WO2012169302A1 - Dye-sensitized solar cell - Google Patents

Abstract

[Problem] To provide a cylindrical dye-sensitized solar cell that suppresses internal resistance of the cell to a low level, does not cause a decrease in voltage, and has: a photoelectrode that is within a tube vessel comprising transparent glass and comprises a semiconductor layer that carries a sensitizing dye; a collector electrode provided contacting the photoelectrode; a counter electrode that faces the collector electrode; and an electrolyte liquid that is sealed in the tube vessel. [Solution] The dye-sensitized solar cell is characterized by the photoelectrode being provided by being coated and baked onto the inner surface of the tube vessel, and the collector electrode being provided contacting the photoelectrode and comprising a metal layer having an aperture through which the electrolye liquid can pass.

Description

Dye-sensitized solar cell

The present invention relates to a dye-sensitized solar cell that converts light energy into electric energy.

Conventionally, solar cells that convert solar energy into electrical energy have been actively researched and developed as environmentally friendly and clean energy sources. Among them, a dye-sensitized solar cell has attracted attention as a low-cost solar cell with high photoelectric conversion efficiency, and various proposals have been made.

In this dye-sensitized solar cell, a sensitizing dye is supported on a semiconductor layer as a negative electrode, an electrolyte is sealed between the opposite positive electrode, and sunlight is incident on the negative electrode. This is excited and taken out as electric energy, such as JP 2000-323189 A (Patent Document 1).
The solar cell having the structure shown in FIG. 10 is shown. A transparent conductive layer (for example, an ITO film) is laminated on a transparent substrate 80 such as transparent glass or a transparent resin film to form a collector electrode 81. A porous metal oxide semiconductor layer 82 such as titanium dioxide is provided on the collector electrode 81, and a sensitizing dye (for example, Ru dye) is supported on the semiconductor layer 82 to form a photoelectrode (negative electrode) 83.
On the other hand, a counter electrode (positive electrode) 85 is formed on the substrate 84, the counter electrode 85 is disposed to face the photoelectrode 83, and an electrolyte solution 86 is sealed between them. .

That is, the transparent substrate 80, the collector electrode (transparent conductive layer) 81, the semiconductor layer 82 (photoelectrode 83), the electrolyte layer (electrolyte solution) 86, the counter electrode 85, and the substrate 84 are sequentially laminated from the light incident side. Configured.
In the dye-sensitized solar cell having such a structure, when visible light (sunlight) is irradiated from the photoelectrode (negative electrode) 83 side, the sensitizing dye in the photoelectrode 83 is excited, and from the ground state. Transition to an excited state, the excited electrons of the dye are injected into the conduction band of the porous layer of the semiconductor 81 and move to the counter electrode (positive electrode) 85 through the external circuit 88. The electrons that have moved to the positive electrode 85 are carried by the ions in the electrolyte 86 and return to the dye. Electric energy is extracted by repeating such a process.

As described above, in such a dye-sensitized solar cell, the photoelectrode (semiconductor layer) 83 is generally provided on the translucent substrate 80 via the collector electrode 81 made of a transparent conductive layer. Is. Since this transparent conductive layer 81 has a higher resistance than metal, it increases the internal resistance of the battery, resulting in a significant voltage drop with a small current.
On the other hand, since the voltage of a dye-sensitized solar cell is low with only a single cell, it is necessary to connect a large number of cells in series to increase the voltage value. If the cells are arranged in series, the internal resistance described above also accumulates. Is done. In other words, there is a problem that a very large loss occurs in practical use.

In view of such problems, in recent years, as seen in Japanese Patent Application Laid-Open No. 2010-225317 (Patent Document 2), porous metal vapor deposition is performed on a metal oxide layer provided on a transparent substrate as a collector electrode. And a structure in which mesh metal is laminated is proposed.
FIG. 11 shows this structure.
In FIG. 11, a photoelectrode 83 made of a metal oxide provided on a transparent substrate 80 is provided, and a metal plate having a plurality of openings 90 a is provided thereon to form a collector electrode 90. This is disposed opposite to the counter electrode 85 provided on the substrate 84, and an electrolyte solution 86 is sealed therebetween.
In the above configuration, the electrolyte 86 penetrates the porous photoelectrode 83 from the opening 90a of the collector electrode 90, and the sensitizing dye carried in the photoelectrode 83 reacts to light from the outside.

Thus, since the metal plate having a low resistance value is used as the collector electrode 90 instead of the collector electrode 81 made of the transparent conductive layer of the prior art shown in FIG. 10, the transparent conductive layer 81 made of an ITO layer or the like has It is expected to solve problems such as high resistance and a large voltage drop with a small current.
However, although this structure can be applied to a solar cell having a rectangular box shape as a whole, it cannot be applied to a cylindrical solar cell structure.
This will be described with reference to FIG. A photoelectrode 83 is formed on the outer peripheral surface of a collector electrode 90 made of a cylindrical multi-hole metal plate, and a concentric cylindrical counter electrode 85 is provided so as to face the collector electrode 90, and these collector electrodes An electrolyte 86 is sealed between 90 and the counter electrode 85.
A cylindrical transparent substrate 80 is provided on the outer periphery of the photoelectrode 83.

However, since both the transparent substrate 80 and the photoelectrode 83 have a cylindrical shape, they cannot be brought into contact with each other so as to be in close contact with each other, and it is unavoidable that a gap S is generated between them. Absent.
Therefore, a situation occurs in which the electrolyte solution 86 that has penetrated into the porous photoelectrode 83 through the opening 90a of the collector electrode 90 enters the gap S and is filled therein.
When the gap 86 is filled with the electrolyte solution 86, light from the outside is excessively applied to the electrolyte solution 86, the electrolyte solution 86 is deteriorated, and the photoelectrode 83 is shielded by the electrolyte solution 86. As a result, there is a problem that the amount of light reaching the photoelectrode 83 is insufficient, the conversion efficiency is lowered, and desired power cannot be obtained.

JP 2000-323189 A JP 2010-225317 A

The problems to be solved by the present invention are as follows. In the dye-sensitized solar cell provided with a tubular container, the internal resistance can be lowered and the electrolytic solution is externally provided. It is intended to provide a structure that does not deteriorate due to light from the light source or that the amount of light that reaches the photoelectrode is not reduced by being absorbed by the electrolyte.

In order to solve the above problems, in the dye-sensitized solar cell according to the present invention, a photoelectrode comprising a semiconductor layer carrying a sensitizing dye in the tubular container made of translucent glass, and the photoelectrode A collecting electrode provided in contact with the collecting electrode, a counter electrode facing the collecting electrode, and an electrolyte solution enclosed in the tubular container, and the photoelectrode is applied to the inner surface of the tubular container. The collector electrode is formed by firing, and the collector electrode is made of a metal layer having an opening through which an electrolytic solution can pass, and is provided in contact with the photoelectrode.

The collector electrode is formed by spraying metal.
Further, the collector electrode is provided on the inner surface of the photoelectrode.
Further, the collector electrode is formed by spraying a metal on porous glass fired on the inner surface of the photoelectrode.
In addition, a part of the photoelectrode exists between the collector electrode and the counter electrode, and functions as an insulating spacer between the counter electrode.
The collector electrode is formed on the inner surface of the tubular container.
The collector electrode is embedded in the semiconductor layer of the photoelectrode, spaced from the inner surface of the tubular container.
Further, the photoelectrode has a plurality of protrusions protruding toward the counter electrode,
The collector electrode is formed by being laminated on the photoelectrode, and the protruding portion of the photoelectrode protrudes from the opening formed in the collector electrode toward the counter electrode.

According to the dye-sensitized solar cell of the present invention, since the photoelectrode is directly formed on the inner surface of the tubular container, no gap is formed between them, so that the electrolyte enters between them. Therefore, it is possible to realize a columnar dye-sensitized solar cell using a more efficient metal collector electrode without causing deterioration of the electrolytic solution or reduction of the amount of light.

Schematic of the light irradiation apparatus of this invention. (A) is a cross-sectional view of FIG. (B) is an enlarged view thereof. Thermal spray mask pattern of collector electrode. Explanatory drawing of the manufacturing process of the dye-sensitized solar cell of this invention. (A) is sectional drawing of the other Example of a metal collector electrode. (B) is an enlarged view thereof. The expanded sectional view of other Examples. Furthermore, the expanded sectional view of another Example. Furthermore, the expanded sectional view of another Example. Explanatory drawing of the manufacturing process of the Example of FIG. Sectional drawing of the conventional rectangular box type dye-sensitized solar cell. Sectional drawing of the other conventional rectangular box type dye-sensitized solar cell. Sectional drawing which made the dye-sensitized solar cell of another prior art example cylindrical shape.

FIG. 1 is a cross-sectional view showing the entire dye-sensitized solar cell of the present invention, FIG. 2 (A) is a transverse cross-sectional view thereof, and FIG. 2 (B) is an enlarged view thereof.
The cylindrical tubular container 1 is made of a translucent material, for example, a glass tube such as quartz glass or soda glass, and comprises a central body portion 2 and sealing portions 3 and 3 at both ends thereof. A photoelectrode (negative electrode) 4 is formed on the inner surface of the main body 2 of the tubular container 1.
The photoelectrode 4 is a semiconductor layer for photoelectric conversion of sunlight, and is composed of a porous layer formed by depositing semiconductor fine particles, for example, metal oxide or metal sulfide.
Such semiconductor fine particles can use, for example, titanium oxide, tin oxide, zinc oxide, niobium oxide, tantalum oxide, zirconium oxide, or the like as the metal oxide, and as the metal complex oxide, for example, Strontium titanate, calcium titanate, barium titanate and the like can also be used. In the case of a metal sulfide, for example, zinc sulfide, lead sulfide, bismuth sulfide, etc. can be used.
The semiconductor layer is produced by applying a paste containing the metal oxide and metal sulfide fine particles to the inner surface of the tubular container 1 and firing the paste. As a paste application method, for example, a screen printing method, a doctor blade method, a squeegee method, or the like can be used.

A sensitizing dye is supported on the semiconductor fine particles constituting the photoelectrode 4.
The sensitizing dye is a dye such as a metal complex or an organic dye having absorption characteristics in the visible light region or in addition to the infrared light region, and can be appropriately selected and used.
As the metal complex, for example, a metal phthalocyanine such as copper phthalocyanine or titanyl phthalocyanine, chlorophyll, or a derivative thereof, a complex of hemin, ruthenium, osmium, iron, or zinc can be used.
Examples of organic dyes include metal-free phthalocyanine, cyanine dyes, methocyanine dyes, xanthene dyes, triphenylmethane dyes, phthalocyanine dyes, naphthalocyanine dyes, phthalo / naphthalene mixed phthalocyanine dyes, and dipyridyl ruthenium complexes. A dye, a terpyridyl ruthenium complex dye, a phenanthroline ruthenium complex dye, a phenylxanthene dye, a triphenylmethane dye, a coumarin dye, an acridine dye, or an azo metal complex dye can be suitably used.

A collecting electrode 5 made of metal is formed on the inner surface of the photoelectrode 4 in a laminated state. The collector electrode 5 functions as a current collection assist.
As shown in FIGS. 2A and 2B, the collector electrode 5 is made of a metal layer formed with an opening 5a through which an electrolyte solution 13 to be described later can pass on the photoelectrode 4 side. In addition, a suitable pattern such as a stripe shape is formed.
As a manufacturing method of the collector electrode 5, for example, a mask pattern MP as shown in FIG. 3 is inserted into the tubular container 1, and a predetermined metal is sprayed thereon to form a film.
The thermal spraying method is not limited, but in the case of a gas type, methods such as hot wire flame spraying, powder flame spraying, high-speed flame spraying, and cold spraying can be employed. In the case of the electric type, a method such as arc spraying or reduced pressure plasma spraying can be employed.

Thus, since the collector electrode 5 is formed by thermal spraying, a uniform and homogeneous film can be formed even in a portion where the film forming operation is difficult, such as the inside of the tubular container 1, and furthermore, the photoelectrode 4. Thus, the current collecting function can be sufficiently exhibited.
The metal constituting the collector electrode 5 is not particularly limited, but specific metal materials include, for example, titanium, aluminum, iron, nickel, iron-nickel alloy, copper, copper-nickel alloy, niobium, Tungsten, tantalum, chromium, stainless steel alloy, etc. can be mentioned. Any of these metal materials can suppress the internal resistance more than the transparent electrode (ITO) which is a collector electrode material in the prior art, so that an efficient solar cell can be obtained.
In the present invention, metallic titanium, aluminum, copper, copper-nickel alloy, or stainless steel alloy is preferably used. The reason is that these metal materials are superior in corrosion resistance due to the electrolytic solution, and are superior to those having a configuration in which the collector electrode is in contact with the electrolytic solution as in the solar cell according to the present invention.

A counter electrode (positive electrode) 6 is provided inside the tubular container 1 so as to be separated from the collector electrode 5. In this embodiment, the counter electrode 6 has a coil shape, and the material thereof is, for example, platinum or a conductive material such as a platinum thin film, rhodium, ruthenium, ruthenium oxide, carbon or the like. Materials can be used. These conductive materials are suitable because they have a catalytic ability to perform the reduction reaction of the electrolytic solution at a sufficient speed.
The shape of the counter electrode 6 is not limited to a coil shape, and may be a rod shape or a plate shape.
In addition, insulating spacers 7 are arranged on the outer periphery of the counter electrode 6 so as to be spaced apart from each other in the circumferential direction, thereby preventing the counter electrode 6 and the collector electrode 5 from contacting each other.
In addition, this spacer 7 is not an essential structure, and if the insulating property between the electrodes 5 and 6 can be stably maintained, a structure without the spacer 7 may be provided. Moreover, it is also possible to use the separator used for a secondary battery instead of the spacer 7. FIG. The separator electrically isolates the positive electrode and the negative electrode and allows ions in the electrolytic solution to pass through, and has a function equivalent to that of the spacer in terms of insulation and ion flow.

Both ends of the counter electrode 6 are connected to internal leads 8a and 8b, respectively. These internal leads 8a and 8b are made of metal foils 9a and 9b embedded in sealing portions 3a and 3b at both ends of the tubular container 1, respectively. To the external leads 10a and 10b. At this time, one internal lead 8a is directly connected to the counter electrode 6 and is in an electrically conductive state, while the other internal lead 8b is connected to the counter electrode 6 via the insulating connecting portion 11, The counter electrode 6 and the internal lead 10b are electrically insulated.
The internal lead 8 b is electrically connected to the collector electrode 5 through a collector terminal 12.
In this way, the external lead 8b of the counter electrode (+) and the external lead 8a of the collector electrode 5 (−) are led out from both ends of the tubular container 1, respectively.

The sealing portions 3a and 3b at both ends of the tubular container 1 are similar to a sealing portion structure such as a pinch seal in a lamp, and metal foils 9a and 9b embedded in the sealing portions 3a and 3b at both ends. The inner leads 8a and 8b and the outer leads 10a and 10b are welded to each other, and the sealing portions 3a and 3b are heated to crush and seal the metal foils 9a and 9b as a center. 1 is sealed in a liquid-tight state.

An electrolytic solution 13 is hermetically sealed in the tubular container 1, and the photoelectrode 4, the collecting electrode 5, the counter electrode 6 and the like are immersed in the electrolytic solution 13.
Specifically, this electrolytic solution 13 is made of redox electrolyte such as I− / I ₃ − system, Br− / Br ₃ − system, quinone / hydroquinone system, etc., and electrochemically such as acetonitrile, propylene carbonate, ethylene carbonate and the like. Inert solvents such as water, alcohols, ethers, esters, other inert solvents, or electrolytes dissolved in mixed solvents thereof can be used. For example, as an I− / I ₃ − electrolyte, an ammonium salt of iodine or a mixture of lithium iodide and iodine can be used. Moreover, when setting it as a gel-like electrolyte layer, in addition to the electrolyte mentioned above, you may contain a gelatinizer. In addition, an ionic electrolyte containing no iodine may be used.

A method for producing the dye-sensitized solar cell having the above-described configuration will be described below with reference to FIG.
4A, a photoelectrode 4 and a collecting electrode 5 are laminated on the inner surface of the axial central region of the tubular container 1 from the inner peripheral surface side. In addition, the electrode non-formation area | region X in which the electroconductive substance by the photoelectrode 4, the collector electrode 5, etc. is not formed exists in a part of both ends of the tubular container 1. FIG.
An electrode mount M having a counter electrode 6 is inserted into the tubular container 1.
In this electrode mount M, an internal lead 8a, a metal foil 9a and an external lead 10a are connected to one end of a counter electrode 6 formed in a coil shape, and an insulation is provided to the other end of the counter electrode 6. The connecting portion 11, the internal lead 8b, the metal foil 9b, and the external lead 10b are connected to each other. The internal lead 8 b is electrically connected to the collector electrode 5 via the collector terminal 12.
Insulating spacers 7 are attached to the outer periphery of the counter electrode 6 at intervals in the circumferential direction.

As shown in FIG. 4B, the electrode mount M inserted into the tubular container 1 is held in a state where tension is applied to the counter electrode 6, and the electrode non-formation region X at both ends of the tubular container 1 is maintained. Is heated to soften the glass and crushed from a direction perpendicular to the surface of the metal foil 9 to form flat sealing portions 3a and 3b.
As a result, both openings of the tubular container 1 are sealed with a structure similar to the sealed portion of the arc tube in the lamp, and the inside of the tubular container 1 is sealed.

As shown in FIG. 4C, a thin glass tube 14 is connected to the side surface of the tubular container 1 thus sealed. The glass tube 14 is provided so that the inside thereof communicates with the inside of the tubular container 1 and functions as a tube for injecting an electrolyte.
The electrolytic solution 13 is injected from the electrolytic solution injection glass tube 14 to fill the inside of the tubular container 1, and then the end of the injection tube 14 is heated and sealed. As a result, a state in which the tubular container 1 filled with the electrolytic solution 13 is hermetically sealed is obtained.
In the figure, in order to facilitate understanding of the structure, structures such as an electrode mount in the tubular container 1 are omitted.
In this way, a dye-sensitized solar cell as shown in FIG. 4D is obtained.

As shown in FIG. 2, according to the dye-sensitized solar cell having the above-described configuration, the electrolytic solution 13 sealed in the tubular container 1 is passed through the opening 5 a of the metal collector electrode 5. Infiltrate into 4. Then, the light that has entered the translucent tubular container 1 is applied to the photoelectrode 4.
As a result, the dye supported on the semiconductor layer of the photoelectrode 4 is excited and transitions from the ground state to the excited state, and the electrons of the excited dye are injected into the conduction band of the semiconductor layer, and are collected from the metal. Move to electrode 5.
The dye that has lost the electrons receives electrons from the ions of the electrolytic solution 13. The molecule that has passed the electrons receives the electrons from the counter electrode 6.
Electric energy is extracted by repeating such a process.

Hereinafter, other examples of the present invention will be described.
FIG. 5 is a cross-sectional enlarged view of the tubular container 1 corresponding to FIG. 2 (B) in the second embodiment.
In this embodiment, the shape of the collecting electrode 5 is different from that of the embodiment shown in FIG. 2, and a porous glass film 15 is formed on the photoelectrode 4 and a metal is sprayed thereon. .
That is, a porous glass such as shirasu porous glass (SPG [Shirau Porous Glass]) is applied and fired on the photoelectrode 4 to form a porous glass film 15, and metal is sprayed thereon to form a metallic collection. The electrode 5 is formed.
The sprayed metal penetrates between the porous glass particles 15 a of the porous glass film 15 and is coated on the photoelectrode 4. The porous glass particles 15a function as the openings 4a of the embodiment shown in FIG. 2, and the electrolytic solution 13 passes through the pores of the porous glass particles 15a themselves to enter the photoelectrode 4 It will penetrate into
Also in this embodiment, an insulating spacer 7 is provided on the outer periphery of the counter electrode 6 as necessary.
According to this embodiment, when the collector electrode 5 is formed, the metal may be sprayed on the porous glass film without using the spray mask pattern as shown in FIG. Although the number of processes is increased, workability related to thermal spraying is improved.
Further, as a manufacturing problem, for example, even when the mask pattern cannot be mounted such that the tubular container is formed of a thin tube, it is advantageous that a collector electrode can be provided.
In addition, in the example of forming the collector electrode without using the mask pattern, in addition to using the porous glass film described above, for example, a surfactant is added to the metal spray solution and foamed and applied, or the metal spray solution Alternatively, a heat volatilizing agent (for example, cyclic dimethyl silicone oil) may be added to and heated to volatilize.

In the embodiment shown in FIGS. 6 to 8, a part of the photoelectrode 4 formed in the tubular container 1 exists between the collecting electrode 5 and the counter electrode 6, and insulation between the counter electrode 6 is performed. In the embodiment functioning as a spacer, the insulating spacer 7 provided on the counter electrode 6 in the embodiment shown in FIGS. 2 and 5 can be omitted.

In FIG. 6, the collecting electrode 5 is directly formed on the inner surface of the tubular container 1 by metal spraying. When the semiconductor layer constituting the photoelectrode 4 is applied from above the collecting electrode 5, a large number of the collecting electrodes 5 are formed. Is applied to the inner surface of the tubular container 1 through the opening 5a. At this time, the photoelectrode 4 is applied to the counter electrode 6 side beyond the collecting electrode 4. Thereafter, the photoelectrode 4 is fired.
By doing so, the collector electrode 5 is embedded in the photoelectrode 4, and a part of the collector electrode 5 exists on the counter electrode 6 side from the photoelectrode 5, and insulation between the counter electrode 6 is present. Functions as a spacer. Therefore, it is not necessary to provide an insulating spacer on the counter electrode 6.
Light from the outside is irradiated to the photoelectrode 4 through the opening 5 a of the collector electrode 5 and reacts with the electrolytic solution 13 that has penetrated into the photoelectrode 4.

In the embodiment shown in FIG. 7, the collector electrode 5 is not formed on the inner surface of the tubular container 1 but is completely embedded in the photoelectrode 4.
This form is created by the following procedure.
First, a semiconductor layer constituting the photoelectrode 4 is formed on the inner surface of the tubular container 1 by coating and baking. The semiconductor layer has nano-sized holes, and an appropriate complex dye is supported on the inner surface of the holes. On the inner surface of the photoelectrode 4 thus configured, the collector electrode 5 is laminated and formed by metal spraying. In this case, the thermal spraying using the thermal spray mask pattern as shown in FIG. 3 is the same. Further, a semiconductor layer is applied on the metal collector electrode 5 and fired.
According to this embodiment, since the inner surface of the tubular container 1 is entirely covered with the photoelectrode 4, the external light is irradiated to all of the photoelectrode 4 without being blocked by the collecting electrode 5, and the conversion efficiency is improved. There is no drop due to the collector electrode 5.

In the embodiment shown in FIG. 8, the photoelectrode 4 formed on the tubular container 1 has a protruding portion 4 a, and the protruding portion 4 a is formed from the opening 5 a of the collecting electrode 5 formed on the photoelectrode 4. It is a form which protrudes to the side.
The creation procedure will be described with reference to FIG. First, a paste containing semiconductor fine particles constituting the photoelectrode 4 is applied in the tubular container 1 (A). Next, a jig having an uneven surface is pressed against the semi-sintered semiconductor layer to form a protrusion 4a on the semiconductor layer (B). This is sintered to form the photoelectrode 4 having the protrusions 4a on the surface (C). Then, the collector electrode 5 is formed by metal spraying on the photoelectrode 4 (D). At this time, the protruding portion 4 a of the photoelectrode 4 protrudes from the opening 5 a of the collecting electrode 5 toward the counter electrode 6, and this protruding portion 4 a functions as an insulating spacer with the counter electrode 6.
In order to prevent metal from being sprayed on the tip of the projecting portion 4a, the tip may be sprayed with a mask, or the tip may be polished to remove the metal coating after spraying. Good.
According to this embodiment, as in the embodiment of FIG. 7, the tubular container 1 is entirely covered with the photoelectrode 4, so that external light is not blocked by the collector electrode 5, and the photoelectrode 4 is once There is an advantage that it can be formed by coating and baking.

As described above, according to the dye-sensitized solar cell of the present invention, the photoelectrode is provided by being applied and fired on the inner surface of the tubular container, and the collector electrode has an opening through which the electrolytic solution can pass. The internal resistance of the battery can be kept low compared to the conventional one in which the collector electrode is a transparent electrode, and the voltage drop is reduced. Can be suppressed.
Accordingly, when a large number of cells (batteries) are connected in series for the purpose of increasing the voltage, the loss accumulated by the series connection of the cells can be greatly reduced.
In addition, when producing a cylindrical solar cell using a tubular container, the semiconductor layer constituting the photoelectrode is directly applied and fired on the inner surface of the tubular container, so that the gap between the photoelectrode and the inner surface of the tubular container is It can be provided without forming a gap.
Therefore, the photoelectrode can be provided without forming a portion where only the electrolytic solution exists on the inner surface of the tubular container, so that the photoelectrode can be efficiently irradiated with light and the electrolytic solution is excessively irradiated with light. This can also be avoided, and deterioration of the electrolyte can be suppressed.
In this way, a cylindrical dye-sensitized solar cell having many advantages over the rectangular box-type dye-sensitized solar cell can be realized.
Although the tubular container 1 has been described as having a cylindrical shape, it may have an appropriate tubular cross-sectional shape such as a square tube shape.

DESCRIPTION OF SYMBOLS 1 Tubular container 2 Main-body part 3 Sealing part 4 Photoelectrode 4a Protrusion part 5 Current collection electrode 5a (For electrolyte solution) Opening 6 Counter electrode 7 Insulation spacer 8 Internal lead 9 Metal foil 10 External lead 11 Insulation connection part 12 Current collection terminal 13 Electrolytic solution 15 Porous glass 15a Porous particle MP Mask pattern for metal spraying X Electrode non-formation region M Electrode mount

Claims (8)

In a dye-sensitized solar cell having a tubular container made of translucent glass,
Inside the tubular container, a photoelectrode composed of a semiconductor layer carrying a sensitizing dye, a collector electrode provided in contact with the photoelectrode, a counter electrode facing the collector electrode, and the tubular container An enclosed electrolyte solution,
The photoelectrode is applied and fired on the inner surface of the tubular container,
The dye-sensitized solar cell, wherein the collector electrode is made of a metal layer having an opening through which an electrolytic solution can pass, and is provided in contact with the photoelectrode. The dye-sensitized solar cell according to claim 1, wherein the collector electrode is formed by spraying metal. 3. The dye-sensitized solar cell according to claim 1, wherein the collector electrode is provided on an inner surface of the photoelectrode. 3. The dye-sensitized solar cell according to claim 1, wherein the collector electrode is formed by spraying metal on porous glass fired on the inner surface of the photoelectrode. 4. . 3. The dye sensitization according to claim 1, wherein a part of the photoelectrode exists between the collector electrode and the counter electrode and functions as an insulating spacer between the counter electrode and the counter electrode. Type solar cell. The dye-sensitized solar cell according to claim 5, wherein the collector electrode is formed on an inner surface of the tubular container. 6. The dye-sensitized solar cell according to claim 5, wherein the collector electrode is embedded in the semiconductor layer of the photoelectrode at a distance from the inner surface of the tubular container. The photoelectrode has a plurality of protrusions protruding toward the counter electrode,
The collector electrode is formed by being laminated on the photoelectrode, and a protruding portion of the photoelectrode protrudes from an opening formed in the collector electrode toward the counter electrode. 5. The dye-sensitized solar cell according to 5.

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