WO2023136681A1 - 비수 전해질용 첨가제를 포함하는 비수 전해질 및 이를 포함하는 리튬 이차전지 - Google Patents
비수 전해질용 첨가제를 포함하는 비수 전해질 및 이를 포함하는 리튬 이차전지 Download PDFInfo
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- WO2023136681A1 WO2023136681A1 PCT/KR2023/000701 KR2023000701W WO2023136681A1 WO 2023136681 A1 WO2023136681 A1 WO 2023136681A1 KR 2023000701 W KR2023000701 W KR 2023000701W WO 2023136681 A1 WO2023136681 A1 WO 2023136681A1
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- aqueous electrolyte
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- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- LSUWCXHZPFTZSF-UHFFFAOYSA-N 4-ethyl-5-methyl-1,3-dioxolan-2-one Chemical compound CCC1OC(=O)OC1C LSUWCXHZPFTZSF-UHFFFAOYSA-N 0.000 description 1
- AUXJVUDWWLIGRU-UHFFFAOYSA-N 4-propyl-1,3-dioxolan-2-one Chemical compound CCCC1COC(=O)O1 AUXJVUDWWLIGRU-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- 229910020203 CeO Inorganic materials 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229910003936 Li(Ni0.5Mn0.3Co0.2)O2 Inorganic materials 0.000 description 1
- 229910004406 Li(Ni0.6Mn0.2CO0.2)O2 Inorganic materials 0.000 description 1
- 229910004427 Li(Ni0.7Mn0.15Co0.15)O2 Inorganic materials 0.000 description 1
- 229910004424 Li(Ni0.8Co0.15Al0.05)O2 Inorganic materials 0.000 description 1
- 229910004437 Li(Ni0.8Mn0.1Co0.1)O2 Inorganic materials 0.000 description 1
- 229910004499 Li(Ni1/3Mn1/3Co1/3)O2 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015644 LiMn 2 - z Ni Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 229910008326 Si-Y Inorganic materials 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
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 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
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-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
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021475 bohrium Inorganic materials 0.000 description 1
- 238000010504 bond cleavage reaction Methods 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
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000011329 calcined coke Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 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
- 229910052733 gallium Inorganic materials 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
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000003106 haloaryl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229910021473 hassium Inorganic materials 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000006051 mesophase pitch carbide Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 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
- 239000011259 mixed solution Substances 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 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
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910021481 rutherfordium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910021477 seaborgium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ZMQDTYVODWKHNT-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) phosphate Chemical compound FC(F)(F)COP(=O)(OCC(F)(F)F)OCC(F)(F)F ZMQDTYVODWKHNT-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/10—Homopolymers or copolymers of unsaturated ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
-
- 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
-
- 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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
-
- 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
Definitions
- the present invention relates to a non-aqueous electrolyte including an additive for non-aqueous electrolyte and a lithium secondary battery including the same.
- a high-nickel-content cathode active material having high energy density but low stability may be used, or the secondary battery may be driven at a high voltage.
- the film formed on the surface of the anode/cathode or the surface structure of the electrode deteriorates due to side reactions caused by the deterioration of the electrolyte, and transition metal ions from the surface of the anode may be eluted.
- the eluted transition metal ions are electro-deposited on the negative electrode and lower the passivation ability of the SEI, a problem of deterioration of the negative electrode occurs.
- the deterioration of the secondary battery tends to be accelerated when the potential of the positive electrode increases or the battery is exposed to high temperature, and the deterioration causes a problem in that the cycle characteristics of the secondary battery deteriorate.
- the present invention aims to provide an additive for a nonaqueous electrolyte capable of suppressing deterioration of the anode, reducing side reactions between the anode and the electrolyte, and forming a stable SEI film on the anode.
- the present invention is intended to provide a non-aqueous electrolyte with improved stability at high temperature by including the additive for the non-aqueous electrolyte.
- the present invention intends to provide a lithium secondary battery with improved overall performance by including the non-aqueous electrolyte, thereby improving high-temperature cycle characteristics and high-temperature storage characteristics.
- the present invention is a lithium salt, an organic solvent, a compound represented by Formula 1 as a first additive and a compound represented by Formula 2-1, Formula 2-2 and Formula 2-3 as a second additive
- a non-aqueous electrolyte containing a polymer containing a repeating unit is provided.
- R is a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms
- R 1 to R 3 are each independently H, an alkyl group having 1 to 3 carbon atoms, or a nitrile group.
- R 4 is H, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms.
- a cycloalkenyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom, and a nitrile group is H, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms.
- R a is an alkyl group having 1 to 10 carbon atoms substituted with one or more nitrile groups
- R 5 is H, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alky group having 2 to 20 carbon atoms. It is any one selected from the group consisting of a yl group, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom, and a nitrile group.
- R b is a fluoroalkyl group having 1 to 10 carbon atoms
- R 6 is H, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a carbon atom 1 It is any one selected from the group consisting of an alkoxy group of 1 to 20, a cycloalkyl group of 3 to 12 carbon atoms, a cycloalkenyl group of 3 to 12 carbon atoms, an aryl group of 6 to 12 carbon atoms, a halogen atom and a nitrile group.
- the present invention provides a lithium secondary battery including the non-aqueous electrolyte.
- the first additive according to the present invention is a compound containing both a propargyl group known to have metal ion adsorption performance and an imidazole group effective for forming an SEI film, and can form a stable ion conductive film on the surface of the negative electrode. , As a result, gas generation due to a side reaction between the anode and the electrolyte is suppressed, and cell swelling can be significantly reduced.
- the second additive according to the present invention can form a solid electrolyte interphase (SEI) film that is elastic and durable on the surface of the negative electrode. Therefore, a strong SEI layer is maintained even at high temperatures to prevent deterioration of the negative electrode and to suppress additional SEI formation reactions due to solvent decomposition during the cycle.
- SEI solid electrolyte interphase
- the second additive acts together to impart elasticity to the SEI film, thereby enhancing the strength of the SEI film. Accordingly, since the film is not destroyed even with extreme volume changes of the negative electrode during charging and discharging, a new interface between the negative electrode and the electrolyte is not formed. Accordingly, an additional electrolyte decomposition reaction can be suppressed during the charging and discharging process, thereby reducing expansion of the cell due to gas generation.
- an electrode-electrolyte interface that is stable and highly durable can be formed even at high temperatures, so that high-temperature cycle characteristics and high-temperature storage characteristics are improved.
- a lithium secondary battery with improved performance can be implemented.
- an alkylene group having 1 to 5 carbon atoms refers to an alkylene group containing 1 to 5 carbon atoms, that is, -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, - CH 2 (CH 3 )CH-, -CH(CH 3 )CH 2 - and -CH(CH 3 )CH 2 CH 2 - and the like.
- alkylene group means a branched or unbranched divalent saturated hydrocarbon group.
- an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a cycloalkyl group, a cycloalkenyl group, and an aryl group may be substituted or unsubstituted.
- substitution means that at least one hydrogen bonded to carbon is substituted with an element other than hydrogen, for example, an alkyl group having 1 to 20 carbon atoms or an alkene having 2 to 20 carbon atoms.
- Nyl group alkynyl group of 2 to 20 carbon atoms, alkoxy group of 1 to 20 carbon atoms, cycloalkyl group of 3 to 12 carbon atoms, cycloalkenyl group of 3 to 12 carbon atoms, heterocycloalkyl group of 3 to 12 carbon atoms, heterocycloalkyl group of 3 to 12 carbon atoms Cycloalkenyl group, aryloxy group having 6 to 12 carbon atoms, halogen atom, fluoroalkyl group having 1 to 20 carbon atoms, nitro group, aryl group having 6 to 20 carbon atoms, heteroaryl group having 2 to 20 carbon atoms, and It means substituted with a haloaryl group or the like.
- the non-aqueous electrolyte according to the present invention may include a second additive together with the first additive represented by Chemical Formula 1 below.
- the first additive compound represented by Chemical Formula 1 contains a propargyl group having a triple bond known to have metal ion adsorption performance and an oxygen atom, and thus contains a nitrogen (N) atom and a carbon (C) atom of the imidazole group.
- the propargyl group which has been separated by bond cleavage, adsorbs metal foreign substances such as Fe, Co, Mn, Ni, etc., eluted from the anode during high voltage charging, and the anode deterioration caused by the electrodeposition of these metal foreign substances on the surface of the anode is prevented. can be effectively suppressed.
- the lone pair of nitrogen (N) atoms of the imidazole group reacts with alkyl carbonate, which is a decomposition product of ethylene carbonate (EC) used as an organic solvent, to reduce on the surface of the anode Therefore, a stable ion conductive film can be formed on the surface of the negative electrode. Therefore, it is possible not only to suppress additional electrolyte decomposition reactions during charge and discharge processes, but also to smoothly occlude and release lithium ions from the negative electrode even during overcharging or high temperature storage, thereby improving cycle life characteristics and high temperature storage performance of secondary batteries. can
- the second additive may include repeating units represented by Chemical Formulas 2-1, 2-2, and 2-3 below.
- the repeating unit of Chemical Formula 2-1 included in the second additive contains a hydroxyl group to impart a hydrogen bond to the additive structure, and the hydrogen bond has an effect of helping the battery material to withstand physical degradation.
- R 4 is H, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms. , It may be any one selected from the group consisting of a cycloalkenyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom, and a nitrile group.
- R 4 may be H or an alkyl group having 1 to 10 carbon atoms, most preferably H.
- the repeating unit of Chemical Formula 2-2 included in the second additive includes a nitrile group, so that the SEI layer can be easily formed by electrodeposition to the negative electrode. Thus, it is possible to rapidly form a robust SEI layer.
- R a is an alkyl group having 1 to 10 carbon atoms substituted with one or more nitrile groups, and preferably, R a in Formula 2-2 has 1 to 5 carbon atoms and is a linear or nitrile group substituted with one or more groups. It may be a branched alkyl group, and most preferably, R a in Chemical Formula 2-2 may be an alkyl group having 1 to 3 carbon atoms in which one or more nitrile groups are substituted.
- R a can be CH 2 CN or CH 2 CH 2 CN.
- R 5 is H, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms. , It may be any one selected from the group consisting of a cycloalkenyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom, and a nitrile group.
- R 5 may be H or an alkyl group having 1 to 10 carbon atoms, most preferably H.
- the repeating unit of Chemical Formula 2-3 included in the second additive includes a fluoroalkyl group
- LiF inorganic materials can be easily generated to form a stable polymer-inorganic based SEI layer. Therefore, the deterioration of the passivation ability of the SEI at high temperatures can be suppressed, and deterioration of the negative electrode can be prevented.
- R b may be a fluoroalkyl group having 1 to 10 carbon atoms.
- R b is preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and most preferably a perfluoroalkyl group having 1 to 10 carbon atoms.
- R 6 is H, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms. , It may be any one selected from the group consisting of a cycloalkenyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen atom, and a nitrile group.
- R 6 may be H or an alkyl group having 1 to 10 carbon atoms, most preferably H.
- the non-aqueous electrolyte according to the present invention may include a polymer represented by Formula 2 below as an additive.
- R a is an alkyl group having 1 to 10 carbon atoms substituted with one or more nitrile groups
- R a in Formula 2 is a linear or branched alkyl group having 1 to 5 carbon atoms and with one or more nitrile groups substituted.
- R a in Formula 2 may be an alkyl group having 1 to 3 carbon atoms in which one or more nitrile groups are substituted.
- R a can be CH 2 CN or CH 2 CH 2 CN.
- R b may be a fluoroalkyl group having 1 to 10 carbon atoms.
- R b is preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and most preferably a perfluoroalkyl group having 1 to 10 carbon atoms.
- R 4 to R 6 are each independently H, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 3 to 20 carbon atoms. It may be any one selected from the group consisting of a cycloalkyl group of 12, a cycloalkenyl group of 3 to 12 carbon atoms, an aryl group of 6 to 12 carbon atoms, a halogen atom, and a nitrile group.
- R 4 to R 6 may each independently be H or an alkyl group having 1 to 10 carbon atoms, and most preferably H.
- p, q and r may each independently be an integer of 1 to 100.
- p is an integer from 1 to 99
- q is an integer from 1 to 99
- r may be an integer from 1 to 99
- q is an integer from 1 to 80
- r may be an integer from 1 to 80.
- the first additive may be included in an amount of 0.01 to 2 parts by weight, preferably 0.05 to 2 parts by weight, more preferably 0.10 to 2 parts by weight, based on 100 parts by weight of the non-aqueous electrolyte. It may be included in an amount of 1.5 parts by weight.
- the content of the first additive satisfies the above range, the effect of forming a film on the negative electrode is sufficient, so that lifespan characteristics and high-temperature storage characteristics are excellent at high temperatures.
- the second additive may be included in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.10 to 10 parts by weight, based on 100 parts by weight of the non-aqueous electrolyte. It may be included in an amount of 3 parts by weight.
- the content of the first additive satisfies the above range, the effect of forming a film on the negative electrode is sufficient, so that lifespan characteristics and high-temperature storage characteristics are excellent at high temperatures.
- the first additive and the second additive are in a weight ratio of 1:0.01 to 1:40, preferably 1:1.5 to 1:10, most preferably 1:1.5 to 1:5.
- the elasticity of the formed SEI film is in an appropriate range, so that the SEI film can be firmly maintained during charging and discharging or at a high temperature.
- the non-aqueous electrolyte according to the present invention may contain a lithium salt.
- the lithium salt is used as an electrolyte salt in a lithium secondary battery and is used as a medium for transferring ions.
- a lithium salt contains, for example, Li + as a cation and F - , Cl - , Br - , I - , NO 3 - , N(CN) 2 - , BF 4 - , ClO 4 - as an anion.
- the lithium salt is LiCl, LiBr, LiI, LiBF 4 , LiClO 4 , LiB 10 Cl 10 , LiAlCl 4 , LiAlO 2 , LiPF 6 , LiCF 3 SO 3 , LiCH 3 CO 2 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiCH 3 SO 3 , LiN(SO 2 F) 2 (lithium bis(fluorosulfonyl)imide; LiFSI), LiN(SO 2 CF 2 CF 3 ) 2 (lithium bis(perfluoroethanesul) phonyl)imide; LiBETI) and LiN(SO 2 CF 3 ) 2 (lithium bis(trifluoromethanesulfonyl)imide; LiTFSI).
- lithium salts commonly used in electrolytes of lithium secondary batteries may be used without limitation.
- the lithium salt may be appropriately changed within a commonly usable range, but in order to obtain an optimum effect of forming a film for preventing corrosion of the electrode surface, a concentration of 0.5 M to 4.0 M in the electrolyte, preferably, a concentration of 1.0 M to 3.0 M concentration, more preferably at a concentration of 1.5 M to 2.0 M.
- concentration of the lithium salt satisfies the above range, the effect of improving cycle characteristics during high-temperature storage of the lithium secondary battery is sufficient and the viscosity of the non-aqueous electrolyte is appropriate, so that electrolyte impregnability can be improved.
- the non-aqueous electrolyte according to the present invention may contain an organic solvent.
- the non-aqueous organic solvent may include at least one organic solvent selected from the group consisting of a cyclic carbonate-based organic solvent, a linear carbonate-based organic solvent, a linear ester-based organic solvent, and a cyclic ester-based organic solvent.
- the additives according to the present invention are particularly effective when using cyclic carbonate solvents.
- a conventional electrolyte additive together with a cyclic carbonate solvent the SEI film formed by decomposition of the cyclic carbonate solvent is difficult to maintain the SEI film due to the volume change of the negative electrode occurring during the cycle, so that the solvent decomposition continues. There was a problem. As a result, there is a problem in that the ionic conductivity of the electrolyte solution is lowered and the cycle characteristics are deteriorated.
- the polymer according to the present invention is used as an additive together with a cyclic carbonate solvent, it is possible to form a solid SEI film, thereby maintaining high cycle characteristics.
- the cyclic carbonate-based organic solvent is a high-viscosity organic solvent that can dissociate lithium salts in the electrolyte well due to its high dielectric constant.
- at least one organic solvent selected from the group consisting of 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate and vinylene carbonate may be used, and among these, fluoroethylene carbonate may be included.
- the linear carbonate-based organic solvent is an organic solvent having a low viscosity and a low dielectric constant, and representative examples thereof include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, and ethylmethyl carbonate ( EMC), at least one organic solvent selected from the group consisting of methylpropyl carbonate and ethylpropyl carbonate may be used, and specifically diethyl carbonate (DEC) may be included.
- DMC dimethyl carbonate
- DEC diethyl carbonate
- EMC ethylmethyl carbonate
- DEC diethyl carbonate
- the organic solvent is a linear ester-based organic solvent and a cyclic ester in at least one carbonate-based organic solvent selected from the group consisting of the cyclic carbonate-based organic solvent and the linear carbonate-based organic solvent in order to prepare an electrolyte having high ionic conductivity. It may further include at least one ester-based organic solvent selected from the group consisting of organic solvents.
- linear ester-based organic solvent examples include at least one organic solvent selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, and butyl propionate.
- cyclic ester organic solvent at least one organic solvent selected from the group consisting of ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone and ⁇ -caprolactone is mentioned.
- the organic solvent may be used by adding an organic solvent commonly used in a non-aqueous electrolyte without limitation, if necessary.
- an organic solvent commonly used in a non-aqueous electrolyte
- at least one organic solvent selected from among ether-based organic solvents, glyme-based solvents, and nitrile-based organic solvents may be further included.
- ether-based solvent examples include dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether, ethyl propyl ether, 1,3-dioxolane (DOL) and 2,2-bis (trifluoromethyl). Any one selected from the group consisting of )-1,3-dioxolane (TFDOL) or a mixture of two or more thereof may be used, but is not limited thereto.
- the glyme-based solvent has a higher permittivity and lower surface tension than linear carbonate-based organic solvents, and is less reactive with metals, such as dimethoxyethane (glyme, DME), diethoxyethane, diglyme, Triglyme (Triglyme), and tetra-glyme (TEGDME) may include at least one or more selected from the group consisting of, but is not limited thereto.
- metals such as dimethoxyethane (glyme, DME), diethoxyethane, diglyme, Triglyme (Triglyme), and tetra-glyme (TEGDME) may include at least one or more selected from the group consisting of, but is not limited thereto.
- the nitrile solvent is acetonitrile, propionitrile, butyronitrile, valeronitrile, caprylonitrile, heptanenitrile, cyclopentane carbonitrile, cyclohexane carbonitrile, 2-fluorobenzonitrile, 4-fluorobenzonitrile , Difluorobenzonitrile, trifluorobenzonitrile, phenylacetonitrile, 2-fluorophenylacetonitrile, may be one or more selected from the group consisting of 4-fluorophenylacetonitrile, but is not limited thereto.
- the non-aqueous electrolyte of the present invention prevents the decomposition of the non-aqueous electrolyte in a high-power environment and causes the collapse of the negative electrode, or to further improve low-temperature high-rate discharge characteristics, high-temperature stability, overcharge prevention, and the effect of suppressing battery swelling at high temperatures.
- a known electrolyte additive may be further included in the non-aqueous electrolyte.
- electrolyte additives include cyclic carbonate-based compounds, halogen-substituted carbonate-based compounds, sultone-based compounds, sulfate-based compounds, phosphate-based compounds, borate-based compounds, nitrile-based compounds, benzene-based compounds, amine-based compounds, and silane-based compounds. It may include at least one additive for forming an SEI film selected from the group consisting of compounds and lithium salt-based compounds.
- the cyclic carbonate-based compound may include vinylene carbonate (VC) or vinyl ethylene carbonate.
- the halogen-substituted carbonate-based compound may include fluoroethylene carbonate (FEC).
- FEC fluoroethylene carbonate
- the sultone-based compounds include 1,3-propane sultone (PS), 1,4-butane sultone, ethensultone, 1,3-propene sultone (PRS), 1,4-butene sultone and 1-methyl-1,3 - At least one or more compounds selected from the group consisting of propene sultone.
- the sulfate-based compound may include ethylene sulfate (Esa), trimethylene sulfate (TMS), or methyl trimethylene sulfate (MTMS).
- Esa ethylene sulfate
- TMS trimethylene sulfate
- MTMS methyl trimethylene sulfate
- the phosphate-based compound is lithium difluoro (bisoxalato) phosphate, lithium difluorophosphate, tetramethyl trimethyl silyl phosphate, trimethyl silyl phosphite, tris (2,2,2-trifluoroethyl) phosphate and tris and at least one compound selected from the group consisting of (trifluoroethyl) phosphites.
- borate-based compound examples include tetraphenylborate, lithium oxalyldifluoroborate (LiODFB), and lithium bisoxalate borate (LiB(C 2 O 4 ) 2 , LiBOB).
- the nitrile-based compound is succinonitrile, adiponitrile, acetonitrile, propionitrile, butyronitrile, valeronitrile, caprylonitrile, heptanenitrile, cyclopentane carbonitrile, cyclohexane carbonitrile, 2-fluorobenzo
- nitrile, 4-fluorobenzonitrile, difluorobenzonitrile, trifluorobenzonitrile, phenylacetonitrile, 2-fluorophenylacetonitrile, and 4-fluorophenylacetonitrile compounds can be mentioned.
- the benzene-based compound may include fluorobenzene
- the amine-based compound may include triethanolamine or ethylene diamine
- the silane-based compound may include tetravinylsilane.
- the lithium salt-based compound is a compound different from the lithium salt included in the non-aqueous electrolyte, and may include lithium difluorophosphate (LiDFP), LiPO 2 F 2 or LiBF 4 .
- LiDFP lithium difluorophosphate
- LiPO 2 F 2 LiPO 2 F 2
- LiBF 4 lithium difluorophosphate
- initial secondary battery when a combination of vinylene carbonate (VC), 1,3-propane sultone (PS), ethylene sulfate (Esa), and lithium difluorophosphate (LiDFP) is further included, initial secondary battery During the activation process, a more durable SEI film may be formed on the surface of the anode, and gas generation that may be generated due to electrolyte decomposition at high temperature may be suppressed, thereby improving high-temperature stability of the secondary battery.
- VC vinylene carbonate
- PS 1,3-propane sultone
- Esa ethylene sulfate
- LiDFP lithium difluorophosphate
- the other electrolyte additives may be used in combination of two or more, and may be included in an amount of 0.050 to 20% by weight, specifically 0.10 to 15% by weight, preferably 0.30 to 10% by weight, based on the total weight of the non-aqueous electrolyte.
- the content of the other electrolyte additives satisfies the above range, the effect of improving ionic conductivity and cycle characteristics is more excellent.
- the present invention also provides a lithium secondary battery including the non-aqueous electrolyte.
- the lithium secondary battery includes a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, a separator interposed between the positive electrode and the negative electrode, and the above-described non-aqueous electrolyte.
- the lithium secondary battery of the present invention can be manufactured according to a conventional method known in the art. For example, after forming an electrode assembly by sequentially stacking a positive electrode, a negative electrode, and a separator between the positive electrode and the negative electrode, the electrode assembly is inserted into the battery case, and the non-aqueous electrolyte according to the present invention is injected. .
- the positive electrode may be prepared by coating a positive electrode mixture slurry including a positive electrode active material, a binder, a conductive material, and a solvent on a positive electrode current collector.
- the cathode current collector is not particularly limited as long as it does not cause chemical change in the battery and has conductivity.
- the cathode active material is a compound capable of reversible intercalation and deintercalation of lithium, and may specifically include a lithium metal oxide containing lithium and one or more metals such as cobalt, manganese, nickel, or aluminum.
- the lithium metal oxide is a lithium-manganese-based oxide (eg, LiMnO 2 , LiMn 2 O 4 , etc.), a lithium-cobalt-based oxide (eg, LiCoO 2 , etc.), a lithium-nickel-based oxide ( For example, LiNiO 2 , etc.), lithium-nickel-manganese-based oxide (eg, LiNi 1-Y Mn Y O 2 (where 0 ⁇ Y ⁇ 1), LiMn 2-Z Ni Z O 4 (here) , 0 ⁇ Z ⁇ 2), etc.), lithium-nickel-cobalt-based oxides (eg, LiNi 1-Y1 Co Y1 O 2 (where 0 ⁇ Y1 ⁇ 1), etc.),
- the lithium metal oxide is LiCoO 2 , LiMnO 2 , LiNiO 2 , lithium nickel manganese cobalt oxide (for example, Li(Ni 1/3 Mn 1/3 Co 1/ 3 ) O 2 , Li(Ni 0.6 Mn 0.2 Co 0.2 ) O 2 , Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 , Li(Ni 0.7 Mn 0.15 Co 0.15 )O 2 and Li(Ni 0.8 Mn 0.1 Co 0.1 )O 2 , etc.), or lithium nickel cobalt aluminum oxide (eg, Li (Ni 0.8 Co 0.15 Al 0.05 ) O 2 , etc.), and any one or a mixture of two or more of them may be used.
- the positive electrode active material may be included in an amount of 60 to 99% by weight, preferably 70 to 99% by weight, and more preferably 80 to 98% by weight, based on the total weight of solids excluding the solvent in the positive electrode mixture slurry.
- the binder is a component that assists in the binding between the active material and the conductive material and the binding to the current collector.
- binders examples include polyvinylidene fluoride, polyvinyl alcohol, starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene (PE), polypropylene, ethylene-propylene-diene monomers, sulfonated ethylene-propylene-diene monomers, styrene-butadiene rubbers, fluororubbers, various copolymers, and the like.
- the binder may be included in an amount of 1 to 20 wt%, preferably 1 to 15 wt%, and more preferably 1 to 10 wt%, based on the total weight of the solid content excluding the solvent in the positive electrode mixture slurry.
- the conductive material is a component for further improving the conductivity of the positive electrode active material, and may be added in an amount of 1 to 20% by weight based on the total weight of the solid content in the positive electrode mixture slurry.
- the conductive material is not particularly limited as long as it has conductivity without causing chemical change to the battery. For example, carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black.
- carbon powder such as natural graphite, artificial graphite, or graphite having a highly developed crystal structure
- conductive fibers such as carbon fibers and metal fibers
- Fluorinated carbon powder such as aluminum powder and nickel powder
- conductive whiskers such as zinc oxide and potassium titanate
- conductive metal oxides such as titanium oxide
- Conductive materials such as polyphenylene derivatives may be used.
- the conductive material may be included in an amount of 1 to 20 wt%, preferably 1 to 15 wt%, and more preferably 1 to 10 wt%, based on the total weight of solids excluding the solvent in the positive electrode mixture slurry.
- the solvent may include an organic solvent such as NMP (N-methyl-2-pyrrolidone), and may be used in an amount that provides a desired viscosity when the cathode active material and optionally a binder and a conductive material are included.
- NMP N-methyl-2-pyrrolidone
- the solid content including the positive electrode active material and, optionally, the binder and the conductive material may be included so that the concentration is 50 to 95% by weight, preferably 70 to 95% by weight, and more preferably 70 to 90% by weight. .
- the negative electrode may be prepared by coating a negative electrode mixture slurry including a negative electrode active material, a binder, a conductive material, and a solvent on a negative electrode current collector, or a graphite electrode made of carbon (C) or a metal itself may be used as the negative electrode.
- a negative electrode mixture slurry including a negative electrode active material, a binder, a conductive material, and a solvent on a negative electrode current collector, or a graphite electrode made of carbon (C) or a metal itself may be used as the negative electrode.
- the negative electrode current collector when manufacturing a negative electrode by coating the negative electrode mixture slurry on the negative electrode current collector, the negative electrode current collector generally has a thickness of 3 to 500 ⁇ m.
- the negative electrode current collector is not particularly limited as long as it does not cause chemical change in the battery and has high conductivity.
- it is made of copper, stainless steel, aluminum, nickel, titanium, fired carbon, copper or stainless steel.
- a surface treated with carbon, nickel, titanium, silver, or the like, an aluminum-cadmium alloy, or the like may be used.
- fine irregularities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as films, sheets, foils, nets, porous bodies, foams, and nonwoven fabrics.
- the anode active material is a lithium metal, a carbon material capable of reversibly intercalating / deintercalating lithium ions, a metal or an alloy of these metals and lithium, a metal composite oxide, and a lithium dope and undope. It may include at least one selected from the group consisting of materials and transition metal oxides.
- any carbon-based negative electrode active material commonly used in lithium ion secondary batteries may be used without particular limitation, and typical examples thereof include crystalline carbon, Amorphous carbon or a combination thereof may be used.
- the crystalline carbon include graphite such as amorphous, plate-like, flake-like, spherical or fibrous natural graphite or artificial graphite, and examples of the amorphous carbon include soft carbon (low-temperature calcined carbon). or hard carbon, mesophase pitch carbide, calcined coke, and the like.
- Examples of the above metals or alloys of these metals and lithium include Cu, Ni, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al And a metal selected from the group consisting of Sn or an alloy of these metals and lithium may be used.
- metal composite oxide examples include PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , Bi 2 O 5 , Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1) and Sn x Me 1-x Me' y O z (Me: Mn, Fe, Pb, Ge; Me': Al, B, P, Si, Groups 1, 2, and 3 elements of the periodic table, halogen; 0 ⁇ x ⁇ 1;1 ⁇ y ⁇ 3; 1 ⁇ z ⁇ 8) A selection from can be used.
- Materials capable of doping and undoping the lithium include Si, SiO x (0 ⁇ x ⁇ 2), Si—Y alloys (Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, It is an element selected from the group consisting of rare earth elements and combinations thereof, but not Si), Sn, SnO 2 , Sn—Y (Y is an alkali metal, an alkaline earth metal, a group 13 element, a group 14 element, a transition metal, and a rare earth element). It is an element selected from the group consisting of elements and combinations thereof, but not Sn), and the like, and at least one of these and SiO 2 may be mixed and used.
- the element Y is Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ge, P, As, Sb, Bi, S, Se, It may be selected from the group consisting of Te, Po, and combinations thereof.
- transition metal oxide examples include lithium-containing titanium composite oxide (LTO), vanadium oxide, and lithium vanadium oxide.
- the additive according to the present invention is particularly effective when Si or SiO x (0 ⁇ x ⁇ 2) is used as an anode active material. Specifically, when a Si-based negative electrode active material is used, if a solid SEI layer is not formed on the surface of the negative electrode during initial activation, degradation of life characteristics is promoted due to extreme volume expansion-shrinkage during cycles. However, since the additive according to the present invention can form an elastic and strong SEI layer, it can improve lifespan and storage characteristics of a secondary battery using a Si-based negative electrode active material.
- the negative electrode active material may be included in an amount of 60 to 99% by weight, preferably 70 to 99% by weight, and more preferably 80 to 98% by weight, based on the total weight of solids in the negative electrode mixture slurry.
- binder examples include polyvinylidene fluoride (PVDF), polyvinyl alcohol, starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomers, sulfonated ethylene-propylene-diene monomers, styrene-butadiene rubber, fluororubber, various copolymers thereof, and the like.
- PVDF polyvinylidene fluoride
- SBR styrene-butadiene rubber
- CMC carboxymethyl cellulose
- the binder may be included in an amount of 1 to 20% by weight, preferably 1 to 15% by weight, more preferably 1 to 10% by weight, based on the total weight of the solids excluding the solvent in the negative electrode mixture slurry.
- the conductive material is a component for further improving the conductivity of the negative electrode active material, and may be added in an amount of 1 to 20% by weight based on the total weight of the solid content in the negative electrode mixture slurry.
- the conductive material is not particularly limited as long as it has conductivity without causing chemical change to the battery. For example, carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black.
- carbon powder such as natural graphite, artificial graphite, or graphite having a highly developed crystal structure
- conductive fibers such as carbon fibers and metal fibers
- Fluorinated carbon powder such as aluminum powder and nickel powder
- conductive whiskers such as zinc oxide and potassium titanate
- conductive metal oxides such as titanium oxide
- Conductive materials such as polyphenylene derivatives may be used.
- the conductive material may be included in an amount of 1 to 20% by weight, preferably 1 to 15% by weight, more preferably 1 to 10% by weight, based on the total weight of solids excluding the solvent in the negative electrode mixture slurry.
- the solvent may include water or an organic solvent such as NMP (N-methyl-2-pyrrolidone), and may be used in an amount that provides a desired viscosity when including the negative electrode active material, and optionally a binder and a conductive material.
- NMP N-methyl-2-pyrrolidone
- the concentration of the solid content including the negative electrode active material and, optionally, the binder and the conductive material may be 50 wt% to 95 wt%, preferably 70 wt% to 90 wt%.
- a metal itself in the case of using a metal itself as the cathode, it may be manufactured by physically bonding, rolling, or depositing a metal on the metal thin film itself or the anode current collector.
- a metal As the deposition method, an electrical deposition method or a chemical vapor deposition method may be used for the metal.
- the metal thin film itself or the metal bonded/rolled/deposited on the anode current collector is a group consisting of lithium (Li), nickel (Ni), tin (Sn), copper (Cu), and indium (In). It may include an alloy of one type of metal or two types of metals selected from.
- porous polymer films such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer, etc.
- a porous polymer film made of the same polyolefin-based polymer may be used alone or by laminating them, or a conventional porous nonwoven fabric, for example, a nonwoven fabric made of high melting point glass fiber or polyethylene terephthalate fiber may be used. It is not limited.
- a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be selectively used in a single-layer or multi-layer structure.
- the separator included in the electrode assembly of the present invention may be a safety reinforced separator (SRS) separator having a coating layer containing a ceramic component or a polymer material to secure heat resistance or mechanical strength.
- SRS safety reinforced separator
- the separators included in the electrode assembly of the present invention include a porous separator substrate and a porous coating layer entirely coated on one or both surfaces of the separator substrate, and the coating layer includes metal oxides, metalloid oxides, metal fluorides, It may include a mixture of inorganic particles selected from metal hydroxide and combinations thereof and a binder polymer that connects and fixes the inorganic particles to each other.
- the coating layer is inorganic particles of Al 2 O 3 , SiO 2 , TiO 2 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , SrTiO 3 , BaTiO 3 , Mg(OH) 2 , And may include one or more selected from MgF.
- the inorganic particles can improve the thermal stability of the separation membrane. That is, the inorganic particles can prevent the separator from shrinking at high temperatures.
- the binder polymer can improve the mechanical stability of the separator by fixing the inorganic particles.
- the appearance of the lithium secondary battery of the present invention is not particularly limited, but may be a cylindrical shape using a can, a prismatic shape, a pouch shape, or a coin shape.
- PVA-CN (3 g, 0.01925 mol) and 87.5 ml of dimethylformamide were added to a 250 ml round flask and stirred. After adding perfluorobutanoic acid (3,3 g, 0.0288 mol) and dicyclohexylcarbodiimide (5.94 g, 0.0288 mol) to the mixed solution, the round flask was immersed in ice water. After dissolving 4-dimethylaminopyridine (0.15 g, 0.0012 mol) in 12 ml of dimethylformamide, it was slowly added to a round flask. After 10 minutes, the ice water was removed and reacted at room temperature for 67 hours.
- the obtained polymer was a substance represented by formula (2a).
- a non-aqueous electrolyte was prepared by adding 0.1 g and 0.1 g of a polymer of Formula 2a below.
- Cathode active material LiNi 0.85 Co 0.05 Mn 0.08 Al 0.02 O 2 : conductive material (carbon nanotube): binder (polyvinylidene fluoride) in a weight ratio of 97.74:0.7:1.56, N-methyl-2-pyrrolidone as a solvent (NMP) to prepare a positive electrode slurry (solid content: 75.5% by weight).
- the positive electrode slurry was coated on one surface of a positive electrode current collector (Al thin film) having a thickness of 15 ⁇ m, and dried and roll pressed to prepare a positive electrode.
- Anode active material (silicon; Si): conductive material (carbon black): binder (styrene-butadiene rubber (SBR)-carboxymethyl cellulose (CMC)) at a weight ratio of 70:20.3:9.7, N-methyl-2- It was added to pyrrolidone (NMP) to prepare a negative electrode slurry (solid content: 26% by weight).
- NMP pyrrolidone
- the negative electrode slurry was coated on one surface of a negative electrode current collector (Cu thin film) having a thickness of 15 ⁇ m, and dried and roll pressed to prepare a negative electrode.
- a polyolefin-based porous separator coated with inorganic particles Al2O3 was interposed between the prepared positive electrode and the negative electrode, and then the prepared non-aqueous electrolyte was injected to prepare a secondary battery.
- a secondary battery was prepared in the same manner as in Example 1, except that 0.1 g of the compound of Formula 1a and 3 g of the polymer of Formula 2a were added to 96.9 g of the non-aqueous solvent prepared in Example 1 to prepare a non-aqueous electrolyte.
- a secondary battery was prepared in the same manner as in Example 1, except that 1.5 g of the compound of Formula 1a and 0.1 g of the polymer of Formula 2a were added to 98.4 g of the non-aqueous solvent prepared in Example 1 to prepare a non-aqueous electrolyte. .
- a secondary battery was prepared in the same manner as in Example 1, except that 0.5 g of the compound of Formula 1a and 2 g of the polymer of Formula 2a were added to 97.5 g of the non-aqueous solvent prepared in Example 1 to prepare a non-aqueous electrolyte.
- a secondary battery was prepared in the same manner as in Example 1, except that 1.5 g of the compound of Formula 1a and 3 g of the polymer of Formula 2a were added to 95.5 g of the non-aqueous solvent prepared in Example 1 to prepare a non-aqueous electrolyte.
- a non-aqueous electrolyte was prepared by adding 0.1 g and 0.1 g of a polymer of Formula 2b below.
- a secondary battery was manufactured in the same manner as in Example 1 except that the non-aqueous electrolyte was used.
- a non-aqueous electrolyte was prepared by adding 0.1 g and 0.1 g of a polymer of Formula 2c below.
- a secondary battery was manufactured in the same manner as in Example 1 except that the non-aqueous electrolyte was used.
- a secondary battery was manufactured in the same manner as in Example 1, except that a non-aqueous electrolyte was prepared using 100 g of the non-aqueous solvent prepared in Example 1.
- a secondary battery was prepared in the same manner as in Example 1, except that 1.5 g of the compound of Formula 1a was added to 98.5 g of the non-aqueous solvent prepared in Example 1 to prepare a non-aqueous electrolyte.
- a secondary battery was manufactured in the same manner as in Example 1, except that 3 g of the polymer of Chemical Formula 2a was added to 97 g of the non-aqueous solvent prepared in Example 1 to prepare a non-aqueous electrolyte.
- each of the batteries prepared in Examples 1 to 7 and Comparative Examples 1 to 3 was charged to 4.2V with a 1C constant current at 45° C., and discharged to 3.0V with a 0.5C constant current as one cycle, 250 cycles After charging and discharging, the capacity retention rate compared to the initial capacity after one cycle was measured. The results are shown in Table 1 below.
- the secondary batteries of Examples 1 to 7 and Comparative Examples 1 to 3 were fully charged to 4.2V, respectively, and stored at 60° C. for 8 weeks.
- the capacity of the fully charged secondary battery was measured and set to the capacity of the initial secondary battery.
- the capacity of the preserved secondary battery was measured to calculate the capacity decreased during the storage period of 8 weeks.
- the capacity retention rate after one week was derived by calculating the percent ratio of the reduced capacity to the capacity of the initial secondary battery. The results are shown in Table 2 below.
- Examples 1 to 7 using a combination of the first additive and the second additive are Comparative Example 1 without using the additive, Comparative Example 2 using only the first additive, and Comparative Example using only the second additive. Compared to the secondary battery of Example 3, the capacity retention rate after 8 weeks was high, and stable performance at high temperatures was confirmed.
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Abstract
Description
용량 유지율 (%) | |
실시예 1 | 82.5 |
실시예 2 | 83.4 |
실시예 3 | 83.8 |
실시예 4 | 84.5 |
실시예 5 | 85.7 |
실시예 6 | 83.6 |
실시예 7 | 84.0 |
비교예 1 | 77.4 |
비교예 2 | 79.6 |
비교예 3 | 81.2 |
용량 유지율 (%) | |
실시예 1 | 91.6 |
실시예 2 | 92.7 |
실시예 3 | 93.5 |
실시예 4 | 95.8 |
실시예 5 | 96.5 |
실시예 6 | 92.1 |
실시예 7 | 92.9 |
비교예 1 | 45.4 |
비교예 2 | 88.6 |
비교예 3 | 90.3 |
Claims (15)
- 리튬염;유기용매;제1첨가제로서 하기 화학식 1로 표시되는 화합물; 및제2첨가제로서 하기 화학식 2-1, 화학식 2-2 및 화학식 2-3으로 표시되는 반복단위를 포함하는 폴리머를 포함하는 비수 전해질:[화학식 1]상기 화학식 1에서,R은 치환 또는 비치환된 탄소수 1 내지 3의 알킬렌기이고,R1 내지 R3는 각각 독립적으로 H, 탄소수 1 내지 3의 알킬기 또는 니트릴기이며,[화학식 2-1]상기 화학식 2-1에서,R4 는 H, 탄소수 1 내지 10의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 2 내지 20의 알키닐기, 탄소수 1 내지 20의 알콕시기, 탄소수 3 내지 12의 사이클로알킬기, 탄소수 3 내지 12의 사이클로알케닐기, 탄소수 6 내지 12의 아릴기, 할로겐 원자 및 니트릴기로 이루어지는 군으로부터 선택된 어느 하나이고,[화학식 2-2]상기 화학식 2-2 에서,Ra 는 니트릴기가 하나 이상 치환된 탄소수 1 내지 10 의 알킬기이며,R5 는 H, 탄소수 1 내지 10의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 2 내지 20의 알키닐기, 탄소수 1 내지 20의 알콕시기, 탄소수 3 내지 12의 사이클로알킬기, 탄소수 3 내지 12의 사이클로알케닐기, 탄소수 6 내지 12의 아릴기, 할로겐 원자 및 니트릴기로 이루어지는 군으로부터 선택된 어느 하나이고,[화학식 2-3]상기 화학식 2-3 에서,Rb 는 탄소수 1 내지 10 의 플루오로알킬기이며,R6 은 H, 탄소수 1 내지 10의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 2 내지 20의 알키닐기, 탄소수 1 내지 20의 알콕시기, 탄소수 3 내지 12의 사이클로알킬기, 탄소수 3 내지 12의 사이클로알케닐기, 탄소수 6 내지 12의 아릴기, 할로겐 원자 및 니트릴기로 이루어지는 군으로부터 선택된 어느 하나임.
- 청구항 1에 있어서,상기 제2첨가제로서 하기 화학식 2 의 폴리머를 포함하는 것인 비수 전해질:[화학식 2]상기 화학식 2에서,R4 내지 R6 는 각각 독립적으로 H, 탄소수 1 내지 10의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 2 내지 20의 알키닐기, 탄소수 1 내지 20의 알콕시기, 탄소수 3 내지 12의 사이클로알킬기, 탄소수 3 내지 12의 사이클로알케닐기, 탄소수 6 내지 12의 아릴기, 할로겐 원자 및 니트릴기로 이루어지는 군으로부터 선택된 어느 하나이고,Ra 는 니트릴기가 하나 이상 치환된 탄소수 1 내지 10 의 알킬기이며,Rb 는 탄소수 1 내지 10 의 플루오로알킬기이며,p, q 및 r은 각각 독립적으로 1 내지 100의 정수임.
- 청구항 1에 있어서,상기 화학식 2-2에서 Ra 는 CH2CN 또는 CH2CH2CN 인 비수 전해질.
- 청구항 1에 있어서,상기 화학식 2-3에서 Rb는 탄소수 1 내지 5 의 퍼플루오로알킬기인 비수 전해질.
- 청구항 1에 있어서,상기 제1첨가제는 비수 전해질 100 중량부에 대하여 0.01 중량부 내지 2 중량부의 함량으로 포함되는 것인 비수 전해질.
- 청구항 1에 있어서,상기 제2첨가제는 비수 전해질 100 중량부에 대하여 0.01 중량부 내지 10 중량부의 함량으로 포함되는 것인 비수 전해질.
- 청구항 1에 있어서,상기 제1첨가제 및 제2첨가제는 1 : 0.01 내지 1 : 40의 중량비로 포함되는 것인 비수 전해질.
- 청구항 1에 있어서,상기 리튬염은 LiCl, LiBr, LiI, LiBF4, LiClO4, LiB10Cl10, LiAlCl4, LiAlO2, LiPF6, LiCF3SO3, LiCH3CO2, LiCF3CO2, LiAsF6, LiSbF6, LiCH3SO3, LiN(SO2F)2, LiN(SO2CF2CF3)2 및 LiN(SO2CF3)2로 이루어진 군으로부터 선택된 하나 이상인 것인 비수 전해질.
- 청구항 1에 있어서,상기 리튬염은 0.5 M 내지 5.0 M의 농도로 포함되는 것인 비수 전해질.
- 청구항 1에 있어서,상기 유기용매는 환형 카보네이트계 유기용매, 선형 카보네이트계 유기용매, 선형 에스테르계 유기용매 및 환형 에스테르계 유기용매로 이루어진 군으로부터 선택된 적어도 하나 이상의 유기용매를 포함하는 비수 전해질.
- 청구항 1에 있어서,상기 유기 용매는 환형 카보네이트계 유기용매를 포함하는 비수 전해질.
- 청구항 12에 있어서,상기 환형 카보네이트계 유기용매는 플루오로 에틸렌 카보네이트(FEC)인 비수 전해질.
- 양극;음극; 및청구항 1의 비수 전해질을 포함하는 리튬 이차전지.
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