JP2009117215A - Dye-sensitized solar cell inclusion body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell inclusion body increasing the power generation amount of a dye-sensitized solar cell and capable of using for a long time without volatilization or leakage of an electrolyte, and to provide a dye-sensitized solar cell inclusion body capable of increasing the power generation amount of a dye-sensitized solar cell housed in a transparent case by increasing the transmission light amount into the transparent case. <P>SOLUTION: The dye-sensitized solar cell inclusion body is formed by housing the dye-sensitized solar cell in a transparent case having a prism structure. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a dye-sensitized solar cell enclosure in which a dye-sensitized solar cell is housed in a transparent case.

In recent years, solar energy has attracted attention from the viewpoint of effectively using resources, and development of solar cells that convert the energy into electric energy has been promoted.
At present, most products on the market as solar cells are provided with silicon, and examples thereof include single crystal silicon, polycrystalline silicon, and amorphous silicon. These silicon-based solar cells are superior in photoelectric conversion efficiency as compared with solar cells not including silicon. However, the production of silicon that constitutes a silicon-based solar cell requires a large amount of energy for a heat source and the like, and thus has a problem of high costs, and also has a limitation on the supply of silicon itself. there were.

In recent years, dye-sensitized solar cells have attracted attention as solar cells that do not use silicon (see, for example, Patent Document 1). Since dye-sensitized solar cells do not use silicon, it is possible to achieve cost reduction.

A conventional dye-sensitized solar cell has an electrolyte layer sandwiched between a photoelectrode comprising a transparent conductive layer and a semiconductive layer supporting a dye on a transparent substrate, and a positive electrode having a conductive layer formed on the substrate. It has a configuration.
When the dye-sensitized solar cell is irradiated with light, the dye supported on the semiconductive layer absorbs light, and electrons in the dye molecule are excited to generate electrons. The generated electrons are transferred to the transparent conductive layer through the semiconductive layer, move to the positive electrode through the electric circuit, and then return to the photoelectrode through the electrolyte layer. By repeating such a process, electric energy is generated.

JP 2007-115513 A

The dye-sensitized solar cell according to the prior art has an advantage that the load on the environment is small and the cost can be reduced. However, since the photoelectric conversion efficiency is low, the power generation amount as the solar cell is low.
In addition, since an electrolytic solution is used for the electrolyte layer interposed between the conductive layer and the semiconductive layer, the electrolytic solution volatilizes or leaks when the dye-sensitized battery is used. As a result, the amount of power generation as a solar cell is reduced, and thus there is a problem in using it for a long time.

Therefore, the present invention improves the amount of power generation of the dye-sensitized solar cell constituting the present invention, and includes a dye-sensitized solar cell enclosure that can be used for a long time without causing volatilization or leakage of the electrolyte. The purpose is to provide.
The present invention also provides a dye-sensitized solar cell encapsulant that can improve the amount of power generated by the dye-sensitized solar cell housed in the transparent case by increasing the amount of light transmitted into the transparent case. With the goal.

The present invention is a dye-sensitized solar cell enclosure in which a dye-sensitized solar cell is housed in a transparent case having a prism structure.
The dye-sensitized solar cell is preferably formed into a sheet.
The dye-sensitized solar cell is preferably formed in a spiral shape.
In the dye-sensitized solar cell, a semiconductive layer carrying a dye, a light-transmitting porous layer, and a second conductive substrate are preferably sequentially laminated on a first conductive substrate. .
Preparing a plurality of dye-sensitized solar cells in which a semiconductive layer carrying a dye, a light-transmitting porous layer, and a second conductive substrate are sequentially laminated on the first conductive substrate; It is preferable that the first conductive substrates or the second conductive substrates are overlapped.
It is preferable that a non-conductive substrate is laminated on the first conductive substrate and / or the second conductive substrate.
It is preferable that wiring is applied to the dye-sensitized solar cell in which the light-transmitting porous layer is preferably filled with an electrolyte.
The transparent case is preferably filled with an electrolyte.
It is preferable that at least a part of the transparent case is removable.
It is preferable that a wiring hole is provided in the transparent case.

According to the dye-sensitized solar cell enclosure of the present invention, it is difficult for the electrolyte to volatilize or leak, and the power generation efficiency as a solar cell can be maintained over a long period of time.
Moreover, according to this invention, the dye-sensitized solar cell enclosure which can improve the electric power generation amount of a dye-sensitized solar cell by increasing the transmitted light amount in a transparent case can be provided.

Hereinafter, the present invention will be described with reference to the drawings.
As the dye-sensitized solar cell constituting the present invention, for example, as shown in FIG. 1, a semiconductive layer 20 having a dye supported on a first conductive substrate 10, a light-transmitting porous layer 30 and A dye-sensitized solar cell 40 in which the second conductive base material 11 is sequentially laminated can be used.
In another dye-sensitized solar cell 41 constituting the present invention, a non-conductive substrate 50 may be laminated on the other surface of the first conductive substrate 10 as shown in FIG. As shown in FIG. 3, a dye-sensitized solar cell 42 may be formed by laminating a non-conductive substrate 50 on the other surface of the second conductive substrate 11. The non-conductive substrate 50 may be laminated on both the first conductive substrate 10 and the second conductive substrate 11.
As the dye-sensitized solar cell that can be used in the present invention, in addition to the dye-sensitized solar cell having the above layer structure, a transparent base material / transparent conductive layer / semiconductive layer carrying a dye / conductive layer / It may be a layer structure in which the base materials are sequentially laminated, or a layer structure in which the transparent base material / transparent conductive layer / semiconductive layer carrying a dye / electrolyte layer / conductive layer / base material are sequentially laminated. It may have.

The light transmissive porous layer 30 may or may not be filled with an electrolyte. When the transparent case is not filled with the electrolyte solution, it is necessary to fill the electrolyte in the light transmissive porous layer 30. As the electrolyte, a solid or gel electrolyte may be used, or a liquid electrolyte may be used.

The dye-sensitized solar cell constituting the present invention is a flexible sheet and can be wound up. A dye-sensitized solar cell 44 wound up in a spiral shape is shown in FIG. The winding method and direction are not limited. For example, when the dye-sensitized solar cells 40, 41, and 42 are wound up, the surface portion 12 of the wound dye-sensitized solar cell 44 has the first conductive substrate 10 and the second conductive substrate 11. Alternatively, the non-conductive substrate 50 is obtained. Therefore, the light transmissive porous layer 30 exists in a multi-layered state in the thickness direction of the dye-sensitized solar cell 44.
By winding the dye-sensitized solar cell in a spiral shape, the area of the portion that generates power increases, so that the amount of power generation can be improved. In other words, the amount of power generation can be improved in a space-saving manner.

FIG. 5 is a view of the dye-sensitized solar cell 44 wound up in a spiral shape as viewed from A shown in FIG. When the non-conductive substrate 50 is present on the first conductive substrate 10 and / or the second conductive substrate 11, the dye-sensitized solar cell 44 has the first conductive substrate 10 side and The second conductive substrate 11 side may be in close contact, or a gap 60 may be provided as shown in FIG.
In addition, when the nonconductive base material 50 is not laminated | stacked on either the 1st conductive base material 10 or the 2nd conductive base material 11, the 1st conductive base material 10 and the 2nd conductive base material Since 11 discharges when 11 contacts, it is preferable to provide the space | gap 60 so that it may not contact mutually. The space | interval of the space | gap 60 can be determined suitably.
Further, an insulating base material may be provided in the gap 60. As the insulating base material, any insulating base material can be used as long as it can maintain the insulation between the first conductive base material 10 and the second conductive base material 11, and it may be transparent. You may not have. As an insulating base material, insulating paper and a resin component can be mentioned, for example.

Furthermore, like the dye-sensitized solar cell 43 shown in FIG. 6, the dye-sensitized solar cell 40 shown in FIG. 1 is prevented so that the first conductive substrate 10 and the second conductive substrate 11 do not contact each other. May be prepared, and the other dye-sensitized solar cell 40 may be laminated on the one dye-sensitized solar cell 40 by rotating 180 °. That is, the dye-sensitized solar cell 43 is formed by laminating the second conductive base materials 11. Similarly, in the plurality of dye-sensitized solar cells 40, the first conductive base materials 10 may be stacked. In addition, since the dye-sensitized solar cell in which these conductive base materials are laminated is also flexible, it can be wound in a spiral shape, and the dye-sensitized solar cell 44 shown in FIG. 4 is obtained. Can do.

The dye-sensitized solar cell 44 wound up in a spiral shape needs to be stored in a transparent case. FIG. 7 shows an example of the transparent case constituting the present invention. The transparent case 80 only needs to be hermetically sealed, and the shape thereof is not particularly limited, and may be the cylinder shown in FIG. 7, or may be a quadrangular prism, a triangular prism, or a sphere.

The transparent case constituting the present invention needs to have a prism structure in at least a part thereof. That at least a part of the transparent case has a prism structure means that, for example, the transparent case 80 including the lid part 70, the bottom part 71, and the side part 72 shown in FIG. Anything is acceptable. Further, it is not necessary that all of these portions constituting the transparent case have a prism structure. Therefore, for example, in the case of the transparent case 80 shown in FIG. 7, the entire lid portion 70 may have a prism structure, or may have a prism structure only near the center of the lid portion 70. . The part having the prism structure can be appropriately determined according to the shape of the transparent case.

Since the transparent case has a prism structure, the angle of light transmitted through the transparent case can be adjusted. For example, in the case where the lid 70 of the transparent case 80 shown in FIG. 8 has a prism structure, when the light irradiation A is made from an oblique direction to the lid 70, the angle of the transmitted light B is changed as shown in FIG. It can be directed toward the bottom 71. In addition, since the light C perpendicularly incident on the lid 70 reaches the bottom 71, the light intensity at the bottom 71 can be improved.

It is preferable that at least one part of the transparent case constituting the present invention is removable.
For example, in the case of the transparent case 80 shown in FIG. 7, it is preferable that at least one of the lid part 70 or the bottom part 71 can be removed. Thus, after the dye-sensitized solar cell 44 is accommodated in the transparent case 80, it can be sealed by the lid portion 71 or the bottom portion 72.
Further, the transparent case 80 may be sealed with a resin component. As the resin component, those having transparency are preferable, and for example, ultraviolet curable acrylic, isocyanate and the like can be used.
In addition, the lid 70 or the bottom 71 may be sealed with the resin component.

In order to take out electrical energy generated by light irradiation, as shown in FIG. 9, on the first conductive substrate 10 and the second conductive substrate 11 of the dye-sensitized solar cell constituting the present invention, Wirings 90 and 91 are preferably provided, respectively. FIG. 9 shows an example of the dye-sensitized solar cell in which the wirings 90 and 91 are provided on the dye-sensitized solar cell 40. The wirings 90 and 91 in the present invention are the first conductive substrate 10 and the first conductive substrate 10 respectively. It is only necessary to be in contact with the two conductive base materials 11, and the formation position and number thereof can be determined as appropriate.
The method for connecting the wirings 90 and 91 on the first conductive base material 10 and the second conductive base material 11 is not particularly limited. For example, solder or conductive paste can be employed. .

In addition, in the case where the non-conductive substrate 50 is provided as in the dye-sensitized solar cells 41 and 42 shown in FIGS. 2 and 3, after removing a part of the non-conductive substrate 50, the wiring Can be provided. A method for partially removing is not particularly limited, but physical treatment or chemical treatment can be performed. For example, the non-conductive substrate 50 may be partially peeled directly, or when the non-conductive substrate 50 is an organic film, the organic film is contracted by partially heating the first film. The conductive substrate 10 and the second conductive substrate 11 may be exposed.
In the dye-sensitized solar cell 40 shown in FIG. 9, after providing the wirings 90 and 91, the nonconductive base material 50 may be provided. For example, when the non-conductive substrate 50 is an organic film, a varnish is applied on the wiring 90 and / or 91 provided on the first conductive substrate 10 and / or the second conductive substrate 11. Thus, the non-conductive substrate 50 can be formed.

As shown in FIG. 10, it is preferable to provide a wiring hole 73 in the transparent case constituting the present invention. As a result, the wirings 90 and 91 for extracting electric energy from the dye-sensitized solar cell 44 housed in the transparent case 81 can be guided out of the transparent case through the wiring hole 73.
The site where the wiring hole 73 is formed can be determined as appropriate, and may be provided on the lid 70 shown in FIG. 10 or on the bottom 71 shown in FIG. In addition, the number of wiring holes 73 formed can be determined as appropriate.

FIG. 11 shows a diagram in which the dye-sensitized solar cell 44 wound up in a spiral shape is housed in a transparent case 81. The transparent case 81 is preferably filled with an electrolytic solution. After the dye-sensitized solar cell 44 is housed in the transparent case 81, the electrolyte is filled with the electrolyte so that the electrolyte penetrates the light-transmitting porous layer 30 by capillary action. When light is irradiated to the light, electrons are emitted and power generation occurs. Therefore, if the transparent case 81 is filled with the electrolytic solution, the light transmissive porous layer 30 may not be filled with the electrolyte in advance.
In addition, by housing the dye-sensitized solar cell 44 in the transparent case 81, the volatilization of the electrolyte solution outside the transparent case 81 can be prevented. Further, in the dye-sensitized solar cell in which the electrolyte is included in the light-transmitting porous layer 30, even if the electrolyte leaks, it does not leak out of the transparent case 70 and can be used as a solar cell for a long time. It is.
After the wirings 90 and 91 provided in the dye-sensitized solar cell 44 are guided from the wiring hole 73 to the outside of the transparent case, the wiring hole 73 can be sealed with a resin component or the like. As a resin component, it is preferable to use what has transparency, such as ultraviolet curable acryl and isocyanate, for example. Thereby, volatilization of the electrolyte filled in the transparent case can be prevented.

Since the transparent case constituting the present invention has a prism structure, the angle of light transmitted through the transparent case can be adjusted. For example, in the case where the lid portion 70 of the transparent case 81 shown in FIG. 11 has a prism structure, when light is irradiated obliquely from above the lid portion 70, the angle of the transmitted light is changed to the bottom portion 71 and the dye-sensitized solar cell. 43. Here, since the light perpendicularly incident on the lid 70 reaches the bottom 71 and the dye-sensitized solar cell 43, the amount of light reaching the dye-sensitized solar cell 43 is increased by providing the lid 70 with a prism structure. Thereby, the power generation efficiency of the dye-sensitized solar cell 43 can be improved.

Hereinafter, materials constituting the present invention will be described.
<Transparent case>
The shape of the transparent case is not limited so long as the electrolyte filled in the transparent case or the electrolyte solution of the electrolyte layer constituting the dye-sensitized solar cell does not leak out of the transparent case. It may be a triangular pyramid or a spherical shape and is not limited. Further, the size of the transparent case is only required to accommodate the dye-sensitized solar cell, and can be determined as appropriate.
In addition, the amount of electrolyte filled in the transparent case can be determined as appropriate.

The transparent case should just have a part in transparency. A part means that it is not necessary to have transparency in all the parts of a transparent case. In the case of the transparent case shown in FIG. 7, for example, the lid portion 70 only needs to have transparency, and other portions do not need to have transparency. Moreover, the bottom part 71 may have transparency, and the site | part which has transparency is not restrict | limited. In addition, the lid portion 70 may be locally transparent, and the transparent portion can be determined as appropriate.
Having transparency is not particularly limited as long as the dye-sensitized solar cell housed in the transparent case is irradiated with light, but the total light transmittance measured according to JIS-K7105 is 70%. The above is preferable. The total light transmittance is more preferably 80% or more, and particularly preferably 90% or more.

As the material having transparency, for example, glass, organic film, plastic, or the like can be used. In the transparent case, only a material having transparency may be used alone, or a material having transparency and / or a material having no transparency may be used in combination.

The prism structure in the present invention refers to a structure having a function capable of adjusting the angle of light.
As the material having a prism structure, the same materials as those having transparency described above can be used. In the present invention, since a prism structure can be provided in any part of the transparent case, it is preferable to use an organic film as the material having the prism structure.
Specific product names of the organic film having a prism structure include BEFII90 / 50, BEFIII90 / 50T, RBEF90 / 50-8T, Thick RBEF, DBEF-D (manufactured by Sumitomo 3M). These organic films are also called brightness enhancement films.
When an organic film is used as the material having a prism structure, it can be laminated on a transparent material via an adhesive or an adhesive.

<Light transmissive porous layer>
The light transmissive porous layer may be any material as long as it has light permeability and allows the electrolyte solution to permeate. For example, paper, woven fabric, nonwoven fabric, stretched porous membrane, polymer porous membrane, ceramics, etc. Can be used. The light transmissive porous layer made of these materials has pores between fibers or particles constituting the layer.
Since the present invention has such a light-transmitting porous layer, the electrolyte solution penetrates into the light-transmitting porous layer by filling the light-transmitting porous layer with the electrolyte solution. is there. In the case of a dye-sensitized solar cell enclosure, the electrolyte solution penetrates into the light-transmitting porous layer by capillary action by filling the transparent case with the electrolyte solution.
As a material for the light-transmitting porous layer constituting the present invention, it is preferable to use a woven fabric, a non-woven fabric, or a polymer porous membrane.
The light-transmitting porous layer transmits light from the light-transmitting porous layer and emits electrons from the dye supported on the semiconductive layer when the dye-sensitized solar cell constituting the present invention is irradiated with light. In addition, any material may be used as long as it generates electric energy, and the light transmittance is not particularly limited. Specifically, it suffices that at least a part of the light transmissive porous layer communicates from one surface to the other surface through the pores of the light transmissive porous layer.

Specifically, the materials constituting the woven fabric, the nonwoven fabric, the stretched porous membrane, and the polymer porous membrane include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyvinylidene fluoride, polyamide, Resins such as polyamide imide, polyimide, polyacrylonitrile, polymethyl methacrylate, polyethylene oxide, polysulfone, polyether sulfone, polyether sulfone, polyphenyl sulfone, and polyphenylene sulfide can be used. In addition, nitrocellulose, acetylcellulose, cellulose acetate and the like, which are cellulose materials, may be used as the resin component. Those selected from a copolymer of the monomer constituting the single polymer and another monomer can also be used.
Moreover, you may use what combined any 2 or more out of the cellulosic material, the glass material, and the ceramic material for the said resin material.

As the woven fabric and the nonwoven fabric, those obtained by a conventionally known method can be used with the fibers made of the resin.

As the stretched porous film, for example, a film obtained by stretching a film made of the resin containing an additive that dissolves in a solvent in a solvent can be used.
Moreover, as a polymeric porous membrane, what was obtained by apply | coating and drying the solution which melt | dissolved the said resin in the mixed solvent of the good solvent and poor solvent from which boiling points differ, for example can be used.

As a method for producing a polymer porous membrane, for example, a porous layer forming step of applying a resin solution to a substrate and drying to form a porous layer, and a peeling step of peeling the substrate from the porous layer are performed. And the like.

Examples of the substrate on which the resin solution is applied include a sheet or film made of a resin such as polyethylene terephthalate, polybutylene terephthalate, polyamideimide, polyethylene naphthalate, polytetrafluoroethylene, and polyimide.

Examples of the resin solution coating apparatus include a dip coater, a spray coater, a roll coater, a doctor blade, a gravure coater, an applicator, and a screen printing machine.

When peeling the resin formed on the substrate, a peeling means may be used, or it may be peeled manually.

As ceramics, oxide ceramics and non-oxide ceramics can be used, and metals may be mixed.
Examples of oxide ceramics include simple oxides such as titania, alumina, magnesia, beryllia, zirconia, and silica, silicates such as silica, forsterite, steatite, wollastonite, zircon, mullite, cordierite, and spojemen, and titanic acid. Double oxides such as aluminum, spinel, apatite, barium titanate, PZT, PLZT, ferrite and lithium niobate can be used.
Non-oxide ceramics include nitrides such as silicon nitride, sialon, aluminum nitride, boron nitride, titanium nitride, carbides such as silicon carbide, boron carbide, titanium carbide, tungsten carbide, amorphous carbon, graphite, diamond, single crystal sapphire. Carbon such as can be used. In addition, borides, sulfides, and silicides can be used.
Gold, silver, iron, copper, nickel or the like can be used as the metal.
At least one of these may be used as a raw material, and silica, titania, and alumina are more preferable, and other components and blends are not particularly limited.

The method for forming the ceramic as a light transmissive porous layer on the first conductive substrate may be either a wet process or a dry process, and is not particularly limited. preferable. In the wet process, the substrate may be coated (applied) by a known method. As the coating method, for example, gravure coating, offset coating, comma coating, die coating, slit coating, spray coating, plating method, sol-gel method, LB film method and the like can be used, and sol-gel method is particularly preferable. .

As a starting material in the sol-gel method, for silica, for example, tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane; organoalkoxysilane such as methyltriethoxysilane and ethyltriethoxysilane; tetra Examples include tetrahalosilanes such as chlorosilane and tetrabromosilane. Examples of alumina include trialkoxyaluminum such as aluminum tri-sec-butoxide; aluminum (III) 2,4-pentanedionate. The above starting materials cause the sol-gel reaction to proceed in the presence of a catalyst and water, but these hydrolysates (reaction intermediates) in which the sol-gel reaction has already progressed may be used as the starting materials. Moreover, you may add suitably other components, such as resin and surfactant, as needed.

Alternatively, a sol-gel reaction may be performed by adding an oxide ceramic filler to the sol containing the starting material. In this case, the content of the filler may be about 5 to 100 parts by weight with respect to 100 parts by weight of the starting material. The average particle diameter of the filler is usually about 10 to 100 nm.

In addition, as a dry process, CVD, vapor deposition, sputtering, ion plating etc. can be used, for example.

The light-transmitting porous layer made of the above materials and methods is in the form of a sheet or plate. In the case of a film shape or a sheet shape, the thickness of the light transmissive porous layer may be about 5 to 1000 μm, preferably about 20 to 500 μm. In the case of a plate shape, the thickness may be about 0.5 to 5 mm, preferably about 1 to 3 mm.

Further, when the light-transmitting porous layer is made of an aggregate (aggregate) of fine particles mainly composed of at least one selected from the group consisting of oxide ceramics, non-oxide ceramics and metals, the average particle size of the fine particles The diameter is about 10 to 100 nm, and the pore diameter is about 10 to 100 nm.

<Conductive substrate>
The first conductive substrate and the second conductive substrate need only have conductivity, and need not have transparency. For example, a metal substrate can be used. By using a metal substrate, it is possible to reduce the resistance of the electrode, so that electrons generated from the dye supported on the semiconductive layer can be taken out as power without loss.
Specific examples of the metal substrate include copper, aluminum, gold, silver, platinum, chromium, nickel, tungsten, and the like and a substrate made of two or more metals selected from these metals.

The first conductive substrate and the second conductive substrate preferably have flexibility. Thereby, it can wind up in a spiral. The thickness of the first conductive substrate and the second conductive substrate is preferably 5 μm to 3 mm, and more preferably 10 μm to 300 μm. By setting the thickness within the range of 5 μm to 3 mm, appropriate strength and flexibility can be provided.

<Semiconductive layer>
The semiconductive layer includes titanium oxide (TiO ₂ ), tin oxide (SnO ₂ ), tungsten oxide (WO ₃ ), zinc oxide (ZnO), niobium oxide (Nb ₂ O ₅ ), indium oxide (In ₂ O ₃ ), Zirconium oxide (ZrO ₂ ), tantalum oxide (Ta ₂ O ₅ ), lanthanum oxide (La ₂ O ₃ ), strontium titanate (SrTiO ₃ ), yttrium oxide (Y ₂ O ₃ ), holmium oxide (Ho ₂ O ₃ ) Main components are oxide semiconductor fine particles having an average particle diameter of 1 to 1000 nm obtained by combining one or more of bismuth oxide (Bi ₂ O ₃ ), cerium oxide (CeO ₂ ), alumina (Al ₂ O ₃ ), and the like. The thickness is preferably a porous thin film having a thickness of about 0.5 to 50 μm.

As a method for forming the semiconductive layer on the first conductive substrate, for example, a dispersion in which oxide semiconductor fine particles are dispersed in a desired dispersion medium, or a colloid solution that can be adjusted by a sol-gel method, After adding a desired additive as required, it can be applied on the transparent conductive layer by a screen printing method, an ink jet printing method, a roll coating method, a doctor blade method, a spin coating method, a spray coating method or the like. Alternatively, an electrophoretic electrodeposition method may be used in which a transparent substrate and a transparent conductive layer are immersed in a colloidal solution, and oxide semiconductor fine particles are deposited on the transparent conductive layer by electrophoresis. In addition, after applying polymer microbeads to a colloidal solution or dispersion and applying it to the transparent conductive layer, the polymer microbeads are removed by heat treatment or chemical treatment to form voids to make it porous. Also good.
A method in which a foaming agent is mixed with a colloidal solution or dispersion and applied to the first conductive substrate, and then sintered to make it porous can be used. When using a material, the temperature at which the dispersion is fired is preferably about 400 to 500 ° C. By setting the firing temperature to about 400 to 500 ° C., the bonding force between the oxide semiconductor fine particles becomes dense, so that electrons generated from the sensitizing dye by light irradiation are easily transmitted to the transparent conductive layer through the semiconductive layer. Therefore, it is preferable.

The dye to be carried on the semiconductive layer is not particularly limited as long as it absorbs visible light. For example, a ruthenium complex having a ligand containing a bipyridine structure, a terpyridine structure, an iron complex, or a porphyrin type. And organic dyes such as phthalocyanine-based metal complexes, eosin, rhodamine, merocyanine, and coumarin, and the like, which can be appropriately selected according to the use and the material of the semiconductive layer.
Examples of the method for adsorbing the dye to the semiconductive layer include a method of impregnating the semiconductive layer on the transparent conductive layer with the dye solution.

<Electrolyte layer>
The electrolyte layer may be made of an electrolyte solution, or may be a semi-solidified electrolyte solution with a gelling agent. The electrolyte layer is not particularly limited as long as it is a substance that can transport electrons, holes, ions, and the like. For example, a p-type semiconductor solid hole transport material such as CuI, CuSCN, NiO, Cu ₂ O, and KI, iodine A solution in which a redox electrolyte such as / iodide and bromine / bromide is dissolved in an organic solvent can be used.
Examples of the organic solvent include polyhydric alcohols such as nitrile acetonitrile, methoxypropionitrile, hydrocarbon propylene carbonate, diethyl carbonate, γ-butyrolactan, and polyethylene glycol.
Among these, a solution in which the redox electrolyte is dissolved in an organic solvent is preferable because it is bulky and the dye adsorbed on the semiconductive layer is difficult to desorb.

<Wiring>
After connecting the wiring to the dye-sensitized solar cell, electrical energy can be taken out by guiding the wiring out of the transparent case. The material constituting the wiring is not particularly limited as long as it is a conductive substance capable of inducing electric energy from the dye-sensitized solar cell to the outside of the transparent case. For example, gold, silver, copper, Nickel or the like can be used.
The wiring is preferably covered with an insulating material.

<Non-conductive substrate>
The non-conductive substrate is only required to suppress discharge even when the first conductive substrate and the second conductive substrate of the dye-sensitized solar cell constituting the present invention are in contact with each other. The material is not particularly limited, and examples thereof include insulating paper and organic film. In the present invention, it is preferable to use an organic film. An organic film can be produced by applying a varnish on the first conductive substrate and / or the second conductive substrate.

The organic film may be transparent or non-transparent, and is not particularly limited. Specifically, polyesters such as polyethylene terephthalate, polyethylene Polyolefins such as polyimide, polyamide, polyamideimide, polyethersulfone, polyphenylene sulfide, polyetherketone, polyetherimide, triacetylcellulose, silicone rubber, polytetrafluoroethylene, and the like. Among these, it is preferable to use polyesters, polyolefins, polyimides, silicone rubbers, polyetherimides, polyethersulfones, polytetrafluoroethylenes and the like because of their excellent insulating properties.

<Transparent substrate>
Although it will not specifically limit as a transparent base material if it has moderate intensity | strength without preventing incident light, For example, glass, an organic film, etc. can be mentioned.
The glass may be a plate-like glass plate, a sheet containing glass as a fiber, or a glass formed in a spiral shape.

Since an organic film has flexibility, it can be formed into a sheet when used as a transparent substrate, and a dye-sensitized solar cell can be wound in a spiral shape, which is preferable. Specific examples of the organic film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide, polyamide, polyamideimide, polyethersulfone, polyphenylene sulfide, polyetherketone, polyetherimide, triacetylcellulose, Organic films such as polytetrafluoroethylene, polyarylate, cyclic polyolefin, and aramid can be used.
The thickness of the organic film is preferably 5 μm to 3 mm, and more preferably 10 μm to 300 μm. By setting the thickness within the range of 5 μm to 3 mm, appropriate strength and flexibility can be provided.

When an organic film is used as the transparent substrate and a semiconductive layer is provided on the organic film, it is difficult to fire the semiconductive layer at about 400 to 500 ° C., and thus a device is required. For example, after baking a laminated body in which a release layer made of a metal oxide and a resin, a transparent conductive layer, and a semiconductive layer are sequentially laminated on a heat-resistant substrate made of a glass plate or a metal plate at 400 to 500 ° C., silicone An organic film on which a release layer is laminated is prepared as a transparent substrate, and the semiconductive layer and the silicone release layer are bonded together. After bonding these together, the heat-resistant substrate is peeled from the release layer. Then, the organic film provided with the contact bonding layer is prepared, and the dye-sensitized solar cell which has flexibility can be produced by bonding the said peeling layer and the said contact bonding layer.
As the metal oxide constituting the release layer, the same metal oxide as the semiconductive layer can be used. As the resin constituting the release layer, cellulose resin, polyester resin, polyamide resin, polyacrylate resin, polycarbonate resin, polyurethane resin, polyolefin resin, polyvinyl acetal resin, fluorine resin, polyimide resin In addition, polyhydric alcohols such as polyethylene glycol can be mentioned.

Moreover, as another example using an organic film as a transparent base material, after laminating | stacking a transparent conductive layer and a semiconductive layer sequentially on the said transparent base material, the 1st metal plate heated at about 100-400 degreeC is used. You may sinter by pressing to the said semiconductive layer. When pressing, the second metal plate can be brought into contact with the other surface of the transparent substrate, but the temperature of the second metal plate is lower than the softening temperature of the transparent substrate. There is a need to.
Although it does not specifically limit as a 1st metal plate and a 2nd metal plate, It is preferable to use a stainless steel plate.

<Transparent conductive layer>
There are no particular restrictions on the transparent conductive layer, from the viewpoint of light transmittance, for example, indium tin oxide (ITO), fluorine-doped tin oxide (FTO), tin oxide _(SnO 2), zinc oxide (ZnO) It is preferable to use a transparent oxide semiconductor such as. These oxide semiconductors may be used alone or in combination.

As a method for forming a transparent conductive layer on a transparent substrate, a method corresponding to the material of the transparent conductive layer may be used. For example, when an oxide semiconductor such as ITO is formed on a transparent substrate, a sputtering method is used. And thin film forming methods such as CVD, SPD, and vapor deposition. The thickness of the transparent conductive layer is preferably 0.05 to 2.0 μm in consideration of light transmittance and conductivity.

<Base material>
As a base material, what is necessary is just to have moderate intensity | strength, and it does not necessarily need to have transparency. Therefore, even if it uses a metal plate, you may use the glass plate, organic film, etc. which have transparency.

<Others>
The dye-sensitized solar cell of the present invention can prevent leakage and volatilization of the electrolyte by sealing the entire dye-sensitized solar cell with a resin component after filling the light-transmitting porous layer with the electrolyte. preferable. Alternatively, the dye-sensitized solar cell may be wound with a resin component and then sealed with a resin component.
The dye-sensitized solar cell encapsulant of the present invention can be accommodated in order to allow the electrolyte solution to penetrate into the light-transmitting porous layer constituting the dye-sensitized solar cell because the electrolyte solution can be present in the transparent case. The dye-sensitized solar cell is preferably partially sealed with a resin component. Further, after the dye-sensitized solar cell is wound up in a spiral shape, partial sealing with a resin component may be performed.
The term “partial” means that the electrolyte solution only needs to permeate the light-transmitting porous layer, and the sealing portion and the sealing method are not particularly limited.
Moreover, as a resin component here, it is preferable to use what has transparency, such as ultraviolet curable acryl and isocyanate.
Hereinafter, the present invention will be described by way of examples.

The dye-sensitized solar cell shown in FIG. 1 was produced as follows.
A reactive vacuum deposition method using an electrolytic copper foil having a thickness of 12 μm (trade name: TQ-LP, manufactured by Mitsui Mining & Smelting Co., Ltd.) as the first conductive substrate, and oxygen gas is introduced as a semiconductive layer thereon. Thus, titanium oxide having a thickness of 9 μm was formed. The film forming pressure at this time was 2.5 × 10 ⁻¹ Pa. The obtained laminate was fired at 450 ° C. for 30 minutes.
Next, the dried laminate is immersed in a 2.5 × 10 ⁻⁴ M ethanol solution of bis (4,4-dicarboxy-2,2-pipyridyl) dithiocyanate ruthenium, whereby the dye is converted into a semiconductive layer. After being supported on, it was washed with ethanol and dried.
In the electrolytic copper foil used as the first conductive substrate, copper wire was soldered to the surface where the semiconductive layer was not laminated.

Subsequently, an electrolytic copper foil having a thickness of 12 μm (trade name: TQ-LP, manufactured by Mitsui Kinzoku Mining Co., Ltd.) was used as the second conductive substrate, and a copper wire was soldered on one surface thereof.

A light transmissive porous layer was prepared by the following method.
Polyamideimide was dissolved in N, N-dimethylacetamide (good solvent), and dibutyl phthalate (poor solvent) was added to prepare a coating solution having a solid content concentration of 10% by weight. The obtained coating solution was coated on a support made of a polyethylene terephthalate film so that the film thickness after drying was 20 μm, and dried in a blow dryer at 120 ° C. Then, the polyamideimide porous membrane (polymer porous membrane, porosity 65%) was produced by peeling the support.

On the semiconductive layer laminated | stacked on the 1st electroconductive base material, the polyamide imide porous film produced by said method was laminated | stacked as a light transmissive porous layer. Then, the 2nd electroconductive base material (surface which has not soldered the copper wire) was laminated | stacked on the polyamide-imide porous film, and the dye-sensitized solar cell shown in FIG. 9 was produced.

Next, the dye-sensitized solar cell shown in FIG. 4 was produced by winding it around the second conductive substrate in a spiral shape. The produced dye-sensitized solar cell was accommodated in the transparent case shown in FIG. 10, and the dye-sensitized solar cell enclosure shown in FIG. 11 was produced.
In addition, an organic film having a prism structure via an adhesive (manufactured by Sumitomo 3M Ltd., trade name: DBEF-D) is provided in advance on the back surface (the dye-sensitized solar cell side) of the lid portion constituting the transparent case. The protrusion-like continuum constituting the prism structure was arranged to face the dye-sensitized solar cell. Further, the front luminance of the organic film was measured by the following method, and as a result, an improvement in front luminance was recognized.

Subsequently, an electrolyte solution having the following composition is filled in the transparent case, the wiring is led out of the transparent case, and then the transparent case is sealed with an ultraviolet curable acrylic resin, whereby the dye-sensitized solar cell encapsulant of the present invention is sealed. Was made.
・ 0.05M iodine ・ 0.1M lithium iodide ・ 0.1M Dimethylpropylimidazolium iodide
・ 0.5M 4-tert-butylpyridine
・ Solvent Butyronitrile (Measurement method of front luminance)
A transparent support made of polycarbonate having a thickness of 2 mm is placed 5 mm away from the surface of a cold cathode tube (luminance on the light source: about 10,000 cd / m ² ), and an organic film having the above prism structure is placed thereon. did. A luminance meter (BM-7, manufactured by Topcon) was fixed at a position 50 cm away from the sample, and the luminance on the light source was measured.

<Evaluation>
When the current-voltage characteristics of the dye-sensitized solar cell encapsulant of Example 1 were examined according to JIS C8913, it was confirmed that energy conversion was performed.

As described above, according to the present invention, it is possible to improve the power generation amount of the dye-sensitized solar cell constituting the present invention, and to increase the amount of dye that can be used for a long time without causing volatilization or leakage of the electrolyte. A solar cell encapsulant can be provided.
Further, since the transparent case constituting the present invention has a prism structure, the amount of light transmitted into the transparent case can be increased. As a result, the power generation amount of the dye-sensitized solar cell housed in the transparent case can be improved, and electric energy can be recovered well.

It is sectional drawing of a dye-sensitized solar cell. It is sectional drawing of a dye-sensitized solar cell. It is sectional drawing of a dye-sensitized solar cell. It is the figure which wound up the dye-sensitized solar cell spirally It is the figure which looked at the dye-sensitized solar cell shown in FIG. 4 from the A direction. It is sectional drawing of a dye-sensitized solar cell. It is a figure which shows an example of a transparent case. It is a figure which shows that light goes to a specific direction It is sectional drawing of a dye-sensitized solar cell. It is a figure which shows an example of a transparent case. It is a dye-sensitized solar cell encapsulant of one embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 1st electroconductive base material 11 2nd electroconductive base material 12 Surface part 20 Semiconductive layer 30 Light transmissive porous layer 40, 41, 42, 43, 44 Dye-sensitized solar cell 50 Nonelectroconductive base material 60 Gap 70 Lid 71 Bottom 72 Side 73 Wiring holes 80 and 81 Transparent cases 90 and 91 Wiring 100 Dye-sensitized solar cell enclosure

Claims (11)

A dye-sensitized solar cell enclosure, wherein the dye-sensitized solar cell is housed in a transparent case having a prism structure. The dye-sensitized solar cell enclosure according to claim 1, wherein the dye-sensitized solar cell is formed into a sheet. The dye-sensitized solar cell enclosure according to claim 1 or 2, wherein the dye-sensitized solar cell is formed in a spiral shape. The dye-sensitized solar cell is formed by sequentially laminating a semiconductive layer carrying a dye, a light-transmitting porous layer, and a second conductive substrate on a first conductive substrate. The dye-sensitized solar cell enclosure according to any one of claims 1 to 3. Preparing a plurality of dye-sensitized solar cells in which a semiconductive layer carrying a dye, a light-transmitting porous layer, and a second conductive substrate are sequentially laminated on the first conductive substrate; The dye-sensitized solar cell enclosure according to any one of claims 1 to 3, wherein the first conductive substrates or the second conductive substrates are overlapped with each other. 5. The dye-sensitized solar cell enclosure according to claim 4, wherein a non-conductive base material is laminated on the first conductive base material and / or the second conductive base material. 6. The dye-sensitized solar cell enclosure according to claim 4, wherein the light-transmitting porous layer is filled with an electrolyte. The dye-sensitized solar cell enclosure according to any one of claims 1 to 7, wherein the dye-sensitized solar cell is provided with wiring. The dye-sensitized solar cell enclosure according to any one of claims 1 to 8, wherein the transparent case is filled with an electrolyte. The dye-sensitized solar cell enclosure according to any one of claims 1 to 9, wherein at least a part of the transparent case is removable. The dye-sensitized solar cell enclosure according to any one of claims 1 to 10, wherein a wiring hole is provided in the transparent case.

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