JP5214681B2 - Photoelectric conversion element - Google Patents

Description

 The present invention relates to a photoelectric conversion element such as a dye-sensitized solar cell.

 Examples of the photoelectric conversion element include a dye-sensitized solar cell that is inexpensive and can provide high photoelectric conversion efficiency.

 A dye-sensitized solar cell includes, for example, a transparent substrate made of a light-transmitting material such as a glass substrate, a working electrode made of a transparent conductive film and a porous oxide semiconductor layer sequentially formed on one surface thereof, and glass The substrate is generally composed of a substrate made of an insulating material such as a substrate, a counter electrode made of a conductive film formed on one surface thereof, and an electrolyte layer made of a gel electrolyte enclosed between them.

Conventionally, such a dye-sensitized solar cell has been manufactured by the following manufacturing method.
FIG. 7 is a schematic cross-sectional view showing a conventional method for producing a dye-sensitized solar cell.
First, a working electrode 104 comprising a transparent substrate 101, a transparent conductive film 102 and a porous oxide semiconductor layer 103 formed in order on one surface of the transparent substrate 101 is formed, and a sensitizing dye is supported on the porous oxide semiconductor layer 103. .

Next, the working electrode 104 and the counter electrode 108 made of the conductive film 107 formed on one surface of the substrate 106 are bonded to each other using a hot melt adhesive 110 at a predetermined interval.
Next, the organic electrolyte 115 is filled between the working electrode 104 and the counter electrode 108 through a through-hole 109 provided in the counter electrode 108 in advance to form an electrolyte layer made of the organic electrolyte 115, and dye A sensitized solar cell is obtained.

 In recent years, development of a flexible dye-sensitized solar cell in which a substrate made of a flexible material such as synthetic resin is used as the transparent substrate 101 and the substrate 106 instead of a glass substrate (for example, , Patent Document 1, Patent Document 2, and Patent Document 3.)

However, when a dye-sensitized solar cell using a substrate made of such a flexible material is manufactured by the above-described conventional manufacturing method, there are the following problems.
As shown in FIG. 8, when the organic electrolyte 115 is filled with pressure between the working electrode 104 and the counter electrode 108 through the through-hole 109, the arrow shown in the figure is applied to the working electrode 104 and the counter electrode 108. A pressure is applied in the direction, and the dye-sensitized solar cell swells, and there is a problem that the distance between the working electrode 104 and the counter electrode 108 cannot be kept constant. If the distance between the working electrode and the counter electrode (hereinafter sometimes referred to as “dipole distance”) is not kept constant, the photoelectron conversion efficiency of the dye-sensitized solar cell deteriorates.

In particular, when using a high-viscosity electrolyte solution such as an ionic liquid electrolyte as the organic electrolyte solution, the electrolyte solution cannot be filled between the working electrode and the counter electrode unless a high pressure is applied. Such a problem appears remarkably.
In addition, when the size of the dye-sensitized solar cell is increased, the same problem may occur even if a glass substrate is used as a substrate serving as a working electrode and a counter electrode as in the prior art.

JP-A-11-288745 JP 2001-357896 A JP 11-329519 A

 The present invention has been made in view of the above circumstances, and an object thereof is to provide a photoelectric conversion element in which the distance between the working electrode and the counter electrode is kept constant.

The photoelectric conversion element of the present invention is a photoelectric conversion element provided with a working electrode, a counter electrode, and an electrolyte layer formed therebetween, and the electrolyte constituting the electrolyte layer is maintained at a pressure maintained after encapsulation. Is sealed at a pressure lower than atmospheric pressure.

At least one of the substrate forming the working electrode or the substrate forming the counter electrode is a flexible substrate, and an adhesive is provided around the porous oxide semiconductor layer forming the working electrode, and the working electrode and the counter electrode It is preferable that at least a part of the portion corresponding to the porous oxide semiconductor layer is shorter than the portion corresponding to the adhesive.
The method for producing a photoelectric conversion element of the present invention is a method for producing a photoelectric conversion element comprising a working electrode, a counter electrode, and an electrolyte layer formed therebetween, and an electrolytic solution for forming the electrolyte layer, The sealing is performed so that the pressure maintained after the sealing is lower than the atmospheric pressure.
At least one of the substrate forming the working electrode or the substrate forming the counter electrode is a flexible substrate, an adhesive is provided around the porous oxide semiconductor layer forming the working electrode, and the working electrode and the counter electrode It is preferable that the distance between them be shorter than at least a part corresponding to the adhesive in at least a part corresponding to the porous oxide semiconductor layer.

 In the photoelectric conversion element of the present invention, since the electrolytic solution constituting the electrolyte layer is sealed at a pressure lower than atmospheric pressure, either the working electrode or the counter electrode, or the material forming both of them is flexible. Even when the electrode is made of a material, the distance between the working electrode and the counter electrode is kept constant. Therefore, the photoelectric conversion element of the present invention has excellent photoelectron conversion efficiency.

It is a schematic sectional drawing which shows the manufacturing method of a dye-sensitized solar cell as 1st embodiment which concerns on this invention. It is a schematic sectional drawing which shows a dye-sensitized solar cell as 1st embodiment which concerns on this invention. It is a schematic perspective view which shows the manufacturing method of a dye-sensitized solar cell as 2nd embodiment which concerns on this invention. It is a schematic perspective view which shows the manufacturing method of a dye-sensitized solar cell as 3rd embodiment which concerns on this invention. It is the schematic which shows 3rd embodiment which concerns on this invention, (a) is a perspective view, (b) is sectional drawing which follows the AA line of (a). It is a graph which shows the result of having measured the relationship between a voltage and a current density about the dye-sensitized solar cell in the Example and comparative example of this invention. It is a schematic sectional drawing which shows the manufacturing method of the conventional dye-sensitized solar cell. It is a schematic sectional drawing which shows the manufacturing method of the conventional dye-sensitized solar cell.

Embodiments of the photoelectric conversion element of the present invention will be described.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.

A first embodiment according to the present invention will be described with reference to FIGS. 1 and 2.
FIG. 1 is a schematic cross-sectional view showing a method for producing a dye-sensitized solar cell as a first embodiment according to the present invention. FIG. 2 is a schematic sectional view showing a dye-sensitized solar cell as a first embodiment according to the present invention.
1 and 2, reference numeral 11 is a transparent substrate, 12 is a transparent conductive film, 13 is a porous oxide semiconductor layer, 14 is a working electrode, 15 is a substrate, 16 is a conductive film, 17 is a counter electrode, and 18 is an adhesive. , 19 is a laminate, 20 is a through-hole, 21 is an electrolytic solution, 22 is a sealing member, and 23 is an electrolyte layer.

 In this embodiment, in order to manufacture a dye-sensitized solar cell, first, the transparent substrate 11, the transparent conductive film 12 and the working electrode 14 formed of the porous oxide semiconductor layer 13 sequentially formed on one surface thereof are provided. And a sensitizing dye is supported on the surface of the porous oxide semiconductor layer 13.

 Moreover, the counter electrode 17 which consists of the board | substrate 15 and the electrically conductive film 16 formed in the one surface is formed.

 Next, the working electrode 14 and the counter electrode 17 are bonded via the adhesive 18 to form the laminate 19. By forming this laminate 19, a space of a predetermined size (a space filled with an electrolytic solution in a subsequent process) is formed between the working electrode 14 and the counter electrode 17.

 Next, the electrolytic solution 21 is filled between the working electrode 14 and the counter electrode 17 from one of the two through holes 20, 20 provided in the counter electrode 17 in advance, and most of the electrolytic solution 21 is formed in the gap of the porous semiconductor layer 13. Impregnate the part.

 Next, one of the two through holes 20 and 20 is sealed with a sealing member 22.

Next, a part of the electrolytic solution 21 filled in the space between the working electrode 14 and the counter electrode 17 is sucked out from the through-hole 20 not sealed with the sealing member 22 by using a vacuum pump or the like, so that this space. The inside is depressurized. Then, due to the atmospheric pressure, the working electrode 14 and the counter electrode 17 are pushed in the direction of the surfaces facing each other (the direction of the arrow shown in FIG. 1), and as a result, the laminate 19 contracts in this direction, The distance between the working electrode 14 and the counter electrode 17 is reduced. At this time, a check valve or the like is provided in the through hole 20 that is not sealed with the sealing member 22. By providing a check valve or the like, the decompressed state in the space is maintained even when the suction of the electrolytic solution 21 in the space by the vacuum pump is finished.
In this process, a part of the excess electrolyte solution 21 is sucked out from the through-hole 20, but the electrolyte solution 21 is sucked while the void portion of the porous semiconductor layer 13 is completely filled with the electrolyte solution 21. Is issued. In addition, the pressure is preferably reduced until the working electrode 14 and the counter electrode 17 come into contact with each other.

 Next, the suction of the electrolytic solution 21 in the space by the vacuum pump is finished, and the through hole 20 used for sucking out the electrolytic solution 21 is maintained while the space between the working electrode 14 and the counter electrode 17 is decompressed. Is sealed with a sealing member 22 to form an electrolyte layer 23 between the working electrode 14 and the counter electrode 17 to obtain a dye-sensitized solar cell.

 In addition, in this embodiment, although the example which provided the through-hole 20 in the counter electrode 17 was shown, this invention is not limited to this. In the present invention, at least one through hole is provided in the working electrode or the counter electrode, and after the electrolyte is filled through the one through hole, a part of the electrolyte is sucked out from the one through hole. The through hole may be sealed. Alternatively, after providing three through holes on the working electrode or the counter electrode, sealing all but one of the through holes, and sucking out a part of the electrolyte from one unsealed through hole, You may seal this through-hole which is not sealed.

 As the transparent substrate 11, a substrate made of a light-transmitting material is used, and any substrate made of glass, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethersulfone, etc., which is usually used as a substrate for solar cells. Even things can be used. In order to realize a flexible dye-sensitized solar cell, it is preferable to use a substrate made of a flexible material as the transparent substrate 11. As the substrate made of a flexible material, a substrate made of a synthetic resin is usually used. For example, a substrate made of the above-described polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethersulfone, or the like can be given.

The transparent conductive film 12 is a thin film made of metal, carbon, conductive metal oxide, or the like formed on one surface of the transparent substrate 11 in order to impart conductivity.
When a metal thin film or a carbon thin film is formed as the transparent conductive film 12, the transparent substrate 11 has a structure that does not significantly impair the transparency. Examples of the conductive metal oxide that forms the transparent conductive film 12 include indium-tin oxide (ITO), tin oxide (SnO ₂ ), and fluorine-doped tin oxide.

The porous oxide semiconductor layer 13 is provided on the transparent conductive film 12. The semiconductor that forms the porous oxide semiconductor layer 13 is not particularly limited, and any semiconductor that can be used to form a porous semiconductor for solar cells can be used. As such a semiconductor, for example, titanium oxide (TiO ₂ ), tin oxide (SnO ₂ ), tungsten oxide (WO ₃ ), zinc oxide (ZnO), niobium oxide (Nb ₂ O ₅ ), or the like can be used. .
Examples of the method of forming the porous oxide semiconductor layer 13 include a method of forming the porous oxide semiconductor layer 13 by applying a paste containing the semiconductor nanoparticles on the transparent conductive film 12 and then baking it. Is not to be done.

 As the sensitizing dye, a ruthenium complex containing a bipyridine structure, a terpyridine structure or the like as a ligand, a metal-containing complex such as porphyrin or phthalocyanine, an organic dye such as eosin, rhodamine or merocyanine can be applied. From these, a sensitizing dye exhibiting an excitation behavior suitable for the application and the semiconductor used can be selected without particular limitation.

As the substrate 15, a metal plate, a synthetic resin plate, or the like is used because it is not necessary to have the same properties as those of the transparent substrate 11 or light transmittance. In order to realize a flexible dye-sensitized solar cell, it is preferable to use a substrate made of a flexible material as the substrate 15. As a substrate made of a flexible material, a synthetic resin plate is usually used. Examples of such synthetic resin plates include substrates made of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethersulfone, and the like.

 The conductive film 16 is a thin film made of metal, carbon or the like formed on one surface of the substrate 15 in order to impart conductivity. As the conductive film 16, for example, a layer of carbon, platinum, or the like, which has been heat-treated after vapor deposition, sputtering, and application of chloroplatinic acid, is preferably used. is not.

 The adhesive 18 is not particularly limited as long as it has excellent adhesion to the transparent conductive film 12 and the conductive film 16, but in particular, when the transparent conductive film 12 and the conductive film 16 are made of metal, the adhesive 18 has excellent adhesion to metal. An excellent one is desirable. As an adhesive having excellent adhesion to metal, an adhesive made of a thermoplastic resin having a carboxylic acid group in its molecular chain is desirable. Polychemical Co., Ltd.).

 As the electrolytic solution 21, an electrolytic component such as iodine, iodide ion, and tertiary butyl pyridine dissolved in an organic solvent such as ethylene carbonate or methoxyacetonitrile, an ionic liquid, or the like is used.

 The sealing member 22 is not particularly limited as long as it has excellent adhesion to the substrate 15 forming the counter electrode 17. For example, an adhesive made of a thermoplastic resin having a carboxylic acid group in the molecular chain is desirable. Specifically, high Milan (made by Mitsui DuPont Polychemical Co., Ltd.), binel (made by Mitsui DuPont Polychemical Co., Ltd.), Aron Alpha (made by Toagosei Co., Ltd.) and the like can be mentioned.

 As described above, in this embodiment, the electrolytic solution is filled between the working electrode 14 and the counter electrode 17 through the through holes 20 and 20 provided in the counter electrode 14, and then the one through hole 20 is sealed. Then, after part of the electrolytic solution 21 is sucked out from the other through-hole 20, the other through-hole 20 is also sealed and the electrolytic solution 21 is sealed between the working electrode 14 and the counter electrode 17. 21 is enclosed in the dye-sensitized solar cell at a pressure lower than atmospheric pressure. Therefore, since the working electrode 14 and the counter electrode 17 are fixed in a state where atmospheric pressure is applied in the direction of the surface where they face each other, either the working electrode 14 or the counter electrode 17 or both of them can be used. Even when made of a flexible material, a dye-sensitized solar cell in which the distance between the working electrode 14 and the counter electrode 17 is kept constant can be realized. Therefore, the dye-sensitized solar cell obtained in this embodiment has excellent photoelectron conversion efficiency.

Next, a second embodiment according to the present invention will be described with reference to FIG.
FIG. 3: is a schematic perspective view which shows the manufacturing method of a dye-sensitized solar cell as 2nd embodiment which concerns on this invention.
This embodiment is different from the first embodiment in a method of keeping the distance between the working electrode 14 and the counter electrode 17 constant in the laminate 19. In FIG. 3, the same components as those of the first embodiment shown in FIGS. 1 and 2 are denoted by the same reference numerals, and the description thereof is omitted.

 In this embodiment, in the same manner as in the first embodiment, after the laminate 19 is formed, the laminate 19 is composed of a pair of flat plates 31 and 31 from the outer surfaces of the working electrode 14 and the counter electrode 17. The pressure member 30 is sandwiched. By this pressurizing member 30, the working electrode 14 and the counter electrode 17 are uniformly pressed in the direction of the surface where they face each other (the direction of the arrow shown in FIG. 3), thereby narrowing the distance between the two electrodes. At this time, pressure may be applied until the working electrode 14 and the counter electrode 17 come into contact with each other.

 Next, in this state, the electrolytic solution is filled between the working electrode 14 and the counter electrode 17 through the at least one through hole 20 provided in advance in the counter electrode 17, and most of the electrolytic solution is formed in the porous oxide semiconductor layer. Impregnate the voids.

 Next, while the working electrode 14 and the counter electrode 17 are kept pressurized with the pressurizing member 30, the through hole 20 is sealed with a sealing member, and the electrolyte solution is placed between the working electrode 14 and the counter electrode 17. An electrolyte layer is formed.

 Next, the pressure applied to the working electrode 14 and the counter electrode 17 is gradually released by the pressure member 30, and finally the pressure member 30 is removed to obtain a dye-sensitized solar cell.

 As the pressing member 30, for example, flat plates 31 and 31 made of a pair of silicon rubber are used, but the present invention is not limited to this. The pressurizing member 30 is not particularly limited as long as the surface in contact with the working electrode 14 or the counter electrode 17 is flat and can be configured to apply a predetermined pressure uniformly to both electrodes.

 Further, as the sealing member for sealing the through hole 20, the same member as the sealing member 22 is used.

 As described above, in this embodiment, the working electrode 14 and the counter electrode are maintained in a state in which the working electrode 14 and the counter electrode 17 are uniformly pressed in the direction of the surfaces facing each other by the pressing member 30. 17, the electrolytic solution is sealed between them and the electrolytic solution is sealed in the dye-sensitized solar cell at a pressure lower than atmospheric pressure. Therefore, since the working electrode 14 and the counter electrode 17 are fixed in a state where atmospheric pressure is applied in the direction of the surface where they face each other, either the working electrode 14 or the counter electrode 17 or both of them can be used. Even when made of a flexible material, a dye-sensitized solar cell in which the distance between the working electrode 14 and the counter electrode 17 is kept constant can be realized. Therefore, the dye-sensitized solar cell obtained in this embodiment has excellent photoelectron conversion efficiency.

Next, a third embodiment according to the present invention will be described with reference to FIGS. 4 and 5.
FIG. 4: is a schematic perspective view which shows the manufacturing method of a dye-sensitized solar cell as 3rd embodiment which concerns on this invention. 5A and 5B are schematic views showing a third embodiment according to the present invention, in which FIG. 5A is a perspective view, and FIG. 5B is a cross-sectional view taken along line AA in FIG.

 4 and 5, reference numeral 41 is a transparent substrate, 42 is a transparent conductive film, 43 is a porous oxide semiconductor layer, 44 is a working electrode, 45 substrates, 46 is a conductive film, 47 is a counter electrode, 49 is a laminate, 52 electrolyte layers, 55 and 56 are conductors, and 60 is a bag.

 In this embodiment, in order to manufacture a dye-sensitized solar cell, first, the working electrode 44 including the transparent substrate 41, the transparent conductive film 42 and the porous oxide semiconductor layer 43 formed in order on one surface thereof is provided. Form. In addition, a conductor 55 is provided on the surface of the transparent conductive film 42 forming the working electrode 44 on the side in contact with the porous oxide semiconductor layer 43 for leading the power generated in the dye-sensitized solar cell to the outside. Further, a sensitizing dye is supported on the surface of the porous oxide semiconductor layer 43.

 Next, an electrolyte solution is dropped and impregnated into the porous oxide semiconductor layer 43 to form an electrolyte layer 52 that is integral with the porous oxide semiconductor layer 43.

 In addition, a counter electrode 47 made of the substrate 45 and the conductive film 46 formed on one surface thereof is formed. Furthermore, a conductor 56 for deriving the power generated in the dye-sensitized solar cell to the outside on the surface of the conductive film 46 forming the counter electrode 47 in contact with the electrolyte layer 52 (porous oxide semiconductor layer 43). Is provided.

 Next, the counter electrode 47 is overlapped with the working electrode 44 so that the conductive film 46 overlaps the electrolyte layer 52, and a laminate 49 is formed in which the electrolyte layer 52 is sandwiched between the working electrode 44 and the counter electrode 47.

 Next, as shown in FIGS. 4A and 4B, the laminated body 49 is accommodated in the bag body 60 formed by forming the laminate film into a bag shape from the opening. At this time, the laminated body 49 is accommodated in the bag body 60 in a state where the conductors 55 and 56 are led out of the bag body 60.

 Next, as shown in FIG. 5A, the bag body 60 is uniformly adhered to the entire outer surface of the laminated body 49 by vacuum packaging. In this vacuum packaging, the bag body 60 is contracted by sucking out air from the inside of the bag body 60 using a vacuum pump, and the bag body 60 is uniformly adhered to the entire outer surface of the laminated body 49. Then, the working electrode 44 and the counter electrode 47 are uniformly pressed by the bag body 60 in the direction of the surface where they face each other.

 Next, in this state, the bag body 60 is sealed by, for example, fusing the opening of the bag body 60 to obtain a dye-sensitized solar cell.

As the transparent substrate 41, the same one as the transparent substrate 11 is used.
The transparent conductive film 42 is the same as the transparent conductive film 12 described above.
As the porous oxide semiconductor layer 43, the same semiconductor as that forming the porous oxide semiconductor layer 13 is used.

As the sensitizing dye, those similar to those in the first embodiment described above are used.
As the electrolytic solution, an electrolyte component such as iodine, iodide ion or tertiary butyl pyridine dissolved in an organic solvent such as ethylene carbonate or methoxyacetonitrile, an ionic liquid, an ionic gel, or the like is used.

 Examples of the gelling agent used for gelling the electrolytic solution include polyvinylidene fluoride, polyethylene oxide derivatives, amino acid derivatives, and nanocomposite gels.

As the substrate 45, the same one as the substrate 15 is used.
As the conductive film 46, the same one as the conductive film 16 is used.

 As a material for forming the conductors 55 and 56, any material can be used as long as it does not adversely affect the dye-sensitized solar cell as an electrical wiring. Examples of such a conductive material include nickel (Ni), chromium (Cr), titanium (Ti), cobalt (Co), and the like.

 The laminate film forming the bag body 60 is not particularly limited as long as it is a light transmissive material and can be applied to vacuum packaging. For example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyvinyl chloride, etc. The film etc. which consist of are used.

 In this embodiment, as the electrolyte layer 52, the porous oxide semiconductor layer 43 is impregnated with an electrolytic solution, and then the electrolytic solution is gelled (pseudo-solidified) using an appropriate gelling agent. In this example, the porous oxide semiconductor layer 43 and the porous oxide semiconductor layer 43 are exemplified, but the present invention is not limited to this. In the present invention, the electrolyte layer may be formed by impregnating a porous oxide semiconductor layer with an electrolytic solution.

 As described above, in this embodiment, the bag body 60 is contracted, and the bag body 60 is uniformly brought into close contact with the entire area of the outer surface of the laminated body 49, and the bag body 60 is hermetically sealed. Since the electrolyte layer 52 is sealed between the working electrode 44 and the counter electrode 47 while keeping the state where the pressure electrode 44 and the counter electrode 47 are uniformly pressed in the direction of the surface where the two electrodes face each other, the electrolysis forming the electrolyte layer 52 is performed. The liquid is enclosed in the dye-sensitized solar cell at a pressure lower than atmospheric pressure. Therefore, since the working electrode 44 and the counter electrode 47 are fixed in a state where atmospheric pressure is applied in the direction of the surface where they face each other, either the working electrode 44 or the counter electrode 47 or both of them can be used. Even when made of a flexible material, a dye-sensitized solar cell in which the distance between the working electrode 44 and the counter electrode 47 is kept constant can be realized. Therefore, the dye-sensitized solar cell obtained in this embodiment has excellent photoelectron conversion efficiency.

 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

Example 1
A dye-sensitized solar cell was produced using the method for producing a photoelectric conversion element shown in the second example.
As the transparent substrate, a 10 cm × 10 cm conductive PET film (trade name; OTEC, manufactured by Oji Tobi Co., Ltd., conductive 10Ω / □) in which a transparent conductive film was provided on one surface of the PET film was used.
A thin conductive film made of titanium oxide having a thickness of 25 nm was formed on the transparent conductive film forming the conductive PET film by a sputtering method, thereby preparing a flexible conductive substrate.
Next, a paste of titanium oxide nanoparticles is applied by a doctor blade method so as to cover the titanium oxide film so as to have a thickness of 10 μm, and then fired at 150 ° C. for 3 hours to form a porous oxide semiconductor layer. Formed.
Next, an N3 dye was supported on the porous oxide semiconductor layer to obtain a working electrode.
In addition, a conductive PET film similar to that used for the production of the working electrode was used, and a thin film made of platinum was formed on the transparent conductive film forming the conductive PET film by a sputtering method. Obtained.
Next, two through holes were formed in this counter electrode.
Next, a sheet made of a thermoplastic resin having a width of 2 mm and a thickness of 50 μm (trade name: High Milan, manufactured by Mitsui Dupont Polychemical Co., Ltd.) is disposed on the peripheral edge of the working electrode or the counter electrode as an adhesive. The sheets were stacked via a sheet made of this thermoplastic resin so that a space of a predetermined size was formed between them.
Subsequently, the sheet | seat which consists of thermoplastic resins was heated and fuse | melted, the working electrode and the counter electrode were adhere | attached, and the laminated body was formed.
Next, the laminate is sandwiched from the outer surface of the working electrode and the counter electrode with a pressure member made of a pair of silicon rubber plates at a pressure of 15 kg / 100 cm ² , and in this state, from the through hole provided in the counter electrode An electrolytic solution was filled between the working electrode and the counter electrode, and most of the electrolytic solution was impregnated in the void portion of the porous oxide semiconductor layer.
After the filling of the electrolytic solution was completed, the through hole was sealed with a sealing member while applying pressure to the laminate by the pressure member.
Next, the pressure applied to the working electrode and the counter electrode was gradually released by the pressure member, and finally the pressure member was removed to obtain a dye-sensitized solar cell.

(Example 2)
A dye-sensitized solar cell was produced using the method for producing a photoelectric conversion element shown in the second example.
As the transparent substrate, 10 cm × 10 cm conductive glass (conductive 10 Ω / □) in which a transparent conductive film was provided on one surface of the glass substrate was used.
A thin film made of titanium oxide having a thickness of 25 nm was formed on the transparent conductive film forming the conductive glass by sputtering to produce a conductive substrate.
Next, a paste of titanium oxide nanoparticles is applied by a doctor blade method so as to cover the titanium oxide film so as to have a thickness of 10 μm, and then fired at 150 ° C. for 3 hours to form a porous oxide semiconductor layer. Formed.
Next, an N3 dye was supported on the porous oxide semiconductor layer to obtain a working electrode.
In addition, a conductive glass similar to that used for the production of the working electrode was used, and a thin film made of platinum was formed on the transparent conductive film forming the conductive glass by a sputtering method to obtain a counter electrode. .
Next, two through holes were formed in this counter electrode.
Next, a sheet made of a thermoplastic resin having a width of 2 mm and a thickness of 50 μm (trade name: High Milan, manufactured by Mitsui Dupont Polychemical Co., Ltd.) is disposed on the peripheral edge of the working electrode or the counter electrode as an adhesive. The sheets were stacked via a sheet made of this thermoplastic resin so that a space of a predetermined size was formed between them.
Subsequently, the sheet | seat which consists of thermoplastic resins was heated and fuse | melted, the working electrode and the counter electrode were adhere | attached, and the laminated body was formed.
Next, the laminate is sandwiched from the outer surface of the working electrode and the counter electrode with a pressure member made of a pair of silicon rubber plates at a pressure of 15 kg / 100 cm ² , and in this state, from the through hole provided in the counter electrode An electrolytic solution was filled between the working electrode and the counter electrode, and most of the electrolytic solution was impregnated in the void portion of the porous oxide semiconductor layer.
After the filling of the electrolytic solution was completed, the through hole was sealed with a sealing member while applying pressure to the laminate by the pressure member.
Next, the pressure applied to the working electrode and the counter electrode was gradually released by the pressure member, and finally the pressure member was removed to obtain a dye-sensitized solar cell.

(Example 3)
A dye-sensitized solar cell was produced using the method for producing a photoelectric conversion element shown in the third example.
As the transparent substrate, a 10 cm × 10 cm conductive PET film (trade name; OTEC, manufactured by Oji Tobi Co., Ltd., conductive 10Ω / □) in which a transparent conductive film was provided on one surface of the PET film was used.
A thin conductive film made of titanium oxide having a thickness of 25 nm was formed on the transparent conductive film forming the conductive PET film by a sputtering method, thereby preparing a flexible conductive substrate.
Next, a paste of titanium oxide nanoparticles is applied by a doctor blade method so as to cover the titanium oxide film so as to have a thickness of 10 μm, and then fired at 150 ° C. for 3 hours to form a porous oxide semiconductor layer. Formed.
Next, an N3 dye was supported on the porous oxide semiconductor layer to obtain a working electrode.
In addition, a conductive PET film similar to that used for the production of the working electrode was used, and a thin film made of platinum was formed on the transparent conductive film forming the conductive PET film by a sputtering method. Obtained.
Next, an electrolyte solution was dropped and impregnated into the porous oxide semiconductor layer forming the working electrode, and then an electrolyte layer integrated with the porous oxide semiconductor layer was formed.
Next, the working electrode and the counter electrode were overlapped to form a laminate in which the electrolyte layer was sandwiched between the working electrode and the counter electrode.
Next, the laminate is accommodated from the opening in an 11 cm × 12 cm bag formed by forming a PET film into a bag shape.
Next, the bag body was contracted by sucking air from the inside of the bag body using a vacuum pump, and the bag body was uniformly adhered to the entire area of the outer surface of the laminate.
Next, in this state, the opening of the bag was fused, the bag was sealed, and a dye-sensitized solar cell was obtained.

(Comparative example)
A working electrode and a counter electrode were produced in the same manner as in Example 1.
Next, two through holes were formed in the counter electrode.
Next, a sheet made of a thermoplastic resin having a width of 2 mm and a thickness of 50 μm (trade name: High Milan, manufactured by Mitsui Dupont Polychemical Co., Ltd.) is disposed on the peripheral edge of the working electrode or the counter electrode as an adhesive. The sheets were stacked via a sheet made of this thermoplastic resin so that a space of a predetermined size was formed between them.
Subsequently, the sheet | seat which consists of thermoplastic resins was heated and fuse | melted, the working electrode and the counter electrode were adhere | attached, and the laminated body was formed.
Next, the electrolytic solution was filled between the working electrode and the counter electrode from the through hole provided in the counter electrode, and the void portion of the porous oxide semiconductor layer was impregnated with most of the electrolytic solution.
After the filling of the electrolytic solution was completed, the through hole was sealed with a sealing member to obtain a dye-sensitized solar cell.

 Regarding the dye-sensitized solar cells obtained in Examples 1 and 2 and the comparative example, the relationship between voltage and current density was examined using the measurement method defined in C8913 of JIS standard. The results are shown in FIG.

 From the results shown in FIG. 6, the dye-sensitized solar cells of Example 1 and Example 2, which were manufactured so that the distance between the two electrodes was constant by applying pressure to the working electrode and the counter electrode, It was confirmed that the resistance was low and the power generation efficiency was excellent. On the other hand, it was confirmed that the dye-sensitized solar cell of the comparative example produced without applying pressure to the working electrode and the counter electrode had high resistance between the two electrodes and was inferior in power generation efficiency.

DESCRIPTION OF SYMBOLS 11,141 ... Transparent substrate, 12, 42 ... Transparent substrate, 13 ... Porous oxide semiconductor layer, 14, 44 ... Working electrode, 15, 45 ... Substrate, 16, 46. .... Conductive film, 17, 47 ... Counter electrode, 18 ... Adhesive, 19, 49 ... Laminate, 20 ... Through-hole, 21 ... Electrolyte, 22 ... Sealing member , 23, 52 ... electrolyte layer, 30 ... pressure member, 31 ... flat plate, 55, 56 ... conductor, 60 ... bag.

Claims (4)

A photoelectric conversion element comprising a working electrode, a counter electrode, and an electrolyte layer formed therebetween,
The electrolytic solution constituting the electrolyte layer is sealed with a pressure maintained after sealing at a pressure lower than atmospheric pressure. At least one of the substrate forming the working electrode or the substrate forming the counter electrode is a flexible substrate, and an adhesive is provided around the porous oxide semiconductor layer forming the working electrode,
The distance between the working electrode and the counter electrode is shorter in at least a part of a portion corresponding to the porous oxide semiconductor layer than in a portion corresponding to the adhesive. The photoelectric conversion element as described in 2. A method for producing a photoelectric conversion element comprising a working electrode, a counter electrode, and an electrolyte layer formed therebetween,
A method for producing a photoelectric conversion element, wherein an electrolytic solution forming the electrolyte layer is sealed so that a pressure maintained after the sealing is lower than an atmospheric pressure. At least one of the substrate forming the working electrode or the substrate forming the counter electrode is a flexible substrate, and an adhesive is provided around the porous oxide semiconductor layer forming the working electrode,
The distance between the working electrode and the counter electrode is shorter than at least a portion corresponding to the porous oxide semiconductor layer than at a portion corresponding to the adhesive. Manufacturing method of the photoelectric conversion element.

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