JP4813819B2 - Dye-sensitized solar cell with capacitor - Google Patents

Description

  The present invention relates to a dye-sensitized solar cell with a capacitor that can directly convert light energy into electric energy and store it. More specifically, the present invention relates to a dye-sensitized solar cell with a capacitor that can output even when light is not received.

At present, in solar power generation, solar cells using single crystal silicon, polycrystalline silicon, amorphous silicon, a combination of these with HIT (Heterojunction with Intrinsic Thin-layer), etc. have been put into practical use and have become the main technology. These solar cells are excellent with photoelectric conversion efficiency of nearly 20%. However, silicon-based solar cells are expensive in terms of energy production, have many problems in terms of environmental impact, and have limitations in price and material supply. On the other hand, a dye-sensitized solar cell proposed by Gratzel et al. Has attracted attention as an inexpensive solar cell (see, for example, Non-Patent Document 1 and Patent Document 1). This solar cell has a structure in which an electrolyte is interposed between a titania porous electrode supporting a sensitizing dye and a counter electrode, and although the photoelectric conversion efficiency is lower than that of the current silicon-based solar cell, the material, Significant cost reduction is possible in terms of manufacturing method.
In addition, a dye-sensitized solar cell and an electric double layer capacitor are integrated so that output can be performed regardless of the presence or absence of light, and a common electrolyte and electrode have been proposed (for example, see Patent Document 2). .

Nature (Vol. 353, pp. 737-740, 1991) Japanese Patent Laid-Open No. 1-220380 Japanese Patent Laid-Open No. 2004-221531

However, when the dye-sensitized solar cell and the electric double layer capacitor are integrated, it is not easy to provide an electrolyte and electrodes having properties necessary for both. In addition, since the electric double layer capacitor has a large capacity, when it is not fully charged, there is a problem that all the electric power generated by the solar cell is consumed for charging and is not output.
The present invention has been made in view of the above situation, and an object of the present invention is to provide a dye-sensitized solar cell with a capacitor that can output even when light is not received.

The dye-sensitized solar cell with a capacitor of the present invention is as follows.
1. Intermediate substrate 11, translucent substrate 12 arranged to face one surface of intermediate substrate 11, catalyst electrode 21 disposed on the one surface side of intermediate substrate 11, and translucent substrate 12 A semiconductor electrode 22 having a sensitizing dye disposed on one side facing the intermediate substrate 11, and contained in at least a part of the semiconductor electrode 22, and between the catalyst electrode 21 and the semiconductor electrode 22. The filled first electrolyte 23, the capacitor substrate 13 disposed to face the other surface side of the intermediate substrate 11, and the first porous electrode 31 disposed on the other surface side of the intermediate substrate 11. And the second porous electrode 32 disposed on the one surface side of the capacitor substrate 13 facing the intermediate substrate 11, the first porous electrode 31, and the second porous electrode 32. Between the first porous electrode 31 and the second porous electrode 32 A second electrolyte 33 filled, provided with, the catalytic electrode 21 and the first porous electrode 31 is electrically connected to the dye-sensitized solar cell with a capacitor, characterized by being mutually.
2. The intermediate substrate 11 and the capacitor substrate 13 are made of ceramic. The dye-sensitized solar cell with a capacitor as described.
3. The electrical connection is performed by the above-described 1. .., which is performed by the via conductive portion 4 provided in the intermediate substrate 11. Or 2. The dye-sensitized solar cell with a capacitor as described.
4). The said 1st porous electrode 31 and the said 2nd porous electrode 32 contain said activated carbon containing said 1 .. To 3. The dye-sensitized solar cell with a capacitor according to any one of the above.
5). The electrical connection further includes a current limiting circuit on the way. To 4. The dye-sensitized solar cell with a capacitor according to any one of the above.

  According to the dye-sensitized solar cell with a capacitor of each invention of the present invention, it is possible to store and output photovoltaic power, so that it can be output even when it is not receiving light, or it can be replenished by receiving light. can do. Moreover, since the electrolyte and electrode which comprise a dye-sensitized solar cell and an electric double layer capacitor are independent, what was suitable for each function can be selected. Further, since the dye-sensitized solar cell portion and the electric double layer capacitor portion are stacked by sharing a part of the substrate, the thickness can be reduced. And the electrode area of an electric double layer capacitor part can be made the same area as a dye-sensitized solar cell part, and it can be made larger capacity | capacitance.

Further, when the intermediate substrate 11 and the capacitor substrate 13 are made of ceramic, the form can be stabilized even in a laminated structure, and manufacture and attachment can be facilitated.
Furthermore, by electrically connecting the dye-sensitized solar cell portion and the electric double layer capacitor portion with vias provided in the intermediate substrate 11, it is not necessary to secure a separate place for connection, and the size can be reduced. it can.
Moreover, when the 1st porous electrode 31 and the 2nd porous electrode 32 are made into activated carbon, the surface area of a porous electrode can be easily enlarged and it can be made large capacity | capacitance.
Furthermore, when the current limiting circuit is further provided, it is possible to suppress the consumption of all the photovoltaic power generated for charging, and to output during light reception even when it is not fully charged.

Hereinafter, the dye-sensitized solar cell with a capacitor of the present invention will be described in detail with reference to FIG.
As illustrated in FIG. 1, the dye-sensitized solar cell with a capacitor includes an intermediate substrate 11 and a translucent substrate 12, a dye-sensitized solar cell portion 101 configured therebetween, an intermediate substrate 11, and a capacitor substrate 13. In addition, the electric double layer capacitor unit 102 is formed between them.
The dye-sensitized solar cell unit 101 includes an intermediate substrate 11, a translucent substrate 12 disposed to face one surface of the intermediate substrate 11, and a catalyst electrode 21 disposed on one surface of the intermediate substrate 11. A semiconductor electrode 22 having a sensitizing dye disposed on one side of the translucent substrate 12 facing the intermediate substrate 11, and contained in at least a part of the semiconductor electrode 22, and the catalyst electrode 21 and the semiconductor electrode 22. A first electrolyte 23 filled in between.
In addition, the electric double layer capacitor unit 102 includes an intermediate substrate 11, a capacitor substrate 13 disposed opposite to the other surface side of the intermediate substrate 11, and a first porous layer disposed on the other surface side of the intermediate substrate 11. Contained in the first porous electrode 31, the second porous electrode 32 disposed on the one surface side of the capacitor substrate 13 facing the intermediate substrate 11, the first porous electrode 31 and the second porous electrode 32, and the first porous electrode 32. And a second electrolyte 33 filled between the porous electrode 31 and the second porous electrode.

The “intermediate substrate 11” and the “capacitor substrate 13” may have a light-transmitting property or may not have a light-transmitting property. The intermediate substrate 11 and the capacitor substrate 13 that do not have translucency can be formed of ceramics, for example. The ceramic substrate has high strength, and this substrate can be used as a support substrate to provide a dye-sensitized solar cell having excellent durability. Moreover, a catalyst electrode and a current collecting electrode can be fired.
The ceramic used for forming the ceramic substrate is not particularly limited, and various ceramics such as oxide ceramics, nitride ceramics, and carbide ceramics can be used. Examples of the oxide ceramic include alumina, mullite, zirconia and the like. Examples of the nitride ceramic include silicon nitride, sialon, titanium nitride, and aluminum nitride. Further, examples of the carbide-based ceramic include silicon carbide, titanium carbide, and aluminum carbide. As the ceramic, alumina, silicon nitride, zirconia and the like are preferable, and alumina is particularly preferable.

  When the intermediate substrate 11 and the capacitor substrate 13 are made of ceramics, the thickness is not particularly limited, but may be 100 μm to 5 mm, 300 μm to 4 mm, particularly 500 μm to 2 mm, and more preferably 700 μm to 1.5 mm. it can. When the thickness of the ceramic substrate is 100 μm to 5 mm, particularly 500 μm or more, the substrate having this high strength becomes a support substrate, and a dye-sensitized solar cell having excellent durability can be obtained.

The intermediate substrate 11 and the capacitor substrate 13 having translucency can be formed using glass, a resin sheet, or the like. When the intermediate substrate 11 and the capacitor substrate 13 are made of a resin sheet, various resins such as polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyphenylene sulfide, polycarbonate, polysulfone, and polyethylidene norbornene are used as the resin sheet. These thermoplastic resins can be mentioned. The thicknesses of the intermediate substrate 11 and the capacitor substrate 13 vary depending on the material and are not particularly limited. However, the following transmittance, which is a light transmission index, is 60 to 99%, particularly 85 to 99%. Is preferred.
The translucency here means that the transmittance of visible light having a wavelength of 400 to 900 nm is 10% or more. This transmittance is preferably 60% or more, particularly 85% or more. Hereinafter, the meaning of translucency and preferable transmittance are all the same.
Transmittance (%) = (transmitted light amount / incident light amount) × 100

Examples of the “translucent substrate 12” disposed to face the intermediate substrate 11 include a substrate made of glass, a resin sheet, or the like as in the case where the intermediate substrate 11 and the capacitor substrate 13 have translucency. . A resin sheet is not specifically limited, The sheet | seat which consists of said various resin is mentioned.
When incident light from the intermediate substrate 11 and capacitor substrate 13 side cannot be expected, the substrates 11 and 13 are preferably ceramic substrates, and the translucent substrate 12 is preferably a glass substrate. The substrates 11 and 13 are ceramic substrates made of alumina, silicon nitride, zirconia, etc., and the translucent substrate 12 is more preferably a glass substrate, and the substrates 11 and 13 are alumina substrates, and the translucent substrate. 12 is particularly preferably a glass substrate.
The thickness of the translucent substrate 12 varies depending on the material and is not particularly limited. However, the above-described transmittance is preferably 60 to 99%, particularly 85 to 99%.

  The “catalyst electrode 21” is disposed on one surface side of the intermediate substrate 11 (see FIG. 1). This catalyst electrode 21 is made of at least one of a metal having a catalytic activity or a conductive oxide used for forming a light-transmitting conductive film and the like, containing a substance having a catalytic activity, and a conductive plastic. Can be formed. As a substance having catalytic activity, noble metals such as platinum and rhodium (however, gold and silver are not preferred because of their low corrosion resistance to electrolytes, etc. Hereinafter, silver is also not preferred in the parts where the electrolytes can contact) .), Carbon black and the like, and these have conductivity together. The catalyst electrode 21 is preferably formed of a noble metal that has catalytic activity and is electrochemically stable, and it is particularly preferable to use platinum that has high catalytic activity and high corrosion resistance to the electrolyte.

In the case of using a metal, a conductive oxide, a conductive polymer, or the like that does not have catalytic activity, examples of the metal used by being mixed with the catalyst electrode 21 include aluminum, copper, chromium, nickel, and tungsten. Furthermore, examples of the conductive polymer used by being mixed with the catalyst electrode 21 include polyaniline, polypyrrole, and polyacetylene. Furthermore, examples of the conductive polymer include those prepared by blending various conductive substances with a resin having no conductivity. The resin not having conductivity is not particularly limited, and may be a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin include thermoplastic polyester resin, polyamide, polyolefin, and polyvinyl chloride. Furthermore, examples of the thermosetting resin include an epoxy resin, a thermosetting polyester resin, and a phenol resin. Also, the conductive material is not particularly limited, and examples thereof include metals such as carbon black, aluminum, nickel, chromium, and tungsten, and conductive plastics such as polyaniline, polypyrrole, and polyacetylene. As the conductive substance, a noble metal and carbon black having both conductivity and catalytic activity are particularly preferable. Only one type of conductive material may be used, or two or more types may be used.
When metals, conductive oxides, conductive polymers, etc. that do not have catalytic activity are used, the content of the above-mentioned substances having catalytic activity is 100 masses of metals, conductive oxides, conductive polymers, etc. Parts, preferably 1 to 99 parts by mass, particularly 50 to 99 parts by mass.

  Thus, the catalyst electrode 21 can be formed of a substance having conductivity and catalytic activity. Further, it can be formed of at least one of a metal, a conductive oxide and a conductive polymer containing a substance having catalytic activity. Furthermore, the catalyst electrode 21 may be a layer made of only one kind of material or a mixed layer made of two or more kinds of materials. Further, the catalyst electrode 21 may be a single layer, or a metal layer, a conductive oxide layer, a conductive polymer layer, and a mixed layer composed of two or more of metal, conductive oxide, and conductive polymer. A multilayer catalyst electrode composed of two or more of them may be used. The thickness of the catalyst electrode 21 is not particularly limited, but can be 3 nm to 10 μm, particularly 3 nm to 2 μm, in both cases of a single layer and a multilayer. When the thickness of the catalyst electrode 21 is 3 nm to 10 μm, the catalyst electrode 21 having a sufficiently low resistance can be obtained.

  The catalytic electrode 21 made of a substance having catalytic activity can be formed by applying a paste containing fine particles of a substance having catalytic activity to the surface of the intermediate substrate 11 or the like. Further, the catalyst electrode 21 made of a metal containing a substance having catalytic activity or a conductive oxide can also be formed by the same method as that for the substance having catalytic activity. Examples of the coating method include various methods such as a screen printing method, a doctor blade method, a squeegee method, and a spin coating method. Furthermore, these catalyst electrodes 21 can also be formed by depositing metal or the like on the surface of the intermediate substrate 11 or the like by sputtering, vapor deposition, ion plating or the like.

  Further, the catalyst electrode 21 made of a conductive polymer containing a substance having a catalytic activity is composed of a conductive polymer and a substance having a catalytic activity such as a powder or a fiber, a Banbury mixer, an internal mixer, an open The resin composition prepared by kneading with an apparatus such as a roll can be formed into a film, and the film can be formed by bonding to the surface of the intermediate substrate 11 or the like. Further, a solution or dispersion prepared by dissolving or dispersing the resin composition in a solvent is applied to the surface of the intermediate substrate 11 and the like, dried, removed to remove the solvent, and heated as necessary. it can. In addition, when the catalyst electrode 21 is a mixed layer, it can be formed by an appropriate method among the above-described various methods according to the type of the material contained.

  The “semiconductor electrode 22” is disposed on one side of the translucent substrate 12 (see FIG. 1). The semiconductor electrode base constituting the semiconductor electrode 22 can be formed of metal oxide, metal sulfide or the like. Examples of the metal oxide include titania, tin oxide, zinc oxide, niobium oxide such as niobium pentoxide, tantalum oxide, and zirconia. Also, double oxides such as strontium titanate, calcium titanate, and barium titanate can be used. Furthermore, examples of the metal sulfide include zinc sulfide, lead sulfide, and bismuth sulfide.

  The method for producing the semiconductor electrode substrate is not particularly limited. For example, a paste containing semiconductor fine particles such as a metal oxide or metal sulfide is applied to the surface of the light-transmitting substrate 12 or the like to form an unfired semiconductor electrode substrate. And it can produce by baking after that. The method for applying the paste is not particularly limited, and examples thereof include a screen printing method, a doctor blade method, a squeegee method, and a spin coating method. The semiconductor electrode substrate thus fabricated is formed in the form of an aggregate formed by aggregating semiconductor fine particles.

  In addition, the semiconductor electrode substrate is formed by applying a colloidal solution in which semiconductor fine particles such as metal oxides and metal sulfides and a small amount of organic polymer are dispersed on the surface of the translucent substrate 12 and the like. And then dried, and then heated to decompose and remove the organic polymer. This colloidal solution can also be applied by various methods such as a screen printing method, a doctor blade method, a squeegee method, and a spin coating method. The semiconductor electrode substrate produced by this method is also formed in the form of an aggregate formed by aggregating semiconductor fine particles.

  The thickness of the semiconductor electrode 22 is not particularly limited, but may be 0.1 to 100 μm, preferably 1 to 50 μm, particularly 2 to 40 μm, and more preferably 5 to 30 μm. When the thickness of the semiconductor electrode 22 is 0.1 to 100 μm, photoelectric conversion is sufficiently performed and power generation efficiency is improved. In addition, the semiconductor electrode 22 is preferably heat-treated in order to improve its strength and adhesion to the translucent substrate 12 or the like. The temperature and time of the heat treatment are not particularly limited, but the heat treatment temperature is preferably 40 to 700 ° C., particularly 100 to 500 ° C., and the heat treatment time is preferably 10 minutes to 10 hours, particularly preferably 20 minutes to 5 hours. In addition, when using a resin sheet as the translucent board | substrate 12, it is preferable to heat-process at appropriate temperature so that resin may not thermally deteriorate.

  As the “sensitizing dye” of the semiconductor electrode 22, complex dyes and organic dyes that improve the action of photoelectric conversion can be used. Examples of complex dyes include metal complex dyes, and examples of organic dyes include polymethine dyes and merocyanine dyes. Examples of the metal complex dye include a ruthenium complex dye and an osmium complex dye, and a ruthenium complex dye is particularly preferable. Furthermore, in order to expand the wavelength range in which photoelectric conversion is performed and improve the photoelectric conversion efficiency, two or more sensitizing dyes having different wavelength ranges in which a sensitizing action is exhibited can be used in combination. In this case, it is preferable to set the type of sensitizing dye to be used in combination and the amount ratio thereof depending on the wavelength range and intensity distribution of the irradiated light. The sensitizing dye preferably has a functional group for bonding to the semiconductor electrode 22. Examples of this functional group include a carboxyl group, a sulfonic acid group, and a cyano group.

  The method for attaching the sensitizing dye to the semiconductor electrode substrate is not particularly limited. For example, the semiconductor electrode substrate is immersed in a solution in which the sensitizing dye is dissolved in an organic solvent, the solution is impregnated, and then the organic solvent is removed. It can be made to adhere. Alternatively, this solution can be applied to a semiconductor electrode substrate and then adhered by removing the organic solvent. Examples of the coating method include a wire bar method, a slide hopper method, an extrusion method, a curtain coating method, a spin coating method, and a spray coating method. Furthermore, this solution can also be applied by a printing method such as offset printing, gravure printing or screen printing.

  The adhesion amount of the sensitizing dye is preferably 0.01 to 1 mmol, particularly 0.5 to 1 mmol with respect to 1 g of the semiconductor electrode. When the adhesion amount is 0.01 to 1 mmol, photoelectric conversion in the semiconductor electrode is efficiently performed. Moreover, if the sensitizing dye that has not adhered to the semiconductor electrode is liberated around the electrode, the conversion efficiency may be lowered. For this reason, it is preferable to remove the excess sensitizing dye by washing the semiconductor electrode after the treatment for attaching the sensitizing dye. This removal can be performed by washing with a polar solvent such as acetonitrile and an organic solvent such as an alcohol solvent using a washing tank. In order to attach a large amount of sensitizing dye to the electrode substrate, it is preferable to heat the semiconductor electrode and perform a treatment such as dipping or coating. In this case, in order to avoid water adsorbing on the surface of the semiconductor electrode, it is preferable to perform the treatment promptly at 40 to 80 ° C. without heating to room temperature after heating.

  In addition, the dye-sensitized solar cell can be provided with the wall part 6 which seals the 1st electrolyte 23 contained in the dye-sensitized solar cell part 101 in a battery. The material of the wall portion 6 can be arbitrarily selected, and examples of the material include resin and glass. As resin used for the wall part 6, thermosetting resins, such as an epoxy resin, a urethane resin, and a thermosetting polyester resin, are mentioned.

Further, a collector electrode provided adjacent to the catalyst electrode 21 and / or the semiconductor electrode 22 can be provided (see, for example, the collector electrodes 51 and 52 shown in FIG. 1). By providing the current collecting electrode, the low conductivity of the catalyst electrode 21 and the semiconductor electrode 22 can be compensated, and the internal resistance of the battery can be lowered. Examples of the current collecting electrode include a metal and carbon or other conductive material having an arbitrary pattern such as a lattice shape, a translucent conductive film, and a conductor and a translucent conductive film.
Among these, metals having excellent corrosion resistance such as tungsten, titanium and nickel are preferable. Moreover, the material of the translucent conductive film is not particularly limited, and examples thereof include a thin film made of a conductive oxide, a metal thin film, and a carbon thin film. Examples of the conductive oxide include tin oxide, fluorine-doped tin oxide, indium oxide, tin-doped indium oxide, and zinc oxide. Examples of the metal include platinum, gold, copper, aluminum, rhodium and indium. The thickness of the translucent conductive film is also different depending on the material, but are not limited to, surface resistance 100 [Omega / cm ² or less, particularly preferably 1~10Ω / cm ² become thick.

The “first electrolyte 23” is contained in at least a part of the semiconductor electrode 22 and is filled between the semiconductor electrode 22 and the catalyst electrode 21. The first electrolyte 23 is usually contained in the entire semiconductor electrode 22 and is filled in the entire area between the semiconductor electrode 22 and the catalyst electrode 21.
Examples of the electrolyte include (1) I ₂ and iodide, (2) Br ₂ and bromide, (3) metal complexes such as ferrocyanate-ferricyanate, ferrocene-ferricinium ion, and (4) sodium polysulfide. And electrolytes containing sulfur compounds such as alkylthiol-alkyldisulfides, (5) viologen dyes, (6) hydroquinone-quinones, and the like. As iodide in (1) is, LiI, NaI, KI, CsI, metal iodide such as CaI _2, and tetraalkylammonium iodide, pyridinium iodide, imidazolium iodide iodine salt of quaternary ammonium compounds such as id, etc. Is mentioned. As the bromide in (2), LiBr, NaBr, KBr, CsBr, CaBr 2 , etc. of the metal bromide, and tetra-alkyl ammonium bromide, bromine salts of quaternary ammonium compounds such as pyridinium bromide and the like. Among these electrolytes, an electrolyte obtained by combining I ₂ and an iodine salt of a quaternary ammonium compound such as LiI, pyridinium iodide, and imidazolium iodide is particularly preferable. These electrolytes may use only 1 type and may use 2 or more types.

  The first electrolyte 23 can be blended in a solvent together with various additives and used as an electrolyte solution. This solvent preferably has a low viscosity, a high ion mobility, and sufficient ion conductivity. Examples of such solvents include (1) carbonates such as ethylene carbonate and propylene carbonate, (2) heterocyclic compounds such as 3-methyl-2-oxazolidinone, (3) ethers such as dioxane and diethyl ether, (4 ) Chain ethers such as ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, (5) methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl Monoalcohols such as ether and polypropylene glycol monoalkyl ether, (6) ethylene glycol, propylene glycol, polyethylene Polyhydric alcohols such as ethylene glycol, polypropylene glycol and glycerin, (7) nitriles such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, and (8) aprotic such as dimethyl sulfoxide and sulfolane. Examples include polar substances. These solvent may use only 1 type and may use 2 or more types.

  Furthermore, a normal temperature molten salt can be used as the first electrolyte 23. In this case, it can be set as an electrolyte solution using a solvent. Also, the electrolyte can be used alone. As this room temperature molten salt, a room temperature molten salt of iodide can be used. Examples of room temperature molten salts of iodide include various room temperature molten salts such as imidazolium salts, pyridinium salts, pyrrolidinium salts, pyrazolidium salts, isothiazolidinium salts, and isoxazolidinium salts. Of the room temperature molten salts of iodide, imidazolium salts are preferred. These room temperature molten salts may be used in combination of two or more different types.

  When an electrolyte solution is used, the electrolyte solution can be injected, contained, and filled in the space formed by the intermediate substrate 11, the translucent substrate 12, and the wall 6. The electrolyte solution may be injected into the space from the intermediate substrate 11 side or the translucent substrate 12 side, and it is preferable to provide an injection port on the side where it is easily perforated and to inject from this injection port. In addition, although one injection port is sufficient, another hole can also be provided for air venting. Thus, by providing the hole for air venting, the electrolyte solution can be injected more easily.

In addition, the element which comprises the dye-sensitized solar cell part 101 is not restricted above, For example, the light-scattering layer which consists of light-scattering particles can be provided. By providing the light scattering layer, light that has not been used for power generation can be scattered and generated again toward the semiconductor electrode 22.
The position at which the light scattering layer is provided can be arbitrarily selected, and can be provided at any position between the semiconductor electrode 22 and the intermediate substrate 11. In addition, the catalyst electrode 21 and / or the semiconductor electrode 22 can contain light scattering particles to form a light scattering layer. As the light scattering particles, any particles that can scatter light having a wavelength that can be used for photovoltaic power generation can be used. As this particle | grain, what consists of metal oxides etc. is mentioned. Examples of the metal oxide include titania, tin oxide, zinc oxide, niobium oxide such as niobium pentoxide, tantalum oxide, and zirconia. Also, double oxides such as strontium titanate, calcium titanate, and barium titanate can be used.

The “first porous electrode 31” and the “second porous electrode 32” are not particularly limited as long as they have a large surface area with voids leading to the outside. Moreover, it is good also considering the electroconductive woven fabric and a nonwoven fabric as the porous electrodes 31 and 32. FIG.
Examples of the material used for the porous electrodes 31 and 32 include carbon and metal. Among these, activated carbon is preferable because it has a large surface area and is inexpensive. Carbon black, fullerene, carbon nanotubes, carbon nanohorns, and the like may also be included. When these carbons are used as electrodes, they are disposed on the substrate using a resin such as a fluororesin and polyvinyl alcohol.

  The “second electrolyte 33” only needs to have characteristics necessary for an electric double layer capacitor, and examples thereof include an electrolyte used for a normal electric double layer capacitor and an electrolyte containing the electrolyte. Examples thereof include a mineral acid such as sulfuric acid, an aqueous electrolyte containing an alkali metal salt or an alkali, and a non-aqueous electrolyte. Various non-aqueous electrolytes can be selected, and examples include propylene carbonate, γ-butyrolactone, acetonitrile, dimethylformamide, sulfolane, and derivatives thereof.

  A separator 34 can be provided between the first porous electrode 31 and the second porous electrode 32. The separator may be any ion-permeable and insulating material. Examples of the separator that can be arbitrarily selected include glass fiber nonwoven fabrics and resin films such as polyphenylene sulfide, polyethylene terephthalate, polyamide, and polyimide. be able to.

The above “electrically connected” means that the catalyst electrode 21 and the first porous electrode 31 are electrically connected by some means. As an example of this, it is possible to use means such as connection by the conductive intermediate substrate 11 and connection by providing a wiring for connection to the intermediate substrate 11. Examples of the conductive intermediate substrate 11 include the use of a conductive material and the inclusion of a conductive material. In addition, as a method of providing connection wiring on the intermediate substrate 11, a method of forming a conductive pattern on the surface of the intermediate substrate 11 and conducting the front and back can be cited. Further, there is a method of providing a “via conductive portion 4” filled with a conductive material in a via hole penetrating the intermediate substrate 11 and connecting the via conductive portion 4 to the catalyst electrode 21 and the first porous electrode 31. Can do. Of these, the method using the via conductive portion 4 is preferable because it does not require complicated wiring.
Moreover, the catalyst electrode 21 and the 1st porous electrode 31 can also be connected via several electroconductive members, such as a current collection electrode.

  The above “current limiting circuit” limits the current flowing from the dye-sensitized solar cell to the electric double layer capacitor to a certain value or less, and receives light even if the electric double layer capacitor is not fully charged. This is a circuit for obtaining a constant output. This current limiting circuit can be arbitrarily selected. For example, the current limiting circuit may be limited by a current limiting resistor, or a circuit combining transistors and the like may be configured. Furthermore, the via conductive portion 4 can be used as a current limiting resistor. The electrical resistance value of the via conductive portion 4 can be selected by appropriately selecting the diameter of the via hole and the conductive material filling the via hole.

Hereinafter, the dye-sensitized solar cell with a capacitor of the present invention will be specifically described by way of examples.
In this example, as shown in FIG. 1, this dye-sensitized solar cell with a capacitor was produced according to the following procedure.
(1) Production on the side of the intermediate substrate 11 After a through hole was formed on the intermediate substrate 11 made of alumina as a flat plate to form a via hole, a conductive paste containing tungsten powder was filled. Subsequently, tungsten paste to be the collecting electrodes 51 and 53 was applied to the front and back surfaces of the intermediate substrate 11 by screen printing. Thereafter, the via conductive portion 4 and the collector electrode 51 were formed by firing. Next, a platinum thin film serving as the catalyst electrode 21 was formed on the collecting electrode 51 by sputtering. Next, a thermosetting resin sheet having a thickness of 50 μm was laminated on the surface on which the collecting electrode 51 was formed to form an uncured wall portion having a predetermined height.

(2) Production of Translucent Substrate 12 Provided with Semiconductor Electrode 22 An FTO transparent conductive film, which is a part of the current collecting electrode 51, was formed in a pattern capable of connecting the semiconductor electrode 22 on one surface of a glass plate substrate. Next, a paste containing titania particles having a particle size of 5 to 300 nm (Ti-Nanoxide D / SP 13um / 300um) was applied by a screen printing method and dried at 120 ° C for 30 minutes to form an unsintered semiconductor electrode substrate. . Next, the unfired semiconductor electrode substrate was fired.
Then, ruthenium organic complex ([Ru2,2bipyridil-4,4-dicarboxylate (TBA) ₂ (NCS) ₂ ]) is dissolved in a mixed solvent of acetonitrile and t-butanol, and 5 × 10 ⁻⁴ M acetonitrile / t-butanol solution. Was prepared. A semiconductor electrode substrate was immersed in this solution for 18 hours, and a ruthenium complex serving as a sensitizing dye was supported on the electrode surface, whereby a light-transmitting substrate 12 having a semiconductor electrode 22 laminated thereon was produced.

(3) Joining of Intermediate Substrate 11 and Translucent Substrate 12 Subsequently, the intermediate substrate 11 and the translucent substrate 12 were opposed to each other, and the uncured wall portion was cured by heating to form the wall portion 6. Next, an iodine electrolyte was injected into the space formed by these from an inlet provided separately, and then the adhesive was filled to seal the inlet.
The iodine electrolyte was butyronitrile, 0.1 mol of lithium iodide, 0.05 mol of iodine, 0.5 mol of 4-tert-butylpyridine, and 0.6 mol of 1,2-dimethyl-3. A solution in which propylimidazolium iodide was dissolved was used.

(4) Production on the Capacitor Substrate 13 Side A tungsten paste to be the collecting electrode 54 was applied by a screen printing method on the flat capacitor substrate 13 made of alumina. Thereafter, the collector electrode 54 was formed by firing at 500 ° C. for 30 minutes in a muffle furnace. Next, an activated carbon paste composed of 80% by mass of activated carbon, 10% by mass of carbon black as a conductive material, and 10% by mass of ethylene tetrafluoride was applied and formed on the collecting electrode 51 and cured to form the second porous electrode 32. .

(3) Bonding of Intermediate Substrate 11 and Capacitor Substrate 13 The activated carbon paste was applied and formed on the collecting electrode 53 of the intermediate substrate 11 and cured to form the first porous electrode 31. Thereafter, after placing a non-woven fabric made of polyphenylene sulfide on the second porous electrode 32 of the capacitor substrate 13, the intermediate substrate 11 and the capacitor substrate 13 are opposed to each other and heated to cure the uncured wall portion. Part 6 was formed. Next, after injecting an electrolytic solution into the space formed by these from an inlet provided separately, the inlet is filled with an adhesive, and the dye-sensitized solar cell 1 with a capacitor shown in FIG. Produced.
In addition, 30 mass% sulfuric acid aqueous solution was used for electrolyte solution.

As shown in FIG. 1, the dye-sensitized solar cell 1 with a capacitor produced in this way includes an intermediate substrate 11, a light-transmitting substrate 12, and a dye-sensitized solar cell portion 101 formed therebetween, and an intermediate substrate. 11 and a capacitor substrate 13 and an electric double layer capacitor portion 102 formed therebetween.
The dye-sensitized solar cell unit 101 includes an intermediate substrate 11, a translucent substrate 12 disposed to face one surface of the intermediate substrate 11, and a current collecting electrode 52 disposed on one surface of the intermediate substrate 11. And at least part of the semiconductor electrode 22, the catalyst electrode 21, the collector electrode 51 disposed on the one surface side of the translucent substrate 12 facing the intermediate substrate 11, the semiconductor electrode 22 having a sensitizing dye, and the like. And a first electrolyte 23 filled between the catalyst electrode 21 and the semiconductor electrode 22.
The electric double layer capacitor unit 102 includes an intermediate substrate 11, a capacitor substrate 13 disposed to face the other surface side of the intermediate substrate 11, a current collecting electrode 53 disposed on the other surface side of the intermediate substrate 11, and The first porous electrode 31, the current collecting electrode 54 and the second porous electrode 32 disposed on one side of the capacitor substrate 13 facing the intermediate substrate 11, the first porous electrode 31 and the second porous electrode 32, and a second electrolyte 33 filled between the first porous electrode 31 and the second porous electrode.
Moreover, the 1st electrolyte 23 and the 2nd electrolyte 33 are hold | maintained in the dye-sensitized solar cell with a capacitor by the wall part 6 formed in the circumference | surroundings. Further, the catalyst electrode 21 and the first porous electrode 31 are connected by the collector electrode 52, the via conductive portion 4, and the collector electrode 53.

The dye-sensitized solar cell 1 with a capacitor can be connected to an external circuit by connection terminals 71, 72, 73 formed by extending the collecting electrodes 51, 52, 54 from the wall 6. Further, the dye-sensitized solar cell unit 101 can be used by using the connection terminals 71 and 72, and the electric double layer capacitor unit 102 can be used by using the connection terminals 72 and 73. Furthermore, by connecting the connection terminal 71 and the connection terminal 73, the electricity generated by the dye-sensitized solar cell unit 101 can be stored in the electric double layer capacitor unit 102 and output to an external circuit, and cannot be photovoltaic. In this case, the electricity stored in the electric double layer capacitor unit 102 can be output to an external circuit.
In addition, since the via conductive portion 4 connecting the catalyst electrode 21 and the first porous electrode 31 is also a current limiting circuit using tungsten, the current flowing to the electric double layer capacitor portion 102 can be limited, and charging is completed. Even when it is not, the electricity generated by photovoltaic power generation can be output to an external circuit.

  The present invention is not limited to the description of the above-described embodiments, and various modifications can be made within the scope of the present invention depending on the purpose, application, and the like. For example, as the first electrolyte 23, an ionic liquid such as a non-volatile imidazolium salt, a gel obtained by gelling this ionic liquid, and a solid such as copper iodide or copper thiocyanide can be used. Moreover, the 2nd electrolyte 33 is not restricted to the sulfuric acid aqueous solution quoted in the Example, The aqueous electrolyte containing an alkali metal salt or an alkali and a non-aqueous electrolyte can be used.

It is a schematic cross section for demonstrating the structure of the dye-sensitized solar cell with a capacitor of a present Example.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1; Dye-sensitized solar cell with a capacitor, 101; Dye-sensitized solar cell part, 102; Electric double layer capacitor part, 11; Intermediate substrate, 12; Translucent substrate, 13; Capacitor substrate, 21; 22; Semiconductor electrode, 23; First electrolyte, 31; First porous electrode, 32; Second porous electrode, 33; Second electrolyte, 34; Separator, 4; Via conductive part (current limiting circuit), 5 Current collecting electrode, 6; wall.

Claims (5)

Intermediate substrate 11, translucent substrate 12 arranged to face one surface of intermediate substrate 11, catalyst electrode 21 disposed on the one surface side of intermediate substrate 11, and translucent substrate 12 A semiconductor electrode 22 having a sensitizing dye disposed on one side facing the intermediate substrate 11, and contained in at least a part of the semiconductor electrode 22, and between the catalyst electrode 21 and the semiconductor electrode 22. Filled first electrolyte part 23;
The capacitor substrate 13 disposed opposite to the other surface side of the intermediate substrate 11, the first porous electrode 31 disposed on the other surface side of the intermediate substrate 11, and the intermediate portion of the capacitor substrate 13 A second porous electrode 32 disposed on one side facing the substrate 11, the first porous electrode 31 and the second porous electrode 32, and the first porous electrode 31 and the second porous electrode 32; A second electrolyte part 33 filled between the two porous electrodes 32,
The dye-sensitized solar cell with a capacitor, wherein the catalyst electrode 21 and the first porous electrode 31 are electrically connected to each other.   The dye-sensitized solar cell with a capacitor according to claim 1, wherein the intermediate substrate 11 and the capacitor substrate 13 are made of ceramic.   3. The dye-sensitized solar cell with a capacitor according to claim 1, wherein the electrical connection is performed by a via conductive portion 4 provided on the intermediate substrate 11.   The dye-sensitized solar cell with a capacitor according to any one of claims 1 to 3, wherein the first porous electrode 31 and the second porous electrode 32 contain activated carbon.   The dye-sensitized solar cell with a capacitor according to any one of claims 1 to 4, wherein the electrical connection further includes a current limiting circuit in the middle.

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