JPH03238704A - High polymer solid electrolyte - Google Patents
High polymer solid electrolyteInfo
- Publication number
- JPH03238704A JPH03238704A JP2035449A JP3544990A JPH03238704A JP H03238704 A JPH03238704 A JP H03238704A JP 2035449 A JP2035449 A JP 2035449A JP 3544990 A JP3544990 A JP 3544990A JP H03238704 A JPH03238704 A JP H03238704A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- bridged
- polymer
- room temperature
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 15
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 11
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229920001940 conductive polymer Polymers 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 16
- VETIYACESIPJSO-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound OCCOCCOCCOC(=O)C=C VETIYACESIPJSO-UHFFFAOYSA-N 0.000 abstract description 2
- QUASZQPLPKGIJY-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound OCCOCCOCCOCCOC(=O)C=C QUASZQPLPKGIJY-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 230000036425 denaturation Effects 0.000 abstract 1
- 238000004925 denaturation Methods 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 27
- 239000010408 film Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- -1 alkali metal salt Chemical class 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 239000005518 polymer electrolyte Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000012456 homogeneous solution Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BJSBGAIKEORPFG-UHFFFAOYSA-N [[6-amino-1,2,3,4-tetramethoxy-4-(methoxyamino)-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CONC1(N(C(N(C(=N1)N)OC)(N(CO)OC)OC)OC)OC BJSBGAIKEORPFG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- MZGMQAMKOBOIDR-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCO MZGMQAMKOBOIDR-UHFFFAOYSA-N 0.000 description 1
- WBIOHYFEXBPYSK-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-methoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(O)COCCOCCOCCO WBIOHYFEXBPYSK-UHFFFAOYSA-N 0.000 description 1
- TVFJLSWPPLFHKR-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-phenoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOCCOCCOCC(O)OC1=CC=CC=C1 TVFJLSWPPLFHKR-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 101100229939 Mus musculus Gpsm1 gene Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical class OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-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
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- QGWKRYREOQNOCC-UHFFFAOYSA-N hydrogen peroxide;1-methyl-4-propan-2-ylbenzene Chemical compound OO.CC(C)C1=CC=C(C)C=C1 QGWKRYREOQNOCC-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000002827 triflate group Chemical class FC(S(=O)(=O)O*)(F)F 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- PADPILQDYPIHQQ-UHFFFAOYSA-L zinc;diperchlorate;hexahydrate Chemical compound O.O.O.O.O.O.[Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O PADPILQDYPIHQQ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- Y02E60/122—
Landscapes
- Primary Cells (AREA)
- Secondary Cells (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の目的〕
（産業上の利用分野）
本発明は、−次電池、二次電池、エレクトロクロミック
（Ｅ ＣＤ）表示素子など、従来、電解質が使用されて
いたところに使用することができるイオン伝導性高分子
固体電解質に関する。[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention is applicable to devices where electrolytes have been conventionally used, such as secondary batteries, secondary batteries, and electrochromic (ECD) display elements. The present invention relates to an ion-conductive polymer solid electrolyte that can be used for.
（従来の技術）
一次電池、二次電池、エレクトロクロミック（ＥＣＤ）
表示素子などの電解質には従来より液体のものが用いら
れてきた。(Prior technology) Primary battery, secondary battery, electrochromic (ECD)
Liquid electrolytes have traditionally been used in display elements and the like.
このため２部品外部への液漏れ、電極物質の溶出などが
発生しやすいために長期信頼性に問題がある。For this reason, liquid leakage to the outside of the two parts, elution of the electrode material, etc. are likely to occur, resulting in problems in long-term reliability.
それに対して、固体電解質はそのような問題がなく、ま
た薄膜にすることも可能となる。In contrast, solid electrolytes do not have such problems and can also be made into thin films.
特に、高分子物質を使用したものは、無機物に比べ１種
々の形状に加工できるメリットがある。In particular, materials using polymeric materials have the advantage of being able to be processed into a variety of shapes compared to inorganic materials.
こういった高分子電解質には、アルカリ金属塩をポリエ
チレンオキシド中に含有させた複合体が知られている（
例えば、Ｆａｓｔ Ｉｏｎ Ｔｒａｎｓｐｏｒｔ
ｉｎ ５ｏｌｉｄ、１３１．１９７９）。A complex of polyethylene oxide containing an alkali metal salt is known as such a polymer electrolyte (
For example, Fast Ion Transport
in 5olid, 131.1979).
（発明が解決しようとする課題） ポリエチレンオキシドとアルカリ金属塩とを複合した。(Problem to be solved by the invention) A composite of polyethylene oxide and an alkali metal salt.
上記の高分子固体電解質は耐熱性に乏しく。The above solid polymer electrolyte has poor heat resistance.
６０℃以上の温度では溶融してしまう。It will melt at temperatures above 60°C.
また、２５℃程度の室温下では固体状態であるが。Moreover, it is in a solid state at room temperature of about 25°C.
イオン伝導性が低いので、前述した一次電池、二次電池
、エレクトロクロミフク（Ｅ ＣＤ）表示素子などの電
解質に使用した場合、性能上充分に満足できるものでは
なかった。Because of its low ionic conductivity, when used as an electrolyte for the aforementioned primary batteries, secondary batteries, electrochromic display devices, etc., the performance was not fully satisfactory.
本発明は、イオン伝導性高分子固体電解質における高分
子として、上記ポリエチレンオキシドとは異なる特定の
高分子を用いることによって、室温下においても良好な
イオン伝導性を有し、６０℃以上の温度でも溶融しない
高分子固体電解質を提供するものである。The present invention uses a specific polymer different from the above-mentioned polyethylene oxide as the polymer in the ion-conducting polymer solid electrolyte, so that it has good ionic conductivity even at room temperature and even at temperatures of 60°C or higher. The present invention provides a solid polymer electrolyte that does not melt.
（課題を解決するための手段）
本発明は、上記の目的を達成するために鋭意研究を重ね
た結果、アクリロイル変性ポリアルキレンオキシド（１
）と１分子内に二重結合を有し、且つ少なくとも１つ以
上の官能基をもつ有機化合物■とを共重合してなるポリ
マー（Ａ）を架橋させて得られる架橋型樹脂、および金
属塩（Ｂ）とからなることを特徴とするイオン伝導性高
分子固体電解質を用いる事により、室温下においても良
好なイオン伝導性を示し、６０℃以上の温度でも溶融し
ない高分子固体電解質が得られることを見出した。(Means for Solving the Problems) As a result of extensive research in order to achieve the above object, the present invention has been developed using acryloyl-modified polyalkylene oxide (1
) and an organic compound (2) having a double bond and at least one functional group in one molecule, and a crosslinked resin obtained by crosslinking a polymer (A), and a metal salt. By using an ion-conductive polymer solid electrolyte characterized by consisting of (B), a polymer solid electrolyte that exhibits good ion conductivity even at room temperature and does not melt even at temperatures of 60°C or higher can be obtained. I discovered that.
また、上記の共重合ポリマーに自己架橋性のない場合に
は、アクリロイル変性ポリアルキレンオキシドと１分子
内に二重結合を有し、且つ少なくとも１つ以上の官能基
をもつ有機化合物■とを共重合してなるポリマー（Ａ＞
を架橋させて得られる架橋型ポリマー（Ａ）と架橋剤（
Ｃ）を架橋させて得られる架橋型樹脂、および金属塩（
Ｂ）とからなることを特徴とするイオン伝導性高分子固
体電解質を用いる事により、室温下においても良好なイ
オン伝導性を示し、６０℃以上の温度でも溶融しない高
分子固体電解質が得られることを見出した。In addition, if the above copolymer does not have self-crosslinking properties, acryloyl-modified polyalkylene oxide and an organic compound (2) having a double bond in one molecule and at least one functional group may be used. Polymer formed by polymerization (A>
A crosslinked polymer (A) obtained by crosslinking and a crosslinking agent (
A crosslinked resin obtained by crosslinking C), and a metal salt (
By using an ion-conductive polymer solid electrolyte characterized by B), it is possible to obtain a polymer solid electrolyte that exhibits good ionic conductivity even at room temperature and does not melt even at temperatures of 60°C or higher. I found out.
以下１本発明のイオン伝導性高分子固体電解質について
詳述する。The ion conductive polymer solid electrolyte of the present invention will be described in detail below.
本発明を構成する組成物の成分■であるアクリロイル変
性ポリアルキレンオキシドとしては１例えばトリエチレ
ングリコールモノアクリレート、テトラエチレングリコ
ールモノアクリレート、ポリエチレングリコールモノア
クリレート、メトキシテトラエチレングリコールモノア
クリレート、フェノキシテトラエチレングリコールモノ
アクリレート、メトキシポリエチレングリコールモノア
クリレート、トリエチレングリコールモノメタクリレー
ト、ポリエチレングリコールモノメタクリレート、メト
キシポリエチレングリコールモノメタクリレートポリエ
チレングリコールジアクリレーロポリエチレングリコー
ルジメタクリレート、および、これらの化合物のエチレ
ングリコール構造をプロピレングリコール構造に、また
エチレンオキサイドとプロピレンオキサイドとを任意の
割合で共重合構造にかえた化合物などが挙げられる。Examples of the acryloyl-modified polyalkylene oxide which is component (1) of the composition of the present invention include triethylene glycol monoacrylate, tetraethylene glycol monoacrylate, polyethylene glycol monoacrylate, methoxytetraethylene glycol monoacrylate, and phenoxytetraethylene glycol monoacrylate. Acrylate, methoxypolyethylene glycol monoacrylate, triethylene glycol monomethacrylate, polyethylene glycol monomethacrylate, methoxypolyethylene glycol monomethacrylate polyethylene glycol diacrylopolyethylene glycol dimethacrylate, and the ethylene glycol structure of these compounds to a propylene glycol structure, Also included are compounds in which ethylene oxide and propylene oxide are changed into a copolymer structure in an arbitrary ratio.
上記アクリロイル変性ポリアルキレンオキシドは。The above acryloyl-modified polyalkylene oxide is.
分子量には特に制限はない。There are no particular restrictions on the molecular weight.
また、上記アクリロイル変性ポリアルキレンオキシドは
２種以上併用してもよい。Furthermore, two or more of the above acryloyl-modified polyalkylene oxides may be used in combination.
本発明を構成する組成物の成分■である分子内に一重結
合を有し、且つ少なくとも１つ以上の官能基を持つ有機
化合物において、官能基としては、カルボキシル基、水
酸基、グリシジル基、イソシアネート基、アミノ基など
が挙げられる。In the organic compound having a single bond in the molecule and at least one functional group, which is component (1) of the composition constituting the present invention, the functional group includes a carboxyl group, a hydroxyl group, a glycidyl group, an isocyanate group. , amino group, etc.
具体的には、アクリル酸、メタクリル酸、２−ヒドロキ
シエチル（メタ）アクリレート グリシジル（メタ）ア
クリレート、２−イソシアナトエチル（メタ）アクリレ
ート、アミノエチル（メタ）アクリレートなどのアクリ
ルモノマーなどや、或いは、 （無水）マレイン酸、
（無水）イタコン酸、 （無水）テトラヒドロフタル酸
などが挙げられる。Specifically, acrylic monomers such as acrylic acid, methacrylic acid, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, 2-isocyanatoethyl (meth)acrylate, and aminoethyl (meth)acrylate, or, (maleic anhydride,
(anhydrous) itaconic acid, (anhydrous) tetrahydrophthalic acid, etc.
また、上記成分■である分子内に二重結合を有し。In addition, it has a double bond in the molecule which is the component (2) above.
且つ少なくとも１つ以上の官能基を持つ有機化合物は２
種類以上併用することができる。And the organic compound having at least one functional group is 2
More than one type can be used together.
前述の成分（１）と成分（２）を共重合してなるポリマ
ー（Ａ）を得る方法としては、必要ならば、成分（１）
と成分■に開始剤ならびに適当な溶剤を加え、これを加
熱しながら撹拌することによ゛って得られる。As a method for obtaining the polymer (A) formed by copolymerizing the above-mentioned component (1) and component (2), if necessary, component (1)
It can be obtained by adding an initiator and a suitable solvent to component (1) and stirring the mixture while heating.
開始剤としては例えば、ｔｅｒｔ−ブチルヒドロパーオ
キサイド、１，１．３．３−テトラメチルブチルヒドロ
パーオキサイド、ｐ−メンタンヒドロパーオキサイド、
クメンヒドロパーオキサイド、メチルエチルケトンパー
オキサイド、ｐ−サイメンヒドロパーオキサイド、ジイ
ソプロピルベンゼンヒドロパーオキサイド、２．５−ジ
メチルヘキサン−２゜５−ジヒドロパーオキサイド、シ
クロヘキサノンパ−オキサイド、３．３．５−）リメチ
ルヘキサノンバーオキサイド、などのヒドロパーオキサ
イド類。Examples of the initiator include tert-butyl hydroperoxide, 1,1.3.3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide,
Cumene hydroperoxide, methyl ethyl ketone peroxide, p-cymene hydroperoxide, diisopropylbenzene hydroperoxide, 2.5-dimethylhexane-2°5-dihydroperoxide, cyclohexanone peroxide, 3.3.5-) Hydroperoxides such as methylhexanone peroxide.
ジーｔｅｒｔ−ブチルパーオキサイド、ｔｅｒｔ−ブチ
ルクミルパーオキサイド、ジクミルパーオキサイド、ベ
ンゾイルパーオキサイド、アセチルパーオキサイドなど
のパーオキサイド類の過酸化物が用いられる。Peroxides of peroxides such as di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, benzoyl peroxide, and acetyl peroxide are used.
また、溶剤としては、共重合反応を阻害せず、かつ、ポ
リマーを充分に溶解するものでなければならない０例え
ば、水、アセトン、メチルエチルケトン。Further, the solvent must be one that does not inhibit the copolymerization reaction and can sufficiently dissolve the polymer. For example, water, acetone, methyl ethyl ketone.
メタノール、エタノール、プロパツール、ブタノール、
酢酸エチル、酢酸ブチル、アセトニトリル、セロソルブ
、ブチルセロソルブ、セロソルブアセテート、ブチルセ
ロソルブアセテート、キシレン、トルエン、テトラヒド
ロフランなどが挙げられる。methanol, ethanol, propatool, butanol,
Examples include ethyl acetate, butyl acetate, acetonitrile, cellosolve, butyl cellosolve, cellosolve acetate, butyl cellosolve acetate, xylene, toluene, and tetrahydrofuran.
以上の方法で得られる共重合物の分子量には、特に制限
はない。There is no particular restriction on the molecular weight of the copolymer obtained by the above method.
また、上記成分（１）と成分■の共重合させる比率にも
特に制限はないが２通常は重量比で成分■／酸成分の比
は９９．９１０．１−１０／９０．好ましくは９９／１
〜５０１５ Ｇの範囲で共重合させるのが良い。There is no particular restriction on the copolymerization ratio of component (1) and component (2), but the usual weight ratio of component (1)/acid component is 99.910.1-10/90. Preferably 99/1
It is preferable to copolymerize within the range of 5015G to 5015G.
成分■が、これ以上だとイオン伝導成分である成分■が
少な過ぎてイオン伝導性が著しく低下する。また、成分
■が、これ以下だと充分な架橋反応がなされない。If component (2) exceeds this range, component (2), which is an ion-conducting component, will be too small and the ionic conductivity will drop significantly. Furthermore, if component (2) is less than this, sufficient crosslinking reaction will not occur.
本発明の組成物を構成する成分（Ｂ）である金属塩には
、特に制限はなく、Ｌｉ、Ｎａ、に、Ｒｂ。The metal salt that is component (B) constituting the composition of the present invention is not particularly limited, and may include Li, Na, and Rb.
Ｃｓ、Ｃａ、Ｍｇ、Ｂａ、Ｃｕ、Ａ１．Ｚｎ、Ｎｉ。Cs, Ca, Mg, Ba, Cu, A1. Zn, Ni.
Ａｇ、およびＨｇの過塩素酸塩、チオシアン酸塩。Ag, and Hg perchlorate and thiocyanate.
はう酸塩、テトラフルオロはう酸塩、トリフルオロ酢酸
塩、トリフルオロメタンスルホン酸塩、ヘキサフルオロ
りん酸塩、およびハロゲン化物、特に好ましくは、Ｌｉ
ＣｌＯ４，Ｌｉ５ＣＮ、ＮａＣｌ０ａ。oxalates, tetrafluorophosphates, trifluoroacetates, trifluoromethanesulfonates, hexafluorophosphates, and halides, particularly preferably Li
ClO4, Li5CN, NaCl0a.
ＫＣｌ０ａ 、Ｃｕ （Ｃ１０ａ ）ｔ ９Ｍｇ （Ｃ
ｌ０ａ ）ｔ、Ｚｎ （Ｃ１０４）ｚ 、Ｚｎ （Ｃ１
０４）ｔ・６Ｈ，０，などの金属塩が挙げられる。また
、上記金属塩はそのまま、上記ポリマー（Ａ）、或いは
硬化剤（Ｃ）に添加しても、上記金属塩を充分に溶解す
る適当な溶媒に溶解してから添加しても良い。KCl0a, Cu(C10a)t9Mg(C
l0a)t, Zn (C104)z, Zn (C1
04) Metal salts such as t.6H,0, etc. can be mentioned. Further, the metal salt may be added to the polymer (A) or curing agent (C) as it is, or may be added after being dissolved in an appropriate solvent that sufficiently dissolves the metal salt.
また、金属塩の含有量は、アクリロイル変性ポリアルキ
レンオキシドのアルキレンオキシドユニット（以下、Ｅ
Ｏと称する）に対して（金属塩／ＥＯ）Ｘ１００ （モ
ル％）が、好ましくは０．０５〜５０モル％、より好ま
しくは０．１〜３０モル％となる量である。In addition, the content of metal salt is the alkylene oxide unit (hereinafter referred to as E) of the acryloyl-modified polyalkylene oxide.
The (metal salt/EO)
上記金属塩の含有量が多くなり過ぎると、過剰となった
金属塩が解離しなくなり、単に混在するだけとなるので
、イオン伝導性は逆に低下する。If the content of the metal salt becomes too large, the excess metal salt will not dissociate and will simply coexist, resulting in a decrease in ionic conductivity.
しかし、含有量が少なすぎても、解離するイオン数が小
さくなり、やはりイオン伝導性は低下する。However, if the content is too low, the number of dissociated ions will be small, and the ionic conductivity will also be reduced.
また、上記金属塩は、２種以上併用することができる。Furthermore, two or more of the above metal salts can be used in combination.
本発明を構成する組成物の成分（Ｃ）である架橋剤とし
ては、前述の共重合ポリマー（Ａ）の官能基に対応して
、これと付加、縮合反応をおこすような官能基を２個以
上もっていることによって、架橋がおこなわれる有機物
が用いられる。The crosslinking agent, which is component (C) of the composition constituting the present invention, has two functional groups that cause an addition or condensation reaction with the functional groups of the above-mentioned copolymer (A). An organic substance that can be crosslinked by having the above-mentioned properties is used.
上記の２官能以上をもった有機物としては、ヘキサメチ
レンジイソシアネート、２．４−）リレンジイソシアネ
ートなどや、それらの誘導体、マレイン酸、フタル酸な
どや、それらの誘導体、エチレングリコール、ジエチレ
ングリコール、グリセリンなどや、それらの誘導体、エ
チレンジアミン、テトラメチレンジアミンなどやそれら
の誘導体、アミノ樹脂。Examples of organic substances having two or more functionalities include hexamethylene diisocyanate, 2,4-)lylene diisocyanate, derivatives thereof, maleic acid, phthalic acid, derivatives thereof, ethylene glycol, diethylene glycol, glycerin, etc. , their derivatives, ethylene diamine, tetramethylene diamine, etc. and their derivatives, amino resins.
エポキシ樹脂、フェノール樹脂、アクリル樹脂などが挙
げられる。Examples include epoxy resin, phenol resin, and acrylic resin.
また９本発明の電解質には、その性能を阻害しない範囲
で、必要に応じて、難燃剤、易燃化荊、帯電防止剤、防
曇剤、劣化防止剤、粘着性付与剤、界面活性剤、滑剤８
発泡剤、消泡剤、レベリング剤、シランカフプリング剤
、硬化触媒、導電側、無機充填剤などの添加剤を適宜添
加することができる。In addition, the electrolyte of the present invention may contain flame retardants, flame retardants, antistatic agents, antifogging agents, deterioration inhibitors, tackifiers, and surfactants, as necessary, to the extent that they do not impair its performance. , lubricant 8
Additives such as a foaming agent, an antifoaming agent, a leveling agent, a silane cuff pulling agent, a curing catalyst, a conductive agent, and an inorganic filler can be added as appropriate.
これらの添加剤の添加時期は１本発明の高分子固体電解
質の性能を阻害しない限り、特に制限はない。There is no particular restriction on the timing of adding these additives as long as they do not impair the performance of the solid polymer electrolyte of the present invention.
本発明の高分子固体電解質は、注型、押出しなどの成形
法によりフィルム状、パイプ状、チューブ状などの形に
成形され、あるいは、ロールコート、スプレーコート、
スピンコード、スクリーン印刷などの塗工印刷法により
９種々の形状の基材上に塗工印刷され、実用に供される
。The solid polymer electrolyte of the present invention can be formed into a film, pipe, tube, etc. by a molding method such as casting or extrusion, or can be formed by roll coating, spray coating, etc.
It is coated and printed on base materials of 9 various shapes by coating printing methods such as spin cord and screen printing, and put into practical use.
（実施例） 以下、実施例により本発明を説明する。(Example) The present invention will be explained below with reference to Examples.
合成例１
メトキシポリエチレングリコールモノアクリレート（新
中村化学ＡＭ−９０Ｇ）を６０ｇ、メタクリル酸グリシ
ジル４ｇ、メタクリル酸３ｇ、過酸化ベンゾイル４ｇ、
メチルエチルケトン３１ｇの混合溶液を８０℃に加熱し
た４０ｇのメチルエチルケトン中に撹拌しながら４時間
かけて滴下した。Synthesis Example 1 60 g of methoxypolyethylene glycol monoacrylate (Shin Nakamura Chemical AM-90G), 4 g of glycidyl methacrylate, 3 g of methacrylic acid, 4 g of benzoyl peroxide,
A mixed solution of 31 g of methyl ethyl ketone was added dropwise to 40 g of methyl ethyl ketone heated to 80° C. over 4 hours with stirring.
その後、２時間撹拌した後１合成終了とした。Thereafter, after stirring for 2 hours, 1 synthesis was completed.
合成例２
メトキシポリエチレングリコールモノアクリレート（新
中村化学ＡＭ−９０Ｇ）を８０ｇ、アクリル＃２−ヒド
ロキシエチル５ｇ、過酸化ベンゾイル４ｇ、メチルエチ
ルケトン４４ｇの混合溶液を８０℃に加勢した４５ｇメ
チルエチルケトン中に撹拌しながら４時間かけて滴下し
た。Synthesis Example 2 A mixed solution of 80 g of methoxypolyethylene glycol monoacrylate (Shin Nakamura Chemical AM-90G), 5 g of acrylic #2-hydroxyethyl, 4 g of benzoyl peroxide, and 44 g of methyl ethyl ketone was stirred into 45 g of methyl ethyl ketone heated to 80°C. The mixture was added dropwise over 4 hours.
その後、２時間撹拌した後１合成終了とした。Thereafter, after stirring for 2 hours, 1 synthesis was completed.
実施例１
合成例１で得られた共重合物１０ｇに過塩素酸リチウム
のメチルエチルケトン溶液（濃度０．２ ｇ ／ ｃｃ
）１．２５ｃｃを混合し、均一溶液とした。Example 1 A solution of lithium perchlorate in methyl ethyl ketone (concentration 0.2 g/cc) was added to 10 g of the copolymer obtained in Synthesis Example 1.
) were mixed to form a homogeneous solution.
得られた液状組成物を１４０℃で１０分間加熱硬化し、
フィルムを得た。The obtained liquid composition was heated and cured at 140°C for 10 minutes,
Got the film.
得られたフィルムの室温における導電率を交流インピー
ダンス法により測定した結果と７０℃での状態を第１表
に示す。Table 1 shows the results of measuring the electrical conductivity of the obtained film at room temperature by an AC impedance method and the state at 70°C.
実施例２
合成例２で得られた共重合物１０ｇに過塩素酸リチウム
のメチルエチルケトン溶液（濃度０．２ ｇ ／ ｃｃ
）１．２５ｃｃ、ヘキサメトキシメチロールメラミンを
１ｇ混合し均一溶液とした。Example 2 A solution of lithium perchlorate in methyl ethyl ketone (concentration 0.2 g/cc) was added to 10 g of the copolymer obtained in Synthesis Example 2.
) 1.25 cc and 1 g of hexamethoxymethylolmelamine were mixed to form a homogeneous solution.
得られた液状組成物を１４０℃で１０分間加熱硬化し、
フィルムを得た。The obtained liquid composition was heated and cured at 140°C for 10 minutes,
Got the film.
得られたフィルムの室温における導電率を交流インピー
ダンス法により測定した結果と７０℃での状態を第１表
に示す。Table 1 shows the results of measuring the electrical conductivity of the obtained film at room temperature by an AC impedance method and the state at 70°C.
実施例３
合成例２で得られた共重合物１０ｇに過塩素酸リチウム
のメチルエチルケトン溶液（濃度０．２ｇ／ｃｃ）１．
２５ｃｃ、）リイレンー２．４−シイソバ／アネートを
１ｇ混合し均一溶液とした。Example 3 A solution of lithium perchlorate in methyl ethyl ketone (concentration 0.2 g/cc) was added to 10 g of the copolymer obtained in Synthesis Example 2.
25 cc,) 1 g of liiren-2.4-shiisoba/anate was mixed to form a homogeneous solution.
得られた液状組成物を１４０℃で１０分間加熱硬化し、
フィルムを得た。The obtained liquid composition was heated and cured at 140°C for 10 minutes,
Got the film.
得られたフィルムの室温における導電率を交流インピー
ダンス法により測定した結果と７０℃での状態を第１表
に示す。Table 1 shows the results of measuring the electrical conductivity of the obtained film at room temperature by an AC impedance method and the state at 70°C.
実施例４
合成例２で得られた共重合物１０ｇに過塩素酸亜鉛６水
和物のメチルエチルケトン溶液（濃度０．２ｇ／ｃ ｃ
） １．２５ ｃ ｃ、 ヘキサメトキシメチロール
メラミンを１ｇ混合し均一溶液とした。Example 4 A solution of zinc perchlorate hexahydrate in methyl ethyl ketone (concentration 0.2 g/cc) was added to 10 g of the copolymer obtained in Synthesis Example 2.
) 1.25 cc, 1 g of hexamethoxymethylolmelamine was mixed to form a homogeneous solution.
得られた液状組成物を１４０℃で１０分間加熱硬化し、
フィルムを得た。The obtained liquid composition was heated and cured at 140°C for 10 minutes,
Got the film.
得られたフィルムの室温における導電率を交流インピー
ダンス法により測定した結果と７０℃での状態を第１表
に示す。Table 1 shows the results of measuring the electrical conductivity of the obtained film at room temperature by an AC impedance method and the state at 70°C.
比較例１
数平均分子量１００，０００のポリエチレンオキサイド
５ｇに過塩素酸リチウムのアセトニトリル溶液（濃度０
．２ｇ／ｃｃ）１．２５ｃｃ、アセトニトリル５ｇを混
合し均一溶液とした。Comparative Example 1 A solution of lithium perchlorate in acetonitrile (concentration 0) was added to 5 g of polyethylene oxide with a number average molecular weight of 100,000.
．． 2g/cc) and 5g of acetonitrile were mixed to form a homogeneous solution.
得られた液状組成物を１４０℃で１０分間加熱すること
で溶媒を除去し、フィルムを得た。The solvent was removed by heating the obtained liquid composition at 140° C. for 10 minutes to obtain a film.
得られたフィルムの室温における導電率を交流インピー
ダンス法により測定した結果と７０℃での状態を第１表
に示す。Table 1 shows the results of measuring the electrical conductivity of the obtained film at room temperature by an AC impedance method and the state at 70°C.
第 １ 表
〔発明の効果〕
本発明により、室温下でも良好なイオン導電性を示し、
６０℃以上の温度でも溶融しない高分子量体電解質が得
られるようになった。Table 1 [Effects of the invention] The present invention shows good ionic conductivity even at room temperature,
It has become possible to obtain a polymer electrolyte that does not melt even at temperatures of 60° C. or higher.
Claims (1)
分子内に二重結合を有し、且つ少なくとも、１つ以上の
官能基をもつ有機化合物（２）を共重合してなるポリマ
ー（Ａ）を架橋させて得られる架橋型樹脂、および金属
塩（Ｂ）とからなることを特徴とするイオン伝導性高分
子固体電解質。 ２、アクリロイル変性ポリアルキレンオキシド（１）と
分子内に二重結合を有し、且つ少なくとも、１つ以上の
官能基をもつ有機化合物（２）を共重合してなるポリマ
ー（Ａ）と架橋剤（Ｃ）を架橋させて得られる架橋型樹
脂、および金属塩（Ｂ）とからなることを特徴とするイ
オン伝導性高分子固体電解質。[Claims] 1. A polymer obtained by copolymerizing an acryloyl-modified polyalkylene oxide (1) with an organic compound (2) having a double bond in the molecule and having at least one or more functional groups. An ion-conductive polymer solid electrolyte comprising a crosslinked resin obtained by crosslinking (A) and a metal salt (B). 2. A polymer (A) obtained by copolymerizing acryloyl-modified polyalkylene oxide (1) and an organic compound (2) having a double bond in the molecule and having at least one functional group, and a crosslinking agent. An ion-conductive polymer solid electrolyte comprising a crosslinked resin obtained by crosslinking (C) and a metal salt (B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2035449A JPH03238704A (en) | 1990-02-16 | 1990-02-16 | High polymer solid electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2035449A JPH03238704A (en) | 1990-02-16 | 1990-02-16 | High polymer solid electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03238704A true JPH03238704A (en) | 1991-10-24 |
Family
ID=12442129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2035449A Pending JPH03238704A (en) | 1990-02-16 | 1990-02-16 | High polymer solid electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03238704A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2292945B (en) * | 1994-09-06 | 1998-07-01 | Hydro Quebec | LPB Electrolyte compositions based on mixtures of copolymers and interpenetrated networks |
| WO1999028986A1 (en) * | 1997-11-27 | 1999-06-10 | Yuasa Corporation | Thin lithium secondary cell |
| EP0822608A3 (en) * | 1996-07-30 | 1999-08-04 | Samsung Electronics Co., Ltd. | Polymeric solid electrolyte and lithium secondary cell adopting the same |
| US6335818B1 (en) * | 1999-10-26 | 2002-01-01 | Xerox Corporation | Bichromal beads having electrolytes therein |
| US6362915B1 (en) * | 1999-10-26 | 2002-03-26 | Xerox Corporation | Bichromal beads having crystalline materials therein |
| US6496298B1 (en) * | 1999-10-26 | 2002-12-17 | Xerox Corporation | Bichromal beads having charge adjuvants therein |
| JP2004213940A (en) * | 2002-12-27 | 2004-07-29 | Nippon Soda Co Ltd | Composite for solid polyelectrolyte |
| US20170327650A1 (en) * | 2014-11-03 | 2017-11-16 | HYDRO-QUéBEC | Crosslinked polymer based on a random copolymer and a volatile polyaminated crosslinking agent and processes for producing same |
| JP2021527243A (en) * | 2018-09-13 | 2021-10-11 | アンビライト・インコーポレイテッド | Method for manufacturing solid-state electrochromic device, solid-state electrochromic device and its application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60232243A (en) * | 1984-04-28 | 1985-11-18 | Res Dev Corp Of Japan | Adsorbent comprising crosslinked high-molecular polymer |
| JPS6147713A (en) * | 1984-08-14 | 1986-03-08 | Hidetoshi Tsuchida | Polymeric compound and ionic conductive material |
| JPH01135856A (en) * | 1987-10-16 | 1989-05-29 | Eniricerche Spa | Solid polymer electrolyte and battery |
| JPH02298504A (en) * | 1989-05-15 | 1990-12-10 | Fuji Photo Film Co Ltd | High polymer solid electrolyte |
-
1990
- 1990-02-16 JP JP2035449A patent/JPH03238704A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60232243A (en) * | 1984-04-28 | 1985-11-18 | Res Dev Corp Of Japan | Adsorbent comprising crosslinked high-molecular polymer |
| JPS6147713A (en) * | 1984-08-14 | 1986-03-08 | Hidetoshi Tsuchida | Polymeric compound and ionic conductive material |
| JPH01135856A (en) * | 1987-10-16 | 1989-05-29 | Eniricerche Spa | Solid polymer electrolyte and battery |
| JPH02298504A (en) * | 1989-05-15 | 1990-12-10 | Fuji Photo Film Co Ltd | High polymer solid electrolyte |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2292945B (en) * | 1994-09-06 | 1998-07-01 | Hydro Quebec | LPB Electrolyte compositions based on mixtures of copolymers and interpenetrated networks |
| EP0822608A3 (en) * | 1996-07-30 | 1999-08-04 | Samsung Electronics Co., Ltd. | Polymeric solid electrolyte and lithium secondary cell adopting the same |
| JP4669980B2 (en) * | 1997-11-27 | 2011-04-13 | 株式会社Ｇｓユアサ | Thin lithium secondary battery |
| US6673496B1 (en) | 1997-11-27 | 2004-01-06 | Yuasa Corporation | Thin lithium secondary cell |
| WO1999028986A1 (en) * | 1997-11-27 | 1999-06-10 | Yuasa Corporation | Thin lithium secondary cell |
| US6335818B1 (en) * | 1999-10-26 | 2002-01-01 | Xerox Corporation | Bichromal beads having electrolytes therein |
| US6362915B1 (en) * | 1999-10-26 | 2002-03-26 | Xerox Corporation | Bichromal beads having crystalline materials therein |
| US6496298B1 (en) * | 1999-10-26 | 2002-12-17 | Xerox Corporation | Bichromal beads having charge adjuvants therein |
| JP2004213940A (en) * | 2002-12-27 | 2004-07-29 | Nippon Soda Co Ltd | Composite for solid polyelectrolyte |
| JP4612272B2 (en) * | 2002-12-27 | 2011-01-12 | 日本曹達株式会社 | Composition for polymer solid electrolyte |
| US20170327650A1 (en) * | 2014-11-03 | 2017-11-16 | HYDRO-QUéBEC | Crosslinked polymer based on a random copolymer and a volatile polyaminated crosslinking agent and processes for producing same |
| US10745526B2 (en) * | 2014-11-03 | 2020-08-18 | Hydro-Quebec | Crosslinked polymer based on a random copolymer and a volatile polyaminated crosslinking agent and processes for producing same |
| JP2021527243A (en) * | 2018-09-13 | 2021-10-11 | アンビライト・インコーポレイテッド | Method for manufacturing solid-state electrochromic device, solid-state electrochromic device and its application |
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