JP6280797B2 - Method for producing anode for dye-sensitized solar cell and method for producing dye-sensitized solar cell - Google Patents

Description

  The present invention relates to a method for producing a dye-sensitized solar cell anode and a method for producing a dye-sensitized solar cell.

The dye-sensitized solar cell has been proposed by a group such as Gretzel in Switzerland, and has attracted attention as a photoelectric conversion element that can be obtained at low cost and with high conversion efficiency.
The dye-sensitized solar cell includes an anode in which a porous semiconductor layer having a sensitizing dye adsorbed is formed on a transparent substrate, a cathode in which a conductive layer is formed, and an electrolyte filled between the anode and the cathode. The layer is configured as a main component (see, for example, Patent Document 1).
In use, when the dye-sensitized solar cell is irradiated with sunlight, the electrons in the sensitizing dye are excited, and the excited electrons are injected from the porous semiconductor layer to the anode via an external load. And move to the cathode. Electricity is generated by repeating this cycle.

The above-described dye-sensitized solar cell has less influence on the performance due to the incident angle of light compared to a conventional solar cell (for example, a solar cell using silicon), and there is no decrease in photoelectric conversion efficiency even at low illuminance. Therefore, there are few restrictions on an installation place, for example, the installation to a window surface or a wall surface is possible.
However, solar cells installed in these places need to be in harmony with, for example, cityscapes and interior spaces in order to be exposed to human eyes, and high designability and light transmission are required.
For this reason, in the development of a light transmissive solar cell, it is important to control the amount of photovoltaic power generation and the amount of light transmission. Generally, light transmittance can be improved by thinning a titanium dioxide electrode (porous semiconductor layer) which is a photovoltaic layer of a dye-sensitized solar cell.

JP2013-16369A

However, as described above, if the titanium dioxide electrode is thinned to obtain a light transmission amount that can be installed on the window surface, the amount of photovoltaic power generation is greatly reduced.
In addition, there is a method of forming a titanium dioxide electrode by a thermal spraying method in order to shorten the film formation time of the titanium dioxide electrode. However, in order to achieve high designability by using the thermal spraying method, an accurate masking technique is required. It becomes. Here, when the titanium dioxide electrode is formed using the thermal spraying method, the temperature of the thermal spray frame is 1000 ° C. or higher, and therefore a metal mask is generally used. However, when a metal mask is used, it is costly for the precision processing of the mask, and a metal with good thermal conductivity comes into contact with the glass substrate (transparent substrate). There is a concern that the production yield may decrease due to cracking.

  The present invention has been made in view of such circumstances, and has a superior design and a method for producing an anode for a dye-sensitized solar cell and a method for producing a dye-sensitized solar cell in which the amount of photovoltaic power generation and the amount of light transmission can be freely controlled. The purpose is to provide.

The method for producing an anode for a dye-sensitized solar cell according to the first aspect of the present invention is the method for producing an anode for a dye-sensitized solar cell having a porous semiconductor layer on which a sensitizing dye is adsorbed on a transparent substrate. ,
A semiconductor which forms a porous semiconductor layer using a thermal spraying method on the transparent substrate on which the mask is formed after forming a mask made of a heat-resistant resin in a predetermined region on the transparent substrate A layer forming step;
A dye adsorption step of adsorbing the sensitizing dye to the porous semiconductor layer outside the area on the transparent substrate after removing the mask from the area on the transparent substrate.

  In the method for producing an anode for a dye-sensitized solar cell according to the first invention, the heat-resistant resin is preferably an ultraviolet curable resin.

  In the method for manufacturing an anode for a dye-sensitized solar cell according to the first invention, the material of the porous semiconductor layer is preferably fine particles of titanium oxide.

  A method for producing a dye-sensitized solar cell according to the second aspect of the present invention that meets the above-described object comprises: a dye-sensitized solar cell anode produced using the method for producing a dye-sensitized solar cell anode according to the first invention; A cathode is arranged opposite to each other with a gap, and an electrolyte is filled between the anode for the dye-sensitized solar cell and the cathode.

The method for producing an anode for a dye-sensitized solar cell and the method for producing a dye-sensitized solar cell according to the present invention are formed in a predetermined region on a transparent substrate in a semiconductor layer forming step, and are porous using a spraying method. After the semiconductor layer is formed, the mask removed from the transparent substrate in the dye adsorption step is made of a heat-resistant resin, so that it can withstand heat generated during thermal spraying.
Therefore, by changing the shape of the area covered with the mask, it is excellent in design, and by adjusting the area of the area covered with the mask, the amount of light transmission and the amount of photovoltaic power generation can be controlled freely. An anode for a solar cell and a dye-sensitized solar cell can be manufactured.

(A)-(D) are explanatory drawings of the manufacturing method of the anode for dye-sensitized solar cells which concerns on one embodiment of this invention, respectively. It is explanatory drawing of the thermal spraying apparatus used for the manufacturing method of the anode for the same dye-sensitized solar cell. (A) is a graph showing the relationship between the number of thermal spray passes during the formation of the titanium dioxide film on the FTO substrate and the film thickness formed, and (B) is the film thickness of the titanium dioxide film adsorbed with the dye. It is a graph which shows the relationship with light transmittance. (A) is a graph showing the relationship between the number of thermal spray passes during the formation of the platinum film on the FTO substrate and the film thickness formed, and (B) shows the relationship between the film thickness of the platinum film and the light transmittance. FIG. (A) is the graph which shows the relationship between the photoelectric conversion efficiency of the produced dye-sensitized solar cell, and the film thickness of a titanium dioxide film, (B) is the photoelectric conversion efficiency of the produced dye-sensitized solar cell, and the light transmittance. It is a graph which shows a relationship. It is a graph which shows the measurement result of the IV characteristic of the produced dye-sensitized solar cell. It is a graph which shows the relationship between the light transmittance of the produced dye-sensitized solar cell, and photoelectric conversion efficiency.

Next, embodiments of the present invention will be described with reference to the accompanying drawings for understanding of the present invention.
First, the dye-sensitized solar cell anode manufactured by the method for manufacturing a dye-sensitized solar cell anode (photoelectromotive electrode) according to the first embodiment of the present invention will be described.
As shown in FIGS. 1A to 1D, a dye-sensitized solar cell anode (hereinafter also simply referred to as an anode) 10 is a porous semiconductor layer (hereinafter also simply referred to as a semiconductor layer) on a transparent substrate 11. 12 is formed by a thermal spraying method, and a sensitizing dye is adsorbed (supported) on the porous semiconductor layer 12. This will be described in detail below.

The transparent substrate 11 is a substrate (for example, having a thickness of about 2 to 5 mm) provided with a conductive film. For example, transparent glass (glass with a conductive film) can be used. The conductive film is, for example, an FTO film (tin oxide film doped with fluorine), an ITO film (indium film doped with tin), a SnO ₂ film (tin oxide film), or the like.
Thereby, when forming the semiconductor layer 12 on the transparent substrate 11 using a thermal spraying method, the transparent substrate 11 can have high heat resistance with respect to the heat | fever at the time of the thermal spraying applied.
The transparent substrate is not limited to the above materials, and for example, a transparent resin film having a thickness of about 50 to 300 μm made of PEN resin, PET resin or the like having appropriate heat resistance can be used. Thus, when using a transparent resin, a flexible anode can be obtained by using a flexible resin film.

The porous semiconductor layer 12 is made of, for example, titanium (Ti), tin (Sn), zirconium (Zr), zinc (Zn), indium (In), tungsten (W), iron (Fe), nickel (Ni), or Although it is composed of a metal oxide such as silver (Ag), titanium oxide (TiO ₂ ) is more preferable from the viewpoint of durability. Note that these materials are not limited to pure substances such as titanium oxide, and may contain other metal oxides in appropriate amounts.
In addition, the metal oxide material is preferably fine particles having an average particle diameter of, for example, about 10 to 200 nm from the viewpoint of balancing the denseness and porosity of the porous semiconductor layer in a balanced manner.

The thickness of the porous semiconductor layer 12 is not particularly limited, but from the viewpoint of obtaining a high amount of photovoltaic power generation (photoelectric conversion efficiency), for example, about 5 to 40 μm (preferably the lower limit is 10 μm and the upper limit is 30 μm). It is preferable that
Here, when the thickness of the porous semiconductor layer is less than 5 μm, the function of the semiconductor layer cannot be sufficiently exhibited, and conversion efficiency may be reduced. On the other hand, when the thickness of the porous semiconductor layer exceeds 40 μm, the function of the semiconductor layer is saturated, and the light transmission amount may be reduced.

Further, the formation region of the porous semiconductor layer 12 is not particularly limited, but from the viewpoint of obtaining a high light transmission amount, for example, 20 to 80% of the area of the transparent substrate (preferably, the lower limit is 30%, Further, it is preferable that the upper limit is about 35% and the upper limit is about 70%, and further about 65%.
Here, when the formation region of the porous semiconductor layer is less than 20% of the area of the transparent substrate, the function of the semiconductor layer cannot be sufficiently exhibited, and conversion efficiency may be reduced. On the other hand, when the formation region of the porous semiconductor layer exceeds 80%, the function of the semiconductor layer is saturated, and the light transmission amount may be reduced.

The shape of the porous semiconductor layer 12 formed on the transparent substrate 11 is not particularly limited. For example, the shape is a triangular or quadrangular (rectangular or square) polygon, a circular shape, an elliptical shape, a star shape, or the like. By using any one of the above shapes or a combination of two or more, it is possible to form a slit portion or the like without a semiconductor layer, and to form a pattern such as a landscape or portrait.
Further, as a thermal spraying method for forming the porous semiconductor layer 12 on the transparent substrate 11, for example, high-speed flame spraying (HVOF), cold spray, flame spraying, explosive spraying (D gun), or electric spraying can be used. Among these, high-speed flame spraying and cold spray are preferable, and high-speed flame spraying is more preferable.

The sensitizing dye adsorbed on the porous semiconductor layer 12 has absorption at a wavelength of 400 to 1000 nm, for example. For example, a metal complex such as a ruthenium dye or a phthalocyanine dye, or an organic dye such as a cyanine dye can be used.
In addition, as a method for adsorbing the sensitizing dye to the porous semiconductor layer 12, an appropriate method such as a commonly used impregnation method can be used.

Then, the dye-sensitized solar cell manufactured with the manufacturing method of the dye-sensitized solar cell which concerns on the 2nd Embodiment of this invention is demonstrated.
The dye-sensitized solar cell uses the dye-sensitized solar cell anode 10 having the porous semiconductor layer 12 on which the sensitizing dye is adsorbed on the transparent substrate 11, and this dye-sensitized solar cell. The anode 10 and the cathode (counter electrode) are opposed to each other with a gap, and an electrolyte is filled between the anode 10 for the dye-sensitized solar cell and the cathode. This will be described in detail below.

The cathode is obtained by forming a conductive layer (for example, a platinum film) on the entire surface (or a part thereof) of a substrate (conductive substrate) provided with a conductive film. The conductive film is, for example, an FTO film (tin oxide film doped with fluorine), an ITO film (indium film doped with tin), a SnO ₂ film (tin oxide film), or the like.
This substrate may be a glass plate or a resin plate like the transparent substrate described above. In addition, the thickness of a board | substrate is about 2-5 mm, for example.

The thickness of the conductive layer is not particularly limited, but is preferably about 10 to 40 μm (preferably the lower limit is 15 μm and the upper limit is 30 μm) from the viewpoint of obtaining a high light transmission amount. In addition, when the thickness of a conductive layer is less than 10 micrometers, the function of a conductive layer cannot fully be exhibited, and when the thickness of a conductive layer exceeds 40 micrometers, there exists a possibility of causing the fall of the amount of light transmission.
In addition, as a method for forming the conductive layer on the substrate, for example, the above-described spraying method, a generally used film forming method, or the like can be used.

As the electrolyte, for example, an electrolyte containing iodine, lithium ion, ionic liquid, t-butylpyridine and the like can be used. In the case of iodine, an oxidation-reduction body composed of a combination of iodide ions and iodine can be used. The redox form contains an appropriate solvent that can dissolve the redox form.
In the dye-sensitized solar cell, an electrolyte is filled between the anode 10 for the dye-sensitized solar cell and the cathode, and this electrolyte is sealed.

Next, the manufacturing method of the anode for dye-sensitized solar cells which concerns on the 1st Embodiment of this invention is demonstrated. In addition, the manufacturing method of the anode 10 for dye-sensitized solar cells has a preparatory process, a semiconductor layer formation process, and a dye adsorption process.
(Preparation process)
First, the transparent substrate 11 shown in FIG. 1A is cleaned by a commonly used method.

(Semiconductor layer formation process)
Next, as shown in FIG. 1B, a mask 13 made of a heat resistant resin is formed in a preset region on the transparent substrate 11 cleaned in the above preparation process.
The mask 13 is not particularly limited as long as it is made of a resin that has heat resistance during the subsequent thermal spraying and can withstand the collision of the fine particles of the material. A resin is preferred.

Note that the shape of the mask 13 (that is, the preset region) is formed so that the transparent substrate 11 looks like a slit in FIG. 1B. However, the necessary photovoltaic power generation amount and light transmission amount are taken into consideration. Can be determined as appropriate. Further, the method for forming the mask 13 is not particularly limited, and for example, a screen print that is usually used can be used.
After the mask 13 is formed on the transparent substrate 11 by the above-described method, the porous material described above is used on the transparent substrate 11 on which the mask 13 is formed, as shown in FIG. A porous semiconductor layer 14 having the same thickness as the semiconductor layer 12 is formed.

Although various methods described above can be used for the thermal spraying method, when the high-speed flame spraying method is used, the thermal spraying apparatus 20 shown in FIG. 2 is used.
The thermal spraying device 20 burns fuel such as kerosene together with oxygen in the combustion chamber 21 to generate a high-speed flame, mixes the atomized material slurry and the high-speed flame in the injection nozzle 22 directly connected to the combustion chamber 21, This is a device for conveying the material in the flow of a high-speed frame through a barrel (jet nozzle) 23 while partially melting the surface layer portion of the material, and depositing it on the transparent substrate 11 arranged perpendicular to the flow of the high-speed frame. . Note that the flow rate of oxygen is set to be greater than the flow rate of kerosene.
A porous semiconductor layer formed by this high-speed flame spraying method is preferable because fine particles of a material (particularly titanium oxide) are highly bonded and dense, and good electron mobility can be obtained.

In the case of the high-speed flame spraying method, the temperature of the high-speed flame at a distance of 100 mm from the tip of the spray nozzle is preferably 1500 ° C. or less, preferably 1000 ° C. or less.
The speed of the high-speed frame ejected from the ejection nozzle is preferably 500 m / sec or more at the tip of the ejection nozzle. When the speed is lower than this, sufficient adhesion strength cannot be obtained between the deposited material particles, which may cause a decrease in battery performance.
The distance between the spray nozzle and the transparent substrate is preferably 100 to 500 mm from the tip of the spray nozzle, but varies depending on temperature conditions and the like.
Furthermore, the dispersion medium used for the slurry of material particles is not particularly limited, and may be, for example, water or a mixed liquid of water and an organic solvent. The content of the material in the slurry is not particularly limited, but is 5 to 50% by mass in order to achieve an efficient deposition rate and prevent the injection nozzle from clogging. It is preferable.

In addition, when performing high-speed flame spraying using the above-described thermal spraying apparatus, the number of times of spraying (number of passes) by spraying the material on the transparent substrate is made two or more passes, and the thickness of the porous semiconductor layer 14 is increased. Use the target thickness.
In this case, first, in the first pass, a barrel having a standard material supply port (hereinafter also referred to as a standard barrel) is used to improve the adhesion of the material to the transparent substrate. In the second pass or more, a tip (hereinafter also referred to as a tip barrel) for expanding the spraying range of the material is provided at the tip of the barrel to improve the specific surface area of the sprayed material.
As a result, the porous semiconductor layer 14 is formed directly on the transparent substrate 11 in the region where the mask 13 exists on the transparent substrate 11 via the mask 13 and in the region where the mask 13 does not exist. .

(Dye adsorption process)
As shown in FIG. 1D, the mask 13 is removed from the transparent substrate 11.
As a result, the porous semiconductor layer in the porous semiconductor layer 14 in the region where the mask 13 existed (preset region) is removed from the transparent substrate 11 together with the mask 13, and the mask 13 does not exist. The porous semiconductor layer in the region (outside the preset region) remains, and the porous semiconductor layer 12 is formed on the transparent substrate 11.
In addition, although the removal method of the mask 13 is not specifically limited, When the above-mentioned ultraviolet curable resin is used as the mask 13, for example, it is immersed in water heated to about 50 ° C. for about 10 minutes. The mask 13 can be peeled off from the transparent substrate 11 and removed.

As described above, after removing the mask 13 from the transparent substrate 11, the sensitizing dye is adsorbed to the porous semiconductor layer 12 on the transparent substrate 11.
This sensitizing dye can be adsorbed to the porous semiconductor layer 12 by an appropriate method such as a commonly used impregnation method.
After the sensitizing dye is adsorbed on the porous semiconductor layer 12 by the above-described method, it is sufficiently washed.

Then, the manufacturing method of the dye-sensitized solar cell which concerns on the 2nd Embodiment of this invention is demonstrated.
The above-described dye-sensitized solar cell anode 10 and cathode are prepared.
The cathode is obtained by washing a substrate having a conductive film by a commonly used method and then spraying an aqueous solution of a conductive material onto the substrate by, for example, a thermal spraying method (the conductive layer on the surface of the substrate). Is obtained). Note that after the conductive layer is formed on the substrate, for example, baking is performed at a predetermined temperature.
A dye-sensitized solar cell can be manufactured by disposing the dye-sensitized solar cell anode 10 and the cathode so as to face each other with a gap therebetween, and filling and sealing the electrolyte therebetween.

Next, examples carried out for confirming the effects of the present invention will be described.
First, the anode and cathode used in the test and the method for producing the dye-sensitized solar cell will be described below.

(Preparation of anode and cathode by thermal spraying method)
The porous semiconductor layer of the anode and the conductive layer of the cathode were formed by a high-speed flame spraying method using the thermal spraying apparatus 20 shown in FIG.
The anode transparent substrate and the cathode substrate are 3 mm thick glass substrate with transparent conductive film (FTO substrate), and the porous semiconductor layer is made of titanium dioxide powder P90 (Nippon Aerosil). As the material for the conductive layer, an aqueous solution of chloroplatinic acid (manufactured by Kanto Chemical Co., Inc.) was used.

As the thermal spraying conditions, the supply amounts of oxygen and kerosene (combustion conditions) were all constant. In addition, the flow rate of oxygen was adjusted so as to be rich in oxygen with respect to kerosene.
In the formation of the porous semiconductor layer, the above-described P90 powder added with 20% by mass of pure water was used as a slurry, and in the formation of the conductive layer, the chloroplatinic acid powder was added to pure water in an amount of 0.1%. What added 1 mass% was used as a precursor solution.
In producing the anode and the cathode, a slurry or a solution was sprayed onto the above-described substrate to form a titanium dioxide film as a porous semiconductor layer and a platinum film as a conductive layer.

(Adjusting the thickness of titanium dioxide film and platinum film)
The film thickness was adjusted by changing the number of spraying times (number of passes) by thermal spraying.
Here, regarding the formation of the titanium dioxide film, the standard barrel was used for the first pass, and the tip barrel was used for the second pass and beyond. A standard barrel was used for the formation of the platinum film.

The anode was prepared by immersing a transparent substrate on which a titanium dioxide film was formed in a sensitizing dye for 24 hours. This sensitizing dye solution was prepared by dissolving 3 × 10 ⁻⁴ M (mol) of the sensitizing dye in a mixed solution (volume ratio: 1: 1) of t-butyl alcohol and acetonitrile. In addition, after taking out the said transparent substrate from this solution, it fully wash | cleaned with the organic solvent.
The cathode was prepared by baking a substrate on which a platinum film was formed at 450 ° C. for 30 minutes.

With respect to the anode and cathode manufactured by changing the number of passes by the above-described method, the film thickness and the light transmittance were measured.
This film thickness measurement is performed using an ultra-precision non-contact surface property measuring instrument (Talysurf CCI-Lite: AMETEK), and the light transmittance is measured using a haze meter (HZ-V3: manufactured by Suga Test Instruments Co., Ltd.). I went there.

Dye-sensitized solar cells were prepared using anodes and cathodes having various film thicknesses.
The anode and the cathode were sealed using a photocurable resin containing a spacer.
In addition, the electrolyte between the anode and the cathode was filled by encapsulating the electrolyte using a capillary phenomenon through a gap between the resin previously provided. As the electrolytic solution, a solution obtained by adding lithium iodide (500 mM), t-butylpyridine (580 mM), iodine (50 mM), and ionic liquid (600 mM) to acetonitrile was used.

After the electrolytic solution was sealed, the resin gap was sealed.
About the dye-sensitized solar cell produced by the said method, the light transmittance and the photoelectric conversion efficiency were measured. In addition, the measurement of photoelectric conversion efficiency was measured using the IV characteristic measurement apparatus under the pseudo-sunlight irradiation adjusted to 100 mW / cm ² .

(Preparation of dye-sensitized solar cell with a changed porous semiconductor layer formation region)
After cleaning the glass substrate having a thickness of 3 mm, the anode was screen-printed with an ultraviolet curable heat-resistant resin using a hand print device (SHP-2530V-AJ: manufactured by SERIA).
Next, after the heat resistant resin was cured with ultraviolet rays to form a mask, a titanium dioxide film was formed on the glass substrate by a thermal spraying method. Here, the number of spraying passes of titanium dioxide was fixed to two.
On the other hand, for the cathode, after a glass substrate having a thickness of 3 mm was washed, a platinum film was formed on the glass substrate by a thermal spraying method. Here, the number of sprays of the chloroplatinic acid solution was fixed to 5 times.

After the above thermal spraying, the anode was removed by removing the mask from the transparent substrate by immersing the heat resistant resin in water heated to about 50 ° C. for about 10 minutes. And the sensitizing dye was made to adsorb | suck to a titanium dioxide film by the above-mentioned method.
On the other hand, for the cathode, a platinum film was baked at 450 ° C. for 30 minutes.
The anode has a configuration in which eight 1 cm × 10 cm strip-shaped cells (titanium dioxide films) are arranged in parallel (see FIG. 1D), and the total area is 80 cm ² . Further, another anode having a total area of 40 cm ² was prepared by arranging four 1 cm × 10 cm strip cells in parallel by the same method as described above.

A dye-sensitized solar cell was produced using the produced anode and cathode.
Metal wiring and a protective layer were provided between adjacent strip cells.
Further, after an electrolyte injection hole was perforated on the cathode side, the gap between the anode and the cathode was sealed using an ultraviolet curable resin containing a spacer. And after filling electrolyte solution from an injection port, the injection port was sealed and the dye-sensitized solar cell was formed.
About each dye-sensitized solar cell using two types of above-mentioned anodes, the light transmittance and the photoelectric conversion efficiency were measured.

  The results of various tests conducted using the anode and cathode obtained by the above method and the dye-sensitized solar cell will be described below.

(Transmittance control by adjusting the thickness of titanium dioxide film and platinum film)
FIG. 3A shows the film thickness with respect to the number of passes of a titanium dioxide film formed by thermal spraying on a glass substrate. FIG. 3B shows the light transmittance with respect to the thickness of the titanium dioxide film on which the sensitizing dye is adsorbed.
As shown in FIG. 3A, the film thickness increased as the number of passes increased. On the other hand, as shown in FIG. 3B, the light transmittance of the glass substrate before forming the titanium dioxide film was 83.7%, whereas the thickness of the titanium dioxide film was 1.9 μm. The light transmittance of the glass substrate was 40.2%, and 4.18% when the thickness was 12 μm. The light transmittance was greatly reduced as the film thickness increased.

FIG. 4A shows the film thickness with respect to the number of passes of a platinum film formed by thermal spraying on a glass substrate. FIG. 4B shows the light transmittance with respect to the thickness of the platinum film.
As shown in FIG. 4A, the film thickness increased with an increase in the number of passes, similar to the titanium dioxide film described above. On the other hand, as shown in FIG. 4B, when the film thickness of the platinum film is 20 nm or more, the light transmittance is remarkably reduced. When the film thickness is 45 nm, the light transmittance is 43.1%, which is a non-formed film. The light transmittance was halved compared to the film.

Next, the dye-sensitized solar cell was produced using the titanium dioxide film from which film thickness differs. The cathode used was a platinum film having a thickness of 21 nm with a slight decrease in light transmittance.
First, the result of the photoelectric conversion efficiency of the dye-sensitized solar cell is shown in FIG.
As shown in FIG. 5A, the photoelectric conversion efficiency of the dye-sensitized solar cell increased with an increase in the thickness of the titanium dioxide film.

Next, the result of the light transmittance of the whole dye-sensitized solar cell with respect to the photoelectric conversion efficiency of the dye-sensitized solar cell is shown in FIG.
As shown in FIG. 5B, when the photoelectric conversion efficiency of the dye-sensitized solar cell is 2.06% (thickness of the titanium dioxide film: 1.9 μm), the light transmittance of the dye-sensitized solar cell is 20 When the photoelectric conversion efficiency of the dye-sensitized solar cell is 4.30% (thickness of the titanium dioxide film: 12 μm), the light transmittance of the dye-sensitized solar cell is 5.2%. there were.
That is, the light transmittance decreased as the photoelectric conversion efficiency of the dye-sensitized solar cell increased, that is, the thickness of the titanium dioxide film increased.

From the above, when using a dye-sensitized solar cell in which the thickness of the titanium dioxide film is adjusted, for example, for a window surface, a light transmittance of about 20% is insufficient, but the light transmittance is further increased. Therefore, the photoelectric conversion efficiency is unavoidably reduced.
Therefore, it can be seen that it is very difficult to achieve both power generation and light transmission by adjusting the thickness of the titanium dioxide film.

(Dye-sensitized solar cell with changed porous semiconductor layer formation region)
FIG. 6 shows the results of measuring the IV characteristics when the formation region of the titanium dioxide film is variously changed. The formation region of the titanium dioxide film, 80 cm ² (○ mark in Fig. 6), 40 cm ² (× mark in FIG. 6), 0.25 cm ² (◆ mark in FIG. 6), and a.
As a result of the decrease in short circuit current density (Jsc) and fill factor (FF) due to the increase in the formation region (area) of the titanium dioxide film, the photoelectric conversion efficiency is 0.25 cm ^{2 in} the formation region of the titanium dioxide film from FIG. 2.79% at 80 cm ² , 2.44% at 80 cm ² and 2.54% at 40 cm ² . Here, the cause of the decrease in the short-circuit current density and the fill factor may be that the current collection effect by the metal wiring is insufficient, and that the distance between the anode and the cathode is increased by forming the current collection wiring. .

The output of the dye-sensitized solar cell is 194.8 mW when the titanium dioxide film forming region is 80 cm ² , 101.7 mW when 40 cm ² , and the output when 40 cm ² is the output when 80 cm ^2. About half of that. Moreover, the relationship between the photoelectric conversion efficiency and the light transmission amount of the dye-sensitized solar cell in which the formation region of the titanium dioxide film was changed was a proportional relationship. On the other hand, the light transmittance attenuates exponentially with respect to the film thickness.

Here, the photoelectric conversion efficiency with respect to the light transmittance is shown in FIG. 7 about the dye-sensitized solar cell which changed the formation area of the titanium dioxide film, and the dye-sensitized solar cell which adjusted the film thickness of the titanium dioxide film.
As shown in FIG. 7, it can be seen that the method of changing the formation region of the titanium dioxide film can suppress the decrease in light conversion efficiency accompanying the increase in the amount of light transmission, compared with the method of adjusting the film thickness of the titanium dioxide film. It was.

  From the above, by using the method for producing an anode for a dye-sensitized solar cell and the method for producing a dye-sensitized solar cell of the present invention, the design is excellent and the amount of photovoltaic power generation and the amount of light transmission can be freely controlled. It was confirmed that an anode for a dye-sensitized solar cell and a dye-sensitized solar cell could be provided.

  As described above, the present invention has been described with reference to the embodiment. However, the present invention is not limited to the configuration described in the above embodiment, and the matters described in the scope of claims. Other embodiments and modifications conceivable within the scope are also included. For example, the present invention can also be applied to the case where the method for producing an anode for a dye-sensitized solar cell and the method for producing a dye-sensitized solar cell of the present invention are configured by combining some or all of the above-described embodiments and modifications. Included in the scope of rights.

10: Anode for dye-sensitized solar cell, 11: Transparent substrate, 12: Porous semiconductor layer, 13: Mask, 14: Porous semiconductor layer, 20: Thermal spraying device, 21: Combustion chamber, 22: Injection nozzle, 23: barrel

Claims (4)

In the method for producing an anode for a dye-sensitized solar cell having a porous semiconductor layer on which a sensitizing dye is adsorbed on a transparent substrate,
A semiconductor which forms a porous semiconductor layer using a thermal spraying method on the transparent substrate on which the mask is formed after forming a mask made of a heat-resistant resin in a predetermined region on the transparent substrate A layer forming step;
A dye adsorption step of adsorbing the sensitizing dye to the porous semiconductor layer outside the region on the transparent substrate after removing the mask from the region on the transparent substrate. A method for producing an anode for a solar cell.   The method for producing an anode for a dye-sensitized solar cell according to claim 1, wherein the heat-resistant resin is an ultraviolet curable resin.   3. The method for producing an anode for a dye-sensitized solar cell according to claim 1, wherein the material of the porous semiconductor layer is fine particles of titanium oxide.   A dye-sensitized solar cell anode manufactured using the method for manufacturing a dye-sensitized solar cell anode according to any one of claims 1 to 3 and a cathode, with a gap therebetween, A method for producing a dye-sensitized solar cell, wherein an electrolyte is filled between the anode for the dye-sensitized solar cell and the cathode.

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