JP2009009722A - Dye-sensitized solar cell and dye-sensitized solar cell sealed body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell having a high conductivity and light transmission, and a dye-sensitized solar cell sealed body which has no volatilization and leakage or the like of an electrolytic liquid and can be used for a long period. <P>SOLUTION: The dye-sensitized solar cell has a semiconductive layer carrying a dye, a light transmitting porous layer, and a second conductive substrate laminated in the order on a first conductive substrate. It is preferable that an electrolyte is filled in the light transmitting porous layer. Furthermore, it is preferable that the dye-sensitized solar cell is made a dye-sensitized solar cell sealed body that is housed in a transparent case. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a dye-sensitized solar cell having a light-transmitting porous layer, and a dye-sensitized solar cell enclosure in which the 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 structure of a dye-sensitized solar cell according to the prior art is formed by sequentially laminating a transparent conductive layer, a semiconductive layer carrying a dye, an electrolyte layer, a conductive layer, and a substrate on a transparent substrate such as glass. is there. In a dye-sensitized solar cell, since no electrical energy is generated unless light is applied to a semiconductive layer carrying a dye, a transparent substrate or a transparent conductive layer may have transparency in a conventional dye-sensitized solar cell. It was necessary.

Examples of the transparent conductive layer laminated on the transparent substrate include transparent oxide semiconductors such as tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), tin oxide (SnO ₂ ), and zinc oxide (ZnO). used. The thickness of the transparent conductive layer in the conventional dye-sensitized solar cell is designed to be about 0.05 to 2.0 μm in order to satisfy light transmittance and conductivity. If the thickness of the transparent conductive layer is less than 0.05 μm, the light transmission is improved, but the electrical conductivity is insufficient, so that it is difficult to recover electrical energy. On the other hand, when the thickness of the transparent conductive layer is more than 2.0 μm, the conductivity is improved, but the light transmittance is insufficient, so that it is difficult to generate electric energy.
Further, when 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.

In the structure of a conventional dye-sensitized solar cell, it has been difficult to solve the above problems. Then, an object of this invention is to provide the dye-sensitized solar cell which has a high electroconductivity and also has a light transmittance.
Another object of the present invention is to provide a dye-sensitized solar cell encapsulant that can be used over a long period of time without causing volatilization or leakage of the electrolyte.

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

In the dye-sensitized solar cell of the present invention, a semiconductive layer carrying a dye, a light-transmitting porous layer, and a second conductive substrate are sequentially laminated on a first conductive substrate. The resistance of the first conductive base material that becomes the electrode can be reduced. Therefore, the generated power can be taken out without deteriorating. Electric power can be generated by guiding light from the light-transmitting porous layer to a semiconductive layer carrying a dye.
Since the dye-sensitized solar cell of the present invention can be formed in a spiral shape, the power generation amount can be improved.
According to the inclusion body of the dye-sensitized solar cell of the present invention, since the electrolyte can be filled in the transparent case, 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. .

Hereinafter, the present invention will be described with reference to the drawings.
As shown in FIG. 1, the dye-sensitized solar cell of the present invention has a semiconductive layer 20, a light-transmitting porous layer 30, and a second conductive material in which a dye is supported on a first conductive substrate 10. This is a dye-sensitized solar cell 40 in which the base material 11 is sequentially laminated.
In another dye-sensitized solar cell 41 of the present invention, as shown in FIG. 2, a nonconductive substrate 50 may be laminated on the other surface of the first conductive substrate 10, and FIG. As shown in FIG. 4, the non-conductive substrate 50 may be laminated on the other surface of the second conductive substrate 11 to form the dye-sensitized solar cell 42. Further, the nonconductive substrate 50 may be laminated on both the first conductive substrate 10 and the second conductive substrate 11.

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 cells 40, 41, and 42 are flexible sheet-like materials that can be wound up. A dye-sensitized solar cell 44 wound up in a spiral shape is shown in FIG. When winding, it may be wound around the first conductive substrate 10 side or may be wound around the second conductive substrate 11 side. Accordingly, the wound surface portion 12 of the dye-sensitized solar cell 41 becomes the first conductive substrate 10, the second conductive substrate 11, or the nonconductive substrate 50. 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 which laminated | stacked these electroconductive base materials also has flexibility, it can be wound up in the shape of a spiral, and it is set as the dye-sensitized solar cell 43 shown in FIG. 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 in the present invention. The transparent case 70 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.

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 70 shown in FIG. 7, it is preferable that at least one of the lid portion 71 or the bottom portion 72 is removable. Thus, after the dye-sensitized solar cell 44 is accommodated in the transparent case 70, it can be sealed with the lid portion 71 or the bottom portion 72.
Further, the transparent case 70 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 71 or the bottom 72 may be sealed with the resin component.

In order to take out the electric energy generated by the light irradiation, as shown in FIG. 8, the wiring 80 is provided on the first conductive substrate 10 and the second conductive substrate 11 of the dye-sensitized solar cell of the present invention. And 81 are preferably provided. FIG. 8 shows an example of the dye-sensitized solar cell in which the wirings 80 and 81 are provided on the dye-sensitized solar cell 40. The wirings 80 and 81 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 80 and 81 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. 8, after providing the wirings 80 and 81, the nonconductive substrate 50 may be provided. For example, when the non-conductive substrate 50 is an organic film, a varnish is applied on the wiring 80 and / or 81 provided on the first conductive substrate 10 and / or the second conductive substrate 11. Thus, the non-conductive substrate 50 can be formed.

The transparent case in the present invention is preferably provided with a wiring hole 73. As a result, the wirings 80 and 81 for extracting electric energy from the dye-sensitized solar cell 44 housed in the transparent case 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 71 shown in FIG. 7 or on the bottom 72 shown in FIG. In addition, the number of wiring holes 73 formed can be determined as appropriate.

FIG. 9 shows a diagram in which the dye-sensitized solar cell 44 wound up in a spiral shape is housed in a transparent case 70. The transparent case 70 is preferably filled with an electrolytic solution. After the dye-sensitized solar cell 44 is accommodated in the transparent case 70, the electrolyte solution is filled, so that the electrolyte solution penetrates the light-transmitting porous layer 30 by capillary action. When light is irradiated to the light, electrons are emitted and power generation occurs.
Moreover, by storing the dye-sensitized solar cell 44 in the transparent case 70, it is possible to prevent volatilization of the electrolytic solution. Further, when the electrolyte is included in the light-transmitting porous layer 30 of the dye-sensitized solar cell, it does not leak out of the transparent case 70 even if the electrolyte leaks. Is possible.
After the wirings 80 and 81 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.

Hereinafter, materials constituting the present invention will be described.
<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.

<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 and is not particularly 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. 9, for example, it is sufficient that the lid 71 has transparency, and other portions do not need to have transparency. Moreover, the bottom part 72 may have transparency, and the site | part which has transparency is not restrict | limited in particular. In addition, the lid portion 71 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 44 housed in the transparent case 70 is irradiated with light, but the total light transmittance measured by JIS-K7105 is not limited. 70% or more 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.

<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 transparent conductive layer, for example, a dispersion in which oxide semiconductor fine particles are dispersed in a desired dispersion medium or a colloidal solution that can be adjusted by a sol-gel method is used as necessary. After adding a desired additive, it can be coated 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.
In these, since the pigment | dye adsorb | sucked to the metal oxide semiconductor porous layer is bulky and it is hard to remove | eliminate, the solution which melt | dissolved the oxidation reduction electrolyte in the organic solvent is preferable.

<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.

<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 (dye 4), thereby obtaining the dye. Was supported on the semiconductive layer, and then 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. Subsequently, after laminating the second conductive base material (the surface on which the copper wire is not soldered) on the polyamideimide porous film, the light transmissive porous layer is impregnated with an electrolytic solution having the following composition. Thus, a dye-sensitized solar cell of Example 1 was produced.
・ 0.05M iodine ・ 0.1M lithium iodide ・ 0.1M Dimethylpropylimidazolium iodide
・ 0.5M 4-tert-butylpyridine
・ Solvent Butyronitrile

Two dye-sensitized solar cells of Example 1 were prepared, the first conductive substrates were overlapped with each other, and then wound in a spiral shape around the second conductive substrate, thereby dye sensitization. A solar cell was produced.

The entire dye-sensitized solar cell of Example 2 was sealed with ultraviolet curable acrylic to prepare a dye-sensitized solar cell.

The dye-sensitized solar cell of Example 2 was housed in a transparent case having the shape shown in FIG. 8, and an electrolytic solution having the following composition was filled in the transparent case.
・ 0.05M iodine ・ 0.1M lithium iodide ・ 0.1M Dimethylpropylimidazolium iodide
・ 0.5M 4-tert-butylpyridine
・ Solvent Butyronitrile

After the wiring was led out of the transparent case, the transparent case was sealed with an ultraviolet curable acrylic resin to produce a dye-sensitized solar cell enclosure shown in FIG.

<Evaluation>
In the dye-sensitized solar cell of Examples 1 to 3 and the dye-sensitized solar cell enclosure of Example 4, the current-voltage characteristics were examined according to JIS C8913, and it was confirmed that energy conversion was performed. .

The dye-sensitized solar cell of the present invention can use the first conductive substrate and the second conductive substrate by using the light-transmitting porous layer. As a result, it is possible to provide a dye-sensitized solar cell having high conductivity and light transmittance.
Moreover, leakage and volatilization of the electrolyte can be prevented by using the dye-sensitized solar cell enclosure of the present invention.

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 sectional drawing of a dye-sensitized solar cell. It is a dye-sensitized solar cell enclosure in which a dye-sensitized solar cell wound up in a transparent spiral is housed in a transparent case.

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 Transparent case 71 Lid 72 Bottom 73 Wiring holes 80, 81 Wiring 90 Dye-sensitized solar cell enclosure

Claims (11)

A dye-sensitized solar cell in which a semiconductive layer carrying a dye, a light-transmitting porous layer, and a second conductive substrate are sequentially laminated on a first conductive substrate. The dye-sensitized solar cell according to claim 1, wherein the light-transmitting porous layer is filled with an electrolyte. The dye-sensitized solar cell according to claim 1 or 2, wherein the dye-sensitized solar cell is formed into a sheet. The dye-sensitized solar cell according to any one of claims 1 to 3, wherein the dye-sensitized solar cell is formed in a spiral shape. A dye-sensitized solar cell in which a plurality of the dye-sensitized solar cells according to claim 1 are overlapped, wherein the first conductive substrates or the second conductive substrates are overlapped. The dye-sensitized solar cell according to claim 1, wherein: The dye-sensitized solar cell according to any one of claims 1 to 4, wherein a non-conductive substrate is laminated on the first conductive substrate and / or the second conductive substrate. The dye-sensitized solar cell according to any one of claims 1 to 6, wherein wiring is applied to the first conductive substrate and the second conductive substrate. A dye-sensitized solar cell encapsulated body, wherein the dye-sensitized solar cell according to claim 1 is housed in a transparent case. 9. The dye-sensitized solar cell enclosure according to claim 8, wherein an electrolyte is filled in the transparent case. The dye-sensitized solar cell enclosure according to claim 8, wherein at least a part of the transparent case is removable. The dye-sensitized solar cell enclosure according to claim 8, wherein a wiring hole is provided in the transparent case.

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