WO2013128797A1 - Procédé de fabrication de collecteur de courant pour cellule solaire sensibilisée aux colorants comprenant une feuille métallique poreuse, collecteur de courant pour cellule solaire sensibilisée aux colorants comprenant une feuille métallique poreuse et une cellule solaire sensibilisée aux colorants - Google Patents

Procédé de fabrication de collecteur de courant pour cellule solaire sensibilisée aux colorants comprenant une feuille métallique poreuse, collecteur de courant pour cellule solaire sensibilisée aux colorants comprenant une feuille métallique poreuse et une cellule solaire sensibilisée aux colorants Download PDF

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WO2013128797A1
WO2013128797A1 PCT/JP2013/000558 JP2013000558W WO2013128797A1 WO 2013128797 A1 WO2013128797 A1 WO 2013128797A1 JP 2013000558 W JP2013000558 W JP 2013000558W WO 2013128797 A1 WO2013128797 A1 WO 2013128797A1
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dye
sensitized solar
solar cell
current collector
sheet
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PCT/JP2013/000558
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English (en)
Japanese (ja)
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早瀬　修二
能弘 山口
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新日鉄住金化学株式会社
国立大学法人九州工業大学
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Publication of WO2013128797A1 publication Critical patent/WO2013128797A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/002—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—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

Definitions

  • the present invention relates to a method for producing a current collector for a dye-sensitized solar cell, a current collector for a dye-sensitized solar cell, and a dye-sensitized solar cell.
  • Dye-sensitized solar cells are called wet solar cells or Gretzel cells, and are characterized by having an electrochemical cell structure that uses an electrolyte without using a silicon semiconductor.
  • a porous semiconductor layer such as a titania layer formed by baking a titanium dioxide powder or the like on an anode electrode using a transparent conductive film such as a transparent conductive glass plate and adsorbing a dye thereto, and a conductive glass plate (conductive A simple structure in which an iodine solution or the like is disposed as an electrolyte between a counter electrode (cathode electrode) composed of a conductive substrate)
  • the power generation mechanism of the dye-sensitized solar cell is as follows. Light incident from the transparent conductive film surface, which is the light-receiving surface, is absorbed by the dye adsorbed on the porous semiconductor layer, causing electronic excitation, and the excited electrons move to the semiconductor and are guided to the conductive glass. . Next, the electrons that have returned to the counter electrode are led to the dye that has lost the electrons through an electrolyte such as iodine, and the dye is regenerated.
  • Dye-sensitized solar cells are attracting attention as low-cost solar cells because they are less expensive than silicon-based solar cells and do not require large-scale production facilities. For example, it is considered to omit an expensive transparent conductive film. In addition, since the transparent conductive film has a large electric resistance, there is also a problem that it is not suitable for increasing the size of the battery.
  • One method for omitting the transparent conductive film is to provide a wiring made of a conductive metal instead of the transparent conductive film disposed on the glass surface. However, in this case, a part of the incident light is blocked by the metal wiring part, resulting in a decrease in efficiency.
  • a photoelectric conversion element in which a dye-carrying semiconductor layer is formed on a transparent substrate that does not have a transparent conductive film on the light irradiation side, and a perforated current collecting electrode is disposed on the dye-carrying semiconductor layer Is disclosed (see Patent Document 1).
  • the perforated current collecting electrode has a network-like or grid-like structure in which fine wire or thin plate electrode materials are combined vertically and horizontally, for example, and this current collecting electrode is placed on a coating film on a porous semiconductor substrate. For example, baking is performed at 500 ° C. for 30 minutes.
  • a wire mesh having a wire diameter of 1 ⁇ m to 10 mm is used as a collecting electrode having holes, a paste which is a material of the porous semiconductor layer is applied to the wire mesh, and the paste is fired to form a porous semiconductor layer.
  • a technique has been disclosed in which a wire mesh is disposed with a porous semiconductor layer facing a glass transparent substrate having no transparent conductive film (see Patent Document 2).
  • a method of depositing a metal such as tungsten, titanium, nickel or the like as a collecting electrode by a method such as sputtering or vapor deposition and then patterning by photolithography or the like is disclosed (see Patent Document 3). ).
  • the resulting collector electrode is a very thin metal film.
  • the thickness of the formed metal film is very thin, for example, if it is less than 50 nm, there is a possibility that the area resistance of the metal film is increased and the power extraction efficiency is not improved.
  • the film becomes dense, the porosity is remarkably lowered, and the flow of the electrolytic solution may be hindered, resulting in insufficient performance. Furthermore, since this method is based on the premise that a metal film is formed on a certain base material, the metal film itself does not exist as a self-supporting film, which limits the design freedom of the dye-sensitized solar cell.
  • the present inventors have disclosed a technique of using a porous metal sheet made of a sintered metal obtained by sintering metal powder as a collecting electrode of a dye-sensitized solar cell (Patent Document 4).
  • This porous titanium sheet is a porous metal body in which a large number of pores communicate isotropically.
  • the metal porous body has a porosity of 30 to 60% by volume and a pore diameter of 1 to 40 ⁇ m.
  • the collector electrode having such a void structure contributes to the improvement of power generation efficiency.
  • the metal porous sheet is preferably thin.
  • the lower limit of the thickness of the metal porous sheet that can be manufactured is the particle size of the metal powder that can be manufactured industrially (industrial Specifically, it is limited to 20 ⁇ m or more.
  • the problem to be solved is that further improvement of the current collecting electrode is required in order to contribute to further improvement of the photoelectric conversion efficiency of the dye-sensitized solar cell.
  • a method for producing a current collector for a dye-sensitized solar cell comprising a porous metal sheet according to the present invention is as follows: Forming a sheet comprising an alloy of a first metal component and a second metal component; A third metal component having a positive heat of mixing with the first metal component and a negative heat of mixing with the second metal component and having a freezing point lower than the melting point of the alloy Immersing the sheet in a metal melting bath of the alloy and treating the sheet at a temperature lower than the minimum liquidus temperature in the phase diagram of the alloy; Removing the treated sheet from the molten metal bath; It is characterized by having.
  • the method for producing a current collector for a dye-sensitized solar cell comprising a porous metal sheet according to the present invention is preferably characterized in that a single roll quenching method is used in the step of forming the alloy sheet.
  • the treated sheet is taken out of the molten metal bath and then washed with an acid or an alkali. It further has a process.
  • the first metal component is selected from Ti, W, Zr, Nb and Ta. It is a seed or two or more kinds.
  • the second metal component is one selected from Cu, Ni, Co and Fe, or It is characterized by being 2 or more types.
  • the manufacturing method of the collector for dye-sensitized solar cells which consists of a porous metal sheet which concerns on this invention
  • the said 3rd metal component is 1 type or 2 types chosen from Mg, Ca, and Bi. It is the above.
  • the current collector for a dye-sensitized solar cell comprising the porous metal sheet according to the present invention has a large number of nano-order diameters in which molten spherical metal lumps are fused to each other in a three-dimensional direction and communicated isotropically. Through-holes.
  • the current collector for a dye-sensitized solar cell comprising the porous metal sheet according to the present invention is preferably characterized in that the porosity is 20 to 90% and the sheet thickness is 50 nm to 100 ⁇ m.
  • the current collector for a dye-sensitized solar cell comprising the porous metal sheet according to the present invention is preferably composed of one or more metals selected from Ti, W, Zr, Nb and Ta.
  • the dye-sensitized solar cell according to the present invention is A transparent substrate, a conductive substrate serving as a cathode electrode, a porous semiconductor layer that is disposed between or in contact with the transparent substrate and adsorbs a dye, between the transparent substrate and the conductive substrate; Comprising a current collector disposed in contact with the opposite side of the transparent semiconductor layer to the transparent substrate and serving as an anode, and the electrolyte is sealed;
  • the current collector is a porous metal sheet produced by the method for producing a current collector for a dye-sensitized solar cell comprising the porous metal sheet.
  • the dye-sensitized solar cell according to the present invention is A transparent substrate, a conductive substrate serving as a cathode electrode, a porous semiconductor layer that is disposed between or in contact with the transparent substrate and adsorbs a dye, between the transparent substrate and the conductive substrate; Comprising a current collector disposed in contact with the opposite side of the transparent semiconductor layer to the transparent substrate and serving as an anode, and the electrolyte is sealed;
  • the current collector is a current collector for a dye-sensitized solar cell made of the porous metal sheet.
  • the obtained current collector is isotropically fused with a molten spherical metal mass in a three-dimensional direction. Since there are a large number of nano-sized through-holes communicating with each other, the mobility of charges in the electrolyte that permeates the current collector is large. For this reason, it can be expected to obtain high photoelectric conversion efficiency when used in a dye-sensitized solar cell.
  • the current collector for a dye-sensitized solar cell comprising the porous metal sheet according to the present invention has a large number of nano-order diameters in which molten spherical metal lumps are fused to each other in a three-dimensional direction and communicated isotropically. Therefore, the charge mobility in the electrolyte that permeates the current collector is large. For this reason, it can be expected to obtain high photoelectric conversion efficiency when used in a dye-sensitized solar cell.
  • FIG. 1 is a diagram showing a schematic configuration of a dye-sensitized solar cell according to the present embodiment.
  • FIG. 2 is a view showing an SEM photograph of the porous titanium sheet of the example as viewed from the main surface (surface).
  • Metal materials having nanopores with nano-order (nm dimensions) are not limited to current collectors for dye-sensitized solar cells, and are generally difficult to produce.
  • a metal bath comprising the first component and the second component and the third component simultaneously having positive and negative heats of mixing with respect to the first component, respectively.
  • the liquidus temperature within a composition variation range from a metal material having a melting point higher than the solidification point of the metal, consisting of a compound, alloy or non-equilibrium alloy until the third component decreases from the metal material to the second component.
  • a method for producing a metal member which is obtained by selectively leaching the third component into the metal bath by dipping in a metal bath controlled at a temperature lower than the minimum value of the above. ing.
  • the metal member obtained in this way has an extremely large specific surface area compared to a bulk metal body, and therefore has high functionality that cannot be obtained with conventional materials in terms of catalyst characteristics, electrode characteristics, gas storage characteristics, and sensing characteristics. It is shown that it can be greatly expected to demonstrate.
  • no quantitative data is shown for nano-order pores, and no specific application examples are shown.
  • the present inventors thought that a useful current collector could be obtained by using the above-described method for producing a metal member as a method for producing a current collector for a dye-sensitized solar cell. did. Unlike other electrode materials, current collectors for dye-sensitized solar cells are resistant to electrolytes, electrically inert to the electrolyte, mobility and diffusivity between electrodes of electrolytes and carriers, and metal electrodes. Therefore, heat resistance and oxidation resistance during sintering of the oxide semiconductor are required. Furthermore, in order to combine the bonding strength with the porous semiconductor and the flowability of the electrolyte, it is necessary to control the structure such as thickness, porosity, and pore diameter.
  • the method of manufacturing a current collector includes a step of forming a sheet made of an alloy of a first metal component and a second metal component, and positive mixing heat with respect to the first metal component. And having a negative heat of mixing with the second metal component, and immersing the sheet in a metal melting bath of the third metal component having a freezing point lower than the melting point of the alloy, and in the phase diagram of the alloy And a step of processing at a temperature lower than the minimum value of the phase line temperature, and a step of removing the processed sheet from the metal melting bath.
  • the first metal component is preferably one or more selected from Ti, W, Zr, Nb and Ta, and more preferably Ti.
  • the second metal component is one or more selected from Cu, Ni, Co and Fe, and more preferably Cu.
  • the third metal component is preferably one or more selected from Mg, Ca and Bi, and more preferably Mg.
  • the raw material for each of these metal components is preferably a high-purity metal powder, but may be a sponge metal powder, a gas atomized metal powder, a metal lump or the like.
  • a method for forming a sheet composed of an alloy of the first metal component and the second metal component is not particularly limited, but it is a preferred embodiment to use a single-roll quenching method.
  • the single roll quenching method is known as a method for producing an amorphous alloy having no crystal structure, and the obtained amorphous alloy is excellent in properties such as strength.
  • the first metal component and the second metal component are melted by, for example, an arc melting method in a pure Ar atmosphere to form an alloy, which is then remelted, for example, rapidly cooled on the surface of a rotating drum, to thereby form an amorphous alloy.
  • a ribbon can be obtained.
  • the alloy sheet has a positive heat of mixing with the first metal component, a negative heat of mixing with the second metal component, and a third metal having a freezing point lower than the melting point of the alloy.
  • the sheet is immersed in the metal melting bath of the components and processed at a temperature lower than the minimum value of the liquidus temperature in the alloy phase diagram.
  • the treated sheet is removed from the metal melting bath. For example, according to the calculation using the Miedemma model, between Mg as the third metal component and Ti as the first metal component and between Mg as the second metal component and Cu as the second metal component, respectively, A heat of mixing of 16 kJ / mol and -3 kJ / mol is generated (refer to the Metallurological Society of Japan, Volume 46, 2818, 2005).
  • Mg and Ti are phase-separated while Mg and Cu have a property of forming an admixture. That is, while Cu remains in the sheet, Cu elutes from the sheet into the metal bath. Ti remaining in the sheet repeats bonding with surrounding Ti to form fine particles having a nano-order size. These fine particles are partially bonded to form a large number of through holes having a nano-order diameter.
  • a nano-sized Ti molten droplet is generated where Cu is eluted.
  • the nanosized droplets generated by melting are connected to each other as time elapses from the generation stage, and a dendritic mass of molten metal Ti having a shape in which the droplets are connected in the shape of branches of a tree is formed. If this molten state is maintained, the shape of the molten metal lump that has grown in a branch shape will change to a shape similar to that of a spherical lump while coalescing with surrounding fine droplets due to the influence of the surface tension of the molten metal. Get closer to a sphere via shape.
  • the molten spherical metal mass of the present invention includes all the shapes of the above-mentioned generational stage dendritic mass, spherical mass, confetti, and the process of changing to a spherical shape.
  • the diameter of the fine particles and the diameter of the through-hole both increase to the micron order.
  • the nano-order dimension literally means less than 1 ⁇ m, more preferably an average pore diameter of 10 to 990 nm.
  • the treatment temperature in the metal molten bath is lower than the temperature that is the minimum value of the liquidus in the alloy phase diagram.
  • the processing temperature is higher than the temperature that is the minimum value of the liquidus, the alloy components are melted, so that the effect of the present invention cannot be obtained.
  • the processing temperature lower than the temperature that is the minimum value of the liquidus line varies depending on the type of alloy component. For example, when Ti is used as the first metal component and Cu is used as the second metal component, respectively, the temperature is preferably lower than 1141 K, which is the minimum value of the liquidus, and is set to 973 K or more.
  • the lower limit of the treatment temperature is a temperature at which Mg can reliably maintain a molten state when Mg is used as the third metal component of the metal melting bath.
  • the time for immersing the sheet in the molten metal bath is not particularly limited, and for example, about several seconds is sufficient.
  • the diameter dimension and the porosity of the through hole are also controlled by changing the composition of the alloy. Both the rate and the average pore diameter increase.
  • the current collector for a dye-sensitized solar cell comprising a porous metal sheet obtained by the method for manufacturing a current collector according to the present embodiment has a molten spherical metal mass fused in a three-dimensional direction, and isotropic It has a large number of through-holes of nano-order diameter that are in continuous communication.
  • Mg—Cu alloy liquid adheresive admixture
  • a current collector for a dye-sensitized solar cell made of a porous metal sheet according to this embodiment (hereinafter simply referred to as a current collector for a dye-sensitized solar cell according to this embodiment). ).
  • the current collector for a dye-sensitized solar cell has a large number of through holes having a nano-order diameter in which molten spherical metal lumps are fused to each other in a three-dimensional direction and communicated isotropically. It consists of a porous metal sheet.
  • the dye-sensitized solar cell current collector preferably has all through holes having a nano-order diameter.
  • the present invention is not necessarily limited thereto, and a certain number of through-holes have a nano-order diameter.
  • the other through holes may be of the order of microns.
  • the porosity and the average pore (through hole) diameter are values obtained by measurement by a mercury intrusion method.
  • a mercury intrusion type pore distribution measuring device (Pascal I 140 and Pascal 440 manufactured by CARLOERBA INSTRUMENTS, measurable range: specific surface area 0.1 m 2 / g or more, pore distribution 0.0034 to 400 ⁇ m), pressure range 0.
  • the press-fit volume is calculated and measured as a side area according to the cylindrical pore model.
  • the dye-sensitized solar cell current collector according to this embodiment can be suitably obtained by the above-described method for producing a current collector according to this embodiment, but the production method is limited to this method. It is not a thing.
  • the current collector for the dye-sensitized solar cell preferably has a porosity of 20 to 90% and a (sheet) thickness of 50 nm to 100 ⁇ m.
  • the porosity is more preferably 40 to 90%.
  • the thickness is more preferably 200 nm to 25 ⁇ m. If the porosity is less than 20%, the flowability and diffusibility of the electrolyte inside the sheet may be deteriorated, and if it exceeds 90%, the adhesion and bonding force with the porous semiconductor layer may be impaired. . Moreover, when it exceeds 90%, there exists a possibility that the intensity
  • the thickness is less than 50 nm, the strength of the sheet may be impaired, and the sheet resistance may be increased.
  • the thickness exceeds 100 ⁇ m, the flow resistance of the electrolyte solution inside the sheet increases and the flowability and diffusibility of the electrolyte inside the sheet or between both surfaces deteriorates. Uniform penetration may be impaired.
  • the dye-sensitized solar cell using the current collector for the dye-sensitized solar cell according to the present embodiment as the current collector has a high charge mobility in the electrolyte that passes through the current collector. For this reason, it can be expected to obtain high photoelectric conversion efficiency when used in a dye-sensitized solar cell.
  • the mechanism by which the through-hole having a nano-order diameter of the current collector contributes to the improvement of photoelectric conversion efficiency is not clear, but the following effects are assumed.
  • the improvement in the photoelectric conversion efficiency is considered to be due to the improvement in the conductivity of the electrolyte (electrolyte solution).
  • a so-called electron hopping effect is considered to improve the conductivity of the electrolyte (electrolyte solution).
  • ion pairs of solvated iodine ions, etc. which are electron carriers, and cations are regularly aligned in the process of passing through a through hole having a nano-order diameter, and redox between adjacent ion pairs.
  • a phenomenon occurs in which only electrons move even if the ion pair does not move, that is, the charge is transported at a high speed.
  • the hopping effect is further increased if the ratio of through holes having a nano-order diameter in the entire through holes is increased.
  • a dye-sensitized solar cell 10 includes a transparent substrate 12, a conductive substrate 14 serving as a cathode electrode, and a space between the transparent substrate 12 and the conductive substrate 14. Further, a porous semiconductor layer 16 that is disposed in the vicinity of or in contact with the transparent substrate 12 and adsorbs the dye, and a collector that is disposed in contact with the opposite side of the porous semiconductor layer 16 to the transparent substrate 12 and serves as an anode electrode. An electric body 18 is provided, and the electrolyte 20 is sealed.
  • the current collector 18 is a porous metal sheet manufactured by the method for manufacturing a current collector for a dye-sensitized solar cell including the porous metal sheet according to the above-described embodiment, or the above-described embodiment. This is a current collector for a dye-sensitized solar cell comprising such a porous metal sheet.
  • reference numeral 22 indicates a sealing material.
  • the components of the dye-sensitized solar cell 10 other than the dye-sensitized solar cell current collector 18 can be manufactured by an appropriate method using an appropriate material that is usually employed.
  • the transparent substrate 12 may be, for example, a glass plate or a plastic plate, but using a plastic plate is preferable because flexibility can be imparted to the dye-sensitized solar cell.
  • a plastic plate for example, PET, PEN, polyimide, cured acrylic resin, cured epoxy resin, cured silicone resin, various engineering plastics, cyclic polymers obtained by metathesis polymerization, and the like can be mentioned.
  • the conductive substrate 14 a substrate similar to the transparent substrate 12 is used. For example, ITO (indium oxide film doped with tin) or FTO (fluorine is doped) on a part of the surface of the substrate facing the electrolyte 20.
  • a conductive film such as a tin oxide film), a SnO 2 film, a metal film such as Ti, W, Mo, Rh, Pt, or Ta is laminated, and a catalyst film such as a platinum film is provided on the conductive film.
  • the transparent substrate may be omitted, and a catalyst film or layer such as a platinum film may be provided on the metal foil.
  • the metal foil is preferably Ti.
  • the porous semiconductor layer 16 can be made of any suitable material such as ZnO or SnO 2, but TiO 2 is preferred.
  • the shape of fine particles such as TiO 2 is not particularly limited, but is preferably about 1 nm to 100 nm.
  • the porous semiconductor layer 16 is preferably formed into a desired thick film by repeating the operation of baking at a temperature of 300 to 550 ° C., for example, after forming a thin film of TiO 2 paste.
  • a dye is adsorbed on the surface of the fine particles constituting the porous semiconductor layer 16.
  • the dye has absorption in at least a part of the wavelength region of 400 nm to 1000 nm. Examples thereof include organic dyes such as dyes and polymethine dyes.
  • the adsorption method is not particularly limited.
  • a so-called impregnation method in which a dye-sensitized solar cell current collector 18 in which a porous semiconductor layer 16 is formed in a dye solution is immersed and the dye is chemically adsorbed on the surface of the fine particles can be used.
  • a so-called impregnation method in which a dye-sensitized solar cell current collector 18 in which a porous semiconductor layer 16 is formed in a dye solution is immersed and the dye is chemically adsorbed on the surface of the fine particles can be used.
  • the transparent substrate 12 and the porous semiconductor layer 16 may or may not be in contact with each other, but the distance between the two is preferably as short as possible. Further, since the conductive metal layer 18 and the conductive substrate (counter electrode) 14 are arranged so as not to contact each other, for example, the conductive metal layer 18 is sufficiently resistant to the electrolyte 20 and does not hinder the diffusion of the electrolyte ions. There is also a method of insulating with a spacer such as glass paper having holes. The distance between the dye-sensitized solar cell current collector 18 and the conductive substrate 14 is preferably 100 ⁇ m or less, and more preferably 25 ⁇ m or less.
  • the electrolyte 20 is not particularly limited, but includes, for example, iodine, lithium ion, ionic liquid, t-butylpyridine, and the like.
  • iodine an oxidation-reduction body composed of a combination of iodide ions and iodine is used. Can do.
  • a metal complex such as cobalt may be used as the redox pair.
  • it contains a solvent capable of dissolving this redox substance, and examples thereof include acetonitrile, ⁇ -butyrolactone, propionitrile, ethylene carbonate, and ionic liquid.
  • the method for injecting the electrolyte 20 is not particularly limited, and for example, a part of the sealing material 22 may be left as an opening, and the electrolyte 20 may be injected from the opening to seal the opening. Alternatively, an opening may be provided in advance in a part of the conductive substrate 14, and the opening may be sealed after injecting the electrolyte 20 therefrom.
  • the sealing material 22 for sealing by injecting the electrolyte 20 between the transparent substrate 12 and the conductive substrate 14 is a thermoplastic resin sheet having a thickness of 100 ⁇ m or less after curing, a photocurable resin, a thermosetting resin. Etc. can be used.
  • the dye-sensitized solar cell may be one in which the stacking order in the thickness direction is the same as described above, and the entire electrode is cylindrical.
  • the dye-sensitized solar cell according to the present embodiment can obtain high photoelectric conversion efficiency.
  • the dye-sensitized solar cell other than the dye-sensitized solar cell according to the present embodiment described above for example, the dye-sensitized solar cell according to the present embodiment is provided on a transparent substrate provided with a transparent conductive film.
  • Dyes such as those provided with current collectors, or those in which one or more current collectors are arranged at a different site from those arranged on the opposite side of the porous semiconductor layer from the transparent substrate
  • a porous metal sheet produced by a method for producing a current collector for a dye-sensitized solar cell comprising a porous metal sheet according to the present embodiment for the entire sensitized solar cell, or the porous material according to the present embodiment described above
  • a dye-sensitized solar cell current collector made of a porous metal sheet can be used as appropriate.
  • Example 1 ⁇ Preparation of porous titanium sheet (A)>
  • a pure argon gas atmosphere approximately 30 g of Cu 70 Ti 30 having a composition with a Cu: Ti atomic ratio of 7: 3 was produced by an arc melting method.
  • a single-roll type quenching method was used to produce a foil-like metal material having approximate dimensions of width 10 mm, thickness 25 ⁇ m, and length 50 mm.
  • the copper element in the foil-like metal material elutes into the magnesium metal molten bath, and the remaining titanium repeats bonding to form fine particulates, which are partially bonded.
  • the adhering admixture of the magnesium component from which copper is eluted is filled in the generated gap.
  • the foil-like metal material that has been pulled up and cooled from the magnesium metal molten bath is treated by placing it in an aqueous nitric acid solution adjusted to a 0.1 molar concentration in a beaker container at room temperature for 30 minutes, and the magnesium and copper components are used as described above. After the adhering admixture was eluted and removed, it was pulled up into the atmosphere and dried to obtain a porous titanium sheet (A).
  • FIG. 2 shows an SEM photograph of the porous titanium sheet (A) viewed from the main surface (front surface) side.
  • the porosity is about 47% and the specific surface area defined by the ratio of the surface area to the volume is about 2.4 ⁇ 10 7 m 2 / m 3. Was calculated.
  • Table 1 shows the thickness of the porous titanium sheet (A) obtained, the average particle diameter of titanium, the porosity, and the average pore diameter.
  • the value of the porosity obtained by measuring by the mercury intrusion method was 50%.
  • ⁇ Preparation of dye-sensitized solar cell (C-1)> A titania paste (trade name Nanoxide D, manufactured by Solaronics) was printed in a range of 5 mm ⁇ 5 mm of the porous titanium sheet (A) cut to 10 mm ⁇ 10 mm, dried, and baked in air at 450 ° C. for 30 minutes. . On the titania after firing, the operation of further printing and firing the titania base was repeated a total of 3 times to obtain a porous Ti sheet substrate with a titania layer.
  • Nanoxide D manufactured by Solaronics
  • the prepared porous Ti sheet substrate with titania layer was impregnated with a mixed solvent solution of N719 dye (manufactured by SOLARONIX) in acetonitrile and t-butyl alcohol for 64 hours, and the dye was adsorbed on the titania surface.
  • the substrate after adsorption was washed with a mixed solvent of acetonitrile and t-butyl alcohol to obtain a porous Ti sheet substrate with a dye-adsorbed titania layer.
  • a titanium foil having a thickness of 12 mm ⁇ 30 mm and a thickness of 25 ⁇ m was laminated on the end portion 2 mm of the surface of the porous Ti sheet substrate with the dye-adsorbing titania layer on which the titania paste was not formed to obtain an anode electrode with a takeout electrode.
  • Platinum was sputtered to 400 nm on one side of a 12 mm ⁇ 30 mm titanium foil having a thickness of 30 ⁇ m to obtain a Ti substrate with a Pt catalyst layer. Further, a 15 mm ⁇ 40 mm titanium foil having a thickness of 20 ⁇ m was laminated on the end portion 2 mm of the Pt-free surface of the Ti substrate with the Pt catalyst layer to obtain a cathode electrode with a takeout electrode.
  • a PEN film having a thickness of 125 ⁇ m bonded with a resin sheet having a thickness of 60 ⁇ m (trade name MELTONIX 1170-60 manufactured by SOLARONIX) was laminated so that the resin sheet surface and the titanium foil surface of the cathode electrode with the extraction electrode face each other. Furthermore, glass paper having a thickness of 50 ⁇ m and a porosity of 85% or more was laminated on the Pt catalyst layer surface of the counter electrode with the extraction electrode. Furthermore, it laminated
  • the PEN film having a thickness of 125 ⁇ m obtained by laminating the resin sheet having a thickness of 60 ⁇ m was laminated so that the surface of the resin adsorbing titania layer of the anode electrode with the extraction electrode faced each other.
  • an electrolyte solution insertion hole of ⁇ 3 mm was provided in the PEN film on the cathode electrode side. These were roll-pressed at a temperature of 130 ° C.
  • the short-circuit current value was measured when the obtained dye-sensitized solar cell was irradiated with pseudo-sunlight having an intensity of 35, 50, 70, 100 mW / cm 2 from the anode electrode side.
  • Table 2 shows the short-circuit current value for each light quantity (light intensity) as a relative value when the value of Example 1 when the light quantity is 35 mw / cm 2 is 1.00.
  • Example 2 A dye-sensitized solar cell (C-2) was obtained in the same manner as in Example 1 except that a glass substrate was used instead of the PEN film. Table 2 shows the characteristics of the dye-sensitized solar cell (C-2).
  • a dye-sensitized solar cell (C-3) was prepared in the same manner as in Example 1 except that the porous titanium sheet (B) (trade name Typorus) made of Osaka Titanium was used instead of the porous titanium sheet (A). Obtained.
  • Table 1 shows the characteristics of Osaka titanium porous titanium sheet (B), and Table 2 shows the characteristics of the dye-sensitized solar cell (C-3).
  • the short-circuit current value greatly increases as the amount of light (light hardness) to be irradiated increases, whereas in the comparative example, even if the amount of light (light hardness) to be irradiated increases, the short-circuit current It can be seen that the value has not increased significantly. This is because the electron hopping phenomenon is added in Examples 1 and 2, and the amount of electrons generated with the increase in the amount of light increases, whereas in the comparative example, even if the amount of light (light hardness) increases, the titanium sheet penetrates. It is considered that a remarkable electron hopping phenomenon does not appear because the hole size is as large as micron order.

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Abstract

L'invention concerne un collecteur de courant capable d'obtenir une efficacité de conversion photoélectrique plus élevée lorsqu'il est utilisé pour une cellule solaire sensibilisée aux colorants. Un procédé de fabrication d'un collecteur de courant pour cellule solaire sensibilisée aux colorants comprenant une feuille métallique poreuse comprend : un procédé de formation d'une feuille réalisée à partir d'un alliage d'un premier composant métallique et d'un second composant métallique ; un procédé de traitement de la feuille à une température inférieure à la valeur minimale de température du liquide dans le diagramme de phase de l'alliage par immersion de la feuille dans un bain de métal en fusion d'un troisième composant métallique qui présente un mélange à chaleur positive pour le premier composant métallique et un mélange à chaleur négative pour le deuxième composant métallique, tout en ayant un point de durcissement inférieur à la température de fusion de l'alliage et un procédé consistant à prendre la feuille traitée du bain de métal en fusion. Le collecteur de courant pour cellule solaire sensibilisée aux colorants comprenant une feuille métallique poreuse comporte un certain nombre de trous avec des diamètres de l'ordre du nanomètre, communiquant entre eux de manière isotrope avec des masses de métal en fusion sphériques étant mutuellement fusionnées dans toutes les directions d'un espace.
PCT/JP2013/000558 2012-02-29 2013-02-01 Procédé de fabrication de collecteur de courant pour cellule solaire sensibilisée aux colorants comprenant une feuille métallique poreuse, collecteur de courant pour cellule solaire sensibilisée aux colorants comprenant une feuille métallique poreuse et une cellule solaire sensibilisée aux colorants WO2013128797A1 (fr)

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JP5689202B1 (ja) * 2014-08-26 2015-03-25 株式会社昭和 集光装置を設けた色素増感型太陽電池
KR20180023465A (ko) * 2016-08-26 2018-03-07 서울대학교산학협력단 수용해성 합금 용탕 치환 공정 및 이를 통해 제조된 다공성 금속

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RU2648520C2 (ru) * 2016-05-20 2018-03-26 Акционерное общество "Информационные спутниковые системы" имени академика М.Ф. Решетнёва" Космическая платформа
CN117026171B (zh) * 2023-08-16 2024-02-06 上海亿氢能源科技有限公司 基于脉冲激光沉积技术制备pem电解槽多孔扩散层的方法

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JP5689202B1 (ja) * 2014-08-26 2015-03-25 株式会社昭和 集光装置を設けた色素増感型太陽電池
JP2015142130A (ja) * 2014-08-26 2015-08-03 株式会社昭和 集光装置を設けた色素増感型太陽電池
KR20180023465A (ko) * 2016-08-26 2018-03-07 서울대학교산학협력단 수용해성 합금 용탕 치환 공정 및 이를 통해 제조된 다공성 금속
US10538826B2 (en) 2016-08-26 2020-01-21 Seoul National University R&Db Foundation Water-leachable alloy-melt-swapping process and porous metal manufactured using the same

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