WO2004092269A1 - 電解質組成物および電池 - Google Patents
電解質組成物および電池 Download PDFInfo
- Publication number
- WO2004092269A1 WO2004092269A1 PCT/JP2004/005370 JP2004005370W WO2004092269A1 WO 2004092269 A1 WO2004092269 A1 WO 2004092269A1 JP 2004005370 W JP2004005370 W JP 2004005370W WO 2004092269 A1 WO2004092269 A1 WO 2004092269A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrolyte
- electrolyte composition
- polymer
- lithium
- group
- Prior art date
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 100
- 239000000203 mixture Substances 0.000 title claims abstract description 83
- -1 ether compound Chemical class 0.000 claims abstract description 121
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 83
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 82
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 34
- 239000000654 additive Substances 0.000 claims abstract description 28
- 230000000996 additive effect Effects 0.000 claims abstract description 27
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims description 34
- 229920001577 copolymer Polymers 0.000 claims description 19
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 abstract 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 56
- 238000004090 dissolution Methods 0.000 description 38
- 239000005518 polymer electrolyte Substances 0.000 description 31
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 30
- 239000010408 film Substances 0.000 description 30
- 238000004132 cross linking Methods 0.000 description 29
- 238000006116 polymerization reaction Methods 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 28
- 238000001556 precipitation Methods 0.000 description 27
- 229940117927 ethylene oxide Drugs 0.000 description 22
- 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 18
- 239000003054 catalyst Substances 0.000 description 17
- 230000008021 deposition Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000011888 foil Substances 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 13
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000003999 initiator Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 9
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 229920000768 polyamine Polymers 0.000 description 9
- 239000004342 Benzoyl peroxide Substances 0.000 description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 8
- 229920002799 BoPET Polymers 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000004014 plasticizer Substances 0.000 description 7
- 239000007784 solid electrolyte Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 5
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 4
- 238000012935 Averaging Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229920006027 ternary co-polymer Polymers 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 3
- NTIFKWPEJRPCOU-UHFFFAOYSA-N carbonic acid;hex-1-ene Chemical compound OC(O)=O.CCCCC=C NTIFKWPEJRPCOU-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical class SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 3
- 229910052990 silicon hydride Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JZFMNFJEQDUBPL-UHFFFAOYSA-N 1-sulfanyl-4,5-dihydroimidazole Chemical class SN1CCN=C1 JZFMNFJEQDUBPL-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 241001314535 Ophrys apifera Species 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229960002130 benzoin Drugs 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
- 239000012965 benzophenone Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- OWUVDWLTQIPNLN-GGWOSOGESA-N (4e,8e)-13-oxabicyclo[10.1.0]trideca-4,8-diene Chemical compound C1C\C=C\CC\C=C\CCC2OC21 OWUVDWLTQIPNLN-GGWOSOGESA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- GGSRTHRSSCWGGK-UHFFFAOYSA-L 2,2-dibutyl-5-hydroxy-1,3,2-dioxastannepane-4,7-dione Chemical compound CCCC[Sn]1(CCCC)OC(=O)CC(O)C(=O)O1 GGSRTHRSSCWGGK-UHFFFAOYSA-L 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- RIZUCYSQUWMQLX-UHFFFAOYSA-N 2,3-dimethylbenzoic acid Chemical compound CC1=CC=CC(C(O)=O)=C1C RIZUCYSQUWMQLX-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical group CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- LELKUNFWANHDPG-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)oxirane;prop-2-enoic acid Chemical compound OC(=O)C=C.C1OC1COCC1CO1 LELKUNFWANHDPG-UHFFFAOYSA-N 0.000 description 1
- VUDVPVOIALASLB-UHFFFAOYSA-N 2-[(2-cyano-1-hydroxypropan-2-yl)diazenyl]-3-hydroxy-2-methylpropanenitrile Chemical compound OCC(C)(C#N)N=NC(C)(CO)C#N VUDVPVOIALASLB-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- AUNOCGWVFDDCAD-UHFFFAOYSA-N 2-[(4-ethenylcyclohexyl)oxymethyl]oxirane Chemical compound C1CC(C=C)CCC1OCC1OC1 AUNOCGWVFDDCAD-UHFFFAOYSA-N 0.000 description 1
- AECMQTCXISKOGO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethyl]phenol Chemical compound CN(C)CCC1=CC=CC=C1O AECMQTCXISKOGO-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- VXZBYIWNGKSFOJ-UHFFFAOYSA-N 2-[4-[5-(2,3-dihydro-1H-inden-2-ylamino)pyrazin-2-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC=1N=CC(=NC=1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 VXZBYIWNGKSFOJ-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- SZERAFCDZCHRQS-UHFFFAOYSA-N 2-ethenyl-3-methyloxirane Chemical compound CC1OC1C=C SZERAFCDZCHRQS-UHFFFAOYSA-N 0.000 description 1
- HPUWVIVMBKTDES-UHFFFAOYSA-N 2-hydroxy-2-[2-(oxiran-2-ylmethoxy)-2-oxoethyl]butanedioic acid Chemical compound C(C1CO1)OC(CC(O)(C(=O)O)CC(=O)O)=O HPUWVIVMBKTDES-UHFFFAOYSA-N 0.000 description 1
- YDCANTZAVGJEFZ-UHFFFAOYSA-N 2-methyl-2-(oxiran-2-yl)oxirane Chemical compound C1OC1C1(C)CO1 YDCANTZAVGJEFZ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- KOHBFAGTEWFCBI-UHFFFAOYSA-N 2-prop-1-enyloxirane Chemical compound CC=CC1CO1 KOHBFAGTEWFCBI-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- UVTIZRNEWKAOEM-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylbutane Chemical compound CCC(C)(C)OOC(C)(C)C UVTIZRNEWKAOEM-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
- RAFAYWADRVMWFA-UHFFFAOYSA-N 4,6-dimethyl-1h-pyrimidine-2-thione Chemical compound CC1=CC(C)=NC(S)=N1 RAFAYWADRVMWFA-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NGZJXCFNBVJLQN-UHFFFAOYSA-N 4-methylimidazolidine-2-thione Chemical compound CC1CNC(=S)N1 NGZJXCFNBVJLQN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SPANOECCGNXGNR-UITAMQMPSA-N Diallat Chemical compound CC(C)N(C(C)C)C(=O)SC\C(Cl)=C\Cl SPANOECCGNXGNR-UITAMQMPSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- LGCMKPRGGJRYGM-UHFFFAOYSA-N Osalmid Chemical compound C1=CC(O)=CC=C1NC(=O)C1=CC=CC=C1O LGCMKPRGGJRYGM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 101001012040 Pseudomonas aeruginosa (strain ATCC 15692 / DSM 22644 / CIP 104116 / JCM 14847 / LMG 12228 / 1C / PRS 101 / PAO1) Immunomodulating metalloprotease Proteins 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- AVTOEKKTKXLWDL-UHFFFAOYSA-N acetylene;1,3-dioxolan-2-one Chemical compound C#C.O=C1OCCO1 AVTOEKKTKXLWDL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000006866 deterioration Effects 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
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- GKCPCPKXFGQXGS-UHFFFAOYSA-N ditert-butyldiazene Chemical compound CC(C)(C)N=NC(C)(C)C GKCPCPKXFGQXGS-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- QPMJENKZJUFOON-PLNGDYQASA-N ethyl (z)-3-chloro-2-cyano-4,4,4-trifluorobut-2-enoate Chemical compound CCOC(=O)C(\C#N)=C(/Cl)C(F)(F)F QPMJENKZJUFOON-PLNGDYQASA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- WTNTZFRNCHEDOS-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-methylpropanamide Chemical compound CC(C)C(=O)NCCO WTNTZFRNCHEDOS-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- JFOJYGMDZRCSPA-UHFFFAOYSA-J octadecanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JFOJYGMDZRCSPA-UHFFFAOYSA-J 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- AVNANMSIFNUHNY-MQQKCMAXSA-N oxiran-2-ylmethyl (2e,4e)-hexa-2,4-dienoate Chemical compound C\C=C\C=C\C(=O)OCC1CO1 AVNANMSIFNUHNY-MQQKCMAXSA-N 0.000 description 1
- NZSXYXVUIOHHSF-UHFFFAOYSA-N oxiran-2-ylmethyl hex-4-enoate Chemical compound CC=CCCC(=O)OCC1CO1 NZSXYXVUIOHHSF-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000323 polyazulene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000414 polyfuran Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- HILHCDFHSDUYNX-UHFFFAOYSA-N trimethoxy(pentyl)silane Chemical compound CCCCC[Si](OC)(OC)OC HILHCDFHSDUYNX-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to an electrolyte composition comprising a lithium salt compound and a cyclic carbonate having an unsaturated group, and more particularly to an electrolyte composition suitable as a material for electrochemical devices such as batteries, capacitors, and sensors.
- an electrolyte or a polymer electrolyte containing an electrolyte to form a gel is used from the viewpoint of ionic conductivity. It has been pointed out that there is a risk of damage to the equipment due to leakage of the electrolyte, and that the electrolyte reacts with the positive electrode and the negative electrode, resulting in deterioration of electrochemical characteristics.
- solid electrolytes such as inorganic crystalline substances, inorganic glasses, and organic polymer substances have been proposed.
- Organic polymer-based substances generally have excellent processability and formability, and the resulting solid electrolyte has flexibility and bendability, and the progress has been made in terms of increasing the degree of freedom in designing devices to be applied. Is expected. However, it is currently inferior to other materials in terms of ion conductivity.
- Japanese Patent Application Laid-Open No. 9-324114 proposes an attempt to incorporate a specific metal salt into a crosslinked diethyleneglyconolemethyldaricidinoleatethrethylene oxide and apply it to a polymer solid electrolyte.
- practically sufficient conductivity values have not been obtained.
- a solid polymer electrolyte containing an aprotic organic solvent or a derivative of a branched polyethylene glycol has been proposed in WO98 / 07772 including the present applicant.
- lithium metal is used for the electrodes, these electrolytes react with the lithium metal or precipitate dendrites on the surface of the lithium metal, and the electrochemical characteristics are significantly reduced. Disclosure of the invention
- An object of the present invention is to provide an electrolyte composition having excellent ionic conductivity and electrochemical properties, particularly a polymer electrolyte.
- the present invention is a.
- an electrolyte composition comprising at least one of the components (1) and (2).
- the present invention also provides a battery using the electrolyte composition.
- the solid electrolyte composition of the present invention is excellent in processability, moldability, mechanical strength, flexibility, heat resistance, and the like, and its electrochemical properties to lithium metal are remarkably improved. Therefore, including solid-state batteries (especially secondary batteries), large-capacity capacitors, It can be applied to display devices, for example, electronic devices such as elect-open chromic displays. Preferred embodiments of the invention
- the electrolyte composition of the present invention contains at least one of the polymer (1) and the additive (2).
- the electrolyte composition may include both the polymer (1) and the additive (2).
- the polymer having an ether bond (1) is a copolymer having a structural unit represented by the following formula (i) and a structural unit represented by the following formula (ii), or the structural unit (i) It is preferable that the copolymer is a copolymer having a structural unit (ii) and a crosslinkable structural unit represented by the following formula (iii). Further, a random copolymer is preferred. -CH 2 -CH -0 +
- R 1 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group or -C3 ⁇ 40_R 2
- R 2 represents an alkyl group having 1 to 6 carbon atoms or a fuel group or-(-CH 2 -CH 2 -0_ ) a -R 2 'or -CH [CH 2 -0- (-CH 2 -CH 2 _0-) b -R 2 '] 2
- R 2 ' is an alkyl group having 1 to 6 carbon atoms
- a and b is an integer from 0 to 12.
- R 3 represents (a) a reactive silicon group, (b) a methyl epoxy group, (c) an ethylenically unsaturated group, or (d) a reactive group having a halogen atom]
- the monomer constituting the structural unit (i) in the polymer (1) is ethylene oxide.
- the oxysilane compound constituting the structural unit (ii) in the polymer (1) includes an alkylene oxide which may have a substituent, a glycidyl ether compound, and the like.
- an alkylene oxide which may have a substituent, a glycidyl ether compound, and the like.
- propylene compounds methyldaricidyl ether, butyl glycidyl / leatenole, styreneoxide, phenyldaricide / leetezole, 1,2-epoxyhexane and other oxysilane compounds, ethylene glycol methyldaricidyl ether, diethylene glycol methyl davisidyl Ether, triethylene glycol methyldaricidyl ether, 1,3_bis (2-methoxetoxy) propane 2-glycidyl ether, 1,3_bis [2- (2-methoxetoxy) ethoxy] propane 2-glycidyl Ether
- the reactive functional groups of the oxysilane compound forming the crosslinkable structural unit (iii) in the polymer (1) include (a) a reactive silicon group, (b) a methyl epoxy group,
- Oxysilane compounds having a reactive silicon group (a) include 2-glycidoxyshethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-dalicydoxypropyltrimethoxysilane, and 4-glycidoxybutyl. Methyltrimethoxysilane, 3- (1,2-epoxy) propyltrimethoxysilane, 4- (1,2-epoxy) ptinoletrimethoxysilane, 5- (1,2-epoxy) pentyltrimethoxysilane,
- Examples thereof include 1- (3,4-epoxycyclohexyl) methylmethinoresimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Of these, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane are particularly preferred.
- the oxysilane compounds having a methyl epoxy group (b) include 2,3-epoxypropyl-2 ', 3, -epoxy-2'-methinolepropynoleatenoate, ethylene glycol-2,3-epoxypropyl- 2 ', 3'-epoxy-2'-methylpropyl ether, and diethylene glycol 1,2,3-epoxypropinole 2', 3'-epoxy-2'-methinolepropynoleether, 2-methyl- 1,2,3,4-diepoxybutane, 2-methyl-1,2,4,5-diepoxypentane, 2-methyl-1,2,5,6-diepoxyhexane, hydroquinone-2,3- Epoxypropyl-
- 2,3-epoxypropyl-2 ', 3'-epoxy-2, -methylpropylether, and ethylene glycol-2,3-epoxypropyl-2', 3, -epoxy-2'- Methyl propyl ether is preferred.
- Oxysilane compounds having an ethylenically unsaturated group (c) include aryl glycidyl ether, 4-vinylcyclohexyl glycidyl ether, ⁇ -tervinyl darici dinore enoate, cyclohexenyl methyl daricidinoreatenore, ⁇ -vinylinvenezinole glycidyl.
- Ether phenylphenyldaricidyl ether, bulglycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-1-pentene, 4,5-epoxy-2-pentene, 1,2-epoxy -5,9-cyclododecadiene, 3,4-epoxy-1-vinyl bin hexene, 1,2-epoxy-5-cycline otaten, glycidyl acrylate, glycidyl methacrylate, glycidyl sorbate, cay skin Glycidyl acid, glycidyl crotonate, and glycidyl-4-hexenoate are used.
- allylic glycidyl ether, glycidyl acrylate, and glycidyl methacrylate are exemplified.
- Examples of the oxysilane compound having a halogen atom (d) include epibromohydrin, epipodhydrin, and epichlorohydrin.
- Polymerization of a polymer having an ether bond is a polymerization method for obtaining a multi-component copolymer by a ring-opening reaction of an ethylene oxide portion, and is described in JP-A-63-154736 and JP-A-62-169823. It is performed in the same way as the method.
- the polymerization reaction can be performed as follows. Each monomer is used in the presence or absence of a solvent using a catalyst system mainly composed of organic aluminum, a catalyst system mainly composed of organic zinc, a catalyst system composed of an organotin-phosphate ester condensate, etc. as a catalyst for ring-opening polymerization.
- the reaction is carried out at a reaction temperature of 10 to 80 ° C. under stirring to obtain a polyether copolymer.
- an organic tin-phosphate ester condensate catalyst system is particularly preferred in view of the degree of polymerization or the properties of the copolymer to be produced.
- the reactive functional groups do not react in the polymerization reaction, and a polymer (1) having a reactive functional group is obtained.
- the proportion of ethylene oxide constituting the structural unit (i) is 10 to 95% by weight, preferably 20 to 90% by weight, based on the polymer (1) having an ether bond used in the electrolyte composition of the present invention.
- the amount of the oxysilane compound constituting the structural unit (ii) is 90 to 5% by weight, preferably 80 to 10% by weight, and the amount of the oxirane compound constituting the crosslinkable structural unit (iii) is 0 to 30% by weight, preferably Is 0 ⁇ 20 weight ° / 0 , especially 0.1 ⁇ 20 weight ° / 0 It is.
- the crosslinked polymer has good ionic conductivity.
- the lithium salt compound When the amount of ethylene oxide constituting the structural unit (i) is 10% by weight or more, the lithium salt compound is easily dissolved even at a low temperature, so that the ionic conductivity is high.
- the ion conductivity is improved by lowering the glass transition temperature.
- the effect of improving the ion conductivity was found to be extremely large.
- the molecular weight of the polymer used in the polymer electrolyte composition should be in the range of 10 4 to 10 8 , preferably 10 5 to 10 to obtain good processability, moldability, mechanical strength, and flexibility. Those within the range of 10 7 are suitable.
- crosslinking can be performed by reacting the reactive silicon group with water.
- tin compounds such as dibutyltin diallate and dibutyltin malate, titanium conjugates such as tetrabutyl titanate and tetrapropyl titanate, aluminum trisacetyl acetate, aluminum trisethyl acetate and aluminum trisethyl acetate
- An organic metal compound such as an aluminum compound such as aluminum such as tate, or an amine compound such as butylamine and octylamine may be used as a catalyst.
- polyamines examples include aliphatic polyamines such as diethylenetriamine and dipropylenetriamine, and aromatic polyamines such as 4,4′-diaminodiphenylether, diaminodiphenylinolenolephone, m-phenylenediamine, and xylylenediamine.
- the amount of the polyamine varies depending on the type of the polyamine, but is usually in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer electrolyte composition excluding the plasticizer (i.e., the additive (2)).
- acid anhydrides examples include maleic anhydride, phthalic anhydride, methylhexahydroanhydrophthalic acid, tetramethylene maleic anhydride, tetrahydrophthalic anhydride and the like.
- the amount of acid anhydride to be added depends on the type of acid anhydride, but usually plasticizer Is in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer electrolyte composition excluding the above. Accelerators may be used for these cross-links.
- Examples of the cross-linking reaction of polyamines include phenol, cresol, and resorcinol, and those for the cross-linking reaction of acid anhydrides include benzyldimethylamine and 2- (dimethylaminoethyl) phenol. , Dimethylaniline and the like.
- the amount of the accelerator added varies depending on the accelerator, but is usually in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the crosslinking agent.
- the reactive functional group is an ethylenically unsaturated group (c)
- a radical initiator selected from organic peroxides, azo compounds, etc., ultraviolet rays, electron beams, etc. Active energy rays are used.
- a crosslinking agent having silicon hydride can be used.
- organic peroxides those commonly used for cross-linking, such as ketone peroxides, hydroxyketals, hide peroxides, dialkyl peroxides, disilyl oxides, and peroxide esters, are used. , 1, 1-bis ( ⁇ -butylperoxy)-3,3,5-trimethylcyclohexane, di-t-butylperoxide, t-butyltamyl peroxide, dicumyl peroxide, 2,5-dimethyl- 2,5-di (t-butylperoxy) hexane, benzoyl peroxide, and the like.
- the amount of the organic peroxide varies depending on the type of the organic peroxide, but is usually in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer electrolyte composition excluding the plasticizer.
- azo compound azonitrile compounds, azomido compounds, azamidine compounds, and the like, which are usually used for cross-linking applications, are used.
- Nitrile 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2-methynole-N-phenyllpionamidine) dihydrochloride, 2, 2'- Azobis [2- (2-imidazoline-2-inole) propane], 2,2, -zozobis [2-methyl-N- (2-hydroxyethyl) propionamide],
- the amount of the azo compound to be added varies depending on the type of the azo compound, but is usually in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer electrolyte composition excluding the plasticizer.
- active energy rays such as ultraviolet rays
- glycidyl ether acrylate, glycidyl methacrylate, and glycidyl citrate are particularly preferable.
- acetophenones such as jetoxyacetophenone, 2-hydroxy-2-methinole-1-phenylpropan-1-one, and phenylketone
- benzoins such as benzoin and benzoin methinooleatenole.
- benzophenone, benzophenones such as 4-phenobenzobenzophenone
- thioxanthones such as 2-isopropylthioxanthone and 2,4-dimethylthioxanthone
- 3-sulfonyl azide benzoic acid 3-sulfonyl azide benzoic acid
- 4-sulfonyl azide benzoate Azides such as acids can be used arbitrarily.
- a compound having at least two silicon hydrides is used.
- a polysiloxane compound or a polysilane compound is preferable.
- Examples of the catalyst for the hydrosilylation reaction include transition metals such as palladium and platinum, or compounds and complexes thereof. Also, peroxides, amines and phosphines are used. The most common catalysts are dichlorobis (acetonitrile) palladium (II), chlorotris (triphenylphosphine) rhodium (I), and chloroplatinic acid.
- crosslinking agents such as polyamines, mercaptoimidazolines, mercaptopyrimidines, thiopereas, and polymercapbutanes are used.
- polyamines include triethylenetetramine, hexamethylenediamine and the like.
- mercaptoimidazolines include 2-mercaptoimidazoline, 4-methyl-2-mercaptoimidazoline, and the like.
- mercaptopyrimidines include 2-mercaptopyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, and the like. No.
- Examples of the thiorea include ethylene thiorea and dibutyl thiourea.
- Examples of the polymercaptans include 2-dibutylamino-4,6-dimethylcapto-s-triazine, 2_phenylamino-4,6-dimercaptotriazine, and the like.
- the amount of the crosslinking agent varies depending on the type of the crosslinking agent, but is usually in the range of 0.1 to 30 parts by weight based on 100 parts by weight of the polymer electrolyte composition excluding the plasticizer. Further, it is effective to further add a metal compound serving as an acid acceptor to the solid polymer electrolyte, in view of the thermal stability of the NOGEN-containing polymer.
- the metal oxide serving as the acid acceptor examples include oxides, hydroxides, carbonates, carbonates, silicates, borates, and phosphites of Group II metals of the periodic table. And Periodic Table VI Group a metal oxides, basic carbonates, basic carboxylates, basic phosphites, basic sulfites, tribasic sulfates and the like. Specific examples include magnesia, magnesium hydroxide, magnesium carbonate, calcium silicate, calcium stearate, lead gall, tin stearate, and the like.
- the amount of the metal compound serving as the acid acceptor varies depending on the type, but is usually in the range of 0.1 to 30 parts by weight based on 100 parts by weight of the polymer electrolyte composition excluding the plasticizer.
- the additive (2) containing an ether compound having an ethylene oxide unit functions as a plasticizer.
- an additive (2) containing an ether compound having an ethylene oxide unit is added to the polymer electrolyte composition, crystallization of the polymer is suppressed, the glass transition temperature is reduced, and many amorphous phases are formed even at a low temperature. Therefore, the ion conductivity increases. .
- an additive represented by any of the following formulas (iv) to (vii) is preferable.
- R 18 is an alkyl group having 1 to 6 carbon atoms, and cr is a number of 0 to 12.
- the mixing ratio of the additive (2) is arbitrary, but the total of the polymer (1) and the additive (2) is 100 parts by weight.
- the lithium salt compound (3) used in the present invention is preferably soluble in the mixture of the polymer (1), the additive (2) and the cyclic carbonate (4). In the present invention, the following lithium salt compounds are preferably used.
- X 2 , 3 ⁇ 4, and Y are electron-withdrawing groups.
- X 2 , and 3 ⁇ 4 each independently have 1 to 6 carbon atoms A perfluoroalkyl group or a perfluoroalkyl group;
- Y is a nitro group, a nitroso group, a carboxy group, a carboxy group or a cyano group.
- 3 ⁇ 4, x 2 and x 3 may be the same or different.
- the amount of the lithium salt compound (3) used is 0.1 to 100 parts by weight, preferably 100 parts by weight, based on 100 parts by weight of the polymer (1) and the additive (2) in total.
- the ff is less than 100 parts by weight, the stiffness, the moldability, the mechanical strength and the flexibility of the obtained solid electrolyte are high, and the heat conductivity is also high.
- Flame retardants include brominated epoxy compounds, halides such as tetrabromobisphenol, chlorinated paraffin, antimony trioxide, antimony pentoxide, aluminum hydroxide, magnesium hydroxide, phosphate esters, and polyphosphoric acid.
- An effective amount (for example, 10 parts by weight or less based on 100 parts by weight of the total of the polymer (1) and the additive (2)) is selected from acid salts and zinc borate.
- the unsaturated group is generally a carbon-carbon double bond.
- the cyclic carbonate (4) reacts with the lithium metal of the negative electrode to form a stable film, and suppresses the reaction between the electrolyte and the lithium metal and the growth of dendrites.
- the cyclic carbonate (4) is preferably biene carbonate or a derivative thereof, or ethylene carbonate having an unsaturated group.
- bilene carbonate or a derivative thereof is a compound represented by the following formula (viii-1)! / ,.
- R 21 is H or an alkyl group having 1 to 6 carbon atoms
- R 22 is an alkenyl group having 1 to 6 carbon atoms or -C3 ⁇ 4R 22 ′
- R 22 ′ is a carbon atom having 1 to 6 carbon atoms. 6 alkenyl groups.
- the amount of the cyclic carbonate (4) used is in the range of 1 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the total of the components (1) and (2).
- the optimal amount is such that the surface of the lithium metal reacts with the cyclic carbonate to form a stable film. If excess cyclic carbonate is present in the polymer electrolyte composition, the electrochemical properties will be reduced.
- the method for containing the cyclic carbonate (4) is not particularly limited as long as the components (1), (2) and (3) are not crosslinked.
- the cyclic carbonate (4) is obtained from the components (1), (2) and (3). It is necessary to impregnate the electrolyte compound after crosslinking. If the crosslinking is carried out after the inclusion of the cyclic carbonate (4) before the crosslinking of the electrolyte compound comprising the components (1), (2) and (3), the electrochemical properties are not improved. This is probably because the ethylenically unsaturated group of the cyclic carbonate (4) has disappeared due to crosslinking.
- the method of impregnating the cyclic carbonate (4) is not particularly limited, but the components (1) and (2)
- the method for producing the polymer electrolyte composition of the present invention is not particularly limited, but each component may be usually mechanically mixed.
- the components are mechanically mixed and then cross-linked. good.
- mechanically mixing various kinds of eders, open rolls, extruders and the like can be arbitrarily used.
- the amount of water used for the cross-linking reaction is not particularly limited because it is easily caused by moisture in the atmosphere.
- Cross-linking can also be achieved by passing the mixture through a cold or hot water bath for a short time, or by exposing it to a steam atmosphere.
- the crosslinking reaction is completed in a temperature of 10 ° C to 200 ° C for 1 minute to 20 hours.
- an energy ray such as an ultraviolet ray
- a sensitizer is generally used.
- the crosslinking reaction is completed in 0.1 second to 1 hour under the temperature condition of 10 ° C. to 150 ° C.
- the crosslinking reaction is completed within 10 minutes to 10 hours at a temperature of 10 ° C to 180 ° C.
- the method of mixing the lithium salt conjugate (3) and the additive (2) with the polymer (1) is not particularly limited, but an organic solvent may be used if necessary. Can be. When using an organic solvent, various polar solvents such as tetrahydrofuran, acetone, acetonitrile, dimethylformamide, dimethylsulfoxide, dioxane, methylethylketone, and methylisobutylketone are used alone or in combination. Used.
- the polymer electrolyte composition shown in the present invention is excellent in mechanical strength and flexibility, and can be easily obtained as a large area thin film solid electrolyte by utilizing its properties.
- a battery can be produced using the polymer electrolyte composition of the present invention.
- the positive electrode material lithium-manganese composite oxide, lithium cobalt oxide, vanadium pentoxide, olivine-type iron phosphate, polyacetylene, polypyrene, polyaniline, polyphenylene, polyphenylene sulfide, polyphenylene oxide , Polypyrrole, polyfuran, polyazulene, etc.
- the negative electrode material examples include an intercalation compound in which lithium is occluded between graphite and a carbon layer, lithium metal, lithium-lead alloy, and the like.
- cations such as metal ions, Cu ions, Ca ions, and Mg ions can be used as a diaphragm for ion electrodes.
- the polymer electrolyte composition of the present invention is particularly suitable as a material for electrochemical devices such as batteries, capacitors and sensors.
- the monomer-equivalent composition of the polyether copolymer was determined by using the R spectrum.
- the molecular weight of the polyether copolymer was measured by gel permeation chromatography, and the molecular weight was calculated in terms of standard polystyrene.
- Genoleme permeation chromatography was performed using Shimadzu Corporation's RID-6A measuring instrument, Showa Denko KK column Showdex KD-807, KD-806, KD-806M and KD-803, and solvent dimethylformamide. (DMF) at 60 ° C.
- the glass transition temperature was measured using a DSC 220 manufactured by Seiko Iden Kogyo Co., Ltd., and the heat of fusion was measured using a differential scanning calorimeter DSC 7 manufactured by PerkinElmer, Inc., in a nitrogen atmosphere, in the temperature range of -100 to 80 ° C, and the temperature was raised. Measured at a rate of 10 ° C / min.
- the sample film was vacuum dried at 30 ° C. for 12 hours in advance to measure the conductivity ⁇ .
- the conductivity was measured at 10 ° C, the film was sandwiched between SUS electrodes, and the complex impedance method was used, using an AC method with a voltage of 30 mV and a frequency range of 10 Hz to 10 MHz.
- the stability evaluation with lithium metal in the battery system was determined by a lithium deposition dissolution efficiency test.
- Nagano Corporation BTS-2004W charge / discharge tester was used for the lithium deposition dissolution efficiency test.
- a test cell was prepared by using metallic lithium for the copper foil and the counter electrode, and sandwiching the polymer electrolyte composition between the two electrodes. Li was deposited at room temperature at a current density of 0.1 IraA / cm 2 for 10 hours, and then dissolved at a current density of 0.1 mA m 2 to a final voltage of 2.0 V.
- Lithium deposition The melting angle / efficiency was determined by the following equation.
- Lithium precipitation dissolution efficiency (%) (time required for dissolution of nth cycle / time required for precipitation of nth cycle) X100 Synthesis example (manufacture of catalyst)
- the inside of a three-liter glass four-necked flask was replaced with nitrogen, and as a catalyst, 2 g of the condensed substance shown in the preparation example of the catalyst, 100 g of propylene oxide adjusted to a water content of 100 ppm or less, 10 g of glycidyl methacrylate, and a solvent Then, 1,000 g of n-hexane was charged, and 200 g of ethylene oxide was added successively while tracking the polymerization rate of propylene oxide by gas chromatography. The polymerization reaction was stopped with methanol.
- a 3-liter glass four-necked flask was replaced with nitrogen, and the catalyst was replaced with 2 g of the condensed substance shown in the catalyst production example and adjusted to less than lOppm of water.
- 100 g, 10 g of arylglycidyl ether, and 1,000 g of n_hexane as a solvent were charged, and 120 g of ethylene oxide was added successively while tracking the polymerization rate of GM by gas chromatography.
- the polymerization reaction was stopped with methanol. After removing the polymer by decantation, it was dried at 40 ° C under normal pressure for 24 hours, and further reduced at 45 ° C for 10 hours under reduced pressure to obtain 205 g of a polymer.
- the glass transition temperature of this copolymer was -74 ° C, the weight-average molecular weight was 1.15 million, and the amount of heat generated was 3 J / g. 3 ⁇ 4 ⁇ ⁇ ⁇ ⁇ ⁇
- the monomer analysis result of this copolymer based on R spectrum was 53 wt% ethylene oxide, 43 wt% GM, and 4 wt ° / aryl glycidyl ether. Met.
- iv-1 lithium bis (trifluoromethylsulfonyl) imide
- 1 g an ether compound having an ethylene oxide unit of the above formula (iv-1) was prepared.
- Example 3 Example 3
- LiBETI lithium bis (perfluoroethylsulfoninole) imide
- LiTFSI lithium bis (trifluoromethylsulfonyl) imide
- Example 8 The electrolyte crosslinked film of Example 3 0.2 wt. /.
- the results are shown in Table 1.
- Example 8 The average value of the lithium precipitation dissolution efficiency of the electrolyte composition impregnated with 0.02 g of the ether compound having an ethylene oxide unit of the above formula (vii-1) containing vinylene carbonate was 92%. The results are shown in Table 1.
- Example 8 The results are shown in Table 1.
- Example 9 The electrolyte crosslinked film of Example 3 40 wt / Og. /.
- the results are shown in Table 1.
- Lithium deposition dissolution efficiency of electrolyte composition impregnated with 0.02 g of ether compound having ethylene oxide unit of the above formula (vii-1) containing 60 wt% of vinylene carbonate with respect to Olg was 91%.
- the result See Table 1. Comparative Example 1
- Ethylene oxide / EM / aryl glycidyl ether ternary copolymer lg having a weight-average molecular weight of S1.3 million obtained in Polymerization Example 3 lg, an ether compound having an ethylene oxide unit of the above formula (iv-1) 2 g of an additive containing, 0.7 g of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) as a lithium salt compound, 0.015 g of benzoyl peroxide as an initiator, and ethylene glycol diacrylate as a crosslinking aid After mixing 0.3 g of the rate and 20 wt% of vinylene carbonate with respect to the electrolyte in 50 g of acetonitrile until uniform, the mixture was uniformly applied to a PET film.
- LiTFSI lithium bis (trifluoromethylsulfonyl) imide
- Ethylene oxide / GM / aryl glycidyl ether ternary copolymer lg having a weight average molecular weight of 1.3 million obtained in Polymerization Example 4, an ether compound having an ethylene oxide unit of the above formula (vii-1) 2 g, containing lithium bis (perfluoroethylsulfoninole) imide (LiBETI) 0.8 g as a lithium salt compound, 0.015 g benzoyl peroxide as an initiator, and ethylene glycol diamine as a crosslinking aid After mixing 0.3 g of acrylate and 50 wt% of vinylene carbonate with respect to the electrolyte in 50 g of acetonitrile until uniform, the mixture was uniformly applied to a PET film.
- LiBETI lithium bis (perfluoroethylsulfoninole) imide
- Lithium deposition efficiency of the electrolyte composition impregnated with 0.02 g of an athenole compound having an ethylene oxide unit of the above formula (vii-1) containing 120 wt% of vinylene carbonate with respect to Olg in the electrolyte crosslinked film of Example 2 was 71%. The results are shown in Table 1.
- a secondary battery was formed using the electrolyte composition obtained in Example 6, a lithium metal foil as a negative electrode, and lithium cobalt oxide (LiCoO 2 ) as a positive electrode active material.
- Lithium copartate was prepared by mixing predetermined amounts of lithium carbonate and cobalt carbonate powder and then calcining at 900 ° C for 5 hours. Next, this was ground, and 5 parts by weight of acetylene black and 10 parts by weight of the polymer obtained in Polymerization Example 2 were added to 85 parts by weight of the obtained lithium cobaltate, and lithium bis (trifluoromethylsulfonyl) was used. After adding 5 parts by weight of imid (LiTFSI) and mixing with a roll, press molding at a pressure of 30 MPa Positive electrode of the pond.
- LiTFSI imid
- Example 6 The electrolyte composition obtained in Example 6 was sandwiched between a lithium metal foil and a positive electrode plate, and the charge / discharge characteristics of the battery were examined at room temperature while applying a pressure of 1 MPa so that the interface was in close contact. Charging was performed at a constant current and voltage up to 4.2 V, and discharging was performed at a constant current. The discharge current was 0.1 mA m 2 , and charging was performed at 0.1 mA / cm 2 . The discharge capacity after 100 cycles of charge and discharge showed 90% of the initial capacity.
- Example 11 The discharge capacity after 100 cycles of charge and discharge showed 90% of the initial capacity.
- Example 7 Using the electrolyte composition obtained in Example 7, a lithium metal foil as the negative electrode, and the positive electrode prepared in Example 10, a secondary battery was prepared, and the charge / discharge characteristics were examined in the same manner. The discharge capacity after charge / discharge of 100 ital showed 91% of the initial capacity. Comparative Example 5
- Example 1 2 Using the electrolyte composition obtained in Comparative Example 3, a lithium metal foil as a negative electrode, and the positive electrode prepared in Example 10, a secondary battery was prepared, and charge / discharge characteristics were examined in the same manner. The discharge capacity after charge / discharge of 100 tals was 78% of the initial capacity.
- Example 1 2 Using the electrolyte composition obtained in Comparative Example 3, a lithium metal foil as a negative electrode, and the positive electrode prepared in Example 10, a secondary battery was prepared, and charge / discharge characteristics were examined in the same manner. The discharge capacity after charge / discharge of 100 tals was 78% of the initial capacity.
- Example 1 2 Using the electrolyte composition obtained in Comparative Example 3, a lithium metal foil as a negative electrode, and the positive electrode prepared in Example 10, a secondary battery was prepared, and charge / discharge characteristics were examined in the same manner. The discharge capacity after charge / discharge of 100 tals was 78% of the initial capacity.
- Example 1 2 Using the electrolyte composition obtained in Comparative Example 3,
- Example 18 Using 0.060 g (50 wt%) of vinylene carbonate and 0.060 g (50 wt%) of an ether compound having an ethylene oxide unit represented by the above formula (vii-1), and using the same lithium electrolyte as in Example 12 except for the above. The average value of the precipitation dissolution efficiency was 91%. The results are shown in Table 2.
- Example 18
- the average value was obtained by averaging the values of the lithium precipitation dissolution efficiency up to the 20th cycle.
- Example 13 A porous separator impregnated with the electrolyte of Example 3 (E25MMS thickness 25 ⁇ , manufactured by Tonen Tapils Co., Ltd., porosity 38%), a lithium metal foil as a negative electrode, and lithium cobalt oxide as a positive electrode active material were used. To form a secondary battery.
- Lithium conolate was prepared by mixing predetermined amounts of lithium carbonate and cobalt carbonate powder and then calcining at 900 ° C for 5 hours. (7) The mixture is ground on a fire, 4 parts by weight of acetylene black and 6 parts by weight of polyvinylidene fluoride are added to 90 parts by weight of the obtained lithium cobaltate, mixed with a roll, and press-molded at a pressure of 30 MPa. Used as the positive electrode of the battery.
- Example 20 The porous separator impregnated with the electrolyte of Example 13 was sandwiched between a lithium metal foil and a positive electrode plate, and the charge / discharge characteristics of the battery were examined at 25 ° C while applying IMPa pressure so that the interface was in close contact. Charging current density 0. 1 mA N m 2, line Le , discharged at a constant current and constant voltage up to the upper limit voltage 4. 2V was performed at a constant current of m 2 N current density 0. 1 mA. The discharge capacity after 100 cycles of charge and discharge was 86% of the initial capacity.
- Example 20 The porous separator impregnated with the electrolyte of Example 13 was sandwiched between a lithium metal foil and a positive electrode plate, and the charge / discharge characteristics of the battery were examined at 25 ° C while applying IMPa pressure so that the interface was in close contact. Charging current density 0. 1 mA N m 2, line Le , discharged at a constant current and constant voltage up to the upper limit voltage 4. 2V was performed at
- a secondary battery was prepared using the porous separator impregnated with the electrolyte of Example 15, a lithium metal foil as the negative electrode, and the positive electrode prepared in Example 19, as in Example 19.
- the charge and discharge characteristics were examined in the same manner.
- the discharge capacity after 100 cycles of charge / discharge showed 88% of the initial capacity. Comparative Example 9
- a secondary battery was prepared using the porous separator impregnated with the electrolyte of Comparative Example 7, a lithium metal foil as the negative electrode, and the positive electrode prepared in Example 19, and the charge / discharge characteristics were examined in the same manner as in Example 19 Was.
- the discharge capacity after 100 cycles of charge and discharge showed 64% of the initial capacity. Comparative Example 10
- a secondary battery was prepared using the porous separator impregnated with the electrolyte of Comparative Example 8, a lithium metal foil as the negative electrode, and the positive electrode prepared in Example 19, and the charge / discharge characteristics were examined in the same manner as in Example 19 Was.
- the discharge capacity after 100 cycles of charging and discharging represents 43% of the initial capacity.
- a lithium salt compound 0.7 g of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) is mixed in 50 g of acetonitrile until uniform, and both sides are coated on a porous film having a thickness of 20 ⁇ . Drying under reduced pressure at 12 ° C for 12 hours gave a 63 ⁇ 4mi electrolyte film including a porous membrane.
- Example 22 1 g of an ethylene oxide / propylene oxide / glycidyl methacrylate terpolymer having a weight average molecular weight of 1.7 million obtained in Polymerization Example 2, containing an ether compound having an ethylene oxide unit of the above formula (iv-1) 2 g of additive, 0.7 g of LiTFSI as lithium chloride, 0.015 g of benzoyl peroxide as initiator, and 0.3 g of ethylene glycol diacrylate as a cross-linking aid are mixed in 50 g of acetonitrile until uniform. After that, it was uniformly applied to a polyethylene terephthalate resin (PET) film. Thereafter, the resultant was dried under reduced pressure at 30 ° C. for 12 hours, and further heated at 100 ° C. for 3 hours under a nitrogen atmosphere to obtain a 50 ⁇ ⁇ ⁇ electrolyte crosslinked film.
- PET polyethylene terephthalate resin
- Example 21 6 wt% with respect to the electrolyte film O. Olg of 1. /.
- Example 26
- Example 22 Crosslinked electrolyte film excluding PET film of Example 2 0.Ether compound having an ethylene oxide unit of the above formula (vii-1) containing 12% by weight of vinylethylene carbonate and 1 mol / kg of LiTFSI based on Olg. The average value of the lithium precipitation dissolution efficiency of the polymer electrolyte composition impregnated with 02 g was 82%. The results are shown in Table 3.
- Example 2 7
- Example 23 Electrolyte crosslinked film of 3. 18 wt ° / Og to Olg.
- the results are shown in Table 3.
- Example 24 Electrolyte cross-linked film of 4. 20 wt ° / with respect to Olg. The average value of the lithium precipitation dissolution efficiency of the polymer electrolyte composition impregnated with 0.02 g of the ether compound having ethylene oxide units of the above formula (vii-1) containing Bier ethylene carbonate was 93%. The results are shown in Table 3.
- Example 24 The electrolyte crosslinked film of 4 O / Olg 50wt ° /. The average value of the lithium precipitation dissolution efficiency of a polymer electrolyte composition impregnated with 0.02 g of an ethylene oxide compound having an ethylene oxide unit of the above formula (vii-1) containing butyl ethylene carbonate was 90%. The results are shown in Table 3. Comparative Example 1 1
- Example 22 A polymer electrolyte composition impregnated with 0.02 g of an ether compound having an ethylene oxide unit of the above formula (vii-1) containing no vinyl ethylene carbonate with respect to the electrolyte crosslinked film O. Olg of 2 The average value of the lithium precipitation dissolution efficiency was 62%. The results are shown in Table 3. Comparative Example 1 2
- Example 23 A polymer impregnated with 0.02 g of an ether compound having an ethylene oxide unit of the above formula (vii-1) containing 20% by weight of ethylene carbonate based on the electroporous crosslinked film O. Olg of 3 The average value of the lithium deposition dissolution efficiency of the electrolyte composition was 58%. The results are shown in Table 3. Comparative Example 1 3
- Example 23 An ether compound having an ethylene oxide unit of the above formula (vii-1) containing 20 wt% of propylene carbonate with respect to the electrolyte crosslinked film O. Olg of 3
- Example 22 A polymer impregnated with 0.02 g of an ether compound having an ethylene oxide unit of the above formula (vii-1) containing 120 wt% of ethylene oxide / bottle with respect to 0.01 g of the electrolyte crosslinked film of 2
- the average lithium deposition efficiency of the electrolyte composition was 65%.
- Table 3 The results are shown in Table 3.
- a secondary battery was formed using the polymer electrolyte composition obtained in Example 26, a lithium metal foil as a negative electrode, and lithium cobalt oxide (LiCo02) as a positive electrode active material.
- Lithium conoretate was prepared by mixing predetermined amounts of lithium carbonate and cobalt carbonate powder and then calcining at 900 ° C for 5 hours. This was pulverized on fire, and 5 parts by weight of acetylene black, 10 parts by weight of the polymer obtained in Polymerization Example 2 and 5 parts by weight of LiTFSI were added to 85 parts by weight of the obtained lithium cobaltate, and mixed with a roll. Press forming was performed at a pressure of 30 MPa to obtain a positive electrode of the battery.
- Example 26 The polymer electrolyte composition obtained in Example 26 was sandwiched between a lithium metal foil and a positive electrode plate, and the charge / discharge characteristics of the battery were examined at room temperature while applying a pressure of 1 MPa so that the interface was in close contact. Charging was performed at a constant current and voltage up to 4.2 V, and discharging was performed at a constant current. The discharge current was 0.1 mA / cm 2 , and charging was performed at 0.1 mA m 2 . The discharge capacity after 100 cycles of charge and discharge showed 90% of the initial capacity.
- Example 3 1 The discharge capacity after 100 cycles of charge and discharge showed 90% of the initial capacity.
- Example 15 Using the polymer electrolyte composition obtained in Example 28, the lithium metal foil as the negative electrode, and the positive electrode prepared in Example 30, a secondary battery was prepared, and the charge / discharge characteristics were examined in the same manner. The discharge capacity after 100 cycles of charge and discharge showed 91% of the initial capacity. Comparative Example 15
- Example 3 2 Using the polymer electrolyte composition obtained in Comparative Example 11, a lithium metal foil as a negative electrode, and the positive electrode prepared in Example 30, a secondary battery was prepared, and the charge / discharge characteristics were similarly examined. The discharge capacity after 100 cycles of charge and discharge showed 80% of the initial capacity.
- Example 3 2 Using the polymer electrolyte composition obtained in Comparative Example 11, a lithium metal foil as a negative electrode, and the positive electrode prepared in Example 30, a secondary battery was prepared, and the charge / discharge characteristics were similarly examined. The discharge capacity after 100 cycles of charge and discharge showed 80% of the initial capacity.
- Example 3 2 Using the polymer electrolyte composition obtained in Comparative Example 11, a lithium metal foil as a negative electrode, and the positive electrode prepared in Example 30, a secondary battery was prepared, and the charge / discharge characteristics were similarly examined. The discharge capacity after 100 cycles of charge and discharge showed 80% of the initial capacity.
- Example 3 2 Using the polymer electrolyte composition obtained in Comparative Example 11, a lithium metal foil as
- Example 3 5 The same electrolyte as in Example 32 was used except that 0.012 g (10 wt%) of vinylene ethylene carbonate and 0.108 g (90 wt%) of an ether compound having an ethylene oxide unit represented by the above formula (iv-2) were used. The average value of the lithium precipitation dissolution efficiency was 93%. The results are shown in Table 4.
- Example 3 5 The same electrolyte as in Example 32 was used except that 0.012 g (10 wt%) of vinylene ethylene carbonate and 0.108 g (90 wt%) of an ether compound having an ethylene oxide unit represented by the above formula (iv-2) were used. The average value of the lithium precipitation dissolution efficiency was 93%. The results are shown in Table 4.
- Example 3 5 The same electrolyte as in Example 32 was used except that 0.012 g (10 wt%) of vinylene ethylene carbonate and 0.108 g (90 wt%) of an ether compound having an ethylene oxide unit represented by the above formula (iv-
- Example 3 7 Using 0.024 g (20 wt%) of butyl ethylene carbonate and 0.096 g (80 wt%) of an ether compound having an ethylene oxide unit of the above formula (vii_l), and otherwise dissolving lithium in the electrolyte in the same manner as in Example 35 The average efficiency was 89%. The results are shown in Table 4.
- Example 3 7 Using 0.024 g (20 wt%) of butyl ethylene carbonate and 0.096 g (80 wt%) of an ether compound having an ethylene oxide unit of the above formula (vii_l), and otherwise dissolving lithium in the electrolyte in the same manner as in Example 35 The average efficiency was 89%. The results are shown in Table 4.
- Example 3 7 Using 0.024 g (20 wt%) of butyl ethylene carbonate and 0.096 g (80 wt%) of an ether compound having an ethylene oxide unit of the above formula (vii_l), and otherwise dissolving lithium in the electrolyte in the same manner as
- the average value was obtained by averaging the values of lithium deposition and dissolution efficiency up to the 20th cycle.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Secondary Cells (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Primary Cells (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005505441A JP4640172B2 (ja) | 2003-04-15 | 2004-04-15 | 電解質組成物および電池 |
CA002522234A CA2522234A1 (en) | 2003-04-15 | 2004-04-15 | Electrolyte composition and cell |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003110011 | 2003-04-15 | ||
JP2003-110011 | 2003-04-15 | ||
JP2003-177688 | 2003-06-23 | ||
JP2003177688 | 2003-06-23 | ||
JP2004-082155 | 2004-03-22 | ||
JP2004082155 | 2004-03-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004092269A1 true WO2004092269A1 (ja) | 2004-10-28 |
Family
ID=33303690
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2004/005370 WO2004092269A1 (ja) | 2003-04-15 | 2004-04-15 | 電解質組成物および電池 |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP4640172B2 (ja) |
KR (1) | KR20060002984A (ja) |
CA (1) | CA2522234A1 (ja) |
WO (1) | WO2004092269A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006147279A (ja) * | 2004-11-18 | 2006-06-08 | Daiso Co Ltd | 電解質組成物および電池 |
JP2010165498A (ja) * | 2009-01-14 | 2010-07-29 | Panasonic Corp | リチウム一次電池 |
JP2018505538A (ja) * | 2015-02-09 | 2018-02-22 | ソリッドエナジー システムズ | 充電式リチウム電池の高塩濃度電解質 |
CN112713306A (zh) * | 2020-12-24 | 2021-04-27 | 清华大学深圳国际研究生院 | 一种遇空气或湿气可固化的电解液及制备方法和应用 |
CN113136159A (zh) * | 2021-04-27 | 2021-07-20 | 西南科技大学 | 一种通电可按需剥离的环氧结构胶黏剂的制备及使用方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102005448B1 (ko) | 2012-09-13 | 2019-07-31 | 삼성전자주식회사 | 리튬전지 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0525353A (ja) * | 1991-07-18 | 1993-02-02 | Matsushita Electric Ind Co Ltd | 高分子固体電解質 |
WO1998007772A1 (en) * | 1996-08-20 | 1998-02-26 | Daiso Co., Ltd. | Solid polyelectrolyte |
WO1998025990A1 (fr) * | 1996-12-09 | 1998-06-18 | Daiso Co., Ltd. | Electrolyte polymere solide comprenant du copolyether |
JPH10176105A (ja) * | 1996-12-17 | 1998-06-30 | Daiso Co Ltd | 高分子固体電解質 |
JP2000306425A (ja) * | 1999-04-19 | 2000-11-02 | Daiso Co Ltd | 架橋高分子固体電解質及びその用途 |
JP2000323170A (ja) * | 1999-05-07 | 2000-11-24 | Lion Corp | 電気化学的安定性に優れた非プロトン性溶媒 |
JP2003016835A (ja) * | 2001-07-04 | 2003-01-17 | Ube Ind Ltd | 高分子電解質及びその製造方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040146786A1 (en) * | 2001-05-10 | 2004-07-29 | Takaya Sato | Nonaqueous electolytic solution, composition for polymer gel electrolyte, polymer gel electrolyte, secondary cell, and electric double-layer capacitor |
JP5239106B2 (ja) * | 2001-05-23 | 2013-07-17 | 三菱化学株式会社 | 非水系電解液二次電池 |
JP2003031259A (ja) * | 2001-07-12 | 2003-01-31 | Japan Storage Battery Co Ltd | 非水電解質二次電池 |
-
2004
- 2004-04-15 CA CA002522234A patent/CA2522234A1/en not_active Abandoned
- 2004-04-15 KR KR1020057019410A patent/KR20060002984A/ko not_active Application Discontinuation
- 2004-04-15 JP JP2005505441A patent/JP4640172B2/ja not_active Expired - Fee Related
- 2004-04-15 WO PCT/JP2004/005370 patent/WO2004092269A1/ja active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0525353A (ja) * | 1991-07-18 | 1993-02-02 | Matsushita Electric Ind Co Ltd | 高分子固体電解質 |
WO1998007772A1 (en) * | 1996-08-20 | 1998-02-26 | Daiso Co., Ltd. | Solid polyelectrolyte |
WO1998025990A1 (fr) * | 1996-12-09 | 1998-06-18 | Daiso Co., Ltd. | Electrolyte polymere solide comprenant du copolyether |
JPH10176105A (ja) * | 1996-12-17 | 1998-06-30 | Daiso Co Ltd | 高分子固体電解質 |
JP2000306425A (ja) * | 1999-04-19 | 2000-11-02 | Daiso Co Ltd | 架橋高分子固体電解質及びその用途 |
JP2000323170A (ja) * | 1999-05-07 | 2000-11-24 | Lion Corp | 電気化学的安定性に優れた非プロトン性溶媒 |
JP2003016835A (ja) * | 2001-07-04 | 2003-01-17 | Ube Ind Ltd | 高分子電解質及びその製造方法 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006147279A (ja) * | 2004-11-18 | 2006-06-08 | Daiso Co Ltd | 電解質組成物および電池 |
JP4560721B2 (ja) * | 2004-11-18 | 2010-10-13 | ダイソー株式会社 | 電解質組成物および電池 |
JP2010165498A (ja) * | 2009-01-14 | 2010-07-29 | Panasonic Corp | リチウム一次電池 |
JP2018505538A (ja) * | 2015-02-09 | 2018-02-22 | ソリッドエナジー システムズ | 充電式リチウム電池の高塩濃度電解質 |
CN112713306A (zh) * | 2020-12-24 | 2021-04-27 | 清华大学深圳国际研究生院 | 一种遇空气或湿气可固化的电解液及制备方法和应用 |
CN113136159A (zh) * | 2021-04-27 | 2021-07-20 | 西南科技大学 | 一种通电可按需剥离的环氧结构胶黏剂的制备及使用方法 |
CN113136159B (zh) * | 2021-04-27 | 2022-07-19 | 西南科技大学 | 一种通电可按需剥离的环氧结构胶黏剂的制备及使用方法 |
Also Published As
Publication number | Publication date |
---|---|
JP4640172B2 (ja) | 2011-03-02 |
KR20060002984A (ko) | 2006-01-09 |
CA2522234A1 (en) | 2004-10-28 |
JPWO2004092269A1 (ja) | 2006-07-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3215440B2 (ja) | 高分子固体電解質 | |
JP3223978B2 (ja) | ポリエーテル共重合体および高分子固体電解質 | |
JP3215436B2 (ja) | 架橋高分子固体電解質及びその用途 | |
JP3301378B2 (ja) | ポリエーテル共重合体および架橋高分子固体電解質 | |
EP0994143B1 (en) | Solid polymer electrolyte and use thereof | |
JP4089221B2 (ja) | 高分子固体電解質および電池 | |
US6858351B2 (en) | Polyethylene oxide-based electrolyte containing silicon compound | |
JP4164131B2 (ja) | ポリエーテル共重合体、高分子固体電解質および電池 | |
WO2004113443A1 (ja) | 架橋高分子電解質及びその用途 | |
Mindemark et al. | Hydroxyl-functionalized poly (trimethylene carbonate) electrolytes for 3D-electrode configurations | |
JP3484974B2 (ja) | 新規なリチウムポリマー電池 | |
WO2000063292A1 (en) | Solid crosslinked-polymer electrolyte and use thereof | |
JP3282565B2 (ja) | 架橋高分子固体電解質及びその用途 | |
WO2004092269A1 (ja) | 電解質組成物および電池 | |
JP3427730B2 (ja) | リチウムポリマー電池 | |
JP4269648B2 (ja) | 電解質組成物および電池 | |
JP4089246B2 (ja) | 架橋高分子固体電解質および電池 | |
JP2006134817A (ja) | 電解質組成物および電池 | |
JP2000150308A (ja) | 電気二重層キャパシタ |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2005505441 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2522234 Country of ref document: CA Ref document number: 1020057019410 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 1020057019410 Country of ref document: KR |
|
122 | Ep: pct application non-entry in european phase |