JPH11329519A - Photocell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocell capable of effectively preventing entrance of bubbles in an electrolyte layer and thickness change of the electrolyte layer generating when the photocell is bent. SOLUTION: In a photocell having (a) a light transmitting first conductive layer and a first electrode containing a semiconductor layer electrically connected to the first conductive layer, (b) a second electrode containing a second conductive layer, and (c) an oxidation-reduction electrolyte arranged between the semiconductor layer of the first electrode and the second conductive layer, and electrically connected to the semiconductor layer and the second conductive layer, the electrolyte layer is constituted with a gelled electrolyte film containing an electrolyte solution and a gelling agent polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to photovoltaic cells, and more particularly to photovoltaic cells that utilize photoelectrochemical reactions and are therefore also referred to as "electrochemical solar cells." The photovoltaic cell of the present invention particularly relates to a photovoltaic cell in which the form of the electrolyte is improved so as to be suitable for use in a flexible film cell.

[0002]

2. Description of the Related Art A photovoltaic cell, also known as an electrochemical solar cell, is known, for example, from US Pat. No. 5,350,644. This photovoltaic cell
Generally, the following means: (a) a first electrode including a light-transmitting first conductive layer and a semiconductor layer electrically connected to the first conductive layer;
A second electrode including a conductive layer; and (c) a redox property disposed between the semiconductor layer and the second conductive layer and electrically connected to both the semiconductor layer and the second conductive layer. And an electrolyte layer.

The electrolyte layer of this photovoltaic cell usually has a first electrode and a second electrode arranged to face each other, and then a liquid electrolyte is filled in a relatively small gap (typically 1 mm or less) formed therebetween. It is formed by pouring, but at that time, there is a difficulty in production that bubbles easily enter the electrolyte layer. On the other hand, it is very difficult to manufacture a flexible sheet-shaped photovoltaic cell using a conventional liquid electrolyte as it is. Flexible sheet photovoltaic cells typically include a first electrode including a flexible support bonded to a first conductive layer, and a second electrode including a flexible support bonded to a second conductive layer. The electrolyte layer is formed by arranging an electrolyte layer between them.However, when the sheet-shaped photovoltaic cell manufactured in this manner is relatively curved, the electrolyte layer flows to change its thickness. However, this causes a problem that battery performance such as electromotive force is reduced.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the conventional photovoltaic cell and to dispose an electrolyte layer in a gap between the first electrode and the second electrode. In addition, since bubbles can be effectively prevented from entering the electrolyte layer, manufacturing is easy, and even when a flexible sheet-shaped photovoltaic cell is formed, a change in the thickness of the electrolyte layer when the photovoltaic cell is curved. An object of the present invention is to provide an improved photovoltaic cell capable of effectively preventing the occurrence of a battery and preventing a decrease in battery performance such as electromotive force.

[0005]

In order to achieve the above object, the present invention comprises, in a first aspect, the following means: (a) a light-transmitting first conductive layer and a first conductive layer; A first electrode including a layer and a semiconductor layer electrically connected thereto;
A second electrode including a conductive layer, and (c) disposed between the semiconductor layer of the first electrode and the second conductive layer, and electrically connected to both the semiconductor layer and the second conductive layer. A photovoltaic cell comprising a redox electrolyte layer, wherein the electrolyte layer comprises a gelled electrolyte membrane containing an electrolyte solution and a gelling agent polymer.

[0006] The present invention also provides, in a second aspect thereof,
The following means: (a) a first electrode including a light-transmissive first conductive layer and a semiconductor layer electrically connected to the first conductive layer;
A second electrode including a conductive layer; and (c) disposed between the semiconductor layer of the first electrode and the second conductive layer, and electrically connected to both the semiconductor layer and the second conductive layer. A photovoltaic cell comprising a redox electrolyte layer, wherein the electrolyte layer comprises an electrolyte sheet including an electrolyte solution and a fibrous sheet impregnated with and holding the electrolyte solution. I will provide a.

In these photovoltaic cells provided by the present invention, the first electrode (a) further comprises a flexible support adhered to the first conductive layer, and the second electrode (b) Preferably further comprises a flexible support adhered to the second conductive layer.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in terms of its operation and embodiments. In the photovoltaic cell according to the first embodiment of the present invention, the electrolyte layer is characterized by comprising a gelled electrolyte membrane containing an electrolyte solution and a gelling agent polymer. Therefore, this electrolyte layer (1) maintains its performance as an electrolyte,
(2) It is possible to effectively prevent air bubbles from being mixed into the electrolyte layer, and (3) it is possible to form a flexible sheet-shaped photovoltaic cell which can be used by being relatively curved.

The electrolyte layer of this photovoltaic cell, that is, the gelled electrolyte membrane can be formed, for example, as follows. First, the gelling agent polymer is composed of water alone or dissolved in an aqueous solvent composed of a mixture of water and an organic solvent compatible with water to form a solution, and a redox agent is further added to the solution. Then, a coating liquid for forming an electrolyte layer is prepared. Then, the coating liquid is cast at a predetermined distance, that is, between two substrates opposed to each other with a gap therebetween to form a coating film, the coating film is gelated, and has a predetermined thickness. A gelled electrolyte membrane is obtained. As the gelling method, for example, a low-temperature crystallization method can be used.

In order to form the photovoltaic cell of the present invention, the base material on both sides thereof is removed from the gelled electrolyte membrane obtained as described above, and one of the two electrodes, ie, the first
The surface of a semiconductor layer of the electrode (or a photosensitizing layer described later),
Alternatively, the second electrode is disposed on the surface of the second conductive layer, and the other electrode is disposed on the surface of the electrolyte membrane. Therefore, there is no need to directly inject the solution into the gap between the first electrode and the second electrode, so that bubbles can be effectively prevented from entering the electrolyte layer. In addition, since the electrolyte layer is a gelled film, the fluidity can be suppressed as much as possible, and even when a flexible sheet-shaped photovoltaic cell is configured, a change in the thickness of the electrolyte layer when the photovoltaic cell is curved can be prevented. It can be effectively prevented.

[0011] In a photovoltaic cell according to a second aspect of the present invention, the electrolyte layer is characterized by comprising an electrolyte sheet comprising an electrolyte solution and a fibrous sheet impregnated with and holding the electrolyte solution. Therefore, this electrolyte layer can have the above-mentioned properties (1) to (3), similarly to the electrolyte layer of the photovoltaic cell in the first embodiment described above.

The electrolyte layer of the photovoltaic cell, that is, the electrolyte sheet, can be formed, for example, as follows. First, an electrolyte solution in which a redox agent is dissolved in a solvent is prepared. Then, this electrolyte solution is transferred to Japanese paper, woven cloth,
An electrolyte sheet is obtained by impregnating a sheet-shaped absorber such as a nonwoven fabric, that is, a fibrous sheet. As the fibrous sheet, for example, Japanese paper is suitable. This is because Japanese paper is relatively thin and durable, and is easily available, and has high retention of the impregnated electrolyte solution.

To form a photovoltaic cell, the electrolyte sheet obtained as described above is placed on one of two electrodes, ie, the surface of the semiconductor layer of the first electrode, or the second conductive layer of the second electrode. And the other electrode is disposed on the surface of the electrolyte membrane. Therefore, there is no need to directly inject the solution into the gap between the first electrode and the second electrode, so that bubbles can be effectively prevented from entering the electrolyte layer. Further, the fluidity of the electrolyte solution can be suppressed as much as possible, and even when a flexible sheet-shaped photovoltaic cell is formed, a change in the thickness of the electrolyte layer when the photovoltaic cell is curved can be effectively prevented. .

The flexible sheet-shaped photovoltaic cell according to the present invention comprises:
One of the above-mentioned gelled electrolyte membrane or electrolyte sheet is used as the electrolyte layer. In order to more effectively suppress the fluidity of the electrolyte layer, the electrolyte may be gelled after impregnating the fibrous sheet with an electrolyte solution containing a gelling agent polymer. Next, the formation of the photovoltaic cell of the present invention using the first electrode, the second electrode, and the electrolyte layer constituting the photovoltaic cell and their components will be described. First Electrode The first electrode has a structure including a light-transmitting first conductive layer and a semiconductor layer electrically connected to the first conductive layer.

The first conductive layer usually comprises a polymer film,
It is formed by applying a conductive material to the surface of a light-transmitting support such as glass. As a conductive material for forming the first conductive layer, ITO (indium tin oxide) or tin oxide is preferable from the viewpoint of light transmittance. The thickness of the first conductive layer is usually 10 nm to 1 mm, and the surface resistance value is usually 500 Ω / □ or less. The light transmittance of the first conductive layer is usually 70% or more. In addition,
The term "light transmission", as used herein, refers to the use of an ultraviolet / visible spectrophotometer at a wavelength of 55
It means the light transmittance measured using 0 nm light.

More specifically, the first conductive layer is formed by ordinary film forming means such as vapor deposition, sputtering, and application of a paste. For example, a conductive layer can be formed by directly providing a support on a support or providing a primer layer on a support and then forming a conductive layer on the primer layer. Also, instead of the primer layer,
The surface of the support may be subjected to an easy adhesion treatment such as a corona treatment. Alternatively, after a conductive layer is provided on a photosensitizing layer described later, a support can be laminated thereon. Further, the conductive layer provided on the release-treated surface of the temporary substrate can be transferred to the surface of the support via a transparent adhesive.
As such a temporary base material, a release paper, a release film, a low molecular weight polyethylene film or the like can be used.

When forming a flexible sheet-shaped photovoltaic cell,
As the light-transmitting support, for example, polyester resins such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate); acrylic resins such as polymethyl methacrylate and modified polymethyl methacrylate;
A film made of a fluororesin such as polyvinylidene fluoride or acryl-modified polyvinylidene fluoride; a polycarbonate resin; or a vinyl chloride resin such as a vinyl chloride copolymer can be used. As the support, a single-layer film can be used, but a multilayer film can also be used.

The light transmittance of the support is usually 60% or more, preferably 70% or more. The thickness of the support is usually 10 to 1,000 when forming a sheet-shaped photovoltaic cell.
μm. In addition, as long as the effects of the present invention are not impaired, the support may contain additives such as an ultraviolet absorber, a moisture absorbent, a coloring agent, a fluorescent substance, and a phosphorescent substance.

The semiconductor layer is a layer that is excited by the irradiated light and has a function of generating holes and free electrons. The semiconductor layer is usually formed from a titanium oxide film. The titanium oxide film usually has an anatase type crystal structure.
The anatase type titanium oxide film is formed, for example, by applying a raw material liquid formed by dissolving a titanium alkoxide in an alcohol to the surface of the first conductive layer, drying the coated liquid, and then heating at 400 to 500 ° C.
And formed by baking. As the raw material liquid, a dispersion liquid of fine particles of titania or a titania sol solution obtained by hydrolyzing titanium alkoxide can be used. An ordinary coating method such as spin coating, dip coating and spray coating can be used for coating the raw material liquid. Further, polyethylene glycol may be added to the raw material liquid so that a porous titanium oxide film can be obtained after firing. The thickness of the semiconductor layer is usually 10 nm to 1 mm. Note that the semiconductor layer is not limited to a titanium oxide film as long as the effects of the present invention are not impaired. For example, a zinc oxide film, a cadmium sulfide film, or the like can be suitably used.

Further, in order to effectively enhance the excitation action of the semiconductor layer, it is preferable to dispose a photosensitizing layer between the semiconductor layer and the electrolyte layer. The photosensitizing layer is provided by, for example, applying a coating solution containing a photosensitive agent on the surface of the semiconductor layer and drying the coating solution. In this case, the photosensitizing layer and the semiconductor layer can be easily electrically connected. Various metal complexes and organic dyes can be used as the photosensitive agent. As the metal complex, copper phthalocyanine, ruthenium complex, osmium complex and the like can be used, and as the organic dye, cyanine dye, merocyanine dye, xanthene dye, triphenylmethane dye and the like can be used. The thickness of the photosensitizing layer is usually 100
nm or less. In addition, the coating solution for the photosensitizing layer can be coated by a usual coating method such as spin coating, dip coating, spray coating and the like.

When a photosensitizing layer is used, usually, an electrolyte layer is brought into close contact with the surface of the photosensitizing layer, and a second layer is formed on the surface of the electrolyte layer.
The electrodes are brought into close contact to form the photovoltaic cell of the present invention. In this case, the irradiated light excites the photosensitizing layer, and can efficiently generate holes and free electrons. However, in this case, the semiconductor layer needs to be light-transmitting. The light transmittance of the semiconductor layer is usually 60% or more, preferably 70% or more.

The photosensitizing layer is preferably adsorbed on the semiconductor layer. In particular, the photosensitizer (photosensitizer) is completely adsorbed on the semiconductor layer and the "semiconductor layer on which the photosensitizer is adsorbed" And the electrolyte layer are preferably in direct contact with each other. In the latter case, the thickness of the photosensitizing layer is substantially zero. When the semiconductor layer is a porous titanium oxide film, the adsorption of the photosensitive agent as described above can be effectively performed. Second electrode The second electrode can also be formed in the same manner as the first electrode described above. For example, a conductive material is applied to the surface of the support to form the support. Such conductive materials include the above-described ITO.
And a light-transmitting conductive film such as tin oxide; a metal film such as gold and platinum; and a conductive film such as a conductive carbon film. The metal film is
For example, a deposition film, a sputtered film, or a metal foil is used. The thickness of the second electrode is usually 0.1 to 1,000 μm.

When the second electrode includes a support, the same as the first electrode can be used. When a flexible sheet-shaped photovoltaic cell is formed, a film made of the above-described resin can be used as a support for the second electrode. The thickness of the support is usually 10 to 1,000 when forming a sheet-shaped photovoltaic cell.
0 μm. Electrolyte layer The electrolyte layer is electrically connected to both the semiconductor layer and the second conductive layer. The state of such an electrical connection is
Usually, 1. 1. When the electrolyte layer is in direct contact with both the semiconductor layer and the second conductive layer, or The photovoltaic cell further includes a photosensitizing layer containing a photosensitizer or the like in direct contact with the electrolyte layer, wherein the photosensitizing layer and the semiconductor layer are in direct contact,
When the electrolyte layer and the second conductive layer are in direct contact with each other, it can be defined as one of the following. In the latter case, the photovoltaic effect can be effectively increased,
It is suitable.

The electrolyte forming the electrolyte layer is usually composed of a redox agent. As the redox agent, for example, a mixture of iodine and tetrapropylammonium iodide can be used. In addition, a mixture of iodine and potassium iodide can be used. When the gelled electrolyte membrane is formed, for example, it can be formed as follows. First, polyvinyl alcohol as a gelling agent polymer is dissolved in a mixed solvent of water and dimethyl sulfoxide while heating to form a polymer solution. The heating is performed, for example, in an autoclave, and the heating temperature is usually 80 to 100 ° C. Next, about 30-50
An oxidation-reduction agent is added to and dissolved in the polymer solution cooled to ° C to prepare a raw material solution. Finally, this raw material solution is
A coating film formed by casting in a gap between two substrates (temporary supports) or by coating on a substrate is gelled to obtain a gelled electrolyte membrane. The so-called low-temperature crystallization method in which the coating solution is cooled at −10 to −30 ° C. to form a gel when the raw material solution as described above is used is preferable. Thereby, a gelled electrolyte membrane having a desired thickness can be easily formed. The thickness of the electrolyte membrane is usually 0.01 to 500 μm.
m. The amount of the redox agent in the gelled electrolyte membrane is usually 0.1 to 1 mol per 100 g of the electrolyte membrane. Polymers such as polyethylene oxide and polyphosphazene can also be used as the gelling agent polymer.

In forming the photovoltaic cell, the substrate is removed from the gelled electrolyte membrane obtained as described above, and the gelled electrolyte membrane is disposed between two electrodes, and the first electrode, the electrolyte membrane and the second The target photovoltaic cell can be formed by bringing the three electrodes into close contact with each other. In addition, as long as the effects of the present invention are not impaired, one of the two electrodes, that is, the surface of the semiconductor layer of the first electrode (or the photosensitizing layer described above) or the second conductive layer of the second electrode. Apply the raw material solution directly to the surface,
It may be gelled to form an electrolyte membrane.

On the other hand, when the electrolyte sheet is formed, for example, it can be formed as follows. First, an electrolyte solution is prepared by dissolving the above-described redox agent (tetrapropylammonium iodide and iodine) in a mixed solvent of ethylene carbonate and acetonitrile. The mixed solvent has good solubility in the redox agent, has a relatively low volatilization rate, effectively suppresses a change in the redox agent concentration in the solution, has a relatively low surface tension, and has a low fiber content. This is preferable in that the impregnation into the porous sheet is easy. The weight ratio (E: A) of ethylene carbonate (E) and acetonitrile (A) in the above mixed solvent is usually 5
0:50 to 90:10. In addition, as the solvent, methanol can be used in addition to the above-mentioned mixed solvent. In short, any solvent that can dissolve (solvate) iodide ions can be used.

Next, a fibrous sheet such as Japanese paper is impregnated with the above-mentioned electrolyte solution to form an electrolyte sheet. The impregnation of the solution into the sheet can be performed, for example, by dropping a predetermined amount of an electrolyte solution on a fibrous sheet spread and arranged on a base material. Alternatively, the fibrous sheet may be immersed in the electrolyte solution, or the fibrous sheet may be used as a substrate to be applied, and the electrolyte solution may be applied and impregnated by applying means such as a brush, a spray, a knife coater, or a roll coater. The thickness of the fibrous sheet is usually 1 to 1,000 μm,
Density is usually 0.1-5 g / cm ^3. The amount of the oxidation-reduction agent in the impregnated electrolyte solution is determined by the amount of the electrolyte solution 1
The amount of impregnation of the electrolyte solution is usually 1 to 1 mol per 1 cm ^{3 of} the electrolyte sheet.
0 g.

In forming a photovoltaic cell, the electrolyte sheet obtained as described above is disposed so as to be sandwiched between two electrodes, and the first electrode, the electrolyte sheet and the second electrode are adhered to each other. Thus, a desired photovoltaic cell can be formed. In addition, as long as the effect of the present invention is not impaired, one of the two electrodes, that is, the surface of the semiconductor layer of the first electrode (or the photosensitizing layer described above) or the second electrode of the second electrode.
After disposing the fibrous sheet on the surface of the conductive layer, the electrolyte solution may be directly applied to form the electrolyte sheet.

[0029]

Next, the present invention will be described with reference to examples. It should be understood that the present invention is not limited to these examples. Example 1 In this example, a photovoltaic cell in which the electrolyte layer was formed of a gelled electrolyte membrane containing an electrolyte solution and a gelling agent polymer was produced.

First, 0.5 g of polyvinyl alcohol (PVA) having a polymerization degree of 1,750 was prepared.
Was added to 10 mL (milliliter) of a mixed solvent obtained by mixing dimethyl sulfoxide and water at a weight ratio of 7: 3.
Melt in an autoclave at 30 ° C for 30 minutes,
It was made by preparing a clear, viscous solution. After cooling the obtained PVA solution to 40 ° C., a redox agent composed of 0.025 g of iodine and 0.78 g of tetrapropylammonium iodide was dissolved therein to prepare a coating solution for forming an electrolyte layer. This coating solution was cast in a gap between the two substrates, and then cooled in a freezer at a temperature of -20 ° C for 24 hours to obtain a gelled electrolyte membrane having a thickness of 0.1 mm.

Subsequently, a glass support with an ITO film [made by Asahi Glass Co., Ltd., (product name) ITO glass substrate thickness = about 1.1 m]
m] was prepared, and a titanium oxide film (light-transmitting semiconductor layer) was formed on the ITO film as follows. First,
0.01 mol titanium alkoxide [manufactured by Wako Pure Chemical Industries, Ltd., (product name) titanium tetraisopropoxide No.207-0
8176] and 0.01 mol of tetraethanolamine (reaction inhibitor) dissolved in 60 mL of isopropyl alcohol to prepare an alcohol solution. This alcohol solution was spin-coated on the ITO film, and then sintered in an oven at 450 ° C. to form a semiconductor layer electrically connected to the first conductive layer. Thereby, the glass support /
A laminate was obtained by laminating the first conductive layer / semiconductor layer in this order.

Further, a ruthenium metal complex and cis- (S
CN) ₂ -bis (2,2'-bipyridyl-4,4'-dicarboxylate) ruthenium (II) [Ruthenium 535 (product name, manufactured by Solaronix)
Was dissolved in N, N-dimethylformamide (DMF), and the laminate was immersed in this solution to adsorb a photosensitive agent to the semiconductor layer. Since the semiconductor layer obtained as described above was a porous titanium oxide film, adsorption of the photosensitive agent was easy. As a result, a first electrode was obtained in which the glass support / the first conductive layer / the semiconductor layer on which the photosensitive agent was adsorbed were laminated in this order.

The second electrode is made of the same ITO as the first electrode.
A glass support with a membrane was used. The gelled electrolyte film is attached to the surface of the photosensitized layer of the first electrode, and the second electrode is laminated thereon, and only by light pressure contact, air bubbles are generated between the electrolyte film and the two electrodes. Without entering, the photovoltaic cell of this example could be produced very easily. Comparative Example 1 A photovoltaic cell of this example was produced in the same manner as in Example 1, except that the electrolyte layer was formed as follows.

First, as an electrolyte solution, a redox agent consisting of 0.5 mol of tetrapropylammonium iodide and 0.04 mol of iodine was mixed with 80% by volume of ethylene carbonate and 20% by volume of ethylene carbonate. A solution dissolved in a mixed solvent with acetonitrile was prepared. Next, the first electrode and the second electrode were opposed to each other at a distance, and the electrolyte solution was carefully and gradually sealed so as to prevent air bubbles from entering the gap.
The thickness of the liquid electrolyte layer was 0.1 mm. Example 2 In this example, a photovoltaic cell in which an electrolyte layer was formed of an electrolyte sheet including an electrolyte solution and a fibrous sheet impregnated with and holding the electrolyte solution was manufactured. A photovoltaic cell of this example was produced in the same manner as in Example 1, except that the electrolyte sheet produced as described below was used.

First, as an electrolyte solution, a redox agent consisting of 0.5 mol of tetrapropylammonium iodide and 0.04 mol of iodine was mixed with 80% by volume of ethylene carbonate and 20% by volume of ethylene carbonate. A solution dissolved in a mixed solvent with acetonitrile was prepared. Next, this electrolyte solution was placed in a glass petri dish, Japanese paper having a thickness of 24 μm and a density of 0.66 g / cm was immersed in the solution, and the electrolyte solution was impregnated at a rate of 2.8 g / cm ³ to prepare an electrolyte sheet. did.

The electrolyte sheet is sandwiched between the first electrode and the second electrode and pressed lightly, so that no air bubbles enter between the electrolyte membrane and the two electrodes. Was manufactured. Comparative Example 2 A photovoltaic cell of this example was produced in the same manner as in Comparative Example 1, except that the thickness of the electrolyte layer was changed to 24 μm. [Evaluation of Photovoltaic Cell Performance] With respect to the photovoltaic cells produced in Examples 1 and 2 and Comparative Examples 1 and 2, the photocurrent and electromotive force were measured by irradiating each photocell with a halogen lamp from the first electrode side. . The measurement of the photocurrent and the electromotive force was performed by connecting the ammeter and voltmeter probes directly to the electrodes of the photovoltaic cell. The plane size of the measurement sample was 2 cm × 2 cm, and the output (wattage) of the halogen lamp was 360 in Example 1 and Comparative Example 1.
W, 500 W in Example 2 and Comparative Example 2.

When the photocurrent and the electromotive force of Example 1 and Comparative Example 1 were compared, Example 1: Photocurrent = 2.60 mA, electromotive force = 0.59 V, Comparative Example 1: Photocurrent = 2. 23 mA, electromotive force = 0.40 V. That is, the battery performance of the photovoltaic cell of the first embodiment of the present invention is at the same level as that of the conventional photovoltaic cell, and since the gelled electrolyte membrane is used, the cell performance is higher than that of the conventional photovoltaic cell (Comparative Example 1). Manufacturing was easy. In addition, even when the glass support is changed to a flexible support such as a PET film to form a flexible sheet-shaped photovoltaic cell, a change in the thickness of the electrolyte layer when the photovoltaic cell is curved is effectively prevented. did it.

Further, comparing the photocurrent and the electromotive force of Example 2 and Comparative Example 2, it can be seen that Example 2: Photocurrent = 1.31 mA, Electromotive force = 0.26 V, Comparative Example 2: Photocurrent = 1.05 mA, electromotive force = 0.29 V. That is, the battery performance of the photovoltaic cell according to the second embodiment of the present invention is at the same level as that of the conventional photovoltaic cell, and since the electrolyte sheet is used, the production is smaller than that of the conventional photovoltaic cell (Comparative Example 2). It was easy. In addition, even when the glass support is changed to a flexible support such as a PET film to form a flexible sheet-shaped photovoltaic cell, a change in the thickness of the electrolyte layer when the photovoltaic cell is curved is effectively prevented. did it.

[0039]

As described above, according to the present invention, when the photovoltaic cell is manufactured, when the electrolyte layer is arranged in the gap between the first electrode and the second electrode, bubbles are generated in the electrolyte layer. It can be effectively prevented from entering, so that it is easy to manufacture, and even when a flexible sheet-shaped photovoltaic cell is formed, a change in the thickness of the electrolyte layer when the photovoltaic cell is curved is effectively prevented. It is possible to prevent a decrease in battery performance such as electromotive force.

Continued on the front page (72) Inventor Takashi Harada 3-8-8 Minamihashimoto, Sagamihara City, Kanagawa Prefecture Sumitomo 3M Limited

Claims (4)

[Claims] 1. The following means: (a) a first electrode including a light-transmitting first conductive layer and a semiconductor layer electrically connected to the first conductive layer; (b) a second conductive layer And (c) a redox disposed between the semiconductor layer of the first electrode and the second conductive layer and electrically connected to both the semiconductor layer and the second conductive layer. A photovoltaic cell comprising: a neutral electrolyte layer, wherein the electrolyte layer comprises a gelled electrolyte membrane containing an electrolyte solution and a gelling agent polymer. 2. The flexible substrate according to claim 1, wherein said first electrode further comprises a flexible support adhered to said first conductive layer, and said second electrode comprises a flexible support adhered to said second conductive layer. The photovoltaic cell according to claim 1, further comprising a volatile support. 3. The following means: (a) a first electrode including a light-transmitting first conductive layer and a semiconductor layer electrically connected to the first conductive layer; (b) a second conductive layer And (c) a redox disposed between the semiconductor layer of the first electrode and the second conductive layer and electrically connected to both the semiconductor layer and the second conductive layer. A photovoltaic cell comprising: an electrolyte layer, comprising: an electrolyte sheet including an electrolyte solution and a fibrous sheet impregnated with and holding the electrolyte solution. 4. The flexible electrode according to claim 1, wherein said first electrode further comprises a flexible support adhered to said first conductive layer, and said second electrode comprises a flexible support adhered to said second conductive layer. 4. The photovoltaic cell according to claim 3, further comprising a porous support.