CN109075387B - Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery including the same - Google Patents
Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery including the same Download PDFInfo
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- CN109075387B CN109075387B CN201880001466.XA CN201880001466A CN109075387B CN 109075387 B CN109075387 B CN 109075387B CN 201880001466 A CN201880001466 A CN 201880001466A CN 109075387 B CN109075387 B CN 109075387B
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- electrolyte solution
- secondary battery
- lithium
- lithium secondary
- additive
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 80
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 76
- 239000000654 additive Substances 0.000 claims abstract description 70
- 230000000996 additive effect Effects 0.000 claims abstract description 53
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 31
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims abstract description 29
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 239000007774 positive electrode material Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- OQYOVYWFXHQYOP-UHFFFAOYSA-N 1,3,2-dioxathiane 2,2-dioxide Chemical compound O=S1(=O)OCCCO1 OQYOVYWFXHQYOP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 claims description 4
- 229910004427 Li(Ni0.7Mn0.15Co0.15)O2 Inorganic materials 0.000 claims description 3
- 229910004170 Li(NiaCObMnc)O2 Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 41
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- 230000000052 comparative effect Effects 0.000 description 24
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 22
- 229910052799 carbon Inorganic materials 0.000 description 21
- 239000008151 electrolyte solution Substances 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 19
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- 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 description 3
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006773 Si—Y Inorganic materials 0.000 description 1
- 229910020997 Sn-Y Inorganic materials 0.000 description 1
- 229910008859 Sn—Y Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NXPZICSHDHGMGT-UHFFFAOYSA-N [Co].[Mn].[Li] Chemical compound [Co].[Mn].[Li] NXPZICSHDHGMGT-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910000417 bismuth pentoxide Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 239000002180 crystalline carbon material Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011326 fired coke Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N germanium monoxide Inorganic materials [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006051 mesophase pitch carbide Substances 0.000 description 1
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
-
- 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
- H01M10/056—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
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to a nonaqueous electrolyte solution for a lithium secondary battery and a lithium secondary battery including the same, and in particular, to a nonaqueous electrolyte solution for a lithium secondary battery including an ionizable lithium salt, an organic solvent, and an additive, and a lithium secondary battery including the same, wherein the additive includes an additive in a weight ratio of 1: 3-20: 3-20 of tetravinylsilane, lithium difluorophosphate and 1, 3-propenyl sulfate, and the total amount of the additive is in the range of 1 to 4% by weight based on the total weight of the non-aqueous electrolyte solution for a lithium secondary battery.
Description
Cross Reference to Related Applications
The present application claims the rights of korean patent application No. 2017-0010043 filed in the korean intellectual property office at 20.1.2017 and korean patent application No. 2018-0006125 filed in the korean intellectual property office at 17.1.2018, the disclosures of which are incorporated herein by reference in their entireties.
Technical Field
The present invention relates to a nonaqueous electrolyte solution for a lithium secondary battery and a lithium secondary battery including the same.
Background
Recently, interest in energy storage technology has been increasing, and as the application of energy storage technology is expanded to mobile phones, video cameras, notebook computers, and even electric vehicles, efforts to develop high-capacity electrochemical devices have been gradually implemented.
Among these electrochemical devices, rechargeable secondary batteries have attracted interest, and in particular, lithium secondary batteries developed in the early 90 s of the 20 th century received attention because they have advantages in that they have a higher operating voltage and a significantly higher energy density.
The lithium secondary battery is composed of a carbon negative electrode capable of intercalating and deintercalating lithium ions, a positive electrode formed of a lithium-containing composite oxide, and a nonaqueous electrolyte solution in which a lithium salt is dissolved in a mixed organic solvent.
In the lithium secondary battery, lithium ions react with an electrolyte solution during initial charge in a voltage range of 0.5V to 3.5V to form lithium ions such as Li2CO3、Li2And compounds such as O and LiOH, by which a Solid Electrolyte Interface (SEI) as a kind of passivation layer (passivation layer) is formed on the surface of the negative electrode.
The SEI film formed at the initial stage of charging may prevent lithium ions from reacting with a carbon negative electrode or other materials during charging and discharging. In addition, the SEI film can pass only lithium ions by acting as an Ion channel (Ion Tunnel). Since the ion channel can prevent the structural destruction of the carbon negative electrode due to the co-intercalation of the carbon negative electrode with a non-aqueous organic solvent having a high molecular weight, which solvates and moves lithium ions together therewith, the cycle-life characteristics and output characteristics of the lithium secondary battery can be improved.
In the case where an organic solvent used in a non-aqueous electrolyte solution of a lithium secondary battery is generally stored at a high temperature for a long time, gas is generated due to a side reaction of the organic solvent with a transition metal oxide of a released positive electrode active material. In addition, high temperature storage under full load conditionDuring which the SEI film gradually collapses (e.g., storage at 60 ℃ after charging to 100% at 4.2V), the negative electrode is exposed, and the exposed negative electrode continuously reacts with the electrolyte solution to generate CO, etc2、CH4And C2H6And the like.
When the internal pressure of the battery is increased by the gas thus generated, deformation of the electrode assembly and swelling of the battery are induced, and as a result, the battery may be deteriorated due to internal short circuit of the battery, or ignition or explosion of the battery may occur.
In order to solve these limitations, it is necessary to develop an electrolyte solution for a lithium secondary battery that can suppress side reactions during high-temperature storage.
Documents of the prior art
Japanese patent application laid-open publication No. 2010-116475.
Disclosure of Invention
Technical problem
An aspect of the present invention provides a nonaqueous electrolyte solution for a lithium secondary battery, which includes an additive capable of forming a stable layer on an electrode surface and suppressing a side reaction of the electrolyte solution during high-temperature storage.
Another aspect of the present invention provides a lithium secondary battery in which high-temperature storage characteristics and cycle-life characteristics are improved by including the non-aqueous electrolyte solution for a lithium secondary battery.
Technical scheme
In accordance with one aspect of the present invention,
providing a non-aqueous electrolyte solution for a lithium secondary battery, the non-aqueous electrolyte solution including an ionizable lithium salt; an organic solvent; and an additive, wherein the additive is a mixture of,
wherein the additive is a mixed additive comprising Tetravinylsilane (TVS), lithium difluorophosphate (LiDFP) and 1, 3-propylene sulfate (PPS) in a weight ratio of 1: 3 to 20, and
the additive is included in an amount of 1 to 4 wt% based on the total weight of the non-aqueous electrolyte solution for a lithium secondary battery.
The weight ratio of tetravinylsilane to lithium difluorophosphate to 1, 3-propene sulfate as additive may be in the range from 1: 3 to 17: 5 to 20, for example from 1: 5 to 15: 5 to 20.
Further, the additive may be included in an amount of 1.8 to 4 wt% based on the total weight of the nonaqueous electrolyte solution for a lithium secondary battery.
In addition, the non-aqueous electrolyte solution of the present invention may further comprise a solvent selected from the group consisting of Vinylene Carbonate (VC), LiBF41, 3-propanesultone and tetraphenylboronic acid ester.
The additional additive may be included in an amount of 0.1 to 5 wt% based on the total weight of the non-aqueous electrolyte solution for a lithium secondary battery.
In the case of including 1, 3-Propanesultone (PS) as an additional additive, tetravinylsilane and 1, 3-Propanesultone (PS) may be included in a weight ratio of 1: 5 to 1: 15.
In addition, in the case of VC or LiBF4As additional additives, tetravinylsilanes with VC or LiBF4May be included in a weight ratio of 1: 1 to 1: 3.
In accordance with another aspect of the present invention,
there is provided a lithium secondary battery comprising a negative electrode, a positive electrode, a separator disposed between the positive electrode and the negative electrode, and a nonaqueous electrolyte solution,
wherein the nonaqueous electrolyte solution includes the nonaqueous electrolyte solution for a lithium secondary battery of the present invention, and
the positive electrode includes a lithium nickel manganese cobalt based oxide as a positive electrode active material.
Specifically, the positive active material may include a lithium transition metal oxide represented by the following formula 1.
[ formula 1]
Li(NiaCobMnc)O2
Wherein, in the formula 1,
a is more than or equal to 0.55 and less than or equal to 0.9, b is more than or equal to 0.05 and less than or equal to 0.22, c is more than or equal to 0.05 and less than or equal to 0.23, and a + b + c is equal to 1.
A typical example of the positive electrode active material may be Li (Ni)0.6Mn0.2Co0.2)O2、Li(Ni0.7Mn0.15Co0.15)O2And Li (Ni)0.8Mn0.1Co0.1)O2At least one of (1).
Advantageous effects
In the present invention, since a stable Solid Electrolyte Interface (SEI) film can be formed on the surface of the negative electrode by including a mixing additive in which three types of compounds are mixed in a specific ratio, a non-aqueous electrolyte solution for a lithium secondary battery in which side reactions during high-temperature storage are suppressed can be prepared. In addition, a lithium secondary battery in which high-temperature storage characteristics and cycle-life characteristics are improved by including the non-aqueous electrolyte solution can be prepared.
Detailed Description
Hereinafter, the present invention will be described in more detail.
It will be understood that the words or terms used in the specification and claims should be interpreted as having meanings consistent with their meanings in the context of the technical idea of the present invention and the related art, based on the principle that the inventor can appropriately define the meanings of the words or terms to best explain the present invention.
Specifically, in an embodiment of the present invention, there is provided a nonaqueous electrolyte solution for a lithium secondary battery, including:
an ionizable lithium salt; an organic solvent; and an additive, wherein the additive is a mixture of,
wherein the additive is a mixed additive including Tetravinylsilane (TVS), lithium difluorophosphate (LiDFP), and 1, 3-propylene sulfate (PPS) in a weight ratio of 1: 3 to 20, and
the additive is included in an amount of 1 to 4 wt% based on the total weight of the non-aqueous electrolyte solution for a lithium secondary battery.
First, in the non-aqueous electrolyte solution for a lithium secondary battery according to an embodiment of the present invention, any lithium salt generally used in the electrolyte solution for a lithium secondary battery may be used without limitation as an ionizable lithium salt, and, for example, the lithium salt may include Li+As a cation, and may include a cation selected from the group consisting of F-、Cl-、Br-、I-、NO3 -、N(CN)2 -、BF4 -、ClO4 -、AlO4 -、AlCl4 -、PF6 -、SbF6 -、AsF6 -、B10Cl10 -、BF2C2O4 -、BC4O8 -、PF4C2O4 -、PF2C4O8 -、(CF3)2PF4 -、(CF3)3PF3 -、(CF3)4PF2 -、(CF3)5PF-、(CF3)6P-、CF3SO3 -、C4F9SO3 -、CF3CF2SO3 -、(CF3SO2)2N-、(FSO2)2N-、CF3CF2(CF3)2CO-、(CF3SO2)2CH-、CH3SO3 -、CF3(CF2)7SO3 -、CF3CO2 -、CH3CO2 -、SCN-And (CF)3CF2SO2)2N-Formed group ofAs an anion. Specifically, the lithium salt may include one or more selected from the group consisting of LiCl, LiBr, LiI, and LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCH3CO2、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、LiAlO4And LiCH3SO3A single material of the group consisting of, or a mixture of two or more of them, and, in addition thereto, a lithium salt generally used in an electrolyte solution of a lithium secondary battery, such as an imide lithium salt represented by: lithium bis (perfluoroethanesulfonyl) imide (1ithium bisperfluoroethanesulfonamide, LiBETI, LiN (SO)2C2F5)2) Lithium fluorosulfonylimide (1ithium fluorosulfenyl imide, LiFSI, LiN (SO)2F)2) And lithium bistrifluoromethanesulfonimide (1ithium (bis) trifluoromethanesulfonimide, LiTFSI, LiN (SO)2CF3)2). Specifically, the lithium salt may include one selected from the group consisting of LiPF6、LiBF4、LiCH3CO2、LiCF3CO2、LiCH3SO3LiFSI, LiTFSI, and LiBETI, or a mixture of two or more thereof. However, the lithium salt does not include the LiDFP as a mixed additive.
In the electrolyte solution, the lithium salt may be appropriately changed within a generally usable range, but specifically may be included at a concentration of 0.1M to 3M, for example, 0.8M to 2.5M. In the case where the concentration of the lithium salt is more than 3M, the film forming effect may be reduced.
Further, in the nonaqueous electrolyte solution for a lithium secondary battery according to the embodiment of the present invention, the type of the organic solvent is not limited as long as it can minimize decomposition caused by an oxidation reaction during charge and discharge of the secondary battery and can exhibit desired characteristics together with additives. For example, an ether solvent, an ester solvent, or an amide solvent may be used alone, or a mixture of two or more of them may be used.
As the ether solvent among these organic solvents, any one selected from the group consisting of: dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether, and ethyl propyl ether, or a mixture of two or more thereof, but the present invention is not limited thereto.
Further, the ester solvent may include at least one compound selected from the group consisting of a cyclic carbonate compound, a linear ester compound, and a cyclic ester compound.
Among these compounds, specific examples of the cyclic carbonate compound may be any one selected from the group consisting of: ethylene Carbonate (EC), 1, 2-butylene carbonate, 2, 3-butylene carbonate, 1, 2-pentylene carbonate, 2, 3-pentylene carbonate, vinylene carbonate, and fluoroethylene carbonate (FEC), or a mixture of two or more thereof, and the cyclic carbonate compound may specifically include any one selected from the group consisting of: ethylene carbonate, 1, 2-butylene carbonate, 2, 3-butylene carbonate, vinylene carbonate, and fluoroethylene carbonate (FEC), or a mixture of two or more thereof.
Regarding Propylene Carbonate (PC) among cyclic carbonate compounds, since propylene carbonate undergoes an irreversible decomposition reaction with a carbon-based anode material, and depending on the thickness of an electrode, an electrode exfoliation (exfoliation) phenomenon caused by propylene carbonate occurs during high-temperature cycling, and thus the capacity of a lithium secondary battery may be decreased. In particular, in propylene carbonate with a solvent such as LiPF6Such a lithium salt is used together, since solvated propylene carbonate does not separate from lithium ions during the formation of an SEI film on the surface of a carbon-based negative electrode and during intercalation of lithium ions solvated by propylene carbonate between carbon layers, solvated propylene carbonate and lithium ions damage the negative electrode layer while intercalated, and thus a large number of irreversible reactions may occur. In addition, since a strong SEI film is not formed on the surface of the anode, operation (working) of the lithium secondary battery may not be possibleAnd (4) the stability is stable.
Therefore, the non-aqueous electrolyte solution for a lithium secondary battery of the present invention may have the effect of improving high-temperature storage characteristics and cycle characteristics by including ethylene carbonate having a high melting point as an essential component, rather than including propylene carbonate as a cyclic carbonate compound.
Further, specific examples of the linear carbonate compound may be any one selected from the group consisting of: dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, Ethyl Methyl Carbonate (EMC), methyl propyl carbonate, and ethyl propyl carbonate, or a mixture of two or more thereof, and the linear carbonate compound may specifically include any one selected from the group consisting of: dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and ethyl methyl carbonate, or a mixture of two or more thereof.
Specific examples of the linear ester compound may be any one selected from the group consisting of: methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, and butyl propionate, or a mixture of two or more thereof, but the present invention is not limited thereto.
Specific examples of the cyclic ester compound may be any one selected from the group consisting of: gamma-butyrolactone, gamma-valerolactone, gamma-caprolactone, delta-valerolactone, and epsilon-caprolactone, or mixtures of two or more thereof, although the invention is not limited thereto.
It is known that a cyclic carbonate compound in an ester solvent is a solvent that well dissociates a lithium salt in an electrolyte due to a high dielectric constant as a highly viscous organic solvent. In addition, when the cyclic carbonate-based compound is mixed with a low-viscosity, low-dielectric constant linear carbonate-based compound (such as dimethyl carbonate and diethyl carbonate) and a linear ester-based compound in an appropriate ratio, an electrolyte solution having high conductivity can be prepared.
The cyclic carbonate compound and the linear carbonate compound may be mixed and used as an organic solvent, and in the organic solvent, the cyclic carbonate compound: the weight ratio of the linear carbonate-based compound may be in the range of 10: 90 to 70: 30.
Further, in the non-aqueous electrolyte solution for a lithium secondary battery according to an embodiment of the present invention, as one of additive components, Tetravinylsilane (TVS) represented by the following formula 2 is a compound that can form a strong SEI film on the surface of a negative electrode through physical adsorption and electrochemical reaction, wherein the tetravinylsilane can improve the durability of the lithium secondary battery during high-temperature storage since the tetravinylsilane can suppress an increase in resistance caused by an additional reaction of the electrolyte solution at high temperature.
[ formula 2]
Further, as one of the additive components, lithium difluorophosphate represented by the following formula 3 is a component that electrochemically decomposes on the surfaces of the cathode and anode to contribute to the formation of SEI. Lithium difluorophosphate may have an effect of improving long-term cycle-life characteristics of the secondary battery.
[ formula 3]
Further, as one of the additive components, 1, 3-propenyl sulfate represented by the following formula 4 can form a stable protective layer on the surface of the anode that does not crack even during high-temperature storage. The anode coated with the protective layer can prevent gas generation by suppressing decomposition of the non-aqueous organic solvent caused by the anode active material even in the case where a highly crystalline carbon material such as natural graphite or artificial graphite is used as the anode active material or even during high-temperature storage. In addition, the protective layer does not interfere with the charge/discharge reaction of the battery. Accordingly, the performance of the secondary battery, such as cycle life, capacity, and resistance, and stability at room temperature and high temperature, can be improved.
[ formula 4]
Further, as the mixed additive, tetraenylsilane, lithium difluorophosphate and 1, 3-propenyl sulfate may be specifically included in a weight ratio of 1: 3 to 17: 5 to 20, for example, 1: 5 to 15: 5 to 20.
When the weight ratio of the tetravinylsilane is greater than the above range, the resistance of the battery may increase due to a side reaction caused by the excessive tetravinylsilane, and thus the cycle life characteristics may be degraded. In contrast, if the weight ratio of the tetravinylsilane is less than the above range, the gas generation reducing effect and the SEI film forming effect are not significant.
Further, in the case where the weight ratio of lithium difluorophosphate is more than 20 or the weight ratio of 1, 3-propenyl sulfate is more than 20 based on 1 part by weight of tetravinylsilane, the cycle life characteristics are degraded since the internal resistance of the battery is increased due to the excessive use of the additive.
In the case where the weight ratio of lithium difluorophosphate to 1, 3-propenyl sulfate is less than 3 based on 1 part by weight of tetravinylsilane, high-temperature storage characteristics and cycle life characteristics may be degraded since the stabilizing effect during SEI film formation is insignificant.
According to these results, in the nonaqueous electrolyte solution of the present invention, in the case where the weight ratio of the compounds constituting the mixed additive satisfies the above range, a stable SEI film can be formed without increasing resistance, and therefore, an effect of suppressing side reactions of the electrolyte solution can be obtained.
Further, the total amount of the additive of the present invention may be in the range of 1 to 4 wt%, for example, 1.8 to 4 wt%, based on the total weight of the non-aqueous electrolyte solution for a lithium secondary battery.
The amount of the additive in the nonaqueous electrolyte solution may be determined by the reaction specific surface area of the positive electrode and the negative electrode, wherein in the case where the amount of the additive is 1% by weight or more as described above, the intended effect produced by the addition of each component may be satisfied, for example, not only a stable SEI film may be formed on the surface of the negative electrode, but also the effect of reducing gas generation may be achieved by suppressing decomposition of the electrolyte solution caused by the reaction between the electrolyte solution and the negative electrode. Further, in the case where the amount of the additive is 4% by weight or less, not only the effect of reducing gas generation can be improved, but also a stable SEI film can be formed on the electrode surface while preventing side reactions and thus an increase in resistance due to the excessive use of the additive.
In the case where the amount of the additive is more than 4% by weight, the effect of reducing gas generation can be further improved due to the excessive use of the additive, but an excessively thick layer is formed due to the excessive remaining amount of each component, and thus an increase in resistance and a decrease in output may be caused.
Therefore, in the case where the nonaqueous electrolyte solution according to the embodiment of the present invention includes the additive in an amount of 1 to 4 wt% based on the total weight of the nonaqueous electrolyte solution while including tetraenylsilane, lithium difluorophosphate, and 1, 3-propenyl sulfate as the additive in a weight ratio of 1: 3 to 20, decomposition of the electrolyte solution due to a reaction between the electrolyte solution and the negative electrode is minimized due to formation of a stable SEI film on the surface of the negative electrode, and thus the characteristics of the secondary battery may be improved.
In addition, the nonaqueous electrolyte solution according to the embodiment of the invention may further include additional additives, if necessary, in order to further obtain the effects of improving cycle-life characteristics, low-temperature high-rate discharge characteristics, high-temperature stability, overcharge protection, and high-temperature expansion.
The additional additive is not particularly limited as long as it is an additive that can form a stable layer on the surfaces of the positive and negative electrodes while not significantly increasing the initial resistance.
Additional additives may include one or more additives selected from the group consisting of Vinylene Carbonate (VC), LiBF41, 3-Propane Sultone (PS) and tetraphenyl borate (TPB).
In the case of the inclusion of 1, 3-Propane Sultone (PS) in the additional additive, the ratio of tetravinylsilane: the weight ratio of 1, 3-Propane Sultone (PS) is in the range of 1: 5 to 1: 15.
In a cell comprising VC or LiBF4As additional additives, tetravinylsilanes VC or LiBF4In the range of 1: 1 to 1: 3.
Specifically, the additional additive may be included in an amount of 0.1 to 5 wt% based on the total weight of the non-aqueous electrolyte solution for a lithium secondary battery, for example, 0.1 to 4 wt%. In the case where the amount of the additional additive is less than 0.1 wt%, the effect obtained from the additional additive may not be significant, and in the case where the amount of the additional additive is greater than 5 wt%, a side reaction may occur due to surplus additional additive.
Generally, in a secondary battery, during initial charging, lithium ions from a lithium metal oxide serving as a positive electrode are intercalated while moving to a carbon-based electrode serving as a negative electrode, wherein the lithium ions react with the carbon-based negative electrode and an electrolyte solution to form an organic material Li since the lithium ions are highly reactive2CO3LiO, or LiOH, which form an SEI film on the surface of the anode. Once the SEI film is formed during initial charging, the SEI film may serve as an ion channel for transferring only lithium ions between the electrolyte solution and the negative electrode, while preventing reaction of the lithium ions with the carbon-based negative electrode or other materials during repeated charge and discharge due to subsequent use of the battery. Since the SEI film blocks the movement of an organic solvent having a high molecular weight (e.g., EC, DMC, DEC, or PP) for a non-aqueous electrolyte solution to a carbon-based negative electrode by an ion channel effect, the organic solvent is not inserted (intercalation) into the carbon-based negative electrode together with lithium ions, and thus the structural collapse of the carbon-based negative electrode can be prevented. That is, once the SEI film is formed, since side reactions of lithium ions with the carbon-based negative electrode or other materials do not occur any more, lithium ions required during charge and discharge due to subsequent use of the battery can be reversibly maintainedThe amount of (c).
In other words, since the carbon material of the anode reacts with the electrolyte solution to form the passivation layer during initial charge, stable charge and discharge are allowed to be maintained without further decomposition of the electrolyte solution, and, in this case, the amount of charge consumed to form the passivation layer on the surface of the anode is an irreversible capacity having a characteristic of reacting irreversibly during discharge, and, for this reason, the lithium ion battery no longer exhibits an irreversible reaction after the initial charge reaction, and a stable life cycle can be maintained.
However, in the case where the lithium secondary battery is stored at high temperature in a fully charged state (for example, stored at 60 ℃ after being charged to 100% at 4.15V or more), it is disadvantageous that the SEI film gradually collapses due to electrochemical energy and thermal energy increasing with time.
The collapse of the SEI film exposes the surface of the negative electrode, which is decomposed as the negative electrode reacts with a carbonate-based solvent in an electrolyte solution, and thus, a continuous side reaction occurs.
The side reaction can generate gas continuously, in this case, the main gas generated can be CO, CO2、CH4And C2H6In which the generated gas may vary depending on the type of the negative electrode active material, and regardless of the type, continuous gas generation increases the internal pressure of the lithium ion battery, thereby causing the thickness of the battery to expand.
Therefore, in the present invention, since tetravinylsilane, lithium difluorophosphate and 1, 3-propenyl sulfate are mixed in the above ratio and used as additives during the preparation of the nonaqueous electrolyte solution, a stable layer is formed on the surface of the electrode to suppress side reactions of the electrolyte solution, and thus, the battery swelling during high-temperature storage can be prevented and the battery characteristics can be improved.
In addition, in the embodiment of the present invention,
there is provided a lithium secondary battery comprising a negative electrode, a positive electrode, a separator disposed between the positive electrode and the negative electrode, and a nonaqueous electrolyte solution,
wherein the nonaqueous electrolyte solution includes the nonaqueous electrolyte solution of the present invention, and
the positive electrode includes a lithium nickel manganese cobalt based oxide as a positive electrode active material.
Specifically, in the lithium secondary battery of the present invention, an electrode assembly may be prepared by sequentially stacking a cathode, an anode, and a separator disposed between the cathode and the anode, in which case all of those cathodes, anodes, and separators prepared by typical methods and used in the preparation of the lithium secondary battery may be used as the cathode, the anode, and the separator constituting the electrode assembly.
First, the positive electrode may be prepared by forming a positive electrode material mixed layer on a positive electrode current collector. The cathode material mixed layer may be prepared by: a positive electrode current collector is coated with a positive electrode slurry including a positive electrode active material, a binder, a conductive agent, and a solvent, and then the coated positive electrode current collector is dried and roll-pressed.
The positive electrode current collector is not particularly limited as long as it has conductivity and does not cause adverse chemical changes in the battery, and, for example, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel surface-treated with one of carbon, nickel, titanium, silver, or the like may be used.
In addition, the positive active material may include a lithium transition metal oxide represented by formula 1 below.
[ formula 1]
Li(NiaCobMnc)O2
Wherein, in the formula 1,
a is more than 0.55 and less than or equal to 0.9, b is more than or equal to 0.05 and less than or equal to 0.22, c is more than or equal to 0.05 and less than or equal to 0.23, and a + b + c is equal to 1.
A typical example of the positive electrode active material may be Li (Ni)0.6Mn0.2Co0.2)O2、Li(Ni0.7Mn0.15Co0.15)O2Or Li (Ni)0.8Mn0.1Co0.1)O2。
In addition, if necessary, except fromThe positive active material may further include any one of the following compounds in addition to the lithium transition metal oxide represented by formula 1: lithium manganese based oxides (e.g., LiMnO)2、LiMn2O4Etc.); lithium cobalt based oxides (e.g., LiCoO)2Etc.); lithium nickel-based oxides (e.g., LiNiO)2Etc.); lithium nickel manganese-based oxides (e.g., LiNi)1-YMnYO2(wherein 0 < Y < 1), LiMn2-ZNiZO4(wherein 0 < Z < 2), etc.); lithium nickel cobalt based oxides (e.g., LiNi)1-Y1CoY1O2(wherein 0 < Y1 < 1)); lithium manganese cobalt based oxides (e.g., LiCo)1-Y2MnY2O2(wherein 0 < Y2 < 1), LiMn2-Z1CoZ1O4(wherein 0 < Z1 < 2)); or lithium nickel cobalt transition metal (M) oxide (e.g., Li (Ni)p2Coq2Mnr3Ms2)O2(wherein M is selected from the group consisting of aluminum (Al), iron (Fe), vanadium (V), chromium (Cr), titanium (Ti), tantalum (Ta), magnesium (Mg), and molybdenum (Mo), p2, q2, r3, and s2 are atomic fractions of each individual element, where 0 < p2 < 1,0 < q2 < 1,0 < r3 < 1,0 < s2 < 1, and p2+ q2+ r3+ s2 ═ 1), and the like), or a mixture of two or more thereof.
The positive active material may include LiCoO2、LiMnO2、LiNiO2Or lithium nickel cobalt aluminum oxide (e.g., Li (Ni)0.8Co0.15Al0.05)O2Etc.).
The cathode active material may be included in an amount of 80 wt% to 99 wt%, for example, 93 wt% to 98 wt%, based on the total weight of the solid content in the cathode slurry. When the amount of the positive electrode active material is 80 wt% or less, the capacity may be decreased due to a decrease in energy density.
The binder is a component that contributes to the binding between the active material and the conductive agent and to the current collector, wherein the binder is generally added in an amount of 1 to 30 wt% based on the total weight of the solid content in the cathode slurry. Examples of the binder may be polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluororubber, various copolymers, and the like.
Any conductive agent may be used as the conductive agent without limitation as long as it has conductivity and does not cause adverse chemical changes in the battery, and for example, the following conductive materials such as: carbon powder such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black; graphite powder such as natural graphite, artificial graphite, or graphite having a good crystal structure; conductive fibers such as carbon fibers or metal fibers; metal powders such as carbon fluoride powder, aluminum powder, and nickel powder; conductive whiskers such as zinc oxide whiskers and potassium titanate whiskers; conductive metal oxides such as titanium oxide; or polyphenylene derivatives.
The conductive agent is generally added in an amount of 1 to 30% by weight based on the total weight of the solid content in the cathode slurry.
Those having trade names such as acetylene black series (Chevron Chemical Company, Denka black (Denka Singapore Private Limited), or Gulf Oil Company), Ketjen black, Ethylene Carbonate (EC) series (Armak Company), Vulcan XC-72(Cabot Company), and SuperP (Timcal Graphite & Carbon) are used as the conductive agent.
The solvent may include an organic solvent such as N-methyl-2-pyrrolidone (NMP), and may be used in an amount such that a desired viscosity is obtained when a positive electrode active material is included and, optionally, a binder and a conductive agent. For example, the solvent may be included in an amount such that the concentration of the solid content in the slurry including the positive electrode active material and optionally the binder and the conductive agent is in the range of 10 to 70 wt%, for example, 20 to 60 wt%.
In addition, the anode may be prepared by forming an anode material mixed layer on an anode current collector. The anode material mixed layer may be formed by: an anode current collector is coated with an anode slurry including an anode active material, a binder, a conductive agent, and a solvent, and then the coated anode current collector is dried and roll-pressed.
The negative electrode current collector generally has a thickness of about 3 to 500 μm. The anode current collector is not particularly limited as long as it has high conductivity and does not cause undesirable chemical changes in the battery, and for example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, or copper or stainless steel surface-treated with one of carbon, nickel, titanium, silver, or the like, aluminum-cadmium alloy, or the like may be used. Further, the anode current collector may have fine surface roughness to improve the binding strength with the anode active material, similar to the cathode current collector, and the anode current collector may be used in various forms such as a film, a sheet, a foil, a mesh, a porous body, a foam, a non-woven fabric body, and the like.
In addition, the anode active material may include at least one selected from the group consisting of: lithium metal, carbon materials capable of reversibly intercalating/deintercalating lithium ions, metals or alloys of lithium with the metals, metal composite oxides, materials that can be doped and undoped with lithium, and transition metal oxides.
As the carbon material capable of reversibly intercalating/deintercalating lithium ions, a carbon-based anode active material generally used in a lithium ion secondary battery may be used without limitation, and, as a typical example, crystalline carbon, amorphous carbon, or both thereof may be used. Examples of the crystalline carbon may be graphite such as irregular, planar, flaky (flake), spherical or fibrous natural graphite or artificial graphite, and examples of the amorphous carbon may be soft carbon (soft carbon) or hard carbon (hard carbon), mesophase pitch carbide, and fired coke.
As the metal or the alloy of lithium and the metal, a metal selected from the group consisting of: copper (Cu), nickel (Ni), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), silicon (Si), antimony (Sb), lead (Pb), indium (In), zinc (Zn), barium (Ba), radium (Ra), germanium (Ge), aluminum (Al), and tin (Sn), or alloys of lithium with the metals.
As the metal composite oxide, one selected from the group consisting of: PbO, PbO2、Pb2O3、Pb3O4、Sb2O3、Sb2O4、Sb2O5、GeO、GeO2、Bi2O3、Bi2O4、Bi2O5、LixFe2O3(0≤x≤1)、LixWO2(x is 0. ltoreq. x.ltoreq.1), and SnxMe1-xMe′yOz(Me: manganese (Mn), Fe, Pb or Ge; Me': Al, boron (B), phosphorus (P), Si, an element of groups I, II or III of the periodic table or halogen; x is more than 0 and less than or equal to 1; y is more than or equal to 1 and less than or equal to 3; and z is more than or equal to 1 and less than or equal to 8).
The material capable of doping and undoped lithium can comprise Si and SiOx(0 < x < 2), a Si-Y alloy (wherein Y is an element selected from the group consisting of alkali metals, alkaline earth metals, group 13 elements, group 14 elements, transition metals, rare earth elements, and combinations thereof, and Y is not Si), Sn, SnO, and combinations thereof2And Sn-Y (wherein Y is an element selected from the group consisting of alkali metals, alkaline earth metals, group 13 elements, group 14 elements, transition metals, rare earth elements, and combinations thereof, and Y is not Sn), and SiO may also be used2And mixtures with at least one of them. The element Y may be selected from the group consisting of: mg, Ca, Sr, Ba, Ra, scandium (Sc), yttrium (Y), Ti, zirconium (Zr), hafnium (Hf), shovel (Rf), V, niobium (Nb), Ta, and,
(Db), Cr, Mo, tungsten (W),
(Sg), technetium (Tc), rhenium (Re),
(Bh), Fe, Pb, ruthenium (Ru), osmium (Os),
(Hs)、Rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt), Cu, silver (Ag), gold (Au), Zn, cadmium (Cd), B, Al, gallium (Ga), Sn, In, Ge, P, arsenic (As), Sb, bismuth (Bi), sulfur (S), selenium (Se), tellurium (Te), polonium (Po), and combinations thereof.
The transition metal oxide may include lithium-containing titanium composite oxide (LTO), vanadium oxide, and lithium vanadium oxide.
The anode active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of the solid content in the anode slurry.
The binder is a component that facilitates bonding between the conductive agent, the active material, and the current collector, wherein the binder is generally added in an amount of 1 to 30 wt% based on the total weight of the solid content in the anode slurry. Examples of the binder may be polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluororubber, and various copolymers thereof.
The conductive agent is a component that further improves the conductivity of the anode active material, wherein the conductive agent may be added in an amount of 1 to 20 wt% based on the total weight of the solid content in the anode slurry. Any conductive agent may be used without limitation as long as it has conductivity and does not cause adverse chemical changes in the battery, and, for example, the following conductive materials such as: carbon powder such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black; graphite powder such as natural graphite, artificial graphite, or graphite having a good crystal structure; conductive fibers such as carbon fibers and metal fibers; metal powders such as carbon fluoride powder, aluminum powder, and nickel powder; conductive whiskers such as zinc oxide whiskers and potassium titanate whiskers; conductive metal oxides such as titanium oxide; or polyphenylene derivatives.
The solvent may include water or an organic solvent such as NMP and alcohol, and may be used in an amount such that a desired viscosity is obtained when the anode active material is included and the binder and the conductive agent are selectively included. For example, the solvent may be included in an amount such that the concentration of the solid content in the slurry including the anode active material and optionally the binder and the conductive agent is in the range of 50 to 75 wt%, for example, 50 to 65 wt%.
Further, a typical porous polymer film used as a typical separator, for example, a porous polymer film made from polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer, may be used alone as a separator or a laminate formed therefrom as a separator, and a typical porous nonwoven fabric, for example, a nonwoven fabric formed from high-melting glass fibers or polyethylene terephthalate fibers, may be used, but the present invention is not limited thereto.
The shape of the lithium secondary battery of the present invention is not particularly limited, but a cylindrical type, a prismatic type, a pouch type (pouch), or a coin type (coin) using a can may be used.
Hereinafter, the present invention will be described in more detail according to examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these exemplary embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Examples
Example 1.
(preparation of nonaqueous electrolyte solution)
By adding a mixed additive (0.2g of tetravinylsilane, 1.0g of lithium difluorophosphate and 1.0g of 1, 3-propenyl sulfate) to 97.8g of a solution in which 1M LiPF is dissolved6The non-aqueous electrolyte solution of the present invention was prepared in an organic solvent (ethylene carbonate (EC): methyl ethyl carbonate (EMC) ═ 3: 7 by volume ratio) (see table 1 below).
(Secondary Battery production)
A positive electrode active material (Li (Ni))0.6Mn0.2Co0.2)O2)、A conductive agent (carbon black) and a binder (polyvinylidene fluoride) were added to N-methyl-2-pyrrolidone (NMP) as a solvent at a weight ratio of 90: 5 to prepare a positive electrode slurry (solid content of 40 wt%). One surface of a 20 μm-thick cathode current collector (Al thin film) was coated with the cathode slurry, dried and rolled to prepare a cathode.
Subsequently, a negative electrode active material (artificial graphite), a conductive agent (carbon black), and a binder (polyvinylidene fluoride) were added to N-methyl-2-pyrrolidone (NMP) as a solvent at a weight ratio of 90: 5 to prepare a negative electrode slurry (solid content of 40 wt%). One surface of a 20 μm-thick negative electrode current collector (Cu film) was coated with the negative electrode slurry, dried and rolled, thereby preparing a negative electrode.
Next, a coin type battery was prepared by a typical method in which the above-prepared cathode and anode were sequentially stacked with a polyethylene porous film, and then a lithium secondary battery (battery capacity 340mAh) was prepared by injecting the prepared non-aqueous electrolyte solution of example 1 thereinto.
Example 2.
A nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in example 1, except that: during the preparation of the nonaqueous electrolyte solution, 0.1g of tetravinylsilane, 1.5g of lithium difluorophosphate and 2g of 1, 3-propylene sulfate were included as mixed additives in 96.4g of an organic solvent (see table 1 below).
Example 3.
(preparation of nonaqueous electrolyte solution)
A nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in example 1, except that: during the preparation of the nonaqueous electrolyte solution, 0.05g of tetravinylsilane, 0.75g of lithium difluorophosphate and 1.0g of 1, 3-propylene sulfate were included as additives in 98.2g of an organic solvent (see table 1 below).
Example 4.
A nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in example 1, except that: during the preparation of the nonaqueous electrolyte solution, 0.1g of tetravinylsilane, 1.0g of lithium difluorophosphate and 1.5g of 1, 3-propylene sulfate were included as additives in 97.4g of an organic solvent (see table 1 below).
Example 5.
A nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in example 1, except that: during the preparation of the nonaqueous electrolyte solution, 0.1g of tetravinylsilane, 1.0g of lithium difluorophosphate and 1.0g of 1, 3-propylene sulfate were included as additives in 97.9g of an organic solvent (see table 1 below).
Example 6.
A nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in example 1, except that: during the preparation of the nonaqueous electrolyte solution, 0.1g of tetravinylsilane, 2.0g of lithium difluorophosphate and 1g of 1, 3-propylene sulfate were included as mixed additives in 96.9g of an organic solvent (see table 1 below).
Comparative example 1.
A nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in example 1, except that: during the preparation of the nonaqueous electrolyte solution, 3g of Vinylene Carbonate (VC) was included in 97g of a solution having 1M LiPF dissolved therein6In an organic solvent (ethylene carbonate (EC): Ethyl Methyl Carbonate (EMC) ═ 3: 7 by volume ratio) (see table 1 below).
Comparative example 2.
A nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in example 1, except that: 2g of LiBF during preparation of non-aqueous electrolyte solution4Included in 98g of a solution of 1M LiPF6In an organic solvent (ethylene carbonate (EC): Ethyl Methyl Carbonate (EMC) ═ 3: 7 by volume ratio) (see table 1 below).
Comparative example 3.
A nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in example 1, except that: during the preparation of the nonaqueous electrolyte solution, 0.5g of tetravinylsilane, 1.25g of lithium difluorophosphate and 1.25g of 1, 3-propylene sulfate were included as mixed additives in 97g of an organic solvent (see table 1 below).
Comparative example 4.
A nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in comparative example 3, except that: during the preparation of the nonaqueous electrolyte solution, 0.1g of tetravinylsilane, 0.5g of lithium difluorophosphate, and 2.5g of 1, 3-propylene sulfate were included as mixed additives in 96.9g of an organic solvent (see table 1 below).
Comparative example 5.
A nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in comparative example 3, except that: during the preparation of the nonaqueous electrolyte solution, 0.1g of tetravinylsilane, 0.3g of lithium difluorophosphate, and 2.4g of 1, 3-propylene sulfate were included as mixed additives in 97.15g of an organic solvent (see table 1 below).
Comparative example 6.
A nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in comparative example 3, except that: during the preparation of the nonaqueous electrolyte solution, 0.15g of tetravinylsilane, 2.1g of lithium difluorophosphate and 0.3g of 1, 3-propylene sulfate were included as mixed additives in 97.45g of an organic solvent (see table 1 below).
Comparative example 7.
A nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in comparative example 3, except that: during the preparation of the nonaqueous electrolyte solution, 1.5g of lithium difluorophosphate and 1.5g of 1, 3-propenyl sulfate were included as mixed additives in 97g of an organic solvent (see table 1 below).
Comparative example 8.
A nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in comparative example 3, except that: during the preparation of the nonaqueous electrolyte solution, 0.25g of tetravinylsilane and 2.5g of 1, 3-propene sulfate were included as a mixed additive in 97.25g of an organic solvent (see table 1 below).
Comparative example 9.
A nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in comparative example 3, except that: during the preparation of the nonaqueous electrolyte solution, 0.25g of tetravinylsilane and 2.5g of lithium difluorophosphate were included as a mixed additive in 97.25g of an organic solvent (see table 1 below).
Comparative example 10.
A positive electrode, a negative electrode, and a lithium secondary battery including the positive electrode and the negative electrode were prepared in the same manner as in example 1, except that: including lithium cobalt composite oxide (LiCoO) during the preparation of secondary batteries2) Instead of Li (Ni)0.6Mn0.2Co0.2)O2As a positive electrode active material.
Test examples
Test example 1.: cycle life characteristic test
Each of the secondary batteries prepared in examples 1 to 6 and comparative examples 1 to 10 was charged to 4.25V/55mA at 45 ℃ under a constant current/constant voltage (CC/CV) condition at 1C, and then discharged to a voltage of 3.0V (1,000 cycles/1 cycle × 100) at a Constant Current (CC) of 2C to measure the life of 1,00 cycles at high temperature, the results of which are listed in table 1 below.
In addition, each of the secondary batteries prepared in examples 1 to 6 and comparative examples 1 to 10 was charged to 4.25V/55mA at 1C under CC/CV conditions at 25C and then discharged to a voltage of 3.0V (1,000 cycles/1 cycle × 100) at CC of 2C to measure the life characteristics of 100 cycles at room temperature, the results of which are listed in table 1 below.
Test example 2.: high temperature storage characteristic test
After each of the secondary batteries prepared in examples 1 to 6 and comparative examples 1 to 10 was stored at a high temperature of 60 ℃ for 16 weeks, each of the secondary batteries was charged at 1C to 4.25V/55mA under constant current/constant voltage (CC/CV) conditions at room temperature, and then discharged at a Constant Current (CC) of 2C to a voltage of 2.5V, and the capacity after high-temperature storage was measured by calculating the discharge capacity after 16 weeks as a percentage (capacity after 16 weeks/initial discharge capacity × 100 (%)). The results are set forth in table 1 below.
Further, after each of the secondary batteries prepared in examples 1 to 6 and comparative examples 1 to 10 was stored at a high temperature of 60 ℃ for 16 weeks, the output was measured by measuring the voltage difference generated by discharging each of the secondary batteries at 50% state of charge (SOC) at room temperature for 10 seconds at 3C, and the output after 16 weeks of storage was calculated as a percentage (output after 16 weeks/initial output × 100), the results of which are listed in table 1 below.
Further, after each of the secondary batteries prepared in examples 1 to 6 and comparative examples 1 to 10 was stored at a high temperature of 60 ℃ for 16 weeks, the change in thickness was measured, and the results thereof are listed in table 1 below.
[ Table 1]
As shown in table 1, when the life characteristics after 1,000 cycles were tested, it could be confirmed that the secondary batteries prepared in examples 1 to 6 had significantly better room-temperature and high-temperature cycle life characteristics than the secondary batteries prepared in comparative examples 1 to 10.
In addition, when the high-temperature storage characteristics were tested, it could be confirmed that the capacity and output characteristics of the secondary batteries prepared in examples 1 to 6 were improved as compared to the secondary batteries prepared in comparative examples 1 to 10.
In particular, regarding the secondary battery of comparative example 10 including LCO as a cathode active material, since the stability of the SEI film formed on the surface of the cathode is relatively lower than that of the secondary batteries of examples 1 to 6 including lithium nickel manganese cobalt based oxide, it can be understood that the cycle life characteristics and the high temperature storage characteristics are deteriorated.
Claims (7)
1. A nonaqueous electrolyte solution for a lithium secondary battery, comprising:
an ionizable lithium salt; an organic solvent; and an additive, wherein the additive is a mixture of,
wherein the additive is prepared from the following components in a weight ratio of 1: 3-20: 3-20 of a mixed additive consisting of tetraenylsilane, lithium difluorophosphate and 1, 3-propylene sulfate, and
the additive is included in an amount of 1 to 4 wt% based on the total weight of the nonaqueous electrolyte solution.
2. The non-aqueous electrolyte solution for a lithium secondary battery according to claim 1, wherein the ratio of tetravinylsilane: lithium difluorophosphate: the weight ratio of the 1, 3-allyl sulfate is 1: 3-17: 5-20.
3. The non-aqueous electrolyte solution for a lithium secondary battery according to claim 1, wherein the ratio of tetravinylsilane: lithium difluorophosphate: the weight ratio of the 1, 3-allyl sulfate is 1: 5-15: 5-20.
4. The nonaqueous electrolyte solution for a lithium secondary battery according to claim 1, wherein the additive is included in an amount of 1.8 to 4 wt% based on the total weight of the nonaqueous electrolyte solution for a lithium secondary battery.
5. A lithium secondary battery comprising a negative electrode, a positive electrode, a separator provided between the positive electrode and the negative electrode, and a nonaqueous electrolyte solution,
wherein the nonaqueous electrolyte solution includes the nonaqueous electrolyte solution for a lithium secondary battery according to claim 1, and
the positive electrode includes a lithium nickel manganese cobalt based oxide as a positive electrode active material.
6. The lithium secondary battery according to claim 5, wherein the positive active material comprises a lithium transition metal oxide represented by formula 1:
[ formula 1]
Li(NiaCobMnc)O2
Wherein, in the formula 1,
a is more than or equal to 0.55 and less than or equal to 0.9, b is more than or equal to 0.05 and less than or equal to 0.22, c is more than or equal to 0.05 and less than or equal to 0.23, and a + b + c is equal to 1.
7. The lithium secondary battery according to claim 6, wherein the positive electrode active material comprises Li (Ni)0.6Mn0.2Co0.2)O2、Li(Ni0.7Mn0.15Co0.15)O2And Li (Ni)0.8Mn0.1Co0.1)O2At least one of (1).
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| KR1020180006125A KR102053313B1 (en) | 2017-01-20 | 2018-01-17 | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
| PCT/KR2018/000873 WO2018135889A1 (en) | 2017-01-20 | 2018-01-18 | Non-aqueous electrolyte for lithium secondary battery, and lithium secondary battery comprising same |
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| KR102529247B1 (en) * | 2019-05-02 | 2023-05-08 | 주식회사 엘지에너지솔루션 | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
| KR20200132024A (en) * | 2019-05-15 | 2020-11-25 | 현대자동차주식회사 | Electrolyte solution for lithium iron phosphate based lithium secondary battery and lithium secondary battery comprising the same |
| CN110416606B (en) * | 2019-05-30 | 2022-07-15 | 贵州兴锂新能源科技有限公司 | Electrolyte for silicon-carbon cathode lithium ion battery |
| CN111146500A (en) * | 2019-12-23 | 2020-05-12 | 东莞市杉杉电池材料有限公司 | Fast-charging type lithium ion battery non-aqueous electrolyte and lithium ion battery containing electrolyte |
| CN111313086B (en) * | 2019-12-24 | 2022-11-01 | 安徽圣格能源科技有限公司 | Electrolyte and lithium ion battery |
| CN112531212B (en) * | 2020-12-09 | 2021-12-07 | 远景动力技术(江苏)有限公司 | Non-aqueous electrolyte with high-temperature characteristic and low impedance, application thereof and lithium ion battery |
| CN112531213A (en) * | 2020-12-09 | 2021-03-19 | 远景动力技术(江苏)有限公司 | Non-aqueous electrolyte with high-temperature characteristics and normal-temperature cycle, application thereof and lithium ion battery |
| CN113764738B (en) * | 2021-10-12 | 2024-05-14 | 远景动力技术(江苏)有限公司 | Electrolyte for improving high-temperature storage characteristics of battery and lithium ion battery |
| CN114373981A (en) * | 2022-01-18 | 2022-04-19 | 香河昆仑新能源材料股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery thereof |
| CN114447435A (en) * | 2022-01-21 | 2022-05-06 | 恒实科技发展(南京)有限公司 | Non-aqueous electrolyte for lithium secondary battery and preparation method and application thereof |
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| CN104025353A (en) * | 2011-10-04 | 2014-09-03 | 旭化成株式会社 | Materials for battery electrolytes and methods for use |
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| CN104025353A (en) * | 2011-10-04 | 2014-09-03 | 旭化成株式会社 | Materials for battery electrolytes and methods for use |
| KR20160036810A (en) * | 2014-09-26 | 2016-04-05 | 주식회사 엘지화학 | Non-aqueous liquid electrolyte and lithium secondary battery comprising the same |
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