CN116979143A - Additive composition for lithium secondary battery electrolyte, and lithium secondary battery - Google Patents
Additive composition for lithium secondary battery electrolyte, and lithium secondary battery Download PDFInfo
- Publication number
- CN116979143A CN116979143A CN202210425458.6A CN202210425458A CN116979143A CN 116979143 A CN116979143 A CN 116979143A CN 202210425458 A CN202210425458 A CN 202210425458A CN 116979143 A CN116979143 A CN 116979143A
- Authority
- CN
- China
- Prior art keywords
- component
- electrolyte
- lithium
- secondary battery
- lithium secondary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000654 additive Substances 0.000 title claims abstract description 81
- 230000000996 additive effect Effects 0.000 title claims abstract description 68
- 239000003792 electrolyte Substances 0.000 title claims abstract description 67
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 67
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 8
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 150000002900 organolithium compounds Chemical class 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims description 20
- -1 lithium hexafluorophosphate Chemical group 0.000 claims description 19
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims description 13
- 159000000002 lithium salts Chemical class 0.000 claims description 13
- 239000002210 silicon-based material Substances 0.000 claims description 13
- 239000007773 negative electrode material Substances 0.000 claims description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910013716 LiNi Inorganic materials 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- 239000006183 anode active material Substances 0.000 claims description 4
- 229940093499 ethyl acetate Drugs 0.000 claims description 3
- 235000019439 ethyl acetate Nutrition 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- AUBNQVSSTJZVMY-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] AUBNQVSSTJZVMY-UHFFFAOYSA-M 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims 1
- KAEZJNCYNQVWRB-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Li+].C(C(=O)F)(=O)F.[Li+].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Li+].C(C(=O)F)(=O)F.[Li+].[Li+] KAEZJNCYNQVWRB-UHFFFAOYSA-K 0.000 claims 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims 1
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims 1
- QJHDFBAAFGELLO-UHFFFAOYSA-N sec-butyl butyrate Chemical compound CCCC(=O)OC(C)CC QJHDFBAAFGELLO-UHFFFAOYSA-N 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 41
- 229910052759 nickel Inorganic materials 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 17
- 239000011255 nonaqueous electrolyte Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- 230000014759 maintenance of location Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002904 solvent Substances 0.000 description 11
- 239000011149 active material Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 9
- 239000010406 cathode material Substances 0.000 description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 7
- 101150058243 Lipf gene Proteins 0.000 description 7
- 239000013543 active substance Substances 0.000 description 7
- 238000009830 intercalation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- 229910021383 artificial graphite Inorganic materials 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000007600 charging Methods 0.000 description 6
- 230000002687 intercalation Effects 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 5
- 238000004770 highest occupied molecular orbital Methods 0.000 description 5
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- DCBKFUVWBRFDDD-UHFFFAOYSA-N 4-fluoro-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC(C#N)=CC=C1F DCBKFUVWBRFDDD-UHFFFAOYSA-N 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 2
- 229910013914 LiPF6 + 0.1 M Inorganic materials 0.000 description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 206010016766 flatulence Diseases 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- PKRKCDBTXBGLKV-UHFFFAOYSA-N tris(ethenyl)-methylsilane Chemical compound C=C[Si](C)(C=C)C=C PKRKCDBTXBGLKV-UHFFFAOYSA-N 0.000 description 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical compound CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 235000019766 L-Lysine Nutrition 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- NHNSSGSIAOTLKL-UHFFFAOYSA-N N=C=O.S=P(OC1=CC=CC=C1)(OC1=CC=CC=C1)OC1=CC=CC=C1 Chemical compound N=C=O.S=P(OC1=CC=CC=C1)(OC1=CC=CC=C1)OC1=CC=CC=C1 NHNSSGSIAOTLKL-UHFFFAOYSA-N 0.000 description 1
- SXDASMFNTHIRRS-UHFFFAOYSA-M P(=O)([O-])(F)F.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] Chemical class P(=O)([O-])(F)F.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] SXDASMFNTHIRRS-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- QABDZOZJWHITAN-UHFFFAOYSA-F [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O Chemical class [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O QABDZOZJWHITAN-UHFFFAOYSA-F 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical group [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- UVVUGWBBCDFNSD-UHFFFAOYSA-N tetraisocyanatosilane Chemical compound O=C=N[Si](N=C=O)(N=C=O)N=C=O UVVUGWBBCDFNSD-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- VMZOBROUFBEGAR-UHFFFAOYSA-N tris(trimethylsilyl) phosphite Chemical compound C[Si](C)(C)OP(O[Si](C)(C)C)O[Si](C)(C)C VMZOBROUFBEGAR-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- 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
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Abstract
The application relates to the field of nonaqueous electrolyte of lithium secondary batteries, and discloses an additive composition for the electrolyte of a lithium secondary battery, the electrolyte of the lithium secondary battery and the lithium secondary battery. The composition contains a component A selected from fluoroethylene carbonate and/or bis-fluoroethylene carbonate, a component C is an organolithium compound containing carboxyl and phosphorus oxy, and a structural formula of a component B is as follows:
Description
Technical Field
The application belongs to the field of electrolyte of lithium secondary batteries, and particularly relates to an additive composition of electrolyte of a lithium secondary battery, the electrolyte of the lithium secondary battery and the lithium secondary battery containing the electrolyte.
Background
The lithium ion battery has been widely used in the fields of consumer electronics, electric automobiles, energy storage and the like with the advantages of high specific energy, long cycle life, environmental friendliness and the like. With the development of transportation and the proposal of a carbon neutralization concept, the demand of lithium ion batteries in the field of Electric Vehicles (EV) is rapidly increased, and the lithium ion batteries are urgently required to have good performances in the aspects of energy and power density, cycle life, wide temperature suitability and the like. At present, the main development route of the domestic vehicle power battery is that a high-nickel ternary positive electrode is matched with a silicon-carbon negative electrode, and the high-nickel ternary positive electrode material has higher specific capacity, and the silicon-carbon negative electrode has more lithium removal/insertion capacity, so that the overall energy density of the lithium ion battery breaks through 300 wh/kg.
However, due to the fact that the battery has higher discharge voltage caused by the increase of the nickel content in the positive electrode, electrolyte in the battery is easier to decompose at the interface between the positive electrode and the electrolyte, so that gas is generated to cause the expansion of the battery, potential safety hazards are brought, and meanwhile, the stability of the layered structure and the thermal stability of the positive electrode material are also reduced; on the negative electrode side, since the lithium intercalation/deintercalation capacity of graphite is 1:6, i.e. 6 carbon atoms are only able to absorb/desorb 1 lithium atom, whereas silicon has an intercalation/deintercalation capacity of 4.4:1, i.e. 1 silicon atom, can be combined with 4.4 lithium atoms. Therefore, the silicon-based material has a larger volume change during charging (lithium removal)/discharging (lithium intercalation) than the graphite material, and the volume change consumes organic substances in the electrolyte during the first charging, and a stable passivation film (solid electrolyte film, SEI film) formed on the surface of the anode expands and contracts, so that the SEI film is repeatedly regenerated and ruptured through charging/discharging, the consumption of the positive electrode active material and the electrolyte is caused, the diffusion resistance of lithium ions on the electrode is increased, and the discharge capacity of the battery is continuously attenuated, the rate performance of the battery is reduced until the battery is failed. Therefore, the application of the lithium ion battery with the high-nickel ternary cathode material and the silicon-carbon anode material in the aspect of power batteries has great challenges.
CN 113270632A discloses a lithium ion battery electrolyte for high nickel ternary cathode material, comprising a non-aqueous organic solvent, lithium salt and additives. The additive used is a compound with more than three isocyanate groups, including L-lysine triisocyanate, 1,3, 6-hexane triisocyanate, triisocyanated vinyl silane, triphenyl phosphorothioate isocyanate, (2, 4, 6-trioxytriazine-1, 3,5 (2H, 4H, 6H) -tri-tris (hexamethylene) isocyanate and tetraisocyanatosilane; the negative film forming additive is fluoroethylene carbonate, ethylene sulfate, vinylene carbonate, tris (trimethylsilyl) phosphite and 1, 3-propane sultone. By adopting the material, the patent solves the problem of normal-temperature gas production of the high-nickel ternary battery, and improves the normal-temperature cycle performance. However, the patent does not solve the problems of capacity retention and gas production in a high-temperature environment, so that the application of the high-nickel ternary cathode material is still different.
CN 108808071B also discloses a lithium ion battery electrolyte for high nickel ternary cathode materials, employing cathode and anode film forming additives (cathode film forming additive trivinylmethylsilane and anode film forming additive 5-cyano-2-fluorobenzeneboronic acid pinacol ester). The lowest unoccupied molecular orbital energy (LUMO) of the 5-cyano-2-fluorobenzeneboronic acid pinacol ester is lower, the reduction potential is higher than that of a solvent, a stable SEI film can be preferentially formed on a negative electrode, the highest occupied molecular orbital energy (HOMO) of the trivinylmethylsilane is higher, the oxidation potential is lower than that of the solvent, a thin cathode electrolyte film (CEI) film with lower impedance can be formed on a positive electrode, and the cycle performance and the high-low temperature performance of the high-nickel ternary battery are improved. The patent adopts 0.2C multiplying power charge and discharge, and the negative electrode material adopts graphite with lower expansion rate, so that the lithium removal/insertion capacity of the material is not too high, the expansion rate of the battery pack reaches 8.7% (volume ratio), and the working condition of the negative electrode and the actual power battery for the vehicle is still greatly different.
CN 109193029B discloses a non-aqueous electrolyte of a high-nickel ternary lithium ion battery and a high-nickel ternary lithium ion battery containing the same, which adopts a phosphate compound additive containing halogenated groups. The patent indicates that the additive can obviously improve the cycle performance of the battery and the capacity retention rate after high-temperature storage, and can speculate that the phosphate additive of the type can form a layer of uniform and compact protective film on the surface of the ternary material, inhibit the corrosion of HF on NCM particles, avoid the generation of cracks in the NCM particles in the cycle process, and reduce the dissolution of transition metal elements at high temperature. However, the negative electrode material used in the patent is also graphite, and although the capacity of the high-nickel ternary lithium ion battery under the working condition of high temperature (55 ℃) can be well maintained in the patent, the technical problem of silicon-based negative electrode gas expansion is not solved, and therefore, the high-nickel ternary lithium ion battery is started up for a certain distance.
CN 107210486B discloses a nonaqueous electrolyte for a secondary battery, which contains isocyanurate (allyl isocyanurate) having a c=c group, and improves cycle performance of the secondary battery by introducing the substance, and simultaneously improves residual capacity and discharge rate characteristics of the battery. However, the positive electrode material used in the patent is nickel-manganese-lithium system, namely binary material, and the discharge rate performance is only 0.2 ℃.
CN 111244546A discloses an electrolyte for a lithium ion battery suitable for quick charge, which contains an imidazole carboxylate compound with c≡c or c≡n group, and further indicates that the use of the imidazole carboxylate compound containing the two groups as an electrolyte additive can effectively improve the high-temperature holding capacity retention rate and low-temperature cycle performance of the prepared battery, and does not generate gas after being stored at a high temperature of 85 ℃ for 6 hours.
CN 110612632A discloses an electrolyte for lithium ion batteries composed of a c≡c compound compounded with lithium difluorophosphate, which can form a film having excellent stability on the electrode surface, and can suppress side effects caused in the battery by positive electrode metal ions or metal foreign matters possibly contained in the production process, also improves abnormal voltage drop phenomenon during high-temperature storage, and improves cycle life characteristics and high-temperature storage performance even during high-voltage charging.
Disclosure of Invention
The application aims to solve the problems of high-temperature flatulence and poor cycle performance of a high-nickel ternary anode matched with a silicon-carbon negative electrode material in the prior art, and provides an additive composition for a lithium secondary battery electrolyte, the lithium secondary battery electrolyte and a lithium secondary battery. The battery containing the additive can form stable interfacial films on the surfaces of an anode and a cathode of the battery respectively during the first charge and discharge, and prevent active substances in the battery from reacting with electrolyte when the temperature is too high so as to reduce the gas yield and further increase the capacity of the battery during normal temperature and high temperature use.
In order to achieve the above object, the first aspect of the present application provides an additive composition for an electrolyte of a lithium secondary battery, the composition containing a component a, a component B and a component C, wherein,
component A is selected from fluoroethylene carbonate and/or bis-fluoroethylene carbonate,
component C is an organolithium compound containing both carboxyl and phosphorus oxy groups,
the structural formula of the component B is as follows:
wherein R1, R2 and R3 are hydrocarbon groups with 1-6 carbon atoms, and the tail end of at least one hydrocarbon group chain of R1, R2 and R3 contains a carbon-carbon triple bond.
In a second aspect, the application provides an electrolyte of a lithium secondary battery, which contains an additive, wherein the additive is the additive composition provided by the application.
The third aspect of the application also provides a lithium secondary battery comprising the electrolyte provided by the application.
Through the technical scheme, the lithium secondary battery electrolyte and the lithium secondary battery assembled by the lithium secondary battery electrolyte have at least the following beneficial effects:
(1) The lithium secondary battery electrolyte provided by the application is matched with the high-nickel ternary anode and silicon-based cathode materials, and has better cycle capacity retention rate at normal temperature and high temperature;
(2) By adopting the lithium secondary battery electrolyte provided by the application, the gas expansion phenomenon at high temperature is obviously improved by matching with the high-nickel ternary anode and silicon-based cathode materials;
(3) The lithium secondary battery electrolyte provided by the application is matched with the high-nickel ternary anode and the silicon-based cathode materials, and has excellent multiplying power performance at normal temperature and high temperature;
(4) The lithium secondary battery electrolyte provided by the application has excellent matching property with a high-nickel ternary anode and a silicon-based cathode, and can be applied to a vehicle power battery.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present application provides an additive composition for an electrolyte of a lithium secondary battery, the composition comprising a component a, a component B and a component C, wherein,
component A is selected from fluoroethylene carbonate and/or bis-fluoroethylene carbonate,
component C is an organolithium compound containing both carboxyl and phosphorus oxy groups,
the structural formula of the component B is as follows:
wherein R1, R2 and R3 are hydrocarbon groups with 1-6 carbon atoms, and the tail end of at least one hydrocarbon group chain of R1, R2 and R3 contains a carbon-carbon triple bond.
In some embodiments of the application, wherein, preferably, component B is selected from one of the following:
preferably, the component B is selected from one of the following:
preferably, the component B is tripropylenimine, i.e. the compound indicated as B1.
The preferred conditions are used, the main purpose being to raise the unsaturation of the additive, raise the Highest Occupied Molecular Orbital (HOMO) energy value of the B component of the electrolyte additive, and allow the primary solvent of the electrolyte to participate in forming the positive CEI film before undergoing oxidation. And after the additive components with preferable conditions are adopted, the formed SEI film has lower resistance, so that the cycle performance under the low-temperature or normal-temperature conditions can be improved.
In some embodiments of the application, the component C is selected from lithium difluorophosphate bisoxalates or lithium tetrafluorophosphates.
By adopting the preferable condition, the oxalic acid radical contained in the additive C can also participate in the effect of forming the SEI film on the surface of the negative electrode-electrolyte, so that the strength of the film is enhanced, and the tolerance to volume change is improved.
In some embodiments of the present application, wherein component A is selected from the group consisting of fluoroethylene carbonate, the fluoroethylene carbonate may be at least one of 1-fluoroethylene carbonate, 2-fluoroethylene carbonate, 3-fluoroethylene carbonate, 4-fluoroethylene carbonate, unless specifically stated in the present application.
In some embodiments of the application, preferably, the component a is selected from 1-fluoroethylene carbonate and/or 2-fluoroethylene carbonate.
In some embodiments of the application, preferably, 2F in the 2-fluoroethylene carbonate of component a are each on two different C.
With the preferred conditions, it is more advantageous to decompose composition component A at the anode-electrolyte interface during charging to give F - 、ROCO 2 - 、RO - 、O 2- 、OH - Equivalent to free Li + Combined, at the negative electrode-electrolyte interface, liF and ROCO are generated 2 Li、ROLi、Li 2 CO 3 And an SEI film of equal composition, making the SEI film easier to form, thereby increasing stability at the time of recycling.
The inventors of the present application have surprisingly found that with additive component B it is possible to co-act with additive component a: the isocyanurate contains nitrogen atoms that complex transition metal ions to passivate the positive electrode and inhibit the corrosive effect of HF on the alkaline high nickel positive electrode due to fluoroethylene carbonate (FEC) decomposition. The isocyanurates with alkynyl groups on the branched chains, and the alkynyl groups impart high unsaturation to the substances, so that the substances have higher HOMO energy values and can participate in forming a catholyte film (CEI) before the electrolyte main solvent undergoes oxidation reaction. Compared with the nitrile additive with similar effect, the resistance is increased less, so that the nitrile additive has better circularity under the working condition of low temperature or normal temperature.
The inventors of the present application have also surprisingly found that, when additive component C is used, oxalic acid groups (-COO) are contained in C - ) The film forming function of the additive component A at the anode-electrolyte interface is also participated, the strength of the film is enhanced, and the tolerance to volume change is improved. The effect on the battery containing the silicon-based negative electrode is that the combination of the FEC with lower concentration can achieve the same level of improvement on the cycle performance, and the degradation effect of the FEC with high content under the high temperature condition is weakened. However, similar conventional additives containing oxalic acid structure, lithium dioxaborate LiBOB and lithium difluorooxalato borate LiDFOB, do not have this effect because they do not improve FEAnd C, the effect of high-temperature flatulence. Presumably, the reason is that the two are easy to fall off oxalic acid radical under the condition of strong oxidizing property, and then are decomposed to generate CO and CO 2 The additive C is lithium phosphate, and the reaction is not easy to occur due to the steric hindrance effect of coordination.
In some embodiments of the application, the volume ratio between the component a, the component B, the component C satisfies: component A: component b=100: (4-30), and component a: (component b+component C) =100: (6-40).
In some embodiments of the application, preferably, the volume ratio between the component a, the component B, the component C satisfies the following component a: component b=100: (5-25), and component a: (component b+component C) =100: (10-30). The adoption of the preferable conditions is more favorable for exerting the synergistic effect of the component A, the component B and the component C.
In a second aspect, the application provides an electrolyte of a lithium secondary battery, which contains an additive, wherein the additive is the additive composition provided by the application.
In some embodiments of the application, the additive comprises component A in an amount of 1 to 10wt%, component B in an amount of 0.1 to 2.5wt%, and component C in an amount of 0.1 to 2wt%, based on the total amount of the electrolyte.
In some embodiments of the application, preferably, the content of component B is 0.2-2%; the content of the component C is 0.2-1.5%. The improvement effect produced by adopting the preferable conditions is better, and adverse effects such as price increase, toxic gas generation and the like caused by excessive addition of the fluorine-containing electrolyte are avoided.
In some embodiments of the application, the electrolyte contains lithium salts that are lithium hexafluorophosphate and/or lithium bis-fluorosulfonyl imide.
In some embodiments of the application, the lithium salt in the electrolyte is a mixture of lithium hexafluorophosphate and lithium bis-fluorosulfonyl imide.
In some embodiments of the present application, preferably, when a mixed lithium salt of lithium hexafluorophosphate and lithium difluorosulfonimide is used, the molar concentration ratio of the two is preferably 1 (0.05-1).
In some embodiments of the present application, preferably, when a mixed lithium salt of lithium hexafluorophosphate and lithium difluorosulfonimide is used, the molar concentration ratio of the two is preferably 3 (0.3-2). The main purpose of the preferred conditions is that within the preferred molar concentration ratio range, the improvement of high/low temperature performance by lithium bis-fluorosulfonyl imide can be exerted and the corrosion of aluminum current collector by lithium hexafluorophosphate can be improved.
In some embodiments of the application, the total concentration of the lithium salt in the organic solvent is 0.5 to 1.5mol/L.
In some embodiments of the application, preferably, the total concentration of the lithium salt in the organic solvent is 0.8 to 1.3mol/L.
The main purpose of the preferred conditions is that when a lower concentration of electrolyte is used, the ionic conductivity of the electrolyte will decrease, thereby affecting the rate performance and cycle performance of the battery. If an electrolyte with a higher concentration is used, the viscosity of the electrolyte increases, the ionic conductivity decreases, and the rate performance of the battery is also affected.
In some embodiments of the present application, preferably, the organic solvent contained in the electrolyte is selected from at least one of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate, ethylacetate, propyl acetate, methyl propionate, ethylacrylate, propylate, methyl butyrate, ethylacrylate, propylate, butylate, γ -butyrolactone, and ethylene carbonate, ethylene carbonate.
Preferably, the electrolyte contains an organic solvent selected from the group consisting of ethylene carbonate, ethylmethyl carbonate, and diethyl carbonate.
The main purpose of adopting the preferred conditions is to maximize the synergistic effect of additive A, additive B and additive C when the preferred organic solvent is used.
The third aspect of the application also provides a lithium secondary battery comprising the electrolyte provided by the application.
The positive electrode active material is: compounds capable of reversibly intercalating and deintercalating lithium include, in particular, lithium composite metal oxides comprising lithium and at least one metal, such as cobalt, manganese, nickel or aluminum.
In some embodiments of the present application, preferably, the lithium composite metal oxide is a material in which the atomic ratio of nickel element to all metal elements of the positive electrode material is not less than 65%, and preferably, the positive electrode active material of the lithium secondary battery is a material of the general formula LiNi x Co y M (1-x-y) O 2 (M＝Mn、Al)，x≥0.65，y＞0。
In some embodiments of the present application, more preferably, the lithium composite metal oxide is such that the atomic proportion of nickel element to all metal elements of the positive electrode material is not less than 80%, i.e., liNi is preferred x Co y M (1-x-y) O 2 (M＝Mn、Al)，x≥0.8，y＞0。
The main purpose of adopting the preferable condition is that the content of nickel element in the positive electrode is improved, and the lithium removal/intercalation capacity and voltage of the battery can be improved. The increase of the nickel content can enhance the oxidizing property of the positive electrode material, and more easily lead the components of the electrolyte to be oxidized and decomposed to generate gas under the action of high voltage on the surface of the positive electrode, thereby causing the gas expansion phenomenon. And the increase of the nickel element content requires more cobalt element to stabilize the structure of the positive electrode material. This also better illustrates that the effects of additive A, additive B, additive C according to the application are suitable for positive electrode materials with high nickel content.
In some embodiments of the present application, it is preferable that the negative electrode active material of the lithium secondary battery is a composite of a carbon-based material and a silicon-based material.
In some embodiments of the present application, preferably, the carbon-based material comprises one of graphite, soft carbon, hard carbon, and the silicon-based material comprises one of silicon oxide, elemental silicon, and a silicon-containing alloy.
In some embodiments of the present application, more preferably, the carbon-based material is graphite and the silicon-based material is silicon oxide (SiO).
In some embodiments of the present application, preferably, the silicon-based material comprises 1 to 25% wt of the anode active material.
In some embodiments of the present application, preferably, the silicon-based material comprises 2 to 20% wt of the anode active material.
The main purpose of adopting the preferred conditions is that the increase of the lithium removal/intercalation capacity of the negative electrode is not obvious by using a small amount of silicon-based material; however, due to the limited amount of lithium elements in the positive electrode material, the use of excessive silicon-based materials is not much beneficial in increasing the overall lithium removal/intercalation capacity of the battery. The use of the silicon-based material can lead the negative electrode to have larger volume change during charging, lead the SEI film formed on the inner side surface of the negative electrode to be repeatedly cracked and regenerated, consume electrolyte active materials and increase diffusion resistance at the same time, thereby leading the capacity of the battery to be attenuated and even leading the battery to be invalid. By adopting the preferable scheme, on one hand, the capacity of the lithium battery can be effectively increased; on the other hand, the excessive use of silicon does not increase the total cost of the battery. The electrolyte provided by the application contains the additive A, the additive B and the additive C, can synergistically act to form a stable SEI film at a negative electrode-electrolyte interface, and slows down the degradation effect of the negative electrode on FEC under the condition of high temperature.
The present application will be described in detail by examples.
In the examples and the discussion of results, the chemicals used are indicated by the acronyms in english, and the compounds involved and their acronyms in english are:
lithium salt: lithium hexafluorophosphate (LiPF) 6 ) The method comprises the steps of carrying out a first treatment on the surface of the Lithium bis (fluorosulfonyl) imide (LiFSI);
solvent: ethylene Carbonate (EC); ethyl Methyl Carbonate (EMC); diethyl carbonate (DEC);
component A: fluoroethylene carbonate (FEC); bis-fluoroethylene carbonate (DiFEC);
component B: b1 The structures of B2, B3 and B4 are as described above;
component C: lithium difluorodioxalate phosphate (LiDODFP); lithium tetrafluorooxalate phosphate (LiOTFP);
other additives: triallyl isocyanurate (TAIC); adiponitrile (ADN);
and (2) a binder: carboxymethyl cellulose (CMC); styrene Butadiene Rubber (SBR); polyvinylidene fluoride (PVDF); polyacrylic acid (PAA).
In the following examples, unless otherwise specified, the charge and discharge test conditions, the calculation of the cycle retention rate, the 60 ℃ cycle gas production rate evaluation method, the positive and negative electrode material preparation method, and the battery specifications were as follows:
(1) Charge and discharge test conditions:
I. pre-cycling: constant-current constant-voltage charging is carried out at 25 ℃, constant current is carried out at 0.2C until the current is reduced to below 0.05C, and then constant voltage is maintained until the current is reduced to 3V by constant current at 0.2C;
II, normal temperature circulation: after the pre-circulation is finished, cutting off a gas bag part in a glove box of inert gas, carrying out final sealing on the battery, and carrying out charge-discharge circulation test in an incubator at 25 ℃ after final sealing, wherein the conditions are that the constant voltage is kept after the constant current is charged to 4.25V at 1C until the current is reduced to below 0.05C, the interval is 10 minutes, and then the constant current is discharged to 3V at 1C, and repeating the steps;
III, high temperature circulation: after the pre-circulation is finished, cutting off a gas bag part in a glove box of inert gas, carrying out final sealing on the battery, and carrying out charge-discharge circulation test in an incubator at 60 ℃ after final sealing, wherein the conditions are that the constant voltage is kept after the constant current is charged to 4.25V at 1C until the current is reduced to below 0.05C, the interval is 10 minutes, and then the constant current is discharged to 3V at 1C, and repeating the steps;
(2) Calculation of cycle retention:
i.25 ℃,300 cycle discharge capacity retention = 300 th 25 ℃ cycle discharge capacity/1 st 25 ℃ cycle discharge capacity x 100%;
ii.60 ℃, discharge capacity maintenance rate of 100 cycles = discharge capacity of 100 th 60 ℃ cycle/discharge capacity of 1 st 60 ℃ cycle x 100%;
(3) Evaluation of gas production in 60℃cycle:
the change in volume of the cell was determined by archimedes' method, after the first measurement was completed at 60 c for the second measurement, after 100 cycles were completed (taken out and cooled to room temperature), and the difference in volume was calculated from the two measurements, i.e., the volume corresponding to the generated gas.
(4) The preparation method of the anode and cathode materials comprises the following steps:
the anode and the cathode are prepared and processed by a common method well known in the art
(5) Specification of battery:
the batteries adopted by the application are all soft package batteries with the design capacity of 0.9 Ah.
Electrode material-containing portion: 8cm multiplied by 6cm of positive pole piece; 8.4cm multiplied by 6.3cm of negative pole piece
The lamination mode is as follows: positive electrode 3 pieces and negative electrode 4 pieces.
Examples 1 to 11 and comparative examples 1 to 9
The positive and negative electrodes were prepared and processed by a general method well known in the art to prepare a soft pack battery having a design capacity of 0.9Ah, and 3.5g of an electrolyte containing the additives in the table was injected for testing.
Examples 1 to 11 and comparative examples 1 to 9 used the same positive electrode materials, the same negative electrode materials, and the same solvent ratios in the electrolyte:
(1) Positive electrode material:
active material: nickel cobalt lithium manganate (LiNi) 0.82 Co 0.12 Mn 0.06 O 2 )；
Conductive agent: carbon black;
and (2) a binder: PVDF;
the composition ratio is as follows: the mass ratio is 97:1.5:1.5 (active substance: conductive agent: binder).
(2) Negative electrode material:
active material: silicon oxide composite artificial graphite;
the active material ratio: mass ratio 95:5 (artificial graphite: silica);
conductive agent: carbon black;
and (2) a binder: CMC and SBR;
the composition ratio is as follows: the mass ratio was 96.5:0.5:1.5:1.5 (active substance: carbon black: CMC: SBR).
(3) Electrolyte solution
Solvent: EC. EMC, DEC, volume ratio 3:5:2;
lithium salt: liPF (LiPF) 6 +lifsi, molar concentration: 1.0M LiPF 6 +0.1M LiFSI
Additive: the proportion and composition of the additives are shown in Table 1
TABLE 1
The performance parameters of the cells after adding additive A, additive B, additive C and other additives in different proportions are shown in Table 2.
TABLE 2
Examples 12 to 15, comparative example 10
Examples 12 to 15 and comparative example 10 used the same solvent ratios of the positive electrode material and the negative electrode material and the electrolyte:
(1) Positive electrode material:
active material: nickel cobalt lithium manganate (LiNi) 0.86 Co 0.08 Mn 0.06 O 2 )；
Conductive agent: carbon black;
and (2) a binder: PVDF;
the composition ratio is as follows: the mass ratio is 97:1.5:1.5 (active substance: conductive agent: binder).
(2) Negative electrode material:
active material: silicon oxide composite artificial graphite;
the active material ratio: mass ratio 88:12 (artificial graphite: silica);
conductive agent: carbon black;
and (2) a binder: CMC, SBR, and PAA;
the composition ratio is as follows: the mass ratio is 96:1:0.5:1:1.5 (active substance: carbon black: CMC: SBR: PAA).
(3) Electrolyte solution:
solvent: EC. EMC, DEC, volume ratio 3:3:4 (EC: EMC: DEC)
Lithium salt: liPF (LiPF) 6 +lifsi, molar concentration: 1.0M LiPF 6 +0.1M LiFSI
Additive: additive composition and formulation table 3.
TABLE 3 Table 3
The performance data of the cells after the above additives are shown in table 4.
TABLE 4 Table 4
Example 16, control 11
The same solvent ratios of the positive electrode material, the negative electrode material and the electrolyte were used in example 16 and comparative example 11:
(1) Positive electrode material:
active material: nickel cobalt lithium manganate (LiNi) 0.8 Co 0.15 Al 0.05 O 2 )；
Conductive agent: carbon black;
and (2) a binder: PVDF;
the composition ratio is as follows: the mass ratio is 97:1.5:1.5 (active substance: conductive agent: binder).
(2) Negative electrode material:
active material: silicon simple substance composite artificial graphite;
the active material ratio: mass ratio 95:5 (artificial graphite: elemental silicon);
conductive agent: carbon black;
and (2) a binder: CMC, SBR, and PAA;
the composition ratio is as follows: the mass ratio is 96:1:0.5:1:1.5 (active substance: carbon black: CMC: SBR: PAA).
(3) Electrolyte solution:
solvent: EC. EMC, DEC, volume ratio 3:3:4 (EC: EMC: DEC)
Lithium salt: liPF (LiPF) 6 +lifsi, molar concentration: 1.0MLiPF 6 +0.1M LiFSI
Additive: additive composition and formulation table 5.
TABLE 5
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The performance data of the cells after the above additives are shown in table 6.
TABLE 6
From the data of examples 1 to 11 and Table 2, it can be seen that the battery performance was improved in both normal temperature cycle and high temperature cycle and the gas production in the high temperature cycle state was also reduced by using the additive combinations and electrolytes satisfying the requirements of the present application, as compared with comparative examples 1 to 9 not satisfying the requirements of the present application.
The sample of comparative example 1 used no additive, and had a capacity retention of 84.2% at 25℃for 300 cycles, 79.8% at 60℃for 100 cycles, and a gas yield of 3.8cm 3 . Comparative examples 2 and 3 were samples in which additive a and additive B were only present, and their capacity retention rates at 25 ℃ and 300 cycles were 85.8% and 83.8%, respectively; capacity retention rates of 100 times at 60 ℃ were 79.5% and 80.7%, respectively, and gas production rates during the period were 5.3cm, respectively 3 And 3.6cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Control 7 is a sample in which additives A and B were present at the same time, and the capacity retention rate at high temperature cycle was higher than that of control 2 and 3, and the generation of gas was also smaller than that of control 2 and 3, indicating that there was a synergistic effect between additives A, B, improving high temperature performance.
Comparative examples 5, 6 and 7 were inferior to example 6 in capacity retention at both normal and high temperatures, and slightly higher in gas yield at high temperatures, indicating that there was a synergistic effect between additive A, B, C between a and B, B and C, and between a and C.
In example 5, however, it was found that the addition of a reasonable amount of additive B significantly increased the capacity retention at high temperatures and further reduced the gas production rate, as compared with example 8. In example 1, it was found that the addition of a reasonable amount of additives B and C significantly increased the capacity retention at normal and high temperatures and further reduced the gas production rate, as compared with example 5. Example 5 shows a modest decrease in the amount of additive a compared to example 7, and a significant decrease in gas production during high temperature cycles.
As can be seen from the cases of example 3 and comparative example 8, the additive containing c=c does not have a synergistic effect on additives a and C as compared with that containing c≡c.
As can be seen from the cases of example 3 and comparative example 9, the additive containing C.ident.N does not have a synergistic effect on the addition of A and additive C as does the additive containing C.ident.C.
In the second battery composition scheme, nickel cobalt lithium manganate with higher nickel content is used as a positive electrode, and a material with higher SiO ratio is used as a negative electrode. Examples 13 to 15, in which a larger amount of additive A, B, C was used, were more effective than example 12, which was more preferable, in that the effect of improving the normal temperature and high temperature cycle performance and suppressing the generation of gas was possibly reduced, but the effect was still advantageous as compared with comparative example 10.
In the third battery composition scheme, nickel cobalt lithium aluminate is used as the positive electrode, and silicon simple substance and graphite are mixed to be used as the negative electrode. It is seen from example 16 and comparative example 11 that the combination of the additive A, B, C also provides a good improvement effect.
The preferred embodiments of the present application have been described in detail above, but the present application is not limited thereto. Within the scope of the technical idea of the application, a number of simple variants of the technical solution of the application are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the application, all falling within the scope of protection of the application.
Claims (10)
1. An additive composition for a lithium secondary battery electrolyte, the composition comprising a component a, a component B and a component C; wherein,,
component A is selected from fluoroethylene carbonate and/or bis-fluoroethylene carbonate,
component C is an organolithium compound containing both carboxyl and phosphorus oxy groups,
the structural formula of the component B is as follows:
wherein R1, R2 and R3 are hydrocarbon groups with 1-6 carbon atoms, and the tail end of at least one hydrocarbon group chain of R1, R2 and R3 contains a carbon-carbon triple bond.
2. The additive composition of claim 1, wherein component B is selected from one of the following:
preferably, the component B is selected from one of the following:
preferably, the component B is tripyristoyl isocyanurate;
preferably, the component C is lithium difluorooxalate phosphate and/or lithium tetrafluorooxalate phosphate.
3. Additive composition according to claim 1 or 2, wherein the volume ratio between component a, component B and component C satisfies the following relationship:
component A: component b=100: (4-30), and component a: (component b+component C) =100: (6-40);
preferably, component a: component b=100: (5-25), and component a: (component b+component C) =100: (10-30).
4. An electrolyte for a lithium secondary battery, which contains an additive, the additive composition according to any one of claims 1 to 3.
5. The electrolyte according to claim 4, wherein the additive contains component a in an amount of 1 to 10wt%, component B in an amount of 0.1 to 2.5wt%, and component C in an amount of 0.1 to 2wt%, based on the total amount of the electrolyte;
preferably, the content of component B is from 0.2 to 2% by weight; the content of the component C is 0.2-1.5wt%.
6. The electrolyte according to claim 4 or 5, wherein the lithium salt contained in the electrolyte is lithium hexafluorophosphate and/or lithium difluorosulfonimide;
preferably, the organic solvent contained in the electrolyte is at least one selected from ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate, ethylacetate, propylacetate, methyl propionate, ethylacetate, propylate, methylpropyl butyrate, ethylbutyrate, propylbutyrate, butylbutyrate, gamma-butyrolactone, vinylene carbonate, and ethylene carbonate; preferably at least one selected from ethylene carbonate, ethylmethyl carbonate and diethyl carbonate;
preferably, the total concentration of the lithium salt in the organic solvent is 0.5 to 1.5mol/L, preferably 0.8 to 1.3mol/L.
7. The electrolyte according to claim 6, wherein when lithium hexafluorophosphate and lithium difluorosulfonimide are contained in the electrolyte at the same time, the molar ratio of lithium hexafluorophosphate to lithium difluorosulfonimide is 1 (0.05-1), preferably 3 (0.3-2).
8. A lithium secondary battery comprising the electrolyte as claimed in any one of claims 4 to 7.
9. The lithium secondary battery according to claim 8, wherein the positive electrode active material of the lithium secondary battery is of the general formula LiNi x Co y M (1-x-y) O 2 The compound is shown, wherein x is more than or equal to 0.65, y is more than 0, and M is selected from Mn and/or Al;
preferably x is greater than or equal to 0.8 and y is greater than 0.
10. The lithium secondary battery according to claim 8 or 9, wherein a negative electrode active material of the lithium secondary battery is a composite of a carbon-based material and a silicon-based material;
preferably, the carbon-based material is selected from at least one of graphite, soft carbon, hard carbon; the silicon-based material is at least one selected from silicon oxide, silicon simple substance and silicon-containing alloy;
further preferably, the carbon-based material is graphite and the silicon-based material is silica;
preferably, the silicon-based material is contained in the anode active material in an amount of 1 to 25% by weight, preferably 2 to 20% by weight, based on the total amount of the anode active material.
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