CN102859786A - Method for producing electrode for photoelectric conversion element - Google Patents
Method for producing electrode for photoelectric conversion element Download PDFInfo
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- CN102859786A CN102859786A CN2010800663368A CN201080066336A CN102859786A CN 102859786 A CN102859786 A CN 102859786A CN 2010800663368 A CN2010800663368 A CN 2010800663368A CN 201080066336 A CN201080066336 A CN 201080066336A CN 102859786 A CN102859786 A CN 102859786A
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- Prior art keywords
- photocatalysis membrana
- electrode
- alcohol
- photoelectric conversion
- transparency carrier
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 claims description 59
- 238000007146 photocatalysis Methods 0.000 claims description 59
- 239000011248 coating agent Substances 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 33
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000003086 colorant Substances 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000003504 photosensitizing agent Substances 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 abstract 6
- 230000002165 photosensitisation Effects 0.000 abstract 2
- 239000000975 dye Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 238000002485 combustion reaction Methods 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 229910044991 metal oxide Inorganic materials 0.000 description 11
- 150000004706 metal oxides Chemical class 0.000 description 11
- 239000002245 particle Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 150000004703 alkoxides Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 239000008393 encapsulating agent Substances 0.000 description 3
- 238000002803 maceration Methods 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- -1 Merlon Polymers 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000012327 Ruthenium complex Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009503 electrostatic coating Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 1
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000004698 iron complex Chemical class 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
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 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
- 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
- 239000003960 organic solvent Substances 0.000 description 1
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
-
- 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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—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
- Y02E10/542—Dye sensitized solar cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Electromagnetism (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Computer Hardware Design (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
Disclosed is a method for producing an electrode for a photoelectric conversion element, which is capable of dehydrating a photocatalyst film in a short time at low cost without requiring large-scale equipment. Specifically disclosed is a method for producing an electrode for a photoelectric conversion element, wherein: a transparent conductive film is formed on a transparent substrate (2); a photocatalyst film is formed on the transparent conductive film; and the photocatalyst film is caused to adsorb a photosensitizing dye. Before the adsorption of the photosensitizing dye by the photocatalyst film, the transparent substrate (2), which has been provided with the photocatalyst film, is immersed in an alcohol (5) that has an azeotropic temperature with water of 150 DEG C or less and then heated therein, thereby dehydrating the photocatalyst film by azeotropy of water and the alcohol.
Description
Technical field
The present invention relates to a kind of photo-electric conversion element, it will have at transparency carrier the electrode and at a certain distance subtend configuration of the opposite pole that has at least conductive component on the opposite pole substrate of nesa coating and the photocatalysis membrana on it, and configure electrolyte between the two poles of the earth; The present invention is specifically related to the preparation method of the electrode of described photo-electric conversion element.
Background technology
Usually, the known photo-electric conversion elements such as dye-sensitized solar cell, it forms nesa coating at transparency carriers such as glass plates, and form the photocatalysis membrana that the metal oxide by titanium oxide and so on consists of thereon, then form electrode at the light-sensitive coloring agent (photosensitizer dye) such as this film absorption ruthenium complex, thereby form nesa coating at opposite pole with transparency carrier and form opposite pole, subtend is prepared described electrode and opposite pole, gets involved the dielectric substrate (patent documentation 1) that is made of iodine electrolyte etc. between two electrodes.
Photocatalysis membrana by the metal oxide of above-mentioned titanium oxide and so on consists of if contain moisture, can hinder the absorption light-sensitive coloring agent, thus the problem that causes photoelectric conversion efficiency to reduce.Therefore, proposed before the absorption light-sensitive coloring agent, photocatalysis membrana is configured in the combustion chamber that has added dehydrating agent and drier, and the method for the indoor atmosphere of circulating combustion, or by photocatalysis membrana is configured in the combustion chamber, to the method such as reducing pressure in the combustion chamber, photocatalysis membrana is carried out processed, thereby improve the adsorptivity (patent documentation 2) of light-sensitive coloring agent.
The prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2002-93475 communique
Patent documentation 2: Japanese Patent Laid-Open 2005-251591 communique
Summary of the invention
The technical problem that (one) will solve
But, when stating dewatering on the implementation, the high cost that needs the main equipment such as combustion chamber or decompressor and be used for described equipment.And, in the method based on dehydrating agent or drier, spended time on processed, in the method based on decompression, although self of dewatering needed time can shorten decompression and turned back to the operation spended time of atmospheric pressure state by decompression state.No matter adopt any method, all spended times on processed, and the substrate that needs to have photocatalysis membrana are configured in the combustion chamber, and therefore the processed of large-area substrate or continuous dehydration have difficulties in processing.
Therefore, technical scheme of the present invention provides a kind of large-scale plant that do not need, and can carry out at short notice with low cost the preparation method of the electrode for photoelectric conversion elements of processed to photocatalysis membrana.
(2) technical scheme
The related invention of claim 1 is a kind of preparation method of electrode for photoelectric conversion elements, it forms nesa coating at transparency carrier, and form photocatalysis membrana thereon, then adsorb light-sensitive coloring agent at this photocatalysis membrana, it is characterized in that, before photocatalysis membrana absorption light-sensitive coloring agent, being impregnated into the photocatalysis membrana of transparency carrier with the water azeotropic temperature is in the alcohol below 150 ℃, subsequently heating, the azeotropic by water and alcohol makes photocatalysis membrana dehydration.
The related invention of claim 2 is the preparation method of electrode for photoelectric conversion elements according to claim 1, it is characterized in that, described alcohol is 1-propyl alcohol or n-butyl alcohol.
The related invention of claim 3 is the preparation method of electrode for photoelectric conversion elements according to claim 1 and 2, transparency carrier is the substrate of film or sheet, and carry out continuously photocatalysis membrana formation, photocatalysis membrana dehydration and make photocatalysis membrana absorption light-sensitive coloring agent.
(3) invention effect
In the related invention of claim 1, before photocatalysis membrana absorption light-sensitive coloring agent, being impregnated into azeotropic temperature with water by the transparency carrier that will have above-mentioned photocatalysis membrana is in the alcohol below 150 ℃, subsequently heating, therefore do not need such as large-scale plants such as combustion chambers of the prior art, can carry out processed to photocatalysis membrana at short notice with low cost.
In addition, do not need as prior art, to be configured in photocatalysis membrana in the combustion chamber that has added dehydrating agent and drier and the atmosphere in the combustion chamber is circulated, or be configured in photocatalysis membrana in the combustion chamber and to reducing pressure in the combustion chamber, therefore large-area electrode can be tackled, continued operation can be carried out simultaneously.
The invention that claim 2 is related, as alcohol use 1-propyl alcohol or the n-butyl alcohol of dipping usefulness, therefore except above-mentioned effect, the azeotropic content of water is many, also has the effect of excellent in safety.
The invention that claim 3 is related except above-mentioned effect, by the transparency carrier of film or sheet is provided continuously, can comprise the preparation of the electrode of above-mentioned dehydration procedure continuously.
Description of drawings
Fig. 1 is preparation method's the flow chart that roughly represents the electrode for photoelectric conversion elements of embodiment 1.
Fig. 2 is the vertical sectional arrangement drawing of the photo-electric conversion element of expression reference example 1.
Embodiment
In the preparation method of electrode for photoelectric conversion elements of the present invention, at first, form nesa coating at transparency carrier, then form photocatalysis membrana at nesa coating.
As transparency carrier, be fit to use synthetic resin board, glass plate etc., but preferred PEN(PEN) thermoplastic resin film such as film.Except PEN, synthetic resin can also be PETG, polyester, Merlon, polyolefin etc.The preferred tens μ m to 1mm of the thickness of transparency carrier.
The formation method of nesa coating has ion evaporation, CVD method etc. multiple, it is not limited, but particularly preferably implement by sputter (spatter) method.As the metallic target in the sputtering method, suitable use becomes tin-doped indium oxide (ITO), fluorine doped tin oxide (FTO), the tin oxide (SnO of nesa coating
2), the In-Sn alloy of indium-zinc oxide (IZO), zinc oxide (ZnO) material, Zn, In-Zn alloy, Sn, Ga-Zn alloy, Al-Zn alloy etc., but so long as can form nesa coating by enough non-oxide metals, just have no particular limits.The thickness of nesa coating is preferred tens of to hundreds of nm.
Metal oxide layer (photocatalysis membrana) the preferential oxidation titanium, the zinc oxide that form at above-mentioned nesa coating.Formation method as photocatalysis membrana, though be not particularly limited, be fit to using and will being dispersed in particle diameter in the pure equal solvent by roller bearing etc. is that the paste-like mixed solution of the metal oxide particle of 20 ~ 60 μ m is coated on method on the nesa coating or the method for electrostatic applications metal oxide sol.
Electrostatic applications about metal oxide sol, with electrostatic coating apparatus as negative side, as the nesa coating of the transparency electrode of applied thing as side of the positive electrode, apply high voltage at two interpolars and form electrostatic field, make the metal oxide that goes out from the nozzle ejection of electrostatic coating apparatus charged in negative side, thereby be coated on the nesa coating surface.
As the metallic compound of metal oxide sol initiation material, in metallo-organic compound, can exemplify such as metal alkoxide, acetyl acetone salt, metal carboxylate; In metal inorganic compound, can exemplify nitrate such as metal, oxychloride, chloride etc.
As above-mentioned metal oxide, the preferential oxidation titanium, other can exemplify tin oxide, tungsten oxide, zinc oxide, niobium oxide etc.
As an example that uses titanium oxide, can exemplify such as tetramethyl alcohol titanium, titanium ethanolate, isopropyl titanate, butanols titanium etc. as metal alkoxide, can exemplify titanium acetylacetone etc. as acetyl acetone salt, carboxylic acid titanium etc. can be exemplified as metal carboxylate, Titanium Nitrate, titanium oxychloride, titanium tetrachloride etc. can also be exemplified.
In addition, by in above-mentioned metallic compound, adding solvent, acid or the ammonia of water, methyl alcohol, ethanol, 1-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 2-butanols, isobutanol, the tert-butyl alcohol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol etc., and other additives, carry out solation, gelation.
In the situation of using above-mentioned metal alkoxide, preferably containing particle diameter in metal alkoxide is the above-mentioned metal oxide particle of 20 ~ 60nm, and further containing as required as light scattering is the particle of the metal oxide of 100 ~ 400 μ m with the particle diameter of particle.
After having carried out above-mentioned coating or electrostatic applications, dry and/or burn till.Drying is preferably at room temperature carried out about 5 ~ 15 minutes.Burn till preferably under 120 ~ 1 50 ℃, carry out about 10 ~ 30 minutes.The thickness of the photocatalysis membrana that forms according to said method is preferably 5 ~ 20 μ m.
Then, it is in the alcohol below 150 ℃ that above-mentioned photocatalysis membrana is impregnated into azeotropic temperature with water, and subsequently heating makes the photocatalysis membrana dehydration by the azeotropic by water and alcohol.
In preferred embodiment, be impregnated into the transparency carrier that forms above-mentioned photocatalysis membrana in the above-mentioned alcohol after, drying is burnt till subsequently, thereby makes the photocatalysis membrana dehydration.
The preferred normal temperature of above-mentioned dipping temperature in alcohol, but also alcohol can be heated to the degree that thermal deformation does not occur transparency carrier.Dip time, preferred about 30 seconds ~ 10 minutes.
As alcohol, though preferred transparency carrier used can not cause in the situation of synthetic resin etc. yet thermal deformation and with the azeotropic point of water be alcohol below 150 ℃, the more preferably alcohol many with water azeotropic content.For example, can use the alcohol shown in the table 1.
Table 1
In addition, consider fail safe, more preferably 1-propyl alcohol, n-butyl alcohol.
Drying is preferably at room temperature carried out about 5 ~ 15 minutes.Burn till preferably under 120 ~ 150 ℃, carry out about 5 ~ 10 minutes.
By above-mentioned drying and burn till, so that be included in moisture and pure azeotropic in the photocatalysis membrana, the photocatalysis membrana dehydration.In addition, by photocatalysis membrana is maintained in the high temperature, thereby improve the adsorptivity of follow-up dyestuff.
Then, make the photocatalysis membrana absorbing dye.Preferably, shorten as much as possible the time that is dewatered to Dye Adsorption from above-mentioned.This is in order to prevent that photocatalysis membrana from reuptaking moisture, and the drop in temperature that prevents photocatalysis membrana.
The absorption of dyestuff was for example flooded in the maceration extract that contains light-sensitive coloring agent 30 ~ 60 minutes by photocatalysis membrana is immersed in, and made this dyestuff of adsorption of photocatalysis membrana and implemented.Behind the preferred dipping, drying is also burnt till.The metal complex of light-sensitive coloring agent such as the ruthenium complex that can think parts such as containing bipyridine structure, terpyridyl structure or iron complex, porphyrin system or phthalocyanine system, can also be the organic dyestuff such as eosin, rhodamine, merocyanine, cumarin etc.By above operation, make the electrode that is formed with photocatalysis membrana at transparency carrier.
Use the photo-electric conversion element of above-mentioned electrode, for example mainly consisted of by the transparency electrode that possesses the photocatalysis membrana that has adsorbed above-mentioned dyestuff, opposite pole opposed with it and the dielectric substrate that configures at two interpolars.
As electrolyte, for example, can use iodine class electrolyte, can enumerate particularly, the electrolyte ingredients such as iodine, iodide ion, tert .-butylpyridine are dissolved in the electrolyte that forms in the organic solvents such as ethylene carbonate or methoxyacetonitrile.Electrolyte is not limited to the electrolyte that is made of electrolyte, also can be solid electrolyte.As solid electrolyte, can exemplify such as DMPImI(dimethyl propyl iodate imidazoles), also can suitably use LiI, NaI, KI, CsI, CaI in addition
2Deng metal iodide and iodide and the I such as salt compounded of iodine of the quaternary ammonium compound such as tetraalkyl ammonium iodide
2The material of combination; LiBr, NaBr, KBr, CsBr, CaBr
2Deng metal bromide, and bromide and the Br such as bromine salt of the quaternary ammonium compound such as tetraalkyl ammonium bromide
2The material of combination etc.
Opposite pole can be to form nesa coating at opposite pole with transparency carrier to form, and perhaps can also be to be provided with the metal sheets such as aluminium, copper, tin to form at same substrate.In addition, can be in the mesh electrodes such as metal (aluminium, copper, tin etc.) or carbon goods, keep the gelatinous solid electrolyte to consist of opposite pole, in addition, also can at opposite pole with on the face of substrate, form the conductive adhesive layer, to cover this substrate, by this bond layer, the brush shape carbon nano-tube group that forms in addition is transferred on the substrate, thereby consists of opposite pole.
When the assembling photo-electric conversion element, for example, to possess electrode and the configuration of opposite pole subtend of the photocatalysis membrana that has adsorbed dyestuff, with hot melt adhesive film or encapsulant two interpolars be sealed, inject electrolyte from the hole or the slit that set in advance at opposite pole or electrode etc.In addition, use in the situation of solid electrolyte, stack the two poles of the earth make and accompany photocatalysis membrana and dielectric substrate between the two poles of the earth, to carrying out caking between its circumference.Can heat by mould, also can be by irradiation plasma (long wavelength), microwave, visible light (more than the 600nm) or infrared ray homenergic Shu Jinhang heating.
Photo-electric conversion element, for example, by using between the transparency carrier with transparency carrier and square opposite pole in square-shaped electrode, form with nesa coating, collector electrode, dielectric substrate and photocatalysis membrana with nesa coating, opposite pole with the predetermined distance configured electrodes, being connected between this moment electrode and the opposite pole can be series connection, also can be in parallel.Any situation no matter, dielectric substrate and photocatalysis membrana all are to be spaced from each other between adjacent by the encapsulant material.In the situation that be connected in series, electrode with nesa coating and collector electrode, forms gap between adjacent with nesa coating, opposite pole, and adjacent electrode is connected by conductor with nesa coating with opposite pole with nesa coating.In the situation that be connected in parallel, electrode, is and does not have apertured shape between adjacent with nesa coating and collector electrode with nesa coating, opposite pole.
Embodiment
In Fig. 1, form the nesa coating (ITO) of 150nm thickness at transparency carrier (PEN) film (thickness 100 μ m).Send successively transparency carrier 2 with conducting film from the roll shaft 1 that is wound with above-mentioned transparency carrier with conducting film, supply with the paste that contains the titanium oxide that anatase-type titanium oxide, ethanol and water by 20 ~ 50nm consists of on the nesa coating of transparency carrier 2 by paste apparatus for coating 3, being applied to thickness is 10 μ m.After the coating, will film at room temperature dry 10 minutes, and in heater 4, under 1 50 ℃, burn till 10 minutes, thereby form photocatalysis membrana at nesa coating.
Then, the transparency carrier 2 that will be formed with photocatalysis membrana flooded 10 minutes in propyl alcohol 5, and then at room temperature dry 10 minutes, and under 150 ℃, burnt till 10 minutes by heater 6.After like this photocatalysis membrana being carried out processed, dipping is 45 minutes in the maceration extract 7 that contains dyestuff (N719), makes Dye Adsorption on photocatalysis membrana.
Thereby, make electrode.
Comparative example 1
Except do not carry out in propyl alcohol dipping and burn till and carry out to the photocatalysis membrana processed, operate according to the method identical with embodiment, thereby make electrode.
Reference example 1
Fig. 2 represents to utilize the example of the photo-electric conversion element that is made of the transparency electrode for preparing among the embodiment 1.Photo-electric conversion element is mainly by the transparency electrode that possesses the photocatalysis membrana that has adsorbed dyestuff, opposite pole opposed with it and be configured in the dielectric substrate of two interpolars and consist of.
In same figure, the 21st, transparency carrier, the 22nd, at the nesa coating of transparency carrier 21 formation, the 24th, opposite pole consists of at the opposite pole of these substrate 24 settings and by platinum with substrate, the 25th.The 26th, stride across a plurality of sheet materials that arrange between the two poles of the earth dividing plate of holding concurrently, between the two poles of the earth, form a plurality of zones by these.The 23rd, the photocatalysis membrana that forms at nesa coating 22 in each zone, absorption has photosensitive dye.In each zone, be injected with electrolyte.The 27th, a plurality of interpolar electrodes, 28th of frame in the two poles of the earth, interpolar electrode protection encapsulant.
The dye-sensitized solar cell that is prepared the 100mm angle by said structure is with AM1.5,100mW/cm
2Standard sources when shining to measure power conversion efficiency, efficiency eta=4.5%, thus obtained high efficiency.
Reference example 2
Except the electrode that uses preparation in comparative example 1 as electrode, other are identical with reference example 1, the formation photo-electric conversion element.
The dye-sensitized solar cell that is prepared the 100mm angle by said structure is with AM1.5,100mW/cm
2Standard sources when shining to measure power conversion efficiency, efficiency eta is 1.8% low value.
Industrial applicibility
The present invention relates to the preparation method of electrode for photoelectric conversion elements, do not need large-scale plant, can carry out processed to photocatalysis membrana at short notice with low cost, the electrode that forms thus is suitable as the electrode of the photo-electric conversion element of dye-sensitized solar cell etc.
[description of reference numerals]
1: roll shaft
2: transparency carrier
3: the paste apparatus for coating
4,6: heater
5: propyl alcohol
7: maceration extract
Claims (3)
1. the preparation method of an electrode for photoelectric conversion elements, it forms nesa coating at transparency carrier, and form photocatalysis membrana thereon, then adsorb light-sensitive coloring agent at this photocatalysis membrana, it is characterized in that, before photocatalysis membrana absorption light-sensitive coloring agent, it is in the alcohol below 150 ℃ that the photocatalysis membrana of transparency carrier is impregnated into azeotropic temperature with water, subsequently heating, the azeotropic by water and alcohol makes photocatalysis membrana dehydration.
2. the preparation method of electrode for photoelectric conversion elements according to claim 1 is characterized in that, described alcohol is 1-propyl alcohol or n-butyl alcohol.
3. the preparation method of electrode for photoelectric conversion elements according to claim 1 and 2, it is characterized in that, described substrate is film or sheet substrate, and carry out continuously photocatalysis membrana formation, photocatalysis membrana dehydration and make photocatalysis membrana absorption light-sensitive coloring agent.
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| PCT/JP2010/057145 WO2011132288A1 (en) | 2010-04-22 | 2010-04-22 | Method for producing electrode for photoelectric conversion element |
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| CN106471594A (en) * | 2014-08-19 | 2017-03-01 | 积水化学工业株式会社 | The colouring method of porous plastid, optoelectronic pole and optical-electric module |
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| JP5824384B2 (en) * | 2012-02-28 | 2015-11-25 | 積水化学工業株式会社 | Method for producing dye-sensitized solar cell |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1736877A (en) * | 2005-07-12 | 2006-02-22 | 武汉大学 | Method for preparing high dispersibility antimony doped stannic hydroxide nanometer powder |
| JP2007242544A (en) * | 2006-03-10 | 2007-09-20 | Sony Corp | Photoelectric converter and its manufacturing method, and surface treatment solution of metal oxide porous layer |
| CN101226966A (en) * | 2008-01-22 | 2008-07-23 | 西安交通大学 | Customizing electroconductive film of dye sensitization TiO2 nanocrystalline solar battery and preparation thereof |
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| JP4129103B2 (en) * | 1999-09-09 | 2008-08-06 | Ｔｄｋ株式会社 | Dye-coupled electrode for dye-sensitized solar cell and dye-sensitized solar cell using the same |
| JP2005251591A (en) * | 2004-03-04 | 2005-09-15 | Toyo Seikan Kaisha Ltd | Manufacturing method of negative electrode in dye-sensitized solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1736877A (en) * | 2005-07-12 | 2006-02-22 | 武汉大学 | Method for preparing high dispersibility antimony doped stannic hydroxide nanometer powder |
| JP2007242544A (en) * | 2006-03-10 | 2007-09-20 | Sony Corp | Photoelectric converter and its manufacturing method, and surface treatment solution of metal oxide porous layer |
| CN101226966A (en) * | 2008-01-22 | 2008-07-23 | 西安交通大学 | Customizing electroconductive film of dye sensitization TiO2 nanocrystalline solar battery and preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106471594A (en) * | 2014-08-19 | 2017-03-01 | 积水化学工业株式会社 | The colouring method of porous plastid, optoelectronic pole and optical-electric module |
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