KR100976959B1 - Electrolyte including eutectic mixture and electrochemical device having same - Google Patents
Electrolyte including eutectic mixture and electrochemical device having same Download PDFInfo
- Publication number
- KR100976959B1 KR100976959B1 KR1020080006869A KR20080006869A KR100976959B1 KR 100976959 B1 KR100976959 B1 KR 100976959B1 KR 1020080006869 A KR1020080006869 A KR 1020080006869A KR 20080006869 A KR20080006869 A KR 20080006869A KR 100976959 B1 KR100976959 B1 KR 100976959B1
- Authority
- KR
- South Korea
- Prior art keywords
- electrolyte
- group
- eutectic mixture
- polymer
- electrochemical device
- Prior art date
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- 239000000374 eutectic mixture Substances 0.000 title claims abstract description 70
- 239000003792 electrolyte Substances 0.000 title claims abstract description 68
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 26
- -1 amide compound Chemical class 0.000 claims abstract description 25
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 24
- 125000003277 amino group Chemical group 0.000 claims abstract description 14
- 239000005518 polymer electrolyte Substances 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011244 liquid electrolyte Substances 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 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
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 3
- 108010000020 Platelet Factor 3 Proteins 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 3
- 125000001425 triazolyl group Chemical group 0.000 claims description 3
- 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
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002338 polyhydroxyethylmethacrylate Polymers 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
- 229920002981 polyvinylidene fluoride 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
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- 241000501667 Etroplus Species 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 230000008020 evaporation Effects 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 27
- 229910001290 LiPF6 Inorganic materials 0.000 description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- JGOVRLXUZIFZNY-UHFFFAOYSA-N N1CCCC1.C(N)(OC)=O Chemical compound N1CCCC1.C(N)(OC)=O JGOVRLXUZIFZNY-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- CVMDTFQZMGWOST-UHFFFAOYSA-N C(N)(OC)=O.N1C=NC=C1 Chemical compound C(N)(OC)=O.N1C=NC=C1 CVMDTFQZMGWOST-UHFFFAOYSA-N 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- JIMIVFAAUJSQKI-UHFFFAOYSA-N C(N)(OC)=O.N1CCOCC1 Chemical compound C(N)(OC)=O.N1CCOCC1 JIMIVFAAUJSQKI-UHFFFAOYSA-N 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- YEOQADWSIVJWNU-UHFFFAOYSA-N methylcarbamic acid pyrrolidine Chemical compound CNC(=O)O.C1CCNC1 YEOQADWSIVJWNU-UHFFFAOYSA-N 0.000 description 4
- JTGQJFWCKVKMFA-UHFFFAOYSA-N 1H-imidazole methylcarbamic acid Chemical compound CNC(O)=O.N1C=NC=C1 JTGQJFWCKVKMFA-UHFFFAOYSA-N 0.000 description 3
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 description 3
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 102100026735 Coagulation factor VIII Human genes 0.000 description 3
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229920001427 mPEG Polymers 0.000 description 3
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 241000981595 Zoysia japonica Species 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
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 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
- 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
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- 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
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 206010015535 Euphoric mood Diseases 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 1
- 108010013381 Porins Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 230000002743 euphoric effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003211 polymerization photoinitiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 102000007739 porin activity proteins Human genes 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007790 solid phase Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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Abstract
본 발명은 (a) 특정 구조의 아민기가 고리로 묶여진 아미드 화합물; 및 (b) 이온화 가능한 리튬염으로 구성된 공융혼합물(eutectic mixture)을 포함하는 전해질 및 이를 구비한 전기화학소자를 개시한다.The present invention (a) an amide compound in which an amine group of a specific structure is bound with a ring; And (b) an electrolyte comprising an eutectic mixture composed of ionizable lithium salts and an electrochemical device having the same.
본 발명의 전해질에 포함된 공융혼합물은 우수한 열적 안정성과 화학적 안정성 등 공융혼합물의 고유 특성을 갖으므로, 전해질의 증발 및 인화에 따른 문제점이 개선된다. Since the eutectic mixture contained in the electrolyte of the present invention has inherent properties of the eutectic mixture such as excellent thermal stability and chemical stability, problems due to evaporation and ignition of the electrolyte are improved.
전기화학소자, 전해질, 공융혼합물, 아민기, 고리 Electrochemical device, electrolyte, eutectic mixture, amine group, ring
Description
본 발명은 공융혼합물(eutectic mixture)을 포함하는 전해질 및 이를 구비한 전기화학소자에 관한 것이다.The present invention relates to an electrolyte comprising an eutectic mixture and an electrochemical device having the same.
근래 많이 사용되고 있는 전기화학소자, 예컨대 리튬 이차전지, 전해 컨텐서(condenser), 전기 이중층 커패시터(capacitor), 전기변색(electrochromic) 표시소자, 장래 실용화를 위해 다양한 연구가 진행되고 있는 색소증감형 태양전지 등에는 다양한 종류의 전해질이 사용되고 있으며, 이들의 중요성이 날로 높아져 가고 있다.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. Various kinds of electrolytes are used in the back, and the importance thereof is increasing day by day.
현재 가장 널리 사용되고 있는 전해질은, 리튬염과 같이 이온화 가능한 염을 에틸렌 카보네이트(ethylene carbonate), 프로필렌 카보네이트(propylene carbonate), 디메톡시 에탄(dimethoxy ethane), g-부틸로 락톤(GBL), N,N-디메틸 포름아미드(dimethyl formamide), 테트라하이드로푸란 (tetrahydrofurane) 또는 아세토니트릴(acetonitrile) 등의 유기용매에 용해시킨 비수계(非水系) 전해액이다.Currently, the most widely used electrolytes include ionizable salts such as lithium salts such as ethylene carbonate, propylene carbonate, dimethoxy ethane, g-butyl lactone (GBL), N, N It is a non-aqueous electrolyte solution dissolved in an organic solvent such as dimethyl formamide, tetrahydrofurane or acetonitrile.
그런데, 이러한 비수계 전해액에 사용되는 유기용매는 점도가 낮아 누수가 쉬울 뿐만 아니라, 휘발성이 매우 강하여 증발될 우려가 있다. 또한 인화성도 강하다. 이에 따라, 이를 구비한 전기화학소자는 내구성 및 안정성에 문제가 있다.By the way, the organic solvent used in such a non-aqueous electrolyte solution is not only easy to leak due to the low viscosity, but also highly volatile and may evaporate. It is also highly flammable. Accordingly, the electrochemical device having the same has problems in durability and stability.
이러한 문제점을 해결하기 위하여, 이미다졸륨 계열과 암모늄 계열의 이온성 액체를 리튬 이차전지의 전해질로 사용하는 방법이 제안되었다. 그러나, 이러한 이온성 액체는 음극에서 리튬 이온보다 높은 전압에서 환원되거나, 리튬 이온과 함께 이미다졸륨, 암모늄 양이온이 함께 음극에 삽입되어, 오히려 전지 성능이 열화되는 문제가 있다.In order to solve this problem, a method of using an imidazolium-based and ammonium-based ionic liquid as an electrolyte of a lithium secondary battery has been proposed. However, such an ionic liquid is reduced at a higher voltage than lithium ions at the negative electrode, or imidazolium and ammonium cations are inserted together at the negative electrode together with lithium ions, thereby degrading battery performance.
한편, 한국 특허등록공보 10-751203호, 한국 특허공개공보 10-2007-85575호 등에는 전해질로서, 아세트아미드, 우레아, 메틸우레아, 카프로락탐, 발레르락탐, 트리플루오르아세트아미드, 카바메이트, 포름아미드 등, 소정 화학식으로 표시되는 아미드 화합물과 리튬염의 공융혼합물이 개시되어 있다. 이러한 공융혼합물은 비교적 넓은 전기화학적 창(electrochemical window) 외에 높은 열적 및 화학적 안정성을 나타내므로, 종래의 유기용매 사용에 따른 전해액의 증발, 인화 등의 문제점이 해결된다.On the other hand, Korean Patent Registration Publication No. 10-751203, Korean Patent Publication No. 10-2007-85575 and the like have acetamide, urea, methylurea, caprolactam, valerictam, trifluoroacetamide, carbamate, formamide as electrolytes. And the like, and a eutectic mixture of an amide compound represented by a predetermined chemical 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.
이에 따라, 전해질로서 유용한 다양한 공융혼합물의 개발이 가속화되고 있다.Accordingly, the development of various eutectic mixtures useful as electrolytes is accelerating.
따라서, 본 발명의 목적은 높은 열적 및 화학적 안정성을 나타내는 신규한 공융 혼합물을 포함하는 전해질 및 이를 구비한 전기화학소자를 제공하는데 있다.Accordingly, it is an object of the present invention to provide an electrolyte comprising a novel eutectic mixture exhibiting high thermal and chemical stability and an electrochemical device having the same.
상기 목적을 달성하기 위하여, 본 발명의 전해질은 (a) 하기 화학식 1로 표시되는 아민기가 고리로 묶여진 아미드 화합물; 및 (b) 이온화 가능한 리튬염으로 구성된 공융혼합물(eutectic mixture)을 포함한다.In order to achieve the above object, the electrolyte of the present invention (a) an amide compound in which the amine group represented by the following formula (1) is bound with a ring; And (b) an eutectic mixture consisting of ionizable lithium salts.
상기 화학식 1에 있어서, In Formula 1,
R은 수소, 탄소수 1 내지 10의 알킬기, 알킬아민기, 알케닐기, 아릴기 및 알킬아릴기로 이루어진 군으로부터 선택된 어느 하나이고,R is any one selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkylamine group, an alkenyl group, an aryl group, and an alkylaryl group,
X는 탄소, 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 탄소 또는 규소이면 m은 3이며,X is any one selected from the group consisting of carbon, 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, i) M is 2 if X is nitrogen or phosphorus i) m is 3 if X is carbon or silicon,
W는 수소 또는 탄소수 1 내지 10의 알킬기이고,W is hydrogen or an alkyl group having 1 to 10 carbon atoms,
Z는 탄소, 산소 및 질소로 이루어진 군으로부터 선택된 어느 하나로서, i)Z가 산소이면 p은 0이고, ii)Z가 질소이면 p는 1이고, iii)Z가 탄소이면 p는 2이며,Z is any one selected from the group consisting of carbon, oxygen and nitrogen, i) p is 0 if Z is oxygen, ii) p is 1 if Z is nitrogen, iii) p is 2 if Z is carbon,
n은 1 내지 5의 정수이다.n is an integer of 1-5.
본 발명의 전해질에 있어서, 상기 아민기가 고리로 묶여진 아미드 화합물은 모포린기, 트리아졸기 및 피리미딘기로 이루어진 군으로부터 선택된 어느 하나를 포함하는 것이 바람직한데, 예를 들어 모포린 메틸 카바메이트, 피롤리딘 메틸 카바메이트, 이미다졸 메틸 카바메이트 등을 들 수 있다.In the electrolyte of the present invention, the amide compound in which the amine group is ringed preferably includes any one selected from the group consisting of a morpholine group, a triazole group and a pyrimidine group, for example, morpholine methyl carbamate and pyrroli Dine methyl carbamate, imidazole methyl carbamate and the like.
또한, 본 발명의 전해질에 있어서, 상기 리튬염의 음이온으로는 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-, (CF3CF2SO2)2N- 등을 예시할 수 있다.Further, in the electrolyte of the present invention, as the lithium salt, 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 - and the like can be given -, (CF 3 CF 2 SO 2) 2 N.
본 발명의 전해질에 있어서, 상기 공융혼합물의 아민기가 고리로 묶여진 아미드 화합물과 리튬염의 몰비가 1 내지 8 : 1인 것이 바람직하다.In the electrolyte of the present invention, it is preferable that the molar ratio of the amide compound and lithium salt in which the amine group of the eutectic mixture is bound by a ring is 1 to 8: 1.
또한, 본 발명의 전해질에 있어서, 전해질이 액체 전해질일 때 공융혼합물은 액체 전해질 총 중량을 기준으로 50 내지 100중량% 포함할 수 있다.In addition, in the electrolyte of the present invention, when the electrolyte is a liquid electrolyte, the eutectic mixture may include 50 to 100% by weight based on the total weight of the liquid electrolyte.
전술한 본 발명의 전해질은 리튬 이차전지와 같은 전기화학소자에 유용하게 적용될 수 있다. The electrolyte of the present invention described above may be usefully applied to an electrochemical device such as a lithium secondary battery.
본 발명의 전해질에 포함된 신규한 공융혼합물은 우수한 열적 안정성과 화학적 안정성 등 공융혼합물의 고유 특성을 나타내므로, 종래의 유기용매 사용에 따른 전해액의 증발, 인화, 부반응 등의 문제점이 크게 개선된다. Since 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, problems such as evaporation, ignition, side reaction of the electrolyte according to the conventional organic solvents are greatly improved.
이하, 본 발명에 대하여 상세히 설명한다. 이에 앞서, 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. Prior to this, terms or words used in the specification and claims should not be construed as having a conventional or dictionary meaning, and the inventors should properly explain the concept of terms in order to best explain their own invention. Based on the principle that can be defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention.
본 발명의 전해질은 (a) 하기 화학식 1로 표시되는 아민기가 고리로 묶여진 아미드 화합물; 및 (b) 이온화 가능한 리튬염으로 구성된 공융혼합물(eutectic mixture)을 포함한다.The electrolyte of the present invention includes (a) an amide compound in which an amine group represented by the following formula (1) is bound with a ring; And (b) an eutectic mixture consisting of ionizable lithium salts.
<화학식 1> <Formula 1>
상기 화학식 1에 있어서, In Formula 1,
R은 수소, 탄소수 1 내지 10의 알킬기, 알킬아민기, 알케닐기, 아릴기 및 알킬아릴기로 이루어진 군으로부터 선택된 어느 하나이고,R is any one selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkylamine group, an alkenyl group, an aryl group, and an alkylaryl group,
X는 탄소, 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 탄소 또는 규소이면 m은 3이며,X is any one selected from the group consisting of carbon, 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, i) M is 2 if X is nitrogen or phosphorus i) m is 3 if X is carbon or silicon,
W는 수소 또는 탄소수 1 내지 10의 알킬기이고,W is hydrogen or an alkyl group having 1 to 10 carbon atoms,
Z는 탄소, 산소 및 질소로 이루어진 군으로부터 선택된 어느 하나로서, i)Z가 산소이면 p은 0이고, ii)Z가 질소이면 p는 1이고, iii)Z가 탄소이면 p는 2이며,Z is any one selected from the group consisting of carbon, oxygen and nitrogen, i) p is 0 if Z is oxygen, ii) p is 1 if Z is nitrogen, iii) p is 2 if Z is carbon,
n은 1 내지 5의 정수이다.n is an integer of 1-5.
본 발명자들은 전술한 구조의 아민기가 고리로 묶여진 아미드 화합물을 이용하여 리튬염과의 공융혼합물(eutectic mixture)을 형성하였는데, 이는 알려진 아세트 아미드, 메틸 카바메이트 등의 아미드계 화합물과 리튬염의 공융혼합물과 같이, 공융혼합물 특유의 높은 열적 및 화학적 안정성을 나타낸다.The present inventors formed an eutectic mixture with a lithium salt using an amide compound in which the amine group having the structure described above is bound with a ring, which is known as an eutectic mixture of an amide compound such as acetamide, methyl carbamate and lithium salt As such, they exhibit high thermal and chemical stability inherent to eutectic mixtures.
본 발명의 전해질에 있어서, 공융혼합물을 구성하는 화학식 1의 아민기가 고리로 묶여진 아미드 화합물은 모포린기, 트리아졸기 및 피리미딘기로 이루어진 군으로부터 선택된 어느 하나를 포함하는 것이 바람직한데, 예를 들어 모포린 메틸 카바메이트, 피롤리딘 메틸 카바메이트, 이미다졸 메틸 카바메이트 등을 들 수 있다. 특히, 모포린 메틸 카바메이트 또는 피롤리딘 메틸 카바메이트를 사용하면, 전기화학적 창(electrochemical window)의 환원 전위가 낮아져서, 다양한 음극재를 적용한 전기화학소자의 전해질로서 유용하게 적용될 수 있어 더욱 바람직하다.In the electrolyte of the present invention, the amide compound in which the amine group of the formula (1) constituting the eutectic mixture is ringed preferably includes any one selected from the group consisting of a morpholine group, a triazole group, and a pyrimidine group. Porin methyl carbamate, pyrrolidine methyl carbamate, imidazole methyl carbamate and the like. In particular, when the morpholine methyl carbamate or pyrrolidine methyl carbamate is used, the reduction potential of the electrochemical window is low, and thus it is more preferable because it can be usefully used as an electrolyte of an electrochemical device to which various negative electrode materials are applied. .
또한, 본 발명의 전해질에 있어서, 전술한 아민기가 고리로 묶여진 아미드 화합물과 함께 공융혼합물을 구성하는 리튬염은 이온화 가능한 리튬염으로서 Li+X-로 표현할 수 있다. 이러한 리튬염의 음이온으로는 특별히 제한되지 않으나, 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-, (CF3CF2SO2)2N- 등을 예시할 수 있다.In the electrolyte of the present invention, the lithium salt constituting the eutectic mixture together with the amide compound in which the aforementioned amine group is ringed can be represented by Li + X - as an ionizable lithium salt. In 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 -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -, SCN - and the like can be given -, (CF 3 CF 2 SO 2) 2 N.
본 발명에 따른 전해질의 공융혼합물의 용융온도는 화학식 1의 R, X, W 등에 따라 달라질 수 있으나, 바람직하게는 상온(25℃)에서 액체인 것이 바람직하다, 또한, 공융혼합물의 점도(viscosity)는 특별한 제한은 없으나, 2000cP 이하가 바람직하다.Melting temperature of the eutectic mixture of the electrolyte according to the present invention may vary according to R, X, W, etc. of the formula (1), preferably a liquid at room temperature (25 ℃), also, the viscosity (viscosity) of the eutectic mixture There is no particular limitation, but 2000 cP or less is preferable.
본 발명에 따른 전해질의 공융혼합물은 당업계에 알려진 통상적인 방법에 따라 제조할 수 있는데, 예를 들어 전술한 아민기가 고리로 묶여진 아미드 화합물과 리튬염을 상온에서 혼합한 다음, 70℃ 이하의 적절한 온도에서 반응시킨 후 정제하여 제조할 수 있다. 이 때, 제조된 공융혼합물의 아민기가 고리로 묶여진 아미드 화합물과 리튬염의 몰비는 바람직하게는 1 내지 8 : 1, 더욱 바람직하게는 2 내지 6:1이다.The eutectic mixture of the electrolyte according to the present invention may be prepared according to a conventional method known in the art, for example, by mixing an amide compound in which the aforementioned amine group is bound with a lithium salt at room temperature, and then suitable at 70 ° C. or lower. After the reaction at the temperature can be prepared by purification. At this time, the molar ratio of the amide compound and lithium salt in which the amine group of the prepared eutectic mixture is bound by a ring is preferably 1 to 8: 1, more preferably 2 to 6: 1.
본 발명의 전해질은 리튬 이온을 자체에 포함하는 공융혼합물을 포함하므로, 리튬 이차전지에 적용하는 경우에도 리튬염을 별도로 첨가하지 않을 수 있으나, 리튬염과 같은 염을 예를 들어 0 내지 1M/L의 농도로 더 포함할 수 있음은 물론이다. 전해질에 리튬염을 더 첨가시, 전해질에 대한 용해성을 향상시키기 위하여, 공융혼합물을 구성하는 리튬염의 음이온과 동일한 음이온을 갖는 리튬염을 사용하는 것이 바람직하다.Since the electrolyte of the present invention includes a eutectic mixture containing lithium ions in itself, even when applied to a lithium secondary battery, a lithium salt may not be added separately, but a salt such as lithium salt may be, for example, 0 to 1 M / L. Of course, the concentration may further include. When further adding a lithium salt to the electrolyte, in order to improve solubility in the electrolyte, it is preferable to use a lithium salt having the same anion as that of the lithium salt constituting the eutectic mixture.
또한, 본 발명의 전해질은 본 발명의 목적을 저해하지 않는 한도 내에서 다양한 종류의 첨가제나 유기용매를 더 포함할 수 있음은 당업자에게 자명하다고 할 것이다.In addition, it will be apparent to those skilled in the art that the electrolyte of the present invention may further include various kinds of additives or organic solvents without departing from the object of the present invention.
본 발명의 전해질은 전해질 형태에 관계없이 모두 적용이 가능한데, 예를 들어 액체 전해질이나, 폴리머 자체로 된 고체상 또는 겔상과 같은 폴리머 전해질로 이용될 수 있다. 본 발명의 전해질이 액체 전해질로 사용되는 경우, 전술한 공융혼합물을 단독으로 사용하거나 또는 염, 유기용매, 첨가제 등을 더 첨가하여 사용할 수 있는데, 전해질 내의 전술한 공융혼합물의 바람직한 함량은 전해질 총 중량을 기준으로 50 내지 100중량%이다.Regardless of the type of electrolyte, all of the electrolytes of the present invention may be applied. For example, the electrolyte may be used as a liquid electrolyte or a polymer electrolyte such as a solid or gel phase of the polymer itself. When the electrolyte of the present invention is used as a liquid electrolyte, the above-mentioned eutectic mixture may be used alone, or further added with a salt, an organic solvent, an additive, and the like. The preferred content of the above eutectic mixture in the electrolyte is the total weight of the electrolyte. It is 50 to 100% by weight based on the.
한편, 본 발명의 전해질이 폴리머 전해질인 경우, 공융혼합물 및 중합반응에 의해 폴리머를 형성할 수 있는 단량체(monomer)를 함유하는 전구체 용액의 중합에 의해 겔상의 폴리머 전해질로, 또는 공융혼합물이 고체상 또는 겔상과 같은 폴리머에 함침된 형태의 폴리머 전해질로 제조될 수 있다.On the other hand, when the electrolyte of the present invention is a polymer electrolyte, the polymer electrolyte is a gel-like polymer by polymerization of a precursor solution containing a eutectic mixture and a monomer capable of forming a polymer by a polymerization reaction, or the eutectic mixture is a solid phase or It may be made of a polymer electrolyte in a form impregnated with a polymer such as gel.
① 우선, 전구체 용액의 중합 반응에 의해 제조된 겔상의 폴리머 전해질에 대해 설명한다.(1) First, the gel polymer electrolyte produced by the polymerization reaction of the precursor solution will be described.
본 발명의 일측면에 따른 겔상의 폴리머 전해질은 (i) 전술한 화학식 1의 공융혼합물; 및 (ii) 중합 반응에 의해 폴리머를 형성할 수 있는 단량체(monomer)를 함유하는 전구체 용액을 중합시켜 형성될 수 있다.Gel-like polymer electrolyte according to an aspect of the present invention is (i) the eutectic mixture of Formula 1; And (ii) a precursor solution containing a monomer capable of forming a polymer by a polymerization reaction.
단량체(monomer)는 중합반응이 진행됨에 따라 공융혼합물과 함께 겔 폴리머를 형성할 수 있는 모든 종류의 단량체가 적용 가능하며, 이의 비제한적인 예로는 비닐 모노머 등이 있다. 비닐 모노머는 공융혼합물과 혼합되어 겔 폴리머를 형성하는 경우 중합이 매우 간단하다는 장점이 있다.As the monomer (monomer) as the polymerization proceeds, all kinds of monomers capable of forming a gel polymer with the eutectic mixture is applicable, non-limiting examples thereof include vinyl monomers. Vinyl monomers have the advantage of very simple polymerization when mixed with eutectic mixtures to form gel polymers.
사용 가능한 비닐 모노머의 비제한적인 예로는 아크릴로니트릴, 메틸메타크릴레이트, 메틸아크릴레이트, 메타크릴로니트닐, 메틸스티렌, 비닐에스테르류, 염화비닐, 염화비닐리덴, 아크릴아마이드, 테트라플루오로에틸렌, 비닐아세테이트, 비닐클로라이드, 메틸비닐케톤, 에틸렌, 스티렌, 파라메톡시스티렌, 파라시아노스티렌 등이 있으며, 이들은 각각 단독으로 또는 이들을 2종 이상 혼합하여 사용할 수 있다.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.
전구체 용액은 통상적인 중합개시제 또는 광개시제를 추가적으로 포함할 수 있는데, 개시제(initiator)는 열이나 자외선에 의해 분해되어 라디칼(radical)을 형성하고, 자유라디칼 중합에 의해 모노머와 반응하여 겔 폴리머 전해질을 형성한다. 또한, 개시제를 사용하지 않고 모노머의 중합을 진행할 수도 있다. 일반적으로 자유라디칼 중합은 반응성이 강한 일시적인 분자들 또는 활성점이 형성되는 개시반 응, 활성연쇄말단에 단량체가 부가되어 다시 사슬 끝에 활성점이 형성되는 성장반응, 활성점을 다른 분자들에게 이동시키는 연쇄이동반응, 활성연쇄 중심이 파괴되는 정지반응의 과정을 거치게 된다.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 | polymerization of a monomer can also be advanced, without using an initiator. In general, 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 the chain, and a chain transfer that transfers the active point to other molecules. Reaction, a stop reaction in which the active chain center is destroyed.
사용 가능한 열중합 개시제로의 비제한적인 예로는 Benzoyl peroxide, Acetyl peroxide, Dilauryl peroxide, Di-tert-butyl peroxide, Cumyl hydroperoxide, Hydrogen peroxide 등의 유기과산화물류나 히드로과산화물류, 2,2-Azobis(2-cyanobutane), 2,2-Azobis(Methylbutyronitrile), AIBN(Azobis(iso-butyronitrile), AMVN (Azobisdimethyl-Valeronitrile) 등의 아조화합물류, 알킬화은류와 같은 유기금속 등이 있다. 또한, 자외선과 같은 빛에 의해 라디칼이 형성되는 광 개시제의 비제한적인 예로는 Chloroacetophenone, Diethoxy Acetophenone(DEAP), 1-phenyl-2-hydroxy-2-methyl propaneone(HMPP), 1-Hydroxy cyclrohexyl phenyl ketone, α-Amino Acetophenone, Benzoin Ether, Benzyl Dimethyl ketal, Benzophenone, Thioxanthone, 2-ethylAnthraquinone(2-ETAQ) 등이 있다.Non-limiting examples of thermal initiators that can be used 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, α-Amino Acetophenone, Benzoin Ether, Benzyl Dimethyl ketal, Benzophenone, Thioxanthone and 2-ethylAnthraquinone (2-ETAQ).
상기 기재된 성분들 이외에, 본 발명에 따른 겔 폴리머 전해질의 전구체 용액은 당업계에 알려진 기타 첨가제 등을 선택적으로 함유할 수 있다.In addition to the components described above, 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.
전술한 전구체 용액을 이용하여 당업계에 알려진 통상적인 방법에 따라 겔 폴리머 전해질을 형성하게 되는데, 전기 화학 소자 내부에서 In - Situ 중합 반응에 의하여 겔 폴리머 전해질을 제조하는 것이 바람직하다. In - Situ 중합 반응은 열 또는 자외선 조사를 통해 가능하다. 전구체 용액 내의 공융혼합물과 모노머의 함량비 는 0.5~0.95 : 0.05~0.5로 조절하는 것이 바람직하다.. 겔 폴리머의 중합 정도는 반응 인자인 중합 시간, 중합 온도 또는 광조사량 정도에 따라 조절할 수 있으므로, 전해질이 누출되지 않으면서도 폴리머가 과중합되어 부피가 수축되지 않을 정도로 조절한다.Using the precursor solution described above to form a gel polymer electrolyte according to a conventional method known in the art, it is preferable to prepare a gel polymer electrolyte by the In - Situ polymerization reaction in the electrochemical device. In - Situ polymerization reaction is possible by heat or ultraviolet irradiation. The content ratio of the eutectic mixture and the monomer in the precursor solution is preferably adjusted to 0.5-0.95: 0.05-0.5. Since the degree of polymerization of the gel polymer can be controlled according to the polymerization time, polymerization temperature or light irradiation degree, which are reaction factors, The polymer is superpolymerized without leaking the electrolyte so that the volume does not shrink.
② 본 발명에 따라 공융혼합물을 포함하는 폴리머 전해질의 다른 제조방법으로서, 공융혼합물을 이미 형성된 고체상 폴리머 또는 겔상 폴리머에 주입하여, 공융혼합물이 폴리머에 함침된 형태로 제조할 수 있다.(2) As another method for producing a polymer electrolyte containing a eutectic mixture according to the present invention, the eutectic mixture may be injected into a solid polymer or a gel polymer already formed, so that the eutectic mixture is impregnated into the polymer.
사용 가능한 폴리머의 비제한적인 예로는 폴리메틸메타크릴레이트, 폴리비닐리덴 디플루라이드, 폴리비닐 클로라이드, 폴리에틸렌 옥사이드, 폴리하이드록시에틸메타크릴레이트 등을 각각 단독으로 또는 이들을 2종 이상 혼합하여 사용할 수 있다. 이 방법은 전술한 In - Situ 방법에 비해 제조 공정이 단순화될 수 있다.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.
③ 본 발명에 따라 공융혼합물을 포함하는 폴리머 전해질의 또 다른 제조방법으로서, 폴리머와 공융혼합물을 용매에 용해시킨 후 용매를 제거함으로써 폴리머 전해질을 형성하는 방법이 이용돌 수 있다. 이때, 공융혼합물은 폴리머 매트릭스 내부에 함유된 형태가 된다.(3) According to the present invention, as another method for preparing a polymer electrolyte containing a eutectic mixture, a method of forming a polymer electrolyte by dissolving the polymer and the eutectic mixture in a solvent and then removing the solvent may be used. At this time, the eutectic mixture is in the form contained in the polymer matrix.
사용 가능한 용매로는 특별한 제한은 없으며, 이의 비제한적인 예로는 톨루엔, 아세톤, 아세토니트릴, THF 등이 있다. 또한 용매 제거 방법도 특별한 제한은 없으며, 열을 가하는 등의 통상적인 방법이 이용될 수 있다.The solvent that can be used is not particularly limited, and non-limiting examples thereof include toluene, acetone, acetonitrile, THF, and the like. In addition, the solvent removal method is not particularly limited, and conventional methods such as applying heat may be used.
본 발명에 따라 공융혼합물을 포함하는 전해질은 사용 목적에 따라 다양한 전기화학적 특성이 요구되는 당 업계에 알려진 통상적인 전기화학소 자(electrochemical device)에 적용 가능하다.The electrolyte comprising the eutectic mixture according to the present invention is applicable to conventional electrochemical devices known in the art which require various electrochemical properties depending on the purpose of use.
상기 전기화학소자의 비제한적인 예로는 모든 종류의 1차, 2차 전지, 연료 전지, 태양 전지, 전기 변색 소자, 전해 컨텐서(condenser) 또는 캐퍼시터(capacitor) 등이 있으며, 이의 구체예로는 리튬 이차전지, 전기 이중층 캐패시터, 색소증감형 태양전지, 전기변색소자 등이 있다.Non-limiting examples of the electrochemical device include all kinds of primary, secondary cells, fuel cells, solar cells, electrochromic devices, electrolytic condenser or capacitor (capacitor), specific examples thereof Lithium secondary batteries, electric double layer capacitors, dye-sensitized solar cells, electrochromic devices and the like.
이하, 본 발명을 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 발명에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되어져서는 안된다. 본 발명의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되어지는 것이다.Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
실시예Example 1 One
1-1. 1-1. MorpholineMorpholine methylcarbamatemethylcarbamate 합성 synthesis
둥근 바닥 플라스크에 메틸 클로로포메이트(Methyl chloroformate) 15g을 넣고 0℃이하로 냉각시킨다. 모포린(Morpholine) 27.6g(2당량)을 테트라히드로푸란(THF)용매에 녹인 후 서서히 적가한다. 적가가 완료되면 상온으로 승온시킨 후 2시간 동안 서서히 교반하고 반응 후 생긴 염을 여과한다. 테트라히드로푸란(THF)용매를 제거한 후 단순 증류하여 원하는 화합물을 18g을 수득하였다.15 g of methyl chloroformate is added to a round bottom flask and cooled to below 0 ° C. 27.6 g (2 equivalents) of Morpholine is dissolved in tetrahydrofuran (THF) solvent and slowly added dropwise. When the dropping is completed, the temperature is raised to room temperature and then slowly stirred for 2 hours, and the salt generated after the reaction is filtered. The tetrahydrofuran (THF) solvent was removed and then distilled to give 18 g of the desired compound.
1-2. 1-2. 모포린Morpholine 메틸카바메이트Methyl carbamate (( MorpholineMorpholine methylcarbamatemethylcarbamate )/) / LiPF6LiPF6 공융혼합물Eutectic mixture 합성 synthesis
정제된 모포린 메틸카바메이트(Morpholine methylcarbamate) 2.86g과 LiPF6 1g을 둥근 바닥 플라스크에 넣고, 질소 분위기하에서 2시간 동안 서서히 교반시켜 원하는 공융혼합물 3.8g을 수득하였다.2.86 g of purified Morpholine methylcarbamate and 1 g of LiPF6 were placed in a round bottom flask, and stirred slowly under a nitrogen atmosphere for 2 hours to obtain 3.8 g of the desired eutectic mixture.
1-3. 1-3. 모포린Morpholine 메틸카바메이트Methyl carbamate /Of LiPF6LiPF6 공융혼합물의Eutectic mixture 열중합을Heat polymerization 통한 젤 Through gel 폴리머Polymer 전해질 Electrolyte
상기 실시예 1-2에서 합성된 모포린 메틸카바메이트/LiPF6 공융혼합물, HEMA(2-hydroxyethylmethacrylate) 단량체, 열중합 개시제로서 AMVN(azobisdimethyl-valeronitrile)를 무게비 8:2:0.01로 혼합하여 55℃의 온도에서 1시간 중합시켜 젤 폴리머 전해질을 형성하였다.Morpholine methyl carbamate / LiPF6 eutectic mixture, HEMA (2-hydroxyethylmethacrylate) monomer, synthesized in Example 1-2, AMVN (azobisdimethyl-valeronitrile) as a thermal polymerization initiator was mixed in a weight ratio of 8: 2: 0.01 55 ℃ Polymerization was carried out at temperature for 1 hour to form a gel polymer electrolyte.
1-4. 1-4. 아세트아미드Acetamide -- NaSCNNaSCN 공융혼합물의Eutectic mixture 자외선 중합을 통한 젤 Gel by UV Polymerization 폴리머Polymer 전해질 Electrolyte
상기 1-2에서 제조된 모포린 메틸카바메이트/LiPF6 공융혼합물, 가교제로 TAEI(tris[2-(acryloyloxy) ethyl] isocyanurate), 단량체인 MPEGM(methoxy poly(ethylene glycol) methacrylate), 자외선 중합 개시제인 Irgacure-184(시바)을 50:0.5:50:10의 질량%로 혼합한 전해질 전구체를 준비하여 자외선을 조사하여 30분간 중합시킴으로써 젤 폴리머 전해질을 형성하였다.Morphorin methyl carbamate / LiPF6 eutectic mixture prepared in 1-2, TAEI (tris [2- (acryloyloxy) ethyl] isocyanurate) as a crosslinking agent, MPEGM (methoxy poly (ethylene glycol) methacrylate) monomers, UV polymerization initiator An electrolyte precursor prepared by mixing Irgacure-184 (Shiba) at a mass% of 50: 0.5: 50: 10 was prepared and polymerized by irradiation with ultraviolet rays for 30 minutes to form a gel polymer electrolyte.
실시예Example 2 2
2-1. 2-1. 피롤리딘Pyrrolidine 메틸카바메이트Methyl carbamate (( PyrrolidinePyrrolidine methylcarbamatemethylcarbamate ) 합성) synthesis
둥근 바닥 플라스크에 메틸 클로로포메이트(Methyl chloroformate) 15g을 넣고 0℃이하로 냉각시킨다. 피롤리딘(Pyrrolidine) 22.6g(2당량)을 테트라히드로푸란(THF)용매에 녹인 후 서서히 적가한다. 적가가 완료되면 상온으로 승온시킨 후 2 시간 동안 서서히 교반하고 반응 후 생긴 염을 여과한다. 테트라히드로푸란(THF)용매를 제거한 후 단순 증류하여 원하는 화합물을 17g을 수득하였다.15 g of methyl chloroformate is added to a round bottom flask and cooled to below 0 ° C. 22.6 g (2 equivalents) of pyrrolidine is dissolved in tetrahydrofuran (THF) solvent and slowly added dropwise. When the dropwise addition is completed, the temperature is raised to room temperature, then slowly stirred for 2 hours, and the salt generated after the reaction is filtered. The tetrahydrofuran (THF) solvent was removed and then distilled to give 17 g of the desired compound.
2-2. 2-2. 피롤리딘Pyrrolidine 메틸카바메이트Methyl carbamate (( PyrrolidinePyrrolidine methylcarbamatemethylcarbamate )/) / LiPF6LiPF6 공융혼Euphoric 합물 합성Compound synthesis
정제된 피롤리딘 메틸카바메이트( Pyrrolidine methylcarbamate) 2.71g과 LiPF6 1g을 둥근 바닥 플라스크에 넣고, 질소 분위기하에서 2시간 동안 서서히 교반시켜 원하는 공융혼합물 3.7g을 수득하였다.The purified insert pyrrolidin-methylcarbamate (Pyrrolidine methylcarbamate) 2.71g and 1g LiPF6 in a round bottom flask, was slowly stirred for 2 hours under a nitrogen atmosphere to give the desired eutectic mixture 3.7g.
2-3. 2-3. 피롤리딘Pyrrolidine 메틸카바메이트Methyl carbamate /Of LiPF6LiPF6 공융혼합물의Eutectic mixture 열중합을Heat polymerization 통한 젤 Through gel 폴리머Polymer 전해질 Electrolyte
상기 실시예 2-2에서 합성된 피롤리딘 메틸카바메이트/LiPF6 공융혼합물, HEMA(2-hydroxyethylmethacrylate) 단량체, 열중합 개시제로서 AMVN(azobisdimethyl-valeronitrile)를 무게비 8:2:0.01로 혼합하여 55℃의 온도에서 1시간 중합시켜 젤 폴리머 전해질을 형성하였다.Pyrrolidine methyl carbamate / LiPF6 eutectic mixture, HEMA (2-hydroxyethylmethacrylate) monomer, synthesized in Example 2-2, AMVN (azobisdimethyl-valeronitrile) as a thermal polymerization initiator is mixed in a weight ratio of 8: 2: 0.01 55 ℃ The polymer was polymerized at a temperature of 1 hour to form a gel polymer electrolyte.
2-4. 2-4. 피롤리딘Pyrrolidine 메틸카바메이트Methyl carbamate /Of LiPF6LiPF6 공융혼합물의Eutectic mixture 자외선 중합을 통한 젤 폴리머 전해질 Gel polymer electrolyte through ultraviolet polymerization
상기 2-에서 제조된 피롤리딘 메틸카바메이트/LiPF6 공융혼합물, 가교제로 TAEI(tris[2-(acryloyloxy) ethyl] isocyanurate), 단량체인 MPEGM(methoxy poly(ethylene glycol) methacrylate), 자외선 중합 개시제인 Irgacure-184(시바)을 50:0.5:50:10의 질량%로 혼합한 전해질 전구체를 준비하여 자외선을 조사하여 30분간 중합시킴으로써 젤 폴리머 전해질을 형성하였다.Pyrrolidine methyl carbamate / LiPF6 eutectic mixture prepared in 2-, TAEI (tris [2- (acryloyloxy) ethyl] isocyanurate) as a crosslinking agent, MPEGM (methoxy poly (ethylene glycol) methacrylate) monomers, UV polymerization initiator An electrolyte precursor prepared by mixing Irgacure-184 (Shiba) at a mass% of 50: 0.5: 50: 10 was prepared and polymerized for 30 minutes by irradiation with ultraviolet rays to form a gel polymer electrolyte.
실시예Example 3 3
3-1. 3-1. 이미다졸Imidazole 메틸카바메이트Methyl carbamate (( ImidazoleImidazole methylcarbamatemethylcarbamate ) 합성) synthesis
둥근 바닥 플라스크에 메틸 클로로포메이트(Methyl chloroformate) 10g을 넣고 0℃이하로 냉각시킨다. 이미다졸(Imidazole) 14.4g(2당량)을 테트라히드로푸란(THF)용매에 녹인 후 서서히 적가한다. 적가가 완료되면 상온으로 승온시킨 후 2시간 동안 서서히 교반하고 반응 후 생긴 염을 여과한다. 테트라히드로푸란(THF)용매를 제거한 후 증류하여 원하는 화합물을 11g을 수득하였다.10 g of methyl chloroformate is added to a round bottom flask and cooled to 0 ° C or lower. 14.4 g (2 equivalents) of imidazole is dissolved in tetrahydrofuran (THF) solvent and slowly added dropwise. When the dropping is completed, the temperature is raised to room temperature and then slowly stirred for 2 hours, and the salt generated after the reaction is filtered. The tetrahydrofuran (THF) solvent was removed and distilled to give 11 g of the desired compound.
3-2. 3-2. 이미다졸Imidazole 메틸카바메이트Methyl carbamate (( ImidazoleImidazole methylcarbamatemethylcarbamate )/) / LiPF6LiPF6 공융혼합Eutectic mixing 물 합성Water synthesis
정제된 이미다졸 메틸카바메이트(Imidazole methylcarbamate) 2.63g과 LiPF6 1g을 둥근 바닥 플라스크에 넣고, 질소 분위기하에서 2시간 동안 서서히 교반시켜 원하는 공융혼합물 3.6g을 수득하였다.2.63 g of purified imidazole methylcarbamate and 1 g of LiPF6 were placed in a round bottom flask and stirred slowly for 2 hours under a nitrogen atmosphere to obtain 3.6 g of the desired eutectic mixture.
3-3. 3-3. 이미다졸Imidazole 메틸카바메이트Methyl carbamate /Of LiPF6LiPF6 공융혼합물의Eutectic mixture 열중합을Heat polymerization 통한 젤 Through gel 폴리머Polymer 전해질 Electrolyte
상기 실시예 3-2에서 합성된 이미다졸 메틸카바메이트/LiPF6 공융혼합물, HEMA(2-hydroxyethylmethacrylate) 단량체, 열중합 개시제로서 AMVN(azobisdimethyl-valeronitrile)를 무게비 8:2:0.01로 혼합하여 55℃의 온도에서 1시간 중합시켜 젤 폴리머 전해질을 형성하였다.The imidazole methyl carbamate / LiPF6 eutectic mixture, HEMA (2-hydroxyethylmethacrylate) monomer, and the AMVN (azobisdimethyl-valeronitrile) as a thermal polymerization initiator were mixed in a weight ratio of 8: 2: 0.01 at 55 ° C. Polymerization was carried out at temperature for 1 hour to form a gel polymer electrolyte.
3-4. 3-4. 이미다졸Imidazole 메틸카바메이트Methyl carbamate /Of LiPF6LiPF6 공융혼합물의Eutectic mixture 자외선 중합을 통한 젤 폴리머 전해질 Gel polymer electrolyte through ultraviolet polymerization
상기 3-에서 제조된 이미다졸 메틸카바메이트/LiPF6 공융혼합물, 가교제로 TAEI(tris[2-(acryloyloxy) ethyl] isocyanurate), 단량체인 MPEGM(methoxy poly(ethylene glycol) methacrylate), 자외선 중합 개시제인 Irgacure-184(시바)을 50:0.5:50:10의 질량%로 혼합한 전해질 전구체를 준비하여 자외선을 조사하여 30분간 중합시킴으로써 젤 폴리머 전해질을 형성하였다.Imidazole methyl carbamate / LiPF6 eutectic mixture prepared in 3-, TAEI (tris [2- (acryloyloxy) ethyl] isocyanurate) as a crosslinking agent, MPEGM (methoxy poly (ethylene glycol) methacrylate) as monomer, Irgacure as UV polymerization initiator A gel polymer electrolyte was prepared by preparing an electrolyte precursor obtained by mixing -184 (Ciba) at a mass% of 50: 0.5: 50: 10 and polymerizing for 30 minutes by irradiating with ultraviolet rays.
전술한 실시예에 따른 공융혼합물의 물성을 평가하기 위하여, 하기와 같이 실시하였다.In order to evaluate the physical properties of the eutectic mixture according to the above-described embodiment, it was carried out as follows.
시료로는 실시예 1 내지 3에서 제조된 공융혼합물을 사용하였으며, 이때 사용된 공융혼합물의 비율은 아미드 화합물과 염의 비가 모두 3:1이었다. 점도 측정은 RS150 점도계를 사용하여 25℃에서 측정하였고, 전도도는 Inolab 740기기를 이용하여 측정하였다. 이의 결과는 하기 표 1에 기재하였다.As a sample, a eutectic mixture prepared in Examples 1 to 3 was used, and the ratio of the eutectic mixture used was 3: 1 in both amide compound and salt ratio. Viscosity measurements were measured at 25 ° C. using an RS150 viscometer and conductivity was measured using an Inolab 740 instrument. The results are shown in Table 1 below.
표 1의 결과를 참조할 때, 모포린 메틸 카바메이트, 피롤리딘 메틸 카바메이트의 경우, 전기화학적 창(electrochemical window)의 환원 전위가 유의있게 종래의 공융혼합물보다 낮으므로, 다양한 음극재를 적용한 전기화학소자의 전해질로서 유용하게 적용될 수 있다.Referring to the results of Table 1, in the case of morpholine methyl carbamate and pyrrolidine methyl carbamate, the reduction potential of the electrochemical window was significantly lower than that of the conventional eutectic mixtures, so that various negative electrode materials were applied. It can be usefully applied as an electrolyte of an electrochemical device.
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