CN114583268A - Lithium ion battery electrolyte and application thereof - Google Patents
Lithium ion battery electrolyte and application thereof Download PDFInfo
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- CN114583268A CN114583268A CN202110777330.1A CN202110777330A CN114583268A CN 114583268 A CN114583268 A CN 114583268A CN 202110777330 A CN202110777330 A CN 202110777330A CN 114583268 A CN114583268 A CN 114583268A
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- lithium
- ion battery
- lithium ion
- compound
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 104
- 239000003792 electrolyte Substances 0.000 title claims abstract description 91
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- 239000000654 additive Substances 0.000 claims abstract description 42
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 229940126062 Compound A Drugs 0.000 claims abstract description 20
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 20
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 20
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- VWEYDBUEGDKEHC-UHFFFAOYSA-N 3-methyloxathiolane 2,2-dioxide Chemical compound CC1CCOS1(=O)=O VWEYDBUEGDKEHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 t-butoxy group Chemical group 0.000 claims description 51
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 13
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 13
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 6
- 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 6
- 229910013872 LiPF Inorganic materials 0.000 claims description 5
- 229910012258 LiPO Inorganic materials 0.000 claims description 5
- 101150058243 Lipf gene Proteins 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- PFJLHSIZFYNAHH-UHFFFAOYSA-N 2,2-difluoroethyl acetate Chemical compound CC(=O)OCC(F)F PFJLHSIZFYNAHH-UHFFFAOYSA-N 0.000 claims description 4
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 4
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 4
- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical compound CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 claims description 4
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 claims description 4
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 4
- VMVNZNXAVJHNDJ-UHFFFAOYSA-N methyl 2,2,2-trifluoroacetate Chemical compound COC(=O)C(F)(F)F VMVNZNXAVJHNDJ-UHFFFAOYSA-N 0.000 claims description 4
- 229940017219 methyl propionate Drugs 0.000 claims description 4
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 4
- CDXJNCAVPFGVNL-UHFFFAOYSA-N propyl 2,2,2-trifluoroacetate Chemical compound CCCOC(=O)C(F)(F)F CDXJNCAVPFGVNL-UHFFFAOYSA-N 0.000 claims description 4
- 229940090181 propyl acetate Drugs 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910013075 LiBF Inorganic materials 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004991 fluoroalkenyl group Chemical group 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 125000004368 propenyl group Chemical group C(=CC)* 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
- 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 3
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000004428 fluoroalkoxy group Chemical group 0.000 claims description 2
- 125000006005 fluoroethoxy group Chemical group 0.000 claims description 2
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 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
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 33
- 230000000052 comparative effect Effects 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 239000002253 acid Substances 0.000 description 8
- 238000007600 charging Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- CTYRPMDGLDAWRQ-UHFFFAOYSA-N phenyl hydrogen sulfate Chemical compound OS(=O)(=O)OC1=CC=CC=C1 CTYRPMDGLDAWRQ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 150000007945 N-acyl ureas Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 230000008859 change Effects 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
- 239000011889 copper foil Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010340 shenyuan Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000009966 trimming Methods 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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 a lithium ion battery electrolyte and application thereof, wherein the lithium ion battery electrolyte comprises lithium salt, an organic solvent and an additive, the additive comprises a compound A shown in a formula (I) and a compound B shown in a formula (II), and the additive can also further comprise other additives such as 2, 4-butane sultone and the like. The lithium ion battery electrolyte can improve the high-temperature storage performance of the lithium ion battery, inhibit high-temperature gas generation, reduce impedance, improve low-temperature charge and discharge performance and improve the cycle performance at normal temperature and high temperature.
Description
Technical Field
The invention relates to the field of electrolytes for lithium ion batteries, in particular to a lithium ion battery electrolyte 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. With the expansion of the application scenes of lithium ion batteries, people pay more and more attention to the high-temperature storage performance, the low-temperature charge and discharge performance, the charge and discharge cycle performance and the like of the lithium ion batteries.
The lithium ion battery electrolyte is used as an important component of the lithium ion battery, and has great influence on the high-temperature storage performance, the low-temperature charge and discharge performance and the cycle performance of the battery. However, in general, from the perspective of lithium ion battery electrolyte, it is difficult to improve both the high temperature performance and the low temperature performance of the lithium ion battery, for example, the high temperature performance can be improved by adding a film forming additive to passivate the positive and negative electrode interfaces, but the low temperature performance of the lithium ion battery is seriously deteriorated due to the increase of the positive and negative electrode interface impedance, and in addition, the increase of the impedance is not favorable for the long-term cycle performance.
In view of the above, there is a need for a lithium ion battery electrolyte that has high-temperature storage performance, low-temperature charge and discharge performance, and charge and discharge cycle performance of a lithium battery.
Patent application CN103107355A discloses an electrolyte for lithium ion battery, wherein the branched cyclic ethylene sulfate is mixed with the unbranched cyclic ethylene sulfate or sulfonate to reduce the resistance of the battery and improve the high temperature performance and cycle performance of the battery. However, it is still insufficient in low-temperature discharge performance and high-temperature storage performance, and the acid value tends to increase, so that improvement is required.
Patent application CN108701864A discloses an electrolyte for a nonaqueous electrolyte battery, in which at least one of (1) a silane compound, (2) a cyclic sulfonic acid compound and a cyclic sulfate compound is used in a mixed manner, whereby the high-temperature storage characteristics at 70 ℃ or higher can be improved in a well-balanced manner, and the amount of gas generated during high-temperature storage can be reduced. However, the resistance is high, and the acid value of the electrolyte tends to increase during storage at high temperatures, and the storage state is unstable, so that there is a need for improvement.
Patent application CN107017433B discloses a lithium ion battery electrolyte, which comprises a non-aqueous organic solvent, a lithium salt, and an additive, wherein the additive contains aryl sulfate, etc., which is beneficial to improving capacity retention rate, discharge capacity and high temperature performance, but the volume expansion rate and internal resistance increase rate are relatively large, which is not beneficial to industrial manufacture and practical application.
Disclosure of Invention
In view of the problems in the background art, an object of the present invention is to provide a lithium ion battery electrolyte and an application thereof, which can improve the high-temperature storage performance of a lithium ion battery, suppress high-temperature gas generation and reduce impedance, and simultaneously improve the low-temperature charge and discharge performance and improve the cycle performance at normal temperature and high temperature.
The invention provides the following technical scheme:
[1] the lithium ion battery electrolyte is characterized by comprising a lithium salt, an organic solvent and an additive, wherein the additive comprises a compound A shown in a formula (I) and a compound B shown in a formula (II),
wherein, in the formula (I), R1、R2、R3、R4Independently selected from any one of hydrogen atom, fluorine atom, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, alkenyloxy with 2-10 carbon atoms, cyano and phenyl;
in the formula (II), R5、R6、R7、R8Each independently selected from any one of a hydrogen atom, 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, a carbonyl group having 1 to 10 carbon atoms, a cyano group, and a phenyl group.
[2]According to [1]The lithium ion battery electrolyte is characterized in that in the formula (II), R is5、R6、R7、R8Each independently selected from hydrogen atom, fluorine atom, methyl, ethyl, fluoromethylFluoroethyl, methoxy, ethoxy, t-butoxy, fluoromethoxy, fluoroethoxy, fluoro-t-butoxy, ethenyl, propenyl, fluoroethenyl, fluoropropenyl, ethyleneoxy, propyleneoxy, fluoroethyleneoxy, fluoropropenyloxy, formyl, acetyl, cyano, phenyl.
[3] The lithium ion battery electrolyte solution according to [1] or [2], wherein the compound A represented by the structural formula (I) contains one or more of the following compounds,
[4] the lithium ion battery electrolyte solution according to [1] or [2], wherein the compound B represented by the structural formula (II) is one or more compounds selected from the following compounds,
[5] the lithium ion battery electrolyte according to any one of [1] to [4], wherein,
the lithium salt is 5.0-20.0 parts by mass, the compound A is 0.1-5.0 parts by mass, and the compound B is 0.1-5.0 parts by mass, relative to 70.0 parts by mass of an organic solvent.
[6] The lithium ion battery electrolyte according to any one of [1] to [3], wherein the additive further contains other additives, and the other additives include one or two or more of 2, 4-butane sultone, 1, 3-propane sultone, 1, 3-propylene sultone, fluoroethylene carbonate, vinylene carbonate, triallylisocyanurate, tris (trimethylsilyl) phosphate, triallyl phosphate, and tris (trimethylsilyl) borate.
[7] The lithium ion battery electrolyte according to [6], which is characterized by comprising, by mass, 5.0 to 20.0 parts of the lithium salt, 0.1 to 5.0 parts of the compound A, 0.1 to 5.0 parts of the compound B, and 0.5 to 5.0 parts of other additives, relative to 70.0 parts of an organic solvent.
[8]According to [1]～[7]The lithium ion battery electrolyte of any of the above claims, wherein the lithium salt comprises lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium trifluoromethanesulfonate (LiSO)3CF3) Lithium perchlorate (LiClO)4) Lithium bistrifluoromethanesulfonylimide (LiN (CF)3SO2)2) Tris (trifluoromethanesulfonyl) methyllithium (LiC (CF)3SO2)3) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (lidob), lithium bis (fluorosulfonyl) imide (LiFSI), lithium difluoro (LiPO)2F2) And lithium difluorobis (oxalato) phosphate (LiDFOP), preferably lithium hexafluorophosphate and lithium difluorophosphate.
[9] The lithium ion battery electrolyte according to any one of [1] to [8], wherein the organic solvent includes one or more of ethylene carbonate, propylene carbonate, butylene carbonate, ethyl methyl 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, difluoroethyl acetate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, tetrahydrofuran, and 2-methyltetrahydrofuran, and preferably includes one or more of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, and diethyl carbonate.
[10] A lithium ion battery is characterized by comprising an electrolyte, a positive plate, a negative plate and a diaphragm, wherein the electrolyte is the lithium ion battery electrolyte in any one of the following items [1] to [9 ].
Compared with the prior art, the invention has the following beneficial effects:
the electrolyte of the lithium ion battery comprises a compound A (methylene methane disulfonate compound) shown in a formula (I) and a compound B (aryl sulfate compound) shown in a formula (II) with specific structures, and the like, and further comprises other additives, the content ratio of the compounds A (methylene methane disulfonate compound) and the compound B (aryl sulfate compound) is precisely controlled, and the synergistic effect of various additives is exerted, so that the high-temperature storage performance of the lithium ion battery can be improved, the high-temperature gas generation is inhibited, the impedance is reduced, the low-temperature charge and discharge performance is improved, and the cycle performance at normal temperature and high temperature is improved.
Detailed Description
In the present specification, unless otherwise specified, the following meanings are given to the symbols, units, abbreviations and terms. For example, when numerical ranges are expressed using "or", they include both endpoints, 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, which comprises lithium salt, an organic solvent and an additive, wherein the additive comprises a compound A shown in a formula (I) and a compound B shown in a formula (II),
wherein, in the formula (I), R1、R2、R3、R4Independently selected from any one of hydrogen atom, fluorine atom, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, alkenyloxy with 2-10 carbon atoms, cyano and phenyl;
in the formula (II), R5、R6、R7、R8Independently selected from any one of hydrogen atom, fluorine atom, alkyl group with 1-10 carbon atoms, fluoroalkyl group with 1-10 carbon atoms, alkoxyl group with 1-10 carbon atoms, fluoroalkoxyl group with 1-10 carbon atoms, alkenyl group with 2-10 carbon atoms, fluoroalkenyl group with 2-10 carbon atoms, alkenyloxy group with 2-10 carbon atoms, fluoroalkenyloxy group with 2-10 carbon atoms, carbonyl group with 1-10 carbon atoms, cyano group and phenyl group。
The methane disulfonic acid methylene ester compound shown in the formula (I) can be decomposed on the surface of a negative electrode in the first charging process of the battery, and compared with an electrolyte solvent molecule, the methane disulfonic acid methylene ester compound is preferentially decomposed to form a passivation film, so that the decomposition of the electrolyte is inhibited, the high-temperature gas production is inhibited, and the high-temperature storage performance of the lithium ion battery is improved.
The aryl sulfate represented by the formula (II) can be reduced at a negative electrode to form a Solid Electrolyte Interface (SEI) film. The aryl sulfate can form a film on a negative electrode, is compact in texture, inhibits the decomposition of a solvent, has higher conductivity, can reduce interfacial impedance, improves the low-temperature charge and discharge performance, can passivate the positive electrode by oxidizing the aryl into a film on the positive electrode, improves the cycle performance at normal temperature and high temperature, has higher stability and oxidation potential than alkyl sulfate, and can improve the high-temperature stability, overcharge resistance and other safety performances of the electrolyte.
In the above lithium ion battery electrolyte, in the formula (II), R is5、R6、R7、R8Each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a fluoromethyl group, a fluoroethyl group, a methoxy group, an ethoxy group, a t-butoxy group, a fluoromethoxy group, a fluoroethoxy group, a fluoro-t-butoxy group, a vinyl group, a propenyl group, a fluorovinyl group, a fluoropropenyl group, an ethyleneoxy group, an propyleneoxy group, a fluoroethyleneoxy group, a fluoropropyleneoxy group, a formyl group, an acetyl group, a cyano group and a phenyl group.
In the lithium ion battery electrolyte, the compound A shown in the structural formula (I) comprises one or more than two of the following compounds,
in the above lithium ion battery electrolyte, the compound B represented by the structural formula (II) is selected from one or more than two of the following compounds,
preferably aryl sulfate compounds represented by the formulae B1 to B6,
the lithium ion battery electrolyte comprises, by mass, 5.0 to 20.0 parts of the lithium salt, 0.1 to 5.0 parts of the compound A, and 0.1 to 5.0 parts of the compound B, with respect to 70.0 parts of an organic solvent.
Further, the lithium ion battery electrolyte contains 0.1 to 5.0 parts by mass of the compound a, preferably 0.2 to 2.0 parts by mass of the compound a, and more preferably 0.5 to 1.0 part by mass of the compound a, relative to 70.0 parts by mass of an organic solvent.
When the addition amount of the compound A (methylene methanedisulfonate compound) is too large, the impedance is easy to rise, the formed film is loose, the thermal stability is poor, and the decomposition is easy, so that the performance of the battery is reduced; when the amount of the additive is too small, the film forming effect is not remarkable, and the damaged SEI film cannot be repaired in the subsequent cycle.
Further, the lithium ion battery electrolyte contains 0.1 to 5.0 parts by mass of the compound B, preferably 0.5 to 2.0 parts by mass of the compound B, with respect to 70.0 parts by mass of an organic solvent.
When the addition amount of the compound B (aryl sulfate compound) is too large, the film formation is too thick, so that the impedance of the battery is increased, and the cycle performance and the rate discharge performance are deteriorated; when the addition amount is too small, the film forming effect is not obvious, and the effect of improving the battery performance is small.
In the above lithium ion battery electrolyte, the additive further comprises other additives, the other additives include one or more of 2, 4-butane sultone, 1, 3-propane sultone, 1, 3-propene sultone, fluoroethylene carbonate, vinylene carbonate, triallyl isocyanurate, tris (trimethylsilyl) phosphate, triallyl phosphate, and tris (trimethylsilyl) borate; from the viewpoint of obtaining better properties, 2, 4-butane sultone, 1, 3-propane sultone, fluoroethylene carbonate, tris (trimethylsilyl) borate are preferable.
The other additives can further improve the high-temperature storage performance and the charge-discharge cycle performance of the lithium battery by being combined with the compound A and the compound B.
For example, 2, 4-butane sultone can be reduced to form a film on a negative electrode, so that the interface impedance is reduced, and the low-temperature discharge performance is good.
The 1, 3-propane sultone can form a film on the anode to protect the anode, the vinylene carbonate can be reduced on the cathode to form a compact protective film, the triallyl isocyanurate unsaturated bond can be reduced on the cathode to form a film, and the ureide structure of the compound has a stabilizing effect on the anode.
The fluoroethylene carbonate can be reduced to form a film at a negative electrode, the film forming impedance is low, a formed solid electrolyte interface film (SEI film) is compact, the cycle performance of the battery, particularly the cycle performance at normal temperature, can be improved, the low-temperature discharge performance and the rate discharge performance can be improved, and the electric conductivity of the negative electrode SEI film formed by the fluoroethylene carbonate is high. However, when the amount of the catalyst is too large, the gas is generated at high temperature seriously, and when the amount is too small, the film formation of the negative electrode is unstable, and the cycle performance and the discharge performance are deteriorated.
The tri (trimethylsilyl) borate can form a film on the anode, reduces the interface impedance, and is beneficial to improving the cycle performance and the discharge performance of the battery.
The lithium ion battery electrolyte comprises, by mass, 5.0-20.0 parts of the lithium salt, 0.1-5.0 parts of the compound A, 0.1-5.0 parts of the compound B and 0.5-5.0 parts of other additives, relative to 70.0 parts of an organic solvent.
Further, the lithium ion battery electrolyte contains 0.5 to 5.0 parts by mass of other additives relative to 70.0 parts by mass of the organic solvent, and preferably contains 0.5 to 3.0 parts by mass of other additives, and more preferably contains 0.5 to 2.0 parts by mass of other additives, in view of obtaining better battery performance.
In the above lithium ion battery electrolyte, the lithium salt comprises lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium trifluoromethanesulfonate (LiSO)3CF3) Lithium perchlorate (LiClO)4) Lithium bistrifluoromethanesulfonylimide (LiN (CF)3SO2)2) Tris (trifluoromethanesulfonyl) methyllithium (LiC (CF)3SO2)3) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), lithium bis (fluorosulfonyl) imide (LiFSI), lithium difluorophosphate (LiPO)2F2) And lithium difluorobis (oxalato) phosphate (LiDFOP); from the viewpoint of obtaining better performance, it is preferable to contain 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 the above lithium ion battery electrolyte, the organic solvent includes one or more of ethylene carbonate, propylene carbonate, butylene carbonate, ethyl methyl 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, difluoroethyl acetate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, tetrahydrofuran, and 2-methyltetrahydrofuran; from the viewpoint of compatibility of the electrical core system, it is preferable to contain one or two or more of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, and diethyl carbonate. The blending 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 invention also provides a lithium ion battery, which comprises the electrolyte, a positive plate, a negative plate and a diaphragm, wherein the electrolyte is the lithium ion battery electrolyte.
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.
The raw material reagents in the synthesis examples of the present invention were analytically pure products from the alatin chemical reagent net, the mylin chemical reagent net, and the solvent was from the taitan great. Lithium salt of raw materials of the electrolyte is purchased from polyfluoro multi-chemical industry Co., Ltd, an organic solvent is purchased from Su Wen electronic materials Co., Ltd, fluoroethylene carbonate is purchased from Jiangsu Huasheng lithium materials Co., Ltd, ethylene sulfate is purchased from Fujian Xin scientific and technological development Co., Ltd, and a compound A (methane disulfonic acid methylene ester compound) shown in the formula (I) and a compound B (aryl sulfate compound) shown in the formula (II) are analytical pure products purchased from an avadin chemical reagent net and a milin chemical reagent net, and are used after water is removed to below 20 ppm. The battery material nickel cobalt lithium manganate is purchased from Ningbo Bai New energy science and technology, Inc., the negative electrode artificial graphite material is purchased from Beibei New energy materials, Inc., and the diaphragm is purchased from Shenzhen Shenyuan materials, science and technology, Inc. The method for producing the lithium ion battery electrolyte of the present invention is explained below.
Example 1
Preparation of lithium ion battery electrolyte
At 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 Ethyl Methyl Carbonate (EMC) were uniformly mixed, the temperature was controlled to 15 ℃, and 15.0 parts by mass of lithium hexafluorophosphate (LiPF) was added6) And 0.5 part by mass of lithium difluorophosphate (LiPO)2F2) The resulting solution was dissolved in the organic solvent, and 0.5 part by mass of compound a1, 1.0 part by mass of compound B1, and 2.0 parts by mass of 2, 4-butane sultone were added thereto, and the mixture was stirred with a stirrer at 200rpm for 30 minutes until uniform, to obtain the lithium ion battery electrolyte of example 1.
Preparation of lithium ion battery
(1) Preparation of positive plate
The preparation method comprises the following steps of (1) mixing a positive active material nickel cobalt lithium manganate (NCM811), a conductive agent SuperP, a carbon nano tube and a binder polyvinylidene fluoride (PVDF) according to a mass part ratio of 97: 1: 0.5: 1.5 and N-methyl pyrrolidone (NMP) are evenly 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 aluminum foil is dried at 70 ℃, cold pressing is carried out at the room temperature of 4Mpa, and then the anode plate is prepared by welding lugs after edge cutting, sheet cutting and strip dividing.
(2) Preparation of negative plate
The method comprises the following steps of mixing a negative active material artificial graphite, a conductive agent SuperP, a thickening agent CMC and a binding agent SBR according to a mass ratio of 97: 1.0: 1.0: 1.5 mixing with purified water to prepare negative electrode slurry, coating the slurry on a current collector copper foil according to the thickness of 100 mu m, drying at 70 ℃, cold pressing at 4Mpa at room temperature, then trimming, cutting into pieces, slitting, welding a tab and preparing a negative electrode piece.
(3) Assembly of lithium ion batteries
Taking a PE porous polymer film as a diaphragm, sequentially laminating the prepared positive plate, the diaphragm and the prepared negative plate to enable the diaphragm to be positioned between the positive plate and the negative plate, and winding to obtain a bare cell; placing the bare cell in an aluminum plastic shell package under vacuum pressure of-0.95 × 105Drying at 100 ℃ under Pa until the water content is below 100 ppm. And injecting the prepared lithium ion battery electrolyte into the dried bare cell, packaging, standing, forming (0.05C constant current charging for 2h, 0.15C constant current charging for 2.5h), shaping, and grading (capacity testing) to obtain the soft package lithium ion battery.
Example 2
A lithium ion battery electrolyte and a lithium ion battery were prepared by referring to the method of example 1, except that 2.0 parts by mass of compound a2 and 2.0 parts by mass of compound B2 were added, and no other additives were added, when preparing the lithium ion battery electrolyte.
Example 3
A lithium ion battery electrolyte and a lithium ion battery were prepared by referring to the method of example 1, except that 0.2 parts by mass of compound a3, 0.5 parts by mass of compound B3, and 3.0 parts by mass of 1, 3-propane sultone were added in the preparation of the lithium ion battery electrolyte.
Example 4
A lithium ion battery electrolyte and a lithium ion battery were prepared with reference to the method of example 1, except that 1.0 parts by mass of compound a4, 1.5 parts by mass of compound B4, and 0.5 parts by mass of fluoroethylene carbonate were added in the preparation of the lithium ion battery electrolyte.
Example 5
A lithium ion battery electrolyte and a lithium ion battery were prepared by referring to the method of example 1, except that 0.5 parts by mass of compound a5, 1.0 parts by mass of compound B5, and 1.0 parts by mass of tris (trimethylsilyl) borate were added at the time of preparing the lithium ion battery electrolyte.
Example 6
A lithium ion battery electrolyte and a lithium ion battery were prepared with reference to the method of example 1, except that, in preparing the lithium ion battery electrolyte, 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 Ethyl Methyl Carbonate (EMC) were uniformly mixed, and 0.5 parts by mass of compound a6 and 1.0 part by mass of compound B6 were added, without adding other additives.
Comparative example 1
A lithium ion battery electrolyte and a lithium ion battery were prepared with reference to the method of example 1, except that 1.0 part by mass of the compound B1 was changed to 1.0 part by mass of vinyl sulfate (DTD) in preparing the lithium ion battery electrolyte.
Comparative example 2
A lithium ion battery electrolyte and a lithium ion battery were prepared with reference to the method of example 2, except that 2.0 parts by mass of compound B2 was changed to 2.0 parts by mass of vinyl sulfate (DTD) in preparing the lithium ion battery electrolyte.
Comparative example 3
A lithium ion battery electrolyte and a lithium ion battery were prepared with reference to the method of example 1, except that 1.0 part by mass of compound B1 was not used in preparing the lithium ion battery electrolyte.
Comparative example 4
A lithium ion battery electrolyte and a lithium ion battery were prepared with reference to the method of example 1, except that 0.5 part by mass of compound a1 was not used in preparing the lithium ion battery electrolyte.
The compositions of the electrolytes of the lithium ion batteries of examples 1 to 6 and comparative examples 1 to 3 are shown in table 1. In table 1, EC represents ethylene carbonate, PC represents propylene carbonate, DEC represents diethyl carbonate, and EMC represents ethyl methyl carbonate.
TABLE 1
The following describes the test procedure and test results of the lithium ion battery.
1. And (3) testing low-temperature discharge performance:
the cells prepared above were charged at 25 ℃ to 4.2V at constant current and constant voltage of 0.33C, current cut off 0.02C, left for 5min, discharged at 25 ℃ to 2.75V at 0.33C, and the cell discharge capacity at 25 ℃ was recorded and left for 5 min. Charging to 4.2V at constant current and constant voltage of 0.33C, cutting off current of 0.02C, placing the battery in a low-temperature box at minus 10 ℃ for 5h, discharging to 2.75V at 0.33C, and recording the discharge capacity at minus 10 ℃.
-10 ℃ discharge capacity retention (%) -10 ℃ discharge capacity/25 ℃ discharge capacity × 100%
2. And (3) testing the high-temperature storage performance:
firstly, charging the prepared battery to 4.2V at a constant current and a constant voltage of 0.33C and stopping the current at 0.02C at 25 ℃, standing for 5min, discharging to 2.75V at 0.33C, and recording the discharge capacity C0 before the battery is stored. Then charging the battery to a full state of 4.2V at a constant current and a constant voltage at 0.33C, measuring the volume V0 of the battery before high-temperature storage by using a drainage method, then placing the battery into a constant temperature box at 60 ℃ for storage for 7 days, taking out the battery after the storage is finished, placing the battery for 12 hours at 25 ℃, measuring the volume V1 after the storage, and calculating the thickness expansion rate of the battery after the constant temperature storage at 60 ℃ for 7 days; the cell was discharged to 2.5V at 0.33C constant current, left for 5min and the discharge capacity C1 was recorded. Then, the charge and discharge were cycled 2 times at 0.33C, and the highest one-time discharge capacity was recorded as C2. And (3) calculating the capacity residual rate of the battery after being stored for 7 days at the constant temperature of 60 ℃, wherein the calculation formula is as follows:
the battery volume expansion rate after 7 days of storage at 60 ═ (V1-V0)/V0 × 100%;
the capacity remaining rate after 7 days of storage at 60 ═ C1/C0 × 100%;
3. and (3) testing the normal-temperature cycle performance:
charging the prepared battery to 4.2V at constant current and constant voltage of 0.5C and stopping current of 0.02C at 25 deg.C, standing for 5min, and discharging to 2.75V at constant current of 1C, standing for 5 min. According to the cycle, after 500 cycles of charge/discharge, the capacity retention rate of the 500 th cycle is calculated, and the calculation formula is as follows:
the 500 th cycle capacity retention ratio (%) (500 th cycle discharge capacity/first cycle discharge capacity) × 100%.
4. And (3) testing high-temperature cycle performance:
firstly, charging the prepared battery to 4.2V at a constant current and a constant voltage of 0.5C and stopping current of 0.02C at 25 ℃, standing for 5min, discharging at 1C to 2.75V, and recording the initial discharge capacity of the battery. And (3) placing the battery in a high-temperature box at 45 ℃, charging the battery to 4.2V at a constant current and a constant voltage of 0.5C, standing for 5min, discharging the battery to 2.75V at 1C, standing for 5min, circulating according to the above, and calculating the capacity retention rate of the 500-week circulation after 500 cycles of charging/discharging. The calculation formula is as follows:
the 500 th cycle capacity retention ratio (%) (500 th cycle discharge capacity/first cycle discharge capacity) × 100%.
5. Discharge DC internal resistance test (DCR test)
The battery prepared above was first discharged at a constant current of 0.5C to 2.75V at 25 ℃, left for 5min, charged at a constant current of 0.5C for 1h (SOC adjusted to 50%), the battery adjusted to 50% SOC was left for 5min at 25 ℃, discharged at a constant current of 4C for 30s, left for 5min, and the initial voltage V0 and the voltage V1 after discharge for 30s were recorded. The calculation formula of the discharging direct current internal resistance at 50% SOC is as follows:
DCR (m Ω) — (V0-V1)/4C discharge current × 1000.
6. High temperature storage Property test of electrolyte (acid value Change test)
Firstly, testing the prepared electrolyte by adopting a potentiometric titration method at 25 ℃, recording an initial acid value, then placing the electrolyte packaged by an aluminum-plastic film in a 45 ℃ high-temperature box for storage for 30 days, taking out the electrolyte after the storage is finished, testing the acidity again at 25 ℃, and recording the acidity as the acid value after the storage for 30 days at 45 ℃.
The specific results of the tests are shown in table 2.
TABLE 2
As is apparent from comparative analysis of examples 1 to 6 with comparative examples 1 and 2 based on tables 1 and 2, since methylene methyldisulfonate compound A and vinyl sulfate (DTD) represented by formula (I) and other additives, 2, 4-butane sultone, were used as additives in comparative example 1 and methylene methyldisulfonate compound A and vinyl sulfate (DTD) represented by formula (I) were used as additives in comparative example 2, and aryl sulfate compound B represented by formula (II) of the present invention was not used in both comparative examples, the acid value of the electrolytes in comparative examples 1 and 2 was significantly increased after high-temperature storage. This shows that the arylsulfate compound B represented by the formula (II) used in the present invention can suppress an increase in the acid value, reduce the generation of hydrofluoric acid, and improve the high-temperature storage stability of the electrolyte. The possible mechanism is that the aryl sulfate compound B shown in the formula (II) contains benzene rings, so that the structure is more stable, and the increase of the acid value of the electrolyte caused by the instability of the additive in the high-temperature storage process is inhibited; however, the vinyl sulfate in comparative examples 1 and 2 is deteriorated in stability after storage at high temperature, ring opening may occur to generate undesirable impurities.
From tables 1 and 2, comparing examples 1 to 6 with comparative example 3, it is found that the lithium ion battery is inferior in low-temperature charge and discharge properties and cycle properties because only methylene methyldisulfonate compound a represented by formula (I) and 2, 4-butanesultone are used as additives in comparative example 3 and aryl sulfate compound B represented by formula (II) is not used. This shows that the aryl sulfate compound B represented by formula (II) used in the present invention can reduce the interface impedance of a lithium ion battery, improve low-temperature charge and discharge performance, and improve cycle performance at normal temperature and high temperature, and the possible mechanism is that the reduction potential of unsaturated bonds in the aryl sulfate compound B represented by formula (II) is low, and the reduction film formation is preferentially performed on the negative electrode, and the film formation impedance is low, reducing the impedance of the entire lithium ion battery.
From tables 1 and 2, comparing examples 1 to 6 with comparative example 4, it is found that in comparative example 4, only the arylsulfonate compound B represented by the formula (II) and 2, 4-butanesultone were used as additives, and the methylene methyldisulfonate compound A represented by the formula (I) was not used, and thus the high-temperature storage performance of the lithium ion battery was poor. This shows that the methylene methyldisulfonate compound a represented by formula (I) used in the present invention can suppress volume expansion and capacity loss of the lithium ion battery during high temperature storage, and the possible mechanism is that the methylene methyldisulfonate compound a represented by formula (I) is preferentially decomposed on the surface of the negative electrode during the first charge of the battery compared to electrolyte solvent molecules to form a passivation film, thereby suppressing decomposition of the electrolyte, suppressing high temperature gas generation, and improving the high temperature storage performance of the lithium ion battery.
The electrolyte of the lithium ion battery contains the methylene methane disulfonate compound shown in the formula (I) and the aryl sulfate compound shown in the formula (II) with specific structures, and further contains other additives, and the content proportion of the methylene methane disulfonate compound and the aryl sulfate compound 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, high-temperature gas generation is inhibited, the impedance is reduced, the low-temperature charge and discharge performance is improved, and the cycle performance at normal temperature and high temperature is improved.
Although the present application has been described with reference to preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the application.
In examples 1 to 15 and comparative examples 1 to 13, only ethylene carbonate, propylene carbonate, diethyl carbonate and ethyl methyl carbonate were used as the organic solvent, but butylene carbonate, dimethyl 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, difluoroethyl acetate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, tetrahydrofuran and 2-methyltetrahydrofuran were all used as the organic solvent in the reaction for preparing the electrolyte solution of the present invention, and the same action and technical effects as those of the organic solvent used in the examples were obtained, and thus the present invention was applied.
In examples 1 to 15 and comparative examples 1 to 13, lithium hexafluorophosphate (LiPF) alone was used as the lithium salt6) Lithium difluorophosphate (LiPO)2F2) Lithium tetrafluoroborate (LiBF4), lithium difluorooxalato borate (LiODFB), lithium bis (fluorosulfonyl) imide (LiFSI) due to lithium trifluoromethanesulfonate (LiSO)3CF3) Lithium bistrifluoromethanesulfonylimide (LiN (CF)3SO2)2) Lithium perchlorate (LiClO)4) Tris (trifluoromethanesulfonyl) methyllithium (LiC (CF)3SO2)3) Lithium bis (oxalato) borate (LiBOB) and the like can be used as lithium salts in the reaction for preparing the electrolyte of the present invention, and the lithium salts have the same or similar effects in action and technical effects as those of the substances used as the lithium salts in the examples, and are therefore suitable for the present invention.
The above description is only for the purpose of illustrating the present invention, but not for the purpose of limiting the same, and the present invention is not limited thereto. Numerous simple deductions, modifications or substitutions may be made by those skilled in the art in light of the teachings of the present invention. Such deductions, modifications or alternatives also fall within the scope of the claims of the present invention.
Claims (10)
1. The lithium ion battery electrolyte is characterized by comprising a lithium salt, an organic solvent and an additive, wherein the additive comprises a compound A shown in a formula (I) and a compound B shown in a formula (II),
wherein, in the formula (I), R1、R2、R3、R4Independently selected from any one of hydrogen atom, fluorine atom, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, alkenyloxy with 2-10 carbon atoms, cyano and phenyl;
in the formula (II), R5、R6、R7、R8Each independently selected from any one of a hydrogen atom, 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, a carbonyl group having 1 to 10 carbon atoms, a cyano group, and a phenyl group.
2. The lithium ion battery electrolyte of claim 1, wherein in the formula (II), R is5、R6、R7、R8Each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a fluoromethyl group, a fluoroethyl group, a methoxy group, an ethoxy group, a t-butoxy group, a fluoromethoxy group, a fluoroethoxy group, a fluoro-t-butoxy group, a vinyl group, a propenyl group, a fluorovinyl group, a fluoropropenyl group, an ethyleneoxy group, an propyleneoxy group, a fluoroethyleneoxy group, a fluoropropenyloxy group, a formyl group, an acetyl group, a cyano group, and a phenyl group.
3. The lithium ion battery electrolyte of claim 1 or 2, wherein the compound A represented by the structural formula (I) comprises one or more of the following compounds,
4. the lithium ion battery electrolyte of claim 1 or 2, wherein the compound B represented by the structural formula (II) is one or more selected from the following compounds,
5. the lithium ion battery electrolyte according to any one of claims 1 to 4, wherein the lithium salt is contained in an amount of 5.0 to 20.0 parts by mass, the compound A is contained in an amount of 0.1 to 5.0 parts by mass, and the compound B is contained in an amount of 0.1 to 5.0 parts by mass, relative to 70.0 parts by mass of the organic solvent.
6. The lithium ion battery electrolyte of any one of claims 1-3, wherein the additive further comprises other additives, and the other additives comprise one or more of 2, 4-butane sultone, 1, 3-propane sultone, 1, 3-propene sultone, fluoroethylene carbonate, vinylene carbonate, triallylisocyanurate, tris (trimethylsilyl) phosphate, triallyl phosphate, and tris (trimethylsilyl) borate.
7. The lithium ion battery electrolyte according to claim 6, wherein the lithium salt is contained in an amount of 5.0 to 20.0 parts by mass, the compound A is contained in an amount of 0.1 to 5.0 parts by mass, the compound B is contained in an amount of 0.1 to 5.0 parts by mass, and other additives are contained in an amount of 0.5 to 5.0 parts by mass, based on 70.0 parts by mass of the organic solvent.
8. The lithium ion battery electrolyte of any of claims 1-7Wherein the lithium salt comprises lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium trifluoromethanesulfonate (LiSO)3CF3) Lithium perchlorate (LiClO)4) Lithium bistrifluoromethanesulfonylimide (LiN (CF)3SO2)2) Tris (trifluoromethanesulfonyl) methyllithium (LiC (CF)3SO2)3) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (lidob), lithium bis (fluorosulfonyl) imide (LiFSI), lithium difluoro (LiPO)2F2) And lithium difluorobis (oxalato) phosphate (LiDFOP), preferably lithium hexafluorophosphate and lithium difluorophosphate.
9. The lithium ion battery electrolyte of any one of claims 1-8, wherein the organic solvent comprises one or more of ethylene carbonate, propylene carbonate, butylene carbonate, ethyl methyl 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, difluoroethyl acetate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, tetrahydrofuran, and 2-methyltetrahydrofuran, and preferably comprises one or more of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, and diethyl carbonate.
10. A lithium ion battery, characterized in that, it includes electrolyte, positive plate, negative plate, and diaphragm, the electrolyte is the lithium ion battery electrolyte of any claim 1-9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115141175A (en) * | 2022-07-04 | 2022-10-04 | 多氟多新材料股份有限公司 | Method for preparing cyclic sulfate |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103178291A (en) * | 2011-12-26 | 2013-06-26 | 索尼公司 | Electrolytic solution, secondary battery, battery pack, electric vehicle, and electric power storage system |
| JP2015162289A (en) * | 2014-02-26 | 2015-09-07 | 三井化学株式会社 | Nonaqueous electrolyte for batteries, and lithium secondary battery |
| CN105895955A (en) * | 2016-06-02 | 2016-08-24 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery |
| CN107017433A (en) * | 2016-01-28 | 2017-08-04 | 宁德新能源科技有限公司 | Nonaqueous electrolytic solution and lithium ion battery |
| CN109119685A (en) * | 2017-06-23 | 2019-01-01 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery |
| CN109776485A (en) * | 2019-01-04 | 2019-05-21 | 蜂巢能源科技有限公司 | Compound, electrolyte and lithium ion battery |
| CN109873206A (en) * | 2019-04-16 | 2019-06-11 | 威马智慧出行科技（上海）有限公司 | Lithium-ion battery electrolytes and lithium ion battery |
| CN112436189A (en) * | 2020-11-30 | 2021-03-02 | 广州天赐高新材料股份有限公司 | Composition, electrolyte containing composition and lithium ion battery |
-
2021
- 2021-07-09 CN CN202110777330.1A patent/CN114583268A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103178291A (en) * | 2011-12-26 | 2013-06-26 | 索尼公司 | Electrolytic solution, secondary battery, battery pack, electric vehicle, and electric power storage system |
| JP2015162289A (en) * | 2014-02-26 | 2015-09-07 | 三井化学株式会社 | Nonaqueous electrolyte for batteries, and lithium secondary battery |
| CN107017433A (en) * | 2016-01-28 | 2017-08-04 | 宁德新能源科技有限公司 | Nonaqueous electrolytic solution and lithium ion battery |
| CN105895955A (en) * | 2016-06-02 | 2016-08-24 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery |
| CN109119685A (en) * | 2017-06-23 | 2019-01-01 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery |
| CN109776485A (en) * | 2019-01-04 | 2019-05-21 | 蜂巢能源科技有限公司 | Compound, electrolyte and lithium ion battery |
| CN109873206A (en) * | 2019-04-16 | 2019-06-11 | 威马智慧出行科技（上海）有限公司 | Lithium-ion battery electrolytes and lithium ion battery |
| CN112436189A (en) * | 2020-11-30 | 2021-03-02 | 广州天赐高新材料股份有限公司 | Composition, electrolyte containing composition and lithium ion battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115141175A (en) * | 2022-07-04 | 2022-10-04 | 多氟多新材料股份有限公司 | Method for preparing cyclic sulfate |
| CN115141175B (en) * | 2022-07-04 | 2024-02-02 | 多氟多新材料股份有限公司 | Method for preparing cyclic sulfate |
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