CN110690501B - Electrolyte solution and electrochemical device - Google Patents
Electrolyte solution and electrochemical device Download PDFInfo
- Publication number
- CN110690501B CN110690501B CN201911120583.0A CN201911120583A CN110690501B CN 110690501 B CN110690501 B CN 110690501B CN 201911120583 A CN201911120583 A CN 201911120583A CN 110690501 B CN110690501 B CN 110690501B
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- additive
- electrolyte
- lithium
- carbon atoms
- battery
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- 239000008151 electrolyte solution Substances 0.000 title claims description 3
- 239000000654 additive Substances 0.000 claims abstract description 190
- 230000000996 additive effect Effects 0.000 claims abstract description 168
- 239000003792 electrolyte Substances 0.000 claims abstract description 96
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 54
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 50
- -1 cyclic carbonate compounds Chemical class 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 16
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 125000001424 substituent group Chemical group 0.000 claims description 15
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 13
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 5
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 5
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 3
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 claims description 3
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 3
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 abstract description 22
- 238000003860 storage Methods 0.000 abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 26
- 229910001416 lithium ion Inorganic materials 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 22
- 239000007789 gas Substances 0.000 description 18
- 210000004027 cell Anatomy 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 8
- 230000002195 synergetic effect Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 125000000542 sulfonic acid group Chemical group 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- 229910013883 LiNi0.3Co0.3Mn0.3O2 Inorganic materials 0.000 description 2
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 2
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000002153 silicon-carbon composite material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 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 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-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
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 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
- 230000000670 limiting effect Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 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
- 230000010287 polarization Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- OIIWPAYIXDCDNL-UHFFFAOYSA-M sodium 3-(trimethylsilyl)propionate Chemical compound [Na+].C[Si](C)(C)CCC([O-])=O OIIWPAYIXDCDNL-UHFFFAOYSA-M 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
An electrolyte and an electrochemical device are disclosed. The electrolyte comprises a non-aqueous organic solvent, lithium salt and additives, wherein the additives comprise an additive A, an additive B, an additive C, an additive D and an additive E. The additive A is selected from at least one of cyclic carbonate compounds; the additive B is selected from at least one of sulfate-containing compounds; the additive C is at least one selected from siloxane compounds; the additive D is selected from at least one of fluorine-containing lithium salt; the additive E is selected from at least one of boron-containing lithium salts. The electrolyte disclosed by the application can effectively inhibit low-temperature lithium precipitation and high-temperature storage gas generation of the battery, and remarkably improves the cycle performance of the battery under high voltage (more than or equal to 4.2V).
Description
Technical Field
The application relates to the technical field of energy storage, in particular to electrolyte and an electrochemical device.
Background
Lithium ion batteries have higher mass and volume energy density and better cycle performance than zinc-manganese batteries, nickel-metal hydride batteries, lead-acid batteries and the like, and are widely applied to various fields such as mobile energy storage, 3C digital products, electric tools and the like.
Currently, the commercial positive electrode material is mainly nickel-cobalt-manganese ternary material, lithium cobaltate material and lithium iron phosphate material, and particularly, the ternary material has the most potential for development. In order to develop a higher energy density battery, increasing the nickel content of the ternary material anode and increasing the working voltage of the battery are two very effective ways. However, the oxidation of the positive electrode and the aggravation of side reactions between the electrode plate and the electrolyte are accompanied, so that the electrolyte is easily oxidized and decomposed, and a large amount of gas is generated in the storage process of the battery at high temperature and high potential, and potential safety hazards are brought. Meanwhile, the stability of the SEI film formed by the positive electrode and the negative electrode is reduced under high voltage, which also causes the reduction of the cycling stability and the capacity retention rate of the battery and influences the performance of the battery. In addition, electrochemical polarization of the graphite electrode is obviously intensified in the process of low-temperature charging, metal lithium is easily precipitated on the surface of the negative electrode, lithium ions which can be repeatedly charged and discharged in the battery are consumed by the reaction, the capacity of the battery is greatly reduced, and the precipitated metal lithium dendrites can pierce through the diaphragm, so that the safety performance is influenced.
Disclosure of Invention
In order to solve the above technical problem, embodiments of the present application provide an electrolyte and an electrochemical device. The electrolyte provided by the embodiment of the application can effectively inhibit low-temperature lithium precipitation and high-temperature storage gas generation of the battery, and remarkably improves the cycle performance of the battery under high voltage (> 4.2V).
In one embodiment of the present application, there is provided an electrolyte including a non-aqueous organic solvent, a lithium salt, and an additive. The additives comprise an additive A, an additive B, an additive C, an additive D and an additive E; wherein, the additive A is selected from at least one of cyclic carbonate compounds; the additive B is at least one selected from the group consisting of sulfate-containing compounds; the additive C is at least one selected from siloxane compounds; the additive D is selected from at least one of fluorine-containing lithium salt; the additive E is selected from at least one of boron-containing lithium salts.
According to an embodiment of the present application, the additive A is at least one selected from the group consisting of a compound of formula I and a compound of formula II,
wherein R1 and R2 are each independently one selected from the group consisting of C1-3 alkyl, alkenyl, C1-3 alkyl substituted with substituent A, alkenyl substituted with substituent A, and halogen;
the substituent A is at least one selected from halogen atoms, alkoxy, carboxyl, sulfonic acid groups, alkyl groups with 1-20 carbon atoms, halogenated alkyl groups with 1-20 carbon atoms, unsaturated hydrocarbon groups with 2-20 carbon atoms and halogenated unsaturated hydrocarbon groups with 2-20 carbon atoms.
According to an embodiment of the present application, the additive a is selected from at least one of vinylene carbonate, ethylene carbonate, fluoroethylene carbonate.
According to the embodiment of the application, the mass percentage of the additive A in the electrolyte is 0.1-2%; preferably 0.1% to 0.5%.
According to an embodiment of the present application, the additive B includes at least one of ethylene sulfate, 1, 3-propane sultone, 1, 4-butane sultone, 1, 3-propene sultone, 1, 4-butene sultone, ethylene sulfite, propylene sulfite, and methylene methane disulfonate.
According to the embodiment of the application, the mass percentage of the additive B in the electrolyte is 0.5-2.5%; preferably 1% to 2%.
According to an embodiment of the present application, the additive C includes at least one selected from the group consisting of a compound of formula III, a compound of formula IV, and a compound of formula V,
wherein R is 3 ～R 29 Each independently is selected from C 1～3 Alkyl and C substituted by substituent B 1～3 One of alkyl groups; wherein the substituent B is at least one selected from the group consisting of halogen, alkoxy, carboxyl, sulfonic acid group, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, unsaturated hydrocarbon group having 2 to 20 carbon atoms and halogenated unsaturated hydrocarbon group having 2 to 20 carbon atoms.
According to the embodiment of the application, the mass percentage of the additive C in the electrolyte is 1-2%.
According to the embodiment of the application, the mass percentage of the additive C in the electrolyte is 0.1-1%.
According to an embodiment of the present application, additive D comprises at least one of lithium bis-fluorosulfonylimide, lithium difluorophosphate.
According to the embodiment of the application, the mass percentage of the additive D in the electrolyte is 0.1-2%.
According to the embodiment of the application, the mass percentage of the additive D in the electrolyte is 0.1-1%.
According to an embodiment of the application, the additive E comprises at least one of lithium difluorooxalato borate, lithium tetrafluoroborate.
According to the embodiment of the application, the mass percentage of the additive E in the electrolyte is 0.5-2.5%.
According to the embodiment of the application, the mass percentage of the additive E in the electrolyte is 1-2%.
According to the embodiment of the application, the total mass percentage of the additive A, the additive B, the additive C, the additive D and the additive E in the electrolyte is 3-5%.
According to an embodiment of the present application, the non-aqueous organic solvent includes at least one of a cyclic carbonate and a linear carbonate.
The invention also provides an electrochemical device which comprises the positive plate, the negative plate, the isolating membrane and any electrolyte.
According to the embodiment of the application, the positive plate comprises a positive current collector and a positive diaphragm coated on the positive current collector, wherein the positive diaphragm comprises a positive active material, a binder and a conductive agent. Further, in the present application, the positive active material is selected from at least one lithium-containing transition metal oxide, wherein the Ni content in the lithium-containing transition metal oxide is 30% to 90%. Further, the positive electrode active material in the present application includes LiNi 0.3 Co 0.3 Mn 0.3 O 2 ，LiNi 0.5 Co 0.2 Mn 0.3 O 2 ，LiNi 0.6 Co 0.2 Mn 0.2 O 2 ，LiNi 0.8 Co 0.1 Mn 0.1 O 2 At least one of (a).
According to the invention, the additive A, the additive B, the additive C, the additive D and the additive E are added into the electrolyte, so that a stable composite solid electrolyte interface film (SEI) is formed on the surfaces of a positive electrode and a negative electrode, the SEI is relatively stable under a high potential, and the storage performance of the battery under the high potential and the cycle performance of the battery under the high voltage can be obviously improved; meanwhile, the interface impedance between the formed SEI film and the electrolyte is small, and the low-temperature lithium ion transmission rate is high, so that the low-temperature lithium precipitation of the battery can be effectively inhibited.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application clearer, the technical solutions of the present application will be clearly and completely described below with reference to the embodiments of the present application. It should be apparent that the described embodiments are only some of the embodiments of the present application, not all of the embodiments, and the embodiments of the present application should not be construed as limiting the present application. All other embodiments obtained by those skilled in the art without any creative effort based on the technical solutions and the given embodiments provided in the present application belong to the protection scope of the present application.
As used herein, the following terms have the meanings indicated below, unless explicitly indicated otherwise.
The term "about" is used to describe and account for small variations. When used in conjunction with an event or circumstance, the terms can refer to instances where the event or circumstance occurs precisely as well as instances where the event or circumstance occurs in close proximity. For example, when used in conjunction with data, the terms can refer to a range of variation of less than or equal to ± 10% of the stated value, e.g., less than or equal to ± 5%, less than or equal to ± 4%, less than or equal to ± 3%, less than or equal to ± 2%, less than or equal to ± 1%, less than or equal to ± 0.5%, less than or equal to ± 0.1%, or less than or equal to ± 0.05%. It is to be understood that such range format is used for convenience and brevity, and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or ranges encompassed within that range as if each numerical value and subrange is explicitly recited.
The term "halogen" encompasses fluorine (F), chlorine (Cl), bromine (Br), iodine (I).
The term "alkyl" is intended to be a straight chain saturated hydrocarbon structure having from 1 to 20 carbon atoms. "alkyl" is also contemplated to be a branched or cyclic hydrocarbon structure having from 3 to 20 carbon atoms. When an alkyl group having a particular carbon number is specified, all geometric isomers having that carbon number are intended to be encompassed; thus, for example, "butyl" is meant to include n-butyl, sec-butyl, isobutyl, tert-butyl, and cyclobutyl; "propyl" includes n-propyl, isopropyl and cyclopropyl. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, n-ethyl, hexyl, cyclohexyl, n-heptyl, octyl, cyclopropyl, cyclobutyl, norbornyl, and the like. In addition, the alkyl group may be optionally substituted.
The term "alkenyl" refers to a monovalent unsaturated hydrocarbon group that can be branched or branched and has at least one and typically 1, 2, or 3 carbon-carbon double bonds. Unless otherwise defined, the alkenyl groups typically contain 2 to 20 carbon atoms and include, for example, -C 2-4 Alkynyl, -C 3-6 Alkynyl and-C 3-10 Alkynyl. Representative alkynyl groups include, for example, ethynyl, prop-2-ynyl (n-propynyl), n-but-2-ynyl, n-hex-3-ynyl, and the like.
In the detailed description and claims, a list of items linked by the term "at least one of can mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" means a only; only B; or A and B. In another example two, if items a, B, and C are listed, the phrase "at least one of a, B, and C" means a only; only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or all of A, B and C. Item a may comprise a single element or multiple elements. Item B may comprise a single element or multiple elements. Item C may comprise a single element or multiple elements.
As used herein, the relative amounts of the components are based on the total mass of the electrolyte.
The present application relates to an electrolyte comprising a non-aqueous organic solvent, a lithium salt and an additive. The additives comprise an additive A, an additive B, an additive C, an additive D and an additive E; wherein, the additive A is selected from at least one of cyclic carbonate compounds; the additive B is at least one selected from the group consisting of sulfate-containing compounds; the additive C is at least one selected from siloxane compounds; the additive D is selected from at least one of fluorine-containing lithium salt; the additive E is selected from at least one of boron-containing lithium salts.
In the process of charging and discharging of the battery, the positive electrode and the negative electrode can generate volume change (expansion/contraction) due to lithium intercalation/lithium separation, and the phenomenon is particularly obvious under high potential (more lithium intercalation amount); the electrolyte containing the additive A can form an SEI film which mainly comprises polymers on the surfaces of the positive electrode and the negative electrode, the SEI film has good mechanical toughness, is not easy to break and break due to volume change, and can continuously protect the positive electrode and the negative electrode in the circulating process, so that the circulating performance of the battery under high voltage can be effectively improved.
However, the inventors of the present application found through research that an SEI film formed by using the additive a alone in the electrolyte is not dense enough, and it is difficult to completely avoid direct contact between the electrolyte and the electrode plate; the addition of additive B to the electrolyte makes it possible to remedy this drawback. The sulfonic acid group contained in the additive B can form a compact inorganic salt SEI film on the surfaces of the anode and the cathode, and can effectively prevent the anode and the cathode from continuously reacting with the electrolyte; in addition, additive B and additive A have synergistic film-forming effects. The additive B is used as electrophilic secondary additive and can form a film product Li through reduction with the additive A 2 The A substance reacts to form a new SEI component which is a multifunctional polymer with lithium sulfonate and lithium organosulfate ester functional groups and has good toughness and compact protection capability, so that active sites on the surface of the anode can be effectively covered under high potential, the possibility of oxidation of the electrolyte is reduced, and gas generation during storage under high temperature and high potential is further inhibited.
Generally speaking, because the film formation is dense, the battery using the A and B additives has high impedance, and low-temperature lithium precipitation is easily caused. Adding additivesThe additive C can effectively improve the transmission capability of lithium ions in the electrolyte and reduce the partial resistance (Rs) of the electrolyte so as to reduce the resistance of the battery; the additive D can improve the content of components such as lithium alkyl ester and lithium carbonate with better ion transmission performance in SEI, and reduce the interface impedance (RCT) of the electrolyte/pole piece. In conclusion, the additive can effectively reduce the battery impedance and reduce low-temperature lithium precipitation. In addition, the use of additive E in the electrolyte also leads to improved electrical core performance. During the storage or circulation process of the battery under high temperature and high voltage, the decomposition of lithium hexafluorophosphate in the electrolyte is accelerated, and the generated high-activity PF 5 The electrolyte is easy to react with SEI components to cause poor cycle performance and bring about battery expansion along with gas generation; lithium borate salt additive as Lewis acid, containing electron-deficient B atom and capable of reacting with strong Lewis base PF 5 The complexing occurs, thereby effectively inhibiting the high-temperature storage and gas production of the battery.
Further, in the application, the additive A is at least one selected from the compound with the structural formula I and the compound with the structural formula II,
wherein R1 and R2 are each independently selected from C 1～3 Alkyl, alkenyl, C substituted by substituent A 1～3 Alkyl, alkenyl substituted by substituent A and halogen.
Wherein the substituent A is at least one selected from the group consisting of halogen, alkoxy, carboxyl, sulfonic acid group, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, unsaturated hydrocarbon group having 2 to 20 carbon atoms and halogenated unsaturated hydrocarbon group having 2 to 20 carbon atoms.
Further, in the present application, the additive a is at least one selected from vinylene carbonate, ethylene carbonate, and fluoroethylene carbonate. The electrolyte containing the additive A can form an SEI film which mainly comprises polymers on the surfaces of the positive electrode and the negative electrode, the SEI film has good mechanical toughness, is not easy to break and break due to volume change of the positive electrode and the negative electrode in the circulating process, and can continuously protect the positive electrode and the negative electrode in the circulating process, so that the circulating performance of the battery under high voltage can be effectively improved. The phenomenon of low-temperature lithium precipitation of the battery core is aggravated by using the additive A in an excessive amount.
According to the embodiment of the application, the mass percentage of the additive A in the electrolyte is 0.1-2%; further, in the application, the mass percentage of the additive A in the electrolyte is 0.1-0.5%.
Further, in the present application, the additive B includes at least one of ethylene sulfate, 1, 3-propane sultone, 1, 4-butane sultone, 1, 3-propene sultone, 1, 4-butene sultone, ethylene sulfite, propylene sulfite, and methylene methane disulfonate. The sulfonic acid group contained in the additive B can form a compact inorganic salt SEI film on the surfaces of the anode and the cathode, and can effectively prevent the anode and the cathode from continuously reacting with the electrolyte; in addition, additive B and additive A have a synergistic film-forming effect. The additive B is not enough in dosage, so that the phenomenon of gas generation during high-temperature storage is difficult to fully inhibit; the excessive dosage of the additive B can increase the cost of the electrolyte, and is not beneficial to popularization and application in industrial production.
According to the embodiment of the application, the mass percentage of the additive B in the electrolyte is 0.5-2.5%; further, in the application, the mass percentage of the additive B in the electrolyte is 1-2%.
Further, in the present application, the additive C includes at least one selected from the group consisting of a compound of formula III, a compound of formula IV, and a compound of formula V,
wherein R3 to R29 are independently selected from C 1～3 Alkyl and C substituted by substituent B 1～3 One of the alkyl groups. Wherein the substituent B is at least one selected from the group consisting of a halogen, an alkoxy group, a carboxyl group, a sulfonic acid group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group having 2 to 20 carbon atoms and a halogenated unsaturated hydrocarbon group having 2 to 20 carbon atoms.
The additive C can effectively improve the transmission capability of lithium ions in the electrolyte, and reduce Rs so as to reduce the impedance of the battery. The gas generation phenomenon of the battery cell is aggravated by adding the additive C excessively.
According to the embodiment of the application, the mass percentage of the additive C in the electrolyte is 1-2%; further, in the application, the mass percentage of the additive C in the electrolyte is 0.1-1%.
Further, in the present application, the additive D includes at least one of lithium bis (fluorosulfonyl) imide and lithium difluorophosphate. The additive D can improve the content of the components of alkyl lithium and lithium carbonate with better ion transmission performance in SEI and reduce RCT. However, excessive addition of the additive D can aggravate the gas generation phenomenon of the cell.
According to the embodiment of the application, the mass percentage of the additive D in the electrolyte is 0.1-2%; further, in the application, the mass percentage of the additive D in the electrolyte is 0.1-1%.
Further, in the present application, the additive E includes at least one of lithium difluorooxalato borate and lithium tetrafluoroborate. The additive E can bring about an improvement in the cell performance. The lithium salt is decomposed and aggravated under high temperature and high voltage, and substances generated by decomposition are easy to react with SEI film components, so that the cycle performance of the battery is deteriorated, and the battery is often expanded along with the generation of acid gas; the lithium borate additive is used as Lewis acid, contains an electron-deficient B atom and can be complexed with acid gas, so that the high-temperature storage and gas generation of the battery are effectively inhibited. In some embodiments, when the lithium salt in the electrolyte comprises lithium hexafluorophosphate, the decomposition of the lithium hexafluorophosphate is accelerated at high temperature and high voltage, and the PF generated by the decomposition is 5 The electrolyte is easy to react with SEI film components to cause poor cycle performance and gas generation to cause battery swelling; lithium borate saltClass of additives as Lewis acids, containing electron-deficient B atoms, capable of reacting with a strong Lewis base PF 5 The complexing occurs, thereby effectively inhibiting the high-temperature storage and gas production of the battery. However, the improvement effect of the excessive borate additive on the high-temperature gas production performance of the battery is relatively reduced, and the low-temperature lithium precipitation phenomenon is possibly aggravated to a certain extent because the interface impedance of the negative electrode is increased by forming a large amount of films on the negative electrode.
According to the embodiment of the application, the mass percentage of the additive E in the electrolyte is 0.5-2.5%; further, in the application, the mass percentage of the additive E in the electrolyte is 1-2%.
Further, in the application, the total mass percentage of the additive A, the additive B, the additive C, the additive D and the additive E in the electrolyte is 3-5%. Too little total amount of additives provides relatively little improvement in battery performance, and too much additives may have some negative effects and increase battery cost.
Further, in the present application, the non-aqueous organic solvent includes at least one of a cyclic carbonate and a linear carbonate.
In different positive electrode systems, the lithium salt concentration range related to the system is set, so that the increase of the interface impedance of the pole piece/electrolyte in the circulating process can be effectively inhibited, and the circulating performance of the battery is improved. The selection of the particular type and concentration range of the lithium salt is not specifically limited in this application.
The application also relates to an electrochemical device which comprises the positive plate, the negative plate and any electrolyte. The electrochemical device of the present application includes any device in which electrochemical reactions occur, and specific examples thereof include all kinds of primary batteries, secondary batteries, fuel cells, solar cells, and capacitors. Specifically, the electrochemical device includes a lithium secondary battery, specifically, it includes a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery and a lithium ion polymer secondary battery. In the following specific embodiments of the present application, only an embodiment of a lithium ion battery is shown, but the present application is not limited thereto.
The application also provides a lithium ion battery, which comprises a positive plate, a negative plate, an isolating membrane arranged between the positive plate and the negative plate at intervals, electrolyte and packaging foil; the positive plate comprises a positive current collector and a positive diaphragm coated on the positive current collector, and the negative plate comprises a negative current collector and a negative diaphragm coated on the negative current collector; the electrolyte is any one of the above electrolytes.
The positive electrode membrane comprises a positive electrode active material, a binder and a conductive agent. Further, the positive active material is selected from at least one lithium-containing transition metal oxide, wherein the content of Ni in the lithium-containing transition metal oxide is 30-90%. The gram capacity of the cathode material with lower nickel content is lower, so that the energy density of the battery cell can be greatly reduced; and the cathode material with too high nickel content has unstable structure, which results in poor cycle performance of the battery core. Further, the positive electrode active material in the present application includes LiNi 0.3 Co 0.3 Mn 0.3 O 2 ，LiNi 0.5 Co 0.2 Mn 0.3 O 2 ，LiNi 0.6 Co 0.2 Mn 0.2 O 2 ，LiNi 0.8 Co 0.1 Mn 0.1 O 2 At least one of (1).
In some embodiments, the binder and the conductive agent in the positive electrode membrane may be selected from those commonly used in the art, and the content or the use ratio may be within a range commonly used in the art.
Further, the negative electrode membrane of the present application includes a negative electrode active material, a binder, and a conductive agent. Further, the negative active material of the present application may be selected from any one of graphite, silicon, or a silicon-carbon composite material, wherein the silicon-carbon composite material refers to a negative active material obtained by doping silicon-carbon in any ratio.
In some embodiments, the binder and the conductive agent in the negative electrode membrane may be selected from those commonly used in the art, and the content or the use ratio may be within a range commonly used in the art.
The technical solution of the present application is exemplarily described by specific embodiments as follows:
preparing an electrolyte:in an argon atmosphere glove box (H) 2 O<10ppm,O 2 <1 ppm), uniformly mixing ethylene carbonate (simple EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) at a mass ratio of 30 6 Dissolving in the non-aqueous solvent to obtain basic electrolyte. In the specific examples of the present application, liPF was contained in the base electrolyte in comparative examples 1 to 10 and examples 1 to 17 6 Is 1.0mol/L, and LiPF is contained in the base electrolyte in comparative examples 11 to 18 and examples 18 to 25 6 The concentration of (2) is 1.2mol/L.
As shown in table 1, additive a, additive B, additive C, additive D, and additive E were added to the base electrolyte.
Examples of additives A are: vinylene carbonate (VC, A1); ethylene carbonate (VEC, A2), fluoroethylene carbonate (FEC, A3);
examples of additives B are: ethylene sulfate (DTD, B1), 1, 3-propanesultone (PS, B2), methylene methanedisulfonate (MMDS, B3);
examples of additives C are: tris (trimethylsilyl) phosphate (TMSP, C1), tris (trimethylsilyl) phosphite (TMSPi, C2);
examples of additives D are: lithium bis (fluorosulfonyl) imide (LiFSI, D1), lithium difluorophosphate (LiPO) 2 F 2 ，D2)；
Examples of additives E are: lithium difluorooxalato borate (LiODFB, E1), lithium tetrafluoroborate (LiBF 4, E2).
TABLE 1 electrolyte additives and addition amounts for examples 1-25 and comparative examples 1-18
Preparing a lithium ion battery:
1) Preparing a positive plate: mixing lithium nickel cobalt manganese (LiNi) as positive electrode active material 0.8 Co 0.1 Mn 0.1 O 2 ) Fully stirring and mixing acetylene black serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder in a proper amount of N-methylpyrrolidone (NMP) solvent according to a weight ratio of 97; coating the slurry on an aluminum foil of a positive current collector, and drying, rolling and cutting into pieces to obtain the positive plate.
2) Preparing a negative plate: fully stirring and mixing a negative electrode active material graphite, a conductive agent acetylene black and a binder Styrene Butadiene Rubber (SBR) in a proper amount of deionized water solvent according to a weight ratio of 96; and coating the slurry on a copper foil of a negative current collector, and drying, rolling and cutting into pieces to obtain the negative plate.
3) Preparing a lithium ion battery: stacking the positive plate, the isolating film and the negative plate in sequence to enable the isolating film to be positioned between the positive plate and the negative plate to play an isolating role, and then winding, hot-pressing and shaping, and welding tabs to obtain a bare cell; and (3) placing the bare cell in an outer packaging foil, injecting the prepared electrolyte into the dried battery, and performing vacuum packaging, standing, formation, shaping and other processes to complete the preparation of the lithium ion battery.
The electrolytes of examples 1 to 25 and comparative examples 1 to 18 and lithium ion batteries were prepared according to the above preparation methods; the additives in the electrolyte and the respective amounts added are shown in table 1.
The lithium ion batteries of the comparative examples and examples of the present application were tested for performance by experiment as follows.
Test for volume expansion
The lithium ion batteries obtained by the preparation were subjected to the following tests, respectively:
charging to 4.2V at 25 deg.C under constant current and constant voltage at 1C, measuring volume by drainage method, and recording as V 0 Then stored at 80 ℃ and after 20 days the volume is measured again and recorded as V 1 . Wherein the volume expansion rate = (V) 1 -V 0 )/V 0 *100%, the obtained record result is shown inTable 2.
TABLE 2 volumetric expansion ratios of lithium ion batteries of examples 1 to 25 and comparative examples 1 to 18
Test two, cycle experiment
The lithium ion batteries obtained by the preparation were subjected to the following tests, respectively:
under the condition of 25 ℃, carrying out charge-discharge cycle test in a voltage range of 2.8-4.3V and a voltage range of 2.8-4.2V by using the charge-discharge rate of 1C/1C, respectively recording the first charge-discharge capacity of the battery and the discharge capacity after each cycle, cycling for 1000 times, and calculating the Nth capacity retention rate of each lithium battery, wherein the Nth capacity retention rate = Nth cycle discharge capacity/battery first discharge capacity 100%. The electrolyte selected for each lithium ion battery and the data of the capacity retention rate after 1000 cycles are shown in table 3.
TABLE 3 Capacity Retention ratio 1000 cycles of lithium ion batteries of examples 1-25 and comparative examples 1-18
Test III, low temperature lithium precipitation test
The lithium ion batteries obtained by the preparation were subjected to the following tests, respectively:
(1) placing the battery cell at-10 deg.C, and standing for 120min; then charging to 4.2V with constant current and constant voltage of k C, stopping current at 0.05C, and standing for 5min; discharging to 2.8V at 1C, and standing for 5min;
(2) repeating the step (1) for 10 times;
(3) charging the battery cell to 4.2V at constant current and constant voltage of k C;
wherein, for comparative examples 1-10 and examples 1-17, k =0.23; for comparative examples 11-18 and examples 18-25, k =0.5;
(4) and (3) disassembling the battery cell in a drying room (with dew point lower than-35 ℃) with lower water content in the air, photographing the obtained negative plate, observing the lithium precipitation condition, and completing the test. Defining the area ratio of lithium deposition = partial area of lithium deposition on the pole piece/total area of the pole piece X100%. Dividing the lithium precipitation area into five grades of 0-4 according to the severity of lithium precipitation, wherein 0 represents no lithium precipitation and corresponds to the lithium precipitation area accounting for 0 percent; 1 represents slight lithium precipitation, and the corresponding lithium precipitation area ratio is 0-20% (excluding end values); 2 represents medium lithium separation, and the area ratio of the corresponding lithium separation is 20-50% (without 50%); 3 represents a large amount of lithium precipitation, and the corresponding lithium precipitation area ratio is 50-90% (not containing 90%); 4 represents that the negative electrode is almost completely covered by lithium, and the lithium deposition area ratio is 90-100%; the results are reported in Table 4.
TABLE 4 degree of low-temperature lithium deposition of lithium ion batteries of examples 1 to 25 and comparative examples 1 to 18
The following conclusions can be drawn in conjunction with the data in tables 1-6:
1) Comparative examples 1-18, which use only some of the additives a-E and combinations thereof, all have certain drawbacks in cell performance. The absence of a part of key additives makes the battery insufficient to form a composite solid electrolyte interface film (SEI film) stable at high potential, affecting the cycle performance of the battery; in addition, part of the batteries have high impedance, low-temperature lithium ion transmission is inhibited, and low-temperature lithium precipitation of the batteries is serious.
2) Comparing examples 1-5 with comparative example 6, and examples 18-20 with comparative example 14, respectively, the results show that additive A has a good synergistic effect with other additives. The additive A added into the electrolyte can form a polymer SEI film with excellent mechanical properties together with other additives, and the battery can be effectively protected in the circulating process. The combination use of the additive A can effectively improve the normal-temperature cycle performance of the battery. The results of comparing example 2 with example 3 show that the improvement degree of the low-temperature lithium precipitation phenomenon of the battery is different according to the different dosage of the additive A.
3) Comparing examples 1 to 14 with comparative example 1, and comparative example 2 with comparative example 1, respectively, the results all show that additive B has a good synergistic effect with other additives. The characteristic of compact film formation of the additive B can effectively inhibit the storage and gas generation of the battery at high temperature and high potential, and the effect is more obvious by increasing the using amount of the additive B. Comparing example 5 with example 6, it is shown that insufficient amount of additive B affects the cycle improvement effect.
4) Comparing examples 10-12 with comparative example 8, and examples 18-23 with comparative example 15, respectively, the results all show that additive C has a good synergistic effect with other additives. The additive C in the electrolyte can effectively reduce the impedance of the battery so as to improve the transmission rate of lithium ions in the electrolyte. The combined use of the additive C can obviously reduce the low-temperature lithium precipitation degree of the battery. The results of comparing example 11 with example 10 show that excessive use of additive C aggravates the high-temperature gassing of the battery, and therefore, an appropriate amount of additive B needs to be added.
5) Comparing examples 13 to 14 with comparative example 9, the results show that the additive D has a good synergistic effect with other additives, and can effectively reduce the interfacial resistance of the battery, thereby increasing the transmission rate of lithium ions at the interface. The combined use of the additive D can also relieve the low-temperature lithium precipitation of the battery. Comparing examples 22-23 with example 21, it is shown that excessive use of additive D aggravates the high-temperature gassing of the battery.
6) The results of comparing examples 15 to 17 with comparative example 10 show that the additive E has a good synergistic effect with other additives, the combined use of the additive E can significantly reduce the gas generation during the high-temperature storage of the battery, and the combined use of the additive E can also improve the cycle performance of the battery at high voltage. Comparing example 13 with example 14, it is shown that the effect of improving the high-temperature gassing property of the battery is relatively reduced by the excess borate additive, and the low-temperature lithium deposition phenomenon may be intensified to some extent by the increase of the interface resistance of the negative electrode due to the large amount of film formation on the negative electrode. In addition, the results of comparing example 24 with comparative examples 16 to 18 show that the use of additive E in combination can significantly reduce the gas evolution during the high-temperature storage of the battery; meanwhile, the combined use of the additive E can also improve the cycle performance of the battery under high voltage. Comparing example 25 with example 24, the results show that the use of additive E in excess can deteriorate the low temperature lithium extraction from the cells.
Compared with the comparative example, the five additive synergistic embodiment has obvious advantages in three performances of high-pressure cycle (4.3V), high-temperature storage gas generation and low-temperature lithium precipitation.
In conclusion, the performance of the lithium ion battery using the electrolyte is obviously improved, and the lithium ion battery can be stored and used more safely under high voltage and low temperature. The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (16)
1. An electrolyte comprises a non-aqueous organic solvent, lithium salt and an additive, wherein the additive comprises an additive A, an additive B, an additive C, an additive D and an additive E; wherein,
the additive A is at least one selected from cyclic carbonate compounds, the additive A is at least one selected from compounds with a structural formula I and compounds with a structural formula II,
wherein R1 and R2 are respectively and independently selected from C1-3 alkyl substituted by substituent A or alkenyl substituted by substituent A, and the substituent A is selected from at least one of alkyl with 1-20 carbon atoms, halogenated alkyl with 1-20 carbon atoms, unsaturated hydrocarbon with 2-20 carbon atoms and halogenated unsaturated hydrocarbon with 2-20 carbon atoms;
the additive B is selected from at least one of sulfate-containing compounds;
the additive C is selected from at least one of siloxane compounds;
the additive D is at least one selected from fluorine-containing lithium salts, the additive D comprises lithium bis (fluorosulfonyl) imide or the additive D comprises lithium bis (fluorosulfonyl) imide and lithium difluorophosphate, and the mass percentage of the additive D in the electrolyte is 0.1-2%;
the additive E is selected from at least one of boron-containing lithium salts.
2. The electrolyte of claim 1, wherein the additive a is selected from ethylene carbonate.
3. The electrolyte according to claim 1, wherein the additive A is contained in the electrolyte in an amount of 0.1-2% by mass.
4. The electrolyte of claim 3, wherein the additive A is present in the electrolyte in an amount of 0.1 to 0.5% by weight.
5. The electrolyte of claim 1, wherein the additive B comprises at least one of ethylene sulfate, 1, 3-propane sultone, 1, 4-butane sultone, 1, 3-propene sultone, 1, 4-butene sultone, ethylene sulfite, propylene sulfite, and methylene methane disulfonate.
6. The electrolyte of claim 1, wherein the additive B is present in the electrolyte in an amount of 0.5 to 2.5% by weight.
7. The electrolyte according to claim 6, wherein the additive B is present in the electrolyte in an amount of 1-2% by weight.
8. The electrolyte of claim 1, wherein the additive C comprises at least one selected from the group consisting of a compound of formula III, a compound of formula IV, and a compound of formula V,
wherein, R is 3 ～R 29 Each independently is selected from C 1～3 Alkyl and C substituted by substituent B 1～3 One of alkyl groups;
the substituent B is at least one selected from halogen, alkoxy, carboxyl, sulfonic group, alkyl with 1-20 carbon atoms, halogenated alkyl with 1-20 carbon atoms, unsaturated hydrocarbon with 2-20 carbon atoms and halogenated unsaturated hydrocarbon with 2-20 carbon atoms.
9. The electrolyte according to claim 1, wherein the additive C is present in the electrolyte in an amount of 1-2% by weight.
10. The electrolyte of claim 1, wherein the additive C is present in the electrolyte in an amount of 0.1-1% by weight.
11. The electrolyte according to claim 1, wherein the additive D is contained in the electrolyte in an amount of 0.1-1% by mass.
12. The electrolyte of claim 1, wherein the additive E comprises at least one of lithium difluorooxalato borate and lithium tetrafluoroborate.
13. The electrolyte of claim 1, wherein the additive E is present in the electrolyte in an amount of 0.5 to 2.5% by weight.
14. The electrolyte of claim 13, wherein the additive E is present in the electrolyte in an amount of 1-2% by weight.
15. The electrolyte according to claim 1, wherein the total mass percentage of the additive A, the additive B, the additive C, the additive D and the additive E in the electrolyte is 3-5%.
16. An electrochemical device comprising a positive electrode sheet, a negative electrode sheet, a separator and the electrolyte solution according to any one of claims 1 to 15.
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| CN113782831A (en) * | 2021-08-03 | 2021-12-10 | 华中科技大学 | High-voltage-resistant lithium ion battery electrolyte and preparation method and application thereof |
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| CN102332607A (en) * | 2011-03-22 | 2012-01-25 | 东莞新能源科技有限公司 | Nonaqueous electrolyte for secondary lithium ion battery |
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