JP6694372B2 - Photoelectric conversion device - Google Patents

Description

  The present invention relates to a photoelectric conversion device.

  A photoelectric conversion device using a dye, such as a dye-sensitized solar cell, is a next-generation photoelectric conversion device that has attracted attention because it has advantages such as high photoelectric conversion efficiency and low manufacturing cost.

  A photoelectric conversion device using such a dye includes a photoelectric conversion element. The photoelectric conversion element generally includes a substrate and at least one photoelectric conversion cell provided on the substrate. However, in the photoelectric conversion element, an annular and soft adhesive portion such as butyl rubber is further provided on the peripheral portion of the substrate. Some of them have a back sheet which is fixed via the substrate and at least one photoelectric conversion cell is arranged between the substrate and the substrate (see Patent Document 1 below).

  On the other hand, as a photoelectric conversion device, a device having a housing for holding a photoelectric conversion element is also known. This housing generally has a housing portion that houses the photoelectric conversion element, and a fixing portion that is provided in the housing portion and presses the back sheet to fix the photoelectric conversion element to the housing portion. In this case, the fixed part of the housing presses the adhesive part via the back sheet.

JP, 2014-192008, A

  However, the photoelectric conversion device described in Patent Document 1 has the following problems.

  That is, in the photoelectric conversion device described in Patent Document 1, the fixing portion of the housing presses the adhesive portion via the back sheet, so when the photoelectric conversion device is placed in a high temperature environment, the adhesive portion softens, As a result, a gap may occur between the backsheet and the fixed portion of the housing, and in that case, it is conceivable that the photoelectric conversion element may be displaced from its original position with respect to the housing.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photoelectric conversion device capable of sufficiently suppressing positional deviation of a photoelectric conversion element with respect to a housing.

  In order to solve the above problems, the present invention includes a photoelectric conversion element and a housing that holds the photoelectric conversion element, wherein the photoelectric conversion element is a substrate and at least one photoelectric element provided on one surface of the substrate. A conversion cell and a hard layer provided on the peripheral surface of the substrate on the one surface of the substrate, the photoelectric conversion cell, a conductive layer provided on the one surface of the substrate, and the conductive layer A housing portion that houses the photoelectric conversion element, and a fixing portion that is provided in the housing portion and that fixes the photoelectric conversion element to the housing portion. And the durometer hardness of the hard part is greater than 50 according to the type D durometer, and the hard part is sandwiched between the substrate and the fixed part.

  According to this photoelectric conversion device, the hard portion is sandwiched between the substrate of the photoelectric conversion element and the fixed portion of the housing, and the durometer hardness of the hard portion of the type D durometer is greater than 50. It becomes possible to firmly fix the photoelectric conversion element to the housing portion of the housing. Therefore, according to the photoelectric conversion device of the present invention, it is possible to sufficiently suppress the positional deviation of the photoelectric conversion element with respect to the housing.

  In the photoelectric conversion device, the photoelectric conversion element is provided on the one surface side of the substrate, further has a protective layer that covers and protects the photoelectric conversion cell, the peripheral portion of the protective layer is the hard portion. It is preferably configured.

  In this case, when the peripheral portion of the protective layer does not form a hard portion, for example, the hard portion exists separately from the protective layer, and when the hard portion and the protective layer are viewed in the direction orthogonal to the one surface of the substrate, Compared to the case where it is provided on the one surface and outside the protective layer, it is possible to omit the area for installing the hard portion on one surface of the substrate. Therefore, the area of one surface of the substrate can be reduced, and the photoelectric conversion element can be further downsized. Therefore, the photoelectric conversion device can be further downsized.

  In the present invention, for the durometer hardness by the type D durometer, a test piece having a thickness of 2 mm or more and a radius of 12 mm or more is separately prepared by using the material used for the hard portion. The value measured in accordance with JIS standard K7215 "Plastic durometer hardness test method".

  ADVANTAGE OF THE INVENTION According to this invention, the photoelectric conversion element which can fully suppress the position gap of a photoelectric conversion element with respect to a housing | casing is provided.

It is a top view which shows one Embodiment of the photoelectric conversion apparatus of this invention. FIG. 2 is a sectional end view taken along line II-II of FIG. 1. FIG. 6 is a sectional end view showing another embodiment of the photoelectric conversion device of the present invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to FIGS. 1 and 2. 1 is a plan view showing an embodiment of a photoelectric conversion device of the present invention, and FIG. 2 is a sectional end view taken along line II-II of FIG.

  As shown in FIGS. 1 and 2, the photoelectric conversion device 100 includes a photoelectric conversion element 110 and a housing 120 that holds the photoelectric conversion element 110. The photoelectric conversion element 110 is provided on the transparent substrate 11 as a substrate, the photoelectric conversion cell 50 provided on the one surface 11a of the transparent substrate 11, and the photoelectric conversion cell 50 provided on the one surface 11a side of the transparent substrate 11 to cover and protect the photoelectric conversion cell 50. It has a protective layer 60.

  The transparent substrate 11 has a light receiving surface 11b for receiving light on the side opposite to the surface 11a on which the photoelectric conversion cells 50 are provided (hereinafter referred to as "cell installation surface").

  The photoelectric conversion cell 50 includes a transparent conductive layer 12 as an electrode provided on the cell installation surface 11 a of the transparent substrate 11, a counter substrate 20 provided to face the transparent conductive layer 12, a transparent conductive layer 12 and a counter substrate 20. Between the oxide semiconductor layer 13 provided on the transparent conductive layer 12 and the transparent substrate 11 and the counter substrate 20, and a ring-shaped sealing portion 30 connecting these, and the sealing portion 30, The electrolyte 40 is provided in the cell space formed by the transparent conductive layer 12 and the counter substrate 20. A dye is carried on the oxide semiconductor layer 13.

  The counter substrate 20 is composed of a counter electrode, and has a metal substrate 21 that also serves as a substrate and an electrode, and a catalyst layer 22 provided on the transparent substrate 11 side of the metal substrate 21.

  The protective layer 60 is provided on the cell mounting surface 11a of the transparent substrate 11 so as to cover the photoelectric conversion cell 50 inside the annular hard portion 61 provided on the peripheral portion of the transparent substrate 11 and the annular hard portion 61. And a covered portion 62. Further, the durometer hardness of the hard portion 61 according to the type D durometer (hereinafter, simply referred to as “durometer hardness”) is larger than 50.

  On the other hand, the housing 120 has a housing portion 121 that houses the photoelectric conversion element 110, and a fixing portion 122 that is provided in the housing portion 121 and that fixes the photoelectric conversion element 110 to the housing portion 121. The accommodating portion 121 is composed of a bottom portion 121 a that comes into contact with the surface of the transparent substrate 11 opposite to the photoelectric conversion cell 50, and a side wall portion 121 b that surrounds the photoelectric conversion element 110. One end (lower end) of the side wall 121b is connected to the bottom 121a, and the fixing part 122 is provided at the other end (upper end) of the side wall 121b. The photoelectric conversion element 110 is sandwiched between the fixed portion 122 and the bottom portion 121a. An opening 121c is formed in the bottom 121a of the housing 121 so that light can enter the transparent substrate 11 of the photoelectric conversion element 110.

  The hard portion 61 of the protective layer 60 is sandwiched between the transparent substrate 11 and the fixed portion 122 of the housing 120. In this embodiment, since the hard portion 61 is annular, when the fixed portion 122 and the hard portion 61 of the housing 120 are viewed along the thickness direction of the oxide semiconductor layer 13, as shown in FIG. The hard portion 61 extends to a portion that does not overlap the fixed portion 122. That is, the fixed portion 122 overlaps only a part of the hard portion 61.

  According to this photoelectric conversion device 100, the hard portion 61 is sandwiched between the transparent substrate 11 and the fixing portion 122, and the durometer hardness of the hard portion 61 is larger than 50. Therefore, the fixing portion 122 of the housing 120 is the photoelectric conversion element. The 110 can be firmly fixed to the housing 121 of the housing 120. Therefore, according to the photoelectric conversion device 100, the positional deviation of the photoelectric conversion element 110 with respect to the housing 120 can be sufficiently suppressed.

  Further, the photoelectric conversion device 100 has a protective layer 60 which is provided on the cell installation surface 11a side of the transparent substrate 11 and covers and protects the photoelectric conversion cell 50, and a peripheral portion of the protective layer 60 forms a hard portion 61. There is. Therefore, when the peripheral portion of the protective layer 60 does not form the hard portion 61, for example, the hard portion 61 exists separately from the protective layer 60, and the hard portion 61 and the protective layer 60 are provided on the cell mounting surface 11a of the transparent substrate 11. Compared with the case where the transparent substrate 11 is provided on the cell installation surface 11a of the transparent substrate 11 and in the outer region of the protective layer 60 when viewed in a direction orthogonal to, It is possible to omit the area for installing 61. Therefore, the area of the cell installation surface 11a of the transparent substrate 11 can be reduced, and the photoelectric conversion element 110 can be further downsized. Therefore, the photoelectric conversion device 100 can be further downsized. Further, on the cell installation surface 11a of the transparent substrate 11, it is possible to omit the region for installing the hard portion 61, and therefore, the ratio of the area of the oxide semiconductor layer 13 to the area of the light receiving surface 11b of the transparent substrate 11. Can be increased, and the aperture ratio of the photoelectric conversion element 110 can be increased.

  Further, in the photoelectric conversion device 100, when the fixed portion 122 and the hard portion 61 of the housing 120 are viewed along the thickness direction of the oxide semiconductor layer 13, the hard portion 61 is annular, and thus the hard portion 61 is formed. Extends to a portion that does not overlap the fixed portion 122. Therefore, when the fixed portion 122 of the housing 120 and the hard portion 61 are viewed along the thickness direction of the oxide semiconductor layer 13, the fixed portion 122 of the housing 120 is displaced from the hard portion 61. However, the hard portion 61 can be maintained in a state of being sandwiched between the transparent substrate 11 and the fixing portion 122 of the housing 120. Further, since the area of the hard portion 61 on the side of the fixed portion 122 increases, the force applied from the hard portion 61 to the photoelectric conversion cell 50 can be dispersed.

  Next, the photoelectric conversion element 110 and the housing 120 will be described in detail.

<< Photoelectric conversion element >>
The photoelectric conversion element 110 has a transparent substrate 11, a photoelectric conversion cell 50, and a protective layer 60. Therefore, these will be described in detail below.

<Transparent substrate>
The material forming the transparent substrate 11 may be, for example, a transparent material, and examples of such a transparent material include borosilicate glass, soda lime glass, white plate glass, glass such as quartz glass, and polyethylene terephthalate (PET). , Polyethylene naphthalate (PEN), polycarbonate (PC), and polyether sulfone (PES). The thickness of the transparent substrate 11 is appropriately determined according to the size of the photoelectric conversion element 100 and is not particularly limited, but may be in a range of 0.05 to 10 mm, for example.

<Photoelectric conversion cell>
The photoelectric conversion cell 50 includes the transparent conductive layer 12, the counter substrate 20, the oxide semiconductor layer 13, the sealing unit 30, the electrolyte 40, and the dye carried on the oxide semiconductor layer 13. .. Hereinafter, these will be described in detail.

(Transparent conductive layer)
Examples of the material forming the transparent conductive layer 12 include conductive metal oxides such as tin-added indium oxide (ITO), tin oxide (SnO ₂ ), and fluorine-added tin oxide (FTO). The transparent conductive layer 12 may be a single layer or a stacked body of a plurality of layers made of different conductive metal oxides. When the transparent conductive layer 12 is composed of a single layer, the transparent conductive layer 12 is preferably composed of FTO because it has high heat resistance and chemical resistance. The thickness of the transparent conductive layer 12 may be in the range of 0.01 to 2 μm, for example.

(Counter substrate)
As described above, the counter substrate 20 includes the metal substrate 21 also serving as a substrate and an electrode, and the conductive catalyst layer 22 provided on the transparent substrate 11 side of the metal substrate 21 and contributing to the reduction of the electrolyte 40.

  The metal substrate 21 may be made of metal, but is made of a corrosion-resistant metal material such as titanium, nickel, platinum, molybdenum, tungsten, aluminum, and stainless. The thickness of the metal substrate 21 is appropriately determined according to the size of the photoelectric conversion element 110 and is not particularly limited, but may be, for example, 0.01 to 4 mm.

  The catalyst layer 22 is made of platinum, a carbon-based material, a conductive polymer, or the like. Here, carbon black or carbon nanotubes are preferably used as the carbon-based material. The counter electrode 20 may not have the catalyst layer 22 when the metal substrate 21 has a catalytic function (for example, when carbon or the like is contained).

(Oxide semiconductor layer)
The oxide semiconductor layer 13 is composed of oxide semiconductor particles. Examples of the oxide semiconductor particles include titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), zinc oxide (ZnO), tungsten oxide (WO ₃ ), niobium oxide (Nb ₂ O ₅ ), and strontium titanate (SrTiO ₃ ). , Tin oxide (SnO ₂ ), or two or more of these. The oxide semiconductor layer 13 may have a thickness of 0.1 to 100 μm, for example.

(Sealing part)
Examples of the material forming the sealing portion 30 include a modified polyolefin resin, a thermoplastic resin such as a vinyl alcohol polymer, and a resin such as an ultraviolet curable resin. Examples of the modified polyolefin resin include ionomers, ethylene-vinyl acetic anhydride copolymers, ethylene-methacrylic acid copolymers and ethylene-vinyl alcohol copolymers. These resins can be used alone or in combination of two or more kinds.

  The thickness of the sealing portion 30 is usually 10 to 50 μm, preferably 20 to 40 μm. In this case, it is possible to more sufficiently suppress the entry of water into the inside of the sealing portion 30.

(Electrolytes)
The electrolyte 40 contains a redox couple and an organic solvent. As the organic solvent, acetonitrile, methoxyacetonitrile, methoxypropionitrile, propionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, γ-butyrolactone, valeronitrile, pivalonitrile, etc. can be used. Examples of the redox couple include redox couples containing halogen atoms such as iodide ion / polyiodide ion (for example, I ⁻ / I ₃ ⁻ ) and bromide ion / polybromide ion, as well as zinc complex, iron complex, and cobalt complex. Redox pairs such as. The iodide ion / polyiodide ion can be formed by iodine (I ₂ ) and a salt (ionic liquid or solid salt) containing iodide (I ⁻ ) as an anion. When using an ionic liquid having iodide as the anion, only iodine needs to be added. When an ionic liquid other than iodide is used as the anion, as an anion such as LiI or tetrabutylammonium iodide. A salt containing iodide (I ⁻ ) may be added. The electrolyte 40 may use an ionic liquid instead of the organic solvent. As the ionic liquid, for example, a known iodine salt such as a pyridinium salt, an imidazolium salt, a triazolium salt, or the like is used. Examples of such an iodine salt include 1-hexyl-3-methylimidazolium iodide, 1-ethyl-3-propylimidazolium iodide, 1-ethyl-3-methylimidazolium iodide, 1,2- Dimethyl-3-propylimidazolium iodide, 1-butyl-3-methylimidazolium iodide, or 1-methyl-3-propylimidazolium iodide is preferably used.

  The electrolyte 40 may use a mixture of the ionic liquid and the organic solvent instead of the organic solvent.

  Additives can be added to the electrolyte 40. Examples of the additive include benzimidazoles such as 1-methylbenzimidazole (NMB) and 1-butylbenzimidazole (NBB), LiI, tetrabutylammonium iodide, 4-t-butylpyridine, and guanidinium thiocyanate. .. Among them, benzimidazole is preferable as the additive.

Further, as the electrolyte 40, a nanocomposite gel electrolyte, which is a pseudo-solid electrolyte formed into a gel by kneading the above electrolyte with nanoparticles such as SiO ₂ , TiO ₂ , and carbon nanotubes, or polyvinylidene fluoride may be used. An electrolyte gelated with an organic gelling agent such as a polyethylene oxide derivative or an amino acid derivative may be used.

(Pigment)
As the dye, for example, a ruthenium complex having a ligand containing a bipyridine structure, a terpyridine structure, or the like, a photosensitizing dye such as an organic dye such as porphyrin, eosin, rhodamine, or merocyanine, or an organic material such as a lead halide perovskite crystal. -Inorganic composite pigments and the like can be mentioned. As the lead halide perovskite, for example, CH ₃ NH ₃ PbX ₃ (X = Cl, Br, I) is used. Among the above dyes, a ruthenium complex having a ligand containing a bipyridine structure or a terpyridine structure is preferable. In this case, the photoelectric conversion characteristics of the photoelectric conversion device 100 can be further improved. When a photosensitizing dye is used as the dye, the photoelectric conversion device 100 is a dye-sensitized photoelectric conversion device.

<Protective layer>
The protective layer 60 has a hard portion 61 and a covering portion 62.

  The material of the protective layer 60 is composed of at least one layer made of a resin material. Examples of the resin material include polyimide resin, epoxy resin, polyurethane resin, polyethylene terephthalate (PET) resin and the like. Of these, polyimide resin is preferable. In this case, more excellent insulation can be imparted to the protective layer 60.

(Hard part)
The durometer hardness of the hard portion 61 is not particularly limited as long as it is greater than 50, but the durometer hardness of the hard portion 61 is preferably 65 or more. In this case, the positional deviation of the photoelectric conversion element 110 with respect to the housing 120 can be suppressed more sufficiently.

  The durometer hardness of the hard portion 61 is preferably 80% or more of the smaller durometer hardness of the durometer hardness of the transparent substrate 11 and the fixing portion 122 of the housing 120. In this case, the positional deviation of the photoelectric conversion element 110 with respect to the housing 120 can be suppressed more sufficiently.

≪Case≫
Next, the housing 120 will be described in detail.

  The housing 120 has a housing portion 121 and a fixed portion 122.

<Container>
The housing portion 121 may have a shape capable of housing the photoelectric conversion element 110 by the bottom portion 121a and the side wall portion 121b.

  As the material forming the housing portion 121, for example, polypropylene, polycarbonate, polyimide, polybutylene terephthalate, resin such as phenol resin or epoxy resin, metal such as aluminum, or ceramics can be used.

<Fixed part>
The fixed portion 122 sandwiches the hard portion 61 together with the photoelectric conversion element 110. In this embodiment, one annular hard portion 61 is fixed by the two fixing portions 122. The fixing portion 122 is usually integrally molded with the housing portion 121. That is, the fixing portion 122 is usually made of the same material as the accommodating portion 121. However, the fixed portion 122 may be made of a material different from that of the accommodation portion 121.

  The present invention is not limited to the above embodiment. For example, in the above-described embodiment, the photoelectric conversion element 110 has the hard portion 61 and the covering portion 62, but the photoelectric conversion element has the covering portion 62 as in the photoelectric conversion device 200 shown in FIG. 3, for example. You don't have to. In this case, the photoelectric conversion element 210 has only the hard portion 61. Further, in the present embodiment, the hard portion 61 is annular, but when the photoelectric conversion element 210 does not have the covering portion 62 as in the photoelectric conversion device 200 shown in FIG. 3, the hard portion 61 is annular. You don't have to. In addition, in FIG. 3, the same or equivalent components as those shown in FIGS. 1 and 2 are denoted by the same reference numerals.

  Further, in the above embodiment, a part of the hard part 61 overlaps with the fixed part 122, but the whole hard part 61 may overlap with the fixed part 122.

  Furthermore, in the photoelectric conversion device 100 of the above-described embodiment, the oxide semiconductor layer 13 is provided on the transparent conductive layer 12, but the oxide semiconductor layer 13 may be provided on the counter substrate 20. However, in this case, the catalyst layer 22 is provided on the transparent conductive layer 12.

  Furthermore, in the above embodiment, the counter substrate 20 is composed of the counter electrode, but the counter substrate 20 may be composed of an insulating substrate. However, in this case, the oxide semiconductor layer 13, the porous insulating layer impregnated with the electrolyte 40, and the counter electrode are sequentially arranged between the transparent conductive layer 12 and the counter substrate 20 from the transparent conductive layer 12 side. A stack is provided.

  Further, in the above embodiment, the photoelectric conversion device 100 has only one photoelectric conversion cell 50, but the photoelectric conversion device 100 may include a plurality of photoelectric conversion cells 50. Here, the plurality of photoelectric conversion cells 50 may be connected in series or in parallel.

11 ... Transparent substrate (substrate)
12 ... Transparent conductive layer (conductive layer)
20 ... Counter substrate 50 ... Photoelectric conversion cell 60 ... Protective layer 61 ... Hard part 100,200 ... Photoelectric conversion device 110,210 ... Photoelectric conversion element 120 ... Case 121 ... Accommodation part 122 ... Fixed part

Claims (2)

A photoelectric conversion element,
A housing for holding the photoelectric conversion element,
The photoelectric conversion element,
Board,
At least one photoelectric conversion cell provided on one surface of the substrate;
A hard portion provided on a peripheral portion of the substrate on the one surface of the substrate,
The photoelectric conversion cell,
A conductive layer provided on the one surface of the substrate;
A counter substrate provided to face the conductive layer,
The housing is
An accommodating portion that accommodates the photoelectric conversion element,
And a fixing portion which is provided in the housing portion and fixes the photoelectric conversion element to the housing portion.
The durometer hardness of the hard part according to the type D durometer is greater than 50,
The photoelectric conversion device, wherein the hard portion is sandwiched between the substrate and the fixing portion. The photoelectric conversion element,
The protective layer is provided on the one surface side of the substrate and covers and protects the photoelectric conversion cell.
The photoelectric conversion device according to claim 1, wherein a peripheral portion of the protective layer constitutes the hard portion.

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