WO2006067969A1 - 光電変換素子用の対極及び光電変換素子 - Google Patents
光電変換素子用の対極及び光電変換素子 Download PDFInfo
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- WO2006067969A1 WO2006067969A1 PCT/JP2005/022485 JP2005022485W WO2006067969A1 WO 2006067969 A1 WO2006067969 A1 WO 2006067969A1 JP 2005022485 W JP2005022485 W JP 2005022485W WO 2006067969 A1 WO2006067969 A1 WO 2006067969A1
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Classifications
-
- 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
- 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
- H01M14/005—Photoelectrochemical storage cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/022—Electrodes made of one single microscopic fiber
-
- 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
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
- H10K30/821—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes comprising carbon nanotubes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/221—Carbon nanotubes
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a counter electrode structure used in a photoelectric conversion element such as a dye-sensitized solar cell.
- wet solar cells such as Dye Sensitized Solar Cell (DSC)
- DSC Dye Sensitized Solar Cell
- a diacid salt on one surface of a transparent substrate made of a material such as glass having excellent light transmittance.
- the electrode is roughly structured by enclosing a counter electrode made of a conductive film and an electrolyte containing an oxidation-reduction pair such as iodine between the electrodes.
- Patent Document 1 Japanese Patent No. 2664191
- Patent Document 2 Japanese Patent Laid-Open No. 2001-160427
- Non-Patent Document 1 M. Graetzel et al, Nature, 737, p.353, 1991
- FIG. 4 is a schematic cross-sectional view showing an example of the structure of a conventional dye-sensitized solar cell.
- This dye-sensitized solar cell 50 includes a porous semiconductor electrode (hereinafter referred to as a photoconductive dye) carrying a photosensitizing dye. (Also referred to as a dye-sensitized semiconductor electrode or working electrode).
- a first substrate 51 having 53 formed on one side thereof, a second substrate 55 having a conductive film 54 formed thereon, and enclosed between them.
- the main component is an electrolyte layer 56 such as a gel electrolyte.
- the first substrate 51 a light-transmitting plate material is used, and a transparent conductive film 52 is disposed on the surface of the first substrate 51 on the side of the dye-sensitized semiconductor electrode 53 in order to provide conductivity. And The first substrate 51, the transparent conductive film 52, and the dye-sensitized semiconductor electrode 53 constitute a window electrode 58.
- a conductive transparent substrate or a metal substrate is used as the second substrate 55.
- a transparent conductive electrode substrate or a transparent conductive electrode substrate is used to provide conductivity to the surface on the electrolyte layer 56 side.
- the second substrate 55 and the conductive film 54 constitute a counter electrode 59.
- a window electrode 58 and a counter electrode 59 are arranged at a predetermined interval so that the dye-sensitized semiconductor electrode 53 and the conductive film 54 face each other, and a sealing material 57 made of thermoplastic resin is provided around the periphery of both electrodes. Provide. Then, the window electrode 58 and the counter electrode 59 are bonded together through the sealing material 57 to assemble the cell, and iodine 'iodide ion ( ⁇ I 3 -1) is used as an electrolyte between the electrodes 58 and 59 through the electrolyte inlet 60.
- the electrolyte layer 56 for charge transfer is formed by filling an electrolytic solution in which an oxidation / reduction pair such as) is dissolved in an organic solvent such as acetonitrile.
- Ionic liquids are also called room temperature fusible salts and are wide, including around room temperature! It is a salt that exists only as a stable liquid in the temperature range, and that has only positive and negatively charged ions. This ionic liquid has substantially no vapor and is not expected to volatilize or ignite like a general organic solvent. Therefore, it is expected as a solution to the deterioration of cell characteristics due to volatilization.
- This type of dye-sensitized solar cell absorbs incident light such as sunlight, sensitizes oxide semiconductor fine particles with the photosensitizing dye, and generates an electromotive force between the working electrode and the counter electrode. As a result, it functions as a light conversion element that converts light energy into electrical energy. Disclosure of the invention
- the present invention has been made in view of the above circumstances, and an object thereof is to realize faster transfer of electrons from a counter electrode to an electrolyte.
- a window electrode having a transparent substrate, a semiconductor layer provided on the surface of the transparent substrate and carrying a sensitizing dye, a substrate, and the surface of the substrate.
- a photoelectric electrode having a counter electrode having a conductive film disposed on the window electrode and facing the semiconductor layer, and an electrolyte layer disposed on at least a part between the window electrode and the counter electrode.
- a counter electrode for a conversion element wherein the counter electrode is a counter electrode for a photoelectric conversion element having carbon nanotubes provided on the substrate surface via the conductive film.
- the carbon nanotube may be a brush-like carbon nanotube.
- the brush-like carbon nanotubes may be oriented perpendicular to the substrate surface.
- the interval between the brush-like carbon nanotubes may be 1 to: LOOOnm.
- the substrate constituting the counter electrode may be subjected to an acid treatment on the surface on which the conductive film and the carbon nanotube are provided.
- the second aspect of the present invention is a window electrode having a transparent substrate and a semiconductor layer provided on the surface of the transparent substrate and carrying a sensitizing dye, the substrate, and provided on the surface of the substrate.
- a counter electrode having a conductive film disposed opposite to the semiconductor layer of the window electrode, a carbon nanotube provided on the substrate surface via the conductive film, and disposed on at least a part of the window electrode and the counter electrode.
- a photoelectric conversion element having a formed electrolyte layer.
- the semiconductor layer may be a porous oxide semiconductor. Yes.
- the semiconductor particles or conductive particles can play a role of charge transfer, and the gel electrolyte composition
- the electrical conductivity of the product is improved, and photoelectric conversion characteristics comparable to those obtained when a liquid electrolyte is used are obtained.
- the carbon nanotubes play a role of charge transfer, and the electrolyte enters between the carbon nanotubes. Therefore, in the electrolyte near the counter electrode, the same effect as that obtained by using the nanocomposite gel electrolyte is obtained, and the electron The moving speed increases and high photoelectric conversion efficiency can be obtained.
- FIG. 1 is a schematic view showing an example of a cross-sectional structure of a photoelectric conversion element of the present invention.
- FIG. 2 is a diagram conceptually showing an enlarged perspective view of the structure of the counter electrode of the present invention.
- FIG. 3 is a diagram showing a cross-sectional structure of a counter electrode of the present invention.
- FIG. 4 is a diagram showing an example of a cross-sectional structure of a conventional photoelectric conversion element.
- FIG. 1 schematically shows an example of the structure of the photoelectric conversion element of the present invention.
- the photoelectric conversion element 10 of the present invention includes a counter electrode 1 on which carbon nanotubes 13 are formed, a window electrode 2 on which a porous semiconductor film 23 carrying a sensitizing dye is formed, and an electrolyte sealed therebetween. It is mainly composed of layer 3 and so on.
- the counter electrode 1 is provided with brush-like carbon nanotubes 13 via a transparent conductive film 12 formed to give conductivity to the surface of the transparent first substrate 11.
- a light transmissive second substrate 21 is used for the window electrode 2, and a porous semiconductor film 23 carrying a sensitizing dye is provided through a transparent conductive film 22 for providing conductivity.
- the window electrode and the counter electrode are arranged at a predetermined interval so that the brush-like carbon nanotube 13 and the porous semiconductor film 23 carrying the sensitizing dye face each other, and the thermoplastic A sealing material 4 made of fat is provided and bonded together to assemble the cell.
- I_Zl 3_ iodine 'iodide ions
- FIG. 2 conceptually shows an enlarged perspective view of the structure of the counter electrode 1 of the present invention
- FIG. 3 schematically shows the cross-sectional structure thereof.
- the counter electrode 1 of the present invention has a thickness h of about 0.:m in order to provide conductivity to the surface of the first substrate 11 that also has a transparent glass isotropic force.
- a transparent conductive film 12 having a fluorine-doped tin oxide (FTO) force is formed, and carbon nanotubes 13 are provided on the surface of the transparent conductive film 12.
- the carbon nanotubes 13 are formed in a brush shape in which one end is fixed to a transparent conductive film 12 provided on one surface of the first substrate 11.
- the growth direction of the brush-like carbon nanotube 13 is not particularly limited, but it is particularly preferable that the brush-like carbon nanotube 13 is formed so as to be substantially perpendicular to the surface of the transparent conductive film 12.
- the electrolytic solution is filled between the carbon nanotubes 13, and the conductivity of the iodine electrolyte is further improved.
- the present invention employs a carbon nanotube instead of a conventional carbon film or platinum film as a counter electrode.
- Carbon nanotubes have a structure in which a graphite sheet is rolled into a cylindrical shape with a diameter of 0 It is a material with a very large aspect ratio having a hollow structure with a length of about 7-50 nm and a length of several zm.
- the electrical properties of carbon nanotubes show semiconducting properties from metals depending on their diameter and chirality.
- As a mechanical property it has a large Young's modulus and also has a feature that can relieve stress by buckling.
- Carbon nanotubes have the unique properties described above, and as electron sources, they are used as electron emission sources and flat panel displays, as electronic materials, as electrode materials for nanoscale devices and lithium batteries, as well as for probe probes and gas storage. It is expected to be applied to materials, nanoscale test tubes, additives for reinforcing grease.
- the carbon nanotube has a cylindrical structure in which a graph end sheet is formed in a cylindrical shape or a truncated cone shape.
- single-wall carbon nanotubes SWCNT: single-wall carbon nanotubes
- MWCNT multi-wall carbon nanotubes
- nanotubes and the like can be used for the counter electrode of the present invention.
- Single-walled carbon nanotubes have diameters of about 0.5 nm to 10 nm and lengths of about 10 nm, and multi-walled carbon nanotubes have diameters of about lnm to 100 nm and lengths of about 50 nm to 50 ⁇ m. There is something.
- the diameter d of the brush-like carbon nanotube 13 of the present invention shown in FIG. 3 is 5 to 75 nm, and the height H is about 0.1 to 500 nm.
- the interval D between the carbon nanotubes 13 is suitably about 1 to 1 OOOnm.
- Carbon nanotubes have high electron emission performance due to their large aspect ratio so that they can be used as electron emitter emitters. This is because electron emission occurs from the tip of the carbon nanotube, and it is considered that the electron emission ability is enhanced by orienting vertically. Therefore, when applied to the counter electrode of the photoelectric conversion element, it is possible to make a counter electrode with high photoelectric conversion efficiency.
- the conductivity of the iodine electrolyte is improved because the electrolyte easily enters between the carbon nanotubes and the carbon nanotubes. It is thought to be up.
- the same effect as a nanocomposite gel electrolyte is acquired. That is, in a nanocomposite gel electrolyte in which conductive particles such as carbon fiber and carbon black are mixed in an ionic liquid and then gelled, the semiconductor particles or conductive particles can play the role of charge transfer, and the gel electrolyte composition
- the electrical conductivity of the material is improved, and a photoelectric conversion characteristic that is inferior to that of the case where a liquid electrolyte is used can be obtained.
- the carbon nanotubes play a role of charge transfer, and the electrolyte enters between the carbon nanotubes. Therefore, in the electrolyte near the counter electrode, the same effect as that obtained by using the nanocomposite gel electrolyte is obtained, and the electron The moving speed increases and high photoelectric conversion efficiency can be obtained.
- Carbon nanotubes can be produced by a known chemical vapor deposition method (CVD method).
- CVD method chemical vapor deposition method
- a metal such as nickel, connold, iron or the like is formed on a silicon substrate by sputtering or vapor deposition, and is preferably 500 to 900 in an inert atmosphere, hydrogen atmosphere or vacuum.
- Heat for 1 to 60 minutes at a temperature of ° C then use a general chemical vapor deposition (CVD) method using a hydrocarbon gas such as acetylene or ethylene or an alcohol gas as the source gas.
- CVD general chemical vapor deposition
- the length and thickness of the brush-like carbon nanotubes can be controlled by controlling the temperature and time.
- the diameter of the brush-like carbon nanotube used in the present invention is preferably 5 to 75 nm, the length is 0.1 to 500 ⁇ m, and the distance between the carbon nanotubes is preferably 1 to 1000 nm.
- the aspect ratio is lowered and the electron emission ability is lowered.
- the length of the brush-like carbon nanotube is out of the proper range, it becomes difficult to align the brush-like carbon nanotube perpendicularly to the substrate surface.
- the distance between the brush-like carbon nanotubes is wider than the appropriate range, it is difficult to obtain the same effect as the nanocomposite gel electrolyte.
- the transparent base material used as the first substrate 11 and the second substrate 21 is a light transmissive material.
- a substrate having a material strength is used, and any glass, polyethylene terephthalate, polyethylene naphtharate, polycarbonate, polyethersulfone, or the like that is usually used as a transparent base material for solar cells can be used.
- a transparent base material is appropriately selected from these in consideration of resistance to an electrolytic solution.
- a substrate having excellent light transmittance is preferred as much as possible, and a substrate having a transmittance of 90% or more is more preferable.
- the transparent conductive films 12 and 22 are thin films formed on one surface of the transparent substrates 11 and 21 in order to impart conductivity.
- the transparent conductive films 12 and 22 are preferably thin films having a conductive metal oxide strength in order to obtain a structure that does not significantly impair the transparency of the transparent substrate.
- Examples of conductive metal oxides include tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), and tin oxide (SnO).
- ITO tin-doped indium oxide
- FTO fluorine-doped tin oxide
- SnO tin oxide
- the transparent conductive films 12 and 22 may be a single-layer film made only of ridges or a laminated film in which an FTO film is laminated on a ridge film. If such a transparent conductive film is used, a transparent conductive film having a high conductivity and a small amount of light absorption in the visible region can be formed.
- the brush-like carbon nanotubes described above are formed on the transparent conductive film 12 of the first substrate 11 on which the transparent conductive film 12 is formed.
- a photosensitizing dye is supported on the transparent conductive film 22 of the second substrate 21 on which the transparent conductive film 22 is formed, with the aid of oxide semiconductor fine particles such as oxide titanium.
- oxide semiconductor fine particles such as oxide titanium.
- a porous semiconductor film 23 is formed.
- the porous semiconductor film 23 is composed of titanium oxide (TiO 2), tin oxide (SnO 2), tungsten oxide (
- a dispersion liquid in which commercially available oxide semiconductor fine particles are dispersed in a desired dispersion medium or a colloid solution that can be adjusted by a sol-gel method is necessary.
- the screen printing method after adding the desired additives
- the electrode substrate is immersed in a colloidal solution, and the oxide semiconductor particles are electroded by electrophoresis.
- Electrophoretic deposition method that adheres to the substrate, a method in which a foaming agent is mixed and applied to a colloidal solution or dispersion, and then sintered to make it porous. After polymer microbeads are mixed and applied, this polymer micro It is possible to apply a method of removing the beads by heat treatment or chemical treatment to form voids to make them porous.
- the sensitizing dye supported on the porous oxide semiconductor film 23 is not particularly limited.
- a ruthenium complex-iron complex having a ligand containing a biviridine structure, a terpyridine structure, or the like.
- the power of organic dyes such as porphyrin-based and phthalocyanine-based metal complexes as well as eosin, rhodamine, merocyanine, coumarin and the like can be appropriately selected and used depending on the application and the material of the oxide semiconductor porous film.
- a known electrolyte layer can be used for the electrolyte layer 3 sealed between the counter electrode 1 and the window electrode 2.
- an electrolyte solution is contained in the porous oxide semiconductor layer 23. What is impregnated is mentioned.
- the electrolyte is gelled (pseudo-solidified) using an appropriate gelling agent to form the porous oxide semiconductor layer 23. Examples thereof include those formed integrally, or gel electrolytes containing ionic liquid oxide semiconductor particles and conductive particles.
- electrolytic solution those dissolved in an electrolyte component such as iodine, iodide ion, and tertiary butyl pyridine, or an organic solvent such as ethylene carbonate or methoxyacetonitrile are used.
- an electrolyte component such as iodine, iodide ion, and tertiary butyl pyridine, or an organic solvent such as ethylene carbonate or methoxyacetonitrile are used.
- Examples of the gelling agent used for gelling this electrolytic solution include polyvinylidene fluoride, a polyethylene oxide derivative, and an amino acid derivative.
- the ionic liquid is not particularly limited, but is a room temperature molten salt that is a liquid at room temperature and a compound having a quaternized nitrogen atom as a cation or a cation. Is mentioned.
- Room temperature molten salt ions include BF-, PF-, F (HF) n-, bis (trifluoromethyl)
- the ionic liquid include salts such as quaternized imidazolium cation and iodide ion or bis (trifluoromethylsulfonyl) imide ion.
- the photoelectric conversion element of the present invention obtained by assembling the above components as shown in Fig. 1 uses brush-like carbon nanotubes having a high electron emission ability as the counter electrode, so that the counter electrode is as much as possible.
- a photoelectric conversion element with high photoelectric conversion efficiency with high electron mobility to the electrolyte can be obtained.
- a photoelectric conversion element having the structure shown in FIG. 1 having a counter electrode as shown in FIGS. 2 and 3 was prepared using the following materials.
- Example The electrolyte of Example 3 and Example 4 includes an ionic liquid containing 1 iodine-iodide ion redox couple (1 ethyl 3 methylimidazolim-bis (trifluoromethylsulfol) imide). was prepared.
- Example 5 As electrolytes of Example 2, Example 5 and Example 6, nanocomposite gel electrolytes prepared by mixing 10 wt% of acid titanium nanoparticles and centrifuging them were used. (Window pole)
- a glass substrate with an FTO film was used as the transparent electrode substrate, and a slurry-like aqueous dispersion of titanium oxide with an average particle diameter of 20 nm was applied to the surface of the transparent electrode plate on the FTO film side.
- a heat treatment was performed for a period of time to form an oxide semiconductor porous film having a thickness of 7 m.
- a window electrode was fabricated by immersing the dye in an ethanol solution of ruthenium piperidine complex (N3 dye) for 1 hour.
- Example 1 and Example 2 using a conventional chemical vapor deposition (CVD) method using acetylene gas as a source gas on a glass substrate with an FTO film, the diameter is 10 to 50 nm and the length is 0.5.
- a brush-like carbon nanotube of ⁇ 10 m was formed as a counter electrode. The carbon nanotubes were formed almost perpendicular to the substrate, and the interval between the carbon nanotubes was 10-50 nm.
- Example 3 and Example 5 a conventional chemical vapor deposition (CVD) method using acetylene gas as a raw material gas on a titanium plate was used, and a diameter of 10 to 50 nm and a length of 0.5 to 10 m were used.
- a carbon-like carbon nanotube was formed as a counter electrode. The carbon nanotubes were formed almost perpendicular to the substrate, and the interval between the carbon nanotubes was 10 to 50 nm.
- a titanium plate that was not subjected to anodizing treatment was used.
- Example 4 and Example 6 a counter electrode was prepared in the same manner as Example 3 except that a titanium plate subjected to anodizing treatment was used.
- Table 1 summarizes the photoelectric conversion efficiency.
- the CNT in Table 1 means the brush-like carbon nanotube described above.
- “Yes” indicates the case where the treatment is performed
- “None” indicates the case where the treatment is not performed
- “No. 1” indicates the titanium plate. The case where it is not applicable because it is not used is shown respectively.
- Example 1 CNT / FTO ionic liquid 6.
- Example 2 CNT / FTO nanocomposite gel 6.5
- Example 3 CNTZ titanium plate None Ionic liquid 6.
- Example 4 CNT / Titanium plate Yes Ionic liquid 6.8
- Example 5 CNTZ titanium plate None Nanocomposite gel 6.4
- Example 6 CNT no titanium plate Yes Nanocomposite gel 6.6 Comparative example 1 Platinum ZFTO —— Nanocomposite gel 5, 9
- a nanocomposite gel electrolyte prepared by mixing 10 wt% of titanium oxide nanoparticles and centrifuging was used as the electrolyte. Sputtering an electrode film made of platinum as the counter electrode A glass substrate with FTO film formed by the method was used. The same window electrode as in the example was used.
- a photoelectric conversion element having the structure shown in FIG. 4 was prepared.
- the photoelectric conversion characteristics were measured using the photoelectric conversion element thus prepared.
- the photoelectric conversion efficiency is also shown in Table 1.
- the electrolyte used was the same ionic liquid electrolyte as in the previous example.
- the same glass substrate with an FTO film on which an electrode film made of platinum was formed by sputtering as in Comparative Example 1 was used.
- the same window electrode as in the example was used.
- a photoelectric conversion element having the structure shown in FIG. 4 was prepared.
- the photoelectric conversion characteristics of the photoelectric conversion element were measured.
- the photoelectric conversion efficiency is also shown in Table 1.
- the same ionic liquid electrolyte as in Example 1 was used.
- the same counter electrode the same titanium plate on which an electrode film made of platinum was formed by sputtering as in Comparative Example 1 was used.
- the same window electrode as in the example was used.
- a titanium plate that was anodized was used.
- a photoelectric conversion element having the structure shown in FIG. 4 was prepared.
- the photoelectric conversion characteristics of the photoelectric conversion element were measured.
- the photoelectric conversion efficiency is also shown in Table 1.
- the photoelectric conversion element incorporating the counter electrode using the carbon nanotube according to the present invention has excellent photoelectric conversion efficiency.
- the thickness of the oxide layer formed by this processing is preferably 500 nm or less. If it is thicker than 500 nm, current will not flow easily from the CNT synthesized on the oxide layer to the substrate (titanium plate).
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Abstract
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KR1020077013782A KR101145322B1 (ko) | 2004-12-22 | 2005-12-07 | 광전변환소자용의 대극 및 광전변환소자 |
US11/722,167 US20090272431A1 (en) | 2004-12-22 | 2005-12-07 | Counter electrode for a photoelectric conversion element and photoelectric conversion element |
EP05814481.7A EP1830431B1 (en) | 2004-12-22 | 2005-12-07 | Counter electrode for photoelectric converter and photoelectric converter |
AU2005320306A AU2005320306B2 (en) | 2004-12-22 | 2005-12-07 | Counter electrode for photoelectric converter and photoelectric converter |
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2005
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- 2005-12-07 EP EP05814481.7A patent/EP1830431B1/en not_active Ceased
- 2005-12-07 KR KR1020077013782A patent/KR101145322B1/ko active IP Right Grant
- 2005-12-07 WO PCT/JP2005/022485 patent/WO2006067969A1/ja active Application Filing
- 2005-12-07 AU AU2005320306A patent/AU2005320306B2/en not_active Ceased
- 2005-12-07 US US11/722,167 patent/US20090272431A1/en not_active Abandoned
- 2005-12-16 TW TW094144703A patent/TWI301000B/zh not_active IP Right Cessation
Patent Citations (5)
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EP1357607A1 (en) | 2000-12-26 | 2003-10-29 | Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo | Solar cell |
JP2004111216A (ja) * | 2002-09-18 | 2004-04-08 | Inst Of Research & Innovation | 色素増感型太陽電池およびナノカーボン電極 |
JP2004241228A (ja) * | 2003-02-05 | 2004-08-26 | Toin Gakuen | プラスチックフィルム電極及びそれを用いた光電池 |
JP2004288985A (ja) * | 2003-03-24 | 2004-10-14 | Japan Science & Technology Agency | 太陽電池 |
JP2004319661A (ja) | 2003-04-15 | 2004-11-11 | Fujikura Ltd | 光電変換素子用基材およびその製造方法ならびに光電変換素子およびその製造方法 |
Non-Patent Citations (2)
Title |
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See also references of EP1830431A4 |
SUZUKI ET AL.: "Application of Carbon Nanotubes to Counter Electrodes of Dye-sensitized Solar Cells", CHEMISTRY LETTERS, vol. 32, no. 1, 2003 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2005216861A (ja) * | 2004-01-28 | 2005-08-11 | Samsung Sdi Co Ltd | ファイバ状太陽電池及びその製造方法 |
EP1879203A1 (en) | 2006-07-13 | 2008-01-16 | Samsung Electronics Co., Ltd | Photovoltaic cell using catalyst-supporting carbon nanotube and method for producing the same |
US7939748B2 (en) * | 2006-12-11 | 2011-05-10 | Fujikura Ltd. | Photoelectric conversion element |
WO2009008495A1 (ja) * | 2007-07-12 | 2009-01-15 | Hitachi Zosen Corporation | 光電変換素子およびその製造方法 |
WO2009008494A1 (ja) * | 2007-07-12 | 2009-01-15 | Hitachi Zosen Corporation | 光電変換素子およびその製造方法 |
CN101743662A (zh) * | 2007-07-12 | 2010-06-16 | 日立造船株式会社 | 光电转换元件及其制造方法 |
CN101689689B (zh) * | 2007-07-12 | 2014-04-02 | 日立造船株式会社 | 光电转换元件及其制造方法 |
US20110100440A1 (en) * | 2007-08-14 | 2011-05-05 | William Marsh Rice University | Optical Rectification Device and Method of Making Same |
JP2009231224A (ja) * | 2008-03-25 | 2009-10-08 | Hitachi Zosen Corp | 光電変換素子およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JP4937560B2 (ja) | 2012-05-23 |
EP1830431A4 (en) | 2011-08-31 |
TW200635100A (en) | 2006-10-01 |
EP1830431A1 (en) | 2007-09-05 |
US20090272431A1 (en) | 2009-11-05 |
EP1830431B1 (en) | 2013-05-22 |
KR101145322B1 (ko) | 2012-05-14 |
JP2006202721A (ja) | 2006-08-03 |
TWI301000B (en) | 2008-09-11 |
AU2005320306A1 (en) | 2006-06-29 |
KR20070091294A (ko) | 2007-09-10 |
AU2005320306B2 (en) | 2010-10-21 |
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