JP4495414B2 - Dye-sensitized solar cell and method for producing the same - Google Patents

Description

【発明の効果】
本発明によれば、酸化物半導体層の結着剤に、上記電解質層に含有された高分子成分と同様の主鎖を持つ高分子材料を用いることにより、酸化物半導体層と電解質層との密着性を高めることができ、両者の接触面積の拡大を図ることができることから、エネルギー変換効率の向上に効果を奏する。
【図面の簡単な説明】
【図１】本発明の色素増感型太陽電池の一例を示す概略断面図である。
【図２】本発明の色素増感型太陽電池の製造方法の一例を示す工程図である。
【図３】本発明の色素増感型太陽電池の製造方法の他の例を示す工程図である。
【図４】本発明の色素増感型太陽電池の一例を示す概略断面図である。
【符号の説明】
１ … 透明基板
２ … 透明電極
３ … 酸化物半導体層
４ … 高分子固体電解質層
５ … 対向電極
６ … 対向基板[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dye-sensitized solar cell in which an electrolyte layer is solidified or gelled and a method for producing the same.
[0002]
[Prior art]
In recent years, global warming caused by carbon dioxide has become a global problem. In recent years, solar cells that use solar energy have attracted attention as environmentally friendly and clean energy sources, and active research and development has been promoted. It has been. As such a solar cell, a single crystal silicon solar cell, a polycrystalline silicon solar cell, an amorphous silicon solar cell and the like have already been put into practical use. However, the solar cell has a low environmental load and may be reduced in cost. As a result, dye-sensitized solar cells are attracting attention and research and development are underway.
[0003]
The dye-sensitized solar cell is, for example, from the light incident side, a transparent substrate, a transparent electrode formed on the transparent substrate, an oxide semiconductor layer carrying a dye sensitizer, an electrolyte layer having an electrolyte, And a counter electrode board | substrate is laminated | stacked in order, and a cell is formed. Among such dye-sensitized solar cells, among them, the dye-sensitized solar cell in which the electrolyte layer is liquid is called a wet dye-sensitized solar cell. This wet dye-sensitized solar cell needs to be shielded strictly to prevent liquid leakage from the liquid electrolyte layer, but it is difficult to maintain the shield over a long period of time. Inconveniences such as evaporation of molecules and disappearance of solvent due to liquid leakage may occur, and there are problems in terms of durability and stability.
[0004]
Therefore, researches have been actively conducted to solve the problems of wet dye-sensitized solar cells by solidifying or gelling the electrolyte layer.
[0005]
For example, Patent Document 1 includes (i) a repeating unit derived from a glycidyl compound of 5 to 95 mol%, a repeating unit derived from ethylene oxide of 95 to 5 mol%, and a reactive group-containing monomer. Having a weight average molecular weight of 10 to 15%^Four-10⁷(Ii) a redox couple comprising a combination of iodine and iodine compound or bromine and bromine compound, and if necessary (iii) a plasticizer A photoelectric conversion element using a polymer component is disclosed.
[0006]
Patent Document 2 discloses a technique in which, in a polymer component containing an electrolyte salt and an organic solvent, the organic solvent is a fluorinated organic solvent.
[0007]
Further, Patent Document 3 includes 1-methyl-3-propylimidazolium iodide, 1-methyl-3-isopropylimidazolium iodide, 1-methyl-3-butylimidazolium iodide, 1-methyl-3- An electrolyte containing at least one imidazolium salt selected from the group consisting of isobutylimidazolium iodide and 1-methyl-3-sbutylimidazolium iodide, a halogen-containing compound, and the halogen-containing compound and onium salt A dye-sensitized solar cell comprising a compound containing at least one element selected from the group consisting of N, P and S that can be formed is disclosed.
[0008]
However, when the electrolyte layer is solidified or gelled in this way, the durability and stability of the dye-sensitized solar cell can be improved, but the member in contact with the electrolyte layer, that is, the oxide semiconductor Since the contact area with the layer is smaller than that of the liquid electrolyte layer, the problem is that the energy conversion efficiency is inferior to that of the wet dye-sensitized solar cell.
[0009]
[Patent Document 1]
JP 2000-150006 A
[Patent Document 2]
Japanese Patent Laid-Open No. 11-172096
[Patent Document 3]
JP 2001-160427 A
[0010]
[Problems to be solved by the invention]
The present invention has been made in view of the above problems, and in a dye-sensitized solar cell having a solidified or gelled electrolyte layer, the contact area between such an electrolyte layer and an oxide semiconductor layer is reduced. The main object is to provide a dye-sensitized solar cell that can be increased and energy conversion efficiency can be improved, and a method for manufacturing the same.
[0011]
[Means for Solving the Problems]
In the present invention, a substrate, a first electrode layer formed on the substrate, a metal oxide semiconductor fine particle and a binder formed on the first electrode layer, and a dye sensitizer carried An oxide semiconductor layer that conducts charges generated from the dye sensitizer by light irradiation, a counter substrate that opposes the substrate, and a counter substrate that is formed on the counter substrate and that opposes the first electrode layer. A second electrode layer that is an electrode, and a polymer component, and the charge that is located between the oxide semiconductor layer and the second electrode layer and is conducted by the oxide semiconductor layer is A dye-sensitized solar cell that transports when transported to the oxide semiconductor layer through the second electrode layer and has a solidified or gelled electrolyte layer,
The binder of the oxide semiconductor layer provides a dye-sensitized solar cell characterized by having a polymer component having the same main chain as the polymer component contained in the electrolyte layer.
[0012]
In the present invention, a polymer material having the same main chain as the polymer component contained in the electrolyte layer is used as the binder for the oxide semiconductor layer, thereby allowing the oxide semiconductor layer and the electrolyte layer to adhere to each other. Therefore, it is possible to increase the contact area between the two, thereby improving the energy conversion efficiency.
[0013]
In the present invention, the substrate is preferably a film substrate. This is because the processability is excellent, so it is easy to combine with other devices, and the range of applications can be expanded. It is also effective in reducing weight, improving productivity, and reducing manufacturing costs.
[0014]
Furthermore, in the present invention, a first electrode layer forming step of forming a first electrode layer on the substrate,
On the first electrode layer, an oxide semiconductor layer containing metal oxide semiconductor fine particles and a binder, carrying a dye sensitizer, and conducting charges generated from the dye sensitizer by light irradiation is formed. An oxide semiconductor layer forming step,
The polymer material contained in the binder of the oxide semiconductor layer and a polymer component having the same main chain, and the charge conducted by the oxide semiconductor layer is the first electrode layer, A polymer that forms a solid polymer electrolyte layer on the oxide semiconductor layer for transporting when transported to the oxide semiconductor layer via a second electrode layer that is an electrode facing the first electrode layer A solid electrolyte layer forming step;
A pressurizing step of pressurizing the polymer solid electrolyte layer;
A counter electrode substrate forming step of forming the second electrode layer and the counter substrate on the polymer solid electrolyte layer;
A method for producing a dye-sensitized solar cell, comprising:
[0015]
In the present invention, after the polymer solid electrolyte layer is formed, the pressure between the polymer solid electrolyte layer is increased by a pressurizing step, thereby improving the adhesion between the oxide semiconductor layer and the polymer solid electrolyte layer. Can do. Furthermore, since the polymer material used for the binder of the oxide semiconductor layer and the polymer component contained in the polymer solid electrolyte layer have the same main chain, this also causes oxidation. The adhesion between the physical semiconductor layer and the polymer solid electrolyte layer can be increased. Therefore, the contact area between the oxide semiconductor layer and the polymer solid electrolyte layer can be increased, which has an effect of improving energy conversion efficiency.
[0016]
In the present invention, in the oxide semiconductor layer forming step, it is preferable to perform a pressure treatment before or after the treatment for supporting the dye sensitizer.
[0017]
This is because the mechanical strength of the oxide semiconductor layer and the adhesiveness to the substrate can be improved by performing a pressurizing process in the oxide semiconductor layer forming step.
[0018]
Furthermore, in the present invention, a first electrode layer forming step of forming a first electrode layer on the substrate,
On the first electrode layer, an oxide semiconductor layer containing metal oxide semiconductor fine particles and a binder, carrying a dye sensitizer, and conducting charges generated from the dye sensitizer by light irradiation is formed. An oxide semiconductor layer forming step,
A counter electrode substrate disposing step of disposing a counter substrate having at least a second electrode layer, which is an electrode facing the first electrode layer, so that the oxide semiconductor layer and the second electrode layer oppose each other;
A gel electrolyte that forms a gel electrolyte layer, which is a gelled electrolyte layer, having a polymer component having the same main chain as the polymer material contained in the binder of the oxide semiconductor layer A layer-forming coating solution is injected between the oxide semiconductor layer and the second electrode layer, and the charge conducted by the oxide semiconductor layer is oxidized through the first electrode layer and the second electrode layer. A method for producing a dye-sensitized solar cell comprising a gel electrolyte layer forming step of forming a gel electrolyte layer for transporting when transported to a physical semiconductor layer,
In the oxide semiconductor layer forming step, there is provided a method for producing a dye-sensitized solar cell, wherein a pressurizing process is performed before or after the process of supporting the dye sensitizer.
[0019]
In the present invention, the mechanical strength of the oxide semiconductor layer itself and the adhesion to the substrate can be improved by performing a pressure treatment in the oxide semiconductor layer forming step. Furthermore, by using a polymer material having the same main chain as the polymer component contained in the gel electrolyte layer as a binder for the oxide semiconductor layer, the oxide semiconductor layer and the gel electrolyte layer Affinity can be increased. Therefore, the contact area between the oxide semiconductor layer and the gel electrolyte layer can be increased, which is effective in improving energy conversion efficiency.
[0020]
Furthermore, in the present invention, the substrate is preferably a film substrate. This is because a film substrate is excellent in workability and can be easily subjected to a pressurizing process.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the dye-sensitized solar cell of the present invention and the manufacturing method thereof will be described.
[0022]
A. Dye-sensitized solar cell
First, the manufacturing method of a dye-sensitized solar cell is demonstrated. The dye-sensitized solar cell of the present invention includes a substrate, a first electrode layer formed on the substrate, a metal oxide semiconductor fine particle and a binder formed on the first electrode layer, A dye sensitizer is supported, and is formed on the counter substrate, an oxide semiconductor layer that conducts charges generated from the dye sensitizer by light irradiation, a counter substrate facing the substrate, and the first substrate. A second electrode layer, which is an electrode facing one electrode layer, and a polymer component, located between the oxide semiconductor layer and the second electrode layer, and the electric charge conducted by the oxide semiconductor layer, A dye-sensitized solar cell that transports when transported to the oxide semiconductor layer through the first electrode layer and the second electrode layer and has a solidified or gelled electrolyte layer. And
The binder of the oxide semiconductor layer is characterized by having a polymer material having the same main chain as the polymer component contained in the electrolyte layer.
[0023]
In the present invention, a polymer material having the same main chain as the polymer component contained in the electrolyte layer is used as the binder for the oxide semiconductor layer, thereby allowing the oxide semiconductor layer and the electrolyte layer to adhere to each other. Therefore, it is possible to increase the contact area between the two, thereby improving the energy conversion efficiency.
[0024]
The dye-sensitized solar cell of the present invention having such advantages will be specifically described with reference to the drawings.
[0025]
FIG. 1 is a schematic cross-sectional view showing an example of the dye-sensitized solar cell of the present invention. As shown in FIG. 1, a transparent substrate 1 and a transparent electrode 2 are formed on the surface of the transparent substrate 1 from the side on which light indicated by an arrow is incident. Furthermore, an oxide semiconductor layer 3 is formed on the surface of the transparent electrode 2 opposite to the direction in which light enters. The oxide semiconductor layer 3 is porous, and a dye sensitizer is supported on the surface thereof. A solid polymer electrolyte layer 4 is formed on the surface of the oxide semiconductor layer 3 opposite to the direction in which light enters.
[0026]
In the present invention, the binder used for forming the oxide semiconductor layer 3 includes a polymer component contained in the polymer solid electrolyte layer 4 and a polymer material having the same main chain. It is what. Thus, in the oxide semiconductor layer 3 and the polymer solid electrolyte layer 4, by using the same type of polymer material, the affinity between the two can be suitably increased, and the adhesion between the two can be increased. it can. Therefore, the contact area between the oxide semiconductor layer 3 and the polymer solid electrolyte layer 4 can be increased, which is effective in improving energy conversion efficiency.
[0027]
Furthermore, a counter electrode 5 and a counter substrate 6 that are electrodes facing the transparent electrode 2 are formed on the surface of the polymer solid electrolyte layer 4 opposite to the light incident direction.
[0028]
In such a dye-sensitized solar cell, the photocurrent is obtained by utilizing the charge generated from the dye sensitizer. Generally, the charge generated from the dye sensitizer includes electrons. it can. Hereinafter, the principle of the dye-sensitized solar cell will be described using the charges generated from the dye-sensitizer as electrons. First, when light is incident from the direction of the arrow shown in FIG. 1, the dye sensitizer carried on the oxide semiconductor layer 3 absorbs light and shifts to an excited state. The dye sensitizer in the excited state generates electrons, and the generated electrons are passed to the oxide semiconductor layer 3. Further, it is carried to the counter electrode 5 through the lead wire 7 connected to the transparent electrode 2. Thereby, a photocurrent can be obtained. The dye sensitizer is oxidized by passing generated electrons to the oxide semiconductor layer 3. In addition, the generated electrons move to the counter electrode 5 and then are redox pairs I existing in the electrolyte layer 4.⁻/ I₃ ⁻I₃ ⁻Reduced to I⁻And In addition, I⁻Can be returned to the ground state by reducing the oxidized dye sensitizer.
[0029]
Hereinafter, the dye-sensitized solar cell of the present invention will be described in detail for each member.
[0030]
1. Substrate and counter substrate
The substrate and the counter substrate used in this embodiment are not particularly limited, even if they are transparent or opaque. However, when the substrate and the counter substrate are located on the light receiving surface side, the light transmission property is not limited. It is preferable that the transparent substrate is excellent. Furthermore, it is preferable that it is excellent in heat resistance, weather resistance, water vapor, and other gas barrier properties. Specifically, transparent flexible materials such as quartz glass, Pyrex (registered trademark), synthetic quartz plate, etc. that are not flexible, ethylene / tetrafluoroethylene copolymer film, biaxially stretched polyethylene terephthalate film, polyethersulfone (PES) film, polyetheretherketone (PEEK) film, polyetherimide (PEI) film, polyimide (PI) film, polyester naphthalate (PEN) and other plastic films. In this embodiment, among these, it is preferable to use a film substrate using a plastic film. This is because the processability is excellent, so it is easy to combine with other devices, and the range of applications can be expanded. It is also effective in improving productivity and reducing manufacturing costs. In addition, for example, when the oxide semiconductor layer and the electrolyte layer described later are formed by performing pressure treatment, even if the oxide semiconductor layer and the electrolyte layer are formed by firing at a temperature within the heat resistance range of the film substrate, In the binding property between the physical semiconductor fine particles and the adhesion to the substrate, the same effects can be obtained as in the case where it is formed by firing under sufficiently high temperature conditions. Therefore, there is little fear of inconveniences such as film peeling and cracking, and a film substrate that is slightly inferior in heat resistance to the glass substrate can be suitably used.
[0031]
Such a film may be used alone or may be a composite film in which two or more kinds of films are laminated.
[0032]
2. First electrode layer and second electrode layer
Next, the first electrode layer and the second electrode layer used in the present invention will be described. Hereinafter, both may be collectively referred to as an electrode layer.
[0033]
The material for forming the first electrode layer and the second electrode layer is not particularly limited as long as it is excellent in conductivity and does not corrode with respect to the electrolyte, but is located on the light receiving surface side. The electrode layer is preferably excellent in light transmittance. For example, as a material excellent in light transmittance, SnO₂, ITO, IZO, ZnO and the like. Among them, fluorine doped SnO₂It is preferable that it is ITO. It is because it is excellent in both electroconductivity and permeability.
[0034]
In addition, it is preferable to select materials for the first electrode layer and the second electrode layer in consideration of each work function and the like. For example, materials having a high work function include Au, Ag, Co, Ni, Pt, C, ITO, SnO.₂, Fluorine doped SnO₂, ZnO and the like. On the other hand, examples of the material having a low work function include Li, In, Al, Ca, Mg, Sm, Tb, Yb, Zr, and LiF.
[0035]
In addition, each electrode layer may be formed of a single layer, or may be stacked using materials having different work functions. For example, as shown in FIG. 4, when light enters from the direction of the arrow, a transparent electrode is used as the first electrode layer 40, and further, as the second electrode layer 43 that is an electrode facing the first electrode layer 40. As an example, a case where a layer in which a layer 41 made by depositing Pt and a layer 42 made of ITO are laminated is used.
[0036]
Furthermore, as the film thickness of the electrode layer, the film thickness is in the case of a single electrode layer, and the total film thickness is in the range of 0.1 to 500 nm in the case of a plurality of layers, among which 1 nm to 300 nm. It is preferable to be within the range.
[0037]
A method for forming such an electrode layer is not particularly limited, and examples thereof include a vapor deposition method, a sputtering method, and a CVD method. Among these, the sputtering method is preferable.
[0038]
3. Oxide semiconductor layer
Next, the oxide semiconductor layer is described. The oxide semiconductor layer in the present invention is formed on the first electrode layer, has metal oxide semiconductor fine particles and a binder, carries a dye sensitizer, and is sensitized by light irradiation. It is a member having a function of conducting charges generated from the agent.
[0039]
Since such an oxide semiconductor layer carries a dye sensitizer, it is preferably porous having communication holes. This is because such a porous structure can increase the surface area of the oxide semiconductor layer, and can support a sufficient amount of the dye sensitizer. Moreover, the contact area with the electrolyte layer to be described later can be increased, which is effective in improving energy conversion efficiency.
[0040]
The thickness of the oxide semiconductor layer is preferably in the range of 1 μm to 100 μm, and more preferably in the range of 5 μm to 30 μm. This is because, within the above range, the film resistance of the oxide semiconductor layer itself is small, and light absorption is sufficiently performed by the oxide semiconductor layer.
[0041]
As described above, the oxide semiconductor layer in the present invention has metal oxide semiconductor fine particles and a binder, and further carries a dye sensitizer. Hereinafter, the oxide semiconductor layer will be described in detail by dividing into metal oxide semiconductor fine particles, a binder, a dye sensitizer, and the like.
[0042]
(1) Metal oxide semiconductor fine particles
The metal oxide semiconductor fine particles are not particularly limited as long as they can conduct charges generated from the dye sensitizer to the first electrode layer. Specifically, TiO₂ZnO, SnO₂, ITO, ZrO₂, SiOX, MgO, Al₂O₃, CeO₂, Bi₂O₃, Mn₃O₄, Y₂O₃, WO₃, Ta₂O₅, Nb₂O₅, La₂O₃Etc. These metal oxide fine particles are suitable for forming a porous oxide semiconductor layer, and are preferable because energy conversion efficiency can be improved and costs can be reduced. In addition, any one of the above fine particles may be used, or two or more kinds may be mixed and used. Above all, TiO₂Can be preferably used. Furthermore, it is good also as a core-shell structure which makes one type | mold core microparticles | fine-particles, and includes a core microparticle and forms a shell with another metal oxide microparticle.
[0043]
In the present invention, the content of the metal oxide semiconductor fine particles in the oxide semiconductor layer is preferably in the range of 40 to 99.9% by weight, and more preferably in the range of 85 to 99.5% by weight. .
[0044]
The particle size of the metal oxide semiconductor fine particles is preferably in the range of 1 nm to 10 μm, and more preferably in the range of 10 nm to 500 nm. When the particle diameter is smaller than the above range, it is difficult to produce such fine particles per se, and each particle aggregates to form secondary particles, which is not preferable. On the other hand, a particle diameter larger than the above range is not preferable because the oxide semiconductor layer may be thickened and resistance becomes high.
[0045]
In addition, the same or different kinds of metal oxide semiconductor fine particles having a particle diameter within the above range and different particle diameters may be mixed and used. Accordingly, the light scattering effect can be enhanced and more light can be confined in the oxide semiconductor layer, so that light absorption in the dye sensitizer can be efficiently performed. For example, the metal oxide semiconductor fine particles in the range of 10 to 50 nm and the metal oxide semiconductor fine particles in the range of 50 to 200 nm can be mixed and used.
[0046]
(2) Binder
Next, the binder will be described.
[0047]
The binder in the present invention is characterized by having a polymer component having the same main chain as the polymer component contained in the electrolyte layer described later.
[0048]
Thus, by using the same type of polymer material in the oxide semiconductor layer and the electrolyte layer, the affinity between the two can be suitably increased, and good adhesion can be maintained between the two. . Accordingly, since the contact area between the oxide semiconductor layer and the electrolyte layer can be increased, charge can be efficiently received between the two. Therefore, it has an effect on improvement of energy conversion efficiency.
[0049]
Here, having the same main chain means that the main chain structure is the same in the polymer material used for the binder and the polymer component contained in the electrolyte layer described later. means. Further, the side chain may be composed of the same substituent or may be composed of different substituents. However, in order to obtain better adhesion in the oxide semiconductor layer and the electrolyte layer, the side chain may be composed of the same substituent. preferable.
[0050]
In the binder in the present invention, the polymer component contained in the electrolyte layer described later and the polymer material having the same main chain include polyether, polyester, polyacrylic acid, polymethacrylic acid, and polyalkyl acrylate. Ester, polymethacrylic acid alkyl ester, polycaprolactone, polyhexamethylene carbonate, polysiloxane, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyhexafluoropropylene, Polyfluoroethylene, polyethylene, polypropylene, polycarbonate, polyolefin, polybutadiene, polyisoprene, polystyrene, polyvinyl pyridine, polyvinyl methyl ether, polyvinyl Sobutyl ether, polyacrylamide, polyacrylonitrile, polyvinylidene anide, polyvinyl acetate, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl pyrrolidone, polyvinyl carbazole, polyethylene terephthalate, nylon, polyamide, polyimide, polycarbonate, polybenzimidazole, polyamine, Examples thereof include polymers having a main chain of polyimine, polysulfide, polyphosphazene, natural polymer (cellulosic), or copolymers of two or more of these monomer components. For example, in the case of polyvinylidene fluoride, a polymer of vinylidene fluoride, a copolymer of vinylidene fluoride and other radical polymerizable monomers, and the like can be exemplified.
[0051]
The amount of the binder added is not particularly limited. Specifically, when the binder is formed as an oxide semiconductor layer, the ratio of the binder in the oxide semiconductor layer is 0.1. It is preferable to be within the range of ˜30% by weight, and in particular within the range of 0.2 to 10% by weight.
[0052]
When the ratio is lower than the above range, the adhesion to the first electrode layer and the like and the binding property between the metal oxide semiconductor particles are insufficient, or the mechanical strength of the oxide semiconductor layer itself is reduced. In some cases, it is not preferable. On the other hand, when the ratio is higher than the above range, since a large amount of insulating binder is present, the function of conducting charges generated from the dye sensitizer may be inhibited, which is not preferable.
[0053]
(3) Dye sensitizer
The dye sensitizer in the present invention is not particularly limited as long as it can absorb light and generate an electromotive force. Specifically, an organic dye or a metal complex dye can be used. Examples of organic dyes include acridine, azo, indigo, quinone, coumarin, merocyanine, and phenylxanthene dyes. Among these, a coumarin type is preferable.
[0054]
Further, as the metal complex dye, a ruthenium dye is preferable, and a ruthenium bipyridine dye and a ruthenium terpyridine dye, which are ruthenium complexes, are particularly preferable. The oxide semiconductor layer can hardly absorb visible light (light having a wavelength of about 400 to 800 nm). For example, by supporting a ruthenium complex on the oxide semiconductor layer, the visible light can be greatly absorbed. Conversion can be caused, and the wavelength region of light that can be photoelectrically converted can be greatly expanded.
[0055]
(4) Other
The oxide semiconductor layer in the present invention can be formed by dissolving or dispersing the above-described metal oxide semiconductor fine particles and a binder in an appropriate solvent and applying a coating solution.
[0056]
The solvent used at this time is not particularly limited as long as it can dissolve the binder described above. Specifically, alcohol solvents, ester solvents, ether solvents, pyrrolidone solvents, chain carbonate solvents, cyclic carbonate solvents, lactone solvents, glycol solvents, nitrile solvents, ketone solvents, pyrrolidone solvents Examples thereof include a solvent, an organic solvent such as toluene, and pure water.
[0057]
Various additives may be used in order to improve the coating suitability of the coating liquid prepared by dissolving or dispersing the binder and the metal oxide semiconductor fine particles in the solvent. For example, as the additive, a surfactant, a viscosity modifier, a dispersion aid, a pH adjuster, or the like can be used. For example, examples of the pH adjuster include nitric acid, hydrochloric acid, acetic acid, dimethylformamide, ammonia and the like.
[0058]
4). Electrolyte layer
Next, the electrolyte layer will be described.
[0059]
The electrolyte layer in the present invention has a polymer component and is solidified or gelled. Further, the charge conducted by the oxide semiconductor layer located between the oxide semiconductor layer and the second electrode layer described above is transported to the oxide semiconductor layer through the first electrode layer and the second electrode layer. It will be transported when
[0060]
Here, the solidified or gelled electrolyte layer means that a liquid electrolyte layer is not included.
[0061]
In the present invention, the polymer component contained in the electrolyte layer and the polymer material contained in the binder of the oxide semiconductor layer have the same main chain. Features. Thereby, the affinity between the oxide semiconductor layer and the electrolyte layer can be suitably increased, and good adhesion can be maintained between them, so that the contact area between the two can be increased. Accordingly, charge can be efficiently received between the oxide semiconductor layer and the electrolyte layer, which is effective in improving energy conversion efficiency.
[0062]
In the polymer component contained in such an electrolyte layer, the polymer material used for the binder of the electrolyte layer is the same as that described in “3. Oxide semiconductor layer” described above. The description here is omitted.
[0063]
The content of such a polymer component is not particularly limited. Specifically, when the ratio of the polymer component in the electrolyte layer is a solidified electrolyte layer, the content is 50% by weight to 99% by weight. %, Particularly 70 to 98% by weight is preferable. On the other hand, in the case of a gelled electrolyte layer, it is preferably in the range of 10% by weight to 95% by weight, and more preferably in the range of 30% by weight to 90% by weight. When the ratio is lower than the above range, adhesiveness with the oxide semiconductor layer may not be sufficiently obtained, and the mechanical strength of the electrolyte layer itself may be decreased, which is not preferable. On the other hand, if the ratio is higher than the above range, a large amount of insulating polymer components are present, which is not preferable because the function of transporting charges may be hindered.
[0064]
Hereinafter, each of the electrolyte layers in the present invention will be described assuming that the solidified electrolyte layer is a polymer solid electrolyte layer and the gelled electrolyte layer is a gel electrolyte layer.
[0065]
(1) Polymer solid electrolyte layer
The polymer solid electrolyte layer in the present invention is a solidified electrolyte layer. By solidifying the electrolyte layer in this way, there is no concern that the composition of the electrolyte layer will change due to solvent outflow and solvent volatilization because there is no solvent inside, durability and long-term stability And a dye-sensitized solar cell excellent in.
[0066]
Such a polymer solid electrolyte layer is one in which a redox counter electrolyte is held in the above-described polymer component. In the present invention, this polymer component is used as a binder for the oxide semiconductor layer. Because it has the same main chain as the contained polymer material, the contact area between the polymer solid electrolyte layer and the oxide semiconductor layer can be increased, which is effective in improving energy conversion efficiency. It has.
[0067]
The polymer component in the polymer solid electrolyte layer is a polyether, polymethacrylic acid, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester, among the polymer materials used for the binder of the oxide semiconductor layer described above. , Polycaprolactone, polyhexamethylene carbonate, polysiloxane, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, polyvinyl fluoride, polyhexafluoropropylene, polyfluoroethylene, polyethylene, polypropylene, polyacrylonitrile in the main chain Polymers or copolymers of two or more of these monomer components can be preferably used.
[0068]
Furthermore, in the polymer solid electrolyte layer in the present invention, the redox counter electrolyte is not particularly limited as long as it is generally used in the polymer solid electrolyte layer. Specifically, a combination of iodine and iodide and a combination of bromine and bromide are preferable. For example, combinations of iodine and iodide include LiI, NaI, KI, and CaI.₂And metal iodides such as I₂And combinations thereof. Further, bromine and bromide combinations include LiBr, NaBr, KBr, CaBr.₂A metal bromide such as₂And combinations thereof.
[0069]
In addition, the content of the redox electrolyte is not particularly limited, and specifically, the ratio of the redox electrolyte to the solid polymer electrolyte layer is in the range of 1 to 50% by weight. Especially, it is preferable to exist in the range of 5-35 weight%. This is because when the content of the redox counter electrolyte is within the above range, a function of transporting charges from the second electrode layer to the oxide semiconductor layer can be sufficiently obtained.
[0070]
The film thickness of such a polymer solid electrolyte layer is not particularly limited as long as it is a film thickness generally employed in the polymer solid electrolyte layer, but it is in the range of 2 μm to 100 μm, among which 2 μm It is preferable to be within a range of ˜50 μm.
[0071]
(2) Gel electrolyte layer
The gel electrolyte layer in the present invention is a gelled electrolyte layer. For example, an electrolyte layer in the case of gelation near room temperature due to physical interaction, or in the case of gelation by chemical bonding by a crosslinking reaction or the like can be mentioned.
[0072]
Such a gel electrolyte layer contains at least the polymer component described above, a redox counter electrolyte, and a solvent that dissolves the polymer component, and holds the solvent in the three-dimensional crosslinked body portion that does not participate in ionic conductivity. It is made. For example, as a method of gelation, in the case of using the above-described polymer component that gels by irradiating energy rays such as heat, X-rays and ultraviolet rays, a low molecular gelling agent such as an amino acid derivative, etc. It may be made to gel by adding.
[0073]
In the present invention, the polymer component contained in such a gel electrolyte layer has the same main chain as the polymer material contained in the binder of the oxide semiconductor layer described above. Therefore, the contact area between the gel electrolyte layer and the oxide semiconductor layer can be increased, which has an effect of improving energy conversion efficiency.
[0074]
In the present invention, the polymer component contained in the gel electrolyte layer includes polyether, polyester, polyacrylic acid, polymethacrylic acid, polyacrylic among the polymer materials used for the binder of the oxide semiconductor layer described above. Acid alkyl ester, polymethacrylic acid alkyl ester, polycaprolactone, polyhexamethylene carbonate, polysiloxane, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyhexafluoro Propylene, polyfluoroethylene, polyethylene, polypropylene, polycarbonate, polyolefin, polybutadiene, polyisoprene, polystyrene, polyvinyl pyridine, polyvinyl methyl ether, poly vinyl Isobutyl ether, polyacrylamide, polyacrylonitrile, polyvinylidene anide, polyvinyl acetate, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl pyrrolidone, polyvinyl carbazole, polyethylene terephthalate, nylon, polyamide, polyimide, polycarbonate, polybenzimidazole, polyamine, Polymers having polyimine, polysulfide, polyphosphazene in the main chain or copolymers of two or more of these monomer components can be preferably used.
[0075]
Furthermore, in the gel electrolyte layer according to the present invention, usable solvents are not particularly limited as long as the above-described polymer component is dissolved. In particular,
Chain carbonate solvent, cyclic carbonate solvent, ether solvent, alcohol solvent, polyhydric alcohol solvent, nitrile solvent, especially carbonate solvents such as ethylene carbonate and propylene carbonate, nitrile solvents such as acetonitrile and methoxyacetonitrile A solvent is preferred.
[0076]
The oxidation-reduction counter electrolyte is the same as that described in “(1) Polymer solid electrolyte layer” described above, and a description thereof is omitted here.
[0077]
The film thickness of such a gel electrolyte layer is not particularly limited as long as it is a film thickness generally employed in the gel electrolyte layer, but the oxide semiconductor layer is a porous film having communication holes. Since it is preferable that there is a gel electrolyte layer filled in such an oxide semiconductor layer, the thickness of the oxide semiconductor layer including the thickness of the oxide semiconductor layer is within a range of 2 μm to 100 μm. Especially, it is preferable that it exists in the range of 2 micrometers-50 micrometers.
[0078]
B. Method for producing dye-sensitized solar cell
Next, the manufacturing method of the dye-sensitized solar cell of this invention is demonstrated.
[0079]
The method for producing a dye-sensitized solar cell of the present invention can be divided into two modes depending on the difference in the electrolyte layer. That is, the electrolyte layer can be divided into a solid polymer electrolyte layer that is a solidified electrolyte layer and a gel electrolyte layer that is a gelled electrolyte layer. Hereinafter, the method for producing the dye-sensitized solar cell of the present invention will be described in two aspects.
[0080]
1. First embodiment
The method for producing a dye-sensitized solar cell according to this embodiment includes a first electrode layer forming step of forming a first electrode layer on a substrate,
On the first electrode layer, an oxide semiconductor layer containing metal oxide semiconductor fine particles and a binder, carrying a dye sensitizer, and conducting charges generated from the dye sensitizer by light irradiation is formed. An oxide semiconductor layer forming step,
The polymer material contained in the binder of the oxide semiconductor layer and a polymer component having the same main chain, and the charge conducted by the oxide semiconductor layer is the first electrode layer, A polymer that forms a solid polymer electrolyte layer on the oxide semiconductor layer for transporting when transported to the oxide semiconductor layer via a second electrode layer that is an electrode facing the first electrode layer A solid electrolyte layer forming step;
A pressurizing step of pressurizing the polymer solid electrolyte layer;
A counter electrode substrate forming step of forming the second electrode layer and the counter substrate on the polymer solid electrolyte layer;
It is characterized by having.
[0081]
In this embodiment, after forming the solid polymer electrolyte layer, the pressure between the solid polymer electrolyte layer and the solid polymer electrolyte layer is increased by applying a pressure to increase the adhesion between the oxide semiconductor layer and the solid polymer electrolyte layer. be able to. Furthermore, since the polymer material used for the binder of the oxide semiconductor layer and the polymer component contained in the polymer solid electrolyte layer have the same main chain, this also causes oxidation. The adhesion between the physical semiconductor layer and the polymer solid electrolyte layer can be increased. Therefore, the contact area between the oxide semiconductor layer and the polymer solid electrolyte layer can be increased, which has an effect of improving energy conversion efficiency.
[0082]
A method for producing the dye-sensitized solar cell of this embodiment having such advantages will be described with reference to the drawings. FIG. 2 is a process diagram illustrating an example of a method for producing a dye-sensitized solar cell according to this embodiment.
[0083]
First, as shown in FIG. 2A, a transparent electrode 21 is formed on a transparent substrate 20, and an oxide semiconductor layer forming coating solution for forming an oxide semiconductor layer is applied onto the transparent electrode 21. Then, an oxide semiconductor film is formed. This oxide semiconductor film is immersed in a solution in which a dye sensitizer is dissolved, and the dye sensitizer is adsorbed on the oxide semiconductor film. Thereby, the oxide semiconductor layer 22 carrying the dye sensitizer can be formed.
[0084]
Next, a polymer solid electrolyte layer forming coating solution for forming a polymer solid electrolyte layer is applied on the oxide semiconductor layer 22 and dried. As shown in FIG. Layer 23 is formed. In this embodiment, the polymer component contained in the polymer solid electrolyte layer 23 and the polymer material used for the binder contained in the oxide semiconductor layer 22 are both the same main chain. By having it, the affinity of the oxide semiconductor layer 22 and the polymer solid electrolyte layer 23 can be increased, and the adhesion between them can be improved. Alternatively, a polymer solid electrolyte film prepared in advance is laminated on the oxide semiconductor layer.
[0085]
Further, after the polymer solid electrolyte layer 23 is formed, the polymer solid electrolyte layer 23 is pressed from above as shown in FIG. Thereby, since the adhesiveness in the oxide semiconductor layer 22 and the polymer solid electrolyte layer 23 can be further increased, the contact area between the both increases, which has an effect of improving energy conversion efficiency.
[0086]
Then, as shown in FIG. 2 (d), a dye-sensitized solar cell is manufactured by disposing the counter substrate 25 on which the second electrode layer 24 is formed on the polymer solid electrolyte layer 23. Can do.
[0087]
Hereafter, the manufacturing method of the dye-sensitized solar cell of this embodiment is demonstrated in detail divided into each process.
[0088]
(1) First electrode layer forming step
The first electrode layer forming step is a step of forming the first electrode layer on the substrate.
[0089]
In this step, the substrate to be used is not particularly limited, but in the present embodiment, a film substrate is preferable. This is because in the pressurizing step described later, a pressurizing process can be easily performed if the film substrate has excellent workability.
[0090]
Moreover, as a method of forming the first electrode layer on the substrate, a known method can be used, and examples thereof include a vapor deposition method, a sputtering method, and a CVD method. Among these, the sputtering method is preferable.
[0091]
In addition, since it is the same as that of what was described in the item of "A. dye-sensitized solar cell" mentioned above about a board | substrate and a 1st electrode layer, description here is abbreviate | omitted.
[0092]
(2) Oxide semiconductor layer formation process
The oxide semiconductor layer forming step in this embodiment includes metal oxide semiconductor fine particles and a binder on the first electrode layer, and a dye sensitizer is supported, and is generated from the dye sensitizer by light irradiation. This is a step of forming an oxide semiconductor layer that conducts the charged charges.
[0093]
The method for forming the oxide semiconductor layer in this step is not particularly limited. For example, a coating liquid in which metal oxide semiconductor fine particles and a binder are dispersed or dissolved in an appropriate solvent is used as the first electrode. After forming an oxide semiconductor film by coating on the layer and drying, an oxide semiconductor layer carrying the dye sensitizer is formed by adsorbing the dye sensitizer to the surface of the oxide semiconductor film be able to.
[0094]
In such a forming method, the method for applying the coating liquid is not particularly limited as long as it is a known application method, but specifically, die coating, gravure coating, gravure reverse coating, roll coating, reverse roll. Examples thereof include coat, bar coat, blade coat, knife coat, air knife coat, slot die coat, slide die coat, dip coat, micro bar coat, micro bar reverse coat, and screen printing (rotary method). Using such a coating method, the oxide semiconductor film is formed to have a desired film thickness by repeating coating and drying one or more times.
[0095]
Further, the method for supporting the dye sensitizer after forming the oxide semiconductor film by applying the coating liquid by the above coating method and drying it is not particularly limited, but as described above, the oxide semiconductor Since the layer is preferably porous having communication holes, the layer is preferably a method capable of adsorbing the dye sensitizer to the pores of the oxide semiconductor layer. For example, a method of immersing an oxide semiconductor film in a dye sensitizer solution, allowing the oxide semiconductor film to penetrate and then drying, or applying a dye sensitizer solution on the oxide semiconductor film, allowing the oxide semiconductor film to penetrate, and then drying. The method etc. can be mentioned. In such a method, the solvent used in the dye sensitizer solution is selected from an aqueous solvent and an organic solvent according to the dye sensitizer used.
[0096]
Furthermore, in this embodiment, it is preferable to perform a pressurizing process in this step before or after performing the process of supporting the dye sensitizer. That is, in this step, an oxide semiconductor film is formed by applying a coating liquid in which metal oxide semiconductor fine particles and a binder are dispersed or dissolved in an appropriate solvent on the first electrode layer and drying it. Then, when the oxide semiconductor film is subjected to a pressure treatment, or the oxide semiconductor film is formed, the dye sensitizer is adsorbed on the surface, and the oxide semiconductor layer supported by the dye sensitizer is formed. In this case, after the formation, the oxide semiconductor layer is pressurized. As described above, in the step of forming the oxide semiconductor layer, by performing the pressurizing treatment, the adhesion between the substrate and the oxide semiconductor layer can be increased, and further, the mechanical strength of the oxide semiconductor layer is increased. be able to.
[0097]
Further, since the oxide semiconductor layer contains a binder, the metal oxide is compared with the oxide semiconductor layer formed by firing at a sufficient temperature by applying pressure. The same effect can be obtained in terms of the binding property between the semiconductor fine particles. Therefore, since the firing temperature in this step can be lowered, a film substrate that is slightly inferior in heat resistance to the glass substrate can be suitably used, which is useful in terms of workability and cost.
[0098]
The method of pressurizing in this step will be described in detail in the pressurizing step described later.
[0099]
In addition, since the oxide semiconductor layer is the same as that described in the item “A. Dye-sensitized solar cell” described above, description thereof is omitted here.
[0100]
(3) Polymer solid electrolyte layer forming step
The polymer solid electrolyte layer forming step in the present embodiment includes a polymer component having the same main chain as the polymer material contained in the binder of the oxide semiconductor layer described above, and the oxide semiconductor layer A step of forming a solid polymer electrolyte layer on the oxide semiconductor layer for transporting the electric charge conducted by the step of being transported to the oxide semiconductor layer via the first electrode layer and the second electrode layer. .
[0101]
In this embodiment, the polymer component contained in the solid polymer electrolyte layer formed in this step and the polymer material contained in the binder of the oxide semiconductor layer described above are the same main components. By having a chain, adhesion between the oxide semiconductor layer and the polymer solid electrolyte layer can be improved, and energy conversion efficiency can be increased.
[0102]
In this step, the method for forming the solid polymer electrolyte layer is not particularly limited. For example, after the polymer component and the redox counter electrolyte are mixed by heating and dissolved, the oxide semiconductor layer is impregnated. Alternatively, a method of forming by solidification by causing a two-dimensional or three-dimensional crosslinking reaction by pouring and cooling, or addition of a polymer component, a redox counter electrolyte and a crosslinking agent, a photopolymerization initiator, etc. An example is a method of preparing a coating liquid in which an agent is dispersed or dissolved in an appropriate solvent, and applying the coating liquid on the oxide semiconductor layer, followed by curing by irradiation with actinic rays. be able to. Furthermore, the polymer solid electrolyte layer can be formed separately as a solid polymer film and disposed on the oxide semiconductor layer.
[0103]
In addition, since it is the same as that of what was described in the item of the above-mentioned "A. dye-sensitized solar cell" regarding a polymer solid electrolyte layer, description here is abbreviate | omitted.
[0104]
(4) Pressurization process
Next, the pressurizing process will be described. The pressurizing step in this embodiment is a step of applying pressure from above the polymer solid electrolyte layer.
[0105]
In this embodiment, since the adhesion between the oxide semiconductor layer and the polymer solid electrolyte layer can be increased by applying pressure from above the polymer solid electrolyte layer in this step, the contact area between the two is increased. Can do. Therefore, the efficiency of charge reception between the two increases, and the energy conversion efficiency can be improved.
[0106]
In this step, the method of pressurizing is not particularly limited as long as the method can uniformly apply pressure to the polymer solid electrolyte layer. For example, a press process can be mentioned. Specific examples of the press treatment include a roll press or a flat plate press method.
[0107]
Moreover, as a pressure at the time of pressurizing, it is preferable to exist in the range of 50-2000 MPa, and within the range of 200-1500 MPa among them.
[0108]
When performing such press processing, it may be performed at normal temperature or may be performed while heating. For example, in this step, when pressure is applied to the solid polymer electrolyte layer while heating, the temperature is not particularly limited as long as the solid polymer electrolyte layer is not deteriorated. However, in the case where the polymer solid electrolyte layer is solidified by causing two-dimensional or three-dimensional physical cross-linking by cooling, it may be liquefied by heating. It is preferable to heat the polymer component to a temperature that does not liquefy the polymer component. Specifically, it varies depending on the polymer component to be used, but generally it is preferably in the range of 40 ° C to 200 ° C, and more preferably in the range of 60 ° C to 150 ° C.
[0109]
Further, in this step, pressure is applied from above the polymer solid electrolyte layer, but as described above, the oxide semiconductor layer forming step is the same as this step before forming the polymer solid electrolyte layer. It is preferable to perform a process of applying pressure. By performing the pressure treatment in the oxide semiconductor layer forming step, the oxide semiconductor layer can be homogenized and densified, and between the metal oxide semiconductor fine particles contained in the oxide semiconductor layer. This is because the binding property can be improved, which has an effect of improving the charge transportability and can improve the energy conversion efficiency.
[0110]
(5) Counter electrode formation process
The counter electrode substrate forming step in this embodiment is a step of forming a second electrode layer and a counter substrate, which are electrodes facing the first electrode layer, on the polymer solid electrolyte layer.
[0111]
In such a process, as a method for forming the second electrode layer and the counter substrate on the solid polymer electrolyte layer, for example, a counter electrode on which the second electrode layer is formed in advance is prepared, and such counter A method of forming the electrode by bonding the second electrode layer and the solid polymer electrolyte layer so as to contact each other can be exemplified.
[0112]
In addition, since the second electrode layer and the counter substrate are the same as those described in the item “A. Dye-sensitized solar cell” described above, description thereof is omitted here.
[0113]
2. Second embodiment
Next, the manufacturing method of the dye-sensitized solar cell of 2nd embodiment is demonstrated.
[0114]
The method for producing a dye-sensitized solar cell according to this embodiment includes a first electrode layer forming step of forming a first electrode layer on a substrate,
On the first electrode layer, an oxide semiconductor layer containing metal oxide semiconductor fine particles and a binder, carrying a dye sensitizer, and conducting charges generated from the dye sensitizer by light irradiation is formed. An oxide semiconductor layer forming step,
A counter electrode substrate disposing step of disposing a counter substrate having at least a second electrode layer, which is an electrode facing the first electrode layer, so that the oxide semiconductor layer and the second electrode layer face each other;
A gel electrolyte having a polymer component contained in the binder of the oxide semiconductor layer and a polymer component having the same main chain and forming a gel electrolyte layer that is a gelled electrolyte layer A layer-forming coating solution is injected between the oxide semiconductor layer and the second electrode layer, and the charge conducted by the oxide semiconductor layer is oxidized through the first electrode layer and the second electrode layer. A method for producing a dye-sensitized solar cell comprising a gel electrolyte layer forming step of forming a gel electrolyte layer for transporting when transported to a physical semiconductor layer,
In the oxide semiconductor layer forming step, a pressure treatment is performed before or after the treatment for supporting the dye sensitizer.
[0115]
In this embodiment, the mechanical strength of the oxide semiconductor layer itself and the adhesion to the substrate can be improved by performing a pressure treatment in the oxide semiconductor layer forming step. Furthermore, by using a polymer material having the same main chain as the polymer component contained in the gel electrolyte layer as a binder for the oxide semiconductor layer, the oxide semiconductor layer and the gel electrolyte layer Affinity can be increased. Therefore, the contact area between the oxide semiconductor layer and the gel electrolyte layer can be increased, which is effective in improving energy conversion efficiency.
[0116]
A method for producing such a dye-sensitized solar cell of this embodiment will be described with reference to the drawings.
[0117]
FIG. 3 is a process diagram showing an example of a method for producing a dye-sensitized solar cell according to this embodiment. First, the transparent substrate 30 on which the first electrode layer 31 and the oxide semiconductor layer 32 are formed and the counter substrate 33 on which the second electrode layer 34 is formed are prepared. Such a transparent substrate 30 and the counter substrate 33 are disposed so that the oxide semiconductor layer 32 and the second electrode layer 34 face each other as shown in FIG.
[0118]
Next, a gel electrolyte layer forming coating solution for forming the gel electrolyte layer is injected between the oxide semiconductor layer 32 and the second electrode layer 34 as shown in FIG. Thereby, as shown in FIG. 3C, a gel electrolyte layer 35 can be formed between the oxide semiconductor layer 32 and the second electrode layer 34. Furthermore, as shown in FIG. 3D, a dye-sensitized solar cell can be produced by sealing with an organic polymer 36 or the like.
[0119]
A method for producing such a dye-sensitized solar cell of this embodiment will be described separately for each step.
[0120]
(1) First electrode layer forming step
The first electrode layer forming step of this embodiment is a step of forming the first electrode layer on the substrate.
[0121]
Since this step is the same as the first electrode layer forming step in the first embodiment described above, description thereof is omitted here.
[0122]
(2) Oxide semiconductor layer formation process
The oxide semiconductor layer forming step in this embodiment includes metal oxide semiconductor fine particles and a binder on the first electrode layer, a dye sensitizer is supported, and the dye sensitizer is irradiated with light. This is a step of forming an oxide semiconductor layer that conducts the generated charges.
[0123]
Further, in the oxide semiconductor layer forming step in the present embodiment, a pressure treatment is performed before or after the treatment for supporting the dye sensitizer. As a result, the oxide semiconductor layer can be homogenized and densified, and the binding property between the metal oxide semiconductor fine particles contained in the oxide semiconductor layer can be increased. It is possible to improve the conductivity of charges such as. In addition, the oxide semiconductor layer itself has an effect of improving the mechanical strength.
[0124]
Further, since the oxide semiconductor layer contains a binder, the metal oxide is compared with the oxide semiconductor layer formed by firing at a sufficient temperature by applying pressure. The same effect can be obtained in terms of the binding property between the semiconductor fine particles. Therefore, when forming the oxide semiconductor layer in this embodiment, since the firing temperature can be lowered, a film substrate that is slightly inferior in heat resistance to the glass substrate can be preferably used. This is useful in terms of cost.
[0125]
In this step, the oxide semiconductor layer, the pressurizing method, and the like are the same as those described in the first embodiment described above, and a description thereof is omitted here.
[0126]
(3) Counter electrode substrate placement process
Next, the counter electrode substrate placement step will be described. In the counter electrode substrate disposing step in this embodiment, the counter substrate having at least a second electrode layer that is an electrode facing the first electrode layer is disposed so that the oxide semiconductor layer and the second electrode layer face each other. It is a process to do.
[0127]
In this embodiment, since the electrolyte layer to be formed is in a gel form, in order to form such a gel electrolyte layer, in this step, the gap in which the gel electrolyte layer is formed is defined as a substrate and a counter substrate. To form.
[0128]
In this step, when the substrate and the counter substrate are arranged so that the oxide semiconductor layer and the second electrode layer face each other, the gap between the oxide semiconductor layer and the second electrode layer is a gel electrolyte between the two. There is no particular limitation as long as the layer can be formed. Specifically, it is preferably within a range of 0.01 μm to 100 μm, and more preferably within a range of 0.1 μm to 50 μm.
[0129]
In order to adjust the gap within the above range, a spacer may be formed on either the substrate or the counter substrate. Since the distance between the substrate and the counter substrate can be controlled by the spacer, the gap between the two can be kept constant with high accuracy. As such a spacer, a known glass spacer, resin spacer, olefin-based porous film, or the like can be used.
[0130]
(4) Gel electrolyte layer forming step
Next, the gel electrolyte layer forming step will be described. The gel electrolyte layer forming step in this embodiment includes a polymer material having the same main chain as the polymer material contained in the above-described binder of the oxide semiconductor layer, and a gelled electrolyte. A gel electrolyte layer forming coating solution for forming a gel electrolyte layer, which is a layer, is injected between the oxide semiconductor layer and the second electrode layer, and the charge conducted by the oxide semiconductor layer is transferred to the first electrode layer and the second electrode layer. This is a step of forming a gel electrolyte layer that performs transport when transported to the oxide semiconductor layer via the second electrode layer.
[0131]
The coating solution for forming a gel electrolyte layer used in this step is not particularly limited as long as it is a solution that can form a gel electrolyte layer. What has dissolved or disperse | distributed the electrolyte, the gelatinizer, etc. in the solvent can be used.
[0132]
Since each material constituting such a coating solution for forming a gel electrolyte layer is the same as that described in the item of “A. Dye-sensitized solar cell” described above, description thereof is omitted here. To do.
[0133]
In addition, as a method for injecting the coating solution for forming the gel electrolyte layer between the second electrode layer and the oxide semiconductor layer in this step, it is a method generally used when forming the gel electrolyte layer. There is no particular limitation. Specific examples include a method using a capillary phenomenon.
[0134]
Furthermore, after injecting the gel electrolyte layer forming coating solution, the gel electrolyte layer forming coating solution is gelled by performing treatment such as cooling or heating according to the gelling agent used. An electrolyte layer is formed.
[0135]
(5) Other
In this embodiment, since the electrolyte layer is a gel electrolyte layer, sealing or the like is performed to prevent evaporation of the solvent from the gel electrolyte layer, outflow of the gel electrolyte layer itself, and the like. As the sealing method, a method generally used when producing a dye-sensitized solar cell having a gel electrolyte layer can be used.
[0136]
In addition, this invention is not limited to the said embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
[0137]
【Example】
The following examples further illustrate the present invention.
[0138]
Example 1
A dye-sensitized solar cell having the configuration shown below was produced as follows, and the conversion efficiency was evaluated.
[0139]
A biaxially stretched polyethylene terephthalate film (thickness: 125 μm) was used as a film substrate, and an ITO vapor deposition layer having a surface resistivity of 10Ω / □ was formed on the film substrate. An oxide semiconductor layer was formed on the ITO deposited layer as follows.
[0140]
As a coating liquid for forming an oxide semiconductor layer, TiO having a particle diameter of 20 nm in pure water.₂Fine particles (P25, manufactured by Nippon Aerosil Co., Ltd.) and a polyether copolymer as a binder were kneaded using a mixer, and then a slurry was prepared with a paint shaker. This was applied by a die coating method so that the film thickness upon drying was 12 μm, and dried to form an oxide semiconductor layer (TiO 2).₂A coating film of fine particles) was formed. In the above slurry, TiO₂Was 20% by weight, and the polyether copolymer was 4% by weight. In this case, TiO in the oxide semiconductor layer at the time of drying is used.₂The content of was 92% by weight.
[0141]
Next, ruthenium dye in absolute ethanol at a concentration of 3 × 10^{− Four}A solution of a dye sensitizer for adsorption is prepared by dissolving at mol / L, and the TiO is used at room temperature for 24 hours.₂The membrane was impregnated to adsorb ruthenium dye.
[0142]
Next, a solid polymer electrolyte layer was prepared as follows. After mixing 1 g of a polyether copolymer and 1 g of oligoethylene glycol dimethyl ether as a plasticizer, 0.2 g of lithium iodide and 0.05 g of iodine in 10 g of acetonitrile, the mixture was cast on a PTFE film and heated at 100 ° C. for 10 minutes. The polymer solid electrolyte layer film in which the polymer solid electrolyte layer was formed on the pressed PTFE film was obtained.
[0143]
The polymer solid electrolyte layer film was laminated on the oxide semiconductor layer prepared above, and then press molded at a pressure of 1 giga Pa.
[0144]
Then, the counter substrate which equipped the platinum film | membrane as a counter electrode was arrange | positioned, and it was set as the dye-sensitized solar cell.
[0145]
The evaluation of the created element is AM1.5, simulated sunlight (100 mW / cm²) Was used as a light source, and current-voltage characteristics were evaluated by applying voltage with a source measure unit (Caseley 2400 type). The evaluation results include a short circuit current (mA / cm²), Open circuit voltage (V), and conversion efficiency%. The evaluation results are shown in Table 1 below.
[0146]
(Example 2)
After forming the oxide semiconductor layer in the same manner as in Example 1, the oxide semiconductor layer was directly formed at 8 ton / cm.²The press molding was performed.
[0147]
Then, the polymer solid electrolyte layer film was laminated | stacked similarly to Example 1, and press molding was performed. The evaluation results are shown in Table 1 below.
[0148]
(Example 3)
As a coating liquid for forming an oxide semiconductor layer, TiO having a particle diameter of 20 nm in pure water.₂Fine particles (P25 manufactured by Nippon Aerosil Co., Ltd.) and poly (4-vinylpyridine) as a binder were kneaded using a mixer, and then a slurry was prepared with a paint shaker. This was applied by a die coating method so that the film thickness upon drying was 12 μm, and dried to form an oxide semiconductor layer (TiO 2).²A coating film of fine particles) was formed. In the above slurry, TiO₂Was 20% by weight, and poly (4-vinylpyridine) was 0.5% by weight. In this case, TiO in the oxide semiconductor layer at the time of drying is used.₂The content of was 92% by weight.
[0149]
Next, a gel electrolyte layer was formed as follows. As an electrolyte solution, a solution in which tetrapropylammonium iodide 0.5 M, potassium iodide 0.02 M, and iodine 0.09 M were dissolved in 1-methyl-3-propylimidazolium iodide was prepared.
[0150]
For 10 g of this electrolyte solution, 0.3 g of poly (4-vinylpyridine),
A coating solution for forming a gel electrolyte layer was prepared by dissolving 0.3 g of 1,6-dibromohexane.
[0151]
After that, the counter substrate having platinum as a counter electrode and the substrate on which the oxide semiconductor layer is formed are bonded together by providing an opening with an epoxy resin at the periphery, and then the gel electrolyte layer is formed from the opening. The coating liquid for injection was injected.
[0152]
Then, it heated for 30 minutes on the hotplate heated at 60 degreeC.
[0153]
The characteristics of the dye-sensitized solar cell thus prepared were evaluated. The evaluation results are shown in Table 1 below.
[0154]
(Comparative Example 1)
A dye-sensitized solar cell was produced in the same manner as in Example 2 except that the binder was not used. The evaluation results are shown in Table 1 below.
[0155]
(Comparative Example 2)
A dye-sensitized solar cell was produced in the same manner as in Example 3 except that the binder was not used. The evaluation results are shown in Table 1 below.
[0156]
[Table 1]

【The invention's effect】
According to the present invention, by using a polymer material having the same main chain as the polymer component contained in the electrolyte layer as the binder for the oxide semiconductor layer, the oxide semiconductor layer and the electrolyte layer are separated. Adhesion can be improved and the contact area between the two can be increased, which is effective in improving energy conversion efficiency.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an example of a dye-sensitized solar cell of the present invention.
FIG. 2 is a process diagram showing an example of a method for producing a dye-sensitized solar cell of the present invention.
FIG. 3 is a process diagram showing another example of a method for producing a dye-sensitized solar cell of the present invention.
FIG. 4 is a schematic cross-sectional view showing an example of the dye-sensitized solar cell of the present invention.
[Explanation of symbols]
1 ... Transparent substrate
2… Transparent electrode
3 ... Oxide semiconductor layer
4 ... Polymer solid electrolyte layer
5 ... Counter electrode
6 ... Counter substrate

Claims (6)

A substrate, a first electrode layer formed on the substrate, a metal oxide semiconductor fine particle and a binder formed on the first electrode layer, carrying a dye sensitizer, An oxide semiconductor layer that conducts charges generated from the dye sensitizer by irradiation, a counter substrate facing the substrate, and an electrode formed on the counter substrate and facing the first electrode layer An electrode layer, having a polymer component, is located between the oxide semiconductor layer and the second electrode layer, and the electric charge conducted by the oxide semiconductor layer passes through the first electrode layer and the second electrode layer. A dye-sensitized solar cell that transports when transported to the oxide semiconductor layer and has a solidified or gelled electrolyte layer,
The dye-sensitized solar cell, wherein the binder of the oxide semiconductor layer has a polymer material having the same main chain structure as the polymer component contained in the electrolyte layer.   The dye-sensitized solar cell according to claim 1, wherein the substrate is a film substrate. A first electrode layer forming step of forming a first electrode layer on the substrate;
On the first electrode layer, an oxide semiconductor layer containing metal oxide semiconductor fine particles and a binder, carrying a dye sensitizer, and conducting charges generated from the dye sensitizer by light irradiation is formed. An oxide semiconductor layer forming step,
The polymer material contained in the binder of the oxide semiconductor layer has a polymer component having the same main chain structure, and the electric charge conducted by the oxide semiconductor layer is the first electrode layer. And forming a solid polymer electrolyte layer on the oxide semiconductor layer for transporting when transported to the oxide semiconductor layer via the second electrode layer, which is an electrode facing the first electrode layer. A polymer solid electrolyte layer forming step;
A pressurizing step of pressurizing the polymer solid electrolyte layer;
A counter electrode substrate forming step of forming the second electrode layer and the counter substrate on the polymer solid electrolyte layer;
A method for producing a dye-sensitized solar cell, comprising:   4. The dye-sensitized solar cell according to claim 3, wherein in the oxide semiconductor layer forming step, a pressurizing process is performed before or after performing the process of supporting the dye sensitizer. 5. Production method. A first electrode layer forming step of forming a first electrode layer on the substrate;
On the first electrode layer, an oxide semiconductor layer containing metal oxide semiconductor fine particles and a binder, carrying a dye sensitizer, and conducting charges generated from the dye sensitizer by light irradiation is formed. An oxide semiconductor layer forming step,
A counter electrode substrate disposing step of disposing a counter substrate having at least a second electrode layer, which is an electrode facing the first electrode layer, so that the oxide semiconductor layer and the second electrode layer face each other;
Forming a gel electrolyte layer, which is a gelled electrolyte layer, having a polymer component having the same main chain structure as the polymer material contained in the binder of the oxide semiconductor layer A coating solution for forming a gel electrolyte layer is injected between the oxide semiconductor layer and the second electrode layer, and electric charges conducted by the oxide semiconductor layer are passed through the first electrode layer and the second electrode layer. A method for producing a dye-sensitized solar cell comprising a gel electrolyte layer forming step of forming a gel electrolyte layer for transporting when transported to the oxide semiconductor layer,
In the oxide semiconductor layer forming step, a method of applying pressure is performed before or after the treatment for supporting the dye sensitizer is performed.   The method for producing a dye-sensitized solar cell according to any one of claims 3 to 5, wherein the substrate is a film substrate.

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