JP2011060495A - Manufacturing method for laminated body of dye-sensitized solar cell and electrode laminated body of dye-sensitized solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a laminated body of a dye-sensitized solar cell capable of manufacturing the laminated body of the dye-sensitized solar cell in a simple process, which can produce a dye-sensitized solar cell element having high performance and high current-collecting effect. <P>SOLUTION: The manufacturing method for a laminated body of a dye-sensitized solar cell has a porous layer forming layer formation process of forming a porous layer forming layer including metal oxide semiconductor fine particles and binder resin on a surface opposite to the surface of the metal layer where a thermal decomposition layer is formed with the use of an electrode laminated body for a dye-sensitized solar cell having a metal layer with through-holes formed and made of a metal material, and the thermal decomposition layer formed so as to cover the through-holes of the metal layer and made of a resin material with a thermal decomposition nature; and a calcining process of removing the binder resin in the porous layer forming layer and the thermal decomposition layer by calcining the electrode laminated body of the dye-sensitized solar cell wherein the porous layer forming layer is formed. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a laminate for a dye-sensitized solar cell used for producing a dye-sensitized solar cell element, and a dye sensitization used for producing a laminate for a dye-sensitized solar cell. The present invention relates to an electrode laminate for a sensitive solar cell.

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, as a solar cell that has a small environmental load and can reduce the manufacturing cost, a dye-sensitized solar cell has attracted attention and research and development has 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. 6, 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 base 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. It has the structure formed inside. 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 112 through the external circuit. Conducted to the second electrode layer 122. Thereafter, electricity is generated by returning the electrons to the ground level of the dye sensitizer through the redox pair.

  By the way, at present, in the dye-sensitized solar cell, a transparent conductive film such as ITO or ZnO is used as the first electrode layer from the viewpoint of effective utilization of transmitted light. However, with the expansion of the area of the solar cell, it has been pointed out that there is a problem that sufficient electrical current cannot be collected with the conductivity of ITO or ZnO, leading to performance degradation. That is, since the ITO, ZnO, and the like have a relatively high electric resistance, when the dye-sensitized solar cell having a large area is manufactured, the electric resistance of the first electrode layer is increased. There was a problem in that the performance degradation was significant.

In view of such a problem, a method of forming an auxiliary electrode made of metal wiring or the like so as to be in contact with the first electrode layer is known (Patent Document 1). The purpose of this method is to supplement the conductivity of the first electrode layer and assist current collection by forming an auxiliary electrode having a low electrical resistance so as to be in contact with the first electrode layer.
However, when such an auxiliary electrode is used, there is a problem in that the effective area contributing to power generation is reduced without being exposed to light at the lower portion where the auxiliary electrode is installed. Such problems will be described with reference to the drawings.

  FIG. 7 is a schematic view showing an example of a dye-sensitized solar cell element in which the auxiliary electrode is used. As illustrated in FIG. 7, when the auxiliary electrode 114 is used, it is generally formed between the porous layer 113 and the first electrode layer 112. Here, the dye-sensitized solar cell generally generates power in the porous layer 113 when irradiated with sunlight from at least the first electrode side (direction indicated by X in the figure). When the auxiliary electrode 114 is formed, light irradiation to the porous layer 113 is shielded in the region where the auxiliary electrode 114 is formed. Therefore, the effective area of the porous layer that contributes to power generation There was a problem that would decrease.

Therefore, in recent years, a method of laminating porous metal deposition or mesh metal on a metal oxide layer provided on a transparent substrate has been studied (Patent Document 2). By using this method, it was possible to effectively use light and to collect current using a metal having excellent conductivity.
However, when these methods are used, it is necessary to sinter the metal oxide on the transparent base material in order to obtain high performance, which is unsuitable for flexibility such as a film base material. In addition, there is a method for producing a perforated metal after laminating a metal oxide on a plastic film using a paste that can be fired at low temperature. However, a baking process cannot be added. There was a problem such as having to. As a method of avoiding these problems, there is a method of baking after applying a titanium oxide paste on a metal mesh. However, there are problems such as leakage of the paste from the mesh at the time of applying the paste, and generation of cracks due to the unevenness of the mesh after baking. It was.

JP 2001-283941 A JP 2003-123855 A

  The present invention has been made in view of such problems, and a simple structure of a dye-sensitized solar cell laminate capable of producing a dye-sensitized solar cell element having high performance and current collecting effect is provided. The main object is to provide a method for producing a laminate for a dye-sensitized solar cell that can be produced in a process.

  In order to solve the above-described problems, the present invention provides a metal layer made of a metal material having a through-hole, and a pyrolysis made of a resin material that is formed so as to cover the through-hole of the metal layer and has a thermal decomposability. A porous layer containing metal oxide semiconductor fine particles and a binder resin on the surface of the metal layer opposite to the surface on which the thermal decomposition layer is formed, using a dye-sensitized solar cell electrode laminate having a layer A porous layer forming layer forming step for forming a layer forming layer, and the porous layer forming step by firing the electrode laminate for a dye-sensitized solar cell on which the porous layer forming layer is formed. There is provided a method for producing a laminate for a dye-sensitized solar cell, comprising: a binder resin in an application layer; and a firing step for removing the thermal decomposition layer.

According to the present invention, as the electrode laminate for a dye-sensitized solar cell, one having a configuration in which the pyrolysis layer is laminated on the metal layer in which a through hole is formed is used, and the pyrolysis is performed. When the layer is made of a thermally decomposable resin material, the thermally decomposed layer is thermally decomposed together with the binder resin in the porous layer forming layer in the firing step, and the dye-sensitized solar produced The battery laminate is composed of a metal layer and a porous layer of a porous body formed on the metal layer.
And since the laminated body for dye-sensitized solar cells manufactured in this way becomes a thing in which the porous layer was formed on the said metal layer, it is for dye-sensitized solar cells manufactured by this invention By producing a dye-sensitized solar cell element so that an electrolyte layer is formed on the metal layer side using the laminate, the power generation efficiency can be reduced without reducing the effective area contributing to power generation of the porous layer. A high dye-sensitized solar cell element can be produced. Further, in the dye-sensitized solar cell element thus produced, the metal layer functions as an auxiliary electrode, so that even when the area is increased, a dye-sensitized solar cell element with high power generation efficiency is obtained. Can do.
Furthermore, in the present invention, since the porous layer forming layer is formed on the metal layer in the porous layer forming layer forming step, sufficient baking can be performed in the baking step. It is possible to form a laminate for a dye-sensitized solar cell in which the layer and the porous layer are firmly adhered.
Therefore, according to the present invention, a laminate for a dye-sensitized solar cell capable of producing a dye-sensitized solar cell element having a high performance and a current collecting effect can be manufactured by a simple process. Can do.

  In the present invention, the electrode laminate for a dye-sensitized solar cell has a support substrate having self-supporting property on the thermal decomposition layer, and the firing step is performed by the dye-sensitized solar cell. It is preferable that firing be performed after the support substrate is peeled from the electrode laminate. When a layer having insufficient self-supporting property is used as the pyrolysis layer, the pyrolysis layer is formed when the porous layer formation layer is formed on the metal layer in the porous layer formation layer formation step. This is because the porous layer forming layer may be deformed and become non-uniform, and this problem can be remarkably suppressed by using the support substrate.

  The present invention also provides a metal layer in which a through hole is formed, a thermal decomposition layer that is formed so as to cover the through hole of the metal layer and is made of a thermally decomposable resin, and the thermal decomposition layer of the metal layer. An electrode laminate for a dye-sensitized solar cell, comprising a porous layer forming layer containing metal oxide semiconductor fine particles and a binder resin formed on a surface opposite to the surface on which the metal oxide is formed I will provide a. Moreover, it is preferable that the laminated body for dye-sensitized solar cells of this invention has a support substrate which has a self-supporting property on the said thermal decomposition layer.

  The electrode laminate for a dye-sensitized solar cell of the present invention is a laminate for a dye-sensitized solar cell capable of producing a dye-sensitized solar cell element having high performance and current collecting effect by firing the electrode laminate. It has the advantage that the body can be manufactured in a simple process.

  The method for producing a laminate for a dye-sensitized solar cell according to the present invention is a simple method of preparing a laminate for a dye-sensitized solar cell capable of producing a dye-sensitized solar cell element having high performance and current collecting effect. There exists an effect that it can manufacture in a process.

It is the schematic which shows an example of the manufacturing method of the laminated body for dye-sensitized solar cells of this invention. It is a schematic sectional drawing which shows an example of the dye-sensitized solar cell element produced using the laminated body for dye-sensitized solar cells manufactured by this invention. It is a schematic sectional drawing which shows an example of the electrode laminated body for dye-sensitized solar cells used for this invention. It is a schematic sectional drawing which shows an example of the electrode laminated body for dye-sensitized solar cells of this invention. It is a schematic sectional drawing which shows the other of the electrode laminated body for dye-sensitized solar cells of this invention. It is the schematic which shows the example of a general dye-sensitized solar cell. It is the schematic which shows the example of the conventional dye-sensitized solar cell.

The present invention relates to a method for producing a laminate for a dye-sensitized solar cell and a laminate for a dye-sensitized solar cell electrode.
Hereinafter, each of these inventions will be described in order.

A. First, the manufacturing method of the laminated body for dye-sensitized solar cells of this invention is demonstrated.
As described above, the method for producing a laminate for a dye-sensitized solar cell according to the present invention is formed so that a through hole is formed and a metal layer made of a metal material and the through hole of the metal layer are covered. Using a dye-sensitized solar cell electrode laminate having a thermal decomposition layer made of a thermally decomposable resin material, metal oxidation is performed on the surface of the metal layer opposite to the surface on which the thermal decomposition layer is formed. Porous layer forming layer forming step for forming a porous layer forming layer containing fine semiconductor particles and a binder resin, and the dye-sensitized solar cell electrode laminate in which the porous layer forming layer is formed By firing the binder resin in the porous layer forming layer and the firing step of removing the thermal decomposition layer.

A method for producing such a laminate for 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 laminate for a dye-sensitized solar cell of the present invention. As illustrated in FIG. 1, the method for producing a laminate for a dye-sensitized solar cell according to the present invention includes a metal layer 1 made of a metal material in which a through hole H is formed, and the through hole H of the metal layer 1. The electrode layered body 10a for a dye-sensitized solar cell having a thermal decomposition layer 2 made of a thermally decomposable resin material is used (FIG. 1 (a)), and the metal layer 1 described above is used. A porous layer forming layer forming step of forming a porous layer forming layer 3 containing metal oxide semiconductor fine particles and a binder resin on the surface opposite to the surface on which the pyrolysis layer 2 is formed (FIG. 1 ( b)) and a firing step (FIG. 1C) for firing the dye-sensitized solar cell electrode laminate 10 b on which the porous layer forming layer 3 is formed.
Here, since the thermal decomposition layer 2 is made of a thermally decomposable resin material, in the baking step (FIG. 1 (c)), the binder resin in the porous layer forming layer 3 and the above The pyrolysis layer 2 is removed. Therefore, the laminate 10 for a dye-sensitized solar cell produced according to the present invention has the metal layer 1 and the porous layer 3 ′ of the porous body formed on the metal layer 1. (FIG. 1 (c)).

The laminate for a dye-sensitized solar cell produced by the present invention is used for producing a dye-sensitized solar cell element. FIG. 2 is a schematic cross-sectional view showing an example of a dye-sensitized solar cell element produced using the laminate for a dye-sensitized solar cell produced by the present invention. As illustrated in FIG. 2, the dye-sensitized solar cell element 30 in which the dye-sensitized solar cell laminate 10 manufactured according to the present invention is used is usually a dye-sensitized solar cell manufactured according to the present invention. The counter electrode 20 for a dye-sensitized solar cell having the battery stack 10, the counter base material 21, and the counter electrode layer 22 formed on the counter base material 21 includes the metal layer 1 and the counter electrode layer 22. Are arranged so as to face each other, and an electrolyte layer 31 is formed between the dye-sensitized solar cell laminate 10 and the dye-sensitized solar cell counter electrode 20.
Here, as illustrated in FIG. 2, in the dye-sensitized solar cell element 30 produced using the laminate 10 for a dye-sensitized solar cell produced according to the present invention, the porous layer 3 ′ described above is used. It is preferable that the transparent substrate 33 is disposed thereon. This is because a dye-sensitized solar cell element with high power generation efficiency can be produced without reducing the effective area contributing to power generation of the porous layer due to the presence of the metal layer 1.
In FIG. 2, 32 represents a sealing material.

According to the present invention, as the electrode laminate for a dye-sensitized solar cell, one having a configuration in which the pyrolysis layer is laminated on the metal layer in which a through hole is formed is used, and the pyrolysis is performed. When the layer is made of a thermally decomposable resin material, the thermally decomposed layer is thermally decomposed together with the binder resin in the porous layer forming layer in the firing step, and the dye-sensitized solar produced The battery laminate is composed of a metal layer and a porous layer of a porous body formed on the metal layer.
And since the laminated body for dye-sensitized solar cells manufactured in this way becomes a thing in which the porous layer was formed on the said metal layer, it is for dye-sensitized solar cells manufactured by this invention By producing a dye-sensitized solar cell element so that an electrolyte layer is formed on the metal layer side using the laminate, the power generation efficiency can be reduced without reducing the effective area contributing to power generation of the porous layer. A high dye-sensitized solar cell element can be produced. Moreover, in the dye-sensitized solar cell element thus manufactured, the metal layer functions as an auxiliary electrode, so that a dye-sensitized solar cell element having a high current collecting effect can be obtained.
Furthermore, in the present invention, since the porous layer forming layer is formed on the metal layer in the porous layer forming layer forming step, sufficient baking can be performed in the baking step. It is possible to form a laminate for a dye-sensitized solar cell in which the layer and the porous layer are firmly adhered.
In addition to the above, it is difficult to form a layer made of a metal oxide semiconductor in the opening portion of the mesh by the conventional method of applying a paste such as titanium oxide on the metal mesh and baking it. However, according to the present invention, it is possible to form the porous layer also in the opening portion of the metal layer. There is an advantage that you can.
Therefore, according to the present invention, a laminate for a dye-sensitized solar cell capable of producing a dye-sensitized solar cell element having a high performance and a current collecting effect can be manufactured by a simple process. Can do.

The method for producing a laminate for a dye-sensitized solar cell according to the present invention includes at least a porous layer forming layer forming step and the firing step, and has other optional steps as necessary. It may be.
Hereafter, each process used for this invention is demonstrated in order.

1. Porous layer forming layer forming step First, the porous layer forming layer forming step used in the present invention will be described. In this step, a dye sensitization having a metal layer made of a metal material with a through-hole formed therein and a thermal decomposition layer made of a resin material having a heat-decomposability formed so as to cover the through-hole of the metal layer. A porous layer forming layer containing metal oxide semiconductor fine particles and a binder resin is formed on the surface of the metal layer opposite to the surface on which the thermal decomposition layer is formed, using an electrode laminate for a solar cell. It is a process.

(1) Dye-sensitized solar cell electrode laminate The dye-sensitized solar cell electrode laminate used in this step will be described. As described above, the electrode laminate for a dye-sensitized solar cell used in this step has a through hole, is formed so as to cover the metal layer made of a metal material, and the through hole of the metal layer. And a thermal decomposition layer made of a decomposable resin material.

(Metal layer)
The metal layer is made of a metal material that can be used as a current collecting auxiliary electrode when a dye-sensitized solar cell element is produced using the dye-sensitized solar cell laminate manufactured according to the present invention. If it is a thing, it will not specifically limit. Examples of such a metal material include titanium, aluminum, iron, nickel, iron-nickel alloy, copper, copper-nickel alloy, niobium, tungsten, tantalum, chromium, stainless steel alloy, and the like. In this step, a metal layer made of any of these metal materials can be suitably used, but among these, a metal layer made of titanium, aluminum, or a stainless alloy is preferably used. As described above, the laminate for a dye-sensitized solar cell produced according to the present invention is used for producing a dye-sensitized solar cell element in which the metal layer is disposed so as to be in contact with the electrolyte layer. This is because these metal materials have excellent corrosion resistance due to the electrolyte layer.

  The metal layer used in this step is one in which a through hole is formed. However, the shape of the through hole is not particularly limited, and the through hole can be formed with a desired opening ratio. Any shape can be used as long as the electrical resistance is within a predetermined range. Examples of such a shape include a circle, a polygon, a stripe, a skewer, and a spiral.

  Moreover, it does not specifically limit about each magnitude | size of the said through-hole, The shape which can achieve the aperture ratio mentioned later after formation of a through-hole is preferable. The shape of the through hole is not particularly limited, but the opening size is appropriately set within a range that can be formed by a photoetching process according to the plate thickness.

  Furthermore, the aperture ratio of the metal layer, that is, the ratio of the area occupied by the through holes per unit area of the metal layer is determined by using the dye-sensitized solar cell laminate manufactured according to the present invention. When the solar cell element is manufactured, it is not particularly limited as long as the electric resistance that can function as an auxiliary electrode can be maintained, and can be appropriately determined in relation to the thickness of the metal layer. is there. In particular, the opening ratio of the metal layer in this step is preferably in the range of 10% to 90%, more preferably in the range of 20% to 80%, and in the range of 30% to 50%. More preferably it is.

(Pyrolysis layer)
Next, the thermal decomposition layer used for the said electrode laminated body for dye-sensitized solar cells is demonstrated. The thermal decomposition layer is made of a thermally decomposable resin material, and is decomposed and removed in a firing step described later.

The resin material used for the thermal decomposition layer is not particularly limited as long as it has thermal decomposability and can be decomposed and removed in the firing step described later. It is preferable that the thermal decomposition start temperature is higher than the boiling point of the solvent contained in the layer forming coating solution. For this reason, the resin material used in the present invention preferably has a thermal decomposition starting temperature in the range of 200 ° C to 500 ° C, more preferably in the range of 250 ° C to 480 ° C, and more preferably in the range of 300 ° C to 450 ° C. More preferably, it is within the range of ° C.
In addition, the said thermal decomposition start temperature can be calculated | required by measuring thermal decomposition temperature, for example using the automatic TG / DTA simultaneous measuring apparatus DTG-60A of Shimadzu Corporation.

  Examples of the resin material used in the present invention include cellulose resins, polyester resins, polyamide resins, polyacrylate resins, polyacryl resins, polycarbonate resins, polyurethane resins, polyolefin resins, and polyvinyl acetal resins. , Fluorine resin, polyimide resin, polyethylene glycol natural rubber, polyacetal, polyvinyl alcohol, polyacrylamide, polyacrylate, N-vinylacetamide-sodium acrylate copolymer, phenol resin, ionomer resin, melamine resin, Examples thereof include resin materials such as urea resin and alkyd resin, and derivatives thereof. In the present invention, any of these resin materials can be suitably used, and among them, it is particularly preferable to use a polyolefin resin, a cellulose resin, or an ionomer resin.

  In addition, the thickness of the pyrolysis layer in the present invention is not particularly limited as long as it is within a range in which the pyrolysis layer can be decomposed and removed in the baking step described later, and depending on the type of resin material used for the pyrolysis layer. It is determined as appropriate. Among these, the thickness of the pyrolysis layer in the present invention is preferably in the range of 1 μm to 200 μm, more preferably in the range of 5 μm to 80 μm, and particularly preferably in the range of 10 μm to 50 μm.

(Other configurations)
The electrode laminate for a dye-sensitized solar cell used in this step has at least the metal layer and the thermal decomposition layer, but may have any other configuration as necessary. Good. As such an arbitrary configuration, for example, a support substrate which is used by being disposed on the thermal decomposition layer and has a self-supporting property can be mentioned. The use of such a support substrate as an arbitrary configuration has the following advantages. That is, when a layer having insufficient self-supporting property is used as the pyrolysis layer, when the porous layer forming layer is formed on the metal layer in the step, the pyrolysis layer is deformed and formed. Where the porous layer forming layer is likely to be non-uniform, the use of the support substrate has the advantage of eliminating such problems.

  The case where the said support substrate is used for the said electrode laminated body for dye-sensitized solar cells is demonstrated, referring a figure. FIG. 3 is a schematic cross-sectional view showing an example where a support substrate is used in the dye-sensitized solar cell electrode laminate. As exemplified in FIG. 3, the dye-sensitized solar cell electrode laminate 10 a used in this step preferably has a support substrate 4 on the thermal decomposition layer 2.

  The support substrate is not particularly limited as long as it has self-supporting properties. Examples of such a support substrate include glass, a metal plate, a resin film, and the like.

  In addition, when what has the said support substrate is used as an electrode laminated body for dye-sensitized solar cells used for this process, in the baking process mentioned later, after peeling the said support substrate from a thermal decomposition layer, baking Will be done.

(2) Formation of porous layer forming layer Next, a method of forming the porous layer forming layer on the metal layer of the dye-sensitized solar cell electrode laminate in this step will be described.

  Here, the layer for forming a porous layer formed in this step is a porous layer made of a porous body by being baked in a baking step described later. Therefore, in this step, an unfired porous layer forming layer that is not a porous body is formed.

  As a method of forming a porous layer forming layer on the metal layer in this step, a porous body is obtained by containing metal oxide semiconductor fine particles and a binder resin and firing in a firing step described later. The method is not particularly limited as long as it can form a porous layer forming layer. In the present invention, a porous layer forming coating solution containing metal oxide semiconductor fine particles and a binder resin is usually used, and a method of coating this on the metal layer is used.

  The coating liquid for forming the porous layer is not particularly limited as long as it contains the metal oxide semiconductor fine particles and a binder resin that can be decomposed and removed by a firing step described later. Further, in this step, other compounds may be contained depending on the specific method for forming the porous layer forming layer.

The metal oxide semiconductor fine particles used in the porous layer forming coating solution 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, Al ₂ O ₃ , CeO ₂ , Bi ₂ O ₃ , and 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 layer for forming a 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.

The average particle diameter 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 formed after firing is within a desired range, but usually 1 nm. It is preferably within the range of 10 μm, particularly preferably within the range of 10 nm to 1000 nm. If the average particle size is smaller than the above range, the respective metal oxide semiconductor fine particles may aggregate to form secondary particles, and if the average particle size is larger than the above range, the porous material formed after firing This is because not only the layer becomes thicker, but also the porosity of the porous layer, that is, the specific surface area may decrease.
In addition, the said average particle diameter shall mean a primary particle size.

  In the present invention, all of the metal oxide semiconductor fine particles having the same average particle diameter may be used, or two or more kinds of metal oxide semiconductor fine particles having different average particle diameters may be used. Here, since the light scattering effect in the porous layer formed after firing can be enhanced by using the metal oxide semiconductor fine particles having different average particle sizes in combination, for example, the dye-sensitized type produced by the present invention In the dye-sensitized solar cell element produced using the solar cell laminate, there is an advantage that light absorption by the dye sensitizer can be efficiently performed.

  In the present invention, when two or more kinds of metal oxide semiconductor fine particles having different average particle diameters are used, examples of combinations of different average particle diameters include, for example, metal oxide semiconductor fine particles having an average particle diameter in the range of 10 nm to 50 nm. A combination with metal oxide semiconductor fine particles having an average particle diameter in the range of 50 nm to 800 nm can be exemplified.

On the other hand, the binder resin used in the porous layer forming coating solution is not particularly limited as long as it is decomposed and removed in the baking step described later. Examples of such binder resins include cellulose resins, polyester resins, polyamide resins, polyacrylate resins, polyacryl resins, polycarbonate resins, polyurethane resins, polyolefin resins, polyvinyl acetal resins, fluorine In addition to the base resin and polyimide resin, polyhydric alcohols such as polyethylene glycol can be used.
The binder resin used in the present invention preferably has a thermal decomposition starting temperature in the range of 200 ° C to 500 ° C, more preferably in the range of 250 ° C to 480 ° C, and more preferably in the range of 300 ° C to 450 ° C. More preferably, it is in the range.
In addition, the said thermal decomposition start temperature can be calculated | required by measuring thermal decomposition temperature, for example using the automatic TG / DTA simultaneous measuring apparatus DTG-60A of Shimadzu Corporation.

  When a solvent is used for the porous layer forming coating solution, the solvent used is not particularly limited as long as the above-described binder resin can be dissolved. Therefore, the said solvent can be suitably determined according to the kind of binder resin used for the coating liquid for porous layer formation. Specific examples of the solvent used in the present invention include various solvents such as water or methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether, terpineol, dichloromethane, acetone, acetonitrile, and ethyl acetate.

  In this step, a generally known coating method can be used as a method for coating the porous layer forming coating solution on the metal layer, and is not particularly limited. Examples of such coating methods include die coating, gravure coating, gravure reverse coating, roll coating, reverse roll coating, bar coating, blade coating, knife coating, air knife coating, slot die coating, slide die coating, dip coating, and micro bar coating. , Microbar reverse coating, screen printing (rotary method) and the like.

  The thickness of the porous layer forming layer formed in this step is usually preferably in the range of 1 μm to 100 μm, particularly preferably in the range of 5 μm to 30 μm. This is because if the thickness of the layer for forming the porous layer is larger than the above range, the porous layer formed after firing is likely to cause cohesive failure of the porous layer itself and may easily become membrane resistance. . Further, if it is thinner than the above range, it becomes difficult to form a porous layer forming layer having a uniform thickness, for example, it is produced using a laminate for a dye-sensitized solar cell produced by the present invention. In a dye-sensitized solar cell element, the porous layer formed after firing may not be able to obtain sufficient performance because the porous layer containing the dye sensitizer cannot sufficiently absorb sunlight. Because there is.

2. Next, the firing process in the present invention will be described. This step is a step of removing the binder resin and the thermal decomposition layer in the porous body by firing the dye-sensitized solar cell electrode laminate on which the porous layer forming layer is formed. is there.

  The temperature at which the dye-sensitized solar cell electrode laminate is fired in this step is particularly within the range in which the binder resin contained in the porous layer forming layer and the thermal decomposition layer can be decomposed and removed. It is not limited and can be suitably determined according to the thermal decomposition temperature of the binder resin and the resin material used for the thermal decomposition layer. Among these, the firing temperature in this step is preferably in the range of 250 ° C to 550 ° C, more preferably in the range of 350 ° C to 550 ° C, and in the range of 400 ° C to 550 ° C. Further preferred.

  In addition, when the electrode laminate for a dye-sensitized solar cell used in the layer forming step for forming the porous layer is one in which a support substrate is disposed on the thermal decomposition layer, this step is performed as described above. After the substrate is peeled from the thermal decomposition layer, baking is performed.

B. Next, the electrode laminated body for dye-sensitized solar cells of the present invention will be described. As described above, the electrode laminate for a dye-sensitized solar cell of the present invention is formed from a metal layer in which a through hole is formed and a resin having a thermal decomposability formed so as to cover the through hole of the metal layer. And a porous layer forming layer formed on the surface of the metal layer opposite to the surface on which the pyrolysis layer is formed and containing metal oxide semiconductor fine particles and a binder resin. It is a feature.

  Such a dye-sensitized solar cell electrode laminate of the present invention will be described with reference to the drawings. FIG. 4 is a schematic cross-sectional view showing an example of a dye-sensitized solar cell electrode laminate of the present invention. As illustrated in FIG. 4, the electrode laminate 40 for a dye-sensitized solar cell of the present invention is formed so as to cover the metal layer 1 in which a through hole is formed and the through hole of the metal layer 1. A porous layer containing a thermal decomposition layer 2 made of a resin having thermal decomposition property and a surface of the metal layer 1 opposite to the surface on which the thermal decomposition layer 2 is formed and containing metal oxide semiconductor fine particles and a binder resin And a layer 3 for forming a quality layer.

  The electrode laminate for a dye-sensitized solar cell of the present invention is a laminate for a dye-sensitized solar cell capable of producing a dye-sensitized solar cell element having high performance and current collecting effect by firing the electrode laminate. It has the advantage that the body can be manufactured in a simple process.

  The electrode laminate for a dye-sensitized solar cell of the present invention has at least the metal layer and the porous layer forming layer, and may have any other configuration as necessary. . Here, as an arbitrary structure used for this invention, the support substrate which has a self-supporting property arrange | positioned on the said metal layer can be mentioned, for example. The use of such a support substrate as an arbitrary configuration has the following advantages. That is, when a layer having insufficient self-supporting property is used as the thermal decomposition layer, the thermal decomposition is performed when the porous layer forming layer is formed on the metal layer in the porous layer forming layer forming step. There is a possibility that the layer may be deformed and the formed porous layer forming layer may be non-uniform. However, the use of the support substrate has an advantage that such a problem is eliminated.

  The case where the electrode laminate for a dye-sensitized solar cell of the present invention has the support substrate will be described with reference to the drawings. FIG. 5 is a schematic cross-sectional view showing an example in which the support substrate is used in the electrode laminate for a dye-sensitized solar cell of the present invention. As illustrated in FIG. 5, in the dye-sensitized solar cell electrode laminate 40 of the present invention, the support substrate 4 is preferably disposed on the thermal decomposition layer 2.

  About each structure, such as a metal layer, a thermal decomposition layer, a layer for porous layer formation, and a support substrate used for the electrode laminated body for dye-sensitized solar cells of this invention, said "A. dye-sensitized solar cell". Since it is the same as that of the electrode laminated body for dye-sensitized solar cells used in the porous layer forming layer forming step in the section “Method for producing battery laminated body”, description thereof is omitted here.

  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]
Using an SUS304 (made by Nilaco) mesh produced by etching so that the aperture ratio is 30% as a metal layer, with an ethyl cellulose resin (thermal decomposition start temperature 300 ° C.) made into a 30 μm thick film while applying a temperature of 100 ° C. A thermal decomposition layer was formed by heat laminating with 180 μm PET resin. Thereafter, a titanium oxide paste Nanooxide D-SP (manufactured by solaronix) was used as a porous layer forming coating solution, and this was laminated several times by a squeegee method to obtain a 15 μm porous layer forming layer. Thereafter, the PET was peeled off from the resin and baked at 500 ° C.

Then, using the electrode prepared above as a dye sensitizer, a ruthenium complex (Nyes made by Dyesol) was dissolved in a 1: 1 volume ratio solution of acetonitrile and tert-butyl alcohol so that the concentration would be 3 × 10 ⁻⁴ mol / l. It was immersed in the dye-carrying coating solution for 20 hours at room temperature. Next, the pigment-carrying coating solution was pulled up from the pigment-carrying coating solution, washed with acetonitrile, and then air-dried. As a result, a laminate for a dye-sensitized solar cell having a substrate size of 100 × 100 mm in which the dye sensitizer was carried on the surface of the titanium oxide fine particles forming the porous layer was obtained. Thereafter, a PET film was placed so as to cover the porous layer carrying the dye, and the periphery was sealed with a thermoplastic resin.

(Preparation of counter electrode substrate for dye-sensitized solar cell)
A transparent conductive glass (made by Nippon Sheet Glass Co., Ltd.) is used as a counter substrate, and a platinum film (film thickness: 300 nm) is formed as a counter electrode layer on the counter substrate by a sputtering method. A counter electrode for a battery was produced. Thereafter, a hole was drilled near the center of the counter substrate using a drill.

(Electrolyte preparation)
A mixture of 0.6M hexyl metyl imidazolum iodide (Toyama Pharmaceutical), 0.03MI ₂ (Aldrich), and 0.1M n-metyl benzoimidazole (Aldrich) was used.

(Cell assembly)
A thermoplastic film having a thickness of 100 μm was laminated on the counter electrode for the dye-sensitized solar cell, bonded to the electrode, and then an electrolyte was injected under vacuum from the hole of the counter electrode.

(result)
The obtained dye-sensitized solar cell was measured for photoelectric conversion efficiency using a spectral sensitivity meter CEP-2000 (spectrometer) with pseudo-sunlight (100 mW / cm ² , AM (AirMass) 1.5) as a light source. . As a result, the solar cell had a conversion efficiency η = 3.0%.

[Example 2]
Using SUS304 (made by Nilaco) mesh produced by etching so that the aperture ratio is 30% as a metal layer, it is bonded to 180μm PET resin with ethyl cellulose resin (pyrolysis start temperature 300 ° C) dissolved in ethanol and pressed. The pyrolysis layer was formed by drying and fixing. Thereafter, a titanium oxide paste Nanooxide D-SP (manufactured by solaronix) was laminated several times on the mesh as a porous layer forming coating solution by a squeegee method to obtain a porous layer forming layer having a thickness of 15 μm. Thereafter, the PET was peeled off from the thermal decomposition layer and baked at 500 ° C.
A dye-sensitized solar cell was prepared in the same manner as in Example 1 except that the thus prepared dye-sensitized solar cell laminate was used.

(result)
The obtained dye-sensitized solar cell was measured for photoelectric conversion efficiency using a spectral sensitivity meter CEP-2000 (spectrometer) with pseudo-sunlight (100 mW / cm ² , AM (AirMass) 1.5) as a light source. . As a result, the solar cell had a conversion efficiency η = 3.1%.

[Comparative example]
A dye-sensitized solar cell was produced in the same manner as in Example 1 except that the resin was not heat-laminated on a SUS304 (made by Nilaco) mesh.

For the dye-sensitized solar cell thus produced, the photoelectric conversion efficiency was determined by the same method as in Example 1. The conversion efficiency η was 2.5%. In the comparative example, it is considered that the performance was slightly deteriorated because there was no TiO _{2 in} the opening portion of the mesh.

DESCRIPTION OF SYMBOLS 1 ... Metal layer 2 ... Thermal decomposition layer 3 ... Porous layer formation layer 3 '... Porous layer 4 ... Support substrate 10 ... Laminated body for dye-sensitized solar cells 10a, 10b ... Electrode for dye-sensitized solar cells Laminate 20 ... Counter electrode for dye-sensitized solar cell 21 ... Counter substrate 22 ... Counter electrode layer 30 ... Dye-sensitized solar cell element 31 ... Electrolyte layer 32 ... Sealing material 33 ... Transparent substrate 40 ... Dye-sensitized type Solar cell electrode stack H ... Through hole

Claims (4)

For a dye-sensitized solar cell having a metal layer made of a metal material having a through-hole, and a thermal decomposition layer formed to cover the through-hole of the metal layer and made of a thermally decomposable resin Using an electrode stack,
A porous layer forming layer forming step of forming a porous layer forming layer containing metal oxide semiconductor fine particles and a binder resin on the surface opposite to the surface of the metal layer on which the thermal decomposition layer is formed;
And the binder resin in the said layer for porous layer formation, and the said thermal decomposition layer are removed by baking the said electrode laminated body for dye-sensitized solar cells in which the said layer for porous layer formation was formed Firing step,
A method for producing a laminate for a dye-sensitized solar cell, comprising:   The dye-sensitized solar cell electrode laminate has a self-supporting support substrate on the thermal decomposition layer, and the firing step is performed from the dye-sensitized solar cell electrode laminate. The method for producing a laminate for a dye-sensitized solar cell according to claim 1, wherein firing is performed after peeling off the support substrate.   A metal layer in which a through hole is formed, a thermal decomposition layer made of a resin having thermal decomposability formed so as to cover the through hole of the metal layer, and a surface on which the thermal decomposition layer of the metal layer is formed And a porous layer forming layer containing metal oxide semiconductor fine particles and a binder resin, the electrode laminate for a dye-sensitized solar cell.   The electrode laminate for a dye-sensitized solar cell according to claim 3, further comprising a support substrate having self-supporting property on the pyrolysis layer.

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