CN117154218A - Electrolyte and battery comprising same - Google Patents
Electrolyte and battery comprising same Download PDFInfo
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- CN117154218A CN117154218A CN202311067798.7A CN202311067798A CN117154218A CN 117154218 A CN117154218 A CN 117154218A CN 202311067798 A CN202311067798 A CN 202311067798A CN 117154218 A CN117154218 A CN 117154218A
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- Prior art keywords
- unsubstituted
- lithium
- substituted
- negative electrode
- group
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 47
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910013872 LiPF Inorganic materials 0.000 claims abstract description 6
- 101150058243 Lipf gene Proteins 0.000 claims abstract description 6
- 239000007773 negative electrode material Substances 0.000 claims description 41
- 125000000217 alkyl group Chemical group 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000000654 additive Substances 0.000 claims description 25
- 230000000996 additive effect Effects 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- -1 lithium hexafluorophosphate Chemical group 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 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 4
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 125000006570 (C5-C6) heteroaryl group Chemical group 0.000 claims description 2
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 18
- 239000002253 acid Substances 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 5
- 238000004146 energy storage Methods 0.000 abstract description 5
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 17
- 239000010405 anode material Substances 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 9
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 4
- 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 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000005392 carboxamide group Chemical group NC(=O)* 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical group 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 125000005463 sulfonylimide group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The application provides an electrolyte and a battery comprising the same. The application reduces fluoroethylene carbonate molecules and LiPF by adding steric hindrance groups and/or electron donating groups to FEC molecules 6 Thereby generating less HF acid, further improving the high temperature performance of the battery, simultaneously overcoming the problem that the prior fluoroethylene carbonate can cause thermal failure of the battery in a high temperature environment, and further improving the electrochemical performance and the safety performance of the lithium ion battery in the high temperature environment. The electrolyte is expected to provide lithium ion batteries with higher electrochemical performance and safety performance for electric automobiles, mobile electronic equipment and large-scale energy storage systems, thereby promoting the further development of the fields.
Description
The application claims the priority of the prior application of the patent application number 202310812444.4 which is filed by the China national intellectual property agency on the 7 th and 4 th days of 2023 and is named as an electrolyte and a battery comprising the electrolyte. The entirety of this prior application is incorporated by reference into the present application.
Technical Field
The application belongs to the technical field of electrolyte, and particularly relates to electrolyte and a battery comprising the same.
Background
Lithium Ion Batteries (LIBs) are considered suitable power sources in mobile electronic devices, electric vehicles, and mass energy storage systems due to their high energy density and long cycle life. In order to increase the energy density of lithium ion batteries, researchers have developed electrode materials with high reversible capacities, including high voltage cathode materials and near 0V (relative to Li/Li + ) Is a low operating potential negative electrode material.
However, degradation of the electrode-electrolyte interface may result in poor battery cycling performance. In order to stabilize the electrode-electrolyte interface, various methods such as electrode material surface coating and the use of electrolyte additives have been proposed. The formation of an artificial Solid Electrolyte Interface (SEI) by using reducible and oxidizable compounds is one of the most effective strategies for improving the stability of electrode-electrolyte interfaces.
Silicon (Si) is considered as the most promising negative electrode material in next generation lithium ion batteries because of its high theoretical capacity. However, as the silicon anode undergoes a large volume change during cycling, the silicon particles break up and create new active surface sites, which may lead to further irreversible electrolyte decomposition. To improve the electrochemical performance of silicon negative electrodes, fluoroethylene carbonate (FEC) is used as a highly efficient reducible additive to be incorporated into the cells of silicon negative electrode systems. It has been shown that FEC as an additive can effectively change the properties of the negative electrode surface SEI layer and improve the electrochemical properties of the negative electrode such as graphite and silicon.
Although FEC has a beneficial effect on the negative electrode, its decomposition mechanism is still under investigation. FEC can be decomposed into components such as Vinyl Carbonate (VC), hydrofluoric acid (HF), etc. However, studies have reported that FEC-derived SEI films may adversely affect electrochemical performance in certain battery systems. Koeun Kim et al studied the effect of FEC and EC-based electrolytes on LCO-NCM/Si-C electrode cycling performance and showed that the capacity loss of FEC was greater at 60℃ than that of the EC-based electrolyte. They believe that at high temperatures, FEC reacts with lithium hexafluorophosphate to produce relatively much hydrofluoric acid, leading to dissolution of the positive metal ions and ultimately to capacity degradation.
Thus, although FEC has a positive effect in improving electrochemical performance of a silicon anode, it has become important to seek improved FEC because it is decomposed to generate hydrofluoric acid (HF) under a high temperature environment, and reacts with some organic salts while damaging a positive electrode material to cause a problem of thermal failure of a battery.
Disclosure of Invention
In order to solve the problem that fluoroethylene carbonate (FEC) can cause thermal failure of a battery under a high-temperature environment, the application aims to provide an electrolyte and a battery comprising the electrolyte. The application reduces fluoroethylene carbonate molecules and LiPF by adding steric hindrance groups and/or electron donating groups to FEC molecules 6 Thereby generating less HF acid, further improving the high temperature performance of the battery, simultaneously overcoming the problem that the prior fluoroethylene carbonate can cause thermal failure of the battery in a high temperature environment, and further improving the electrochemical performance and the safety performance of the lithium ion battery in the high temperature environment. The electrolyte is expected to provide lithium ion batteries with higher electrochemical performance and safety performance for electric automobiles, mobile electronic equipment and large-scale energy storage systems, thereby promoting the further development of the fields.
The application aims at realizing the following technical scheme:
an electrolyte comprising an organic solvent, an electrolyte lithium salt, and an additive; the additive is a fluoroethylene carbonate compound modified by an R group; the R group is a steric hindrance group and/or an electron donating group.
According to an embodiment of the present application, the electron donating group refers to a group that can raise the electron cloud density on the ethylene carbonate ring.
According to an embodiment of the present application, the steric hindrance group refers to a group that causes mutual repulsion of the internal molecular structure of fluoroethylene carbonate in the steric arrangement.
According to an embodiment of the application, the R group is selected from the group consisting of-CHO, -OH, -NR 1 R 2 、-S(＝O)NR 1 R 2 、-S(＝O) 2 NR 1 R 2 、-CONR 1 R 2 -OC (=o) H, -NHCOH, substituted or unsubstituted-S-C 1-12 Alkyl, substituted or unsubstituted-OC (=o) C 1-12 Alkyl, substituted or unsubstituted-NHCOC 1-12 Alkyl, substituted or unsubstituted C 1-12 Alkyl, substituted or unsubstituted C 6-12 Aryl, substituted or unsubstituted C 2-12 Alkenyl, substituted or unsubstituted 5-12 membered heteroaryl; in the case of substitution, the substituent is C 1-12 An alkyl group; r is R 1 And R is 2 Identical or different, independently of one another, from H, C 1-12 An alkyl group.
According to an embodiment of the application, the R group is selected from the group consisting of-CHO, -OH, -NR 1 R 2 、-S(＝O)NR 1 R 2 、-S(＝O) 2 NR 1 R 2 、-CONR 1 R 2 -OC (=o) H, -NHCOH, substituted or unsubstituted-S-C 1-6 Alkyl, substituted or unsubstituted-OC (=o) C 1-6 Alkyl, substituted or unsubstituted-NHCOC 1-6 Alkyl, substituted or unsubstituted C 1-6 Alkyl, substituted or unsubstituted C 6-8 Aryl, substituted or unsubstituted C 2-6 Alkenyl, substituted or unsubstituted 5-8 membered heteroaryl; in the case of substitution, the substituent is C 1-6 An alkyl group; r is R 1 And R is 2 Identical or different, independently of one another, from H, C 1-6 An alkyl group.
According to an embodiment of the application, the R group is selected from the group consisting of-CHO, -OH, -NR 1 R 2 、-S(＝O)NR 1 R 2 、-S(＝O) 2 NR 1 R 2 、-CONR 1 R 2 -OC (=o) H, -NHCOH, substituted or unsubstituted-S-C 1-3 Alkyl, substituted or unsubstituted-OC (=o) C 1-3 Alkyl, substituted or unsubstituted-NHCOC 1-3 Alkyl, substituted or unsubstituted C 3-6 Alkyl, substituted or unsubstituted C 6-7 Aryl, substituted or unsubstituted C 3-6 Alkenyl, substituted or unsubstituted 5-6 membered heteroaryl; in the case of substitution, the substituent is C 1-3 An alkyl group; r is R 1 And R is 2 Identical or different, independently of one another, from H, C 1-3 An alkyl group.
According to an embodiment of the application, the R group is selected from the group consisting of-CHO, -OH, -NH 2 、-S(＝O)NH 2 、-S(＝O) 2 N(CH 3 ) 2 、-CONH 2 、-OC(＝O)H、-NHCOH、-S-CH 3 、-OC(＝O)CH 3 、-NHCOCH 3 Tertiary butyl, benzyl, cyclopentadienyl, and pyridyl.
According to an embodiment of the application, the additive is selected from at least one of the compounds having the formula I:
wherein R is defined as above.
According to an embodiment of the present application, the additive is selected from at least one of the compounds represented by formulas 1 to 5:
according to an embodiment of the application, the electrolyte lithium salt is selected from lithium hexafluorophosphate (LiPF) 6 ) Or is selected from lithium hexafluorophosphate (LiPF) 6 ) A combination with at least one of the following electrolyte lithium salts: lithium difluorophosphate (LiPO) 2 F 2 ) Lithium difluorooxalato borate (LiDFOB), lithium bistrifluoromethylsulfonyl imide, lithium difluorobisoxalato phosphate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium hexafluoroantimonate, lithium hexafluoroarsenate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (pentafluoroethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methyl lithium, lithium bis (trifluoromethylsulfonyl) imide.
According to an embodiment of the present application, the organic solvent is selected from carbonates and/or carboxylates selected from at least one of Ethylene Carbonate (EC), propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethylmethyl carbonate; the carboxylic acid ester is at least one selected from propyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, propyl Propionate (PP), ethyl Propionate (EP), methyl butyrate and ethyl n-butyrate.
According to an embodiment of the application, the weight of the additive is 5% to 20%, preferably 10% to 15%, for example 10%, 12%, 13%, 14% or 15% of the total weight of organic solvents in the electrolyte.
According to an embodiment of the application, the electrolyte is used in a battery, preferably in a lithium ion battery.
The application also provides a battery, which comprises the electrolyte.
According to an embodiment of the present application, the battery further includes a positive electrode sheet containing a positive electrode active material, a negative electrode sheet containing a negative electrode active material, and a separator.
According to an embodiment of the present application, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer coated on one or both side surfaces of the positive electrode current collector, the positive electrode active material layer including a positive electrode active material, a conductive agent, and a binder.
According to an embodiment of the present application, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer coated on one or both side surfaces of the negative electrode current collector, the negative electrode active material layer including a negative electrode active material, a conductive agent, and a binder.
According to an embodiment of the present application, the positive electrode active material layer comprises the following components in percentage by mass: 80 to 99.8 weight percent of positive electrode active material, 0.1 to 10 weight percent of conductive agent and 0.1 to 10 weight percent of binder.
Preferably, the positive electrode active material layer comprises the following components in percentage by mass: 90 to 99.6 weight percent of positive electrode active material, 0.2 to 5 weight percent of conductive agent and 0.2 to 5 weight percent of binder.
According to an embodiment of the present application, the mass percentage of each component in the anode active material layer is: 80 to 99.8 weight percent of negative electrode active material, 0.1 to 10 weight percent of conductive agent and 0.1 to 10 weight percent of binder.
Preferably, the mass percentage of each component in the anode active material layer is as follows: 90 to 99.6 weight percent of negative electrode active material, 0.2 to 5 weight percent of conductive agent and 0.2 to 5 weight percent of binder.
According to an embodiment of the present application, the conductive agent is at least one selected from conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, metal powder, and carbon fiber.
According to an embodiment of the present application, the binder is at least one selected from sodium carboxymethyl cellulose, styrene-butadiene latex, polytetrafluoroethylene, and polyethylene oxide.
According to an embodiment of the present application, the anode active material includes a carbon-based anode material and/or a silicon-based anode material.
According to an embodiment of the present application, the silicon-based negative electrode material is selected from nano silicon, silicon oxygen negative electrode material (SiO x (0<x<2) At least one of a silicon carbon anode material).
According to an embodiment of the present application, the carbon-based negative electrode material is selected from at least one of artificial graphite, natural graphite, mesophase carbon microspheres, hard carbon, and soft carbon.
According to an embodiment of the present application, the mass ratio of the silicon-based anode material and the carbon-based anode material in the anode active material is 9:1 to 1:9, for example, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, or 9:1.
According to an embodiment of the present application, the positive electrode active material is selected from one or more of lithium cobaltate, lithium manganate, lithium iron phosphate, and ternary materials.
According to an embodiment of the application, the battery satisfies at least one of the following relations:
(1) If the positive electrode active material is lithium cobaltate, the mass ratio of the additive to lithium cobaltate in the battery is in the range of 0.01352-0.1352, preferably 0.027;
(2) If the negative electrode active material is a carbon-based negative electrode material, the mass ratio of the additive to the carbon-based negative electrode material in the battery is in the range of 0.025 to 0.25, preferably 0.049;
(3) If the negative electrode active material is a silicon-based negative electrode material, the mass ratio of the additive in the battery to the silicon-based negative electrode material is in the range of 0.02-0.3, preferably 0.049;
(4) If the negative electrode active material is a carbon-based negative electrode material and a silicon-based negative electrode material, the mass ratio of the additive in the battery to the total mass of the carbon-based negative electrode material and the silicon-based negative electrode material is between 0.034 and 0.34, preferably 0.068.
The application has the beneficial effects that:
the application provides an electrolyte and a battery comprising the same. The electrolyte provided by the application can solve the problem that the battery is likely to be thermally invalid in a high-temperature environment, and simultaneously brings at least one of the following beneficial effects for the lithium ion battery:
1. the safety of the battery is improved: by reducing the likelihood of FEC generating HF in high temperature environments, R group modified fluoroethylene carbonate compounds help reduce the risk of thermal failure of the battery in high temperature environments. This benefit is particularly important for battery systems that operate in harsh environments, such as electric vehicles and large-scale energy storage systems.
2. Enhancing battery performance: the R group modified fluoroethylene carbonate compound is favorable for maintaining the cycle performance and capacity of the battery in a high-temperature environment, so that the overall performance of the lithium ion battery is improved. This is of great importance for meeting the demands for high performance batteries, such as mobile electronic devices and electric vehicles.
3. Optimizing Solid Electrolyte Interface (SEI) layers: the R group modified fluoroethylene carbonate compound is favorable for forming a more stable SEI layer, so that the electrochemical performance and the safety performance of the battery are maintained in a high-temperature environment. This has a positive effect on improving the cycle life and durability of the lithium ion battery.
4. The method is suitable for various anode materials: the R group modified fluoroethylene carbonate compound can be applied to silicon-based anode materials and/or carbon-based anode materials, and the electrochemical properties of the silicon-based anode materials and the carbon-based anode materials are improved. This means that the application has a wide application potential and can be used for various types of lithium ion batteries.
5. Promote the development of the related fields: the application provides important support for technical progress and market development of electric automobiles, mobile electronic equipment and large-scale energy storage systems by providing the lithium ion battery with higher electrochemical performance and safety performance.
In a word, the electrolyte provided by the application not only solves the problem that the battery is possibly thermally invalid in a high-temperature environment, but also makes an important contribution to improving the electrochemical performance and the safety performance of the lithium ion battery. This will help to meet the ever-increasing demand for high performance batteries and drive the development of the relevant art.
Drawings
Fig. 1 is a graph showing the cycle capacity retention ratio of the batteries of comparative example 1 and examples 1-2.
Fig. 2 is a graph of impedance versus 200 cycles of the cells of comparative example 1 and examples 1-2.
Fig. 3 is a graph showing the cycle capacity retention ratio of the batteries of comparative example 1 and examples 3 to 5.
Fig. 4 is a graph of impedance comparison after 200 cycles of the cells of comparative example 1 and examples 3-5.
Detailed Description
The additive shown in the formulas 1 to 5 can be prepared by adopting a method known in the art, and can also be prepared by the following method:
the preparation method comprises the following steps:
(1) The fluoroepoxy compounds are prepared by nucleophilic epoxidation starting from the general formula (1).
X in the general formula (1) may be a group having a certain steric hindrance such as a tetraphenylmethoxy group, a sulfonylimide group, a cyclopentadienyl group, a tert-butyl group, or a group having a certain electron donating property such as an aldehyde group, an alcohol group, a benzyl group, an amino group, a methylthio group, a carboxamide group, a formyloxy group, a pyridyl group, an acetate amine group, or the like.
The synthetic route is as follows: a certain amount of the compound shown in the general formula (1) is dissolved in DMF, and is stirred and added dropwise into the solution by using 0.3mol/L hydrogen peroxide or tert-butyl peroxide alkaline solution catalyst, the temperature is maintained at about 80 ℃, and the reaction is carried out for 12 hours to obtain the general formula (2).
(2) The general formula (2) reacts with carbon dioxide to form a fluorinated saturated cyclic carbonate.
Dissolving the general formula (2) in ethyl acetate, and adding a proper amount of AlCl 3 Introducing carbon dioxide into the catalyst, keeping the temperature at 80 ℃, reacting for 12 hours, adding water to cool the reaction temperature to room temperature, extracting the target product dissolved in ethyl acetate, and finally obtaining the purer additive through centrifugation, washing and centrifugation.
The present application will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the application. All techniques implemented based on the above description of the application are intended to be included within the scope of the application.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
The lithium ion batteries of examples 1 to 10 and comparative example 1 were prepared by the following steps:
1) Preparation of positive plate
Lithium cobalt oxide (LiCoO) as a positive electrode active material 2 ) Mixing polyvinylidene fluoride (PVDF) and conductive carbon black (super P) according to the mass ratio of 7:1:2, adding N-methyl pyrrolidone (NMP), and stirring under the action of a vacuum stirrer until the mixed system becomes anode active slurry with uniform fluidity; uniformly coating the positive electrode active slurry on two surfaces of an aluminum foil with the thickness of 10 mu m; and (3) placing the coated aluminum foil in an oven at 60 ℃ for drying for 24 hours, and then rolling and slitting to obtain the required positive plate.
2) Preparation of negative plate
Mixing a silicon-carbon negative electrode active material, artificial graphite, conductive carbon black (SP) and styrene-butadiene rubber (SBR) according to a mass ratio of 2:6:1:1, adding deionized water, and obtaining negative electrode active slurry under the action of a vacuum stirrer; uniformly coating the anode active slurry on two surfaces of copper foil with the thickness of 8 mu m; and (3) airing the coated copper foil at room temperature, transferring to a 60 ℃ oven for drying for 24 hours, and then carrying out cold pressing and slitting to obtain the negative plate.
3) Preparation of electrolyte
In a glove box filled with argon (H 2 O<0.1ppm，O 2 <0.1 ppm), EC/DMC was mixed uniformly in a volume ratio of 1:1, and then lithium hexafluorophosphate (LiPF) was added rapidly to it, dried well 6 ) Forming the concentration of 1mol/L, adding an additive accounting for Xwt% of the total mass of the organic solvent after dissolving, and uniformly mixing to prepare the electrolyte of the example and the electrolyte of the comparative example.
4) Preparation of lithium ion batteries
Laminating the positive plate in the step 1), the negative plate in the step 2) and the isolating film according to the sequence of the positive plate, the isolating film and the negative plate, and then winding to obtain the battery cell; and (3) placing the battery cell in an outer packaging aluminum foil, injecting the electrolyte in the step (3) into the outer packaging, and performing the procedures of vacuum packaging, standing, formation, shaping, sorting and the like to obtain the lithium ion battery. In the lithium ion battery, the mass of the additive and the mass of lithium cobaltate are shown in a table 1; the mass ratio of the additive to the total mass of the carbon-based anode material and the silicon-based anode material is shown in table 1.
5) Performance testing
Capacity retention rate: constant temperature of 45 ℃ is kept for 30min, constant current charging is carried out at 1C until the temperature reaches 4.5V, constant voltage charging is carried out at 4.5V, and the temperature is cut off at 0.3C; 0.7C was discharged to 3V. The charging cycle was performed 200 times in accordance with this charging schedule, and the capacity retention rate was calculated.
Furnace temperature: and (3) placing the full-charged battery into a test box, heating the test box at a heating rate of 5 ℃/min, keeping the temperature constant for 60min after the temperature in the test box reaches 130+/-2 ℃, and heating at a heating rate of 1 ℃/min until the temperature of the battery body changes suddenly if the battery reaches 130 ℃ and does not fail.
Acidity: the cell after 200 cycles of circulation was disassembled to obtain an electrolyte and the free HF acid content in the electrolyte was titrated with sodium formate.
Table 1 results of performance test of batteries of examples and comparative examples
From the results in Table 1, the furnace temperature failure temperatures of examples 1-2 were higher than those of comparative example 1, indicating that the furnace temperature failure temperatures were significantly increased after the introduction of the sulfonimide and the cyclopentadienyl group in FEC, demonstrating that the increase in steric hindrance caused by the sulfonimide and the cyclopentadienyl group can effectively enhance the thermal stability of the battery. The furnace temperature failure temperature of examples 3-5 is higher than that of comparative example 1, which shows that the introduction of electron donating groups at the ortho position of F element can effectively reduce the electron density of ortho hydrogen atoms, reduce the acidity thereof, and make it more difficult to deviate to form HF acid, thereby improving the furnace temperature performance of the battery.
The cell after 200 cycles was disassembled to obtain an electrolyte and the free HF acid content of the electrolyte was titrated with sodium formate, and the results are shown in table 1, with HF content of examples 1-2 being significantly lower than that of comparative example 1, indicating that the addition of sterically bulky groups can block attack of lewis acids on F and H. The HF content of examples 3-5 is significantly lower than that of comparative example 1, indicating that the addition of electron donating groups can reduce the probability of FEC stripping out of hydrofluoric acid.
Fig. 1 is a graph showing the cycle capacity retention ratio of the batteries of comparative example 1 and examples 1-2, specifically, a cycle capacity graph of the battery at 45 ℃. As can be seen from fig. 1, the capacity retention rates of examples 1 and 2 were significantly higher than comparative example 1 after 200 cycles of the battery, indicating that the introduction of the sulfonimide and the cyclopentadienyl group can effectively prevent the capacity fade problem caused by the side reaction due to FEC.
Fig. 2 is an EIS diagram of full power after 200 cycles of battery cycles of comparative example 1 and examples 1-2 are completed. As can be seen from fig. 2, the film resistance and the load carrying resistance of the batteries of examples 1-2 were significantly smaller than those of the battery of comparative example 1, indicating that the introduction of the sulfonimide and the cyclopentadienyl group can form an SEI film having a lower resistance.
Fig. 3 is a graph showing the cycle capacity retention ratio of the batteries of comparative example 1 and examples 3 to 5, specifically, a cycle capacity graph of the battery at 45 ℃. As can be seen from fig. 3, the capacity retention rates of the batteries of examples 3 to 5 were all higher than that of comparative example 1 after 200 cycles of the battery, indicating that the introduction of aldehyde groups, carboxamide groups, pyridine groups and acetate groups at the vicinal carbon positions can prevent rapid decomposition thereof by the electron donating effect, and improve the capacity retention rate during the cycles thereof.
Fig. 4 is an EIS diagram of full power after 200 cycles of the battery cycle of comparative example 1 and examples 3-5 are completed. As can be seen from fig. 4, the film resistance and the load carrying resistance of the batteries of examples 3 to 5 were significantly lower than those of the battery of comparative example 1, indicating that the introduction of aldehyde groups, carboxamide groups, pyridine groups and acetate groups can form SEI films having lower resistances while reducing the load carrying resistance.
The embodiments of the present application have been described above. However, the present application is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. An electrolyte is characterized by comprising an organic solvent, electrolyte lithium salt and an additive; the additive comprises R-group modified fluoroethylene carbonate compounds; the R group is a steric hindrance group and/or an electron donating group.
2. The electrolyte of claim 1 wherein the R groups are selected from the group consisting of-CHO, -OH, -NR 1 R 2 、-S(＝O)NR 1 R 2 、-S(＝O) 2 NR 1 R 2 、-CONR 1 R 2 -OC (=o) H, -NHCOH, substituted or unsubstituted-S-C 1-12 Alkyl, substituted or unsubstituted-OC (=o) C 1-12 Alkyl, substituted or unsubstituted-NHCOC 1-12 Alkyl, substituted or unsubstituted C 1-12 Alkyl, substituted or unsubstituted C 6-12 Aryl, substituted or unsubstituted C 2-12 Alkenyl, substituted or unsubstituted 5-12 membered heteroaryl; in the case of substitution, the substituent is C 1-12 An alkyl group; r is R 1 And R is 2 Identical or different, independently of one another, from H, C 1-12 An alkyl group.
Preferably, the R group is selected from the group consisting of-CHO, -OH, -NR 1 R 2 、-S(＝O)NR 1 R 2 、-S(＝O) 2 NR 1 R 2 、-CONR 1 R 2 -OC (=o) H, -NHCOH, substituted or unsubstituted-S-C 1-6 Alkyl, substituted or unsubstituted-OC (=o) C 1-6 Alkyl, substituted or unsubstituted-NHCOC 1-6 Alkyl, substituted or unsubstituted C 1-6 Alkyl, substituted or unsubstituted C 6-8 Aryl, substituted or unsubstituted C 2-6 Alkenyl, substituted or unsubstituted 5-8 membered heteroaryl; in the case of substitution, the substituent is C 1-6 An alkyl group; r is R 1 And R is 2 Identical or different, independently of one another, from H, C 1-6 An alkyl group.
Preferably, the R group is selected from the group consisting of-CHO, -OH, -NR 1 R 2 、-S(＝O)NR 1 R 2 、-S(＝O) 2 NR 1 R 2 、-CONR 1 R 2 -OC (=o) H, -NHCOH, substituted or unsubstituted-S-C 1-3 Alkyl, substituted or unsubstituted-OC (=o) C 1-3 Alkyl, substituted or unsubstituted-NHCOC 1-3 Alkyl, substituted or unsubstituted C 3-6 Alkyl, substituted or unsubstituted C 6-7 Aryl, substituted or unsubstituted C 3-6 Alkenyl, substituted or unsubstituted 5-6 membered heteroaryl; in the case of substitution, the substituent is C 1-3 An alkyl group; r is R 1 And R is 2 Identical or different, independently of one another, from H, C 1-3 An alkyl group.
3. The electrolyte according to claim 1 or 2, wherein the R group is selected from the group consisting of-CHO, -OH, -NH 2 、-S(＝O)NH 2 、-S(＝O) 2 N(CH 3 ) 2 、-CONH 2 、-OC(＝O)H、-NHCOH、-S-CH 3 、-OC(＝O)CH 3 、-NHCOCH 3 Tertiary butyl, benzyl, cyclopentadienyl, and pyridyl.
4. The electrolyte according to any one of claims 1 to 3, wherein the additive is selected from at least one of the compounds having formula I:
wherein R is as defined in any one of claims 1 to 3.
5. The electrolyte according to any one of claims 1 to 4, wherein the additive is at least one selected from the group consisting of compounds represented by formulas 1 to 5:
6. the electrolyte of any one of claims 1-5 wherein the electrolyte lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ) Or is selected from lithium hexafluorophosphate (LiPF) 6 ) A combination with at least one of the following electrolyte lithium salts: lithium difluorophosphate (LiPO) 2 F 2 ) Lithium difluorooxalato borate (LiDFOB), lithium bistrifluoromethylsulfonyl imide, lithium difluorobisoxalato phosphate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium hexafluoroantimonate, lithium hexafluoroarsenate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (pentafluoroethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methyl lithium, lithium bis (trifluoromethylsulfonyl) imide.
7. Electrolyte according to any one of claims 1-6, wherein the weight of the additive is 5-20%, preferably 10-15% of the total weight of organic solvents in the electrolyte.
8. A battery comprising the electrolyte of any one of claims 1-7.
9. The battery according to claim 8, further comprising a positive electrode sheet containing a positive electrode active material, a negative electrode sheet containing a negative electrode active material, a separator;
the negative electrode active material comprises a carbon-based negative electrode material and/or a silicon-based negative electrode material selected from nano silicon, silicon oxygen negative electrode material (SiO) x (0<x<2) At least one of) or a silicon carbon negative electrode material, wherein the carbon-based negative electrode material is at least one selected from artificial graphite, natural graphite, mesophase carbon microspheres, hard carbon and soft carbon;
the positive electrode active material is selected from one or more of lithium cobaltate, lithium manganate, lithium iron phosphate and ternary materials.
10. The battery according to claim 8 or 9, wherein the battery satisfies at least one of the following relationships:
(1) If the positive electrode active material is lithium cobaltate, the mass ratio of the additive to the lithium cobaltate in the battery is within the range of 0.01352-0.1352;
(2) If the negative electrode active material is a carbon-based negative electrode material, the mass ratio of the additive to the carbon-based negative electrode material in the battery is in the range of 0.025-0.25;
(3) If the negative electrode active material is a silicon-based negative electrode material, the mass ratio of the additive in the battery to the silicon-based negative electrode material is within the range of 0.02-0.3;
(4) If the negative electrode active material is a carbon-based negative electrode material and a silicon-based negative electrode material, the mass ratio of the mass of the additive in the battery to the total mass of the carbon-based negative electrode material and the silicon-based negative electrode material is between 0.034 and 0.34.
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