WO2010011110A2 - 공융혼합물을 포함하는 전해질 및 이를 구비한 전기화학소자 - Google Patents
공융혼합물을 포함하는 전해질 및 이를 구비한 전기화학소자 Download PDFInfo
- Publication number
- WO2010011110A2 WO2010011110A2 PCT/KR2009/004146 KR2009004146W WO2010011110A2 WO 2010011110 A2 WO2010011110 A2 WO 2010011110A2 KR 2009004146 W KR2009004146 W KR 2009004146W WO 2010011110 A2 WO2010011110 A2 WO 2010011110A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrolyte
- methyl
- carbonate
- methoxyethyl
- group
- Prior art date
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 109
- 239000000374 eutectic mixture Substances 0.000 title claims abstract description 55
- -1 amide compound Chemical class 0.000 claims abstract description 49
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims abstract description 28
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 24
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 239000005518 polymer electrolyte Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000003282 alkyl amino group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 4
- FYRSBLKIFWXJSA-UHFFFAOYSA-N 3-(2-methoxyethyl)-1,3-oxazolidin-2-one Chemical compound COCCN1CCOC1=O FYRSBLKIFWXJSA-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 4
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- QAQJKDRAJZWQCM-UHFFFAOYSA-N 2-methoxyethyl carbamate Chemical compound COCCOC(N)=O QAQJKDRAJZWQCM-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 108010000020 Platelet Factor 3 Proteins 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- FVALQWWEQUWPEA-UHFFFAOYSA-N 1-(2-methoxyethyl)azepan-2-one Chemical compound COCCN1CCCCCC1=O FVALQWWEQUWPEA-UHFFFAOYSA-N 0.000 claims description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 claims description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 claims description 2
- WQBZJYMVYGBAEL-UHFFFAOYSA-N methoxymethyl carbamate Chemical compound COCOC(N)=O WQBZJYMVYGBAEL-UHFFFAOYSA-N 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 28
- 239000000243 solution Substances 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 8
- 229910013870 LiPF 6 Inorganic materials 0.000 description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 3
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 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 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- NRKYWOKHZRQRJR-UHFFFAOYSA-N 2,2,2-trifluoroacetamide Chemical compound NC(=O)C(F)(F)F NRKYWOKHZRQRJR-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
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- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
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- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
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- 230000000593 degrading effect Effects 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
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- 125000006850 spacer group Chemical group 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- 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
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- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to an electrolyte comprising an eutectic mixture and an electrochemical device having the same.
- Electrochemical devices such as lithium secondary batteries, electrolytic condensers, electric double layer capacitors, electrochromic display devices, and dye-sensitized solar cells, which are being researched for practical use in the future, are widely used in recent years.
- electrolytes are used in the back, and the importance thereof is increasing day by day.
- a lithium secondary battery includes an anode made of a carbon material or a lithium metal alloy, a cathode made of a lithium metal oxide, and an electrolyte in which lithium salt is dissolved in an organic solvent.
- Lithium metal oxides have structural safety and capacity determined by the insertion and desorption reaction of lithium ions. Their capacity increases as the charging potential increases, but the lithium metal oxide becomes structurally unstable. This instability of the electrode structure leads to the generation of oxygen, which not only causes overheating in the battery, but also may explode by reacting with the electrolyte.
- Organic solvents widely used in electrolytes of lithium secondary batteries are ethylene carbonate, propylene carbonate, dimethoxy ethane, ⁇ -butyrolactone (GBL), and N, N-dimethyl. Dimethyl formamide, tetrahydrofurane or acetonitrile. Since these organic solvents generally have high volatility and flammability, lithium secondary batteries employing the organic solvents have problems of stability, particularly high temperature safety.
- Korean Patent Registration Publication No. 10-751203, Korean Patent Publication No. 10-2007-85575, etc. include acetamide, urea, methylurea, caprolactam, valerictam, trifluoroacetamide, carbamate, and formamide as electrolytes. And the like, and a eutectic mixture of an amide compound represented by a predetermined formula and a lithium salt is disclosed. Since the eutectic mixture exhibits high thermal and chemical stability in addition to a relatively wide electrochemical window, problems such as evaporation and ignition of the electrolyte according to conventional organic solvents are solved.
- an object of the present invention is to provide an electrolyte and an electrochemical device having the same showing high thermal and chemical stability.
- the other object of the present invention in addition to the above-mentioned object, in particular exhibits a lower limit of the low electrochemical window with higher high temperature stability, an electrolyte exhibiting sufficiently low viscosity and high ionic conductivity and an electric with the same To provide a chemical device.
- the electrolyte of the present invention comprises (a) an eutectic mixture of an alkoxy alkyl group-containing amide compound represented by the following formula (1) or (2) and an ionizable lithium salt; And (b) a carbonate compound.
- R, R 1 and R 2 are each independently selected from hydrogen, halogen and alkyl group having 1 to 20 carbon atoms, alkylamine group, alkenyl group and aryl group, at least one of R 1 and R 2 is CH
- X is any one selected from the group consisting of silicon, oxygen, nitrogen, phosphorus, sulfur and hydrogen, i) m is 0 if X is hydrogen, ii) m is 1 if X is oxygen or sulfur, and M is 2 if nitrogen or phosphorus; i) m is 3 if X is silicon.
- R is any one selected from the group consisting of hydrogen, alkyl groups having 1 to 20 carbon atoms, alkylamine groups, alkenyl groups, aryl groups and allyl groups, and R 1 is represented by CH 3- (CH 2 ) pO (CH 2 ) q As the alkoxy alkyl group to be, p is an integer of 0 to 8, q is an integer of 1 to 8,
- X is any one selected from the group consisting of silicon, oxygen, nitrogen, phosphorus and sulfur, i) m is 0 if X is oxygen or sulfur, ii) m is 1 if X is nitrogen or phosphorus, iii) X is If silicon, m is 2.
- n is an integer from 1 to 10.
- the alkoxy alkyl group-containing amide compound is N-methoxyethyl methyl carbamate, N-methoxyethyl-N-methyl methyl carbamate, N-methoxymethyl-N-methyl methyl carbamate, N , N-dimethyl methoxyethyl carbamate, N-methyl-methoxymethyl methoxyethyl carbamate, N-methyl-N-methoxyethyl methoxyethyl carbamate, N-methyl-N-methoxyethyl methoxymethyl Carbamate, N-methoxyethylcaprolactam, N-methoxyethyl oxazolidinone, N-methoxyethyl-N-methyl phenylthiocarbamate, N-methoxyethyl-N-methyl piperidine carbamate, and the like. Can be mentioned.
- the anion is F -, Cl -, Br - , I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 - , (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 -, ( CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5 ) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -, SCN -, (CF 3 CF 2 SO 2) 2 N - and the like can
- the reduction potential window of the eutectic mixture of the alkoxy alkyl group-containing amide compound represented by the formula (1) and the ionizable lithium salt is 0.4 to 0.55 V, and is ionizable with the alkoxy alkyl group-containing amide compound represented by the formula (2).
- the reduction potential window of the eutectic mixture of lithium salt is preferably 0.7 to 0.9V.
- the carbonate compound may be a carbonate compound commonly used as an organic solvent of the electrolyte.
- linear carbonate and cyclic carbonate may be used alone or in combination thereof.
- the viscosity of the electrolyte is preferably 4 to 30 cP or less.
- the electrolyte of the present invention may be a liquid electrolyte, and may be a polymer electrolyte such as a solid phase or a gel phase of the polymer itself, and the polymer electrolyte may include a monomer capable of forming a polymer by the eutectic mixture and a polymerization reaction.
- the polymer electrolyte may be a gel-like polymer electrolyte formed by polymerization of a precursor solution containing it, or a form in which the eutectic mixture is impregnated into a polymer.
- the electrolyte of the present invention described above may be usefully applied to an electrochemical device such as a lithium secondary battery.
- the electrolyte according to the present invention has the following effects.
- the novel eutectic mixture contained in the electrolyte of the present invention exhibits inherent properties of the eutectic mixture such as excellent thermal stability and chemical stability, and thus, problems such as evaporation, ignition and side reaction of the electrolyte are greatly improved.
- the electrolyte of the present invention can exhibit a lower limit value of the electrochemical window, that is, a low reduction potential window, it can be usefully applied as an electrolyte of an electrochemical device requiring various electrochemical properties.
- the electrochemical device having the same exhibits good charge and discharge performance.
- FIG. 1 is a schematic cross-sectional view of a coin-type secondary battery
- FIG. 2 is a graph measuring charge and discharge efficiency of secondary batteries according to Example 7 and Comparative Example 4.
- FIG. 2 is a graph measuring charge and discharge efficiency of secondary batteries according to Example 7 and Comparative Example 4.
- FIG. 3 is a graph illustrating differential scanning calorimetry (DSC) analysis results of a charged LiCoO 2 electrode and an electrolyte in a lithium secondary battery of Example 7.
- DSC differential scanning calorimetry
- DSC differential scanning calorimetry
- the electrolyte is an electrolyte (a) an eutectic mixture of an alkoxy alkyl group-containing amide compound represented by Formula 1 or Formula 2 and an ionizable lithium salt; And (b) a carbonate compound.
- R, R 1 and R 2 are each independently selected from hydrogen, halogen and alkyl group having 1 to 20 carbon atoms, alkylamine group, alkenyl group and aryl group, at least one of R 1 and R 2 is CH
- X is any one selected from the group consisting of silicon, oxygen, nitrogen, phosphorus, sulfur and hydrogen, i) m is 0 if X is hydrogen, ii) m is 1 if X is oxygen or sulfur, and M is 2 if nitrogen or phosphorus; i) m is 3 if X is silicon.
- R is any one selected from the group consisting of hydrogen, alkyl groups having 1 to 20 carbon atoms, alkylamine groups, alkenyl groups, aryl groups and allyl groups, and R 1 is represented by CH 3- (CH 2 ) pO (CH 2 ) q As the alkoxy alkyl group to be, p is an integer of 0 to 8, q is an integer of 1 to 8,
- X is any one selected from the group consisting of silicon, oxygen, nitrogen, phosphorus and sulfur, i) m is 0 if X is oxygen or sulfur, ii) m is 1 if X is nitrogen or phosphorus, iii) X is If silicon, m is 2.
- n is an integer from 1 to 10.
- Electrochemical devices have high heat generation and are frequently exposed to high temperatures, so stability at high temperatures is a very important factor.
- the present inventors formed an eutectic mixture with a lithium salt using an alkoxy alkyl group-containing amide compound having the above-described structure.
- the eutectic mixture has a high thermal and chemical characteristic unique to the eutectic mixture. It shows stability, which shows higher temperature stability than the eutectic mixture of amide-based compounds such as acetamide, methyl carbamate, and lithium salts as disclosed in the prior art.
- the eutectic mixture of the alkoxy alkyl group-containing amide compound and the lithium salt of the present invention may exhibit a low lower limit of the electrochemical window (also called a potential window).
- the reduction potential window of the eutectic mixture of the alkoxy alkyl group-containing amide compound represented by the formula (1) and the ionizable lithium salt is 0.4 to 0.55 V
- the eutectic of the alkoxy alkyl group-containing amide compound represented by the formula (2) and the ionizable lithium salt The reduction potential window of the mixture is preferably 0.7 to 0.9V.
- the electrolyte including the eutectic mixture of the alkoxy alkyl group-containing amide compound and the lithium salt not only contributes to improving the high temperature stability of the secondary battery, but may be usefully applied as an electrolyte of a secondary battery to which various negative electrode materials are applied.
- the alkoxy alkyl group-containing amide compound constituting the eutectic mixture is N-methoxyethyl methyl carbamate, N-methoxyethyl-N-methyl methyl carbamate, N-methoxymethyl-N-methyl Methyl carbamate, N, N-dimethyl methoxyethyl carbamate, N-methyl-methoxymethyl methoxyethyl carbamate, N-methyl-N-methoxyethyl methoxyethyl carbamate, N-methyl-N-meth Methoxyethyl methoxymethyl carbamate, N-methoxyethyl caprolactam, N-methoxyethyl oxazolidinone, N-methoxyethyl-N-methyl phenylthiocarbamate, N-methoxyethyl-N-methyl piperi Din carbamate etc. are mentioned.
- the lithium salt constituting the eutectic mixture together with the alkoxy alkyl group-containing amide compound described above can be represented by Li + X - as an ionizable lithium salt.
- this lithium salt anion is not particularly limited, F -, Cl -, Br -, I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, (CF 3 ) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2 ) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C - , (CF 3 SO 2) 3 C -
- the melting temperature of the eutectic mixture contained in the electrolyte according to the present invention may vary according to the formula (I) or (II) of R, R 1, R 2, X, a melting temperature is liquid at below 25 °C, namely room temperature (25 °C) It is preferable to exist as.
- the electrolyte of the present invention contains a carbonate-based compound.
- ionic conductivity is generally determined by the mobility of ions moving in the electrolyte solution
- the factors affecting the ionic conductivity are the viscosity of the electrolyte solution and the ion concentration in the solution.
- the lower the viscosity of the solution the more free the movement of ions in the solution and the higher the ionic conductivity.
- the higher the concentration of ions in the solution the more the amount of ions, the charge transporter, increases the ionic conductivity.
- the carbonate compound is mixed with the eutectic mixture, thereby lowering the viscosity of the electrolyte to improve ionic conductivity.
- the preferred viscosity of the electrolyte according to the present invention is 50 cP or less, and more preferably 4 to 30 cP in consideration of the ionic conductivity and thermal stability of the electrolyte.
- the preferred ionic conductivity of the electrolyte is 5 to 10 mS / cm.
- the carbonate-based compound is preferably mixed in an amount of 5 to 200 parts by weight based on 100 parts by weight of the eutectic mixture.
- the carbonate compound included in the electrolyte of the present invention may be used as long as it is a carbonate compound commonly used in the nonaqueous electrolyte of a lithium secondary battery.
- the linear carbonate compound and the cyclic carbonate compound may be used alone or in combination thereof.
- Non-limiting examples of such carbonate compounds include propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), butylene carbonate, methylpropyl carbonate, Ethylpropyl carbonate, dimethyl sulfoxide, acetonitrile, dimethoxyethane, diethoxyethane, tetrahydrofuran, N-methyl-2-pyrrolidone (NMP), ethylmethyl carbonate (EMC), gamma butyrolactone, and the like.
- PC propylene carbonate
- EC ethylene carbonate
- DEC diethyl carbonate
- DMC dimethyl carbonate
- DPC dipropyl carbonate
- butylene carbonate methylpropyl carbonate
- Ethylpropyl carbonate dimethyl sulfoxide
- NMP N-methyl-2-pyrrolidone
- EMC eth
- the electrolyte according to the present invention can be prepared according to a conventional method known in the art, for example, the above-described alkoxy alkyl group-containing amide compound and a lithium salt are mixed at room temperature, and then a carbonate-based compound is added or an amide group-containing compound , A carbonate-based compound and a lithium salt may be prepared by mixing at room temperature, adding a suitable temperature of 70 ° C. or lower, and then reacting to purify. At this time, the molar ratio of the alkoxy alkyl group-containing amide compound and the lithium salt of the eutectic mixture contained in the electrolyte is preferably 1 to 8: 1, more preferably 2 to 6: 1, in consideration of the ionic conductivity and viscosity.
- electrolyte of the present invention may further include various kinds of additives or organic solvents without departing from the object of the present invention.
- the electrolyte may be used as a liquid electrolyte or a polymer electrolyte such as a solid or gel phase of the polymer itself.
- the electrolyte of the present invention is a polymer electrolyte
- a precursor solution containing a mixture of a eutectic mixture and a carbonate compound and a monomer at the same time is polymerized to a gel polymer electrolyte, or a mixture of the eutectic mixture and a carbonate compound is a solid phase or It may be made of a polymer electrolyte in a form impregnated with a polymer such as gel.
- the gel polymer electrolyte according to one aspect of the present invention is prepared by polymerizing (i) a mixture of the eutectic mixture of (a) and the carbonate compound of (b) and a precursor solution simultaneously adding (ii) a monomer. Can be formed.
- all kinds of monomers capable of forming a gel polymer together with a mixture of a eutectic mixture and a carbonate-based compound are applicable, and non-limiting examples thereof include vinyl monomers.
- Vinyl monomers have the advantage of very simple polymerization when mixed with a mixture of eutectic mixtures and carbonate-based compounds to form gel polymers.
- Non-limiting examples of vinyl monomers that can be used include acrylonitrile, methyl methacrylate, methyl acrylate, methacrylonitrile, methyl styrene, vinyl esters, vinyl chloride, vinylidene chloride, acrylamide, tetrafluoroethylene , Vinyl acetate, vinyl chloride, methyl vinyl ketone, ethylene, styrene, paramethoxy styrene, paracyano styrene, and the like, each of which may be used alone or in combination of two or more thereof.
- the precursor solution may additionally include conventional polymerization initiators or photoinitiators, initiators are decomposed by heat or ultraviolet light to form radicals and react with monomers by free radical polymerization to form gel polymer electrolytes. do. Moreover, superposition
- free radical polymerization is a reaction of initiation where active molecules or active points are formed, a growth reaction in which monomers are added at the end of an active chain to form an active point at the end of a chain, and a chain transfer reaction that moves an active point to other molecules. In addition, the reaction chain undergoes a stop reaction in which the active chain center is destroyed.
- thermal initiators include organic peroxides such as Benzoyl peroxide, Acetyl peroxide, Dilauryl peroxide, Di-tert-butyl peroxide, Cumyl hydroperoxide, and Hydrogen peroxide, and hydroperoxides, 2,2-Azobis (2).
- azo compounds such as -cyanobutane), 2,2-Azobis (Methylbutyronitrile), AIBN (Azobis (iso-butyronitrile), AMVN (Azobisdimethyl-Valeronitrile), and organic metals such as silver alkylated compounds.
- Non-limiting examples of photoinitiators formed by radicals include Chloroacetophenone, Diethoxy Acetophenone (DEAP), 1-phenyl-2-hydroxy-2-methyl propaneone (HMPP), 1-Hydroxy cyclrohexyl phenyl ketone, ⁇ -Amino Acetophenone, Benzoin Ether, Benzyl Dimethyl ketal, Benzophenone, Thioxanthone and 2-ethylAnthraquinone (2-ETAQ).
- the precursor solution of the gel polymer electrolyte according to the present invention may optionally contain other additives and the like known in the art.
- a polymer gel electrolyte There is to form a polymer gel electrolyte according to the conventional method known in the art using the above precursor solution, it is preferable to prepare the gel polymer electrolyte by In-Situ polymerization inside an electrochemical device. In-Situ polymerization reaction is possible by heat or ultraviolet irradiation.
- the content ratio of component (i) and component (ii) in the precursor solution can be controlled, for example, from 0.5 to 0.95: 0.05 to 0.5.
- the degree of polymerization of the gel polymer is about the polymerization time, polymerization temperature or light irradiation amount, which is a reaction factor. It can be adjusted according to, so that the polymer is not polymerized without leaking the electrolyte so that the volume does not shrink.
- a mixture of a eutectic mixture and a carbonate compound may be injected into a solid polymer or gel polymer already formed, so that the electrolyte may be prepared in the form of impregnating the polymer.
- Non-limiting examples of the polymers that can be used include polymethyl methacrylate, polyvinylidene difluoride, polyvinyl chloride, polyethylene oxide, polyhydroxyethyl methacrylate, etc., alone or in combination of two or more thereof. have. This method can simplify the manufacturing process compared to the In-Situ method described above.
- a method of forming a polymer electrolyte by dissolving a mixture of a eutectic mixture and a carbonate compound and a polymer in a solvent and then removing the solvent may be used. At this time, the electrolyte is in the form contained in the polymer matrix.
- the solvent that can be used is not particularly limited, and non-limiting examples thereof include toluene, acetone, acetonitrile, THF, and the like.
- the solvent removal method is not particularly limited, and conventional methods such as applying heat may be used.
- the electrolyte of the present invention described above may be usefully applied to an electrochemical device such as a lithium secondary battery.
- the lithium secondary battery to which the electrolyte of the present invention is applied has good thermal stability. Therefore, even after charging the pouch type secondary battery to which the electrolyte of the present invention is applied to 4.2 V and then left at 90 ° C. for 4 hours, the thickness change rate may be 10% or less.
- the electrolyte of the present invention is significantly improved in viscosity and ionic conductivity than the electrolyte of the conventional eutectic mixture.
- the potential window was measured for the eutectic mixture of Example 4 and the eutectic mixture of Comparative Example 3, which contain the amide compound corresponding to Formula 2, and the results are shown in Table 3 below. Referring to the results of Table 3, it can be seen that the reduction potential window (lower limit value of the potential window) of the eutectic mixture of Example 4 composed of an amide compound containing an alkoxy alkyl group was lower than that of the comparative examples, so that the reduction stability was improved. have.
- LiCoO 2 as a positive electrode active material artificial graphite as a conductive material, polyvinylidene fluoride as a binder was mixed in a weight ratio of 94: 3: 3, and N-methylpyrrolidone was added to the resulting mixture to prepare a slurry.
- the prepared slurry was applied to aluminum foil, and dried at 130 ° C. for 2 hours to prepare a positive electrode.
- a negative electrode active material, artificial graphite, a conductive material, and a binder were mixed in a weight ratio of 94: 3: 3, and N-methylpyrrolidone was added to prepare a slurry.
- the prepared slurry was applied to a copper foil and dried at 130 ° C. for 2 hours to prepare a negative electrode.
- a positive electrode and a negative electrode prepared as described above were prepared in 1 cm 2 , and a separator was interposed therebetween. Injecting the electrolyte prepared in Example 1 here to complete the secondary battery as shown in FIG.
- reference numeral 1 denotes an anode, 2 a cathode, 3 a separator and an electrolyte, 4 a spacer, 5 a coin can container, 6 a coin can lid, and 7 a sealing rubber.
- a secondary battery was manufactured by injecting 2.3 g of the electrolyte prepared in Example 1 into a commercial pouch-type battery having a separator interposed between the cathode and the anode manufactured as described above.
- a secondary battery was manufactured in the same manner as in Example 7, except that 4.2 g of ethylene carbonate and 6.3 g of ethyl methyl carbonate were mixed as an electrolyte, and then an electrolyte solution prepared by dissolving 1.5 g of LiPF6 was used.
- a secondary battery was manufactured in the same manner as in Example 8, except that the electrolyte of Comparative Example 1 was used instead of the electrolyte of Example 1.
- the secondary batteries manufactured according to the above method were charged and discharged at 0.5 mA, respectively, and the discharge capacity and the charge and discharge efficiency according to the cycles were measured.
- the battery of Comparative Example 4 using an electrolyte containing a conventional carbonate solvent and the battery of Example 7 using an electrolyte of the present invention had a discharge capacity of 90% or more after the thirtieth cycle, as shown in FIG. It showed a charge-discharge efficiency of 99%.
- the solid line represents Example 7 and the dotted line represents Comparative Example 4.
- Example 7 and Comparative Example 4 After charging the batteries of Example 7 and Comparative Example 4 to 4.2V at 23 °C, the battery was disassembled to collect a positive electrode. Then, the thermal safety of the positive electrode and the electrolyte was evaluated using differential scanning calorimetry (DSC) on the collected positive electrode.
- DSC differential scanning calorimetry
- the battery of Example 7 has a peak at the highest calorific value starting at 249 ° C., whereas the battery of Comparative Example 4 having an electrolytic solution mixed with conventional EC and EMC has a lower temperature of 203 ° C. You can see that it starts from. Therefore, it was confirmed that the lithium secondary battery of Example 7 according to the present invention significantly inhibited side reactions between the electrode active material and the electrolyte, thereby improving thermal safety of the battery.
- Example 8 using the electrolyte of the present invention showed better high temperature stability than the battery of Comparative Example 5 using the conventional eutectic mixture as an electrolyte.
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Abstract
Description
점도(cP) | 이온 전도도(mS/cm) | |
실시예 1 | 7.4 | 7.1 |
실시예 2 | 10.2 | 5.6 |
실시예 3 | 9.2 | 5.9 |
실시예 4 | 15.6 | 5.1 |
실시예 5 | 11.3 | 6.2 |
실시예 6 | 13.1 | 5.5 |
비교예 1 | 62.0 | 1.7 |
비교예 2 | 100.0 | 1.1 |
실시예 1 | 실시예 2 | 실시예 3 | 비교예 1 | 비교예 2 | |
전위창(V) | 0.45~4.5 | 0.5~4.7 | 0.45~4.55 | 0.6~4.7 | 0.7~4.9 |
전위창 | |
실시예 4 | 0.8~4.7 |
비교예 3 | 1.1~4.8 |
실시예 7 | 비교예 4 | |||
Onset Temp(℃) | 220 | 249 | 203 | 241 |
Peak area(W/g) | 66 | 501 | 539 | 174 |
초기 두께(mm) | 후기 두께(mm) | 증가량(%) | |
실시예 8 | 3.85 | 3.92 | 1.8% |
비교예 5 | 3.86 | 4.53 | 17.3% |
Claims (21)
- (a) 하기 화학식 1 또는 하기 화학식 2로 표시되는 알콕시 알킬기 함유 아미드 화합물과 이온화 가능한 리튬염의 공융혼합물(eutectic mixture) 및(b) 카보네이트계 화합물을 포함하는 전해질.<화학식 1>상기 화학식 1에 있어서,R, R1 및 R2는 서로 독립적으로 수소, 할로겐 및 탄소수가 1 내지 20인 알킬기, 알킬아민기, 알케닐기 및 아릴기로 이루어진 군으로부터 선택된 어느 하나이되, R1과 R2 중 적어도 하나는 CH3-(CH2)p-O(CH2)q로 표시되는 알콕시 알킬기로서, p는 0 내지 8의 정수이고, q는 1 내지 8의 정수이고,X는 규소, 산소, 질소, 인, 황 및 수소로 이루어진 군으로부터 선택된 어느 하나로서, i) X가 수소이면 m은 0이고, ii) X가 산소 또는 황이면 m은 1이고, ⅲ) X가 질소 또는 인이면 m은 2이고, ⅳ) X가 규소이면 m은 3이다.<화학식 2>상기 화학식 2에 있어서,R은 수소, 탄소수가 1 내지 20인 알킬기, 알킬아민기, 알케닐기, 아릴기 및 알릴기로 이루어진 군으로부터 선택된 어느 하나이고, R1은 CH3-(CH2)p-O(CH2)q로 표시되는 알콕시 알킬기로서, p는 0 내지 8의 정수이고, q는 1 내지 8의 정수이고,X는 규소, 산소, 질소, 인 및 황으로 이루어진 군으로부터 선택된 어느 하나로서, i) X가 산소 또는 황이면 m은 0이고, ii) X가 질소 또는 인이면 m은 1이고, iii) X가 규소이면 m은 2이며,n은 1 내지 10의 정수이다.
- 제 1항에 있어서, 상기 알콕시 알킬기 함유 아미드 화합물은 N-메톡시에틸 메틸카바메이트, N-메톡시에틸-N-메틸 메틸카바메이트, N-메톡시메틸-N-메틸 메틸카바메이트, N,N-디메틸 메톡시에틸 카바메이트, N-메틸-메톡시메틸 메톡시에틸 카바메이트, N-메틸-N-메톡시에틸 메톡시에틸 카바메이트, N-메틸-N-메톡시에틸 메톡시메틸 카바메이트, N-메톡시에틸카프로락탐, N-메톡시에틸 옥사졸리디논, N-메톡시에틸-N-메틸 페닐티오카바메이트 및 N-메톡시에틸-N-메틸 피페리딘카바메이트로 이루어진 군으로부터 선택된 어느 하나인 것을 특징으로 하는 전해질.
- 제 1항에 있어서, 상기 리튬염의 음이온은 F-, Cl-, Br-, I-, NO3 -, N(CN)2 -, BF4 -, ClO4 -, PF6 -, (CF3)2PF4 -, (CF3)3PF3 -, (CF3)4PF2 -, (CF3)5PF-, (CF3)6P-, CF3SO3 -, CF3CF2SO3 -, (CF3SO2)2N-, (FSO2)2N-, CF3CF2(CF3)2CO-, (CF3SO2)2CH-, (SF5)3C-, (CF3SO2)3C-, CF3(CF2)7SO3 -, CF3CO2 -, CH3CO2 - , SCN- 및 (CF3CF2SO2)2N-로 이루어진 군으로부터 선택된 어느 하나인 것을 특징으로 하는 전해질.
- 제 1항에 있어서, 상기 공융혼합물은 상기 알콕시 알킬기 함유 아미드 화합물과 리튬염의 몰비가 1 내지 8 : 1인 것을 특징으로 하는 전해질.
- 제 1항에 있어서, 상기 화학식 1로 표시되는 알콕시 알킬기 함유 아미드 화합물과 이온화 가능한 리튬염의 공융혼합물의 환원전위창은 0.4 내지 0.55V이고, 상기 화학식 2로 표시되는 알콕시 알킬기 함유 아미드 화합물과 이온화 가능한 리튬염의 공융혼합물의 환원전위창은 0.7 내지 0.9V인 것을 특징으로 하는 전해질.
- 제 1항에 있어서, 상기 카보네이트계 화합물은 선형 카보네이트, 환형 카보네이트 및 이들의 혼합물로 이루어진 군으로부터 선택된 어느 하나인 것을 특징으로 하는 전해질.
- 제 6항에 있어서, 상기 카보네이트계 화합물은 프로필렌 카보네이트(PC), 에틸렌 카보네이트(EC), 디에틸카보네이트(DEC), 디메틸카보네이트(DMC), 디프로필카보네이트(DPC), 부티렌 카보네이트, 메틸프로필 카보네이트, 에틸프로필 카보네이트, 디메틸설폭사이드, 아세토니트릴, 디메톡시에탄, 디에톡시에탄, 테트라하이드로퓨란, N-메틸-2-피롤리돈(NMP), 에틸메틸카보네이트(EMC) 및 감마 부티로락톤으로 이루어진 군으로부터 선택된 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 전해질.
- 제 1항에 있어서, 상기 카보네이트계 화합물의 함량은 상기 공융혼합물 100 중량부를 기준으로 5 내지 200 중량부인 것을 특징으로 하는 전해질.
- 제 1항에 있어서, 점도가 50 cP 이하인 것을 특징으로 하는 전해질.
- 제 9항에 있어서, 점도가 4 내지 30 cP 이하인 것을 특징으로 하는 전해질.
- 제 1항에 있어서, 상기 전해질의 이온 전도도는 5 내지 10 mS/cm인 것을 특징으로 하는 전해질.
- 제 1항에 있어서, 상기 전해질은 폴리머 전해질인 것을 특징으로 하는 전해질.
- 제 12항에 있어서, 상기 폴리머 전해질은 (i) 상기 (a)의 공융혼합물과 (b)의 카보네이트계 화합물의 혼합물 및 (ii) 단량체(monomer)를 동시에 함유하는 전구체 용액을 중합하여 형성된 겔상의 폴리머 전해질인 것을 특징으로 하는 전해질.
- 제 13항에 있어서, 상기 단량체는 비닐 모노머인 것을 특징으로 하는 전해질.
- 제 14항에 있어서, 상기 비닐 모노머는 아크릴로니트릴, 메틸메타크릴레이트, 메틸아크릴레이트, 메타크릴로니트닐, 메틸스티렌, 비닐에스테르류, 염화비닐, 염화비닐리덴, 아크릴아마이드, 테트라플루오로에틸렌, 비닐아세테이트, 비닐크로라이드, 메틸비닐케톤, 에틸렌, 스티렌, 파라메톡시스티렌 및 파라시아노스티렌으로 이루어진 군으로부터 선택된 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 전해질.
- 제 13항에 있어서, 상기 겔상의 폴리머 전해질은 전기 화학 소자 내부에서 In-situ 중합하여 제조된 것을 특징으로 하는 전해질.
- 제 12항에 있어서, 상기 폴리머 전해질은 상기 (a)의 공융혼합물과 (b)의 카보네이트계 화합물의 혼합물이 폴리머에 함침된 폴리머 전해질인 것을 특징으로 하는 전해질.
- 제 17항에 있어서, 상기 폴리머는 폴리메틸메타크릴레이트, 폴리비닐리덴 디플루라이드, 폴리비닐 클로라이드, 폴리에틸렌 옥사이드 및 폴리하이드록시에틸메타크릴레이트로 이루어진 군으로부터 선택된 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 전해질.
- 양극, 음극 및 전해질을 포함하는 전기화학소자에 있어서,상기 전해질은 제1항의 전해질인 것을 특징으로 하는 전기화학소자.
- 제 19항에 있어서, 상기 전기화학소자는 리튬 이차전지인 것을 특징으로 하는 전기화학소자.
- 제 20항에 있어서, 상기 리튬 이차전지는 파우치형 이차전지이고, 상기 파우치형 이차전지를 4.2V까지충전한 다음 90℃에서 4시간 방치한 후의 두께 변화율이 10% 이하인 것을 특징으로 하는 전기화학소자.
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