JP2010080275A - Dye-sensitized solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell having no injection hole while suppressing degradation caused by heat in heat sealing without applying load to an electrode substrate in manufacturing. <P>SOLUTION: The dye-sensitized solar cell is formed by laminating a photoelectrode substrate formed by providing at least part of a support body including a transparent conductive film, with an oxide semiconductor layer carrying coloring matter, and a counter electrode substrate facing the oxide semiconductor layer, through an electrolyte layer. The photoelectrode substrate, the electrolyte layer and the counter electrode substrate are sealed in a sealed bag body with the peripheral edge parts of a pair of base material sheets being bonded to each other, and at least part of the photoelectrode substrate and at least part of the counter electrode substrate are projected from the sealed bag body. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a dye-sensitized solar cell, and more particularly to a dye-sensitized solar cell having an electrolyte injection hole.

  In recent years, environmental problems such as global warming have been pointed out worldwide, and solar power generation has attracted attention as clean energy with a low environmental load, and active research and development of solar cell elements has been promoted. As solar cells, single crystal silicon solar cells, polycrystalline silicon solar cells, amorphous silicon solar cells, compound semiconductor solar cells, etc. have already been put into practical use, but there are problems in manufacturing costs and energy consumption at the manufacturing stage is large. Such a problem has been pointed out. From such a viewpoint, a dye-sensitized solar cell has begun to attract attention as a novel solar cell that can be manufactured at a relatively low cost and can reduce energy consumption at the manufacturing stage.

  In general, a dye-sensitized solar cell includes a transparent substrate, a transparent electrode (first electrode layer), an oxide semiconductor layer carrying a dye sensitizer, an electrolyte layer made of an electrolyte, from the light incident side, And the counter electrode board | substrate provided with the 2nd electrode layer has the cell structure laminated | stacked in order. The electrolyte layer is filled with an electrolytic solution.

  In a dye-sensitized solar cell, the electrolyte is formed with a hole in either the counter electrode substrate or the transparent electrode substrate, and the periphery of the second electrode substrate and the transparent electrode substrate is sealed with an adhesive or the like Then, it is generally filled by a method of injecting from the hole (Japanese Patent Laid-Open No. 2004-319112: Patent Document 1). However, when the solar cell is used for a long time, the electrolytic solution may be depleted, and the photoelectric conversion efficiency may be significantly reduced due to the depletion of the electrolytic solution. Moreover, since the electrolyte solution containing the organic solvent leaks from the solar cell when the solar cell is damaged, a safety problem has been pointed out.

  To solve this problem, a method has been proposed in which an electrolytic solution is made into a paste and applied directly onto a transparent electrode (International Publication WO2005 / 006482: Patent Document 2). However, when adopting a method of applying the electrolytic solution in a paste, it may be difficult to strictly control the filling amount of the electrolytic solution.

In JP 2007-335228 A (Patent Document 3), after leaving a part of the transparent electrode substrate and the counter electrode substrate, the peripheral portion thereof is heat-sealed to form a bag shape, and the electrolyte is injected from the non-sealed portion. A solar cell has been proposed in which an electrolyte can be injected without providing a hole by sealing the non-sealed portion and leakage of the electrolyte can be suppressed.
JP 2004-319112 A International Publication WO2005 / 006482 JP 2007-335228 A

  However, if the peripheral portions of the transparent electrode substrate and the counter electrode substrate are sealed to form a bag shape, the electrode substrate is bent and bent due to the thickness of the electrolyte, separator, and the like filled therein. In particular, since the transparent electrode substrate is generally formed using a transparent electrode material such as ITO, the electrode may be cracked due to bending or distortion of the transparent electrode substrate.

  In addition, the electrodes themselves may be thermally deteriorated by heat when the peripheral portions of both electrode substrates are heat sealed, leading to a decrease in photoelectric efficiency.

  Accordingly, an object of the present invention is to provide a dye-sensitized solar cell having no injection hole, in which an electrode substrate is not loaded during manufacture and deterioration due to heat during heat sealing can be suppressed. .

  Another object of the present invention is to provide a method for producing a dye-sensitized solar cell, in which a load is not applied to an electrode substrate during production, and deterioration due to heat during heat sealing can be suppressed.

The dye-sensitized solar cell according to the present invention includes a photoelectrode substrate in which an oxide semiconductor layer carrying a dye is provided on at least a part of a support having a transparent conductive film, and the oxide semiconductor layer. A counter electrode substrate is a dye-sensitized solar cell laminated via an electrolyte layer so as to face each other,
The photoelectrode substrate, the electrolyte layer, and the counter electrode substrate are enclosed in a sealed bag body in which peripheral portions of a pair of base material sheets are bonded to each other,
At least a part of the photoelectrode substrate and at least a part of the counter electrode substrate protrude from the sealed bag body.

In addition, a method for producing a dye-sensitized solar cell according to another aspect of the present invention includes an oxide having a dye supported on at least a part of a support provided with a transparent conductive film between a pair of substrate sheets. Superposing a photoelectrode substrate provided with a semiconductor layer and a counter electrode substrate so as to face the oxide semiconductor layer;
Forming a non-sealed bag by adhering the peripheral edges of the pair of base material sheets to each other, leaving a part thereof;
Filling the electrolyte solution into the non-sealed bag body from the opening portion to which the base material sheets are not bonded, and bonding the base sheet peripheral edge of the opening portion to form a sealed bag body, It is characterized by comprising.

  Furthermore, in the present invention, a dye-sensitized solar cell module in which a plurality of the dye-sensitized solar cells are connected, and a photoelectrode substrate protruding from the sealed bag body of one of the dye-sensitized solar cells, There is also provided a dye-sensitized solar cell module in which the counter electrode substrate protruding from the sealed bag body of the other dye-sensitized solar cell is connected to each other.

  In the present invention, since it is an electrolyte-sealed dye-sensitized solar cell having no injection hole, the electrolyte does not run out and does not leak during use. In addition, even when a sealed dye-sensitized solar cell is manufactured, the electrode substrate is not loaded, so that the electrode substrate can be prevented from being damaged. Furthermore, when the sealed dye-sensitized solar cell is manufactured by heat-sealing the base material sheet, the electrode substrate itself is not heated, so that thermal degradation of the electrode substrate can be suppressed.

  Also, when directly heat-sealing the photoelectrode substrate and the counter electrode substrate, as suggested in Japanese Patent Application Laid-Open No. 2007-335228, considering the heat resistance and thermal degradation of the electrode substrate, the heat seal temperature is as low as possible. However, in the present invention, in order to heat-seal the peripheral edge of the base sheet in order to form a bag made of a pair of base sheets, heat is directly applied to the photoelectrode substrate and the counter electrode substrate. Since there is no influence, heat sealing can be performed at a relatively high temperature, and a bag body having high sealing properties can be formed. As a result, it is possible to realize a dye-sensitized solar cell that has high durability and can prevent leakage of the electrolytic solution.

<Dye-sensitized solar cell>
The dye-sensitized solar cell according to the present invention will be described below with reference to the drawings.

  FIG. 1 is a schematic sectional view of a dye-sensitized solar cell according to the present invention. The dye-sensitized solar cell according to the present invention includes a photoelectrode substrate 3 in which an oxide semiconductor layer carrying a dye is provided on at least a part of a support having a transparent conductive film, and the oxide semiconductor layer. The counter electrode substrate 2 has a structure in which the counter electrode substrate 2 is laminated via the electrolyte solution layer 4, and the photoelectrode substrate 3, the electrolyte solution layer 4, and the counter electrode substrate 2 are a pair of base material sheets. It has a structure in which 1, 5 peripheral portions are enclosed in a sealed bag body bonded to each other. Then, at least a part 9 of the photoelectrode substrate and at least a part 8, 9 of the counter electrode substrate 2 protrude from the sealed bag body. The two protruding portions 9 and 8 function as electrode terminals for taking out electromotive force from the solar cell to the outside.

  That is, in the dye-sensitized solar cell according to the present invention, the photoelectrode substrate including the electrolyte layer and the counter electrode substrate are arranged in a sealed bag body in which the peripheral portions of a pair of base material sheets are bonded, It does not have an electrolyte injection hole like a solar cell. Accordingly, the electrolytic solution is not leaked or depleted while using the solar cell, and photoelectric conversion can be performed stably over a long period of time. In addition, the injection method of electrolyte solution of the dye-sensitized solar cell having a structure having such injection holes will be described later.

  Further, as shown in FIG. 1, the portion of the photoelectrode substrate 3 where the oxide semiconductor layer and the electrolyte solution layer 4 are laminated has a thickness greater than the protruding portions 8 and 9. However, in this invention, only this thick part is covered with a pair of base material sheets 1 and 5, and the protrusion parts 9 and 8 without thickness go to the exterior of the bag body which consists of the base material sheets 1 and 5. It has an extended structure. By adopting such a structure, when manufacturing the dye-sensitized solar cell, even if pressure and heat are applied to the periphery of the base sheet, the photoelectrode substrate and the counter electrode substrate are not distorted. Can be prevented.

  FIG. 2 schematically shows a laminated structure of the dye-sensitized solar cell according to the present invention. The photoelectrode substrate 3 has a shape having a protruding portion 9 for taking out electromotive force to the outside. Although this protrusion part needs to protrude toward the exterior from the bag body which adhere | attached the peripheral part of a pair of base material sheets 1 and 5, and was sealed, the shape of protrusion part itself is as shown in FIG. It may be not only a rectangular shape but also a rod shape, and is not particularly limited.

  Moreover, this protrusion part 9 functions as an electrode for taking out electromotive force outside, and is formed by laminating | stacking a transparent electrode film | membrane on a support body.

  As described above, the photoelectrode substrate 3 has a structure in which a transparent electrode film is laminated on a support, but an oxide semiconductor layer carrying a dye is provided on at least a part of the photoelectrode substrate 3. Preferably, an oxide semiconductor layer is provided on the photoelectrode substrate 3 other than the protruding portion 9. And the part in which the oxide semiconductor layer was provided among the photoelectrode substrates 3 will be arrange | positioned in the bag body which consists of a pair of base material sheet.

  The counter electrode substrate 2 is disposed so as to face the oxide semiconductor layer of the photoelectrode substrate 3, and has a shape having a protruding portion 8 for taking out an electromotive force to the outside like the photoelectrode substrate 3. It is. Although this protrusion part needs to protrude toward the exterior from the bag body which adhere | attached the peripheral part of a pair of base material sheets 1 and 5, and was sealed, the shape of protrusion part itself is as shown in FIG. It may be not only a rectangular shape but also a rod shape, and is not particularly limited. Moreover, although the position of the protrusion is not particularly limited, it is preferable to dispose the protrusion at a location different from the position of the protrusion 9 of the photoelectrode substrate 3 in order to prevent a short circuit. For example, as shown in FIG. 2, the photoelectrode substrate 3 can be protruded from one side of a bag body made of a pair of base material sheets 1, 5, and the counter electrode substrate 2 can be protruded from the opposite side.

  The dye-sensitized solar cell according to the present invention has a structure in which a photoelectrode substrate 3 and a counter electrode substrate 2 are laminated via an electrolyte layer 4. This electrolytic solution layer may be composed only of the electrolytic solution, but in order to prevent the photoelectrode substrate 3 and the counter electrode substrate 2 from coming into direct contact and short-circuiting, both layers are laminated via an electrical insulating layer. Can do.

  Next, each member which comprises the dye-sensitized solar cell by this invention is demonstrated.

<Support>
The support for the photoelectrode substrate is usually the light-receiving surface of the dye-sensitized solar cell element. Therefore, the support is preferably excellent in light transmittance. In the present invention, the kind of the support is not particularly limited, and the same support as a general dye-sensitized solar cell element can be used. Specific examples thereof include glass, a non-plastic rigid material, and a film base material, but are not limited thereto. Examples of the rigid material include quartz glass, Pyrex (registered trademark), and a synthetic quartz plate. Examples of the film substrate include an ethylene / tetrafluoroethylene copolymer film, a biaxially stretched polyethylene terephthalate film, a polyethersulfone (PES) film, a polyetheretherketone (PEEK) film, and a polyetherimide (PEI). ) Film, polyimide (PI) film, polyester naphthalate (PEN), polycarbonate (PC) and other resin film base materials, among others, biaxially oriented polyethylene terephthalate film (PET), polyester naphthalate (PEN) Polycarbonate (PC) is preferred. The film substrate is excellent in processability and can reduce the manufacturing cost.

  Moreover, the said support body may be used individually by 1 type, and may laminate | stack and use 2 or more types.

  Although the thickness of a support body is not specifically limited, About 12-200 micrometers is preferable from a viewpoint of the intensity | strength of a support body and workability.

<Transparent electrode film>
The transparent electrode film is formed on the above support and has a function of collecting charges generated by light irradiation. Therefore, the transparent electrode film is preferably excellent in light transmittance and conductivity. In the present invention, the type and the like of the transparent electrode film are not particularly limited, and those similar to general dye-sensitized solar cell elements can be used.

The transparent electrode film is usually made of a metal oxide. Examples of the metal oxide include SnO ₂ , FTO (fluorine-doped tin oxide), ATO (antimony-doped tin oxide), ITO, and ZnO. Of these, FTO and ITO are preferable. This is because FTO and ITO are excellent in light transmission and conductivity.

  The transparent electrode film may have a single layer structure or a multilayer structure. As the transparent electrode film having a multilayer structure, for example, a layer in which layers having different work functions are stacked, a layer in which different metal oxide layers are stacked, and the like can be exemplified.

  Although it does not specifically limit as thickness of the said transparent electrode film, For example, it is preferable to exist in the range of 5 nm-2000 nm, especially the range of 10 nm-1000 nm. If the thickness of the transparent electrode film is too small, sufficient conductivity may not be obtained. If the thickness of the transparent electrode film is too large, it may be difficult to form a homogeneous transparent electrode layer. Because there is.

<Oxide semiconductor layer>
The oxide semiconductor layer is formed on the transparent electrode film, and is generally a porous layer containing a dye sensitizer. In the present invention, the type and the like of the oxide semiconductor layer are not particularly limited, and those similar to general dye-sensitized solar cell elements can be used.

The oxide semiconductor layer usually contains metal oxide semiconductor fine particles. Examples of the metal oxide semiconductor fine particles include TiO ₂ , ZnO, SnO ₂ , ITO, ZrO ₂ , MgO, Al ₂ O ₃ , CeO ₂ , Bi ₂ O ₃ , Mn ₃ O ₄ , Y ₂ O ₃ , WO ₃ , Ta ₂ O ₅ , Nb ₂ O ₅ , La ₂ O _{3 and the} like, and TiO ₂ is particularly preferable. Since these metal oxide semiconductor fine particles are suitable for forming a porous oxide semiconductor layer, they are preferably used. The metal oxide semiconductor fine particles may have a core-shell structure. Furthermore, the oxide semiconductor layer may be one using the metal oxide semiconductor fine particles, or may be two or more types.

  The particle size of the metal oxide semiconductor fine particles is not particularly limited, but is preferably in the range of, for example, 1 nm to 10 μm, and more preferably in the range of 10 nm to 1000 nm. If the particle size of the metal oxide semiconductor fine particles is too small, the respective metal oxide semiconductor fine particles may aggregate to form secondary particles. If the particle size of the metal oxide semiconductor fine particles is too large, the oxide semiconductor This is because the layer may be thickened and the film resistance may be increased.

  On the other hand, the oxide semiconductor layer usually carries a dye sensitizer. The dye sensitizer is not particularly limited, and examples thereof include organic dyes and metal complex dyes. Specific examples of the organic dyes include acridine dyes, azo dyes, indigo dyes, quinone dyes, coumarin dyes, merocyanine dyes, and phenylxanthene dyes. Of these, coumarin dyes are preferable. On the other hand, specific examples of the metal complex dye include a ruthenium dye, and among them, a ruthenium bipyridine dye and a ruthenium terpyridine dye, which are ruthenium complexes, are preferable.

  Although it does not specifically limit as thickness of the said oxide semiconductor layer, For example, it is preferable to exist in the range of 1 micrometer-100 micrometers, especially in the range of 5 micrometers-30 micrometers. If the thickness of the oxide semiconductor layer is too small, it may be difficult to form an oxide semiconductor layer having a uniform thickness, and the amount of light absorption decreases because the amount of dye absorption is reduced. On the other hand, if the thickness of the oxide semiconductor layer is too large, the film resistance of the oxide semiconductor layer may be increased.

<Electrolyte layer>
The electrolyte layer is provided between the oxide semiconductor layer described above and a counter electrode substrate described later. The electrolyte layer has a function of charge transport between the dye sensitizer carried on the oxide semiconductor layer and the counter electrode layer.

  As the electrolytic solution, the same one as a general dye-sensitized solar cell element can be used. Specifically, propylene carbonate, iodine, N-methylbenzimidazole, guanidinium thiocyanate, lithium iodide. An electrolytic solution in which is dissolved can be preferably used.

  The electrolyte layer contains a redox couple. Examples of the oxidation-reduction pair include iodine-iodine compounds and bromine-bromine compounds used in the dye-sensitized solar cell electrolyte as described above.

  The form of the electrolyte layer is not particularly limited as long as it can perform charge transport, and a liquid form, a solid form, or a semisolid form can be used. In the case where the electrolyte layer is made of a liquid electrolyte, it is preferable to dispose the electrical insulating layer between the oxide semiconductor layer and the counter electrode substrate in order to prevent a short circuit due to contact between the photoelectrode substrate and the counter electrode substrate.

  As the electrical insulating layer, those used for general dye-sensitized solar cells can be used, and for example, Hypore (Asahi Kasei Chemicals) and the like can be preferably used. Moreover, you may use the separator generally used for the lithium ion battery as an electrically insulating layer.

<Counter electrode substrate>
The counter electrode substrate is provided to face the above-described oxide semiconductor layer. In the present invention, the type and the like of the counter electrode substrate are not particularly limited, and those similar to general dye-sensitized solar cell elements can be used. Further, as the counter electrode substrate, a material similar to that obtained by providing a transparent electrode film on the above-described support can be used. Furthermore, in the present invention, the counter electrode substrate preferably has a metal having a function as a catalyst layer, such as Pt, C, or a conductive polymer, on the surface of the oxide semiconductor layer.

  The dye-sensitized solar cell element used in the present invention is formed by laminating the above constituent members. The shape of the dye-sensitized solar cell element is not particularly limited, and examples thereof include a strip shape, a circular shape, and a spiral shape.

<Base material sheet>
Of the pair of substrate sheets, the substrate sheet on the photoelectrode substrate side is preferably formed from a transparent material. This is because the photoelectric efficiency is improved by using a material having a high light transmittance.

  The transparent material is not limited to a colorless and transparent material, and a colored transparent material may be used. A translucent material can also be used.

  Since the base sheet constitutes the outermost layer of the dye-sensitized solar cell, impact resistance to protect the packaging material and contents from external physical impact, and heat resistance to withstand heat sealing And a resin film or sheet having printability can be used.

  Specifically, it is preferable to use a film or sheet made of a resin such as polyester or polyamide from the viewpoint of mechanical characteristics, thermal characteristics, and the like.

  As the above-mentioned resin film or sheet, any of a stretched film stretched in a uniaxial direction or a biaxial direction can be used, but it is particularly preferable to use a film subjected to a biaxial stretching process. The heat resistance and impact resistance can be further improved.

  Although the thickness of a base film can be about 5-1000 micrometers, about 100-400 micrometers is preferable.

  In the present invention, the base sheet preferably has gas barrier properties. By having a gas barrier property, not only can the depletion of the electrolyte be suppressed, but also the entry of oxygen or the like from the outside can be suppressed, so that deterioration due to oxidation of the dye-sensitized solar cell can be suppressed.

  Examples of the base sheet material having gas barrier properties include resins such as polyvinylidene chloride resin, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer, polyamide resin, polyester resin, and the like. A base sheet made of these resins may be used, or a transparent base sheet in which sheets made of these resins are laminated may be used.

  As the base sheet made of the above resin, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used. It is preferable at an excellent point.

  In the present invention, the base sheet preferably has heat sealability. The heat-sealable base sheet is a material that can be melted by heat and fused to each other as long as it is transparent, and a melt-extruded resin layer or a synthetic resin film layer can be used. Specifically, a thermoplastic resin as described above can be used. Any transparent thermoplastic resin may be used, for example, low density polyethylene resin, medium density polyethylene resin, high density polyethylene resin, linear low density polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, ionomer resin, acrylic resin. Resin, ethylene-acrylic acid copolymer resin, ethylene-ethyl acrylate copolymer resin, ethylene-methacrylic acid copolymer resin, ethylene-propylene copolymer resin, methylpentene resin, polybutene resin, acid-modified polyolefin Resins such as resins and urethane resins can be used. In addition, the material of the outermost surface heat-sealed of a base material sheet should just be formed from the above heat-sealable resin, and the base material sheet laminated | stacked with the above gas barrier property sheets can be used conveniently.

<Method for producing dye-sensitized solar cell>
As shown in FIG. 2, the method for producing a dye-sensitized solar cell according to the present invention includes the above-described photoelectrode substrate 3 and counter electrode substrate 2 stacked between a pair of base material sheets 1 and 5. The non-sealed bag body is formed by bonding the peripheral edge portions 6 of the base material sheets 1 and 5 to each other leaving a part to form a non-sealed bag body. Filling the body with an electrolytic solution, and bonding the base sheet peripheral edge portion 7 of the opening portion to form a sealed bag body.

  In order to form a bag by bonding the peripheral portions of the base sheets, the base sheets are bonded to each other by bonding the peripheral portions. The bonding method is not particularly limited, and an adhesive such as a thermosetting resin or an ultraviolet curable resin can be used, or a heat sealing method can be used, but in the present invention, the heat sealing method is preferably used. . To heat-seal the peripheral edge 6 of the base sheet 1, 5, a method of laminating a normal packaging material, for example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a T-die extrusion It can be carried out by a molding method, a coextrusion lamination method, an inflation method, a coextrusion inflation method, or the like.

  In the present invention, the heat seal surface 6 may be subjected to, for example, corona treatment, ozone treatment, flame treatment, or other pretreatment. By such treatment, stronger adhesion can be realized.

  Examples of the adhesive layer include anchor coating agents such as polyester-based, isocyanate-based (urethane-based), polyethyleneimine-based, polybutadiene-based, and organic titanium-based materials, or polyurethane-based, polyacrylic-based, polyester-based, epoxy-based, and polyvinyl acetate. It is preferable to use anchor coating agents such as adhesives for laminating, cellulose, and the like, adhesives, and the like because of excellent interlayer adhesion.

  Specifically, as the anchor coat layer, for example, an organic titanium anchor coating agent, an isocyanate anchor coating agent, a polyethyleneimine anchor coating agent, a polybutadiene anchor coating agent, or the like can be used.

In the present invention, the above-described anchor coating agent can be used to form a primer layer by coating with a normal coating method such as gravure coating or roll coating. Further, examples of the coating ^{amount, 0.1g / m 2 ~3g / m} 2 position is preferred. Moreover, in order to raise the adhesive force, you may give a corona discharge process to such a formation surface side previously.

  In the above, as a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.

  The bag body is formed by stacking two base sheet sheets, and further heat-sealing the peripheral edge of the outer periphery in a heat-sealing form such as a three-side seal type, and having an opening in a part After forming the body first, as shown in FIG. 3, after injecting an electrolyte from the opening, the periphery of the base sheet of the opening is heat-sealed in the same manner as described above, thereby making a sealed bag. The body can be formed.

<Dye-sensitized solar cell module>
The dye-sensitized solar cell module according to the present invention has a structure in which a plurality of dye-sensitized solar cells are arranged and connected. Connection of each battery may be connected in series, or may be connected in parallel. For example, as shown in FIG. 4, a photoelectrode substrate 9 protruding from a sealed bag body of one dye-sensitized solar cell and a counter electrode substrate 8 protruding from the sealed bag body of the other dye-sensitized solar cell are provided. Can be connected to each other.

  Hereinafter, although an example and a comparative example explain the present invention still in detail, the present invention is not limited to these examples.

<Production of photoelectrode substrate>
On a support made of polyethylene terephthalate, ITO was vapor-deposited with a sputter to produce an ITO-PET substrate having a surface resistance of 20Ω / □. On this substrate, a titanium oxide paste (Nanoxide DL, manufactured by Solaronix) was applied with an applicator so as to have a film thickness of 10 μm to form an oxide semiconductor layer. Thereafter, the ITO-PET substrate provided with the oxide semiconductor layer was dried by heating at 120 ° C. for 10 minutes. After cooling, a ruthenium complex (manufactured by Soalronix) as a dye sensitizer is dissolved in a 1: 1 mixed solution of acetonitrile and tert-butyl alcohol so as to have a concentration of 3 × 10 ⁻⁴ mol / l. A solution was prepared, and the ITO-PET substrate provided with the oxide semiconductor layer was immersed in the solution for 24 hours to carry the sensitizing dye on the oxide semiconductor layer.

  The substrate is processed into a shape like that of the photoelectrode substrate 3 in FIG. 2, and only the protruding portions are removed from the oxide semiconductor layer by trimming, so that the ITO layer becomes the outermost surface and is used as an electrode outlet. A substrate was obtained.

<Production of counter electrode substrate>
A substrate obtained by sputtering platinum on an ITO-PET substrate similar to the above was processed into a shape like the counter electrode substrate 2 of FIG. 2 to obtain a counter electrode substrate.

<Preparation of electrolyte>
For 10 ml of propylene carbonate (made by Junsei Kagaku), iodine (made by Merck) 0.2 mol / l, N-methylbenzimidazole (made by Aldrich) 0.5 mol / l, guanidinium thiocyanate (made by Aldrich) 0.1 mol / l 1 and 2 mol / l of lithium iodide (manufactured by Wako) were dissolved to prepare an electrolytic solution.

<Cell assembly>
As the base material sheet 1 disposed on the photoelectrode substrate side, an ionomer resin having a thickness of 50 μm was used. Moreover, as the board | substrate sheet | seat 2 arrange | positioned at the counter-electrode board | substrate side, an aluminum foil (thickness 40 micrometers) and a polyethylene terephthalate film (thickness 125 micrometers) are laminated | stacked via a two-component curing type polyurethane-type adhesive agent, Then, aluminum foil A non-stretched polypropylene layer side of a 30 μm-thick CPP film (manufactured by FILAX) was used on the polyethylene terephthalate film surface not provided with a film.

  The counter electrode substrate was arranged on the base material sheet 2 so that the peripheral edge portion 0.5 cm of the base material sheet 2 became a margin. At this time, it arrange | positioned so that the protrusion part of a counter electrode board might protrude from the base material sheet 2. FIG. On this counter electrode substrate, a hypo (made by Asahi Kasei Chemicals Co., Ltd.) processed to 9 cm □ as a separator was disposed so as to have a margin of 0.5 cm from the peripheral edge of the base sheet 2. After the photoelectrode substrate obtained above was placed on this separator, a laminate was produced in which the base sheet 1 was placed thereon.

  Next, three sides of the base material sheet peripheral portion of the laminate were bonded to each other with a width of 0.5 cm using a heat sealer to form a bag having an opening on one side. The electrolyte solution was injected from the opening, and the opening was heat-sealed under vacuum to bond the base sheet together, thereby producing a sealed bag-shaped dye-sensitized solar cell.

<Performance evaluation of solar cells>
The photoelectric conversion efficiency was measured when the obtained solar cell was irradiated with light from the substrate sheet 2 side using AM1.5 and pseudo-sunlight (incident intensity 100 mW / cm ² ) as a light source. Conversion efficiency was measured by using a source measure unit (Keutley Model 2400) and measuring the current-voltage characteristics due to voltage application. As a result, the voltage was 0.6 V and the conversion efficiency was 2.04%.

<Production of solar cell module>
A solar cell similar to the solar cell obtained above was produced, and a projecting portion of one photoelectrode substrate and a projecting portion of the other counter electrode substrate were joined to produce a solar cell module connected in series.

  When the performance evaluation of the obtained solar cell module was performed in the same manner as described above, the voltage was 1.15V.

1 is a schematic cross-sectional view of a dye-sensitized solar cell according to the present invention. It is a figure which shows the laminated structure of the dye-sensitized solar cell by this invention. It is the figure which showed one embodiment of the process of inject | pouring electrolyte solution in the manufacturing method of the dye-sensitized solar cell by this invention. It is the figure which showed the dye-sensitized solar cell module of the structure which connected the some dye-sensitized solar cell.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material sheet 2 Counter electrode board 3 Photoelectrode board | substrate 4 Electrolyte layer 5 Base material sheet 6 The peripheral part (sealing part) of a base material sheet
7 Unheat-sealed part 8 Protruding part of counter electrode substrate 9 Protruding part of photoelectrode substrate

Claims (8)

A photoelectrode substrate in which an oxide semiconductor layer carrying a dye is provided on at least a part of a support including a transparent conductive film, and a counter electrode substrate so as to face the oxide semiconductor layer include an electrolyte solution. A dye-sensitized solar cell laminated through layers,
The photoelectrode substrate, the electrolyte layer, and the counter electrode substrate are enclosed in a sealed bag body in which peripheral portions of a pair of base material sheets are bonded to each other,
At least a part of the photoelectrode substrate and at least a part of the counter electrode substrate protrude from the sealed bag body.   The dye-sensitized solar cell according to claim 1, wherein the photoelectrode substrate and the counter electrode substrate protrude from an adhesive interface of the pair of base material sheets.   The dye-sensitized solar cell according to claim 1 or 2, wherein a base material sheet on the photoelectrode substrate side of the pair of base material sheets is transparent.   The dye-sensitized solar cell according to any one of claims 1 to 3, wherein the pair of substrate sheets is made of a sheet having gas barrier properties.   The dye-sensitized solar cell according to any one of claims 1 to 4, wherein the electrolyte layer is composed of an electrolyte solution and an electrical insulating layer.   The dye-sensitized solar cell according to any one of claims 1 to 5, wherein the pair of substrate sheets is made of a sheet having heat sealability. A method for producing the dye-sensitized solar cell according to any one of claims 1 to 6,
A photoelectrode substrate in which an oxide semiconductor layer carrying a dye is provided on at least a part of a support provided with a transparent conductive film between a pair of base material sheets, and the oxide semiconductor layer. So that the counter electrode substrate is overlaid,
Forming a non-sealed bag by adhering the peripheral edges of the pair of base material sheets to each other, leaving a part thereof;
Filling the electrolyte solution into the non-sealed bag body from the opening portion to which the base material sheets are not bonded, and bonding the base sheet peripheral edge of the opening portion to form a sealed bag body, A method comprising the steps of:   A dye-sensitized solar cell module in which a plurality of the dye-sensitized solar cells according to any one of claims 1 to 6 are connected, and protrudes from a sealed bag body of one of the dye-sensitized solar cells. A dye-sensitized solar cell module in which a photoelectrode substrate and a counter electrode substrate protruding from a sealed bag body of the other dye-sensitized solar cell are connected to each other.

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