JP2002367686A - Dye sensitization type solar cell and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solar cell in which transmission of carbon is prevented and the carbon does not directly contact the transparent conductive membrane installed on the photo-electrode side, and, after firing and installation on the solar cell, electrical potential is generated between the photo-electrode and the counter electrode when light is irradiated on it and performs completely as a battery, and which has improved yield of manufacture and improved conversion efficiency. SOLUTION: This is a dye sensitization type solar cell in which a transparent conductive membrane 31 is laminated on a glass substrate 31 and a first photo-electrode 34 made of a dense material is laminated on the transparent conductive membrane 32, and a second photo-electrode 35 made of a porous material is laminated on the first photo-electrode 34, and a separator 36 made of a porous material is laminated on the second photo-electrode 35, and a counter electrode 37 made of a porous carbon layer is laminated on the separator, and a photo-sensitization dye is carried by the above first photo-electrode 34 and the second photo-electrode 35, and an electrolyte is filled between the above transparent conductive membrane 32 and the counter electrode 37. The mean particle size of the constituting particles of the first photo-electrode 34 is smaller than the mean particle size of the constituting particles of the second photo-electrode 35.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dye-sensitized solar cell and a method for manufacturing the same.

[0002]

2. Description of the Related Art The use of energy and electric power has been rapidly increasing due to recent industrial development. As a result, the emission of environmental pollutants such as carbon monoxide has also increased, and has become a considerable amount to protect the global environment. BACKGROUND ART Solar cells that convert solar energy into electricity can produce electric power without directly discharging pollutants, and thus are expected to spread. However, the conventional solar cell using silicon has a problem of high manufacturing cost, and has not yet spread as expected for large-scale electric power.

As a solar cell having a low manufacturing cost in place of a solar cell using silicon, a dye-sensitized solar cell having a photoelectric conversion active material layer in which semiconductor particles carry a dye that absorbs visible light (also referred to as a wet solar cell). ) Is attracting attention. When the dye is irradiated with light, conduction electrons and holes are generated, the conduction electrons move to the semiconductor particles carrying the dye, and the holes receive electrons from the redox species in the contacting electrolyte and disappear. I do. The flow of electrons is generated by these photoelectrochemical reactions, and light energy can be converted into electric energy.

[0004] References relating to dye-sensitized solar cells and modules thereof include AndreausKay, Micae.
l Graetzel's Solar Energy M
materials Solar Cells "(vol.
44 (1996) pp. 99-117).
t photovoltanic modules ba
sed on dye sensitive nan
ocrystaline titanium diox
Ide and carbon powder are disclosed.

This document discloses a three-layer structure including a photoelectrode 235, a separator 236 made of a porous layer, and a counter electrode 237 made of porous carbon, as shown in FIG. As a manufacturing method of this three-layer structure, first, the entire surface of the photoelectrode 235 of the first layer is printed by gravure printing or screen printing, and after drying and firing, patterning is performed by machining, air jet, laser scribing, or the like. Next, the entire surface of the separator 236 as the second layer is printed, dried and fired. At this time, the same processing as that for the first layer is performed. Third
After printing the entire surface of the counter electrode 237 of the layer, drying and firing, the same processing as described above is performed.

[0006]

However, in the above technique, the photoelectrode 235 and the separator 236 are required to be porous in order to increase the electrochemical reaction area and to reduce the diffusion resistance of ions. Counter electrode 2 of layer
When printing carbon 37, fine carbon may pass through the porous separator 236 and the photoelectrode 235 and reach the transparent conductive film 232 in some cases. For this reason, even after firing, the counter electrode potential becomes the same as that of the photoelectrode 235, and a short circuit inside the battery occurs frequently, and the battery may not function.

Further, the photoelectrode 23 for forming a series cell is used.
5, the separator 236 and the counter electrode 237 are printed on the entire surface, but processing for separating cells is required for each process, which is complicated. In addition, there are differences in the amount of drying shrinkage and the coefficient of thermal expansion of each layer, cracks are easily formed during drying and firing, and the size that can be manufactured is limited.

Further, in order to form a series cell, the cells are separated from each other by machining, air jet, or laser scribing for each layer. Processing and processing accuracy cannot be obtained sufficiently.

Further, it is difficult to machine only one layer contributing to the photoelectrochemical reaction by machining or laser scribing, and sometimes a layer which must be completely removed remains, or even the transparent conductive film 232 is worked. As a result, the seriality of cells may be lost.

[0010] A problem common to the three processes of machining, air jet, and laser scribing is that a large amount of processing chips are generated during processing, and the processing chips cannot be completely removed and are partially left in the processing grooves. Debris can form conductive paths and cause shorts and micro shorts inside the battery. In addition, such processing wastes impede the complete fusion of the heat-sealing sheet serving as a seal between the cells, and the electrolyte is shared with the adjacent cells. As a result, there is a possibility that a short circuit occurs inside the battery.

The present invention has solved the above-mentioned problems. In the present invention, the photoelectrode has two layers of a first photoelectrode and a second photoelectrode, and when printing a porous counter electrode mainly composed of carbon, for example, a porous separator or Even if it penetrates into the second photoelectrode, the dense first photoelectrode layer that is in contact with the transparent conductive film is provided to prevent carbon from directly contacting the transparent conductive film on the first photoelectrode side. . Therefore, when the solar cell is assembled after firing, a potential is generated between the first photoelectrode and the second photoelectrode and the counter electrode, which completely functions as a solar cell, has good conversion efficiency, and has a high conversion efficiency. An object of the present invention is to provide a dye-sensitized solar cell with improved battery production yield and a method for manufacturing the same.

[0012] Further, when pattern printing is performed by dividing each layer constituting the cell one by one, the printed area becomes smaller and the amount of shrinkage during drying and baking becomes smaller than when printing the entire area. Is difficult to enter. Furthermore, in the production of batteries, there is a merit that not only there is no machining process such as machining but the process can be simplified, but also there is an advantage that no processing waste is generated, and in each process, contamination by a photoelectrode, a separator, and particles of a counter electrode can occur. Absent. It is another object of the present invention to provide a dye-sensitized solar cell free from short-circuits in the battery and short-circuits in the electrolyte caused by poor sealing caused by processing waste and a method for manufacturing the same.

In addition, during printing of a porous counter electrode mainly composed of carbon, it is possible to prevent the carbon from coming into contact with the transparent conductive film due to the leveling after printing and to generate a photoelectrode and a counter electrode potential even after firing. The present invention provides a dye-sensitized solar cell which completely functions as a photovoltaic cell and significantly improves the yield of battery production, and a method for manufacturing the same.

[0014]

According to a first aspect of the present invention, there is provided a first photoelectrode comprising a transparent conductive film laminated on a glass substrate and the transparent conductive film formed of a dense material. Are stacked, a second photoelectrode made of porous is stacked on the first photoelectrode, a separator made of porous is stacked on the second photoelectrode, and a counter electrode made of a porous carbon layer is formed on the separator. A dye-sensitized solar cell stacked, wherein the first photoelectrode and the second photoelectrode carry a photosensitizing dye, and an electrolyte is filled between the transparent conductive film and the counter electrode; The dye-sensitized solar cell is characterized in that the average particle diameter of the constituent particles of the first photoelectrode is smaller than the average particle diameter of the constituent particles of the second photoelectrode.

According to the first aspect of the present invention, the second photoelectrode is provided with the second photoelectrode.
By using constituent particles having a finer average particle diameter than the photoelectrode, the first photoelectrode is more compact than the second photoelectrode. When printing a porous counter electrode mainly composed of carbon, for example, even if it permeates a porous separator or a second photoelectrode, the first photoelectrode layer that is in contact with the transparent conductive film is densified, and Prevents the passage of carbon that has passed through the electrode and prevents the carbon from directly contacting the transparent conductive film provided on the photoelectrode side.When assembled in a solar cell even after firing, the potential is applied to the photoelectrode and counter electrode when irradiated with light. Occurs, functioning completely as a battery, improving the yield of battery production and improving the conversion efficiency.

According to a second aspect of the present invention, there is provided an image forming apparatus, wherein the average pore size of the first photoelectrode is smaller than the average pore size of the second photoelectrode; The dye-sensitized solar cell according to claim 1, wherein the average particle diameter is smaller than the average particle diameter of the dye-sensitized solar cell.

According to the second aspect of the present invention, the average pore size of the first photoelectrode is smaller than the average pore size of the second photoelectrode and smaller than the average particle size of the secondary particles of carbon. It is possible to prevent the passage of carbon that has passed through, and the same effect as in claim 1, wherein the direct carbon does not come into contact with the transparent conductive film provided on the photoelectrode side, and when baked into the solar cell even after firing, light Upon irradiation, a potential is generated between the photoelectrode and the counter electrode, which fully functions as a battery, improves the yield of battery production, and improves conversion efficiency.

According to a third aspect of the present invention, which is made to solve the above technical problem, the average thickness of the first photoelectrode is set to be larger than the average thickness of any of the second photoelectrode, the separator, and the counter electrode. 2. The dye-sensitized solar cell according to claim 1, wherein the solar cell is also thin.

According to the third aspect of the present invention, cracks in the dense first photoelectrode which are apt to crack can be eliminated, and carbon which has passed through the pores of the second photoelectrode can be prevented from passing through the cracks. The same effect as in item 1 does not directly contact carbon with the transparent conductive film provided on the photoelectrode side, and when assembled into a solar cell even after firing, a potential is generated between the photoelectrode and the counter electrode when irradiated with light. It functions completely as a battery, improves the yield of battery production, and improves conversion efficiency.

The reason why the cracks disappear is as follows.
Since the first electrode is desired to be dense and almost free of pores, it is composed of fine particles. However, if the electrode film is thin, the bonding force between the substrate and the particles is dominant, and the film does not peel off.
As the film becomes thicker, the bonding force between the particles becomes dominant, the bonding force between the substrate and the particles becomes relatively weaker, and the distance between the particles shrinks three-dimensionally during firing, and the electrode film may stop. No, cracks. On the other hand, porous membranes such as the second electrode, the separator, and the counter electrode have pores that shrink the distance between particles and buffer the bonding force between particles. It is presumed that growth of ceases at the stomata.

According to a fourth aspect of the present invention, there is provided a liquid crystal display device, wherein the constituent particles of the second photoelectrode are smaller than the average particle diameter of the constituent particles of the separator. 2. The dye-sensitized solar cell according to item 1.

According to the fourth aspect of the present invention, by using constituent particles having an average particle diameter smaller than that of the separator for the second photoelectrode, the porosity of the second photoelectrode is reduced as compared with the separator, and the pores of the separator are reduced. The amount of carbon that has passed can be reduced by the second photoelectrode, and the same effect as in claim 1 can be achieved without direct carbon contacting the transparent conductive film provided on the photoelectrode side, and even after firing. When assembled in a cell, a potential is generated between the photoelectrode and the counter electrode when irradiated with light, so that the cell functions completely as a battery, and the yield of battery production is improved and the conversion efficiency is also improved. In addition, by using large constituent particles for a separator which does not directly act as a reaction field electrochemically, there is an effect that incident light reflection and scattering are increased, which contributes to an improvement in conversion efficiency.

According to a fifth aspect of the present invention, which is made to solve the above technical problem, an average thickness of the second photoelectrode is larger than an average thickness of the separator. Is a dye-sensitized solar cell.

According to the fifth aspect of the present invention, by increasing the average film thickness of the second photoelectrode to be greater than that of the separator, the amount of carbon passing through the pores of the separator can be reduced by the second photoelectrode. Direct carbon, which is the same effect as 1, does not come into contact with the transparent conductive film provided on the photoelectrode side, and when assembled into a solar cell after firing, a potential is generated at the photoelectrode and the counter electrode when irradiated with light, It functions perfectly as a battery, improves the yield of battery production and improves conversion efficiency. Also, by relatively reducing the volume of the separator that does not act as a reaction field electrochemically in the battery cell, the reaction field between the second photoelectrode and the counter electrode increases, which contributes to an improvement in conversion efficiency.

According to a sixth aspect of the present invention, which has been made to solve the above technical problem, the counter electrode is laminated inward from the end face of the separator. It is a solar cell.

According to the sixth aspect of the present invention, by inserting one end of the counter electrode inside the separator, it is possible to prevent paste-like carbon from flowing outside the separator and the second photoelectrode and directly reaching the transparent conductive film. Is what you do. When the solar cells are connected in series, the carbon of the counter electrode comes in contact with the transparent conductive film of the adjacent cell which is insulated by scribe so as to have the same potential as the photoelectrode of the adjacent cell. If there is a portion where the counter electrode contacts the transparent conductive film in the same cell, a short circuit occurs inside the battery. In order to avoid this, the yield can be improved by installing the counter electrode carbon inside the separator.

In order to solve the above technical problems, the invention according to claim 7 is a step of laminating a transparent conductive film on a glass substrate, and a step of laminating a dense first photoelectrode on the transparent conductive film. And a second porous electrode formed on the first photoelectrode.
A dye-sensitized solar cell comprising: a step of laminating a photoelectrode; a step of laminating a porous separator on the second photoelectrode; and a step of laminating a counter electrode composed of a porous carbon layer on the separator. The method according to claim 1, wherein
A method for producing a dye-sensitized solar cell, wherein the constituent particle diameter of the photoelectrode is smaller than the average particle diameter of the constituent particles of the second photoelectrode.

According to the seventh aspect, when printing the porous counter electrode mainly composed of carbon, for example, even if the carbon penetrates into the separator or the second photoelectrode made of the porous layer, the first light contacting the transparent conductive film is obtained. By forming the electrode in a dense layer,
Prevents the passage of carbon that has passed through the photoelectrode, without directly touching the transparent conductive film installed on the photoelectrode side,
When the solar cell is assembled after firing, a potential is generated between the photoelectrode and the counter electrode when irradiated with light, so that the cell functions completely as a battery, the yield of battery production is improved, and the conversion efficiency is improved.

[0029] The invention of claim 8 made in order to solve the above technical problem is characterized in that the lamination in each of the steps is performed by printing, drying and firing in a screen printing with a pattern formed in each step. A method for producing a dye-sensitized solar cell according to claim 7.

According to claim 8, each layer constituting the cell is defined as 1
Since printing is performed by screen printing in which a pattern is formed in a desired shape by dividing into sections one by one, compared to printing the entire area, the printing area is smaller and the amount of shrinkage during drying and firing is small, so cracks are formed. Hateful. Furthermore, in the production of batteries, there is no processing step such as mechanical processing, which not only simplifies the process, but also has the advantage that no processing dust is generated.In each step, the cell is formed by photoelectrodes, separators, and counter electrode carbon particles. No pollution.

Further, there is no short circuit inside the battery due to the direct contact between the photoelectrode and the counter electrode induced by the processing dust, and there is no short circuit of the electrolytic solution of the adjacent cell due to defective sealing caused by the processing dust being involved in the seal portion. In addition, the merit of baking in each step of forming a layer to be laminated is that, during printing, the baking layer makes the lower layer robust and printing accuracy is easily obtained, and the organic components contained in the paste can be removed in a short time. The point is that organic components remaining in each layer can be reduced as much as possible.

According to a ninth aspect of the present invention, there is provided a method according to claim 9, wherein the laminating in each of the steps is performed in each step by printing and drying by a screen printing method in which a pattern is formed. After drying, the first photoelectrode at once,
8. The method according to claim 7, wherein the second photoelectrode, the separator, and the counter electrode are fired.

According to the ninth aspect, each layer constituting the cell is defined as 1
Since printing is performed by screen printing in which a pattern is formed in a desired shape by dividing into sections one by one, compared to printing the entire area, the printing area is smaller and the amount of shrinkage during drying and firing is small, so cracks are formed. Hateful. Furthermore, in the production of batteries, there is an advantage that not only there is no machining process such as machining but the process can be simplified, but also there is an advantage that no processing dust is generated.In each process, the cell is contaminated with particles of the photoelectrode, separator and counter electrode carbon. There is no.

A dye-sensitized solar cell in which the electrolytic solution in an adjacent cell is not short-circuited due to short-circuiting inside the battery due to direct contact between the photoelectrode and the counter electrode induced by processing debris or a defective seal caused by entrapping processing debris in the seal portion. It is possible to provide a battery, its module, and its manufacturing method. The merit of firing at once is that four firings can be performed only once, so that energy cost and lead time can be significantly reduced.

According to a tenth aspect of the present invention which has been made to solve the above technical problem, the first photoelectrode has an average particle diameter of 2 μm.
The dye-sensitized solar cell according to claim 1 or 7, wherein the thickness is 5 nm or less, and a method for manufacturing the same.

According to the tenth aspect, when the average particle diameter of the first photoelectrode is 25 nm or less, densification progresses, and the passage of carbon that has passed through the second photoelectrode can be prevented by the first photoelectrode.
When the carbon is not directly in contact with the transparent conductive film installed on the photoelectrode side and assembled to the solar cell even after firing, a potential is generated at the photoelectrode and the counter electrode when irradiated with light, and the battery functions completely, Also, the yield of battery production is improved and the conversion efficiency is improved. If the average particle diameter of the first photoelectrode is larger than 25 nm, densification does not proceed and carbon may pass through the first photoelectrode and reach the transparent conductive film directly.

According to an eleventh aspect of the present invention, which has been made to solve the above technical problem, the first photoelectrode has an average pore diameter of 50%.
The dye-sensitized solar cell according to claim 1 or 7, and a method for producing the same.

According to the eleventh aspect, when the average pore diameter of the first photoelectrode is 50 nm or less, the passage of carbon that has passed through the second photoelectrode can be prevented by the first photoelectrode, and the carbon can be directly transferred to the photoelectrode side. If it is assembled to a solar cell even after firing without contacting the transparent conductive film installed in the cell, a potential is generated between the photoelectrode and the counter electrode when irradiated with light, and the battery functions completely as a battery, and the yield of battery production is reduced. The conversion efficiency is improved. If the average pore diameter of the first photoelectrode is larger than 50 nm, carbon may pass through the first photoelectrode and reach the transparent conductive film directly.

According to a twelfth aspect of the present invention for solving the above technical problem, the first photoelectrode has an average film thickness of 1 μm.
8. The dye-sensitized solar cell according to claim 1 or 7, and a method for producing the same.

According to the twelfth aspect, when the average film thickness of the first photoelectrode is 1 μm or less, cracks in the dense first photoelectrode that are apt to crack are eliminated, and the passage of carbon that has passed through the second photoelectrode is prevented. It can be prevented by one photoelectrode, and carbon is not directly in contact with the transparent conductive film installed on the photoelectrode side. If it is assembled to the solar cell even after firing, a potential is generated between the photoelectrode and the counter electrode when irradiated with light. It functions completely as a battery, improves the yield of battery production, and improves conversion efficiency. If the average thickness of the first photoelectrode is larger than 1 μm, cracks may occur, and carbon may pass through the first photoelectrode and reach the transparent conductive film directly.

According to a thirteenth aspect of the present invention, an average particle diameter of the second photoelectrode is smaller than 250 nm, and an average particle diameter of the separator is larger than 250 nm. The dye-sensitized solar cell according to claim 1 or 7, and a method for manufacturing the same.

According to the thirteenth aspect, when the average particle size of the second photoelectrode is smaller than 250 nm and the average particle size of the separator is larger than 250 nm, the porosity of the second photoelectrode is reduced as compared with the separator, and the separator is thinner. The amount of carbon passing through the hole can be reduced by the second photoelectrode,
The same effect as in claim 1, wherein the potential is generated between the photoelectrode and the counter electrode when irradiated with light when the carbon is assembled to the solar cell even after firing without direct contact with the transparent conductive film provided on the photoelectrode side. However, it functions completely as a battery, improves the yield of battery production, and improves the conversion efficiency. In addition, by using large constituent particles for a separator which does not directly act as a reaction field electrochemically, there is an effect that incident light reflection and scattering are increased, which contributes to an improvement in conversion efficiency.

When the average particle diameter of the second photoelectrode is 250 nm or more and the average particle diameter of the separator is 250 nm or less, carbon passing through the separator can easily pass through the second photoelectrode and directly reach the transparent conductive film. Gender increases.

In order to solve the above-mentioned technical problem, the invention of claim 14 is directed to an invention wherein the average thickness of the second photoelectrode is 7 μm.
The dye-sensitized solar cell according to claim 1 or 7, wherein the average thickness of the separator is smaller than 7 µm.

According to a fourteenth aspect, the average thickness of the second photoelectrode is 7 mm.
If the average thickness of the second photoelectrode is larger than that of the separator, the carbon that has passed through the pores of the separator is reduced to the second thickness.
2. The amount of passage can be reduced by the photoelectrode,
The same effect as above, without direct carbon contacting the transparent conductive film installed on the photoelectrode side, when assembled into a solar cell even after firing, a potential is generated at the photoelectrode and the counter electrode when irradiated with light, and as a battery It is fully functional and improves battery production yield and conversion efficiency. Also, by relatively reducing the volume of the separator that does not act as a reaction field electrochemically in the battery cell, the reaction field between the second photoelectrode and the counter electrode increases, which contributes to an improvement in conversion efficiency.
If the average film thickness of the second photoelectrode is 7 μm or less and the average film thickness of the separator is larger than 7 μm, the possibility that carbon passing through the separator easily passes through the second photoelectrode and directly reaches the transparent conductive film increases. I do.

[0046]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to FIGS.
This will be described with reference to FIG.

According to the present invention, as shown in FIG. 2, a transparent conductive film 32 is
A first photoelectrode 34 made of dense material is laminated on the first
A second photoelectrode 35 made of porous material is laminated on the photoelectrode 34, and the separator 3 made of porous material is formed on the second photoelectrode 35.
6, a counter electrode 37 made of a porous carbon layer is laminated on the separator, a photosensitizing dye is carried on the first photoelectrode 34 and the second photoelectrode 35, and the transparent conductive film 32 is And a counter-electrode 37 filled with an electrolyte, wherein the average particle diameter of the constituent particles of the first photoelectrode 34 is larger than the average particle diameter of the constituent particles of the second photoelectrode 35. Is also small.

The average pore size of the first photoelectrode 34 is smaller than the average particle size of the carbon secondary particles of the counter electrode 37. First
The average particle diameter of the photoelectrode 34 is preferably 25 nm or less. The average particle size is preferably 50 nm or less.

As shown in FIG. 3, the counter electrode 37 has a structure in which the counter electrode 37 is laminated inward from the end face of the separator 36, so that an effect of preventing a short circuit inside the battery can be achieved.

In the method of manufacturing the dye-sensitized solar cell, as shown in FIG.
2, a step of stacking a dense first photoelectrode 34 on the transparent conductive film 32, and a step of stacking a porous second photoelectrode 35 on the first photoelectrode 34. A porous separator 36 is provided on the second photoelectrode 35.
And a step of laminating a counter electrode 37 made of a porous carbon layer on the separator 36, wherein the particle diameter of the first photoelectrode 34 is Is smaller than the average particle diameter of the constituent particles of the second photoelectrode 35.

In the above-mentioned steps, the lamination in each of the steps is performed by a printing method in which printing, drying and baking are performed in each step by screen printing in which a pattern is formed, and the lamination in each step is performed by a screen printing method in which a pattern is formed. Then, there is a manufacturing method in which printing and drying are performed in respective steps, and after drying the counter electrode, the first photoelectrode, the second photoelectrode, the separator, and the counter electrode are fired at once.

Next, the embodiment will be specifically described based on Embodiments 1 to 3.

(Example 1) In order to confirm the effect of preventing the dense layer of the first photoelectrode 34 from purely contacting the carbon and the transparent conductive film 32, only one cell was used.

FIG. 1A is a process diagram showing the processing of a glass substrate. To connect cells in series to a glass substrate 31 having a transparent conductive film 32 made of 0.5 μm fluorine-doped tin oxide on 1.1 mm thick glass, a 50 μm width scribe 33 is applied to a YAG laser for the purpose of insulating between cells. Processed.

FIG. 1B shows a first photoelectrode (photoelectrode dense layer).
It is a flowchart showing the screen printing of the mask for 34 formation. FIG. 1C is a process diagram showing dip coating or screen printing (pattern printing) of the first photoelectrode 34.

As shown in FIGS. 1B and 1C, the first photoelectrode (dense layer) 34 is formed as follows. A portion which is not applied in advance is masked with a mask M made of a paste material which is thermally decomposed and gasified at a firing temperature, and dip-coated several times with a titania sol having anatase 100% titanium oxide having an average primary particle diameter of 6 nm or an average particle diameter of 25 nm or less. Titanium oxide was dispersed and a cellulosic binder was mixed.

Thereafter, mixing was performed while replacing the solvent such as butyl carbitol, and finally, the solid content of titanium oxide was 16 wt.
% Of a paste for screen printing is used. After printing, it was dried and baked at 450 ° C. The first photoelectrode 34 is formed with a thickness within 1 μm.

FIG. 1D is a process diagram showing printing (pattern printing), drying and baking of the second photoelectrode 35.

The second photoelectrode 35 is formed as follows. Mean particle size of titanium oxide of 100% anatase 250
Particles of nm or less were dispersed, and a cellulose-based binder was mixed. Thereafter, mixing was carried out while replacing the solvent with butyl carbitol or the like, and a paste for screen printing was finally prepared so as to have a titanium oxide solid content concentration of 10 wt%. After printing and drying, it was baked at 450 ° C. The second photoelectrode 35 having a thickness of 8 to 17 μm (average thickness of 12.5 μm) was formed.

FIG. 1E is a process diagram showing printing (pattern printing), drying and baking of the separator 36.

The separator (porous layer) 36 is formed as follows. Rutile 100% titanium oxide particles having an average particle diameter of more than 250 nm and zirconium oxide having an average particle diameter of 20 nm were dispersed and mixed with a cellulose binder. Thereafter, mixing was performed while replacing the solvent such as butyl carbitol, and a paste for screen printing was finally prepared so as to have a solid content of titanium oxide and zirconium oxide of 15 wt%. Film thickness 3-7μ
m (average film thickness: 5 μm) was formed.

FIG. 1F shows a counter electrode (porous carbon layer) 3
FIG. 7 is a process chart showing printing (pattern printing), drying, and baking of No. 7;

The counter electrode 37 is formed as follows. Carbon black having a specific surface area of 800 m ² / g or more, graphite having an average particle diameter of 5 μm, and titanium oxide having an average primary particle diameter of 6 nm were 1: 5: 1, and a cellulose binder was mixed. Thereafter, mixing was performed while replacing the solvent with butyl carbitol or the like, and a paste was prepared so that the solid content concentration was finally 30 wt%. After printing and drying, the paste was baked at 450 ° C. The counter electrode 37 having a thickness of 50 to 60 μm was formed.

In the separator 36, the counter electrode 37 (porous carbon layer) directly connected must exceed the scribe line, and the first photoelectrode 34 and the second photoelectrode 35
To avoid direct contact on the side of the counter electrode 37,
One end (the lower end in FIGS. 1 and 2) is in contact with the scribe 33 of the glass substrate 31.

The counter electrode 37 is also formed in an L-shaped cross section. One end (lower end in FIGS. 1 and 2) of the counter electrode 37 is in contact with the transparent conductive film 32 as a battery interconnection when forming a direct junction.

FIG. 2 is a sectional perspective view of the electrode body D1 of the first embodiment formed by the above steps. FIG. 3 is a cross-sectional perspective view of the electrode body D2 in which the counter electrode 37 is retracted inside the end face of the separator 36 and stacked. In this configuration, the counter electrode 37 is stacked inward from the end face of the separator 36 by a distance d. The distance of d is generally 0.2 mm
To 0.5 mm is desirable.

FIG. 4 is a cross-sectional perspective view of an electrode DP without a first photoelectrode (dense layer) 34 according to the prior art as a comparative example.

Next, a dye cis-Di (tiocyanato) -bis was added to acetonitrile for each of the above electrodes.
(2,2-bipyridyl-4,4'-dicar
boxylate) -Rurhenium 3 × 10
^-4 mol / L, dissolved in a dye solution, and baked to the above counter electrode D1, D2, D
P was impregnated, and the dye was adsorbed on the first photoelectrode 34 and the second photoelectrode 35.

Further, as shown in FIG. 5, a PET film 38 laminated with an ionomer Surlyn (trade name: manufactured by DuPont) was used as a heat-sealing sheet as a top cover, and the portion where the transparent conductive film 32 was exposed was heat-sealed. And the cells C1, C2 corresponding to the electrode bodies D1, D2, DP
2. CP was created.

Then, 0.03 mol was added to acetonitrile.
/ L of I ₂ (iodine) and 0.3 mol / L of LiI
A solution in which (lithium iodine) was dissolved was used as an electrolytic solution, injected into the space V of the cell C1, and sealed to produce a dye-sensitized solar cell C11. For cells C2 and CP, dye-sensitized solar cells C22 and CPP were manufactured in the same manner.

Five dye-sensitized solar cells obtained by the above-described method were manufactured, and five of them were manufactured by a solar simulator using a xenon lamp having an AM1.5 spectral distribution.
The solar cell characteristics under the condition of 00 mW / cm2 were measured.
Table 1 shows the results.

[0072]

[Table 1] From Table 1, it can be seen that the sample No. 6-10, 11-1
5, the first and second photoelectrodes 34 and 35
No. 2 and the first photoelectrode was a dense layer. The yield was improved as compared with 1-5.

Further, the effect of preventing the internal short circuit due to the penetration of the counter electrode carbon into the transparent conductive film 32 on the photoelectrode side was confirmed. Observation of the dense layer of the first electrode 34 with an electron microscope revealed that no carbon penetrated the dense layer and reached the transparent conductive film on the light electrode side.

No. In the short circuit of No. 15, the carbon did not penetrate the dense layer, and the counter electrode 37 was originally printed in an L-shape, dried and fired at the leveling after printing.
It was found that the paste of No. 7 flowed, became U-shaped, and was in contact with the transparent conductive film 32.

In the first embodiment, the conversion efficiency is good and the performance is improved. The reason for this is that the photoelectrode has two or more layers, such as the first photoelectrode 32 and the second photoelectrode 33, so that the light scattering efficiency is improved, the current that can be taken out increases according to the scattering efficiency, and the output power increases. It is considered that (conversion efficiency) was improved.

In the case of No. 1 of the first embodiment, Counter electrode 3 of 16-25
In the dye-sensitized solar cell including the cell C2 in which 6 is smaller than the separator layer, the counter electrode 36 does not have a U-shape, but is printed, dried, and fired in an L-shape. Further improved. Although the conversion efficiency was slightly reduced as the area of the counter electrode was reduced due to the reduced area, the effect of preventing short circuit inside the battery was confirmed.

(Embodiment 2) Next, Embodiment 1 has been described with reference to a unit cell.
(A) to FIG. 6 (e).

FIG. 6A: 100 × 100 mm thickness 1.
Glass substrate 131 with 500 nm 1 mm transparent conductive film
In order to connect cells in series, 50
A scribe 133 having a width of μm was processed using a YAG laser.

FIG. 6B: First photoelectrode (dense layer) 134
Was prepared by dispersing titanium oxide having an average particle size of 25 nm or less in water and mixing a cellulose binder. Thereafter, mixing was performed while replacing the solvent such as butyl carbitol, and a paste for screen printing was finally prepared so as to have a titanium oxide solid content concentration of 16% by weight. Using a screen having a pattern of 10 mm in width, 90 mm in length, and a pattern capable of simultaneously printing 7 cells, after printing, dried and fired at 450 ° C. The film thickness is 1μ
m or less.

FIG. 6C: Second photoelectrode (porous layer) 13
In No. 5, particles having an average primary particle diameter of titanium oxide of 25 nm were dispersed, and a cellulose-based binder was mixed. Thereafter, mixing was carried out while replacing the solvent with butyl carbitol or the like, and a paste for screen printing was finally prepared so as to have a titanium oxide solid content concentration of 10 wt%.

FIG. 6 (d): The screen has the same pattern as the first photoelectrode (dense layer) 134, but the mesh is coarse. The thickness of the film fired at 450 ° C. after printing and drying so as to overlap the first photoelectrode (dense layer) 134 was 8 to 17 μm.

The separator 136 contains particles having a mean particle diameter of titanium oxide of 100% rutile and larger than 250 nm.
Zirconium oxide having a primary particle diameter of 20 nm was dispersed and mixed with a cellulose binder. Thereafter, mixing was performed while replacing the solvent with butyl carbitol or the like, and a paste for screen printing was prepared so that the solid content of titanium oxide and zirconium oxide finally became 15 wt%. 11mm in width 90m in length
m, the pattern is aligned with the end face of the first photoelectrode 134 for 7 cells, and as shown in FIG.
34 was printed in an L-shape to cover one side. After printing and drying 4
It was fired at 50 ° C. The thickness was 3-7 μm.

Thereafter, the carbon at the counter electrode 137 was prepared by mixing carbon black having a specific surface area of 800 m ² / g or more, graphite having an average particle diameter of 5 μm, and titanium oxide having an average primary particle diameter of 6 nm in a ratio of 1: 5: 1 and a cellulose-based binder. did.

Thereafter, mixing was carried out while replacing the solvent such as butyl carbitol, and a paste was prepared so as to finally have a solid concentration of 30 wt%, and finally the paste was prepared so as to have a solid concentration of 30 wt%. 90mm length
The pattern was aligned with the end faces of the first photoelectrode 134 and the second photoelectrode 135 for 7 cells, and 1 mm was printed in an L shape so as to cover one side of the separator 136 as shown in FIG.
After printing and drying, it was baked at 450 ° C. Film thickness is 20-60μ
m. The total thickness of all four layers was 30-75 μm. No crack due to drying shrinkage or firing shrinkage was observed in each of the layers repeatedly dried and fired.

[0086] Three modules connected in series with 7 cells were produced by the above method. In each cell, the dye cis-Di (tiocyanato) -bis (2,2) was added to acetonitrile.
2-bipyridyl-4,4'-dicarbox
ylate) -Rurhenium 3 × 10 ⁻⁴ mo
1 / L was dissolved to a concentration of 3 × 10 ⁻⁴ mol / L, and a dye solution was impregnated with the cell fired up to the counter electrode to adsorb the dye. Then, as shown in FIG.
Using a PET film 138 laminated with Surlyn, an ionomer, as a heat-sealing sheet as a top cover, a portion where the transparent conductive film was exposed was heat-sealed to form a cell. Then, 0.03 mol / L of I ₂ was added to acetonitrile.
(Iodine) and 0.3 mol / L of LiI (lithium iodide) dissolved therein were used as an electrolytic solution.
To complete sealing. The module M was completed.

After that, 100 mW by a solar simulator using a xenon lamp having an AM1.5 spectrum distribution.
The solar cell characteristics were measured under the conditions of / cm 2. (Embodiment 3) Next, a manufacturing method using the dye-sensitized solar cell module of Embodiment 3 of the present invention will be described. The drawings of the respective process diagrams are the same as those in Example 2, and the method for manufacturing the module is shown in FIGS. 6 (a) to 6 (e). The present manufacturing method changed the firing timing.

FIG. 6 (a): 50 μm for the purpose of inter-cell insulation for connecting cells in series to a glass substrate having a transparent conductive film of 500 nm having a thickness of 100 mm × 100 mm and 1.1 mm.
A scribe 133 having a width of m was processed using a YAG laser.

FIG. 6B: First photoelectrode (dense layer) 134
Was prepared by dispersing titanium oxide having an average primary particle diameter of 25 nm and mixing with a cellulose binder. Thereafter, mixing was performed while replacing the solvent such as butyl carbitol, and a paste for screen printing was finally prepared so as to have a titanium oxide solid content concentration of 16% by weight. Using a screen having a pattern of 10 mm in width and 90 mm in length and capable of printing 7 cells simultaneously, the printing was sufficiently dried. The dry film thickness was 2 μm or less.

FIG. 6C: Second photoelectrode (porous layer) 13
In No. 5, particles having an average primary particle diameter of titanium oxide of 25 nm were dispersed and mixed with a cellulose binder. Thereafter, mixing was performed while replacing the solvent with butyl carbitol or the like, and a paste for screen printing was finally prepared so as to have a titanium oxide solid content concentration of 10 wt%.

FIG. 6 (d): The screen has the same pattern as the second photoelectrode (dense layer) 135, but the mesh is coarse. The thickness of the film printed and sufficiently dried so as to overlap the dense layer of the photoelectrode was 25 to 50 μm.

In the separator 136, 100% rutile particles of titanium oxide having an average particle diameter of 250 nm or more and zirconium oxide having an average particle diameter of 20 nm were dispersed and mixed with a cellulose binder. Thereafter, mixing was performed while replacing the solvent with butyl carbitol or the like, and a paste for screen printing was finally prepared so as to have a solid content concentration of titanium oxide and zirconium oxide of 15% by weight. The pattern is aligned with the end faces of the first photoelectrode 134 and the second photoelectrode 135 for a width of 11 mm, a length of 90 mm, and 7 cells, and a cross section L of 1 mm covers one side of the separator 136 as shown in FIG. Printed in a letter shape. It dried sufficiently after printing. Dry film thickness is 10-25 μm
Met.

Next, the carbon of the counter electrode 137 has a specific surface area of 8
00m ² / g or more carbon black, average particle size 5μ
m of graphite, titanium oxide having an average primary particle diameter of 6 nanometers was 1: 5: 1, and a cellulosic binder was mixed.

Then, the mixture was mixed while replacing the solvent with butyl carbitol or the like, and a paste was prepared so that the solid content concentration was finally 30 wt%. The pattern was matched, and as shown in FIG. 6E, 1 mm was printed so as to cover one side of the photoelectrode in an L-shape. After printing, dry thoroughly
At 2 ° C., the two fired photoelectrode layers, the separator and the counter electrode were fired at once. The overall film thickness was 30-85 μm.

In each of the layers that were repeatedly dried, no crack due to drying shrinkage was found, and no crack was observed after firing. Three modules with 7 cells connected in series by the above method were produced.

In each cell, the dye cis- was added to acetonitrile.
Di (tiocyanato) -bis (2,2-bi
pyridyl-4,4'-dicarboxylat
The e) -Rurhenium dissolved so that a ^3X10 -4 mol / L to ^3X10 -4 mol / L concentration, to that the dye solution to impregnate the cells that are firing to the counter electrode, to adsorb the dye. After that, as shown in FIG. 7, a PET film 138 laminated with ionomer Surlyn was used as a heat-sealing sheet as a top cover, and a portion where the transparent conductive film was exposed was heat-sealed to form a cell. Next, 0.03 mol / L of I ₂ (iodine) and 0.3 mol / L of LiI (lithium iodine) were added to acetonitrile.
Was dissolved in each of the above-mentioned void portions V, and the resulting solution was sealed to complete a dye-sensitized solar cell module M.

Thereafter, 100 mW was applied to a solar simulator using a xenon lamp having an AM1.5 spectral distribution.
The solar cell characteristics were measured under the conditions of / cm 2.

Comparative Example FIG. 8 shows, as a comparative example, a method of manufacturing a dye-sensitized solar cell module having three layers of cells based on the above-mentioned literature.

As shown in FIG. 8A, 100 × 100
mm 1.1 mm thick transparent conductive film 232 (thickness 500
scribe 233 having a width of 50 μm for the purpose of insulating cells from each other in order to connect cells in series to a glass substrate 231 with
Was processed using a YAG laser.

The photoelectrode 235 has a titanium oxide average particle diameter of 25.
Particles of nm or less were dispersed and a cellulose binder was mixed. Thereafter, mixing was performed while replacing the solvent with butyl carbitol or the like, and a paste for screen printing was finally prepared so as to have a titanium oxide solid content concentration of 10 wt%.

As shown in FIG. 8B, the screen is
A screen with a printable pattern having a width of 90 mm and a length of 90 mm was used. After printing and drying, it was baked at 450 ° C. The thickness of the film was 10-15 μm.

As shown in FIG. 8C, the baked film of the photoelectrode 235 was scribed at a predetermined position with a carbide needle so that seven cells could be connected in series. At this time, microcracks, which are considered to have been locally formed during firing, had occurred.

[0102] As shown in FIG.
No. 6 has an average particle diameter of titanium oxide of 100% rutile of 0.3 μm.
m and zirconium oxide having an average primary particle diameter of 20 nm were dispersed and mixed with a cellulose binder.

As shown in FIG. 8 (e), mixing was performed while replacing the solvent with butyl carbitol or the like, and a paste for screen printing was finally prepared so that the solid content of titanium oxide and zirconium oxide became 15 wt%. 90m width
Using a screen having a printable pattern with a length of 90 mm and a length of 90 mm, printing was performed so as to overlap the scribed film of the photoelectrode 235. The thickness of the separator 236 was 3-5 μm. Like the photoelectrode, the fired film was scribed at a predetermined position so that seven cells could be connected in series with a carbide needle. At this time, generation of microcracks was not recognized in the separator 236.

Then, as shown in FIG.
Carbon No. 7 was prepared by mixing carbon black having a specific surface area of 800 m ² / g or more, graphite having an average particle diameter of 5 μm, and titanium oxide having an average primary particle diameter of 6 nm in a ratio of 1: 5: 1 and a cellulose binder. After that, mixing was performed while replacing the solvent such as butyl carbitol, and finally the solid concentration was 30 wt%.
Mix paste to make 90mm width 90m
m, printing was performed so as to overlap the film of the scribed separator 237 using a screen having a printable pattern.

Thereafter, the printed matter is dried and dried.
The counter electrode was fired at 50 ° C. The film thickness of the counter electrode is 20-60
μm. The thickness of the entire photoelectrode to the counter electrode is 30 to 85.
μm.

As shown in FIG. 8 (g), the counter electrode film after firing was scribed at a predetermined position so that seven cells could be connected in series with a carbide needle. Three modules with 7 cells connected in series by the above method were produced.

The other steps such as dye adsorption, completion of the module, and measurement of the characteristics of the solar cell are the same as those in the first to third embodiments, so that the description will be omitted.

Table 2 shows measurement results showing the results of Example 2, Example 3, and Comparative Example.

[0109]

[Table 2] No. 2 of Comparative Example 2. 1-3 showed unstable behavior even during the measurement of the module, and the module stopped showing photoelectric conversion for the third time in the repeated measurement. When the details of the failure were partially disassembled and investigated, the heat-sealing seal could not be completely removed and the photoelectrode layer was involved. The electrolyte leaked out of the layer and short-circuited with the next cell. The carbon was partially in contact with the transparent conductive film 232, and a micro short circuit occurred. Further, a defect in which a part of the transparent conductive film 232 was damaged when the photoelectrode 235 was scribed was observed. In general, black carbon particles of the counter electrode material floated and adhered to the electrolyte and the inside of the photoelectrode.

On the other hand, in Example 2, the seal between the cells of the module was good, and the electrolytic solution observed in the comparative example oozed, and there was no liquid short circuit with the adjacent cell. The black counter electrode material carbon particles float inside the electrolyte or photoelectrode,
It is considered that such carbon particles did not adhere, and were caused by processing chips that could not be completely removed when scribing.

Also in Example 3, the intercellular seal of the module was good in each case, and there was no leakage of the electrolytic solution and no liquid short-circuit with the adjacent cells as seen in Comparative Example 2.

It was confirmed that both Examples 2 and 3 had higher conversion efficiency than Comparative Example 2.

From the above, the photoelectrode has two or more layers,
It has become clear that a dye-sensitized solar cell in which one layer in contact with a transparent conductive film is composed of a dense layer has improved conversion efficiency and improved reliability.

Also, after printing on a screen in which the photoelectrode, separator, and counter electrode of each cell of the module composed of cells connected in series are separated by a pattern, and firing, printing is performed on the entire surface, and processing is performed on the cell. It has been found that the effect of eliminating the trouble caused by the processing dust is greater than that of the conventional method of forming the pattern of (1).

[0115]

According to the first aspect of the present invention, a transparent conductive film is laminated on a glass substrate, a dense first photoelectrode is laminated on the transparent conductive film, and a porous material is formed on the first photoelectrode. A second photoelectrode comprising: a second electrode; a second electrode having a porous separator laminated thereon; a second electrode having a porous carbon layer laminated on the separator;
A dye-sensitized solar cell, in which a photosensitizing dye is supported on a photoelectrode and the second photoelectrode, and an electrolyte is filled between the transparent conductive film and the counter electrode, wherein the configuration of the first photoelectrode is Since the dye-sensitized solar cell is characterized in that the average particle size of the particles is smaller than the average particle size of the constituent particles of the second photoelectrode, the first photoelectrode has a finer average particle size than the second photoelectrode. By using constituent particles having a particle diameter, the first photoelectrode is more dense than the second photoelectrode. When printing a porous counter electrode mainly composed of carbon, for example, the first photoelectrode layer that is in contact with the transparent conductive film even if it permeates the porous separator or the second photoelectrode is dense, and the second photoelectrode Prevents the passage of carbon that has passed through, and the carbon is not directly in contact with the transparent conductive film installed on the photoelectrode side, and when assembled into a solar cell even after firing, a potential is generated at the photoelectrode and the counter electrode when irradiated with light In addition, it functions completely as a battery, and the yield of battery production is improved and the conversion efficiency is improved.

[0116] The invention of claim 7 relates to the invention relating to the production method of claim 1 of the present invention, wherein a step of laminating a transparent conductive film on a glass substrate and a step of forming the first photoelectrode made of dense material on the transparent conductive film are performed. Laminating, laminating a porous second photoelectrode on the first photoelectrode, laminating a porous separator on the second photoelectrode, and porous the separator. Laminating a counter electrode comprising a carbon layer, wherein the constituent particle diameter of the first photoelectrode is smaller than the average particle diameter of the constituent particles of the second photoelectrode. Since the method for manufacturing a dye-sensitized solar cell is characterized in that, when printing a porous counter electrode mainly composed of carbon, for example, even if carbon permeates the separator or the second photoelectrode made of a porous layer Contacts the transparent conductive film By making one photoelectrode a dense layer, the passage of carbon that has passed through the second photoelectrode is prevented, and the carbon is not directly in contact with the transparent conductive film provided on the photoelectrode side, but is assembled to the solar cell even after firing. When light is applied, a potential is generated between the photoelectrode and the counter electrode, which fully functions as a battery, improves the yield of battery production, and improves conversion efficiency.

[Brief description of the drawings]

FIG. 1 is a process chart for manufacturing a cell according to a first embodiment.

FIG. 2 is a sectional perspective view of the cell of the first embodiment.

FIG. 3 is a cross-sectional perspective view of an electrode main body in which a counter electrode is laminated inward from an end face of a separator in the first embodiment.

FIG. 4 is a sectional perspective view of a comparative example.

FIG. 5 is a cross-sectional view of the dye-sensitized solar cell of the first embodiment.

FIG. 6 is a process chart for manufacturing the module of the second embodiment.

FIG. 7 is a sectional view of a module according to a second embodiment.

FIG. 8 is a process chart for manufacturing a module of a comparative example.

FIG. 9 is a sectional view of a module according to a comparative example.

[Explanation of symbols]

 31, 131, 231 ... glass substrate 34, 132 ... first photoelectrode 35, 135, 136 ... second photoelectrode 36, 136, 236 ... separator 37, 137, 237 ... counter electrode

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5F051 AA14 5H032 AA06 AS12 AS16 BB00 BB02 BB10 CC06 CC11 CC14 CC16 EE01 EE08 EE16 HH04

Claims (14)

[Claims] 1. A transparent conductive film is laminated on a glass substrate, and a dense first photoelectrode is laminated on the transparent conductive film.
A second photoelectrode made of a porous material is laminated on the first photoelectrode, a separator made of a porous material is laminated on the second photoelectrode, a counter electrode made of a porous carbon layer is laminated on the separator, A dye-sensitized solar cell in which a photosensitizing dye is supported on the first photoelectrode and the second photoelectrode, and an electrolyte is filled between the transparent conductive film and the counter electrode,
A dye-sensitized solar cell, wherein the average particle diameter of the constituent particles of the first photoelectrode is smaller than the average particle diameter of the constituent particles of the second photoelectrode. 2. The method according to claim 1, wherein the average diameter of the first photoelectrode is equal to the second pore size.
Carbon 2 which is smaller than the average pore diameter of the photoelectrode,
The dye-sensitized solar cell according to claim 1, wherein the average particle diameter of the secondary particles is smaller than that of the secondary particles. 3. An average film thickness of the first photoelectrode is equal to the second film thickness of the second photoelectrode.
The dye-sensitized solar cell according to claim 1, wherein the average thickness of the photoelectrode, the separator, and the counter electrode is smaller than any of the average thickness. 4. The dye-sensitized solar cell according to claim 1, wherein constituent particles of the second photoelectrode are smaller than an average particle diameter of constituent particles of the separator. 5. The dye-sensitized solar cell according to claim 1, wherein the average thickness of the second photoelectrode is larger than the average thickness of the separator. 6. The dye-sensitized solar cell according to claim 1, wherein said counter electrode is laminated inside said separator end face. 7. A step of laminating a transparent conductive film on a glass substrate, a step of laminating a dense first photoelectrode on the transparent conductive film, and a step of laminating a porous second photoelectrode on the first photoelectrode. Manufacturing a dye-sensitized solar cell, comprising: stacking a porous separator on the second photoelectrode; and stacking a counter electrode made of a porous carbon layer on the separator. A method of manufacturing a dye-sensitized solar cell, wherein the constituent particle diameter of the first photoelectrode is smaller than the average particle diameter of the constituent particles of the second photoelectrode. 8. The method for producing a dye-sensitized solar cell according to claim 7, wherein the lamination in each of the steps is performed by printing, drying, and baking in screen printing with a pattern formed in each of the steps. 9. The lamination in each step is performed by printing and drying in each step by a screen printing method in which a pattern is formed, and after the counter electrode is dried, the first photoelectrode and the second photoelectrode are simultaneously formed. The method for producing a dye-sensitized solar pond according to claim 7, wherein the separator and the counter electrode are fired. 10. An average particle diameter of the first photoelectrode is 25n.
The dye-sensitized solar cell according to claim 1 or 7, and a method for producing the same. 11. An average pore diameter of the first photoelectrode is 50 nm.
9. The method according to claim 1, wherein:
The dye-sensitized solar cell according to the above and a method for producing the same. 12. The dye-sensitized solar cell according to claim 1, wherein an average film thickness of the first photoelectrode is 1 μm or less. 13. The second photoelectrode having an average particle diameter of 250.
nm, the average particle size of the separator is 250
8. The dye-sensitized solar cell according to claim 1 or 7, and a method for producing the same. 14. The dye-sensitized solar cell according to claim 1, wherein the average thickness of the second photoelectrode is larger than 7 μm, and the average thickness of the separator is smaller than 7 μm. Battery and manufacturing method thereof.