one or a combination of at least two of a carbonaceous material, an alloy-like material, and a metal composite material containing lithium, preferably a combination of at least two of any one of natural graphite, artificial graphite, soft carbon, hard carbon, lithium titanate, silicon, a silicon-carbon alloy, and a silicon-oxygen alloy.
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