JP5106866B2 - Photoelectric conversion element - Google Patents

Description

  The present invention relates to a photoelectric conversion element and a first electrode used therefor. More specifically, the present invention relates to a photoelectric conversion element having a novel configuration that eliminates the need for a conductive substrate and a first electrode used therefor.

  The dye-sensitized solar cell has been proposed by a group such as Gretzel of Switzerland, and has attracted attention as a photoelectric conversion element that can be obtained at low cost and high conversion efficiency (for example, Patent Document 1 and Non-Patent Document 1). reference.).

FIG. 7 is a cross-sectional view showing an example of a conventional dye-sensitized solar cell.
The dye-sensitized solar cell 100 includes a first substrate 101 having a porous semiconductor electrode 103 (hereinafter also referred to as a dye-sensitized semiconductor electrode) 103 carrying a sensitizing dye formed on one surface, and a conductive film 104. And the electrolyte layer 106 including a redox pair such as iodine / iodide ions enclosed between them is a main component.

A light-transmitting plate material is used as the first substrate 101, and a transparent conductive layer 102 is disposed on the surface of the first substrate 101 in contact with the dye-sensitized semiconductor electrode 103 in order to provide conductivity. A working electrode (window electrode) 108 is formed by the substrate 101, the transparent conductive layer 102, and the dye-sensitized semiconductor electrode 103.
On the other hand, as the second substrate 105, a conductive layer 104 made of, for example, carbon or platinum is provided on the surface on the side in contact with the electrolyte layer 106, and the counter electrode 109 is formed by the second substrate 105 and the conductive layer 104. Is configured.

  The first substrate 101 and the second substrate 105 are arranged at a predetermined interval so that the dye-sensitized semiconductor electrode 103 and the conductive layer 104 face each other, and a peripheral portion between the two substrates is sealed with, for example, a thermoplastic resin Agent 107 is provided. Then, the two substrates 101 and 105 are bonded together through the sealant 107 to assemble a cell, and an oxidation / reduction pair such as iodine / iodide ions is included between the electrodes 108 and 109 through the electrolyte injection port 110. Examples thereof include an organic electrolyte solution filled and an electrolyte layer 106 for charge transfer formed.

Such a dye-sensitized photoelectric conversion element is said to be capable of drastically reducing costs as compared with a conventional photoelectric conversion element, and is expected to be put to practical use at an early stage. At that time, as one of the obstacles to reduce the cost, the use of a conductive substrate can be mentioned. That is, in the photoelectric conversion element having a conventional structure, the electrode (window electrode) on the light incident side is particularly required to have visible light transmittance and high conductivity. A substrate coated with a transparent conductive metal oxide such as indium (ITO) or fluorine-doped tin oxide (FTO) has been used. Indium (In) used here is a rare metal and becomes a factor that hinders cost reduction of the photoelectric conversion element, as is apparent from the recent rapid increase in price. Therefore, if a dye-sensitized photoelectric conversion element having a completely new structure that does not require such a conductive substrate is realized, the cost can be greatly reduced, and development thereof is expected.
Japanese Patent Laid-Open No. 1-220380 M. Graetzel et al., Nature, 737, p.353, 1991

  The present invention has been devised in view of such a conventional situation, and provides a photoelectric conversion element having a new structure that does not require a conductive substrate and can achieve cost reduction.

The photoelectric conversion element according to claim 1 of the present invention is a photoelectric conversion element in which a first electrode and a second electrode forming separate bodies are arranged at least one by way of an electrolyte. The one electrode, the second electrode, and the electrolyte are housed in a substantially cylindrical casing, and both the first electrode and the second electrode have a linear shape extending in the longitudinal direction in the casing. And the first electrode is composed of at least a conductive first wire and a porous oxide semiconductor that is disposed on the outer periphery of the first wire and carries a dye. And
The photoelectric conversion element according to claim 2 of the present invention is the photoelectric conversion element according to claim 1, wherein either one of the first electrode and the second electrode is disposed between the other electrode and the housing. The one electrode is plural.
According to a third aspect of the present invention, in the photoelectric conversion element according to the second aspect, the one electrode is arranged in a spiral shape or a mesh shape along the outer surface of the other electrode. .
According to a fourth aspect of the present invention, in the photoelectric conversion element according to the second aspect, the one electrode is disposed so as to be included in the other electrode.
The photoelectric conversion element according to claim 5 of the present invention is the photoelectric conversion element according to claim 1, wherein either one of the first electrode and the second electrode is disposed between the other electrode and the housing. There are a plurality of both of the one electrode and the second electrode.

  In the present invention, the first electrode forming the working electrode is composed of at least a conductive first wire and a porous oxide semiconductor that is disposed on the outer periphery of the first wire and carries a dye, and is substantially cylindrical. Photoelectric conversion with a new structure that eliminates the need for a conductive substrate and accommodates the first and second electrodes, which are linearly extending in the longitudinal direction, and the electrolyte in a cylindrical housing. An element can be provided.

<First embodiment>
Hereinafter, embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is a cross-sectional view showing an example of the photoelectric conversion element of the present invention.
This photoelectric conversion element 1A (1) is a photoelectric conversion element in which a first electrode 10 and a second electrode 13 which are separate members are arranged via an electrolyte layer 14 at least one by one. The one electrode 10, the second electrode 13 and the electrolyte layer 14 are accommodated in a substantially cylindrical casing 15.
In the photoelectric conversion element of the present invention, both the first electrode 10 and the second electrode 13 are linearly extending in the longitudinal direction in the casing 15, and the first electrode 10 Is composed of at least a conductive first wire and a porous oxide semiconductor disposed on the outer periphery of the first wire and carrying a dye.

In this invention, the structure of the photoelectric conversion element 1 which does not require a conductive substrate and is completely different from the conventional one is proposed. Conductivity is assigned to a metal wire (first wire 11) having good corrosion resistance.
In such a photoelectric conversion element 1, since the outer peripheral surface of the linear first electrode 10 becomes a light receiving surface, the projected area with respect to the irradiation light can be increased, and the dependency on the light incident angle can be reduced. Be expected.
In addition, since both the first electrode 10 and the second electrode 13 are linear, the degree of freedom in system design is improved.

1, reference numeral 1 is a dye-sensitized photoelectric conversion element, 10 is a first electrode (working electrode), 11 is a first wire, 12 is a porous oxide semiconductor layer, 13 is a second electrode (counter electrode), Reference numeral 14 denotes an electrolyte layer, and 15 denotes a housing.
In the photoelectric conversion element 1, the first electrode 10, the second electrode 13, and the electrolyte layer 14 are housed and sealed in a substantially cylindrical casing 15 and function as a photoelectric conversion element. The first electrode 10 and the second electrode 13 both have a linear shape extending in the longitudinal direction in the housing 15.

  In the photoelectric conversion element 1 according to the present embodiment, one of the first electrode 10 and the second electrode 13 (second electrode 13) is the other electrode (first electrode 10) and the casing. 15 and a plurality of the one electrode (second electrode 13). Since a plurality of linear second electrodes 13 are arranged outside the linear first electrode 10, the power generation efficiency is excellent.

  As shown in FIG. 1, the first electrode 10 includes a first wire 11 having at least conductivity, a porous oxide semiconductor layer 12 disposed on the outer periphery of the first wire 11 and carrying a sensitizing dye, It is composed of and is linear.

  The conventional electrode (working electrode) using a transparent conductive substrate in which a transparent conductive film such as FTO or ITO is formed on a transparent substrate made of glass, plastic or the like has a problem of heat resistance of the transparent substrate. From the above, when the porous oxide semiconductor layer was formed, firing at high temperature was difficult. However, the first electrode 10 does not have the above-described problem and can be sufficiently fired at high temperature. Suitable as (working electrode).

In addition, since a linear wire is used without using a plate-like substrate, it has flexibility and can be used as electrodes for photoelectric conversion elements having various structures.
Furthermore, unlike a conventional electrode, a glass substrate or a transparent conductive film is not used, so that the electrode can be manufactured at low cost.

Specific examples of the first wire 11 include a wire made of any one of Ti, Ni, W, Rh, and Mo, or an alloy thereof, a hollow wire, and a rod. Further, a linear base material made of a material that is electrically conductive and electrochemically inactive with respect to the electrolyte is made of, for example, any one of Ti, Ni, W, Rh, Mo, or an alloy thereof. What was covered is also used as the first wire 11.
The thickness (diameter) of the first wire 11 is not particularly limited, but is preferably 10 [μm] to 5 [m], for example. However, in order to fully exhibit flexibility, the thickness of the first wire 11 is better as it is thinner.

The porous oxide semiconductor layer 12 is provided around the first wire 11, and a sensitizing dye is supported on at least a part of the surface of the porous oxide semiconductor layer 12.
Note that the porous oxide semiconductor layer 12 may cover only a part of the outer periphery of the first wire 11. However, the porous oxide semiconductor layer 12 has a decrease in light collection capability, promotion of reverse electron transfer reaction, etc. It is preferable to completely cover the outer periphery of the wire 11.

The semiconductor for forming the porous oxide semiconductor layer 12 is not particularly limited, and any semiconductor can be used as long as it is generally used for forming a porous oxide semiconductor for the photoelectric conversion element 1. . As such a semiconductor, for example, titanium oxide (TiO ₂ ), tin oxide (SnO ₂ ), zinc oxide (ZnO), niobium oxide (Nb ₂ O ₅ ), tungsten oxide (WO ₃ ), or the like can be used. .

As a method for forming the porous oxide semiconductor layer 12, for example, a dispersion in which commercially available oxide semiconductor fine particles are dispersed in a desired dispersion medium or a colloidal solution that can be prepared by a sol-gel method is used as necessary. Then, after adding a desired additive, it is arranged on the outer periphery of the first wire 11 by a method such as dipping, coating, or extrusion, and then formed by firing.
The thickness of the porous oxide semiconductor layer 12 is not particularly limited, but is preferably 1 [μm] to 50 [μm], for example.

  Examples of sensitizing dyes include ruthenium complexes containing bipyridine or terpyridine structures as ligands, metal-containing complexes such as porphyrins and phthalocyanines, and organic dyes such as eosin, rhodamine and merocyanine. From these, those having an excitation behavior suitable for the application and the semiconductor used may be appropriately selected.

The second electrode 13 has a linear shape and is made of, for example, platinum (Pt), carbon, or a conductive polymer. Also, a linear substrate made of a material that is electrically conductive and electrochemically inert to the electrolyte is coated with Pt, or the linear substrate is coated with carbon or a conductive polymer. This is also used as the second electrode 13. In such a second electrode 13, transfer of charges with the electrolyte proceeds promptly.
Specific examples of such a linear substrate include inert metals such as Ti, Ni, W, Rh, and Mo, or carbon fibers.

Specifically, as the carbon, for example, particles such as graphitized (crystallized) 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 second electrode 13 include PEDOT [Poly (3,4-ethylenedioxythiophene): “polyethylenedioxythiophene]] derivative, PANI [Polyaniline] derivative, and the like. .

  The electrolyte layer 14 is formed by impregnating the porous oxide semiconductor layer 12 with the electrolytic solution, or after impregnating the porous oxide semiconductor layer 12 with the electrolytic solution, the electrolytic solution is applied to an appropriate gel. That is formed into a gel (pseudo-solid) by using an agent and formed integrally with the porous oxide semiconductor layer 12, or based on an ionic liquid, and further oxide semiconductor particles and conductive A gel electrolyte containing 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.

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 ambient temperature molten _{^{salt, BF 4 -, PF 6 -}} , (HF) n -, bis (trifluoromethylsulfonyl) imide _{[N (CF 3 S0 2)} 2 -], and the like iodide ion.
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 those that are excellent in miscibility with an electrolytic solution mainly composed of an ionic liquid and that gel the electrolytic solution are used. Further, the oxide semiconductor particles are required to have excellent chemical stability against other coexisting components contained in the electrolyte without reducing the semiconductivity of the electrolyte. In particular, even when the electrolyte contains 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 this electrolytic solution are used. Furthermore, it is necessary to be excellent in chemical stability against other coexisting components contained in the electrolyte. In particular, even when the electrolyte contains an oxidation / reduction pair such as iodine / iodide ion or bromine / bromide ion, an electrolyte that does not deteriorate due to 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.

  As the casing 15, a member having optical characteristics that transmits sunlight is used. Although it does not specifically limit as a member which has the optical characteristic which permeate | transmits sunlight, For example, the member which consists of a transparent and rigid material, such as an acryl, a polycarbonate, glass, is mentioned. Further, for example, by using a transparent and flexible or flexible material such as polyethylene terephthalate or polyethylene naphthalate, the photoelectric conversion element 1 can be provided with flexibility or flexibility.

The photoelectric conversion element (FIG. 1) of the first embodiment described above can be formed by, for example, a series of manufacturing processes A (FIG. 5) described in the following steps (1) to (4).
(1) First, as shown in FIG. 5, one Ti wire having an outer diameter of 0.5 mm.phi. Is passed through a suspension of fine semiconductor particles (hereinafter also referred to as "semiconductor solution"). A film having a thickness of 50 [μm] to 100 [μm] is formed on the outer periphery of the film, and then a drying process is performed. As a method for forming this film, for example, there is a method in which one desired hole having a substantially round shape is provided at the bottom of a container containing a semiconductor solution, and the wire is moved so as to pass through this hole. Thereafter, this coating film is sintered by passing through a constant temperature bath having an internal temperature of 450 [° C.] to 550 [° C.], whereby a thickness of 1 [μm] is formed on the outer periphery of the wire 11 as shown in FIG. The first electrode 10 having the porous semiconductor layer 12 of ˜50 [μm] is obtained.
(2) Next, the porous semiconductor layer 12 constituting the skin of the first electrode 10 is loaded with a dye. The treatment is performed, for example, by dipping.
(3) Next, in the cross-sectional structure, the first electrode 10 is arranged at the center, and a plurality of second electrodes 13 (eight in FIG. 1) made of platinum are extruded while being vertically attached to the first electrode 10. Using a method or the like, the casing 15 is provided so as to wrap around and cover these outer circumferences.
(4) Then, it cut | disconnects to suitable length, and fills electrolyte solution between the 1st electrode 10 and the housing | casing 15, and seals a terminal part. In sealing, the first electrode 10 and the second electrode 13 are exposed from the sealing portion so as to be electrically connected to the outside.
Here, the sealing may be a technique of melting the end portion of the casing 15 or a technique of covering with a material having excellent weather resistance. Examples of the material having excellent weather resistance include butyl rubber, fluororesin, silicon resin, high Milan, and binel.

<Second embodiment>
Hereinafter, a second embodiment of the photoelectric conversion element according to the present invention will be described with reference to the drawings.
FIG. 2 is a schematic perspective view showing an example of the photoelectric conversion element 1B (1) according to the present embodiment. In the present embodiment, differences from the first embodiment described above will be mainly described, and description of similar parts will be omitted. However, in FIG. 2, only the internal structure is clearly shown, and the electrolyte layer 14 and the casing 15 that forms the jacket are omitted.

  This embodiment is substantially the same as the first embodiment except that the arrangement of the first electrode 10 and the second electrode 13 provided in the photoelectric conversion element 1 is different. That is, in the first embodiment, the second electrode 13 is arranged in parallel with the first electrode 10, but the photoelectric conversion element 1 </ b> B of the present embodiment has the one electrode (second electrode 13) as the other electrode. It is characterized by being arranged in a spiral shape or a mesh shape along the outer surface of the first electrode (first electrode 10).

  As in the first embodiment, the photoelectric conversion element 1B has a structure in which the second electrode 13 is disposed around the first electrode 10 poles, but the second electrode 13 is spirally wound around the first electrode 10. ing. By arranging the second electrode 13 in a spiral shape, the photoelectric conversion element 1 is excellent in flexibility.

  In FIG. 2, the single second electrode 13 is spirally wound around the first electrode 10. However, the first embodiment is within a range that does not prevent the light from entering the first electrode 10. Similarly to the above, a plurality of second electrodes 13 may be provided, or they may be arranged in a mesh shape. By making the mesh shape, the diameter of the element can be reduced, and the shape stability is excellent.

  Alternatively, the first electrode 10 and the second electrode 13 may be interchanged so that the first electrode 10 is on the outside. Thereby, it is avoided that a shadow is formed on the first electrode 10 by the second electrode 13, and incident light can be used effectively.

The manufacturing process B for forming the photoelectric conversion element (FIG. 2) of the second embodiment is substantially the same as the manufacturing process A of the first embodiment described above, and spirals with respect to the first electrode 10 in the step (3). The only difference is that the second electrode 13 is provided so as to have a shape wound in a shape, and the other points are the same as in the first embodiment.
Therefore, the photoelectric conversion element of the second embodiment can be formed by a series of manufacturing processes substantially similar to those of the first embodiment described above.

<Third embodiment>
Hereinafter, a third embodiment of the photoelectric conversion element according to the present invention will be described with reference to the drawings.
FIG. 3 is a cross-sectional view illustrating an example of the photoelectric conversion element 1C (1) according to the present embodiment. In this embodiment, differences from the above-described embodiment will be mainly described, and description of similar parts will be omitted.

  This embodiment is substantially the same as the first embodiment except that the arrangement of the first electrode 10 and the second electrode 13 provided in the photoelectric conversion element is different. That is, in the first embodiment, the second electrode 13 is arranged around the first electrode 10. However, in the present embodiment, one electrode (second electrode 13) is the other electrode (first electrode 10). ) Is included.

In the structure shown in FIG. 1, the amount of necessary electrolyte increases and the element becomes thick. Therefore, in the photoelectric conversion element 1 </ b> C of this embodiment, as shown in FIG. 3, the base material ( A U-shaped or V-shaped recess 16 is provided in the first wire 11, and the second electrode 13 is arranged in the recess 16. Since the shadow portion by the second electrode 13 is reduced, the light collection efficiency is improved.
Thus, by making the 2nd electrode 13 resident in the 1st electrode 10, while being able to reduce the quantity of the electrolyte inject | poured inside an element, the diameter reduction of an element can be achieved.

The manufacturing process C for forming the photoelectric conversion element (FIG. 3) of the third embodiment is substantially the same as the manufacturing process A of the first embodiment described above, and the cross-sectional structure is substantially circular in the step (1). The point which used the 1st electrode 10 which replaced with the 1st electrode 10 and provided the dent 16 for dropping the 2nd electrode 13 differs from 1st embodiment, and the other point is the same as that of 1st embodiment.
By providing the recess 16 in the first electrode 10, only the step (3) needs to be changed slightly. That is, after loading the pigment in the step (2), in the step (3), the first electrode 10 provided with the recess 16 is arranged at the center, and the second electrode 13 is placed inside the recess 16 of the first electrode 10. While dropping, the casing 15 is provided so as to wrap around and cover the outer periphery using an extrusion method or the like.
Therefore, the photoelectric conversion element of the third embodiment can be formed by a series of manufacturing processes substantially similar to those of the first embodiment described above.

<Fourth embodiment>
Hereinafter, 4th embodiment of the photoelectric conversion element which concerns on this invention is described based on drawing.
FIG. 4 is a cross-sectional view showing an example of the photoelectric conversion element 1D (1) according to this embodiment. In this embodiment, differences from the above-described embodiment will be mainly described, and description of similar parts will be omitted.

In the photoelectric conversion element 1D of the present embodiment, one of the first electrode 10 and the second electrode 13 is disposed between the other electrode and the housing 15, and the one electrode Both of the second electrodes 13 are plural.
In the photoelectric conversion element 1D shown in FIG. 4, a plurality of second electrodes 13 are embedded in a porous body 17 and a plurality of first electrodes 10 are arranged around the second electrodes 13 like a coaxial cable. By adopting such a structure, it is avoided that a shadow is formed on the first electrode 10 by the second electrode 13, and incident light can be used effectively.

The manufacturing process D (FIG. 6) for forming the photoelectric conversion element (FIG. 4) of the fourth embodiment is almost the same as the manufacturing process A of the first embodiment described above. In step (1), a plurality of wires are used. (3 in FIG. 4) is used to form a structure in which the second electrode 13 made of a wire is embedded in the porous body 17, and then in step (3), a plurality ( 4 is different from the first embodiment in that 16 first electrodes 10 are provided, and the other points are the same as in the first embodiment.
By using a plurality of second electrodes 13, only the step (1) needs to be changed slightly. That is, in step (1) of the manufacturing process D, in order to form a structure in which the three second electrodes 13 are embedded in the porous body 17, when forming the porous body 17, for example, a semiconductor solution is used. There may be mentioned a method in which three holes having a desired substantially round shape are provided at the bottom of the container, and individual wires are moved so as to pass through these holes. At that time, in order to obtain an arrangement example of the second electrode 13 as shown in FIG. 4, the arrangement of the three holes is such that the center point of each hole forms an apex of an equilateral triangle and the wires do not contact each other ( A porous body always exists between adjacent wires. Thereby, the cross-sectional shape (outer peripheral shape of the porous body 17) of the structure described above can be a shape close to a circle.
Therefore, the photoelectric conversion element of the fourth embodiment can be formed by a series of manufacturing processes substantially similar to those of the first embodiment described above.

  The photoelectric conversion element of the present invention has been described above, but the present invention is not limited to the above example, and can be appropriately changed as necessary.

  For example, in the above-described embodiment, the case where the cross sections of the first electrode and the second electrode are substantially circular has been described as an example, but the present invention is not limited to this, and the cross section of each electrode is an ellipse. , Triangles, squares, stars, other polygons, etc. Moreover, you may combine these shapes. Above all, if the working electrode is a circle or an ellipse, it shows almost the same sensitivity to light incident from any direction, and if the cross section of the second electrode is circular, it will be a shadow on the first electrode. Since the area of the portion is minimized, a configuration in which the conversion efficiency with respect to the incident direction of light as a whole of the element is less changed and reduced can be obtained. Furthermore, since the metal wire having a circular cross section can be manufactured most inexpensively by stretching, a configuration with high cost merit can be obtained.

  The number of first electrodes and second electrodes is not limited to the example described above. For example, FIG. 1 shows a configuration example in which eight second electrodes 13 having the same thickness are arranged on the outer side of one first electrode 10. However, the number of second electrodes 13 may be increased or decreased. . Also, it is possible to use a configuration in which several types of second electrodes 13 having different thicknesses are used and these are mixed in order or randomly. Further, although not shown, a configuration in which the second electrode 13 is the center and the first electrode 10 is disposed on the outer periphery may be adopted. However, when the first electrode 10 is arranged on the outer periphery, the close-packed arrangement is preferable. However, when the second electrode 13 is arranged on the outer periphery, it is difficult for light to reach the first electrode 10 arranged in the center. It is important to consider the arrangement method of the two electrodes 13.

  Further, the configuration example of FIG. 2 described above shows an example in which one electrode (second electrode 13) is arranged in a spiral shape or a mesh shape along the outer surface of the other electrode (first electrode 10). However, for example, the power generation characteristics can be controlled by appropriately adjusting the separation distance between both electrodes according to the characteristics of the electrolyte layer 14 disposed so as to satisfy both electrodes. In particular, in the case of a spiral shape, power generation can also be performed by appropriately adjusting the interval between adjacent ones of the electrodes (second electrodes 13) arranged similarly in a spiral shape, the angle wound around the spiral shape, and the like. The characteristics can be controlled.

  Here, various optional arrangements have been described by taking the configuration examples of FIGS. 1 and 2 as an example. However, the various optional arrangements described above can also be adopted in the configuration examples of FIGS. 3 and 4. Yes, as needed.

  The present invention can be applied as a photoelectric conversion element that does not require a conductive substrate and can achieve cost reduction. In addition, the photoelectric conversion element according to the present invention is suitable for applications that are difficult to apply in the past, such as applications that require little angle dependency of incident light, and applications that require flexibility.

It is sectional drawing which shows an example of the photoelectric conversion element which concerns on this invention. It is a perspective view which shows the example of arrangement | positioning of an outer electrode in the photoelectric conversion element of FIG. It is sectional drawing which shows another example of the photoelectric conversion element which concerns on this invention. It is sectional drawing which shows another example of the photoelectric conversion element which concerns on this invention. It is a figure which shows the manufacturing process A of the photoelectric conversion element which concerns on this invention. It is a figure which shows the manufacturing process D of the photoelectric conversion element which concerns on this invention. It is sectional drawing which shows an example of the conventional photoelectric conversion element.

Explanation of symbols

  1A, 1B, 1C, 1D (1) photoelectric conversion element, 10 first electrode, 11 first wire, 12 porous oxide semiconductor layer, 13 second electrode, 14 electrolyte layer, 15 housing, 16 dent, 17 porous Body.

Claims (5)

The first electrode and the second electrode forming separate bodies are at least one photoelectric conversion element arranged via an electrolyte,
The first electrode, the second electrode, and the electrolyte are housed in a substantially cylindrical casing,
Each of the first electrode and the second electrode has a linear shape extending in the longitudinal direction in the casing, and the first electrode includes at least a first wire having conductivity, and the first electrode A photoelectric conversion element comprising a porous oxide semiconductor that is disposed on an outer periphery of a single wire and carries a dye.   2. The electrode according to claim 1, wherein one of the first electrode and the second electrode is disposed between the other electrode and the casing, and the plurality of the one electrode are plural. The photoelectric conversion element as described in 2.   The photoelectric conversion element according to claim 2, wherein the one electrode is arranged in a spiral shape or a mesh shape along an outer surface of the other electrode.   The photoelectric conversion element according to claim 2, wherein the one electrode is disposed so as to be included in the other electrode.   One of the first electrode and the second electrode is disposed between the other electrode and the housing, and both the one electrode and the second electrode are plural. The photoelectric conversion element according to claim 1.

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