JP2014007264A - Gel electrolyte capacitor, and method of manufacturing the same - Google Patents
Gel electrolyte capacitor, and method of manufacturing the same Download PDFInfo
- Publication number
- JP2014007264A JP2014007264A JP2012141481A JP2012141481A JP2014007264A JP 2014007264 A JP2014007264 A JP 2014007264A JP 2012141481 A JP2012141481 A JP 2012141481A JP 2012141481 A JP2012141481 A JP 2012141481A JP 2014007264 A JP2014007264 A JP 2014007264A
- Authority
- JP
- Japan
- Prior art keywords
- gel
- water
- organic
- polymer
- inorganic composite
- 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.)
- Granted
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 74
- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 105
- 239000002131 composite material Substances 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000000178 monomer Substances 0.000 claims abstract description 50
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 40
- 239000002734 clay mineral Substances 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000011888 foil Substances 0.000 claims description 54
- 239000006185 dispersion Substances 0.000 claims description 46
- -1 amidine phthalate Chemical class 0.000 claims description 24
- 239000007863 gel particle Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 4
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001741 Ammonium adipate Substances 0.000 claims description 3
- 235000019293 ammonium adipate Nutrition 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 230000000717 retained effect Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 11
- 239000000499 gel Substances 0.000 description 137
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 43
- 239000000047 product Substances 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000000123 paper Substances 0.000 description 11
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 239000002655 kraft paper Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- 229940094522 laponite Drugs 0.000 description 7
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 7
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 125000004185 ester group Chemical group 0.000 description 6
- 230000010354 integration Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 125000001033 ether group Chemical group 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 5
- 229920000620 organic polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920002939 poly(N,N-dimethylacrylamides) Polymers 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000003908 quality control method Methods 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- OWCLRJQYKBAMOL-UHFFFAOYSA-N 2-butyloctanedioic acid Chemical compound CCCCC(C(O)=O)CCCCCC(O)=O OWCLRJQYKBAMOL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 238000010382 chemical cross-linking Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000008393 encapsulating agent Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 108010025899 gelatin film Proteins 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 235000010355 mannitol Nutrition 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 3
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920001977 poly(N,N-diethylacrylamides) Polymers 0.000 description 3
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical group C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- KGFNCEVZZDDBTR-UHFFFAOYSA-N 1-piperazin-1-ylbut-3-en-2-one Chemical compound C=CC(=O)CN1CCNCC1 KGFNCEVZZDDBTR-UHFFFAOYSA-N 0.000 description 2
- RESPXSHDJQUNTN-UHFFFAOYSA-N 1-piperidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCCC1 RESPXSHDJQUNTN-UHFFFAOYSA-N 0.000 description 2
- WLPAQAXAZQUXBG-UHFFFAOYSA-N 1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCC1 WLPAQAXAZQUXBG-UHFFFAOYSA-N 0.000 description 2
- KWIPUXXIFQQMKN-UHFFFAOYSA-N 2-azaniumyl-3-(4-cyanophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC=C(C#N)C=C1 KWIPUXXIFQQMKN-UHFFFAOYSA-N 0.000 description 2
- VSKIZLPBNBFXMZ-UHFFFAOYSA-N 2-carboxybenzoate;1-ethyl-2,3-dimethylimidazolidin-1-ium Chemical compound CC[NH+]1CCN(C)C1C.OC(=O)C1=CC=CC=C1C([O-])=O VSKIZLPBNBFXMZ-UHFFFAOYSA-N 0.000 description 2
- SFPNZPQIIAJXGL-UHFFFAOYSA-N 2-ethoxyethyl 2-methylprop-2-enoate Chemical compound CCOCCOC(=O)C(C)=C SFPNZPQIIAJXGL-UHFFFAOYSA-N 0.000 description 2
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 2
- XJMMNTGIMDZPMU-UHFFFAOYSA-N 3-methylglutaric acid Chemical compound OC(=O)CC(C)CC(O)=O XJMMNTGIMDZPMU-UHFFFAOYSA-N 0.000 description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 229920000936 Agarose Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PMDCZENCAXMSOU-UHFFFAOYSA-N N-ethylacetamide Chemical compound CCNC(C)=O PMDCZENCAXMSOU-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229940090948 ammonium benzoate Drugs 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 229910000271 hectorite Inorganic materials 0.000 description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 2
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 2
- FIBUWQFQYAAXHD-UHFFFAOYSA-N n-cyclopropyl-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1CC1 FIBUWQFQYAAXHD-UHFFFAOYSA-N 0.000 description 2
- LCXIFAOALNZGDO-UHFFFAOYSA-N n-cyclopropylprop-2-enamide Chemical compound C=CC(=O)NC1CC1 LCXIFAOALNZGDO-UHFFFAOYSA-N 0.000 description 2
- ZOTWHNWBICCBPC-UHFFFAOYSA-N n-ethyl-n-methylprop-2-enamide Chemical compound CCN(C)C(=O)C=C ZOTWHNWBICCBPC-UHFFFAOYSA-N 0.000 description 2
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 2
- COYVWKMZTCAFHO-UHFFFAOYSA-N n-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)N(C)C(=O)C=C COYVWKMZTCAFHO-UHFFFAOYSA-N 0.000 description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- CKMXAIVXVKGGFM-UHFFFAOYSA-N p-cumic acid Chemical compound CC(C)C1=CC=C(C(O)=O)C=C1 CKMXAIVXVKGGFM-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920001078 poly (N-Isopropyl methacrylamide) Polymers 0.000 description 2
- 229920000333 poly(propyleneimine) Polymers 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- AZJYLVAUMGUUBL-UHFFFAOYSA-A u1qj22mc8e Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 AZJYLVAUMGUUBL-UHFFFAOYSA-A 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- XLSXKCPCBOMHON-UHFFFAOYSA-N 1,1-dimethoxypropan-1-ol Chemical compound CCC(O)(OC)OC XLSXKCPCBOMHON-UHFFFAOYSA-N 0.000 description 1
- KYRYHBRYSSBWLU-UHFFFAOYSA-N 1,2,3,4-tetramethylimidazolidine Chemical compound CC1CN(C)C(C)N1C KYRYHBRYSSBWLU-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- JJNFHWKVZWAKEB-UHFFFAOYSA-N 1,3,4-trimethylimidazolidin-2-one Chemical compound CC1CN(C)C(=O)N1C JJNFHWKVZWAKEB-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- NYCCIHSMVNRABA-UHFFFAOYSA-N 1,3-diethylimidazolidin-2-one Chemical compound CCN1CCN(CC)C1=O NYCCIHSMVNRABA-UHFFFAOYSA-N 0.000 description 1
- SOKQNFRUHLVLHI-UHFFFAOYSA-N 1,3-dimethylnonane-1,3,9-tricarboxylic acid Chemical compound OC(=O)C(C)CC(C)(C(O)=O)CCCCCCC(O)=O SOKQNFRUHLVLHI-UHFFFAOYSA-N 0.000 description 1
- GXOVLFMZQUTYBX-UHFFFAOYSA-N 1,3-dimethyloctane-1,3,8-tricarboxylic acid Chemical compound OC(=O)C(C)CC(C)(C(O)=O)CCCCCC(O)=O GXOVLFMZQUTYBX-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- IFSLDAPFCPZGMR-UHFFFAOYSA-N 1-(1,4-diazepan-1-yl)but-3-en-2-one Chemical compound C=CC(=O)CN1CCCNCC1 IFSLDAPFCPZGMR-UHFFFAOYSA-N 0.000 description 1
- ARKIFHPFTHVKDT-UHFFFAOYSA-N 1-(3-nitrophenyl)ethanone Chemical compound CC(=O)C1=CC=CC([N+]([O-])=O)=C1 ARKIFHPFTHVKDT-UHFFFAOYSA-N 0.000 description 1
- WVUYYXUATWMVIT-UHFFFAOYSA-N 1-bromo-4-ethoxybenzene Chemical compound CCOC1=CC=C(Br)C=C1 WVUYYXUATWMVIT-UHFFFAOYSA-N 0.000 description 1
- OEYNWAWWSZUGDU-UHFFFAOYSA-N 1-methoxypropane-1,2-diol Chemical compound COC(O)C(C)O OEYNWAWWSZUGDU-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- DWFUTNJGNBYHNN-UHFFFAOYSA-N 2,2,4-trimethylhexanedioic acid Chemical compound OC(=O)CC(C)CC(C)(C)C(O)=O DWFUTNJGNBYHNN-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-N 2,2-diethylpropanedioic acid Chemical compound CCC(CC)(C(O)=O)C(O)=O LTMRRSWNXVJMBA-UHFFFAOYSA-N 0.000 description 1
- DIRSQLKNZQKDBK-UHFFFAOYSA-N 2,2-dipropylpropanedioic acid Chemical compound CCCC(C(O)=O)(C(O)=O)CCC DIRSQLKNZQKDBK-UHFFFAOYSA-N 0.000 description 1
- BQNDPALRJDCXOY-UHFFFAOYSA-N 2,3-dibutylbutanedioic acid Chemical compound CCCCC(C(O)=O)C(C(O)=O)CCCC BQNDPALRJDCXOY-UHFFFAOYSA-N 0.000 description 1
- RLEQVGMLDNITBW-UHFFFAOYSA-N 2,4,4-trimethylhexanedioic acid Chemical compound OC(=O)C(C)CC(C)(C)CC(O)=O RLEQVGMLDNITBW-UHFFFAOYSA-N 0.000 description 1
- JKEPCPLWGHIECQ-UHFFFAOYSA-N 2,4-dimethylnonanedioic acid Chemical compound OC(=O)C(C)CC(C)CCCCC(O)=O JKEPCPLWGHIECQ-UHFFFAOYSA-N 0.000 description 1
- WKFQMDFSDQFAIC-UHFFFAOYSA-N 2,4-dimethylthiolane 1,1-dioxide Chemical compound CC1CC(C)S(=O)(=O)C1 WKFQMDFSDQFAIC-UHFFFAOYSA-N 0.000 description 1
- AUZBAWMCVFJYAU-UHFFFAOYSA-N 2,8-dimethylnonanedioic acid Chemical compound OC(=O)C(C)CCCCCC(C)C(O)=O AUZBAWMCVFJYAU-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical class O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 description 1
- VIKBNMWOLLIQPG-UHFFFAOYSA-N 2-methyldecanedioic acid Chemical compound OC(=O)C(C)CCCCCCCC(O)=O VIKBNMWOLLIQPG-UHFFFAOYSA-N 0.000 description 1
- XWVFEDFALKHCLK-UHFFFAOYSA-N 2-methylnonanedioic acid Chemical compound OC(=O)C(C)CCCCCCC(O)=O XWVFEDFALKHCLK-UHFFFAOYSA-N 0.000 description 1
- KIBVFIDMXQZCBS-UHFFFAOYSA-N 2-methyloctanedioic acid Chemical compound OC(=O)C(C)CCCCCC(O)=O KIBVFIDMXQZCBS-UHFFFAOYSA-N 0.000 description 1
- ZDFKSZDMHJHQHS-UHFFFAOYSA-N 2-tert-butylbenzoic acid Chemical compound CC(C)(C)C1=CC=CC=C1C(O)=O ZDFKSZDMHJHQHS-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 1
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZKXBLNXJQIBQOX-UHFFFAOYSA-N 4-ethyl-2-methylnonanedioic acid Chemical compound OC(=O)C(C)CC(CC)CCCCC(O)=O ZKXBLNXJQIBQOX-UHFFFAOYSA-N 0.000 description 1
- XPEFVGMKDOHGPH-UHFFFAOYSA-N 4-methoxycarbonyl-2,4-dimethyldecanedioic acid Chemical compound OC(=O)C(C)CC(C)(C(=O)OC)CCCCCC(O)=O XPEFVGMKDOHGPH-UHFFFAOYSA-N 0.000 description 1
- HWEXOZJZJZBHKA-UHFFFAOYSA-N 4-methoxycarbonyl-2,4-dimethyldodecanedioic acid Chemical compound OC(=O)C(C)CC(C)(C(=O)OC)CCCCCCCC(O)=O HWEXOZJZJZBHKA-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- CWJJAFQCTXFSTA-UHFFFAOYSA-N 4-methylphthalic acid Chemical compound CC1=CC=C(C(O)=O)C(C(O)=O)=C1 CWJJAFQCTXFSTA-UHFFFAOYSA-N 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- SLBQXWXKPNIVSQ-UHFFFAOYSA-N 4-nitrophthalic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1C(O)=O SLBQXWXKPNIVSQ-UHFFFAOYSA-N 0.000 description 1
- UZIWMCAWBNTWDN-UHFFFAOYSA-N 7-methoxy-7-phenyloctanoic acid Chemical compound OC(=O)CCCCCC(C)(OC)C1=CC=CC=C1 UZIWMCAWBNTWDN-UHFFFAOYSA-N 0.000 description 1
- IQWKYRKBHFUUKH-UHFFFAOYSA-N 8,13-dimethylicosanedioic acid Chemical compound OC(=O)CCCCCCC(C)CCCCC(C)CCCCCCC(O)=O IQWKYRKBHFUUKH-UHFFFAOYSA-N 0.000 description 1
- WOJVMZGXOWNAIG-UHFFFAOYSA-N 8,9,12,13-tetramethylicosanedioic acid Chemical compound OC(=O)CCCCCCC(C)C(C)CCC(C)C(C)CCCCCCC(O)=O WOJVMZGXOWNAIG-UHFFFAOYSA-N 0.000 description 1
- KTFVECGOKBNPEK-UHFFFAOYSA-N 8,9-dimethylhexadecanedioic acid Chemical compound OC(=O)CCCCCCC(C)C(C)CCCCCCC(O)=O KTFVECGOKBNPEK-UHFFFAOYSA-N 0.000 description 1
- JHRJYXZOXJXEJJ-UHFFFAOYSA-N 8-ethyloctadecanedioic acid Chemical compound OC(=O)CCCCCCC(CC)CCCCCCCCCC(O)=O JHRJYXZOXJXEJJ-UHFFFAOYSA-N 0.000 description 1
- LXRALFGPYZLNBT-UHFFFAOYSA-N 8-methoxy-8-phenylnonanoic acid Chemical compound OC(=O)CCCCCCC(C)(OC)C1=CC=CC=C1 LXRALFGPYZLNBT-UHFFFAOYSA-N 0.000 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NTOXAXQNZZXUQQ-UHFFFAOYSA-N C1(OC(=C(C)C)O1)=O Chemical compound C1(OC(=C(C)C)O1)=O NTOXAXQNZZXUQQ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229920002148 Gellan gum Polymers 0.000 description 1
- 101000720524 Gordonia sp. (strain TY-5) Acetone monooxygenase (methyl acetate-forming) Proteins 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920001311 Poly(hydroxyethyl acrylate) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- CGBYBGVMDAPUIH-UHFFFAOYSA-N acide dimethylmaleique Natural products OC(=O)C(C)=C(C)C(O)=O CGBYBGVMDAPUIH-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000005340 bisphosphate group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- KTHXBEHDVMTNOH-UHFFFAOYSA-N cyclobutanol Chemical compound OC1CCC1 KTHXBEHDVMTNOH-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N cyclohexene-1,2-dicarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- CGBYBGVMDAPUIH-ARJAWSKDSA-N dimethylmaleic acid Chemical compound OC(=O)C(/C)=C(/C)C(O)=O CGBYBGVMDAPUIH-ARJAWSKDSA-N 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000010492 gellan gum Nutrition 0.000 description 1
- 239000000216 gellan gum Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001584 poly(acrylomorpholines) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-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
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920006268 silicone film Polymers 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000007984 tetrahydrofuranes Chemical class 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000005068 transpiration Effects 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
本発明は、ゲル電解質を用いたコンデンサ、及びその製造方法に関する。 The present invention relates to a capacitor using a gel electrolyte and a manufacturing method thereof.
各種電子機器において、電解コンデンサ、電気二重層コンデンサといったコンデンサが用いられている。かかるコンデンサは、例えば以下のように構成される。
（１）陽極箔と陰極箔を、セパレータを介して重ね合わせ、電極箔を形成する。セパレータには、マニラ紙やクラフト紙等の薄い低密度の紙が用いられる。
（２）電極箔にリード線を接続し、電解液を含浸させる。電解液は、有機溶媒に無機酸塩又は有機酸塩を溶解させた液状の電解質である。
In various electronic devices, capacitors such as electrolytic capacitors and electric double layer capacitors are used. Such a capacitor is configured as follows, for example.
(1) An anode foil and a cathode foil are overlapped via a separator to form an electrode foil. As the separator, thin low density paper such as Manila paper or kraft paper is used.
(2) A lead wire is connected to the electrode foil and impregnated with an electrolytic solution. The electrolytic solution is a liquid electrolyte in which an inorganic acid salt or an organic acid salt is dissolved in an organic solvent.
海外の電力事情の悪い地域などにおいてコンデンサが使用される場合、コンデンサに過電圧が印加される事態が発生しやすい。その際、コンデンサ内部の電解液が漏れだし、コンデンサを搭載した機器の故障をもたらすという問題が発生していた。 When a capacitor is used in an area where the power situation of overseas is poor, an overvoltage is likely to be applied to the capacitor. At that time, the electrolyte in the capacitor leaked, causing a problem of failure of the device equipped with the capacitor.
このような問題を解決するために、ゲル電解質をコンデンサに使用することが検討されてきた。ゲル電解質は、有機架橋剤で三次元網目を形成させるゲル（以後このゲルを有機架橋ゲルと称する）に電解液を含浸させたものである。このゲル電解質を、従来のセパレータの代わりに陽極箔及び陰極箔の間に挟んでコンデンサを構成することができる（例えば、特許文献１参照）。このようなコンデンサは、ゲルの保持力によって過電圧印加時の電解液の漏れを抑制できる。 In order to solve such problems, it has been studied to use a gel electrolyte for a capacitor. The gel electrolyte is obtained by impregnating an electrolyte with a gel (hereinafter, this gel is referred to as an organic crosslinking gel) that forms a three-dimensional network with an organic crosslinking agent. A capacitor can be formed by sandwiching the gel electrolyte between an anode foil and a cathode foil instead of a conventional separator (see, for example, Patent Document 1). Such a capacitor can suppress leakage of the electrolyte when an overvoltage is applied due to the retention force of the gel.
しかしながら、上述した有機架橋ゲルからなる高分子ゲルは力学的に脆弱であり、コンデンサの部品としては取扱いが難しかった。 However, the polymer gel composed of the above-mentioned organic crosslinked gel is mechanically fragile and difficult to handle as a capacitor part.
本発明者らは、水溶性有機モノマーの重合体とナノサイズの層状粘土鉱物とが架橋されて形成された三次元網目を有する有機無機複合ゲル（以下、単に「複合ゲル」ともいう）が、力学的に優れていることに着目した（例えば、特許文献２参照）。 The inventors of the present invention provide an organic-inorganic composite gel having a three-dimensional network formed by crosslinking a polymer of a water-soluble organic monomer and a nano-sized layered clay mineral (hereinafter also simply referred to as “composite gel”). It was noted that it is mechanically superior (for example, see Patent Document 2).
しかしながら、かかる複合ゲルは、一般に層状剥離したクレイの存在下で水溶性有機モノマーをインシチュ重合して得られるが、重合は酸素フリー、すなわち、酸素を遮断して行う必要があった。また場合によっては、重合後に残存モノマーを除去したりする精製工程が必要であった。したがって、複合ゲルを作製してから、コンデンサに使用するまでの期間が長い場合、含水率を一定に保つなどの保護手段が必要であり、品質管理、取り扱いにおいて特段の注意が必要であった。 However, such a composite gel is generally obtained by in-situ polymerization of a water-soluble organic monomer in the presence of layered exfoliated clay. However, the polymerization has to be performed free of oxygen, that is, by blocking oxygen. In some cases, a purification step for removing the residual monomer after the polymerization is necessary. Therefore, when the period from the preparation of the composite gel to the use of the capacitor is long, a protective means such as keeping the moisture content constant is necessary, and special care is required in quality control and handling.
本発明は、上述の課題を解決して、電解液の漏れを抑制でき、力学的強度に優れたゲル電解質を用いたコンデンサや、それらの簡便な製造方法を提供すること目的とする。 An object of the present invention is to solve the above-mentioned problems, and to provide a capacitor using a gel electrolyte that can suppress leakage of an electrolytic solution and has excellent mechanical strength, and a simple manufacturing method thereof.
上記課題を解決するために、本発明は次の特徴を有するゲル電解質を用いたコンデンサ（以下、単にゲル電解質コンデンサともいう）を提供する。
（１）有機無機複合ゲルの粒子を一体化した高分子ゲル中に、電解液が保持されているものを使用する。
（２）有機無機複合ゲルは、重合性不飽和基含有水溶性有機モノマーの重合体と水膨潤性粘土鉱物との架橋により形成された、三次元網目構造を有するものである。
In order to solve the above problems, the present invention provides a capacitor using a gel electrolyte having the following characteristics (hereinafter also simply referred to as a gel electrolyte capacitor).
(1) A polymer gel in which particles of an organic-inorganic composite gel are integrated is used in which an electrolytic solution is held.
(2) The organic-inorganic composite gel has a three-dimensional network structure formed by crosslinking of a polymer of a polymerizable unsaturated group-containing water-soluble organic monomer and a water-swellable clay mineral.
さらに、本発明は上記ゲル電解質を用いたコンデンサの製造方法を提供する。該製造方法は、以下の工程を有する。
（Ａ）重合性不飽和基含有水溶性有機モノマーの重合体と水膨潤性粘土鉱物との架橋により形成された三次元網目構造を有する有機無機複合ゲルを、粉砕及び乾燥して粒子状乾燥物を形成する。
（Ｂ）該粒子状乾燥物を、水、溶質又は溶質を含有する水溶液と混合して高分子ゲル分散液を調製する。
（Ｃ）上記（Ａ）、（Ｂ）の代わりに、重合性不飽和基含有水溶性有機モノマーの重合体と水膨潤性粘土鉱物との架橋により形成された三次元網目構造を有する有機無機複合ゲルを、水中にて粉砕して、スラリー状の高分子ゲル分散液を調製する。
（Ｄ）上記（Ａ）、（Ｂ）の代わりに、重合性不飽和基含有水溶性有機モノマーの重合体と水膨潤性粘土鉱物との架橋により形成された三次元網目構造を有する有機無機複合ゲル粒子を合成し、それを含む高分子ゲル分散液を調製する。
（Ｅ）該高分子ゲル分散液を素子構成材料上に塗布して乾燥する。
（Ｆ）素子構成材料に電解液を含浸してコンデンサを形成する。
Furthermore, this invention provides the manufacturing method of the capacitor | condenser using the said gel electrolyte. The manufacturing method includes the following steps.
(A) An organic-inorganic composite gel having a three-dimensional network structure formed by crosslinking a polymer of a polymerizable unsaturated group-containing water-soluble organic monomer and a water-swellable clay mineral is pulverized and dried to obtain a particulate dried product Form.
(B) The particulate dried product is mixed with water, a solute, or an aqueous solution containing a solute to prepare a polymer gel dispersion.
(C) An organic-inorganic composite having a three-dimensional network structure formed by cross-linking of a polymer of a polymerizable unsaturated group-containing water-soluble organic monomer and a water-swellable clay mineral instead of the above (A) and (B) The gel is pulverized in water to prepare a slurry polymer gel dispersion.
(D) An organic-inorganic composite having a three-dimensional network structure formed by crosslinking a polymer of a polymerizable unsaturated group-containing water-soluble organic monomer and a water-swellable clay mineral instead of the above (A) and (B) A gel particle is synthesized and a polymer gel dispersion containing the same is prepared.
(E) The polymer gel dispersion is applied onto the element constituent material and dried.
(F) Capacitors are formed by impregnating the element constituent material with an electrolytic solution.
上述の特徴により、本発明のゲル電解質コンデンサは、以下の効果を得られる。
（１）ゲルの保持力によって、コンデンサに過電圧が印加された時の電解液の漏れが抑制される。長寿命のコンデンサが得られる。
（２）有機無機複合ゲルを用いることによって、高い力学的強度を得ることができ、取り扱いが容易である。
Due to the above-described characteristics, the gel electrolyte capacitor of the present invention can obtain the following effects.
(1) The leakage of the electrolyte when the overvoltage is applied to the capacitor is suppressed by the gel holding force. A long-life capacitor is obtained.
(2) By using the organic-inorganic composite gel, high mechanical strength can be obtained, and handling is easy.
さらに、本発明のゲル電解質コンデンサ及びコンデンサの製造方法は、上述の工程により以下の効果を得られる。
（３）有機無機複合ゲルをいったん乾燥粒状物とし、もしくは、有機無機複合ゲルをスラリー状とし、もしくは粒子状の有機無機複合ゲルを合成して、この複合ゲル粒子をコンデンサの製造に使用する。そのため、大気下中で製造作業を行うことができ、簡便で、品質管理等が容易な製造方法を提供できる。
Furthermore, the gel electrolyte capacitor and the method for manufacturing the capacitor of the present invention can obtain the following effects by the above-described steps.
(3) The organic-inorganic composite gel is once made into a dry granular material, or the organic-inorganic composite gel is made into a slurry, or a particulate organic-inorganic composite gel is synthesized, and the composite gel particles are used for manufacturing a capacitor. Therefore, it is possible to perform a manufacturing operation in the atmosphere, and to provide a manufacturing method that is simple and easy in quality control and the like.
［ゲル電解質］
本実施形態におけるゲル電解質は、有機無機複合ゲルの粒子が一体化した高分子ゲル中に、電解液が保持されているものである。図１に示すように、ゲル電解質を製造する工程は、大別すると以下のようになる。
（Ａ）有機無機複合ゲルを、乾燥後に粉砕し又は粉砕後に乾燥して、該複合ゲルの粒子状乾燥物を作製する。
（Ｂ）該粒子状乾燥物を水、溶質又は溶質を含む水溶液と混合して、高分子ゲル分散液を調整する。
（Ｃ）上記（Ａ）、（Ｂ）の代わりに、重合性不飽和基含有水溶性有機モノマーの重合体と水膨潤性粘土鉱物との架橋により形成された三次元網目構造を有する有機無機複合ゲルを、水中にて粉砕してスラリー状の高分子ゲル分散液を調製する。
（Ｄ）上記（Ａ）、（Ｂ）の代わりに、重合性不飽和基含有水溶性有機モノマーの重合体と水膨潤性粘土鉱物との架橋により形成された三次元網目構造を有する有機無機複合ゲル粒子を合成し、それを含む高分子ゲル分散液を調製する。
（Ｅ）該高分子ゲル分散液を基板上に塗布した後、乾燥して高分子ゲルシートを作製する。この基板としては、金属や樹脂等の板状部材や、コンデンサの素子を構成する陽極箔、陰極箔やセパレータなどが挙げられる。
（Ｆ）該高分子ゲルシートに電解液を含浸し、ゲル電解質を作製する。
[Gel electrolyte]
The gel electrolyte in the present embodiment is one in which an electrolytic solution is held in a polymer gel in which particles of an organic-inorganic composite gel are integrated. As shown in FIG. 1, the process for producing a gel electrolyte is roughly classified as follows.
(A) The organic-inorganic composite gel is pulverized after drying or dried after pulverization to produce a particulate dried product of the composite gel.
(B) The particulate dried product is mixed with water, a solute or an aqueous solution containing a solute to prepare a polymer gel dispersion.
(C) An organic-inorganic composite having a three-dimensional network structure formed by cross-linking of a polymer of a polymerizable unsaturated group-containing water-soluble organic monomer and a water-swellable clay mineral instead of the above (A) and (B) The gel is pulverized in water to prepare a slurry polymer gel dispersion.
(D) An organic-inorganic composite having a three-dimensional network structure formed by crosslinking a polymer of a polymerizable unsaturated group-containing water-soluble organic monomer and a water-swellable clay mineral instead of the above (A) and (B) A gel particle is synthesized and a polymer gel dispersion containing the same is prepared.
(E) After apply | coating this polymer gel dispersion liquid on a board | substrate, it dries and produces a polymer gel sheet. Examples of the substrate include plate members such as metals and resins, and anode foils, cathode foils, and separators that constitute capacitor elements.
(F) The polymer gel sheet is impregnated with an electrolytic solution to produce a gel electrolyte.
（Ａ）有機無機複合ゲルおよびその粒子状乾燥物の作製
（有機無機複合ゲルの合成）
本実施形態における有機無機複合ゲルは、重合性不飽和基含有水溶性有機モノマーから得られる重合体と層状に剥離した水膨潤性粘土鉱物が分子レベルで複合化し、三次元網目を形成している。この三次元網目の形成は、水素結合、イオン結合、配位結合、共有結合などのいずれかまたは複数による。このことは、（１）該複合ゲルが水又は親水性有機溶剤により膨潤し、且つ該複合ゲルを２０℃で５００時間以上処理しても構成成分である水膨潤性粘土鉱物及び水溶性有機モノマー重合体が抽出されないことや、（２）延伸や圧縮の力学試験において、大きな可逆的伸張性や圧縮性を示すこと、から推定される。
(A) Preparation of organic-inorganic composite gel and particulate dried product (synthesis of organic-inorganic composite gel)
In the organic-inorganic composite gel in this embodiment, a polymer obtained from a polymerizable unsaturated group-containing water-soluble organic monomer and a water-swellable clay mineral separated in layers are combined at a molecular level to form a three-dimensional network. . The three-dimensional network is formed by any one or a plurality of hydrogen bonds, ionic bonds, coordination bonds, covalent bonds, and the like. This is because (1) the composite gel swells with water or a hydrophilic organic solvent, and the water-swellable clay mineral and water-soluble organic monomer which are constituents even if the composite gel is treated at 20 ° C. for 500 hours or longer It is presumed from the fact that the polymer is not extracted and (2) that it exhibits a large reversible stretchability and compressibility in a mechanical test of stretching and compression.
有機無機複合ゲルは公知の方法で作製することができる。例えば、水に均一分散した水膨潤性粘土鉱物に、重合性不飽和基含有水溶性有機モノマー、ラジカル重合開始剤、及び触媒を添加して、不酸素雰囲気下にて重合を行うことにより作製することができる。またはラジカル重合開始剤の代わりに光重合開始剤を用いて不酸素雰囲気下にて紫外線照射を行う光重合により作製することもできる。 The organic-inorganic composite gel can be produced by a known method. For example, it is prepared by adding a polymerizable unsaturated group-containing water-soluble organic monomer, a radical polymerization initiator, and a catalyst to a water-swellable clay mineral uniformly dispersed in water, and performing polymerization in an oxygen-free atmosphere. be able to. Alternatively, the photopolymerization initiator can be used instead of the radical polymerization initiator, and it can be prepared by photopolymerization in which ultraviolet irradiation is performed in an oxygen-free atmosphere.
（重合性不飽和基含有水溶性有機モノマー）
本発明における重合性不飽和基含有水溶性有機モノマーとしては、水に溶解する性質を有し、水に均一分散可能な水膨潤性粘土鉱物と相互作用を有するものが好ましい。例えば、粘土鉱物と水素結合、イオン結合、配位結合、共有結合等を形成できる官能基を有するものが好ましい。これらの官能基を有する重合性不飽和基含有水溶性有機モノマーとしては、具体的には、アミド基、アミノ基、エステル基、水酸基、エーテル基、テトラメチルアンモニウム基、シラノール基、エポキシ基などを有する重合性不飽和基含有水溶性有機モノマーが挙げられる。なかでもアミド基、エステル基、水酸基、エーテル基を有する重合性不飽和基含有水溶性有機モノマーが好ましく、特に好ましくはアミド基、エステル基を有する重合性不飽和基含有水溶性有機モノマーである。なお、本発明で言う水には、水単独以外に、水と混和する有機溶媒をとの混合溶媒で水を主成分とするものが含まれる。
(Polymerizable unsaturated group-containing water-soluble organic monomer)
As the polymerizable unsaturated group-containing water-soluble organic monomer in the present invention, those having a property of being dissolved in water and interacting with a water-swellable clay mineral that can be uniformly dispersed in water are preferable. For example, those having a functional group capable of forming a hydrogen bond, an ionic bond, a coordinate bond, a covalent bond and the like with a clay mineral are preferable. Specific examples of polymerizable unsaturated group-containing water-soluble organic monomers having these functional groups include amide groups, amino groups, ester groups, hydroxyl groups, ether groups, tetramethylammonium groups, silanol groups, and epoxy groups. Examples thereof include a polymerizable unsaturated group-containing water-soluble organic monomer. Among these, a polymerizable unsaturated group-containing water-soluble organic monomer having an amide group, an ester group, a hydroxyl group, or an ether group is preferable, and a polymerizable unsaturated group-containing water-soluble organic monomer having an amide group or an ester group is particularly preferable. The water referred to in the present invention includes a mixture of water and an organic solvent miscible with water in addition to water alone.
アミド基を有する重合性不飽和基含有水溶性有機モノマーの具体例としては、Ｎ−アルキルアクリルアミド、Ｎ，Ｎ−ジアルキルアクリルアミド、アクリルアミド等のアクリルアミド類、または、Ｎ−アルキルメタクリルアミド、Ｎ，Ｎ−ジアルキルメタクリルアミド、メタクリルアミド等のメタクリルアミド類が挙げられる。ここでアルキル基としては炭素数が１〜４のものが特に好ましく選択される。またエステル基を有する重合性不飽和基含有水溶性有機モノマーの具体例としては、メトキシエチルアクリレート、エトキシエチルアクリレート、メトキシエチルメタクリレート、エトキシエチルメタクリレートなどがあげられる。またエーテル基を有する重合性不飽和基含有水溶性有機モノマーの具体例としては、側鎖にポリエチレングリコール鎖を有するアクリレート、具体的には、メトキシポリエチレングリコールアクリレートが挙げられる。ここでポリエチレングリコール鎖のエチレンオキサイドユニットの数としては１〜２０が用いられ、特に好ましくは２〜１５が用いられる。 Specific examples of the polymerizable unsaturated group-containing water-soluble organic monomer having an amide group include acrylamides such as N-alkylacrylamide, N, N-dialkylacrylamide, and acrylamide, or N-alkylmethacrylamide, N, N- And methacrylamides such as dialkylmethacrylamide and methacrylamide. Here, an alkyl group having 1 to 4 carbon atoms is particularly preferably selected. Specific examples of the polymerizable unsaturated group-containing water-soluble organic monomer having an ester group include methoxyethyl acrylate, ethoxyethyl acrylate, methoxyethyl methacrylate, and ethoxyethyl methacrylate. Specific examples of the polymerizable unsaturated group-containing water-soluble organic monomer having an ether group include acrylate having a polyethylene glycol chain in the side chain, specifically, methoxypolyethylene glycol acrylate. Here, 1-20 are used as the number of ethylene oxide units of the polyethylene glycol chain, and 2-15 are particularly preferably used.
（水溶性有機モノマー重合体）
かかる水溶性有機モノマー重合体としては、例えば、ポリ（Ｎ−メチルアクリルアミド）、ポリ（Ｎ−エチルアクリルアミド）、ポリ（Ｎ−シクロプロピルアクリルアミド）、ポリ（Ｎ−イソプロピルアクリルアミド）、ポリ（アクリロイルモルフォリン）、ポリ（メタクリルアミド）、ポリ（Ｎ−メチルメタクリルアミド）、ポリ（Ｎ−シクロプロピルメタクリルアミド）、ポリ（Ｎ−イソプロピルメタクリルアミド）、ポリ（Ｎ，Ｎ−ジメチルアクリルアミド）、ポリ（Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド）、ポリ（Ｎ−メチル−Ｎ−エチルアクリルアミド）、ポリ（Ｎ−メチル−Ｎ−イソプロピルアクリルアミド）、ポリ（Ｎ−メチル−Ｎ−ｎ−プロピルアクリルアミド）、ポリ（Ｎ，Ｎ−ジエチルアクリルアミド）、ポリ（Ｎ−アクリロイルピロリディン）、ポリ（Ｎ−アクリロイルピペリディン）、ポリ（Ｎ−アクリロイルメチルホモピペラディン）、ポリ（Ｎ−アクリロイルメチルピペラディン）、ポリ（アクリルアミド）、ポリ（メトキシエチルアクリレート）、ポリ（エトキシエチルアクリレート）、ポリ（メトキシエチルメタクリレート）、ポリ（エトキシエチルメタクリレート）、ポリ（メトキシポリエチレングリコール）アクリレートが例示される。また水溶性有機モノマー重合体としては、以上のような単一の重合性不飽和基含有水溶性有機モノマーからの重合体の他、これらから選ばれる複数の異なる重合性不飽和基含有水溶性有機モノマーを重合して得られる共重合体を用いることも有効である。具体的には、Ｎ−アルキルアクリルアミド、Ｎ，Ｎ−ジアルキルアクリルアミド、アクリルアミド等のアクリルアミド類、または、Ｎ−アルキルメタクリルアミド、Ｎ，Ｎ−ジアルキルメタクリルアミド、メタクリルアミド等のメタクリルアミド類と、エステル基を有する重合性不飽和基含有水溶性有機モノマーとの共重合体、もしくは、かかるアミド基含有モノマーもしくはエステル基含有モノマーとエーテル基含有モノマーとの共重合体が好ましく用いられる。特に好ましい具体例としては、Ｎ，Ｎ−ジメチルアクリルアミドとメトキシエチルアクリレートの共重合体やメトキシエチルアクリレートとメトキシポリエチレングリコールアクリレートの共重合体があげられる。また上記水溶性有機モノマーとそれ以外の有機溶媒可溶性重合性不飽和基含有有機モノマーとの共重合体も、本発明にいう一体化した高分子ゲルが達成出来るものであれば使用することができる。
(Water-soluble organic monomer polymer)
Examples of the water-soluble organic monomer polymer include poly (N-methylacrylamide), poly (N-ethylacrylamide), poly (N-cyclopropylacrylamide), poly (N-isopropylacrylamide), and poly (acryloylmorpholine. ), Poly (methacrylamide), poly (N-methylmethacrylamide), poly (N-cyclopropylmethacrylamide), poly (N-isopropylmethacrylamide), poly (N, N-dimethylacrylamide), poly (N, N-dimethylaminopropylacrylamide), poly (N-methyl-N-ethylacrylamide), poly (N-methyl-N-isopropylacrylamide), poly (N-methyl-Nn-propylacrylamide), poly (N, N-diethylacrylamide), poly (N-acryloylpyrrolidine), poly (N-acryloylpiperidine), poly (N-acryloylmethylhomopiperadine), poly (N-acryloylmethylpiperazine), poly (acrylamide), poly (methoxyethyl acrylate) , Poly (ethoxyethyl acrylate), poly (methoxyethyl methacrylate), poly (ethoxyethyl methacrylate), poly (methoxypolyethylene glycol) acrylate. The water-soluble organic monomer polymer may be a polymer from a single polymerizable unsaturated group-containing water-soluble organic monomer as described above, or a plurality of different polymerizable unsaturated group-containing water-soluble organic materials selected from these. It is also effective to use a copolymer obtained by polymerizing monomers. Specifically, acrylamides such as N-alkyl acrylamide, N, N-dialkyl acrylamide and acrylamide, or methacrylamides such as N-alkyl methacrylamide, N, N-dialkyl methacrylamide and methacrylamide and ester groups A copolymer with a polymerizable unsaturated group-containing water-soluble organic monomer having the above or a copolymer of such an amide group-containing monomer or ester group-containing monomer with an ether group-containing monomer is preferably used. Particularly preferred specific examples include a copolymer of N, N-dimethylacrylamide and methoxyethyl acrylate and a copolymer of methoxyethyl acrylate and methoxypolyethylene glycol acrylate. A copolymer of the above water-soluble organic monomer and other organic solvent-soluble polymerizable unsaturated group-containing organic monomer can also be used as long as the integrated polymer gel according to the present invention can be achieved. .
本発明における重合性不飽和基含有水溶性有機モノマー重合体は、上記水溶性有機モノマーを重合したものであり、水溶性または水を吸湿する性質を有する親水性または両親媒性を有する。具体的には、ポリ（Ｎ，Ｎ−ジメチルアクリルアミド）のような親水性を示すもの、ポリ（Ｎ−イソプロピルアクリルアミド）のような親水性／疎水性が温度により変化するもの、ポリ（Ｎ，Ｎ−ジメチルアクリルアミド）とポリ（メトキシエチルアクリレート）の共重合体のように重合比率により親水〜疎水の中間の性質をしめすものなどが含まれる。 The polymerizable unsaturated group-containing water-soluble organic monomer polymer in the present invention is obtained by polymerizing the above-mentioned water-soluble organic monomer, and has hydrophilicity or amphiphilicity that has water-soluble or water-absorbing properties. Specifically, those having hydrophilic properties such as poly (N, N-dimethylacrylamide), those having hydrophilicity / hydrophobicity changing with temperature, such as poly (N-isopropylacrylamide), poly (N, N -A dimethylacrylamide) and poly (methoxyethyl acrylate) copolymer, which has a hydrophilic to hydrophobic intermediate property depending on the polymerization ratio.
（水膨潤性粘土鉱物）
本実施形態における有機無機複合ゲルに用いる水膨潤性粘土鉱物としては、水に膨潤性を有するものであり、好ましくは水によって層間が膨潤する性質を有するものが用いられる。より好ましくは少なくとも一部が水中で層状に剥離して分散できるものであり、特に好ましくは水中で１ないし１０層以内の厚みの層状に剥離して均一分散できる層状粘土鉱物である。例えば、水膨潤性スメクタイトや水膨潤性雲母などが用いられる。具体的には、ナトリウムを層間イオンとして含む水膨潤性ヘクトライト、水膨潤性モンモロナイト、水膨潤性サポナイト、水膨潤性合成雲母などが挙げられる。この中でも、特に層状剥離後の基本サイズ（直径）が３０ｎｍ前後と小さい合成ヘクトライトは三次元網目構造を効果的に形成するのに有効であり、一方、層状剥離後の基本サイズ（直径）が３００〜１０００ｎｍと大きな天然モンモリロナイトは耐久性、耐水和性、耐熱性に優れたゲル電解質を調製するのに有効である。
(Water-swelling clay mineral)
As the water-swellable clay mineral used in the organic-inorganic composite gel in the present embodiment, water-swellable clay minerals, preferably those having the property of swelling between layers by water, are used. More preferably, it is a layered clay mineral that can be at least partially exfoliated and dispersed in layers in water, and particularly preferably a lamellar clay mineral that can be exfoliated and dispersed uniformly in water with a thickness of 1 to 10 layers. For example, water-swellable smectite or water-swellable mica is used. Specific examples include water-swellable hectorite containing sodium as an interlayer ion, water-swellable montmoronite, water-swellable saponite, and water-swellable synthetic mica. Among these, synthetic hectorite having a small basic size (diameter) after delamination of about 30 nm is particularly effective for effectively forming a three-dimensional network structure, while the basic size (diameter) after delamination is effective. Natural montmorillonite as large as 300 to 1000 nm is effective for preparing a gel electrolyte excellent in durability, hydration resistance and heat resistance.
本実施形態における重合性不飽和基含有水溶性有機モノマー重合体に対する水膨潤性粘土好物の質量比は、０．０３〜２．０であることが好ましく、より好ましくは、０．０５〜１．５、特に好ましくは、０．１〜０．７である。０．０３以下では得られる一体化された高分子ゲルの強度が弱い場合が多く、２．０以上では一体化が進みにくくなる。また、溶質を用いないで一体化する高分子ゲルの場合のより好ましい範囲は、０．０５〜０．７である。 In the present embodiment, the mass ratio of the water-swellable clay favorite to the polymerizable unsaturated group-containing water-soluble organic monomer polymer is preferably 0.03 to 2.0, more preferably 0.05 to 1. 5, particularly preferably 0.1 to 0.7. If it is 0.03 or less, the strength of the integrated polymer gel obtained is often weak, and if it is 2.0 or more, the integration becomes difficult to proceed. Moreover, the more preferable range in the case of the polymer gel integrated without using a solute is 0.05-0.7.
（粒子状乾燥物）
本発明における粒子状乾燥物は、有機無機複合ゲルを乾燥した粉末状のものである。従って、水を含んだヒドロゲルと異なり、水分の放出を防ぐための密封、カビの発生を抑えるための抗菌成分の添加、ヒドロゲルの変形を防ぐための無圧力下での保存などヒドロゲルに必要な特段の管理項目が必要でない特徴を有する。
(Particulate dry matter)
The particulate dried product in the present invention is a powdered product obtained by drying an organic-inorganic composite gel. Therefore, unlike hydrogels containing water, the special features necessary for hydrogels such as sealing to prevent the release of moisture, addition of antibacterial components to suppress mold generation, storage under no pressure to prevent deformation of the hydrogel, etc. The management item is not necessary.
本発明に用いる粒子状乾燥物の大きさは、最終的に粒子状乾燥物が一体化した高分子ゲルが得られればよく特に限定されない。しかし、例えば、早い一体化時間や高強度の高分子ゲルを得るためには、平均粒径が０．１μｍ〜１０００μｍであることが好ましく、より好ましくは、１μｍ〜３００μｍ、更に好ましくは２μｍ〜２００μｍ、特に好ましくは、３μｍ〜１００μｍである。平均粒径が０．１μｍ以下は調製が困難であったり、取り扱い性が悪くなる問題が生じ、１０００μｍ以上では一体化が不均一となる問題が生じてくる場合がある。また、粒子状乾燥物の形状は種々のものが用いられ特に限定されない。例えば、球状、直方体状、扁平状、繊維状などが用いられ、表面も平滑なものと凹凸を有するものがいずれも可能である。このうち、有機無機複合ゲルを延伸、圧縮などの方法で変形した状態で乾燥粒子化したものは、その後の一体化力を高めるのに有効である。変形倍率としては、必ずしも限定されないが、延伸変形の場合、延伸倍率が２倍〜２０倍が特に有効に用いられる。圧縮変形の場合は、圧縮率が３０％〜９５％が有効に用いられる。また、有機無機複合ゲルを凍結した状態で乾燥する方法も有効に用いられる。この場合、粒子状とするのは凍結乾燥させる前でも、凍結乾燥した後でもよい。一方、粒子状乾燥物における乾燥度合いは粉末状態を保つものであれば良く、必ずしも水分率０％の絶乾状態である必要はない。乾燥粉末の水分率（粉末全体に対する水含有率）としては、好ましくは、６０％以下、より好ましくは３０％以下、特に好ましくは２０％以下である。 The size of the particulate dried product used in the present invention is not particularly limited as long as a polymer gel integrated with the particulate dried product is finally obtained. However, for example, in order to obtain a fast integration time and a high-strength polymer gel, the average particle size is preferably 0.1 μm to 1000 μm, more preferably 1 μm to 300 μm, and even more preferably 2 μm to 200 μm. Particularly preferably, the thickness is 3 μm to 100 μm. If the average particle size is 0.1 μm or less, preparation may be difficult or the handleability may be poor, and if it is 1000 μm or more, integration may be uneven. Various shapes of the particulate dried material are used and are not particularly limited. For example, a spherical shape, a rectangular parallelepiped shape, a flat shape, a fiber shape, or the like is used, and a smooth surface or an uneven surface can be used. Among these, what formed the dry particle | grains in the state which deform | transformed organic-inorganic composite gel by methods, such as extending | stretching and compression, is effective in raising the subsequent integration force. The deformation ratio is not necessarily limited, but in the case of stretch deformation, a stretch ratio of 2 to 20 times is particularly effectively used. In the case of compression deformation, a compression rate of 30% to 95% is effectively used. Moreover, the method of drying the organic-inorganic composite gel in a frozen state is also used effectively. In this case, the particulate form may be before lyophilization or after lyophilization. On the other hand, the degree of drying in the particulate dried product is not limited as long as it maintains a powder state, and does not necessarily need to be in an absolutely dry state with a moisture content of 0%. The moisture content of the dry powder (water content relative to the whole powder) is preferably 60% or less, more preferably 30% or less, and particularly preferably 20% or less.
本発明における有機無機複合ゲルの粒子状乾燥物を得る方法としては、有機無機複合ゲルを粉砕後乾燥する方法、有機無機複合ゲルを乾燥後粉砕する方法、両者を併せて用いる方法のいずれもが用いられる。粉砕方法としては、通常知られている機械的力および／または熱による方法が用いられ特に限定されない。 As a method for obtaining a particulate dried product of the organic-inorganic composite gel in the present invention, any of a method of pulverizing and drying the organic-inorganic composite gel, a method of drying and pulverizing the organic-inorganic composite gel, and a method of using both in combination. Used. As the pulverization method, a conventionally known method using mechanical force and / or heat is used and is not particularly limited.
（Ｂ）高分子ゲル分散液の調製
本発明において、粒子状乾燥物を水、溶質または溶質を含む水溶液と混合することにより、特異的な高分子ゲル分散液が得られる。高分子ゲル分散液の特性は、粒子状乾燥物の性質のほか、分散液中での粒子状乾燥物の含有量や溶質の性質および濃度によって決まる。用いる溶質としては、水に溶解または混和することができる有機分子、有機高分子および水膨潤性粘土鉱物である。具体的には、エーテル基、水酸基、カルボキシル基、アミド基、アミノ基などの親水性官能基を有する有機分子または有機高分子であり、例として、メタノール、エタノール、プロパノール、アセトン、エチレングリコール、プロピレングリコール、ジエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、１，３ブチレングリコール、グリセリン、ポリビニルアルコール、ポリビニルピロリドン、ポリ（ヒドロキシエチルアクリレート）、ポリ（ヒドロキシエチルメタクリレート）、ポリ（Ｎ−メチルアクリルアミド）、ポリ（Ｎ−エチルアクリルアミド）、ポリ（Ｎ−シクロプロピルアクリルアミド）、ポリ（Ｎ−イソプロピルアクリルアミド）、ポリ（アクリロイルモルフォリン）、ポリ（メタクリルアミド）、ポリ（Ｎ−メチルメタクリルアミド）、ポリ（Ｎ−シクロプロピルメタクリルアミド）、ポリ（Ｎ−イソプロピルメタクリルアミド）、ポリ（Ｎ，Ｎ−ジメチルアクリルアミド）、ポリ（Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド）、ポリ（Ｎ−メチル−Ｎ−エチルアクリルアミド）、ポリ（Ｎ−メチル−Ｎ−イソプロピルアクリルアミド）、ポリ（Ｎ−メチル−Ｎ−ｎ−プロピルアクリルアミド）、ポリ（Ｎ，Ｎ−ジエチルアクリルアミド）、ポリ（Ｎ−アクリロイルピロリディン）、ポリ（Ｎ−アクリロイルピペリディン）、ポリ（Ｎ−アクリロイルメチルホモピペラディン）、ポリ（Ｎ−アクリロイルメチルピペラディン）、ポリ（アクリルアミド）、ポリアクリル酸、ヒアルロン酸、ポリエチレンイミン、ポリプロピレンイミン、アガロース、アルギン酸、カラギーナン、コラーゲン、メチルセルロース、カルボキシメチルセルロース、ヒドロキシプロピルセルロース、セルロース誘導体、キタンサンガム、ジェランガム、キトサンなどが挙げられ、好ましくは、メタノール、エタノール、プロパノール、アセトン、エチレングリコール、プロピレングリコール、ジエチレングリコール、１，３ブチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、グリセリン、ポリ（Ｎ，Ｎ−ジメチルアクリルアミド、ポリ（Ｎ，Ｎジエチルアクリルアミド）、ポリビニルピロリドン、ポリアクリル酸、ポリエチレンイミン、ポリプロピレンイミンが用いられる。また、特に好ましくは、エタノール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ポリエチレングリコール、グリセリン、ポリプロピレングリコール、ポリ（Ｎ，Ｎ−ジメチルアクリルアミド）、ポリビニルピロリドンが用いられる。これらは単独または複数を組み合わせて用いられる。また、これら溶質をあらかじめ水に溶解または分散しておいたものは有効に用いられる。高分子ゲル分散液における粒子状乾燥物の含有量は０．２〜２０ｗｔ％であることが好ましく、より好ましくは１〜１０ｗｔ％、特に好ましくは２〜５ｗｔ％である。
(B) Preparation of polymer gel dispersion In the present invention, a specific polymer gel dispersion can be obtained by mixing the particulate dried product with water, a solute or an aqueous solution containing a solute. The characteristics of the polymer gel dispersion liquid are determined not only by the properties of the particulate dry matter, but also by the content of the particulate dry matter in the dispersion and the nature and concentration of the solute. Solutes used are organic molecules, organic polymers and water-swellable clay minerals that can be dissolved or miscible in water. Specifically, it is an organic molecule or organic polymer having a hydrophilic functional group such as an ether group, a hydroxyl group, a carboxyl group, an amide group, an amino group, and examples thereof include methanol, ethanol, propanol, acetone, ethylene glycol, propylene. Glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, 1,3 butylene glycol, glycerin, polyvinyl alcohol, polyvinyl pyrrolidone, poly (hydroxyethyl acrylate), poly (hydroxyethyl methacrylate), poly (N-methylacrylamide), poly (N- Ethyl acrylamide), poly (N-cyclopropyl acrylamide), poly (N-isopropyl acrylamide), poly (acryloylmorpholine), poly (methacrylamide), (N-methylmethacrylamide), poly (N-cyclopropylmethacrylamide), poly (N-isopropylmethacrylamide), poly (N, N-dimethylacrylamide), poly (N, N-dimethylaminopropylacrylamide), Poly (N-methyl-N-ethylacrylamide), poly (N-methyl-N-isopropylacrylamide), poly (N-methyl-Nn-propylacrylamide), poly (N, N-diethylacrylamide), poly ( N-acryloylpyrrolidine), poly (N-acryloylpiperidine), poly (N-acryloylmethylhomopiperazine), poly (N-acryloylmethylpiperazine), poly (acrylamide), polyacrylic acid, hyaluronic acid, Polyethylene imine, polypropylene imine , Agarose, alginic acid, carrageenan, collagen, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, cellulose derivatives, chitansan gum, gellan gum, chitosan, etc., preferably methanol, ethanol, propanol, acetone, ethylene glycol, propylene glycol, diethylene glycol, 1,3 butylene glycol, polyethylene glycol, polypropylene glycol, glycerin, poly (N, N-dimethylacrylamide, poly (N, N diethylacrylamide), polyvinylpyrrolidone, polyacrylic acid, polyethyleneimine, polypropyleneimine are used. Particularly preferably, ethanol, ethylene glycol, propylene glycol, diethylene Glycol, polyethylene glycol, glycerin, polypropylene glycol, poly (N, N-dimethylacrylamide), and polyvinylpyrrolidone are used. These may be used alone or in combination. Moreover, what dissolved or disperse | distributed these solutes beforehand in water is used effectively. The content of the particulate dried product in the polymer gel dispersion is preferably 0.2 to 20 wt%, more preferably 1 to 10 wt%, and particularly preferably 2 to 5 wt%.
（Ｃ）スラリー状高分子ゲル分散液の調製
本発明においてスラリー状高分子ゲル分散液は、前述した（有機無機複合ゲルの合成）で記した方法により有機高分子／粘土鉱物架橋体からなる一体化した有機無機複合ゲルをいったん合成した後、該ゲルを多量の水中に投入し、ミキサーで撹拌・粉砕することにより得られる。用いる水の量は有機無機複合ゲルより多く、好ましくはゲル質量の２倍〜２０倍量の水が用いられる。撹拌条件は目的に応じて広い範囲から設定できる。得られたスラリー状高分子ゲル分散液はそのまま、もしくは、その後、余分な水を除いたり、逆に水を追加して用いられる。
(C) Preparation of Slurry Polymer Gel Dispersion In the present invention, the slurry polymer gel dispersion is formed of an integrated organic polymer / clay mineral by the method described in the above (Synthesis of organic-inorganic composite gel). After synthesizing the organic-inorganic composite gel, the gel is put into a large amount of water, stirred and pulverized with a mixer. The amount of water to be used is larger than that of the organic-inorganic composite gel, and preferably 2 to 20 times the amount of gel mass is used. The stirring conditions can be set from a wide range according to the purpose. The obtained slurry polymer gel dispersion is used as it is, or after that, excess water is removed or water is added.
（Ｄ）粒子合成による高分子ゲル分散液の調製
前述した（有機無機複合ゲルの合成：水中に分散した水膨潤性粘土鉱物の存在下で、重合性不飽和基含有水溶性有機モノマーを重合する）において、反応水溶液の水量の割合を高くすることにより、粒子状の有機無機複合ゲルを含む高分子ゲル分散液を一段で合成することができる。一体化した有機無機複合ゲルが得られるか、粒子状の有機無機複合ゲル分散液が得られるかは、用いる水量により主に決定される。粒子合成のための適した水量は、用いる有機高分子や粘土鉱物の種類や濃度によって変化するため一概には限定できないが、一般には、水溶性有機モノマーと層状粘土鉱物の合計量の１０〜３００倍が好ましく用いられ、より好ましくは２０〜１５０倍、特に好ましくは２５〜１００倍が用いられる。水量が３００倍以上では濃度が低すぎて粒子合成の効率が悪い。得られた有機無機複合ゲル粒子の大きさは安定した分散状態を保つものであれば、目的により任意に選ばれ必ずしも限定されないが、好ましくは平均粒子径が０．０１〜３μｍ、より好ましくは０．０２〜０．５μｍ、特に好ましくは０．０３〜０．３μｍの範囲である。
(D) Preparation of polymer gel dispersion by particle synthesis As described above (Synthesis of organic-inorganic composite gel: polymerization of polymerizable unsaturated group-containing water-soluble organic monomer in the presence of water-swellable clay mineral dispersed in water. ), The polymer gel dispersion containing the particulate organic-inorganic composite gel can be synthesized in one step by increasing the ratio of the amount of water in the reaction aqueous solution. Whether an integrated organic-inorganic composite gel or a particulate organic-inorganic composite gel dispersion is obtained is mainly determined by the amount of water used. The amount of water suitable for particle synthesis varies depending on the type and concentration of the organic polymer and clay mineral to be used, and thus cannot be generally limited. However, generally, the total amount of water-soluble organic monomer and layered clay mineral is 10 to 300. Is preferably used, more preferably 20 to 150 times, and particularly preferably 25 to 100 times. When the amount of water is 300 times or more, the concentration is too low and the efficiency of particle synthesis is poor. The size of the obtained organic-inorganic composite gel particles is arbitrarily selected depending on the purpose as long as it maintains a stable dispersion state, but preferably has an average particle diameter of 0.01 to 3 μm, more preferably 0. The range is 0.02 to 0.5 μm, particularly preferably 0.03 to 0.3 μm.
（Ｅ）高分子ゲルシートの作製
上述した（Ｂ）〜（Ｃ）で得られた高分子ゲル分散液を、大気中にてアルミ箔、セパレータ等の基板に塗布し、さらに乾燥処理を行う。これによって、シート状の高分子ゲルが得られる。
このようにして得られた高分子ゲルは、優れた吸収性、力学物性、機能性を示す。例えば、力学物性としては、水含水率が８５重量％である時の引っ張り強度が１ｋＰａ以上、より好ましくは３ｋＰａ以上、特に好ましくは５ｋＰａ以上であり、引っ張り破断伸びが５０％以上、より好ましくは１００％以上、特に好ましくは２００％以上である。
(E) Production of polymer gel sheet The polymer gel dispersion obtained in (B) to (C) described above is applied to a substrate such as an aluminum foil or a separator in the air, and further dried. Thereby, a sheet-like polymer gel is obtained.
The polymer gel thus obtained exhibits excellent absorptivity, mechanical properties and functionality. For example, as mechanical properties, the tensile strength when the water content is 85% by weight is 1 kPa or more, more preferably 3 kPa or more, particularly preferably 5 kPa or more, and the tensile elongation at break is 50% or more, more preferably 100 % Or more, particularly preferably 200% or more.
これに対して、比較として、有機無機複合ゲルではなく、例えば一般に知られている化学架橋ゲル（例：ポリジメチルアクリルアミドの化学架橋ゲル）や物理架橋ゲル（例：アガロースの物理架橋ゲル）を用いた場合は、それらを粒子状乾燥物とした後、同様に水、溶質または溶質を含む水溶液と混合させても、いずれも一体化された高い力学物性を有する高分子ゲルは得られなかった。本発明における有機無機複合ゲルを用いることで極めて効果的に粒子状乾燥物を経て最終的に一体化された高分子ゲルが調製されることが明らかとなった。一体化する機構は必ずしも限定されていないが、例えば、粒子ゲルの表面にある片末端が自由な高分子鎖（もう一方の末端はクレイと結合）が媒体中で、隣接する他のクレイと再結合することにより一体化が生じることが考えられる。
また本発明における高分子ゲル分散液を経て調製された一体化した高分子ゲルは、粒子の融合体であるため電解液が容易に浸透し、且つ、安定して含まれる特徴を有する。
On the other hand, for comparison, for example, generally known chemical cross-linking gel (eg, polydimethylacrylamide chemical cross-linking gel) or physical cross-linking gel (eg: agarose physical cross-linking gel) is used instead of organic-inorganic composite gel. In such a case, even if they were made into a particulate dry product and then mixed with water, a solute, or an aqueous solution containing a solute in the same manner, a polymer gel having high integrated mechanical properties could not be obtained. It was revealed that by using the organic-inorganic composite gel in the present invention, a polymer gel finally integrated through a particulate dried product is prepared extremely effectively. The mechanism of integration is not necessarily limited. For example, a polymer chain on one surface of the particle gel is free from a polymer chain (the other end is bonded to clay) in the medium and re-laminated with other adjacent clay. It is conceivable that integration is caused by bonding.
In addition, the integrated polymer gel prepared through the polymer gel dispersion in the present invention is a particle fusion, so that the electrolyte solution easily permeates and is stably contained.
（Ｆ）ゲル電解質の作製
本実施形態におけるゲル電解質は、シート状の高分子ゲルに電解液を含浸させることによって得られる。
(F) Production of Gel Electrolyte The gel electrolyte in the present embodiment is obtained by impregnating a sheet-like polymer gel with an electrolytic solution.
（電解液）
電解液としては、溶媒に溶質としてイオン解離性の塩を溶解させたものが挙げられる。
電解コンデンサに用いる場合は、溶媒として、水、プロトン性極性溶媒、非プロトン性溶媒、及びこれらの混合物を用いることができる。プロトン性極性溶媒としては、一価アルコール類（エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、シクロブタノール、シクロペンタノール、シクロヘキサノール、ベンジルアルコール等）、多価アルコール類およびオキシアルコール化合物類（エチレングリコール、プロピレングリコール、グリセリン、メチルセロソルブ、エチルセロソルブ、メトキシプロピレングリコール、ジメトキシプロパノール等）などが挙げられる。また、非プロトン性の極性溶媒としては、アミド系（Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−エチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−エチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、ヘキサメチルホスホリックアミド等）、ラクトン類（γ−ブチロラクトン、δ−バレロラクトン、γ−バレロラクトン等）、スルホラン系（スルホラン、３−メチルスルホラン、２，４−ジメチルスルホラン等）、環状アミド系（Ｎ−メチル−２−ピロリドン等）、カーボネイト類（エチレンカーボネイト、プロピレンカーボネイト、イソブチレンカーボネイト等）、ニトリル系（アセトニトリル等）、スルホキシド系（ジメチルスルホキシド等）、２−イミダゾリジノン系〔１，３−ジアルキル−２−イミダゾリジノン（１，３−ジメチル−２−イミダゾリジノン、１，３−ジエチル−２−イミダゾリジノン、１，３−ジ（ｎ−プロピル）−２−イミダゾリジノン等）、１，３，４−トリアルキル−２−イミダゾリジノン（１，３，４−トリメチル−２−イミダゾリジノン等）〕などが代表として、挙げられる。
(Electrolyte)
Examples of the electrolytic solution include those obtained by dissolving an ion dissociable salt as a solute in a solvent.
When used for an electrolytic capacitor, water, a protic polar solvent, an aprotic solvent, and a mixture thereof can be used as a solvent. Protic polar solvents include monohydric alcohols (ethanol, propanol, butanol, pentanol, hexanol, cyclobutanol, cyclopentanol, cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols and oxyalcohol compounds (ethylene glycol) Propylene glycol, glycerin, methyl cellosolve, ethyl cellosolve, methoxypropylene glycol, dimethoxypropanol, etc.). Examples of aprotic polar solvents include amides (N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, hexamethylphosphoricamide, etc.), lactones (γ-butyrolactone, δ-valerolactone, γ-valerolactone, etc.), sulfolanes (sulfolane, 3-methylsulfolane, 2 , 4-dimethylsulfolane, etc.), cyclic amides (N-methyl-2-pyrrolidone, etc.), carbonates (ethylene carbonate, propylene carbonate, isobutylene carbonate, etc.), nitriles (acetonitrile, etc.), sulfoxides (dimethylsulfoxide, etc.) , -Imidazolidinone series [1,3-dialkyl-2-imidazolidinone (1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-di (n- And propyl) -2-imidazolidinone), 1,3,4-trialkyl-2-imidazolidinone (1,3,4-trimethyl-2-imidazolidinone, etc.)] and the like.
また、溶質としては、有機酸および／または無機酸のオニウム塩が挙げられ、有機酸成分の具体例としては、安息香酸、トルイル酸、クミン酸、ｔ−ブチル安息香酸、サリチル酸、アニス酸などの芳香族モノカルボン酸類；ギ酸、酢酸、プロピオン酸、７−フェニル−７−メトキシ−１−オクタンカルボン酸、６−フェニル−６−メトキシ−１−ヘプタンカルボン酸などの脂肪族モノカルボン酸類；フタル酸、４−メチルフタル酸、４−ニトロフタル酸など芳香族ジカルボン酸類；マレイン酸、シトラコン酸、ジメチルマレイン酸、１，２−シクロヘキセンジカルボン酸などの不飽和脂肪族ジカルボン酸類；シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、トリデカン二酸などの直鎖状飽和脂肪族ジカルボン酸類；ジメチルマロン酸、ジエチルマロン酸、ジプロピルマロン酸、２−メチルグルタル酸、３−メチルグルタル酸、３，３−ジメチルグルタル酸、３−メチルアジピン酸、２，２，４−トリメチルアジピン酸、２，４，４−トリメチルアジピン酸、１，６−デカンジカルボン酸、５，６−デカンジカルボン酸、１，７−オクタンジカルボン酸、７−メチル−７−カルボメトキシ−１，９−デカンジカルボン酸、２，８−ノナンジカルボン酸、７，８，１１，１２−テトラメチル−１，１８−オクタデカンジカルボン酸、１−メチル−３−エチル−１，７−ヘプタンジカルボン酸、１，３−ジメチル−１，７−ヘプタンジカルボン酸、５−メチル−１，７−オクタンジカルボン酸、７，１２−ジメチル−１，１８−オクタデカンジカルボン酸、７−エチル−１，１６−ヘキサデカンジカルボン酸、７，８−ジメチル−１，１４−テトラデカンジカルボン酸、１，６−ヘプタンジカルボン酸、６−メチル−６−カルボメトキシ−１，８−ノナンジカルボン酸、１，８−ノナンジカルボン酸、８−メチル−８−カルボメトキシ−１，１０−ウンデカンジカルボン酸、６−エチル−１，４−テトラデカンジカルボン酸、シクロヘキサンジカルボン酸などの分岐鎖を有する飽和脂肪族ジカルボン酸類；７−メチル−１，７，９−デカントリカルボン酸、６−メチル−１，６，８−ノナントリカルボン酸、８−メチル−１，８，１０−ウンデカントリカルボン酸などのトリカルボン酸類等あるいはこれらの混合物が挙げられる。また、無機酸成分の具体例としては、ホウ酸、燐酸などが挙げられる。 Examples of the solute include onium salts of organic acids and / or inorganic acids. Specific examples of the organic acid component include benzoic acid, toluic acid, cumic acid, t-butylbenzoic acid, salicylic acid, anisic acid and the like. Aromatic monocarboxylic acids; aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, 7-phenyl-7-methoxy-1-octanecarboxylic acid, 6-phenyl-6-methoxy-1-heptanecarboxylic acid; phthalic acid Aromatic dicarboxylic acids such as 4-methylphthalic acid and 4-nitrophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, citraconic acid, dimethylmaleic acid and 1,2-cyclohexene dicarboxylic acid; oxalic acid, malonic acid, succinic acid , Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, Linear saturated aliphatic dicarboxylic acids such as decanedioic acid and tridecanedioic acid; dimethylmalonic acid, diethylmalonic acid, dipropylmalonic acid, 2-methylglutaric acid, 3-methylglutaric acid, 3,3-dimethylglutaric acid 3-methyladipic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, 1,6-decanedicarboxylic acid, 5,6-decanedicarboxylic acid, 1,7-octanedicarboxylic acid 7-methyl-7-carbomethoxy-1,9-decanedicarboxylic acid, 2,8-nonanedicarboxylic acid, 7,8,11,12-tetramethyl-1,18-octadecanedicarboxylic acid, 1-methyl-3 -Ethyl-1,7-heptanedicarboxylic acid, 1,3-dimethyl-1,7-heptanedicarboxylic acid, 5-methyl-1,7-octanedicarbo Acid, 7,12-dimethyl-1,18-octadecanedicarboxylic acid, 7-ethyl-1,16-hexadecanedicarboxylic acid, 7,8-dimethyl-1,14-tetradecanedicarboxylic acid, 1,6-heptanedicarboxylic acid, 6-methyl-6-carbomethoxy-1,8-nonanedicarboxylic acid, 1,8-nonanedicarboxylic acid, 8-methyl-8-carbomethoxy-1,10-undecanedicarboxylic acid, 6-ethyl-1,4- Saturated aliphatic dicarboxylic acids having a branched chain such as tetradecanedicarboxylic acid and cyclohexanedicarboxylic acid; 7-methyl-1,7,9-decanetricarboxylic acid, 6-methyl-1,6,8-nonanetricarboxylic acid, 8-methyl Examples thereof include tricarboxylic acids such as -1,8,10-undecane tricarboxylic acid, and mixtures thereof. Specific examples of the inorganic acid component include boric acid and phosphoric acid.
上記した有機酸成分及び無機酸成分のうちでも定格電圧１００Ｖ以下の低圧用コンデンサ向けには電気伝導率の高い電解液が得られるフタル酸、マレイン酸、安息香酸、アジピン酸が好ましい。定格電圧３００Ｖ以上の高圧用コンデンサ向けには耐電圧の高い電解液が得られるアゼライン酸、セバシン酸、１，６−デカンジカルボン酸、１，７−オクタンジカルボン酸、ホウ酸が好ましい。定格電圧１００Ｖを越え、３００Ｖ未満の中圧用コンデンサ向けには適度の電気伝導率と耐電圧を有する電解液が得られる安息香酸、アジピン酸、アゼライン酸が好ましい。 Of the organic acid components and inorganic acid components described above, phthalic acid, maleic acid, benzoic acid, and adipic acid are preferred for low voltage capacitors having a rated voltage of 100 V or less, which can provide an electrolytic solution with high electrical conductivity. For high voltage capacitors having a rated voltage of 300 V or more, azelaic acid, sebacic acid, 1,6-decanedicarboxylic acid, 1,7-octanedicarboxylic acid, and boric acid are preferred because an electrolytic solution having a high withstand voltage can be obtained. Benzoic acid, adipic acid, and azelaic acid are preferable for medium-pressure capacitors that exceed the rated voltage of 100 V and less than 300 V to obtain an electrolytic solution having appropriate electrical conductivity and withstand voltage.
オニウム塩の具体例としては、アンモニウム；メチルアンモニウム；ジメチルアンモニウム；トリメチルアンモニウム、エチルジメチルアンモニウム、ジエチルメチルアンモニウム、トリエチルアンモニウムなどの三級アンモニウム類；テトラメチルアンモニウム、トリエチルメチルアンモニウム、テトラエチルアンモニウムなどの四級アンモニウム類等あるいはこれらの混合物が挙げられる。 Specific examples of the onium salt include ammonium; methylammonium; dimethylammonium; tertiary ammoniums such as trimethylammonium, ethyldimethylammonium, diethylmethylammonium, and triethylammonium; quaternary such as tetramethylammonium, triethylmethylammonium, and tetraethylammonium. Examples thereof include ammoniums and mixtures thereof.
中高圧用コンデンサに用いる場合は、エチレングリコール溶媒と１，６−デカンジカルボン酸などのジカルボン酸類との組み合わせにおいて高い耐電圧を有する電解液が得られるアンモニアが好ましい。低圧用コンデンサにはγ−ブチロラクトン溶媒とフタル酸などの組み合わせにおいて高い電気伝導率を有する電解液が得られる１，２，３，４−テトラメチルイミダゾリニウム、１−エチル−２，３−ジメチルイミダゾリニウム、テトラメチルアンモニウム、トリエチルメチルアンモニウム、テトラエチルアンモニウムが好ましい。溶質の使用量は溶媒と溶質との合計重量に対して５〜３０重量％の範囲で含有させるのが好ましい。 When used for a medium- or high-voltage capacitor, ammonia is preferable because an electrolytic solution having a high withstand voltage can be obtained by a combination of an ethylene glycol solvent and a dicarboxylic acid such as 1,6-decanedicarboxylic acid. For low-voltage capacitors, 1,2,3,4-tetramethylimidazolinium, 1-ethyl-2,3-dimethyl, which can obtain an electrolytic solution having high electrical conductivity in a combination of γ-butyrolactone solvent and phthalic acid, etc. Preference is given to imidazolinium, tetramethylammonium, triethylmethylammonium and tetraethylammonium. The amount of the solute used is preferably in the range of 5 to 30% by weight with respect to the total weight of the solvent and the solute.
また、必要に応じて電解液にさらに添加剤を含有させることもできる。添加剤としては、ホウ酸、ホウ酸と多価アルコール類（エチレングリコール、マンニトール、ソルビトールなど）との錯化合物などのホウ素化合物類；リン酸、酸性リン酸エステル類〔リン酸ジブチル、リン酸ビス（２−エチルヘキシル）〕、酸性ホスホン酸エステル類〔２−エチルヘキシルホスホン酸（２−エチルヘキシル）など〕のリン化合物類；ｐ−ニトロ安息香酸、ｍ−ニトロアセトフェノンなどのニトロ化合物類などが挙げられる。 Moreover, an additive can also be further contained in electrolyte solution as needed. Additives include boron compounds such as boric acid, complex compounds of boric acid and polyhydric alcohols (ethylene glycol, mannitol, sorbitol, etc.); phosphoric acid, acidic phosphate esters (dibutyl phosphate, bisphosphate) (2-ethylhexyl)], phosphoric compounds such as acidic phosphonic acid esters [2-ethylhexylphosphonic acid (2-ethylhexyl) and the like]; and nitro compounds such as p-nitrobenzoic acid and m-nitroacetophenone.
また、コンデンサが電気二重層コンデンサ（キャパシタ）の場合は、電解液としてその主溶媒として、γ−ブチロラクトン、スルホランまたはその誘導体、プロピレンカーボネートを用いることができる。また、副溶媒として、エチレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、ジエチルカーボネートなどのカーボネート類；トリメトキシメタン、１，２−ジメトキシエタン、ジエチルエーテル、２−エトキシエタン、テトラヒドロフラン、２−メチルテトラヒドロフランなどのエーテル類；ジメチルスルホキシドなどのスルホキシド類；１，３−ジオキソラン、４−メチル−１，３−ジオキソランなどのオキソラン類；アセトニトリルやニトロメタンなどの含窒素類；ギ酸メチル、酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル、プロピオン酸エチルなどの有機酸エステル類；リン酸トリエステルや炭酸ジメチル、炭酸ジエチル、炭酸ジプロピルのような炭酸ジエステルなどの無機酸エステル類；ジグライム類；トリグライム類；３−メチル−２−オキサゾリジノンなどのオキサゾリジノン類；１，３−プロパンスルトン、１，４−ブタンスルトン、ナフタスルトンなどのスルトン類等を用いることができる。 When the capacitor is an electric double layer capacitor (capacitor), γ-butyrolactone, sulfolane or a derivative thereof, and propylene carbonate can be used as the main solvent as the electrolyte. Further, as a co-solvent, carbonates such as ethylene carbonate, butylene carbonate, dimethyl carbonate, and diethyl carbonate; ethers such as trimethoxymethane, 1,2-dimethoxyethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran, and 2-methyltetrahydrofuran Sulfoxides such as dimethyl sulfoxide; oxolanes such as 1,3-dioxolane and 4-methyl-1,3-dioxolane; nitrogen-containing compounds such as acetonitrile and nitromethane; methyl formate, methyl acetate, ethyl acetate, butyl acetate, Organic acid esters such as methyl propionate and ethyl propionate; inorganic acid esters such as phosphoric acid triester and diester carbonate such as dimethyl carbonate, diethyl carbonate and dipropyl carbonate; diglyme ; Triglyme like; oxazolidinones such as 3-methyl-2-oxazolidinone; 1,3-propane sultone, 1,4-butane sultone can be used sultone like such Nafutasuruton.
溶質としては金属の陽イオン、４級アンモニウムカチオン、カルボニウムカチオン等のカチオンと、ＢＦ4 -、ＰＦ6 -、ＣｌＯ4 -、ＡｓＦ6 -、ＳｂＦ6 -、ＡｌＣｌ4 -、またはＲｆＳＯ3 -、（ＲｆＳＯ2）2Ｎ-、ＲｆＣＯ2 -(Ｒｆは炭素数１〜８のフルオロアルキル基)から選ばれるアニオンの塩を挙げることができる。その他、電気化学キャパシタでは、上述の主溶媒及び副溶媒が用いられ、溶質としては特に第４級アンモニウム塩、第４級ホスホニウム塩を使用することができる。 Solutes include cations such as metal cations, quaternary ammonium cations, carbonium cations, BF 4 − , PF 6 − , ClO 4 − , AsF 6 − , SbF 6 − , AlCl 4 − , or RfSO 3 − , An anionic salt selected from (RfSO 2 ) 2 N − and RfCO 2 − (Rf is a fluoroalkyl group having 1 to 8 carbon atoms). In addition, in the electrochemical capacitor, the above-mentioned main solvent and auxiliary solvent are used, and quaternary ammonium salts and quaternary phosphonium salts can be used as solutes.
［コンデンサ］
本実施形態のゲル電解質をコンデンサに応用する場合は、図２に示すように、以下の工程によってコンデンサを製造することができる。
（Ｅ）図１の工程（Ｂ）、（Ｃ）または（Ｄ）で得られた高分子ゲル分散液を、素子構成材料上に塗布して乾燥させる（高分子ゲルシートの作製）。図２（Ｅ）では一例として陽極箔に塗布しているが、他の素子構成材料、例えば陰極箔やセパレータに塗布しても良い。
（Ｆ）陽極箔及び陰極箔を重ね合わせ、高分子ゲルが該陽極箔及び陰極箔の間に配置されるようにする。なお、セパレータを該陽極箔及び陰極箔の間に配置してもよい。電極箔にリード線を接続する。電極箔とリード線との接続部をあて紙で覆った後、電解液を含浸させる（ゲル電解質の作製）。
（Ｇ）電解液含浸後の電極箔をフィルム状封止体で覆うことにより、ラミネート型のコンデンサを得る。
[Capacitor]
When the gel electrolyte of the present embodiment is applied to a capacitor, the capacitor can be manufactured by the following steps as shown in FIG.
(E) The polymer gel dispersion obtained in step (B), (C) or (D) of FIG. 1 is applied onto the element constituent material and dried (production of a polymer gel sheet). In FIG. 2 (E), it is applied to the anode foil as an example, but may be applied to other element constituent materials such as a cathode foil and a separator.
(F) The anode foil and the cathode foil are overlapped so that the polymer gel is disposed between the anode foil and the cathode foil. A separator may be disposed between the anode foil and the cathode foil. Connect the lead wires to the electrode foil. The connecting portion between the electrode foil and the lead wire is covered with paper and impregnated with an electrolytic solution (production of a gel electrolyte).
(G) A laminated capacitor is obtained by covering the electrode foil impregnated with the electrolytic solution with a film-shaped encapsulant.
陽極箔及び陰極箔としては、コンデンサの種類に応じて、公知の電極材料を使用することができる。例えば、コンデンサがアルミニウム電解コンデンサの場合には、アルミニウム箔の表面積をエッチング処理によって拡大した後、表面に酸化皮膜の誘電体層を形成した箔を陽極とし、エッチング処理を施した同種又は他の金属の箔を陰極とすることができる。 As the anode foil and cathode foil, known electrode materials can be used depending on the type of capacitor. For example, in the case where the capacitor is an aluminum electrolytic capacitor, the surface of the aluminum foil is enlarged by etching, and then a foil having an oxide film dielectric layer formed on the surface is used as an anode, and the same or other metal subjected to the etching treatment. The foil can be used as a cathode.
セパレータには、不織布、マニラ紙、クラフト紙、セルロース紙等が使用され、また、ガラス、合成高分子の繊維を用いたセパレータを使用することもできる。 As the separator, non-woven fabric, manila paper, kraft paper, cellulose paper, or the like is used, and a separator using glass or synthetic polymer fibers can also be used.
一対の電極及びこれらの間に挟持されたゲル電解質を覆うフィルム状封止体としては、シリコーンフィルム、アルミニウム箔とポリプロピレン、ポリエチレンテレフタレート等の樹脂フィルムとを積層させたラミネートフィルムなどを使用することができる。 As the film-like encapsulant covering the pair of electrodes and the gel electrolyte sandwiched between them, it is possible to use a silicone film, a laminate film in which an aluminum foil and a resin film such as polypropylene and polyethylene terephthalate are laminated, and the like. it can.
なお、図２の工程（Ｆ）では、陽極箔と陰極箔を重ね合わせた後、電解液を含浸しているが、陽極箔と陰極箔とを交互に複数枚重ね合わせた後、電解液を含浸してもよい。 In the step (F) of FIG. 2, the anode foil and the cathode foil are overlapped and then impregnated with the electrolytic solution. After the anode foil and the cathode foil are alternately stacked, the electrolyte solution is It may be impregnated.
アルミニウム電解コンデンサに用いられる電極箔は、アルミニウム箔の表面積をエッチング処理によって拡大しており、このエッチング処理によってアルミニウム箔の表面には、1μｍ以下の極小のエッチングピットが形成されている。粒子状乾燥物は、その粒子径によりエッチングピットの深部にまで入り込ませにくいが、電解液がこのエッチングピットの深部にまで入り込ませることができる。これにより、静電容量が向上し、アルミニウム箔の表層に形成される高分子ゲル層によってＥＳＲが改善されていると推定される。 In the electrode foil used for the aluminum electrolytic capacitor, the surface area of the aluminum foil is enlarged by an etching process, and a very small etching pit of 1 μm or less is formed on the surface of the aluminum foil by this etching process. Although the particulate dried product is difficult to penetrate into the deep part of the etching pit due to its particle diameter, the electrolytic solution can penetrate into the deep part of the etching pit. Thereby, it is presumed that the electrostatic capacity is improved and the ESR is improved by the polymer gel layer formed on the surface layer of the aluminum foil.
［効果］
以上詳述したように、本実施形態によれば、以下の効果を得られる。
（１）水膨潤性粘土鉱物を含有する有機無機複合ゲルの粒子が一体化したものを用いることによって、高い力学的強度を有し、取り扱いが容易なゲル電解質を得ることができる。
（２）該高分子ゲル内に、容易に、且つ、安定して電解液が保持されることによって、過電圧印加時の電解液の漏れが抑制されるため、長寿命の電気化学素子が得られる。
（３）いったん乾燥粒状物とした有機無機複合ゲルを用いたり、有機無機複合ゲルをスラリー状としたものを用いたり、粒子状に合成した有機無機複合ゲルを用いて、ゲル電解質及びコンデンサの製造を行うことによって、大気下中で製造作業を行うことができるため、製造工程が簡便となり、品質管理等も容易である。
（４）ゲル電解質を作製するための電解液の含浸はコンデンサ製造と同時に行うため、高分子ゲルを作製してからコンデンサへの使用までに期間が空く場合も、電解液の保持率を維持する管理が必要ないため、高分子ゲルの保管取扱いも容易である。
（５）より具体的方法として、陽極箔、陰極箔又はセパレータから選択した素子構成材料に高分子ゲル分散液を塗布して乾燥した後に、素子構成材料全体を巻回又は積層し、その後に電解液を含浸してコンデンサ素子を形成する。これによって、製造工程が簡便となり、品質管理等も容易となる。また、ゲル電解質の作製及びコンデンサ素子の形成が同時に行われるので、作業効率を上げることができる。
[effect]
As described above in detail, according to the present embodiment, the following effects can be obtained.
(1) By using an integrated organic-inorganic composite gel particle containing a water-swellable clay mineral, a gel electrolyte having high mechanical strength and easy handling can be obtained.
(2) Since the electrolyte solution is easily and stably held in the polymer gel, leakage of the electrolyte solution during overvoltage application is suppressed, and thus a long-life electrochemical device can be obtained. .
(3) Manufacture of gel electrolytes and capacitors using organic-inorganic composite gels that have been once dried, using slurries of organic-inorganic composite gels, or using organic-inorganic composite gels synthesized into particles Since the manufacturing operation can be performed in the air, the manufacturing process becomes simple, and quality control and the like are easy.
(4) Since the impregnation of the electrolytic solution for producing the gel electrolyte is performed simultaneously with the production of the capacitor, the retention rate of the electrolytic solution is maintained even when there is a period between the production of the polymer gel and the use for the capacitor. Since management is not required, storage and handling of the polymer gel is easy.
(5) As a more specific method, after coating and drying a polymer gel dispersion on an element constituent material selected from an anode foil, a cathode foil or a separator, the entire element constituent material is wound or laminated, and then electrolyzed. A capacitor element is formed by impregnating the solution. This simplifies the manufacturing process and facilitates quality control and the like. Moreover, since the production of the gel electrolyte and the formation of the capacitor element are performed simultaneously, the working efficiency can be increased.
（実施例１）
（高分子ゲル分散液）
水膨潤性粘土鉱物には、［Ｍｇ５．３４Ｌｉ０．６６Ｓｉ８Ｏ２０（ＯＨ）４］Ｎａ＋ ０．６６の組成を有する水膨潤性合成ヘクトライト（商標ラポナイトＸＬＧ）を、水溶性有機モノマーには、Ｎ，Ｎ−ジメチルアクリルアミド（ＤＭＡＡ：興人株式会社製）を用いた。ＤＭＡＡは精製により重合禁止剤を取り除いてから使用した。水溶性有機モノマー（ＤＭＡＡ）を０．６８ｇ、粘土鉱物（ラポナイトＸＬＧ）を０．２１ｇ、水を４０ｇを混合したものに、重合開始剤として、光開始重合剤（Ｉｒｇａｃｕｒｅ１８４：チバガイギー社製：２％メタノール溶液）を１００μｌ、及び、ペルオキソ二硫酸カリウム（ＫＰＳ）水溶液（２％水溶液）１４０μｌを添加して反応水溶液を調製した。石英製透明容器に反応水溶液を入れ、３６５ｎｍ、強度４０ｍＷ／ｃｍ２の紫外線を１０分間照射した後、８０℃恒温槽に移し１時間保持した。その結果、ゲル粒子が分散した高分子ゲル分散液が得られた。重合収率は９９％以上であり、動的光散乱装置（堀場製作所製LD550V）を用いて測定したゲル粒子の平均粒子径は１００ｎｍであった。また、ゲル粒子乾燥物の熱重量分析、透過型電子顕微鏡測定、エネルギー分散Ｘ線スペクトラム（ＥＤＸ）マッピング測定、ＦＴＩＲ測定から、ゲル粒子は高分子（ＰＤＭＡＡ）と層状剥離した粘土鉱物（ヘクトライト）が複合した有機無機複合ゲル粒子であることが確認された。更に、この有機無機複合ゲル粒子は空気中および水中で可逆的に乾燥−膨潤を繰り返すこと及び下記に示す力学試験の結果から、有機無機複合ゲル粒子は層状剥離した粘土鉱物と高分子（ＰＤＭＡＡ）が三次元網目構造を形成していることが確認された。
得られた高分子ゲル分散液の一部をポリ容器（５ｃｍ×７ｃｍ×１ｃｍ深さ）内に充填し２５℃で静置して徐々に水分を乾燥除去し、含水率を５０％以下にした結果、一体化した高分子ゲルフィルムが得られ、これを水中に浸漬すると再び膨潤した。含水率を８５ｗｔ％に調整した一体化高分子ゲルフィルムの引っ張り試験を、引っ張り試験装置（株式会社島津製作所製、卓上型万能試験機ＡＧＳ−Ｈ）を用い、評点間距離＝３０ｍｍ、引っ張り速度＝１００ｍｍ／分にて行った。高分子ゲルは、大きな力学的タフネスおよび延伸性（弾性率＝３．５ｋＰａ、強度＝３７ｋＰａ、破断伸び＝１１００％）を有するゴム的な力学物性を示した。また水中で大きな膨潤性（２０℃水中での吸水量は乾燥物の２０倍以上）を示した。このように、本実施形態の高分子ゲルは高い力学的強度と保持力を有する。
（ゲル電解質・コンデンサ）
上述の高分子ゲル分散液の一部を、１４．５ｍｍ×２２．０ｍｍのサイズのアルミニウム陽極箔上に塗布し、８０℃で１時間乾燥した。この高分子ゲル分散液の塗布及び乾燥工程を、３回繰り返し、乾燥後の高分子ゲル層の厚みを２０μｍとなるようにした。さらに、高分子ゲル分散液が塗布された面を内側にして、アルミニウム陰極と重ね合わせた。重ね合わせた電極箔にリード線を接続し、接続部分をクラフト紙のあて紙で覆った。その後、エチレングリコール１００、ホウ酸６、Ｄ−マンニトール９を溶解した電解液に、減圧下で電極箔を浸漬した。これによって、陽極箔に塗布された高分子ゲル中に電解液が保持されるため、本実施形態のゲル電解質が得られる。なお、ゲル電解質の厚みは、含浸後４０μｍとなるようにした。
含浸後の電極箔を、さらにフィルム状封止体で覆うことにより、ラミネートセルを作製した。
Example 1
(Polymer gel dispersion)
For the water-swellable clay mineral, water-swellable synthetic hectorite (trademark Laponite XLG) having a composition of [Mg 5.34 Li 0.66 Si 8 O 20 (OH) 4 ] Na + 0.66 is dissolved in water. N, N-dimethylacrylamide (DMAA: manufactured by Kojin Co., Ltd.) was used as the organic monomer. DMAA was used after removing the polymerization inhibitor by purification. As a polymerization initiator, 0.68 g of water-soluble organic monomer (DMAA), 0.21 g of clay mineral (Laponite XLG) and 40 g of water were mixed as a polymerization initiator (Irgacure 184: manufactured by Ciba Geigy: 2%) 100 μl of methanol solution) and 140 μl of potassium peroxodisulfate (KPS) aqueous solution (2% aqueous solution) were added to prepare a reaction aqueous solution. The reaction aqueous solution was put into a quartz transparent container, irradiated with ultraviolet rays of 365 nm and an intensity of 40 mW / cm 2 for 10 minutes, and then transferred to a constant temperature bath at 80 ° C. for 1 hour. As a result, a polymer gel dispersion having gel particles dispersed therein was obtained. The polymerization yield was 99% or more, and the average particle size of the gel particles measured using a dynamic light scattering device (LD550V manufactured by Horiba, Ltd.) was 100 nm. In addition, the thermogravimetric analysis, transmission electron microscope measurement, energy dispersive X-ray spectrum (EDX) mapping measurement, and FTIR measurement of the gel particle dry matter, the gel particle is a clay mineral (hectorite) exfoliated from the polymer (PDMAA). Was confirmed to be a composite organic-inorganic composite gel particle. Furthermore, the organic-inorganic composite gel particles are repeatedly dried and swollen in air and water, and from the results of the mechanical tests shown below, the organic-inorganic composite gel particles are delaminated clay mineral and polymer (PDMAA). Was confirmed to form a three-dimensional network structure.
Part of the obtained polymer gel dispersion was filled in a plastic container (5 cm × 7 cm × 1 cm depth) and allowed to stand at 25 ° C. to gradually dry and remove moisture, thereby reducing the water content to 50% or less. As a result, an integrated polymer gel film was obtained, which swelled again when immersed in water. A tensile test of an integrated polymer gel film with a moisture content adjusted to 85 wt% was performed using a tensile test device (manufactured by Shimadzu Corporation, desktop universal testing machine AGS-H), distance between ratings = 30 mm, tensile speed = It was performed at 100 mm / min. The polymer gel exhibited rubber-like mechanical properties having large mechanical toughness and stretchability (elastic modulus = 3.5 kPa, strength = 37 kPa, elongation at break = 1100%). In addition, it showed a large swellability in water (the amount of water absorption in water at 20 ° C. was 20 times or more that of a dried product). Thus, the polymer gel of this embodiment has high mechanical strength and holding power.
(Gel electrolyte / capacitor)
A part of the polymer gel dispersion described above was applied onto an aluminum anode foil having a size of 14.5 mm × 22.0 mm and dried at 80 ° C. for 1 hour. The polymer gel dispersion application and drying steps were repeated three times, so that the thickness of the polymer gel layer after drying was 20 μm. Further, the surface coated with the polymer gel dispersion was placed on the inside, and was superposed on the aluminum cathode. Lead wires were connected to the overlapped electrode foils, and the connected portions were covered with kraft paper. Thereafter, the electrode foil was immersed in an electrolytic solution in which ethylene glycol 100, boric acid 6, and D-mannitol 9 were dissolved. Thereby, since the electrolytic solution is held in the polymer gel applied to the anode foil, the gel electrolyte of this embodiment is obtained. The thickness of the gel electrolyte was 40 μm after the impregnation.
A laminate cell was produced by covering the impregnated electrode foil with a film-like sealing body.
なお、実施例１のラミネートセルのゲル電解質の厚みを変更したものについて、高温槽にて１０５℃で長時間放置した後のＥＳＲを測定した。測定結果は、図３に示すとおりである。ゲル厚さは、セル全体をマイクロメータ（ミツトヨ社製・ＭＤＣ−２５ＭＪ）で測定し、陰極箔や陽極箔等の材料の厚さを減じて算出した。ＥＳＲは２０℃で測定した。
図３からわかるように、ＥＳＲ特性は、ゲル電解質の厚みが１０〜１７０μｍまでは良好であることがわかる。
In addition, about what changed the thickness of the gel electrolyte of the laminate cell of Example 1, ESR after leaving it to stand at 105 degreeC for a long time in a high-temperature tank was measured. The measurement results are as shown in FIG. The gel thickness was calculated by measuring the whole cell with a micrometer (MDC-25MJ, manufactured by Mitutoyo Co., Ltd.) and subtracting the thickness of the material such as cathode foil or anode foil. ESR was measured at 20 ° C.
As can be seen from FIG. 3, it can be seen that the ESR characteristics are good when the thickness of the gel electrolyte is 10 to 170 μm.
（実施例２）
電解液を、エチレングリコール１００に、水１４、安息香酸アンモニウム１０、アジピン酸アンモニウム５を溶解して調製した。その他の部分は、実施例１と同様にしてラミネートセルを作製した。
(Example 2)
An electrolytic solution was prepared by dissolving water 14, ammonium benzoate 10, and ammonium adipate 5 in ethylene glycol 100. Other parts were made in the same manner as in Example 1 to produce a laminate cell.
（実施例３）
電解液を、γ―ブチロラクトン７５ｗｔ％に、フタル酸水素１−エチル−２，３−ジメチルイミダゾリニウム２５ｗｔ％を溶解して調製した。その他の部分は、実施例１と同様にしてラミネートセルを作製した。
(Example 3)
An electrolytic solution was prepared by dissolving 25 wt% of 1-ethyl-2,3-dimethylimidazolinium hydrogen phthalate in 75 wt% of γ-butyrolactone. Other parts were made in the same manner as in Example 1 to produce a laminate cell.
（実施例４、５、６、７、８）
実施例４では粘土鉱物（ラポナイトＸＬＧ）を０．４２ｇ用いること及び水を５３ｇ用いること、実施例５では反応水溶液にクエン酸を０．２５ｍＭを添加すること、実施例６では粘土鉱物としてモンモリロナイト（クニミネ工業（株）製クニピアＦ）を０．２１ｇ用いること、実施例７では有機架橋剤（Ｎ，Ｎ−メチレンビスアクリルアミド）を水溶性モノマー（ＤＭＡＡ）の０．０５モル比を添加すること、実施例８では水溶性有機モノマーとしてＤＭＡＡ０．３４ｇと２−メトキシエチルアクリレート（ＭＥＡ：東亞合成）０．４１ｇを用いること及び粘土鉱物（ラポナイトＸＬＧ）を０．１０５ｇ用いること及び水を２７ｇ用いることを除くと、全て実施例１と同様にして重合を行い、いずれも有機無機複合ゲル粒子からなる均一な高分子ゲル分散液が得られた。ＤＬＳで測定した平均粒子径はそれぞれ６０ｎｍ（実施例４）、１０３ｎｍ（実施例５）、５５０ｎｍ（実施例６）、９４ｎｍ（実施例７）、１３３ｎｍ（実施例８）であった。また、得られた高分子ゲル分散液を用いて、実施例１と同様にしてゲル電解質およびコンデンサを調製した。
(Examples 4, 5, 6, 7, 8)
In Example 4, 0.42 g of clay mineral (Laponite XLG) and 53 g of water were used, in Example 5, 0.25 mM citric acid was added to the aqueous reaction solution, and in Example 6, montmorillonite ( 0.21 g of Kunimine Kogyo Co., Ltd. Kunipia F) is used, and in Example 7, an organic cross-linking agent (N, N-methylenebisacrylamide) is added in a 0.05 molar ratio of a water-soluble monomer (DMAA). In Example 8, 0.34 g of DMAA and 0.41 g of 2-methoxyethyl acrylate (MEA: Toagosei) are used as water-soluble organic monomers, 0.105 g of clay mineral (Laponite XLG) and 27 g of water are used. Except for the above, the polymerization is carried out in the same manner as in Example 1, all of which are composed of organic-inorganic composite gel particles. Molecular gel dispersion was obtained. The average particle diameter measured by DLS was 60 nm (Example 4), 103 nm (Example 5), 550 nm (Example 6), 94 nm (Example 7), and 133 nm (Example 8), respectively. Further, a gel electrolyte and a capacitor were prepared in the same manner as in Example 1 using the obtained polymer gel dispersion.
（実施例９）
ガラス容器に、純水３８ｇ、ラポナイトＸＬＧ１．２３ｇ、ＤＭＡＡ３．９６ｇを加えて無色透明水溶液を得た。この水溶液に、重合開始剤として、ペルオキソ二硫酸カリウム（ＫＰＳ）をＫＰＳ／水＝０．４０／２０（ｇ／ｇ）の割合で水溶液にして２．０ｇ、また触媒として、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン（ＴＥＭＥＤ：和光純薬工業株式会社製）３２μｌを攪拌しながら加え、反応水溶液を調製した。この溶液を直径が３．５ｃｍ、長さが１０ｃｍの密閉したガラス容器にして移した後、２０℃の恒温水槽中で２０時間静置して重合を行った。これらの溶液調製から重合までの操作は、全て酸素を遮断した窒素雰囲気下で行った。重合開始から２０時間後に、容器内に有機モノマー重合体と層状剥離した粘土鉱物からなる無色透明で均一な有機・無機複合ゲルが生成した。
得られた有機・無機複合ゲルを約５ｍｍ角に切断後、最終固形分が２ｗｔ％となるように水を加え、ミキサー（岩谷産業（株）製）に投入して１０分間粉砕を行って、スラリー状の高分子ゲル分散液が得られた。得られた高分子ゲル分散液を用いて、実施例１と同様にしてゲル電解質およびコンデンサを調製した。
Example 9
To a glass container, 38 g of pure water, 1.23 g of Laponite XLG, and 3.96 g of DMAA were added to obtain a colorless transparent aqueous solution. To this aqueous solution, 2.0 g of potassium peroxodisulfate (KPS) as a polymerization initiator at a ratio of KPS / water = 0.40 / 20 (g / g) as an initiator and N, N, N as a catalyst 32 μl of ', N'-tetramethylethylenediamine (TEMED: manufactured by Wako Pure Chemical Industries, Ltd.) was added with stirring to prepare a reaction aqueous solution. This solution was transferred to a sealed glass container having a diameter of 3.5 cm and a length of 10 cm, and then left to stand in a constant temperature water bath at 20 ° C. for 20 hours for polymerization. All operations from preparation of the solution to polymerization were performed in a nitrogen atmosphere in which oxygen was blocked. 20 hours after the start of the polymerization, a colorless transparent and uniform organic / inorganic composite gel composed of an organic monomer polymer and layered exfoliated clay mineral was formed in the container.
After cutting the obtained organic-inorganic composite gel into about 5 mm square, water is added so that the final solid content is 2 wt%, and the mixture is put into a mixer (manufactured by Iwatani Corporation) and pulverized for 10 minutes. A slurry polymer gel dispersion was obtained. A gel electrolyte and a capacitor were prepared in the same manner as in Example 1 using the obtained polymer gel dispersion.
（実施例１０，１１）
実施例１０では、水溶性有機モノマーとしてアクリロイルモルホリン（ＡＣＭＯ：興人株式会社製）を０．７３ｇ、及び粘土鉱物としてラポナイトＸＬＧを０．１０５ｇを用いること、及び水を３３ｇ用いること、また実施例１１では水溶性有機モノマーとして、ＤＭＡＡ０．４２ｇとメトキシポリエチレングリコールアクリレート（エチレンオキシド単位＝１７）０．３４ｇを用いること、更にいずれの実施例でも、光開始重合剤を添加せず、且つ、光照射をしないで、熱重合（８０℃１時間）のみを行うことを除くと実施例１と同様にして重合を行った。その結果、有機・無機複合ゲル粒子からなる高分子ゲル分散液を得た。重合収率はいずれも９９％以上であり、粘土鉱物は全量がゲル粒子中に含まれていた。得られた高分子ゲル分散液を用いて実施例１と同様にしてまた、得られた高分子ゲル分散液を用いて、実施例１と同様にしてゲル電解質およびコンデンサを調製した。
(Examples 10 and 11)
In Example 10, 0.73 g of acryloylmorpholine (ACMO: manufactured by Kojin Co., Ltd.) is used as a water-soluble organic monomer, 0.105 g of Laponite XLG is used as a clay mineral, and 33 g of water is used. In Example 11, 0.42 g of DMAA and 0.34 g of methoxypolyethylene glycol acrylate (ethylene oxide unit = 17) are used as water-soluble organic monomers. Further, in any of the examples, a photoinitiator is not added and light irradiation is performed. However, polymerization was carried out in the same manner as in Example 1 except that only thermal polymerization (80 ° C. for 1 hour) was carried out. As a result, a polymer gel dispersion composed of organic / inorganic composite gel particles was obtained. The polymerization yield was 99% or more in all cases, and the entire amount of clay mineral was contained in the gel particles. A gel electrolyte and a capacitor were prepared using the obtained polymer gel dispersion in the same manner as in Example 1, and using the obtained polymer gel dispersion in the same manner as in Example 1.
（実施例１２）
（有機無機複合ゲル）
平底ガラス容器に、純水３８．０４ｇと１．２３ｇのラポナイトＸＬＧを加え、無色透明の溶液を調製した。これにＤＭＡＡ３．９６ｇを加えて無色透明溶液を得た。次にＫＰＳ／水＝０．４０／２０（ｇ／ｇ）の割合で調製したＫＰＳ水溶液２．０ｇとＴＥＭＥＤ３２μｌを攪拌しながら加え、この溶液を直径が３．５ｃｍ、長さが１０ｃｍの密閉したガラス容器にして移した後、２０℃の恒温水槽中で２０時間静置して重合を行った。これらの溶液調製から重合までの操作は、全て酸素を遮断した窒素雰囲気下で行った。重合開始から２０時間後に、容器内に有機モノマー重合体と層状剥離した粘土鉱物からなる無色透明で均一な有機・無機複合ゲルが生成した。
（高分子ゲル分散液）
得られた有機ポリマー（ＰＤＭＡＡ）／クレイ複合ゲルを約５ｍｍ角に切断後、室温にて２４時間、引き続き４０℃にて３時間、更に、４０℃真空乾燥にて１時間乾燥後、ミキサーにて粉末化を行った。得られたものを分級して３〜４０μｍ範囲の粒子状乾燥物を得た（平均粒径＝１９μｍ）。次いで、この粒子状乾燥物にその６倍量のポリエチレングリコール水溶液（ポリエチレングリコール２００００（平均分子量２００００）（和光純薬工業（株）製）を１重量％含む水溶液）及び４０倍量の水を加えて高分子ゲル分散液を得た。
高分子ゲル分散液の一部をポリ容器（５ｃｍ×７ｃｍ×１ｃｍ深さ）内に充填し２５℃で静置して、元の粒子状乾燥物の７倍量の水分含有量になるまで、徐々に水分を乾燥除去した。３０分後にポリ容器内から一体化した高分子ゲルフィルム（厚み約２ｍｍ）を取り出した。得られた高分子ゲル（含水率（１００×水／高分子ゲル）＝８９ｗｔ％）の引っ張り試験を、引っ張り試験装置（株式会社島津製作所製、卓上型万能試験機ＡＧＳ−Ｈ）を用い、評点間距離＝３０ｍｍ、引っ張り速度＝１００ｍｍ／分にて行った。高分子ゲルは、大きな延伸性（弾性率＝３．０ｋＰａ、強度＝３３ｋＰａ、破断伸び＝１０５０％）を有するゴム的な力学物性を示した。また大きな膨潤性（２０℃水中での吸水量は粒子状乾燥物の２０倍以上）を示した。このように、本実施形態の高分子ゲルは高い力学的強度と保持力を有する。
次いで、得られた高分子ゲル分散液を用いて、実施例１と同様にしてゲル電解質およびコンデンサを調製した。
(Example 12)
(Organic inorganic composite gel)
To a flat bottom glass container, 38.04 g of pure water and 1.23 g of Laponite XLG were added to prepare a colorless and transparent solution. To this was added 3.96 g of DMAA to obtain a colorless transparent solution. Next, 2.0 g of KPS aqueous solution prepared at a rate of KPS / water = 0.40 / 20 (g / g) and 32 μl of TEMED were added with stirring, and this solution was sealed with a diameter of 3.5 cm and a length of 10 cm. After being transferred to a glass container, the polymerization was carried out by leaving it in a constant temperature water bath at 20 ° C. for 20 hours. All operations from preparation of the solution to polymerization were performed in a nitrogen atmosphere in which oxygen was blocked. 20 hours after the start of the polymerization, a colorless transparent and uniform organic / inorganic composite gel composed of an organic monomer polymer and layered exfoliated clay mineral was formed in the container.
(Polymer gel dispersion)
The obtained organic polymer (PDMAA) / clay composite gel was cut to about 5 mm square, then dried at room temperature for 24 hours, subsequently at 40 ° C. for 3 hours, and further dried at 40 ° C. under vacuum for 1 hour, and then with a mixer. Powdered. The obtained product was classified to obtain a particulate dried product in the range of 3 to 40 μm (average particle size = 19 μm). Next, a 6-fold amount of an aqueous polyethylene glycol solution (an aqueous solution containing 1% by weight of polyethylene glycol 20000 (average molecular weight 20000) (manufactured by Wako Pure Chemical Industries, Ltd.)) and 40 times the amount of water are added to the dried particulate matter. Thus, a polymer gel dispersion was obtained.
Fill a portion of the polymer gel dispersion in a plastic container (5 cm × 7 cm × 1 cm depth) and let it stand at 25 ° C. until the water content is 7 times the amount of the original particulate dried product. The water was gradually removed by drying. After 30 minutes, an integrated polymer gel film (thickness: about 2 mm) was taken out from the inside of the plastic container. The tensile test of the obtained polymer gel (water content (100 × water / polymer gel) = 89 wt%) was evaluated using a tensile test device (manufactured by Shimadzu Corporation, desktop universal testing machine AGS-H). The distance was 30 mm and the pulling speed was 100 mm / min. The polymer gel exhibited rubber-like mechanical properties having large stretchability (elastic modulus = 3.0 kPa, strength = 33 kPa, elongation at break = 1050%). Moreover, the big swelling property (The amount of water absorption in 20 degreeC water was 20 times or more of the particulate dried material) was shown. Thus, the polymer gel of this embodiment has high mechanical strength and holding power.
Next, a gel electrolyte and a capacitor were prepared in the same manner as in Example 1 using the obtained polymer gel dispersion.
（比較例１）
厚さ約５０μｍのクラフトパルプ二重紙を酸化被膜を有するアルミニウム陽極と、アルミニウム陰極とで挟んだ。重ね合わせた電極箔にリード線を接続し、接続部分をクラフト紙のあて紙で覆った。その後、実施例１と同様にエチレングリコール１００、ホウ酸６、Ｄ−マンニトール９を溶解した電解液に電極箔を浸漬した。含浸後の電極箔をフィルム状封止体で覆うことにより、ラミネートセルを作製した。
(Comparative Example 1)
Kraft pulp double paper having a thickness of about 50 μm was sandwiched between an aluminum anode having an oxide film and an aluminum cathode. Lead wires were connected to the overlapped electrode foils, and the connected portions were covered with kraft paper. Thereafter, the electrode foil was immersed in an electrolytic solution in which ethylene glycol 100, boric acid 6 and D-mannitol 9 were dissolved in the same manner as in Example 1. A laminate cell was produced by covering the impregnated electrode foil with a film-shaped encapsulant.
（比較例２）
電解液を実施例２と同様にエチレングリコール１００に、水１４、安息香酸アンモニウム１０、アジピン酸アンモニウム５を溶解して調製した。その他の部分は、比較例１と同様にしてラミネートセルを作製した。
(Comparative Example 2)
An electrolytic solution was prepared by dissolving water 14, ammonium benzoate 10 and ammonium adipate 5 in ethylene glycol 100 in the same manner as in Example 2. Other parts were made in the same manner as in Comparative Example 1 to produce a laminate cell.
（比較例３）
比較例１のクラフトパルプ二重紙をマニラ紙に替え、さらに電解液を、実施例３と同様にγ―ブチロラクトン７５ｗｔ％に、フタル酸水素１−エチル−２，３−ジメチルイミダゾリニウム２５ｗｔ％を溶解して調製した。その他の部分は、比較例１と同様にしてラミネートセルを作製した。クラフトパルプ二重紙の代わりにマニラ紙を用いた理由は、クラフト紙がγ―ブチロラクトンとの濡れ性が悪く、ＥＳＲが高くなってしまい、実施例との比較対象として不適当だからである。
(Comparative Example 3)
The kraft pulp double paper of Comparative Example 1 was replaced with Manila paper, and the electrolyte was further added to 75 wt% of γ-butyrolactone and 25 wt% of 1-ethyl-2,3-dimethylimidazolinium hydrogen phthalate as in Example 3. Was prepared by dissolving. Other parts were made in the same manner as in Comparative Example 1 to produce a laminate cell. The reason why Manila paper is used instead of kraft pulp double paper is that kraft paper has poor wettability with γ-butyrolactone and has high ESR, which is not suitable for comparison with Examples.
（比較例４）
有機架橋剤（Ｎ，Ｎ−メチレンビスアクリルアミド）をモノマー（ＤＭＡＡ）の１モル％を用いて化学架橋ゲルを作製した。この化学架橋ゲルを実施例１２と同様の方法で粒子状乾燥物とした。その後、実施例１２と同様に、粒子乾燥物をその６倍量のエチレングリコールと混合し、水分量の調整（減水、乾燥）を行ったが、化学架橋ゲルの分散状態のままで、それらが一体となることはなかった。また、実施例１２と同様にしてゲル分散液を塗布してコンデンサを調製したが、十分な電解液保持性がなかった。
(Comparative Example 4)
A chemical cross-linking gel was prepared using 1 mol% of an organic cross-linking agent (N, N-methylenebisacrylamide) as a monomer (DMAA). This chemically crosslinked gel was made into a particulate dried product in the same manner as in Example 12. Thereafter, similar to Example 12, the dried particles were mixed with 6 times the amount of ethylene glycol, and the water content was adjusted (reduced water, dried). It was never united. Further, a capacitor was prepared by applying the gel dispersion in the same manner as in Example 12, but it did not have sufficient electrolyte retention.
（高温寿命試験）
実施例１〜３、及び比較例１〜３において作製したラミネートセルについて、高温槽にて１０５℃で長時間放置した後のゲル厚さ及びＥＳＲを測定した。ゲル厚さは、セル全体をマイクロメータ（ミツトヨ社製・ＭＤＣ−２５ＭＪ）で測定し、陰極箔や陽極箔等の材料の厚さを減じて算出した。ＥＳＲは２０℃で測定した。
(High temperature life test)
About the laminated cell produced in Examples 1-3 and Comparative Examples 1-3, the gel thickness and ESR after leaving at 105 degreeC for a long time in a high-temperature tank were measured. The gel thickness was calculated by measuring the whole cell with a micrometer (MDC-25MJ, manufactured by Mitutoyo Co., Ltd.) and subtracting the thickness of the material such as cathode foil or anode foil. ESR was measured at 20 ° C.
表１及び表２に示すように、実施例１〜３及び実施例４〜１２のラミネートセルは、同一の電解液を用いている比較例と比べると、ＥＳＲが低く抑えられている。さらに、ゲル厚さの減少が少ないことから、高分子ゲルの保持力により電解液の漏れや蒸散が抑制されていると考えられる。 As shown in Tables 1 and 2, the laminate cells of Examples 1 to 3 and Examples 4 to 12 have a low ESR compared to the comparative example using the same electrolytic solution. Furthermore, since the decrease in the gel thickness is small, it is considered that leakage and transpiration of the electrolyte are suppressed by the holding power of the polymer gel.
なお、本発明は上述した実施形態に限定されない。例えば、本発明に係るゲル電解質を巻回型コンデンサに用いることも可能である。従来の巻回型コンデンサは、マニラ紙等のセパレータを陽極箔及び陰極箔で挟んで巻回し電解液を含浸してコンデンサ素子を形成する。その後、コンデンサ素子をケースに収納し、開口部を封口部材で封口する。封口部材はゴム等の樹脂材で形成されるが、ガス透過性であるため、含浸された電解液が封口部材を透過して蒸散してしまい、コンデンサ素子の特性劣化が生じていた。本発明に係るゲル電解質を用いる場合には、セパレータの代わりにゲル電解質を陽極箔及び陰極箔で挟んで巻回し、電解液に含浸する。電解液はゲル内に保持されているため、封口部材を透過して蒸散する電解液の量を低減することができる。これによって、コンデンサ素子の特性劣化を低減することができる。 In addition, this invention is not limited to embodiment mentioned above. For example, the gel electrolyte according to the present invention can be used for a wound capacitor. A conventional winding type capacitor is wound by sandwiching a separator such as manila paper between an anode foil and a cathode foil, and impregnated with an electrolytic solution to form a capacitor element. Thereafter, the capacitor element is housed in a case, and the opening is sealed with a sealing member. Although the sealing member is formed of a resin material such as rubber, it is gas permeable. Therefore, the impregnated electrolytic solution permeates through the sealing member and evaporates, resulting in deterioration of the characteristics of the capacitor element. When the gel electrolyte according to the present invention is used, the gel electrolyte is wound between the anode foil and the cathode foil instead of the separator, and the electrolyte is impregnated. Since the electrolyte is held in the gel, the amount of electrolyte that permeates through the sealing member can be reduced. Thereby, characteristic deterioration of the capacitor element can be reduced.
Claims (7)
The element constituent material to which the polymer gel dispersion is applied is selected from an anode foil, a cathode foil or a separator, and after application and drying of the polymer gel dispersion, the element constituent material is wound or laminated, and then The method for producing a gel electrolyte capacitor according to claim 6, wherein the capacitor element is formed by impregnating with an electrolytic solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012141481A JP6190575B2 (en) | 2012-06-22 | 2012-06-22 | Gel electrolyte, gel electrolyte for capacitor and gel electrolyte capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012141481A JP6190575B2 (en) | 2012-06-22 | 2012-06-22 | Gel electrolyte, gel electrolyte for capacitor and gel electrolyte capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014007264A true JP2014007264A (en) | 2014-01-16 |
| JP6190575B2 JP6190575B2 (en) | 2017-08-30 |
Family
ID=50104745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012141481A Active JP6190575B2 (en) | 2012-06-22 | 2012-06-22 | Gel electrolyte, gel electrolyte for capacitor and gel electrolyte capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6190575B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017164003A1 (en) * | 2016-03-22 | 2017-09-28 | Dic株式会社 | Method for producing organic-inorganic composite hydrogel |
| JPWO2016159078A1 (en) * | 2015-03-31 | 2018-02-01 | 株式会社大阪ソーダ | Electrochemical capacitor |
| JPWO2019044044A1 (en) * | 2017-08-31 | 2020-08-13 | 昭和電工株式会社 | Method for manufacturing solid electrolytic capacitor |
| WO2022050331A1 (en) * | 2020-09-04 | 2022-03-10 | Dic株式会社 | Organic-inorganic complex liquid dispersion and method for producing same |
| CN114672043A (en) * | 2022-04-12 | 2022-06-28 | 武汉纺织大学 | PNIPAM-HPC (para-vinyl acetate-HPC) -based synthesis method and application of temperature-sensitive intelligent hydrogel |
| CN115249590A (en) * | 2021-12-27 | 2022-10-28 | 沈阳大学 | All-solid-state stretchable supercapacitor based on double-network gel and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002075453A (en) * | 2000-08-31 | 2002-03-15 | Hitachi Ltd | Electrolyte and electrochemical device |
| JP2002324732A (en) * | 2001-04-24 | 2002-11-08 | Showa Denko Kk | Electrolytic capacitor, material thereof and method for manufacturing the same |
| JP3635302B2 (en) * | 1997-02-17 | 2005-04-06 | 株式会社リコー | Secondary battery |
| JP2005142077A (en) * | 2003-11-07 | 2005-06-02 | Nitto Denko Corp | Gel electrolyte, its manufacturing method and its utilization |
| JP2010245133A (en) * | 2009-04-01 | 2010-10-28 | Nippon Chemicon Corp | Gel electrolyte and method for producing the same, and electrochemical element using the gel electrolyte |
| JP2011001482A (en) * | 2009-06-19 | 2011-01-06 | Kawamura Inst Of Chem Res | Polymer gel, polymer gel dispersion, polymer gel composite, and method for producing the same |
| WO2011087029A1 (en) * | 2010-01-15 | 2011-07-21 | 株式会社クラレ | Gel polymer electrolyte composition |
| JP2013196942A (en) * | 2012-03-21 | 2013-09-30 | Kawamura Institute Of Chemical Research | Secondary battery electrolyte gel and manufacturing method thereof and secondary battery including the same |
-
2012
- 2012-06-22 JP JP2012141481A patent/JP6190575B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3635302B2 (en) * | 1997-02-17 | 2005-04-06 | 株式会社リコー | Secondary battery |
| JP2002075453A (en) * | 2000-08-31 | 2002-03-15 | Hitachi Ltd | Electrolyte and electrochemical device |
| JP2002324732A (en) * | 2001-04-24 | 2002-11-08 | Showa Denko Kk | Electrolytic capacitor, material thereof and method for manufacturing the same |
| JP2005142077A (en) * | 2003-11-07 | 2005-06-02 | Nitto Denko Corp | Gel electrolyte, its manufacturing method and its utilization |
| JP2010245133A (en) * | 2009-04-01 | 2010-10-28 | Nippon Chemicon Corp | Gel electrolyte and method for producing the same, and electrochemical element using the gel electrolyte |
| JP2011001482A (en) * | 2009-06-19 | 2011-01-06 | Kawamura Inst Of Chem Res | Polymer gel, polymer gel dispersion, polymer gel composite, and method for producing the same |
| WO2011087029A1 (en) * | 2010-01-15 | 2011-07-21 | 株式会社クラレ | Gel polymer electrolyte composition |
| JP2013196942A (en) * | 2012-03-21 | 2013-09-30 | Kawamura Institute Of Chemical Research | Secondary battery electrolyte gel and manufacturing method thereof and secondary battery including the same |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2016159078A1 (en) * | 2015-03-31 | 2018-02-01 | 株式会社大阪ソーダ | Electrochemical capacitor |
| WO2017164003A1 (en) * | 2016-03-22 | 2017-09-28 | Dic株式会社 | Method for producing organic-inorganic composite hydrogel |
| JPWO2017164003A1 (en) * | 2016-03-22 | 2018-04-05 | Dic株式会社 | Method for producing organic-inorganic composite hydrogel |
| JPWO2019044044A1 (en) * | 2017-08-31 | 2020-08-13 | 昭和電工株式会社 | Method for manufacturing solid electrolytic capacitor |
| US11591480B2 (en) | 2017-08-31 | 2023-02-28 | Showa Denko K.K. | Method for manufacturing solid electrolytic capacitor |
| WO2022050331A1 (en) * | 2020-09-04 | 2022-03-10 | Dic株式会社 | Organic-inorganic complex liquid dispersion and method for producing same |
| JPWO2022050331A1 (en) * | 2020-09-04 | 2022-03-10 | ||
| CN116018357A (en) * | 2020-09-04 | 2023-04-25 | 富士胶片株式会社 | Organic-inorganic composite dispersion and method for producing same |
| JP7545485B2 (en) | 2020-09-04 | 2024-09-04 | 富士フイルム株式会社 | Organic-inorganic composite dispersion and method for producing same |
| CN115249590A (en) * | 2021-12-27 | 2022-10-28 | 沈阳大学 | All-solid-state stretchable supercapacitor based on double-network gel and preparation method thereof |
| CN114672043A (en) * | 2022-04-12 | 2022-06-28 | 武汉纺织大学 | PNIPAM-HPC (para-vinyl acetate-HPC) -based synthesis method and application of temperature-sensitive intelligent hydrogel |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6190575B2 (en) | 2017-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6190575B2 (en) | Gel electrolyte, gel electrolyte for capacitor and gel electrolyte capacitor | |
| Han et al. | Design and fabrication of conductive polymer hydrogels and their applications in flexible supercapacitors | |
| Shi et al. | Energy gels: A bio-inspired material platform for advanced energy applications | |
| Qiu et al. | Surface activated polyethylene separator promoting Li+ ion transport in gel polymer electrolytes and cycling stability of Li-metal anode | |
| Wang et al. | Flexible solid-state supercapacitors based on a conducting polymer hydrogel with enhanced electrochemical performance | |
| JP4499795B2 (en) | Electric current collector for electric double layer capacitor, electrode for electric double layer capacitor, electric double layer capacitor, and manufacturing method thereof | |
| Xiao et al. | A novel sandwiched membrane as polymer electrolyte for application in lithium-ion battery | |
| Sakakibara et al. | Fabrication of surface skinless membranes of epoxy resin-based mesoporous monoliths toward advanced separators for lithium ion batteries | |
| JP5445885B2 (en) | Separator for electrochemical device and manufacturing method thereof | |
| JP5461745B2 (en) | Microporous membrane and method for producing the same | |
| JP7137929B2 (en) | Composition for gel electrolyte | |
| US9972451B2 (en) | Polyelectrolyte and a method for manufacturing an energy storage device | |
| JP5461744B2 (en) | Microporous membrane and method for producing the same | |
| KR20150084116A (en) | Ceramic coated separator having excellent thermal property and electro-chemical stability and the manufacturing method of it | |
| WO2017051734A1 (en) | Hydrogel and method for producing same | |
| WO2015174056A1 (en) | Electrolytic capacitor manufacturing method | |
| CN110809598A (en) | Hydrogel, use thereof, and method for producing same | |
| Sheng et al. | Use of an [EMIM][OAc]/GVL-based organic electrolyte solvent to engineer chitosan into a nanocomposite organic ionogel electrolyte for flexible supercapacitors | |
| JP3848435B2 (en) | Electric double layer capacitor and manufacturing method thereof | |
| JP5834482B2 (en) | Method for producing organic-inorganic composite electrolyte layer for battery | |
| CN106548872A (en) | Treatment fluid and the solid electrolyte capacitor with which | |
| JP2017135043A (en) | Cellulose microporous film and method of producing the same, and electrochemical element | |
| JP2005285377A (en) | Polysiloxane-polyolefin complex gel electrolyte, and lithium battery using the same | |
| WO2012144332A1 (en) | Organic-inorganic composite gel, secondary battery electrolyte gel, and secondary battery, and manufacturing method therefor | |
| WO2010113516A1 (en) | Gel electrolyte, method for producing same and electrochemical element using the gel electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20140623 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20140623 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150609 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160328 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160405 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20160603 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160728 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20161220 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170217 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170711 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170807 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6190575 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |