WO2012096170A1 - 光電変換素子 - Google Patents
光電変換素子 Download PDFInfo
- Publication number
- WO2012096170A1 WO2012096170A1 PCT/JP2012/000125 JP2012000125W WO2012096170A1 WO 2012096170 A1 WO2012096170 A1 WO 2012096170A1 JP 2012000125 W JP2012000125 W JP 2012000125W WO 2012096170 A1 WO2012096170 A1 WO 2012096170A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- photoelectric conversion
- methyl
- conversion element
- electrode
- formula
- Prior art date
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- YCBLEHMSAYLVKL-UHFFFAOYSA-M 1-methyl-1-propylpyrrolidin-1-ium;hydroxide Chemical compound [OH-].CCC[N+]1(C)CCCC1 YCBLEHMSAYLVKL-UHFFFAOYSA-M 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- KLEPTKBBYYYALG-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxin-5-ylmethanamine Chemical compound O1CCOC2=C(CN)SC=C21 KLEPTKBBYYYALG-UHFFFAOYSA-N 0.000 description 1
- LRWVQOFWMRDMHM-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxin-5-ylmethanol Chemical compound O1CCOC2=C(CO)SC=C21 LRWVQOFWMRDMHM-UHFFFAOYSA-N 0.000 description 1
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 description 1
- VMISXESAJBVFNH-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid;ruthenium(2+);diisothiocyanate Chemical compound [Ru+2].[N-]=C=S.[N-]=C=S.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 VMISXESAJBVFNH-UHFFFAOYSA-N 0.000 description 1
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- ZDQZVKVIYAPRON-UHFFFAOYSA-N 3-phenylthiophene Chemical compound S1C=CC(C=2C=CC=CC=2)=C1 ZDQZVKVIYAPRON-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- ABSXMLODUTXQDJ-UHFFFAOYSA-N 4-(4-sulfophenyl)benzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1C1=CC=C(S(O)(=O)=O)C=C1 ABSXMLODUTXQDJ-UHFFFAOYSA-N 0.000 description 1
- QIWLEULVJYJBFW-UHFFFAOYSA-N 5-hexyl-2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=C(CCCCCC)SC=C21 QIWLEULVJYJBFW-UHFFFAOYSA-N 0.000 description 1
- FPVUWZFFEGYCGB-UHFFFAOYSA-N 5-methyl-3h-1,3,4-thiadiazole-2-thione Chemical compound CC1=NN=C(S)S1 FPVUWZFFEGYCGB-UHFFFAOYSA-N 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- ILFFFKFZHRGICY-UHFFFAOYSA-N anthracene-1-sulfonic acid Chemical compound C1=CC=C2C=C3C(S(=O)(=O)O)=CC=CC3=CC2=C1 ILFFFKFZHRGICY-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- RXKLBLXXQQRGJH-UHFFFAOYSA-N bis(fluorosulfonyl)azanide 1-methyl-1-propylpyrrolidin-1-ium Chemical compound CCC[N+]1(C)CCCC1.FS(=O)(=O)[N-]S(F)(=O)=O RXKLBLXXQQRGJH-UHFFFAOYSA-N 0.000 description 1
- MIOPJNTWMNEORI-UHFFFAOYSA-N camphorsulfonic acid Chemical compound C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ZRZKFGDGIPLXIB-UHFFFAOYSA-N fluoroform;sulfuric acid Chemical compound FC(F)F.OS(O)(=O)=O ZRZKFGDGIPLXIB-UHFFFAOYSA-N 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- ZJYYHGLJYGJLLN-UHFFFAOYSA-N guanidinium thiocyanate Chemical compound SC#N.NC(N)=N ZJYYHGLJYGJLLN-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- HYFMZOAPNQAXHU-UHFFFAOYSA-N naphthalene-1,7-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(S(=O)(=O)O)=CC=C21 HYFMZOAPNQAXHU-UHFFFAOYSA-N 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 125000005031 thiocyano group Chemical group S(C#N)* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- 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
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2018—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte characterised by the ionic charge transport species, e.g. redox shuttles
-
- 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
-
- 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
- Y02E10/52—PV systems with concentrators
-
- 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 a photoelectric conversion element suitably used as a dye-sensitized solar cell or the like.
- a dye-sensitized solar cell includes a semiconductor electrode having a photoelectric conversion layer made of a semiconductor having a dye adsorbed on a conductive substrate, and a catalyst layer on a conductive substrate provided facing the semiconductor electrode. It is comprised from the provided counter electrode and the electrolyte layer hold
- the electrolyte of the dye-sensitized solar cell generally uses an iodine redox couple dissolved in an organic solvent.
- Iodine-based redox couples have excellent performance, such as high ion conductivity and a high rate of reducing oxidized dyes, while low reactivity on the conductive glass surface and titanium oxide surface of the working electrode. ing.
- iodine-based redox couples have strong absorption in the visible light range, and when high-viscosity solvents such as ionic liquids are used, it is necessary to increase the concentration of iodine-based redox couples in order to operate sufficiently as a solar cell element. As a result, the light absorption of the dye is hindered, causing a decrease in performance. Further, when the colorfulness of solar cells is emphasized using various pigments, especially in the case of blue elements, the color of iodine is an obstacle, and it cannot be said that the element design is appropriate.
- Non-Patent Documents 1 to 6, Patent Document 1 disclose a redox couple that replaces the iodine-based one.
- Non-Patent Documents 1 to 3 have proposed using a cobalt complex as a redox pair.
- Cobalt complexes are said to exhibit the same performance as iodine-based redox couples under low light conditions, but due to the large molecular size, the redox couple transfer speed is slow, and the performance is approximately half under simulated sunlight irradiation conditions. To drop.
- cobalt complexes are expensive compared to iodine, and are not practical.
- Non-Patent Documents 4 to 5 have proposed using (SCN) 2 / SCN ⁇ , (SeCN) 2 / SeCN ⁇ as a redox pair.
- (SCN) 2 / SCN ⁇ operates as a redox couple, it is less than half the performance of an iodine-based redox couple .
- (SeCN) 2 / SeCN ⁇ shows higher performance than that, but has a problem in safety and cannot be said to have high practicality.
- Non-Patent Document 6 shows that high photoelectric conversion performance is achieved by using a sulfide-based redox couple and an organic solvent as an electrolyte.
- Non-Patent Document 6 when a volatile organic solvent such as acetonitrile and ethylene carbonate as shown in Non-Patent Document 6 is used as the electrolyte solution of the dye-sensitized solar cell, it is difficult to seal the electrolyte solution, which is practical. It is difficult to obtain element durability. Therefore, in many cases, an ionic liquid having very low volatility is used as an electrolyte solvent. However, since the ionic liquid has a higher viscosity than a general volatile organic solvent, the device performance is organic as described in Patent Document 1. The problem is that it is lower than the solvent electrolyte.
- Non-Patent Document 6 shows that a tetramethylammonium salt of a sulfide compound is used as a reductant of a redox pair, and in that case, the solubility in an ionic liquid is insufficient, and a satisfactory element There is a problem that performance cannot be demonstrated.
- Patent Document 1 discloses a sulfide compound having a thiadiazole skeleton as an oxidation-reduction pair, but a disulfide compound that is an oxidant of the oxidation-reduction pair has particularly low solubility in an electrolyte solution such as an ionic liquid ( (Less than 0.2M), but the volatile properties of ionic liquids and the like are low, but there is a problem that the device performance deteriorates when a solvent having high viscosity is used. Furthermore, when the concentration of the redox couple is increased, there is a problem that the stability of the redox itself is lowered.
- an iodine substitute electrolyte solution that does not have sublimation property or light absorption property in the visible light region, has high solubility in an electrolyte solution solvent, and is stable and high performance in the solvent.
- the present invention has been made in view of the above points, and is more transparent than iodine-based redox couples, easy to seal, and highly practical photoelectric conversion using high-performance redox couples. It is an object to provide an element.
- the electrolyte layer is a redox pair of a photoelectric conversion element comprising a compound represented by the following general formula (1) and formula (2). It has been found that it has high performance and stability as a pair, and the above redox couple dissolves in a high concentration in the ionic liquid represented by the formula (3), and exhibits high performance as an electrolytic solution using the ionic liquid. Based on these findings, we have found that by using a conductive polymer catalyst as the counter electrode, it is possible to produce a photoelectric conversion element that exhibits high element photoelectric conversion efficiency almost equivalent to that using a conventional iodine redox pair. The present invention has been completed.
- the photoelectric conversion element of the present invention is a photoelectric conversion element including a semiconductor electrode, a counter electrode, and an electrolyte layer held between the semiconductor electrode and the counter electrode. And an ionic liquid having a redox pair consisting of a compound represented by the general formula (1) and a compound represented by the formula (2) and a bis (fluorosulfonyl) imide anion represented by the formula (3).
- A is Li, an imidazolium compound represented by the following formula (4), or a pyrrolidinium compound represented by the following formula (5).
- R 1 represents an alkyl group having 1 to 12 carbon atoms
- R 2 represents a hydrogen atom or a methyl group
- R 3 represents an alkyl group having 1 to 12 carbon atoms. Indicates.
- the concentration of the compound represented by the general formula (1) in the electrolyte layer is 0.5 mol / L or more, and the concentration of the compound represented by the formula (2) is 0.5 mol / L or more. Preferably there is.
- the counter electrode preferably contains a conductive polymer catalyst having catalytic activity for the redox couple.
- the photoelectric conversion device of the present invention has photoelectric conversion efficiency and stability comparable to devices using conventional iodine-based redox couples, and solves the transparency problem that was a weak point of conventional iodine-based redox couples.
- the redox couple used in the present invention does not have strong absorption in the visible light region, the design of the device is improved, and a low-volatile ionic liquid is dissolved at a high concentration. Even when an ionic liquid is used as a solvent, the device performance is not deteriorated due to light absorption of the electrolyte layer as seen in an iodine-based redox couple, and a highly practical photoelectric conversion device can be provided.
- FIG. (A) is a figure which shows the result of the IPCE (incident-photo-to-current conversion ⁇ efficiency) measurement of Example 1
- (B) is a figure which shows the IPCE measurement result of the comparative example 1.
- FIG. (A) is a figure which shows the relationship between the light irradiation intensity
- (B) is a figure which shows the relationship between the light irradiation intensity
- FIG. 1 is a schematic cross-sectional view showing an example of the photoelectric conversion element 10 of the present invention.
- reference numeral 1 is a transparent substrate
- reference numeral 2 is a transparent conductive film
- reference numeral 3 is a porous metal oxide semiconductor layer
- reference numeral 4 is a sensitizing dye
- reference numeral 5 is an electrolyte layer
- reference numeral 6 is a catalyst layer
- reference numeral 7 is Reference numeral 6 denotes an electrode substrate
- reference numeral 8 denotes an electrode substrate
- reference numeral 9 denotes a counter electrode.
- a porous metal oxide semiconductor layer 3 is formed on the surface of an electrode substrate 8 comprising a transparent substrate 1 and a transparent conductive film 2 formed thereon, and this porous metal oxide semiconductor 3 is further formed.
- the sensitizing dye 4 is adsorbed on the surface.
- the counter electrode 9 in which the catalyst layer 6 was formed on the surface of the electrode base material 7 is arrange
- Transparent substrate As the transparent substrate 1 constituting the electrode substrate 8, one that transmits visible light can be used, and transparent glass can be suitably used. Moreover, what processed the glass surface and scattered incident light can also be used. Moreover, not only glass but a plastic plate, a plastic film, etc. can be used if it transmits light.
- the thickness of the transparent substrate 1 is not particularly limited because it varies depending on the shape of the photoelectric conversion element 10 and usage conditions. For example, when glass or plastic is used, 1 mm to 1 cm is considered in consideration of durability during actual use. When a plastic film or the like is used, the thickness is preferably about 1 ⁇ m to 1 mm.
- Transparent conductive film As the transparent conductive film 2, a material that transmits visible light and has conductivity can be used.
- a material that transmits visible light and has conductivity is a metal oxide.
- tin oxide doped with fluorine hereinafter abbreviated as “FTO”
- ITO indium oxide
- ITO indium oxide
- antimony antimony
- Tin oxide, zinc oxide and the like doped with can be preferably used.
- an opaque conductive material can also be used if visible light is transmitted by a treatment such as dispersion.
- Such materials include carbon materials and metals. Although it does not specifically limit as a carbon material, For example, graphite (graphite), carbon black, glassy carbon, a carbon nanotube, fullerene, etc. are mentioned.
- the metal is not particularly limited, and examples thereof include platinum, gold, silver, ruthenium, copper, aluminum, nickel, cobalt, chromium, iron, molybdenum, titanium, tantalum, and alloys thereof.
- the electrode substrate 8 can be formed by providing a conductive material made of at least one of the above-described conductive materials on the surface of the transparent substrate 1.
- a conductive material made of at least one of the above-described conductive materials on the surface of the transparent substrate 1.
- the transparent conductive film 2 on the transparent substrate 1 when using a metal oxide, there are a liquid layer method such as a sol-gel method, a gas phase method such as sputtering or CVD, and a coating of a dispersion paste. Moreover, when using an opaque electroconductive material, the method of fixing powder etc. with a transparent binder etc. is mentioned.
- the transparent substrate 1 and the transparent conductive film 2 there is a method of mixing the conductive film material as a conductive filler when the transparent substrate 1 is molded.
- the thickness of the transparent conductive film 2 is not particularly limited because the conductivity varies depending on the material to be used. However, in the glass with FTO film generally used, it is 0.01 ⁇ m to 5 ⁇ m, preferably 0.1 ⁇ m to 1 ⁇ m. It is. Further, the required conductivity varies depending on the area of the electrode to be used, and a wider electrode is required to have a lower resistance, but is generally 100 ⁇ / ⁇ or less, preferably 10 ⁇ / ⁇ or less, more preferably 5 ⁇ . / ⁇ or less.
- the thickness of the electrode substrate 8 composed of the transparent substrate 1 and the transparent conductive film 2 or the electrode substrate 8 in which the transparent substrate 1 and the transparent conductive film 2 are integrated is the shape and use of the photoelectric conversion element 10 as described above. Since it varies depending on conditions, it is not particularly limited, but is generally about 1 ⁇ m to 1 cm.
- porous metal oxide semiconductor examples include, but are not limited to, titanium oxide, zinc oxide, tin oxide, and the like.
- titanium dioxide and further anatase type titanium dioxide are suitable.
- the metal oxide has few grain boundaries in order to reduce the electric resistance value.
- the semiconductor layer preferably has a large specific surface area, specifically 10 to 200 m 2 / g.
- the particle size of the oxide to be used is widened to scatter light, or large oxide semiconductor particles having a particle size of about 300 to 400 nm are formed in the porous layer. It is desirable to provide it as a reflective layer on top.
- Such a porous metal oxide semiconductor layer 3 is not particularly limited, and can be provided on the transparent conductive film 2 by a known method.
- a sol-gel method for example, there are a sol-gel method, dispersion paste application, electrodeposition and electrodeposition.
- the thickness of the semiconductor layer 3 is not particularly limited because the optimum value varies depending on the oxide to be used, but is usually 0.1 ⁇ m to 50 ⁇ m, preferably 3 to 30 ⁇ m.
- sensitizing dye any dye that can be excited by sunlight and can inject electrons into the metal oxide semiconductor 3 can be used, and a dye generally used in a photoelectric conversion element can be used. In order to improve the light intensity, it is desirable that the absorption spectrum overlaps with the sunlight spectrum in a wide wavelength range and has high light resistance.
- the sensitizing dye 4 is not particularly limited, but is preferably a ruthenium complex, particularly a ruthenium polypyridine-based complex, and more preferably a ruthenium complex represented by Ru (L) 2 (X) 2 .
- L is 4,4′-dicarboxy-2,2′-bipyridine, or a quaternary ammonium salt thereof, and a polypyridine-based ligand into which a carboxyl group is introduced
- X is SCN, Cl, CN.
- Examples thereof include bis (4,4′-dicarboxy-2,2′-bipyridine) diisothiocyanate ruthenium complex.
- dyes examples include metal complex dyes other than ruthenium, such as iron complexes and copper complexes.
- Further examples include organic dyes such as cyan dyes, porphyrin dyes, polyene dyes, coumarin dyes, cyanine dyes, squaric acid dyes, styryl dyes, eosin dyes, and indoline dyes.
- These dyes desirably have a bonding group with the metal oxide semiconductor 3 in order to improve the electron injection efficiency into the metal oxide semiconductor 3.
- the bonding group is not particularly limited, but a carboxyl group, a sulfonic acid group, a hydroxyl group and the like are desirable.
- a blue or transparent photoelectric conversion element can be produced, and uses that require colorfulness, etc.
- the use application of the device can be increased.
- the solvent used for dissolving the dye examples include alcohols such as ethanol, nitrogen compounds such as acetonitrile, ketones such as acetone, ethers such as diethyl ether, halogenated aliphatic hydrocarbons such as chloroform, hexane Aliphatic hydrocarbons such as benzene, aromatic hydrocarbons such as benzene, and esters such as ethyl acetate.
- the concentration of the dye in the solution can be appropriately adjusted depending on the kind of the dye and the solvent to be used. In order to sufficiently adsorb on the semiconductor surface, it is desirable that the concentration is somewhat high. For example, a concentration of 4 ⁇ 10 ⁇ 5 mol / L or more is desirable.
- the method of adsorbing the sensitizing dye 4 to the porous metal oxide semiconductor 3 is not particularly limited.
- the porous material is dissolved in a solution in which the dye is dissolved at room temperature and atmospheric pressure.
- a method of immersing the electrode base 8 on which the metal oxide semiconductor 3 is formed may be mentioned.
- the immersion time is preferably adjusted as appropriate so that the monomolecular film of the sensitizing dye 4 is uniformly formed on the semiconductor layer 3 according to the type of semiconductor, dye, solvent, and dye concentration used.
- suction can be performed efficiently by performing the immersion under a heating.
- the electrolyte layer 5 used in the present invention includes a redox pair composed of a compound represented by the general formula (1) and a compound represented by the formula (2).
- the compound represented by the general formula (1) is a reductant
- the compound represented by the formula (2) is an oxidant.
- A represents Li, an imidazolium compound represented by the following formula (4), or a pyrrolidinium compound represented by the following formula (5).
- R 1 represents an alkyl group having 1 to 12 carbon atoms, preferably 2 to 6 carbon atoms, and R 2 represents a hydrogen atom or a methyl group.
- R 3 represents an alkyl group having 1 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
- the compound represented by the formula (1) include 1-methyl-5-mercapto-1,2,3,4-tetrazole: lithium salt (Li-MTZT), 1-methyl-5-mercapto-1 1,2,3,4-tetrazole: 1-methyl-3-ethylimidazolium salt (EMIm-MTZT), 1-methyl-5-mercapto-1,2,3,4-tetrazole: 1,2-dimethyl-3 -Propylimidazolium salt (DMPIm-MTZT), 1-methyl-5-mercapto-1,2,3,4-tetrazole: 1-methyl-1-propylpyrrolidinium salt (MPPy-MTZT), 1-methyl- 5-mercapto-1,2,3,4-tetrazole: 1-methyl-3-propylimidazolium salt, 1-methyl-5-mercapto-1,2,3,4-tetrazole: 1- Tyl-3-butylimidazolium salt, 1-methyl-5-mercapto-1,2,3,4-tetrazole: 1- 1-methyl
- the compound represented by the formula (2) is 5,5′-dithiobis (1-methyl-1H-tetrazole) ((MTZT) 2 ).
- the solvent for dissolving the redox pair includes an ionic liquid having a bis (fluorosulfonyl) imide anion represented by the formula (3).
- the ionic liquid include 1-methyl-3-ethylimidazolium bis (fluorosulfonyl) imide, 1,3-dimethylimidazolium bis (fluorosulfonyl) imide, 1-methyl-3-propylimidazolium bis (fluoro Sulfonyl) imide, 1-methyl-3-butylimidazolium bis (fluorosulfonyl) imide, 1-methyl-3-hexylimidazolium bis (fluorosulfonyl) imide, 1,2-dimethyl-3-propylimidazolium bis (fluoro Sulfonyl) imide, 1,2-dimethyl-3-butylimidazolium bis (fluorosulfonyl) imide, 1,2-dimethyl-3-hexylimidazolium bis (fluorosulfonyl) imide, 1-methyl-1-ethylpyrrolidinium Bis (fluorosulfo ) Imide, 1,
- the above-mentioned oxidation-reduction pair and ionic liquid can be commercially available, or can be synthesized from commercially available materials by a known method.
- the concentration of the compound (reduced form) represented by the general formula (1) in the electrolyte layer (solvent) is preferably 0.5 mol / L or more, and more preferably 0.5 to 3 mol / L. If the concentration of the compound represented by the general formula (1) is less than 0.5 mol / L, the charge transport capability of the redox couple may be insufficient, and the current value of the device may decrease. If the concentration exceeds 3 mol / L, When the viscosity of the electrolytic solution is increased, the charge transport capability of the redox couple is lowered, and the performance of the device may be lowered.
- the concentration of the compound (oxidant) represented by the formula (2) in the electrolyte layer (solvent) is preferably 0.5 mol / L or more, and preferably 0.5 to 1.4 mol / L. More preferred. If the concentration of the compound represented by the formula (2) is less than 0.5 mol / L, the charge transport capability of the redox pair may be insufficient, and the current value of the device may decrease. If the concentration exceeds 1.4 mol / L There is a possibility that the compound of formula (2) (oxidized substance) is precipitated.
- the ratio (molar ratio) of the compound represented by the general formula (1) to the compound represented by the formula (2) is preferably 0.8 or more, more preferably 1 or more, and 1.2 or more. More preferably.
- the upper limit of the ratio is preferably 5 or less, and more preferably 3 or less.
- a supporting electrolyte, an additive, and the like can be further added as necessary without departing from the object of the present invention and without impairing the characteristics of the electrolyte layer.
- the supporting electrolyte include lithium salts, imidazolium salts, and quaternary ammonium salts.
- the additive include bases such as t-butylpyridine, N-methylimidazole, N-methylbenzimidazole and N-methylpyrrolidone, and thiocyanates such as guanidinium thiocyanate.
- it can also be gelatinized physically or chemically by adding a suitable gelling agent.
- the counter electrode 9 has a structure in which the catalyst layer 6 is formed on the surface of the electrode substrate 7. Since this electrode base material 7 is used as a support and current collector of the catalyst layer 6, it is preferable that the surface portion has conductivity.
- a conductive metal or metal oxide, a carbon material, a conductive polymer, or the like is preferably used.
- the metal include platinum, gold, silver, ruthenium, copper, aluminum, nickel, cobalt, chromium, iron, molybdenum, titanium, tantalum, and alloys thereof.
- a carbon material For example, graphite (graphite), carbon black, glassy carbon, a carbon nanotube, fullerene etc. are mentioned.
- a metal oxide such as FTO, ITO, indium oxide, zinc oxide or antimony oxide is used, the amount of light incident on the sensitizing dye layer 4 can be increased because it is transparent or translucent.
- an insulator such as glass or plastic may be used as long as at least the surface of the electrode substrate 7 is treated.
- a treatment method for maintaining conductivity in such an insulator a method of covering a part or the entire surface of the insulating material with the above-described conductive material, for example, when using a metal, plating, electrodeposition, etc.
- a gas phase method such as a sputtering method or a vacuum deposition method is used.
- a sol-gel method or the like can be used.
- the method of mixing with an insulating material using 1 type or multiple types of the said powder of an electroconductive material, etc. is mentioned.
- the catalyst layer 6 can be formed by providing the current collector and the catalyst independently by providing the highly conductive catalyst layer 6 on the base material 7. Both of these functions can be fulfilled and can be used as the counter electrode 9.
- the shape of the electrode substrate 7 is not particularly limited because it can be changed according to the shape of the photoelectric conversion element 10 used as the catalyst electrode, and may be a plate shape or a film shape that can be curved. Further, the electrode substrate 7 may be transparent or opaque, but can be transparent or translucent because the amount of incident light on the sensitizing dye layer 4 can be increased, and in some cases the design can be improved. Is desirable.
- the thickness of the conductive layer is particularly limited. Not.
- the thickness is 0.01 ⁇ m to 5 ⁇ m, preferably 0.1 ⁇ m to 1 ⁇ m.
- the required conductivity varies depending on the area of the electrode to be used, and a wider electrode is required to have a lower resistance, but is generally 100 ⁇ / ⁇ or less, preferably 10 ⁇ / ⁇ or less, more preferably 5 ⁇ . / ⁇ or less.
- the thickness of the electrode substrate 7 is not particularly limited because it varies depending on the shape and use conditions of the photoelectric conversion element 10 as described above, but is generally about 1 ⁇ m to 1 cm.
- the catalyst layer 6 is not particularly limited as long as it has electrode characteristics capable of promptly proceeding with a reduction reaction for reducing the oxidized form of the redox couple in the electrolyte to a reduced form. , Heat treated materials, platinum catalyst electrodes deposited with platinum, carbon materials such as activated carbon, glassy carbon and carbon nanotubes, inorganic sulfur compounds such as cobalt sulfide, conductive polymers such as polythiophene, polypyrrole and polyaniline, etc. Of these, a conductive polymer catalyst is preferably used.
- the monomer constituting the conductive polymer catalyst used in the present invention include thiophene compounds represented by the following general formula (6).
- R 4 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group, an aryl group having 6 to 12 carbon atoms, a cyano group, a thiocyano group, and a halogen group.
- a nitro group, an amino group, a carboxyl group, a sulfo group, or a phosphonium group, R 4 and R 5 may be linked to form a ring.
- thiophene, tetradecylthiophene, isothianaphthene, 3-phenylthiophene, 3,4-ethylenedioxythiophene and their derivatives can be preferably used, and among them, 3,4-ethylenedioxythiophene and The derivative can be preferably used.
- 3,4-ethylenedioxythiophene derivatives include hydroxymethyl-3,4-ethylenedioxythiophene, aminomethyl-3,4-ethylenedioxythiophene, hexyl-3,4-ethylenedioxythiophene, and octyl. -3,4-ethylenedioxythiophene.
- these thiophene compounds may be used individually by 1 type, and the conductive polymer catalyst layer 6 may be formed using 2 or more types.
- the monomer used to form the conductive polymer catalyst layer 6 is preferably one having a conductivity of 10 ⁇ 9 S / cm or more as a polymerized film.
- a dopant to the conductive polymer catalyst layer 6 in order to improve conductivity.
- a known material can be used without any particular limitation.
- the dopant include halogen anions such as iodine, bromine and chlorine, hexafluorolin, hexafluoroarsenic, hexafluoroantimony, tetrafluoroboron, halide anions such as perchloric acid, methanesulfonic acid, dodecylsulfonic acid and the like.
- the dopant of the low molecular compound is higher than the dopant of the high molecular compound because the catalytic activity for the redox couple of the present invention is high.
- Specific examples include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and the like.
- the amount of dopant used in the conductive polymer catalyst layer is not particularly limited because the optimum value varies depending on the type of dopant used, but is preferably 5 to 60% by mass, more preferably 10 to 45% by mass.
- Such a dopant can coexist with a monomer of a conductive polymer when forming the conductive polymer catalyst layer.
- the conductive polymer catalyst layer 6 is formed on the electrode substrate 7.
- the formation method is not particularly limited, and examples thereof include a method of forming a film from a solution in which a conductive polymer is in a molten state or dissolved.
- the monomer is chemically or electrochemically oxidized, for example, in a state where the solution containing the monomer of the conductive polymer and the electrode substrate 7 are in contact with each other.
- a polymerization method is preferably used.
- the conductive polymer powder is processed into a paste form, an emulsion form, or a mixture form containing a polymer solution and a binder, it is formed on the electrode substrate 7 by screen printing, spray coating, brush coating, or the like. A method can also be used.
- the method for forming the conductive polymer catalyst layer 6 is preferably an electrolytic polymerization method or a chemical polymerization method, and particularly preferably a chemical polymerization method.
- the chemical polymerization method is a method in which a polymerization monomer is oxidatively polymerized using an oxidizing agent.
- the electrolytic polymerization method is a method of forming a conductive polymer film on an electrode such as a metal by performing electrolytic oxidation in a solution containing a polymerization monomer.
- the oxidizing agent used in the chemical polymerization method includes iodine, bromine, bromine iodide, chlorine dioxide, iodic acid, periodic acid, chlorous acid and other halides, antimony pentafluoride, phosphorus pentachloride, phosphorus pentafluoride.
- Metal halides such as aluminum chloride, molybdenum chloride, permanganate, dichromate, chromic anhydride, ferric salt, cupric salt and other high-valent metal salts, sulfuric acid, nitric acid, trifluoromethanesulfuric acid
- Protonic acids such as oxygen compounds such as sulfur trioxide and nitrogen dioxide, peroxo acids such as hydrogen peroxide, ammonium persulfate and sodium perborate or salts thereof, or molybdophosphoric acid, tungstophosphoric acid, tungstomolybdophosphoric acid, etc.
- the electrode substrate 7 is immersed in a solution containing either an aromatic compound monomer or an oxidizing agent, or after applying the solution to them, the electrode substrate 7 is subsequently immersed or applied in a solution in which the other component is dissolved. For example, it is desirable that the polymerization proceeds on the surface of the electrode substrate 7 to form a conductive polymer.
- an additive that lowers the polymerization rate is added to the mixed solution of the monomer and polymerization initiator, and after forming into a film under conditions where polymerization does not occur at room temperature, a porous conductive polymer film is produced by heating reaction. can do.
- the method for forming a film is not particularly limited, and examples thereof include a spin coating method, a casting method, a squeegee method, and a screen printing method.
- the additive for reducing the polymerization rate when the polymerization initiator is a high-valent metal salt, for example, Fe (III) salt, Fe (III) salt Since the oxidation potential changes depending on the pH, the polymerization rate can be slowed by adding a base.
- the base include imidazole and dimethyl sulfoxide.
- the solvent for dissolving and mixing the monomer, the polymerization initiator, and the additive is not particularly limited as long as it dissolves the compound to be used and does not dissolve the electrode substrate 7 and the polymer.
- methanol, ethanol, propanol examples include alcohols such as normal butanol.
- the mixing ratio of the monomer, the polymerization initiator, and the additive varies depending on the compound used, the target degree of polymerization, and the polymerization rate, but the molar ratio to the monomer, that is, the monomer: polymerization initiator is from 1: 0.3 to 1:
- the molar ratio to the polymerization initiator is between 10, ie, the polymerization initiator: additive is between 1: 0.05 and 1: 4.
- the heating conditions in the case of heat polymerization after coating the above mixed solution vary depending on the monomer used, the polymerization catalyst, the type of additives and their mixing ratio, concentration, coating film thickness, etc.
- the heating temperature is 25 ° C. to 120 ° C.
- the heating time is between 1 minute and 12 hours.
- a conductive polymer film is formed on the surface of the electrode substrate 7 or the electrode substrate with the conductive film, and then subjected to the above chemical polymerization to conduct the conductivity.
- a method of growing polymer particles can also be used.
- the thickness of the catalyst layer 6 in the counter electrode 9 is suitably 5 nm to 5 ⁇ m, particularly preferably 50 nm to 2 ⁇ m.
- the photoelectric conversion element 10 can be completed by assembling the metal oxide semiconductor electrode and the catalyst electrode so as to face each other through an electrolyte by a conventionally known method.
- a porous metal oxide semiconductor layer 3 was formed on a transparent conductive film 2 formed by vacuum deposition of a transparent conductive film 2 made of SnO 2 doped with fluorine on a transparent substrate 1 made of glass.
- the electrode substrate 8 having the transparent conductive film 2 formed on the transparent substrate FTO glass (manufactured by Nippon Sheet Glass Co., Ltd.) is used, and a commercially available titanium oxide paste (manufactured by Catalyst Kasei Co., Ltd., trade name TSP-18NR) , A particle size of 20 nm) is printed on the transparent conductive film 2 side by a screen printing method with a film thickness of about 6 ⁇ m and an area of about 5 mm ⁇ 10 mm, and a commercially available titanium oxide paste (catalyst chemical stock) on the same area.
- FTO glass manufactured by Nippon Sheet Glass Co., Ltd.
- a commercially available titanium oxide paste manufactured by Catalyst Kasei Co., Ltd., trade name TSP-18NR
- a particle size of 20 nm is printed on the transparent conductive film 2 side by a screen printing method with a film thickness of about 6 ⁇ m and an area of about 5 mm ⁇ 10 mm, and
- sensitizing dye 4 bis (4-carboxy-4′-tetrabutylammoniumcarboxy-2,2′-bipyridine) diisothiocyanate ruthenium complex (manufactured by Solaronix) generally called N719dye was used.
- the porous titanium oxide semiconductor electrode was immersed in an absolute ethanol solution having a pigment concentration of 0.4 mmol / L and allowed to stand overnight under light shielding. Thereafter, excess pigment was washed with absolute ethanol and then air-dried to produce a semiconductor electrode of a solar cell.
- an electrolytic solution constituting the electrolyte layer 5 was prepared. That is, 1-methyl-3-ethylimidazolium bis (fluorosulfonyl) imide (EMIm-FSI, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name Elexel IL-110) was used as a solvent, and 1.1 mol / L was used.
- EMIm-FSI 1-methyl-3-ethylimidazolium bis (fluorosulfonyl) imide
- counter electrode As the counter electrode 9, a poly (3,4-ethylenedioxythiophene) (hereinafter, PEDOT-PTS) counter electrode doped with p-toluenesulfonic acid was used. Glass with FTO coating (manufactured by Asahi Glass Co., Ltd., 10 ⁇ / ⁇ or less) was used as the electrode substrate 7, and the electrode substrate ultrasonically cleaned in an organic solvent was subjected to 3,4-ethylenedioxythiophene, tris-p-toluenesulfone.
- PEDOT-PTS poly (3,4-ethylenedioxythiophene)
- a reaction solution in which iron (III) acid and dimethyl sulfoxide were dissolved in n-butanol at a weight ratio of 1: 8: 1 was applied by spin coating.
- the spin coating was performed for 30 seconds under a rotation condition of 2000 rpm, and the concentration of 3,4-ethylenedioxythiophene in the solution was 0.48M.
- the electrode substrate coated with the solution was placed in a thermostat kept at 110 ° C., polymerized by heating for 5 minutes, and then washed with methanol to produce a counter electrode.
- the film thickness of the produced PEDOT thin film was about 0.3 ⁇ m.
- the counter electrode 9 produced as described above is provided with a 1 mm ⁇ electrolyte injection hole at an appropriate position with an electric drill, and then the titanium oxide film 3 on the transparent substrate 1 provided with the transparent conductive film 2 produced as described above.
- a thermoplastic sheet (made by Mitsui DuPont Polychemical Co., Ltd., product name: Himilan 1652, film thickness: 25 ⁇ m) is sandwiched between the electrode substrate 8 (working electrode) and the counter electrode, and both electrodes are bonded by thermocompression bonding. Glued.
- a 1 mm-thick glass plate is placed on the electrolyte injection hole, and a UV sealant (manufactured by ThreeBond Co., Ltd., developed product name 30Y) is placed thereon. -727) was applied, and sealing was carried out by irradiating UV light with an intensity of 100 mW / cm 2 for 30 seconds to produce a solar cell element.
- a UV sealant manufactured by ThreeBond Co., Ltd., developed product name 30Y
- Example 2 As the electrolyte layer 5, instead of 1-methyl-5-mercapto-1,2,3,4-tetrazole: 1-methyl-3-ethylimidazolium salt (EMIm-MTZT), 1-methyl-5-mercapto- A solar cell element was produced in the same manner as in Example 1 except that 1,2,3,4-tetrazole: 1-methyl-1-propylpyrrolidinium salt (MPPy-MTZT) was used.
- MEPy-MTZT 1-methyl-1-propylpyrrolidinium salt
- Example 3 As the electrolyte layer 5, instead of 1-methyl-5-mercapto-1,2,3,4-tetrazole: 1-methyl-3-ethylimidazolium salt (EMIm-MTZT), 1-methyl-5-mercapto- A solar cell element was produced in the same manner as in Example 1 except that 1,2,3,4-tetrazole: 1,2-dimethyl-3-propylimidazolium salt (DMPIm-MTZT) was used.
- Example 4 As the electrolyte layer 5, EMIm-FSI was used as a solvent, and 0.5 mol / L (MTZT) 2 , 1.4 mol / L EMIm-MTZT, 0.1 mol / L Li-MTZT, 0.5 mol / L was used as the electrolyte layer 5.
- a solar cell element was produced in the same manner as in Example 1 except that one prepared by dissolving NMBI of L was used.
- Example 5 As the electrolyte layer 5, EMIm-FSI was used as a solvent, and 0.8 mol / L (MTZT) 2 , 1.5 mol / L EMIm-MTZT, 0.1 mol / L Li-MTZT, 0.5 mol / L was used as the electrolyte layer 5.
- a solar cell element was produced in the same manner as in Example 1 except that one prepared by dissolving NMBI of L was used.
- Example 6 As the electrolyte layer 5, EMIm-FSI was used as a solvent, and 0.8 mol / L (MTZT) 2 , 1.1 mol / L EMIm-MTZT, 0.1 mol / L Li-MTZT, 0.5 mol / L A solar cell element was produced in the same manner as in Example 1 except that one prepared by dissolving NMBI of L was used.
- Comparative Example 2 As a counter electrode 9, a solar cell element was produced in the same manner as in Comparative Example 1 except that a Pt counter electrode (manufactured by Geomatec) obtained by depositing Pt on ITO conductive glass by sputtering was used.
- a Pt counter electrode manufactured by Geomatec
- IPCE incident-photo-to-current conversion efficiency
- the element IV characteristics were similarly evaluated under the condition that the irradiation light of the solar simulator was dimmed using a 1% or 10% ND filter (manufactured by Sigma Koki Co., Ltd.). .
- the light irradiation intensity was calculated using a spectrum analyzer (LS-100, manufactured by Eihiro Seiki Co., Ltd.) by comparing the integrated value of irradiation light in the region of ⁇ : 400 to 800 nm with the value of reference sunlight.
- LS-100 manufactured by Eihiro Seiki Co., Ltd.
- Table 1 shows the IV characteristic evaluation results and the stability evaluation results of the photoelectric conversion elements of the examples and comparative examples under simulated sunlight irradiation conditions.
- the photoelectric conversion elements of Examples 1 to 6 according to the present invention have a photoelectric conversion level equal to or higher than that of the element of Comparative Example 1 using the same ionic liquid as a solvent and using a conventional iodine-based redox pair.
- the performance is shown under simulated sunlight irradiation conditions.
- the device performance under pseudo-sunlight irradiation conditions is about half that of iodine, and therefore the redox couple of the present invention is superior.
- the electrolyte layer and the surface of the conductive glass are interposed between the FTO conductive glass and the porous semiconductor layer. It is necessary to provide a dense semiconductor layer such as titanium oxide in order to prevent contact, but since the redox couple of the present invention has low reactivity on FTO conductive glass, it is as described above even without providing a dense layer. High device performance and high practicality.
- FIG. 2 shows the results of IPCE measurement (results normalized by the IPCE maximum value) of the photoelectric conversion element of Example 1 as (A) and Comparative Example 1 as (B). It can be seen that Example 1 using the redox couple of the present invention has a higher IPCE value around ⁇ : 350 to 500 nm than Comparative Example 1 using a conventional iodine-based redox couple. This indicates that in Comparative Example 1, the iodine absorption is in the vicinity of the above wavelength, and the iodine redox couple absorbs light and hinders the light absorption of the dye, resulting in a decrease in the IPCE value. .
- Example 1 since the redox couple of Example 1 does not have large absorption in the visible light region, the IPCE value is high near ⁇ : 350 to 500 nm. This can also be seen from the IV characteristic evaluation results shown in Table 1 in which the short circuit current values (Jsc) of Examples 1 to 3 are higher than those of Comparative Example 1.
- Comparative Example 2 using the Pt electrode as the counter electrode is inferior in element performance to Example 1 using the PEDOT electrode as the counter electrode, and the value of FF is particularly lowered.
- PEDOT has higher catalytic activity for the sulfide-based redox couple used in the present invention than Pt. This can also be confirmed from an interface reaction resistance analysis by impedance measurement described later. Therefore, in this invention, it can be said that the photoelectric conversion element which shows high photoelectric conversion efficiency is producible by using together a specific oxidation-reduction pair and conductive polymer catalysts, such as PEDOT.
- Comparative Example 3 in which 1-methyl-5-mercapto-1,2,3,4-tetrazole: tetramethylammonium salt shown in Non-Patent Document 6 is used as a reduced form is obtained by adding the reduced form to an ionic liquid. Since solubility is lower than the compound of this invention, it can melt
- Comparative Example 4 using a sulfide redox having a thiadiazole skeleton disclosed in Patent Document 1 as a redox pair has a low solubility in a solvent of a disulfide compound as an oxidant, and therefore, compared with Example 1. Since the photoelectric conversion performance was inferior and the electrolyte solution was unstable under high concentration conditions, the device performance retention after 30 days had dropped to about 50%. On the other hand, in Examples 1 to 6 of the present invention, the device performance hardly deteriorated even after 30 days. Therefore, it turns out that a practical photoelectric conversion element can be produced by combining the redox couple of the present invention, a conductive polymer catalyst, and an ionic liquid.
- Example 1 and Examples 4 to 6 are compared, the number of moles of the compound (reduced form) represented by the general formula (1) with respect to the number of moles of the compound represented by the formula (2) (oxidized form). It can be seen that the device performance was improved more when the number was used excessively. The reason is not clear, but when an excessive amount of the reductant is used, a charge transfer complex is formed from the oxidant (T 2 ) and the reductant (T ⁇ ) (indicated as T 2 ⁇ T ⁇ ⁇ T 3 ⁇ ). It is considered that the charge transfer performance is improved. In addition, it is considered that one of the reasons for improving the device performance is that the charge exchange reaction occurring between the oxidant and the reductant is more likely to occur when the reductant is excessive.
- FIG. 3 shows the relationship between the light irradiation intensity and the element power generation performance in the elements of Example 1 and Comparative Example 1.
- (A) is Example 1 and (B) is Comparative Example 1.
- the photoelectric conversion element of the present invention shown in Example 1 has a power generation equivalent to or higher than that of Comparative Example 1 using a conventional iodine-based redox pair. The characteristics are shown. This indicates that the photoelectric conversion element of the present invention operates effectively even under weak light conditions. Therefore, it can be said that the photoelectric conversion element of the present invention is highly practical.
- Example 1 [Production of electrolyte solution evaluation element, evaluation of electrolyte properties]
- the counter electrode PEDOT counter electrode was used instead of the working electrode in Examples 1 to 4 and Comparative Example 1.
- a counter electrode / electrolytic solution / counter electrode element for evaluating an electrolytic solution was prepared by preparing a sandwich cell by the technique. Examples corresponding to Examples 1, 2, 3, 4 and Comparative Example 1 were designated as Examples 1 ′, 2 ′, 3 ′, 4 ′ and Comparative Example 1 ′, respectively.
- CV cyclic voltammetry
- IMP impedance
- IM6 impedance analyzer
- FIG. 4 shows the results of CV measurement.
- (A) is Example 1 ′
- (B) is Example 2 ′
- (C) is Example 3 ′
- (D) is Example 4 ′
- (E) is Comparative Example 1 ′.
- Examples 1 ′ to 4 ′ using the redox couple of the present invention and ionic liquid are all compared with Comparative Example 1 ′ using the conventional iodine-based redox couple and ionic liquid as the electrolyte.
- Comparative Example 1 ′ using the conventional iodine-based redox couple and ionic liquid as the electrolyte.
- the interface resistance between the redox couple of Examples 1 ′ to 4 ′ and the counter electrode catalyst is sufficiently small as the interface resistance between the iodine-based redox couple / counter electrode catalyst of Comparative Example 1 ′. It was confirmed. This indicates that the redox reaction of the redox couple dissolved in the ionic liquid of the present invention is superior to the conventional iodine-based redox couple.
- the photoelectric conversion device of the present invention is superior to the conventional iodine-based redox couple in terms of device performance and transparency, and the redox couple specified in the present invention.
- an ionic liquid and an organic conductive polymer counter electrode By using an ionic liquid and an organic conductive polymer counter electrode, a highly practical solar cell element excellent in performance, durability, cost, and design can be provided.
- the photoelectric conversion element according to the present invention is suitably used as a photoelectric conversion element that can be used indoors and outdoors. Further, by utilizing the characteristics of the electrolyte of the present invention, it can be applied to consumer equipment and the like that are particularly required to be designed. It can be used. Furthermore, it can be used not only as a photoelectric conversion element but also as an optical sensor.
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Abstract
Description
電極基体8を構成する透明基体1は、可視光を透過するものが使用でき、透明なガラスが好適に利用できる。また、ガラス表面を加工して入射光を散乱させるようにしたものも使用できる。また、ガラスに限らず、光を透過するものであれば、プラスチック板やプラスチックフィルム等も使用できる。
透明導電膜2としては、可視光を透過して、かつ導電性を有するものが使用できる。このような材料としては、例えば金属酸化物が挙げられる。特に限定はされないが、例えばフッ素をドープした酸化スズ(以下、「FTO」と略記する。)や、酸化インジウム、酸化スズと酸化インジウムの混合体(以下、「ITO」と略記する。)、アンチモンをドープした酸化スズ、酸化亜鉛などを好適に用いることができる。
多孔質金属酸化物半導体3としては、特に限定はされないが、酸化チタン、酸化亜鉛、酸化スズなどが挙げられ、特に二酸化チタン、さらにはアナターゼ型二酸化チタンが好適である。
増感色素4としては、太陽光により励起されて上記金属酸化物半導体3に電子注入できるものであればよく、一般的に光電変換素子に用いられている色素を用いることができるが、変換効率を向上させるためには、その吸収スペクトルが太陽光スペクトルと広波長域で重なっていて、耐光性が高いことが望ましい。
本発明で用いる電解質層5は、一般式(1)で示される化合物および式(2)で示される化合物からなる酸化還元対を含むものである。なお、一般式(1)で示される化合物が還元体、式(2)で示される化合物が酸化体である。
対向電極9は、電極基材7の表面に触媒層6が形成された構造をしている。この電極基材7は、触媒層6の支持体兼集電体として用いられるため、表面部分に導電性を有していることが好ましい。
[実施例1]
[多孔質金属酸化物半導体の作製]
ガラスからなる透明基板1上にフッ素をドープしたSnO2からなる透明導電膜2を真空蒸着により形成した透明導電膜2上に、以下の方法で多孔質金属酸化物半導体層3を形成した。
増感色素4として、一般にN719dyeと呼ばれるビス(4-カルボキシ-4’-テトラブチルアンモニウムカルボキシ-2,2’-ビピリジン)ジイソチオシアネートルテニウム錯体(Solaronix社製)を使用した。上記多孔質酸化チタン半導体電極を色素濃度0.4mmol/Lの無水エタノール溶液中に浸漬し、遮光下でひと晩静置した。その後無水エタノールにて余分な色素を洗浄してから風乾することで太陽電池の半導体電極を作製した。
次に、電解質層5を構成する電解液を調製した。すなわち、溶媒として1-メチル-3-エチルイミダゾリウムビス(フルオロスルホニル)イミド(EMIm-FSI、第一工業製薬(株)製、製品名エレクセルIL-110)を用い、それに1.1mol/Lの5,5’-ジチオビス(1-メチル-1H-テトラゾール)((MTZT)2)、0.1mol/Lの1-メチル-5-メルカプト-1,2,3,4-テトラゾール:リチウム塩(Li-MTZT)、1.0mol/Lの1-メチル-5-メルカプト-1,2,3,4-テトラゾール:1-メチル-3-エチルイミダゾリウム塩(EMIm-MTZT)、0.5mol/LのN-メチルベンズイミダゾール(NMBI)を溶解させることにより調製した。
対向電極9として、p-トルエンスルホン酸がドープされたポリ(3,4-エチレンジオキシチオフェン)(以下、PEDOT-PTS)対極を使用した。電極基体7としてFTO被膜付きガラス(旭硝子(株)製、10Ω/□以下)を用い、有機溶媒中で超音波洗浄した電極基体に、3,4-エチレンジオキシチオフェン、トリス-p-トルエンスルホン酸鉄(III)、ジメチルスルホキシドを重量比で1:8:1の割合でn-ブタノールに溶解させた反応溶液をスピンコート法にて塗布した。スピンコートは、回転条件2000rpmの条件で30秒間行い、溶液における3,4-エチレンジオキシチオフェンの濃度は0.48Mであった。つづいて、溶液を塗布した電極基板を110℃に保持した恒温槽に入れ、5分間加熱することで重合させた後、メタノールで洗浄することで対向電極を作製した。作製したPEDOT薄膜の膜厚は約0.3μmであった。
上記のように作製した対向電極9に電気ドリルで1mmφの電解液注入孔を適当な位置に設けたのち、上記のように作製した透明導電膜2を具備した透明基板1上の酸化チタン膜3からなる電極基体8(作用極)と、対向電極の間に熱可塑性シート(三井・デュポンポリケミカル(株)製、製品名ハイミラン1652、膜厚25μm)を挟み、熱圧着することにより両電極を接着した。次に、上記のように作製した電解液を両電極間に注入した後、電解液注入孔上に1mm厚のガラス板を置き、その上にUVシール剤(スリーボンド(株)製、開発品名30Y-727)を塗布し、UV光を100mW/cm2の強度で30秒照射することで封止を実施し、太陽電池素子を作製した。
電解質層5として、1-メチル-5-メルカプト-1,2,3,4-テトラゾール:1-メチル-3-エチルイミダゾリウム塩(EMIm-MTZT)の代わりに、1-メチル-5-メルカプト-1,2,3,4-テトラゾール:1-メチル-1-プロピルピロリジニウム塩(MPPy-MTZT)を使用した以外は実施例1と同様にして、太陽電池素子を作製した。
電解質層5として、1-メチル-5-メルカプト-1,2,3,4-テトラゾール:1-メチル-3-エチルイミダゾリウム塩(EMIm-MTZT)の代わりに、1-メチル-5-メルカプト-1,2,3,4-テトラゾール:1,2-ジメチル-3-プロピルイミダゾリウム塩(DMPIm-MTZT)を使用した以外は実施例1と同様にして、太陽電池素子を作製した。
電解質層5として、EMIm-FSIを溶媒として用い、これに0.5mol/Lの(MTZT)2、1.4mol/LのEMIm-MTZT、0.1mol/LのLi-MTZT、0.5mol/LのNMBIを溶解させることにより調製したものを使用した以外は実施例1と同様にして、太陽電池素子を作製した。
電解質層5として、EMIm-FSIを溶媒として用い、これに0.8mol/Lの(MTZT)2、1.5mol/LのEMIm-MTZT、0.1mol/LのLi-MTZT、0.5mol/LのNMBIを溶解させることにより調製したものを使用した以外は実施例1と同様にして、太陽電池素子を作製した。
電解質層5として、EMIm-FSIを溶媒として用い、これに0.8mol/Lの(MTZT)2、1.1mol/LのEMIm-MTZT、0.1mol/LのLi-MTZT、0.5mol/LのNMBIを溶解させることにより調製したものを使用した以外は実施例1と同様にして、太陽電池素子を作製した。
電解質層5として、1-メチル-3-エチルイミダゾリウムビス(トリフルオロメタンスルホニル)イミド(EMIm-FSI)を溶媒として用い、それに0.2mol/Lのヨウ素、2.0mol/Lの1,2-ジメチル-3-エチルイミダゾリウムアイオダイド(DMPIm-I)、0.5mol/LのN-メチルベンズイミダゾール(NMBI)を溶解させたものを使用した以外は実施例1と同様にして太陽電池素子を作製した。
対向電極9として、スパッタ法によりITO導電性ガラス上にスパッタ法によりPtを蒸着したPt対極(ジオマテック製)を使用した以外は比較例1と同様に太陽電池素子を作製した。
電解質層5として、1-メチル-3-エチルイミダゾリウムビス(トリフルオロメタンスルホニル)イミド(EMIm-FSI)を溶媒として用い、それに0.5mol/Lの1-メチル-5-メルカプト-1,2,3,4-テトラゾール:テトラメチルアンモニウム塩、0.5mol/Lの2,2’‐ジチオビス(5-メチル-1,3,4-チアジアゾール)、0.5mol/LのN-メチルベンズイミダゾール(NMBI)を溶解させたものを使用した以外は実施例1と同様に太陽電池素子を作製した。
電解質層5として、1-メチル-3-エチルイミダゾリウムビス(トリフルオロメタンスルホニル)イミド(EMIm-FSI)を溶媒として用い、それに2mol/Lの5-メチル-2-メルカプト-1,3,4-チアジアゾール:1-メチル-3-エチルイミダゾリウム塩(EMIm-MTT)、0.2Mの2,2’-ジチオビス(5-メチル-1,3,4-チアジアゾール)、0.5mol/LのN-メチルベンズイミダゾール(NMBI)を溶解させたものを使用した以外は実施例1と同様に太陽電池素子を作製した。
1-メチル-1,2,3,4-テトラゾール-5-チオール1モル等量と炭酸カリウム0.5モル等量をメタノールに溶かし、攪拌しながら炭酸カリウムが溶けてなくなるまで(約2.5時間)超音波バス処理を行った。その後、ろ紙を使用して固形物を除き、溶媒をロータリーエバポレーターにより留去し、生じた白色固形物をジクロロメタンで洗浄後、真空乾燥することで1-メチル-5-メルカプト-1,2,3,4-テトラゾール:カリウム塩を合成した。上記の反応収率は82%であった。
1-メチル-5-メルカプト-1,2,3,4-テトラゾール:カリウム塩の合成において、炭酸カリウムに代えて炭酸リチウムを用いることで1-メチル-5-メルカプト-1,2,3,4-テトラゾール:リチウム塩を合成した。上記の反応収率は48%であった。
1-メチル-1,2,3,4-テトラゾール-5-チオール1モル等量をメタノールに溶解させたものと1-メチル-3-エチルイミダゾリウム炭酸水素塩(EMIm-HCO3)1モル当量をメタノールに溶解させたものとを混合し、3時間攪拌後、溶媒をロータリーエバポレーターにより留去することにより、常温で液体の1-メチル-5-メルカプト-1,2,3,4-テトラゾール:EMIm塩を合成した。上記の反応収率は98%であった。
1-メチル-1,2,3,4-テトラゾール-5-チオール1モル等量をメタノールに溶解させたものと、1-メチル-1-プロピルピロリジニウムヒドロキシド(MPPy-OH)1モル当量をメタノールに溶解させたものとを混合し、3時間攪拌後、溶媒をロータリーエバポレーターにより留去することにより、常温で液体の1-メチル-5-メルカプト-1,2,3,4-テトラゾール:MPPy塩を合成した。上記の反応収率は96%であった。
1-メチル-1,2,3,4-テトラゾール-5-チオール1モル等量をメタノールに溶解させたものと、1,2-ジメチル-3-プロピルイミダゾリウムヒドロキシド(DMPIm-OH)1モル当量をメタノールに溶解させたものとを混合し、3時間攪拌後、溶媒をロータリーエバポレーターにより留去することにより、常温で液体の1-メチル-5-メルカプト-1,2,3,4-テトラゾール:DMPIm塩を合成した。上記の反応収率は99%であった。
上記により作製した太陽電池の評価を以下の手法で実施した。性能評価には、AMフィルターを具備したキセノンランプのソーラーシュミレーター(関西科学機械株式会社より購入、XES-502S)にて、AM1.5Gのスペクトル調整後、100mW/cm2の照射条件下で、ポテンシオスタットによる負荷特性(I-V特性)を評価した。太陽電池の評価値としては、開放電圧Voc(V)、短絡電流密度Jsc(mA/cm2)、形状因子FF(-)、変換効率η(%)が用いられるが、最終的な太陽電池の性能の良否は、変換効率の大小で評価した。また、暗所、室温条件下での素子性能保持率を合わせて評価した。
各酸化還元対を溶解させた電解液自身の特性を比較するために、実施例1~4、比較例1において、作用極の代わりに対向電極のPEDOT対極を用いた以外は実施例1と同じ手法でサンドイッチセルを作製することで、電解液評価用の対極/電解液/対極素子を作成した。実施例1、2、3、4、比較例1に対応するものを、それぞれ実施例1’、2’、3’、4’、比較例1’とした。
CV測定条件;測定範囲:-1~1V、スイープ速度:10mV/sec
IMP測定条件;測定範囲:1MHz~100mHz、振幅:10mV、印加電圧:0V
2 ・・・透明導電膜
3 ・・・多孔質金属酸化物半導体(層)
4 ・・・増感色素
5 ・・・電解質層
6 ・・・触媒層
7 ・・・電極基材
8 ・・・電極基体(作用極)
9 ・・・対向電極
10・・・光電変換素子
Claims (3)
- 半導体電極と、対向電極と、これら半導体電極と対向電極との間に保持された電解質層とを備えた光電変換素子であって、
前記電解質層が、次の一般式(1)で示される化合物および式(2)で示される化合物からなる酸化還元対、ならびに式(3)で示されるビス(フルオロスルホニル)イミドアニオンを有するイオン液体を含む
ことを特徴とする、光電変換素子。
- 前記電解質層中における一般式(1)で示される化合物の濃度が0.5mol/L以上であり、式(2)で示される化合物の濃度が0.5mol/L以上であることを特徴とする、請求項1に記載の光電変換素子。
- 前記対向電極が、前記酸化還元対に対する触媒活性を有する導電性高分子触媒を含有することを特徴とする、請求項1又は2に記載の光電変換素子。
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JP2012552681A JP5475145B2 (ja) | 2011-01-13 | 2012-01-11 | 光電変換素子 |
KR1020137016631A KR101417700B1 (ko) | 2011-01-13 | 2012-01-11 | 광전변환소자 |
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EP (1) | EP2665121A1 (ja) |
JP (1) | JP5475145B2 (ja) |
KR (1) | KR101417700B1 (ja) |
CN (1) | CN103299478B (ja) |
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Cited By (5)
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JP2014044813A (ja) * | 2012-08-24 | 2014-03-13 | Osaka Gas Co Ltd | 電解液及び光電変換素子 |
WO2014076896A1 (ja) * | 2012-11-15 | 2014-05-22 | 国立大学法人岐阜大学 | 酸化還元対およびそれを用いた光電変換素子 |
JP2014154498A (ja) * | 2013-02-13 | 2014-08-25 | Nsk Ltd | 光電変換素子 |
JP2014157914A (ja) * | 2013-02-15 | 2014-08-28 | Toyo Ink Sc Holdings Co Ltd | 熱電変換素子用組成物およびその用途 |
JP2016004934A (ja) * | 2014-06-18 | 2016-01-12 | カーリットホールディングス株式会社 | 色素増感太陽電池用電解液及びそれを用いた色素増感太陽電池 |
Families Citing this family (4)
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KR20150086050A (ko) * | 2014-01-17 | 2015-07-27 | 동우 화인켐 주식회사 | 신규의 설포닐이미드 염화합물, 이의 제조 방법 및 이를 포함하는 광산 발생제 및 감광성 수지 조성물 |
JP7012660B2 (ja) | 2016-04-01 | 2022-02-14 | ノームズ テクノロジーズ インコーポレイテッド | リン含有修飾イオン性液体 |
CN110915037B (zh) | 2017-07-17 | 2023-11-07 | 诺姆斯科技公司 | 含磷电解质 |
US11267707B2 (en) | 2019-04-16 | 2022-03-08 | Honeywell International Inc | Purification of bis(fluorosulfonyl) imide |
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- 2012-01-11 WO PCT/JP2012/000125 patent/WO2012096170A1/ja active Application Filing
- 2012-01-11 KR KR1020137016631A patent/KR101417700B1/ko active IP Right Grant
- 2012-01-11 US US13/979,200 patent/US8907209B2/en active Active
- 2012-01-11 EP EP12734354.9A patent/EP2665121A1/en not_active Withdrawn
- 2012-01-12 TW TW101101232A patent/TWI499062B/zh active
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2014044813A (ja) * | 2012-08-24 | 2014-03-13 | Osaka Gas Co Ltd | 電解液及び光電変換素子 |
WO2014076896A1 (ja) * | 2012-11-15 | 2014-05-22 | 国立大学法人岐阜大学 | 酸化還元対およびそれを用いた光電変換素子 |
JP2014099364A (ja) * | 2012-11-15 | 2014-05-29 | Gifu Univ | 酸化還元対およびそれを用いた光電変換素子 |
KR20150082274A (ko) | 2012-11-15 | 2015-07-15 | 고꾸리츠 다이가꾸호오징 기후다이가꾸 | 산화환원쌍 및 이를 사용한 광전변환소자 |
JP2014154498A (ja) * | 2013-02-13 | 2014-08-25 | Nsk Ltd | 光電変換素子 |
JP2014157914A (ja) * | 2013-02-15 | 2014-08-28 | Toyo Ink Sc Holdings Co Ltd | 熱電変換素子用組成物およびその用途 |
JP2016004934A (ja) * | 2014-06-18 | 2016-01-12 | カーリットホールディングス株式会社 | 色素増感太陽電池用電解液及びそれを用いた色素増感太陽電池 |
Also Published As
Publication number | Publication date |
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KR101417700B1 (ko) | 2014-07-09 |
KR20130099184A (ko) | 2013-09-05 |
TW201236174A (en) | 2012-09-01 |
JP5475145B2 (ja) | 2014-04-16 |
CN103299478A (zh) | 2013-09-11 |
TWI499062B (zh) | 2015-09-01 |
US8907209B2 (en) | 2014-12-09 |
US20130291943A1 (en) | 2013-11-07 |
CN103299478B (zh) | 2015-05-20 |
JPWO2012096170A1 (ja) | 2014-06-09 |
EP2665121A1 (en) | 2013-11-20 |
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