JP5407681B2 - Counter electrode substrate for dye-sensitized solar cell, dye-sensitized solar cell element, and dye-sensitized solar cell module - Google Patents

Description

  The present invention relates to a counter electrode substrate for a dye-sensitized solar cell used for a dye-sensitized solar cell, a dye-sensitized solar cell element using the counter electrode substrate for the dye-sensitized solar cell, and the dye-sensitized solar cell. The present invention relates to a dye-sensitized solar cell module using a solar cell element.

In recent years, environmental problems such as global warming caused by an increase in carbon dioxide have become serious, and countermeasures are being promoted worldwide. In particular, active research and development on solar cells using solar energy as a clean energy source with a low environmental impact is underway. As such solar cells, single crystal silicon solar cells, polycrystalline silicon solar cells, amorphous silicon solar cells, compound semiconductor solar cells and the like have already been put into practical use, but these solar cells have high production costs, etc. There is a problem. Therefore, a dye-sensitized solar cell has attracted attention as a solar cell that has a low environmental load and can reduce the manufacturing cost, and research and development have been promoted.
In such a dye-sensitized solar cell, an oxide semiconductor electrode having a porous layer containing metal oxide semiconductor fine particles is used.

  An example of a general configuration of the dye-sensitized solar cell is shown in FIG. As illustrated in FIG. 5, a general dye-sensitized solar cell 100 includes a porous layer including metal oxide semiconductor fine particles carrying a first electrode layer 112 and a dye sensitizer on a substrate 111. An electrolyte layer 101 having a redox pair is encapsulated between the oxide semiconductor electrode 110 in which the layers 113 are stacked in this order and the counter electrode substrate 120 in which the second electrode layer 122 is formed on the counter base material 121. 102 has a configuration formed inside 102. Then, the dye sensitizer adsorbed on the surface of the metal oxide semiconductor fine particles is excited by receiving sunlight from the substrate 111 side, and the excited electrons are conducted to the first electrode layer, and are then passed through the external circuit. Conducted to two electrode layers. Thereafter, electricity is generated by returning the electrons to the ground level of the dye sensitizer through the redox pair.

  Such a dye-sensitized solar cell can mention the outstanding design property as the characteristic feature. That is, the dye-sensitized solar cell has attracted attention as a feature not found in conventional solar cells in that it can produce a colorful battery by using various dyes and adopting a light-transmitting constituent member. ing.

  Here, it is necessary for the counter electrode substrate to have a configuration in which at least the counter base material and the second electrode layer are laminated as described above. Today, the power generation efficiency of the dye-sensitized solar cell is improved. Therefore, a mainstream is that a catalyst layer having a catalytic action on the redox couple in the electrolyte layer is formed on the second electrode layer (for example, Patent Document 1). The technique employing such a catalyst layer is one of the useful methods for improving the power generation efficiency of the dye-sensitized solar cell element.

  However, it is known that platinum is used as the catalyst layer. However, regarding the use of platinum, platinum is expensive and dissolves due to the presence of moisture when iodine is used as an electrolyte material. It is regarded as a problem from the point that it ends up, and an alternative technology is required.

  As a catalyst material replacing platinum, for example, studies using activated carbon, conductive polymer, and the like have been reported (for example, Patent Document 2). However, when the catalyst layer is formed in such a manner that the activated carbon used in Patent Document 2 is contained in the range of 50% by mass to 95% by mass, good performance is exhibited, but the color of the counter electrode is Since blackening causes a loss of good color development and see-through properties, there is a problem in that the design characteristics that are one of the characteristics of the dye-sensitized solar cell described above are sacrificed.

  In view of such a problem, it has been studied to solve this problem by using a conductive polymer having a catalytic function with a thin film that can ensure see-through (for example, Patent Document 3). However, its performance is lower than that of platinum, and there is a problem that surface area and conductivity are low.

  Furthermore, when these alternative materials are used, some studies have been reported to achieve catalytic ability close to platinum by increasing the surface area in order to improve catalytic ability (for example, Patent Document 4). When metal particles are added to the layer, the conductivity and surface area are improved, but there is a possibility of corrosion. As described above, when a large amount of particles such as carbon is added, the see-through property and the conductivity are deteriorated. Highly transparent particles can obtain good catalytic ability by increasing the surface area, but there is a problem that the conductivity is not improved.

Japanese Patent Laid-Open No. 2001-102102 JP 2003-297446 A JP 2003-317814 A JP 2001-43908 A

  The present invention has been made in view of such problems, and is capable of producing a dye-sensitized solar cell that is excellent in conductivity and light transmittance, has high power generation efficiency, and has a design property. An object of the present invention is to provide a counter electrode substrate for a dye-sensitized solar cell.

  In order to solve the above problems, the present invention provides a counter substrate, a counter electrode layer formed on the counter substrate, made of a conductive material, has a needle shape, and has light transmittance and conductivity. And a catalyst layer that is formed on the counter electrode layer and contains a material having a catalytic activity with respect to the redox pair and the needle-like transparent conductive particles. A counter electrode substrate is provided.

According to the present invention, the catalyst layer is formed on the counter electrode layer, and the needle-shaped transparent conductive particles having a needle-like shape are contained in the catalyst layer. Can be improved. Moreover, since the said acicular transparent electroconductive particle has a light transmittance, according to this invention, the electroconductivity of the said catalyst layer can be improved, without impairing the light transmittance of a catalyst layer. Therefore, according to the present invention, for example, by using the counter substrate and the counter electrode layer having light transmissivity, the dye-sensitized solar cell counter electrode substrate of the present invention is used. When a solar cell element is manufactured, power can be generated by irradiating light from both sides. In addition, a dye-sensitized solar cell element having see-through property as a whole and excellent in design can be obtained.
Furthermore, according to the present invention, light scattering properties can be imparted to the catalyst layer by containing the acicular transparent conductive particles in the catalyst layer. For this reason, in the dye-sensitized solar cell element manufactured using the counter electrode substrate for the dye-sensitized solar cell of the present invention, the light irradiated inside the element is reflected by the catalyst layer and contributes to power generation again. be able to.
In addition to these, according to the present invention, the needle-shaped transparent conductive particles are contained, thereby increasing the surface area of the catalyst layer, and using the counter electrode substrate for the dye-sensitized solar cell of the present invention, the dye When a sensitized solar cell element is produced, the contact area between the electrolyte layer and the catalyst layer can be improved.
Therefore, according to the present invention, a dye-sensitized solar cell capable of producing a dye-sensitized solar cell element having excellent conductivity and light transmittance, high power generation efficiency, and excellent design properties. A counter electrode substrate for a battery can be provided.

In the present invention, the acicular transparent conductive particles are preferably made of ATO, ITO, FTO, ZnO, SnO ₂ or a composite material thereof. Since ATO, ITO, FTO, ZnO, SnO ₂ or their composite materials have both light transmittance and conductivity, the use of such needle-like transparent conductive particles enables the conductivity and light transmission of the catalyst layer. This is because the property can be further improved.

  Moreover, in this invention, it is preferable that a counter base material and the said counter electrode layer have a light transmittance. Thus, when a dye-sensitized solar cell element is produced using the counter electrode substrate for the dye-sensitized solar cell of the present invention, the dye-sensitized light can be generated by irradiating light from both sides of the element. This is because a type solar cell element can be obtained. In addition, since the see-through property can be imparted to the counter electrode substrate for the dye-sensitized solar cell of the present invention, the dye-sensitized solar cell element excellent in design of the electrode substrate for the dye-sensitized solar cell of the present invention. This is because it can be made to be able to be manufactured.

  In the present invention, the material exhibiting catalytic ability for the redox couple is preferably polypyrrole, polythiophene, ponianiline, or a derivative thereof. This is because, by using these conductive polymers as materials exhibiting catalytic ability for the redox couple, a catalyst layer having further excellent conductivity and light transmittance can be obtained.

  Furthermore, the counter electrode substrate for a dye-sensitized solar cell preferably has a total light transmittance of 10% or more. When the total light transmittance is within such a range, the balance between the light scattering property and the light transmittance of the catalyst layer is maintained, and the electrode substrate for the dye-sensitized solar cell of the present invention is further improved in power generation efficiency. This is because a high dye-sensitized solar cell element can be produced.

The present invention includes a counter substrate, a counter electrode layer formed on the counter substrate and made of a conductive material, a needle-like transparent conductive particle having a needle-like shape and having light transmittance and conductivity, And a counter electrode substrate for a dye-sensitized solar cell, which contains a material exhibiting catalytic ability for a redox pair, and has a catalyst layer formed on the counter electrode layer, and the base material, And an oxide semiconductor electrode having a first electrode layer made of a metal oxide and a porous layer formed on the first electrode layer and containing metal oxide semiconductor fine particles and a dye sensitizer. An electrolyte layer including a redox pair is formed between the oxide semiconductor electrode and the counter electrode substrate for a dye-sensitized solar cell. A dye-sensitized solar cell element is provided.
Furthermore, the present invention provides a dye-sensitized solar cell module in which a plurality of dye-sensitized solar cell elements according to the present invention are connected.

  According to the present invention, since the counter electrode substrate for a dye-sensitized solar cell according to the present invention is used, the dye-sensitized solar cell element and the dye-sensitized type having high power generation efficiency and excellent design properties. A solar cell module can be provided.

  The counter electrode substrate for a dye-sensitized solar cell of the present invention can produce a dye-sensitized solar cell element that is excellent in conductivity, light scattering property, and light transmittance, has high power generation efficiency, and has a design property. There is an effect that can be done.

It is a schematic sectional drawing which shows an example of the counter electrode board | substrate for dye-sensitized solar cells of this invention. It is the schematic explaining the acicular shape of the acicular transparent conductive particle used for this invention. It is the schematic explaining the aspect in which the acicular transparent electroconductive particle contains in a catalyst layer. It is a schematic sectional drawing which shows an example of the dye-sensitized solar cell element of this invention. It is the schematic which shows the example of a general dye-sensitized solar cell.

The present invention relates to a counter electrode substrate for a dye-sensitized solar cell, a dye-sensitized solar cell element, and a dye-sensitized solar cell module.
Hereinafter, each of these inventions will be described in order.

A. First, the counter electrode substrate for a dye-sensitized solar cell of the present invention will be described.
As described above, the counter electrode substrate for a dye-sensitized solar cell of the present invention has a counter substrate, a counter electrode layer formed on the counter substrate, made of a conductive material, a needle-like shape, and It has a needle-like transparent conductive particle having light permeability and conductivity, and a catalyst layer formed on the counter electrode layer, containing a material exhibiting catalytic ability for a redox pair. Is.

Such a counter electrode substrate for a dye-sensitized solar cell of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of a counter electrode substrate for a dye-sensitized solar cell according to the present invention. As illustrated in FIG. 1, a counter electrode substrate 10 for a dye-sensitized solar cell according to the present invention includes a counter substrate 1, a counter electrode layer 2 formed on the counter substrate 1 and made of a conductive material, And a catalyst layer 3 formed on the counter electrode layer 2.
In such an example, the counter electrode substrate 10 for the dye-sensitized solar cell of the present invention has the acicular transparent conductive particles in which the catalyst layer 3 has an acicular shape and has light transmittance and conductivity, and redox. It is characterized by containing a material exhibiting catalytic ability for the pair.

According to the present invention, the catalyst layer is formed on the counter electrode layer, and the acicular transparent conductive particles are contained in the catalyst layer, thereby improving the conductivity of the catalyst layer. it can. Moreover, since the said acicular transparent electroconductive particle has a light transmittance, according to this invention, the electroconductivity of the said catalyst layer can be improved, without impairing the light transmittance of a catalyst layer. Therefore, according to the present invention, for example, a dye-sensitized solar cell counter electrode substrate according to the present invention is used by using a light-transmitting material as the counter base material and the counter electrode layer. When a solar cell element is manufactured, power can be generated by irradiating light from both sides. In addition, a dye-sensitized solar cell element having see-through property as a whole and excellent in design can be obtained.
Furthermore, according to the present invention, light scattering properties can be imparted to the catalyst layer by containing the acicular transparent conductive particles in the catalyst layer. For this reason, in the dye-sensitized solar cell element manufactured using the counter electrode substrate for the dye-sensitized solar cell of the present invention, the light irradiated inside the element is reflected by the catalyst layer and contributes to power generation again. be able to.
In addition to these, according to the present invention, since the surface area of the catalyst layer can be increased by containing the acicular transparent conductive particles, the counter electrode substrate for the dye-sensitized solar cell of the present invention. The contact area between the electrolyte layer and the catalyst layer can be improved when a dye-sensitized solar cell element is fabricated using In addition, the use of needle-like transparent conductive particles can improve the in-plane conductivity of the catalyst layer.
Therefore, according to the present invention, a dye-sensitized solar cell capable of producing a dye-sensitized solar cell element having excellent conductivity and light transmittance, high power generation efficiency, and excellent design properties. A counter electrode substrate for a battery can be provided.

The counter electrode substrate for a dye-sensitized solar cell of the present invention has at least a counter substrate, a counter electrode layer, and a catalyst layer, and may have any other configuration as necessary. .
Hereafter, each structure used for this invention is demonstrated in order.

1. Catalyst Layer First, the catalyst layer used in the present invention will be described. The catalyst layer used for this invention is formed on the counter electrode layer mentioned later, and contains the acicular transparent conductive particle and the material which shows a catalytic ability with respect to a redox pair.

  Here, the catalyst layer used in the present invention is a redox pair contained in the electrolyte layer when a dye-sensitized solar cell element is produced using the counter electrode substrate for the dye-sensitized solar cell of the present invention. It acts as a catalyst. Therefore, even if any configuration is used for the counter electrode substrate for the dye-sensitized solar cell of the present invention, the catalyst layer is always dye-sensitized using the counter electrode substrate for the dye-sensitized solar cell of the present invention. When a solar cell is produced, it is formed so as to be positioned on the outermost surface in contact with the electrolyte layer.

(1) Needle-like transparent conductive particles The needle-like transparent conductive particles contained in the catalyst layer in the present invention have a needle-like shape and have light transmittance and conductivity. By containing such needle-like transparent conductive particles, the counter electrode substrate for the dye-sensitized solar cell of the present invention is excellent in light transmittance and conductivity, and is excellent in power generation efficiency and design. Thus, a dye-sensitized solar cell element can be produced.

  The needle-like transparent conductive particles used in the present invention have a needle-like shape, and the “needle-like shape” means that the length in at least two directions among the X, Y, and Z axis directions orthogonal to each other. It shall mean a different shape.

  Such a needle-like shape will be described with reference to the drawings. FIG. 2 is a schematic diagram illustrating the shape of the needle-like transparent conductive particles. As illustrated in FIG. 2, the needle-like transparent conductive particles A used in the present invention have different lengths in at least two directions among the X, Y, and Z axis directions orthogonal to each other (in FIG. 2, the X axis direction is different from the X axis direction). This means a shape having different lengths in the Y and Z axis directions.

The shape of the acicular transparent conductive particles used in the present invention is not particularly limited as long as it is an acicular shape as described above. In particular, the aspect ratio is preferably 3 or more, and is preferably 10 or more. It is more preferable. In the present invention, the needle-like transparent conductive particles have an acicular shape, so that the conductivity can be improved in the major axis direction of the needle-like transparent conductive particles, but the aspect ratio is more than the above range. This is because the effect of containing needle-shaped transparent conductive particles that improve conductivity in a specific direction may be diminished.
The aspect ratio is the ratio of the length in the direction with the longest distance to the length in the direction with the shortest distance among the X, Y, and Z axis directions constituting the needle-like shape (longest direction / longest direction). Means short direction).

  Specific examples of the needle-like transparent conductive particles include a cylindrical shape and an elliptical disc shape.

  In addition, all the acicular transparent conductive particles used in the present invention may have the same shape, or may have a mixture of different shapes.

Since the acicular transparent conductive particles used in the present invention are conductive, they are composed of a conductive material. The conductive material constituting the needle-like transparent conductive particles used in the present invention is not particularly limited as long as it is a material having desired light transmittance and conductivity. Here, the acicular transparent conductive particles used in the present invention have a light transmittance of the catalyst layer in the range of 5% to 99%, preferably in the range of 30% to 90%, and more preferably in the range of 60% to 90%. It is preferable that it can be within the range. Further, the acicular transparent conductive particles used in the present invention have a conductivity of the catalyst layer in the range of 1.0 × 10 ¹⁵ Ω / □ or less, more preferably in the range of 10 × 10 ¹⁰ Ω / □ or less, More preferably, it can be within the range of 1.0 × 10 ⁶ Ω / □ or less. Therefore, as the conductive material, those capable of obtaining needle-like transparent conductive particles having such conductivity and light transmittance are preferably used. Note that the conductivity and light transmittance of the needle-like transparent conductive particles can be measured by, for example, infrared spectroscopy, scattered light measurement, and conductivity measured by surface resistance measurement and volume resistance measurement. .

Examples of the conductive material used in the present invention include ATO, ITO, FTO, ZnO, SnO ₂ or a composite material thereof. In the present invention, any of these conductive materials can be suitably used, and among them, ITO is preferably used. This is because by using such a conductive material, needle-like transparent conductive particles having particularly excellent conductivity and light transmittance can be obtained.

  In addition, all the acicular transparent conductive particles used in the present invention may be made of the same conductive material, or a mixture of two or more kinds of different conductive materials may be used.

  As the amount of acicular transparent conductive particles contained in the catalyst layer, depending on the type of material exhibiting catalytic ability for the redox pair described later, the type of conductive material constituting the acicular transparent conductive particles, and the like, The catalyst layer is not particularly limited as long as the desired conductivity and light transmittance can be imparted to the catalyst layer. Moreover, since content of the acicular transparent electroconductive particle in a catalyst layer also contributes to the haze of the counter electrode substrate for dye-sensitized solar cells of the present invention, it is determined within a suitable range in relation to haze. As described above, the content of the acicular transparent conductive particles in the catalyst layer is determined within a preferable range in consideration of all factors, and is not uniquely determined. However, usually, the content of the acicular transparent conductive particles in the catalyst layer is preferably in the range of 1% by weight to 99% by weight and in the range of 30% by weight to 85% by weight in terms of solid content ratio. Is more preferable, and it is still more preferable that it exists in the range of 50 weight%-80 weight%.

(2) Material showing catalytic ability for redox couple Next, a material showing catalytic ability for the redox couple contained in the catalyst layer will be described.
The material showing catalytic ability for the redox couple used in the present invention is included in the electrolyte layer when a dye-sensitized solar cell element is produced using the counter electrode substrate for the dye-sensitized solar cell of the present invention. It exhibits a catalytic action on the redox couple to be produced and has conductivity. Therefore, the material showing catalytic ability for the redox couple used in the present invention is determined mainly depending on the presence or absence of the catalytic action for the redox couple. In particular, the material exhibiting catalytic ability for the redox pair used in the present invention is preferably a transparent material capable of forming a catalyst layer having light permeability. As a result, the counter electrode substrate for the dye-sensitized solar cell of the present invention can have light transmittance as a whole, and the dye-sensitized solar cell has see-through property and power generation potential by light irradiation from both sides. This is because an element can be manufactured.

Examples of the material exhibiting catalytic ability for the redox pair used in the present invention include a conductive polymer, platinum, carbon and the like. Here, in the case of using a material such as a conductive polymer or carbon that cannot maintain catalytic ability with a supported amount that can maintain see-through properties, such as platinum, the catalyst should be used so as not to impair the light transmittance of the catalyst layer. It is necessary to reduce the content of these materials in the layer. In this case, the content of these materials in the catalyst layer is not particularly limited as long as the light transmittance of the catalyst layer can be maintained within a desired level, but usually the catalyst layer is constituted. The solid content is preferably less than 50% by mass, more preferably in the range of 0.1% by mass to 49.9% by mass, and in the range of 0.1% by mass to 30% by mass. Is more preferable. When the content is higher than the above range, the light transmittance of the catalyst layer may be insufficient. On the other hand, when the content is lower than the above range, the catalytic action of the catalyst layer on the redox pair may be insufficient. Because there is. Here, conventionally, when a material such as carbon is included in the catalyst layer, there is a problem that sufficient catalytic ability cannot be realized if the content is small, but for the dye-sensitized solar cell of the present invention. The counter electrode substrate can increase the surface area of the catalyst layer by containing the acicular transparent conductive particles in the catalyst layer. For this reason, even if it is the said content, favorable catalytic ability is realizable. In addition, regarding the use of platinum as a catalyst layer, a problem in terms of cost has been pointed out in the past. However, by limiting the platinum content in the catalyst layer to the above range, the problem in terms of cost may be solved. it can.
In the present invention, any of the above-mentioned conductive polymers, platinum, carbon, etc. can be suitably used as the material exhibiting catalytic ability for the redox couple, and among these, conductive polymers are used. It is preferable.

  Specific examples of the conductive polymer used in the present invention include polypyrrole, polythiophene, polyaniline, and derivatives thereof. In the present invention, any of these conductive polymers can be suitably used, and among them, polypyrrole, polythiophene, polyaniline, and derivatives thereof are preferably used.

  In addition, the conductive polymer used for this invention may be only 1 type, or 2 or more types may be sufficient as it.

(3) Catalyst layer Next, the aspect in which the said acicular transparent conductive particle is contained in the said catalyst layer is demonstrated. As described above, the needle-like transparent conductive particles used in the present invention have a needle-like shape, and have a function of improving the conductivity in the longitudinal direction of the needle-like shape in the catalyst layer. Therefore, the catalyst layer used in the present invention can have conductivity anisotropy by controlling the mode in which the acicular transparent conductive particles are contained.
For example, when the needle-shaped transparent conductive particles are randomly contained in the catalyst layer, the catalyst layer has improved conductivity in all directions and does not exhibit conductivity anisotropy. On the other hand, the inclusion of the needle-like transparent particles in the catalyst layer so that the major axis direction is perpendicular to the thickness direction, the conductivity in the in-plane direction can be made higher than the thickness direction. In the aspect, by including the long axis direction so as to be arranged in a certain direction, the in-plane conductivity in a certain direction can be selectively increased.
Moreover, the acicular transparent electroconductive particle can be made higher in the thickness direction than in the in-plane direction by containing the acicular transparent conductive particles in the catalyst layer so that the major axis direction is in the thickness direction.

In the present invention, an embodiment in which the acicular transparent conductive particles are contained in the catalyst layer will be described with reference to the drawings. FIG. 3 is a schematic view illustrating an embodiment in which acicular transparent conductive particles are contained in the catalyst layer.
As illustrated in FIG. 3A, by adding the needle-like transparent conductive particles A to the catalyst layer 3 at random, the catalyst layer 3 has improved conductivity in all directions. Sex anisotropy will not be shown.
As illustrated in FIG. 3B, the acicular transparent particles A are contained in the catalyst layer 3 so that the major axis direction is perpendicular to the thickness direction, so that the in-plane direction is larger than the thickness direction. The conductivity can be increased. Further, as illustrated in FIG. 3C, by including the major axis direction perpendicular to the thickness direction and arranging the major axis direction in a certain direction in the plane, The conductivity can be selectively increased.
Further, as illustrated in FIG. 3D, the needle-like transparent conductive particles A are contained in the catalyst layer 3 so that the major axis direction is in the thickness direction, so that the thickness direction is greater than the in-plane direction. The conductivity can be increased.

  In the present invention, acicular transparent conductive particles may be contained in the catalyst layer in any of these embodiments, but the catalyst layer exhibits a catalytic action on the redox pair by contacting the electrolyte layer. For this reason, it is more preferable that the needle-like transparent conductive particles are contained in such a manner that the contact area with the electrolyte layer becomes larger. From such a viewpoint, as an aspect in which the acicular transparent conductive particles are contained in the catalyst layer, the aspect in which the needle-like transparent conductive particles are contained at random (FIG. 3A) or the major axis direction in the catalyst layer is the thickness direction. It is more preferable that it is an aspect (FIG. 3 (d)) that is contained so as to be suitable, and it is further an aspect (FIG. 3 (a)) that is contained randomly from the viewpoint that the catalyst layer can be easily formed. Would be preferable.

  The thickness of the catalyst layer in the present invention is not particularly limited as long as it has a desired conductivity and light transmittance depending on the size of the needle-like transparent conductive particles and the type of the conductive polymer. It is not limited. In particular, the thickness of the catalyst layer in the present invention is preferably in the range of 10 nm to 10000 nm, more preferably in the range of 50 nm to 1000 nm, and still more preferably in the range of 100 nm to 800 nm.

  In addition, as described above, the catalyst layer in the present invention contains at least a material exhibiting catalytic ability with respect to the needle-shaped transparent conductive particles and the redox couple, and other additives or the like may be added as necessary. It may be contained. As such other additives, for example, as a binder resin, a cellulose resin, a polyester resin, a polyamide resin, a polyacrylic ester resin, a polyacrylic resin, a polycarbonate resin, a polyurethane resin, a polyolefin resin, In addition to polyvinyl acetal resins, fluorine resins, polyimide resins, and the like, polyhydric alcohols such as polyethylene glycol can be used.

2. Next, the counter electrode layer used in the present invention will be described. The counter electrode layer used in the present invention is formed on a counter substrate described later and is made of a conductive material.

  As the conductive material used for the counter electrode layer, in the dye-sensitized solar cell element produced using the counter electrode substrate for the dye-sensitized solar cell of the present invention, the counter electrode layer having an electric resistance within a desired range If it can form, it will not be specifically limited. Examples of such conductive materials include metals and metal oxides. In particular, in the present invention, it is preferable to use a metal oxide as the conductive material. As described later, it is preferable that the counter electrode layer used in the present invention has light transmittance. By using a metal oxide as the conductive material, a counter electrode layer having excellent light transmittance can be formed. Because it can.

Examples of the metal oxide include SnO ₂ , ITO, IZO, and ZnO. In the present invention, any of these metal oxides can be suitably used. Among these, fluorine-doped SnO ₂ (hereinafter referred to as FTO) and ITO are preferably used. This is because FTO and ITO are excellent in both conductivity and sunlight permeability.

  Moreover, the structure which consists of a single layer may be sufficient as the counter electrode layer used for this invention, and the structure by which the several layer was laminated | stacked may be sufficient. Examples of the configuration in which a plurality of layers are laminated include an aspect in which layers made of conductive materials having different work functions are laminated, and an aspect in which layers made of different metal oxides are laminated.

  The thickness of the counter electrode layer used in the present invention is such that, in the dye-sensitized solar cell element produced using the counter electrode substrate for the dye-sensitized solar cell of the present invention, depending on the type of the conductive material, etc. The resistance is not particularly limited as long as the counter electrode layer having a resistance within a desired range can be formed. In particular, in the present invention, it is preferably in the range of 10 nm to 5000 nm, more preferably in the range of 30 nm to 1000 nm, and still more preferably in the range of 50 nm to 800 nm.

  Furthermore, the counter electrode layer used in the present invention preferably has light transmittance. As a result, the counter electrode substrate for the dye-sensitized solar cell of the present invention can have light transmittance as a whole, and the dye-sensitized solar cell has see-through property and power generation potential by light irradiation from both sides. This is because an element can be manufactured.

3. Next, the counter substrate used in the present invention will be described. The counter substrate used in the present invention is not particularly limited as long as it has a self-supporting property that can support the counter electrode layer and the catalyst layer. Therefore, the opposing base material used in the present invention may be a flexible material having flexibility, or a rigid material having no flexibility, such as quartz glass, Pyrex (registered trademark), and synthetic quartz plate. There may be. Especially, it is preferable that the opposing base material used for this invention is a flexible material, and it is preferable that it is a film base material among the said flexible materials. This is because the film substrate is excellent in processability and can reduce the manufacturing cost.

  Moreover, it is preferable that the opposing base material used for this invention has a light transmittance. As a result, the counter electrode substrate for the dye-sensitized solar cell of the present invention can have light transmittance as a whole, and the dye-sensitized solar cell has see-through property and power generation potential by light irradiation from both sides. This is because an element can be manufactured.

  Examples of such an opposing substrate include an ethylene / tetrafluoroethylene copolymer film, a biaxially stretched polyethylene terephthalate film, a polyethersulfone (PES) film, a polyetheretherketone (PEEK) film, and a polyetherimide ( PEI) film, polyimide (PI) film, polyester naphthalate (PEN), polycarbonate (PC) and other resin film base materials. In particular, in the present invention, it is preferable to use a biaxially stretched polyethylene terephthalate film (PET), polyester naphthalate (PEN), or polycarbonate film (PC).

  In addition, the thickness of the counter substrate used in the present invention is usually preferably in the range of 50 μm to 2000 μm, particularly preferably in the range of 75 μm to 1800 μm, and more preferably in the range of 100 μm to 1500 μm. It is preferable.

  Moreover, the opposing base material used for this invention may be provided with the mesh-shaped metal wiring as an auxiliary electrode.

4). Counter electrode substrate for dye-sensitized solar cell The counter substrate for a dye-sensitized solar cell of the present invention has at least the above-mentioned counter base material, counter electrode layer, and catalyst layer. In the present invention, all of these It is preferable that the overall counter electrode substrate for the dye-sensitized solar cell of the present invention has light transmittance. As a result, it becomes possible to produce a dye-sensitized solar cell element having see-through property and power generation potential by light irradiation from both sides, using the counter electrode substrate for the dye-sensitized solar cell of the present invention. is there.

  When the counter electrode substrate for the dye-sensitized solar cell of the present invention has light transmittance, the total light transmittance is preferably 10% or more, preferably in the range of 40% to 90%, More preferably, it is in the range of 60% to 85%. When the total light transmittance is within such a range, the balance between the light scattering property and the light transmittance of the catalyst layer is maintained, and the electrode substrate for the dye-sensitized solar cell of the present invention has high power generation efficiency. This is because a dye-sensitized solar cell element can be produced.

In addition, the counter electrode substrate for a dye-sensitized solar cell of the present invention can have haze when the catalyst layer contains needle-like transparent conductive particles. The counter electrode substrate for the dye-sensitized solar cell of the present invention has a light scattering property by having a haze, and the dye-sensitized solar cell manufactured using the counter electrode substrate for the dye-sensitized solar cell of the present invention. In the battery element, there is an advantage that light irradiated inside the element can be reflected by the catalyst layer and contribute to power generation again. The haze of the electrode substrate for the dye-sensitized solar cell of the present invention is determined in consideration of the balance with the total light transmittance, but is usually preferably in the range of 5% or more. Is more preferably in the range of 50% or more, and further preferably in the range of 70% or more. If the haze is smaller than the above range, the light scattering property may decrease, and the power generation efficiency of the dye-sensitized solar cell element produced using the counter electrode substrate for the dye-sensitized solar cell of the present invention is improved. This is because there is a possibility that it cannot be expected.
The haze value can be adjusted by changing the shape and content of the acicular transparent conductive particles in the catalyst layer.

5. Method for Producing Dye-Sensitized Solar Cell Counter Electrode Substrate The counter substrate for a dye-sensitized solar cell of the present invention is formed, for example, by forming a counter electrode layer on a counter substrate by a generally known method, The electrode layer can be produced by applying a coating liquid for forming a catalyst layer containing a material that exhibits catalytic ability to the acicular transparent conductive particles and the redox couple.

B. Next, the dye-sensitized solar cell element of the present invention will be described. As described above, the dye-sensitized solar cell element of the present invention has a counter substrate, a counter electrode layer formed on the counter substrate, made of a conductive material, a needle-like shape, and transmits light. For a dye-sensitized solar cell, comprising needle-shaped transparent conductive particles having conductivity and conductivity, and a catalyst layer formed on the counter electrode layer, which contains a material exhibiting catalytic ability for a redox couple A counter electrode substrate, a base material, a first electrode layer formed on the base material and made of a metal oxide, and a porous material formed on the first electrode layer and containing metal oxide semiconductor fine particles and a dye sensitizer An oxide semiconductor electrode having a porous layer is disposed so that the porous layer and the catalyst layer face each other, and between the oxide semiconductor electrode and the counter electrode substrate for the dye-sensitized solar cell An electrolyte layer containing a redox pair is formed on Than is. That is, the dye-sensitized solar cell element of the present invention is characterized in that the counter electrode substrate for a dye-sensitized solar cell according to the present invention is used as the counter electrode substrate for the dye-sensitized solar cell. It is.

Such a dye-sensitized solar cell element of the present invention will be described with reference to the drawings. FIG. 4 is a schematic sectional view showing an example of the dye-sensitized solar cell element of the present invention. As illustrated in FIG. 4, the dye-sensitized solar cell element 30 of the present invention is formed on a counter electrode 10 for a dye-sensitized solar cell, a base material 21, and the base material 21, and is a metal oxide. And an oxide semiconductor electrode 20 having a porous layer 23 formed on the first electrode layer 22 and containing metal oxide semiconductor fine particles and a dye sensitizer. It is. And it has the structure by which the electrolyte layer 31 containing a redox pair was formed between the said oxide semiconductor electrode 20 and the said counter electrode substrate 10 for dye-sensitized solar cells.
In such an example, in the dye-sensitized solar cell element 30 of the present invention, the counter electrode substrate for a dye-sensitized solar cell according to the present invention is used as the counter electrode substrate 10 for the dye-sensitized solar cell element. It is characterized by that.
In FIG. 4, 32 represents a sealing material.

  According to the present invention, by using the dye-sensitized solar cell counter substrate according to the present invention, a dye-sensitized solar cell element having high power generation efficiency and excellent design can be obtained. .

The dye-sensitized solar cell element of the present invention includes at least the counter electrode substrate for the dye-sensitized solar cell, the oxide semiconductor electrode, and the electrolyte layer. It may have a configuration.
Hereafter, each structure used for this invention is demonstrated in order.

  The counter substrate for a dye-sensitized solar cell used in the present invention is the same as that described in the above section “A. Counter substrate for a dye-sensitized solar cell”, and is therefore described here. Is omitted.

1. Oxide Semiconductor Electrode First, the oxide semiconductor electrode used in the present invention will be described.
The oxide semiconductor electrode used in the present invention includes a base material, a first electrode layer formed on the base material and made of a metal oxide, a metal oxide semiconductor fine particle and a dye formed on the first electrode layer. And a porous layer containing a sensitizer.

(1) Porous layer The porous layer used for this invention is formed on the 1st electrode layer mentioned later. The porous layer used in the present invention contains metal oxide semiconductor fine particles and a dye sensitizer, and has a property of imparting semiconductor characteristics to the oxide semiconductor electrode used in the present invention.

(Metal oxide semiconductor fine particles)
The metal oxide semiconductor fine particles used in the present invention are not particularly limited as long as they are made of a metal oxide having semiconductor characteristics. Examples of the metal oxide constituting the metal oxide semiconductor fine particles used in the present invention include TiO ₂ , ZnO, SnO ₂ , ITO, ZrO ₂ , MgO, CeO ₂ , Bi ₂ O ₃ , Mn ₃ O ₄ , Y ₂ O ₃ , WO ₃ , Ta ₂ O ₅ , Nb ₂ O ₅ , La ₂ O _{3 and the} like can be mentioned. These metal oxide semiconductor fine particles are suitable for forming a porous porous layer, and can be suitably used in the present invention because energy conversion efficiency can be improved and costs can be reduced.

The metal oxide semiconductor fine particles used in the present invention may be all made of the same metal oxide, or two or more kinds of those made of different metal oxides may be used. In addition, the metal oxide semiconductor fine particles used in the present invention may have a core-shell structure in which one type is a core fine particle and the other metal oxide semiconductor fine particles include the core fine particle to form a shell.
In particular, in the present invention, it is most preferable to use TiO ₂ as the semiconductor oxide fine particles. This is because TiO ₂ is particularly excellent in semiconductor characteristics.

  The particle size of the metal oxide semiconductor fine particles used in the present invention is not particularly limited as long as the surface area of the porous layer can be within a desired range, but is usually within the range of 1 nm to 10 μm. It is preferable that it is in the range of 10 nm-1000 nm especially. If the particle size is smaller than the above range, the respective metal oxide semiconductor fine particles may aggregate to form secondary particles, and if the particle size is larger than the above range, the porous layer becomes thicker. This is because the porosity of the porous layer, that is, the specific surface area may decrease.

  In the present invention, all the metal oxide semiconductor fine particles may have the same particle diameter, or two or more kinds of metal oxide semiconductor fine particles having different particle diameters may be used. Here, since the light scattering effect in the porous layer can be enhanced by using the metal oxide semiconductor fine particles having different particle diameters together, for example, in the dye-sensitized solar cell element of the present invention, There is an advantage that light absorption can be performed efficiently.

  In the present invention, when two or more kinds of metal oxide semiconductor fine particles having different particle diameters are used, as a combination of different particle diameters, for example, metal oxide semiconductor fine particles in a range of 10 nm to 50 nm and a range of 50 nm to 800 nm are used. The combination with the metal oxide semiconductor fine particle in the inside can be illustrated.

(Dye sensitizer)
The dye sensitizer used in the present invention is not particularly limited as long as it can absorb light and generate an electromotive force. Examples of such a dye sensitizer include organic dyes and metal complex dyes. Examples of the organic dye include acridine, azo, indigo, quinone, coumarin, merocyanine, and phenylxanthene dyes. In the present invention, among these organic dyes, a coumarin dye is preferably used. The metal complex dye is preferably a ruthenium dye, and particularly preferably a ruthenium bipyridine dye and a ruthenium terpyridine dye, which are ruthenium complexes. This is because such a ruthenium complex has a wide wavelength range of light to be absorbed, so that the wavelength range of light that can be photoelectrically converted can be greatly expanded.

(Porous layer)
The thickness of the porous layer used in the present invention is usually preferably in the range of 1 μm to 100 μm, and particularly preferably in the range of 1 μm to 20 μm. This is because if the thickness of the porous layer is larger than the above range, the porous layer itself tends to cause cohesive failure, which tends to cause membrane resistance. On the other hand, if the thickness is less than the above range, the dye-sensitized solar cell element of the present invention has a decreased performance because the amount of dye-sensitized agent adsorbed decreases and the porous layer cannot absorb light sufficiently. Because there is a possibility.

  The porous layer in the present invention may be composed of a single layer or may be composed of a plurality of layers. As a structure in which a plurality of layers are stacked, for example, a porous layer is formed on the oxide semiconductor layer in contact with the first electrode layer, and is more porous than the oxide semiconductor layer. A two-layer structure including a layer having a high rate can be given.

(2) First Electrode Layer Next, the first electrode layer used in the present invention will be described. The 1st electrode layer used for this invention consists of metal oxides, and is formed on the said porous layer.

  As a metal oxide which comprises the 1st electrode layer used for this invention, if it has desired electroconductivity, it will not specifically limit. Especially, it is preferable that the metal oxide used for this invention has a transmittance | permeability with respect to sunlight. Thereby, in the dye-sensitized solar cell element of the present invention, it is possible to prevent the power generation efficiency from being impaired.

Examples of such a metal oxide having sunlight permeability include SnO ₂ , ITO, IZO, and ZnO. In the present invention, any of these metal oxides can be suitably used. Among these, fluorine-doped SnO ₂ (hereinafter referred to as FTO) and ITO are preferably used. This is because FTO and ITO are excellent in both conductivity and sunlight permeability.

  The first electrode layer used in the present invention may be composed of a single layer or may be composed of a plurality of layers laminated. Examples of the configuration in which a plurality of layers are stacked include a mode in which layers having different work functions are stacked and a mode in which layers made of different metal oxides are stacked.

The thickness of the first electrode layer used in the present invention is usually preferably in the range of 5 nm to 2000 nm, and particularly preferably in the range of 10 nm to 1000 nm. If the thickness is greater than the above range, it may be difficult to form a homogeneous first electrode layer. If the thickness is less than the above range, the conductivity of the first electrode layer may be insufficient. Because there is.
In addition, the said thickness shall point out the total thickness which added the thickness of all the layers, when the 1st electrode layer is comprised by the laminated | stacked several layer.

(3) Substrate Next, the substrate used in the present invention will be described. The base material used in the present invention is not particularly limited as long as it has a self-supporting property capable of supporting the first electrode layer and the porous layer used in the present invention.
Here, as the base material used in the present invention, the same material as the “opposite base material” described in the section “A. Counter electrode substrate for dye-sensitized solar cell” can be used.

(4) Oxide Semiconductor Electrode The oxide semiconductor electrode used in the present invention has at least the base material, the first electrode layer, and the porous layer, but has any other configuration as necessary. It may be a thing. As an arbitrary structure used for this invention, the contact bonding layer formed between the said base material and a 1st electrode layer and consisting of adhesive resin can be mentioned, for example. By forming such an adhesive layer, when the oxide semiconductor electrode used in the present invention is manufactured by a transfer method, the first electrode layer and the substrate can be bonded to facilitate transfer. it can.

  Examples of the adhesive resin used in the adhesive layer include polyethylene, polypropylene, polyisobutylene, polystyrene, polyolefins such as ethylene-propylene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethyl cellulose, triethylene. Cellulose derivatives such as cellulose acetate, copolymers of poly (meth) acrylic acid and esters thereof, polyvinyl acetal such as polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral, polyacetal, polyamide, polyimide, nylon, polyester resin, urethane resin, An epoxy resin, a silicone resin, a fluororesin, etc. can be mentioned. Moreover, as adhesive resin used for this invention, what was described in Unexamined-Japanese-Patent No. 2006-310256 can be mentioned, for example. In the present invention, any of these adhesive resins can be suitably used. Among them, polyolefin, ethylene-vinyl acetate are preferred from the viewpoints of adhesion, resistance to electrolyte, light transmission and transferability. A copolymer, urethane resin, epoxy resin, silane-modified resin, or acid-modified resin is preferred.

(5) Manufacturing method of oxide semiconductor electrode The oxide semiconductor electrode used in the present invention includes, for example, a first electrode layer forming step of forming a first electrode layer made of a metal oxide on a glass substrate, and a metal oxide. And a porous layer forming step of forming a porous layer containing semiconductor fine particles.
Here, for each of the above steps, since a known method can be used as a method generally used for producing a dye-sensitized solar cell element, the description thereof is omitted here.

2. Electrolyte Layer Next, the electrolyte layer used in the present invention will be described. The electrolyte layer in the present invention includes a redox pair.

  The redox couple used in the electrolyte layer in the present invention is not particularly limited as long as it is generally used in the electrolyte layer of a dye-sensitized solar cell element. Among them, the redox couple used in the present invention is preferably a combination of iodine and iodide and a combination of bromine and bromide.

Examples of the combination of iodine and iodide used in the present invention as the redox couple, for example, can be cited LiI, NaI, KI, and metal iodide such as CaI _2, a combination of I _2.
Further, examples of the combination of bromine and bromide include a combination of a metal bromide such as LiBr, NaBr, KBr, and CaBr ₂ and Br ₂ .

  The electrolyte layer in the present invention may contain additives such as a crosslinking agent, a photopolymerization initiator, a thickener, and a room temperature molten salt as other compounds other than the redox couple.

The electrolyte layer may be an electrolyte layer having any form of gel, solid, or liquid. When the electrolyte layer is in a gel form, either a physical gel or a chemical gel may be used. Here, the physical gel is gelled near room temperature due to physical interaction, and the chemical gel is a gel formed by chemical bonding by a crosslinking reaction or the like.
When the electrolyte layer is in a liquid state, for example, acetonitrile, methoxyacetonitrile, propylene carbonate or the like is used as a solvent, and an ionic liquid containing a redox couple or an imidazolium salt as a cation is used as a solvent. can do.

3. Dye-sensitized solar cell element In the dye-sensitized solar cell element of the present invention, the porous layer of the oxide semiconductor electrode and the counter electrode layer of the counter electrode substrate for the dye-sensitized solar cell are patterned. By doing so, it may have a configuration in which a plurality of cells are connected between a pair of oxide semiconductor electrodes and a counter electrode substrate for a dye-sensitized solar cell. This is because by having such a configuration, the dye-sensitized solar cell element of the present invention can have a high electromotive force.

  Further, the patterning shape can be arbitrarily determined by the electromotive force required for the dye-sensitized solar cell element of the present invention. In particular, in the present invention, the stripe patterning is most preferable. .

4). Next, an example of a method for producing the dye-sensitized solar cell element of the present invention will be described. The dye-sensitized solar cell element of the present invention is formed by forming an electrolyte layer between the porous layer of the oxide semiconductor electrode and the counter electrode layer of the counter electrode substrate for the dye-sensitized solar cell. Can be manufactured.

  In the present invention, the method for forming the electrolyte layer is not particularly limited as long as the electrolyte layer can be formed with high thickness accuracy. As such a method, after forming an electrolyte layer on the porous layer of the oxide semiconductor electrode, a method of arranging a counter electrode substrate for a dye-sensitized solar cell on the electrolyte layer (first method); After the oxide semiconductor electrode and the counter electrode substrate for the dye-sensitized solar cell are arranged so that the porous layer and the counter electrode layer face each other, an electrolyte layer is formed between the porous layer and the counter electrode layer And a second method.

  As the first method, for example, a coating for forming a counter electrode substrate for a dye-sensitized solar cell is formed after an electrolyte layer is formed by applying a composition for forming an electrolyte layer on the porous layer and drying it. Can be used. As the second method, the porous layer of the oxide semiconductor electrode and the counter electrode layer of the counter electrode substrate for the dye-sensitized solar cell are arranged with a predetermined gap so as to face each other. An injection method for forming an electrolyte layer by injecting a composition for forming an electrolyte layer into the gap can be used.

C. Next, the dye-sensitized solar cell module of the present invention will be described. The dye-sensitized solar cell module of the present invention is characterized in that a plurality of dye-sensitized solar cell elements according to the present invention are connected.

  According to the present invention, by using the dye-sensitized solar cell element according to the present invention, a dye-sensitized solar cell module having high power generation efficiency and excellent design can be obtained.

  The aspect in which a plurality of dye-sensitized solar cell elements are connected in the present invention is not particularly limited as long as a desired electromotive force can be obtained by the dye-sensitized solar cell module of the present invention. Absent. As such an aspect, the aspect which each dye-sensitized solar cell element was connected in series may be sufficient, or the aspect connected in parallel may be sufficient.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the technical idea described in the claims of the present invention has substantially the same configuration and exhibits the same function and effect regardless of the case. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described more specifically with reference to examples.

[Example]
1. Preparation of oxide semiconductor electrode Prepare transparent conductive glass (base material) (manufactured by Nippon Sheet Glass) with FTO film formed on a glass plate as the first electrode layer, and prepare titanium oxide paste Nanooxide D-SP (manufactured by solaronix) A 4 mm × 90 mm pattern was applied by screen printing, and then fired at 500 ° C. to obtain a porous layer having a thickness of 10 μm formed of a large number of metal oxide semiconductor fine particles (TiO ₂ fine particles). Thereafter, a dye-supporting coating in which ruthenium complex N719 (manufactured by dyesol) as a dye sensitizer is dissolved in a 1: 1 volume ratio solution of acetonitrile and tert-butyl alcohol so as to have a concentration of 3 × 10 ⁻⁴ mol / l. The porous layer described above was immersed in the working solution at room temperature for 20 hours. Next, the pigment-carrying coating solution was pulled up from the pigment-carrying coating solution, washed with acetonitrile, and then air-dried. Thereby, said sensitizing dye was carry | supported on the titanium oxide fine particle surface which has formed the porous layer. An oxide semiconductor electrode having a substrate size of 10 × 100 mm was obtained.

2. Fabrication of counter electrode substrate for dye-sensitized solar cell
After applying SC-K (manufactured by Sumitomo Metal Mining) on a 10 × 100 mm conductive glass substrate (opposite substrate) with a Miya bar to a dry film thickness of 5 to 10 μm and drying at 120 ° C. for 5 minutes, On top of this, PEDOTPSS dispersion (Clevios, Starck) was spin coated and heated at 120 ° C. for 10 minutes.

3. Electrolyte production
It was prepared by adding 5 wt% of silica particles to 0.6 M hexylmethylimidazolium iodide, 0.03 MI ₂ , 0.1 M N-methylbenzimidazole and mixing them.

4). Application of Electrolyte The gel electrolyte was applied in a 5 mm × 91 mm pattern on the porous semiconductor electrode of the photoelectrode substrate by screen printing. As a result, an electrolyte layer was formed.

5. Preparation of dye-sensitized solar cell element After setting a thermosetting resin film mainly composed of ionomer resin in a 6mm x 92mm pattern on the outer periphery of the porous semiconductor electrode, the catalyst layer surface of the counter electrode substrate and the dye of the photoelectrode A dye-sensitized solar cell element was obtained by pasting the supported semiconductor film surface in an Ar purged glove box.

[Comparative example]
Except that the dye-sensitized solar cell electrode substrate was produced by the following method, dye-sensitized solar cell elements were produced in the same manner as in Examples.
(Counter electrode production)
A PEDOTPSS dispersion was spin-coated on a 10 × 100 mm conductive glass substrate and heated at 120 ° C. for 10 minutes.

[Evaluation]
The photoelectric conversion efficiency of the obtained dye-sensitized solar cell was determined using a spectral sensitivity measuring device CEP-2000 (spectrometer) using pseudo-sunlight (100 mW / cm ² , AM (AirMass) 1.5) as a light source. Moreover, a black shading mask was installed except for the power generation part of the element. As a result of the performance evaluation, the device performance of the example was photoelectric conversion efficiency η = 5%, and the device performance of the comparative example was photoelectric conversion efficiency η = 3.4%.
Moreover, as a result of measuring the total light transmittance using a haze meter (Suga test machine), the total light transmittance of the example counter electrode = 75%, the haze ratio = 76%, the total light transmittance of the comparative example counter electrode = 79% The haze ratio was 2.6%, and no significant reduction in transmittance due to the addition of particles was observed.

DESCRIPTION OF SYMBOLS 1 ... Counter base material 2 ... Counter electrode layer 3 ... Catalyst layer 10 ... Counter electrode board | substrate for dye-sensitized solar cells 20 ... Oxide semiconductor electrode 21 ... Base material 22 ... 1st electrode layer 23 ... Porous layer 30 ... Dye increase Sensitive solar cell element 31 ... Electrolyte layer 32 ... Sealing material A ... Acicular transparent conductive particles

Claims (7)

An opposing substrate;
A counter electrode layer formed on the counter substrate and made of a conductive material;
A needle-shaped transparent conductive particle having a needle-like shape and having light permeability and conductivity, and a catalyst layer formed on the counter electrode layer, the material including a material exhibiting catalytic ability for a redox pair; ,
A counter electrode substrate for a dye-sensitized solar cell, comprising: The counter electrode substrate for a dye-sensitized solar cell according to claim 1, wherein the needle-like transparent conductive particles are made of ATO, ITO, FTO, ZnO, SnO ₂ or a composite material thereof.   The counter electrode substrate for a dye-sensitized solar cell according to claim 1 or 2, wherein the counter substrate and the counter electrode layer have light transmittance.   The dye according to any one of claims 1 to 3, wherein the material exhibiting catalytic ability with respect to the redox couple is polypyrrole, polythiophene, ponianiline, or a derivative thereof. Sensitive solar cell power counter electrode substrate.   The counter electrode substrate for a dye-sensitized solar cell according to any one of claims 1 to 4, wherein the total light transmittance is 10% or more. A counter substrate, a counter electrode layer formed on the counter substrate and made of a conductive material, needle-shaped transparent conductive particles having a needle shape and having light transmission and conductivity, and a redox pair A counter electrode substrate for a dye-sensitized solar cell, which has a catalyst layer formed on the counter electrode layer, and a base material, and is formed on the base material. An oxide semiconductor electrode comprising: a first electrode layer made of a metal oxide; and a porous layer formed on the first electrode layer and containing metal oxide semiconductor fine particles and a dye sensitizer. An electrolyte layer including an oxidation-reduction pair is formed between the oxide semiconductor electrode and the counter electrode substrate for a dye-sensitized solar cell. , Dye-sensitized solar cell element.   A dye-sensitized solar cell module comprising a plurality of the dye-sensitized solar cell elements according to claim 6 connected to each other.

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