WO2005012599A1 - イオン性液体を用いた金属表面酸化皮膜形成法、電解コンデンサ及びその電解質 - Google Patents
イオン性液体を用いた金属表面酸化皮膜形成法、電解コンデンサ及びその電解質 Download PDFInfo
- Publication number
- WO2005012599A1 WO2005012599A1 PCT/JP2004/010996 JP2004010996W WO2005012599A1 WO 2005012599 A1 WO2005012599 A1 WO 2005012599A1 JP 2004010996 W JP2004010996 W JP 2004010996W WO 2005012599 A1 WO2005012599 A1 WO 2005012599A1
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- WO
- WIPO (PCT)
- Prior art keywords
- ionic liquid
- oxide film
- electrolytic capacitor
- electrolyte
- salt
- Prior art date
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 235
- 239000003990 capacitor Substances 0.000 title claims abstract description 213
- 239000003792 electrolyte Substances 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 87
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 64
- 239000002184 metal Substances 0.000 title claims abstract description 64
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 78
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical class CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims abstract description 68
- 150000003839 salts Chemical class 0.000 claims abstract description 51
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- -1 amine salt Chemical class 0.000 claims description 46
- 150000001450 anions Chemical class 0.000 claims description 41
- 230000003647 oxidation Effects 0.000 claims description 37
- 238000007254 oxidation reaction Methods 0.000 claims description 37
- 229910052731 fluorine Inorganic materials 0.000 claims description 22
- 239000011737 fluorine Substances 0.000 claims description 22
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 20
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- AGQRIOQDPGZONW-UHFFFAOYSA-N (1-ethylimidazol-2-yl) acetate Chemical compound CCN1C=CN=C1OC(C)=O AGQRIOQDPGZONW-UHFFFAOYSA-N 0.000 description 1
- GHPYJLCQYMAXGG-WCCKRBBISA-N (2R)-2-amino-3-(2-boronoethylsulfanyl)propanoic acid hydrochloride Chemical compound Cl.N[C@@H](CSCCB(O)O)C(O)=O GHPYJLCQYMAXGG-WCCKRBBISA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- BGBNXIKULUCCOO-BTJKTKAUSA-N (z)-but-2-enedioic acid;n,n-diethylethanamine Chemical compound CCN(CC)CC.OC(=O)\C=C/C(O)=O BGBNXIKULUCCOO-BTJKTKAUSA-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
- AQIFGXUGEFKTEE-UHFFFAOYSA-N 1-butyl-1h-imidazol-1-ium;4-methylbenzenesulfonate Chemical compound CCCC[NH+]1C=CN=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 AQIFGXUGEFKTEE-UHFFFAOYSA-N 0.000 description 1
- VTPVXIGCSXBDLN-UHFFFAOYSA-N 1-butyl-4,5-dihydroimidazole Chemical compound CCCCN1CCN=C1 VTPVXIGCSXBDLN-UHFFFAOYSA-N 0.000 description 1
- KDONBTHXJLBZSW-UHFFFAOYSA-N 1-butylisoquinoline;hydroiodide Chemical compound [I-].C1=CC=C2C(CCCC)=[NH+]C=CC2=C1 KDONBTHXJLBZSW-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- MWPXDSRCADUQLR-UHFFFAOYSA-N 2-(3-methylbutyl)isoquinolin-2-ium Chemical compound C1=CC=CC2=C[N+](CCC(C)C)=CC=C21 MWPXDSRCADUQLR-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- APLNAFMUEHKRLM-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(3,4,6,7-tetrahydroimidazo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)N=CN2 APLNAFMUEHKRLM-UHFFFAOYSA-N 0.000 description 1
- QIPOHFUODFGVHI-UHFFFAOYSA-N 2-butylisoquinolin-2-ium Chemical compound C1=CC=CC2=C[N+](CCCC)=CC=C21 QIPOHFUODFGVHI-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- KCBWAFJCKVKYHO-UHFFFAOYSA-N 6-(4-cyclopropyl-6-methoxypyrimidin-5-yl)-1-[[4-[1-propan-2-yl-4-(trifluoromethyl)imidazol-2-yl]phenyl]methyl]pyrazolo[3,4-d]pyrimidine Chemical compound C1(CC1)C1=NC=NC(=C1C1=NC=C2C(=N1)N(N=C2)CC1=CC=C(C=C1)C=1N(C=C(N=1)C(F)(F)F)C(C)C)OC KCBWAFJCKVKYHO-UHFFFAOYSA-N 0.000 description 1
- 244000291564 Allium cepa Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- UNPLRYRWJLTVAE-UHFFFAOYSA-N Cloperastine hydrochloride Chemical compound Cl.C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)OCCN1CCCCC1 UNPLRYRWJLTVAE-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 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
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 241001251074 Imperator Species 0.000 description 1
- 241001409001 Maera Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- QPFYXYFORQJZEC-FOCLMDBBSA-N Phenazopyridine Chemical group NC1=NC(N)=CC=C1\N=N\C1=CC=CC=C1 QPFYXYFORQJZEC-FOCLMDBBSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 1
- 241000375392 Tana Species 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 150000007960 acetonitrile Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- VQLOCUKZAJRPAO-UHFFFAOYSA-N aluminum oxygen(2-) tantalum(5+) Chemical compound [O--].[O--].[O--].[O--].[Al+3].[Ta+5] VQLOCUKZAJRPAO-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- AOKTVRKVJQRVEP-UHFFFAOYSA-N ethanol;1-ethylimidazole Chemical compound CCO.CCN1C=CN=C1 AOKTVRKVJQRVEP-UHFFFAOYSA-N 0.000 description 1
- VRZVPALEJCLXPR-UHFFFAOYSA-N ethyl 4-methylbenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=C(C)C=C1 VRZVPALEJCLXPR-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-O hydron;pyrimidine Chemical compound C1=CN=C[NH+]=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-O 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-O hydron;quinoline Chemical compound [NH+]1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-O 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- LPAGFVYQRIESJQ-UHFFFAOYSA-N indoline Chemical compound C1=CC=C2NCCC2=C1 LPAGFVYQRIESJQ-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- IOEDDFFKYCBADJ-UHFFFAOYSA-M lithium;4-methylbenzenesulfonate Chemical compound [Li+].CC1=CC=C(S([O-])(=O)=O)C=C1 IOEDDFFKYCBADJ-UHFFFAOYSA-M 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- RLLPVAHGXHCWKJ-UHFFFAOYSA-N permethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- CBQRTOJFWLXNMQ-UHFFFAOYSA-L phthalate;triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC.CC[N+](C)(CC)CC.[O-]C(=O)C1=CC=CC=C1C([O-])=O CBQRTOJFWLXNMQ-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940070891 pyridium Drugs 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- PYLWBTPVPPYFNW-ANIXHHLQSA-M sodium;(2s,5r,6r)-6-[[(2r)-2-(3,4-dihydroxyphenyl)-2-[(4-ethyl-2,3-dioxopiperazine-1-carbonyl)amino]acetyl]amino]-6-formamido-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate Chemical compound [Na+].O=C1C(=O)N(CC)CCN1C(=O)N[C@H](C=1C=C(O)C(O)=CC=1)C(=O)N[C@]1(NC=O)C(=O)N2[C@@H](C([O-])=O)C(C)(C)S[C@@H]21 PYLWBTPVPPYFNW-ANIXHHLQSA-M 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- CIFIGXMZHITUAZ-UHFFFAOYSA-M tetraethylazanium;benzoate Chemical compound CC[N+](CC)(CC)CC.[O-]C(=O)C1=CC=CC=C1 CIFIGXMZHITUAZ-UHFFFAOYSA-M 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/02—Diaphragms; Separators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to a method for forming an oxide film on a metal surface by anodic oxidation or a method for repairing a metal oxide film, an electrolytic capacitor using the principle of forming and repairing an oxide film by those methods, and an electrolyte therefor.
- the anodic oxidation method is a method of forming an oxide film on a metal surface in an acidic solution or a neutral solution using the metal as an anode. This method is often used to form an oxide film on the surface of a valve metal such as aluminum and tantalum.
- a valve metal such as aluminum and tantalum.
- a thick porous film is formed in an acidic solution such as sulfuric acid, oxalic acid, or phosphoric acid.
- Oxide film is formed, and in a neutral solution such as borate, phosphate and adipate, a thin and dense barrier type film is formed.
- a porous aluminum oxide film is used for the purpose of corrosion protection, friction prevention and decoration by coloring, and a barrier type film is widely used as a dielectric for electrolytic capacitors.
- Electrolytic capacitors are generally made of aluminum or tantalum. Such a valve metal is used as an anode, an oxide film formed on its surface is used as a dielectric, and a cathode is formed between the dielectric and an electrolyte.
- the driving electrolyte in this electrolytic capacitor has two important roles. One is the actual function as a cathode, which serves to extract capacitance from the dielectric on the anode, and requires high electrical conductivity, that is, high electronic conductivity.
- the other is the action of protecting and repairing extremely thin oxide films, and the chemical action of forming a new oxide at the defective part of the aluminum-tantalum oxide film based on the ionic conductivity of the electrolyte.
- Anodization is used to form a dielectric oxide film on electrolytic capacitors and to repair defects in the oxide film. Therefore, the electrolytic solution of the electrolytic capacitor Must have anodizing ability.
- an organic solvent such as ethylene glycol or ⁇ -butyrolactone, to which an organic acid, an inorganic acid, or a salt thereof is added, is used as an electrolytic solution for an electrolytic capacitor.
- the added organic acid and inorganic acid or salts thereof include phosphoric acid, formic acid, acetic acid, ammonium adipic acid, ammonium succinate, tertiary amines, and quaternary ammonium salts.
- the reason for using such a composite electrolyte system is to provide an electrolyte having excellent ionic conductivity.
- a conductive polymer such as polypropylene, polyaniline, or a polythiophene derivative is used as an electrolyte.
- These conductive polymers have much higher electrical conductivity (electron conductivity) than the above-mentioned electrolytic solution consisting of an electrolyte and a solvent. Therefore, the internal impedance of a capacitor using them as an electrolyte is high. And can exhibit excellent characteristics, especially when used as capacitors for high frequency circuits. Therefore, such conductive polymer capacitors are forming an important position in the field of electrolytic capacitors.
- a capacitor with a high withstand voltage cannot be produced in a conductive polymer capacitor.
- a conductive polymer capacitor using aluminum as the anode is, for example, about 16 V when forming 70 V
- a conductive polymer capacitor using tantalum is, for example, 34 V
- 70 V conversion means that the DC voltage applied to the valve metal when forming the dielectric oxide film on the surface of the valve metal, that is, the voltage applied to the valve metal is 70 V.
- Patent Document 3 As an attempt to improve the withstand voltage characteristics of such a conductive polymer capacitor, an electrolytic capacitor characterized by using an electrolyte composed of a conductive polymer and an organic acid salt has been disclosed.
- molten salts that are liquid at room temperature have recently been developed and are receiving attention. These are called ionic liquids and are imidazolympi Quaternary salt cation and a suitable Anion such Rijiniumu (B r one, Al C l-, BF 4 one, PF 6 one, etc.) is configured in combination with, often containing halogen.
- Ionic liquids have characteristics such as non-volatility, non-flammability, chemical stability, and high ionic conductivity, and are attracting attention as reusable green solvents used for various chemical reactions such as synthesis and catalytic reactions.
- ionic liquids have been studied from the viewpoint of anodizing properties, that is, from the viewpoint of forming an oxide film on the valve metal surface or restoring the oxide film.
- Patent Document 1 JP-A-5-13278
- Patent Document 2 Japanese Patent Laid-Open No. 5-101983
- Patent Document 3 JP 2003-22938
- Non-Patent Document 1 Review of electrolytic capacitors, Vol. 53, No. 1, page 101 (2002)
- Non-Patent Document 2 Review of electrolytic capacitors, Vol. 53, No. 95, (2002) Disclosure of the Invention
- the present inventors have found that an ionic liquid having no dry-up due to evaporation has excellent oxidizing properties, and completed the present invention. That is, the present invention provides a method for easily forming an oxide film on a metal surface by performing anodic oxidation in the presence of an ionic liquid, or a method for repairing an already formed metal oxide film, and a method for oxidizing in such a method.
- the present invention relates to an electrolytic capacitor that has significantly improved the performance of forming and restoring a dielectric by applying a film forming ability.
- electrolytic capacitors such as conductive polymer electrolytes and TCNQ salt electrolytes
- electrolytes for solid electrolytic capacitors such as conductive polymer electrolytes and TCNQ salt electrolytes
- the present invention includes the following aspects.
- a method for forming an oxide film on a metal surface which comprises anodizing in the presence of an ionizing liquid.
- metal is aluminum and / or its alloy, tantalum and / or its alloy 3.
- An electrolytic capacitor provided with the means described in 1 to 8 above for repairing an oxide film. 10.
- An electrolytic capacitor characterized in that a solution containing at least one type of ionic liquid is used as an electrolyte as a means for repairing an oxide film.
- the conductive polymer is at least one selected from polypyrrole, polyaurine, polythiophene, and derivatives thereof.
- the TCNQ salt is a nitrogen-containing heterocyclic compound in which the N-position is alkyl-substituted as a donor, 15.
- An electrolyte comprising the ionic liquid according to item 18 above, which is used for forming an oxide film on a metal surface by anodic oxidation.
- An electrolyte which is a solution containing the ionic liquid according to 9-22 above, which is used for an electrolytic capacitor.
- the first means has been completed by the present inventor by finding that the ionic liquid has excellent metal oxidizing ability.
- the solution containing the ionic liquid can repair the defect of the metal oxide film formed by another method in advance.
- the third to seventh means it is possible to exhibit particularly excellent ability in forming and repairing an oxide film on the valve metal surface.
- the ability to form an oxide film on the valve metal surface and the ability to repair defects in the oxide film can be controlled.
- a ninth means is an electrolytic capacitor using a method of forming an oxide film on a metal surface by anodic oxidation formed by any of the above means, or a method of repairing the oxide film.
- a tenth means is to apply the method for forming an oxide film on the valve metal surface and the method for repairing a defect of the oxide film to an electrolytic capacitor.
- the electrolytic capacitor is based on the excellent electronic conductivity of the conductive polymer and the excellent ion conductivity of the ionic liquid.
- a high-performance capacitor with excellent impedance characteristics having excellent electron conductivity based on the TCNQ salt and oxide film repairability based on the excellent ion conductivity of the ionic liquid.
- a high-performance capacitor with excellent impedance characteristics having excellent electron conductivity based on the TCNQ salt and oxide film repairability based on the excellent ion conductivity of the ionic liquid.
- the second or second means is an electrolyte that gives the ability to form and repair an oxide film on the valve metal surface in an electrolytic capacitor.
- Figure 1 shows a typical current change observed when the electrolyte has the ability to repair the metal oxide film.
- Figure 2 shows the current change when re-chemical conversion (oxide film repair experiment) was performed using ILS-1 under the following conditions.
- Initialization 200 V voltage rise rate: 1 Y / measurement: room temperature
- Figure 3 Current change when re-formation (oxide film repair experiment) was performed using an adipic acid aqueous solution (1 g / 1) under the following conditions. Show. Initialization voltage 200 V, «JE rise rate: 1 V / sec, Measurement: room temperature
- FIG. 4 is a conceptual diagram of a conductive polymer electrolytic polymerization apparatus.
- the present inventors have conducted various studies in order to solve the above problems, and have found that a series of compounds called ionic liquids exhibit excellent anodizing properties, and have completed the present invention.
- the ionic liquid used in the present invention is also called a room temperature molten salt, and is a liquid which is liquid at room temperature despite being composed of an anion component and a cation component. It is believed that the ionic liquid is not ionized and dissociated as in a general organic solvent, but is formed only of ions, that is, 100% ionized. Normally, ionic liquids are liquids at room temperature.
- the ionic liquids used in the present invention do not necessarily need to be liquids at room temperature, and become liquid during capacitor aging or heat treatment and spread throughout the electrolyte. Any material may be used as long as it becomes liquid by the Joule heat generated when the oxide film is repaired.
- cation used in the ionic liquid suitable for the purpose of the present invention various cations having quaternized nitrogen can be used.
- ammonium and its derivatives, imidazolinium and its derivatives, pyridinium and its derivatives, pyrrolidinium and its derivatives, pyrroleum and its derivatives, pyradium and its derivatives, pyrimidinium and its derivatives, triazonium and its derivatives, triazinium and its derivatives, triazine derivatives Cation, quinolinium and its derivatives, isoquinolium and its derivatives, indolinium and its derivatives, quinoxaluium and its derivatives, pirazium and its derivatives, oxazolinium and its derivatives, thiazolinium and its derivatives, morpholium and its derivatives, Razine and its derivatives can be exemplified.
- imidazolim derivatives ammonium derivatives, and pyridinium derivatives can be preferably used for this purpose.
- derivative refers to hydrogen and a substituent such as an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a carboxylic acid and an ester group, various ether groups, various acyl groups, various amino groups, and the like. These are substituted at any position of the above-mentioned cation component.
- the preferred Anion component used for this purpose can be mentioned Anion containing fluorine, BF 4 -, PF 6 - , R A S 0 3 - (wherein R A fluorinated aliphatic hydrocarbon group, fluorinated Alicyclic hydrocarbon group, fluorinated aromatic hydrocarbon group, ether group, ester group, acyl group, etc. And a fluorinated substituent containing a).
- CF 3 S0 3 —, (CF 3 S 0 2 ) 2 N-, (CF 3 S0 2 ) 3 C_, CHF 2 CF 2 CF 2 CF 2 CH 2 OS0 31 CHF 2 CF 2 CF 2 CF 2 CH 2 S0 3 one it can be exemplified the like, they can be preferably used for this purpose.
- BF 4 one also favorably used as the Anion this purpose.
- the fluorine anion suitable for the present invention is not limited to these examples.
- Anion acid (an S0 3 -) can be exemplified an atomic group containing, R B S0 3 _ (wherein R B is an aliphatic hydrocarbon group, alicyclic It represents a substituent containing a cyclic hydrocarbon group, an aromatic hydrocarbon group, an ether group, an ester group, an acyl group, etc.), and may of course contain fluorine. Specifically, p CH 3 C 6 H 4 S0 3 one, C 6 H 5 S0 3 _ , CH 3 CH 2 OCH 2 CH 2 0 SO 3 one, C 6 H 5 OCH 2 CH 2 OS0 3 -, etc.
- Anion containing both fluorine and sulfonate anion is particularly preferably used for the purpose of the present invention.
- the above-mentioned CHF 2 CF 2 CF 2 CF 2 CH 2 OS0 3 —, CHF 2 CF 2 CF 2 CF 2 CH 2 S0 and the like can be exemplified.
- the sulfonic acid-containing anion suitable for the present invention is not limited to these examples.
- Examples of the anion component preferably used in the present invention include an atomic group containing carboxylate (1-COO-1). Specifically, R c COO—, OOCR c CO OH, _OOCR c CCOO_, NH 2 CHR c COO— (where R c is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group And substituents including an ether group, an ester group, and an acyl group) and), and may of course contain fluorine.
- carboxylate suitable for the present invention is not limited to these examples.
- Anion used in the present invention N0 3 -, R d N_ ⁇ 3 i (where R d is an aliphatic Sumyi ⁇ containing group, an alicyclic hydrocarbon group, an aromatic hydrocarbon A substituent containing a hydrogen group, an ether group, an ester group, an acyl group, etc., and may of course contain fluorine).
- an ionic liquid containing sulfonate anion or an ionic liquid containing fluorine can be preferably used for the purpose of the present invention.
- the ionic liquid of the present invention is a substance obtained by combining the above anion and the above thione, and can be synthesized by a known method. Specifically, methods such as an anion exchange method, an acid ester method, and a neutralization method can be used.
- the anodic oxidation method is widely used as a means for forming a metal oxide film on a metal surface.
- An oxide film is formed by applying a current or applying an electric current in an electrolyte solution using the metal on which the oxide film has been formed as an anode. .
- This method is the most common method for forming an oxide film on the surface of valve metals such as aluminum, tantalum, and niobium.
- valve metals such as aluminum, tantalum, and niobium.
- an example of aluminum as a method of forming an oxide film according to the present invention will be described.
- valve metals such as tantalum and niobium, and aluminum and Z or alloys thereof, tantalum and alloys thereof and alloys thereof.
- Niobium and / or its alloys, and other metals are basically the same.
- the scope of the present invention is not limited to aluminum but also applies to valve metals such as tantalum and niobium.
- a cell having aluminum as an anode and stainless steel copper or platinum as a cathode is immersed in the electrolyte, and a constant pressure is applied between the electrodes.
- the change of the current value flowing during the measurement is measured.
- the ability of the electrolyte to form an oxide film is limited, and as the voltage increases, the oxide film formed cannot withstand the voltage and eventually breaks down. Therefore, the anodic oxidation ability of the electrolytic solution can be estimated by measuring such a current value change.
- anodic oxide film in the existing electrolyte it was necessary to prepare an anodic oxide film in the existing electrolyte at a fixed voltage in advance and boil the oxide film in boiling water. It is convenient to use a method in which a defect is partially introduced by a method. The sample thus prepared is immersed in the electrolytic solution to be evaluated, and the change in current value is measured while increasing the temperature at a constant rate. This is also called the re-chemical evaluation method.
- the voltage for forming the anodic oxide film that is, by changing the thickness of the anodic oxide film
- an experiment similar to the above-described oxide film forming experiment can be performed. That is, for example, when an oxide film is formed at 10 OV in advance, the anodic oxidation ability of the electrolyte can be evaluated in the same way as in the oxide film formation experiment described above by observing how much voltage leads to breakdown. .
- FIG. 1 shows a typical current value change observed when the electrolytic solution has a repair ability for a metal oxide film.
- the current flows through the broken part of the oxide film (region 1), but if the electrolyte has anodizing properties, a new oxide film is formed on the broken part due to its ability to repair the film. Then, the current value decreases below the maximum value (A) (region 2).
- the minimum point of the current value (B) is the time when the restoration is completed, and after that, a linear current rise region proportional to the voltage rise appears (region 3). However, when the voltage is further increased, the current starts to flow from a certain voltage (C), deviating from the linear relationship (region 4). This indicates the effective withstand voltage of the electrolyte and corresponds to the above breakdown voltage. Of course, if there is no anodic oxidation ability, current will flow in the area 1 only, leading to the destruction of the oxide film.
- the dense barrier coatings are phosphoric acid, sulfuric acid,
- a porous film is formed in an acidic solution such as an aqueous solution of oxalic acid. The porous film is formed because local dissolution of the film occurs during anodizing. When the formation of the porous film due to such local dissolution starts, protons in the solution enter the inside of the film due to thermal action against the electric field and a large amount of ion current starts to flow.
- the electrolyte used for anodic oxidation is a boric acid-based chemical solution, an oxalic acid-based chemical solution, a phosphoric acid-based chemical solution, or an adipic acid-based chemical solution.
- a phosphate chemical solution is prepared by dissolving 1.5 g of ammonium phosphate in 1 L of water.
- adipic acid-based chemical solution It is prepared by dissolving 1 g of ammonium adipate in 1 L of water.
- (A) was in the range of 10 V to 100 V
- (B) was in the range of 20 V to 180 V
- (C) was in the range of 60 V to 200 V.
- an acidic solution such as an oxalic acid solution
- the point (A) appears low, but the voltage at the point (C) is relatively low.
- a neutral chemical solution such as adipic acid
- the point (C) can be increased but the point (A) also has a disadvantage.
- Anion'ion liquid suitable for the present invention containing sulfonic acid (one so 3 _) Anion'ion liquid, containing Karupokishirato (one COO-) Ayuon'ion liquid, when evaluated by the reformation evaluation method, for example, the first When the oxide film is formed at 20 OV, the maximum current point (A) is mostly in the range of 10 V to 25 V, and the minimum current point (B) is in the range of 30 V to 50 V. On the other hand, the current increase point (C) was found to be in the range of 100 V to 200 V. These properties vary with the type of ionic liquid, especially the type of anion.
- the fluorine-containing anionic ionic liquid has a characteristic that the voltage at the point (C) is particularly high (160 V or more), and has excellent resistance to heat.
- the point (C) in the sulfonic acid-containing (mono-SO 3- ) anionic ionic liquid and the carboxylate-containing (-COO ") anionic ionic liquid is from 60 V to: L 00 V.
- the first oxide film is formed at 200V or less, eg, 50V or 100V.
- acid (_S0 3 -) acid (_S0 3 -) ⁇ two Onion liquid
- free Karupokishirato (_COO_) in Anion'ion liquid (C) point is around 30 V ⁇ 60V
- the sulfonic acid (_so 3 —) anionic liquid containing no fluorine ion and the carboxylate-containing (one COO_) anionic liquid containing fluorinated ion have a (C) point of 50 V. It is around 120 V to 200 V in the fluorine-containing anionic ionic liquid while it is around 80 V.
- the ionic liquid exhibits an anodic oxidation property that is superior to the relatively low voltage range compared to general organic solvent-soluble organic salt electrolytes (ie, point (A) appears at low voltage).
- point (A) appears at low voltage.
- the ionic liquid such as the sulfonic acid (_so 3 _ ) anionic ionic liquid and the carboxylate (-COO —)-an ionic liquid, the pressure resistance characteristics of the electrolyte in the high voltage region ( In other words, it is necessary to improve (the voltage at point (C) is low).
- ionic liquids contain additives such as ammonium salts, amine salts, quaternary ammonium salts, tertiary amines, and organic acids. It has been found that the addition of the compound can improve the pressure resistance characteristics.
- the ionic liquid can well dissolve ammonium salts, amine salts, quaternary ammonium salts and organic acids.
- ammonium salt-based additives such as ammonium adipate; amine salt-based additives such as triethylamine maleate; quaternary ammonium salt additives such as quaternary ammonium maleate and quaternary ammonium phthalate;
- ammonium phosphate additives such as ammonium dihydrogen phosphate, ammonium borate, quaternized imidazolium salts, malic acid, and succinic acid.
- the addition of these additives to the above-mentioned bibitionic ionic liquid is effective for the purpose of the present invention since the melting point can be lowered.
- the electrolyte of the present invention can improve the performance as an electrolyte by further adding a solute to the ionic liquid which is a component thereof.
- the added solute always exists in a dissolved state because the ionic liquid does not substantially evaporate, so that the anodizing property of the solute is added to the anodizing property of the ionic liquid.
- the capacity as an electrolyte will be higher.
- solutes include ammonium borate, ammonium phosphate, and ammonium adipate.
- Such a method has a particularly high anodizing ability for ionic liquids! /, In which case it is an effective method.
- physical properties can be controlled such that the freezing point of the added solute can lower the melting point of the ionic liquid as a constituent.
- the amount of the solute added to these ionic liquids can be arbitrarily selected as long as the properties of the ionic liquid as a liquid are not lost.
- the strength depends on the type of the ionic liquid.
- the addition amount is preferably within a range not exceeding 50%.
- the addition amount is preferably not more than 10%.
- the solubility of the above-mentioned solutes in the above-mentioned ionic liquid is large, and a relatively large amount of solute can be dissolved, which is an advantage of using an ionic liquid.
- the ionic liquid itself may dissolve the oxide film by corrosion and etching.
- those in which the anion is a molecule containing fluorine are advantageous because they do not adversely affect the oxide film such as etching.
- fluorine-containing anionic liquids in which ionic liquids are hydrophilic have excellent anodizing properties.
- the determination of hydrophilicity / hydrophobicity was made by adding water to the synthesized ionic liquid to make a substance that completely mixes both hydrophilic, and to make a substance that separated into two layers hydrophobic.
- the ionic liquid exhibits excellent anodic oxidation properties.
- the practical advantages of forming an oxide film on a metal surface using an ionic liquid will be described. That is, the vapor pressure of the ionic liquid is extremely low and practically does not evaporate.
- the electrolyte generally used for anodic oxidation is used in the form of an aqueous solution or dissolved in an organic solvent, and naturally, the water and the organic solvent are evaporated.
- the solvent evaporates and becomes a solid solute the ability to form an oxide film on the metal surface is lost. That is, the conventional electrolyte cannot be used in an environment where the solvent evaporates.
- the method for forming an oxide film on a metal surface using an ionic liquid can be used under various conditions that cannot be used with ordinary electrolytes.
- the first advantage is that it has excellent anodic oxidation properties
- the second advantage is that the ionic liquid has a very low vapor pressure, which is a common advantage. It does not substantially evaporate during use.
- a solution obtained by adding a solute to an organic solvent and adding a calorie is used as the electrolysis solution.
- the added solute will be in a solid state in a state after the evaporation of the organic solvent, and it will not be possible to exhibit the anodizing property, which is the ability to repair an oxide film.
- the added solute is a liquid, the solute component remains even if the organic solvent evaporates, and the anodizing performance is not completely lost. Therefore, the use of the ionic liquid of the present invention for an electrolytic liquid type capacitor is useful as one form of application of the present invention.
- the ionic liquid of the present invention is preferably used for a solid electrolytic capacitor.
- a solute such as an ammonium salt, an amine salt, a quaternary ammonium salt, or an organic acid is dissolved in an organic solvent, and the resultant is dissolved in a conductive polymer or TCNQ.
- a solvent has a drawback that the effect of its addition is lost because it evaporates due to long-term use, and the electrolyte according to the present invention is used for a solid capacitor.
- an ionic liquid When used, it is particularly preferable to add (complex) an ionic liquid to the conductive '14 polymer electrolyte or TCNQ salt electrolyte. It is an ideal capacitor for an ideal capacitor by combining the excellent anodizing property of the ionic liquid and the excellent electronic conductivity S of the conductive polymer electrolyte and TCNQ salt electrolyte. .
- the conductive polymer is not particularly limited, but polypyrrole, polythiophene, polyaniline, and derivatives thereof are preferable.
- polypyrrole polypyrrole
- polythiophene polyaniline
- polythiophene obtained from 114 dioxitithiophene monomers.
- a chemical polymerization method an electrolytic polymerization method, and an organometallic chemical condensation polymerization method are used.
- the chemical polymerization method and the electrolytic polymerization method are preferably used.
- a polypyrrole which is a conductive polymer
- a pyrrole monomer is dissolved in a solvent together with a supporting electrolyte and then anodically oxidized to conduct dehydrogenation polymerization.
- oxidation of the polymer skeleton further progresses in the polymerization, and anion of a supporting electrolyte is taken into the polymer as a dopant.
- electropolymerization such a mechanism provides a conductive polymer without the need to add dopants later.
- chemical polymerization is a method of polymerizing and synthesizing a raw material monomer such as pyrrole by oxidative dehydration in the presence of an appropriate oxidizing agent.
- an appropriate oxidizing agent persulfate, hydrogen peroxide, or a transition metal salt such as iron, copper, and manganese can be used.
- the conductive polymer synthesized by chemical polymerization can also obtain a conductive polymer in a one-step reaction because the anion of the oxidizing agent is incorporated into the polymer during the polymerization process as a dopant.
- the aionic component of the ionic liquid may be taken into the conductive polymer as a dopant, which is particularly preferable for the purpose of the present invention.
- the dopant of the conductive polymer which is a component of the electrolyte according to the present invention, is selected in consideration of its effect on the conductivity and thermal stability of the conductive polymer.
- the dopants preferably used in the present invention include 4-fluoroborate ion, p-toluenesulfonic acid ion, anthraquinone-12-sulfonic acid ion, triisopropylnaphthalenesulfonic acid ion, polyvinylsulfonic acid ion, dodecyl Examples thereof include benzenesulfonate ion, alkylsulfonate ion, n-propylphosphate ion, perchlorate ion, and the like.
- sodium p-toluenesulfonate sodium dodecylbenzenesulfonate, n-propylester phosphate, tetra-n-butylammonium perchlorate, etc.
- the dopant may be dissolved in a solvent such as water or a non-aqueous solvent (acetonitrile, dimethylformamide, etc.) in the form of sodium chloride, sodium salt, ester, ammonium salt, etc., and the above-mentioned electrolytic polymerization may be carried out in this solution. .
- the electrolyte When used as an electrolyte for an electrolytic capacitor, the electrolyte is placed on the surface of an oxide film formed on a valve metal such as annealed, tantalum, or niobium. These metals function as anodes of electrolytic capacitors, and are used as etching foils or as sintered metal powders to increase their surface area. Therefore, when a conductive polymer is synthesized by a chemical polymerization method, the conductive polymer must be filled in the holes of the etching foil and the gaps of the sintered powder.
- a valve metal such as annealed, tantalum, or niobium.
- the oxide film on the valve metal is a dielectric, so a conductive film is formed on the dielectric in advance to make it conductive, and the power is supplied from the power supply.
- Electropolymerization must be performed by applying current or voltage.
- the conductive film used for this purpose is synthesized by chemical polymerization. For example, a conductive polymer or hot manganese dioxide can be used.
- the simplest method of the composite method is to form a conductive polymer on a valve metal oxide film by a known method, immerse it in an ionic liquid, and then pull it up from the ionic liquid. Note that a solute may be added to the ionic liquid.
- a cathode forming step, an electrode attaching step, an exterior step, and an aging step may be performed thereafter.
- an aluminum case aluminum case
- the addition amount of the ionic liquid is selected within a range that has sufficient anodizing property and does not impair the electron conductivity of the conductive polymer. Generally, from the viewpoint of not impairing electron conductivity,
- the addition amount of the ionic liquid be less than 110 in terms of the weight ratio of the conductive polymer.
- the amount of the ionic liquid to be added is preferably at least 1100,000 or more, and more preferably at least lZl0,000 of the conductive high molecule. Things are better. That is, the preferred weight ratio of the ionic liquid and the conductive polymer in the electrolyte of the present invention (ionic liquid / conductive polymer) is in the range of less than 1/10 to 1Z1000. The preferred range is from less than 1/10 to 1Z100.
- Such an ionic liquid of the present invention requires a remarkably small amount as compared with an electrolytic capacitor using an electrolyte composed of a conductive polymer and an organic acid salt as described in Patent Document 3, for example. Is also good.
- the preferable ratio of the conductive polymer (A) to the organic acid salt (B) is (A) :( B) -1: 0.
- the preferable addition amount to the conductive polymer is less than 10%, and the addition of the ionic liquid impairs the high level of the conductive polymer and impairs the electric conductivity. As a result, a capacitor with excellent impedance characteristics can be realized.
- the second method of compounding is a method for synthesizing a conductive polymer by electrolytic polymerization or chemical polymerization.
- An ionic liquid is used as a solvent, and the solvent is allowed to remain positively, for example, after an electrolyte forming step of an electrolytic capacitor.
- the preferred weight ratio of the ionic liquid and the conductive polymer is lZi
- the range is less than 0 to 1Z 10000, and the more preferable range is the range of less than 1/10 to 1/1000.
- the anion species of the ionic liquid as the common anion with the conductive polymer dopant.
- the conductive polymer is doped at the same time as the electrolytic polymerization reaction, and an electrolyte having both excellent electronic conductivity and excellent ion conductivity can be obtained. Examples of using an ionic liquid as a solvent during the synthesis of a conductive polymer, actively leaving an ionic liquid after polymerization, or adding an ionic liquid to a polymerized conductive polymer Is not known.
- the TCNQ salt is not particularly limited, but a TCNQ complex salt using an ammonium cation is preferably used.
- a TCNQ complex salt using a nitrogen-containing compound having alkyl substitution at the N-position as a donor and TCNQ as an acceptor examples include pyridin derivatives such as pyridine and lutidine, derivatives such as quinoline and isoquinoline, ataridine, phenazine and phenanthroline.
- N-substituted alkyl group examples include butyl, amyl, hexyl, and phenethyl. These salts are used singly or as a mixture of a plurality of TCNQ salts as an electrolyte, and additives such as a glucose polymer may be added as necessary.
- TCNQ salts use purified or dehydrated acetonitrile, etc. This is performed by adding TCNQ to a storage medium, adding an ammonium salt (eg, Nn-butylisoquinolium iodide, etc.) thereto, and separating and filtering the precipitated TCNQ salt.
- an ammonium salt eg, Nn-butylisoquinolium iodide, etc.
- TCNQ salts N-n-heptyl isoquinolizinyloxy linear ⁇ beam (TCN Q) 2 salt and N- isoamyl isoquinolizinyloxy linear ⁇ beam (TCNQ) 2 salts,, N, N- pentamethylene ( Lutidine) 2 (TCNQ) 4 salt, N-phenethyllutidine (TCNQ) 2 salt, or a mixture of these TCNQ salts can be exemplified.
- TCNQ The reason why salts are preferably used is that these salts have relatively high conductivity and have unique properties as a TCNQ salt that is melted by heating. Normal TCNQ salts do not melt when heated, but decompose or sublime.
- the electrolyte of the electrolytic capacitor is disposed on the surface of a dielectric oxide film formed on a valve metal such as anoremium, tantalum, and niobium.
- a valve metal such as anoremium, tantalum, and niobium.
- These metals function as anodes of electrolytic capacitors, and are used as etching foils or as sintered bodies of metal powder to increase their surface area. Therefore, the TCNQ salt must be filled into the holes of the etching foil and the gaps of the sintered powder.
- the property of the TCNQ salt that it is melted is used for melting and filling the inside of an etched aluminum electrode or a sintered tantalum electrode, and is an excellent manufacturing method.
- the addition amount of the ionic liquid is selected within a range that has sufficient anodizing property and does not impair the electron conductivity of the TCNQ salt.
- the amount of the ionic liquid added is preferably less than 1/2 of the TCNQ salt by weight, more preferably 1 Z 5 or less, and lZl It is most preferable that it is 0 or less.
- the amount of the ionic liquid to be added is preferably at least 11,000, more preferably at least 1/1000, of the TCNQ salt by weight.
- the preferred weight ratio (ionic liquid ZTCNQ salt) of the ionic liquid and the TCNQ salt in the electrolyte of the present invention is in the range of less than 1Z2 to 10000, and the more preferable range is 1 to 5 or less to 1/10000. And the most preferred range is from 110 to 1/1000.
- the simplest method of compounding is to form a TCNQ salt on a valve metal oxide film by a known method, and then immerse it in an ionic liquid and pull it up.
- a cathode forming step, an electrode attaching step, an exterior step, and an aging step may be performed thereafter.
- a capacitor of aluminum type using an aluminum case (aluminum case)
- the ionic liquid and the TCNQ salt are put in an aluminum case (aluminum case) and dissolved by heating, and a capacitor element consisting of an anode and a cathode wound with maera hemp paper is inserted inside the aluminum case.
- a sealing and aging process may be performed thereafter. If it is not a boring type, after forming a TCNQ salt on the valve metal oxide film by a known method, immerse it in an ionic liquid and lift it up with a bow.
- a shading step, an exterior step, and an aging step are performed thereafter.
- the ionic liquid which is a component of the electrolyte of the present invention will be described.
- those described in the synthesis method were synthesized and used. Those not described in the synthesis method were commercially available.
- the molecular formula, physical properties, and abbreviations (ILS-1 to: 1LS-23) of the ionic liquid used are described below. Where Im is imidazolidum and Py is pyridium.
- 1-Ethylimidazolymbenzenesulfonate was synthesized in the same manner as above.
- the product was a clear, colorless liquid having a glass transition point of 16.5 ° C and a melting point of 19.5 ° C.
- the mixture was quickly aspirated on a suction nutsche fitted with a glass filter and filtered on a glass filter to recover 8.10 g of product.
- the yield was 65.5%.
- the product was identified as 1-ethyl-imidazolium-p-tonoreensenorefonato.
- the resulting imidazolym salt had a glass transition temperature (Tg) of 4.3 ° C.
- the mixture was sucked on a suction nut attached with a glass filter and filtered on a glass filter to recover 6.40 g of a white solid.
- the yield was 70.6%.
- the recovered product was identified as 1-butyl-imidazolium p-toluenesulfonate.
- the resulting imidazolyme salt had a glass transition temperature (Tg) of 18.4 ° C. and a crystallization temperature (Tc) of 2.6 ° C.
- ILS-16 1.0 g of the above-mentioned ILS-16 was dissolved in 10 ml of methanol, and azobisisobutyronitrile was added as a polymerization initiator to these at a molar ratio of 1% to the vinyl unit of ILS-16. And radical polymerization at a temperature of 65 ° C for 3 hours to obtain N-butylimidazoline solution. A molten salt polymer (ILS_17) was obtained.
- n-butyl iodide (2 Ommo 1) and isoquinoline (2 Ommo 1) were added to a flask equipped with a reflux condenser, and the mixture was heated to 80 ° C. Since the yellow oily product separated from the liquid phase, heating was discontinued once the product began to form and the reaction was adjusted using warm water (about 40 ° C) to proceed slowly. Since the reaction progressed almost 100%, the reaction was stopped when the whole was oily. The product crystallized (solidified) as soon as the heating was stopped. After washing with ethyl ether, purification by recrystallization was performed using methanol.
- the n-butylisoquinoline iodide (25 mmo 1) obtained by the above method was calothermally dissolved in acetonitrile 3 Om 1 and TCNQ (3 Ommo 1) in acetonitrile 6 Oml, and the two solutions were mixed while gently boiling. did. After mixing, the mixture was heated under reflux for 1 hour to complete the reaction. After completion of the reaction, the mixture was left at room temperature for 1 hour, cooled at 5 ° C. for 24 hours, and the resulting black-purple crystals were separated by filtration. The obtained crystals were washed with a small amount of cooled acetonitrile and further washed with ethyl ether.
- the obtained salt had an electrical conductivity of 3.4 ⁇ cm, a melting point of 210 ° C, and a yield of 80%.
- N- isoamyl isoquinolizinyloxy linear ⁇ beam (TCNQ) 2 salt in the same manner as (A).
- the obtained salt had an electrical conductivity of 4.2 ⁇ cm, a melting point of 213 ° C and a yield of 78%.
- Purity 99.99% aluminum wires (1. 5 mm in diameter) was 70% HNO 3 (15 parts) and 85% H 3 P0 4 was immersed for two minutes in (85 parts) force Ranaru mixture was washed with pure water. Next, it was etched with a 1N, NaOH solution for 10 minutes, washed with pure water, immersed in acetone, and dried. Next, the aluminum wire was subjected to a chemical conversion treatment in an aqueous solution of adipic acid (1 g / L). The dangling was performed at a constant current of 1 OmA / cm 2 , and was performed by maintaining the voltage at 200 ° C. for 10 minutes after 3 ⁇ 4] £ reached 200 V. Next, the above-mentioned chemical conversion film was treated with boiling water for 3 minutes while applying a direct current to 100 V and stamping so that the A1 (aluminum) side became a positive pole. This treatment causes part of the conversion coating to burst.
- FIG. 3 shows the experimental results.
- the aqueous solution of adipic acid was prepared by dissolving 1 g of ammonium adipic acid in 1 L of distilled water.
- the conductivity at 70 ° C was 400 ⁇ cm and the pH was 6.8.
- ILS-1 is an excellent material that exhibits anodic oxidation (re-formation) from low ⁇ voltage. It can be seen that even with a 200V-formed film, a pressure resistance of up to about 80 to 100V cannot be achieved.
- adipic acid has excellent withstand voltage characteristics up to 180 V, but has the disadvantage that it cannot regenerate in the low-voltage region below 40 V and cannot cope with such a voltage region. all right. Examples 2 to 12
- Example 1 The same experiment as in Example 1 was performed using ILS-2 to ILS-12. Table 1 shows the experimental results. In the table, the portion where the numerical value is not described (the portion indicated as 1) indicates that a clear voltage value was not observed.
- Table 1 shows the voltages at points A, B, and C above. In the table, the portion where the numerical value is not described (the portion indicated as 1) indicates that no clear «] £ value was observed.
- ILS-2 to ILS-12 are the ILS according to the present invention and the fluorine-containing anion ILS. From these results, it was found that all ILS have excellent anodizing ability. However, it is clear from these results that the ⁇ at points A, B, and C differ for each ILS, and the performance differs for each ILS. All of the ILSs formed from fluorinated a unions have high resistance to E (C point), including atomic groups including sulfonate anions (-SO s- ) and carboxylate (one C OO-1) ILS formed from an anion composed of atomic groups has excellent anodizing ability (ie, low A and B points), although the breakdown voltage characteristics are inferior to those of fluorine-containing anion ILS. On the other hand, it can be seen that whether the cationic component is imidazolyme, pyridinium, or ammonium does not significantly affect its anodic oxidation characteristics. Comparative Examples 2-3
- Example 2 The same experiment as in Example 1 was performed with the initial formation voltage set to 50 V and 100 V. The results are shown in Table 2. In the table, the parts that are not described in a few numbers (the parts indicated by “1”) indicate that no clear ⁇ value power S was observed. Evaluation of anodizing ability (reforming experiment): Influence of formation voltage
- ILS- 2, ILS- 3 the fluorinated ion ILS (ILS-7, ILS-8, ILS-10) has a breakdown voltage of 120 to 160 V.
- ILS_7 is a fluorine-containing sulfonate anion
- ILS-10 which are anions containing fluorine, from the viewpoint of withstand voltage.
- Having a breakdown ⁇ JE of 50 V or more in a sample formed at 50 V means that these ILS have the same breakdown voltage even if an aluminum electrode without initialization is used. This indicates that these ILS have excellent anodizing ability.
- ILS-2 and I LS-3 are 85 V and 80 V, respectively, which are lower than the breakdown voltage.
- ILS-7, ILS_8, and ILS-10 are 150 V, 180 V, and 200 V, respectively, indicating that the fluorine-containing anion-based liquid has excellent withstand voltage characteristics.
- Table 3 shows the results of the same re-formation (anodic oxidation) experiment performed using an electrolyte solution in which adipic acid was dissolved and added to an ionic liquid at 10% by weight.
- the part where the numerical value is not described indicates that a clear voltage value was not observed.
- the C point can be increased (that is, the withstand voltage of the electrolyte can be improved) as compared with the case of using the ionic liquid alone.
- Such a composite ionic liquid does not lose its characteristic that it can exhibit an anodic oxidation ability from a low voltage region as compared with an adipic acid aqueous solution electrolyte. That is, such a composite electrolyte has an excellent film repairing ability from a low voltage region and becomes an electrolyte having excellent withstand voltage characteristics in a high voltage region.
- Such a method can be widely applied to ionic liquids and can control the oxide film forming characteristics. Examples 28-44
- An electrolytic capacitor was prototyped by forming a conductive polymer on the oxide film of the anoreminium by electrolytic polymerization, and the above-mentioned ionic liquid was added to the obtained electrolytic capacitor, and the capacitor characteristics were measured.
- an aluminum foil aluminum-etched foil with pores formed on the surface by an etching process with a length of 7 mm and a width of 10 mm with an anode lead was immersed in a 3% aqueous solution of ammonium adipic acid at 70 ° C.
- Anodization was performed under the conditions of an applied voltage of 70 V to form a dielectric film as an oxide film on the surface of the aluminum foil.
- this was immersed in a 30% aqueous solution of manganese nitrate, air-dried, and then subjected to a heat treatment at 300 ° C. for 30 minutes to form a conductive layer composed of a manganese oxide layer on the dielectric film. .
- FIG. 4 shows a conceptual diagram of the equipment used.
- the electrolytic solution (6) used for the polymerization was an electrolytic solution consisting of pyropropyl (0.5%), a 30% alcoholic solution of sodium triisopropylnaphthalenesulfonate (0.1M), and water. As shown in Fig.
- an aluminum foil (2) was placed in the electrolytic polymerization solution, the polymerization initiation electrode (1) was brought close to the manganese dioxide conductive layer (4), and the polymerization initiation electrode (1) and the cathode ( A constant voltage of 1.5 V was applied for 50 minutes between and 7) to carry out an electrolytic polymerization reaction to form an electropolymerized polypyrrole layer (5) on the conductive layer.
- Table 4 shows the characteristics of the obtained capacitors.
- the initial capacity, ta ⁇ ⁇ , and impedance were not significantly different from those of Comparative Example 4 in comparison with Comparative Example 4, but the withstand voltage characteristics were significantly improved. It has been found that the application of the electrolyte of the present invention in which an ionic liquid is added to a conductive polymer to an electrolytic capacitor can improve the withstand voltage characteristics of the capacitor.
- Table 4 Initial characteristics of capacitors: Aluminum Z oxide film Z (polypyrrole + ionic liquid) system
- Example 4 An aluminum electrolytic capacitor was experimentally produced by electrolytic polymerization in the same manner as in Example 45.
- the ionic liquids ILS-22 and ILS-23 were added to the obtained electrolytic capacitor, and the capacitor characteristics were measured.
- Table 1 shows the characteristics of the obtained capacitors. It was found that when an ionic liquid containing chlorine and bromine was added, the capacitor characteristics were significantly deteriorated.
- a conductive polymer electrolytic capacitor was fabricated by placing a conductive polymer obtained by chemical polymerization on a tantalum oxide film, and the above-mentioned ionic liquid was added to the obtained electrolytic capacitor to obtain the capacitor characteristics. was measured.
- a rectangular parallelepiped tantalum sintered body (length: 2 mm, height: 1.5 mm, width: 1 mm) with an anode lead was placed in a 0.05% phosphoric acid aqueous solution at 85 ° C for 60 minutes.
- Anodizing was performed under the conditions of an applied voltage of 33.9 V to prepare a sample in which a dielectric film as an oxide film was formed on the tantalum sintered body. This sample was immersed in a 0.75 mol / 1/1 pyrrole aqueous solution for 2 minutes, and then immersed in a 0.1 mol / 1/1 aqueous ferric sulfate solution for 10 minutes.
- Table 6 shows the characteristics of the obtained capacitors. No significant difference was observed in the initial capacity and ta ⁇ ⁇ values compared to the comparative example without addition of the ionizing liquid, but significant improvements were observed in the leakage current value and the withstand voltage characteristics. It has been found that the application of the electrolyte of the present invention in which an ionic liquid is added to a conductive polymer to an electrolytic capacitor can improve the withstand voltage characteristics of the capacitor.
- a conductive polymer aluminum electrolytic capacitor (aluminum electrolytic capacitor) was fabricated by placing a conductive polymer obtained by chemical polymerization of thiophene on an aluminum oxide film.
- an aluminum-etched foil 4 ⁇ 3.3 mm is immersed in a 3% ammonium adipate 7 solution, first raised from 0 to 10 V at a speed of 10 mV / sec, and then kept at a constant 10 V.
- One pound was pressed for 40 minutes to form a dielectric film on the surface of the aluminum-etched foil.
- the foil is washed with running deionized water for 10 minutes, and then dried at 105 ° C for 5 minutes. went.
- the liquid volume of the aluminum-etched foil obtained at this time was 18 F.
- ferric benzenesulfonate, a transition metal salt using benzenesulfonate ion as anion and ferric triisopropylnaphthalenesulfonate, a transition metal salt using triisopropylnaphthalene sulfonate ion as anion.
- 1,4-dioxythiophene was mixed with this solution and stirred to prepare a polymerization solution.
- the anodized aluminum foil is immersed in this solution, heated in an electric furnace at 105 ° C for 5 seconds, and further heated in an electric furnace at 70 ° C for 10 minutes to allow chemical polymerization to proceed. Washing with water and drying were performed.
- Example 28 An ionic liquid was added in the same manner as in Example 28. (That is, as described above, an electropolymerized polythiophene layer is formed on a conductive layer, washed with water, dried, immersed in a methanol solution of an ionic liquid, and then dried to remove methanol. Was added to the electrolytically-polymerized polypyrrole layer to obtain the electrolyte of the present invention in an amount of 0.5 to 5% by weight of the conductive polymer.) Then, on the electrolyte of the present invention, A capacitor was prepared by providing a carbon layer and a silver paste layer. Table 7 shows the characteristics of the obtained capacitors.
- the capacitor characteristics were evaluated using a system in which the following solutes were added to each of the ionic liquids so that the weight ratio between the ionic liquid (ILS-2) and the following solutes was 2: 1.
- the following commercially available solutes were used as the solutes to be added.
- a methanol solution of ILS-2 to which the following solutes were added was boxed, and capacitors were produced in the same manner as in Examples 28 to 44. That is, the immersion step was performed using the methanol-immersion solution of ILS-2 to which the solute was added, with the ILS-2 methanol solution immersion step force S in Example 29.
- Table 8 shows the characteristics of the obtained capacitors. Initial characteristics of capacitor: aluminum / oxide film (polypyrrole + ionic liquid + solute)
- SA to SH are solutes.
- SA to SE are used, but in the following Examples and Comparative Examples, SF to SH are used.
- Phthalic acid tetra E chill ammonium Niu beam ((C 2 H 5) 4 N) + (HOOC-C 6 H 4 -C OO) -, abbreviated as SD).
- Triethylmethylammonium phthalate ((C 2 H 5 ) 3 N-CH 3 ) + (1-HOOC—C 6 H 4 — 2— COO)-, abbreviated as SG)
- Table 9 shows the characteristics of the obtained capacitors in the same manner as in Examples 28 to 44, except for TIE (1) and (2).
- Ionic liquids up to ILS-18 ⁇ 21 Ionic liquids up to ILS-18 ⁇ 21, ionic liquids (ILS-18 ⁇
- the electroconducting liquid was formed from “pyrrole (0.5M), a 30% alcohol solution of sodium triisopropylnaphthalenesulfonate (0.1M), and water.
- pyrrole 0.5M
- a 30% alcohol solution of sodium triisopropylnaphthalenesulfonate 0.1M
- water a 30% alcohol solution of sodium triisopropylnaphthalenesulfonate
- Table 9 shows the characteristics of the obtained capacitors. Compared with Comparative Example 4 in which no ionic liquid was added, there were no significant differences in the values of the initial capacity, ta ⁇ ⁇ , and impedance, but there was a significant improvement in the withstand voltage characteristics. It was found that the addition can improve the withstand voltage characteristics of the capacitor. (Examples 92 to 94)
- An aluminum electrolytic capacitor was experimentally produced by electrolytic polymerization in the same manner as in Example 88, and 15% of each of the solutes S ⁇ , SF, and SG were dissolved in the above-mentioned ionic liquid ILS-18 in the obtained electrolytic capacitor, and the resulting solution was dissolved. After addition, the capacitor characteristics were measured. The characteristics of the obtained capacitors are shown in the lower part of Table 9. Compared with Comparative Example 4 in which no ionic liquid was added, there was no significant difference in the values of the initial capacity, ta ⁇ ⁇ , and impedance, but a significant improvement was observed in the withstand voltage characteristics. It has been found that it is possible to improve the capacitor pressure resistance regardless of the type of solute added.
- a tantalum conductive polymer electrolytic capacitor was prepared by polymerization and added to the obtained electrolytic capacitor with the above-mentioned ionic liquid ILS-18 to 21 (each 15% dissolved in solute SA). was measured.
- a rectangular parallelepiped tantalum sintered body (length: 2 mm, height: 1.5 mm, width: lmm) with an anode lead was placed in a 0.05% phosphoric acid aqueous solution at 85 ° C for 60 minutes, and an applied voltage of 33. Anodization was performed at 9 V to form a dielectric film.
- This device was immersed in a 0.75 mO1 / 1 aqueous solution of pyrrole for 2 minutes, and then immersed in ferric sulfate 0.1 ml of 1/1 water for 10 minutes in a vigorous night. This operation was repeated about 20 times so that the entire device was covered with conductive polymer polypropylene by chemical oxidation polymerization.
- a ionic liquid was added in the same manner as in Example 45.Next, a carbon paste film and a silver paste film were formed by a usual method, a cathode lead was provided on the silver paste film, and aging was performed at 2.5 V. Then, it was covered with resin to obtain an electrolytic capacitor. After aging the thus obtained capacitor of the present invention at 2 OV for 1 hour, the initial capacity, tan S, leakage current value, and withstand voltage (V) were measured.
- Table 10 shows the characteristics of the obtained capacitors. No significant difference was found in the initial capacity and ta ⁇ ⁇ values compared to Comparative Example 11 in which no ionic liquid was added, but a significant improvement was observed in the leakage current value and the resistance characteristics, It was found that the characteristics of the capacitor could be improved by adding liquid.
- Example 9 5 IL S- 18 + SA 1 6.6 2.2 20.0 9 19
- Example 9 6 IL S- 19 + SA 16.2 2.20.19.18
- Example 9 7 ILS- 20 + SA 1 6.4 2.30.26.16
- Example 9 8 ILS-21 + SA 1 6. 0 2.4 0. 1 8 1 6 Comparative example 1 1 None 1 7. 2 2. 0 0. 1 8 1 2 (Example 9 9 to 10 2)
- Conductive polymer aluminum electrolytic capacitors were produced by chemical polymerization of thiophene, and the obtained electrolytic capacitors were added with the above-mentioned ionic liquids ILS-18 to 20 (each 15% dissolved in solute SA). The properties were measured.
- an ethanol solution of ferric benzenesulfonate, a transition metal salt containing benzenesulfonate ion, and ferric triisopropylnaphthalenesulfonate, a transition metal containing triisopropylnaphthalenesulfonate ion as aion is used.
- 1,4-dioxythiophene was mixed with the solution and stirred to prepare a polymerization solution.
- the anodized aluminum foil is immersed in this solution, heated in an electric furnace at 105 ° C for 5 seconds, and further heated in an electric furnace at 70 ° C for 10 minutes to allow chemical polymerization to proceed.
- An electrolytic capacitor was prototyped by forming a TCNQ salt on the aluminum oxide film by melt impregnation, and an ionic liquid was added to the obtained electrolytic capacitor, and the capacitor characteristics were measured.
- high-magnification aluminum etched foil /.
- the aluminum foil was immersed in an aqueous solution of ammonium adipate and subjected to anodization at 70 ° C. under an applied voltage of 50 V to form a dielectric film as an oxide film on the surface of the aluminum foil.
- This was used as an anode foil and a cathode foil, and the lead wire was attached and wound up through a separator made of Manila hemp paper to form a capacitor-type capacitor element.
- the capacitor element was heated to carbonize the separator paper.
- Table 13 shows the obtained capacitor characteristics. Table 13 Initial characteristics of capacitors:
- Ionic liquids ILS-22 and 23 were added in the same manner as in Example 120, and the capacitor characteristics were measured. The measurement results are shown in the lower row of Table 13. It was found that when an ionic liquid containing chlorine and bromine was added, the capacitor characteristics deteriorated significantly. Examples 124 to 131
- ⁇ _ ⁇ - butyl isoquinolizinyloxy linear ⁇ beam (TCNQ) 2 ⁇ - Isoamiruisoki glue instead of salt - but using ⁇ beam (TCNQ) 2 salt was prepared electrolytic capacitors in the same manner as in Example 103.
- the melting 'impregnation temperature was 215 ° C.
- Table 14 shows the characteristics of the obtained capacitors. Experiments were conducted on the ionizable liquid ILS—1 to 5, 10, 13, and 14. Table 14 Initial characteristics of capacitors:
- ILS-18 and 19 which are hydrophilic ionic liquids, showed no significant difference in the values of initial volume, ta ⁇ , and impedance compared to Comparative Example 17 without the addition of the ionic liquid. There was a significant improvement in the withstand voltage characteristics that were not found, and it was found that the addition of an ionic liquid could improve the capacitor withstand voltage characteristics. On the other hand, in the case of ILS_20 and ILS_21, which are hydrophobic ionic liquids, there was almost no effect on the capacitor characteristics, and the withstand voltage characteristics were not significantly improved. This is thought to be due to the lower anodizing ability of ILS_20, 21 compared to ILS-18, 19. Examples 136-140
- a prototype of an aluminum electrolytic capacitor was prepared by forming a TCNQ salt electrolyte containing 5% of an ionizable liquid ILS-18 to 21 (each of which dissolved 15% of a solute SA) by melt impregnation in the same manner as in Example 120. Then, the capacitor characteristics were measured.
- Table 17 shows the characteristics of the obtained capacitors. Although there were no significant differences in the initial capacity, ta ⁇ ⁇ , and impedance values compared to Comparative Example 17 in which no ionizing liquid was added, a significant improvement was observed in the withstand voltage characteristics. It was found that the addition of the dissolved ionic liquid can improve the withstand voltage characteristics of the capacitor.
- Example 141 I LS-18 + SA 6.6 2.2 97 28
- Example 142 I LS-19 + SA 6.4 2.5 90 32
- Example 143 I LS-20 + SA 6.5 2.
- Example 144 I LS-21 + SA 6. 4. 2. 5 95 27
- Example 1 4 5 to 1 4 7
- the amount of the ionic liquid added to the conductive polymer was 0.01 part by weight with respect to 100 parts by weight of the conductive polymer. Also has an effect on improving the pressure resistance characteristics, and the effect is remarkable if it is 0.1 part by weight or more. However, it was found that when the added amount was more than 10 parts by weight, the impedance characteristics became poor, and the capacity also showed a decreasing tendency.
- the most preferable amount of the ionic liquid to be added in the electrolyte composed of the TCNQ salt and the ionic liquid ranges from less than 10% to 0.01% with respect to 100% by weight of the TCNQ. I understood that.
- An oxide film can be easily formed on a valve metal by using the method of the present invention. Further, by using the method of the present invention as an electrolyte of an electrolytic capacitor, the ionic liquid By taking advantage of its non-volatility and excellent oxide film repair ability, a high-performance electrolytic capacitor with excellent high-frequency characteristics and high withstand voltage can be obtained.
Abstract
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JP2012191085A (ja) * | 2011-03-11 | 2012-10-04 | Kaneka Corp | 電解質組成物およびイオン液体 |
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Also Published As
Publication number | Publication date |
---|---|
EP1650328B1 (en) | 2016-10-19 |
US20080304208A1 (en) | 2008-12-11 |
EP1650328A1 (en) | 2006-04-26 |
US7746623B2 (en) | 2010-06-29 |
JP4685631B2 (ja) | 2011-05-18 |
EP1650328A4 (en) | 2007-05-23 |
US20060181835A1 (en) | 2006-08-17 |
KR20060039924A (ko) | 2006-05-09 |
US8014128B2 (en) | 2011-09-06 |
JPWO2005012599A1 (ja) | 2006-09-21 |
JP2011091428A (ja) | 2011-05-06 |
EP2540875A1 (en) | 2013-01-02 |
JP5167333B2 (ja) | 2013-03-21 |
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