JP2005317453A - Dye-sensitized solar cell and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell which can use light incident from a side of a translucent substrate effectively, and its manufacturing method. <P>SOLUTION: The dye-sensitized solar cell comprises: a substrate 1 (such as a ceramic substrate); a translucent substrate 2 (such as a glass substrate) facing the substrate 1; a catalyst electrode 3 (made of platinum or the like) placed on a surface of the translucent substrate 1; a first semiconductor electrode 41 (made of a titania or the like) placed on a surface of the translucent substrate 2 and having a sensitizing dye; a first current collection electrode 51 (made of tungsten or the like) placed away from the catalyst electrode 3 for the first semiconductor electrode 41 on a side facing the catalyst electrode 3; and an electrolyte which at least a portion of the first semiconductor electrode 41 contains and with which a space between the first semiconductor electrode 41 and the catalyst electrode 3 is filled; where the first current collection electrode 51 contains light scattering particles (titania particles or the like). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a dye-sensitized solar cell that directly converts light energy into electric energy. More specifically, the present invention relates to a dye-sensitized solar cell that can efficiently use light incident from the side of a translucent substrate and a method for manufacturing the same.

  At present, in solar power generation, solar cells using single crystal silicon, polycrystalline silicon, amorphous silicon, and HIT (Heterojunction with Intrinsic Thin-layer) combined with these have been put into practical use and have become the main technology. These solar cells have an excellent 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.

  However, this dye-sensitized solar cell has a problem in that light incident on the titania porous electrode is transmitted through the electrode and the incident light is not used sufficiently effectively. In view of this, a method for scattering the light in the titania porous electrode and improving the utilization efficiency of the incident light has been studied. As this method, there is known a photoelectric conversion element having a semiconductor fine particle film which is composed of a plurality of layers having different light scattering properties and in which a layer having the lowest light scattering property is arranged on the light incident side (for example, Patent Document 2). reference.). In addition, a dye-sensitized solar cell including a semiconductor electrode having a light scattering layer containing metal oxide particles such as rods that scatter incident light is known (see, for example, Patent Document 3). Furthermore, there is known a dye-sensitized solar cell that includes a light-absorbing layer made of light-absorbing particles carrying a dye and contains light-scattering particles in the light-absorbing layer (see, for example, Patent Document 4).

Nature (Vol. 353, pp. 737-740, 1991) Japanese Patent Laid-Open No. 1-220380 JP 2002-222968 A JP 2002-289274 A JP 2003-303629 A

  The present invention has been made in view of the above-described situation. Light scattering particles are contained in a negative electrode-side current collecting electrode disposed on a semiconductor electrode to scatter light transmitted through the semiconductor electrode. Dye-sensitized solar cell that can efficiently use light incident from the side of the light-transmitting substrate by making part of the light incident again on the semiconductor electrode and photoelectrically converting it, and this dye-sensitized solar cell are easy It aims at providing the manufacturing method of the dye-sensitized solar cell which can be manufactured in the next.

The present invention is as follows.
1. A substrate 1, a translucent substrate 2 disposed opposite the substrate 1, a catalyst electrode 3 disposed on one surface side of the substrate 1, and a translucent substrate 2 disposed on one surface side; A first semiconductor electrode 41 having a sensitizing dye, and a first negative electrode side collector electrode 51 disposed on the side of the first semiconductor electrode 41 facing the catalyst electrode 3 and spaced apart from the catalyst electrode 3; In the dye-sensitized solar cell including the electrolyte 6 contained in at least a part of the first semiconductor electrode 41 and filled between the first semiconductor electrode 41 and the catalyst electrode 4, The dye-sensitized solar cell, wherein the negative electrode side collecting electrode 51 contains light scattering particles 7.
2. An insulating layer 8 is interposed between the catalyst electrode 3 and the first negative electrode side collecting electrode 51, and the electrolyte 6 is contained in the insulating layer 8. 2. A dye-sensitized solar cell according to 1.
3. On the side of the first negative electrode side collector electrode 51 facing the catalyst electrode 3, the second negative electrode side collector electrode 52 having higher conductivity than the first negative electrode side collector electrode 51 is disposed. . Or 2. 2. A dye-sensitized solar cell according to 1.
4). The second semiconductor electrode 42 having a sensitizing dye is disposed on the side of the first negative electrode side collecting electrode 51 facing the catalyst electrode 3. Or 2. 2. A dye-sensitized solar cell according to 1.
5). The average particle diameter of the light scattering particles 7 is a value of 25 to 75% of a light wavelength at which the light absorption rate of the first semiconductor electrode 41 is 50%. To 4. The dye-sensitized solar cell of any one of these.
6). At least a part of each of the first semiconductor electrode 41 and the light scattering particles 7 is made of the same material. To 5. The dye-sensitized solar cell of any one of these.
7). Each of the first semiconductor electrode 41 and the light scattering particles 7 is made of titania or contains titania. To 6. The dye-sensitized solar cell of any one of these.
8). 1. The substrate 1 is made of ceramic. To 7. The dye-sensitized solar cell of any one of these.
9. Above 1. To 8. A method for producing a dye-sensitized solar cell according to any one of claims 1 to 3, wherein an unfired catalyst electrode 3 'is formed on one side of an unfired ceramic substrate 1', and then the unfired catalyst electrode An unfired insulating layer 8 ′ is formed on one surface side of 3 ′, and then an unfired first negative electrode side collector electrode 51 ′ containing unfired light scattering particles 7 ′ on the one surface side of the unfired insulating layer 8 ′. After that, an unfired laminate including the unfired catalyst electrode 3 ′, the unfired insulating layer 8 ′, and the unfired first negative electrode side collector electrode 51 ′ is cofired, and then the cofired An unsintered semiconductor electrode base body s is formed on one surface side of the first negative electrode side collector electrode 51 manufactured by the above, and then the unsintered semiconductor electrode base body s is fired to produce a semiconductor electrode base body, and then the semiconductor A first semiconductor electrode 41 is produced by impregnating an electrode substrate with a sensitizing dye, and then the first semiconductor electrode 4 1, a translucent substrate 2 is placed on one surface side, and then between the ceramic substrate 1 produced by the co-firing and the translucent substrate 2, the catalyst electrode 3 produced by the co-firing, An uncured bonding layer 9 ′ surrounding the insulating layer 8, the first negative electrode side collector electrode 51, and the first semiconductor electrode 41 produced by the co-firing is formed, and then the uncured bonding layer 9 ′ is heated. In this way, the bonding layer 9 is prepared, and then the dye 6 is made to contain the electrolyte 6 in at least a part of the first semiconductor electrode 41, the first negative electrode side collecting electrode 51, and the insulating layer 8. Type solar cell manufacturing method.

In the dye-sensitized solar cell of the present invention, the light transmitted through the semiconductor electrode is scattered at the negative electrode side collector electrode, and a part of the scattered light is incident again on the semiconductor electrode to perform photoelectric conversion. Utilization efficiency can be improved.
Further, when the insulating layer 8 is interposed between the catalyst electrode 3 and the first negative electrode side collecting electrode 51 and the electrolyte 6 is contained in the insulating layer 8, the negative electrode side and the positive electrode side are surely provided. And a dye-sensitized solar cell having excellent conversion efficiency.
Further, when the second negative electrode side collector electrode 52 having higher conductivity than the first negative electrode side collector electrode 51 is disposed on the side of the first negative electrode side collector electrode 51 facing the substrate 1, The second negative electrode side collecting electrode 52 can provide a dye-sensitized solar cell with high current collecting efficiency.
In addition, when the second semiconductor electrode 42 having a sensitizing dye is disposed on the side of the first negative electrode side collecting electrode 51 facing the substrate 1, the dye-sensitized solar with higher light utilization efficiency. It can be a battery.
Furthermore, when the average particle diameter of the light scattering particles 7 is 25 to 75% of the light wavelength at which the light absorption rate of the first semiconductor electrode 41 is 50%, the scattered light can be used more efficiently. And a dye-sensitized solar cell with particularly high utilization efficiency of incident light.
When at least a part of each of the first semiconductor electrode 41 and the light scattering particles 7 is made of the same material, for example, titania, or contains titania, the first semiconductor electrode 41 and the first negative electrode side collector electrode 51 are used. The dye-sensitized solar cell with high conversion efficiency can be obtained.
Furthermore, when the substrate 1 is made of ceramic, the dye-sensitized solar cell can be more easily manufactured and can be a dye-sensitized solar cell excellent in durability.
According to the method for producing a dye-sensitized solar cell of the present invention, the dye-sensitized solar cell of the present invention can be easily produced by a simple process.

Hereinafter, with reference to FIGS. 1-12, the dye-sensitized solar cell of this invention and its manufacturing method are demonstrated in detail.
The “substrate 1” may have translucency or may not have translucency. The substrate 1 that does not have translucency can be formed of ceramic. 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. 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 board | substrate 1 consists of ceramics, the thickness is not specifically limited, However, It can be referred to as 100 micrometers-5 mm, 300 micrometers-4 mm, Especially 500 micrometers-2 mm, Furthermore, it can be set as 700 micrometers-1.5 mm. 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 light-transmitting substrate 1 can be formed using glass, a resin sheet, or the like. When the substrate 1 is made of a resin sheet, the resins used for forming the resin sheet include various thermoplastic resins such as polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyphenylene sulfide, polycarbonate, polysulfone, and polyethyleneidene norbornene. Can be mentioned. When the substrate 1 is a light-transmitting substrate, its thickness varies depending on the material and is not particularly limited, but the following transmittance, which is a light-transmitting index, is 60 to 99%, particularly 85 to 99%. It is preferable that it is the thickness which becomes.
Translucency 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 2” disposed to face the substrate 1 include a substrate made of glass, a resin sheet, or the like. A resin sheet is not specifically limited, The sheet | seat which consists of said various resin is mentioned. The substrate 1 can be formed of glass, resin, ceramic, and the like, and the translucent substrate 2 can be formed of glass, resin, and the like, but the substrate 1 is a ceramic substrate, and the translucent substrate 2 is A glass substrate is preferred. The substrate 1 is a ceramic substrate made of alumina, silicon nitride, zirconia, or the like, and the translucent substrate 2 is more preferably a glass substrate. The substrate 1 is an alumina substrate, and the translucent substrate 2 is a glass substrate. It is particularly preferable (see FIG. 1 and FIGS. 7 to 11).
The thickness of the translucent substrate 2 varies depending on the material and is not particularly limited. However, it is preferable that the transmissivity is 60 to 99%, particularly 85 to 99%.

  The “catalyst electrode 3” is disposed on one surface side of the substrate 1 (see FIGS. 1 and 7 to 11). The catalyst electrode 3 is composed of a material having catalytic activity, or a material containing a catalytic activity, of a metal, a conductive oxide and a conductive polymer used to form a translucent conductive layer p described later. It can be formed by at least one kind. As a substance having catalytic activity, noble metals such as platinum, gold and rhodium (however, silver is not preferred because of its low corrosion resistance to electrolytes, etc., hereinafter, silver is also not preferred in the part where the electrolyte etc. can contact) .), Carbon black and the like, and these have conductivity together. The catalyst electrode is preferably formed of a noble metal having catalytic activity and electrochemically stable, and it is particularly preferable to use platinum having 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 mixing with the catalyst electrode include aluminum, copper, chromium, nickel, tungsten, and the like. Furthermore, polyaniline, polypyrrole, polyacetylene, etc. are mentioned as a conductive polymer used by mixing with a catalyst electrode. Further, 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. Further, the conductive substance is not particularly limited, and examples thereof include metals such as carbon black, aluminum, nickel, chromium and tungsten, and conductive polymers such as polyaniline, polypyrrole and polyacetylene. As the conductive material, 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.
In the case of using a metal, conductive oxide, conductive polymer, or the like that does not have catalytic activity, the content of the substance having the catalytic activity is 100 masses of metal, conductive oxide, conductive polymer, etc. Parts (hereinafter referred to as “parts”), it is preferably 1 to 99 parts, particularly 50 to 99 parts.

  Thus, the catalyst electrode 3 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 3 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 3 may be a single layer, 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 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 is 3 nm to 10 μm, the catalyst electrode can have a sufficiently low resistance.

  The catalyst electrode 3 made of a substance having catalytic activity can be formed by applying a paste containing fine particles of a substance having catalytic activity on the surface of the substrate 1 or the like. Further, the catalyst electrode 3 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 3 can also be formed by depositing metal or the like on the surface of the substrate 1 or the like by sputtering, vapor deposition, ion plating or the like.

  Further, the catalyst electrode 3 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 a roll or the like can be formed into a film, and the film can be formed by bonding to the surface of the substrate 1 or the like. Further, a solution or dispersion prepared by dissolving or dispersing the resin composition in a solvent can be applied to the surface of the substrate 1 and the like, dried, the solvent removed, and heated as necessary. . In addition, when the catalyst electrode 3 is a mixed layer, it can be formed by an appropriate method among the above-described various methods according to the type of material contained.

  The “first semiconductor electrode 41” is disposed on one surface side of the translucent substrate 2 (see FIGS. 1 and 7 to 11). The semiconductor electrode substrate of the first semiconductor electrode 41 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 fine particles such as metal oxide and metal sulfide is applied to the surface of the translucent substrate 2 and the like to form the unfired semiconductor electrode substrate s. 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 produced in this way is formed in the form of an aggregate made up of fine particles.

  The semiconductor electrode substrate is formed by applying a colloidal solution in which fine particles such as metal oxide and metal sulfide and a small amount of organic polymer are dispersed on the surface of the translucent substrate 2 or the like to form an unfired semiconductor electrode substrate s. Then, it can be produced by a process such as drying and then heating 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 made up of fine particles.

  The thickness of the first semiconductor electrode 41 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 first semiconductor electrode 41 is 0.1 to 100 μm, photoelectric conversion is sufficiently performed and power generation efficiency is improved. Further, the first semiconductor electrode 41 is preferably subjected to heat treatment in order to improve its strength and adhesion with the translucent substrate 2 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 2, it is preferable to heat-process at appropriate temperature so that resin may not thermally deteriorate.

  As the “sensitizing dye” of the first semiconductor electrode 41, a complex dye and an organic dye that improve the photoelectric conversion effect 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. 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.

  The “first negative electrode side collector electrode 51” disposed on the side of the first semiconductor electrode 41 facing the catalyst electrode 3 and spaced apart from the catalyst electrode 3 is a function of collecting current from the first semiconductor electrode 41 and the like. And also has a function of scattering light incident on the first negative electrode current collecting electrode 51 through the first semiconductor electrode 41 by light scattering particles described later (see FIGS. 1 and 7 to 11). A part of the scattered light is incident again on the first semiconductor electrode 41 and undergoes photoelectric conversion. In this way, light incident from the side of the translucent substrate 2 can be used more efficiently. The material of the first negative electrode side collecting electrode 51 is not particularly limited, and metals such as tungsten, titanium, and molybdenum can be used.

  The planar shape of the first negative electrode side collecting electrode 51 is not particularly limited, and may be an electrode made of a planar electrode and a linear electrode and formed by a specific electrode pattern. The first negative electrode side collecting electrode 51 does not need to have translucency, and is preferably planar from the viewpoint of scattering more transmitted light and making it incident on the first semiconductor electrode 41 again. . When the first negative electrode side collector electrode 51 has a planar shape, the first negative electrode side collector electrode 51 has a planar shape similar to that of the first semiconductor electrode 41 in order to obtain a negative electrode side collector electrode with low resistance. It is preferable that the electrode is a planar electrode having an area of 50% or more, particularly 65% or more, and further 80% or more (may be substantially the same area). More preferably, the first semiconductor electrode 41 is disposed in a similar shape.

  When the 1st negative electrode side current collection electrode 51 consists of a linear electrode and is formed by the specific electrode pattern, it can be set as planar electrodes, such as a grid | lattice shape, a comb-tooth shape, and radial shape, for example. In the case of the first negative electrode side collecting electrode 51 made of this linear electrode and formed by a specific electrode pattern, the width and thickness of the linear electrode are not particularly limited, and its electric resistance, cost, etc. It is preferable to set in consideration. The total area of the first negative electrode side collecting electrode 51 is preferably 50% or more, particularly 80% or more, and more preferably 90% or more (or 100%) with respect to the total area of the first semiconductor electrode 41. If the area of the first negative electrode side collecting electrode 51 is 50% or more, particularly 100%, with respect to the total area of the first semiconductor electrode 41, more of the light transmitted through the first semiconductor electrode 41 is the first. It can be scattered at the negative electrode side collector electrode 51. As a result, more light can be made incident again on the first semiconductor electrode 41, so that the light can be used efficiently and the current collection efficiency can be increased.

  The method of providing the first negative electrode side collecting electrode 51 is not particularly limited. For example, titanium is formed by physical vapor deposition such as magnetron sputtering and electron beam vapor deposition using a mask on which a predetermined pattern is formed. There may be mentioned a method of depositing a metal such as molybdenum and then patterning by photolithography or the like. Moreover, it can also form by the method of patterning by the screen printing method etc. using the metallized ink containing each metal component, and baking it after that.

  The electrolyte 6 is filled between the first semiconductor electrode 41 and the catalyst electrode 3 (see FIG. 11) and contained. Therefore, when the first negative electrode side collecting electrode 51 is planar with the same size as the first semiconductor electrolyte 1 and the like, the first negative electrode side collecting electrode 51 needs to be a porous body (FIG. 1). And see FIGS. The porosity of the first negative electrode side collecting electrode 51 made of this porous body is not particularly limited, but may be 2 to 40%, particularly 10 to 30%, and further 15 to 25%. If the porosity is 10 to 30%, the electrolyte can be easily contained without lowering the current collection efficiency. When the first negative electrode side collecting electrode 51 is made of the above-mentioned linear electrode and formed by a specific electrode pattern, it is not necessary to be a porous body.

  The first negative electrode side collecting electrode 51 is disposed away from the catalyst electrode 3, and the negative electrode side and the positive electrode side are electrically insulated. In order to make this electrical insulation more reliable, The insulating layer 8 can be interposed between the 1 negative electrode side current collection electrode 51 and the catalyst electrode 3 (refer FIG.1 and FIG.7-10). The material of the insulating layer 8 is not particularly limited, and examples thereof include ceramic, resin, and glass, and ceramic is preferable. As the ceramic, 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.

  The planar shape of the insulating layer 8 is not particularly limited as long as the negative electrode side and the positive electrode side can be electrically insulated. For example, the insulating layer 8 may have a planar shape, or a specific shape such as a lattice shape, a comb shape, or a radial shape. However, in the case of a planar shape having the same size as the first semiconductor electrode 41 and the like, it needs to be a porous body. When the insulating layer 8 is a porous body, the porosity is not particularly limited, but is preferably 2 to 40%, particularly 10 to 30%, and more preferably 15 to 25%. When the porosity is 10 to 30%, the electrolyte 6 is easily contained, and the function as a dye-sensitized solar cell is not impaired. The thickness of the insulating layer 8 is not particularly limited, but can be 0.5 to 20 μm, particularly 1 to 10 μm, and further 2 to 5 μm. When the thickness of the insulating layer 8 is 0.5 to 20 μm, the negative electrode side and the positive electrode side can be sufficiently electrically insulated.

  The insulating layer 8 may be formed by using a paste containing each ceramic component or the like by forming a coating film on the surface of the catalyst electrode 3 by a screen printing method or the like and then firing at a predetermined temperature. it can. Further, a ceramic such as alumina, silicon nitride, zirconia, or the like may be deposited on the surface of the catalyst electrode 3 by a physical vapor deposition method such as a magnetron sputtering method or an electron beam vapor deposition method.

  The “electrolyte 6” is contained in at least a part of the first semiconductor electrode 41 and is filled between the semiconductor electrode 41 and the substrate 1. The electrolyte 6 is usually contained in the entire first semiconductor electrode 41 and filled in the entire area between the first semiconductor electrode 41 and the substrate 1.

Examples of the electrolyte include (1) I ₂ and iodide, (2) Br ₂ and bromide, (3) metal complexes such as ferrocyanate-ferricyanate and 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 electrolyte 6 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, glycerin, (7) nitriles such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, (8) aprotic such as dimethyl sulfoxide, sulfolane, etc. Examples include polar substances. These solvent may use only 1 type and may use 2 or more types.

  In the case of using an electrolyte solution, this solution is sealed between the substrate 1 and the translucent substrate 2 with resin or glass around the first semiconductor electrode 41 and the like, and the electrolyte solution is injected into the space to be formed. , Can be included and filled. The electrolyte solution may be injected into this space from the substrate 1 side or from the translucent substrate 2 side, and it is preferable to provide an injection port on the side where it is easy to perforate 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.

  When the first negative electrode side collecting electrode 51 is separated from the catalyst electrode 3, that is, when the insulating layer 8 is interposed, the thickness of the insulating layer 8 is not particularly limited, but is 200 μm or less, particularly 100 μm. Hereinafter, it can be further set to 50 μm or less (usually 1 μm or more). If this distance or the thickness of the insulating layer 8 is not more than a predetermined value, the conversion efficiency can be sufficiently increased.

  Examples of the resin used for sealing around the first semiconductor electrode 41 and the like include polyamide resins, thermoplastic polyester resins, modified polyolefin resins such as maleic acid-modified polyethylene, and polyolefins having adhesive properties such as ethylene-ethyl acrylate copolymer resins. Examples thereof include thermoplastic resins such as resins. Moreover, thermosetting resins, such as an epoxy resin, a urethane resin, a polyimide resin, and a thermosetting polyester resin, are mentioned. Furthermore, this sealing can also be performed with glass. In particular, in a dye-sensitized solar cell that requires long-term durability, sealing with glass is preferable.

  As the “light scattering particles 7”, particles that can be contained in the first negative electrode side collector electrode 51 and can scatter light incident on the first negative electrode side collector electrode 51 can be used. (See FIG. 2). As this particle | grain, what consists of a metal oxide, a metal sulfide, 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. Furthermore, examples of the metal sulfide include zinc sulfide, lead sulfide, and bismuth sulfide.

  When the first negative electrode side collecting electrode 51 contains the light scattering particles 7 which are foreign particles made of the above metal oxide and metal sulfide, light is scattered on the surface of the light scattering particles 7. The The particle diameter of the light-scattering particles 7 is not particularly limited, but the average particle diameter is 25 to 25 of the light wavelength (for example, wavelengths A and B in FIG. 3) at which the light absorption rate of the first semiconductor electrode 41 is 50%. A value of 75% is preferred. The average particle diameter of the light scattering particles 7 is more preferably 30 to 70%, particularly 35 to 65%, and more preferably 40 to 60% of the light wavelength at which the light absorption rate of the first semiconductor electrode 41 is 50%. It is preferably 45 to 55%, more preferably around 50% (for example, 48 to 52%). The light having a wavelength at which the light absorption rate of the first semiconductor electrode 41 is 50% is also a lot of transmitted light. However, if much of the transmitted light is scattered and incident on the first semiconductor electrode 41 again, the incident light About 50% of the light is absorbed, and the light utilization efficiency as a whole can be improved.

  Furthermore, the particle diameter of the metal particles constituting the first negative electrode side collecting electrode 51 can be 0.1 to 50 μm, preferably 0.5 to 20 μm, particularly preferably 1 to 10 μm. On the other hand, the particle diameter of the light scattering particles 7 can be 25 to 75% of the particle diameter of λ, where λ (nm) is the wavelength of light having a light absorption rate of 50%, and 40 to 60 of λ. %, Particularly 45 to 55%, more preferably about 50% (48 to 52%).

  It is preferable that at least a part of each of the first semiconductor electrode 41 and the light scattering particles 7 is made of the same material. Thus, if at least a part is the same material, the adhesiveness between the first semiconductor electrode 41 and the first negative electrode side collecting electrode 51 can be increased, and the photoelectric conversion efficiency can also be improved. The semiconductor electrode is often made of titania, but it is preferable that the first semiconductor electrode 41 is made of titania and the light scattering particles 7 are made of titania. In this case, each of the first semiconductor electrode 41 and the light scattering particles 7 may contain 50% by mass or more, particularly 80% by mass or more of titania. More preferably, the whole consists of titania. In this way, the adhesion between the first semiconductor electrode 41 and the first negative electrode side collecting electrode 51 can be sufficiently increased, and the photoelectric conversion efficiency can be further improved.

In this dye-sensitized solar cell, the second negative electrode side collecting electrode 52 having higher conductivity than the first negative electrode side collecting electrode 51 is provided on the side of the first negative electrode side collecting electrode 51 facing the catalyst electrode 3. (See FIG. 7). The conductivity higher than that of the first negative electrode side collecting electrode 51 means that the light scattering particles 7 are contained in the light scattering particles 7 as compared with the first negative electrode side collecting electrode 51 whose conductivity is lowered by containing the light scattering particles 7. If it is not contained or contained, it means that the content of the light scattering particles 7 is less than that of the first negative electrode side and 51. The second negative electrode side collecting electrode 52 does not contain the light scattering particles 7 or, if it is contained, the content thereof is 50% or less of the first negative electrode side collecting electrode 51, particularly 20% or less. Is preferred. Thereby, the fall of the current collection efficiency of the 1st negative electrode side current collection electrode 51 can be supplemented, and the current collection efficiency as the whole current collection electrode can be improved.
The material, planar shape, thickness, formation method, and the like of the second negative electrode side collecting electrode 52 are the same as those of the first negative electrode side collecting electrode 51. Furthermore, for the same reason, when the second negative electrode side collecting electrode 52 is formed in a planar shape having the same size as the first semiconductor electrode 41, the second negative electrode side collecting electrode 52 needs to be a porous body. is there.

In the dye-sensitized solar cell, the second semiconductor electrode 42 can be provided on the side of the first negative electrode side collecting electrode 51 facing the catalyst electrode 3 (see FIG. 8). The first negative electrode side collector electrode 51 is not so light transmissive, but there is also light that passes through the first negative electrode side collector electrode 51. Using this transmitted light, the second semiconductor electrode 42 can also perform photoelectric conversion, and the photoelectric conversion efficiency can be improved.
The material, planar shape, thickness, formation method, and the like of the second semiconductor electrode 42 are the same as those of the first semiconductor electrode 41. Further, the kind of sensitizing dye, the method of attaching the sensitizing dye, the amount of attachment, and the like of the second semiconductor electrode 42 are the same as those of the first semiconductor electrode 41.
When the heat treatment is performed to improve the strength of the second semiconductor electrode 42 and the adhesion with the first negative electrode side collector electrode 51, the temperature and time of the heat treatment can be the same as those of the first semiconductor electrode 41. .

  Furthermore, in this dye-sensitized solar cell, a positive-side collector electrode a for collecting current from the catalyst electrode 3 can be provided between the substrate 1 and the catalyst electrode 3 (see FIG. 9). This positive electrode side collecting electrode a is formed from a noble metal having excellent conductivity, such as platinum, with the catalyst electrode 3 being 20 nm or more, and more preferably 1 μm or more (usually 10 μm or less) from the viewpoint of conductivity. Although it is not necessary to provide it, it is preferable in terms of cost. That is, since platinum etc. are expensive, it is preferable to make the catalyst electrode 3 as thin as possible. However, if it is thin, the resistance becomes high. Therefore, by providing the positive collector electrode, it is possible to improve the current collection efficiency and reduce the cost. Further, when the catalyst electrode 3 is formed of a composition in which the conductive oxide is mixed with a substance having catalytic activity, the resistance of the catalyst electrode 3 becomes higher. It is more preferable to increase the current collection efficiency.

  Although the planar shape of the positive electrode side collector electrode a is not particularly limited, since the light transmitting property is not essential on the substrate 1 side, it can be a planar shape. When the positive electrode side collecting electrode a is planar, it has a planar shape similar to that of the catalyst electrode 3 and 50% or more with respect to the catalyst electrode 3 in order to obtain a positive electrode side collecting electrode a having low resistance. In particular, a flat electrode having an area of 65% or more, more preferably 80% or more (may be substantially the same area) is preferable. More preferably, the catalyst electrode 3 is arranged in a similar shape.

  The positive electrode side collecting electrode a may be an electrode made of a linear electrode and formed by a specific electrode pattern. This specific pattern is not particularly limited, and may be, for example, a lattice shape, a comb shape, a radial shape, or the like. In the case of the positive electrode side current collecting electrode a made of this linear electrode and formed by a specific electrode pattern, the width and thickness of the linear electrode are not particularly limited, taking into account its electrical resistance, cost, etc. It is preferable to set. When the positive electrode side collecting electrode a is an electrode made of a linear electrode and formed by a specific electrode pattern, the total area of the positive electrode side collecting electrode a is not particularly limited, but the total area of the catalyst electrode 3 is On the other hand, it can be 0.1% or more, particularly 5% or more, and further 10% or more. In addition, the total area can be 90% or more, and the current collecting efficiency can be further improved if the positive electrode side current collecting electrode having such a large area is used.

  The method of providing the positive electrode side collecting electrode a is not particularly limited. For example, titanium, molybdenum by physical vapor deposition such as magnetron sputtering and electron beam vapor deposition using a mask on which a predetermined pattern is formed. For example, a method of depositing a metal such as photolithography and then patterning by photolithography or the like may be used. Moreover, it can form by the method of patterning by the screen-printing method etc. using the metallized ink containing each metal component, and baking it after that.

Moreover, in this dye-sensitized solar cell, the translucent conductive layer p can be provided between the translucent substrate 2 and the first semiconductor electrode 41 (see FIG. 10). The translucent conductive layer p only needs to have translucency and conductivity. The material of the translucent conductive layer p 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 transparent conductive layer thickness of the p varies also 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 method for forming the light-transmitting conductive layer p is not particularly limited, and the light-transmitting conductive layer p can be formed by applying a paste containing fine particles such as metal and conductive oxide on the surface of the light-transmitting substrate 1. Examples of the coating method include various methods such as a doctor blade method, a squeegee method, and a spin coating method. The translucent conductive layer p can also be formed by a sputtering method, a vacuum deposition method, an ion plating method, or the like using a metal, a conductive oxide, or the like.

  The method for producing the dye-sensitized solar cell of the present invention is not particularly limited. (1) On one side of the substrate 1, the catalyst electrode 3, the insulating layer 8, the first negative electrode side collector electrode 51, and the first semiconductor electrode 41. Is formed in a laminated state, and then a bonding layer 9 surrounding the catalyst electrode 3 and the like is formed, and then the electrolyte 6 is contained in at least a part of the first semiconductor electrode 41 and the like. (2) The catalyst electrode 3 is formed on one surface side of the substrate 1, and the first semiconductor electrode 41 and the first negative electrode side collecting electrode 51 are stacked on the one surface side of the translucent substrate 2, Thereafter, an insulating frame i (see FIG. 11) made of resin or the like is provided between the catalyst electrode 3 and the first negative electrode side collector electrode 51 so as to face each other and between the catalyst electrode 3 and the first negative electrode side collector electrode 51. There is a method in which the bonding layer 9 surrounding the catalyst electrode 3 or the like is formed in a state of being separated by interposing it or the like, and then the electrolyte 6 is contained in at least a part of the first semiconductor electrode 41 or the like. Among these methods, the method (1) is preferable because it is easy to form the first negative electrode side collecting electrode 51 and the catalyst electrode 3 apart from each other.

  In the production method of (1), the unfired ceramic substrate 1 ′ has a non-fired catalyst electrode 3 ′ that is a conductive coating film that becomes the catalyst electrode 3, and a non-fired insulation that is a conductive coating film that becomes the insulating layer 8. An unfired first negative electrode side collector electrode 51 ′ containing unfired light scattering particles 7 ′, which is a conductive coating film that becomes 8 ′ and the first negative electrode side collector electrode 51, is formed in this order to form an unfired laminate. Thereafter, the unfired laminate is simultaneously fired, and then the unfired semiconductor electrode substrate s, which is a conductive coating film to be the first semiconductor electrode 41, on one surface side of the negative electrode side collecting electrode 51 produced by simultaneous firing. And then firing to produce a semiconductor electrode substrate, and then impregnating the semiconductor electrode substrate with a sensitizing dye to produce a first semiconductor electrode 41, and then to one side of the first semiconductor electrode 41 The translucent substrate 2 is placed, and then the ceramic substrate 1 and the translucent substrate. The joining layer 9 surrounding the catalyst electrode 3 and the like is formed between the conductive substrate 2 and the electrolyte 6 is then contained in at least a part of the first semiconductor electrode 41, the first negative electrode side collecting electrode 51 and the insulating layer 8. It is something to be made.

  The method for forming each conductive coating film is not particularly limited, and examples thereof include a screen printing method, a doctor blade method, a squeegee method, and a spin coating method. Of these methods, the screen printing method is particularly preferable. Also, the firing temperature is not particularly limited, but in the case of an unfired laminate, the type of ceramic contained in the unfired ceramic substrate 1 ', and in the case of an unfired semiconductor electrode substrate s, the metal oxide contained in this substrate s. It is preferable to set according to the type of the product and the metal sulfide. Furthermore, the above description can be applied as it is to the method of attaching the sensitizing dye to the semiconductor electrode substrate and the method of containing the electrolyte 6 in the first semiconductor electrode 41 or the like.

Hereinafter, the present invention will be described specifically by way of examples.
Example 1
The dye-sensitized solar cell 201 of FIG. 1 was produced as follows.
[1] Production of unsintered laminate in which unsintered ceramic substrate 1 'to unsintered first negative electrode side collector electrode 51' are laminated 5 parts as a sintering aid on 100 parts of alumina powder with a purity of 99.9% by mass Part of magnesia, calcia and silica mixed powder, 2 parts of binder and solvent were blended to prepare a slurry, and an alumina green sheet was prepared by the doctor blade method using this slurry. Thereafter, a conductive coating film (unfired catalyst electrode 3 ′) to be the catalyst electrode 3 was formed on one surface side of the alumina green sheet by screen printing using a metallized ink containing a platinum component. Next, a metallized ink containing a tungsten component and a carbon powder having the same volume as the tungsten component (each volume is a volume calculated from a measured particle size) on the surface of the unfired catalyst electrode 3 ′. Was used to form a conductive coating film (unfired insulating layer 8 ′) to be the insulating layer 8 by screen printing. Thereafter, a tungsten component and titania powder (light scattering particles 7) having the same volume as the tungsten component (each volume is an apparent volume measured in the same manner as described above) on the surface of the unfired insulating layer 8 ′. The electroconductive coating film (unbaked 1st negative electrode side current collection electrode 51 ') used as the 1st negative electrode side current collection electrode 51 was formed by screen printing using the metallized ink containing these. Next, it is integrally fired at 1500 ° C. in a reducing atmosphere, and the catalyst electrode 3 having a length of 96 mm, a width of 96 mm, a thickness of 500 nm, a thickness of 5 μm, A laminate in which the porous insulating layer 8 having a porosity of about 30% and the first negative electrode side collector electrode 51 having a thickness of 500 nm was formed was produced.

[2] Fabrication of first semiconductor electrode 41 A slurry containing titania particles having a particle diameter of 10 to 20 nm (manufactured by Solaronix, manufactured on one surface side of the first negative electrode side collecting electrode 51 of the laminate fabricated in [1]. The product name “Ti-Nonoxide D / SP”) was applied by screen printing and dried at 120 ° C. for 1 hour to form an unfired semiconductor electrode substrate s. Then, it baked at 480 degreeC for 30 minutes, and formed the titania sintered layer (semiconductor electrode base | substrate) of length 96mm, width 96mm, and thickness 20 micrometers. Next, the semiconductor electrode substrate is immersed in an ethanol solution of a ruthenium complex (manufactured by Solaronix, trade name “535bis-TBA”) for 10 hours, and the titania sintered particles absorb light in a wavelength region of 400 to 600 nm. A first semiconductor electrode 41 was prepared by attaching a ruthenium complex, which is a dye-sensitive dye.

[3] Production of dye-sensitized solar cell A thermosetting resin is formed on a portion of the laminate including the first semiconductor electrode 41 produced in [2] where the catalyst electrode 3 on one surface side of the alumina substrate 1 is not formed. An uncured bonding layer 9 ′ having a width of 1 mm and a thickness of 60 μm is formed by screen printing using an adhesive made of The substrate 2 is placed, then placed on a hot plate adjusted to 100 ° C. with the glass substrate 2 side down, and heated for 5 minutes to join the alumina substrate 1 and the glass substrate 2 to a width of 2 mm, A bonding layer 9 having a thickness of 30 μm was prepared. Thereafter, an iodine electrolyte solution (trade name “Iodolyte PN-50” manufactured by Solaronix Co., Ltd.) is injected from an electrolyte solution injection port provided at a predetermined position of the glass substrate 2, and the electrolyte 6 is connected to the first semiconductor electrode 41, the first electrode. 1 The negative electrode side collector electrode 51 and the insulating layer 8 were included. After injection of the iodine electrolyte, the inlet was sealed using the above adhesive.

[4] Performance Evaluation of Dye-Sensitized Solar Cell An irradiation intensity of 100 mW / cm ^{2 is} applied to the dye-sensitized solar cell 201 produced by the above [1] to [3] using a solar simulator whose spectrum is adjusted to AM1.5. When the artificial sunlight was irradiated, the conversion efficiency was 7.5%.

  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, the first negative electrode side collecting electrode 51 and the first semiconductor electrode 41 may be disposed on the substrate 1 side, and the catalyst electrode 3 may be disposed on the translucent substrate 2 side. More specifically, the first negative electrode side collecting electrode 51 containing the substrate 1, the translucent substrate 2 disposed opposite to the substrate 1, and the light scattering particles 7 disposed on one surface side of the substrate 1. A first semiconductor electrode 41 having a sensitizing dye disposed away from the catalyst electrode 3 on the side of the first negative electrode side collecting electrode 51 facing the catalyst electrode 3, and one surface of the translucent substrate 2 Dye-sensitized type comprising a catalyst electrode 3 disposed on the side and an electrolyte 6 contained in at least a part of the first semiconductor electrode 41 and filled between the first semiconductor electrode 41 and the catalyst electrode 3 The solar battery 207 can be used. In the dye-sensitized solar cell 207, the insulating layer 8 may be interposed between the catalyst electrode 3 and the first negative electrode side collecting electrode 51 (see FIG. 12), or the electrolyte 6 May be filled. Further, in the case of this embodiment, a translucent conductive layer p similar to the above is usually provided between the translucent substrate 2 and the catalyst electrode 3.

  Furthermore, as the electrolyte 6, it is also possible to use 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.

3 is a schematic diagram showing a cross section of a dye-sensitized solar cell 201 of Example 1. FIG. FIG. 2 is a schematic diagram showing a part of a first negative electrode side collecting electrode 51 in the dye-sensitized solar cell 201 in FIG. It is a graph which shows an example of the light absorption curve of the semiconductor electrode 41 which has a sensitizing dye. In the production of the dye-sensitized solar cell 201 of Example 1, the unfired catalyst electrode 3 ′, the unfired insulating layer 8 ′, and the unfired first negative electrode side collector electrode 51 ′ are formed on one side of the unfired ceramic substrate. It is a schematic diagram which shows a mode that it laminated | stacked. In the production of the dye-sensitized solar cell 201 of Example 1, the unfired catalyst electrode, the unfired insulating layer, and the unfired first negative electrode side collector electrode laminated on one side of the unfired ceramic substrate were co-fired, Furthermore, it is a schematic diagram which shows a mode that the unbaked semiconductor electrode base | substrate s was laminated | stacked. In the production of the dye-sensitized solar cell 201 of Example 1, the semiconductor electrode substrate is impregnated with the sensitizing dye to produce the first semiconductor electrode 41, and the uncured bonding layer 9 ′ surrounding the catalyst electrode 3 and the like is surrounded by the uncured bonding layer 9 ′. It is a schematic diagram which shows a mode that was formed. In the dye-sensitized solar cell of FIG. 1, a schematic view showing a cross section of a dye-sensitized solar cell 202 in which a second negative electrode side collecting electrode 52 is further provided on the side of the first semiconductor electrode 41 facing the catalyst electrode 3. FIG. FIG. 2 is a schematic diagram showing a cross section of a dye-sensitized solar cell 203 in which a second semiconductor electrode 42 is further provided on the side of the first semiconductor electrode 41 facing the catalyst electrode 3 in the dye-sensitized solar cell of FIG. 1. . FIG. 2 is a schematic diagram showing a cross section of a dye-sensitized solar cell 204 in which a positive current collecting electrode a is further provided between a substrate 1 and a catalyst electrode 3 in the dye-sensitized solar cell of FIG. 1. In the dye-sensitized solar cell of FIG. 1, a schematic view showing a cross section of a dye-sensitized solar cell 205 in which a light-transmitting conductive layer p is further provided between the light-transmitting substrate 2 and the first semiconductor electrode 41. It is. FIG. 2 is a schematic diagram showing a cross section of a dye-sensitized solar cell 206 in which a gap is formed between a first semiconductor electrode 41 and a catalyst electrode 3 in the dye-sensitized solar cell of FIG. 1. In the dye-sensitized solar cell of FIG. 10, the first negative electrode side collecting electrode 51 and the first semiconductor electrode 41 are disposed on the substrate 1 side, and the catalyst electrode 3 is disposed on the translucent substrate 2 side. It is a schematic diagram which shows the cross section of the dye-sensitized solar cell 207 made.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1; Substrate, 2; Translucent substrate, 3; Catalyst electrode, 41; First semiconductor electrode, 42; Second semiconductor electrode, 51; First negative electrode side collector electrode, 52; 6; electrolyte, 7; light scattering particles, 8; insulating layer, 9; bonding layer, a; positive electrode side collecting electrode, p; translucent conductive layer, i; resin insulating frame, 1 ′; 3 ′; unsintered catalyst electrode, s; unsintered semiconductor electrode substrate, 51 ′; unsintered first negative electrode side collector electrode, 7 ′; unsintered light scattering particles, 8 ′; unsintered insulating layer, 9 ′; Uncured bonding layer, 201, 202, 203, 204, 205, 206, 207; a dye-sensitized solar cell.

Claims (9)

A substrate 1, a translucent substrate 2 disposed opposite the substrate 1, a catalyst electrode 3 disposed on one surface side of the substrate 1, and a translucent substrate 2 disposed on one surface side; A first semiconductor electrode 41 having a sensitizing dye, and a first negative electrode side collector electrode 51 disposed on the side of the first semiconductor electrode 41 facing the catalyst electrode 3 and spaced apart from the catalyst electrode 3; In the dye-sensitized solar cell including the electrolyte 6 contained in at least a part of the first semiconductor electrode 41 and filled between the first semiconductor electrode 41 and the catalyst electrode 3,
The dye-sensitized solar cell, wherein the first negative electrode side collecting electrode 51 contains light scattering particles 7.   The dye sensitization according to claim 1, wherein an insulating layer 8 is interposed between the catalyst electrode 3 and the first negative electrode side collecting electrode 51, and the electrolyte 6 is contained in the insulating layer 8. Type solar cell.   The second negative electrode side collecting electrode 52 having higher conductivity than the first negative electrode side collecting electrode 51 is disposed on the side of the first negative electrode side collecting electrode 51 facing the catalyst electrode 3. 3. The dye-sensitized solar cell according to 1 or 2.   3. The dye-sensitized solar cell according to claim 1, wherein a second semiconductor electrode having a sensitizing dye is disposed on a side of the first negative electrode side collecting electrode 51 facing the catalyst electrode 3. .   The average particle diameter of the light scattering particles 7 is a value of 25 to 75% of a light wavelength at which the light absorption rate of the first semiconductor electrode 41 is 50%. The dye-sensitized solar cell described.   The dye-sensitized solar cell according to any one of claims 1 to 5, wherein at least a part of each of the first semiconductor electrode 41 and the light scattering particles 7 is made of the same material.   The dye-sensitized solar cell according to any one of claims 1 to 6, wherein each of the first semiconductor electrode 41 and the light scattering particle 7 is made of titania or contains titania.   The dye-sensitized solar cell according to any one of claims 1 to 7, wherein the substrate 1 is made of ceramic.   It is a manufacturing method of the dye-sensitized solar cell of any one of Claims 1 thru | or 8, Comprising: Forming unfired catalyst electrode 3 'on the one surface side of unfired ceramic substrate 1', Then, An unfired first negative electrode side comprising unfired insulating layer 8 ′ formed on one surface side of unfired catalyst electrode 3 ′ and then containing unfired light scattering particles 7 ′ on one surface side of unfired insulating layer 8 ′ Forming the current collecting electrode 51 ′, and then simultaneously firing the unfired laminated body including the unfired catalyst electrode 3 ′, the unfired insulating layer 8 ′, and the unfired first negative electrode side current collecting electrode 51 ′; Next, an unsintered semiconductor electrode substrate s is formed on one surface side of the first negative electrode side collecting electrode 51 manufactured by the simultaneous firing, and then the unsintered semiconductor electrode substrate s is fired to produce a semiconductor electrode substrate. Then, the first semiconductor electrode 41 is produced by impregnating the semiconductor electrode substrate with a sensitizing dye. Thereafter, the translucent substrate 2 is placed on one surface side of the first semiconductor electrode 41, and then between the ceramic substrate 1 and the translucent substrate 2 produced by the co-firing, by the co-firing. An uncured bonding layer 9 ′ surrounding the produced catalyst electrode 3, the insulating layer 8 produced by the co-firing, the first negative electrode current collecting electrode 51, and the first semiconductor electrode 41 is formed. The cured bonding layer 9 ′ is heated to produce the bonding layer 9, and then the electrolyte 6 is contained in at least a part of the first semiconductor electrode 41, the first negative electrode side collecting electrode 51 and the insulating layer 8. A method for producing a dye-sensitized solar cell characterized by

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