JP5398498B2 - Dye-sensitized photoelectric conversion element - Google Patents

Description

  The present invention relates to a photoelectric conversion element such as a dye-sensitized solar cell that can be significantly reduced in price as compared with a silicon-based conventional solar cell.

  Compared to silicon-based conventional solar cells, it is possible to significantly reduce the price, and in the dye-sensitized solar cells that are expected to be put to practical use, the impediment to price reduction is the conductivity The price of the board. However, in a dye-sensitized solar cell having a conventional structure, the electrode (window electrode) on which light enters is particularly required to have visible light transmission and high conductivity. Substrates coated with transparent conductive metal oxides such as tin-doped indium oxide and fluorine-doped tin oxide have been used. Therefore, if a dye-sensitized solar cell having a completely new structure that does not use such a transparent conductive substrate is realized, research and development are being carried out on the assumption that the price of the solar cell can be greatly reduced. .

The general dye-sensitized solar cells so far are mostly flat and stacked structures, and many of them have a structure in which various functional materials are sequentially stacked on a transparent conductive substrate. (See Non-Patent Documents 1, 2, and 3; Patent Document 1). Further, for example, a dye-sensitized solar having a structure in which a window electrode having a transparent conductive film is provided on one surface of a substrate, a porous oxide semiconductor layer supporting a dye is provided as a counter electrode, and an electrolyte layer is provided therebetween. A battery is known (see Patent Document 2).
On the other hand, in addition to the transparent conductive substrate, dye-sensitized solar cells using a metal plate or foil as an electrode are known. In these dye-sensitized solar cells, either the working electrode or the counter electrode is known. The only electrode is a metal plate or foil, and a transparent conductive substrate is always used for the light incident surface (see Patent Documents 2, 3, and 4).
Furthermore, as a dye-sensitized solar cell having another structure, a structure having two or more electrode surfaces (see Patent Documents 3 and 4) is known.

  In addition, a structure using a part of a metal wire or a metal wire network structure as an electrode wire (see Patent Documents 5, 6, 7, and 8), a structure in which a metal wire electrode is wound around a rod-shaped counter electrode, and an electrolyte is provided around the electrode ( Patent Document 9) is known. However, in these structures, since a metal wire is used for the working electrode, it is difficult to configure a large-area solar cell module, and it is inherently an advantage that the dye-sensitized solar cell can easily be enlarged. As a result, Therefore, it is necessary to develop an element structure that does not impair the above advantages.

  As a structure of the emitting electrode that enables large-area elements, a cloth-like structure (textile structure) in which a plurality of metal wires are knitted in a mesh shape is adopted, and a structure using one or more of these emitting electrodes is also proposed. (See Patent Documents 10, 11, 12, and 13). By using the electrode having a textile structure, a large-area element can be formed, and a dye-sensitized photoelectric conversion element having a flexible structure can be provided.

FIG. 4 shows a schematic configuration diagram of a dye-sensitized photoelectric conversion element 100 including a working electrode 103 having a textile structure. FIG. 4A is a plan view of the dye-sensitized photoelectric conversion element 100. FIG. 4B is a cross-sectional view of the dye-sensitized photoelectric conversion element 100 having the working electrode 103a having a high-density textile structure, taken along line BB in FIG. 4A. FIG. 4C is a cross-sectional view of the dye-sensitized photoelectric conversion element 100 having the working electrode 103b having a low-density textile structure.
The dye-sensitized photoelectric conversion element 100 has a structure in which a working electrode 103 having a textile structure and a counter electrode 104 made of a metal plate are overlapped. The working electrode 103 and the counter electrode 104 are sandwiched between transparent films 110 having a slightly larger area than the working electrode 103 and the counter electrode 104. The periphery of the transparent film 110 is bonded with an adhesive 111 made of a thermoplastic resin, whereby the transparent film 110 is formed in a bag shape. An electrolyte 113 is sealed in the bag portion.

  A part of the counter electrode 104 made of a metal plate extends to the outside from the bag portion formed by the transparent film 110. Around the working electrode 103, a collector electrode 135 made of a metal plate is electrically connected by welding, and this collector electrode 135 extends from the bag portion to the outside. With such a configuration, the dye-sensitized photoelectric conversion element 100 can generate electric power at the emitting electrode composed of the working electrode 103 and the counter electrode 104 and extract the generated electrons to the outside.

JP 2003-0777550 A JP 2007-012448 A JP 2007-172916 A JP 2007-172917 A JP 2008-181690 A JP 2008-181691 A JP 2005-196982 A JP 2005-516370 gazette JP 2008-108508 A JP 2000-021460 A JP 2001-283941 A JP 2001-283944 A JP 2001-283945 A

O'Regan B., Graetzel M., Alow cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films, Nature, 1991, 353, 737-739 Japan Patent Office: Standard Technology Collection: “Dye-sensitized solar cell” Japan Patent Office: Patent application technology trend survey: FY 2005 “Dye-sensitized solar cell”

However, in the dye-sensitized photoelectric conversion element having the textile-structure working electrode 103, different problems occur depending on the density of the textile. For example, in the case where the working electrode 103a has a textile density that is too high as shown in the sectional view of FIG. 4B, the working electrode 103a itself diffuses iodine ions (I ₃ ⁻ , I ⁻ ) accompanying power generation. The problem of inhibiting occurs.
On the other hand, as shown in FIG.4 (c), when the density of the textile of the working electrode 103b is too low, the problem of an electric power generation area will arise. For example, when the aperture ratio of the working electrode 103b is 50%, 50% of the irradiated sunlight reaches the counter electrode 104b without being absorbed by the working electrode 103b as indicated by a black arrow. That is, there is a problem that efficiency is lowered because the power generation area is reduced.

  Therefore, when determining the density of the textile, it is necessary to open the textile to an extent that does not inhibit the diffusion of iodine ions. However, when the opening ratio of the textile is increased, it is inevitable that the power generation area is reduced as compared with the case where the density of the textile is made fine. Therefore, improvement in power generation capability is also desired in a dye-sensitized photoelectric conversion element that employs a working electrode having a textile structure.

The invention according to claim 1 of the present invention has a structure in which the first working electrode, the counter electrode, and the second working electrode have a structure in which a plurality of conductive wires are knitted in a mesh shape, and the first working electrode, A dye-sensitized photoelectric conversion element in which the counter electrode and the second working electrode are stacked in order from the light incident side, wherein the opening ratio of the mesh of the first working electrode is a, and the opening of the mesh of the counter electrode A dye-sensitized photoelectric conversion element satisfying a relational expression of a> c and b> c, where b is the rate and c is the aperture ratio of the mesh of the second working electrode.
According to a second aspect of the present invention, the first working electrode and the counter electrode are arranged so that light that has passed through the opening of the mesh of the first working electrode can easily pass through the opening of the mesh of the counter electrode. The dye-sensitized photoelectric conversion elements according to claim 1, wherein are arranged mutually.
The invention according to claim 3 of the present invention is characterized in that the opening of the mesh of the first working electrode and the opening of the mesh of the counter electrode are the same as viewed from the incident direction of light. 1. The dye-sensitized photoelectric conversion element according to 1.

  The dye-sensitized photoelectric conversion element according to the present invention includes a first working electrode, a counter electrode, and a second working electrode having a structure in which a plurality of conductive wires are knitted in a mesh shape, and sequentially from the light incident side. The first working electrode, the counter electrode, and the second working electrode are stacked. Further, when the aperture ratio of the mesh of the first working electrode is a, the aperture ratio of the mesh of the counter electrode is b, and the aperture ratio of the mesh of the second working electrode is c, a> c and b> c By configuring so as to satisfy the above, there are effects that the first working electrode and / or the counter electrode does not inhibit the diffusion of iodine and does not reduce the power generation area.

The schematic block diagram of the dye-sensitized photoelectric conversion element which concerns on this invention is shown, (a) is a top view, (b) is sectional drawing which follows an AA line. It is a perspective view which shows the laminated structure of a 1st working electrode, a counter electrode, and a 2nd working electrode. The enlarged view of a textile structure is shown, (a) is a 1st working electrode, (b) is a counter electrode, (c) is an enlarged view of a 2nd working electrode. The schematic block diagram which showed an example of the conventional dye-sensitized photoelectric conversion element is shown, (a) is a top view, (b) And (c) is sectional drawing which follows the BB line of (a). is there.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a drawing showing an embodiment of the dye-sensitized photoelectric conversion element of the present invention, FIG. 1 (a) is a plan view of the dye-sensitized photoelectric conversion element 1, and FIG. It is sectional drawing which follows the AA line of Fig.1 (a).
The dye-sensitized photoelectric conversion element 1 of the present invention includes working electrodes 3 and 5 and a counter electrode 4 as an electrode pair. As shown in the cross-sectional view of FIG. 1B, a first working electrode 3 and a second working electrode 5 are provided as working electrodes, and the first working electrode 3 and the counter electrode 4 are provided from the light source side. The second working electrode 5 is laminated in order. In addition, a pair of films 10 having at least one of visible light permeability are arranged so as to sandwich the first working electrode 3, the counter electrode 4, and the second working electrode 5, and the periphery of the film 10 is adhered, An electrolyte 13 is enclosed together with a working electrode and a counter electrode.

As best shown in the plan view of FIG. 1A, the first working electrode 3, the counter electrode 4, and the second working electrode 5 constituting the dye-sensitized photoelectric conversion device 1 of the present invention are plural. It is characterized by having a textile structure in which a linear substrate is knitted in a mesh shape.
Since a linear base material (wire) is used without using a plate-like substrate, and a plurality of base materials are knitted like cloth, it is relatively easy to increase the area and is not knitted. Compared to a device manufactured using a single metal wire, a flexible device with better shape stability can be constructed. Furthermore, unlike a conventional photoelectric conversion element, since a transparent conductive substrate (for example, a substrate in which a transparent conductive film is provided on a glass substrate) is not used, the element can be manufactured at low cost.

  Around the first working electrode 3 and the second working electrode 5, a porous oxide semiconductor layer 12 carrying a dye is disposed, and the porous oxide semiconductor layer 12 contains an electrolyte 13 together with a sensitizing dye. Is also impregnated.

FIG. 2 is a perspective view showing a laminated configuration of the first working electrode 3, the counter electrode 4, and the second working electrode 5. The first working electrode 3, the counter electrode 4, and the second working electrode 5 are stacked in the order shown in FIG.
As shown in FIGS. 2 (a) to 2 (c), collector electrodes 35, 45 made of a metal plate are provided on three sides of the outer periphery of the first working electrode 3, the counter electrode 4 and the second working electrode 5 of the textile structure. 55 is attached by welding. Projections 35a, 45a, and 55a are formed on the collector electrode so that a part thereof extends from a bag portion to be described later.

The first working electrode 3, the counter electrode 4, the second working electrode 5, and the collector electrodes 35, 45, 55 thereof are adhesives made of two films 10 and a thermoplastic resin, except for the protruding portions 35 a, 45 a, 55 a. 11 is sealed together with the electrolyte 13 in the bag portion formed by 11. The adhesive 11 is disposed on the peripheral edge of the film 10, and the two films 10 are bonded by thermocompression bonding.
As described above, the first working electrode 3, the counter electrode 4, and the second working electrode 5 are stacked in order from the light source side to form an electrode pair. The electrode pair is immersed in an electrolyte solution, sandwiched between a pair of films 10, and sealed by leaving the protruding portions 35a, 45a, and 55a of the collecting electrode for taking out the generated electricity to the outside. A sensitized photoelectric conversion element 1 is configured.

Next, with reference to FIG. 1 and FIG. 3, the detail of the textile structure of a working electrode and a counter electrode is demonstrated.
The first working electrode 3 has a structure in which a plurality of linear first base materials 31 are knitted in a cloth shape so as to sufficiently come into contact with each other at the overlapping portion. The counter electrode 4 is composed of a linear second base material 41, and the second base material 41 is knitted in a mesh shape as shown in FIG. The 2nd working electrode 5 consists of the linear 3rd base material 51, and is knitted by mesh shape as shown in FIG.3 (c).

The density (opening ratio) of the textile parts of the first working electrode 3, the counter electrode 4, and the second working electrode 5 will be described. Textile part, the wire when weaving cloth, by adjusting the spacing of the wire adjacent (designated C ₃ in FIG. 3 (a)), it is possible to change the density. For example, by increasing the interval C _3, the textile portion is a low density, by reducing the interval C _3, may be a high density.
Further, the density of the textile portion can be represented by an aperture ratio (%). The aperture ratio is a ratio of a portion through which light is transmitted when the textile portion is viewed from the surface direction, and means a ratio of a visible light transmitting portion per unit area.

In the dye-sensitized photoelectric conversion element according to the present invention, the density of the textile portion of the first working electrode 3 and the counter electrode 4 is lower than that of the second working electrode 5. Specifically, for a line width D of 50 μm, the distances C ₃ and C ₄ between the base materials were set to 50 μm. In this case, the aperture ratio is 25%.
As described above, since the first working electrode 3 and the counter electrode 4 are knitted at a low density, a plurality of openings 32a and 42a are formed in the mesh. The plurality of openings 32a and 42a collectively constitute the openings 32 and 42.

  On the other hand, the density of the textile part of the second working electrode 5 was made higher than the density of the first working electrode 3 and the counter electrode 5. Specifically, the wire was knitted at an interval such that the wires were almost in contact with each other. That is, the textile part was formed so that the aperture ratio was substantially 0%.

  However, the aperture ratio of the mesh of the second working electrode 5 is not necessarily 0%, and can be changed according to the thickness of the third base material 51 to be used. However, in order to realize the effect of the present invention, the aperture ratio of the mesh of the second working electrode 5 needs to be lower than the aperture ratio of the mesh of the first working electrode and the second working electrode. That is, when the aperture ratio of the mesh of the first working electrode is a, the aperture ratio of the mesh of the counter electrode is b, and the aperture ratio of the mesh of the second working electrode is c, a> c and b> c. It is necessary to satisfy.

  Further, the first working electrode 3 and the counter electrode 4 need to be arranged so that the light that has passed through the mesh opening 32 of the first working electrode 3 can easily pass through the opening 42 of the counter electrode 4. Needless to say. Of the light that has passed through the openings 32 of the mesh of the first working electrode 3, the more light that is blocked by the second base material 41 of the counter electrode 4, the less the light that reaches the second working electrode 5, As a result, power generation efficiency is lowered.

  As described above, the first working electrode 3, the counter electrode 4, and the second working electrode 5 are arranged in order of the first working electrode 3, the counter electrode 4, and the second working electrode 5 from the light source side. And while making the textile part of the 2nd working electrode 5 into a high-density structure where wires contact, the 1st working electrode 3 and the counter electrode 4 are compared with the 2nd working electrode 5 as a low-density structure. Yes.

Such a configuration has an effect that the diffusion of iodine is not inhibited during power generation because the density of the first working electrode 3 is low.
In addition, light incident from the light source side and transmitted through the first working electrode 3 and the counter electrode 4 is absorbed by the second working electrode 5 to generate power. Since the second working electrode 5 is knitted with high density, the power generation efficiency of the dye-sensitized photoelectric conversion element 1 as a whole is increased.

Hereinafter, the components of the dye-sensitized photoelectric conversion element 1 of the present invention will be described in detail.
The first base material 31 and the third base material 51 constituting the first working electrode 3 and the second working electrode 5 are wires made of Ti. Of course, the material constituting the first base material 31 and the second base material 51 is not limited to Ti, and metals having high corrosion resistance such as W and Pt and alloys thereof can also be used. Further, for example, a Ti-coated metal wire obtained by coating a linear base material made of a material that is electrically conductive and electrochemically inactive with respect to the electrolyte 13 with Ti or the like is also used for the first base material 31 and It can be used as the second substrate 51.
Moreover, as the 1st base material 31 and the 3rd base material 51, it is also possible to use not only a wire with a normal circular cross section but also a deformed wire such as a flat wire or a polygonal wire.

Hereinafter, an example of a method for producing a Ti-coated Cu wire as a Ti-coated metal wire will be described.
First, Ti is formed into a pipe shape by extrusion molding or the like, and Cu is formed into a linear shape by extrusion molding or the like, and while the Ti pipe and the Cu wire are run simultaneously, a Cu wire is inserted inside the Ti pipe, These are squeezed to bring them into close contact to obtain a Ti-coated Cu wire.
The thickness (diameter) of the first base material 31 and the second base material 51 is preferably 10 μm to 1 mm, for example. However, in order to fully exhibit flexibility, the thinner the substrate, the better.

A porous oxide semiconductor layer 12 is disposed on the surfaces of the first working electrode 3 and the second working electrode 5, and a sensitizing dye and an electrolyte 13 are supported at least partially on the surfaces.
The semiconductor that forms the porous oxide semiconductor layer 12 is titanium oxide (TiO ₂ ). The thickness of the titanium oxide is about 5 μm, but is not particularly limited, and may be, for example, 1 μm to 50 μm.
The semiconductor that forms the porous oxide semiconductor layer 12 is not limited to titanium oxide, and is generally zinc oxide (ZnO), tin oxide (SnO ₂ ), oxidation, as long as it is used in dye-sensitized solar cells. Various semiconductor electrodes such as zinc (ZnO), niobium oxide (Nb ₂ O ₅ ), and tungsten oxide (WO ₃ ) can be used without limitation.

  Examples of the sensitizing dye include ruthenium complexes such as N719, N3, and black dye, metal-containing complexes such as porphyrin and phthalocyanine, and organic dyes such as eosin, rhodamine, and merocyanine. From the above, it is only necessary to appropriately select one having an excitation behavior suitable for the application and the semiconductor used.

  The porous oxide semiconductor layer 12 is impregnated with an electrolytic solution, and this electrolytic solution also constitutes a part of the electrolyte 13. In this case, the electrolyte 13 in the porous oxide semiconductor layer 12 is formed by impregnating the porous oxide semiconductor layer 12 with the electrolytic solution, or impregnating the porous oxide semiconductor layer 12 with the electrolytic solution. Then, the electrolytic solution is gelled (pseudo-solidified) using an appropriate gelling agent and formed integrally with the porous oxide semiconductor layer 12, or based on an ionic liquid. Further, a gel electrolyte containing oxide semiconductor particles and conductive particles is used.

As said electrolyte solution, what melt | dissolved electrolyte components, such as an iodine, iodide ion, and tertiary butyl pyridine, in organic solvents and ionic liquids, such as ethylene carbonate and methoxyacetonitrile, is used.
Examples of the gelling agent used for gelling the electrolytic solution include polyvinylidene fluoride, a polyethylene oxide derivative, and an amino acid derivative.
Moreover, if it replaces with a volatile electrolyte solution and is generally used for a dye-sensitized solar cell, not only what a solvent is an ionic liquid or the gelatinized thing but a p-type inorganic semiconductor and an organic hole transport layer Even solids such as these can be used without limitation.

Although it does not specifically limit as said ionic liquid, It is a liquid at room temperature, For example, the normal temperature molten salt which used the compound which has the quaternized nitrogen atom as a cation is mentioned.
Examples of the cation of the room temperature molten salt include quaternized imidazolium derivatives, quaternized pyridinium derivatives, and quaternized ammonium derivatives.
Examples of the anion of the room temperature molten salt include BF ₄ ⁻ , PF ₆ ⁻ , (HF) _n ⁻ , bistrifluoromethylsulfonylimide [N (CF ₃ SO ₂ ) ₂ ⁻ ], and iodide ions.
Specific examples of the ionic liquid include salts composed of quaternized imidazolium-based cations and iodide ions or bistrifluoromethylsulfonylimide ions.

  The oxide semiconductor particles are not particularly limited in terms of the type and particle size of the substance, but are excellent in miscibility with an electrolyte mainly composed of an ionic liquid and gel the electrolyte. Is used. In addition, the oxide semiconductor particles are required to have excellent scientific stability against other coexisting components contained in the electrolyte 13 without reducing the semiconductivity of the electrolyte 13. In particular, even when the electrolyte 13 includes a redox pair such as iodine / iodide ions or bromine / bromide ions, the oxide semiconductor particles are preferably those that do not deteriorate due to an oxidation reaction.

Examples of such oxide semiconductor particles include TiO ₂ , SnO ₂ , SiO ₂ , ZnO, Nb ₂ O ₅ , In ₂ O ₃ , ZrO ₂ , Al ₂ O ₃ , WO ₃ , SrTiO ₃ , Ta ₂ O ₅ , One or a mixture of two or more selected from the group consisting of La ₂ O ₃ , Y ₂ O ₃ , Ho ₂ O ₃ , Bi ₂ O ₃ , CeO ₂ is preferable, and the average particle size is about 2 nm to 1000 nm. preferable.

As the conductive fine particles, conductive particles such as a conductor and a semiconductor are used.
Further, the type and particle size of the conductive particles are not particularly limited, and those that are excellent in miscibility with an electrolytic solution mainly composed of an ionic liquid and that gel the electrolytic solution are used. Furthermore, it is necessary to be excellent in chemical stability against other coexisting components contained in the electrolyte 13.
In particular, even when the electrolyte 13 includes a redox pair such as iodine / iodide ions or bromine / bromide ions, an electrolyte that does not deteriorate due to an oxidation reaction is preferable.

  Examples of such conductive fine particles include those composed mainly of carbon, and specific examples include particles such as carbon nanotubes, carbon fibers, and carbon black. All methods for producing these substances are known, and commercially available products can also be used.

The 2nd base material 41 which comprises the counter electrode 4 is a metal wire which makes a linear shape. The second substrate 41 is made of, for example, platinum (Pt), carbon fiber, and conductive polymer fiber. Also, a linear substrate made of a material that is electrically conductive and electrochemically inactive with respect to the electrolyte 13 is coated with Pt, or the linear substrate is made of carbon or a conductive polymer. The coated one is also used as the counter electrode 4. In such a counter electrode 4, charge transfer with the electrolyte 13 proceeds promptly.
Specific examples of such a linear substrate include inert metals such as Ti, Ni, W, Rh, and Mo, or carbon fibers.
Further, as the second base material 41, not only a normal wire having a circular cross section but also a deformed wire such as a flat wire or a polygonal wire can be used.

Specifically, as the carbon, for example, particles such as graphitized carbon or amorphous carbon, fullerene, carbon nanotube, carbon fiber, and carbon black may be pasted and applied. When such carbon is used, it is preferable to remove unnecessary adsorbate by heating, baking treatment, etc., because the electrode reaction of the iodine redox couple proceeds smoothly.
Examples of the conductive polymer constituting the material of the counter electrode 4 include PEDOT [Poly (3,4-ethylenedioxythiophene): “polyethylenedioxythiophene]] derivatives, PANI [Polyaniline] derivatives, and the like.

  Further, a separator for preventing a short circuit may be inserted between the first working electrode 3 and the counter electrode 4 and / or between the counter electrode 4 and the second working electrode 5. The separator is made of a non-conductive material such as polyethylene, and preferably has a thickness of 20 μm or less. However, if the separator can withstand the electrolytic solution and insulate the working electrode and the counter electrode, There is no limitation.

  The film 10 having visible light permeability is formed of a high gas barrier transparent film using PET as a substrate. In addition to the PET substrate, other glass substrates and resin substrates such as polyethylene naphthalate and fluororesin can be used without limitation as long as they are resins used for dye-sensitized solar cells.

  The thermoplastic resin that functions as the adhesive 11 for adhering the film 5 includes a resin having a polar group or a modified resin film having a polar group introduced therein, for example, a polar group in a molecular chain such as EMAA or ionomer. It is possible to use an ethylene copolymer, an acid-modified product of polyolefin such as polyethylene or polypropylene, and the like. Specific examples include High Milan, Nuclerel (Mitsui DuPont Polychemical), Binnel (DuPont), Adtex (Nippon Polyethylene), Primacol (Dow Chemical).

  The collector electrodes 35, 45, and 55 are preferably Ti plates having a thickness of 100 μm. However, the collector electrodes 35, 45, and 55 are not limited to this as long as they are conductive and can withstand electrolytes.

(Example)
A photoelectric conversion element having the structure shown in FIG. 1 was produced.
First, a Ti wire (first base material 31, second base material 41, third base material 51) having a diameter of 50 μm was woven into a cloth (textile) using a loom. The size of the rectangular portion (textile portion) where the vertical and horizontal Ti wires are woven is 50 mm × 100 mm. The fabric used as the first working electrode 3 and the counter electrode 4 was woven so that the interval (gap) between the Ti wires was 50 μm. The fabric used as the second working electrode 5 was densely woven so that both the warp and the weft were in contact.

  Ti foils having a thickness of 100 μm and a width of 5 mm were attached to the three sides of the outer periphery of the three kinds of woven fabrics as collector electrodes 35, 45, 55 by welding as shown in FIG. In addition, protrusions 35a, 45a, and 55a are provided on one side of the collector electrodes 35, 45, and 55.

Of the textile part to which the collecting electrodes 35, 45, 55 are attached, the first working electrode 3 and the second working electrode 5 are dipped in TiO ₂ paste (catalyst conversion PST-21NR), pulled up, temporarily dried, Sintered at 500 ° C. for 1 hour in a furnace to obtain a Ti textile portion with a porous TiO ₂ film. The film thickness of TiO ₂ was approximately 15 μm.

Next, the first working electrode 3 and the second working electrode 5 are immersed in a 0.3 mM, acetonitrile / tert-butanol = 1: 1 solution of a ruthenium dye (referred to as N719), and left at room temperature for 24 hours to leave TiO. ₂ Dye was supported on the surface. After being lifted from the dye solution, it was washed with the above mixed solvent, and this was used as the first working electrode 3 and the second working electrode 5.

  On the other hand, a counter electrode 4 was obtained by depositing Pt on the textile portion using a ternary RF sputtering apparatus.

As the film 10 for sealing the first working electrode 3, the counter electrode 4, the second working electrode 5, and the electrolyte 13, two PET films having a thickness of 50 μm and 70 mm × 100 mm were used.
Between the two films, the first working electrode 3, the counter electrode 4, and the second working electrode 5 were sandwiched, and the outer periphery of the PET film was bonded by thermocompression bonding to form a cell of the power generation unit. At the time of thermocompression bonding, nucleol which is an ethylene-methacrylic acid copolymer was inserted between two PET films.
A volatile electrolyte using methoxyacetonitrile as a solvent was injected into the cell. Finally, the power generation part was sealed by thermocompression bonding of the electrolyte injection part.

The photoelectric conversion element produced as described above was irradiated with light with a solar simulator (AM1.5, 100 mW / cm ² ), and a current-potential curve was measured. As a result, the photoelectric conversion efficiency was 4.0%.

  From the above, according to the present invention, in the dye-sensitized photoelectric conversion element using the working electrode and the counter electrode of the textile structure, the working electrode and / or the counter electrode itself does not inhibit the diffusion of iodine, and the power generation area is reduced. It has been found that a dye-sensitized photoelectric conversion element that does not decrease can be provided.

  The present invention is widely applicable to photoelectric conversion elements using metal wires as electrodes.

DESCRIPTION OF SYMBOLS 1 ... Dye-sensitized photoelectric conversion element, 3 ... 1st working electrode, 4 ... Counter electrode, 5 ... 2nd working electrode, 10 ... Film, 11 ... Adhesive, 12 ... Porous oxide semiconductor layer, 13 ... Electrolyte, DESCRIPTION OF SYMBOLS 31 ... 1st base material, 32 ... Opening part, 35 ... Current collection electrode, 41 ... 2nd base material, 42 ... Opening part, 45 ... Current collection electrode, 51 ... 3rd base material, 55 ... Current collection electrode.

Claims (3)

The first working electrode, the counter electrode, and the second working electrode have a structure in which a plurality of wires having conductivity are knitted in a mesh shape,
The dye-sensitized photoelectric conversion element in which the first working electrode, the counter electrode, and the second working electrode are sequentially stacked from the light incident side,
When the aperture ratio of the mesh of the first working electrode is a, the aperture ratio of the mesh of the counter electrode is b, and the aperture ratio of the mesh of the second working electrode is c,
A dye-sensitized photoelectric conversion element characterized by satisfying a relational expression of a> c and b> c.   The first working electrode and the counter electrode are arranged mutually so that light that has passed through the opening of the mesh of the first working electrode can easily pass through the opening of the mesh of the counter electrode. The dye-sensitized photoelectric conversion device according to claim 1. Seen from the incident direction of light,
The dye-sensitized photoelectric conversion element according to claim 1, wherein the opening of the mesh of the first working electrode is the same as the opening of the mesh of the counter electrode.

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