JP5422224B2 - Photoelectric conversion element - Google Patents

Description

  The present invention relates to a photoelectric conversion element.

  As a photoelectric conversion element, a dye-sensitized solar cell has attracted attention because it is inexpensive and can provide high photoelectric conversion efficiency, and various developments have been made on dye-sensitized solar cells.

  In general, a dye-sensitized solar cell includes a working electrode, a counter electrode, a photosensitizing dye supported on the working electrode, a sealing portion that connects the working electrode and the counter electrode, and a working electrode, a counter electrode, and a sealing portion. And an electrolyte disposed in an enclosed space (hereinafter referred to as “cell space”) (for example, Patent Document 1 below).

JP 2007-265796 A

  However, the dye-sensitized solar cell described in Patent Document 1 described above has a problem that the electrolyte leaks and the photoelectric conversion efficiency decreases with time, particularly when used in a place where the ambient temperature changes greatly. Had.

  The present invention has been made in view of the above circumstances, and provides a photoelectric conversion element that can sufficiently suppress a decrease in photoelectric conversion efficiency over time even when used in a place where the ambient temperature changes greatly. With the goal.

  As a result of intensive studies to solve the above-mentioned problems, the inventors have given flexibility to at least one of the pair of electrodes by increasing the internal pressure of the cell space. It has been found that stress applied to the electrode is absorbed, and stress applied to the interface between the sealing portion and the flexible electrode can be relaxed. Further, the stress applied to the interface between the sealing portion and the flexible electrode in this way suppresses the bending of the annular fixing portion fixed to the sealing portion of the flexible electrode, or on the inner side of the fixing portion. It has been found that the peeling of the fixed part from the sealing part can be sufficiently suppressed by suppressing the bending of the adjacent movable part. Thus, the inventors have completed the present invention.

  That is, the present invention provides a photoelectric device comprising a pair of electrodes facing each other, a sealing portion that connects the pair of electrodes, an electrolyte that fills the cell space surrounded by the pair of electrodes and the sealing portion. In the conversion element, at least one of the pair of electrodes is a flexible electrode having flexibility, and the flexible electrode is an annular fixed portion fixed by the sealing portion. And a non-fixed part surrounded by the fixed part, the non-fixed part being adjacent to the inner periphery of the fixed part and an annular first movable part and a first movable part surrounded by the first movable part The photoelectric conversion element is configured by two movable parts, and the photoelectric conversion element includes a bending suppression unit that suppresses the bending of the fixed portion of the flexible electrode or the first movable part. .

  According to this photoelectric conversion element, when the ambient environmental temperature increases, the electrolyte expands and the internal pressure of the cell space increases. As a result, stress is applied from the electrolyte to the non-fixed portion of the flexible electrode. At this time, since the flexible electrode has flexibility, the non-fixed portion bends. As a result, the stress applied to the non-fixed part is absorbed, and the stress applied to the interface between the sealing part and the fixed part is relaxed. On the other hand, when the first movable part bends greatly, the fixed part tends to be greatly bent accordingly. At this time, in the photoelectric conversion element of the present invention, the bending of the fixed portion or the first movable portion is suppressed by the bending suppression means. As described above, according to the photoelectric conversion element of the present invention, it is possible to sufficiently suppress the peeling of the fixing portion from the sealing portion while relaxing the stress applied to the interface between the sealing portion and the fixing portion. As a result, according to the photoelectric conversion element, leakage of the electrolyte is effectively suppressed even when used in a place where the surrounding environmental temperature change is large, and a decrease in photoelectric conversion efficiency with time is sufficiently suppressed.

  In the photoelectric conversion element, the deflection suppressing unit includes a reinforcing portion having rigidity higher than that of the flexible electrode, and the reinforcing portion is on the opposite side of the electrolyte from the electrolyte. It is preferable that the fixing portion and the non-fixing portion are disposed so as to cover the fixing portion and at least the fixing portion.

  In this case, the reinforcing part is bonded to at least the fixing part, and the reinforcing part is more difficult to bend than at least the fixing part. For this reason, even if stress is applied to the non-fixed portion from the electrolyte, and the fixed portion tends to bend greatly, the bending of the fixed portion is sufficiently suppressed.

  Here, a part of the reinforcing part is a thick part having a thickness larger than the other part of the reinforcing part, and the thick part is preferably bonded to at least the fixing part. .

  In this case, in the reinforcing part, the thick part has higher rigidity than the other part. And this thick part adhere | attaches at least with a fixing | fixed part, and the thick part becomes much more difficult to bend than at least a fixing | fixed part. For this reason, even if stress is applied to the non-fixed part from the electrolyte, and the fixed part tries to bend greatly, the bending of the fixed part is more sufficiently suppressed.

  Here, it is preferable that the thick part covers at least a part of the fixed part and also covers the first movable part.

  In this case, the bending of the fixed part is sufficiently suppressed by the thick part. In addition, even if the non-fixed part is greatly bent and the first movable part moves to the side opposite to the electrolyte, the first movable part is brought into contact with the thick part, and the movement is restricted by the thick part. For this reason, compared with the case where the thick part has not covered the 1st movable part, peeling of the fixing | fixed part from a sealing part can be suppressed more fully.

  The thick part preferably covers the entire fixed part in addition to covering the first movable part.

  In this case, since the entire fixed part that is easily bent is covered with a thick part having rigidity higher than that of the fixed part, the bending suppression effect of the fixed part is more than when a part of the fixed part is covered with the thick part. And the separation of the fixing portion from the sealing portion is more sufficiently suppressed.

  Further, the deflection suppressing means has a reinforcing portion having higher rigidity than the flexible electrode, and the reinforcing portion is at least a part of the fixing portion on the side opposite to the electrolyte with respect to the flexible electrode. And at least a position facing the non-fixed portion, and may be bonded to at least the fixed portion.

  In this case, since the reinforcing portion has an opening at a position facing the non-fixed portion of the flexible electrode, even if the second movable portion moves to the side opposite to the electrolyte due to an increase in internal pressure of the cell space, the second movable portion The part can enter the opening. That is, the expandable volume of the cell space can be increased as compared with the case where the reinforcing portion does not have an opening. As a result, the stress concentration at the interface between the sealing portion and the fixing portion due to the increase in the internal pressure of the cell space can be sufficiently reduced as compared with the case where the reinforcing portion has no opening.

  Here, it is preferable that the reinforcing portion covers at least a part of the fixed portion and also covers the first movable portion.

  In this case, the bending of the fixed portion is sufficiently suppressed by the reinforcing portion. In addition, even if the non-fixed part is greatly bent and the first movable part moves to the side opposite to the electrolyte, the first movable part is brought into contact with the reinforcing part, and the movement is restricted by the reinforcing part. For this reason, peeling of the fixing part from the sealing part is more sufficiently suppressed.

  Here, in addition to covering the first movable part, the reinforcing part preferably covers the entire fixed part.

  In this case, since the entire fixing portion that is easily bent is covered with the reinforcing portion having higher rigidity than the fixing portion, the bending suppressing effect of the fixing portion is increased as compared with the case where a part of the fixing portion is covered with the reinforcing portion. And the peeling of the fixing part from the sealing part is more sufficiently suppressed.

  The bending suppression means has a reinforcing portion having rigidity higher than that of the flexible electrode, and the reinforcing portion is at least one of the first movable parts on the side opposite to the electrolyte with respect to the flexible electrode. It may be arranged so as to cover the part, and may be bonded to the first movable part.

  Further, the deflection suppressing means is disposed so as to cover the fixed portion and the non-fixed portion on the side opposite to the electrolyte with respect to the flexible electrode and presses the fixed portion or the first movable portion. May be provided.

In the present invention, the term “flexible electrode” means that both edges (5 mm width) of a sheet-like electrode of 50 mm × 200 mm in a 20 ° C. environment are fixed horizontally with a tension of 1 N, The maximum deformation rate of the deflection of the electrode when a load of 20 g weight is applied to the center of the electrode shall be greater than 20%. Here, the maximum deformation rate is the following formula:
Maximum deformation rate (%) = 100 × (maximum displacement / sheet electrode thickness)
The value calculated based on Therefore, for example, when a sheet-like electrode having a thickness of 0.04 mm is bent by applying a load as described above and the maximum deformation amount is 0.01 mm, the maximum deformation rate is 25%. It becomes a flexible electrode. Further, the “reinforcing part having higher rigidity than the flexible electrode” means that both edges on the long side (each having a width of 5 mm) for each of the 50 mm × 200 mm sheet-like reinforcing part and the electrode in an environment of 20 ° C. ), A load of 20 g weight is applied to the center, and the maximum deformation rate is calculated, the reinforcing portion having a maximum deformation rate smaller than that of the flexible electrode shall be said. Therefore, for example, when a load is applied to a plate-shaped reinforcing portion (for example, a glass plate) having a thickness of 4 mm and the maximum displacement of the reinforcing portion is 0.01 mm, the maximum deformation rate of the reinforcing portion is 2.5%. . In contrast, it is assumed that the maximum deformation rate of the sheet-like electrode is 25% as described above. In this case, the maximum deformation rate of the reinforcing portion is smaller than the maximum deformation rate of the sheet-like electrode. Therefore, the reinforcing portion has higher rigidity than the flexible electrode.

  ADVANTAGE OF THE INVENTION According to this invention, even if it uses in the place where the surrounding environmental temperature change is large, the photoelectric conversion element which can fully suppress a time-dependent fall of photoelectric conversion efficiency is provided.

It is sectional drawing which shows 1st Embodiment of the photoelectric conversion element of this invention. It is a top view which shows the photoelectric conversion element of FIG. It is a fragmentary sectional view which shows the 1st modification of the reinforcement part of FIG. It is a fragmentary sectional view which shows the 2nd modification of the reinforcement part of FIG. It is a fragmentary sectional view which shows the 3rd modification of the reinforcement part of FIG. It is sectional drawing which shows the 4th modification of the reinforcement part of FIG. It is sectional drawing which shows 2nd Embodiment of the photoelectric conversion element of this invention. It is a fragmentary sectional view which shows the 1st modification of the reinforcement part of FIG. It is a fragmentary sectional view which shows the 2nd modification of the reinforcement part of FIG. It is a fragmentary sectional view showing the 3rd modification of a reinforcement part of Drawing 7. It is a fragmentary sectional view which shows 3rd Embodiment of the photoelectric conversion element of this invention. It is a fragmentary sectional view which shows 4th Embodiment of the photoelectric conversion element of this invention. It is a fragmentary sectional view which shows 5th Embodiment of the photoelectric conversion element of this invention. It is a fragmentary sectional view which shows 6th Embodiment of the photoelectric conversion element of this invention. It is a top view which shows the modification of the reinforcement part of FIG.

  Hereinafter, embodiments of the present invention will be described in detail.

(First embodiment)
First, a first embodiment of a photoelectric conversion element according to the present invention will be described with reference to FIGS. 1 and 2. FIG. 1 is a sectional view showing a first embodiment of the photoelectric conversion element according to the present invention, and FIG. 2 is a plan view showing the photoelectric conversion element of FIG.

  The photoelectric conversion element 100 shown in FIG. 1 is a dye-sensitized solar cell. As shown in FIG. 1, the photoelectric conversion element 100 includes a working electrode 1 and a counter electrode 2 disposed so as to face the working electrode 1. The working electrode 1 carries a photosensitizing dye. Between the working electrode 1 and the counter electrode 2, a sealing portion 4 that connects the working electrode 1 and the counter electrode 2 is provided. The cell space surrounded by the working electrode 1, the counter electrode 2, and the sealing portion 4 is filled with an electrolyte 3.

  In the photoelectric conversion element 100, the working electrode 1 is not flexible, whereas the counter electrode 2 is a flexible electrode having flexibility. Therefore, as shown in FIG. 2, the counter electrode 2 is surrounded by the annular fixing portion 2B fixed to the sealing portion 4 and the fixing portion 2B, and moves to the side opposite to the electrolyte 3 due to the increase in the internal pressure of the cell space. It is comprised with the fixing | fixed part 2A. Here, the non-fixed portion 2A refers to a region inside the interface between the counter electrode 2 and the sealing portion 4, and the other portion is referred to as a fixed portion 2B. Further, the non-fixed portion 2A is configured by a first movable portion 2A1 adjacent along the inner periphery of the fixed portion 2B, and a second movable portion 2A2 surrounded by the first movable portion 2A1. Here, the second movable portion 2A2 is a case where the flexible electrode is bent when the surface of the flexible electrode on the side of the electrolyte 3 when the flexible electrode is not bent is used as a reference plane. Of the surface of the flexible electrode on the side of the electrolyte 3, the portion surrounded by the annular portion where the inclination with respect to the reference plane is the largest.

  As shown in FIG. 2, a plate-like reinforcing portion 20 having higher rigidity than the counter electrode 2 is disposed on the opposite side of the counter electrode 2 from the electrolyte 3 so as to cover the entire fixing portion 2 </ b> B of the counter electrode 2. Has been. The reinforcing portion 20 has an opening 20 a at a position facing the non-fixed portion 2 </ b> A of the counter electrode 2. The reinforcing portion 20 is bonded to the fixed portion 2B of the counter electrode 2 via the adhesive 21. In the present embodiment, the reinforcing portion 20 constitutes a bending suppression means.

  The working electrode 1 includes a transparent substrate 6, a transparent conductive film 7 provided on the counter electrode 2 side of the transparent substrate 6, and a porous oxide semiconductor layer 8 provided on the transparent conductive film 7. It constitutes an electrode. The photosensitizing dye is supported on the porous oxide semiconductor layer 8 in the working electrode 1.

  The material which comprises the transparent substrate 6 should just be a transparent material, for example, As such a transparent material, glass, such as borosilicate glass, soda lime glass, white plate glass, quartz glass, polyethylene terephthalate (PET), for example , Polyethylene naphthalate (PEN), polycarbonate (PC), polyethersulfone (PES) and the like. The thickness of the transparent substrate 6 is such a thickness that the working electrode 1 does not have flexibility, and may be in the range of 50 μm to 10000 μm, for example.

Examples of the material constituting the transparent conductive film 7 include tin-doped indium oxide (Indium-Tin-Oxide: ITO), tin oxide (SnO ₂ ), and fluorine-doped tin oxide (Fluorine-doped-Tin-Oxide: FTO). Examples include conductive metal oxides. The transparent conductive film 7 may be a single layer or a laminate of a plurality of layers made of different conductive metal oxides. When the transparent conductive film 7 is composed of a single layer, the transparent conductive film 7 is preferably composed of FTO because it has high heat resistance and chemical resistance. Moreover, it is preferable to use a laminated body composed of a plurality of layers as the transparent conductive film 7 because the characteristics of each layer can be reflected. Among these, it is preferable to use a laminate of a layer made of ITO and a layer made of FTO. In this case, the transparent conductive film 7 having high conductivity, heat resistance and chemical resistance can be realized. The thickness of the transparent conductive film 7 may be in the range of 0.01 μm to 2 μm, for example.

The porous oxide semiconductor layer 8 is composed of a porous oxide semiconductor. Examples of the porous oxide semiconductor include titanium oxide (TiO ₂ ), zinc oxide (ZnO), tungsten oxide (WO ₃ ), niobium oxide (Nb ₂ O ₅ ), strontium titanate (SrTiO ₃ ), and tin oxide (SnO ₂ ). ), Indium oxide (In ₃ O ₃ ), zirconium oxide (ZrO ₂ ), thallium oxide (Ta ₂ O ₅ ), lanthanum oxide (La ₂ O ₃ ), yttrium oxide (Y ₂ O ₃ ), holmium oxide (Ho ₂₎ O ₃ ), bismuth oxide (Bi ₂ O ₃ ), cerium oxide (CeO ₂ ), aluminum oxide (Al ₂ O ₃ ), or oxide semiconductor particles composed of two or more thereof. The average particle diameter of these oxide semiconductor particles is 1-1000 nm, the surface area of the oxide semiconductor covered with the dye is increased, that is, the field for photoelectric conversion is increased, and more electrons are generated. Is preferable. Here, it is preferable that the porous oxide semiconductor layer 8 is configured by a stacked body in which oxide semiconductor particles having different particle size distributions are stacked. In this case, it becomes possible to cause reflection of light repeatedly in the laminated body, and light can be efficiently converted into electrons without escaping incident light to the outside of the laminated body. The thickness of the porous oxide semiconductor layer 8 may be, for example, 0.5 to 50 μm. In addition, the porous oxide semiconductor layer 8 can also be comprised with the laminated body of the several semiconductor layer which consists of a different material.

  Examples of the photosensitizing dye include a ruthenium complex having a ligand containing a bipyridine structure, a terpyridine structure, and the like, and organic dyes such as porphyrin, eosin, rhodamine, and merocyanine.

  The counter electrode 2 includes a counter electrode substrate 9 and a conductive catalyst film 10 that is provided on the working electrode 1 side of the counter electrode substrate 9 and promotes a reduction reaction on the surface of the counter electrode 2.

  The counter electrode substrate 9 is made of titanium, nickel, platinum, or an alloy of two or more thereof. These can be used regardless of the type of the electrolyte 3, but are particularly suitable when the electrolyte 3 contains iodine because it has corrosion resistance particularly against iodine. Of these, the counter electrode substrate 9 is preferably made of titanium from the viewpoint of corrosion resistance, cost, and availability. In addition, as the counter electrode substrate 9, what formed the electrically conductive film in resin, such as PET and PEN, can also be used.

  The catalyst film 10 is made of platinum, a carbon-based material, a conductive polymer, or the like.

  In order to impart flexibility to the counter electrode 2, when the counter electrode substrate 9 is made of the above metal, the thickness thereof is, for example, 5 to 35 μm, preferably 5 to 30 μm. In the case of using a material formed with a film, it cannot be generally stated because it differs depending on the material of the resin, but the thickness may be set to, for example, 5 to 300 μm.

The electrolyte 3 is usually composed of an electrolytic solution, and this electrolytic solution contains a redox couple such as I ⁻ / I ₃ ⁻ and an organic solvent. As the organic solvent, acetonitrile, methoxyacetonitrile, methoxypropionitrile, propionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, γ-butyrolactone, and the like can be used. Examples of the redox pair include I ⁻ / I ₃ ⁻ and bromine / bromide ion pairs. The dye-sensitized solar cell 100 is an electrolytic solution that includes a volatile solute such as I ⁻ / I ₃ ⁻ as an oxidation-reduction pair and an organic solvent such as acetonitrile, methoxyacetonitrile, and methoxypropionitrile that easily volatilizes at high temperatures. This is particularly effective when is used as the electrolyte 3. In this case, the change in the internal pressure of the cell space is particularly large due to the change in the ambient temperature around the dye-sensitized solar cell 100, and the interface between the sealing part 20 and the counter electrode 2, and the sealing part 20 and the working electrode 1. This is because the electrolyte 3 easily leaks from the interface. A gelling agent may be added to the volatile solvent. Moreover, the electrolyte 3 may be comprised with the ionic liquid electrolyte which consists of a mixture of an ionic liquid and a volatile component. Also in this case, the change in the internal pressure of the cell space increases due to the change in the ambient temperature around the dye-sensitized solar cell 100. As the ionic liquid, for example, a known iodine salt such as a pyridinium salt, an imidazolium salt, or a triazolium salt, and a room temperature molten salt that is in a molten state near room temperature is used. As such a room temperature molten salt, for example, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide is preferably used. As the volatile component, the above and an organic solvent, 1-methyl-3-methyl imidazolium iodide, _LiI, and the like I 2, 4-t-butylpyridine. Further, as the electrolyte 3, a nanocomposite ionic gel electrolyte, which is a pseudo-solid electrolyte formed by kneading nanoparticles such as SiO ₂ , TiO ₂ , and carbon nanotubes in the ionic liquid electrolyte, may be used. An ionic liquid electrolyte gelled using an organic gelling agent such as vinylidene chloride, polyethylene oxide derivative, or amino acid derivative may be used.

  As shown in FIG. 1, the sealing part 4 is composed of an inorganic sealing part 4A made of an inorganic material, a resin sealing part 4B made of a first resin, and a second resin covering the inorganic sealing part 4A. And a resin layer 13. The inorganic sealing portion 4 </ b> A includes a current collecting wiring 11 and a wiring protective layer 12 that covers and protects the current collecting wiring 11. The current collection wiring 11 should just be comprised with the electrically conductive material which has higher electroconductivity than the transparent conductive film 7, and is normally comprised from metal materials, such as silver and copper. The wiring protective layer 12 protects the current collecting wiring 11 from the electrolyte 3 and is made of, for example, an inorganic insulating material such as a lead-free transparent low melting point glass frit. As the first resin constituting the resin sealing portion 4B, for example, ionomer, ethylene-vinyl acetic anhydride copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl alcohol copolymer, ultraviolet curable resin, and Examples thereof include resins such as vinyl alcohol polymers. Moreover, as 2nd resin which comprises the resin layer 13, resin similar to 1st resin which comprises the resin sealing part 13, polyimide, a fluororesin, etc. can be used, for example. In addition, the resin sealing part 4B may be comprised only with 1st resin, and may be comprised with 1st resin and the inorganic filler.

  The reinforcement part 20 should just have rigidity higher than the counter electrode 2, As such a reinforcement part 20, for example, aluminum, iron, nickel, chromium, copper, zinc, tin, and an alloy containing these metals In addition to a metal plate made of, for example, a resin plate such as ABS resin, PET, or acrylic plate can be used. Although the thickness of the reinforcement part 20 differs depending on the material of the reinforcement part 20, it cannot be said unconditionally. However, when the reinforcement part 20 is made of a metal plate, the thickness is set to 20 to 5000 μm, for example, and the reinforcement part 20 is a resin plate. In the case of being configured, the thickness may be 100 to 5000 μm.

  As the adhesive 21, for example, a resin is used. As this resin, a resin similar to the first resin constituting the resin sealing portion 4B can be used.

  According to the photoelectric conversion element 100 described above, when the ambient environmental temperature rises, the electrolyte 3 expands and the internal pressure of the cell space rises. As a result, stress is applied from the electrolyte 3 to the non-fixed portion 2A of the counter electrode 2, and the non-fixed portion 2A moves to the opposite side of the electrolyte 3, so that the fixed portion 2B tries to bend. To do. At this time, the bending of the fixing portion 2B is suppressed by the reinforcing portion 20. On the other hand, the bending of the second movable part 2A2 is ensured without being suppressed. For this reason, the stress applied to the non-fixed portion 2A is absorbed, and the stress at the interface between the sealing portion 4 and the fixed portion 2B is relaxed. Thus, according to the photoelectric conversion element 100, peeling of the fixing part 2B from the sealing part 4 can be sufficiently suppressed while relaxing stress applied to the interface between the sealing part 4 and the fixing part 2B. As a result, according to the photoelectric conversion element 100, leakage of the electrolyte 3 is effectively suppressed even when used in a place where the ambient temperature change is large, and a decrease in photoelectric conversion efficiency is sufficiently suppressed.

  In the photoelectric conversion element 100, the reinforcing portion 20 has an opening 20a at a position facing the non-fixed portion 2A. For this reason, even if the second movable part 2A2 moves to the side opposite to the electrolyte 3 due to the increase in the internal pressure of the cell space, the second movable part 2A2 can enter the opening 20a. That is, the expandable volume of the cell space can be increased as compared with the case where the reinforcing portion 20 does not have the opening 20a. As a result, compared with the case where the reinforcing part 20 does not have the opening 20a, the stress concentration at the interface between the sealing part 4 and the fixing part 2B due to the increase in the internal pressure of the cell space can be sufficiently relaxed.

  Furthermore, the reinforcement part 20 has covered the whole fixing | fixed part 2B. For this reason, since the whole fixing part 2B which is easy to bend is covered with the reinforcing part 20 having higher rigidity than the fixing part 2B, the bending suppressing effect of the fixing part 2B is more than the case where a part of the fixing part 2B is covered. And the separation of the fixed portion 2B from the sealing portion 4 can be sufficiently suppressed.

  Next, a method for manufacturing the photoelectric conversion element 100 will be described.

  First, the working electrode 1 and the counter electrode 2 are prepared.

  In the working electrode 1, a transparent conductive film 7 is formed on a transparent substrate 6, a porous oxide semiconductor layer 8 is formed on the transparent conductive film 7, and a photosensitizing dye is applied to the porous oxide semiconductor layer 8. It can be obtained by carrying it.

  Examples of the method for forming the transparent conductive film 7 on the transparent substrate 6 include a sputtering method, a vapor deposition method, a spray pyrolysis (SPD) method, and a CVD method.

  The porous oxide semiconductor layer 8 can be obtained, for example, by sintering the oxide semiconductor particles described above.

  Next, the current collector wiring 11 is formed around the porous oxide semiconductor layer 8 in the working electrode 1, and then the porous oxide semiconductor layer 8 is surrounded so as to cover the current collector wiring 11. Thus, the wiring protective layer 12 is formed. In this way, the inorganic sealing portion 4A is obtained around the porous oxide semiconductor layer 8.

  The current collector wiring 11 is, for example, a paste obtained by blending the above-described metal particles and a thickener such as polyethylene glycol, and surrounding the porous oxide semiconductor layer 8 using a screen printing method or the like. It can be obtained by coating a film, heating and baking. When the working electrode 1 is a conductive glass or the like, the current collector wiring 11 is firmly bonded to the working electrode 1 by mixing the above-mentioned paste with a low melting point glass frit.

  The wiring protective layer 12 is made of, for example, a paste obtained by blending a thickening agent, a binder, a dispersant, a solvent, or the like with an inorganic insulating material such as the above-described low-melting glass frit as necessary, by a screen printing method or the like. It can be obtained by coating the current collector wiring 11 so as to cover the whole, heating and baking.

  The wiring protective layer 12 prevents contact between the electrolyte 3 and the current collector wiring 11 over a longer period of time, and the dissolved component of the wiring protective layer 12 when the electrolyte 3 comes into contact with the wiring protective layer 12. In order to prevent the occurrence of this, it is preferable to coat with a chemical-resistant resin layer 13 such as polyimide, fluororesin, or the second resin. The coating of the inorganic sealing portion 4A with the resin layer 13 can be performed as follows, for example. When the resin layer 13 is a thermoplastic resin, the molten second resin is applied to the wiring protective layer 12 and then naturally cooled at room temperature, or the film-like second resin is brought into contact with the wiring protective layer 12. The resin layer 13 can be obtained by naturally cooling at room temperature after the film-like second resin is heated and melted by an external heat source. As the thermoplastic second resin, for example, an ionomer or an ethylene-methacrylic acid copolymer is used. When the second resin is an ultraviolet curable resin, an ultraviolet curable resin that is a precursor of the second resin is applied to the wiring protective layer 12, and then the ultraviolet curable resin described above is cured by ultraviolet rays. The resin layer 13 can be obtained. When the second resin is a water-soluble resin, the resin layer 13 can be obtained by applying an aqueous solution containing the second resin onto the wiring protective layer 12. As the water-soluble second resin, for example, a vinyl alcohol polymer is used.

  Next, in order to carry the photosensitizing dye on the porous oxide semiconductor layer 8 of the working electrode 1, the working electrode 1 in which the porous oxide semiconductor layer 8 is formed on the transparent conductive film 7 is usually used as the light. The photosensitizing dye is immersed in a solution containing a sensitizing dye, the dye is adsorbed on the porous oxide semiconductor layer 8, and then the excess dye is washed away with the solvent component of the solution and dried. Adsorbed on the porous oxide semiconductor layer 8. However, even if the photosensitizing dye is adsorbed to the porous oxide semiconductor layer 8 by applying a solution containing the photosensitizing dye to the porous oxide semiconductor layer 8 and then drying the photosensitizing dye, It can be supported on the porous oxide semiconductor layer 8.

  On the other hand, the counter electrode 2 is prepared as follows. For example, a flexible counter electrode 9 having a thickness of 5 to 35 μm made of titanium, platinum, nickel, or an alloy of two or more thereof is prepared. Or when using what formed the electrically conductive film in resin as the counter-electrode board | substrate 9, the thing of thickness 5-300 micrometers is prepared. Then, the catalyst film 10 is formed on the counter electrode substrate 9. As a method for forming the catalyst film 10, a sputtering method, a vapor deposition method, or the like is used. Of these, sputtering is preferred from the viewpoint of film uniformity. Thus, the flexible counter electrode 2 is prepared.

  Next, a first resin or a precursor thereof for connecting the inorganic sealing portion 4A and the counter electrode 2 is formed on the surface of the counter electrode 2 on the catalyst film 10 side. When the first resin is a thermoplastic resin, the molten first resin is applied on the counter electrode 2 and then naturally cooled at room temperature, or the film-like first resin is brought into contact with the counter electrode 2 and external The first resin can be obtained by heating and melting the film-like second resin with a heat source and then naturally cooling at room temperature. As the thermoplastic first resin, for example, an ionomer or an ethylene-methacrylic acid copolymer is used. When the first resin is an ultraviolet curable resin, an ultraviolet curable resin that is a precursor of the first resin is applied on the counter electrode 2. However, in the case where an ultraviolet curable resin is used, it is necessary that the portion coated with the ultraviolet curable resin on either the working electrode 1 or the counter electrode 2 transmits ultraviolet light. When the first resin is a water-soluble resin, an aqueous solution containing the first resin is applied on the counter electrode 2. As the water-soluble first resin, for example, a vinyl alcohol polymer is used.

  Then, the working electrode 1 and the counter electrode 2 are opposed to each other, and the first resin and the inorganic sealing portion 4A are overlapped to form a laminate. When the first resin is a thermoplastic resin, the first resin is heated and melted to bond the inorganic sealing portion 4A and the counter electrode 2 together. In this way, the resin sealing part 4B which connects these between the inorganic sealing part 4A and the counter electrode 2 is obtained. When the first resin is an ultraviolet curable resin, the ultraviolet curable resin described above is cured with ultraviolet rays after forming the laminate, and the resin is connected between the inorganic sealing portion 4A and the counter electrode 2 The sealing part 4B is obtained. When the first resin is a water-soluble resin, after the laminate is formed, the finger is dried at room temperature and then dried in a low-humidity environment, and between the inorganic sealing portion 4A and the counter electrode 2, A resin sealing portion 4B for connecting the two is obtained. Thus, the sealing portion 4 is formed between the working electrode 1 and the counter electrode 2. The counter electrode 2 is composed of a fixed portion 2B and a non-fixed portion 2A.

  Next, an electrolyte 3 is filled in a cell space surrounded by the working electrode 1, the counter electrode 2, and the sealing portion 4. The electrolyte 3 is filled by, for example, injecting the electrolyte 3 through a preformed electrolyte inlet (not shown) in the working electrode 1 and finally sealing the electrolyte inlet with the first resin. it can.

  On the other hand, the reinforcement part 20 in which the opening 20a was formed is prepared. At this time, the reinforcing part 20 is prepared to have a dimension that covers the entire fixing part 2 </ b> B and has higher rigidity than the counter electrode 2. And the sheet | seat which consists of a thermoplastic resin is pinched | interposed by the reinforcement part 20 and the fixing | fixed part 2B, and the reinforcement part 20 is arrange | positioned so that the whole fixing | fixed part 2B may be covered. And the sheet | seat which consists of thermoplastic resins is heat-melted. Thus, the reinforcing portion 20 is bonded to the fixed portion 2B via the adhesive 21. In this way, the photoelectric conversion element 100 is obtained and the manufacture of the photoelectric conversion element 100 is completed.

  In the photoelectric conversion element 100 of the present embodiment, the reinforcing portion 20 does not cover the first movable portion 2A1 even though it covers the entire fixed portion 2B, but as shown in FIG. Preferably covers not only the entire first fixed portion 2B but also the first movable portion 2A1. In this case, the bending of the fixing portion 2B is sufficiently suppressed by the reinforcing portion 20. In addition, even if the non-fixed portion 2A is greatly bent due to the increase in the internal pressure of the cell space and the first movable portion 2A1 moves to the side opposite to the electrolyte 3, the first movable portion 2A1 is brought into contact with the reinforcing portion 20, The movement is restricted by the reinforcing portion 20. For this reason, the stress concerning the interface of the sealing part 4 and the fixing | fixed part 2B can be relieve | moderated more. In FIG. 3, the reinforcing portion 20 is bonded to the fixed portion 2 </ b> B and the first movable portion 2 </ b> A <b> 1 via an adhesive 21, but the reinforcing portion 20 is bonded to at least the fixed portion 2 </ b> B via the adhesive 21. The reinforcement part 20 may be adhere | attached only on the fixing | fixed part 2B via the adhesive agent 21.

  In FIG. 1, the reinforcing part 20 covers the entire fixed part 2B. However, as shown in FIG. 4, the reinforcing part 20 covers only a part of the fixed part 2B and covers the first movable part 2A1. It may be. In FIG. 4, the reinforcing portion 20 is bonded to the fixed portion 2 </ b> B and the first movable portion 2 </ b> A <b> 1 via the adhesive 21, but the reinforcing portion 20 is bonded to at least the fixed portion 2 </ b> B via the adhesive 21. The reinforcement part 20 may be adhere | attached only on the fixing | fixed part 2B via the adhesive agent 21.

  In FIG. 1, the reinforcing portion 20 covers the entire fixing portion 2B, but as shown in FIG. 5, the reinforcing portion 20 may cover only a part of the fixing portion 2B. In this case, the reinforcing portion 20 is bonded only to the fixing portion 2B via the adhesive 21. Furthermore, in the photoelectric conversion element 100 of this embodiment, although the reinforcement part 20 has the opening 20a, as shown in FIG. 6, the reinforcement part 20 can also be comprised by what does not have the opening 20a. In this case, the reinforcing part 20 covers not only the fixed part 2B but also the non-fixed part 2A. In FIG. 6, the reinforcing portion 20 is bonded only to the fixed portion 2 </ b> B via the adhesive 21, but the reinforcing portion 20 is not only the fixed portion 2 </ b> B via the adhesive 21 but the first movable portion 2 </ b> A <b> 1. It may be adhered to.

(Second Embodiment)
Next, a second embodiment of the photoelectric conversion element of the present invention will be described in detail with reference to FIG. FIG. 7 is a cross-sectional view showing a second embodiment of the photoelectric conversion element of the present invention. In FIG. 7, the same or equivalent components as those in the first embodiment are denoted by the same reference numerals, and redundant description is omitted.

  As shown in FIG. 7, the photoelectric conversion element 200 of the present embodiment is different from the photoelectric conversion element 100 of the first embodiment in that a reinforcing part 220 is used instead of the reinforcing part 20.

  Here, the reinforcement part 220 has comprised the shape where the peripheral part of the plate-shaped member rose and became thick. That is, the reinforcing part 220 is configured by an annular thick part 220A and a thin part 220B surrounded by the thick part 220A, and the thick part 220A has a larger thickness than the thin part 220B. Here, the thick part 220A has higher rigidity than the fixed part 2B. The thick portion 220A is bonded to the fixed portion 2B via the adhesive 21. The reinforcing part 220 has a concave part 220C at a position facing the non-fixed part 2A. As a material constituting the reinforcing portion 220, the same material as that constituting the reinforcing portion 20 can be used. A through hole (not shown) is formed in the thin portion 220B of the reinforcing portion 220. The through hole is for releasing air in a space surrounded by the reinforcing portion 220, the counter electrode 2, and the adhesive 21.

  According to the photoelectric conversion element 200, the thick portion 220A has higher rigidity than the fixed portion 2B, and the thick portion 220A is bonded to the fixed portion 2B via the adhesive 21. For this reason, the thick part 220A is more difficult to bend than the fixed part 2B. Therefore, even if the fixing portion 2B is to be greatly bent, the bending of the fixing portion 2B is more sufficiently suppressed by the thick portion 220A. The reinforcing part 220 has a recess 220C at a position facing the non-fixed part 2A. For this reason, even if the second movable part 2A2 moves to the side opposite to the electrolyte 3 due to the increase in the internal pressure of the cell space, since the recessed part 220C is formed in the reinforcing part 220, the second movable part 2A2 enters the recessed part 220C. It becomes possible. That is, the expandable volume of the cell space can be increased as compared with the case where the reinforcing portion 220 does not have the concave portion 220C. In addition, at this time, the air in the space surrounded by the reinforcing portion 220, the counter electrode 2 and the adhesive 21 can be released through the through hole formed in the thin portion 220B, so that the second movable portion 2A2 is opposite to the electrolyte 3 side. Easy to move to. As a result, the stress concentration at the interface between the sealing portion 4 and the fixing portion 2B due to an increase in the internal pressure of the cell space can be sufficiently relaxed as compared with the case where the reinforcing portion 220 does not have the concave portion 220C.

  In the photoelectric conversion element 200 of the present embodiment, the thick portion 220A of the reinforcing portion 220 covers the entire fixed portion 2B but does not cover the first movable portion 2A1, but as shown in FIG. Moreover, it is preferable that the thick portion 220A of the reinforcing portion 220 not only covers the entire fixed portion 2B but also covers the first movable portion 2A1. In this case, the bending of the fixed portion 2B is sufficiently suppressed by the thick portion 220A of the reinforcing portion 220. In addition, even if the non-fixed portion 2A is greatly bent due to the increase in the internal pressure of the cell space and the first movable portion 2A1 moves to the side opposite to the electrolyte 3, the first movable portion 2A1 is brought into contact with the thick portion 220A, The movement is regulated by the thick portion 220A. For this reason, the stress concerning the interface of the sealing part 4 and the fixing | fixed part 2B can be relieve | moderated more. In FIG. 8, the reinforcing portion 220 is bonded to the fixed portion 2 </ b> B and the first movable portion 2 </ b> A <b> 1 via the adhesive 21, but the reinforcing portion 220 is bonded to at least the fixed portion 2 </ b> B via the adhesive 21. The reinforcement part 20 may be adhere | attached only on the fixing | fixed part 2B via the adhesive agent 21.

  In FIG. 7, the thick part 220A covers the entire fixed part 2B. However, as shown in FIG. 9, the thick part 220A covers only a part of the fixed part 2B and the first movable part 2A1. May be covered. In FIG. 9, the reinforcing portion 220 is bonded to the fixed portion 2 </ b> B and the first movable portion 2 </ b> A <b> 1 via the adhesive 21, but the reinforcing portion 220 is bonded to at least the fixed portion 2 </ b> B via the adhesive 21. The reinforcement part 220 may be adhere | attached only on the fixing | fixed part 2B via the adhesive agent 21. In FIG. 7, the thick portion 220A covers the entire fixed portion 2B. However, as shown in FIG. 10, the thick portion 220A may cover only a part of the fixed portion 2B. . In this case, the reinforcing part 220 is bonded only to the fixing part 2B via the adhesive 21.

(Third embodiment)
Next, a third embodiment of the photoelectric conversion element of the present invention will be described in detail with reference to FIG. FIG. 11 is a partial cross-sectional view showing a third embodiment of the photoelectric conversion element of the present invention. In FIG. 11, the same or equivalent components as those in the first embodiment are denoted by the same reference numerals, and redundant description is omitted.

  As shown in FIG. 11, the photoelectric conversion element 300 according to the present embodiment is a second embodiment in that a pressing member 320 that presses the fixed portion 2 </ b> B of the counter electrode 2 is used as a bending suppression unit for the fixed portion 2 </ b> B of the counter electrode 2. This is different from the photoelectric conversion element 200 of FIG.

  Here, the pressing member 320 includes a reinforcing portion 220 and a pressing portion 320 </ b> C provided on the thick portion 220 </ b> A of the reinforcing portion 220. The pressing portion 320C has an annular shape and has a narrower width than the thick portion 220A. The pressing member 320 is not bonded to the fixing portion 2B with an adhesive, and is different from the reinforcing portion 220 in that the fixing portion 2B is simply pressed by the pressing portion 320C. Further, in order to apply a pressing force to the fixed portion 2B by the pressing member 320, it is necessary to press the pressing member 320 toward the fixed portion 2B. For this purpose, for example, the pressing member 320 and the working electrode 1 may be sandwiched between leaf springs (not shown) having a U-shaped cross section, or the whole may be accommodated in a housing (not shown).

  According to the photoelectric conversion element 300, the pressing member 320 can also suppress the bending of the fixing portion 2B, can sufficiently suppress the peeling of the fixing portion 2B from the sealing portion 4, and the photoelectric conversion efficiency over time. Can be sufficiently suppressed. Moreover, in the photoelectric conversion element 300, since the reinforcement part 320 has the press part 320C with a smaller area which contacts the fixing | fixed part 2B than the thick part 220A, the pressure added to the fixing | fixed part 2B is pressed by the thick part 220A. The fixing portion 2B can be effectively pressed by the pressing member 320.

  Here, it is preferable that the pressing portion 320C is arranged so as to press the edge portion on the non-fixed portion 2A side of the annular fixed portion 2B. In this case, as compared with the case where the pressing part 320C is arranged so as to press a part other than the edge part on the non-fixing part 2A side in the annular fixing part 2B, the bending of the fixing part 2B as a whole is suppressed. There is an advantage that can be.

  Note that the pressing member 320 may be configured by only the reinforcing portion 220. Further, the pressing member 320 includes the reinforcing portion 220 having higher rigidity than the fixing portion 2B, but the pressing member 320 suppresses the bending of the fixing portion 2B by pressing the fixing portion 2B. However, it is not always necessary to use the reinforcing portion 220 having higher rigidity than the fixed portion 2B. Instead of the reinforcing portion 220, for example, a member having lower rigidity than the fixed portion 2B may be used.

(Fourth embodiment)
Next, a fourth embodiment of the photoelectric conversion element of the present invention will be described in detail with reference to FIG. FIG. 12 is a partial cross-sectional view showing a fourth embodiment of the photoelectric conversion element of the present invention. In FIG. 12, the same or equivalent components as those in the first embodiment are denoted by the same reference numerals, and redundant description is omitted.

  As shown in FIG. 12, the photoelectric conversion element 400 according to the present embodiment is directly bonded to the fixing portion 2B of the counter electrode 2 and is harder than the resin constituting the adhesive 21 as a means for suppressing the bending of the fixing portion 2B of the counter electrode 2. It differs from the photoelectric conversion element 100 of the first embodiment in that the resin 420 is used.

  The rigid resin 420 can also suppress the bending of the fixing portion 2B, can sufficiently suppress the peeling of the fixing portion 2B from the sealing portion 4, and can sufficiently suppress the temporal deterioration of the photoelectric conversion efficiency. .

  The hard resin 420 only needs to be a resin that is harder in a higher temperature region than the resin constituting the adhesive 21, and examples of the hard resin 420 include epoxy resins, olefin resins, and isobutylene resins, composite resins thereof, Alternatively, a resin to which an elastomer component such as rubber is appropriately added can be used. In particular, when the adhesive 21 is a resin mainly composed of a thermoplastic resin and softens under a high temperature region, the range of resins that can be used as the hard resin 420 is widened, and the thermoplastic having a higher softening point than the adhesive 21 is used. Resins can also be used widely. It is preferable that the hard resin 420 covers the entire fixing portion 2B because bending can be further suppressed as compared to a case where only a part of the fixing portion 2B is covered.

  Moreover, it is preferable that the hard resin 420 covers up to the first movable part 2A1. In this case, even the bending of the first movable portion 2A1 that causes the fixing portion 2B to peel from the sealing portion 4 is suppressed, and the bending of the fixing portion 2B from the sealing portion 4 is effectively suppressed. it can.

  As shown in FIG. 12, the harder resin 420 includes the side surface 2D of the fixing portion 2B of the counter electrode 2, the boundary B1 between the sealing portion 4 and the counter electrode 2, the sealing portion 4, and the working electrode 1 and the sealing portion 4. It is preferable that the boundary B2 is covered and further bonded to the surface 1a of the working electrode 1. In this case, when the electrolyte 3 leaks through the interface between the counter electrode 2 and the sealing portion 4, the electrolyte 3 is not only the interface between the counter electrode 2 and the resin sealing portion 4 </ b> B but also the side surface 2 </ b> D of the hard resin 420 and the counter electrode 2. And the interface between the hard resin 420 and the fixed portion 2B and the surface on the opposite side of the sealing portion 4, and the interface distance is extended. In addition, when the electrolyte 3 leaks through the interface between the working electrode 1 and the sealing portion 4, the electrolyte 3 is not only the interface between the inorganic sealing portion 4 and the resin layer 13, but also the hard resin 420 and the resin layer 13. , And the interface between the hard resin 420 and the working electrode 1, and the interface distance is extended. For this reason, the leakage of the electrolyte 3 can be more sufficiently suppressed, and the temporal deterioration of the photoelectric conversion efficiency can be more sufficiently suppressed. Further, since the hard resin 420 is also bonded to the surface 1a of the working electrode 1, even if a force for peeling the fixing portion 2B from the sealing portion 4 is applied, the fixing portion 420 is sealed by the hard resin 420. Force to pull back to the 4 side works. For this reason, peeling of the fixing | fixed part 2B from the sealing part 4 can be suppressed more fully.

  The present invention is not limited to the first to fourth embodiments described above. For example, in the second embodiment, the thick portion 220A of the reinforcing portion 220 is bonded to the fixed portion 2B by the adhesive 21, but the thick portion 220A is an adhesive as in the photoelectric conversion element 500 shown in FIG. 21 may be bonded to the first movable part 2A1. In this case, the reinforcing part 220 covers not only the first movable part 2A1 but also the second movable part 2A2. Even in this case, when the internal pressure of the cell space increases and the non-fixed portion 2A moves to the side opposite to the electrolyte 3, the deflection of the first movable portion 2A1 is suppressed by the thick portion 220A. On the other hand, the bending of the second movable part 2A2 is ensured without being suppressed. For this reason, the stress due to the increase in the internal pressure of the cell space is absorbed by the second movable part 2A2, and the stress applied to the interface between the sealing part 4 and the fixing part 4B is relieved, so that the fixing part from the sealing part 4 2B peeling can be sufficiently suppressed.

  In the photoelectric conversion elements 100, 200, 300, and 400 according to the first to fourth embodiments, the reinforcing portions 20 and 220, the pressing member 320, and the hard resin 420 are used as the deflection suppressing means of the fixing portion 2B. As in the photoelectric conversion element 600 shown in FIG. 14, a rigid portion 520 having a higher rigidity by increasing the thickness of the fixed portion 2B than that of the non-fixed portion 2A may be used as a means for suppressing deflection of the fixed portion 2B. In this case, the fixing portion 2B itself also serves as a bending suppression means.

  Furthermore, in the photoelectric conversion element 100 according to the first embodiment, one reinforcing portion 20 covers the entire fixing portion 2B. However, as shown in FIG. 15, a plurality of reinforcing portions 20A that are separated from each other extend along the fixing portion 2B. The reinforcing portions 20 </ b> A may be bonded to the fixing portion 2 </ b> B by the adhesive 21.

  Furthermore, in the photoelectric conversion elements 100, 200, 300, and 400 of the first to fourth embodiments, the sealing unit 4 includes the inorganic sealing unit 4A and the resin sealing unit 4B. 4 may be comprised only by the resin sealing part 4B. The inorganic sealing portion 4A is composed of the current collecting wiring 11 and the wiring protective layer 12, but may be composed of an inorganic material, for example, inorganic insulation such as a non-lead-based transparent low melting point glass frit. It is also possible to configure only with materials.

  Furthermore, in the photoelectric conversion elements 100, 200, 300, and 400 of the first to fourth embodiments, only the counter electrode 2 is a flexible electrode, but both the counter electrode 2 and the working electrode 1 are flexible. It may be a flexible electrode. In order to impart flexibility to the working electrode 1, for example, the thickness of the transparent substrate 6 constituting the working electrode 1 may be set to 300 μm or less. In this case, it is necessary to provide a deflection suppressing means not only on the counter electrode 2 side but also on the working electrode 1 side. Further, the counter electrode 2 may not be flexible, and only the working electrode 1 may be a flexible electrode. In this case, the bending suppression means may be provided only on the working electrode 1 side.

  Hereinafter, the content of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Example 1
First, a 10 cm × 10 cm × 4 mm FTO substrate was prepared. Subsequently, a titanium oxide paste (Solaronix, Ti nanoixide T / sp) was applied on the FTO film by a doctor blade method so that its thickness became 10 μm, and then placed in a hot air circulation type oven. Baking was performed at 500 ° C. for 3 hours, a porous oxide semiconductor layer was formed on the FTO film, and a 5 cm × 5 cm laminate was obtained. Next, two through holes were formed in the laminate to obtain a working electrode.

  Next, the working electrode was immersed in a dehydrated ethanol solution in which 0.2 mM of N719 dye, which is a photosensitizing dye, was dissolved for 24 hours to support the photosensitizing dye on the working electrode.

  On the other hand, a metal substrate made of a titanium foil of 6 cm × 6 cm × 35 μm was prepared. Then, a platinum catalyst film having a thickness of 10 nm was formed on the metal substrate by sputtering to obtain a counter electrode.

  Then, an annular thermoplastic resin sheet made of Himiran (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.), which is an ionomer, was sandwiched between the working electrode and the counter electrode. At this time, the porous oxide semiconductor layer was arranged inside the thermoplastic resin sheet. Then, the thermoplastic resin sheet was heated and melted at 180 ° C. for 35 minutes to bond the working electrode and the counter electrode.

  Next, the acetonitrile-based electrolyte was injected and filled into the cell space surrounded by the working electrode, the counter electrode, and the sealing portion through the through-hole formed in the working electrode. And the through-hole formed in the working electrode was sealed using the thermoplastic resin similar to the said sheet | seat.

  Next, a 6 cm × 6 cm glass plate was prepared as a reinforcing part. In addition, the square through-hole of 5 cm x 5 cm was formed in this glass plate by the sandblast method. Subsequently, the glass plate and the fixing portion of the counter electrode were sandwiched between a thermoplastic resin sheet made of high milan as an ionomer and a 5 cm × 5 cm opening was formed, and the glass plate was disposed so as to cover the entire counter electrode. Then, the thermoplastic resin sheet was heated and melted, and the reinforcing portion was bonded to the fixed portion of the counter electrode via an adhesive. Thus, a dye-sensitized solar cell was obtained.

(Examples 2 and 3)
A dye-sensitized solar cell was produced in the same manner as in Example 1 except that the electrolyte shown in Table 1 was used.

(Comparative Example 1)
A dye-sensitized solar cell was produced in the same manner as in Example 1 except that the glass plate was not bonded to the counter electrode.

(Comparative Examples 2 and 3)
A dye-sensitized solar cell was produced in the same manner as in Example 1 except that the glass plate was not adhered to the counter electrode and the electrolyte shown in Table 1 was used.

[Evaluation of change in photoelectric conversion efficiency by thermal cycle test: Evaluation 1]
About the dye-sensitized solar cell obtained in Examples 1-3 and Comparative Examples 1-3, after measuring photoelectric conversion efficiency, the heat cycle test was done. After the thermal cycle test, the photoelectric conversion efficiency was measured again for the dye-sensitized solar cell, and the decrease rate of the photoelectric conversion efficiency was calculated. Regarding the evaluation, “○” is displayed when the rate of decrease in photoelectric conversion efficiency is 5% or less, and “X” is displayed when the rate of decrease in photoelectric conversion efficiency is greater than 5% and 10% or less. It was decided to. The results are shown in Table 1.

  The thermal cycle test is a cycle in which the temperature is raised from −50 ° C. to 100 ° C., held at 100 ° C. for 10 minutes, then lowered from 100 ° C. to −50 ° C., and held at −50 ° C. for 10 minutes. A cycle was performed 300 times. At this time, the rate of temperature increase and the rate of temperature decrease were both 5 ° C./min.

[Evaluation of electrolyte remaining rate by thermal cycle test: Evaluation 2]
The dye-sensitized solar cells obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were subjected to the same thermal cycle test as described above, and then the volume of the dye-sensitized solar cell (cell), that is, the working electrode and the counter electrode. The ratio of the remaining amount of the electrolyte to the volume of the cell space surrounded by the sealing portion was measured. When the electrolyte remaining ratio is 95% or more, “◯” is displayed, when it is 90% or more and less than 95%, “△” is displayed, and when it is less than 90%, “×” is displayed. I decided to display it. The results are shown in Table 1.

  From the results shown in Table 1, in the dye-sensitized solar cells of Examples 1 to 3, the decrease in photoelectric conversion efficiency after the heat cycle test is sufficiently smaller than the dye-sensitized solar cells of Comparative Examples 1 to 3. I understood that.

  Therefore, according to the photoelectric conversion element of the present invention, it has been confirmed that even if it is used in a place where the ambient temperature changes greatly, it is possible to sufficiently suppress the temporal deterioration of the photoelectric conversion efficiency.

DESCRIPTION OF SYMBOLS 1 ... Working electrode (electrode), 2 ... Counter electrode (electrode), 2A ... Non-fixed part, 2A1 ... 1st movable part, 2A2 ... 2nd movable part, 2B ... Fixed part, 3 ... Electrolyte, 4 ... Sealing part, 4A ... inorganic sealing part, 4B ... resin sealing part, 20, 20A, 220 ... reinforcing part (bending suppression means), 220A ... thick part, 220B ... thin part, 320 ... pressing member (bending suppression means), 420 ... Hard resin, 100, 200, 300, 400, 500, 600 ... Photoelectric conversion element.

Claims (9)

A pair of electrodes facing each other;
A sealing portion connecting the pair of electrodes;
A photoelectric conversion element comprising the pair of electrodes and an electrolyte filled in a cell space surrounded by the sealing portion,
At least one of the pair of electrodes is a flexible electrode having flexibility,
The flexible electrode is
An annular fixing part fixed by the sealing part;
A non-fixed part surrounded by the fixed part,
The non-fixed part is
An annular first movable part adjacent along the inner periphery of the fixed part;
A second movable part surrounded by the first movable part;
The photoelectric conversion element includes a bending suppression unit that suppresses bending of the fixed portion or the first movable portion of the flexible electrode ,
The deflection suppressing means has a reinforcing portion having higher rigidity than the flexible electrode,
The reinforcing portion is arranged to cover the fixed portion and the non-fixed portion on the opposite side of the electrolyte with respect to the flexible electrode, and is bonded to at least the fixed portion;
A photoelectric conversion element characterized by the above. The portion of the reinforcing portion has a thick portion having a thickness greater than other portions of the reinforcing portion, according to claim 1 where the thick portion is bonded to at least the fixed part Photoelectric conversion element. The photoelectric conversion element according to claim 2 , wherein the thick part covers at least a part of the fixed part and also covers the first movable part. The photoelectric conversion element according to claim 3 , wherein the thick part covers the entire fixed part. A pair of electrodes facing each other;
A sealing portion connecting the pair of electrodes;
A photoelectric conversion element comprising the pair of electrodes and an electrolyte filled in a cell space surrounded by the sealing portion,
At least one of the pair of electrodes is a flexible electrode having flexibility,
The flexible electrode is
An annular fixing part fixed by the sealing part;
A non-fixed part surrounded by the fixed part,
The non-fixed part is
An annular first movable part adjacent along the inner periphery of the fixed part;
A second movable part surrounded by the first movable part;
The photoelectric conversion element includes a bending suppression unit that suppresses bending of the fixed portion or the first movable portion of the flexible electrode,
The deflection suppressing means has a reinforcing portion having higher rigidity than the flexible electrode,
The reinforcing portion is disposed so as to cover at least a part of the fixing portion on the side opposite to the electrolyte with respect to the flexible electrode, and has an opening at a position facing at least the non-fixing portion, and at least the Bonded to the fixed part
A photoelectric conversion element characterized by the above. The photoelectric conversion element according to claim 5 , wherein the reinforcing portion covers at least a part of the fixed portion and also covers the first movable portion. The photoelectric conversion element according to claim 6 , wherein the reinforcing portion covers the entire fixing portion. A pair of electrodes facing each other;
A sealing portion connecting the pair of electrodes;
A photoelectric conversion element comprising the pair of electrodes and an electrolyte filled in a cell space surrounded by the sealing portion,
At least one of the pair of electrodes is a flexible electrode having flexibility,
The flexible electrode is
An annular fixing part fixed by the sealing part;
A non-fixed part surrounded by the fixed part,
The non-fixed part is
An annular first movable part adjacent along the inner periphery of the fixed part;
A second movable part surrounded by the first movable part;
The photoelectric conversion element includes a bending suppression unit that suppresses bending of the fixed portion or the first movable portion of the flexible electrode,
The deflection suppressing means has a reinforcing portion having higher rigidity than the flexible electrode,
The reinforcing portion is disposed on the side opposite to the electrolyte with respect to the flexible electrode so as to cover at least a part of the first movable portion, and is bonded to the first movable portion.
A photoelectric conversion element characterized by the above. A pair of electrodes facing each other;
A sealing portion connecting the pair of electrodes;
A photoelectric conversion element comprising the pair of electrodes and an electrolyte filled in a cell space surrounded by the sealing portion,
At least one of the pair of electrodes is a flexible electrode having flexibility,
The flexible electrode is
An annular fixing part fixed by the sealing part;
A non-fixed part surrounded by the fixed part,
The non-fixed part is
An annular first movable part adjacent along the inner periphery of the fixed part;
A second movable part surrounded by the first movable part;
The photoelectric conversion element includes a bending suppression unit that suppresses bending of the fixed portion or the first movable portion of the flexible electrode,
The bending suppression means is a pressing member that is arranged to cover the fixed portion and the non-fixed portion on the side opposite to the electrolyte with respect to the flexible electrode and presses the fixed portion or the first movable portion. To prepare
A photoelectric conversion element characterized by the above.

Images