JP2012038602A - Dye-sensitized solar cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell which has both of high reliability and durability, and which has a high sealing property of an electrolyte solution inlet, thereby causing no swelling and deterioration at the seal portion for a long period of time.SOLUTION: A sealing plug 8 having a shape capable of closing an inlet Q for injecting an electrolyte solution 5 into a gap between a pair of electrode substrates A and B is fitted into the inlet Q. A photopolymerizable composition is applied on an upper side of the sealing plug 8, a cover glass 10 is overlapped, and they are irradiated with ultraviolet ray to form a seal material hardened body (end seal) 9.

Description

  The present invention relates to a dye-sensitized solar cell in which a pair of electrode substrates are sealed facing each other, and an electrolyte solution is sealed in a sealed gap, and the dye has a high electrolyte solution sealing property and excellent durability. The present invention relates to a sensitized solar cell.

A dye-sensitized solar cell in which a redox electrolyte solution is sealed between a transparent conductive substrate with a semiconductor film such as TiO ₂ on which a dye is supported and a counter electrode substrate has high conversion efficiency of sunlight. Promising as a low-generation solar cell.

  However, when a redox electrolyte such as iodine or lithium iodide is injected between a glass substrate or a plastic film substrate and sealed, ethylene-methacrylic acid conventionally used for sealing silicon solar cells is used. When a copolymerized ionomer resin is used as a sealing material, this type of dye-sensitized solar cell has a problem of poor durability because it cannot prevent leakage of the electrolyte solution and moisture absorption from the outside. .

  For this reason, it has been proposed to seal (seal) the electrolyte solution by using a liquid epoxy resin or a silicone resin instead of the ethylene-methacrylic acid copolymerized ionomer resin (see Patent Document 1). Further, as a dye-sensitized solar cell sealing material using an elastomer having excellent electrolyte solution resistance, a polysilane containing a silane coupling agent and containing at least one alkenyl group capable of hydrosilylation in a molecule. A sealing material obtained by polymerizing an isoprene-based polymer and an organohydrogenpolysiloxane with a hydrosilylation catalyst has been proposed (see Patent Document 2). On the other hand, the inventors of the present invention also have one or more (at least one end of molecular end) as a photo-curing (ultraviolet-curing) type sealing material that does not swell or deteriorate in long-term sealing and has extremely high sealing performance. A dye-sensitized solar cell using a photopolymerizable composition containing a hydrogenated elastomer derivative having a (meth) acryloyl group as an essential component as a sealing material has been proposed (see Patent Document 3).

JP 2000-30767 A JP 2004-95248 A JP 2008-140759 A

  However, although all of the above-mentioned sealing materials are heat-cured or photo-cured, the cured product is excellent in electrolyte solution resistance. However, when sealing the inlet into which the electrolyte solution is injected (end seal), the sealing material is Since it is uncured, depending on the solvent used in the electrolyte solution, there is a concern that the components of the sealing material may elute into the electrolyte solution. Since the eluted sealing material component reduces the ionic conductivity of the electrolyte solution, there is a possibility of causing problems in the solar cell, such as a decrease in power generation efficiency of the solar cell and leakage of the electrolyte solution itself, Further improvements are required.

  The present invention has been made in view of such circumstances, and the sealing performance of the electrolyte solution inlet is extremely high, and the sealing portion does not swell or deteriorate over a long period of time, and has high reliability and durability. The object is to provide a dye-sensitized solar cell having both properties.

  In order to achieve the above object, the dye-sensitized solar cell of the present invention has a pair of electrode substrates each provided with an electrolyte solution injection port in at least one electrode substrate, with the conductive electrode surfaces facing each other. The gap between the pair of electrode substrates is sealed by disposing a sealing material on the peripheral edge of the inner side surface of the substrates, and the electrolyte solution is sealed in the sealed gap. The gist of the present invention is that the sealing plug is inserted into the electrolyte solution inlet.

  That is, the present inventors have repeated research in order to obtain a dye-sensitized solar cell having excellent power generation efficiency and high durability. Among them, problems such as a decrease in power generation efficiency and leakage of the electrolyte solution are caused by placing an uncured sealing material on the injection port of the electrolyte solution and placing a thin glass on which it is sealed. When sealing the sealing material by irradiating it with ultraviolet rays or the like, it was conceived that the sealing material before curing was eluted into the electrolyte solution. Therefore, further research has been conducted on whether or not the electrolyte solution inlet can be sealed by a method other than applying an uncured sealing material. As a result, when a sealing plug molded in a shape that can close the injection port is inserted into the injection port and sealed, the components of the uncured sealing material do not elute into the electrolyte solution, and the sealing property Has been found to be high, leading to the present invention. That is, according to the present invention, conventionally, after sealing an electrolyte solution injection port, an uncured sealing material is applied so as to close the injection port, and then a thin glass for sealing it is placed thereon. When it was common sense to cure and seal the sealing material, it was made by breaking this common sense.

  Thus, the dye-sensitized solar cell of the present invention is a dye-sensitized solar cell in which an electrolyte solution is sealed in a gap between a pair of sealed electrode substrates, and at least one of the electrode substrates In this structure, a sealing plug is fitted into the electrolyte solution inlet provided in the container. Therefore, since the uncured sealing material does not come into contact with the inlet as in the prior art, the components of the uncured sealing material do not elute into the electrolyte solution. Therefore, the ionic conductivity of the electrolyte solution does not decrease, and it is possible to suppress the occurrence of problems such as a decrease in power generation efficiency of the solar cell and the cause of leakage of the electrolyte solution itself. That is, the dye-sensitized solar cell of the present invention has an extremely high sealing performance at the electrolyte solution inlet, and does not swell or deteriorate in the sealing portion over a long period of time, and has high reliability and durability. It will be something that combines.

  Further, a transparent sealing plate is stacked on the upper side of the sealing plug via a sealing material, and the electrolyte solution injection port is doubled between the sealing plug and the transparent sealing plate via the sealing material. When sealed, the sealing plug can be effectively prevented from falling off when an impact is applied from the outside. Even if electrolyte solution leaks from the gap between the sealing plug and the injection port, the sealing plug can be sealed. Since the leakage to the outside can be prevented by the stopper and the transparent sealing plate portion via the sealing material, it has both higher reliability and durability.

  And when the said sealing plug is a sealing plug made of a thermoplastic resin, since it is manufactured with dimensional accuracy by injection molding, extrusion molding, etc., there is no gap when the sealing plug is inserted into the injection port. It does not occur and leakage of the electrolyte solution can be further prevented.

  Furthermore, when the sealing plug is a polytetrafluoroethylene sealing plug, the sealing plug is chemically stable and excellent in heat resistance and chemical resistance, so that the components can be eluted into the electrolyte solution. In addition to being able to prevent more effectively, the deterioration of the sealing plug due to the electrolyte solution can also be more effectively prevented.

It is sectional drawing of one Example of this invention. It is explanatory drawing of the electrode substrate A used for the said Example. It is explanatory drawing of the electrode substrate B used for the said Example. It is explanatory drawing of the process of obtaining the said Example. (A) is explanatory drawing which shows the principal part of the said Example, (b), (c) is explanatory drawing of the modification of the said principal part. It is sectional drawing which shows a prior art example.

  Next, an embodiment for carrying out the present invention will be described.

  FIG. 1 is a cross-sectional view of a dye-sensitized solar cell according to an embodiment for carrying out the present invention. 1 and 1 ′ are glass substrates, 2 and 2 ′ are conductive electrode films, 3 is a titanium oxide film, 4 Is a sensitizing dye adsorbed on the titanium oxide film, 5 is an electrolyte solution, 6 is a platinum deposition film, 7 is a cured sealant (main seal), 8 is a sealing plug for sealing the electrolyte solution inlet, and 9 is A sealing material hardened body (end seal), 10 is a cover glass. A is a negative electrode substrate having the above 1, 2, 3 and 4, and B is a positive electrode substrate having 1 ', 2' and 6.

  Such a dye-sensitized solar cell can be obtained, for example, as follows. First, as shown in FIG. 2, a negative electrode substrate A (hereinafter referred to as “electrode substrate A”) in which a titanium oxide film 3 adsorbing a sensitizing dye 4 is formed on the upper surface of a conductive electrode film 2 on a glass substrate 1. And a (meth) acryloxyalkylsilane silane coupling agent is applied to the portion S on the conductive electrode film 2 in contact with the main seal 7 (see FIG. 1) to perform surface coating treatment. On the other hand, as shown in FIG. 3, a positive electrode substrate B (hereinafter referred to as a platinum deposition film 6) formed by vapor deposition on the upper surface of the conductive electrode film 2 ′ on the glass substrate 1 ′ disposed opposite to the electrode substrate A. The electrode substrate B is provided with an inlet Q for the electrolyte solution 5 and a peripheral portion of the inlet Q [part S ′ in contact with the end seal 9 (see FIG. 1)]. In the same manner as described above, a (meth) acryloxyalkylsilane silane coupling agent is applied to the portion S ″ in contact with the main seal 7 (see FIG. 1) to perform surface coating treatment. Then, a photopolymerizable composition comprising a hydrogenated elastomer derivative having at least one (meth) acryloyl group as an essential component on at least one of both molecular terminals, which is an uncured product of the main seal 7 prepared in advance. The at least one of the electrode substrates A and B is applied to the predetermined portion subjected to the surface coating treatment. Then, using the polyimide tape as a spacer, with the conductive electrode films 2 and 2 ′ inside, as shown in FIG. The resulting uncured product (photopolymerizable composition) is irradiated with ultraviolet rays to form a cured seal material (main seal) 7 and the electrode substrates A and B are bonded together.

  Next, the electrolyte solution 5 is injected into the gap R (see FIG. 4) between the bonded electrode substrates A and B from the injection port Q. After the injection is completed, a polytetrafluoroethylene sealing plug 8 manufactured by injection molding having a shape capable of closing the injection port Q is fitted into the injection port Q. Then, the same photopolymerizable composition as that used for forming the main seal 7 is applied, and the cover glass 10 is stacked thereon. In the same manner as described above, the photopolymerizable composition is irradiated with ultraviolet rays to form a cured seal material (end seal) 9, and the injection port Q is covered with the sealing plug 8 and the cured seal material 9. By double sealing with glass 10, the dye-sensitized solar cell shown in FIG. 1 can be obtained (return to FIG. 2).

  According to this configuration, due to the presence of the sealing plug 8, the uncured end seal 9 (photopolymerizable composition) before irradiation with ultraviolet rays does not come into contact with the electrolyte solution 5, so that the components of the photopolymerizable composition are It does not elute into the electrolyte solution 5. Therefore, the ionic conductivity of the electrolyte solution 5 does not decrease due to the elution of the components of the photopolymerizable composition, and the decrease in power generation efficiency of the dye-sensitized solar cell can be suppressed. Moreover, since unnecessary components are not included in the electrolyte solution 5, leakage of the electrolyte solution 5 can be prevented. Since the sealing plug 8 is manufactured by injection molding with high dimensional accuracy, there is no gap between the sealing plug 8 and the sealing plug 8 made of polytetrafluoroethylene. In addition to being excellent in heat resistance and chemical resistance, it is possible to prevent the elution of the components into the electrolyte solution 5 and to effectively prevent the sealing plug 8 from being deteriorated by the electrolyte solution 5, so that the dye-sensitized solar cell It is possible to extend the service life. Furthermore, since the end seal 9 is made of a photopolymerized cured body, heat curing is not required, and there is no problem associated with evaporation of the electrolyte solution 5 due to heating. And since the said photopolymerization hardening body consists of a special photopolymerizable composition, the swelling and deterioration by the electrolyte solution 5 do not arise in the case of sealing over a long term. In addition, combined with the action of a specific silane coupling agent on the electrode substrates A and B, it exhibits high adhesive strength and develops high durability.

  The sealing plug 8 used in the present invention is made of polytetrafluoroethylene in the above example, but is not limited to this, and can be made of thermoplastic resin. Specifically, general-purpose plastics such as polyethylene, polypropylene, vinyl chloride, acrylic resin, polyethylene terephthalate, polyamide, polyacetal, polycarbonate, polybutylene terephthalate, ultrahigh molecular weight polyethylene, polyether ether ketone, polysulfone, polyarylate, polyether sal Examples include engineering plastics such as phonone, polyetherimide, polyphenylsulfone, and super engineering plastics, and fluorine resins such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride. Among these, polytetrafluoroethylene having excellent solvent resistance with respect to a redox electrolyte solution using an organic solvent is particularly preferably used.

  Further, in the above example, the shapes of the inlet Q and the sealing plug 8 are as shown in FIG. 5A. However, the shape is not limited to this, and the inlet Q and the sealing plug 8 are fitted with no gap so that the electrolyte solution 5 does not leak. It only has to match. For example, the shape shown in FIG. 5B makes it easy to fit the sealing plug 8 into the injection port Q, and the shape shown in FIG. 5C inserts the sealing plug 8 into the injection port Q. At the same time, leakage of the electrolyte solution 5 can be more effectively prevented.

  In the above example, the glass substrates 1 and 1 ′ are used as the base material of the electrode substrates A and B. However, organic substances such as plastic can be used instead of glass. Examples of the plastic include polyethylene, polypropylene, polyester, nylon, polyethylene terephthalate, polyethylene naphthalate, vinyl chloride, silicone resin, and polyimide.

  Further, in the above example, the (meth) acryloxy applied to the portions (S, S ′, S ″) of the electrode substrates A, B that are in contact with the respective cured sealing materials (main seal 7, end seal 9). Examples of the alkylsilane silane coupling agent include acryloxyalkylsilane and methacryloxyalkylsilane. Preferable examples include 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and more preferable example includes 3-acryloxypropyltrimethoxysilane having high photopolymerization reactivity. These (meth) acryloxyalkylsilane silane coupling agents may be used alone or in combination of two or more. And the surface coating process using these silane coupling agents is 0.01-5.0 weight% of the said (meth) acryloxyalkylsilane silane coupling agent in organic solvents, such as methanol and ethanol, for example. And is applied to the electrode substrate 1, 1 ′ portion (S, S ′, S ″) in contact with the main seal 7 and end seal 9 and heated in the range of 60 to 150 ° C. Done. When the electrode substrates A and B are firmly sealed only by the main seal 7 and the end seal 9, the surface coating treatment with the (meth) acryloxyalkylsilane silane coupling agent is unnecessary.

  And in said example, the photopolymerizable composition used as a material of sealing material hardening body (main seal) 7 and sealing material hardening body (end seal) 9 has a hydrogenated elastomer derivative as an essential component. The hydrogenated elastomer derivative only needs to have one or more (meth) acryloyl groups at at least one of both molecular ends. Among them, the main chain of the hydrogenated elastomer derivative is preferably made of hydrogenated polybutadiene or hydrogenated polyisoprene. In the present invention, the (meth) acryloyl group means at least one of the following acryloyl groups and methacryloyl groups corresponding thereto.

  Examples of the hydrogenated polybutadiene as the main chain of the hydrogenated elastomer derivative include hydrogenated 1,4-polybutadiene, hydrogenated 1,2-polybutadiene, hydrogenated 1,4-polybutadiene and hydrogenated 1,2-polybutadiene. And the like. Examples of the hydrogenated polyisoprene include hydrogenated 1,4-polyisoprene, hydrogenated 1,2-polyisoprene, hydrogenated 1,4-polyisoprene and hydrogenated 1,2-polyisoprene. For example, coalescence.

  As the hydrogenated elastomer derivative, more preferably, a hydrogenated polybutadiene derivative obtained by reacting a hydrogenated polybutadiene polyol or hydrogenated polyisoprene polyol with a hydroxy (meth) acrylate compound with a polyisocyanate as a linking group, or There are hydrogenated polyisoprene derivatives. Further, there may be mentioned a hydrogenated polybutadiene derivative or a hydrogenated polyisoprene derivative obtained by reacting a hydrogenated polybutadiene polyol or hydrogenated polyisoprene polyol with a (meth) acryloyl group-containing isocyanate compound.

  In addition to the above, the photopolymerizable composition used as a material for the sealing material cured body (main seal) 7 and the sealing material cured body (end seal) 9 includes a layered silicate, an insulating spherical inorganic filler, (Meth) acrylate compounds, photopolymerization initiators, antioxidants, antifoaming agents, surfactants, colorants, inorganic fillers, organic fillers, various spacers, solvents, etc. are appropriately blended as necessary. be able to. These may be used alone or in combination of two or more.

  After the photopolymerizable composition thus obtained is applied to a predetermined location, it is cured by, for example, irradiating ultraviolet rays with a UV lamp or the like and performing post-curing at a predetermined temperature as required. The cured seal material (main seal) 7 and the cured seal material (end seal) 9 are obtained.

  The liquid layer of the electrolyte solution 5 and the cured seal material (main seal) 7 of the dye-sensitized solar cell shown in FIG. 1 have an appropriate thickness (between substrates) and width according to the purpose and application. The thickness is usually about 50 to 500 μm and the width is about 1 to 5 mm.

  Next, examples will be described together with comparative examples. However, the present invention is not limited to this.

  First, prior to the examples, materials for each component shown below were prepared.

[Photopolymerizable composition comprising, as an essential component, a hydrogenated elastomer derivative having at least one (meth) acryloyl group at at least one of both molecular ends]
As a hydrogenated elastomer derivative, 2 g of the following hydrogenated elastomer derivative a, 8 g of dimethylol dicyclopentane diacrylate (tricyclodecane dimethanol diacrylate), and 0.5 g of a radical photopolymerization initiator were blended to perform photopolymerization. A sex composition was prepared.

[Hydrogenated elastomer derivative a]
Hydrogenated polybutadiene having hydroxyl groups at both ends represented by the following general formula (1) (number average molecular weight: about 1500, hydroxyl value: 75 KOH mg / g, iodine value: 10I 2 mg / 100 g, viscosity 30 Pa · s / 25 ° C.) 15 g (0.01 mol), 10.2 g (0.05 mol) of norbornene diisocyanate, and 20 g of toluene were each taken in a glass reactor and heated to 50 ° C. under a nitrogen gas stream. Thereafter, 0.4 g of an ethyl acetate solution of 5% by weight dibutyltin laurate was added and reacted at 50 ° C. for 6 hours. Thereafter, 0.001 g of hydroquinone and 20.7 g (0.09 mol) of 2-hydroxy-1,3-dimethacryloxypropane (glycerin dimethacrylate) were added, and the mixture was further reacted at 60 ° C. for 6 hours. Next, the reaction product was put into excess acetonitrile and stirred for washing, and after solid-liquid separation, the desired hydrogenated elastomer derivative a was obtained by drying under reduced pressure. According to the Fourier transform infrared spectrometer (FT-IR: manufactured by Thermo Electron, Nicolet IR200), the obtained reaction product disappeared from the characteristic absorption band (near 2260 cm-1) derived from the isocyanate group, The standard polystyrene equivalent weight average molecular weight measured by a permeation chromatograph (GPC: manufactured by Tosoh Corporation, HLC-8120) was 6150.

(Electrolyte solution)
An electrolyte solution of acetonitrile solvent containing I ₂ (0.1M), LiI (0.5M), 4-t-butylpyridine (0.5M) was prepared.

[Lamination of electrode substrate]
As shown in FIG. 2, the main seal 7 is disposed on a portion S of a substrate 1 (size: 26 mm × 76 mm × thickness 1.3 mm) made of a borosilicate glass plate provided with a fluorine-doped transparent conductive electrode film 2. A titanium oxide paste was screen printed on the entire inner surface. Thereafter, the substrate 1 was calcined 1 hour at 500 ° C., TiO ₂ semiconductor film 3 having a thickness of 8~12μm was produced an electrode substrate A provided on the conductive electrode film 2. Next, the electrode substrate A was immersed in an ethanol solution of a ruthenium-based sensitizing dye (manufactured by Solaronix, ruthenium 535 dye) for one day and washed with anhydrous ethanol to adsorb the dye 4 to the semiconductor film 3. Furthermore, a 1 wt% methanol solution of 3-acryloxypropyltrimethoxysilane is applied to a portion S of the electrode substrate A where the main seal 7 is to be disposed, dried at 100 ° C. for 10 minutes, and surface coated. A was prepared.
On the other hand, as shown in FIG. 3, an electrode substrate B provided with a fluorine-doped transparent conductive electrode film 2 with a platinum film 6 on a substrate 1 ′ made of borosilicate glass having the same size as described above was prepared. The electrode substrate B is provided with two injection ports Q for the electrolyte solution 5 of 2 mmΦ with a diamond drill, and then the peripheral edge S ′ (portion in contact with the end seal 9) of the injection port Q of the electrode substrate B and the main seal 7. A 1 wt% methanol solution of 3-acryloxypropyltrimethoxysilane was applied to the portion S ″ to be disposed, and dried at 100 ° C. for 10 minutes to prepare a surface-coated electrode substrate B.
The electrode substrate A and the electrode substrate B are used with spacers made of polyimide tape having a thickness of 50 μm, with the conductive electrode surfaces facing each other, so that the electrode substrates A and B are kept at a distance of 50 μm. Then, the photopolymerizable composition was applied, and both were superposed. And the said photopolymerizable composition was UV-cured on condition of 3000 mJ / cm of integrated light quantity under nitrogen stream, and both A and B were bonded together.

[Example 1]
In the electrode substrates A and B bonded together as described above, the prepared electrolyte solution 5 is inserted into the gap R between the electrode substrates A and B from the injection port Q of the electrode substrate B, and a 0.4 mmφ needle (injection needle) is provided. It inject | poured using the attached syringe (syringe). After the injection was completed, the needle was pulled out from the injection port Q. Instead, a sealing plug 8 made of polytetrafluoroethylene resin was fitted into the injection port Q, and the injection port Q was sealed. Thereafter, a photopolymerizable composition similar to that used when the electrode substrates A and B are bonded is further applied to the upper side and the peripheral edge of the sealing plug 8, and a cover glass 10 is placed thereon. Then, the photopolymerizable composition was UV-cured under the condition of an integrated light quantity of 3000 mJ / cm under a nitrogen stream to produce the dye-sensitized solar cell of the present invention.

[Example 2]
A dye-sensitized solar cell of the present invention was manufactured in the same manner as in Example 1 except that a fluorine rubber (manufactured by DuPont Elastomer, Viton) was used as the sealing plug 8.

Example 3
A dye-sensitized solar cell of the present invention was manufactured in the same manner as in Example 1 except that an acrylic thermoplastic elastomer (manufactured by Kuraray Co., Ltd.) was used as the sealing plug 8.

[Comparative Example 1]
A dye-sensitized solar cell was manufactured in the same manner as in Example 1 except that the sealing plug 8 was not used.

  For the dye-sensitized solar cells of Examples 1 to 3 and Comparative Example 1 thus obtained, the following tests were conducted in order to evaluate the electrolyte solution filling retention rate and the leakage location of the electrolyte solution 5. went. Moreover, evaluation was performed according to the following criteria, and the results are also shown in [Table 1] below.

〔Test method〕
The products of Examples 1 to 3 and the product of Comparative Example 1 were left in a high-temperature dryer at 60 ° C. or 85 ° C. for 500 hours, respectively.

[Electrolytic solution filling retention]
About Example 1-3 goods and Comparative Example 1 goods, the filling area of the electrolyte solution 5 when it sees from an upper surface is measured twice immediately after manufacture and after a test, and the filling area after a test with respect to the filling area immediately after manufacture Was calculated as the electrolyte solution filling retention rate. The electrolyte solution filling retention rate is 100% when there is no leakage of the electrolyte solution 5, and the numerical value decreases as the degree of leakage increases. This is calculated in this way because when the electrolyte solution 5 leaks, there is a space in the interior corresponding to the leak, and there is no electrolyte solution 5 in this portion, and the filling area of the electrolyte solution 5 decreases.

[Leakage location]
For the products of Examples 1 to 3 and the product of Comparative Example 1, after the test, whether or not the electrolyte solution 5 leaked was visually observed, and if there was a leak, the location was indicated.

  From the results in Table 1, it can be said that all of the products of Examples 1 to 3 have a very high electrolyte solution filling retention rate (100%) and there is no leakage of the electrolyte solution 5. On the other hand, although the product of Comparative Example 1 has no problem at 65 ° C., the electrolyte solution filling retention rate is slightly lowered when left at 85 ° C. for 500 hours, and the leakage location can be visually confirmed. I knew it was possible.

Example 4
In Example 1, the electrode substrate A and B are not subjected to surface coating treatment with a 1 wt% methanol solution of 3-acryloxypropyltrimethoxysilane, and the cover glass 10 coated with the photopolymerizable composition is not placed. When a dye-sensitized solar cell was manufactured and evaluated in the same manner, an evaluation almost equivalent to that of the product of Example 1 was obtained. However, the product of Example 1 was slightly superior when left at 85 ° C. for over 500 hours.

  As described above, each of the products of the examples can completely seal the inlet Q of the electrolyte solution 5, and the sealing material cured body (main seal) 7, the sealing material cured body (end seal) 9, and the sealing material. The stopper plug 8 has high electrolyte solution resistance and adhesiveness. Therefore, the dye-sensitized solar cell of the present invention is extremely excellent to withstand long-term storage and long-term use.

  INDUSTRIAL APPLICABILITY The present invention can be used for a dye-sensitized solar cell that has high electrolyte liquid sealing properties and excellent durability.

5 Electrolyte liquid 8 Seal plug 9 Sealing material cured body 10 Cover glass A Negative electrode substrate B Positive electrode substrate Q Inlet

Claims (4)

  A pair of electrode substrates provided with electrolyte solution inlets in at least one of the electrode substrates are disposed at a predetermined interval with the conductive electrode surfaces facing each other, and the gap between the pair of electrode substrates is A dye-sensitized solar cell that is sealed by disposing a sealing material on the peripheral edge of the inner side surface of the substrate, and in which the electrolyte solution is sealed in the sealed gap, the electrolyte solution inlet A dye-sensitized solar cell, wherein a sealing plug is inserted into the solar cell.   A transparent sealing plate is stacked on the upper side of the sealing plug via a sealing material, and the inlet for the electrolyte solution is double sealed with the sealing plug and the transparent sealing plate via the sealing material. The dye-sensitized solar cell according to claim 1.   The dye-sensitized solar cell according to claim 1 or 2, wherein the sealing plug is a thermoplastic resin sealing plug.   The dye-sensitized solar cell according to any one of claims 1 to 3, wherein the sealing plug is a polytetrafluoroethylene sealing plug.

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