WO2007052681A1 - Cellule photoelectrochimique - Google Patents

Cellule photoelectrochimique Download PDF

Info

Publication number
WO2007052681A1
WO2007052681A1 PCT/JP2006/321807 JP2006321807W WO2007052681A1 WO 2007052681 A1 WO2007052681 A1 WO 2007052681A1 JP 2006321807 W JP2006321807 W JP 2006321807W WO 2007052681 A1 WO2007052681 A1 WO 2007052681A1
Authority
WO
WIPO (PCT)
Prior art keywords
photoelectrochemical cell
oxide
semiconductor fine
resin
sealant
Prior art date
Application number
PCT/JP2006/321807
Other languages
English (en)
Japanese (ja)
Inventor
Kunihito Miyake
Original Assignee
Sumitomo Chemical Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Publication of WO2007052681A1 publication Critical patent/WO2007052681A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
    • H01G9/2077—Sealing arrangements, e.g. to prevent the leakage of the electrolyte
    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/88—Passivation; Containers; Encapsulations
    • 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
    • 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
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a photoelectrochemical cell. Background art
  • C_ ⁇ 2 released into the atmosphere in order to prevent global warming.
  • a solar using photoelectrochemical cell such as a silicon solar cell of the pn junction type can installed in the roof of the house -.
  • System utilization promotion have been proposed.
  • the single crystal, polycrystal and amorphous silicon used in the above silicon-based photoelectrochemical zero pond have a problem of high cost due to the necessity of high temperature and high vacuum conditions during the manufacturing process.
  • the charge transfer layer proposed in Nature uses iodine, fluoride, etc. as an electrolyte, and uses acetonitrile as a solvent. If a long-term use is required, a sealant is used to prevent the charge transfer layer from volatilizing.
  • BYNEL registered trademark, DuPont
  • an adhesive of polyethylene resin is used as a sealant.
  • the proposed photoelectrochemical cell has been proposed.
  • the present inventors have provided a photoelectrochemical cell obtained using iodine / iodide as an electrolyte contained in a charge transfer layer, using acetonitrile as a solvent, and using the adhesive as a sealant. 8 When stored at 5T: Iodine disappeared, indicating that the durability was not sufficient. Disclosure of the invention
  • An object of the present invention is to provide a photoelectrochemical cell excellent in durability. That is, the present invention provides the following [1] to [5].
  • a photoelectrochemical cell containing a resin comprising:
  • the resin containing a hydroxyl group is at least one resin selected from the group consisting of an ethylene-vinyl alcohol copolymer, a partially saponified polyvinyl alcohol, and a fully saponified polypinyl alcohol.
  • the photoelectrochemical cell described in [3] The photoelectrochemical cell according to [1] or [2], wherein the semiconductor fine particles are titanium oxide. '
  • FIG. 1 is a schematic cross-sectional view of wet photoelectrochemistry of the present invention.
  • the photoelectrochemical cell of the present invention is a photoelectrochemical cell formed by sealing a laminate including a conductive substrate, semiconductor fine particles adsorbed with a photosensitizing dye, a charge transfer layer and a counter electrode with a sealant. It is.
  • an electrolyte is filled between a conductive substrate in contact with a layer of semiconductor fine particles adsorbed with a photosensitizing dye (hereinafter also referred to as a dye adsorbing semiconductor particle layer) and a counter electrode.
  • a photosensitizing dye hereinafter also referred to as a dye adsorbing semiconductor particle layer
  • the conductive substrate and the counter electrode are stacked via a solid hole transport material, and the semi-fine particles adsorbed with the photosensitizing dye are solid hole transport materials. It is contained in.
  • the wet photoelectrochemical cell of the present invention will be described below as an example. A specific example is shown in Fig. 1.
  • the semiconductor particle layer (3) (with the dye adsorbed) is filled with the electrolytic solution (5) and sealed with a sealing material (10).
  • the conductive substrate (8) is composed of a substrate (1) and a conductive layer (2) in order from the top.
  • the counter electrode (9) consists of a substrate (7) and a conductive layer (6) in order from the bottom.
  • the conductive substrate (8) used in the photoelectrochemical cell of the present invention and the conductive layer in the counter electrode (9) ((2) for the conductive substrate, (6) for the counter electrode) The lower the resistance, the better.
  • the conductive layer (2) of the conductive substrate has a high transmittance in the high wavelength region, specifically, a region longer than 350 nm, specifically, a transmittance of 80% or more. It is preferable.
  • Examples of the conductive material used in the conductive layer include iron, nickel, chromium, titanium, aluminum, platinum, gold, silver, cobalt, palladium, .copper, tantalum, ruthenium, tungsten, zinc, tin, and the like;
  • Metal alloy Conductive metal oxide such as indium-muth tin complex oxide (ITO), tin oxide doped with fluorine: Conductivity such as carbon, polyethylene dioxythiophene (EDOT), poly'diphosphorus, etc.
  • the conductive polymer is usually doped with para-toluenesulfonic acid or the like.
  • the conductive layer include a conductive substance itself, or a non-conductive substrate, and a thin film of a conductive substance formed on the surface of the non-conductive substrate by vapor deposition, sputtering, adhesion, or the like. '.
  • the conductive substrate (8) preferably has a textured structure on the surface of the conductive material in order to confine incident light and use it effectively.
  • (1) for conductive substrate and (7) for counter electrode include glass or plastic.
  • Plastics include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PP S), poly force—bonate (PC), polypropylene (PP), polyimide (PI), rear Cetylcellulose (TAC), Syndiotactic polystyrene (SPS), Polyarylate (PAR); Aton (registered trademark of JSR), Zeonex ( ⁇ registered trademark of Nippon Zeon), Zeonor (registered trademark of Nippon Zeon), Cyclic polyolefin (COP) such as Abel (registered trademark of Mitsui Chemicals) and Topas (registered trademark of T icona); Polyester monosulfone (PES), Polyether imide (P, EI), Polysulfone (PSF) And polyamide (PA).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PP S polyphenylene sulfide
  • PC poly force—bonate
  • the conductive substrate (8) and the counter electrode (9) glass or plastic coated with a conductive metal oxide is preferable.
  • conductive glass with a conductive layer made of tin dioxide doped with fluorine and conductive film with a conductive layer made of indium-tin composite oxide (ITO) have low electrical resistance and light transmission. It is particularly preferable because of its excellent properties and availability.
  • the semiconductor fine particles used in the present invention are fine particles having a semiconductor characteristic with a primary particle size of about 1 to 5000 nm, preferably about 5 to 500 nm. For the purpose of improving the photoelectric conversion efficiency by reflection, semiconductor fine particles having different primary particle diameters may be mixed. Tubes and hollow fine particles may be used.
  • Examples of the material of the semiconductor fine particles (2) include titanium oxide, tin oxide, zinc oxide, iron oxide, tungsten oxide, zirconium oxide, hafnium oxide, strontium oxide, indium oxide, cerium oxide, yttrium oxide, lanthanum oxide, Metal oxides such as vanadium oxide, niobium oxide, tantalum oxide, gallium oxide, nickel oxide, strontium titanate, barium titanate, potassium niobate and sodium tantalite; Metal halides such as silver iodide, silver bromide, copper iodide, copper bromide, etc .; zinc sulfide, titanium sulfide, indium sulfide, bismuth sulfide, cadmium sulfide, zirconium sulfide, tantalum sulfide, molybdenum sulfide, silver sulfide, Metal sulfides such as copper sulfide, tin sul
  • Metal selenides such as cadmium selenide, zirconium selenide, zinc selenide, titanium selenide, indium selenide, tungsten selenide, molybdenum selenide, bismuth selenide, lead selenide;
  • Metal tellurides such as cadmium telluride, tungsten telluride, molybdenum telluride, zinc telluride, bismuth telluride;
  • Metal phosphides such as zinc phosphide, gallium phosphide, indium phosphide, cadmium phosphide;
  • Examples include gallium arsenide, copper indium monoselenide, copper indium monosulfide, silicon, germanium, and the like.
  • it may be a mixture of two or more of zinc oxide, Z tin oxide, tin oxide, titanium oxide and the like.
  • Metal oxides such as tantalum, gallium oxide, nickel iodide, strontium titanate, barium titanate, potassium niobate, sodium tantalate, zinc oxide / oxide, tin, tin oxide, titanium oxide, etc. are available at relatively low prices It is preferable because it is easy to absorb and the photosensitizing dye is easily adsorbed.
  • titanium oxide is suitable.
  • the surface of the semiconductor fine particles On the surface of the semiconductor fine particles, chemical plating using a titanium tetrachloride aqueous solution or electrochemical using a titanium trichloride aqueous solution. You may perform a target treatment. As a result, the surface area of the semiconductor fine particles is increased, the purity in the vicinity of the semiconductor fine particles is increased, impurities such as iron existing on the surface of the conductive fine particles are obscured, or the connectivity and integrity of the semiconductor fine particles. Can be increased.
  • the semiconductor fine particles preferably have a large surface area so that many photosensitizing dyes can be adsorbed. Therefore, the surface area of the semiconductor fine particle (2) layer applied on the substrate is preferably 10 times or more, more preferably 100 times or more the projected area. This upper limit is usually around 100 times.
  • the layer of semiconductor fine particles (2) may be a single layer of semiconductor fine particles, but in the case of a wet photoelectrochemical cell, which is usually a layer composed of a plurality of semiconductor fine particles and a plurality of semiconductor fine particles having different particle diameters. After the semiconductor fine particle layer is formed on the conductive substrate, the photosensitizing dye is adsorbed on the fine particles of the layer.
  • a method of forming a semiconductor fine particle layer on a conductive substrate a method of directly forming a semiconductor fine particle as a thin film on a conductive substrate by spray spraying or the like; electrically depositing a semiconductor fine particle thin film using the conductive substrate as an electrode
  • the method include: a method in which a slurry of semiconductor fine particles is applied on a conductive substrate and then dried, cured, or baked.
  • the method for applying the semiconductor fine particle slurry onto the conductive substrate will be described in more detail. Examples thereof include a doctor blade, squeegee, spin coating, date coating, and screen printing.
  • the average particle diameter in the dispersed state of the semiconductor fine particles in the slurry is preferably 0, 0 1 nm to 100 m. ,
  • the dispersion medium for dispersing the slurry is not particularly limited as long as the semiconductor fine particles can be dispersed.
  • the dispersion includes a polymer such as polyethylene glycol; a surfactant such as T r i, t o n—X
  • An organic acid or an inorganic acid such as acetic acid, formic acid, nitric acid or hydrochloric acid; and a cleansing agent such as acetylacetone.
  • a semiconductor fine particle layer by firing a conductive substrate coated with a slurry of semiconductor fine particles.
  • the firing temperature is usually lower than the melting point of the conductive layer or substrate, and the upper limit of the firing temperature is 1200, preferably 600: or less.
  • the firing time is usually within 10 hours.
  • the thickness of the semiconductor fine particle layer on the conductive substrate is usually from 0.:! To 2 0 0, preferably :! ⁇ 50.
  • Other methods for forming a semiconductor fine particle layer on a conductive substrate at a relatively low temperature include, for example, a hydrothermal method in which a porous semiconductor fine particle layer is formed by hydrothermal treatment (dye-sensitized photoelectric for practical use).
  • the photosensitizing dye used in the present invention has absorption in the visible light region and / or infrared light region, and various metal complexes can be used as one or more organic dyes.
  • photosensitizing dyes having functional groups such as force lpoxyl group, hydroxyalkyl group, hydroxyl S., sulfone group, force lpoxyalkyl group in the molecule tend to be adsorbed to semiconductors quickly. It is preferably used because of its presence.
  • a metal complex is preferably used because of excellent photoelectric conversion efficiency and durability.
  • metal complex examples include copper phthalocyanine, metal phthalocyanine such as titanyl phthalocyanine, chlorophyll, hemin, and those described in JP-A No. 1 2 2 0 3 80 and JP-A-5-5 0 4 0 2 3 Ruthenium, osmium, iron, zinc complex, etc. can be used.
  • a more detailed example of a ruthenium complex is c / s-bis (isothiocyanate) bis (2,2'-bibilidyl-4,4'-dicarboxylate) -ruthenium (II) bis-tetrabutyl Ammonium, bis (isothiocyanate) bis (2,2'-bibilyl-4,4'-dicarboxylate) -ruthenium (11), tris (isothiocyanate) monoruthenium (II)- 2, 2 ': 6', 2 "-Te-pyridine-4,4 ', 4" -tricarboxylic acid tristetratetramethyl ammonium, cis-bis (isothiocyanate) (2, 2'-bipyridyl-4 , 4'-dicarboxylate) (2,2'-bibilidyl-4,4'-dinonyl) ruteni Um (II).
  • organic dyes include metal-free phthalocyanine, cyanine dye
  • cyanine dyes include NK 1 1 94, .NK 342 2 (both manufactured by Nippon Photosensitivity Laboratories).
  • merocyanine dyes include NK242 6 and NK 2 5 0 1 (both manufactured by Nippon Photosensitivity Laboratories).
  • xanthene dyes examples include uranin, eosin, rose bengal, rhodamine B, and dibromofluorescein.
  • triphenylmethane dye examples include malachite green and crystal violet.
  • Examples of the coumarin dye include NKX-267 7 (produced by Hayashibara Biochemical Research Institute) (see the following structural formula).
  • indoline-based organic dyes examples include D 149 (manufactured by Mitsubishi Paper Industries) (see the following structural formula). '
  • Examples of the method of adsorbing the photosensitizing dye to the semiconductor fine particles laminated on the conductive substrate include a well-dried semiconductor fine particle layer and a conductive material in a solution containing the photosensitizing dye of the present invention.
  • substrate for several hours is mentioned.
  • Adsorption of the photosensitizing dye may be performed at room temperature (at 25), may be performed under heating, or may be performed while refluxing a solution containing the photosensitizing dye.
  • the photosensitizing dye can be adsorbed before the semiconductor fine particle layer is formed on the conductive substrate, or the semiconductor fine particles and the photosensitizing dye may be applied to the conductive substrate at the same time.
  • the photosensitizing dye adsorption is performed after the heat treatment. After the heat treatment, the photosensitizing dye is adsorbed before water is adsorbed on the surface of the semiconductor fine particle layer. Particularly preferred is a method of making them.
  • 'It is preferable to remove the unadsorbed photosensitizing dye by washing in order to suppress the reduction of the sensitizing effect due to floating of the photosensitizing dye not adhering to the semiconductor fine particles.
  • One type of photosensitizing dye can be adsorbed or a mixture of several types can be used.
  • the application is a photoelectrochemical cell, it is preferable to select a photosensitizing dye to be mixed so that the wavelength range of photoelectric conversion of irradiation light such as sunlight is as wide as possible.
  • the adsorption amount of the photosensitizing dye to the semiconductor fine particles is 0.1. A millimolar is preferred. With such a dye amount, a sufficient sensitizing effect is obtained in the semiconductor fine particles, and there is a tendency to suppress a reduction in the sensitizing effect due to the floating of the dye not attached to the semiconductor fine particles. To preferred. ..
  • the photosensitizing dye adsorbed on the semiconductor fine particle layer (2) may be the same or different.
  • the first layer adsorbs a photosensitizing dye of 300 nm to '500 nm
  • the second layer adsorbs a photosensitizing dye of 500 nm to 700 nm.
  • a photosensitizing dye having a different absorption wavelength may be adsorbed to each layer, for example, a photosensitizing dye having a wavelength of 700 to 90 nm is adsorbed to the third layer.
  • a colorless compound may be co-adsorbed for the purpose of suppressing interactions such as association and aggregation between photosensitizing dyes.
  • the hydrophobic compound after co-adsorption include a steroid compound having a strong lpoxyl group (for example, chenodeoxycholic acid) and the like.
  • the surface of the semiconductor fine particles may be treated with amines after adsorbing the dye.
  • Preferred amines include, for example, pyridine, 4-tert-butylpyridine, polyvinyl pyridine and the like. When these are liquids, they may be used as they are, or when they are solids, they may be dissolved in an organic solvent.
  • Examples of the electrolyte contained in the charge transfer layer of the present invention include combinations of 12 and various iodides, combinations of Br 2 and various bromides, and combinations of ferrocyanate-ferricyanate metal complexes. , Combinations of metal complexes of phenoxy and ferricinium ions, combinations of alkyl compounds of alkylthio-l-alkyldisulfides, combinations of alkylviologens and their reduced forms, combinations of polyhydroxybenzenes and their oxidants, etc. Can be mentioned.
  • the ® ⁇ product that may be combined with I 2, for example, L i I, N a I , KI, C s I and C a I 2 of a metal such as iodides; 1-propyl one 3-methylimidazo Riumuai
  • a metal such as iodides
  • 1-propyl one 3-methylimidazo Riumuai examples include iodine salts of quaternary imidazolium compounds such as iodine, 1-propyl-2,3-dimethyldimethylimidazole, iodine salts of quaternary pyridinium compounds, iodine salts of tetraalkylammonium compounds, and the like.
  • the iodide may be combined with B r 2, for example, L i B r, N a B r, KB r, C s B r and C a B r 2, etc. of the metal bromide; tetraalkyl ammonium Niu beam blow amide Ya pyridinium Examples include bromine salts of quaternary ammonium compounds such as zinc bromide.
  • alkyl viologen examples include methyl viologen chloride, hexyl viologen promide, and benzyl viologen tetrafluoroborate.
  • polyhydroxybenzes and diols examples include, for example, hyde mouth quinone and naphthohyde mouth quinone.
  • the electrolyte is preferably a combination of I 2 and an iodide, and in particular, a metal iodide, an iodine salt of a quaternary imidazolium compound, an iodine salt of a quaternary pyridinium compound, and an iodine salt of a tetraalkylammonium compound.
  • a combination of at least one iodide selected from the group consisting of and I 2 is preferred.
  • the charge transfer layer contains an electrolyte.
  • the electrolytic solution include water and an organic solvent that dissolves the electrolyte.
  • organic solvent examples include nitrile solvents such as acetonitrile and methotisacetonitrile pionitrile; carbonate solvents such as ethylene power and propylene carbonate; Lactone solvents such as lolactone; Amide solvents such as N ,, N-dimethylformamide i 1-Methyl-3 —propylimidazolium ioidaid 1-methyl-3 —hexylimidazole An ionic liquid such as mu-iodide; 1-ethyl-3-methylimidazolium-bis (trifluoromethanesulfonic acid) imide. ..,
  • the electrolysis 3 ⁇ 4 may be gelled with a low molecular gelling agent shown in polyacrylonitrile, polyvinylidene fluoride, poly-4-vinylpyridine, or Chemistry Letters, 1 2 4 1 (1 9 9 8).
  • a solid electrolytic layer such as a solid hole transport material is used for the charge transfer layer.
  • Solid hole transport materials include those made of p-type inorganic semiconductors containing monovalent copper such as Cu I and Cu SCN, and Synthetic M etl, 8 9, 2 1 5 (1 9. 9 7) And aromatic, amines such as those shown by Nature, 3 95, 5 8 3 (1 9 9 8); polythiophene and its derivatives; polypyrrole and its derivatives; poly 7 phosphorus and its derivatives; And (2) vinylene) and derivatives thereof; poly ( ⁇ -phenylenepinylene) and derivatives thereof, and the like.
  • the sealing agent used in the present invention contains a resin containing a hydroxyl group. By using the resin as a sealing agent, when a volatile solvent such as acetonitrile or iodine is used as an electrolytic solution, they are In particular, it is difficult to volatilize at high temperatures, so durability is significantly improved.
  • a thermoplastic resin is preferable because of easy handling.
  • a resin containing a hydroxyl group an ethylene-vinyl alcohol copolymer obtained by hydrolyzing an acetate ester of an ethylene-vinyl acetate copolymer is used.
  • Resin structure such as polyvinyl acetate, partially saponified polyvinyl alcohol partially hydrolyzed with vinyl acetate, and fully saponified polyvinyl alcohol with approximately 98 mol% or more of polyvinyl acetate hydrolyzed Examples thereof include those containing a structural unit obtained by hydrolysis of vinyl ester as a unit.
  • the resin containing a hydroxyl group can be used as a film, and when used as a film, the film may be stretched.
  • the film may be stretched.
  • ethylene-vinyl alcohol copolymer is preferably used.
  • ethylene-vinyl alcohol copolymer examples include Kuraray's Ever, Lu (registered trademark), Nippon Synthetic Chemical's Soanol (registered trademark), Soarlite (registered trademark), and the like. Any grade in the EVAL RE SI N & F I LM catalog (issued in May 2006) can be used. For example, L, F, T, J, H, E, E, G with different ethylene polymerization ratios. Any grade can be used. Also; these films may contain a lubricant. .
  • ethylene-vinyl alcohol copolymer, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol are polyethylene terephthalate (PET), polyamide: (PA), polyethylene (PE), polypropylene (PP) , they may form a multi-layered structure of aluminum S I_ ⁇ 2 film.
  • Kuraray's Kuraray Poval Japan
  • Synthetic Chemical's Gosensenol Shiramoto Vinegar Bipoval's J-Poval
  • 'Ryoke Chemical Company's Denka Poval Examples include Unitika Poval manufactured by Unitica.
  • the poval may contain a plasticizer. '.
  • the spacers of .. • further suppress the evaporation of volatile solvents such as acetonitrile and iodine.
  • a filler such as S i 0 T i '0 2 or A 1 2 0 3 may be mixed.
  • the sealing agent of the present invention includes Hi-Milan (registered trademark, Mitsui DuPont Polychemi).
  • Ionomer resins such as Calf); Glass frits; Hot mesole adhesives such as SX 1 1 70 (Solaronix); Adhesives such as Amo si 1 4 (So 1 aronix); B YNE L (DuPont)
  • Anhydrous-modified LLDPE made by modifying linear low density polyethylene with an acid anhydride such as maleic anhydride
  • epoxy adhesive may be used in combination.
  • pre-molded shapes such as films and sheets, or water before sealing Comprise a liquid, to drying during sealing 'shall and the like 3 ⁇ 4 ease of handling, film, sealing such sheets -. Those preformed in a shape to be sealed are preferred.
  • the thickness of the film is usually about 1 m to 1 mm.
  • a method for sealing using a molded sealant a method in which a sealant is sandwiched between a working electrode and a counter electrode and bonded by an electric heating press can be mentioned.
  • the bonding temperature may be at a temperature higher than the temperature at which the resin melts, and is usually between 50 and 300.
  • the sealing material portion may be locally heated and melted and bonded using laser light or the like.
  • a volatile solvent such as acetonitrile or a sealing agent that can prevent the evaporation of electrolyte such as iodine, the electrolyte contained in the charge transfer layer even when stored at high temperature
  • the charge transfer layer such as water and solvent is not lost and it has excellent durability. Examples, ⁇
  • the conductive surface of a conductive glass with a tin oxide film doped with fluorine (made by Nippon Sheet Glass Co., Ltd., 10 ⁇ / D) is a titanium oxide dispersion. Name, manufactured by Solaronix) was applied using a doctor blade, fired at 500, the glass was cooled, and a semiconductor fine particle layer was formed on a conductive substrate.
  • a 50-thick ethylene-vinyl alcohol copolymer resin (EVAL (registered trademark of Kuraray Co., Ltd.) F 1 0 1) film was installed around the layer as a sealant, A conductive glass with a tin oxide film and pre-deposited with platinum was overlaid with a hole drilled beforehand. After thermocompression bonding with an electrothermal brace machine, the electrolyte solution is passed through a hole in the counter electrode previously opened (solvent is acetonitrile; iodine concentration in the solvent is 0.05 mol liter, and the concentration of lithium iodide is also 0.1 mol) A 4-liter tert-butylpyridine concentration of 0 ...
  • the photoelectrochemical cell produced in this way was put into a xenon weathering tester and irradiated with light. (Light quantity: 0.48W / m 2 (340nm), black panel temperature: 83, humidity: 50% RH , No rain), observed the change in conversion efficiency over time.
  • the conversion efficiency was measured using a solar simulator manufactured by Yamashita Denso.
  • Table 1 shows the retention of conversion efficiency after 3.50 hours when the initial efficiency is 1.
  • a photoelectrochemical cell was obtained in the same manner as in Example 1 except that B YNEL (registered trademark, manufactured by DuPont), which is an anhydride-modified LLDPE, was used as the sealant.
  • B YNEL registered trademark, manufactured by DuPont
  • LLDPE anhydride-modified LLDPE
  • a 50-thick ethylene-vinyl alcohol sealant Copolymer resin (Eval (registered trademark of Kuraray Co., Ltd.) F 1 0 1)
  • the electrolyte solution (the solvent is acetonitrile, the iodine concentration in the solvent is 0.05 mol liters, the concentration of lithium niobate is 5 mol 0.1 mol noritol, 4 tert-butyl lysine concentration is 0.5 mol Z.
  • the glass plate encapsulating the electrolyte was aged in an oven at 85 t: and the time course of the amount of iodine was measured at an absorbance of 36 2 nm.
  • Table 2 shows the absorbance retention when the initial absorbance is 1. Absorbance is high ⁇ , which means that the iodine retained in the photoelectrochemical cell is high. ''
  • a glass plate encapsulating an electrolyte solution was obtained in the same manner as in Example 2 except that BYNEL (registered trademark, manufactured by DuPont), which is an anhydride-modified LLDPE, was used as the sealant.
  • BYNEL registered trademark, manufactured by DuPont
  • the change in absorbance over time was measured in the same manner as in Example 2. The results are shown in Table 2.
  • the photoelectrochemical cell of the present invention has a significant loss of electrolytes such as iodine and volatile solvents even when used at high temperatures or for long periods of time compared to the case of using a conventional sealant.
  • the photoelectrochemical cell of the present invention can be used as an optical sensor because current flows upon receiving light irradiation.

Abstract

La présente invention concerne une cellule photoélectrochimique obtenue en scellant un corps multicouche, lequel comprenant un substrat conducteur, des particules semi-conductrices sur lesquels un colorant photosensible est adsorbé, une couche de transport de charge et une contre-électrode, avec un agent de scellement. Cette cellule photoélectrochimique est caractérisée en ce que l'agent de scellement contient une résine possédant un groupe hydroxyle.
PCT/JP2006/321807 2005-10-31 2006-10-25 Cellule photoelectrochimique WO2007052681A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-315890 2005-10-31
JP2005315890 2005-10-31

Publications (1)

Publication Number Publication Date
WO2007052681A1 true WO2007052681A1 (fr) 2007-05-10

Family

ID=38005834

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/321807 WO2007052681A1 (fr) 2005-10-31 2006-10-25 Cellule photoelectrochimique

Country Status (1)

Country Link
WO (1) WO2007052681A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005093252A (ja) * 2003-09-18 2005-04-07 Hitachi Maxell Ltd 光電変換素子モジュール
JP2005100875A (ja) * 2003-09-26 2005-04-14 Hitachi Maxell Ltd 光電変換素子モジュール
JP2005158621A (ja) * 2003-11-27 2005-06-16 Kyocera Corp 積層型光電変換装置
JP2005213470A (ja) * 2004-02-02 2005-08-11 Nichiban Co Ltd シール材
JP2005243379A (ja) * 2004-02-26 2005-09-08 Kyocera Corp 光電変換装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005093252A (ja) * 2003-09-18 2005-04-07 Hitachi Maxell Ltd 光電変換素子モジュール
JP2005100875A (ja) * 2003-09-26 2005-04-14 Hitachi Maxell Ltd 光電変換素子モジュール
JP2005158621A (ja) * 2003-11-27 2005-06-16 Kyocera Corp 積層型光電変換装置
JP2005213470A (ja) * 2004-02-02 2005-08-11 Nichiban Co Ltd シール材
JP2005243379A (ja) * 2004-02-26 2005-09-08 Kyocera Corp 光電変換装置

Similar Documents

Publication Publication Date Title
US8933328B2 (en) Dye-sensitized solar cell module and method of producing the same
CN101595594B (zh) 染料增感型光电转换器件及其制造方法、电子设备以及半导体电极及其制造方法
US8314329B2 (en) Dye-sensitized solar cell module and method for manufacturing the same
CN100411195C (zh) 光电转换器件的制作方法
CN100588027C (zh) 染料敏化光电变换器及其制备方法和电子装置及其制备方法以及电子设备
JP2007073505A (ja) 光電変換素子
US20050067006A1 (en) Wire interconnects for fabricating interconnected photovoltaic cells
US20030192584A1 (en) Flexible photovoltaic cells and modules formed using foils
CN102077410A (zh) 染料敏化太阳能电池、其制造方法以及染料敏化太阳能电池组件
JP4887694B2 (ja) 光電変換素子およびその製造方法ならびに光電変換素子モジュールならびに電子機器ならびに移動体ならびに発電システムならびにディスプレイおよびその製造方法
JP2007149652A (ja) 光電気化学電池
JP5160045B2 (ja) 光電変換素子
WO2007072970A1 (fr) Compose, convertisseur photoelectrique et cellule photoelectrochimique
JP4377627B2 (ja) 色素増感太陽電池および色素増感太陽電池モジュール
JP2008147154A (ja) 光電気化学電池
JP2002313444A (ja) 光電変換素子及びその製造方法
JP5160051B2 (ja) 光電変換素子
WO2007052681A1 (fr) Cellule photoelectrochimique
JP2006004736A (ja) 光電変換素子及び光電変換素子用色素
WO2005091425A1 (fr) Module de cellule solaire pour sensibilisation à la teinture et procédé de fabrication de celui-ci
US20140130872A1 (en) Photoelectric-conversion device, electronic instrument and building
JP2006339074A (ja) 色素増感太陽電池の製造方法
JP5131732B2 (ja) 色素増感太陽電池用の色素吸着半導体電極の製造方法
JP5130775B2 (ja) 光電気化学電池
JP2008243618A (ja) 光電変換素子

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06822736

Country of ref document: EP

Kind code of ref document: A1