JP5080018B2 - Dye-sensitized solar cell - Google Patents

Dye-sensitized solar cell Download PDF

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JP5080018B2
JP5080018B2 JP2006104727A JP2006104727A JP5080018B2 JP 5080018 B2 JP5080018 B2 JP 5080018B2 JP 2006104727 A JP2006104727 A JP 2006104727A JP 2006104727 A JP2006104727 A JP 2006104727A JP 5080018 B2 JP5080018 B2 JP 5080018B2
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electrode
substrate
surface
dye
solar cell
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JP2007066874A (en
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康生 奥山
一郎 権田
淳矢 高島
拓也 藤井
悟史 江崎
圭三 古崎
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日本特殊陶業株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/54Material technologies
    • Y02E10/542Dye sensitized solar cells

Description

  The present invention relates to a dye-sensitized solar cell that directly converts light energy into electric energy. More specifically, the present invention has a low resistance by providing the collector electrode on the semiconductor electrode side of the counter electrode, which has a low resistance and it is not easy to form a collector electrode having excellent current collection efficiency. Thus, it is possible to easily form a collecting electrode having excellent current collecting efficiency by a simple process, and to reduce the area of the semiconductor electrode by providing the collecting electrode, and to increase the dye having sufficient power generating efficiency. The present invention relates to a sensitive solar cell.

  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. This silicon-based solar cell has an excellent photoelectric conversion efficiency of nearly 20%. However, the energy cost for raw material production is high, there are many problems in terms of environmental impact, and there are 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, Patent Document 1 and Non-Patent Document 1). This solar cell has a structure in which an electrolytic solution is interposed between a titania porous electrode carrying a sensitizing dye and a catalyst electrode, and although the conversion efficiency is lower than that of current silicon solar cells, Cost reduction is possible in terms of manufacturing method and the like.

  In this dye-sensitized solar cell, normally, a collector electrode for efficiently collecting current from each electrode is attached to each of the semiconductor electrode and the catalyst electrode. The current collecting electrode is often formed by applying and baking a silver paste (see, for example, Patent Document 2). In addition, it has been studied to form a collecting electrode by depositing metal by a method such as sputtering and vapor deposition.

Japanese Patent Laid-Open No. 1-220380 Nature (Vol. 353, pp. 737-740, 1991) JP 2000-285777 A

  However, since the electrolytic solution used in the dye-sensitized solar cell is highly volatile and corrosive, for example, in order to prevent contact between the collector electrode made of silver and the electrolyte solution, the collector electrode is usually made of resin. Covered and protected. When the current collecting electrode and the resin layer are thus formed on the substrate surface, the area of the substrate surface on which the semiconductor electrode can be formed is reduced, thereby reducing power generation efficiency. Furthermore, since the electrolytic solution is highly volatile, even if it is protected by the resin, it may penetrate through the resin and corrode the current collecting electrode. In addition, when the current collecting electrode is formed by a method such as sputtering or vapor deposition, a glass substrate and a resin substrate used as a light-transmitting substrate are not sufficiently heat resistant, so that a metal cannot be deposited thickly. For this reason, in order to obtain a collector electrode with low resistance, the area must be increased, and similarly, the area where the semiconductor electrode can be formed is reduced, and power generation efficiency tends to be reduced.

  The present invention has been made in view of the above-described situation, and is characterized in that the negative electrode side collector electrode is provided on the counter electrode side. Thereby, the reduction of the area of the semiconductor electrode in the translucent substrate such as a glass substrate provided with the semiconductor electrode is suppressed. Moreover, the conventionally complicated process can be simplified, and the negative electrode side collecting electrode can be easily formed. Furthermore, when the negative electrode side collector electrode is provided on one surface of the counter electrode substrate, particularly when the counter electrode is a ceramic substrate, it is possible to easily form a collector electrode having low resistance and excellent current collection efficiency. Thus, a dye-sensitized solar cell having higher power generation efficiency can be obtained. Furthermore, when the negative electrode side collecting electrode is provided on the other surface of the counter electrode substrate, the resistance is low regardless of the material of the counter electrode substrate, and a collecting electrode having excellent current collecting efficiency can be easily formed. A dye-sensitized solar cell having high power generation efficiency can be obtained.

The present invention is as follows.
1. A translucent substrate 1, a counter electrode substrate 2 disposed to face one surface of the translucent substrate 1,
The translucent conductive layer 31 provided on the one surface of the translucent substrate 1, the semiconductor electrode 32 provided on the surface of the translucent conductive layer 31 and having a sensitizing dye, and on one surface of the counter electrode substrate 2 A catalyst electrode 33 provided opposite to the semiconductor electrode 32, a negative electrode side collector provided on the one surface or the other surface of the counter electrode substrate 2, spaced apart from the catalyst electrode 33 and connected to the translucent conductive layer 31. And at least one unit having an electrolytic solution 35 contained in at least a part of each of the electric electrode 34 and the semiconductor electrode 32 and the catalyst electrode 33 and filled between the semiconductor electrode 32 and the catalyst electrode 33. A dye-sensitized solar cell comprising the cell structure 3.
2. The counter electrode substrate 2 is a ceramic substrate 2, and the negative electrode side collecting electrode 34 is provided on one surface of the ceramic substrate 2 facing the one surface of the light transmitting substrate 1 and contains tungsten. 2. A dye-sensitized solar cell according to 1.
3. 2. The thickness of the negative electrode side collecting electrode 34 is 10 to 100 μm. 2. A dye-sensitized solar cell according to 1.
4). 2. The light-transmitting conductive layer 31 and the negative electrode side collecting electrode 34 are connected via a conductive adhesive layer 36. Or 3. 2. A dye-sensitized solar cell according to 1.
5. The conductive adhesive layer 36 contains a conductive filler, and the conductive filler is at least one of a carbon filler, a tungsten filler, a titanium filler, and a nickel filler. 2. A dye-sensitized solar cell according to 1.
6). The conductive adhesive layer 36 is formed by curing an uncured conductive adhesive layer with laser light irradiated through the translucent substrate 1. Or 5. 2. A dye-sensitized solar cell according to 1.
7). The negative electrode side collecting electrode 34 is provided on the other surface of the counter electrode substrate 2, and a plurality of interconnectors 37 are interposed between the surface of the translucent conductive layer 31 and the one surface of the counter electrode substrate 2. In addition, each of the plurality of interconnectors 37 and the negative electrode side collector electrode 34 are connected to each other by the via conductor 38 formed on the counter electrode substrate 2. 2. A dye-sensitized solar cell according to 1.
8). 6. The interconnector 37 has a cross-sectional area of 0.15 to 5.0 mm 2 , and the plurality of interconnectors 37 are spaced apart by 4.0 to 11.0 mm. 2. A dye-sensitized solar cell according to 1.
9. The interconnector 37 is formed by curing an uncured conductive adhesive layer containing alkali silicate. Or 8. 2. A dye-sensitized solar cell according to 1.
10. 6. The counter substrate 2 is a ceramic substrate 2 Thru 9. The dye-sensitized solar cell of any one of these.
11. 6. The negative electrode side collecting electrode 34 has a thickness of 0.5 to 100 μm. To 10. The dye-sensitized solar cell of any one of these.
12 Between the one surface of the translucent substrate 1 and the one surface of the ceramic substrate 2, each has between the translucent conductive layers 31, between the semiconductor electrodes 32, between the catalyst electrodes 33, and the negative electrode side collector electrode. A plurality of the single cell constituent bodies 3 that are electrically insulated from each other and between the electrolyte solutions 35 are provided, and each of the plurality of single cell constituent bodies 3 is connected in series. To 6. The dye-sensitized solar cell of any one of these.
13. A space between the one surface of the translucent substrate 1 and the one surface of the ceramic substrate 2 is sealed with a resin or glass around the negative electrode side collecting electrode 34 included in each of the single cell constituting bodies 3. 12. The above insulation is performed. 2. A dye-sensitized solar cell according to 1.
14 Between the one surface of the translucent substrate 1 and the one surface of the counter electrode substrate 2, each has between the translucent conductive layers 31, between the semiconductor electrodes 32, between the catalyst electrodes 33, and the negative electrode side collector electrode. 34, the electrolyte solution 35, and the interconnector 37 are electrically insulated from each other, and a plurality of the single cell structural bodies 3 are provided, and each of the plurality of single cell structural bodies 3 is connected in series. The above 7. To 11. The dye-sensitized solar cell of any one of these.
15. Between the one surface of the translucent substrate 1 and the one surface of the counter electrode substrate 2 is sealed with resin or glass around the semiconductor electrode 32 of each of the unit cell structures 3, and the insulation is performed. 14 above. 2. A dye-sensitized solar cell according to 1.
16. 1. A positive collector electrode 39 provided between the counter electrode substrate 2 and the catalyst electrode 33; To 15. The dye-sensitized solar cell of any one of these.

The dye-sensitized solar cell of the present invention has excellent current collection efficiency on the semiconductor electrode side, suppresses a reduction in the effective area of the semiconductor electrode, and has sufficient power generation efficiency. Moreover, the formation process of the negative electrode side current collection electrode which was complicated conventionally can be simplified.
Furthermore, when the counter electrode substrate 2 is a ceramic substrate 2 and the negative electrode side collecting electrode 34 is provided on one surface of the ceramic substrate 2 facing the one surface of the light transmitting substrate 1 and contains tungsten, A solar cell having excellent durability can be obtained, and the current collecting efficiency can be improved, and a current collecting electrode having high corrosion resistance against the electrolytic solution can be obtained, thereby improving the power generation efficiency.
Moreover, when the thickness of the negative electrode side collector electrode 34 is 10-100 micrometers, it can be set as a collector electrode with low resistance enough.
Further, when the translucent conductive layer 31 and the negative electrode side collector electrode 34 are connected via the conductive adhesive layer 36, the close contact between the translucent conductive layer 31 and the negative electrode side collector electrode 34. Can increase the sex.
In addition, the conductive adhesive layer 36 contains a conductive filler. When the conductive filler is at least one of a carbon filler, a tungsten filler, a titanium filler, and a nickel filler, the anti-corrosion against the electrolytic solution. It can be set as the conductive adhesive layer 36 excellent in property.
Furthermore, when the conductive adhesive layer 36 is formed by curing the uncured conductive adhesive layer with laser light that has been transmitted through the translucent substrate 1 and irradiated, the conductive adhesive layer 36 can be easily formed. Can be formed.
A negative current collecting electrode 34 is provided on the other surface of the counter substrate 2, a plurality of interconnectors 37 are interposed between the surface of the translucent conductive layer 31 and one surface of the counter electrode substrate 2, and a plurality of When each of the interconnectors 37 and the negative electrode side collecting electrode 34 are connected by the via conductor 38 formed on the counter electrode substrate 2, the reduction of the area of the semiconductor electrode in the translucent substrate is further suppressed, and the power generation Efficiency is also improved.
Furthermore, when the cross-sectional area of the interconnector 37 is 0.15 to 5.0 mm 2 and the distance between each of the plurality of interconnectors 37 is 4.0 to 11.0 mm, A reduction in the area of the semiconductor electrode can be suppressed, and the negative electrode side collecting electrode 34 having sufficient current collecting efficiency can be obtained.
Moreover, when the interconnector 37 is formed by curing an inorganic conductive adhesive layer containing an alkali silicate and a conductive filler, the interconnector 37 can be easily formed.
Furthermore, when the counter electrode substrate 2 is the ceramic substrate 2, a solar cell having excellent durability can be obtained.
Moreover, when the thickness of the negative electrode side collector electrode 34 is 0.5-100 micrometers, it can be set as a collector electrode with low resistance enough by adjusting the area and thickness of a collector electrode.
Furthermore, between one surface of the translucent substrate 1 and one surface of the ceramic substrate 2, each has a translucent conductive layer 31, a semiconductor electrode 32, a catalyst electrode 33, and a negative current collector electrode 34. When the plurality of single cell constituent bodies 3 that are electrically insulated from each other and the electrolyte solution 35 are provided and each of the plurality of single cell constituent bodies 3 is connected in series, the output voltage of the solar battery Can be high.
In addition, between one surface of the translucent substrate 1 and one surface of the ceramic substrate 2, at least around the negative electrode side collecting electrode 34 included in each of the two or more single cell constituent bodies 3, resin or glass is used. When sealed and insulated, each single cell component 3 can be electrically insulated reliably.
Furthermore, between one surface of the translucent substrate 1 and one surface of the counter electrode substrate 2, each has a translucent conductive layer 31, a semiconductor electrode 32, a catalyst electrode 33, and a negative current collector electrode 34. In the case where a plurality of single cell constituent bodies 3 are electrically insulated from each other between the electrolyte solution 35 and the interconnector 37, and each of the plurality of single cell constituent bodies 3 is connected in series, The output voltage of the solar cell can be increased.
Further, between one surface of the translucent substrate 1 and one surface of the counter electrode substrate 2 is sealed by resin or glass around the semiconductor electrode 32 included in each of the unit cell structures 3 to be insulated. In this case, each unit cell structure 3 can be electrically and reliably insulated.
Furthermore, when the positive electrode side current collecting electrode 39 is provided between the counter electrode substrate 2 and the catalyst electrode 33, the current collecting efficiency on the positive electrode side is also improved, and a solar cell with higher power generation efficiency can be obtained. .

Hereinafter, the present invention will be described in detail with reference to FIGS.
The dye-sensitized solar cell of the present invention includes a translucent substrate 1, a counter electrode substrate 2 disposed to face one surface of the translucent substrate 1, and a translucent substrate provided on one surface of the translucent substrate 1. Photoconductive layer 31, semiconductor electrode 32 provided on the surface of translucent conductive layer 31 and having a sensitizing dye, catalyst electrode 33 provided on one surface of counter electrode substrate 2 so as to face semiconductor electrode 32, counter electrode substrate 2 The negative electrode side collector electrode 34 provided on one side or the other side of the electrode and separated from the catalyst electrode 33 and connected to the translucent conductive layer 31, and contained in at least a part of each of the semiconductor electrode 32 and the catalyst electrode 33. And at least one unit cell structure 3 having an electrolytic solution 35 filled between the semiconductor electrode 32 and the catalyst electrode 33.

Examples of the “translucent substrate 1” include a substrate made of a glass plate, a resin sheet, or the like. The resin sheet is not particularly limited, and examples thereof include resin sheets prepared using polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyphenylene sulfide, polycarbonate, polysulfone, and polyethyleneidene norbornene.
The “translucency” of the translucent substrate 1 means that the visible light transmittance represented by the following formula is 10% or more.
Visible light transmittance (%) = (amount of light transmitted through the translucent substrate / amount of light incident on the translucent substrate) × 100
The visible light transmittance is preferably 60% or more, particularly preferably 85% or more.
The thickness of the translucent substrate 1 varies depending on the material and is not particularly limited, but it is preferable that the visible light transmittance is 60 to 99%, particularly 85 to 99%.

  The “counter electrode substrate 2” is disposed to face the translucent substrate 1. This counter electrode substrate 2 may or may not have translucency. Examples of the counter electrode substrate 2 having translucency include a substrate made of a glass plate, a resin sheet, or the like. This resin sheet is not particularly limited, and examples thereof include the same resin sheet as that of the above-described translucent substrate 1. Although the counter electrode substrate 2 which does not have translucency is not specifically limited, The ceramic substrate 2 is mentioned. By providing this ceramic substrate 2, the durability of the dye-sensitized solar cell can be improved. As the ceramic for producing the ceramic substrate 2, various ceramics such as oxide ceramics, nitride ceramics, carbide ceramics can be used.

  As the ceramic, alumina, silicon nitride, zirconia and the like are preferable, and alumina is particularly preferable. Alumina has high corrosion resistance, high strength, excellent electrical insulation, and a ceramic substrate 2 made of alumina makes it possible to obtain a dye-sensitized solar cell having more excellent durability. In the case of the ceramic substrate 2 containing alumina, when the total amount of ceramic contained in the substrate is 100% by mass, alumina is 80% by mass or more, particularly 90% by mass or more, and further 95% by mass or more (100% by mass). It may be.

  The thickness of the ceramic substrate 2 is not particularly limited, but may be 100 μm to 5 mm, particularly 500 μm to 5 mm, more preferably 1 to 5 mm, and preferably 300 μm to 3 mm. When the thickness of the ceramic substrate 2 is 100 μm to 5 mm, particularly 300 μm to 3 mm, a dye-sensitized solar cell having sufficient strength as a support layer and excellent durability can be obtained.

Hereinafter, the “single cell structure 3” will be described in detail.
The “translucent conductive layer 31” is provided on one surface of the translucent substrate 1. The translucent conductive layer 31 is not particularly limited as long as it has translucency and conductivity. Examples of the translucent conductive layer 31 include a thin film made of a conductive oxide, a carbon thin film, and the like. Examples of the conductive oxide include indium oxide, tin-doped indium oxide, tin oxide, and fluorine-doped tin oxide (FTO). The thickness of the transparent conductive layer 31 is 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 translucent meaning and preferable visible light transmittance of the translucent conductive layer 31 are the same as those of the translucent substrate 1.

  The “semiconductor electrode 32” is provided on the surface of the translucent conductive layer 31 and has a sensitizing dye. The semiconductor electrode 32 has a porous electrode substrate and a sensitizing dye attached to the porous electrode substrate. The porous electrode substrate can be formed of metal oxides such as titania, tin oxide, and zinc oxide, and metal sulfides such as zinc sulfide and lead sulfide. The method for producing the porous electrode substrate is not particularly limited. For example, the surface of the translucent conductive layer 31 provided on one surface of the translucent substrate 1 with a paste containing fine particles such as metal oxide and metal sulfide. Further, it can be produced by applying and baking by a screen printing method, a doctor blade method or the like.

  Although the firing conditions are not particularly limited, the firing temperature can be 400 to 600 ° C., particularly 450 to 550 ° C., and the firing time can be 10 to 300 minutes, particularly 20 to 40 minutes. The firing atmosphere can be an oxidizing atmosphere such as an air atmosphere or an inert atmosphere such as a rare gas atmosphere such as argon and a nitrogen gas atmosphere.

  The “sensitizing dye” has an effect of improving photoelectric conversion efficiency. As this sensitizing dye, a complex dye and an organic dye can be used. Examples of complex dyes include metal complex dyes. 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. Moreover, in order to expand the wavelength range in which photoelectric conversion is performed and improve the conversion efficiency, two or more sensitizing dyes having different wavelength ranges in which photoelectric conversion is performed can be used in combination. The method for attaching the sensitizing dye to the porous electrode substrate is not particularly limited. For example, the porous electrode substrate is immersed in a solution in which the sensitizing dye is dissolved in an organic solvent to impregnate the solution, and then the organic solvent is used. It can be made to adhere by removing. Alternatively, this solution can be applied to a porous electrode substrate by a wire bar method, a slide hopper method or the like, impregnated, and then adhered by removing the organic solvent. The thickness of the semiconductor electrode 32 is not particularly limited, but may be 0.1 to 100 μm, preferably 1 to 30 μm, and particularly preferably 2 to 25 μm. When the thickness of the semiconductor electrode 32 is 0.1 to 100 μm, photoelectric conversion is sufficiently performed and power generation efficiency is improved.

  The “catalyst electrode 33” is provided on one surface of the counter electrode substrate 2 so as to face the semiconductor electrode 32. The catalyst electrode 33 can be formed of a substance having catalytic activity. Further, by using a metal having no catalytic activity, a conductive oxide used for forming the light-transmitting conductive layer 31 and a conductive polymer such as polyaniline and polypyrrole, and a substance having catalytic activity. It can also be formed. Examples of the substance having catalytic activity include noble metals such as platinum and rhodium, carbon black and the like, and these have conductivity together. The catalyst electrode 33 is preferably formed of a noble metal having catalytic activity and electrochemically stable, and it is particularly preferable to use platinum that has high catalytic activity and is not easily corroded by the electrolyte solution. The thickness of the catalyst electrode 33 is not particularly limited, but can be 3 nm to 10 μm, particularly 3 nm to 1 μm. When the thickness of the catalyst electrode 33 is 3 nm to 10 μm, a sufficiently low resistance catalyst electrode can be obtained.

  The catalyst electrode 33 made of a substance having a catalytic activity is formed by using a paste containing fine particles of a substance having a catalytic activity on one side of the counter electrode substrate 2 or when the positive electrode side collector electrode 39 is provided as described later. It can be produced by coating the surface of the side current collecting electrode 39 by a screen printing method, a doctor blade method or the like and heating. Further, the catalyst electrode 33 made of a metal containing a substance having catalytic activity and the catalyst electrode 33 made of a conductive oxide containing a substance having catalytic activity are also produced by the same method as that for the substance having catalytic activity. be able to. Furthermore, these catalyst electrodes 33 can also be formed by depositing metal or the like on the surface of the counter electrode substrate 2 or the like by sputtering, vapor deposition, ion plating or the like.

  On the one surface or the other surface of the counter electrode substrate 2, the “negative current collecting electrode 34” is provided. The negative electrode side collecting electrode 34 is formed apart from the catalyst electrode 33. This separation means that the negative electrode side collector electrode 34 and the catalyst electrode 33 are electrically insulated. Further, the negative electrode side collecting electrode 34 is electrically connected to the translucent conductive layer 31 and functions as a collecting electrode for the negative electrode side, that is, the semiconductor electrode 32. Thus, by providing the current collecting electrode of the semiconductor electrode 32 on the side of the counter electrode substrate 2 facing the translucent substrate 1, the reduction of the area of the semiconductor electrode due to the provision of the current collecting electrode can be sufficiently suppressed.

  When the negative electrode side collector electrode 34 is provided on one surface of the counter electrode substrate 2 (hereinafter referred to as the negative electrode side collector electrode 341) (see FIGS. 1 to 6), the negative electrode side collector electrode 341 is in contact with the electrolytic solution. Therefore, it is necessary to use the negative electrode side collecting electrode 341 made of a material having high corrosion resistance. Examples of the material having high corrosion resistance include tungsten, titanium, nickel and the like, and tungsten having more excellent corrosion resistance is particularly preferable. The material of the counter electrode substrate 2 is not particularly limited, but the ceramic substrate 2 is preferable. That is, in order to improve the power generation efficiency, it is preferable to increase not only the semiconductor electrode 32 but also the area of the opposing catalyst electrode 33, and in that case, the area of the negative current collecting electrode 341 must be reduced. In order to obtain the negative electrode side collecting electrode 341 having sufficiently low resistance and excellent current collecting efficiency, it is necessary to make the negative electrode side collecting electrode 341 thick. In order to obtain a thick film, the counter electrode substrate 2 having sufficient heat resistance can be used regardless of the method such as depositing metal by sputtering or forming a coating film by screen printing or the like. Preferably, there is a ceramic substrate 2.

  In the case of using tungsten, the negative electrode side collecting electrode 341 is made of pure tungsten (this pure tungsten means that tungsten having a purity of 99.98% or more is used as it is, and other metals are not mixed). It may be. Moreover, it may consist of a mixture of tungsten and another metal. When tungsten and other metals are used in combination, the content of tungsten is 95% by mass or more, particularly 98% by mass or more, and further 99.9% by mass, when the total of tungsten and other metals is 100% by mass. % Or more is preferable. When the tungsten content is 95% by mass or more, a current collecting electrode having high current collecting efficiency and excellent corrosion resistance can be obtained. Among these, the negative electrode side collecting electrode 341 made of pure tungsten is particularly preferable because it is more excellent in corrosion resistance to the electrolytic solution.

  The negative electrode side collecting electrode 341 can be formed by a physical vapor deposition method such as a magnetron sputtering method and an electron beam vapor deposition method using a mask on which a predetermined pattern is formed. Alternatively, it can be formed by a screen printing method using a conductive paste. In particular, in the case of the ceramic substrate 2, the negative electrode side collecting electrode 341 having a sufficient thickness can be obtained by any method, and the thickness is 10 to 100 μm, particularly 30 to 100 μm, and further 30 to 30 μm. It can be 70 μm. When the thickness of the negative electrode side collecting electrode 341 is 10 to 100 μm, the current collecting electrode can have a low resistance and excellent current collecting efficiency.

  The distance between the negative electrode side collector electrode 341 and the catalyst electrode 33, that is, the separation distance (the minimum distance between the negative electrode side collector electrode 341 and the catalyst electrode 33) is 1-1000 μm, in particular 50-500 μm, more preferably 100- It is preferable that it is 500 micrometers. When the separation distance is 1-1000 μm, the negative electrode side collecting electrode 341 and the catalyst electrode 33 can be electrically insulated reliably. Further, the negative electrode side collecting electrode 341 and the translucent conductive layer 31 may be connected by contact with each other, or may be connected via an interconnector. In order to reduce the resistance at the connection surface, it is preferable to interpose an interconnector. The interconnector is not particularly limited, but in the case of the negative electrode side collecting electrode 341 provided on one surface of the ceramic substrate 2, the conductive adhesive layer 36 is preferable.

  The conductive adhesive layer 36 contains a conductive filler. This conductive filler is not particularly limited. Examples of the conductive filler include fillers made of (1) carbon black, (2) metals such as tungsten, copper, silver, aluminum, nickel, and chromium, and (3) conductive polymers such as polyaniline, polypyrrole, and polyacetylene. It is done. Since the conductive adhesive layer 36 is in contact with the electrolytic solution, the conductive filler is preferably at least one of a carbon filler, a tungsten filler, a titanium filler, and a nickel filler having excellent corrosion resistance. In this case, only one type of the four types of fillers may be used, or two or more types may be used in combination. When using 2 or more types together, the combination of fillers to be used and their quantitative ratio are not particularly limited, and any filler may be used in any quantitative ratio. Among these fillers having excellent corrosion resistance, carbon filler, tungsten filler and nickel filler having more excellent corrosion resistance are particularly preferable.

The conductive adhesive layer 36 is formed by curing an uncured conductive adhesive layer or by solidifying an unsolidified conductive hot melt adhesive layer. As the uncured conductive adhesive used for forming the uncured conductive adhesive layer, a thermosetting adhesive containing a conductive filler, a photocurable adhesive, or the like can be used. The thermosetting adhesive contains a thermosetting resin. This thermosetting resin is not particularly limited, and examples thereof include an epoxy resin, a urethane resin, and an isobutylene resin. Among these resins, an isobutylene resin having sufficient corrosion resistance is preferable from the viewpoint of corrosion resistance to the electrolytic solution. This thermosetting adhesive can be cured by heating at a predetermined temperature depending on the type of thermosetting resin. The photocurable adhesive contains various types of photocurable resins, and the photocurable adhesive can be cured by irradiation with laser light, ultraviolet rays, or the like. For example, the conductive adhesive layer 36 can be formed by curing an uncured conductive adhesive with a laser beam irradiated through the transparent substrate 1. This method is preferable because only the uncured conductive adhesive layer can be heated and cured, and the conductive adhesive layer 36 can be efficiently formed. The laser beam is not particularly limited, and usually a YAG laser, a carbon dioxide gas laser, or the like can be used. Irradiation conditions such as the laser frequency and the input current value can be appropriately set so that they can be efficiently cured by the composition and thickness of the uncured conductive adhesive. On the other hand, the conductive hot melt adhesive used for forming the unsolidified conductive hot melt adhesive layer includes a hot melt adhesive made of an olefin resin containing a conductive filler, and the olefin resin is also an electrolytic solution. Is preferable because it has sufficient corrosion resistance. This hot melt adhesive can be solidified by heating at a predetermined temperature depending on the type of thermoplastic resin or the like.
The conductive adhesive layer interposed as an interconnector between the negative electrode side collecting electrode 341 and the translucent conductive layer 31 may be formed by similarly curing using an inorganic conductive adhesive described later. it can.

  When the negative electrode side collecting electrode 34 is provided on the other surface of the counter electrode substrate 2 (hereinafter referred to as the negative electrode side collecting electrode 342) (see FIGS. 7 to 9), the negative electrode side collecting electrode 342 is in contact with the electrolytic solution. Therefore, corrosion resistance is not particularly required. On the other hand, it is preferable that the negative electrode side current collecting electrode 342 has excellent adhesion to the counter electrode substrate 2. The material is not particularly limited, and can be formed of a metal such as tungsten, titanium, nickel, or silver. Further, in the case of this negative electrode side collecting electrode 342, it is preferable to protect the negative electrode side collecting electrode 342 with a resin, glass, or the like in order to prevent damage from the peeling from the counter electrode substrate 2 and contact with other members, or leakage of electric current.

This negative electrode side collecting electrode 342 is similar to the case of the collecting electrode provided on one surface of the counter substrate 2, using a mask on which a predetermined pattern is formed, a magnetron sputtering method, an electron beam evaporation method, etc. The physical vapor deposition method can be used. Alternatively, it can be formed by a screen printing method using a conductive paste. Further, the negative electrode side collecting electrode 342 can be formed on the entire other surface of the counter electrode substrate 2, and in this case, it is preferably formed by a screen printing method or the like. In addition, the thickness can be approximately the same as that of the negative electrode side collecting electrode 341 provided on one surface of the counter electrode substrate 2. In addition, when an area is large, it can also be set as a thinner current collection electrode. For example, when the area of the negative electrode side collecting electrode 342 is 50% or more of the area of the other surface of the ceramic substrate 2, the thickness can be reduced to 0.5 to 20 μm, particularly 0.5 to 5 μm. .
As described above, in the case of the negative electrode side collecting electrode 342, there is no limitation on the material, thickness, and the like. Accordingly, the material of the counter electrode substrate 2 is not particularly limited, but from the viewpoint of durability of the solar cell, the ceramic substrate 2 It is preferable that

The negative electrode side collector electrode 342 provided on the other surface of the counter electrode substrate 2 and the translucent conductive layer 31 are electrically connected via the interconnector 37 and the via conductor 38.
The “interconnector 37” has one end surface in contact with or bonded to the translucent conductive layer 31, and the other end surface in contact with or bonded to one end side of the via conductor 38. The material is not particularly limited, and an interconnector 37 made of the same metal as that used for forming the negative electrode side collecting electrode 341 can be used. Moreover, it can also be set as the interconnector 37 which consists of conductive rubber, anisotropic conductive rubber, pressurization conductive rubber, etc. Further, an interconnector 37 made of an uncured conductive adhesive and a conductive hot melt adhesive similar to the case of the conductive adhesive layer 36 can be used. When a metal is used, a conductive adhesive layer is interposed between the translucent conductive layer 31 and the interconnector 37 in order to improve the adhesion with the translucent conductive layer 31 and to conduct stably. Is preferred. The material and the formation method of the conductive adhesive layer are not particularly limited. For example, by using the same photo-curable adhesive as in the case of the conductive adhesive layer 36, by irradiating laser light in the same manner. Can be formed. When rubber is used, due to its elasticity, it can be stably interposed between the translucent conductive layer 31 and the counter electrode substrate 2, and can be sufficiently adhered at each interface. Even when rubber is used, a conductive adhesive layer may be interposed between the translucent conductive layer 31 and the interconnector 37 in the same manner as described above.

The interconnector 37 can also be formed using an inorganic conductive adhesive containing various inorganic adhesive compounds. The inorganic adhesive compound is not particularly limited, and various inorganic adhesive compounds can be used. As this inorganic adhesive compound, for example, alkali silicate can be used. Examples of the alkali silicate include potassium silicate (SiO 2 · K 2 O), sodium silicate (SiO 2 · Na 2 O), and the like. These alkali silicates are dehydrated and condensed to solidify to form an interconnector 37. The alkali silicate can be dehydrated and condensed at room temperature (for example, 15 to 35 ° C.), and may be dehydrated and condensed by heating as necessary. When heating, temperature is not specifically limited, It can be set as 80-150 degreeC. Furthermore, dehydration condensation may be performed in an air atmosphere, or dehydration condensation may be performed under reduced pressure. The alkali silicate is preferably vacuum-dried at room temperature for dehydration condensation, whereby the dehydration condensation is promoted and the uncured conductive adhesive layer can be sufficiently solidified.

The shape of the interconnector 37 is not particularly limited, and may be a columnar body such as a circular shape, an elliptical shape, a polygonal shape such as a triangle or a quadrangle, and a pad shape having a larger cross-sectional area. The dimension of the interconnector 37 is not particularly limited as long as sufficient electrical connection between the negative electrode side collector electrode 342 and the translucent conductive layer 31 can be obtained. The interconnector 37 has a cross-sectional area of 0.15 to 5.0 mm 2 , particularly 1.0 to 3.5 mm 2 , and each of the plurality of interconnectors 37 is separated from each other (each interconnector). The minimum distance between the 37 edges is preferably 4.0 to 11.0 mm, and particularly preferably 5.0 to 9.0 mm. Furthermore, it is more preferable that the interconnector 37 is provided on one surface of the counter electrode substrate 2 at equal intervals. With the interconnector 37 having such a cross-sectional area and arrangement, it is possible to obtain a negative-side current collecting electrode 342 having excellent current collecting efficiency, and to further suppress a reduction in the area of the semiconductor electrode, thereby improving power generation efficiency. It can be set as the outstanding dye-sensitized solar cell.

In the case where the negative electrode side collector electrode is provided on the other surface of the counter electrode substrate 2 and the negative electrode side collector electrode 342 and the translucent conductive layer 31 are connected by the interconnector 37, as described above, the semiconductor Reduction of the electrode area can be further suppressed. For example, the interconnector 37 has a columnar shape with a diameter of 0.5 mm, and there are portions where the translucent conductive layer 31 with a diameter of 1.5 mm and the catalyst electrode 33 are not provided concentrically around each interconnector. When the distance between the two electrodes 37 (in this case, the distance between the centers of the respective interconnectors 37) is 6 mm, the entire surface of the counter electrode substrate 2 (translucent conductive layer 31) as calculated by the following equation: The semiconductor electrode 32 can be provided in 95% of the portion. This ratio varies depending on the area of the portion where the translucent conductive layer 31 and the catalyst electrode 33 are not provided around the interconnector 37 and the separation distance between the interconnectors 37, but is 69 to 99%, particularly It may be 86 to 99%.
Area ratio (95%) at which a semiconductor electrode can be formed = [36 − {(3.14 × 0.75 × 0.75) × 1/4} × 4] / 36 (× 100)
The meaning of each numerical value in the above formula is as follows.
In the above formula, 36 (mm 2 ) is a square area formed by connecting the centers of the four interconnectors 37, and 3.14 × 0.75 × 0.75 (mm 2 ) is transparent. The area of each of the four circular portions where the photoconductive layer 31 and the catalyst electrode 33 are not provided. Further, in each square area, the portion where the semiconductor electrode 32 cannot be formed is 1/4 of the area of each circular portion, and since there are four circular portions, the semiconductor electrode 32 is formed. The total area of the parts that cannot be done is four times that.

  The “via conductor 38” (see FIGS. 8 to 9) has one end in contact with or joined to the interconnector 37 and the other end joined to the negative current collecting electrode 342. The via conductor 38 can be provided by forming a conductor in a via hole provided through the front and back of the ceramic substrate 2. Moreover, it can provide by forming a conductor layer in the wall surface of a via hole. The via hole provided in the ceramic substrate 2 can be formed by various methods such as irradiation with laser light such as YAG laser and carbon dioxide laser, drilling, punching using a punch. Among these, a method of forming a via hole in an unfired ceramic sheet that becomes the ceramic substrate 2 using a punch is simple and preferable.

  The conductor can be formed by filling a conductor paste from at least one opening of a via hole by a hole-filling printing method or the like, and then firing it. The conductor paste is not particularly limited, but a paste prepared by mixing a metal powder, an organic binder, an organic solvent, a solvent such as water, and the like can be used. The metal powder is not particularly limited, and examples thereof include powders of metals such as silver, gold, platinum, palladium, copper, tungsten, nickel, and titanium, and powders of alloys such as silver-platinum alloys and silver-palladium alloys. Furthermore, the paste for conductors can also contain a glass component. A glass component is preferable because it can be fired at a lower temperature. Further, the conductor layer on the wall surface of the via hole can be formed by sputtering, electroless plating, or the like using the same metal as that of the conductor.

  Since the via conductor 38 is formed, the cross-sectional shape of the via hole formed in the ceramic substrate 2 is not particularly limited, and may be a circle, an ellipse, a polygon such as a triangle, a quadrangle, or the like. This cross-sectional shape is often circular. Moreover, the dimension of the radial direction of a via hole is not specifically limited, either, When it is circular in cross section, it can be set as a through-hole with a diameter of 0.05-1 mm, especially 0.1-0.8 mm. Furthermore, when it is not circular in cross section, it can be a through hole having an opening size equivalent to that in the case of circular cross section. The via conductors 38 are provided corresponding to the interconnectors 37, and the number of via conductors 38 can be the same as the interconnectors 37.

  When the interconnector 37 is made of conductive rubber, anisotropic conductive rubber, pressurized conductive rubber, or the like, the interconnector 37 and the via conductor 38 can be sufficiently adhered to each other due to their elasticity. In this case, a conductive adhesive layer may be interposed between the interconnector 37 and the via conductor 38 in order to further improve the adhesion and to conduct stably. The material and the formation method of the conductive adhesive layer are not particularly limited. For example, a thermosetting adhesive and a hot melt adhesive among the uncured conductive adhesives in the case of the conductive adhesive layer 36 are used. Then, it can be formed by heating. Further, when the interconnector 37 is made of the same uncured conductive adhesive and conductive hot melt adhesive as in the case of the conductive adhesive layer 36, and when it is made of an inorganic conductive adhesive, the same as described above. And can be cured or solidified. Further, when the interconnector 37 is made of metal, the ceramic substrate 2 is used as the counter electrode substrate 2, and each of the interconnector 37, the via conductor 38, the negative current collecting electrode 342, and the ceramic substrate 2 is respectively fired. Can be formed at a time by simultaneously firing the unfired laminate. In this way, the process can be simplified.

When the interconnector 37, the via conductor 38, the negative electrode side current collecting electrode 342, and the ceramic substrate 2 are formed at a time as described above, the materials of each are not particularly limited, but the interconnector 37, the via conductor 38, and the negative electrode side current collector are not particularly limited. The electrode 342 is preferably formed of tungsten or molybdenum, and the ceramic substrate 2 is preferably formed of alumina. Further, it is particularly preferable that the interconnector 37, the via conductor 38, and the negative electrode side collecting electrode 342 are formed of tungsten, and the ceramic substrate 2 is formed of alumina. Tungsten is easy to be co-fired with alumina and has excellent corrosion resistance, so there is no problem even if it is used as the interconnector 37 in contact with the electrolytic solution.
In addition, an extraction electrode can be connected to the negative electrode side collecting electrodes 341 and 342, and electric power can be extracted from the extraction electrode. This take-out electrode can be integrally formed simultaneously with the formation of the negative electrode side collector electrode.

The “electrolytic solution 35” is contained in at least a part of each of the semiconductor electrode 32 and the catalyst electrode 33 and is filled between the semiconductor electrode 32 and the catalyst electrode 33. The electrolytic solution 35 is normally contained in the entirety of each of the semiconductor electrode 32 and the catalyst electrode 33, thereby improving the photoelectric conversion efficiency. The distance between the semiconductor electrode 32 and the catalyst electrode 33 is not particularly limited, but can be 200 μm or less, particularly 50 μm or less (usually 1 μm or more). When the thickness is 200 μm or less, a dye-sensitized solar cell having sufficient power generation efficiency can be obtained. In addition to the electrolyte, the electrolytic solution 35 usually contains a solvent such as carbonates such as ethylene carbonate and propylene carbonate, various additives, and the like. This electrolyte is not particularly limited, and various electrolytes can be used. As the electrolyte, 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. Only one type of electrolyte may be used, or two or more types of electrolytes may be used.

  In the case of the negative electrode side current collecting electrode 341 provided on one surface of the ceramic substrate 2, the electrolytic solution 35 is provided between the translucent conductive layer 31 and the counter electrode substrate 2, particularly the ceramic substrate 2. By sealing with resin or glass around the negative electrode side collecting electrode 341 and injecting it into the formed sealed space, it can be contained in each of the semiconductor electrode 32 and the catalyst electrode 33 and filled between them. (See FIGS. 2-3 and 5-6). Further, in the case where the negative electrode side current collecting electrode 34 is a negative electrode side current collecting electrode 342 provided on the other surface of the ceramic substrate 2, the electrolytic solution 35 is formed between the translucent conductive layer 31 and the counter electrode substrate 2, particularly the ceramic substrate 2. The gap is sealed with resin or glass around the semiconductor electrode 32 and injected into the formed sealed space so that it is contained in each of the semiconductor electrode 32 and the catalyst electrode 33 and filled between them. Yes (see FIGS. 8-9).

  The electrolytic solution 35 may be injected into the sealed space from the translucent substrate 1 side or the counter electrode substrate 2 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. Furthermore, the electrolytic solution 35 can also be injected from an injection port provided in the joint portion 4 formed by sealing between the translucent conductive layer 31 and the counter electrode substrate 2 with resin or glass. 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 can be injected more easily.

  The injection port may be provided in any of the translucent substrate 1, the counter electrode substrate 2, and the bonding portion 4. For example, when the translucent substrate 1 is a glass substrate, it is not easy to perforate. On the other hand, when the counter electrode substrate 2 is the ceramic substrate 2, it is easier to perforate than the glass substrate, and in particular, it can be extremely easily perforated using a punch or the like in the unfired sheet. Also, the joint can be easily drilled. Therefore, it is preferable to provide an injection port in the ceramic substrate 2 and / or the joint portion 4.

  The resin used for sealing around the negative electrode current collecting electrode 341 or the semiconductor electrode 32 is not particularly limited. Examples of this resin include thermosetting resins such as epoxy resins, urethane resins, and isobutylene resins, and thermoplastic resins such as olefin resins and ionomer resins. Furthermore, this sealing can also be performed with glass such as inorganic glass and organic glass such as acrylic glass. In particular, in a dye-sensitized solar cell that requires long-term durability, sealing with glass is preferable.

  When the negative electrode side collector electrode 341 is provided on one surface of the counter electrode substrate 2, the ceramic substrate 2 is used as the counter electrode substrate 2, and a plurality of single cells are provided between one surface of the translucent substrate 1 and one surface of the ceramic substrate 2. The structure 3 can be provided (refer FIG.11 and FIG.12). In each of the plurality of unit cell structures 3, each of the translucent conductive layers 31, the semiconductor electrodes 32, the catalyst electrodes 33, the negative electrode current collecting electrodes 34, and the electrolyte solution 35 is electrically connected. Each of the single cell constituent bodies 3 can be connected in series to form a dye-sensitized solar cell module 201. Each member is insulated between one surface of the translucent substrate 1 and one surface of the ceramic substrate 2 by a joint portion 4 formed by sealing with resin or glass around the plurality of unit cell structures 3. (See FIG. 11). As the resin or glass used for the sealing, the same ones as described above can be used. Further, in this dye-sensitized solar cell module 201, each single cell constituent body 3 includes a catalyst electrode 33 (positive electrode side collector electrode 39) and a negative electrode side collector electrode 341, for example, as shown in FIG. It can be connected in series by connecting.

  Even when the negative electrode side current collecting electrode 342 is provided on the other surface of the counter electrode substrate 2, a plurality of unit cell structures 3 can be provided between one surface of the translucent substrate 1 and one surface of the ceramic substrate 2 ( (See FIGS. 13, 14 and 15). In this case, the counter electrode substrate 2 is not particularly limited, but the ceramic substrate 2 is preferably used. In the plurality of single cell constituting bodies 3, each of the plurality of single cell constituting bodies 3 includes between the translucent conductive layers 31, between the semiconductor electrodes 32, between the catalyst electrodes 33, between the negative electrode side collecting electrodes 34, between the electrolyte solution 35, and between the interconnectors 37. Are electrically insulated from each other, and the unit cell structures 3 can be connected in series to form a dye-sensitized solar cell module 202. Between each member, between one surface of the translucent substrate 1 and one surface of the ceramic substrate 2 is sealed with a resin or glass around the semiconductor electrode 32 of each of the unit cell structures 3. It can be insulated by the joint 4. As the resin or glass used for the sealing, the same ones as described above can be used. Further, in this dye-sensitized solar cell module 202, each unit cell structure 3 includes the catalyst electrode 33 (positive electrode side collecting electrode 39), the via conductor 38, and the negative electrode side collecting electrode 342, for example, FIG. And it can connect in series by connecting like FIG.

  Thus, when the several single cell structure 3 is provided, these single cell structures 3 can be connected and used in series as mentioned above. Further, a larger number of unit cell structures 3 may be provided, and a part of these unit cell structures 3 may be connected in series and the other part connected in parallel. In this way, by connecting a large number of single-cell constituent bodies 3 in series or in parallel, the output voltage and power of the dye-sensitized solar cell can be easily adjusted according to the application.

  A positive current collecting electrode 39 can be provided between the counter electrode substrate 2 and the catalyst electrode 33 (see FIGS. 3, 6, and 9). If the catalyst electrode 33 is made of platinum and has a sufficient thickness, the positive electrode side collecting electrode 39 is not necessarily provided. However, since platinum is expensive, when the catalyst electrode 33 is a thin layer, it is preferable to provide the positive collector electrode 39 in order to increase the current collection efficiency. Although the planar shape of the positive electrode side collecting electrode 39 is not particularly limited, in order to obtain the positive electrode side collecting electrode 39 having sufficiently low resistance and excellent current collecting efficiency, the shape and size are similar to those of the catalyst electrode 33. Preferably there is. The area of the positive electrode side collector electrode 39 is more preferably 50% or more, particularly 65% or more, and more preferably 80% or more (or the same area) of the area of the catalyst electrode 33. Further, it is particularly preferable that the catalyst electrode 33 is disposed in a similar shape.

  The positive electrode side collector electrode 39 can be provided on one surface of the counter electrode substrate 2 by a physical vapor deposition method such as a magnetron sputtering method or an electron beam vapor deposition method using a mask on which a predetermined pattern is formed. Further, when the counter electrode substrate 2 is the ceramic substrate 2, it can be provided by forming a coating film on one surface of the ceramic substrate 2 and baking it by a screen printing method using a paste or the like. When the whole of the positive electrode side collecting electrode 39 is covered with the catalyst electrode 33, the corrosion resistance against the electrolytic solution is not required, so the material is not particularly limited and is formed of tungsten, titanium, nickel or the like. can do. In addition, when the edge part of the positive electrode side current collection electrode 39 contacts with the electrolyte solution 35, it has especially excellent corrosion resistance, and at the time of preparation of a ceramic substrate, particularly an alumina substrate, it is fired simultaneously with an unfired substrate. It is particularly preferred to contain tungsten that can be used.

  An extraction electrode can be connected to the positive-side current collecting electrode 39, and electric power can be extracted from the extraction electrode. This take-out electrode can be integrally formed at the same time when the positive electrode side collecting electrode is formed. When the positive electrode side collector electrode 39 is not provided, the positive electrode side extraction electrode can be provided continuously with the catalyst electrode 33. This take-out electrode can be integrally formed simultaneously with the formation of the catalyst electrode.

Hereinafter, the present invention will be described specifically by way of examples.
Example 1
The dye-sensitized solar cell 102 shown in FIG. 3 was manufactured as follows.
(1) Formation of an alumina green sheet and a non-fired positive electrode side current collecting electrode as a part of the ceramic substrate 2 90.5 mass% alumina powder, 1 mass% magnesia powder and 4 mass% as a sintering aid Silica powder was mixed and wet pulverized with a ball mill for 12 hours, then dehydrated and dried. Next, this mixed powder was blended with 3% by weight of methacrylic acid isobutyl ester as an organic binder, 1% by weight of nitrocellulose and 0.5% by weight of dioctyl phthalate, and further trichloroethylene and n-butanol as solvents. To prepare a slurry containing alumina powder. This slurry was degassed under reduced pressure, and then cast into a sheet, and then slowly cooled to volatilize the solvent to form an alumina green sheet that becomes a part of the ceramic substrate 2.

  On the other hand, a metallized ink containing tungsten powder was similarly prepared using a ball mill. Thereafter, using this metallized ink, four conductive coating films having a rectangular planar shape serving as the positive electrode side collecting electrode 39 having a thickness of 10 μm were formed on the surface of the alumina green sheet by a screen printing method.

(2) Formation of unsintered alumina molded body and unsintered negative electrode side current collecting electrode as other part of ceramic substrate 2 The slurry containing the alumina powder prepared in (1) above was degassed under reduced pressure, and then cast. The sheet was then gradually cooled to volatilize the solvent. Thereafter, four rectangular openings were formed by a punching method at positions corresponding to the conductive coating film serving as the positive current collecting electrode 39 in (1). Next, a screen printing method is performed by using the metallized ink containing the tungsten powder prepared in the above (1) on one surface of the unfired alumina molded body that is the other part of the ceramic substrate 2 in which the four openings are formed. Thus, a conductive coating film to be the negative electrode side collecting electrode 341 was formed.

(3) Lamination, co-firing and formation of catalyst electrode The part (2) above is formed on the surface of the alumina green sheet prepared in (1) above where the conductive coating film to be the positive electrode side collecting electrode 39 is not formed. The other surface of the unfired alumina molded body produced in step 1 was laminated. Thereafter, the alumina green sheet, the conductive coating film serving as the positive electrode side collector electrode 39, the unfired alumina molded body, and the conductive coating film serving as the negative electrode side collector electrode 341 were simultaneously fired at 1500 ° C. in a reducing atmosphere. 1 (see FIG. 1), 100 mm × 100 mm × flat plate portion (see FIG. 1, a portion indicated by reference numeral 22 in FIG. 1), 1 mm in thickness, convex part (see FIG. 1, reference numeral 21 in FIG. 1). Of the alumina substrate 2 having a thickness of 60 μm, the positive electrode side collector electrode 39 made of four tungsten of 78 mm × 18 mm × 50 μm in thickness formed on one surface of the flat plate portion, and the alumina substrate 2. A laminate having a negative electrode side collecting electrode 341 having a width of 2 mm and a thickness of 30 μm formed on the upper surface of the convex portion was produced. Next, platinum was deposited on the surface of the positive electrode side collector electrode 39 by sputtering to form a catalyst electrode 33 having a thickness of 1 μm.

(4) Application of conductive adhesive A conductive adhesive containing 98% by mass of tungsten powder in a thermosetting resin is screened on the surface of the negative electrode side collecting electrode 341 of the laminate produced in (3) above. The uncured conductive adhesive layer to be the conductive adhesive layer 36 was formed by coating by a printing method.

(5) Formation of Semiconductor Electrode On the surface of the light-transmitting conductive layer 31 of the glass substrate 1 (translucent substrate 1, manufactured by Nippon Sheet Glass Co., Ltd.) having a thickness of 100 mm × 100 mm × 4 mm on which the light-transmitting conductive layer 31 is formed. Four coating films having a rectangular planar shape to be the semiconductor electrode 32 were formed by a screen printing method using a commercially available titania paste (manufactured by Solaronix, trade name “Ti-Nanoxide D / SP”). Thereafter, preliminary drying is performed at 150 ° C. for 30 minutes, and then the porous electrode for producing the semiconductor electrode 32 is maintained by baking at 500 ° C. for 30 minutes in a muffle furnace (manufactured by Motoyama, model “SK-2030D”). A substrate was formed. On the other hand, ruthenium organic complex [Ru2,2-bipyridil-4,4-dicboxylate (TBA) 2 (NCS) 2 ] (manufactured by Kojima Chemical Co., Ltd., trade name “N-719”) is mixed with acetonitrile and tert-butanol. A solution of 3 × 10 −4 mol / liter acetonitrile / tert-butanol was prepared by dissolving in a solvent. Next, the porous electrode substrate and the glass substrate were immersed in this ruthenium organic complex solution for 12 hours, and the ruthenium organic complex as a sensitizing dye was adhered to the porous electrode substrate to form the semiconductor electrode 32.

(6) Production of dye-sensitized solar cell The laminate produced in (4) above, in which an uncured conductive adhesive layer was formed on the surface of the negative electrode side collecting electrode 341, and produced in (5) above. The glass substrate on which the semiconductor electrode 32 is formed is such that the semiconductor electrode 32 and the catalyst electrode 33 face each other, and an adhesive resin sheet with a thickness of 100 μm (trade name “HIMILAN 1702 manufactured by Mitsui Dupont Polychemical Co., Ltd.). ”) Was provided with an opening of 91 mm × 91 mm in accordance with the outermost dimension of the semiconductor electrode 32, and this was interposed between the translucent conductive layer 31 and the ceramic substrate 2 as a spacer and laminated. Thereafter, the spacer was heated to 100 ° C. using a hot plate, and the translucent conductive layer 31 and the ceramic substrate 2 were joined. Next, the uncured conductive adhesive layer was irradiated with YAG laser from the side of the glass substrate and cured to form a conductive adhesive layer 36. Thereafter, 0.05 mol I 2 , 0.1 mol LiI, 0.6 mol Dimethylpropylimidazolium iodide and 0.5 mol 4-tert-butylpyridine are mixed in the formed space. The electrolyte solution 35 was injected from the injection port provided in the ceramic substrate 2 by a syringe, and immediately after the injection, the gap was sealed with an ultraviolet curable resin, and the dye-sensitized solar cell 102 was manufactured.

(7) Performance Evaluation The dye-sensitized solar cell produced in (6) above was irradiated with 20 mW / cm 2 of light using a halogen lamp, and a standard voltammetry tool (model “HSV-100” manufactured by Hokuto Denko Co., Ltd.) Was used to measure the current-voltage curve, and the photoelectric conversion efficiency (η) was determined. As a result, η was 8.2%.

Example 2
The dye-sensitized solar cell 104 shown in FIG. 6 was manufactured as follows.
(1) Formation of Alumina Green Sheet to be Ceramic Substrate 2 and Unfired Negative Electrode Side Current Collection Electrode A slurry containing alumina powder prepared in the same manner as in Example 1 (1) was degassed under reduced pressure, and then cast. Then, it was gradually cooled to volatilize the solvent to form an alumina green sheet to be the ceramic substrate 2. Thereafter, using a metallized ink containing tungsten powder prepared in the same manner as in Example 1 (1), the planar shape of the positive electrode side current collecting electrode 39 is rectangular on the surface of the alumina green sheet by screen printing. Four conductive coating films were formed. Further, by using a metallized ink containing the above tungsten powder, the surface of the alumina green sheet is surrounded by a screen printing method so as to surround the conductive coating film serving as the positive electrode side collecting electrode 39 and separated from the conductive coating film. Thus, a conductive coating film to be the negative electrode side collecting electrode 341 was formed.

(2) Simultaneous firing The alumina green sheet formed in (1) above, the conductive coating film serving as the positive current collecting electrode 39, and the conductive coating film serving as the negative current collecting electrode 341 are simultaneously produced at 1500 ° C. in a reducing atmosphere. As shown in FIG. 6 (see FIG. 4), the positive electrode side current collector made of 100 mm × 100 mm × 1 mm thick alumina substrate 2 and 78 tungsten × 18 mm × 10 μm thick tungsten formed on one surface thereof. A laminate having the electrode 39 and a negative electrode side collecting electrode 341 having a width of 2 mm and a thickness of 50 μm was produced.

(3) Formation of Catalyst Electrode A catalyst electrode 33 made of platinum having a size of 78 mm × 18 mm × thickness 1 μm was formed on the surface of the positive electrode side collector electrode 39 formed in (2) above by sputtering.

(4) Application of conductive adhesive The conductive adhesive prepared in the same manner as in (4) of Example 1 was applied in the same manner to the surface of the negative electrode side collecting electrode 341 formed in (2) above, An uncured conductive adhesive layer to be the conductive adhesive layer 36 was formed.

(5) Formation of Semiconductor Electrode A porous electrode substrate was formed in the same manner as in Example 1 (5), and a sensitizing dye was attached in the same manner to form a semiconductor electrode 32.

(6) Production of dye-sensitized solar cell The laminate produced in (4) above, in which an uncured conductive adhesive layer was formed on the surface of the negative electrode side collecting electrode 341, and produced in (5) above. The glass substrate on which the semiconductor electrode 32 is formed is placed on the adhesive resin sheet described in (6) of Example 1 so that the semiconductor electrode 32 and the catalyst electrode 33 face each other. An opening of 91 mm × 91 mm was provided according to the outer dimensions, and this was interposed between the translucent conductive layer 31 and the ceramic substrate 2 and laminated. Thereafter, the adhesive resin sheet was heated in the same manner as in (6) of Example 1 to join the translucent conductive layer 31 and the ceramic substrate 2 together. Further, the uncured conductive adhesive layer was cured to form the conductive adhesive layer 36. Next, an electrolytic solution 35 prepared in the same manner as in (6) of Example 1 was injected by a syringe from the injection port provided in the same manner, and after injection, sealed in the same manner, and the dye-sensitized solar cell 104. Manufactured.
Η obtained in the same manner as in Example 1 (7) was 8.2%.

Example 3
The dye-sensitized solar cell 106 shown in FIG. 9 was manufactured as follows.
(1) Preparation of alumina green sheet to be ceramic substrate 2, unfired negative electrode side collector electrode, unfired via conductor and unfired positive electrode side collector electrode Alumina powder prepared in the same manner as (1) of Example 1 The contained slurry was degassed under reduced pressure, then cast into a sheet, and then slowly cooled to volatilize the solvent to form an alumina green sheet to be the ceramic substrate 2. After that, this alumina green sheet was punched using a punch, and 121 cross-sectionally spaced 121 via holes with a circular cross section and a diameter of 0.25 mm (area of 0.05 mm 2 ) and a separation distance of 8 mm. Formed. Next, a metallized ink containing tungsten powder prepared in the same manner as in Example 1 (1) was applied to the other surface of the alumina green sheet by a screen printing method to form a conductive coating film serving as the negative electrode side collecting electrode 342. At the same time, the metallized ink was filled into the via hole by sucking from one surface side to form an unfired via conductor. Further, the metallized ink is applied to one surface of the alumina green sheet by a screen printing method except for a portion having a diameter of 1.5 mm after firing around the interconnector 37 to be provided, whereby the positive electrode side collecting electrode 39 is obtained. A conductive coating was formed.

(2) Simultaneous firing The alumina green sheet produced in the above (1), the conductive coating film serving as the negative electrode side collecting electrode 342, the unfired via conductor and the conductive coating film serving as the positive electrode side collecting electrode 39 are reduced in a reducing atmosphere. As shown in FIG. 9 (see FIG. 7), the alumina substrate 2 having a size of 100 mm × 100 mm × thickness 1 mm and a negative electrode-side collector made of tungsten having a thickness of 100 mm × 100 mm × thickness 10 μm formed on one surface are baked at 1500 ° C. A laminate having a positive electrode side current collecting electrode 39 having an outer dimension of 100 mm × 100 mm × thickness of 10 μm formed on the other surface of the electric electrode 342, the via conductor 38, and the alumina substrate 2 was produced.

(3) Formation of Catalyst Electrode A 1 μm-thick catalyst electrode 33 made of platinum was formed on the surface of the positive electrode current collecting electrode 39 produced in (2) above by sputtering.

(4) Formation of interconnector Using conductive silicon rubber containing tungsten powder as a conductive material, an interconnector 37 made of conductive rubber having a diameter of 500 μm and a length of 200 μm was formed.

(5) Formation of Semiconductor Electrode Same as (5) of Example 1 except for the portion of the surface of the translucent conductive layer 31 except the 1.5 mm diameter portion around the interconnector 37 to be disposed. A porous electrode substrate was formed, and a sensitizing dye was attached in the same manner to form a semiconductor electrode 32.

(6) Manufacture of dye-sensitized solar cell A positive electrode side collector electrode 39 and a catalyst electrode 33 formed on one surface of the ceramic substrate 2 and a negative electrode side collector electrode 342 formed on the other surface, which are prepared in (3) above, are formed. The interconnector 37 produced in the above (4) was disposed on one end side of each via conductor 38 of the laminate in which the via conductors 38 were formed on the substrate 2. Thereafter, the adhesive resin sheet described in (6) of Example 1 is provided with an opening of 81 mm × 81 mm according to the outermost dimension of the semiconductor electrode 32, and this is disposed on the periphery of the ceramic substrate 2. Next, the glass substrate 1 on which the semiconductor electrode 32 formed in (5) was formed was laminated so that the catalyst electrode 33 formed on the ceramic substrate 2 and the semiconductor electrode 32 face each other. Thereafter, the adhesive resin sheet was heated in the same manner as in (6) of Example 1 to join the translucent conductive layer 31 and the ceramic substrate 2 together. Next, the electrolytic solution 35 prepared in the same manner as in (6) of Example 1 was injected by a syringe from the injection port provided in the same manner, and after injection, sealed in the same manner, and the dye-sensitized solar cell 106. Manufactured.
Η obtained in the same manner as in Example 1 (7) was 8.5%.

Example 4
A dye-sensitized solar cell in which the counter electrode substrate was a glass substrate was manufactured as follows.
(1) Production of negative electrode side collector electrode, via conductor, positive electrode side collector electrode and catalyst electrode 100 mm × 100 mm × thickness 1 mm glass substrate 2 (counter electrode substrate 2, Japanese plate glass) on which translucent conductive layer 31 is formed Via holes with a diameter of 0.25 mm were formed at intervals of 8 mm by drilling on the entire surface. Thereafter, a resin paste containing tungsten powder was prepared using a ball mill, and this resin paste was filled in the via hole by hole-filling printing to form an unfired via conductor. Next, the resin paste was applied to the other surface of the glass substrate 2 by a screen printing method to form a conductive coating film serving as the negative electrode side collecting electrode 342. Further, the above resin paste is applied to one surface of the glass substrate 2 by a screen printing method except for a portion with a diameter of 1.5 mm around the interconnector 37 to be disposed, and a conductive coating to be the positive electrode side collecting electrode 39 is applied. A film was formed. Then, it hold | maintained at 150 degreeC for 2 hours, it was made to dry, and the negative electrode side current collection electrode 342, the via conductor 38, and the positive electrode side current collection electrode 39 were formed. Next, a catalyst electrode 33 made of platinum and having a thickness of 1 μm was formed on the surface of the positive electrode side collector electrode 39 by sputtering.

(2) Formation of interconnector The interconnector 37 was formed in the same manner as (4) of Example 3.

(3) Formation of Semiconductor Electrode Same as (5) of Example 1 except for the portion of the surface of the translucent conductive layer 31 except the 1.5 mm diameter portion around the interconnector 37 to be disposed. A porous electrode substrate was formed, and a sensitizing dye was attached in the same manner to form a semiconductor electrode 32.

(4) Production of dye-sensitized solar cell The positive electrode side collector electrode 39 and the catalyst electrode 33 are formed on one surface of the glass substrate 2 prepared in the above (1), and the negative electrode side collector electrode 342 is formed on the other surface. In addition, the interconnector 37 produced in the above (2) was disposed on one end side of each via conductor 38 of the laminated body in which the via conductor 38 was formed on the glass substrate 2. Thereafter, the adhesive resin sheet described in (6) of Example 1 is provided with an opening of 82 mm × 82 mm in accordance with the outermost dimension of the semiconductor electrode 32, and this is disposed on the periphery of the glass substrate 2, Next, the glass substrate 1 formed with the semiconductor electrode 32 formed in the above (3) was laminated so that the catalyst electrode 33 formed on the glass substrate 2 and the semiconductor electrode 32 face each other. Thereafter, the adhesive resin sheet was heated in the same manner as in (6) of Example 1 to join the translucent conductive layer 31 and the glass substrate 2 together. Next, an electrolytic solution 35 prepared in the same manner as in (6) of Example 1 was injected by a syringe from the injection port provided in the same manner, and after the injection, it was sealed in the same manner to obtain a dye-sensitized solar cell. Manufactured.
Η obtained in the same manner as in Example 1 (7) was 8.2%.
The dye-sensitized solar cell of Example 4 has the same structure as the dye-sensitized solar cell 106 of Example 3 except that the counter electrode substrate 2 is a glass substrate 2 having a translucent conductive layer 31. FIG. 9 is substituted for the drawing.

Example 5
A dye-sensitized solar cell in which the interconnector was made of a conductive adhesive was produced as follows.
(1) An alumina green sheet, an unfired negative electrode side current collecting electrode, an unfired via conductor, and an unfired positive electrode side current collecting electrode to be the ceramic substrate 2 were produced in the same manner as in Example 3 (1).

(2) A laminated body having the same structure, which is co-fired in the same manner as (2) of Example 3 and has the same size alumina substrate 2, negative electrode side collecting electrode 342, via conductor 38, and positive electrode side collecting electrode 39. Produced.

(3) The catalyst electrode 33 was formed in the same manner as in Example 3 (1).

(4) Formation of uncured interconnector made of uncured conductive adhesive 25 mass in the portion where the end surface of via conductor 38 is exposed on one surface of alumina substrate 2 of the laminate produced in (3) above. % Inorganic potassium silicate and 75 mass% nickel powder are put into pure water and mixed to apply an inorganic conductive adhesive by screen printing so that it is concentric with the end face of the via conductor 38. An uncured interconnector to be an interconnector 37 having a diameter of 1.5 mm and a length of 100 μm was formed.

(5) Formation of Semiconductor Electrode A porous electrode substrate was formed in the same manner as in Example 1 (5), and a sensitizing dye was attached in the same manner to form a semiconductor electrode 32.

(6) Manufacture of dye-sensitized solar cell A positive electrode side collector electrode 39 and a catalyst electrode 33 formed on one surface of the ceramic substrate 2 and a negative electrode side collector electrode 342 formed on the other surface, which are prepared in (3) above, are formed. Example 6 (6) in which an opening of 81 mm × 81 mm is provided on the periphery of one surface of the ceramic substrate 2 of the laminate in which the via conductors 38 are formed on the substrate 2 in accordance with the outermost dimension of the semiconductor electrode 32. Then, the glass substrate 1 on which the semiconductor electrode 32 formed on the ceramic substrate 2 is formed using the adhesive electrode sheet described in (5) above, and the catalyst electrode 33 and the semiconductor electrode 32 formed on the ceramic substrate 2. Were laminated so that they face each other. Next, the adhesive resin sheet was heated in the same manner as in Example 1 (6) to join the translucent conductive layer 31 and the ceramic substrate 2 together. At the same time, the uncured interconnector formed in the above (4) was cured by a dehydration condensation reaction in the atmosphere, and then put into a vacuum desiccator and dried to form an interconnector 37. Next, an electrolytic solution 35 prepared in the same manner as in (6) of Example 1 was injected by a syringe from the injection port provided in the same manner, and after the injection, it was sealed in the same manner to obtain a dye-sensitized solar cell. Manufactured.
Η obtained in the same manner as in Example 1 (7) was 8.2%.
The dye-sensitized solar cell of Example 5 has the same structure as the dye-sensitized solar cell 106 of Example 3 except that the interconnector 37 is made of a conductive adhesive layer. FIG. 9 is substituted.

Example 6
The dye-sensitized solar cell 107 shown in FIG. 10 in which the counter electrode substrate was a resin substrate was manufactured as follows.
(1) Formation of via conductor, positive electrode side collecting electrode and catalyst electrode 100 mm × 100 mm × thickness 120 μm polyethylene naphthalate resin center 2 made of polyethylene naphthalate resin, using a perforated punch, the cross section is circular Three via holes having a diameter of 0.25 mm and a distance of 0.25 mm between each edge were formed at equal intervals. Thereafter, tungsten is deposited on one surface of the resin substrate 2 by sputtering, and tungsten is deposited on a circular portion having a diameter of 1.5 mm around the via hole on the one surface to form a part of the interconnector 37 having a thickness of 10 μm. The conductive layer 371 for the interconnector is formed, and the via conductor 38 is formed on the wall surface of the via hole. At the same time, the conductive layer 371 is separated from the other portion of the one surface of the resin substrate 2 where the conductive layer 371 is not formed. Thus, a positive electrode side collector electrode 39 having a thickness of 10 μm was formed. Next, platinum was deposited on the surface of the positive electrode side collector electrode 39 by sputtering to form a catalyst electrode 33 having a thickness of 1 μm.

(2) Formation of negative electrode side collector electrode and interconnector A conductive coating film to be the negative electrode side collector electrode 342 was formed on the other surface of the resin substrate 2 by applying a commercially available silver paste by screen printing. Subsequently, the negative electrode side current collection electrode 342 was formed by heating at 150 degreeC for 30 minutes. Thereafter, a resin sealing agent was filled from one surface side of the resin substrate 2 into a hollow portion where the via conductor 38 of the via hole was not formed, and the resin sealing portion 373 was formed by filling the hole. Next, a conductive adhesive prepared in the same manner as in (4) of Example 1 is applied to the surface of the conductive layer 371 that becomes a part of the interconnector 37 formed in (1) above. The adhesive coating film for interconnectors having a thickness of 50 μm was formed.

(3) Formation of semiconductor electrode A portion of the surface of the translucent conductive layer 31 other than a portion having a diameter of 2.0 mm around the interconnector adhesive layer 372 to be disposed is commercially available by screen printing. A titania paste for low-temperature film formation was applied, dried at 150 ° C. to form a porous electrode substrate, and a sensitizing dye was attached in the same manner as in Example 1 (5) to form a semiconductor electrode 32.

(4) Production of dye-sensitized solar cell The positive electrode side collector electrode 39 and the catalyst electrode 33 are formed on one surface of the resin substrate 2 produced in the above (1), and the negative electrode side collector electrode 342 is formed on the other surface. The adhesive resin sheet described in (6) of Example 1 is formed on the periphery of the resin substrate 2 of the laminate in which the via conductors 38 are formed on the resin substrate 2. In addition, an opening of 82 mm × 82 mm is provided and disposed on the periphery of the resin substrate 2, and then the glass substrate 1 formed with the semiconductor electrode 32 formed in the above (3) is formed on the resin substrate 2. The interconnector adhesive coating film was laminated so that the portion where the semiconductor electrode 32 was not formed was opposed. Then, it is heated to 120 ° C. in a dryer to cure the adhesive film for interconnector to form an adhesive layer 372 for interconnector and adhere it to the translucent conductive layer 31, and with an adhesive resin sheet The translucent conductive layer 31 and the glass substrate 2 were joined. Next, the electrolytic solution 35 prepared in the same manner as in (6) of Example 1 was injected by a syringe from the injection port provided in the same manner, and after injection, sealed in the same manner, and the dye-sensitized solar cell 107. Manufactured.
Η obtained in the same manner as in Example 1 (7) was 7.0%.

  It should be noted that the present invention is not limited to the description of the above-described embodiments, and can be variously modified embodiments within the scope of the present invention. For example, as the electrolytic solution, one containing an ionic liquid as a main component can be used. The ionic liquid is contained in an amount of 50% by mass or more, particularly 90% by mass or more (or 100% by mass) when the electrolytic solution is 100% by mass. As this ionic liquid, a room temperature molten salt of iodide can be used. Examples of the room temperature molten salt of iodide include various room temperature molten salts such as imidazolium salt, pyridinium salt, pyrrolidinium salt, pyrazolidium salt, isothiazolidinium salt and isoxazolidinium salt. 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.

It is the typical perspective view which decomposed | disassembled an example of the dye-sensitized solar cell in which the negative electrode side collector electrode was provided in one surface of the counter electrode substrate, and was seen from diagonally upward. It is a schematic diagram which shows the cross section of the dye-sensitized solar cell of FIG. It is a schematic diagram which shows the cross section of the dye-sensitized solar cell of Example 1 in which the positive electrode side collector electrode was further provided in FIG. It is the typical perspective view which decomposed | disassembled the other example of the dye-sensitized solar cell in which the negative electrode side current collection electrode was provided in one surface of the counter electrode substrate, and was seen from diagonally upward. It is a schematic diagram which shows the cross section of the dye-sensitized solar cell of FIG. FIG. 6 is a schematic diagram showing a cross section of the dye-sensitized solar cell of Example 2 in which a positive current collecting electrode is further provided in FIG. 5. It is the typical perspective view which decomposed | disassembled an example of the dye-sensitized solar cell in which the negative electrode side current collection electrode was provided in the other surface of the counter electrode substrate, and was seen from diagonally upward. It is a schematic diagram which shows the cross section of the dye-sensitized solar cell of FIG. It is a schematic diagram which shows the cross section of the dye-sensitized solar cell of Example 3 in which the positive electrode side collector electrode was further provided in FIG. It is a schematic diagram which shows the cross section of the dye-sensitized solar cell by which the counter electrode substrate of Example 5 is a resin substrate, and the negative electrode side current collection electrode was provided in the other surface of this resin substrate. It is a schematic diagram which shows the cross section of an example of the dye-sensitized solar cell module by which a several unit cell structure is connected in series. It is a schematic diagram which shows the connection pattern for connecting each single cell structure in series in the dye-sensitized solar cell module of FIG. It is a schematic diagram which shows the cross section of the other example of the dye-sensitized solar cell module by which a several unit cell structure is connected in series. It is a schematic diagram which shows the connection pattern (one surface side of a counter electrode substrate) for connecting each single cell structure in series in the dye-sensitized solar cell module of FIG. It is a schematic diagram which shows the connection pattern (other surface side of a counter electrode substrate) for connecting each single cell structure in series in the dye-sensitized solar cell module of FIG.

Explanation of symbols

  101, 102, 103, 104, 105, 106, 107; dye-sensitized solar cell, 201, 202; dye-sensitized solar cell module, 1; translucent substrate (glass substrate), 2, 21, 22; Counter electrode substrate (ceramic substrate), 31; Translucent conductive layer, 32; Semiconductor electrode, 33; Catalyst electrode, 34, 341, 342; Negative electrode side collecting electrode, 35; Electrolytic solution, 36; 37; interconnector, 371; conductive layer for interconnector, 372; adhesive layer for interconnector, 373; resin sealing portion, 38; via conductor, 39; positive collector electrode, 4;

Claims (16)

  1. A translucent substrate;
    A counter electrode substrate disposed to face one surface of the translucent substrate;
    A translucent conductive layer provided on the one surface of the translucent substrate; a semiconductor electrode provided on the surface of the translucent conductive layer and having a sensitizing dye; and one surface of the counter electrode substrate facing the semiconductor electrode. Provided on the one or other surface of the counter electrode substrate, separated from the catalyst electrode and connected to the translucent conductive layer, and the semiconductor electrode and the catalyst A dye-sensitized type comprising: at least one unit cell structure having an electrolyte contained in at least a part of each of the electrodes and filled between the semiconductor electrode and the catalyst electrode Solar cell.
  2.   The dye-sensitized type according to claim 1, wherein the counter electrode substrate is a ceramic substrate, and the negative electrode side collecting electrode is provided on one surface of the ceramic substrate facing the one surface of the translucent substrate and contains tungsten. Solar cell.
  3.   The dye-sensitized solar cell according to claim 2, wherein the negative electrode side collector electrode has a thickness of 10 to 100 µm.
  4.   The dye-sensitized solar cell according to claim 2 or 3, wherein the translucent conductive layer and the negative electrode side collecting electrode are connected via a conductive adhesive layer.
  5.   The dye-sensitized dye according to claim 4, wherein the conductive adhesive layer contains a conductive filler, and the conductive filler is at least one of a carbon filler, a tungsten filler, a titanium filler, and a nickel filler. Type solar cell.
  6.   The dye-sensitized solar cell according to claim 4 or 5, wherein the conductive adhesive layer is formed by curing an uncured conductive adhesive layer with a laser beam irradiated through the translucent substrate. .
  7.   The negative current collecting electrode is provided on the other surface of the counter electrode substrate, a plurality of interconnectors are interposed between the surface of the translucent conductive layer and the one surface of the counter electrode substrate, and a plurality of 2. The dye-sensitized solar cell according to claim 1, wherein each of the interconnectors and the negative electrode side collector electrode are connected by a via conductor formed on the counter electrode substrate.
  8. Area of the cross section of the interconnector is 0.15~5.0mm 2, dye-sensitized according to claim 7 each distance of the plurality of the interconnectors is 4.0~11.0mm Solar cell.
  9.   The dye-sensitized solar cell according to claim 7 or 8, wherein the interconnector is formed by curing an uncured conductive adhesive layer containing alkali silicate.
  10.   The dye-sensitized solar cell according to any one of claims 7 to 9, wherein the counter electrode substrate is a ceramic substrate.
  11.   The dye-sensitized solar cell according to any one of claims 7 to 10, wherein the negative electrode side collecting electrode has a thickness of 0.5 to 100 µm.
  12.   Between the one surface of the translucent substrate and the one surface of the ceramic substrate, the translucent conductive layers, between the semiconductor electrodes, between the catalyst electrodes, between the negative electrode current collecting electrodes, and between the electrolyte solutions are respectively included. The plurality of single cell components that are electrically insulated from each other are provided, and each of the plurality of single cell components is connected in series. Dye-sensitized solar cell.
  13.   The insulation between the one surface of the translucent substrate and the one surface of the ceramic substrate is sealed with a resin or glass around the negative current collecting electrode of each of the unit cell constituents. The dye-sensitized solar cell according to claim 12, which is made.
  14.   Between the one surface of the translucent substrate and the one surface of the counter electrode substrate, each has a translucent conductive layer, between semiconductor electrodes, between catalyst electrodes, between negative electrode side collecting electrodes, between electrolyte solutions, and The plurality of single cell constituents each electrically insulated from each other between the interconnectors are provided, and each of the plurality of single cell constituents is connected in series. 2. A dye-sensitized solar cell according to item 1.
  15.   Between the one surface of the translucent substrate and the one surface of the counter electrode substrate is sealed with resin or glass around the semiconductor electrode of each of the unit cell constituents, and the insulation is made. The dye-sensitized solar cell according to claim 14.
  16.   The dye-sensitized solar cell according to any one of claims 1 to 15, wherein a positive-side collector electrode is provided between the counter electrode substrate and the catalyst electrode.
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USRE42567E1 (en) 1995-11-16 2011-07-26 Lifescan, Inc. Electrochemical cell
USRE44330E1 (en) 1995-06-19 2013-07-02 Lifescan Inc. Electrochemical cell
US8486243B2 (en) 2001-10-10 2013-07-16 Lifescan, Inc. Electrochemical cell

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JP5032051B2 (en) * 2006-04-17 2012-09-26 日本特殊陶業株式会社 Dye-sensitized solar cell
JP5013741B2 (en) * 2006-05-08 2012-08-29 京セラ株式会社 Photoelectric conversion device and photovoltaic power generation device
JP2007317454A (en) * 2006-05-24 2007-12-06 Ngk Spark Plug Co Ltd Dye-sensitized solar cell
JP5095226B2 (en) * 2007-01-16 2012-12-12 日本特殊陶業株式会社 Dye-sensitized solar cell and method for producing the same
JP2009211967A (en) * 2008-03-05 2009-09-17 Ngk Spark Plug Co Ltd Dye-sensitized solar cell and its manufacturing method
JP2009218179A (en) * 2008-03-12 2009-09-24 Ngk Spark Plug Co Ltd Dye-sensitized solar cells
JP2010021102A (en) * 2008-07-14 2010-01-28 Sharp Corp Dye-sensitized solar cell, manufacturing method therefor, and dye-sensitized solar cell module
KR20100098745A (en) * 2009-03-02 2010-09-10 주식회사 동진쎄미켐 Dye sensitized solar cell
JP2010211971A (en) * 2009-03-09 2010-09-24 Citizen Holdings Co Ltd Dye-sensitized solar cell and wrist watch equipped with the same
JP2012212615A (en) * 2011-03-31 2012-11-01 Sony Corp Method for manufacturing photoelectric conversion element, photoelectric conversion element, and electronic apparatus
US20150368414A1 (en) * 2012-10-17 2015-12-24 Mitsubishi Rayon Co., Ltd. Acrylic resin film, and laminate and solar cell module each of which uses same
JP6418515B2 (en) * 2014-03-31 2018-11-07 イムラ・ジャパン株式会社 electrode

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JP2007066875A (en) * 2005-08-02 2007-03-15 Ngk Spark Plug Co Ltd Dye-sensitized solar cell

Cited By (4)

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Publication number Priority date Publication date Assignee Title
USRE44330E1 (en) 1995-06-19 2013-07-02 Lifescan Inc. Electrochemical cell
USRE42567E1 (en) 1995-11-16 2011-07-26 Lifescan, Inc. Electrochemical cell
US8486243B2 (en) 2001-10-10 2013-07-16 Lifescan, Inc. Electrochemical cell
US8801907B2 (en) 2001-10-10 2014-08-12 Lifescan, Inc. Electrochemical cell

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