CN117317372A - Electrolyte containing fluoro additive, preparation method and battery - Google Patents
Electrolyte containing fluoro additive, preparation method and battery Download PDFInfo
- Publication number
- CN117317372A CN117317372A CN202311420433.8A CN202311420433A CN117317372A CN 117317372 A CN117317372 A CN 117317372A CN 202311420433 A CN202311420433 A CN 202311420433A CN 117317372 A CN117317372 A CN 117317372A
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- China
- Prior art keywords
- additive
- electrolyte
- methyl
- lithium
- carbonate
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- 239000000654 additive Substances 0.000 title claims abstract description 188
- 230000000996 additive effect Effects 0.000 title claims abstract description 155
- 239000003792 electrolyte Substances 0.000 title claims abstract description 89
- 125000001153 fluoro group Chemical group F* 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- PKGTVIQAQNQQRM-UHFFFAOYSA-N (2-pentylphenyl)-diphenylphosphanium bromide Chemical compound [Br-].CCCCCC1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 PKGTVIQAQNQQRM-UHFFFAOYSA-N 0.000 claims abstract description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 43
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 43
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 42
- -1 cyano, carbonyl Chemical group 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 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
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229940017219 methyl propionate Drugs 0.000 claims description 4
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- LOWMYOWHQMKBTM-UHFFFAOYSA-N 1-butylsulfinylbutane Chemical compound CCCCS(=O)CCCC LOWMYOWHQMKBTM-UHFFFAOYSA-N 0.000 claims description 2
- GNFVFPBRMLIKIM-UHFFFAOYSA-N 2-fluoroacetonitrile Chemical compound FCC#N GNFVFPBRMLIKIM-UHFFFAOYSA-N 0.000 claims description 2
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 claims description 2
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 2
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 claims description 2
- STZZWJCGRKXEFF-UHFFFAOYSA-N Dichloroacetonitrile Chemical compound ClC(Cl)C#N STZZWJCGRKXEFF-UHFFFAOYSA-N 0.000 claims description 2
- 229910013075 LiBF Inorganic materials 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- DRUIESSIVFYOMK-UHFFFAOYSA-N Trichloroacetonitrile Chemical compound ClC(Cl)(Cl)C#N DRUIESSIVFYOMK-UHFFFAOYSA-N 0.000 claims description 2
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 claims description 2
- 229940008406 diethyl sulfate Drugs 0.000 claims description 2
- NVJBFARDFTXOTO-UHFFFAOYSA-N diethyl sulfite Chemical compound CCOS(=O)OCC NVJBFARDFTXOTO-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 2
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 claims description 2
- RBBXSUBZFUWCAV-UHFFFAOYSA-N ethenyl hydrogen sulfite Chemical compound OS(=O)OC=C RBBXSUBZFUWCAV-UHFFFAOYSA-N 0.000 claims description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 2
- YLJRCXSSKLWCDE-UHFFFAOYSA-N methyl ethanesulfonate Chemical compound CCS(=O)(=O)OC YLJRCXSSKLWCDE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims 1
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 claims 1
- 229910013870 LiPF 6 Inorganic materials 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 15
- 229910013872 LiPF Inorganic materials 0.000 description 14
- 101150058243 Lipf gene Proteins 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- 238000007600 charging Methods 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 125000006091 1,3-dioxolane group Chemical group 0.000 description 1
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 description 1
- 125000004918 2-methyl-2-pentyl group Chemical group CC(C)(CCC)* 0.000 description 1
- 125000004922 2-methyl-3-pentyl group Chemical group CC(C)C(CC)* 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 1
- 125000004919 3-methyl-2-pentyl group Chemical group CC(C(C)*)CC 0.000 description 1
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect 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
- 239000011268 mixed slurry Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- 239000002562 thickening agent Substances 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000003466 welding 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of fluoro-additive electrolyte, and particularly discloses electrolyte containing fluoro-additive, a preparation method and a battery, wherein the electrolyte comprises a solvent, lithium salt and an additive; the additives include a first additive, a second additive, and a third additive; the first additive and the second additive are fluoro-additive; the third additive is selected from any one of methyl triphenylphosphine bromide or amyl triphenylphosphine bromide. The electrolyte containing the fluoro additive has the circulation performance at high temperature and the low-temperature discharge performance, and the comprehensive performance of the battery can be comprehensively improved.
Description
Technical Field
The invention belongs to the technical field of fluoro-additive electrolyte, and particularly relates to electrolyte containing fluoro-additive, a preparation method and a battery.
Background
The lithium ion battery has the advantages of high specific capacity, long cycle life, low self-discharge rate, no memory effect, environmental friendliness and the like, and is widely applied to electronic products such as notebook computers, digital cameras and the like. The lithium cobaltate material has the advantages of higher energy density, good cycle stability, good thermal stability and the like, and is widely applied. However, cobalt resources are increasingly scarce, and the cost of lithium ion batteries using lithium cobalt oxide as a positive electrode is also increasing. With the continuous development of social demands, the requirements of lithium ion batteries are higher and higher, and the industry is pursuing higher energy density of lithium batteries. For this reason, researchers have developed positive and negative electrode materials with higher gram capacities to meet the increasing performance demands of commercial lithium ion batteries. At present, a high-nickel ternary material or a high-voltage positive electrode material is generally adopted as the positive electrode, and a silicon-based material is adopted as the negative electrode. The high-nickel ternary material and the high-voltage positive electrode material have strong oxidizing property to electrolyte after lithium removal, so that the problems of gas production, metal element dissolution, capacity attenuation and the like of the lithium ion battery are caused. And the silicon-based anode material has huge volume shrinkage and expansion in the process of lithium intercalation, so that SEI films on the surface of the silicon-based anode material are easy to crack, repeated growth of the SEI films is then carried out, and finally a series of problems of increased battery impedance, gas expansion, capacity attenuation and the like are caused.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention aims to provide an electrolyte containing a fluoro additive, wherein the electrolyte comprises a solvent, lithium salt and the additive; the additives include a first additive, a second additive, and a third additive; the first additive and the second additive are fluoro additives, the structural formula is shown as formula (I), and the second additive is shown as formula (II):
wherein R is 1 Or R is 2 Independently selected from methyl, ethyl, propyl, sulfonic acid, sulfonyl, C 1 ～C 8 Alkyl, phenyl, ester, cyano, carbonyl, methanesulfonyl, amide, heteroaryl, aryl;
R 3 or R is 4 Independently selected from methyl, ethyl, propyl, sulfonic acid, sulfonyl, C 1 ～C 8 Alkyl, phenyl, ester, cyano, carbonyl, methanesulfonyl, amide, heteroaryl,Aryl groups.
Further, the third additive is selected from any one of methyl triphenylphosphine bromide or amyl triphenylphosphine bromide;
and/or the addition amount of the first, second and third additives in the electrolyte is X, Y, Z respectively, and the first, second and third additives are expressed as the following relation:
1.5Z≤(X+Y)≤3.2Z。
the first additive and the second additive of the fluorine-containing electrolyte additive have lower HOMO energy level and further have stronger oxidation resistance; in general, since the compound containing fluorine group (halogen group) has a higher HOMO energy level and is more easily oxidized, the first and second additives have lower HOMO energy levels when they contain fluorine group, such as sulfur-containing long chain, sulfonyl group, etc., and the difference between HOMO energy level and LOMO energy level (about 5 eV) of the two additives is wider, the electrochemical window is wider, so that the fluorine ions can promote Li while the additives form a protective film at the anode and cathode + The transmission capacity of the electrolyte is increased, and the low-temperature discharge capacity of the electrolyte is improved; while the third additive Li under electro-reduction conditions 3 P fast ion conductor for improving high lithium ion mobility and F in the first and second additives - Is easy to coordinate with lithium ion, weaken Li + Acting force between the organic solvent molecules can cooperate with the first additive to improve high-temperature cycle performance at high temperature, and cooperate with the discharge performance of the second additive at low temperature. And the addition of the first, second and third additives reduces the surface activity of the electrode, improves the stability of the electrode and the interface at different temperatures, protects the anode, effectively inhibits the dissolution of metal ions, inhibits the occurrence of side reaction between the motor and the electrolyte, and improves the cycle performance of the electrolyte under high voltage.
Further, the first additive accounts for 0.1 to 5 percent of the total mass of the electrolyte;
and/or the second additive accounts for 0.1-5% of the total mass of the electrolyte;
and/or the third additive accounts for 0.1-5% of the total mass of the electrolyte;
and/or the additive accounts for 0.1-5% of the total mass of the electrolyte.
Further, the first additive is selected from any one of formulas (1-1) to (1-6):
further, the second additive is selected from any one of formulas (2-1) to (2-6):
further, the lithium salt is selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) One or more of lithium dioxalate borate (LiBOB), lithium difluorooxalate borate (LiODFB), lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) in any proportion;
and/or the concentration of the lithium salt in the electrolyte is 0.05M-3M; specifically, 0.1M, 0.2M, 0.3M, 0.4M, 0.5M, 0.51M, 0.52M, 0.53M, 0.54M, 0.55M, 0.56M, 0.57M, 0.58M, 0.59M, 0.6M, 0.62M, 0.64M, 0.66M, 0.68M, 0.7M, 0.75M, 0.78M, 0.79M, 0.8M, 0.85M, 0.9M, 0.95M, 1.1M, 1.2M, 1.3M, 1.4M, 1.5M, 1.6M, 1.7M, 1.8M, 1.9M, 2M.
Further, the solvent is selected from 1, 3-Dioxolane (DOL), ethylene glycol dimethyl ether (DME), ethylene Carbonate (EC), propylene Carbonate (PC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), fluoroethylene carbonate (FEC), vinylene Carbonate (VC), gamma-butyrolactone (GBL), methyl Acetate (MA), ethyl Acetate (EA), methyl Propionate (MP), ethyl Propionate (EP), dimethyl sulfoxide (CH) 3 SOCH 3 ) Butyl sulfoxide, thionyl chloride (SOCl) 2 ) Acetonitrile (CH) 3 CN), chloroacetonitrile (ClCH) 2 CN), dichloroacetonitrile (Cl) 2 CHCN), trichloroacetonitrile (CCl) 3 CN), fluoroacetonitrile (FCH) 2 CN), propionitrile (CH) 3 CH 2 CN), malononitrile (NCCH) 2 CN), succinonitrile (NC (CH) 2 ) 2 CN), dimethyl sulfite ((CH) 3 ) 2 SO 3 ) Diethyl sulfite ((C) 2 H 5 ) 2 SO 3 ) Vinyl sulfite, propylene sulfite, dimethyl sulfate ((CH) 3 O) 2 SO 2 ) Diethyl sulfate ((C) 2 H 5 O) 2 SO 2 ) Vinyl sulfate, 3-chloro-1, 3-propylsultone (3-Cl-PS), methyl methylsulfonate (CH) 3 SO 3 CH 3 ) Methyl ethyl sulfonate (C) 2 H 5 SO 3 CH 3 ) Any one or a plurality of the components in any proportion;
and/or the content of the solvent accounts for 45-98 w% of the total weight of the electrolyte.
Another object of the present invention is to provide a method for preparing an electrolyte containing a fluoro additive, the method comprising the steps of:
s1: mixing and preparing the solvent with a certain volume ratio under the conditions that the temperature is between minus 20 ℃ and 30 ℃ and the oxygen content is less than 5 ppm.
S2: adding the third additive into S1 at 5-10 ℃, stirring, and adding the first and second additives according to the Z of 1.5-3.2Z.
S3: and finally, adding the selected lithium salt into the step S2 to obtain the electrolyte.
Preferably, the temperature of adding lithium salt in the step S3 is controlled to be 1-3 ℃.
A third object of the present invention is to provide a battery comprising a positive electrode, a negative electrode, a separator, and the electrolyte containing a fluorine-substituted additive of the present invention.
Compared with the prior art, the invention has the following beneficial effects:
in the present invention, since the second additive has a benzene ring structure, the benzene ring is substituted with sp 2 Hybrid forms, in which carbon atoms overlap each other in the p-orbitalPi conjugation is formed, the internal energy of the molecules is reduced, the stability of the electrolyte is improved, and the electrolyte has five-membered rings containing carbonyl, so that the compatibility of the additive, an organic solvent and salt is improved, and the low-temperature performance of the electrolyte is improved, but the performance of the electrolyte is rapidly reduced after multiple cycles in the high-temperature cycle process; and the research of the inventor shows that when the content ratio of the first additive, the second additive and the third additive in the electrolyte is in the range of 1.5Z (X+Y) to 3.2Z, the battery performance is optimal at normal temperature and high temperature and low temperature.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a process for preparing an electrolyte containing a fluorinated additive according to the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention is provided on the premise of the technical solution of the present invention, and the detailed implementation manner and specific operation process are provided, and it should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered as the protection scope of the present invention.
Thus, the following detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that: like reference numerals and letters denote like items below, and thus once an item is defined, no further definition or explanation thereof is required later.
In the description of the present invention, it should be noted that, the azimuth or positional relationship indicated by the terms "front", "rear", etc. are based on azimuth or positional relationship, or azimuth or positional relationship that the inventive product is conventionally put in use, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific azimuth, be configured and operated in a specific azimuth, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
In the description of the present invention, it should also be noted that, unless explicitly specified and limited otherwise, the terms "disposed", "connected" and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
In the present invention, unless expressly stated or limited otherwise, a first feature may include first and second features directly contacting each other, either above or below a second feature, or through additional features contacting each other, rather than directly contacting each other.
Moreover, the first feature being above, over, and on the second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is higher in level than the second feature. The first feature being below, beneath, and beneath the second feature includes the first feature being directly below and obliquely below the second feature, or simply indicates that the first feature is less level than the second feature.
What needs to be described here is: "alkyl" as used herein refers to saturated hydrocarbons containing primary (plus) carbon atoms, or secondary carbon atoms, or tertiary carbon atoms, or quaternary carbon atoms, or combinations thereof; examples as follows include but are not limited toNot limited to: methyl (-CH) 3 ) Ethyl (-CH) 2 CH 3 ) 1-propyl (-CH) 2 CH 2 CH 3 ) 2-propyl (-CH (CH) 3 ) 2 ) 1-butyl (-CH) 2 CH 2 CH 2 CH 3 ) 2-methyl-1-propyl (-CH) 2 CH(CH 3 ) 2 ) 2-butyl (-CH (CH) 3 )CH 2 CH 3 ) 2-methyl-2-propyl (-C (CH) 3 ) 3 ) 1-pentyl (-CH) 2 CH 2 CH 2 CH 2 CH 3 ) 2-pentyl (-CH (CH) 3 )CH 2 CH 2 CH 3 ) 3-pentyl (-CH (CH) 2 CH 3 ) 2 ) 2-methyl-2-butyl (-C (CH) 3 ) 2 CH 2 CH 3 ) 3-methyl-2-butyl (-CH (CH) 3 )CH(CH 3 ) 2 ) 3-methyl-1-butyl (-CH) 2 CH 2 CH(CH 3 ) 2 ) 2-methyl-1-butyl (-CH) 2 CH(CH 3 )CH 2 CH 3 ) 1-hexyl (-CH) 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2-hexyl (-CH (CH) 3 )CH 2 CH 2 CH 2 CH 3 ) 3-hexyl (-CH (CH) 2 CH 3 )(CH 2 CH 2 CH 3 ) 2-methyl-2-pentyl (-C (CH) 3 ) 2 CH 2 CH 2 CH 3 ) 3-methyl-2-pentyl (-CH (CH) 3 )CH(CH 3 )CH 2 CH 3 ) 4-methyl-2-pentyl (-CH (CH) 3 )CH 2 CH(CH 3 ) 2 ) 3-methyl-3-pentyl (-C (CH) 3 )(CH 2 CH 3 ) 2 ) 2-methyl-3-pentyl (-CH (CH) 2 CH 3 )CH(CH 3 ) 2 ) 2, 3-dimethyl-2-butyl (-C (CH) 3 ) 2 CH(CH 3 ) 2 ) 3, 3-dimethyl-2-butyl (-CH (CH) 3 )C(CH 3 ) And octyl (- (CH) 2 ) 7 CH 3 )。
Example 1
An electrolyte containing a fluoro additive, wherein the first additive used in this example is of formula (1-1), the second additive is of formula (2-1), and the third additive is methyltriphenylphosphine bromide.
Electrolyte containing fluoro additive: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC: DEC: EMC=1:1:1, and adding 1mol of lithium hexafluorophosphate (LiPF) 6 ) Finally, adding additives accounting for the total mass content of the electrolyte, wherein the content of the first additive, the second additive and the third additive accounts for 0.1%,0.1% and 0.13%.
Example 2
An electrolyte containing a fluoro additive, wherein the first additive used in this example is of formula (1-3), the second additive is of formula (2-2), and the third additive is methyl triphenylphosphine bromide.
Electrolyte containing fluoro additive: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC: DEC: EMC=1:1:1, and adding 1mol of lithium hexafluorophosphate (LiPF) 6 ) And finally, adding additives accounting for the total mass content of the electrolyte, wherein the content of the first additive, the second additive and the third additive accounts for 0.15%,0.15% and 0.15%.
Example 3
An electrolyte containing a fluoro additive, wherein the first additive used in this example is of formula (1-6), the second additive is of formula (2-5), and the third additive is amyl triphenylphosphine bromide.
Electrolyte containing fluoro additive: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC: DEC: EMC=1:1:1, and adding 1mol of lithium hexafluorophosphate (LiPF) 6 ) Finally, adding additives accounting for the total mass content of the electrolyte, wherein the content of the first additive, the second additive and the third additive accounts for 0.22%,0.22% and 0.25%.
Comparative example 1
An electrolyte containing a fluoro additive, wherein the first additive used in this example is of formula (1-1), the second additive is of formula (2-1), and the third additive is methyltriphenylphosphine bromide.
Containing fluoroElectrolyte of additive: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC: DEC: EMC=1:1:1, and adding 1mol of lithium hexafluorophosphate (LiPF) 6 ) Finally, adding additives accounting for the total mass content of the electrolyte, wherein the content of the first additive, the second additive and the third additive accounts for 0.22%,0.22% and 0.13%.
Comparative example 2
An electrolyte containing a fluoro additive, wherein the first additive used in this example is of formula (1-3), the second additive is of formula (2-2), and the third additive is methyl triphenylphosphine bromide.
Electrolyte containing fluoro additive: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC: DEC: EMC=1:1:1, and adding 1mol of lithium hexafluorophosphate (LiPF) 6 ) Finally, adding additives accounting for the total mass content of the electrolyte, wherein the content of the first additive, the second additive and the third additive accounts for 0.2%,0.2% and 0.1%.
Comparative example 3
An electrolyte containing a fluoro additive, wherein the first additive used in this example is of formula (1-6), the second additive is of formula (2-5), and the third additive is amyl triphenylphosphine bromide.
Electrolyte containing fluoro additive: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC: DEC: EMC=1:1:1, and adding 1mol of lithium hexafluorophosphate (LiPF) 6 ) Finally, adding additives accounting for the total mass content of the electrolyte, wherein the content of the first additive, the second additive and the third additive accounts for 0.1%,0.1% and 0.3%.
Comparative example 4
An electrolyte containing a fluoro additive, the additive used in this example is a first additive of formula (1-1).
Electrolyte containing fluoro additive: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC: DEC: EMC=1:1:1, and adding 1mol of lithium hexafluorophosphate (LiPF) 6 )，And finally adding an additive accounting for the total mass content of the electrolyte, wherein the content of the first additive is 0.5%.
Comparative example 5
An electrolyte containing a fluorinated additive, the additive used in this example is a second additive of formula (2-1).
Electrolyte containing fluoro additive: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC: DEC: EMC=1:1:1, and adding 1mol of lithium hexafluorophosphate (LiPF) 6 ) And finally, adding an additive accounting for the total mass content of the electrolyte, wherein the content of the second additive accounts for 0.5 percent.
Comparative example 6
An electrolyte containing a fluoro additive, in this example, methyl triphenylphosphine bromide as a third additive was used.
Electrolyte containing fluoro additive: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC: DEC: EMC=1:1:1, and adding 1mol of lithium hexafluorophosphate (LiPF) 6 ) And finally, adding an additive accounting for the total mass content of the electrolyte, wherein the content of the third additive accounts for 0.5 percent.
Comparative example 7
An electrolyte containing a fluorinated additive, the first additive used in this example was of formula (1-1), and the second additive was of formula (2-1).
Electrolyte containing fluoro additive: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC: DEC: EMC=1:1:1, and adding 1mol of lithium hexafluorophosphate (LiPF) 6 ) And finally, adding additives accounting for the total mass content of the electrolyte, wherein the content of the first additive and the second additive accounts for 0.25 percent and 0.25 percent.
Comparative example 8
An electrolyte containing a fluoro additive, the first additive used in this example is of formula (1-1), and the third additive is methyltriphenylphosphine bromide.
Electrolyte containing fluoro additive: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC: DEC: EMC=1:1:1, and adding 1mol of lithium hexafluorophosphate (LiPF) 6 ) And finally, adding additives accounting for the total mass content of the electrolyte, wherein the content of the first additive and the third additive accounts for 0.25 percent and 0.25 percent.
Comparative example 9
An electrolyte containing a fluoro additive, the second additive used in this example is of formula (2-1) and the third additive is methyltriphenylphosphine bromide.
Electrolyte containing fluoro additive: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC: DEC: EMC=1:1:1, and adding 1mol of lithium hexafluorophosphate (LiPF) 6 ) And finally, adding additives accounting for the total mass content of the electrolyte, wherein the content of the second additive and the third additive accounts for 0.25 percent and 0.25 percent.
Comparative example 10
An electrolyte solution: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC: DEC: EMC=1:1:1, and adding 1mol of lithium hexafluorophosphate (LiPF) 6 ) No additives are added in this example.
Performance test:
1. preparation of a positive plate: ternary material LiNi of nickel cobalt lithium manganate 0.6 Co 0.2 Mn 0.2 O 2 Uniformly mixing a conductive agent SuperP, an adhesive PVDF and a carbon nano tube CNT according to a mass ratio of 97.5:1.5:1:1 to prepare lithium ion battery anode slurry with certain viscosity, and coating the anode slurry on an aluminum foil for a current collector, wherein the coating weight is 320g/m 2 Drying at 85 ℃ and then cold pressing; then trimming, cutting pieces, splitting, drying at 85 ℃ for 4 hours under vacuum condition after splitting, and welding the tab to prepare the lithium ion battery positive plate meeting the requirements.
2. Preparing a negative plate: mixing artificial graphite and silicon according to the mass ratio of 90:10, preparing slurry with a conductive agent SuperP, a thickening agent CMC and an adhesive SBR (styrene butadiene rubber emulsion) according to the mass ratio of 95:1.5:1.0:2.5, uniformly mixing, coating the mixed slurry on two sides of a copper foil, drying and rolling to obtain a negative plate, and preparing the negative plate of the lithium ion battery meeting the requirements.
3. Preparation of electrolyte: see above for details.
4. Preparation of a lithium ion battery: the positive plate, the negative plate and the diaphragm prepared according to the process are manufactured into a lithium ion battery with the thickness of 4.7mm, the width of 55mm and the length of 60mm through a lamination process, the capacity is 1800mAh, the battery is baked for 48h under vacuum at 85 ℃, and the electrolyte is injected to finish the battery manufacturing.
5. And (3) testing:
(1) And (3) carrying out normal-temperature cyclic test at 25 ℃ at 1.0C/1.0C: charging to 4.5V at 25deg.C under constant current of 1.0C, charging to off current of 0.05C under constant voltage of 4.5V, discharging the battery under constant current of 1.0C, and recording discharge capacity as C 0 Repeating the charge and discharge steps for 1000 weeks to obtain discharge capacity C at 1000 weeks 1000 ，
Capacity retention = C 1000 /C 0 ×100％。
(2) High temperature cycle test at 45℃1.0C/1.0C: charging to 4.5V at 45deg.C under constant current of 1.0C, constant voltage charging to cutoff current of 0.05C, discharging the battery under constant current of 1.0C, and recording discharge capacity as C 0 Repeating the charge and discharge steps for 1000 weeks to obtain discharge capacity C at 1000 weeks 1000 ，
Capacity retention = C 1000 /C 0 ×100％。
(3) -20 ℃ low temperature discharge test: charging at 25deg.C to 4.5V with constant current of 1.0C, charging at constant voltage of 4.5V to cutoff current of 0.05C, discharging the battery with constant current of 0.5C, and recording discharge capacity as C 0 . Charging at 25deg.C under constant current of 1.0C to 4.5V, charging at constant voltage of 4.5V to cutoff current of 0.05C, transferring the battery to-20deg.C, standing for 240min, discharging the battery under constant current of 0.5C, and recording discharge capacity as C 1 ，
-20 ℃ discharge rate = C 1 /C 0 ×100％。
After the electrolyte in the above example was prepared into a lithium ion battery, the normal temperature cycle performance, the high temperature cycle performance and the low temperature discharge performance of the lithium ion battery were tested, and the results are shown in table 1, table 1. Test results:
as can be seen from Table 1, the first, second and third additives in comparative examples 1 to 3 were slightly inferior in the properties at normal temperature, high temperature and low temperature to those in comparative examples 1 to 3 in that the ratio of the first, second and third additives was not in accordance with the relation 1.5 Z.ltoreq.X+Y.ltoreq.3.2Z; in comparative examples 4 to 6, since only one additive was used, the high, low and normal temperature properties were excellent; two additives were used in comparative examples 7 to 9, and their normal temperature, low temperature and high temperature properties were deteriorated; the comparative example had the worst performance of the battery since no additive was used.
Claims (10)
1. An electrolyte containing a fluoro additive, characterized in that the electrolyte comprises a solvent, a lithium salt and an additive; the additives include a first additive, a second additive, and a third additive; the first additive and the second additive are fluoro additives, the structural formula is shown as formula (I), and the second additive is shown as formula (II):
wherein R is 1 Or R is 2 Independently selected from methyl, ethyl, propyl, sulfonic acid, sulfonyl, C 1 ～C 8 Alkyl, phenyl, ester, cyano, carbonyl, methanesulfonyl, amide, heteroaryl, aryl;
R 3 or R is 4 Independently selected from methyl, ethyl, propyl, sulfonic acid, sulfonyl, C 1 ～C 8 Alkyl, phenyl, ester, cyano, carbonyl, methanesulfonyl, amide, heteroaryl, aryl.
2. An electrolyte containing a fluoro additive according to claim 1,
the third additive is selected from any one of methyl triphenylphosphine bromide or amyl triphenylphosphine bromide;
and/or the number of the groups of groups,
the addition amounts of the first additive, the second additive and the third additive in the electrolyte are X, Y, Z respectively, and the first additive, the second additive and the third additive are expressed as the following relation:
1.5Z≤(X+Y)≤3.2Z。
3. the electrolyte containing a fluoro additive according to claim 1, wherein the first additive accounts for 0.1-5% of the total mass of the electrolyte;
and/or the second additive accounts for 0.1-5% of the total mass of the electrolyte;
and/or the third additive accounts for 0.1-5% of the total mass of the electrolyte;
and/or the additive accounts for 0.1-5% of the total mass of the electrolyte.
4. The fluorine-additive-containing electrolyte according to claim 1, wherein the first additive is selected from any one of formulas (1-1) to (1-6):
5. the fluorine-additive-containing electrolyte according to claim 1, wherein the second additive is selected from any one of formulas (2-1) to (2-6):
6. the electrolyte containing a fluorine-containing additive according to claim 1, wherein the lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ) Lithium tetrafluoroborate (LiBF) 4 ) One or more of lithium dioxalate borate (LiBOB), lithium difluorooxalate borate (LiODFB), lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) in any proportion; and/or the number of the groups of groups,
the concentration of the lithium salt in the electrolyte is 0.05M-3M; specifically, 0.1M, 0.2M, 0.3M, 0.4M, 0.5M, 0.51M, 0.52M, 0.53M, 0.54M, 0.55M, 0.56M, 0.57M, 0.58M, 0.59M, 0.6M, 0.62M, 0.64M, 0.66M, 0.68M, 0.7M, 0.75M, 0.78M, 0.79M, 0.8M, 0.85M, 0.9M, 0.95M, 1.1M, 1.2M, 1.3M, 1.4M, 1.5M, 1.6M, 1.7M, 1.8M, 1.9M, 2M.
7. The electrolyte containing a fluorine-substituted additive according to claim 1, wherein the solvent is selected from the group consisting of 1, 3-Dioxolane (DOL), ethylene glycol dimethyl ether (DME), ethylene Carbonate (EC), propylene Carbonate (PC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC), fluoroethylene carbonate (FEC), vinylene Carbonate (VC), γ -butyrolactone (GBL), methyl Acetate (MA), ethyl Acetate (EA), methyl Propionate (MP), ethyl Propionate (EP), dimethyl sulfoxide (CH) 3 SOCH 3 ) Butyl sulfoxide, thionyl chloride (SOCl) 2 ) Acetonitrile (CH) 3 CN), chloroacetonitrile (ClCH) 2 CN), dichloroacetonitrile (Cl) 2 CHCN), trichloroacetonitrile (CCl) 3 CN), fluoroacetonitrile (FCH) 2 CN), propionitrile (CH) 3 CH 2 CN), malononitrile (NCCH) 2 CN), succinonitrile (NC (CH) 2 ) 2 CN), dimethyl sulfite ((CH) 3 ) 2 SO 3 ) Diethyl sulfite ((C) 2 H 5 ) 2 SO 3 ) Vinyl sulfite, propylene sulfite, dimethyl sulfate ((CH) 3 O) 2 SO 2 ) Diethyl sulfate((C 2 H 5 O) 2 SO 2 ) Vinyl sulfate, 3-chloro-1, 3-propylsultone (3-Cl-PS), methyl methylsulfonate (CH) 3 SO 3 CH 3 ) Methyl ethyl sulfonate (C) 2 H 5 SO 3 CH 3 ) Any one or a plurality of the components in any proportion;
and/or the number of the groups of groups,
the content of the solvent accounts for 45-98 w% of the total weight of the electrolyte.
8. The method for producing a fluorine-containing additive-containing electrolyte according to any one of claims 1 to 7, characterized in that the method comprises the steps of:
s1: mixing and preparing a solvent with a certain volume ratio under the conditions that the temperature is between 20 ℃ below zero and 30 ℃ and the oxygen content is less than 5 ppm;
s2: adding a third additive into the S1 at the temperature of 5-10 ℃, stirring, and adding the first additive and the second additive according to the temperature of 1.5Z (X+Y) to 3.2Z;
s3: and finally, adding the selected lithium salt into the step S2 to obtain the electrolyte.
9. The method for preparing an electrolyte containing a fluorine-substituted additive according to claim 8, wherein the temperature of adding lithium salt in the step S3 is controlled to be 1-3 ℃.
10. A battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte selected from the group consisting of the fluorine-containing additive-containing electrolyte according to any one of claims 1 to 7.
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| CN111244543A (en) * | 2020-01-15 | 2020-06-05 | 松山湖材料实验室 | High-voltage lithium ion battery electrolyte additive, electrolyte, battery and formation method thereof |
| CN114204106A (en) * | 2021-03-31 | 2022-03-18 | 松山湖材料实验室 | Lithium ion battery electrolyte additive, electrolyte and lithium ion battery |
| CN114361590A (en) * | 2021-12-17 | 2022-04-15 | 松山湖材料实验室 | Lithium ion battery electrolyte additive, electrolyte and lithium ion battery |
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| US20020025477A1 (en) * | 2000-07-14 | 2002-02-28 | Mitsubishi Chemical Corporation | Non-aqueous electrolytic solution and secondary battery containing same |
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