CN116936928A - Lithium ion battery electrolyte additive and preparation method and application thereof - Google Patents
Lithium ion battery electrolyte additive and preparation method and application thereof Download PDFInfo
- Publication number
- CN116936928A CN116936928A CN202210340520.1A CN202210340520A CN116936928A CN 116936928 A CN116936928 A CN 116936928A CN 202210340520 A CN202210340520 A CN 202210340520A CN 116936928 A CN116936928 A CN 116936928A
- Authority
- CN
- China
- Prior art keywords
- group
- lithium
- substituted
- lithium ion
- ion battery
- Prior art date
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 190
- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 34
- 239000003792 electrolyte Substances 0.000 claims abstract description 120
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 44
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 40
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 19
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 125000003302 alkenyloxy group Chemical group 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000005133 alkynyloxy group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000004991 fluoroalkenyl group Chemical group 0.000 claims abstract description 4
- 125000004428 fluoroalkoxy group Chemical group 0.000 claims abstract description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract 2
- -1 t-butoxy group Chemical group 0.000 claims description 130
- 238000006243 chemical reaction Methods 0.000 claims description 76
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 37
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 36
- 150000008064 anhydrides Chemical class 0.000 claims description 33
- 229910052744 lithium Inorganic materials 0.000 claims description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 31
- 239000000654 additive Substances 0.000 claims description 30
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 30
- 230000000996 additive effect Effects 0.000 claims description 27
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 27
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 25
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 24
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 24
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 24
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 21
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 19
- CNTIXUGILVWVHR-UHFFFAOYSA-N diphosphoryl chloride Chemical compound ClP(Cl)(=O)OP(Cl)(Cl)=O CNTIXUGILVWVHR-UHFFFAOYSA-N 0.000 claims description 17
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims description 15
- 159000000002 lithium salts Chemical class 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 150000003871 sulfonates Chemical class 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 11
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 11
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 10
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000012025 fluorinating agent Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 claims description 7
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- CHHOPPGAFVFXFS-UHFFFAOYSA-M [Li+].[O-]S(F)(=O)=O Chemical group [Li+].[O-]S(F)(=O)=O CHHOPPGAFVFXFS-UHFFFAOYSA-M 0.000 claims description 6
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 6
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- VXJAYNWISQFORV-UHFFFAOYSA-M potassium fluorosulfate Chemical compound [K+].[O-]S(F)(=O)=O VXJAYNWISQFORV-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 claims description 4
- SNVCRNWSNUUGEA-UHFFFAOYSA-N dichlorophosphoryloxymethane Chemical compound COP(Cl)(Cl)=O SNVCRNWSNUUGEA-UHFFFAOYSA-N 0.000 claims description 4
- 238000004334 fluoridation Methods 0.000 claims description 4
- 238000006138 lithiation reaction Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 4
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-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 3
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 3
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 3
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910013075 LiBF Inorganic materials 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical compound CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- VMVNZNXAVJHNDJ-UHFFFAOYSA-N methyl 2,2,2-trifluoroacetate Chemical compound COC(=O)C(F)(F)F VMVNZNXAVJHNDJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 3
- CDXJNCAVPFGVNL-UHFFFAOYSA-N propyl 2,2,2-trifluoroacetate Chemical compound CCCOC(=O)C(F)(F)F CDXJNCAVPFGVNL-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 claims description 3
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 claims description 3
- DZXBHDRHRFLQCJ-UHFFFAOYSA-M sodium;methyl sulfate Chemical group [Na+].COS([O-])(=O)=O DZXBHDRHRFLQCJ-UHFFFAOYSA-M 0.000 claims description 3
- BVZSCTHELIHSMP-UHFFFAOYSA-M sodium;trifluoromethyl sulfate Chemical compound [Na+].[O-]S(=O)(=O)OC(F)(F)F BVZSCTHELIHSMP-UHFFFAOYSA-M 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 claims description 3
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 125000006005 fluoroethoxy group Chemical group 0.000 claims description 2
- 125000004785 fluoromethoxy group Chemical group [H]C([H])(F)O* 0.000 claims description 2
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- LDHXNOAOCJXPAH-UHFFFAOYSA-M sodium;prop-2-yne-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC#C LDHXNOAOCJXPAH-UHFFFAOYSA-M 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- BVWQQMASDVGFGI-UHFFFAOYSA-N ethene propyl hydrogen carbonate Chemical compound C(CC)OC(O)=O.C=C BVWQQMASDVGFGI-UHFFFAOYSA-N 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 208000028659 discharge Diseases 0.000 description 42
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 239000000203 mixture Substances 0.000 description 20
- 239000010413 mother solution Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000002161 passivation Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 9
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 9
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 9
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- LOZAIRWAADCOHQ-UHFFFAOYSA-N triphosphazene Chemical compound PNP=NP LOZAIRWAADCOHQ-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000007600 charging Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical class OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 3
- 239000006256 anode slurry Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- FYHLDUXIKXBAAT-UHFFFAOYSA-N prop-1-yne-1-sulfonic acid Chemical group CC#CS(O)(=O)=O FYHLDUXIKXBAAT-UHFFFAOYSA-N 0.000 description 3
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical group OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- MBXNQZHITVCSLJ-UHFFFAOYSA-N methyl fluorosulfonate Chemical compound COS(F)(=O)=O MBXNQZHITVCSLJ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical group OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- BDIBYQORZHGDIR-UHFFFAOYSA-N fluorosulfonyloxybenzene Chemical compound FS(=O)(=O)OC1=CC=CC=C1 BDIBYQORZHGDIR-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- SCLFRABIDYGTAZ-UHFFFAOYSA-N methylphosphonic acid dichloride Chemical compound CP(Cl)(Cl)=O SCLFRABIDYGTAZ-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- TURAMGVWNUTQKH-UHFFFAOYSA-N propa-1,2-dien-1-one Chemical group C=C=C=O TURAMGVWNUTQKH-UHFFFAOYSA-N 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- MRGUSFYIQDLKNZ-UHFFFAOYSA-M sodium;prop-1-yne-1-sulfonate Chemical compound [Na+].CC#CS([O-])(=O)=O MRGUSFYIQDLKNZ-UHFFFAOYSA-M 0.000 description 1
- LWLVRCRDPVJBKL-UHFFFAOYSA-M sodium;prop-2-ynoate Chemical compound [Na+].[O-]C(=O)C#C LWLVRCRDPVJBKL-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical group OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- H01M10/0567—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
- H01M10/05—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
-
- 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
Abstract
The invention relates to the field of electrolyte for lithium ion batteries, in particular to a lithium ion battery electrolyte additive, a preparation method and application thereof. The lithium ion battery electrolyte additive comprises a compound shown in a formula 1,wherein, in the formula 1, R 1 、R 2 Each independently selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluoroalkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a fluoroalkenyloxy group having 2 to 10 carbon atoms, and a fluoroalkenyloxy group having 2 to 10 carbon atoms10, an alkynyloxy group having 2 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. The lithium ion battery electrolyte additive can balance the low-temperature charge and discharge performance and the high-temperature storage performance of a lithium ion battery.
Description
Technical Field
The invention relates to the field of electrolyte for lithium ion batteries, in particular to a lithium ion battery electrolyte additive, a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high voltage, large specific energy, long cycle life, good safety performance, small self-discharge, quick charge, wide working temperature range and the like, and is widely applied to the fields of electronic products, electric tools, energy storage equipment, new energy automobiles and the like. Along with the expansion of application scenes of the lithium ion battery, people increasingly pay attention to high-temperature storage performance, low-temperature charge-discharge performance, charge-discharge cycle performance and the like of the lithium ion battery.
The lithium ion battery electrolyte is used as an important component of a lithium ion battery, and has great influence on the high-temperature storage performance, the low-temperature charge-discharge performance and the cycle performance of the battery. However, in general, it is difficult to improve both high temperature performance and low temperature performance of the lithium ion battery from the standpoint of the electrolyte of the lithium ion battery, for example, the high temperature performance can be improved by passivating the interface between the positive and negative electrodes by adding a film-forming additive, but the low temperature performance of the lithium ion battery is seriously deteriorated due to the simultaneous increase of the interface resistance of the positive and negative electrodes, and in addition, the increase of the resistance is also unfavorable for long-term circulation.
In view of the above, there is a need for developing a lithium ion battery electrolyte that combines high-temperature storage performance, low-temperature charge-discharge performance, and charge-discharge cycle performance of a lithium battery.
JP-A-2000-123867 proposes to improve battery characteristics by adding vinylene carbonate to an electrolyte. The vinylene carbonate can generate reduction decomposition reaction on the surface of the negative electrode in preference to solvent molecules, and can form a passivation film on the surface of the negative electrode to prevent electrolyte from further decomposing on the surface of the electrode, thereby improving the cycle performance of the battery. However, when vinylene carbonate is added, the battery is liable to generate gas during high-temperature storage, resulting in swelling of the battery. In addition, the passivation film formed by vinylene carbonate has high impedance, and lithium is easy to be separated out by low-temperature charging particularly under the low-temperature condition, so that the safety of the battery is influenced.
Chinese patent CN103107355a discloses an electrolyte for lithium ion batteries, wherein the resistance of the battery is reduced and the high temperature performance and cycle performance of the battery are improved by adding branched cyclic ethylene sulfate and unbranched cyclic ethylene sulfate or sulfonate for mixed use. However, in a ternary nickel-cobalt-manganese and nickel-cobalt-aluminum battery anode material system, when the mass fraction of nickel element in an active material is more than or equal to 30%, more gas is generated in the battery formation process, so that the performance is influenced, and meanwhile, the safety risk is high.
Disclosure of Invention
Problems to be solved by the invention: the electrolyte in the prior art cannot simultaneously give consideration to both high-temperature storage performance and low-temperature charge and discharge performance of the lithium ion battery.
In view of the above problems, an object of the present invention is to provide an additive for lithium ion battery electrolyte, which is applied to lithium ion battery electrolyte to improve high-temperature storage performance of lithium ion battery, inhibit high-temperature gas generation, improve low-temperature charge and discharge performance, and inhibit internal resistance increase at low temperature.
In order to solve the problems, the technical scheme of the invention is as follows:
the invention provides a lithium ion battery electrolyte additive, which comprises a compound shown in a formula 1,
wherein, in the formula 1, R 1 、R 2 Each independently selected from any one of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluoroalkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a fluoroalkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
Preferably, in the formula 1, the R 1 、R 2 Each independently selected from fluorine atom, methyl, ethyl, fluoroAny one of methyl, fluoroethyl, methoxy, ethoxy, t-butoxy, fluoromethoxy, fluoroethoxy, fluoro-t-butoxy, ethenyl, propenyl, fluoroethenyl, fluoropropenyl, ethenyloxy, propenyloxy, fluoroethenyloxy, fluoropropenyyloxy, propynyl, propynyloxy and phenyl.
Preferably, the compound represented by the structural formula 1 is selected from one or more of the following compounds,
preferably, the compound represented by the structural formula 1 is selected from one or more of the following compounds,
preferably, the compound shown in the formula 1 is prepared by the following steps: the sulfonic acid group compound and/or the sulfuric acid group compound are reacted with phosphorus oxychloride and then are fluorinated and lithiated to obtain or the sulfonic acid group compound and/or the sulfuric acid group compound and R 2 The substituted dichlorophosphoryl is obtained by lithiation after reaction.
The invention also provides a preparation method of the lithium ion battery electrolyte additive, and the synthetic route of the compound shown in the formula 1 is as follows:
if R is 2 In the case of fluorine atoms, the synthetic route is as follows:
If R is 2 When the fluorine atom is not contained, the synthetic route is as follows:
wherein: a is chlorosulfonic acid, R 1 Substituted sulfonates and R 1 One or more than two of the substituted sulfates;
b is a fluorinating agent;
c is a lithium source;
d is R 1 Substituted sulfonates and/or R 1 Substituted sulfates.
Preferably, in the above preparation method, when R 2 In the case of fluorine atoms, comprising the steps of:
(1) The sulfonic acid group compound and/or sulfuric acid group compound reacts with phosphorus oxychloride to obtain R 1 Substituted sulfonic acid group dichlorophosphoric anhydride and/or R 1 Substituted sulfate dichlorophosphoric anhydrides;
(2) R is obtained in the step (1) 1 Substituted sulfonic acid group dichlorophosphoric anhydride and/or R 1 Reacting substituted sulfuric dichlorophosphoric anhydride with fluoridation reagent to obtain R 1 Substituted sulfonic acid group fluoro chloro phosphoric anhydride and/or R 1 Substituted sulfate-based fluoro chloro phosphoric anhydrides;
(3) Obtaining R in the step (2) 1 Substituted sulfonic acid group fluoro chloro phosphoric anhydride and/or R 1 Substituted sulfuric acid group fluoro chloro phosphoric anhydride reacts with lithium source to obtain R 1 Substituted sulfonic acid group lithium fluorophosphate anhydride salt and/or R 1 Substituted lithium sulfate fluorophosphate anhydride salts;
wherein the sulfonic acid group compound is chlorosulfonic acid, R 1 One or more than two of the substituted sulfonates, the sulfate compound is R 1 Substituted sulfates.
Preferably, the molar ratio of the sulfonic acid-based compound and/or sulfuric acid-based compound to the phosphorus oxychloride in step (1) is 1 (1) to (4).
Preferably, the reaction temperature of the step (1) is 40-150 ℃ and the reaction time is 10-20 h.
Preferably, R in step (2) 1 Substituted sulfonic acid group dichlorophosphoric anhydride and/or R 1 The molar ratio of the substituted sulfuric dichlorophosphoric anhydride to the fluorinating agent is 1 (1-5).
Preferably, the reaction temperature of the step (2) is 40-80 ℃ and the reaction time is 10-24 h.
Preferably, R in step (3) 1 Substituted sulfonic acid group fluoro chloro phosphoric anhydride and/or R 1 The molar ratio of the substituted sulfuric acid group fluoro chloro phosphoric anhydride to the lithium element in the lithium source is (1-1.2): 1.
Preferably, the reaction temperature of the step (3) is 30-120 ℃ and the reaction time is 4-24 h.
Preferably, the fluorinating agent is one or more of potassium fluoride, ammonium fluoride, potassium bifluoride, ammonium bifluoride, hydrogen fluoride and antimony trifluoride.
Preferably, in the above preparation method, when R 2 When the fluorine atom is not contained, the method comprises the following steps:
(1) Combining a sulphonic acid compound and/or a sulphuric acid compound with R 2 Substituted dichlorophosphoryl reacts to obtain sulfonic group chlorophosphoric anhydride and/or sulfuric group chlorophosphoric anhydride;
(2) Reacting the sulfonic acid group chlorophosphoric anhydride and/or sulfuric acid group chlorophosphoric anhydride obtained in the step (1) with a lithium source to obtain a lithium fluorosulfonate group chlorophosphoric anhydride salt and/or a lithium fluorosulfonate group chlorophosphoric anhydride salt;
wherein the sulfonic acid group compound is R 1 Substituted sulfonate, the sulfate compound is R 1 Substituted sulfates.
Preferably, the sulfonic acid group compound and/or sulfuric acid group compound in step (1) and the R 2 The molar ratio of the substituted dichlorophosphoryl is 1 (1-4).
Preferably, the R 2 The substituted dichlorophosphoryl is selected from one or more of phenylphosphoryl dichloride, methyl dichlorophosphate or methylphosphono phthalein dichloride.
Preferably, the reaction temperature in the step (1) is 40-150 ℃ and the reaction time is 10-20 h;
preferably, the molar ratio of the sulfonic acid group chlorophosphoric anhydride and/or sulfuric acid group chlorophosphoric anhydride to the lithium element in the lithium source in the step (2) is (1 to 1.2): 1.
Preferably, the reaction temperature of the step (2) is 30-120 ℃ and the reaction time is 4-24 h.
Preferably, the R 1 The substituted sulfonate is selected from one or more of sodium vinylsulfonate, sodium trifluoromethanesulfonate, sodium propargyl sulfonate, sodium phenylsulfonate, sodium methylsulfonate and sodium 2-fluoro-vinylsulfonate.
Preferably, the R 1 The substituted sulfate is selected from sodium methyl sulfate and/or sodium trifluoromethyl sulfate.
Preferably, the lithium source is one or more of lithium hydroxide, lithium phosphate and lithium acetate.
The invention also provides lithium ion battery electrolyte, which comprises lithium salt, an organic solvent and the lithium ion battery electrolyte additive;
preferably, the organic solvent is 70.0 parts by mass, the lithium salt is 10.0 to 20.0 parts by mass, and the additive is 0.1 to 5.0 parts by mass, preferably 0.2 to 2.0 parts by mass, and more preferably 0.5 to 1.0 parts by mass.
Preferably, the lithium ion battery electrolyte further comprises fluoroethylene carbonate;
preferably, the fluoroethylene carbonate accounts for 0.01 to 15 parts by mass;
preferably, the fluoroethylene carbonate accounts for 0.1 to 12 parts by mass;
preferably, the fluoroethylene carbonate is 1 to 12 parts by mass.
Preferably, the lithium ion battery electrolyte further comprises a film forming additive, wherein the film forming additive comprises one or more than two of vinylene carbonate, 1, 3-propane sultone, 1, 3-propylene sultone, triallyl isocyanurate, tri (trimethylsilyl) phosphate, triallyl phosphate, tri (trimethylsilyl) borate and (ethoxy) pentafluoroethyl cyclotriphosphazene;
Preferably, the film forming additive is 0.1 to 3.0 parts by mass;
preferably, the film-forming additive is 0.5 to 1.0 parts by mass.
Preferably, the lithium salt in the above lithium ion battery electrolyte contains lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium triflate (LiSO) 3 CF 3 ) Lithium perchlorate (LiClO) 4 ) Lithium bis (trifluoromethanesulfonyl) imide (LiN (CF) 3 SO 2 ) 2 ) Tris (trifluoromethanesulfonyl) methyllithium (LiC (CF) 3 SO 2 ) 3 ) Lithium bis (oxalato) borate (LiBOB), lithium difluorooxalato borate (LiDFOB), lithium bis (fluorosulfonyl) imide (LiLSI), lithium difluorophosphate (LiPO) 2 F 2 ) And one or two or more of lithium difluorobis (oxalato) phosphate (LiDFOP);
preferably, the lithium salt comprises lithium hexafluorophosphate and lithium difluorophosphate.
Preferably, the organic solvent in the lithium ion battery electrolyte contains one or more of ethylene carbonate, propylene carbonate, butylene carbonate, ethylmethyl carbonate, dimethylcarbonate, diethylcarbonate, dipropylcarbonate, methylpropylcarbonate, ethylpropylcarbonate, 1, 4-butyrolactone, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl difluoroacetate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, tetrahydrofuran, and 2-methyltetrahydrofuran;
Preferably, the organic solvent comprises one or more of ethylene carbonate, propylene carbonate, ethylmethyl carbonate and diethyl carbonate.
The invention also provides a preparation method of the lithium ion electrolyte, which comprises the step of mixing the raw material components at the temperature of 10-30 ℃.
The invention also provides a lithium ion battery, which comprises the lithium ion battery electrolyte.
The invention has the beneficial effects that:
the invention provides a novel lithium ion battery electrolyte additive, which has a phosphoric acid part (-P (=O) R 2 ) And an alkylsulfonic acid site (-S (=o) 2 R 1 ) Forming passivation film with small impedance at positive and negative electrodesThe low-temperature charge and discharge performance of the lithium ion battery is improved; meanwhile, the passivation film is not easy to decompose at high temperature, so that gas generation during high-temperature storage is inhibited. Therefore, the lithium ion battery electrolyte additive can balance the low-temperature charge and discharge performance and the high-temperature storage performance of the lithium ion battery.
Detailed Description
In the present specification, unless otherwise specified, symbols, units, abbreviations, and terms have the following meanings. For example, when a numerical range is represented by using-or-it includes both end points, and the units are common. For example, 5 to 25% means 5% or more and 25% or less.
In order to better understand the above technical solution, the present invention is further described in detail below.
The invention provides a lithium ion battery electrolyte additive, which comprises a compound shown in a formula 1
Wherein, in the formula 1, R 1 、R 2 Each independently selected from any one of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluoroalkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a fluoroalkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
The lithium ion electrolyte additive of the invention has a phosphate group (-P (=o) R) compared to the electrolyte solvent molecule 2 ) And a sulfonic acid group (-S (=o) 2 R 1 ) The electrolyte can be prevented from being decomposed by the passivation film formed by decomposition on the positive and negative electrode surfaces preferentially in the first charging process of the battery. The formed passivation film is firm, can prevent the increase of the battery resistance, and improves the low-temperature charge and discharge of the lithium ion battery An electrical property; meanwhile, the passivation film is not easy to decompose at high temperature, and gas generation during high-temperature storage is inhibited. Therefore, the lithium ion battery electrolyte additive can balance the low-temperature charge and discharge performance and the high-temperature storage performance of the lithium ion battery.
In a preferred embodiment of the present invention, in the formula 1, the R 1 、R 2 Each independently selected from any one of fluorine atom, methyl group, ethyl group, fluoromethyl group, fluoroethyl group, methoxy group, ethoxy group, t-butoxy group, fluoromethoxy group, fluoroethoxy group, t-butoxy group, vinyl group, propenyl group, fluorovinyl group, fluoropropenyl group, ethyleneoxy group, propyleneoxy group, fluoropropenyloxy group, propynyl group, propynyloxy group and phenyl group.
In still another preferred embodiment of the present invention, the compound represented by structural formula 1 is selected from one or two or more of the following compounds,
in still another preferred embodiment of the present invention, the compound represented by structural formula 1 is selected from one or two or more of the following compounds,
in still another preferred embodiment of the present invention, the compound represented by formula 1 is prepared by the steps of: the sulfonic acid group compound and/or the sulfuric acid group compound are reacted with phosphorus oxychloride and then are fluorinated and lithiated to obtain or the sulfonic acid group compound and/or the sulfuric acid group compound and R 2 The substituted dichlorophosphoryl is obtained by lithiation after reaction.
The invention also provides a preparation method of the lithium ion battery electrolyte additive, and the synthetic route of the compound shown in the formula 1 is as follows:
if R is 2 In the case of fluorine atoms, the synthetic routes are as followsThe following steps:
if R is 2 When the fluorine atom is not contained, the synthetic route is as follows:
wherein: a is chlorosulfonic acid, R 1 Substituted sulfonates and R 1 One or more than two of the substituted sulfates;
b is a fluorinating agent;
c is a lithium source;
d is R 1 Substituted sulfonates and/or R 1 Substituted sulfates.
For example:
when R in the compound of formula 1 1 And R is 2 When none of them is a fluorine atom, the corresponding chemical reaction formula may be as follows:
when R in the compound of formula 1 1 Is a fluorine atom, R 2 When the compound is not fluorine atom, the corresponding chemical reaction formula can be as follows:
when R in the compound of formula 1 1 Not being fluorine atoms, R 2 When the fluorine atom is a fluorine atom, the corresponding chemical reaction formula can be as follows:
when R in the compound of formula 1 1 And R is 2 Are all fluorogensThe corresponding chemical reaction formula may be as follows:
in the preparation method of the lithium ion battery electrolyte additive,
if R is 2 Is fluorine atom, comprising the steps of:
(1) The sulfonic acid group compound and/or sulfuric acid group compound reacts with phosphorus oxychloride to obtain R 1 Substituted sulfonic acid group dichlorophosphoric anhydride and/or R 1 Substituted sulfate dichlorophosphoric anhydrides;
(2) R is obtained in the step (1) 1 Substituted sulfonic acid group dichlorophosphoric anhydride and/or R 1 Reacting substituted sulfuric dichlorophosphoric anhydride with fluoridation reagent to obtain R 1 Substituted sulfonic acid group fluoro chloro phosphoric anhydride and/or R 1 Substituted sulfate-based fluoro chloro phosphoric anhydrides;
(3) Obtaining R in the step (2) 1 Substituted sulfonic acid group fluoro chloro phosphoric anhydride and/or R 1 Substituted sulfuric acid group fluoro chloro phosphoric anhydride reacts with lithium source to obtain R 1 Substituted sulfonic acid group lithium fluorophosphate anhydride salt and/or R 1 Substituted lithium sulfate fluorophosphate anhydride salts;
wherein the sulfonic acid group compound is chlorosulfonic acid, R 1 One or more than two of the substituted sulfonates, the sulfate compound is R 1 Substituted sulfates.
The molar ratio of the sulfonic acid group compound and/or sulfuric acid group compound to the phosphorus oxychloride in the step (1) is 1 (1-4);
the reaction temperature of the step (1) is 40-150 ℃ and the reaction time is 10-20 h;
r is as described in step (2) 1 Substituted sulfonic acid group dichlorophosphoric anhydride and/or R 1 The molar ratio of the substituted sulfuric dichlorophosphoric anhydride to the fluorinating agent is 1 (1-5);
the reaction temperature in the step (2) is 40-80 ℃ and the reaction time is 10-24 h;
R in the step (3) 1 Substituted sulfonic acid group fluoro chloro phosphoric anhydride and/or R 1 The molar ratio of the substituted sulfuric acid group fluoro chloro phosphoric anhydride to the lithium element in the lithium source is (1-1.2): 1;
the reaction temperature in the step (3) is 30-120 ℃ and the reaction time is 4-24 hours;
the fluoridation reagent is one or more than two of potassium fluoride, ammonium fluoride, potassium bifluoride, ammonium bifluoride, hydrogen fluoride and antimony trifluoride.
If R is 2 Is not a fluorine atom, comprising the steps of:
(1) Combining a sulphonic acid compound and/or a sulphuric acid compound with R 2 Substituted dichlorophosphoryl reacts to obtain sulfonic group chlorophosphoric anhydride and/or sulfuric group chlorophosphoric anhydride;
(2) Reacting the sulfonic acid group chlorophosphoric anhydride and/or sulfuric acid group chlorophosphoric anhydride obtained in the step (1) with a lithium source to obtain a lithium fluorosulfonate group chlorophosphoric anhydride salt and/or a lithium fluorosulfonate group chlorophosphoric anhydride salt;
wherein the sulfonic acid group compound is R 1 Substituted sulfonate, the sulfate compound is R 1 Substituted sulfates;
the sulfonic acid-based compound and/or sulfuric acid-based compound and the R in the step (1) 2 The molar ratio of the substituted dichlorophosphoryl is 1 (1-4);
the R is 2 The substituted dichlorophosphoryl is selected from one or more than two of phenylphosphoryl dichloride, methyl dichlorophosphate or methylphosphono phthalein dichloride;
The reaction temperature of the step (1) is 40-150 ℃ and the reaction time is 10-20 h;
the molar ratio of the sulfonic acid group chlorophosphoric anhydride and/or sulfuric acid group chlorophosphoric anhydride to the lithium element in the lithium source in the step (2) is (1-1.2): 1;
the reaction temperature in the step (2) is 30-120 ℃ and the reaction time is 4-24 h.
In the preparation method of the lithium ion battery electrolyte additive, R is as follows 1 Substituted sulphonates or R 1 The substituted sulphates are from commercial sources or are derived from the phase by sulphonic acidReacting corresponding alkali or salt to obtain the catalyst;
the R is 1 The substituted sulfonate is selected from one or more than two of potassium fluorosulfonate, sodium vinylsulfonate, sodium trifluoromethanesulfonate, sodium allylsulfonate, sodium phenylsulfonate, sodium methylsulfonate or sodium 2-fluoro-vinylsulfonate;
the R is 1 The substituted sulfate is selected from sodium methyl sulfate and/or sodium trifluoromethyl sulfate.
The lithium source is one or more than two of lithium hydroxide, lithium phosphate and lithium acetate.
The preparation method further comprises the steps of sequentially filtering and concentrating the reaction liquid of the final lithiation reaction to obtain mother liquid, and then crystallizing and drying, wherein the poor solvent added in the crystallization process is one or more than two of dichloromethane, 1, 2-dichloroethane, tetrahydrofuran and acetonitrile; the volume ratio of the poor solvent to the mother solution is (5-10): 1.
The invention also provides lithium ion battery electrolyte which comprises lithium salt, organic solvent and the lithium ion battery electrolyte additive, preferably, the lithium ion battery electrolyte comprises 70.0 parts of organic solvent, 10.0-20.0 parts of lithium salt and 0.1-5.0 parts of additive, further preferably, the additive is 0.2-2.0 parts, and more preferably, 0.5-1.0 parts; still more preferably, the lithium salt is 10 to 16 parts. The formed passivation film is firmer and more stable by controlling the addition amount of the additive in the electrolyte; the additive is added in proper amount, and the additive can form stable SEI film with good ion conductivity and electronic insulation on the surface of the battery, and has good tolerance to the expansion and contraction of the electrode in the circulation process; when the additive is added in excessive amount, the impedance is easy to rise, the film is loose, the thermal stability is poor, and the decomposition is easy to occur, so that the battery performance is reduced; when the addition amount is too small, the film forming effect is not obvious, the SEI film strength is weak, and the damaged SEI film cannot be repaired in subsequent circulation.
In still another preferred embodiment of the present invention, the above lithium ion battery electrolyte further comprises fluoroethylene carbonate, preferably, the fluoroethylene carbonate is 0.01 to 15 parts by mass, preferably 0.1 to 12 parts by mass, more preferably 1 to 12 parts by mass.
Fluoroethylene carbonate can be reduced to form a film on a negative electrode, the film forming resistance is small, but the consumption is excessive, and the high-temperature gas production is serious. The fluoroethylene carbonate is beneficial to improving the battery cycle performance, especially the normal temperature cycle performance, and can improve the low-temperature discharge and rate discharge performance, and the impedance of a cathode electrolyte interface film (SEI film) formed by participation of the fluoroethylene carbonate is low.
In still another preferred embodiment of the present invention, the above lithium ion battery electrolyte further comprises a film forming additive, wherein the film forming additive comprises one or more of vinylene carbonate, 1, 3-propane sultone, 1, 3-propenolactone, triallyl isocyanurate, tris (trimethylsilyl) phosphate, triallyl phosphate, tris (trimethylsilyl) borate and (ethoxy) pentafluoroethyl cyclotriphosphazene, and preferably the film forming additive is 0.1 to 3.0 parts by mass, preferably 0.5 to 1.0 parts by mass.
The film forming additive can further improve the high-temperature storage performance and the charge-discharge cycle performance of the lithium battery by being combined with the additive. For example, vinylene carbonate can be reduced to form a film on the cathode to prevent electrolyte from further decomposing on the surface of the electrode, so that the cycle performance of the battery is improved; the tri (trimethylsilyl) phosphate can form a film on the positive electrode, reduce interface impedance, and is favorable for improving the cycle performance and the discharge performance of the battery; the (ethoxy) pentafluoroethylene triphosphazene can form a film on the positive electrode to protect the positive electrode, thereby being beneficial to improving the high-temperature storage performance and inhibiting the gas production.
In still another preferred embodiment of the present invention, the lithium salt in the above lithium ion battery electrolyte comprises lithium hexafluorophosphate (LiPF 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium triflate (LiSO) 3 CF 3 ) Lithium perchlorate (LiClO) 4 ) Lithium bis (trifluoromethanesulfonyl) imide (LiN (CF) 3 SO 2 ) 2 ) Tris (trifluoromethanesulfonyl) methyllithium (LiC (CF) 3 SO 2 ) 3 ) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), bis (fluoro)Lithium sulfonimide (LiFSI), lithium difluorophosphate (LiPO) 2 F 2 ) And one or two or more of lithium difluorobis (oxalato) phosphate (LiDFOP); from the viewpoint of obtaining better performance, it is preferable to include lithium hexafluorophosphate and lithium difluorophosphate. The mixing ratio of each lithium salt in the lithium salt composition used in the present invention is not particularly limited as long as a predetermined effect can be achieved.
In still another preferred embodiment of the present invention, the organic solvent in the above lithium ion battery electrolyte contains one or more of ethylene carbonate, propylene carbonate, butylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, 1, 4-butyrolactone, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl difluoroacetate, ethyl acetate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, tetrahydrofuran, and 2-methyltetrahydrofuran; from the viewpoint of suitability of the cell system, it is preferable to contain one or two or more of ethylene carbonate, propylene carbonate, ethylmethyl carbonate and diethyl carbonate. The mixing ratio of each solvent in the solvent composition used in the present invention is not particularly limited as long as a predetermined effect can be achieved.
The application also provides a preparation method of the lithium ion electrolyte, which comprises the step of mixing the raw material components at the temperature of 10-30 ℃.
The application also provides a lithium ion battery, which comprises the lithium ion battery electrolyte.
The application is further illustrated by the following examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application.
The starting reagents in the synthesis examples of the present application were purchased from the products of the Amara Ding Huaxue reagent net, the Michelin chemical reagent net, an Naiji, TCI, admas, and the solvents from the Taitan great. The lithium salt of the electrolyte raw material is purchased from polyfluoro poly chemical industry Co., ltd, the organic solvent is purchased from Zhuhai Siraio electronic materials Co., ltd, the fluoroethylene carbonate is purchased from Jiangsu Shengshui lithium electric materials Co., ltd, the ethylene sulfate is purchased from Fujian Chuan Xin technology development Co., ltd, the raw materials for synthesizing the compound shown in 2-10 are purchased from analytical pure products of an Aba Ding Huaxue reagent net and a microphone chemical reagent net, and the compound is used after water removal to below 20 ppm. The battery material lithium nickel cobalt manganese oxide is purchased from Ningbo hundred new energy science and technology Co., ltd, the negative electrode silicon oxide material is purchased from Bei Terui new energy material Co., ltd, and the diaphragm is purchased from Shenzhen Star source material science and technology Co., ltd.
Example 1
1. Preparation of lithium ion battery electrolyte additive:
0.2mol of potassium fluorosulfonate is weighed and gradually added into 0.4mol of phosphorus oxychloride, and the mixture is stirred at 40 ℃ for reaction for 12 hours. After the reaction is finished, separating to obtain the fluorosulfonyl dichlorophosphoric anhydride through rectification;
weighing 0.2mol of fluorosulfonyl dichlorophosphoric anhydride and 0.2mol of ammonium fluoride, adding into a reaction kettle, and stirring at 40 ℃ for reacting for 12 hours to obtain fluorosulfonyl fluorochlorophosphoric anhydride;
0.1mol of fluorosulfonyl fluorochlorophosphoric anhydride and 0.1mol of lithium hydroxide monohydrate are weighed and added into a reaction kettle, 100mL of acetonitrile solvent is added into the reaction kettle, and the mixture is stirred and reacted for 24 hours at 30 ℃. And after the reaction is finished, filtering and concentrating to obtain a mother solution, adding dichloromethane with the volume of 5 times of the mother solution for crystallization, and finally drying to obtain the compound shown in the formula 2.
2. Preparation of lithium ion battery electrolyte
At the water content<In a 10ppm argon atmosphere glove box, 15.0 parts by mass of Ethylene Carbonate (EC), 5.0 parts by mass of Propylene Carbonate (PC), 35.0 parts by mass of diethyl carbonate (DEC) and 15.0 parts by mass of ethylmethyl carbonate (EMC) were uniformly mixed, and then the temperature was controlled to 15℃to obtain 15.0 parts by mass of lithium hexafluorophosphate (LiPF 6 ) And 0.5 part by mass of lithium difluorophosphate (LiPO) 2 F 2 ) Dissolving in the above organic solvent, adding 0.5 parts by mass of the compound of formula 2, 8.0 parts by mass of fluoroethylene carbonate and 2 parts by mass of (ethoxy) pentafluoroethyl cyclotriphosphazene, stirring at 200rpm with a stirrer for 30 minutes to uniformity, to obtain the lithium ion battery electrolyte of example 1 And (3) liquid.
3. Preparation of lithium ion batteries
(1) Preparation of positive plate
The positive electrode active material nickel cobalt lithium manganate (NCM 811), a conductive agent SuperP, a carbon nano tube and a binder polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 97:1:0.5:1.5 and N-methyl pyrrolidone (NMP) are uniformly mixed to prepare anode slurry, the anode slurry is coated on a current collector aluminum foil according to the thickness of 100 mu m, the anode slurry is dried at 70 ℃ and then cold-pressed at room temperature under 4Mpa, and then the anode sheet is prepared by trimming, cutting and stripping, and then welding the electrode lugs.
(2) Preparation of negative electrode sheet
The negative electrode active material silicon oxide, a conductive agent SuperP, a thickener CMC and a binder SBR are mixed according to the mass ratio of 97:1.0:1.0:1.5 mixing with purified water to prepare negative electrode slurry, coating the negative electrode slurry on a current collector copper foil according to the thickness of 100 mu m, drying at 70 ℃, cold pressing at room temperature under 4Mpa, trimming, cutting pieces, splitting, welding electrode lugs, and preparing the negative electrode sheet.
(3) Assembly of lithium ion batteries
Sequentially stacking the prepared positive plate, the membrane and the negative plate by taking the PE porous polymeric film as the membrane, enabling the membrane to be positioned between the positive plate and the negative plate, and winding to obtain a bare cell; the bare cell is arranged in an aluminum plastic shell package and is subjected to vacuum pressure of-0.95 multiplied by 10 5 Drying at 100deg.C under Pa to water content of 100ppm or less. And injecting the prepared electrolyte of the lithium ion battery of the embodiment 1 into the dried bare cell, packaging, standing, forming (0.05C constant current charging for 2h and 0.15C constant current charging for 2.5 h), shaping and capacity division (capacity test), and preparing the soft-package lithium ion battery.
Example 2
1. Preparation of lithium ion battery electrolyte
A lithium ion battery electrolyte was prepared in the same manner as in example 1, except that in preparing the lithium ion battery electrolyte, fluoroethylene carbonate was added in an amount of 1.0 parts by mass, to obtain the lithium ion battery electrolyte of example 2.
2. Preparation of lithium ion batteries
A soft pack lithium ion battery was prepared as in example 1, except that the electrolyte was the lithium ion battery electrolyte of example 2.
Example 3
1. Preparation of lithium ion battery electrolyte
A lithium ion battery electrolyte was prepared in the same manner as in example 1, except that in preparing the lithium ion battery electrolyte, fluoroethylene carbonate was added in an amount of 15.0 parts by mass, to obtain the lithium ion battery electrolyte of example 3.
2. Preparation of lithium ion batteries
A soft-pack lithium ion battery was prepared as in example 1, except that the electrolyte was the lithium ion battery electrolyte of example 3.
Example 4
1. Preparation of lithium ion battery electrolyte
A lithium ion battery electrolyte was prepared in accordance with the method of example 1, except that fluoroethylene carbonate was not added in the preparation of the lithium ion battery electrolyte, to obtain the lithium ion battery electrolyte of example 4.
2. Preparation of lithium ion batteries
A soft-pack lithium ion battery was prepared as in example 1, except that the electrolyte was the lithium ion battery electrolyte prepared in example 4.
Example 5
1. Preparation of lithium ion battery electrolyte
A lithium ion battery electrolyte was prepared as in example 1, except that (ethoxy) pentafluoroethylene triphosphazene was not added in preparing the lithium ion battery electrolyte, to give the lithium ion battery electrolyte of example 5.
2. Preparation of lithium ion batteries
A soft pack lithium ion battery was prepared as in example 1, except that the electrolyte was the lithium ion battery electrolyte prepared in example 5.
Example 6
1. Preparation of lithium ion battery electrolyte
A lithium ion battery electrolyte was prepared as in example 1, except that fluoroethylene carbonate and (ethoxy) pentafluoroethylene triphosphazene were not added in the preparation of the lithium ion battery electrolyte, to give a lithium ion battery electrolyte of example 6.
2. Preparation of lithium ion batteries
A soft pack lithium ion battery was prepared as in example 1, except that the electrolyte was the lithium ion battery electrolyte of example 6.
Example 7
1. Preparation of lithium ion battery electrolyte additive
0.2mol of sodium trifluoromethanesulfonate is weighed and gradually added into 0.2mol of phosphorus oxychloride, and the mixture is stirred at 150 ℃ for reaction for 10 hours. After the reaction is finished, separating to obtain the trifluoromethyl sulfonic group dichlorophosphoric anhydride through rectification;
weighing 0.2mol of trifluoromethyl sulfonic group dichlorophosphoric anhydride and 0.4mol of ammonium fluoride, adding into a reaction kettle, and stirring at 60 ℃ for reacting for 20 hours to obtain trifluoromethyl sulfonic group fluorochlorophosphoric anhydride;
0.1mol of trifluoromethyl sulfonic acid group fluoro-chloro phosphoric anhydride and 0.12mol of lithium hydroxide monohydrate are weighed and added into a reaction kettle, 100mL of acetonitrile solvent is added into the reaction kettle, and the mixture is stirred and reacted for 4 hours at 120 ℃. And after the reaction is finished, filtering and concentrating to obtain a mother solution, adding dichloromethane with the volume of 3 times of the mother solution for crystallization, and finally drying to obtain the compound shown in the formula 3.
2. Preparation of lithium ion battery electrolyte
At the water content<In a 10ppm argon atmosphere glove box, 15.0 parts by mass of Ethylene Carbonate (EC), 5.0 parts by mass of Propylene Carbonate (PC), 35.0 parts by mass of diethyl carbonate (DEC) and 15.0 parts by mass of ethylmethyl carbonate (EMC) were uniformly mixed, and then the temperature was controlled to 15℃to obtain 15.0 parts by mass of lithium hexafluorophosphate (LiPF 6 ) And 0.5 part by mass of lithium difluorophosphate (LiPO) 2 F 2 ) Dissolving in the organic solvent, adding 2.0 parts by mass of the compound of formula 3 prepared above and 8.0 parts by mass of fluoroethylene carbonate, and stirring at 200rpm for 30min to uniformity by using a stirrer to obtain the lithium ion battery electrolyte of example 7.
3. Preparation of lithium ion batteries
A soft-pack lithium ion battery was prepared as in example 1, except that the electrolyte was the lithium ion battery electrolyte of example 7.
Example 8
1. Preparation of lithium ion battery electrolyte additive
0.2mol of sodium vinylsulfonate is weighed and gradually added into 0.8mol of phosphorus oxychloride, and the mixture is stirred at 80 ℃ for reaction for 20 hours. After the reaction is finished, separating to obtain vinyl sulfonic group dichlorophosphoric anhydride through rectification;
weighing 0.2mol of vinyl sulfonic acid group dichlorophosphoric anhydride and 1mol of ammonium fluoride, adding into a reaction kettle, and stirring and reacting for 10 hours at 150 ℃ to obtain alkenyl sulfonic acid group fluorochlorophosphoric anhydride;
0.1mol of vinyl sulfonic acid group fluoro-chloro-phosphoric anhydride and 0.11mol of lithium hydroxide monohydrate are weighed and added into a reaction kettle, 100mL of acetonitrile solvent is added into the reaction kettle, and the mixture is stirred and reacted for 14h at 70 ℃. And after the reaction is finished, filtering and concentrating to obtain a mother solution, adding dichloromethane with the volume of 5 times of the mother solution for crystallization, and finally drying to obtain the compound shown in the formula 4.
2. Preparation of lithium ion battery electrolyte
At the water content<In a 10ppm argon atmosphere glove box, 15.0 parts by mass of Ethylene Carbonate (EC), 5.0 parts by mass of Propylene Carbonate (PC), 35.0 parts by mass of diethyl carbonate (DEC) and 15.0 parts by mass of ethylmethyl carbonate (EMC) were uniformly mixed, and then the temperature was controlled to 15℃to obtain 15.0 parts by mass of lithium hexafluorophosphate (LiPF 6 ) And 0.5 part by mass of lithium difluorophosphate (LiPO) 2 F 2 ) Dissolving in the organic solvent, adding 0.2 part by mass of the compound shown in formula 4, 8.0 parts by mass of fluoroethylene carbonate and 3 parts by mass of vinylene carbonate, and stirring at 200rpm for 30min to uniformity by using a stirrer to obtain the lithium ion battery electrolyte of example 8.
3. Preparation of lithium ion batteries
A soft-pack lithium ion battery was prepared as in example 1, except that the electrolyte was the lithium ion battery electrolyte of example 8.
Example 9
1. Preparation of lithium ion battery electrolyte additive
0.2mol of sodium allylsulfonate is weighed and gradually added into 0.4mol of phosphorus oxychloride, and the mixture is stirred at 100 ℃ for reaction for 15 hours. After the reaction is finished, separating to obtain allyl sulfonic group dichlorophosphoric anhydride through rectification;
weighing 0.2mol of allyl sulfonic acid group dichlorophosphoric anhydride and 0.6mol of ammonium fluoride, adding into a reaction kettle, and stirring at 80 ℃ for reaction for 15 hours to obtain allyl sulfonic acid group fluorochlorophosphoric anhydride;
0.1mol of allyl sulfonic acid group fluoro-chloro-phosphoric anhydride and 0.1mol of lithium hydroxide monohydrate are weighed and added into a reaction kettle, 100mL of acetonitrile solvent is added into the reaction kettle, and the mixture is stirred and reacted for 20 hours at 60 ℃. And after the reaction is finished, filtering and concentrating to obtain a mother solution, adding dichloromethane with the volume of 1 time of the mother solution for crystallization, and finally drying to obtain the compound shown in the formula 5.
2. Preparation of lithium ion battery electrolyte
At the water content<In a 10ppm argon atmosphere glove box, 15.0 parts by mass of Ethylene Carbonate (EC), 5.0 parts by mass of Propylene Carbonate (PC), 35.0 parts by mass of diethyl carbonate (DEC) and 15.0 parts by mass of ethylmethyl carbonate (EMC) were uniformly mixed, and then the temperature was controlled to 15℃to obtain 15.0 parts by mass of lithium hexafluorophosphate (LiPF 6 ) And 0.5 part by mass of lithium difluorophosphate (LiPO) 2 F 2 ) Dissolving in the above organic solvent, and adding 1.0 parts by mass of the compound of formula 5, 8.0 parts by mass of fluoroethylene carbonate and 0.5 parts by mass of 1, 3-propenesulfonic acid lactone, stirring at 200rpm with a stirrer for 30 minutes until uniform, to obtain the lithium ion battery electrolyte of example 9.
3. Preparation of lithium ion batteries
A soft pack lithium ion battery was prepared as in example 1, except that the electrolyte was the lithium ion battery electrolyte of example 9.
Example 10
1. Preparation of lithium ion battery electrolyte additive
Dissolving 0.5mol of sodium hydroxide in 100ml of water, gradually adding 0.5mol of propiolic acid into the solution, reacting for 1h at 10 ℃, concentrating, drying, and washing for multiple times by using ethanol to obtain a sodium propiolate product.
0.2mol of sodium propynylsulfonate is weighed and gradually added into 0.2mol of phosphorus oxychloride, and the mixture is stirred at 60 ℃ for reaction for 12 hours. After the reaction is finished, rectifying and separating to obtain propyne sulfonic group dichlorophosphoric anhydride;
weighing 0.2mol of propyne sulfonic acid group dichlorophosphoric anhydride and 0.4mol of ammonium fluoride, adding into a reaction kettle, and stirring at 70 ℃ for reaction for 12 hours to obtain propyne sulfonic acid group fluorochlorophosphoric anhydride;
0.1mol of propyne sulfonic acid group fluoro chloro phosphoric anhydride and 0.1mol of lithium hydroxide monohydrate are weighed and added into a reaction kettle, 100mL of acetonitrile solvent is added into the reaction kettle, and the mixture is stirred and reacted for 15 hours at 80 ℃. And after the reaction is finished, filtering and concentrating to obtain a mother solution, adding dichloromethane with the volume of 5 times of the mother solution for crystallization, and finally drying to obtain the compound shown in the formula 6.
2. Preparation of lithium ion battery electrolyte
At the water content<In a 10ppm argon atmosphere glove box, 15.0 parts by mass of Ethylene Carbonate (EC), 5.0 parts by mass of Propylene Carbonate (PC), 35.0 parts by mass of diethyl carbonate (DEC) and 15.0 parts by mass of ethylmethyl carbonate (EMC) were uniformly mixed, and then the temperature was controlled to 15℃to obtain 15.0 parts by mass of lithium hexafluorophosphate (LiPF 6 ) And 0.5 part by mass of lithium difluorophosphate (LiPO) 2 F 2 ) Dissolving in the above organic solvent, and adding 0.5 parts by mass of the compound of formula 6, 8.0 parts by mass of fluoroethylene carbonate and 1.0 parts by mass of tris (trimethylsilyl) phosphate, stirring at 200rpm with a stirrer for 30 minutes until uniform, to obtain the lithium ion battery electrolyte of example 10.
3. Preparation of lithium ion batteries
A soft pack lithium ion battery was prepared as in example 1, except that the electrolyte was the lithium ion battery electrolyte of example 10.
Example 11
1. Preparation of lithium ion battery electrolyte additive
Dissolving 0.5mol of sodium hydroxide in 100ml of water, gradually adding 0.5mol of benzenesulfonic acid into the solution, reacting for 1h at 10 ℃, concentrating, drying, and washing with ethanol for multiple times to obtain sodium benzenesulfonate product.
0.2mol of sodium benzenesulfonate is weighed and gradually added into 0.6mol of phosphorus oxychloride, and the mixture is stirred at 90 ℃ for reaction for 10 hours. After the reaction is finished, obtaining benzenesulfonic acid dichlorophosphoric anhydride through rectification and separation;
weighing 0.2mol of benzenesulfonic acid dichlorophosphoric anhydride and 0.2mol of ammonium fluoride, adding into a reaction kettle, and stirring at 50 ℃ for reacting for 18 hours to obtain benzenesulfonic acid fluorochlorophosphoric anhydride;
0.1mol of benzenesulfonic acid fluoro-chloro-phosphoric anhydride and 0.11mol of lithium hydroxide monohydrate are weighed and added into a reaction kettle, 100mL of acetonitrile solvent is added into the reaction kettle, and the mixture is stirred and reacted for 18 hours at 40 ℃. And after the reaction is finished, filtering and concentrating to obtain a mother solution, adding dichloromethane with the volume of 5 times of the mother solution for crystallization, and finally drying to obtain the compound shown in the formula 7.
2. Preparation of lithium ion battery electrolyte
At the water content<In a 10ppm argon atmosphere glove box, 15.0 parts by mass of Ethylene Carbonate (EC), 10.0 parts by mass of Propylene Carbonate (PC), 30.0 parts by mass of diethyl carbonate (DEC) and 15.0 parts by mass of ethylmethyl carbonate (EMC) were uniformly mixed, and then the temperature was controlled to 15℃to obtain 15.0 parts by mass of lithium hexafluorophosphate (LiPF 6 ) And 0.5 part by mass of lithium difluorophosphate (LiPO) 2 F 2 ) Dissolving in the above organic solvent, and adding 0.5 parts by mass of the compound of formula 7 and 8.0 parts by mass of fluoroethylene carbonate, stirring at 200rpm with a stirrer for 30 minutes until uniform, to obtain the lithium ion battery electrolyte of example 11.
3. Preparation of lithium ion batteries
A soft pack lithium ion battery was prepared as in example 1, except that the electrolyte was the lithium ion battery electrolyte of example 11.
Example 12
1. Preparation of lithium ion battery electrolyte additive
0.2mol of potassium fluorosulfonate is weighed and gradually added into 0.4mol of phenylphosphoryl dichloride, and the mixture is stirred at 40 ℃ for reaction for 12 hours. After the reaction is finished, rectifying and separating to obtain phenyl fluorosulfonic acid chlorophosphoric acid anhydride;
0.1mol of phenyl fluorosulfonic acid chlorophosphoric anhydride and 0.1mol of lithium hydroxide monohydrate are weighed and added into a reaction kettle, 100mL of acetonitrile solvent is added into the reaction kettle, and the mixture is stirred and reacted for 24 hours at 30 ℃. And after the reaction is finished, filtering and concentrating to obtain a mother solution, adding dichloromethane with the volume of 5 times of the mother solution for crystallization, and finally drying to obtain the compound shown in the formula 8.
2. Preparation of lithium ion battery electrolyte
At the water content<In a 10ppm argon atmosphere glove box, 15.0 parts by mass of Ethylene Carbonate (EC), 10.0 parts by mass of Propylene Carbonate (PC), 30.0 parts by mass of diethyl carbonate (DEC) and 15.0 parts by mass of ethylmethyl carbonate (EMC) were uniformly mixed, the temperature was controlled to 15℃and 9.5 parts by mass of lithium hexafluorophosphate (LiPF 6 ) And 0.5 part by mass of lithium difluorophosphate (LiPO) 2 F 2 ) Dissolving in the above organic solvent, and adding 5 parts by mass of the compound of formula 8, 10.0 parts by mass of fluoroethylene carbonate and 1 part by mass of tris (trimethylsilyl) phosphate, and stirring at 200rpm with a stirrer for 30 minutes until uniform, to obtain the lithium ion battery electrolyte of example 12.
3. Preparation of lithium ion batteries
A soft-pack lithium ion battery was prepared as in example 1, except that the electrolyte was the lithium ion battery electrolyte prepared in example 12.
Example 13
1. Preparation of lithium ion battery electrolyte additive
0.2mol of potassium fluorosulfonate is weighed and gradually added into 0.4mol of methyl dichlorophosphate, and the mixture is stirred at 80 ℃ for reaction for 15 hours. After the reaction is finished, obtaining methoxy substituted fluorosulfonic acid chlorophosphoric acid anhydride through rectification and separation;
weighing 0.2mol of methoxy substituted fluorosulfonic acid chlorophosphoric anhydride and 0.2mol of ammonium fluoride, adding into a reaction kettle, and stirring and reacting for 10 hours at 150 ℃ to obtain methoxy substituted fluorosulfonic acid chlorophosphoric anhydride;
0.1mol of methoxy substituted fluorosulfonic acid chlorophosphoric anhydride and 0.1mol of lithium hydroxide monohydrate are weighed and added into a reaction kettle, 100mL of acetonitrile solvent is added into the reaction kettle, and the mixture is stirred and reacted for 24 hours at 30 ℃. And after the reaction is finished, filtering and concentrating to obtain a mother solution, adding dichloromethane with the volume of 5 times of the mother solution for crystallization, and finally drying to obtain the compound shown in the formula 9.
2. Preparation of lithium ion battery electrolyte
At the water content<In a 10ppm argon atmosphere glove box, 15.0 parts by mass of Ethylene Carbonate (EC), 10.0 parts by mass of Propylene Carbonate (PC), 30.0 parts by mass of diethyl carbonate (DEC) and 15.0 parts by mass of ethylmethyl carbonate (EMC) were uniformly mixed, and then the temperature was controlled to 15℃to obtain 15.5 parts by mass of lithium hexafluorophosphate (LiPF 6 ) And 0.5 part by mass of lithium difluorophosphate (LiPO) 2 F 2 ) Dissolving in the above organic solvent, adding 2 parts by mass of the compound of formula 9 and 0.01 parts by mass of fluoroethylene carbonate, and stirring at 200rpm with a stirrer for 30 minutes until uniform, to obtain the lithium ion battery electrolyte of example 13.
3. Preparation of lithium ion batteries
A soft pack lithium ion battery was prepared as in example 1, except that the electrolyte was the lithium ion battery electrolyte prepared in example 13.
Example 14
1. Preparation of lithium ion battery electrolyte additive
0.2mol of potassium fluorosulfonate is weighed and gradually added into 0.4mol of methylphosphonic dichloride, and the mixture is stirred at 80 ℃ for reaction for 15 hours. After the reaction is finished, separating to obtain methyl fluorosulfonic acid chlorophosphoric anhydride through rectification;
0.1mol of methyl fluorosulfonic acid chlorophosphoric anhydride and 0.1mol of lithium hydroxide monohydrate are weighed and added into a reaction kettle, 100mL of acetonitrile solvent is added into the reaction kettle, and the mixture is stirred and reacted for 24 hours at 30 ℃. And after the reaction is finished, filtering and concentrating to obtain a mother solution, adding dichloromethane with the volume of 5 times of the mother solution for crystallization, and finally drying to obtain the compound shown in the formula 10.
2. Preparation of lithium ion battery electrolyte
At the water content<In a 10ppm argon atmosphere glove box, 15.0 parts by mass of Ethylene Carbonate (EC), 10.0 parts by mass of Propylene Carbonate (PC), 30.0 parts by mass of diethyl carbonate (DEC) and 15.0 parts by mass of ethylmethyl carbonate (EMC) were uniformly mixed, the temperature was controlled to 15℃and 11.5 parts by mass of lithium hexafluorophosphate (LiPF 6 ) And 0.5 part by mass of lithium difluorophosphate (LiPO) 2 F 2 ) Dissolving in the organic solvent, and adding 3 parts by mass of compound of formula 10 and 0.1 part by mass of fluorocarbonic acidVinyl ester and 5 parts by mass of tris (trimethylsilyl) phosphate were stirred at 200rpm with a stirrer for 30 minutes to uniformity, to obtain the lithium ion battery electrolyte of example 14.
3. Preparation of lithium ion batteries
A soft-pack lithium ion battery was prepared as in example 1, except that the electrolyte was the lithium ion battery electrolyte prepared in example 14.
Comparative example 1
1. Preparation of lithium ion battery electrolyte
A lithium ion battery electrolyte was prepared in the same manner as in example 3, except that 0.5 parts by mass of the compound of formula 2 was not added in the preparation of the lithium ion battery electrolyte, to obtain a lithium ion battery electrolyte of comparative example 1.
2. Preparation of lithium ion batteries
A soft pack lithium ion battery was prepared as in example 1, except that the electrolyte was the lithium ion battery electrolyte of comparative example 1.
Comparative example 2
1. Preparation of lithium ion battery electrolyte
A lithium ion battery electrolyte was prepared in accordance with the method of example 7, except that in preparing the lithium ion battery electrolyte, 2 parts by mass of the compound of formula 3 was changed to 2 parts by mass of Vinylene Carbonate (VC), to obtain a lithium ion battery electrolyte of comparative example 1.
2. Preparation of lithium ion batteries
A soft pack lithium ion battery was prepared as in example 1, except that the electrolyte was the lithium ion battery electrolyte of comparative example 2.
Application test example
The performance of the lithium ion batteries prepared in examples 1 to 14 and comparative examples 1 to 2 was tested according to the following method:
1. Low temperature discharge performance test:
the battery prepared above was charged to 4.2V at constant current and constant voltage of 0.33C, cut-off current of 0.02C, left for 5min, discharged to 2.75V at 0.33C at 25℃, the battery discharge capacity at 25℃ was recorded, and left for 5min. The battery was charged to 4.2V at a constant current and constant voltage of 0.33C, the off-current was 0.02C, the battery was placed in a low temperature box at-10℃for 5 hours, and the discharge capacity at-10℃was recorded at 0.33C to 2.75V.
-10 ℃ discharge capacity retention rate (%) = -10 ℃ discharge capacity/25 ℃ discharge capacity x 100%
2. And (3) testing normal temperature cycle performance:
the prepared battery is charged to 4.2V at constant current and constant voltage of 0.5C, cut-off current is 0.02C, and the battery is placed for 5min, then discharged to 2.75V at constant current of 1C, and placed for 5min. According to the cycle, the 500 th cycle capacity retention rate is calculated after 500 charge/discharge cycles, and the calculation formula is as follows:
500 th cycle capacity retention (%) = (500 th cycle discharge capacity/first cycle discharge capacity) ×100%.
3. High temperature cycle performance test:
first, the battery prepared above was charged to 4.2V at a constant current and constant voltage of 0.5C, the off current was 0.02C, left for 5min, and 1C discharged to 2.75V at 25 ℃, and the initial discharge capacity of the battery was recorded. The battery is placed in a high-temperature box at 45 ℃ and charged to 4.2V according to constant current and constant voltage of 0.5C, the battery is placed for 5min,1C is discharged to 2.75V, the battery is placed for 5min, and the capacity retention rate of the 500 th cycle is calculated after 500 cycles of charge/discharge according to the circulation. The calculation formula is as follows:
500 th cycle capacity retention (%) = (500 th cycle discharge capacity/first cycle discharge capacity) ×100%.
4. High temperature storage performance test:
firstly, the prepared battery is charged to 4.2V at constant current and constant voltage of 0.33C, cut-off current is 0.02C, the battery is placed for 5min, the battery is discharged to 2.75V at 0.33C, and the discharge capacity C0 of the battery before storage is recorded. Then charging the battery to a full state of 4.2V at a constant current and constant voltage at 0.33 ℃, measuring the volume V0 of the battery before high-temperature storage by using a drainage method, then placing the battery into a 60 ℃ incubator for 7 days, taking out the battery after storage, placing the battery at 25 ℃ for 12 hours, measuring the volume V1 after storage, and calculating the thickness expansion rate of the battery after the battery is stored at the constant temperature of 60 ℃ for 7 days; the battery was subjected to constant current discharge at 0.33C to 2.5V, left for 5min, and the discharge capacity C1 was recorded. Then, the charge and discharge cycle was repeated 2 times at 0.33C, and the highest primary discharge capacity was taken and designated as C2. The capacity remaining rate of the battery after being stored at the constant temperature of 60 ℃ for 7 days is calculated, and the calculation formula is as follows:
cell volume expansion ratio= (V1-V0)/v0×100% after storage at 60 ℃ for 7 days;
capacity remaining after 7 days of storage at 60 ℃ =c1/c0×100%.
5. Low-temperature discharge DC internal resistance test (DCR test)
Firstly, discharging the prepared battery to 2.75V at a constant current of 0.5C at 25 ℃, standing for 5min, charging for 1h at a constant current of 0.5C (adjusting SOC to 50%), standing for 4h at-10 ℃, discharging for 30s at a constant current of 4C, standing for 5min, and recording an initial voltage V0 and a voltage V1 after 30s of discharging. The formula for calculating the discharge DC internal resistance at 50% SOC is as follows:
DCR (mΩ) = (V0-V1)/4C discharge current 1000.
The specific results of each test are shown in table 1.
Table 1 results of performance tests of lithium ion batteries prepared in examples 1 to 14 and comparative examples 1 to 2
As can be seen from Table 1, the battery performance test results show that, relative to comparative examples 1 and 2, the lithium ion batteries prepared in examples 1 to 14 of the present invention have higher discharge capacity retention rates at-10℃than those of the comparative examples, lower DCR resistance at low temperatures than those of the comparative examples, higher volume expansion rate after storage at 60℃for 7 days and higher capacity retention rate after storage at 60℃for 7 days than those of the comparative examples, and higher normal temperature cycle performance and higher high temperature cycle performance than those of the comparative examples. Illustrating that the low-temperature charge-discharge performance and high-temperature storage performance of a lithium ion battery can be balanced by using the electrolyte additive comprising the compound of formula 1.
Compared with example 3, the lithium ion battery electrolyte prepared in comparative example 1 does not use the compound shown in the formula 1 of the invention, the volume expansion rate of comparative example 1 is obviously increased after the lithium ion battery electrolyte is stored for 7 days at 60 ℃, the DCR impedance is increased at low temperature, and the capacity remaining rate is increased after the lithium ion battery electrolyte is stored for 7 days at 60 DEG C The discharge capacity retention at-10 ℃ is also decreased. This demonstrates the effect of using the electrolyte additive comprising the compound of formula 1 of the present invention in the production of lithium ion batteries to suppress gas generation, improve the high-temperature storage performance of lithium ion batteries, improve the low-temperature charge/discharge performance, and suppress the increase in internal resistance at low temperatures. The possible mechanism is that the compound represented by formula 1 has a phosphate site (-P (=o) R 2 ) And an alkylsulfonic acid site (-S (=o) 2 R 1 ) In the first charging process of the battery, the passivation film is formed on the surfaces of the positive electrode and the negative electrode by decomposition preferentially, the formed passivation film is firmer and has higher lithium conductivity, namely the formed passivation film has smaller impedance, the overall impedance of the lithium ion battery is reduced, and meanwhile, the passivation film is not easy to decompose at high temperature, and the gas generation during high-temperature storage is inhibited, so that the high-temperature storage performance of the lithium ion battery is improved.
As is clear from a comparative analysis of example 1 and example 4, since only the compound represented by formula 1 and (ethoxy) pentafluoroethylene triphosphazene are used as additives in example 4, fluoroethylene carbonate (FEC) is not used, and thus the cycle performance of the lithium ion battery is deteriorated. This demonstrates that the fluoroethylene carbonate (FEC) used in the present invention can improve the cycle performance at low and high temperatures, and the possible mechanism is that the fluoroethylene carbonate has a low reduction potential, is preferentially reduced to form a film at the negative electrode, has a low film formation resistance, and reduces the overall resistance of the lithium ion battery.
As is clear from a comparison analysis of example 1 and example 5, since only the compound represented by formula 1 and fluoroethylene carbonate (FEC) were used as additives in example 5, and (ethoxy) pentafluoroethyl cyclotriphosphazene was not used, the high-temperature storage performance of the lithium ion battery was poor. This demonstrates that the (ethoxy) pentafluoroethylene triphosphazene used in the present invention can suppress the volume expansion and capacity loss of lithium ion batteries during high temperature storage, and a possible mechanism is that the (ethoxy) pentafluoroethylene triphosphazene preferentially decomposes on the surface of the positive electrode during the first charge of the battery compared with the solvent molecules of the electrolyte to form a passivation film, thereby suppressing the decomposition of the electrolyte, suppressing the high temperature gas generation, and thus improving the high temperature storage performance of the lithium ion battery.
As can be seen from a comparison of the analysis of example 1 with example 6, in example 6, only the compound represented by formula 1 was used, and (ethoxy) pentafluoroethylphosphazene and fluoroethylene carbonate (FEC) were not used, and the high-temperature storage performance of the lithium ion battery was worse. This also demonstrates that (ethoxy) pentafluoroethylene triphosphazene and fluoroethylene carbonate (FEC) have the effect of improving the high temperature storage performance of the battery.
The lithium ion battery electrolyte provided by the application further comprises fluoroethylene carbonate and a film forming additive, and the content ratio of the fluoroethylene carbonate and the film forming additive is precisely controlled, so that the synergistic effect of various additives is exerted, the high-temperature storage performance of the lithium ion battery can be improved, the high-temperature gas production is inhibited, the low-temperature charge and discharge performance is improved, the effect of inhibiting the increase of internal resistance at low temperature is improved, and the cycle performance at low temperature and high temperature is improved.
While the application has been described in terms of the preferred embodiment, it is not intended to limit the scope of the claims, and any person skilled in the art can make many variations and modifications without departing from the spirit of the application, so that the scope of the application shall be defined by the claims. The above description is not intended to limit the application in any way, but is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (11)
1. A lithium ion battery electrolyte additive is characterized in that the additive comprises a compound shown in a formula 1,
Wherein, in the formula 1, R 1 、R 2 Each independently selected from the group consisting of fluorine atom, alkyl group having 1 to 10 carbon atoms, fluoroalkyl group having 1 to 10 carbon atoms, and carbon atom numberAn alkoxy group having 1 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluoroalkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a fluoroalkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
2. The lithium ion battery electrolyte additive according to claim 1, wherein in the formula 1, the R 1 、R 2 Each independently selected from any one of fluorine atom, methyl group, ethyl group, fluoromethyl group, fluoroethyl group, methoxy group, ethoxy group, t-butoxy group, fluoromethoxy group, fluoroethoxy group, t-butoxy group, vinyl group, propenyl group, fluorovinyl group, fluoropropenyl group, ethyleneoxy group, propyleneoxy group, fluoropropenyloxy group, propynyl group, propynyloxy group and phenyl group.
3. The lithium ion battery electrolyte additive according to claim 1 or 2, wherein the compound represented by structural formula 1 is selected from one or more of the following compounds,
Preferably, the compound represented by the structural formula 1 is selected from one or more of the following compounds,
4. according to claims 1-3The lithium ion battery electrolyte additive is characterized in that the compound shown in the formula 1 is prepared by the following steps: the sulfonic acid group compound and/or the sulfuric acid group compound are reacted with phosphorus oxychloride and then are fluorinated and lithiated to obtain or the sulfonic acid group compound and/or the sulfuric acid group compound and R 2 The substituted dichlorophosphoryl is obtained by lithiation after reaction.
5. The method for preparing the lithium ion battery electrolyte additive according to any one of claims 1 to 4, wherein the synthetic route of the compound represented by formula 1 is as follows:
if R is 2 In the case of fluorine atoms, the synthetic route is as follows:
if R is 2 When the fluorine atom is not contained, the synthetic route is as follows:
wherein: a is chlorosulfonic acid, R 1 Substituted sulphonates or R 1 One or more than two of the substituted sulfates;
b is a fluorinating agent;
c is a lithium source;
d is R 1 Substituted sulfonates and/or R 1 Substituted sulfates.
6. The process according to claim 5, wherein when R 2 In the case of fluorine atoms, comprising the steps of:
(1) The sulfonic acid group compound and/or sulfuric acid group compound reacts with phosphorus oxychloride to obtain R 1 Substituted sulfonic acid group dichlorophosphoric anhydride and/or R 1 Substituted sulfate dichlorophosphoric anhydrides;
(2) R is obtained in the step (1) 1 SubstitutedSulfonic acid group dichlorophosphoric anhydride and/or R 1 Reacting substituted sulfuric dichlorophosphoric anhydride with fluoridation reagent to obtain R 1 Substituted sulfonic acid group fluoro chloro phosphoric anhydride and/or R 1 Substituted sulfate-based fluoro chloro phosphoric anhydrides;
(3) Obtaining R in the step (2) 1 Substituted sulfonic acid group fluoro chloro phosphoric anhydride and/or R 1 Substituted sulfuric acid group fluoro chloro phosphoric anhydride reacts with lithium source to obtain R 1 Substituted sulfonic acid group lithium fluorophosphate anhydride salt and/or R1 substituted sulfuric acid group lithium fluorophosphate anhydride salt;
wherein the sulfonic acid group compound is chlorosulfonic acid, R 1 One or more than two of the substituted sulfonates, the sulfate compound is R 1 Substituted sulfates;
preferably, the molar ratio of the sulfonic acid group compound and/or sulfuric acid group compound to the phosphorus oxychloride in the step (1) is 1 (1-4);
or preferably, the reaction temperature in the step (1) is 40-150 ℃ and the reaction time is 10-20 h;
or preferably, R in step (2) 1 Substituted sulfonic acid group dichlorophosphoric anhydride and/or R 1 The molar ratio of the substituted sulfuric dichlorophosphoric anhydride to the fluorinating agent is 1 (1-5);
Or preferably, the reaction temperature of the step (2) is 40-80 ℃ and the reaction time is 10-24 hours;
or preferably, R in step (3) 1 Substituted sulfonic acid group fluoro chloro phosphoric anhydride and/or R 1 The molar ratio of the substituted sulfuric acid group fluoro chloro phosphoric anhydride to the lithium element in the lithium source is (1-1.2): 1;
or preferably, the reaction temperature of the step (3) is 30-120 ℃ and the reaction time is 4-24 hours;
or preferably, the fluorinating agent is one or more of potassium fluoride, ammonium fluoride, potassium bifluoride, ammonium bifluoride, hydrogen fluoride and antimony trifluoride.
7. The process according to claim 5, wherein when R 2 Not being a fluorine sourceThe method comprises the following steps:
(1) Combining a sulphonic acid compound and/or a sulphuric acid compound with R 2 Substituted dichlorophosphoryl reacts to obtain sulfonic group chlorophosphoric anhydride and/or sulfuric group chlorophosphoric anhydride;
(2) Reacting the sulfonic acid group chlorophosphoric anhydride and/or sulfuric acid group chlorophosphoric anhydride obtained in the step (1) with a lithium source to obtain a lithium fluorosulfonate group chlorophosphoric anhydride salt and/or a lithium fluorosulfonate group chlorophosphoric anhydride salt;
wherein the sulfonic acid group compound is R 1 Substituted sulfonate, the sulfate compound is R 1 Substituted sulfates;
preferably, the sulfonic acid group compound and/or sulfuric acid group compound and the R in the step (1) 2 The molar ratio of the substituted dichlorophosphoryl is 1 (1-4);
or preferably, the R 2 The substituted dichlorophosphoryl is selected from one or more of phenylphosphoryl dichloride, methyl dichlorophosphate and methylphosphono phthalein dichloride;
or preferably, the reaction temperature in the step (1) is 40-150 ℃ and the reaction time is 10-20 h;
or preferably, the molar ratio of the sulfonic acid group chlorophosphoric anhydride and/or sulfuric acid group chlorophosphoric anhydride to lithium element in the lithium source in the step (2) is (1-1.2): 1;
or preferably, the reaction temperature of the step (2) is 30-120 ℃ and the reaction time is 4-24 h.
8. The preparation method according to claim 5 to 7, wherein R 1 The substituted sulfonate is selected from one or more than two of potassium fluorosulfonate, sodium vinylsulfonate, sodium trifluoromethanesulfonate, sodium propargyl sulfonate, sodium phenylsulfonate, sodium methylsulfonate and sodium 2-fluoro-vinylsulfonate; preferably, said R 1 The substituted sulfate is selected from sodium methyl sulfate and/or sodium trifluoromethyl sulfate;
or the lithium source is one or more than two of lithium hydroxide, lithium phosphate and lithium acetate.
9. A lithium ion battery electrolyte comprising a lithium salt, an organic solvent, and the additive of any one of claims 1 to 4 or the additive produced by the production method of any one of claims 5 to 8;
preferably, the organic solvent is 70.0 parts by mass, the lithium salt is 10.0 to 20.0 parts by mass, and the additive is 0.1 to 5.0 parts by mass, preferably 0.2 to 2.0 parts by mass, more preferably 0.5 to 1.0 parts by mass;
or preferably, the lithium ion battery electrolyte further comprises fluoroethylene carbonate; more preferably, the fluoroethylene carbonate is 0.01 to 15 parts by mass, preferably 0.1 to 12 parts by mass, and still more preferably 1 to 12 parts by mass;
or preferably, the lithium ion battery electrolyte further comprises a film forming additive, wherein the film forming additive comprises one or more of vinylene carbonate, 1, 3-propane sultone, 1, 3-propenesulfonic acid lactone, triallyl isocyanurate, tri (trimethylsilyl) phosphate, triallyl phosphate, tri (trimethylsilyl) borate and (ethoxy) pentafluoroethyl cyclotriphosphazene; more preferably, the film-forming additive is 0.1 to 3.0 parts by mass, preferably 0.5 to 1.0 parts by mass.
10. The lithium ion battery electrolyte of claim 9, wherein the lithium salt comprises lithium hexafluorophosphate (LiPF 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium triflate (LiSO) 3 CF 3 ) Lithium perchlorate (LiClO) 4 ) Lithium bis (trifluoromethanesulfonyl) imide (LiN (CF) 3 SO 2 ) 2 ) Tris (trifluoromethanesulfonyl) methyllithium (LiC (CF) 3 SO 2 ) 3 ) Lithium bis (oxalato) borate (LiBOB), lithium difluorooxalato borate (LiDFOB), lithium bis (fluorosulfonyl) imide (LiLSI), lithium difluorophosphate (LiPO) 2 F 2 ) And one or two or more of lithium difluorobis (oxalato) phosphate (LiDFOP); preferably, the lithium salt comprises lithium hexafluorophosphate and lithium difluorophosphate; or alternatively
The organic solvent comprises one or more than two of ethylene carbonate, propylene carbonate, butylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethylene propyl carbonate, 1, 4-butyrolactone, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl difluoroacetate, diethyl acetate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, tetrahydrofuran and 2-methyltetrahydrofuran; preferably, the organic solvent comprises one or more of ethylene carbonate, propylene carbonate, ethylmethyl carbonate and diethyl carbonate.
11. A lithium ion battery, characterized in that it comprises the lithium ion battery electrolyte according to claim 9 or 10.
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