WO2012050140A1 - 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池 - Google Patents
光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池 Download PDFInfo
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- WO2012050140A1 WO2012050140A1 PCT/JP2011/073450 JP2011073450W WO2012050140A1 WO 2012050140 A1 WO2012050140 A1 WO 2012050140A1 JP 2011073450 W JP2011073450 W JP 2011073450W WO 2012050140 A1 WO2012050140 A1 WO 2012050140A1
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- Prior art keywords
- group
- photoelectric conversion
- conversion element
- acid
- electrolyte
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 94
- 239000003792 electrolyte Substances 0.000 title claims abstract description 56
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- 125000001204 arachidyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([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])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])[H] 0.000 description 1
- WXBLLCUINBKULX-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1 WXBLLCUINBKULX-UHFFFAOYSA-N 0.000 description 1
- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 description 1
- PASOAYSIZAJOCT-UHFFFAOYSA-N butanoic acid Chemical compound CCCC(O)=O.CCCC(O)=O PASOAYSIZAJOCT-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-L butyl phosphate Chemical compound CCCCOP([O-])([O-])=O BNMJSBUIDQYHIN-UHFFFAOYSA-L 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
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- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 125000000062 cyclohexylmethoxy group Chemical group [H]C([H])(O*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- YBPJNJSKPUAMKZ-UHFFFAOYSA-N decane Chemical compound CCCCCCCCC[CH2-] YBPJNJSKPUAMKZ-UHFFFAOYSA-N 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([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])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- HCIQUGMKXQZZMG-UHFFFAOYSA-N ethyl hexyl hydrogen phosphate Chemical compound CCCCCCOP(O)(=O)OCC HCIQUGMKXQZZMG-UHFFFAOYSA-N 0.000 description 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 1
- 239000001019 fluorene dye Substances 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- JYDNQSLNPKOEII-CFYXSCKTSA-N hexadec-9-enoic acid;(z)-hexadec-9-enoic acid Chemical compound CCCCCCC=CCCCCCCCC(O)=O.CCCCCC\C=C/CCCCCCCC(O)=O JYDNQSLNPKOEII-CFYXSCKTSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([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])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])[H] 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
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- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- ZJZXSOKJEJFHCP-UHFFFAOYSA-M lithium;thiocyanate Chemical compound [Li+].[S-]C#N ZJZXSOKJEJFHCP-UHFFFAOYSA-M 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([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])C([H])([H])[H] 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- YJBMMHPCGWCCOH-UHFFFAOYSA-N octan-3-yl dihydrogen phosphate Chemical compound CCCCCC(CC)OP(O)(O)=O YJBMMHPCGWCCOH-UHFFFAOYSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
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- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- SXBRULKJHUOQCD-UHFFFAOYSA-N propanoic acid Chemical compound CCC(O)=O.CCC(O)=O SXBRULKJHUOQCD-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 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
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([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])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])[H] 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([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])[H] 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
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- 238000001771 vacuum deposition Methods 0.000 description 1
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- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2013—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Definitions
- the present invention relates to an electrolyte for a photoelectric conversion element, a photoelectric conversion element using the electrolyte, and a dye-sensitized solar cell.
- non-silicon solar cells have attracted attention as solar cells that can reduce environmental impact and reduce manufacturing costs.
- dye-sensitized solar cells developed by Grezel, etc. of Switzerland have high photoelectric conversion efficiency among solar cells using organic materials, and are less expensive to manufacture than silicon-based solar cells. It is also attracting attention as a new type of solar cell due to its advantages such as low price.
- dye-sensitized solar cells are electrochemical cells
- organic electrolytes or ionic liquids are used as electrolytes.
- they may volatilize or be depleted during long-term use.
- ionic liquids volatilization and depletion during long-term use can be prevented, but there are durability problems such as structural deterioration due to liquid leakage. It was.
- Patent Document 1 describes "(i) Layered clay mineral and / or organically modified layered clay mineral and (ii) an electrolyte for a photoelectric conversion element comprising an ionic liquid.” 1]).
- An object of the present invention is to provide an electrolyte for a photoelectric conversion element from which a dye-sensitized solar cell excellent in stability can be obtained as in the invention disclosed in Patent Document 1.
- the inventor of the present invention uses a predetermined organic salt compound and an organically treated layered double hydroxide (LDH) in combination to form a gel.
- LDH organically treated layered double hydroxide
- the present inventors have found that an electrolyte can be obtained and that volatilization, liquid leakage, and the like can be suppressed, and the present invention has been completed. That is, the present invention provides the following (1) to (7).
- An electrolyte for a photoelectric conversion element comprising an organic salt compound (A) having a tertiary or quaternary cation and an organically modified layered double hydroxide (B).
- the organically modified layered double hydroxide (B) is a layered double hydroxide that has been organically treated using an organic anion having 3 or more carbon atoms. Electrolytes.
- the onium base is at least one selected from the group consisting of an imidazolium base, a pyridinium base, a pyrrolidinium base, a piperidinium base, an ammonium base, a sulfonium base, a phosphonium base, and the like. Electrolyte for photoelectric conversion element.
- a dye-sensitized solar cell in which a photosensitizing dye is supported on the photoelectrode of the photoelectric conversion element according to (6).
- an electrolyte for a photoelectric conversion element from which a dye-sensitized solar cell excellent in stability can be obtained can be provided.
- FIG. 1 is a schematic cross-sectional view showing an example of the basic configuration of the photoelectric conversion element of the present invention.
- FIG. 2 is a drawing showing the basic configuration of the solar cell of the present invention used in Examples and the like.
- the electrolyte for photoelectric conversion elements of the present invention (hereinafter also simply referred to as “the electrolyte of the present invention”) is an organic treatment using an organic salt compound (A) having a tertiary or quaternary cation and an organic anion. And an organically modified layered double hydroxide (B) that is a layered double hydroxide.
- Organic salt compound (A) used in the electrolyte of the present invention is an organic salt compound having a tertiary or quaternary cation and an anion which is a counter ion thereof, and is a liquid (so-called ionic liquid) at room temperature. Is preferred.
- the tertiary cation refers to a cation in which a positively charged periodic table group 16 element (for example, an oxygen atom, a sulfur atom, etc.) does not have a hydrogen atom
- the quaternary cation is A cation in which a Group 15 element (for example, a nitrogen atom or a phosphorus atom) having a positive charge does not have a hydrogen atom.
- cation possessed by the organic salt compound (A) include cations represented by the following formula (1) or (2).
- R 1 represents a hydrocarbon group that may contain a heteroatom having 1 to 20 carbon atoms, and has a substituent that may contain a heteroatom having 1 to 20 carbon atoms. May be.
- R 2 and R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may contain a hetero atom. However, when the nitrogen atom contains a double bond, R 3 does not exist.
- Q represents a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom
- R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom or a hydrocarbon having 1 to 8 carbon atoms. Represents a group and may contain a heteroatom. However, when Q is an oxygen atom or a sulfur atom, R 7 does not exist, and when Q is a sulfur atom, R 4 and R 5 may be linked.
- the hydrocarbon group which may contain a hetero atom having 1 to 20 carbon atoms of R 1 in the above formula (1) includes a ring structure together with a nitrogen atom (ammonium ion) in the above formula (1). It is preferable to take it.
- the substituent which may have a hetero atom having 1 to 20 carbon atoms which R 1 in the above formula (1) may have is an alkyl group having 1 to 20 carbon atoms (for example, methyl Group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, ethylhexyl group, nonyl group, decyl group, dodecyl group, undecyl group, hexadecyl group, octadecyl group, cyclopropylmethyl group, tripropyl group Fluoroethyl group, etc.), alkenyl group having 2 to 20 carbon atoms (for example, vinyl group, allyl group, etc.), aryl group having 6 to 20 carbon atoms (for example, phenyl group, tolyl group, naphthyl group, etc.), carbon number 7 -20 aralkyl
- an alkyl group having 1 to 20 carbon atoms for example, , Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, ethylhexyl group, nonyl group, decyl group, dodecyl group, undecyl group, hexadecyl group, octadecyl group, cyclopropylmethyl group , Trifluoroethyl group, etc.), C 2-20 alkenyl group (eg, vinyl group, allyl group, etc.), C 6-20 aryl group (eg, phenyl group, tolyl group, naphthyl group, etc.), carbon 7 to 20 aralkyl groups (for example, Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group,
- the hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms of R 4 , R 5 , R 6 and R 7 is specifically 1 to 1 carbon atom.
- 8 alkyl groups for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc.
- alkoxy groups having 1 to 8 carbon atoms for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, sec-butoxy group, n-pentoxy group, n-hexoxy group, 1,2-dimethylbutoxy group, etc.
- C 2-8 Alkyl alkoxy groups for example, methylene methoxy group (—CH 2 OCH 3 ), ethylene methoxy group (—CH 2 CH 2 OCH 3 ), n-propylene-is
- Examples of the cation represented by the above formula (1) include imidazolium ion, pyridinium ion, pyrrolidinium ion, piperidinium ion, and the like.
- a cation represented by any of the following formulas (3) to (6) is preferably exemplified.
- the cation represented by the following formulas (3) and (5) is the photoelectric conversion of the photoelectric conversion element using the electrolyte of the present invention (hereinafter also referred to as “the photoelectric conversion element of the present invention”). This is preferable because the efficiency tends to be better.
- R each independently represents a hydrocarbon group which may contain a hetero atom having 1 to 20 carbon atoms or a hydrogen atom. More specifically, the following cations are mentioned.
- Examples of the cation represented by the above formula (2) include organic cations such as ammonium ion, sulfonium ion, phosphonium ion, and oxonium ion. Specifically, the following cations are preferably exemplified. Among these, aliphatic quaternary ammonium ions are preferable because the photoelectric conversion efficiency of the photoelectric conversion element of the present invention tends to be better.
- organic salt compound (A) examples include I ⁇ , Br ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , NO 3 ⁇ , BF 4 ⁇ , PF 6 ⁇ and CH 3.
- bromine ions (Br ⁇ ) and iodine ions (I ⁇ ) are preferable because the photoelectric conversion efficiency of the photoelectric conversion element of the present invention tends to be better, and iodine ions (I ⁇ ). More preferably.
- a thiocyanate anion (SCN ⁇ ) is preferable.
- organic salt compound (A) the organic salt compound etc. which consist of a combination of the cation and anion which were illustrated above are mentioned, for example.
- an organic salt compound having an imidazolium ion as a cation and an iodine ion as an anion is preferable because the photoelectric conversion efficiency of the photoelectric conversion element of the present invention becomes better.
- An organic salt compound having a thiocyanate anion is preferable because the heat resistance is good, and an organic salt compound having an imidazolium ion and an iodine ion and an organic salt compound having a thiocyanate anion are more preferably used in combination.
- the method for synthesizing the organic salt compound (A) is not particularly limited, and various organic salt compounds composed of combinations of cations and anions exemplified above can be synthesized by a conventionally known method.
- Examples of the organic salt compound (A) include 1-methyl-3-methylimidazolium iodide, 1-ethyl-3-methylimidazolium iodide, 1-methyl-3-pentylimidazolium iodide, 1-hexyl-
- synthetic products such as 3-methylimidazolium iodide, 1-((2-methoxyethoxy) ethyl) -3-((2-methoxyethoxy) ethyl) imidazolium iodide, commercially available products can be used.
- 1-methyl-3-propylimidazolium iodide manufactured by Tokyo Chemical Industry Co., Ltd.
- 1-methyl-3-butylimidazolium iodide manufactured by Tokyo Chemical Industry Co., Ltd.
- 1-methyl-1- Methyl-pyrrolidinium iodide manufactured by Aldrich
- 1-ethyl-3-methylimidazolium tetracyanoborate Merck
- 1-ethyl-3-methylimidazolium thiocyanate Merck
- 1-ethyl-3-methylimidazolium bis trifluoromethylsulfonyl) imide
- the content of the organic salt compound (A) is preferably 50 to 95% by mass and more preferably 65 to 95% by mass with respect to the total mass of the electrolyte of the present invention. When the content is within this range, the photoelectric conversion efficiency of the photoelectric conversion element of the present invention becomes better.
- the organically modified layered double hydroxide (B) used in the electrolyte of the present invention is obtained by organicizing an untreated layered double hydroxide (hereinafter simply referred to as “layered double hydroxide”) using an organic anion. It has been processed.
- the electrolyte of the present invention becomes a gel electrolyte by containing the organically modified layered double hydroxide (B). Therefore, in a dye-sensitized solar cell using the electrolyte, volatilization or Leakage is suppressed and stability is excellent.
- the layered double hydroxide will be described first, and then the organic treatment will be described.
- the layered double hydroxide generally comprises an oxide layer formed of an oxide composed of a metal ion containing a monovalent metal or a divalent metal and a metal ion containing a trivalent metal, an inorganic anion intermediate layer, However, in the layered structure which is laminated
- This layered double hydroxide usually has a crystal structure.
- the monovalent metal include Li.
- the divalent metal include Mg, Ca, Mn, Fe, Co, Ni, Cu, and Zn.
- the trivalent metal include Al, Fe, Cr, Mn, Co, Ni, La, and Ga.
- the oxide layer refers to a layer in which an oxygen octahedron centered on a metal ion containing a monovalent or divalent metal and a metal ion containing a trivalent metal forms a layer in two dimensions.
- the layered double hydroxide includes “hydrotalcite” and “hydrotalcite-like compound”.
- “Hydrotalcite” is the name given to the natural mineral Mg 6 Al 2 (OH) 16 .CO 3 .4-5H 2 O.
- “Hydrotalcite-like compound” is a name given to minerals having the same or similar crystal structure as “hydrotalcite” (for example, stichtite, pyroaulite, leebesite, tachovit, onesite, iowite, etc.). Yes, it can be synthesized.
- Such a “hydrotalcite-like compound” is represented by the following formula (7) or (8), for example.
- M 2+ is a metal ion of a divalent metal that is at least one selected from the group consisting of Mg, Ca, Mn, Fe, Co, Ni, Cu and Zn.
- M 3+ is a metal of a trivalent metal that is at least one selected from the group consisting of Al, Fe, Cr, Mn, Co, Ni, La, and Ga. Ion.
- a n ⁇ is at least one selected from the group consisting of OH ⁇ , ClO 3 ⁇ , ClO 4 ⁇ , F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , CO 3 2 ⁇ , NO 3 ⁇ , and SO 4 2 ⁇ .
- n-valent inorganic anion that is a seed.
- x is a positive number of 0 ⁇ x ⁇ 0.5
- m is a positive number of 0 ⁇ m
- n is a valence of the inorganic anion.
- the divalent-trivalent system (combination of divalent metal ions and trivalent metal ions) represented by the above formula (7) is a non-stoichiometric compound (0 ⁇ x ⁇ 0.5), and various combinations and compositions Ratios of compounds can be synthesized.
- the general mechanism of the crystal structure of this compound is as follows. First, a part of the divalent metal ion (M 2+ ) is replaced with a trivalent metal ion (M 3+ ), which is similar to brucite (Brucite, Mg (OH) 2 ) having a positive charge. A basic layer ([M 2 + 1 ⁇ x M 3+ x (OH) 2 ] x + ) is formed. In order to maintain electrical neutrality with this basic layer, a negatively charged inorganic anion intermediate layer ([A n ⁇ x / n ⁇ mH 2 O] x ⁇ ) is formed. A layered structure composed of an anionic intermediate layer is formed. And in this layer structure, the water molecule is normally hydrogen-bonded with the hydroxyl group of the basic layer, and maintains the state in harmony with the anion intermediate layer.
- Hydrotalcite and hydrotalcite-like compounds have a structural unit consisting of a positively charged basic layer, an inorganic anionic intermediate layer that electrically neutralizes the positive, and crystal water. These are known to exhibit almost similar properties except for the difference in structural destruction temperature, have solid basicity and anion exchange properties, and perform specific reactions such as intercalation and regeneration reactions. Show.
- the anion exchange capacity of the layered double hydroxide is preferably 150 to 550 meq / 100 g.
- Commercially available products can be used as such layered double hydroxides, for example, Mg—Al carbonate type LDH (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd.), Mg—Zn—Al carbonate.
- Type LDH (trade name: Alma Kaiser, manufactured by Kyowa Chemical Industry Co., Ltd.), Mg-Al carbonate type LDH (trade name: Kyoward 500, manufactured by Kyowa Chemical Industry Co., Ltd.), Mg-Al carbonate type LDH (trade name: Kyoward 1000) , Manufactured by Kyowa Chemical Industry Co., Ltd.), Mg-Al carbonate type LDH (trade name: STABIACE HT-1, manufactured by Sakai Chemical Industry Co., Ltd., Mg-Al carbonate type LDH (trade name: STABIACE HT-7, Sakai Chemical Industry Co., Ltd.)
- Mg-Al carbonate type LDH (trade name: STABIACE HT-P, manufactured by Sakai Chemical Industry Co., Ltd.) is preferably used.
- Organic anion used for the organic treatment is not particularly limited as long as it is an anion containing at least one carbon atom. However, because it is hydrophobized, the moisture resistance of the photoelectric conversion element of the present invention is excellent.
- An organic anion having 3 or more carbon atoms is preferable, an organic anion having 3 to 25 carbon atoms is more preferable, and an organic anion having 5 to 20 carbon atoms is further preferable.
- the organic anion is preferably an organic anion having an onium base as a substituent because the photoelectric conversion efficiency of the photoelectric conversion element of the present invention is improved. Details of such an organic anion will be described later.
- Examples of the organic anion used for the organic treatment include an organic anion derived from an organic acid.
- Examples of the organic anion include a carboxylic acid represented by the following formula (9) and a formula (10) below. Examples thereof include sulfonic acids shown, and organic phosphorus compounds represented by the following formulas (11) to (14).
- R 8 is an alkyl group having 1 to 24 carbon atoms which may have a substituent or a hetero atom, a carbon number which may have a substituent or a hetero atom.
- a plurality of R 8 may be the same or different.
- alkyl group having 1 to 24 carbon atoms which may have a substituent represented by R 8 include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henocosyl, docosyl, tricosyl, tetracosyl, etc.
- alkyl groups may be linear or branched; these groups include fluorine atom, methyl group, ethyl group, hydroxy group, nitrile group, amino group, methoxy group, ethoxy group, isopropyloxy group, Phenyl, naphthyl, phenoxy, naphthyloxy, onium base, etc. And the like; alkyl group having a carbon number of 24 or less.
- Examples of the alkenyl group having 2 to 24 carbon atoms which may have a substituent represented by R 8 include a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group.
- Examples of the aryl group having 6 to 20 carbon atoms which may have a substituent represented by R 8 include aryl groups such as phenyl group and naphthyl group; these groups include fluorine atom, methyl group, ethyl group, hydroxy group
- aryl group having a total number of carbon atoms of 20 or less wherein a group, nitrile group, amino group, methoxy group, ethoxy group, isopropyloxy group, phenyl group, naphthyl group, phenoxy group, naphthyloxy group, onium base, or the like is substituted; Etc.
- Examples of the carboxylic acid represented by the above formula (9) include ethanoic acid (acetic acid), propanoic acid (propionic acid), butanoic acid (butyric acid), pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decane.
- Acid dodecanoic acid (lauric acid), tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid (stearic acid), 9-hexadecenoic acid (palmitoleic acid), cis-9-octadecenoic acid (oleic acid), benzenecarboxylic acid (benzoic acid) Acid), linoleic acid, linolenic acid, arachidonic acid, salicylic acid, phenylpropenoic acid, trihydroxybenzoic acid, carboxylic acids having an onium base as a substituent, and the like. These may be used alone.
- More than one species may be used in combination.
- a carboxylic acid having 3 or more carbon atoms is preferable and a carboxylic acid having 5 to 20 carbon atoms is more preferable because the photoelectric conversion element of the present invention has excellent moisture resistance.
- pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid (lauric acid), tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid (stearic acid), oleic acid, linoleic acid Acid, linolenic acid, arachidonic acid, salicylic acid, phenylpropenoic acid, trihydroxybenzoic acid are preferred, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid (lauric acid), octadecanoic acid (stearic acid) Acid), oleic acid, linoleic acid, salicylic acid, phenylprop
- Examples of the sulfonic acid represented by the above formula (10) include methanesulfonic acid, 1-hexanesulfonic acid, 1-octanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, benzenesulfonic acid, and 4-methyl. Examples thereof include benzenesulfonic acid, 2-dodecylbenzenesulfonic acid, camphorsulfonic acid, and sulfonic acids having an onium base as a substituent. These may be used alone or in combination of two or more. .
- a sulfonic acid having 3 or more carbon atoms is preferable and a sulfonic acid having 5 to 20 carbon atoms is more preferable because the photoelectric conversion element of the present invention has excellent moisture resistance.
- Examples of the phosphoric acid represented by the above formulas (11) to (14) include, for example, methyl phosphate (mono-substituted, di-substituted, mixtures thereof), ethyl phosphate (mono-substituted, di-substituted, mixtures thereof) ), Butyl phosphate (mono-substituted, di-substituted, mixtures thereof), ethylhexyl phosphate (mono-substituted, di-substituted, mixtures thereof), butoxyethyl phosphate mono-substituted, di-substituted, mixtures thereof), Decyl phosphate (mono-substituted, di-substituted, mixtures thereof) Dodecyl phosphate (mono-substituted, di-substituted, mixtures), methoxypolyethylene glycol phosphate (mono-substituted, di-sub
- These phosphoric acid derivatives having an onium base as a substituent may be used, and these may be used alone. Two or more kinds may be used in combination. Among these, a phosphoric acid derivative having 3 or more carbon atoms is preferable, and a phosphoric acid derivative having 5 to 20 carbon atoms is more preferable because the photoelectric conversion element of the present invention has excellent moisture resistance.
- ethyl hexyl phosphate (mono-substituted, di-substituted, mixtures thereof), butoxyethyl phosphate mono-substituted, di-substituted, mixtures thereof), decyl phosphate (mono-substituted, di-substituted, them) Mixture)
- Dodecyl phosphate (mono-substituted, di-substituted, mixtures), methoxypolyethylene glycol phosphate (mono-substituted, di-substituted, mixtures), methacryloyloxypolyethylene glycol phosphate (mono-substituted, di-substituted) Hexylphosphonic acid, octylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, and methoxyphenylphosphonic acid.
- Examples of the cation species (Y + ) in the onium base (—Y + Z ⁇ ) include, for example, imidazolium ions, pyridinium ions, pyrrolidinium ions, piperidinium ions described as cations possessed by the organic salt compound (A). , Ammonium ion, sulfonium ion, phosphonium ion, oxonium ion, and imidazolium ion, pyrrolidinium ion, piperidinium ion, ammonium ion because the photoelectric conversion efficiency of the photoelectric conversion element of the present invention is improved. More preferred are sulfonium ion and phosphonium ion.
- the onium salt includes, for example, those described as anions that the organic salt compound (A) has and the like, also, anion - - anion in (Z) (-Y + Z) (Z -) , the Although it is not necessarily limited because it can be easily exchanged with an anion of the organic salt compound (A), bromine ion (Br ⁇ ), because the photoelectric conversion efficiency of the photoelectric conversion element of the present invention becomes better.
- Iodine ion (I ⁇ ) is preferable, and iodine ion (I ⁇ ) is preferable.
- the onium base (—Y + Z ⁇ ) is arranged along the oxide layer, for example, Since a path of iodine ions (I ⁇ ) is formed, it is assumed that the photoelectric conversion efficiency of the photoelectric conversion element is improved.
- Such an organic anion preferably has an onium base (—Y + Z ⁇ ), and examples thereof include organic anions represented by the following formulas (15) to (18).
- n represents an integer of 1 to 24 and is preferably an integer of 1 to 20.
- Y + and Z ⁇ are as described above.
- Specific examples of the organic anions represented by the above formulas (15) to (18) include those described in Examples described later.
- Ion exchange is performed by intercalating a target anion (organic anion). Examples of such ion exchange include direct ion exchange in an aqueous solution and ion exchange by a regeneration method.
- a layered double hydroxide containing a monovalent anion between layers is used.
- nitrogen gas is preferably bubbled. This is because the layered double hydroxide has a specific affinity for carbonate ions, so when most anions exchange with carbonate ions to form carbonate ion type layered double hydroxides, the target anions ( This is because ion exchange with the organic anion) may not be possible.
- Ion exchange by the regeneration method intercalates the target anion (organic anion) by utilizing the property that when the thermal decomposition product of layered double hydroxide is immersed in an aqueous solution, it is regenerated into layered double hydroxide. It is. That is, when the thermal decomposition product of the layered double hydroxide is immersed in an aqueous solution, the thermal decomposition product takes in the anion present in the aqueous solution and regenerates it. Therefore, the target anion (organic anion) is charged in the aqueous solution in advance. Thus, the organic anion can be intercalated between the layers during regeneration.
- the heating temperature for obtaining the thermal decomposition product of the layered double hydroxide is preferably 400 to 800 ° C. If the heating temperature is within the above upper limit, the tendency to make it difficult to regenerate to the layered double hydroxide is suppressed, and if the heating temperature is at least the above lower limit, the thermal decomposition is insufficient or The tendency for ions to remain is suppressed.
- the content of the organically modified layered double hydroxide (B) thus obtained is preferably 1 to 250 parts by mass in terms of inorganic matter with respect to 100 parts by mass of the organic salt compound (A). It is more preferably 2 to 150 parts by mass.
- inorganic conversion means the mass which excluded the anion between layers in the said organic-ized layered double hydroxide (B), ie, the organic anion mentioned above.
- the organic layered double hydroxide (B) is formed by the ion exchange reaction, but the layers of the layered double hydroxide need not necessarily be completely intercalated with organic anions.
- the electrolyte of the present invention can be added with a redox pair (redox pair).
- redox pair any one generally used or usable in a dye-sensitized solar cell can be used as long as the object of the present invention is not impaired.
- iodine / iodide ions, bromine / bromide ions, and the like can be used.
- metal iodides of iodine and LiI, NaI, KI, etc. iodide salts of iodine and quaternary imidazolium compounds, iodide salts of iodine and quaternary pyridinium compounds, iodine and tetraalkylammonium compounds
- Iodide / iodide ion pairs such as iodide salts with; bromide and metal bromides with LiBr, NaBr, KBr, etc., bromide salts with bromine and quaternary imidazolium compounds, bromide salts with bromine and quaternary pyridinium compounds, Bromine / bromide ions such as bromide salts of bromine and tetraalkylammonium compounds; metal complexes such as ferrocyanate-ferricyanate, ferrocene-ferricinium salts, cobalt complexes; di (
- the electrolyte of this invention can add inorganic salt and / or organic salt from a viewpoint of improving the short circuit current of the photoelectric conversion element of this invention.
- inorganic salts and organic salts include alkali metal, alkaline earth metal salts, and the like.
- lithium iodide sodium iodide, potassium iodide, magnesium iodide, calcium iodide
- examples include lithium trifluoroacetate, sodium trifluoroacetate, lithium thiocyanate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium perchlorate, lithium trifluoromethanesulfonate, and lithium bis (trifluoromethanesulfonyl) imide. These may be used alone or in combination of two or more.
- the amount of the inorganic salt or organic salt added is not particularly limited, and can be the same as before as long as the object of the present invention is not impaired.
- pyridines and benzimidazoles can be added to the electrolyte of this invention from a viewpoint of improving the open circuit voltage of the photoelectric conversion element of this invention.
- alkyl pyridines such as methyl pyridine, ethyl pyridine, propyl pyridine and butyl pyridine
- alkyl imidazoles such as methyl imidazole, ethyl imidazole and propyl imidazole
- alkylbenzimidazoles such as imidazole, and the like. These may be used alone or in combination of two or more.
- the addition amount of pyridines and benzimidazoles is not particularly limited and can be the same as before as long as the object of the present invention is not impaired.
- Organic solvent (C) optionally contained in the electrolyte of the present invention is not particularly limited as long as it is an organic solvent having a boiling point of 150 ° C. or higher and a relative dielectric constant of 20 or higher.
- the boiling point refers to the boiling point at 1 atm
- the relative dielectric constant is measured using a liquid dielectric constant meter (liquid dielectric constant meter M-870, manufactured by Nippon Lucas Co., Ltd.) to which 25 ° C. and 10 kHz are applied. Value.
- Specific examples of the organic solvent (C) include those described in the specification of Japanese Patent Application No. 2010-243682.
- the content is preferably 0.5 to 40 parts by mass with respect to 100 parts by mass of the organic salt compound (A), and is 1 to 30 parts by mass. Is more preferable.
- the photoelectric conversion efficiency of the photoelectric conversion element of the present invention becomes better.
- the ratio (C / A) of the said organic solvent (C) and the said organic salt compound (A) keeps the outstanding moisture resistance of the photoelectric conversion element of this invention.
- the photosensitizing dye especially organic dye
- it is preferably 29/71 to 0.5 / 99.5, and 23/77 More preferably, it is ⁇ 1 / 99.
- the method for producing the electrolyte of the present invention is not particularly limited.
- the organic salt compound (A), the organically modified layered double hydroxide (B) and the like are mixed, a ball mill, a sand mill, a pigment disperser, a grinder, Produced by thoroughly mixing and uniformly dispersing (kneading) at room temperature or under heating (for example, 40 to 150 ° C.) using an ultrasonic disperser, homogenizer, planetary mixer, Hobart mixer, roll, kneader, etc. be able to.
- an organic solvent for example, toluene or the like
- the organic solvent may be distilled off after mixing.
- FIG. 1 is a schematic cross-sectional view showing an example of the basic configuration of the photoelectric conversion element of the present invention.
- the photoelectric conversion element of the present invention includes a photoelectrode having a transparent conductive film and a metal oxide semiconductor porous film, a counter electrode disposed to face the photoelectrode, and the photoelectrode and the counter electrode. And an electrolyte layer disposed thereon.
- the photoelectrode includes a transparent substrate 1, a transparent conductive film 2, and an oxide semiconductor porous film 3.
- the transparent substrate 1 preferably has good light transmittance.
- Specific examples thereof include a glass substrate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyphenylene sulfide, and cyclic olefin polymer.
- resin substrates (films) such as polyethersulfone, polysulfone, polyetherimide, polyarylate, triacetylcellulose, and polymethylmethacrylate.
- the transparent conductive film 2 specifically, for example, conductive metal oxides such as tin oxide doped with antimony or fluorine, zinc oxide doped with aluminum or gallium, indium oxide doped with tin, etc. Is mentioned.
- the thickness of the transparent conductive film 2 is preferably about 0.01 to 1.0 ⁇ m.
- the method for providing the transparent conductive film 2 is not particularly limited, and examples thereof include a coating method, a sputtering method, a vacuum deposition method, a spray pyrolysis method, a chemical vapor deposition method (CVD), and a sol-gel method.
- the oxide semiconductor porous film 3 is obtained by applying a dispersion of oxide semiconductor fine particles on the transparent conductive film 2.
- oxide semiconductor fine particles include titanium oxide, tin oxide, zinc oxide, tungsten oxide, zirconium oxide, hafnium oxide, strontium oxide, vanadium oxide, niobium oxide, and the like. You may use independently and may use 2 or more types together.
- the dispersion is obtained by mixing the oxide semiconductor fine particles and the dispersion medium with a dispersing machine such as a sand mill, a bead mill, a ball mill, a three roll mill, a colloid mill, an ultrasonic homogenizer, a Henschel mixer, or a jet mill.
- the dispersion is preferably obtained by mixing with a disperser and then subjected to ultrasonic treatment using an ultrasonic homogenizer or the like immediately before use (coating). By performing ultrasonic treatment immediately before use, the photoelectric conversion efficiency of the photoelectric conversion element of the present invention becomes better.
- the oxide semiconductor porous film formed using a dispersion subjected to ultrasonic treatment immediately before use is easily filled with the electrolyte of the present invention containing the organic salt compound (A), This is thought to be due to an increase in dye adsorption capacity.
- acetylacetone, hydrochloric acid, nitric acid, a surfactant, a chelating agent, or the like may be added to the dispersion. Therefore, a polymer such as polyethylene oxide and polyvinyl alcohol, a cellulose-based thickener, or the like may be added.
- dispersion examples include titanium oxide pastes SP100 and SP200 (both manufactured by Showa Denko KK), titanium oxide fine particles Ti-Nanoxide® T (manufactured by Solaronics), Ti-Nanoxide® D (manufactured by Solaronics), Ti-Nanoxide®T / SP (manufactured by Solaronics), Ti-Nanoxide® D / SP (manufactured by Solaronics), titania coating paste PECC01 (manufactured by Pexel Technologies), titania particle paste PST-18NR, PST-400C It is also possible to use commercially available products such as those manufactured by the same company.
- a known wet film forming method can be used as a method for applying the dispersion on the transparent conductive film.
- a known wet film forming method can be used.
- Specific examples of the wet film forming method include a screen printing method, an ink jet printing method, a roll coating method, a doctor blade method, a spin coating method, and a spray coating method.
- heat treatment for the purpose of improving electronic contact between the fine particles, improving adhesion with the transparent conductive film, and improving film strength, heat treatment, chemical treatment, plasma, It is preferable to perform ozone treatment or the like.
- the temperature of the heat treatment is preferably 40 ° C. to 700 ° C., and preferably 40 ° C. to 650 ° C.
- the heat treatment time is not particularly limited, but is usually about 10 seconds to 24 hours.
- Specific examples of the chemical treatment include chemical plating treatment using a titanium tetrachloride aqueous solution, chemical adsorption treatment using a carboxylic acid derivative, and electrochemical plating treatment using a titanium trichloride aqueous solution.
- the counter electrode is an electrode 5 disposed to face the photoelectrode 4.
- a metal substrate a glass substrate having a conductive film on the surface, a resin substrate, or the like can be used.
- metal substrate metals such as platinum, gold, silver, copper, aluminum, indium, and titanium can be used.
- resin substrate in addition to the substrate (film) exemplified as the transparent substrate 1 constituting the photoelectrode 4, a general resin substrate which is opaque or inferior in transparency can also be used.
- metals such as platinum, gold, silver, copper, aluminum, indium and titanium; carbon; tin oxide; tin oxide doped with antimony and fluorine; zinc oxide; doped with aluminum and gallium Zinc oxide; indium oxide doped with tin; conductive metal oxides such as;
- the thickness and formation method of the conductive film can be the same as those of the transparent conductive film 2 constituting the photoelectrode 4.
- the counter electrode 5 may be an electrode in which a conductive polymer film is formed on a substrate or a conductive polymer film electrode.
- the conductive polymer include polythiophene, polypyrrole, polyaniline, and the like.
- a method for forming a conductive polymer film on a substrate a conductive polymer film is formed on a substrate from a polymer dispersion using a dipping method, a spin coating method, or the like that is usually known as a wet film formation method. be able to.
- Examples of the conductive polymer dispersion include the polyaniline dispersion disclosed in JP-A-2006-169291, a commercially available polythiophene derivative aqueous dispersion (Vitron P, manufactured by Bayer), Mitsubishi Rayon Co., Ltd. (Aqua Save, polyaniline). Derivative aqueous solution) and the like can be used.
- a conductive polymer film can be formed on the substrate by an electrolytic polymerization method in addition to the above method.
- Conductive polymer film electrode is a casting that is usually known as a wet film-forming method from a self-supporting film or a conductive polymer dispersion obtained by peeling off a conductive polymer film formed on an electrode by electrolytic polymerization. It is also possible to use a self-supporting film formed using a method or a spin coating method.
- the conductive polymer dispersion referred to here is a conductive polymer dispersion in which conductive polymer fine particles are dispersed in a solvent and a conductive polymer is dissolved in a solvent. A functional polymer dispersion.
- the electrolyte layer is an electrolyte layer 6 provided between the photoelectrode 4 and the counter electrode 5, and the above-described electrolyte of the present invention is used in the photoelectric conversion element of the present invention.
- the photoelectric conversion element of the present invention uses the above-described electrolyte of the present invention, excellent moisture resistance can be achieved.
- the dye-sensitized solar cell of the present invention is one type of photoelectric conversion element in which a photosensitizing dye is supported on the photoelectrode that constitutes the above-described photoelectric conversion element of the present invention.
- the photosensitizing dye is not particularly limited as long as it is a dye having absorption in the visible light region and / or the infrared light region, and a metal complex, an organic dye, or the like can be used.
- a ruthenium complex dye for example, a ruthenium complex dye, an iron complex dye, an osmium complex dye, a platinum complex dye, an iridium complex dye or the like coordinated with a ligand such as a bipyridine structure or a terpyridine structure may be used.
- organic dyes include porphyrin dyes, phthalocyanine dyes, cyanine dyes, merocyanine dyes, xanthene dyes, coumarin dyes, indole dyes, fluorene dyes, and triphenylamine dyes.
- dye etc. can be used.
- the method for supporting the photosensitizing dye is not particularly limited. For example, the dye is dissolved in water, an alcohol solvent, a nitrile solvent, and the oxide semiconductor porous film 3 is immersed in the dye solution or the dye solution. Is supported on the oxide semiconductor porous film 3 by coating.
- the organic layered double hydroxide was obtained by a regeneration method using the property of regenerating the layered double hydroxide.
- the layered double hydroxide 1 (Mg—Al-based layered double hydroxide, trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd.), which is a commercial product, is fired at 500 ° C. for 12 hours to obtain the fired layered double hydroxide.
- an aqueous solution of sodium stearate manufactured by Kanto Chemical Co., Inc.
- 0.1M was prepared using ion-exchanged water (bubbled with nitrogen gas and decarboxylated).
- an organic anion represented by the following formula (23) derived from bromopropanephosphonic acid was used in the same manner as the organically modified layered double hydroxide 1 except that bromopropanephosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.
- a precursor of layered double hydroxide intercalated was obtained.
- 0.1 M of an aqueous solution of 1-methylimidazole manufactured by Aldrich
- 2 g of the precursor was added to 1 L of the aqueous solution, followed by stirring at room temperature for 24 hours. Thereafter, filtration and washing were repeated three times, followed by drying and pulverization to prepare an organically modified layered double hydroxide 38 in which an organic anion represented by the following formula (24) was intercalated.
- the solvent ethanol was used for the organic layered double hydroxides 5, 12 and 17, and the layered double hydroxide 1 and toluene was used for the other organic layered double hydroxides. Thereafter, the obtained precipitate was washed with a solvent used and dried to obtain a gel-like substance. Next, iodine and N-methylbenzimidazole shown in the following tables were added to the obtained gel substance at a composition ratio shown in the following tables and mixed. When the organic layered double hydroxide 1 to 45 and the layered double hydroxide 1 were not used, the organic salt compounds 1 and 2 were used as electrolytes as they were.
- a titanium oxide paste Ti-Nanoxide D (manufactured by Solaronix) is applied onto transparent conductive glass (FTO glass, surface resistance 15 ⁇ / ⁇ , manufactured by Nippon Sheet Glass Co., Ltd.), dried at room temperature, and then heated to 450 ° C. Was sintered for 30 minutes to produce a photoelectrode in which a porous titanium oxide film was formed on transparent conductive glass.
- the produced photoelectrode was converted into a ruthenium complex dye (cis- (diisothiocyanate) -N, N′-bis (2,2′-bipyridyl-4,4′-dicarboxyl acid) ruthenium (II) complex) (Ruthenium). It was immersed in a butyl alcohol / acetonitrile solution (volume ratio: 1/1, concentration 3 ⁇ 10 ⁇ 4 mol / L) of 535-bisTBA (manufactured by Solaronix) for 4 hours.
- a heat-sealing film was interposed between the photoelectrode and the platinum counter electrode, and heat-sealing was performed at 150 ° C. to seal between the electrodes, thereby obtaining a dye-sensitized solar cell.
- the dye-sensitized solar cell is the same as the dye-sensitized solar cell (photosensitizing dye: ruthenium complex dye) described above except that an indoline dye (D205, manufactured by Mitsubishi Paper Industries) is used instead of the ruthenium complex dye.
- a battery photosensitizing dye: organic dye was prepared.
- ⁇ Photoelectric conversion efficiency> As shown in FIG. 2, a solar simulator is used as a light source, and AM1.5 simulated sunlight is irradiated from the photoelectrode side with a light intensity of 100 mW / cm 2 , and a current-voltage measuring device (Digital Source Meter 2400 manufactured by Keithley Instruments Co., Ltd.). ) To obtain the conversion efficiency [%].
- ⁇ Moisture resistance (maintenance rate)> The dye-sensitized solar cell whose photoelectric conversion efficiency was measured was allowed to stand for 1000 hours under the conditions of 40 ° C. and 85% RH. Thereafter, the photoelectric conversion efficiency was measured by the same method as described above, and the maintenance rate (photoelectricity after humidification) Conversion efficiency / photoelectric conversion efficiency before humidification ⁇ 100) [%] was calculated. As a result, if the maintenance rate of the photoelectric conversion efficiency is 80 [%] or more, it can be evaluated that the rate of change is small and the moisture resistance is excellent.
- ⁇ Moisture and heat resistance (maintenance rate)> The dye-sensitized solar cell whose photoelectric conversion efficiency has been measured is allowed to stand for 1000 hours under the conditions of 85 ° C. and 85% RH, and then the photoelectric conversion efficiency is measured by the same method as described above, and the retention rate (after heating and humidification) The photoelectric conversion efficiency / photoelectric conversion efficiency before heating / humidification ⁇ 100) [%] was calculated. As a result, if the maintenance rate of the photoelectric conversion efficiency is 80 [%] or more, it can be evaluated that the rate of change is small and the heat and moisture resistance is excellent.
- Organic salt compound 1 (MPImI): 1-methyl-3-propylimidazolium iodide (manufactured by Tokyo Chemical Industry Co., Ltd.)
- Organic salt compound 2 (EMImSCN): 1-ethyl-3-methylimidazolium thiocyanate (Merck)
- Examples 1 to 135 all have a small rate of change in photoelectric conversion efficiency (heat resistance, moisture resistance, heat and humidity resistance), and even when left for a long period of time. It was found that liquid leakage and the like were prevented and the stability was excellent. It was also found that Examples 22 to 32, 66 to 89, 90 to 114, and 126 to 135 using the organic salt compound 2 were all excellent in heat resistance.
- Examples 1 to 6, 8 to 15, 17 to 20 and Examples 7, 16, and 21 are compared, implementation using organic layered double hydroxides 1 to 4, 6 to 11, and 13 to 16 is performed. Examples 1 to 6, 8 to 15, and 17 to 20 were found to be superior in moisture resistance and moist heat resistance to Examples 7, 16, and 21 using the organically modified layered double hydroxides 5, 12, and 17. . This was the same in Examples 22 to 32.
- Examples 33 to 65 using the organically modified layered double hydroxides 18 to 45 are excellent in photoelectric conversion efficiency.
- Example 2 in which the amount of the organically modified layered double hydroxide is the same amount.
- Example 33 and Example 34 were contrasted, it turned out that the direction of Example 33 with much organic-ized layered double hydroxide 18 is more excellent in photoelectric conversion efficiency.
- the same tendency was observed in Examples 35 and 36, Examples 37 and 38, Examples 48 and 49, and Examples 50 and 51.
- This tendency was the same in Examples 90 to 114 in which the organic salt compound and the organic solvent were used in combination.
- This tendency was the same in Examples 115 to 135 using organic dyes as photosensitizing dyes instead of ruthenium complex dyes.
- Comparative Examples 1 to 14 which do not use the organic layered double hydroxides 1 to 45 have a large rate of change in photoelectric conversion efficiency, and liquid leakage occurs when left for a long period of time, which is stable. It turned out to be inferior.
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Abstract
Description
非シリコン系太陽電池の中でも特に、スイスのグレツェルらが開発した色素増感太陽電池は、有機材料を用いた太陽電池の中では光電変換効率が高く、シリコン系太陽電池と比較して製造コストが安い等の利点もあり、新しいタイプの太陽電池として注目を集めている。
例えば、特許文献1には、「(i)層状粘土鉱物及び/又は有機化層状粘土鉱物並びに(ii)イオン性液体を含んでなる光電変換素子用電解質。」が記載されている([請求項1])。
すなわち、本発明は、以下の(1)~(7)を提供する。
本発明の光電変換素子用電解質(以下、単に「本発明の電解質」ともいう。)は、第3級または第4級カチオンを有する有機塩化合物(A)と、有機アニオンを用いて有機化処理された層状複水酸化物である有機化層状複水酸化物(B)と、を含有する光電変換素子用電解質である。
以下では、まず、本発明の電解質の各成分について詳述する。
本発明の電解質で用いられる有機塩化合物(A)は、第3級または第4級カチオンならびにその対イオンであるアニオンを有する有機塩化合物であり、常温で液体(いわゆるイオン性液体)であるのが好ましい。
ここで、第3級カチオンとは、正電荷を有する周期律表第16族元素(例えば、酸素原子、硫黄原子等)が水素原子を有していないカチオンをいい、第4級カチオンとは、正電荷を有する周期律表第15族元素(例えば、窒素原子、リン原子等)が水素原子を有していないカチオンをいう。
式(2)中、Qは、窒素原子、酸素原子、リン原子または硫黄原子を表し、R4、R5、R6およびR7は、それぞれ独立に水素原子または炭素数1~8の炭化水素基を表し、ヘテロ原子を含んでいてもよい。ただし、Qが酸素原子または硫黄原子の場合、R7は存在せず、Qが硫黄原子の場合、R4およびR5は連結していてもよい。
次いで、上記式(1)中のR1が有していてもよい、炭素数1~20のヘテロ原子を含んでいてもよい置換基としては、炭素数1~20のアルキル基(例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、エチルヘキシル基、ノニル基、デシル基、ドデシル基、ウンデシル基、ヘキサデシル基、オクタデシル基、シクロプロピルメチル基、トリフルオロエチル基等)、炭素数2~20のアルケニル基(例えば、ビニル基、アリル基等)、炭素数6~20のアリール基(例えば、フェニル基、トリル基、ナフチル基等)、炭素数7~20のアラルキル基(例えば、ベンジル基、フェニルエチル基、フェニルプロピル基等)、炭素数1~20のアルコキシ基(例えば、メトキシ基、エトキシ基、n-プロポキシ基、イソ-プロポキシ基、n-ブトキシ基、tert-ブトキシ基、sec-ブトキシ基、n-ペントキシ基、n-ヘキソキシ基、1,2-ジメチルブトキシ基、ヘプトキシ基、オクトキシ基、ノニノキシ基、デシロキシ基、フェノキシ基、メチルフェノキシ基、エチルフェノキシ基等)、炭素数2~20のアルキルアルコキシ基(例えば、メチレンメトキシ基(-CH2OCH3)、エチレンメトキシ基(-CH2CH2OCH3)、n-プロピレン-イソ-プロポキシ基(-CH2CH2CH2OCH(CH3)2)、メチレン-t-ブトキシ基(-CH2-O-C(CH3)3、ブチレンメトキシ基、ペンチレンメトキシ基、へキシレンメトキシ基、ヘプチレンメトキシ基、オクチレンメトキシ基、ノニレンメトキシ基、デシレンメトキシ基、メチレンエトキシ基、エチレンエトキシ基、プロピレンエトキシ基、ブチレンエトキシ基、ペンチレンエトキシ基、へキシレンエトキシ基、エチレンエトキシメトキシ基、シクロプロピルメトキシ基、シクロヘキシルメトキシ基、メチルフェノキシ基、メトキシフェノキシ基、エトキシフェノキシ基、フェノキシフェノキシ基等)であるのが好ましい。また、上記式(1)中のR1は、この置換基を2以上有していてもよい。
具体的には、下記式(3)~(6)のいずれかで表されるカチオンが好適に例示される。
このうち、下記式(3)および(5)で表されるカチオンであるのが、本発明の電解質を用いた光電変換素子(以下、「本発明の光電変換素子」ともいう。)の光電変換効率がより良好となる傾向がある理由から好ましい。
より具体的には、以下に示すカチオンが挙げられる。
具体的には、以下に示すカチオンが好適に例示される。
このうち、脂肪族4級アンモニウムイオンであるのが、本発明の光電変換素子の光電変換効率がより良好となる傾向がある理由から好ましい。
このうち、本発明の光電変換素子の光電変換効率がより良好となる傾向がある理由から、臭素イオン(Br-)、ヨウ素イオン(I-)であるのが好ましく、ヨウ素イオン(I-)であるのがより好ましい。
また、本発明の光電変換素子の耐熱性が良好になるという観点からは、チオシアネートアニオン(SCN-)(連結異性体であるイソチオシアネートアニオンを含む。以下同様。)が好ましい。
中でも、本発明の光電変換素子の光電変換効率がより良好になるという理由からは、カチオンとしてイミダゾリウムイオンを有し、アニオンとしてヨウ素イオンを有する有機塩化合物が好ましく、本発明の光電変換素子の耐熱性が良好になるという理由からは、チオシアネートアニオンを有する有機塩化合物が好ましく、イミダゾリウムイオンおよびヨウ素イオンを有する有機塩化合物と、チオシアネートアニオンを有する有機塩化合物とを併用することがより好ましい。
本発明の電解質に用いられる有機化層状複水酸化物(B)は、未処理の層状複水酸化物(以下、単に「層状複水酸化物」という。)を、有機アニオンを用いて有機化処理したものである。
本発明の電解質は、上記有機化層状複水酸化物(B)を含有することにより、ゲル状の電解質となるため、これを用いた色素増感太陽電池においては、長期間放置後も揮発や液漏れが抑制され、安定性に優れる。
以下では、まず、層状複水酸化物について説明し、次いで、有機化処理について説明する。
層状複水酸化物は、一般には、1価金属または2価金属を含む金属イオンと3価金属を含む金属イオンとから構成される酸化物により形成された酸化物層と、無機アニオン中間層とが、交互に積層している層状構造において、その層間に水分子を挟み込んでいる(複水している)構造を有する。この層状複水酸化物は、通常、結晶構造になっている。
上記1価金属としては、例えば、Liが挙げられる。上記2価金属としては、例えば、Mg,Ca,Mn,Fe,Co,Ni,Cu,Zn等が挙げられる。上記3価金属としては、例えば、Al,Fe,Cr,Mn,Co,Ni,La,Ga等が挙げられる。
上記酸化物層とは、1価または2価金属を含む金属イオンと、3価金属を含む金属イオンとが中心に位置する酸素八面体が、2次元に連なって層を構成したものをいう。
「ハイドロタルサイト」は、天然鉱物Mg6Al2(OH)16・CO3・4~5H2Oに与えられた名称である。
「ハイドロタルサイト様化合物」は、「ハイドロタルサイト」と同一または類似の結晶構造をもつ鉱物(例えば、スティヒタイト、パイロオーライト、リーベサイト、タコヴァィト、オネサイト、アイオワイト等)に与えられた名称であり、合成も可能となったものである。このような「ハイドロタルサイト様化合物」は、例えば、下記式(7)または(8)で表わされる。
〔Li+ 1-xM3+ x(OH)2〕(2x-1)+〔An- (2x-1)/n・mH2O〕(2x-1)- (8)
このような層状複水酸化物としては、市販品を用いることができ、例えば、Mg-Al系炭酸型LDH(商品名:DHT-6、協和化学工業社製)、Mg-Zn-Al系炭酸型LDH(商品名:アルマカイザー、協和化学工業社製)、Mg-Al系炭酸型LDH(商品名:キョワード500、協和化学工業社製)、Mg-Al系炭酸型LDH(商品名:キョワード1000、協和化学工業社製)、Mg-Al系炭酸型LDH(商品名:STABIACE HT-1、堺化学工業社製、Mg-Al系炭酸型LDH(商品名:STABIACE HT-7、堺化学工業社製、Mg-Al系炭酸型LDH(商品名:STABIACE HT-P、堺化学工業社製)等が好適に用いられる。
有機化処理では、層状複水酸化物の層間に存在する交換性陰イオン(無機アニオン)を、有機アニオンとイオン交換する。
上記有機化処理に用いられる有機アニオンとしては、炭素原子を少なくとも1つ含有するアニオンであれば、特に限定されないが、疎水化されることで本発明の光電変換素子の耐湿性が優れるという理由から、炭素数3以上の有機アニオンであることが好ましく、炭素数3~25の有機アニオンであることがより好ましく、炭素数5~20の有機アニオンであることがさらに好ましい。
HO3S-R8 (10)
(HO)2P(=O)(OR8) (11)
(HO)P(=O)(OR8)2 (12)
(HO)2P(=O)R8 (13)
(HO)P(=O)R8 2 (14)
上記式(12)および(14)において、複数のR8は、同一であっても異なっていてもよい。
これらのうち、本発明の光電変換素子の耐湿性が優れるという理由からは、炭素数3以上のカルボン酸が好ましく、炭素数5~20のカルボン酸がより好ましい。具体的には、ペンタン酸、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、ドデカン酸(ラウリン酸)、テトラデカン酸、ヘキサデカン酸、ヘプタデカン酸、オクタデカン酸(ステアリン酸)、オレイン酸、リノール酸、リノレン酸、アラキドン酸、サリチル酸、フェニルプロペン酸、トリヒドロキシ安息香酸が好ましく、ペンタン酸、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、ドデカン酸(ラウリン酸)、オクタデカン酸(ステアリン酸)、オレイン酸、リノール酸、サリチル酸、フェニルプロペン酸、トリヒドロキシ安息香酸がより好ましい。
これらのうち、本発明の光電変換素子の耐湿性が優れるという理由からは、炭素数3以上のスルホン酸が好ましく、炭素数5~20のスルホン酸がより好ましい。具体的には、1-ヘキサンスルホン酸、1-オクタンスルホン酸、1-デカンスルホン酸、1-ドデカンスルホン酸、ベンゼンスルホン酸、4-メチルベンゼンスルホン酸、2-ドデシルベンゼンスルホン酸、カンファースルホン酸が好ましく、1-オクタンスルホン酸、1-デカンスルホン酸、1-ドデカンスルホン酸、ベンゼンスルホン酸、4-メチルベンゼンスルホン酸、2-ドデシルベンゼンスルホン酸、カンファースルホン酸がより好ましい。
これらのうち、本発明の光電変換素子の耐湿性が優れるという理由からは、炭素数3以上のリン酸誘導体が好ましく、炭素数5~20のリン酸誘導体がより好ましい。具体的には、リン酸エチルヘキシル(モノ置換体、ジ置換体、それら混合物)、リン酸ブトキシエチルモノ置換体、ジ置換体、それら混合物)、リン酸デシル(モノ置換体、ジ置換体、それら混合物)リン酸ドデシル(モノ置換体、ジ置換体、それら混合物)、リン酸メトキシポリエチレングリコール(モノ置換体、ジ置換体、それら混合物)、リン酸メタクリロイルオキシポリエチレングリコール(モノ置換体、ジ置換体、それら混合物)、ヘキシルホスホン酸、オクチルホスホン酸、デシルホスホン酸、ドデシルホスホン酸、 メトキシフェニルホスホン酸がより好ましい。
このような有機アニオンとしては、上記オニウム塩基(-Y+Z-)を有するものであるのが好ましく、例えば、下記式(15)~(18)で表される有機アニオンが挙げられる。
-OO2S-(CH2)n-Y+Z- (16)
-OP(=O)(OH)-(CH2)n-Y+Z- (17)
-C(CN)2-CO-O-(CH2)n-Y+Z- (18)
このような上記式(15)~(18)で表される有機アニオンの具体例としては、後述する実施例において記載するものが挙げられる。
イオン交換は、目的とする陰イオン(有機アニオン)をインターカレーションすることにより行われる。このようなイオン交換としては、例えば、水溶液中での直接のイオン交換、再生法によるイオン交換等が挙げられる。
すなわち、層状複水酸化物の加熱分解物を水溶液に浸すと、加熱分解物は水溶液中に存在するアニオンを取り込んで再生するため、予め目的とする陰イオン(有機アニオン)を水溶液中に仕込んでおくことで、再生の際に有機アニオンを層間にインターカレーションさせることができる。
ここで、層状複水酸化物の加熱分解物を得る場合の加熱温度としては、400~800℃であることが好ましい。加熱温度が上記上限値以内であれば、層状複水酸化物への再生が困難となる傾向が抑えられ、また、加熱温度が上記下限値以上であれば、加熱分解が不充分であったり炭酸イオンが残存したりする傾向が抑えられる。
ここで、無機物換算とは、上記有機化層状複水酸化物(B)における層間の陰イオン、すなわち上述した有機アニオンを除外した質量をいう。
また、上記有機化層状複水酸化物(B)は、上記イオン交換反応により形成されるが、層状複水酸化物の層間が、必ずしも有機アニオンで完全にインターカレーションされていなくても良い。
本発明の電解質は、本発明の光電変換素子の光電変換効率をより向上させる観点から、酸化還元対(レドックス対)を添加することができる。
酸化還元対としては、色素増感太陽電池において一般的に使用されているまたは使用することができる任意のものを本発明の目的を損なわない範囲で用いることができる。
例えば、ヨウ素/ヨウ化物イオン、臭素/臭化物イオン等を用いることができる。具体的には、ヨウ素とLiI、NaI、KI等との金属ヨウ化物、ヨウ素と4級イミダゾリウム化合物とのヨウ化物塩、ヨウ素と4級ピリジニウム化合物とのヨウ化物塩、ヨウ素とテトラアルキルアンモニウム化合物とのヨウ化物塩等のヨウ素/ヨウ化物イオン対;臭素とLiBr、NaBr、KBr等との金属臭化物、臭素と4級イミダゾリウム化合物との臭化物塩、臭素と4級ピリジニウム化合物との臭化物塩、臭素とテトラアルキルアンモニウム化合物との臭化物塩等の臭素/臭化物イオン;フェロシアン酸塩-フェリシアン酸塩、フェロセン-フェリシニウム塩、コバルト錯体等の金属錯体;ジ(ポリ)スルフィド化合物とメルカプト化合物との硫黄化合物;ハイドロキノン-キノン;ビオロゲン色素;等が挙げられ、これらを1種単独で用いてもよく、2種以上を併用してもよい。
これらのうち、ヨウ素/ヨウ化物イオン、臭素/臭素化物イオンが好ましい。
無機塩、有機塩としては、例えば、アルカリ金属、アルカリ土類金属塩等を挙げることができ、具体的には、ヨウ化リチウム、ヨウ化ナトリウム、ヨウ化カリウム、ヨウ化マグネシウム、ヨウ化カルシウム、トリフルオロ酢酸リチウム、トリフルオロ酢酸ナトリウム、チオシアン酸リチウム、四フッ化ホウ酸リチウム、六フッ化りん酸リチウム、過塩素酸リチウム、トリフルオロメタンスルホン酸リチウム、リチウムビス(トリフルオロメタンスルホニル)イミド等が挙げられ、これらを1種単独で用いてもよく、2種以上を併用してもよい。
無機塩、有機塩の添加量は、特に限定されず、本発明の目的を損なわない限り、従来通りとすることができる。
具体的には、メチルピリジン、エチルピリジン、プロピルピリジン、ブチルピリジン等のアルキルピリジン類;メチルイミダゾール、エチルイミダゾール、プロピルイミダゾール等のアルキルイミダゾール類;メチルベンズイミダゾール、エチルベンズイミダゾール、ブチルベンズイミダゾール、プロピルベンズイミダゾール等のアルキルベンズイミダゾール類;等が挙げられ、これらを1種単独で用いてもよく、2種以上を併用してもよい。
ピリジン類、ベンズイミダゾール類の添加量は、特に限定されず、本発明の目的を損なわない限り、従来通りとすることができる。
本発明の電解質が所望により含有する有機溶媒(C)は、沸点が150℃以上であり、比誘電率が20以上である有機溶媒であれば特に限定されない。
ここで、沸点とは、1気圧における沸点をいい、比誘電率とは、25℃および10kHzを印加させる液体用誘電率計(液体誘電率計M-870、日本ルフト社製)を用いて測定した値をいう。
有機溶媒(C)の具体例としては、特願2010-243682号の明細書に記載されているものを例示できる。
また、上記有機溶媒(C)を含有する場合の含有量は、上記有機塩化合物(A)100質量部に対して0.5~40質量部であるのが好ましく、1~30質量部であるのがより好ましい。含有量がこの範囲であると、本発明の光電変換素子の光電変換効率がより良好となる。
また、上記有機溶媒(C)を含有する場合、上記有機溶媒(C)と上記有機塩化合物(A)との比(C/A)は、本発明の光電変換素子の優れた耐湿性を保持し、かつ、本発明の色素増感太陽電池における光増感色素(特に有機色素)の溶出を抑制する観点から、29/71~0.5/99.5であるのが好ましく、23/77~1/99であるのがより好ましい。
本発明の電解質の製造方法は特に限定されず、例えば、上記有機塩化合物(A)、上記有機化層状複水酸化物(B)等を混合し、ボールミル、サンドミル、顔料分散機、すりつぶし機、超音波分散機、ホモジナイザー、プラネタリーミキサー、ホバートミキサー、ロール、ニーダー等を用いて室温下または加熱下(例えば40~150℃)で十分に混合し、均一に分散(混練)させることにより製造することができる。
ここで、上記混合には、必要に応じて有機溶剤(例えば、トルエン等)を併用し、混合後に有機溶剤を真空留去する方法を用いてもよい。
次に、本発明の光電変換素子および色素増感太陽電池について、図1を用いて詳述する。図1は、本発明の光電変換素子の基本構成の一例を示す模式断面図である。
上記光電極は、例えば、図1に示すように、透明基板1と透明導電膜2と酸化物半導体多孔質膜3により構成されている。
ここで、透明基板1は、光透過性が良好なものが好ましく、その具体例としては、ガラス基板の他、ポリスチレン、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート、ポリフェニレンスルフィド、環状オレフィンポリマー、ポリエーテルサルフォン、ポリスルフォン、ポリエーテルイミド、ポリアリレート、トリアセチルセルロース、ポリメタクリル酸メチル等の樹脂基板(フィルム)が挙げられる。
また、透明導電膜2の厚さは、0.01~1.0μm程度であるのが好ましい。
更に、透明導電膜2を設けるための方法は特に限定されず、例えば、塗布法、スパッタリング法、真空蒸着法、スプレーパイロリシス法、化学気相成長法(CVD)、ゾルゲル法等が挙げられる。
上記酸化物半導体微粒子としては、具体的には、例えば、酸化チタン、酸化スズ、酸化亜鉛、酸化タングステン、酸化ジルコニウム、酸化ハフニウム、酸化ストロンチウム、酸化バナジウム、酸化ニオブ等が挙げられ、これらを1種単独で用いてもよく、2種以上を併用してもよい。
また、上記分散液は、分散機で混合して得た後、使用(塗布)直前に、超音波ホモジナイザー等を用いて超音波処理を施すのが好ましい。使用直前に超音波処理を施すことにより、本発明の光電変換素子の光電変換効率がより良好となる。これは、使用直前に超音波処理を施した分散液を用いて形成した酸化物半導体多孔質膜に対して、上記有機塩化合物(A)を含有する本発明の電解質が充填されやすくなったり、色素の吸着能が高まったりしたためと考えられる。
さらに、上記分散液には、分散液中の上記酸化物半導体微粒子の再凝集を防ぐために、アセチルアセトン、塩酸、硝酸、界面活性剤、キレート剤等を添加してもよく、分散液の増粘のために、ポリエチレンオキシド、ポリビニルアルコール等の高分子やセルロース系の増粘剤等を添加してもよい。
湿式成膜法としては、具体的には、例えば、スクリーンプリント法、インクジェットプリント法、ロールコート法、ドクターブレード法、スピンコート法、スプレー塗布法等が挙げられる。
加熱処理の温度としては、40℃~700℃であるのが好ましく、40℃~650℃であるのが好ましい。また、加熱処理の時間としては、特に制限はないが、通常は10秒~24時間程度である。
化学処理としては、具体的には、例えば、四塩化チタン水溶液を用いた化学メッキ処理、カルボン酸誘導体を用いた化学吸着処理、三塩化チタン水溶液を用いた電気化学的メッキ処理等が挙げられる。
上記対向電極とは、図1に示すように、光電極4に対向して配置される電極5であり、例えば、金属基板、表面に導電膜を有するガラス基板や樹脂基板等を用いることができる。
金属基板としては、白金、金、銀、銅、アルミニウム、インジウム、チタン等の金属を用いることができる。樹脂基板としては、光電極4を構成する透明基板1で例示した基板(フィルム)に加えて、不透明あるいは透明性に劣る一般的な樹脂基板も用いることができる。
また、表面に設ける導電膜としては、白金、金、銀、銅、アルミニウム、インジウム、チタン等の金属;炭素;酸化スズ;アンチモンやフッ素がドープされた酸化スズ;酸化亜鉛;アルミニウムやガリウムがドープされた酸化亜鉛;スズがドープされた酸化インジウム;等の導電性金属酸化物;等が挙げられる。導電膜の厚さや形成方法は、光電極4を構成する透明導電膜2と同様のものを挙げることができる。
導電性高分子としては、具体的には、例えば、ポリチオフェン、ポリピロール、ポリアニリン等が挙げられる。
基板上に導電性高分子膜を形成させる方法は、通常湿式成膜法として知られているディッピング法やスピンコーティング法等を用いて、高分子分散液から基板上に導電高分子膜を形成することができる。
導電性高分子分散液としては、特開2006-169291号公報で開示したポリアニリン分散液や市販品であるポリチオフェン誘導体水分散液(バイトロンP、バイエル社製)、三菱レイヨン社製(アクアセーブ、ポリアニリン誘導体水溶液)等を用いることができる。
また、基板が上記導電基板である場合、上記手法に加えて電解重合法によっても基板上に導電性高分子膜を形成させることができる。導電性高分子フィルム電極は、電解重合法によって電極上に形成された導電性高分子フィルムを電極から剥離した自立性フィルムまたは導電性高分子分散液から通常湿式成膜法として知られているキャスティング法やスピンコーティング法等を用いて形成された自立性フィルム等を用いることもできる。ここで言う導電性高分子分散液は、導電性高分子微粒子が溶媒中に分散している状態と導電性高分子が溶媒中に溶解している状態とが混在しているものを、便宜上導電性高分子分散液としている。
上記電解質層は、図1に示すように、光電極4および対向電極5の間に設けられる電解質層6であり、本発明の光電変換素子においては、上述した本発明の電解質を用いる。
ここで、光増感色素としては、可視光領域および/または赤外光領域に吸収を持つ色素であれば特に限定されなく、金属錯体または有機色素等を用いることができる。
金属錯体としては、具体的には、例えば、ビピリジン構造やターピリジン構造などの配位子が配位したルテニウム錯体色素、鉄錯体色素、オスミウム錯体色素、白金錯体色素、イリジウム錯体色素等を用いることができ、有機色素としては、具体的には、例えば、ポルフィリン系色素、フタロシアニン系色素、シアニン系色素、メロシアニン系色素、キサンテン系色素、クマリン系色素、インドール系色素、フルオレン系色素、トリフェニルアミン系色素等を用いることができる。
光増感色素を担持させる方法に特に制限はないが、上記色素を、例えば、水、アルコール系溶媒、二トリル系溶媒に溶解させ、色素溶液に酸化物半導体多孔質膜3を浸漬または色素溶液を酸化物半導体多孔質膜3に塗布することにより担持される。
有機化層状複水酸化物は、層状複水酸化物の再生する性質を用いた再生法により行
った。
(有機化層状複水酸化物1)
市販品である層状複水酸化物1(Mg-Al系層状複水酸化物、商品名:DHT-6、協和化学工業社製)を500℃、12時間焼成することにより焼成層状複水酸化物を得た。次に、イオン交換水(窒素ガスにてバブリング、脱炭酸処理したもの)を用いて、ステアリン酸ナトリウム(関東化学社製)水溶液0.1Mを調製した。得られた焼成層状複水酸化物2gを上記ステアリン酸ナトリウム水溶液1L中に投入し、室温で24時間攪拌した。その後、ろ過、洗浄を3回繰り返し、乾燥、粉砕して有機化層状複水酸化物1を調製した。
それぞれ、下記第1表に示す有機化処理剤を用いた以外は、有機化層状複水酸化物1と同様にして、有機化層状複水酸化物2~17を調製した。
まず、ヨードプロピオン酸(アルドリッチ社製)を用いた以外は、有機化層状複水酸化物1と同様にして、ヨードプロピオン酸に由来する、下記式(19)で表される有機アニオンがインターカレーションされた層状複水酸化物の前駆体を得た。
次に、1-メチルイミダゾール(アルドリッチ社製)の水溶液0.1Mを調製し、当該水溶液1L中に上記前駆体2gを投入し、室温で24時間攪拌した。その後、ろ過、洗浄を3回繰り返し、乾燥、粉砕して、下記式(20)で表される有機アニオンがインターカレーションされた有機化層状複水酸化物18を調製した。
有機化層状複水酸化物18を調製した方法と同様の方法を用いて、下記第2表に示す有機アニオン(カルボン酸誘導体)がインターカレーションされた有機化層状複水酸化物19~29を調製した。
アセトン中に1-メチルイミダゾール(アルドリッチ社製)と1,3-プロパンスルトン(アルドリッチ社製)とを45℃で反応させることにより、スルホン酸とイミダゾリウム塩とを有する下記式(21)で表されるものを調製した。ステアリン酸ナトリウムの代わりに、得られた有機アニオンおよびヨウ化リチウムを用いた以外は、有機化層状複水酸化物1と同様にして、下記式(22)で表されるものがインターカレーションされた有機化層状複水酸化物30を調製した。
有機化層状複水酸化物30を調製した方法と同様の方法を用いて、下記第2表に示す有機アニオン(スルホン酸誘導体)がインターカレーションされた有機化層状複水酸化物31~37を調製した。
まず、ブロモプロパンホスホン酸(東京化成社製)を用いた以外は、有機化層状複水酸化物1と同様にして、ブロモプロパンホスホン酸に由来する、下記式(23)で表される有機アニオンがインターカレーションされた層状複水酸化物の前駆体を得た。
次に、1-メチルイミダゾール(アルドリッチ社製)の水溶液0.1Mを調製し、当該水溶液1L中に上記前駆体2gを投入し、室温で24時間攪拌した。その後、ろ過、洗浄を3回繰り返し、乾燥、粉砕して、下記式(24)で表される有機アニオンがインターカレーションされた有機化層状複水酸化物38を調製した。
有機化層状複水酸化物38を調製した方法と同様の方法を用いて、下記第2表に示す有機アニオン(リン酸誘導体)がインターカレーションされた有機化層状複水酸化物39~42を調製した。
アセトン中に1-メチルイミダゾール(アルドリッチ社製)とジシアノケテンエチレンアセタール(アルドリッチ社製)とを45℃で反応させることにより、エノラートアニオンとイミダゾリウム塩とを有する下記式(25)で表されるものを調製した。ステアリン酸ナトリウムの代わりに、得られた有機アニオン化合物およびヨウ化リチウムを用いた以外は、有機化層状複水酸化物1と同様にして、下記式(26)で表されるものがインターカレーションされた有機化層状複水酸化物43を調製した。
有機化層状複水酸化物43を調製した方法と同様の方法を用いて、下記第2表に示す有機アニオン(エノラートアニオンを有する有機アニオン)がインターカレーションされた有機化層状複水酸化物44および45を調製した。
混合容器中で、下記第3表~第12表に示す成分を下記各表に示す組成比(質量部)で、撹拌し、混合することにより電解質を調製した。
具体的には、下記各表に示す組成比で、下記各表に示すイオン性液体である有機塩化合物1,2に、あらかじめ溶媒中に有機化層状複水酸化物1~45、層状複水酸化物1を膨潤分散させて得られた分散液を加えて、室温下で3時間撹拌し、静置した後に、溶媒を除去して沈殿物を得た。なお、溶媒は、有機化層状複水酸化物5,12および17、ならびに、層状複水酸化物1にはエタノールを使用した、それ以外の有機化層状複水酸化物にはトルエンを使用した。その後、得られた沈殿物を使用した溶媒で洗浄し、乾燥することによりゲル状物質を得た。次に、得られたゲル状物質に、下記各表に示すヨウ素、および、N-メチルベンズイミダゾールを、下記各表に示す組成比で添加し、混合した。
なお、有機化層状複水酸化物1~45、層状複水酸化物1を使用しない場合には、有機塩化合物1,2をそのまま電解質とした。
透明導電性ガラス(FTOガラス、表面抵抗15Ω/□、日本板硝子社製)上に、酸化チタンペーストTi-Nanoxide D(Solaronix社製)を塗布し、室温下で乾燥させた後、450℃の温度で30分間焼結することにより、透明導電性ガラス上に酸化チタン多孔質膜が形成された光電極を作製した。
作製した光電極を、ルテニウム錯体色素(シス-(ジイソチオシアネート)-N,N′-ビス(2,2′-ビピリジル-4,4′-ジカルボキシリックアシッド)ルテニウム(II)錯体)(Ruthenium 535-bisTBA、Solaronix社製)のブチルアルコール/アセトニトリル溶液(体積比:1/1、濃度3×10-4mol/L)に4時間浸漬させた。
その後、アセトニトリルで洗浄し、暗所において窒素気流下で乾燥することにより光電極の酸化チタン電極に増感色素を担持させたものを光電極として用いた。
光増感色素を担持させた光電極上に調製した上記電解質を塗りつけ、これと、透明導電性ガラス基板(導電面にスズがドープされた酸化インジウム、シート抵抗:8Ω/□、日本板硝子社製)表面にスパッタリング法で厚さ約100nmの白金薄膜を形成させた白金対向電極とを張り合わせた。貼り合せる際、光電極と白金対向電極の間に熱融着フィルムを介在させ、150℃で熱融着させて電極間の封止を行うことにより、色素増感太陽電池を得た。
ルテニウム錯体色素に代えてインドリン系色素(D205、三菱製紙社製)を用いた以外は、上述した色素増感太陽電池(光増感色素:ルテニウム錯体色素)と同様の方法で、色素増感太陽電池(光増感色素:有機色素)を作製した。
得られた2種の色素増感太陽電池について、以下に示す評価を行った。その結果を下記各表に示す。
図2に示すように、光源としてソーラーシミュレーターを用い、AM1.5の擬似太陽光を100mW/cm2の光強度で光電極側から照射し、電流電圧測定装置(ケースレーインスツルメンツ社製デジタルソースメーター2400)を用いて変換効率[%]を求めた。
作製後、100℃、1週間垂直放置された色素増感太陽電池について、揮発や液漏れの有無を確認した。揮発または液漏れのいずれかが確認された場合には、安定性に劣るものとして「×」と評価し、揮発および液漏れがいずれも確認されなかった場合には、安定性に優れるものとして「○」と評価した。
光電変換効率を測定した色素増感太陽電池を、85℃の温度下で1000時間放置し、その後に上記と同様の方法により光電変換効率を測定し、その維持率(加熱後の光電変換効率/加熱前の光電変換効率×100)[%]を算出した。
この結果、光電変換効率の維持率が80[%]以上であれば、変化率が小さく、耐熱性に優れていると評価できる。
光電変換効率を測定した色素増感太陽電池を、40℃、85%RHの条件で1000時間放置し、その後に上記と同様の方法により光電変換効率を測定し、その維持率(加湿後の光電変換効率/加湿前の光電変換効率×100)[%]を算出した。
この結果、光電変換効率の維持率が80[%]以上であれば、変化率が小さく、耐湿性に優れていると評価できる。
光電変換効率を測定した色素増感太陽電池を、85℃、85%RHの条件で1000時間放置し、その後に上記と同様の方法により光電変換効率を測定し、その維持率(加熱・加湿後の光電変換効率/加熱・加湿前の光電変換効率×100)[%]を算出した。
この結果、光電変換効率の維持率が80[%]以上であれば、変化率が小さく、耐湿熱性に優れていると評価できる。
・有機塩化合物1(MPImI):1-メチル-3-プロピルイミダゾリウムアイオダイド(東京化成社製)
・有機塩化合物2(EMImSCN):1-エチル-3-メチルイミダゾリウムチオシアネート(Merck社製)
・有機溶媒(C):メトキシプロピオニトリル(沸点:166℃、比誘電率:25)
また、有機塩化合物2を用いた実施例22~32,66~89,90~114,126~135は、いずれも、耐熱性に優れることが分かった。
また、実施例1~6,8~15,17~20と実施例7,16,21とを対比すると、有機化層状複水酸化物1~4,6~11,13~16を用いた実施例1~6,8~15,17~20は、有機化層状複水酸化物5,12,17を用いた実施例7,16,21よりも、耐湿性および耐湿熱性に優れることが分かった。これは実施例22~32においても同様であった。
また、実施例33と実施例34とを対比すると、有機化層状複水酸化物18がより多い実施例33の方が、光電変換効率により優れることが分かった。これは、実施例35と実施例36、実施例37と実施例38、実施例48と実施例49、実施例50と実施例51においても、同様の傾向が見られた。
この傾向は、有機塩化合物と有機溶媒とを併用した実施例90~114においても、同様であった。
また、この傾向は、光増感色素としてルテニウム錯体色素の代わりに有機色素を用いた実施例115~135においても同様であった。
2:透明導電膜
3:酸化物半導体多孔質膜
4:光電極
5:対向電極
6:電解質層
11:透明基板
12:透明導電膜(ITO、FTO)
13:金属酸化物
14:電解質
15:白金薄膜
16:透明導電膜(ITO、FTO)
17:基板
18:対向電極
Claims (7)
- 第3級または第4級カチオンを有する有機塩化合物(A)と、有機化層状複水酸化物(B)と、を含有する光電変換素子用電解質。
- 前記有機化層状複水酸化物(B)が、炭素数3以上の有機アニオンを用いて有機化処理された層状複水酸化物である、請求項1に記載の光電変換素子用電解質。
- 前記有機化層状複水酸化物(B)が、オニウム塩基を有する有機アニオンを用いて有機化処理された層状複水酸化物である、請求項1または2に記載の光電変換素子用電解質。
- 前記オニウム塩基が、イミダゾリウム塩基、ピリジニウム塩基、ピロリジニウム塩基、ピペリジニウム塩基、アンモニウム塩基、スルホニウム塩基、および、ホスホニウム塩基等からなる群から選ばれる少なくとも1種である、請求項3に記載の光電変換素子用電解質。
- 前記有機塩化合物(A)が、チオシアネートアニオンを有する、請求項1~4のいずれかに記載の光電変換素子用電解質。
- 透明導電膜および金属酸化物半導体多孔質膜を有する光電極と、
前記光電極に対向して配置される対向電極と、
前記光電極と前記対向電極との間に配された電解質層と、を有し、
前記電解質層が、請求項1~5のいずれかに記載の光電変換素子用電解質である、光電変換素子。 - 請求項6に記載の光電変換素子が有する前記光電極に光増感色素を担持させてなる、色素増感太陽電池。
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JP2016535999A (ja) * | 2013-08-28 | 2016-11-24 | コーニンクレッカ ネザーランド アカデミー ヴァン ウェテンシャッペン | 形質導入バッファー |
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TWI828154B (zh) * | 2022-05-20 | 2024-01-01 | 鴻海精密工業股份有限公司 | 碳酸酯類電解液及其製備方法及鋰金屬電池 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007531206A (ja) * | 2004-03-31 | 2007-11-01 | 横浜ゴム株式会社 | 光電変換素子用電解質並びにその電解質を含む光電変換素子及び色素増感太陽電池 |
JP2008071749A (ja) * | 2006-08-14 | 2008-03-27 | Yokohama Rubber Co Ltd:The | 色素増感太陽電池及びその電解質 |
JP2008218180A (ja) * | 2007-03-05 | 2008-09-18 | Japan Carlit Co Ltd:The | 色素増感太陽電池用の対極、及びそれを備えた色素増感太陽電池 |
JP2009238672A (ja) * | 2008-03-28 | 2009-10-15 | Tdk Corp | 光電変換素子および光電変換素子の製造方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6878492B2 (en) * | 2000-07-10 | 2005-04-12 | Showa Denko Kabushiki Kaisha | Polymerizable composition and use thereof |
JP2006169291A (ja) | 2004-12-13 | 2006-06-29 | Yokohama Rubber Co Ltd:The | 変性導電性高分子並びにそれを用いた導電性部材 |
EP2150568B1 (en) | 2007-05-29 | 2016-03-23 | Youl Chon Chemical Co. Ltd. | Chain-end functionalized methoxy poly(ethylene glycol)and metal nano-particles using the same |
ITVA20070085A1 (it) * | 2007-11-21 | 2009-05-22 | Lamberti Spa | Inibitori di rigonfiamento di argille |
JP5312155B2 (ja) | 2009-04-03 | 2013-10-09 | キヤノン株式会社 | 屈折率分布型光学素子及び該屈折率分布型光学素子を有する撮像素子 |
CN101572192B (zh) * | 2009-06-02 | 2011-04-13 | 彩虹集团公司 | 一种染料敏化太阳能电池用电解质及其制备方法 |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007531206A (ja) * | 2004-03-31 | 2007-11-01 | 横浜ゴム株式会社 | 光電変換素子用電解質並びにその電解質を含む光電変換素子及び色素増感太陽電池 |
JP2008071749A (ja) * | 2006-08-14 | 2008-03-27 | Yokohama Rubber Co Ltd:The | 色素増感太陽電池及びその電解質 |
JP2008218180A (ja) * | 2007-03-05 | 2008-09-18 | Japan Carlit Co Ltd:The | 色素増感太陽電池用の対極、及びそれを備えた色素増感太陽電池 |
JP2009238672A (ja) * | 2008-03-28 | 2009-10-15 | Tdk Corp | 光電変換素子および光電変換素子の製造方法 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013218877A (ja) * | 2012-04-09 | 2013-10-24 | Yokohama Rubber Co Ltd:The | 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池 |
JP2016535999A (ja) * | 2013-08-28 | 2016-11-24 | コーニンクレッカ ネザーランド アカデミー ヴァン ウェテンシャッペン | 形質導入バッファー |
JP2020146056A (ja) * | 2013-08-28 | 2020-09-17 | コーニンクレッカ ネザーランド アカデミー ヴァン ウェテンシャッペン | 形質導入バッファー |
US10883116B2 (en) | 2013-08-28 | 2021-01-05 | Koninklijke Nederlandse Akademie Van Wetenschappen | Transduction buffer |
JP7055168B2 (ja) | 2013-08-28 | 2022-04-15 | コーニンクレッカ ネザーランド アカデミー ヴァン ウェテンシャッペン | 形質導入バッファー |
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