JP2007220608A - Method of manufacturing dye-sensitized solar cell, and dye-sensitized solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a dye-sensitized solar cell capable of manufacturing a dye-sensitized solar cell with a large area in a short time. <P>SOLUTION: The manufacturing method comprises a sealing material formation process in which, using a dye-sensitized solar cell substrate 10 wherein a first electrode layer 12 and a porous layer 13 containing metal oxide semiconductor particulates adsorbed with a dye-sensitizing agent on the surface are laminated on a substrate 11 in this order and a counter electrode substrate 20 wherein a second electrode layer 22 consisting of a metal oxide is laminated on a counter substrate 21, a sealing material made of an adhesive resin is formed in a frame shape having an inner circumference wider than the outer circumference of the porous layer on any one of the first electrode layer or the second electrode layer, a formation process of an electrolyte, a substrate pasting process in which the dye-sensitized solar cell substrate and the counter electrode substrate are pasted under reduced pressure, and a fixing process of substrates. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a dye-sensitized solar cell, and more particularly to a method for producing a dye-sensitized solar cell suitable for producing a large-area dye-sensitized solar cell. .

  In recent years, environmental problems such as global warming have progressed globally. In recent years, photovoltaic power generation has attracted attention as a clean energy with a low environmental load, and research and development are being actively promoted. 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. However, these solar cells have problems such as high manufacturing costs and high energy consumption in the manufacturing stage. Under such circumstances, the dye-sensitized solar cell is attracting attention as a novel solar cell with high possibility of cost reduction, and research and development are being conducted energetically.

  A general dye-sensitized solar cell includes a first electrode layer made of a metal oxide on a substrate and a porous layer containing metal oxide semiconductor fine particles adsorbed with a dye sensitizer on the surface. A dye-sensitized solar cell substrate having a structure laminated in this order, and a counter electrode base material in which a second electrode layer made of a metal oxide is formed on a counter base material are used. The dye-sensitized solar cell substrate and the counter electrode base material are arranged so that the porous layer and the second electrode layer face each other through an electrolyte layer including a reducing pair.

As a method for producing such a dye-sensitized solar cell, the dye-sensitized solar cell substrate and the counter electrode base material are sealed so that the porous layer and the second electrode layer face each other. A method of injecting a composition for forming an electrolyte layer containing an oxidation-reduction pair into the above-mentioned interval after using a material to face each other at a certain interval is used.
As a method for injecting such a composition for forming an electrolyte layer, for example, as disclosed in Patent Document 1, a through-hole provided in the counter electrode substrate is used as an injection hole, and the composition for forming an electrolyte layer is used. A method is used in which an object is brought into contact under reduced pressure and then released from the atmosphere and simultaneously injected from the injection hole by capillary action. Further, as another injection method, for example, as disclosed in Patent Document 2, two through holes are provided in the counter electrode base material, one is used as an injection hole, and the other is used as a deaeration hole. A method of injecting using the same capillary phenomenon is used.

However, the method of injecting the composition for forming an electrolyte layer disclosed in Patent Document 1 or Patent Document 2 is useful in that the electrolyte layer can be uniformly injected. There is a disadvantage that it takes. In recent years, dye-sensitized solar cells have a tendency to increase in area, and such a defect may become a problem from the viewpoint of productivity of dye-sensitized solar cells.
Furthermore, recent dye-sensitized solar cells tend to have flexibility as a whole by using a flexible material. In the method described in Patent Document 1, the composition for forming an electrolyte layer is used. There is also a problem that the base material bends when an object is injected, and it is difficult to keep the distance between the dye-sensitized solar cell substrate and the counter electrode base material uniform.

JP 2002-313443 A JP 2000-348783 A

  This invention is made | formed in view of the said problem, and it aims at providing the manufacturing method of a dye-sensitized solar cell which can manufacture a large area dye-sensitized solar cell in a short time. .

  In order to solve the above problems, the present invention provides a first electrode layer made of a metal oxide on a substrate, and a porous layer containing metal oxide semiconductor fine particles adsorbed with a dye sensitizer on the surface, Using the dye-sensitized solar cell substrate laminated in this order, and the counter electrode substrate in which the second electrode layer made of a metal oxide is laminated on the counter substrate, the first electrode layer or the above A sealing material forming step in which a sealing material made of an adhesive resin is formed on any one of the second electrode layers into a frame shape having an inner circumference wider than the outer circumference of the porous layer; An electrolyte layer forming step of forming an electrolyte layer by injecting a composition for forming an electrolyte layer containing an oxidation-reduction pair inside the sealed material, and the electrolyte layer is the first electrode layer and the second electrode layer And the dye sensitization to be sealed by the sealant Substrate laminating step for laminating the solar cell substrate and the counter electrode base material under reduced pressure, and a substrate immobilizing step for fixing the dye-sensitized solar cell substrate and the counter electrode base material by the sealing material And a method for producing a dye-sensitized solar cell, comprising:

According to the present invention, after the electrolyte layer is formed on the dye-sensitized solar cell substrate or the counter electrode substrate in advance by the sealing material forming step and the electrolyte layer forming step, the dye sensitization is performed. Since the electrolyte layer can be formed in a short time by laminating the substrate for the sensitive solar cell and the counter electrode base material, a large-area dye-sensitized solar cell can be manufactured in a short time Can do.
Further, according to the present invention, since the dye-sensitized solar cell substrate and the counter electrode base material are bonded together under reduced pressure, it is possible to prevent air from being enclosed between the two, thereby improving power generation efficiency. An excellent dye-sensitized solar cell can be produced.
Furthermore, according to the present invention, as described above, air can be prevented from being enclosed between the dye-sensitized solar cell substrate and the counter electrode base material. Thus, performance deterioration of the dye-sensitized solar cell produced according to the present invention can be suppressed.

  In the present invention, the composition for forming an electrolyte layer may contain an ionic liquid. Since the ionic liquid has a high viscosity, the conventional method using the capillary phenomenon has a problem that it takes too much time to inject and lacks productivity, but in the present invention, the viscosity of the composition for forming an electrolyte layer is not suitable. This is because a dye-sensitized solar cell can be manufactured in a short time regardless.

  In the present invention, it is preferable that the electrolyte layer forming composition is injected under reduced pressure in the electrolyte layer forming step. By injecting the electrolyte layer forming composition under reduced pressure, air dissolved in the electrolyte layer forming composition can be removed, so that the inside of the dye-sensitized solar cell formed according to the present invention is removed. This is because air can be prevented from being enclosed. In addition, according to such a method, the electrolyte layer can be formed without bringing the composition for forming an electrolyte layer into contact with outside air containing moisture, and therefore, it is possible to prevent moisture from being mixed into the electrolyte layer. This is because a dye-sensitized solar cell having excellent temporal stability can be produced.

  In the present invention, the substrate is preferably a resin film substrate. This is because a dye-sensitized solar cell having flexibility can be manufactured by the above-mentioned base material being a resin film base material. In addition, in the conventional method for forming an electrolyte layer using capillary action, when a flexible material such as a resin film substrate is used as the substrate, the substrate is formed at the time of injection of the electrolyte layer forming composition. Although there was a problem of bending, according to the present invention, there is no such problem. Even when a resin film substrate is used, a dye-sensitized solar cell substrate, a counter electrode substrate, This is because it is possible to manufacture a dye-sensitized solar cell in which are arranged at uniform intervals in a short time.

Furthermore, in the present invention, the adhesive resin is preferably a photocurable resin.
In the substrate fixing step, when the electrolyte layer is heated when the dye-sensitized solar cell substrate and the counter electrode base material are fixed by the sealant, for example, a solvent-based solvent is used as the electrolyte layer. In the case where a material is used, the solvent in the electrolyte layer is vaporized, and there is a possibility that gas is encapsulated between the dye-sensitized solar cell substrate and the counter electrode base material. This is because there is no such problem with a resin.

  In the present invention, the dye-sensitized solar cell substrate may have an adhesive layer made of a resin between the base material and the first electrode layer. This is because such a dye-sensitized solar cell substrate can be manufactured with high productivity by a transfer method.

  The present invention also provides a substrate, a first electrode layer formed on the substrate and made of a metal oxide, and a metal oxide semiconductor formed on the first electrode layer and having a dye sensitizer adsorbed on the surface. A substrate for a dye-sensitized solar cell having a porous layer containing fine particles, a counter substrate, and a counter electrode substrate having a second electrode layer formed on the counter substrate is a redox pair. The porous layer and the second electrode layer are disposed so as to face each other via an electrolyte layer containing a sealing material, and a sealing material is formed so as to seal the electrolyte layer around the electrolyte layer. A dye-sensitized solar cell having the above-described configuration, wherein a through-hole is not formed in the base material and the counter base material, is provided.

  According to the present invention, the through-holes are not formed in the base material and the counter base material, so that the dye-sensitized solar cell of the present invention can be used for electrolyte leakage, volatilization, intrusion of moisture from the outside, and the like. Therefore, a dye-sensitized solar cell excellent in durability can be obtained.

  The present invention has an effect that a dye-sensitized solar cell having a large area can be produced in a short time.

  Hereinafter, the method for producing a dye-sensitized solar cell and the dye-sensitized solar cell of the present invention will be described in detail.

A. First, a method for producing a dye-sensitized solar cell of the present invention will be described. The method for producing a dye-sensitized solar cell of the present invention includes a first electrode layer made of a metal oxide on a substrate, and a porous layer containing metal oxide semiconductor fine particles having a dye sensitizer adsorbed on the surface. And a substrate for a dye-sensitized solar cell laminated in this order, and a counter electrode base material in which a second electrode layer made of a metal oxide is laminated on a counter base material, and the first electrode layer A sealing material forming step of forming a sealing material made of an adhesive resin in a frame shape having an inner circumference wider than an outer circumference of the porous layer on either the upper electrode layer or the second electrode layer; and the frame shape An electrolyte layer forming step of forming an electrolyte layer by injecting an electrolyte layer forming composition containing an oxidation-reduction pair into the inside of the sealing material formed on the first electrode layer, the second electrode layer; The dye enhancement so as to be sealed by the electrode layer and the sealing material. Substrate bonding step of bonding the solar cell substrate and the counter electrode base material under reduced pressure, and fixing the substrate to fix the dye-sensitized solar cell substrate and the counter electrode base material by the sealing material And a process.

A method for producing such a dye-sensitized solar cell of the present invention will be described with reference to the drawings. FIG. 1 is a schematic view showing an example of a method for producing a dye-sensitized solar cell of the present invention. As illustrated in FIG. 1, the method for producing a dye-sensitized solar cell according to the present invention includes a first electrode layer 12 made of a metal oxide on a substrate 11, and a metal oxide having a dye sensitizer adsorbed on the surface. A substrate 10 for dye-sensitized solar cells in which a porous layer 13 containing fine semiconductor particles is laminated in this order, and a counter electrode group having a structure in which a second electrode layer 22 is laminated on a counter substrate 21 Material 20 (FIG. 1A),
A sealing material forming step in which a sealing material 30 made of an uncured ultraviolet curable resin is formed in a frame shape on the first electrode layer 12 so as to surround the porous layer 13 (FIG. 1B);
An electrolyte layer forming step of forming the electrolyte layer 40 by injecting an electrolyte layer forming composition containing a redox couple into the inside of the sealing material 30 formed in the frame shape (FIG. 1C);
The dye-sensitized solar cell substrate and the counter electrode base material are attached under reduced pressure so that the electrolyte layer 40 is surrounded by the first electrode layer 12, the second electrode layer 22, and the sealing material 30. A substrate bonding process to be combined (FIG. 1 (d)),
A substrate immobilization step for immobilizing the dye-sensitized solar cell substrate 10 and the counter electrode base material 20 by curing the ultraviolet curable resin (FIG. 1E). is there.

Although the example in which the sealing material is formed on the first electrode layer has been described with reference to FIG. 1, the sealing material may be formed on the second electrode layer in the present invention. Such an example will be described with reference to FIG. As illustrated in FIG. 2, when the sealing material is formed on the second electrode layer, the method for producing a dye-sensitized solar cell according to the present invention includes a first method comprising a metal oxide on a base material 11. On the substrate 10 for the dye-sensitized solar cell in which the electrode layer 12 and the porous layer 13 containing the metal oxide semiconductor fine particles having the dye sensitizer adsorbed on the surface are laminated in this order, Using the counter electrode base material 20 having a configuration in which the second electrode layer 22 is laminated (FIG. 2A),
A sealing material forming step of forming a sealing material 30 made of an uncured ultraviolet curable resin on the second electrode layer 22 so as to have a frame shape having an inner circumference wider than the outer circumference of the porous layer 13; FIG. 2 (b)),
An electrolyte layer forming step of forming the electrolyte layer 40 by dropping an electrolyte layer forming composition containing a redox couple inside the sealing material 30 formed in the frame shape (FIG. 2 (c));
The dye-sensitized solar cell substrate and the counter electrode base material are attached under reduced pressure so that the electrolyte layer 40 is surrounded by the first electrode layer 12, the second electrode layer 22, and the sealing material 30. A substrate bonding process for matching (FIG. 2 (d)),
A substrate fixing step for fixing the dye-sensitized solar cell substrate 10 and the counter electrode base material 20 by curing the ultraviolet curable resin (FIG. 2E). Become.

Conventionally, as a method for dye-sensitized solar cells using a dye-sensitized solar cell substrate and a counter electrode base material, a certain interval between the dye-sensitized solar cell substrate and the counter electrode base material is used. A method of forming an electrolyte layer by injecting a composition for forming an electrolyte layer between the two by using a capillary phenomenon after being disposed in the space has been used. However, such a method has a problem that it takes time to form an electrolyte and the productivity is insufficient. Further, in the method utilizing the capillary phenomenon, for example, when a flexible resin film substrate is used as a substrate constituting the dye-sensitized solar cell substrate, the resin film is bent. Therefore, there is a problem that the distance between the dye-sensitized solar cell substrate and the counter electrode base material becomes non-uniform when the electrolyte layer is formed.
However, according to the present invention, after the electrolyte layer is formed on the dye-sensitized solar cell substrate or the counter electrode substrate in advance by the electrolyte layer forming step, the dye-sensitized solar cell is used. By attaching the substrate and the counter electrode base material together, the electrolyte layer can be formed in a short time. Therefore, according to the present invention, even a large area dye-sensitized solar cell can be manufactured in a short time.
Further, in the present invention, since the dye-sensitized solar cell substrate and the counter electrode base material are bonded together under reduced pressure, air can be prevented from being enclosed between the two, so that the power generation efficiency is excellent. A dye-sensitized solar cell can be manufactured.

  The method for producing a dye-sensitized solar cell of the present invention includes a sealing material forming step, an electrolyte layer forming step, a substrate bonding step, and a substrate fixing step. Hereinafter, each of these steps will be described in detail.

1. Sealing material forming step First, the sealing material forming step in the present invention will be described. In this step, a dye is formed by laminating a first electrode layer made of a metal oxide and a porous layer containing metal oxide semiconductor fine particles having a dye sensitizer adsorbed on the surface in this order on a substrate. Using a substrate for a sensitized solar cell and a counter electrode base material in which a second electrode layer made of a metal oxide is laminated on a counter base material, either on the first electrode layer or on the second electrode layer On the other hand, it is a step of forming a sealing material made of an adhesive resin into a frame shape having an inner circumference wider than the outer circumference of the porous layer. Hereinafter, such a sealing material forming step will be described.

(1) Sealing material The sealing material used for this process is demonstrated. The sealing material used in the present invention is made of an adhesive resin.

  The sealing material formed in this step has a function of adhering the dye-sensitized solar cell substrate and the counter electrode base material and sealing the electrolyte layer formed in the electrolyte layer forming step described later. Is. Moreover, the said sealing material is contacted with the composition for electrolyte layer formation containing an oxidation reduction pair in the electrolyte layer formation process mentioned later. Therefore, as the adhesive resin used for the sealing material, the adhesiveness capable of bonding the dye-sensitized solar cell substrate and the counter electrode base material, and the durability to the electrolyte layer forming composition are as follows. It is required to have.

  The adhesive resin used in this step is not particularly limited as long as it has the adhesiveness and the durability. Examples of such adhesive resins include thermoplastic resins that are plasticized by heating and exhibit adhesive properties, thermosetting resins that are cured by heating and exhibit adhesive properties, and actinic radiation. An actinic radiation curable resin that cures and exhibits the above-mentioned adhesiveness can be exemplified.

First, the actinic radiation curable resin that can be used as the adhesive resin will be described. The actinic radiation curable resin used in this step is not particularly limited as long as it has durability against an electrolyte layer forming composition to be described later in an uncured state. Here, the actinic radiation refers to radiation that can supply activation energy necessary for a polymerization reaction of a monomer or the like by irradiating the monomer or oligomer of the actinic radiation curable resin.
As such an actinic radiation curable resin, a photocurable resin that is cured by irradiating light (electromagnetic waves) having a wavelength in a specific range, and an electron beam curable resin that is cured by irradiating an electron beam. Can be mentioned.
As the actinic radiation curable resin used in this step, any of the photocurable resin and the electron beam curable resin can be suitably used, and among them, the photocurable resin is used. preferable. This is because photocurable resins are widely used in other fields and are already established techniques, so that they can be easily applied to the present invention.

  Examples of the photocurable resin include an ultraviolet curable resin that is cured by irradiating ultraviolet light, a visible light curable resin that is cured by irradiating visible light, and the like. It is preferable to use an ultraviolet curable resin. By using an ultraviolet curable resin that is cured by ultraviolet rays having a short wavelength, the electrolyte layer is heated when the sealing material is fixed in the substrate fixing step described later, and the liquid in the electrolyte is vaporized. This is because it can be surely prevented.

  Further, from the viewpoint of easiness of the ultraviolet irradiation device, the wavelength range of ultraviolet rays for curing the ultraviolet curable resin is preferably in the range of 150 nm to 500 nm, more preferably in the range of 250 nm to 450 nm, particularly 300 nm to A range of 400 nm is preferable.

  Specific examples of the ultraviolet curable resin used in this step include acrylic resins, epoxy resins, fluorine resins, olefin resins, and the like. Among these, in this step, it is preferable to use an acrylic resin, an epoxy resin, or a fluorine resin.

  In this step, only one type of the actinic radiation curable resin may be used, or two or more types may be used in combination.

Next, the thermosetting resin used as the adhesive resin will be described. The thermosetting resin used in this step is not particularly limited as long as it has durability against an electrolyte layer forming composition to be described later in an uncured state. In particular, in this step, it is preferable to use a material that can be cured at a temperature that does not vaporize the liquid in the electrolyte layer formed in the electrolyte layer forming step described later. More specifically, it is preferable to use a thermosetting resin having a curing temperature in the range of 60 ° C. to 200 ° C., in particular in the range of 80 ° C. to 180 ° C., and further in the range of 100 ° C. to 160 ° C. . When the curing temperature is higher than the above range, the liquid contained in the electrolyte layer described later is vaporized when the sealing material is fixed in the substrate fixing step described later, and manufactured according to the present invention. This is because there is a risk of gas being enclosed inside the dye-sensitized battery. Further, if the curing temperature is lower than the above range, it may be difficult to handle the thermosetting resin without curing it until the substrate fixing step.
Here, the curing temperature of the thermosetting resin is measured, for example, by measuring the internal temperature of a curing oven or the like that cures the thermosetting resin using a temperature measuring instrument HA-200E manufactured by Anritsu Keiki Co., Ltd. and a temperature sensor. Can be measured.

  Specific examples of such thermosetting resins include acrylic resins, epoxy resins, fluorine resins, silicone resins, olefin resins, polyisobutylene resins, and the like. In this step, it is preferable to use acrylic resin, epoxy resin, fluorine resin, or silicone resin among such thermosetting resins.

  In this step, only one type of the thermosetting resin may be used, or two or more types may be mixed and used.

Next, the thermoplastic resin used as the adhesive resin will be described. The thermoplastic resin used in this step is not particularly limited as long as it has durability against the electrolyte layer forming composition described later. In particular, in this step, it is preferable to use a material whose melting point is a temperature at which the liquid in the electrolyte layer formed in the electrolyte layer forming step described later is not vaporized. More specifically, it is preferable to use a thermoplastic resin having a melting point in the range of 80 ° C. to 250 ° C., particularly in the range of 100 ° C. to 200 ° C. When the melting point is higher than the above range, the liquid contained in the electrolyte layer described later is vaporized when the sealing material is fixed in the substrate fixing step described later, and the dye produced by the present invention This is because there is a risk of gas being sealed inside the sensitized battery. Moreover, it is because it will become difficult to form the said sealing material in frame shape when melting | fusing point is lower than the said range.
Here, the melting point of the thermoplastic resin can be generally measured by a known method.

  Specific examples of such a thermoplastic resin include olefin resins, polyisobutylene resins, silicone resins, acrylic resins, polyamide resins, and the like. In this step, among such thermoplastic resins, polyolefin resins and silicone resins can be suitably used.

  In this step, only one kind of the thermoplastic resin may be used, or two or more kinds may be mixed and used.

  In this step, any of the thermoplastic resin, the thermosetting resin, and the actinic radiation curable resin can be suitably used as the adhesive resin. It is preferable to use a resin, and among the active radiation curable resins, it is preferable to use a photocurable resin described later. The reason is as follows. That is, the sealing material formed in this step is subjected to an immobilization treatment for causing the adhesive resin to exhibit the adhesive property in a substrate immobilizing step described later, thereby the dye-sensitized solar cell substrate and Although the counter electrode substrate is fixed, if a thermosetting resin or a thermoplastic resin is used as the adhesive resin, a heat treatment is required in the immobilization process, so the liquid in the electrolyte layer Vaporization may cause gas to be enclosed between the dye-sensitized solar cell substrate and the counter electrode substrate. However, when a photocurable resin is used as the adhesive resin, there is no such problem because no heat treatment is required in the immobilization process.

  The sealing material used in this step has a function of adjusting the distance between the dye-sensitized solar cell substrate and the counter electrode substrate in the substrate bonding step described later. A spacer may be contained. By including such a spacer in the sealing material, it is easy to bond the dye-sensitized solar cell substrate and the counter electrode substrate at a uniform interval in the substrate bonding step described later. can do.

  The spacer is not particularly limited as long as it can control the distance between the dye-sensitized solar cell substrate and the counter electrode base material within a desired range by being present in the sealing material. Fiber-like or columnar ones are used.

  As the material constituting the fine particles, for example, glass, acrylic, silica, aluminum oxide or the like can be used. In particular, in this step, it is preferable to use a spacer made of silica.

  In addition, when a spherical spacer is used as the spacer, the particle diameter is appropriately selected so that the distance between the dye-sensitized solar cell substrate and the counter electrode substrate can be set to a desired value. It is preferably within the range of 10 μm to 100 μm, more preferably within the range of 15 μm to 80 μm, and particularly preferably within the range of 15 μm to 50 μm. If it is smaller than the above range, the distance between the dye-sensitized solar cell substrate and the counter electrode substrate becomes too narrow. For example, the dye-sensitized solar cell substrate and the counter electrode substrate are flexible. This is because there is a risk of short circuiting when both are in contact. If the particle size is larger than the above range, the distance between the dye-sensitized solar cell substrate and the counter electrode substrate becomes too wide, so the power generation efficiency of the dye-sensitized solar cell produced by the present invention This is because there is a possibility that it will be lowered.

  The form of the sealing material used in this step may be liquid or solid, but is preferably liquid. This is because, when the sealing material is in a liquid state, it is easy to form the sealing material in a frame shape having an inner circumference wider than the outer circumference of the porous layer in this step.

  The shape of the sealing material used in this step is not particularly limited as long as it is a continuous frame shape that can surround the electrolyte layer described later, and may be any shape such as a rectangle or a circle. it can.

(2) Formation method of sealing material Next, the method to form the said sealing material on the 1st electrode layer of the said board | substrate for dye-sensitized solar cells or the 2nd electrode layer of the said counter electrode base material is demonstrated.
As a method for forming the sealing material, the sealing material is wider than the outer periphery of the porous layer on the first electrode layer of the dye-sensitized solar cell substrate or the second electrode layer of the counter electrode base material. The method is not particularly limited as long as it can be formed into a frame shape having an inner periphery. As such a method, for example, when the sealing material is in a liquid form, a frame having an inner circumference wider than the outer circumference of the porous layer while continuously discharging the liquid sealing material is used. A method of forming the image so as to draw can be given.
On the other hand, when the sealing material is in a solid state, the solid sealing material is processed in advance into a frame shape having an inner periphery wider than the outer periphery of the porous layer, and a method of forming this is given. You can draw. In the case of using such a method, it is usually necessary to previously adhere a sealing material on the first electrode layer or the second electrode layer before injecting the electrolyte layer forming composition.

(3) Dye-sensitized solar cell substrate Next, the dye-sensitized solar cell substrate used in this step will be described. The dye-sensitized solar cell substrate used in this step comprises a base material, a first electrode layer made of a metal oxide on the base material, and metal oxide semiconductor fine particles having a dye sensitizer adsorbed on the surface. And a porous layer containing a layered structure in this order.
The dye-sensitized solar cell substrate may have an adhesive layer made of a resin between the base material and the first electrode layer. This is because the dye-sensitized solar cell substrate having such an adhesive layer can be manufactured with high productivity by a transfer method.

  Such a dye-sensitized solar cell substrate will be described with reference to the drawings. FIG. 3 is a schematic cross-sectional view showing an example of a dye-sensitized solar cell substrate used in this step. As illustrated in FIG. 3, the dye-sensitized solar cell substrate 10 ′ used in this step includes an adhesive layer 14 made of a resin and a first electrode layer 12 made of a metal oxide on a base material 11. The porous layer 13 containing the metal oxide semiconductor fine particles having the dye sensitizer adsorbed on the surface may be laminated in this order.

  Hereafter, each structure of the board | substrate for dye-sensitized solar cells used for this process is demonstrated in detail.

a. Base Material The base material used for the dye-sensitized solar cell substrate will be described. Since the dye-sensitized solar cell produced according to the present invention is disposed on a light receiving surface that receives sunlight, the base material is required to have transparency to sunlight. . Therefore, the substrate is not particularly limited as long as it can transmit sunlight corresponding to the absorption wavelength of the dye sensitizer according to the type of the dye sensitizer described later. Especially in this process, it is preferable that the transmittance | permeability with respect to the light with a wavelength of 400 nm-1000 nm is 78% or more, Furthermore, it is preferable that it is 80% or more. This is because if the transmittance of the substrate is lower than the above range, the power generation efficiency of the dye-sensitized solar cell produced by this step may be impaired.

Specific examples of the base material include quartz glass, Pyrex (registered trademark), a non-flexible transparent rigid material such as a synthetic quartz plate, an ethylene / tetrafluoroethylene copolymer film, a biaxially stretched polyethylene terephthalate film, Resin film base materials such as polyethersulfone (PES) film, polyetheretherketone (PEEK) film, polyetherimide (PEI) film, polyimide (PI) film, polyester naphthalate (PEN), polycarbonate (PC) Can be mentioned.
In particular, in this step, it is preferable to use the resin film substrate. This is because a dye-sensitized solar cell having flexibility according to the present invention can be manufactured by the above-mentioned base material being a resin film base material. In addition, in the conventional method for forming an electrolyte layer using capillary action, when a flexible material such as a resin film substrate is used as the substrate, the substrate is formed at the time of injection of the electrolyte layer forming composition. Although there was a problem of bending, according to the present invention, there is no such problem. Even when a resin film substrate is used, a dye-sensitized solar cell substrate, a counter electrode substrate, This is because it is possible to manufacture a dye-sensitized solar cell in which are arranged at uniform intervals in a short time.

  Furthermore, it is preferable to use a biaxially stretched polyethylene terephthalate film (PET), polyester naphthalate (PEN), or polycarbonate (PC) among the resin film base materials in this step.

b. First Electrode Layer Next, the first electrode layer used for the dye-sensitized solar cell substrate will be described. The first electrode layer is made of a metal oxide.

  The metal oxide constituting the first electrode layer is not particularly limited as long as it is excellent in conductivity and exhibits resistance to a redox pair described later. In particular, in this step, it is preferable to use a material having excellent sunlight permeability. Since the dye-sensitized solar cell produced by the present invention is usually used in a mode of receiving sunlight from the base material side, it is produced by the present invention when the metal oxide has poor sunlight transmittance. This is because the power generation efficiency of the dye-sensitized solar cell is impaired.

Examples of the metal oxide having excellent sunlight permeability include SnO ₂ , ITO, IZO, and ZnO. In particular, in this step, it is preferable to use fluorine-doped SnO ₂ (hereinafter referred to as FTO) or ITO. This is because FTO and ITO are excellent in both conductivity and sunlight permeability.

  The first electrode layer used in this step may have a single layer structure, or may have a configuration in which a plurality of layers are stacked. Examples of the configuration in which a plurality of layers are stacked include a configuration in which a layer made of ITO and a layer made of FTO are stacked.

c. Next, the porous layer used for the dye-sensitized solar cell substrate will be described. The porous layer contains metal oxide semiconductor fine particles having a dye sensitizer adsorbed on the surface.

i. Metal Oxide Semiconductor Fine Particles The metal oxide semiconductor fine particles contained in the porous layer will be described. The metal oxide semiconductor fine particles are not particularly limited as long as they exhibit a desired energy conversion efficiency. Examples of such metal oxide semiconductor fine particles include TiO ₂ , ZnO, SnO ₂ , ITO, ZrO ₂ , MgO, Al ₂ O ₃ , CeO ₂ , Bi ₂ O ₃ , Mn ₃ O ₄ , and Y ₂ O _3. , WO ₃ , Ta ₂ O ₅ , Nb ₂ O ₅ , La ₂ O _{3 and the} like. In particular, in this step, it is most preferable to use TiO ₂ as the metal oxide semiconductor fine particles.

  The particle size of the metal oxide semiconductor fine particles is not particularly limited as long as a desired surface area can be obtained in the porous layer, but is usually preferably in the range of 1 nm to 10 μm, particularly 10 nm to It is preferable to be in the range of 1000 nm. This is because, if it is smaller than the above range, the respective metal oxide semiconductor fine particles may aggregate to form secondary particles. On the other hand, if it is larger than the above range, not only the porous layer becomes thicker, but also the porosity of the porous layer, that is, the specific surface area decreases, so that the dye sensitizer is sufficient for photoelectric conversion into the porous layer This is because it may not be possible to carry the.

  In this step, it is preferable to use a mixture of a plurality of metal oxide semiconductor particles having different particle diameters as the metal oxide semiconductor particles. This is because by using a mixture of metal oxide semiconductor particles having different particle sizes, the light scattering effect in the porous layer can be enhanced, so that light absorption by the dye sensitizer can be performed efficiently. .

ii. Dye sensitizer The dye sensitizer adsorbed on the surface of the metal oxide semiconductor fine particles will be described. The dye sensitizer is not particularly limited as long as it can generate an electromotive force by absorbing light. Examples of such a dye sensitizer include organic dyes and metal complex dyes.

  Examples of the organic dye include acridine dyes, azo dyes, indigo dyes, quinone dyes, coumarin dyes, merocyanine dyes, and phenylxanthene dyes. Among these organic dyes, a coumarin dye is preferably used in this step.

  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.

The porous layer may be composed of a single layer or may be composed of a plurality of layers laminated. As the structure in which the plurality of layers are laminated, any structure can be appropriately selected and employed according to the method for producing the dye-sensitized solar cell substrate used in the present invention.
A configuration comprising an oxide semiconductor layer formed on the first electrode layer and an intervening layer formed on the oxide semiconductor layer and having a higher porosity than the oxide semiconductor layer; A structure in which a layer made of metal oxide semiconductor fine particles having a small particle size is stacked on a layer made of metal oxide semiconductor fine particles having a large particle size can be given.
In particular, this step includes an oxide semiconductor layer formed on the first electrode layer and an intervening layer formed on the oxide semiconductor layer and having a higher porosity than the oxide semiconductor layer. A two-layer structure is preferable. This is because, when the porous layer has such a two-layer structure, for example, it becomes easy to produce a dye-sensitized solar cell substrate used in the present invention by a transfer method.

  The case where the porous layer has a two-layer structure of the oxide semiconductor layer and the intervening layer will be described with reference to the drawings. FIG. 4 is a schematic cross-sectional view showing an example where the porous layer has a two-layer structure of an oxide semiconductor layer and an intervening layer. As illustrated in FIG. 4, the dye-sensitized solar cell substrate 10 ″ used in this step includes an oxide semiconductor layer 13 a in which the porous layer 13 is formed on the first electrode layer 12, and the above-described process. An intervening layer 13b formed over the oxide semiconductor layer 13a may be stacked. In such an example, the intervening layer 13b has a higher porosity than the oxide semiconductor layer 13a.

d. Adhesive Layer The adhesive layer used for the dye-sensitized solar cell substrate will be described. The adhesive layer is made of a resin that adheres the base material and the first electrode layer. For example, when the dye-sensitized solar cell substrate is produced using a transfer method, a porous layer described later is used. It has a function of improving the transferability of.

  The resin used for the adhesive layer in the present invention is not particularly limited as long as it can adhere the substrate and the first electrode layer with a desired adhesive force. Examples of such resins include thermoplastic resins, thermosetting resins, and active radiation curable resins. Among these, in the present invention, it is preferable to use a thermoplastic resin as the resin.

  The thermoplastic resin used in the present invention preferably has a melting point in the range of 50 ° C. to 200 ° C., particularly preferably in the range of 60 ° C. to 180 ° C., particularly 65 ° C. to 150 ° C. It is preferable to be within the range. When the dye-sensitized solar cell substrate is prepared by a transfer method, the base material and the first electrode layer are thermally fused with the thermoplastic resin, but the melting point of the thermoplastic resin is in the above range. If the temperature is higher than that, the heating temperature at the time of heat-sealing becomes high, and the above-described base material and the like may be damaged by heat. Also, if the melting point is lower than the above range, when the dye-sensitized solar cell produced according to the present invention is used outdoors, the adhesive layer melts depending on the use environment, resulting in a decrease in power generation efficiency. Because there is a risk of doing.

  Specific examples of the thermoplastic resin include polyethylene, polypropylene, polyisobutylene, polystyrene, polyolefin such as ethylene-propylene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethyl cellulose, cellulose triacetate, etc. Cellulose derivatives, copolymers of poly (meth) acrylic acid and esters thereof, polyvinyl acetals such as polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyacetal, polyamide, polyimide, nylon, polyester resin, urethane resin, epoxy resin, silicone Examples thereof include resins and fluororesins. Of these, polyolefins, ethylene-vinyl acetate copolymers, urethane resins, epoxy resins, silane-modified resins, and acid-modified resins are preferable from the viewpoints of adhesiveness, resistance to an electrolytic solution, light transmittance, and transferability.

  In addition, as another example of the thermoplastic resin, for example, homopolymers of α-olefins having about 2 to 8 carbon atoms such as ethylene, propylene, 1-butene, the α-olefins and ethylene, propylene, 1 Other α-olefins having about 2 to 20 carbon atoms such as -butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, Mention may be made of copolymers with vinyl acetate, (meth) acrylic acid, (meth) acrylic acid esters, and the like, (anhydrous) maleic acid-modified resins, silane-modified resins, olefin elastomers and other polyolefin compounds.

  The thermoplastic resin used in this step is a modified polyolefin, particularly a modified ethylene resin (for example, a silane-modified resin composed of a copolymer of an ethylenically unsaturated silane compound and a polyolefin compound, from the viewpoint of adhesiveness among the above resins, Ethylene copolymers such as ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer) are preferred, and the case where a silane-modified resin is used as the adhesive layer is most preferred. This is because the adhesive force exhibited by the adhesive layer can be further strengthened by using the silane-modified resin.

In this step, it is preferable to use a copolymer of a polyolefin compound and an ethylenically unsaturated silane compound among the silane-modified resins. By using such a copolymer, for example, it is easy to adjust various physical properties of the silane-modified resin within a suitable range according to the method for producing the dye-sensitized solar cell substrate used in the present invention. Because it becomes.
Here, in this step, the copolymer may or may not be crosslinked with a silanol catalyst.

  Examples of the polyolefin compound used in the copolymer include homopolymers of α-olefins having about 2 to 8 carbon atoms such as ethylene, propylene, 1-butene, the α-olefins and ethylene, propylene, 1-butene, Other α-olefins having about 2 to 20 carbon atoms such as 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, vinyl acetate, Examples include (meth) acrylic acid, copolymers with (meth) acrylic acid esters, and the like. Specifically, for example, low / medium / high-density polyethylene (branched or linear) ethylene single weight Polymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene -Vinyl acetate Copolymers, ethylene resins such as ethylene- (meth) acrylic acid copolymers, ethylene- (meth) ethyl acrylate copolymers, propylene homopolymers, propylene-ethylene copolymers, propylene-ethylene-1- Examples include propylene resins such as butene copolymers, and 1-butene resins such as 1-butene homopolymers, 1-butene-ethylene copolymers, and 1-butene-propylene copolymers. Of these, a polyethylene resin is preferred in this step.

  The ethylenically unsaturated silane compound used in the copolymer of the polyolefin compound and the ethylenically unsaturated silane compound is not particularly limited as long as it can be polymerized with the polymerization polyethylene to form a thermoplastic resin. Examples of such ethylenically unsaturated silane compounds include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane, vinyl tributoxy silane, vinyl triopentoxy silane, vinyl triphenoxy silane, vinyl tribenzyloxy silane, vinyl It is preferably at least one selected from the group consisting of trimethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, and vinyltricarboxysilane.

  The copolymer of the polyolefin compound and the ethylenically unsaturated silane compound may be any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer. In particular, in this step, a graft copolymer is preferable, and a graft copolymer obtained by polymerizing a main chain of polyethylene for polymerization and an ethylenically unsaturated silane compound as a side chain is more preferable. This is because such a graft copolymer has a higher degree of freedom of silanol groups that contribute to the adhesive strength, and thus can further strengthen the adhesive strength of the adhesive layer.

  The method for producing the graft copolymer of the polyolefin compound and the ethylenically unsaturated silane compound is not particularly limited as long as it can obtain a desired yield, and can be produced by a known polymerization means. Can do. In particular, in this step, a method of obtaining a graft copolymer by heating and mixing a silane-modified resin composition comprising the polyolefin compound, the ethylenically unsaturated silane compound, and a free radical generator is preferable. . This is because such a method makes it easy to obtain the graft copolymer in a high yield.

  The adhesive layer may contain a compound other than the silane-modified resin as necessary. In this step, it is preferable to use a thermoplastic resin as such another compound, and it is particularly preferable to use a polyolefin compound (hereinafter referred to as an additive polyolefin compound). Further, when a copolymer of a polyolefin compound and an ethylenically unsaturated silane compound is used as the silane-modified resin contained in the adhesive layer, the polyolefin used in the copolymer as such a polyolefin compound for addition It is preferable to use a compound and a compound.

  Furthermore, the adhesive layer used in this step preferably contains at least one additive selected from the group consisting of a light stabilizer, an ultraviolet absorber, a heat stabilizer, and an antioxidant. By including these additives, it is possible to obtain a long-term stable mechanical strength, yellowing prevention effect, cracking prevention effect, and workability. Moreover, you may contain a crosslinking agent, a dispersing agent, a leveling agent, a plasticizer, an antifoamer, etc. besides the above.

e. Next, the manufacturing method of the board | substrate for dye-sensitized solar cells used for this process is demonstrated. The dye-sensitized solar cell substrate includes, for example, a porous layer forming step of forming a porous layer on a heat-resistant substrate, and a first electrode layer forming step of forming a first electrode layer on the porous layer. A base material forming step of laminating a base material on the first electrode layer, and a heat resistant substrate-attached laminate forming step of producing a heat resistant substrate-attached laminate,
A heat-resistant substrate peeling step for producing an oxide semiconductor electrode by peeling the heat-resistant substrate of the laminate with a heat-resistant substrate from the porous layer;
It can be produced by a dye sensitizer carrying step for carrying a dye sensitizer on the porous layer of the oxide semiconductor electrode.
Here, as a specific method in each of the above steps, for example, a generally known method as a method for producing a dye-sensitized solar cell substrate such as the method described in JP-A-2005-166648 can be used. Therefore, detailed description is omitted here.

(4) Counter electrode base material Next, the counter electrode base material used for this process is demonstrated. The counter electrode base material used for this process has a counter base material and the 2nd electrode layer formed on the said counter base material. In addition, the counter electrode base material used in this step may include other configurations other than those described above as necessary. Examples of such other layers include a catalyst layer. In this step, by forming a catalyst layer on the second electrode layer, the dye-sensitized solar cell produced by this step can be made more excellent in power generation efficiency. Examples of the catalyst layer include, but are not limited to, an embodiment in which Pt is vapor-deposited on the second electrode layer.

  The second electrode layer is the same as that used for the first electrode layer of the dye-sensitized solar cell substrate, and the description thereof is omitted here. Moreover, since it is the same as that used for the base material of the said board | substrate for dye-sensitized solar cells as said opposing base material, description here is abbreviate | omitted.

  The counter electrode substrate can be prepared by forming the second electrode layer on the counter substrate, but the method for forming the second electrode layer on the counter substrate is not particularly limited and is a general method. Can be used.

2. Electrolyte Layer Formation Step Next, the electrolyte layer formation step in the present invention will be described. This step is a step of forming an electrolyte layer by injecting a composition for forming an electrolyte layer containing an oxidation-reduction pair into the inside of the sealing material formed in a frame shape by the sealing material forming step. Therefore, in this step, when the sealing material is formed on the first electrode layer of the dye-sensitized solar cell substrate in the sealing material forming step, an electrolyte layer is formed on the first electrode layer. On the other hand, when the sealing material is formed on the second electrode layer of the counter electrode base material, the electrolyte layer is formed on the second electrode layer.

(1) Composition for forming an electrolyte layer The composition for forming an electrolyte layer used in this step will be described. The composition for forming an electrolyte layer used in this step contains a redox couple, and usually comprises a redox couple and a solvent that dissolves the redox couple.

The redox couple used for the composition for forming an electrolyte layer will be described. As said oxidation-reduction pair, what is generally used for the electrolyte layer of a dye-sensitized solar cell can be especially used without a restriction | limiting. In particular, in this step, it is preferable to use a combination of iodine and iodide and a combination of bromine and bromide as the redox pair.
As a combination of the iodine and iodide, for example, it can be cited LiI, NaI, KI, and metal iodide such as CaI _2, a combination of _{I 2.}
As the combination of the above bromine and bromide, for example, it can be cited LiBr, NaBr, KBr, and metal bromide such as CaBr _2, a combination of Br _2.

  The solvent used in the electrolyte layer forming composition is not particularly limited as long as it can dissolve the redox couple at a desired concentration. Examples of such a solvent include acetonitrile, methoxyacetonitrile, propylene carbonate, and the like.

An ionic liquid may be used as the solvent. Since the ionic liquid has high viscosity, when using the conventional method using the capillary phenomenon as a method for forming the electrolyte layer, there is a problem that it takes too much time for injection and lacks productivity. Regardless of the viscosity of the electrolyte layer forming composition, it is possible to produce a dye-sensitized solar cell in a short time. For this reason, even if it is a case where an ionic liquid is used as the said solvent in this invention, a dye-sensitized solar cell can be manufactured in a short time. As such an ionic liquid, for example, an ionic liquid having an imidazolium salt as a cation can be exemplified.
When an ionic liquid is used as the solvent, a nanocomposite gel in which nanoparticles are dispersed in the ionic liquid can be used as the composition for forming an electrolyte layer in this step.

  The composition for forming an electrolyte layer in this step may contain other compounds other than the redox couple. Examples of such other compounds include additives such as a crosslinking agent, a photopolymerization initiator, a thickener, and a room temperature molten salt.

In the composition for forming an electrolyte layer used in this step, the distance between the two is adjusted when the dye-sensitized solar cell substrate and the counter electrode base material are bonded in the substrate bonding step described later. A spacer may be included. Even when a large-area dye-sensitized solar cell is produced according to the present invention by including such a spacer in the electrolyte layer forming composition, the dye-sensitized solar cell is used in the substrate bonding step described later. This is because it becomes easy to bond the working substrate and the counter electrode base material at a uniform interval.
Moreover, the electrolyte layer formed by this process contains a spacer by making the said composition for electrolyte layer formation contain a spacer. For this reason, a flexible dye-sensitized solar cell having flexibility according to the present invention is manufactured by using the dye-sensitized solar cell substrate and the counter electrode base material having flexibility. However, when the dye-sensitized solar cell is bent, the substrate for the dye-sensitized solar cell and the counter electrode base material can be prevented from contacting and short-circuiting.

  As the spacer, it is possible to adjust the distance between the dye-sensitized solar cell substrate and the counter electrode base material within a desired range by being present in the electrolyte layer formed in this step. If it does not specifically limit. Such spacers are the same as those described in the above section “1. Sealing material forming step”, and thus description thereof is omitted here.

  Further, when a spacer is contained in the composition for forming an electrolyte layer, the content thereof depends on the area of the dye-sensitized solar cell substrate manufactured according to the present invention, and the dye-sensitized solar cell substrate described above. If it is in the range which can control the space | interval with said counter electrode base material uniformly, it will not specifically limit. Especially in this process, it is preferable that the said content exists in the range of 0.01 mass%-10 mass%, It is preferable that it is especially in the range of 0.05 mass%-8 mass%, Furthermore, It is preferable to be within the range of 0.1% by mass to 5% by mass. When the spacer content is less than the above range, the dye-sensitized solar cell produced according to the present invention may be produced depending on the strength and area of the dye-sensitized solar cell substrate and counter electrode substrate used in the present invention. This is because when the substrate is bent, the dye-sensitized solar cell substrate and the counter electrode base material may come into contact with each other and short-circuit. Moreover, it is because the electric power generation efficiency of the dye-sensitized solar cell manufactured by this invention may fall when there is more content than the said range.

(2) Method for forming electrolyte layer In this step, the electrolyte layer is formed by injecting the composition for forming an electrolyte layer into the inside of the sealing material formed in a frame shape by the sealing material forming step. The method for injecting the composition for forming an electrolyte layer in the process is not particularly limited as long as it is a method that can inject a desired amount of the composition for forming an electrolyte layer inside the sealing material. A method of dropping the electrolyte layer forming composition inside the sealing material is used.

  Moreover, the injection of the composition for forming an electrolyte layer in this step may be performed under reduced pressure or in an inert atmosphere gas (nitrogen, rare gas). The electrolyte layer forming composition is preferably injected under reduced pressure. By injecting the electrolyte layer forming composition under reduced pressure, air dissolved in the electrolyte layer forming composition can be removed at the time of injection, so that air is mixed into the electrolyte layer formed in this step. This is because this makes it possible to dispose the dye-sensitized solar cell substrate and the counter electrode base material at uniform intervals. In addition, according to such a method, the electrolyte layer forming composition can be formed in a state in which the composition for forming an electrolyte layer is never in contact with the outside air containing moisture, so that moisture is mixed into the electrolyte layer. As a result, it is possible to produce a dye-sensitized solar cell with excellent temporal stability according to the present invention.

In this step, the atmospheric pressure when injecting the composition for forming an electrolyte layer under reduced pressure is preferably in the range of 0.1 Pa to 5 × 10 ⁴ Pa, and in particular, 0.5 Pa to 5 × 10 ^3. It is preferably within the range of Pa, and particularly preferably within the range of 1 Pa to 1 × 10 ³ Pa. When the atmospheric pressure is within the above range, the time-dependent stability of the dye-sensitized solar cell produced by the present invention is deteriorated due to the electrolyte layer coming into contact with the outside air containing moisture. It is because it can prevent more effectively.

  Further, the injection amount of the composition for forming an electrolyte layer in this step is such that the dye sensitizing solar cell substrate and the counter electrode base material are bonded together in the substrate bonding step described later. The amount is such that no gap is generated in a region surrounded by the first electrode layer of the substrate for a sensitive solar cell, the second electrode layer of the counter electrode base material, and the sealing material.

(3) Electrolyte layer The form of the electrolyte layer formed by this step may be a gel or liquid form. When the electrolyte layer is in a gel form, it may be either a physical gel or a chemical gel. 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.

3. Substrate bonding step Next, the substrate bonding step in the present invention will be described. In this step, the electrolyte layer formed in the electrolyte layer formation step is a first electrode layer of the dye-sensitized solar cell substrate, a second electrode layer of the counter electrode substrate, and the first electrode layer or In this step, the dye-sensitized solar cell substrate and the counter electrode base material are bonded together under reduced pressure so that the second electrode layer is sealed with the sealing material formed in a frame shape.
When the dye-sensitized solar cell substrate and the counter electrode base material are bonded together in this step, the electrolyte layer is surrounded by the first electrode layer, the second electrode layer, and the sealing material. However, for example, when other layers are laminated on the first electrode layer and / or the second electrode layer, the porous layer is surrounded by these other layers and the sealing material. It will be.

  The reason why the dye-sensitized solar cell substrate and the counter electrode base material are bonded together under reduced pressure in this step is to eliminate air existing between the two during bonding. Thus, air is sealed between the dye-sensitized solar cell substrate and the counter electrode base material by bonding the dye-sensitized solar cell substrate and the counter electrode base material under reduced pressure. Therefore, the dye-sensitized solar cell produced by the present invention can be made excellent in power generation efficiency.

In this step, the pressure at the time of bonding the dye-sensitized solar cell substrate and the counter electrode substrate is selected according to the area of the dye-sensitized solar cell produced according to the present invention. If it is in the range which can prevent air being enclosed between the board | substrate for sensitized solar cells and the said counter electrode base material, it will not specifically limit. Especially in this process, it is preferable that it exists in the range of 0.1 Pa-5x10 < ⁴ > Pa, and it is preferable that it exists in the range of 0.5 Pa-5x10 < ³ > Pa, especially 1 Pa-1x10. It is preferably within the range of ³ Pa. This is because air pressure can be more effectively prevented from being enclosed between the dye-sensitized solar cell substrate and the counter electrode base material because the atmospheric pressure is within the above range.

  In this step, as a method of bonding the dye-sensitized solar cell substrate and the counter electrode base material, the electrolyte layer is the first electrode layer of the dye-sensitized solar cell substrate, A method capable of being bonded so as to be disposed so as to be sealed by the second electrode layer of the electrode base material and the sealing material formed in a frame shape on the first electrode layer or the second electrode layer. There is no particular limitation. As such a method, for example, after bonding under reduced pressure, a method of gradually releasing to atmospheric pressure, and after bonding under reduced pressure, a fixing process is performed in a substrate fixing step described later. And then gradually releasing the pressure to atmospheric pressure. In addition, as a method of bonding, bonding can be performed by a generally used method such as pressurization, and continuous pressurization may be performed when performing immobilization in a substrate immobilization process described later. Is possible.

4). Substrate fixing step Next, the substrate fixing step in the present invention will be described. This step is a step of fixing the dye-sensitized solar cell substrate and the counter electrode base material with a sealing material. That is, in this step, the dye-sensitized solar cell substrate bonded in the substrate bonding step and the pair are subjected to an immobilization treatment that causes the adhesive resin constituting the sealing material to exhibit adhesiveness. In this step, the electrode base material is bonded and fixed via the sealing material.

The immobilization treatment carried out in this step is a treatment for developing an adhesive property for adhering the dye-sensitized solar cell substrate and the counter electrode base material to an adhesive resin constituting the sealing material. In this step, the dye-sensitized solar cell substrate and the counter electrode base material are fixed by performing such an immobilization treatment. The immobilization treatment performed in this step is performed by using the sealing material. What is necessary is just to change suitably according to the kind of adhesive resin which comprises.
For example, when the adhesive resin is the thermoplastic resin, the fixing treatment may be performed by heating to a temperature higher than the melting point of the thermoplastic resin, and the adhesive resin may be heated. In the case of a curable resin, it is only necessary to perform a heat treatment for heating to a temperature higher than the curing temperature of the thermosetting resin as the immobilization treatment, and the adhesive resin is the actinic radiation curable resin. In such a case, irradiation with actinic radiation for curing the actinic radiation curable resin may be performed as the immobilization treatment.

5). Next, the dye-sensitized solar cell produced by the present invention will be described. The dye-sensitized solar cell produced by the present invention includes a base material, a first electrode layer formed on the base material, made of a metal oxide, and formed on the first electrode layer, and a dye on the surface. A substrate for a dye-sensitized solar cell having a porous layer containing metal oxide semiconductor fine particles adsorbed with a sensitizer, a counter substrate, and a second electrode layer formed on the counter substrate The counter electrode substrate having the porous layer and the second electrode layer are disposed so as to face each other with an electrolyte layer including a redox pair interposed therebetween, and the electrolyte layer is disposed around the electrolyte layer. The sealing material is formed so as to be sealed. Since such a dye-sensitized solar cell will be described in detail in the section “B. Dye-sensitized solar cell” described later, description thereof is omitted here.

B. Next, the dye-sensitized solar cell of the present invention will be described. The dye-sensitized solar cell of the present invention includes a base material, a first electrode layer formed on the base material and made of a metal oxide, formed on the first electrode layer, and a dye sensitizer on the surface. A substrate for a dye-sensitized solar cell having a porous layer containing metal oxide semiconductor fine particles adsorbed with metal, a counter electrode, and a counter electrode having a second electrode layer formed on the counter substrate A base material is disposed so that the porous layer and the second electrode layer face each other with an electrolyte layer including a redox pair, and the electrolyte layer is sealed around the electrolyte layer. As described above, the sealing material is formed, and the substrate and the counter substrate are not formed with through holes.

Such a dye-sensitized solar cell of the present invention will be described with reference to the drawings. FIG. 5 is a schematic sectional view showing an example of the dye-sensitized solar cell of the present invention. As illustrated in FIG. 5, in the dye-sensitized solar cell 1 of the present invention, the electrolyte layer 40 is sandwiched between the dye-sensitized solar cell substrate 10 and the counter electrode base material 20. The electrolyte layer 40 is sealed by a sealing material 30 formed around the periphery.
Here, the substrate 10 for dye-sensitized solar cell includes a porous material including a first electrode layer 12 made of a metal oxide and a metal oxide semiconductor fine particle having a dye-sensitized agent adsorbed on the surface thereof on a base material 11. The material layer 13 has a structure laminated in this order.
The counter electrode base material 20 has a configuration in which the second electrode layer is laminated on the counter base material 21.
In such an example, the dye-sensitized solar cell 1 of the present invention is characterized in that no through hole is formed in the base material 11 and the counter base material 21.

  According to the present invention, the through-holes are not formed in the base material and the counter base material, so that the dye-sensitized solar cell of the present invention can be used for electrolyte leakage, volatilization, intrusion of moisture from the outside, and the like. Therefore, a dye-sensitized solar cell excellent in durability can be obtained.

  In the present invention, “the through hole is not formed” does not only mean that the through hole opened in the base material and the counter base material is not formed, but once formed. It also means that the through hole is closed and a closed through hole is not formed.

  The dye-sensitized solar cell of the present invention includes a porous layer of the dye-sensitized solar cell substrate, a second electrode base material of the counter electrode base material, and the like. It may have a configuration in which a plurality of cells are connected to a dye-sensitized solar cell substrate and a counter electrode base material. This is because by having such a configuration, the dye-sensitized solar cell of the present invention can have a high electromotive force.

  An example of a dye-sensitized solar cell having such a configuration will be described with reference to the drawings. FIG. 6 is a schematic cross-sectional view showing an example where the dye-sensitized solar cell of the present invention has a configuration in which a plurality of cells are connected. As illustrated in FIG. 6, the dye-sensitized solar cell 2 of the present invention includes the first electrode layer 12, the porous layer 13, and the counter electrode base material 20 included in the dye-sensitized solar cell substrate 10. By patterning the second electrode layer 22, a plurality of cells C are formed on the pair of dye-sensitized solar cell substrate 10 and counter electrode base material 20, and these cells C are connected by wiring 50. It may have the structure which was made. The example shown in FIG. 6 has a configuration in which three cells C are connected.

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

  Further, the dye-sensitized solar cell substrate used in the dye-sensitized solar cell of the present invention may be one in which an adhesive layer is formed between the base material and the first electrode layer. . This is because such a dye-sensitized solar cell substrate can be easily produced by a transfer method.

  In addition, about each structure of the dye-sensitized solar cell of this invention, since it is the same as that of what was described in the said "A. manufacturing method of a dye-sensitized solar cell", description here is abbreviate | omitted. .

  The method for producing the dye-sensitized solar cell of the present invention is not particularly limited as long as it is a method capable of producing a dye-sensitized solar cell having the above-described configuration. As such a production method, the method described in the section “A. Production method of dye-sensitized solar cell” can be most preferably used.

  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.

(1) Example 1
(Preparation of dye-sensitized solar cell electrode substrate)
As a base material and a first electrode layer, a transparent conductive film (113B-125N manufactured by Tobi Co., Ltd., surface resistance value 13Ω / □) in which an ITO film was formed on a polyethylene terephthalate film substrate was prepared. A titanium oxide paste (PECC01-06 manufactured by Pexel Technologies Co., Ltd.) was applied to the first electrode layer made of the ITO film by a doctor blade method, and then dried at 120 ° C. for 30 minutes to obtain a large number of metal oxide semiconductor fine particles (TiO 2). A porous layer having a film thickness of 8 μm formed as a porous body with ₂ fine particles was formed, thereby obtaining an oxide semiconductor electrode.

Next, a dye obtained by dissolving a ruthenium complex (PECD07 manufactured by Pexel Technologies Co., Ltd.) as a dye sensitizer in a 1: 1 solution of acetonitrile and tert-butyl alcohol in a volume ratio of 3 × 10 −4 mol / L. A supporting coating solution was prepared, and the oxide semiconductor electrode was immersed in the coating solution, followed by stirring at 40 ° C. for 1 hour. Thereafter, the oxide semiconductor electrode was lifted from the dye-supporting coating solution, and the dye-supporting coating solution adhering to the porous layer was washed with acetonitrile and then air-dried. As a result, the sensitizing dye was supported on the surface of the metal oxide semiconductor fine particles (TiO ₂ fine particles) contained in the porous layer.

  Further, the porous layer was trimmed so as to be a 10 cm × 10 cm square when viewed in plan to obtain a dye-sensitized solar cell electrode substrate (hereinafter referred to as electrode substrate A) having a substrate size of 120 mm □. .

(Preparation of counter electrode substrate)
As the counter substrate and the second electrode layer, a transparent conductive film (113B-125N manufactured by Tobi Co., Ltd., surface resistance value 13Ω / □) in which an ITO film is formed on a polyethylene terephthalate film substrate is used, and a platinum thin film is formed on the ITO film. A counter electrode substrate having a size of 120 mm □ was obtained by forming (film thickness 300 nm) by a sputtering method.

(Preparation of dye-sensitized solar cell)
A composition for forming an electrolyte layer was prepared by dissolving 0.5 mol / L of lithium iodide, 0.05 mol / L of iodine, and 0.5 mol / L of tert-butylpyridine in propylene carbonate.
Next, the above-mentioned dye-sensitized solar cell electrode substrate is mounted on a support base equipped with an electrostatic adsorption mechanism, adsorbed, and silica fine particles having an average particle size of 15 μm are enclosed by a dispenser device so as to surround the porous layer. The sealing material which consists of fluorine-type thermosetting resin which has a liquid fluorine elastomer as a main component was formed.
Thereafter, the composition for forming an electrolyte layer was injected into a region surrounded by the sealing material with a separately prepared dispenser device under reduced pressure (5 × 10 ² Pa). Then, the said electrode base material for dye-sensitized solar cells was bonded together with the said counter electrode base material adsorbed-supported on the support stand provided with the adsorption mechanism under pressure reduction (10 Pa). After bonding, the sealing material is cured by heating at 100 ° C. for 1 hour as an immobilization treatment, thereby fixing the dye-sensitized solar cell substrate and the counter electrode base material, A sensitized solar cell was produced.

(2) Example 2
A sealing material comprising silica fine particles having an average particle diameter of 15 μm and comprising an acrylic ultraviolet curable resin mainly composed of an acrylate oligomer and an acrylate monomer, and UV irradiation was performed as the immobilization treatment. Produced a dye-sensitized solar cell by the same method as in Example 1.

(3) Example 3
A porous olefin film (thickness: 15 μm) having the same size as the porous layer without including silica fine particles in the sealing material is placed on the porous layer, and the dye-sensitized solar cell substrate and the pair A dye-sensitized solar cell was produced in the same manner as in Example 2 except that the electrode substrate was bonded.

(4) Example 4
A dye-sensitized solar cell was produced in the same manner as in Example 2 except that 1% by mass of silica fine particles having an average particle diameter of 15 μm was dispersed in the composition for forming an electrolyte layer.

(5) Example 5
After dissolving acrylic resin (molecular weight 25000, glass transition temperature 105 ° C.) whose main component is polymethyl methacrylate (BR87 manufactured by Mitsubishi Rayon Co., Ltd.) in a mixed solution of methyl ethyl ketone and toluene (mixing ratio 1: 1) at 10% by mass. 1 mass% of TiO ₂ fine particles having a primary particle diameter of 20 nm (P25 manufactured by Nippon Aerosil Co., Ltd.) were mixed and dispersed using a homogenizer to prepare a coating solution for forming an intervening layer. This intervening layer forming coating solution was applied with a wire bar on a titanium substrate (thickness 150 μm, size 10 cm × 10 cm) prepared as a heat-resistant substrate, and dried to form an intervening layer forming layer.

  Next, Ti Nanoxide D made by Solaronix SA was prepared as a coating liquid for forming an oxide semiconductor layer, and applied to the intervening layer forming layer formed on the titanium substrate with a doctor blade (5 mil). Then, after leaving at room temperature for 20 minutes, it was dried at 100 ° C. for 30 minutes. Thereafter, firing was performed at 500 ° C. for 30 minutes in an atmospheric pressure atmosphere using an electric muffle furnace (P90 manufactured by Denken). As a result, a porous layer formed as a porous body and having a configuration in which an intervening layer and an oxide semiconductor layer were laminated was obtained.

  Next, a coating solution for forming a first electrode layer in which 0.1 mol / L of indium chloride and 0.005 mol / L of tin chloride are dissolved in ethanol is prepared. The porous layer was heated by placing it on a hot plate (400 ° C.) so as to face upward. Thereafter, the first electrode layer-forming coating liquid is sprayed on the heated porous layer with an ultrasonic sprayer to form an ITO film as a transparent electrode with a thickness of 500 nm. A forming laminate was obtained.

  A PET film (Toyobo E5100, thickness 125 μm) is prepared as a substrate, a Surlyn film (DuPont, thickness 30 μm) having a softening point of 80 ° C. is disposed on the PET film as an adhesive layer, and the oxide semiconductor electrode forming laminate The ITO surface of the body and Surlyn film were combined and heat laminated at 130 ° C. Then, the oxide semiconductor layer electrode was obtained by cooling and peeling the substrate to be transferred to transfer the ITO film and the porous layer onto the PET film.

  Next, a dye-sensitized solar cell substrate was prepared by supporting a dye-sensitizer on the porous layer in the same manner as in Example 1.

  Thereafter, a dye-sensitized solar cell was prepared in the same manner as in Example 2 using the dye-sensitized solar cell substrate thus prepared.

(6) Example 6
As the composition for forming an electrolyte layer, 0.5 mol / L of iodine and 0.45 mol / L of N-methylbenzimidazolium are dissolved in 1-methyl-3-propylimidazolium iodide which is an ionic liquid. A dye-sensitized solar cell was produced in the same manner as in Example 2 except that.

(7) Example 7
As the composition for forming an electrolyte layer, 0.5 mol / L of iodine and 0.45 mol / L of N-methylbenzimidazolium are dissolved in 1-methyl-3-propylimidazolium iodide which is an ionic liquid. Except for the above, a dye-sensitized solar cell was produced in the same manner as in Example 5.

(8) Comparative Example 1
A dye-sensitized solar cell substrate and a counter electrode base material were produced in the same manner as in Example 1. Next, an injection hole and a deaeration hole having a diameter of 0.5 mmΦ were previously formed on the diagonal line of the counter electrode base material, and then the dye-sensitized solar cell substrate and the counter electrode base material were designated as Example 2. Bonding was performed using the same sealing material, and ultraviolet irradiation was performed as a fixing treatment.

  Next, liquid injection is performed by injecting the same electrolyte layer forming composition as in Example 1 into the injection hole. After the injection is completed, the injection hole and the deaeration hole are formed with the sealing material. The dye-sensitized solar cell was produced by sealing and immobilizing this with ultraviolet irradiation.

(9) Comparative Example 2
As the composition for forming an electrolyte layer, 0.5 mol / L of iodine and 0.45 mol / L of N-methylbenzimidazolium are dissolved in 1-methyl-3-propylimidazolium iodide which is an ionic liquid. Except for the above, a dye-sensitized solar cell was produced in the same manner as in Comparative Example 1.

(10) Comparative Example 3
A dye-sensitized solar cell substrate and a counter electrode base material were produced in the same manner as in Example 1. Next, after making a 0.5 mmφ injection hole in the counter electrode base material in advance, the dye-sensitized solar cell substrate and the counter electrode base material are bonded and fixed in the same manner as in Comparative Example 1. The treatment was performed.

  Thereafter, the same electrolyte layer forming composition as in Example 1 is injected into the injection hole, and after injection, the pressure is reduced to 133 Pa, the air inside is sucked, and the pressure is gradually released to atmospheric pressure. Injection was performed by replacing the product. Thereafter, the injection hole was sealed with the sealing material, and a dye-sensitized solar cell was produced by irradiating with ultraviolet rays.

(11) Evaluation In the above examples and comparative examples, the time required to encapsulate the electrolyte and the remaining state of bubbles in the encapsulated electrolyte were evaluated. In the evaluation of the bubble remaining state, the evaluation criteria were as follows.
◎: No bubbles left ○: Some bubbles left △: Bubbles left about 5mmΦ

  The evaluation results are shown in Table 1 below. From Table 1, it can be seen that according to the present invention, the electrolyte can be sealed in a short time. Moreover, according to this invention, it turns out that air is hard to be enclosed with an electrolyte layer.

It is the schematic which shows an example of the manufacturing method of the dye-sensitized solar cell of this invention. It is the schematic which shows the other example of the manufacturing method of the dye-sensitized solar cell of this invention. It is a schematic sectional drawing which shows an example of the board | substrate for dye-sensitized solar cells used for this invention. It is a schematic sectional drawing which shows the other example of the board | substrate for dye-sensitized solar cells used for this invention. It is a schematic sectional drawing which shows an example of the dye-sensitized solar cell of this invention. It is a schematic sectional drawing which shows the other example of the dye-sensitized solar cell of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 2 ... Dye-sensitized solar cell 10 ... Dye-sensitized solar cell substrate 11 ... Base material 12 ... 1st electrode layer 13 ... Porous layer 13a ... Oxide semiconductor layer 13b ... Intervening layer 14 ... Adhesion layer 20 ... Counter electrode base material 21 ... Opposing base material 22 ... Second electrode layer 30 ... Sealing material 40 ... Electrolyte layer 50 ... Wiring

Claims (7)

A dye-sensitized solar in which a first electrode layer made of a metal oxide and a porous layer containing metal oxide semiconductor fine particles adsorbed with a dye sensitizer are laminated in this order on a substrate. Using a battery substrate, and a counter electrode base material in which a second electrode layer made of a metal oxide is laminated on a counter base material,
Forming a sealing material on either the first electrode layer or the second electrode layer by forming a sealing material made of an adhesive resin into a frame shape having an inner circumference wider than the outer circumference of the porous layer Process,
An electrolyte layer forming step of forming an electrolyte layer by injecting an electrolyte layer forming composition containing an oxidation-reduction pair into the inside of the sealing material formed in the frame shape;
A substrate for bonding the dye-sensitized solar cell substrate and the counter electrode base material under reduced pressure so that the electrolyte layer is sealed by the first electrode layer, the second electrode layer, and the sealing material; Bonding process;
A substrate fixing step of fixing the dye-sensitized solar cell substrate and the counter electrode base material by the sealing material;
A method for producing a dye-sensitized solar cell, comprising:   The method for producing a dye-sensitized solar cell according to claim 1, wherein the composition for forming an electrolyte layer contains an ionic liquid.   The method for producing a dye-sensitized solar cell according to claim 1 or 2, wherein, in the electrolyte layer forming step, the composition for forming an electrolyte layer is injected under reduced pressure.   The method for producing a dye-sensitized solar cell according to any one of claims 1 to 3, wherein the substrate is a resin film substrate.   The method for producing a dye-sensitized solar cell according to any one of claims 1 to 4, wherein the adhesive resin is a photocurable resin.   The substrate for a dye-sensitized solar cell has an adhesive layer made of a resin between the base material and the first electrode layer. A method for producing a dye-sensitized solar cell according to any one of the claims. A porous material comprising a base material, a first electrode layer formed on the base material and made of a metal oxide, and metal oxide semiconductor fine particles formed on the first electrode layer and adsorbed with a dye sensitizer on the surface An electrolyte layer in which a counter electrode substrate having a substrate for a dye-sensitized solar cell, a counter substrate, and a second electrode layer formed on the counter substrate includes a redox pair The porous layer and the second electrode layer are disposed so as to face each other, and a sealing material is formed around the electrolyte layer so as to seal the electrolyte layer. A dye-sensitized solar cell,
A dye-sensitized solar cell, wherein a through hole is not formed in the base material and the counter base material.

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