WO2018012392A1 - Élément de conversion photoélectrique - Google Patents

Élément de conversion photoélectrique Download PDF

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Publication number
WO2018012392A1
WO2018012392A1 PCT/JP2017/024784 JP2017024784W WO2018012392A1 WO 2018012392 A1 WO2018012392 A1 WO 2018012392A1 JP 2017024784 W JP2017024784 W JP 2017024784W WO 2018012392 A1 WO2018012392 A1 WO 2018012392A1
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Prior art keywords
photoelectric conversion
oxygen barrier
conversion element
oxygen
transmission coefficient
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PCT/JP2017/024784
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English (en)
Japanese (ja)
Inventor
健治 勝亦
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株式会社フジクラ
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Publication of WO2018012392A1 publication Critical patent/WO2018012392A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices

Definitions

  • the present invention relates to a photoelectric conversion element.
  • photoelectric conversion elements As photoelectric conversion elements, photoelectric conversion elements using dyes are attracting attention because of low production costs and high photoelectric conversion efficiency, and various developments have been made on photoelectric conversion elements using dyes.
  • a photoelectric conversion element using a dye for example, a photoelectric conversion element described in Patent Document 1 below is known.
  • the photoelectric conversion element described in Patent Literature 1 below includes a first electrode, a second electrode facing the first electrode, an annular sealing portion that joins the first electrode and the second electrode, and an inner side of the sealing portion.
  • an ionomer, an ethylene-vinyl acetic anhydride copolymer, an ethylene-methacrylic acid copolymer, an ethylene-vinyl alcohol copolymer, or the like is used as a sealing portion. Yes.
  • Patent Document 1 has room for improvement in terms of durability in a high humidity environment.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a photoelectric conversion element having excellent durability even in a high humidity environment.
  • the present inventor has intensively studied to solve the above problems.
  • oxygen may enter the inside of the sealing portion in a high humidity environment, and as a result, the output of the photoelectric conversion element may not be reduced. I thought.
  • the present inventor has studied to provide an oxygen barrier resin outside the sealing portion in the photoelectric conversion cell. However, even in this case, the output of the photoelectric conversion element may decrease in a high humidity environment. Therefore, as a result of further earnest research, the present inventor has found that the above-described problems can be solved by the following invention.
  • the present invention provides a photoelectric conversion element having at least one photoelectric conversion cell, wherein the photoelectric conversion cell is an annular substrate that joins the electrode substrate, the counter substrate facing the electrode substrate, and the electrode substrate and the counter substrate.
  • an oxygen barrier portion having an oxygen transmission coefficient lower than that of the sealing portion is provided outside the sealing portion, and the oxygen barrier portion covers the sealing portion. is doing. Therefore, the oxygen barrier part sufficiently suppresses the amount of oxygen reaching the sealing part, and sufficiently suppresses oxygen from entering the sealing part.
  • a water shielding part having a water vapor transmission coefficient lower than that of the oxygen barrier part is provided outside the oxygen barrier part, and the water shielding part covers the oxygen barrier part.
  • the photoelectric conversion element of this invention the oxygen barrier part is provided in the outer side of the sealing part, and the electrolyte is arrange
  • the resin having a hydroxyl group preferably contains a vinyl alcohol unit.
  • the photoelectric conversion element may have better durability even in a high humidity environment. It becomes possible.
  • the content of the vinyl alcohol unit in the resin having a hydroxyl group is preferably 20 to 70 mol%.
  • the water vapor transmission coefficient ratio R 1 represented by the following formula (1) is preferably 0.001 to 0.9.
  • R 1 A / B (1)
  • A represents the water vapor transmission coefficient (g ⁇ mm / m 2 ⁇ 24 h) at 40 ° C. and 90% RH of the water shielding portion
  • B represents 40 ° C. and 90% of the oxygen barrier portion.
  • RH (g ⁇ mm / m 2 ⁇ 24h).
  • the water vapor transmission coefficient ratio R 1 exceeds 0.9, water penetration into the oxygen barrier portion can be more sufficiently suppressed, so that the photoelectric conversion element has superior durability even in a high humidity environment. It is possible to have On the other hand, as compared with the case the water vapor permeability coefficient ratio R 1 is less than 0.001, it is possible to easily move the water mixed in the photoelectric conversion cell to the outside by heating in a dry environment, sealed In addition, the moisture in the electrolyte can be reduced more sufficiently.
  • the water vapor transmission coefficient ratio R 1 represented by the formula (1) is preferably 0.001 to 0.4.
  • the photoelectric conversion element As compared with the case where the water vapor permeability coefficient ratio R 1 is greater than 0.4, the photoelectric conversion element, it is possible to have better durability under a high humidity environment.
  • oxygen permeability coefficient ratio R 2 represented by the following formula (2) is less than 1 0.0001 or more.
  • R 2 C / D (2)
  • C represents an oxygen transmission coefficient (cc ⁇ mm / m 2 ⁇ 24 h / atm) at 22 ° C. and 90% RH of the oxygen barrier portion
  • D represents 22 ° C. of the sealing portion
  • the amount of oxygen entering the inside of the sealing portion can be more sufficiently reduced, and oxygen in the sealed electrolyte can be reduced by heating in the absence of oxygen.
  • a water vapor transmission coefficient of the water shielding portion at 40 ° C. and 90% RH is 0.001 to 10 (g ⁇ mm / m 2 ⁇ 24 h).
  • the amount of oxygen entering the inside of the sealing portion can be more sufficiently reduced, and oxygen in the sealed electrolyte can be reduced by heating in the absence of oxygen.
  • the oxygen barrier portion extends from the main body portion to the surface on the opposite side of the electrode substrate from the main body portion and is bonded to the counter substrate. It is preferable to have an extending portion.
  • the surface area of the oxygen barrier portion is increased by an amount corresponding to the extending portion as compared with the case where the oxygen barrier portion is composed only of the main body. For this reason, the oxygen barrier property of the oxygen barrier portion is further improved.
  • the oxygen barrier portion has an extending portion that extends from the main body portion to the surface of the counter substrate on the side opposite to the electrode substrate and is bonded to the counter substrate.
  • the counter substrate includes the sealing portion and the oxygen barrier portion. It is sandwiched between the extension part of the. For this reason, the photoelectric conversion element is placed in a high temperature environment, and the pressure in the space between the electrode substrate, the counter substrate, and the sealing portion increases, and accordingly, the force for peeling the counter substrate from the sealing portion is increased. Even if it works, peeling of the counter substrate from the sealing portion is sufficiently suppressed. Therefore, the photoelectric conversion element can have more excellent durability.
  • the photoelectric conversion element further includes an adhesive part for bonding the oxygen barrier part and the water shielding part between the oxygen barrier part and the water shielding part, and the adhesive part includes a hydroxyl group and the water shielding part. It is preferable to have the same functional group as the functional group contained in.
  • the adhesive force between the oxygen barrier part and the water shielding part is further improved.
  • the water shielding portion is composed of at least one water shielding layer, and the at least one water shielding layer is made of only a resin.
  • the impact resistance of the water shielding portion can be further improved.
  • the water shielding portion is composed of at least one water shielding layer, and the at least one water shielding layer is made of only a resin and an inorganic substance.
  • the impact resistance of the water shielding portion can be further improved, and the water shielding property can be further improved.
  • the inorganic substance is preferably at least one selected from the group consisting of an inorganic filler and a desiccant.
  • the water-impervious portion it becomes possible for the water-impervious portion to have higher water-imperviousness, and the shape stability of the water-impervious portion becomes higher.
  • a photoelectric conversion element having excellent durability even in a high humidity environment is provided.
  • FIG. 1 is a cross-sectional end view showing an embodiment of the photoelectric conversion element of the present invention.
  • the photoelectric conversion element 100 includes one photoelectric conversion cell 90, and the photoelectric conversion cell 90 includes the electrode substrate 10, the counter substrate 20 facing the electrode substrate 10, the electrode substrate 10, and the counter substrate.
  • an adhesion part 80 for bonding the oxygen barrier part 60 or the counter substrate 20 and the water shielding part 70 to each other. Note that a dye is supported on the oxide semiconductor layer 50.
  • the counter substrate 20 is composed of a counter electrode, and includes a conductive substrate 21 serving as a substrate and an electrode, and a catalyst layer 22 provided on the conductive substrate 21.
  • the oxygen barrier part 60 includes a resin having a hydroxyl group, and the oxygen permeability coefficient of the oxygen barrier part 60 at 22 ° C. and 90% RH is lower than the oxygen permeability coefficient of the sealing part 30 at 22 ° C. and 90% RH.
  • the oxygen barrier unit 60 includes a main body 61 that covers the sealing unit 30, and an extension that extends from the main body 61 to the surface of the counter substrate 20 opposite to the electrode substrate 10 and is bonded to the counter substrate 20. 62.
  • the water vapor transmission coefficient at 40 ° C. and 90% RH of the water shielding part 70 is smaller than the water vapor transmission coefficient at 40 ° C. and 90% RH of the oxygen barrier part 60.
  • the oxygen barrier unit 60 having an oxygen transmission coefficient lower than that of the sealing unit 30 is provided outside the sealing unit 30 in the photoelectric conversion cell 90, and the oxygen barrier unit 60 is the sealing unit. 30 is covered. Therefore, the oxygen barrier unit 60 sufficiently suppresses the amount of oxygen reaching the sealing unit 30 and sufficiently suppresses oxygen from entering the sealing unit 30. Further, according to the photoelectric conversion element 100, the water shielding unit 70 having a water vapor transmission coefficient lower than that of the oxygen barrier unit 60 is provided outside the oxygen barrier unit 60, and the water shielding unit 70 covers the oxygen barrier unit 60. is doing.
  • the photoelectric conversion element 100 According to the photoelectric conversion element 100, the oxygen barrier unit 60 is provided outside the sealing unit 30, and the electrolyte 40 is disposed inside the sealing unit 30. That is, the sealing part 30 is interposed between the electrolyte 40 and the oxygen barrier part 60. For this reason, the deterioration of the oxygen barrier section 60 due to the electrolyte 40 is sufficiently suppressed. From the above, according to the photoelectric conversion element 100, it is possible to have excellent durability even in a high humidity environment.
  • the oxygen barrier unit 60 includes the main body 61 that covers the sealing unit 30, and extends from the main body 61 to the opposite surface of the counter substrate 20 to the electrode substrate 10. 20 and an extending portion 62 bonded to 20. Therefore, as compared with the case where the oxygen barrier unit 60 is composed only of the main body unit 61, the surface area of the oxygen barrier unit 60 is increased by the amount of the extending part 62. For this reason, the oxygen barrier property of the oxygen barrier unit 60 is further improved.
  • the oxygen barrier unit 60 includes an extending portion 62 that extends from the main body 61 to the surface of the counter substrate 20 on the side opposite to the electrode substrate 10 and is bonded to the counter substrate 20.
  • the photoelectric conversion element 100 is placed in a high temperature environment, and the pressure in the space between the electrode substrate 10, the counter substrate 20, and the sealing portion 30 increases, and the counter substrate 20 is peeled off from the sealing portion 30 accordingly. Even if the force to be applied works, peeling of the counter substrate 20 from the sealing portion 30 is sufficiently suppressed. Therefore, the photoelectric conversion element 100 can have more excellent durability.
  • the electrode substrate 10, the counter substrate 20, the sealing part 30, the electrolyte 40, the oxide semiconductor layer 50, the dye, the water shielding part 70, the oxygen barrier part 60, and the bonding part 80 will be described in detail.
  • the electrode substrate 10 includes a transparent substrate 11 and a transparent conductive layer 12 provided on the transparent substrate 11.
  • the material which comprises the transparent substrate 11 should just be a transparent material, for example, as such a transparent material, glass, such as borosilicate glass, soda-lime glass, white plate glass, quartz glass, for example; Polyethylene terephthalate (PET) And resins such as polyethylene naphthalate (PEN), polycarbonate (PC), and polyether sulfone (PES).
  • PET Polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • PES polyether sulfone
  • 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 the range of 50 to 4000 ⁇ m, for example.
  • Transparent conductive layer 12 examples 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 laminate 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 ⁇ m, for example.
  • the counter substrate 20 includes the conductive substrate 21 serving as a substrate and an electrode, and the catalyst layer 22 provided on the electrode substrate 10 side of the conductive substrate 21 to promote the catalytic reaction.
  • the conductive substrate 21 is made of a corrosion-resistant metal material such as titanium, nickel, platinum, molybdenum, tungsten, aluminum, and stainless steel.
  • the conductive substrate 21 may be formed of a laminate in which a substrate and an electrode are separated and a conductive layer made of a conductive oxide such as ITO or FTO is formed on a resin film as an electrode.
  • a laminate in which a conductive layer made of a conductive oxide such as FTO is formed may be used.
  • the thickness of the conductive substrate 21 is appropriately determined according to the size of the photoelectric conversion element 100 and is not particularly limited, but may be, for example, 0.01 to 4 mm.
  • the catalyst layer 22 is made of a metal such as platinum, a carbon-based material, or a conductive polymer.
  • the sealing portion 30 examples include thermoplastic resins such as modified polyolefin resins and vinyl alcohol copolymers, and resins such as ultraviolet curable resins.
  • the modified polyolefin resin include maleic anhydride-modified polyethylene, ionomer, ethylene-vinyl acetic anhydride copolymer, ethylene-methacrylic acid copolymer, and ethylene-vinyl alcohol copolymer. These resins can be used alone or in combination of two or more.
  • the sealing part 30 a part having higher durability with respect to the electrolyte 40 than the oxygen barrier part 60 is preferable.
  • the sealing unit 30 is preferably a modified polyolefin resin or an ultraviolet curable resin.
  • the electrolyte 40 includes a redox couple and an organic solvent.
  • organic solvent acetonitrile, methoxyacetonitrile, 3-methoxypropionitrile, propionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, ⁇ -butyrolactone, valeronitrile, pivalonitrile, and the like can be used.
  • the redox pair examples include a redox pair containing a halogen atom such as iodide ion / polyiodide ion (for example, I ⁇ / I 3 ⁇ ), bromide ion / polybromide ion, zinc complex, iron complex, and cobalt complex. And redox pairs.
  • 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 an ionic liquid having an iodide as an anion is used, only iodine may be added.
  • an anion such as LiI or tetrabutylammonium iodide is used as an anion
  • 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.
  • the ionic liquid for example, known iodinated salts such as pyridinium salts, imidazolium salts, triazolium salts and the like are used.
  • Examples of such an iodide salt include 1-hexyl-3-methylimidazolium iodide, 1-ethyl-3-propylimidazolium iodide, 1-ethyl-3-methylimidazolium iodide, 1, -Dimethyl-3-propylimidazolium iodide, 1-butyl-3-methylimidazolium iodide, or 1-methyl-3-propylimidazolium iodide is preferably used.
  • the electrolyte 40 may be a mixture of the ionic liquid and the organic solvent instead of the organic solvent.
  • an additive can be added to the electrolyte 40.
  • the additive include benzimidazoles such as 1-methylbenzimidazole (NMB) and 1-butylbenzimidazole (NBB), 4-t-butylpyridine, and guanidinium thiocyanate. Among them, benzimidazole is preferable as an additive.
  • a nano-composite gel electrolyte which is a pseudo-solid electrolyte formed by kneading nanoparticles such as SiO 2 , TiO 2 , carbon nanotubes, etc. into the electrolyte, may be used, and polyvinylidene fluoride may be used.
  • an electrolyte gelled with an organic gelling agent such as a polyethylene oxide derivative or an amino acid derivative may be used.
  • the oxide semiconductor layer 50 is composed of oxide semiconductor particles.
  • the oxide semiconductor particles include titanium oxide (TiO 2 ), zinc oxide (ZnO), tungsten oxide (WO 3 ), niobium oxide (Nb 2 O 5 ), strontium titanate (SrTiO 3 ), and tin oxide (SnO 2 ).
  • the thickness of the oxide semiconductor layer 50 may be set to 0.1 to 100 ⁇ m, for example.
  • the dye examples include a ruthenium complex having a ligand including a bipyridine structure, a terpyridine structure, and the like, a photosensitizing dye such as an organic dye such as porphyrin, eosin, rhodanine, and merocyanine, and an organic such as a lead halide-based perovskite crystal.
  • a photosensitizing dye such as an organic dye such as porphyrin, eosin, rhodanine, and merocyanine
  • an organic such as a lead halide-based perovskite crystal.
  • a ruthenium complex having a ligand containing a bipyridine structure or a terpyridine structure is preferable.
  • the photoelectric conversion characteristics and durability of the photoelectric conversion element 100 can be further improved.
  • the photoelectric conversion element 100 turns into a dye-sensitized photoelectric conversion element.
  • the water shielding part 70 has water shielding.
  • the water-impervious portion 70 only needs to cover part or all of the outer surface of the oxygen barrier portion 60, but preferably covers the entire surface. In this case, the amount of water vapor entering the oxygen barrier unit 60 can be more sufficiently suppressed, and the durability of the photoelectric conversion element 100 can be further improved.
  • the water vapor transmission coefficient ratio R 1 represented by the following formula (1) is not particularly limited, but is preferably 0.001 to 0.9.
  • Water vapor transmission coefficient ratio R 1 A / B (1)
  • A represents the water vapor transmission coefficient (g ⁇ mm / m 2 ⁇ 24 h) at 40 ° C. and 90% RH of the water shielding portion 70
  • B represents 40 ° C. and 90% of the oxygen barrier portion 60.
  • RH g ⁇ mm / m 2 ⁇ 24h.
  • water vapor permeability coefficient ratio R 1 is as compared with the case of more than 0.9, because the water in the oxygen barrier portion 60 penetrate can be more sufficiently suppressed, the photoelectric conversion element 100 even under high-humidity environment is better It becomes possible to have durability.
  • the water vapor permeability coefficient ratio R 1 is as compared with the case is less than 0.001, the water mixed in the photoelectric conversion cell 90 by heating in a dry environment can make easily move to the outside, sealing The moisture in the electrolyte 40 thus made can be reduced more sufficiently.
  • the water vapor transmission coefficient ratio R 1 represented by the above formula (1) is preferably 0.001 to 0.4. In this case, as compared with the case where the water vapor permeability coefficient ratio R 1 is greater than 0.4, the photoelectric conversion element 100, it is possible to have better durability under a high humidity environment.
  • the water vapor transmission coefficient at 40 ° C. and 90% RH of the water shielding portion 70 is not particularly limited, but is preferably 0.001 to 10 (g ⁇ mm / m 2 ⁇ 24 h). In this case, drying by heating in a dry environment is easy and a sufficient water shielding effect is obtained.
  • the water vapor transmission coefficient of the water shielding part 70 at 40 ° C. and 90% RH is more preferably 0.001 to 0.5 (g ⁇ mm / m 2 ⁇ 24 h), preferably 0.1 to 0.4 (g Particularly preferred is mm / m 2 ⁇ 24h).
  • the water-impervious portion 70 includes at least one water-impervious layer, and the at least one water-impervious layer is made of only a resin. In this case, the impact resistance of the water shielding part 70 can be further improved.
  • the resin contained in the water shielding layer is not particularly limited, and examples of the resin include urethane resin, polyester, nylon resin, polyvinylidene chloride, butyl rubber, polyethylene, and epoxy resin. Of these, epoxy resins are preferred. In this case, the airtightness of the water-impervious portion 70 can be increased, and the permeation of water vapor can be effectively suppressed.
  • the at least one water shielding layer may be composed only of the above-described resin and inorganic substance. In this case, the impact resistance of the water shielding portion 70 can be further improved, and the water shielding property can be further improved.
  • the inorganic material is not particularly limited, but an inorganic filler, a desiccant and a mixture thereof are preferable as the inorganic material.
  • the crack by the shrink deformation of the water shielding part 70 can be more sufficiently suppressed by including the inorganic substance that the water shielding layer does not easily shrink.
  • the water-impervious part 70 it becomes possible for the water-impervious part 70 to have higher water-imperviousness, and the shape stability of the water-impervious part 70 becomes higher.
  • the inorganic filler include clay minerals.
  • the desiccant include silica gel, alumina, and zeolite.
  • the oxygen barrier unit 60 may cover a part or all of the outer surface of the sealing unit 30, but preferably covers the entire surface. In this case, the amount of oxygen that enters the inside of the sealing portion 30 can be more sufficiently reduced, and the durability of the photoelectric conversion element 100 can be further improved.
  • Oxygen permeability of the oxygen barrier section 60 is not particularly limited as lower than the oxygen permeability coefficient of the sealing portion 30, the oxygen permeability coefficient ratio R 2 represented by the following formula (2) is 0.0001 It is preferable that it is less than 1.
  • R 2 C / D (2)
  • C represents the oxygen transmission coefficient (cc ⁇ mm / m 2 ⁇ 24 h / atm) at 22 ° C. and 90% RH of the oxygen barrier portion 60
  • D represents 22 ° C. of the sealing portion 30, Oxygen transmission coefficient at 90% RH (cc ⁇ mm / m 2 ⁇ 24h / atm).
  • the amount of oxygen entering the inside of the sealing portion 30 can be more sufficiently reduced, and the oxygen in the sealed electrolyte 40 can be reduced by heating in the absence of oxygen.
  • the oxygen transmission coefficient ratio R 2 represented by the above formula (2) is more preferably 0.0001 to 0.01, and particularly preferably 0.0002 to 0.001.
  • the oxygen permeability coefficient of the oxygen barrier part 60 is not particularly limited as long as it is lower than the oxygen permeability coefficient of the sealing part 30, but is 0.001 to 10 (cc ⁇ mm / mm) under the conditions of 22 ° C. and 90% RH. m 2 ⁇ 24 h / atm). In this case, the amount of oxygen entering the inside of the sealing portion 30 can be more sufficiently reduced, and the oxygen in the sealed electrolyte 40 can be reduced by heating in the absence of oxygen.
  • the oxygen permeability coefficient of the oxygen barrier section 60 is more preferably 0.01 to 2 (cc ⁇ mm / m 2 ⁇ 24 h / atm) under the conditions of 22 ° C. and 90% RH, and more preferably 0.03 to 0.00. 1 (cc ⁇ mm / m 2 ⁇ 24 h / atm) is particularly preferable.
  • the material constituting the oxygen barrier section 60 only needs to contain a resin having a hydroxyl group.
  • the resin having a hydroxyl group is not particularly limited as long as it has a hydroxyl group, but is preferably a resin containing a vinyl alcohol unit.
  • the oxygen barrier property of the oxygen barrier unit 60 is further improved as compared with the case where no vinyl alcohol unit is included. For this reason, the photoelectric conversion element 100 can have more excellent durability even in a high humidity environment.
  • Examples of such a resin include butenediol-vinyl alcohol copolymer, polyvinyl alcohol polymer, and ethylene-vinyl alcohol copolymer. These can be used alone or in combination of two or more.
  • the content of the vinyl alcohol unit in the resin is not particularly limited, but is preferably 20 to 70 mol%. In this case, since the resin is excellent in moldability, a more stable oxygen barrier structure can be formed.
  • the thickness of the oxygen barrier portion 60 is not particularly limited, but is preferably 5 to 50 ⁇ m. In this case, the moldability is better and the strength of the oxygen barrier portion 60 is sufficiently increased, so that a more stable oxygen barrier structure can be formed.
  • the bonding portion 80 is not particularly limited as long as it can bond the water shielding portion 70 and the oxygen barrier portion 60, but the bonding portion 80 is the same as the hydroxyl group and the functional group included in the water shielding portion 70. It is preferable to include a material having a functional group of In this case, the adhesive force between the oxygen barrier part 60 and the water shielding part 70 is further improved.
  • an adhesive which comprises such an adhesion part 80 bisphenol A type epoxy resin, its modified resin, etc. are mentioned, for example.
  • an electrode substrate 10 having a transparent conductive layer 12 formed on one transparent substrate 11 is prepared.
  • a sputtering method, a vapor deposition method, a spray pyrolysis method, a CVD method, or the like is used as a method for forming the transparent conductive layer 12.
  • a sputtering method, a vapor deposition method, a spray pyrolysis method, a CVD method, or the like is used as a method for forming the transparent conductive layer 12.
  • the spray pyrolysis method is preferable from the viewpoint of apparatus cost.
  • the oxide semiconductor layer 50 is formed on the transparent conductive layer 12 of the electrode substrate 10.
  • the oxide semiconductor layer 50 can be formed by printing a porous oxide semiconductor layer forming paste containing oxide semiconductor particles, followed by firing.
  • the oxide semiconductor layer forming paste contains a resin such as polyethylene glycol and a solvent such as terpineol in addition to the oxide semiconductor particles described above.
  • a printing method of the oxide semiconductor layer forming paste for example, a screen printing method, a doctor blade method, a bar coating method, or the like can be used.
  • the firing temperature varies depending on the material of the oxide semiconductor particles, but is usually 350 ° C. to 600 ° C.
  • the firing time also varies depending on the material of the oxide semiconductor particles, but is usually 0.5 to 5 hours.
  • a dye is supported on the oxide semiconductor layer 50 of the electrode substrate 10.
  • the electrode substrate 10 is immersed in a solution containing a dye, the dye is adsorbed on the oxide semiconductor layer 50, and then the excess dye is washed away with the solvent component of the solution and dried.
  • the dye may be adsorbed on the oxide semiconductor layer 50.
  • the dye can be supported on the oxide semiconductor layer 50 even when the dye is adsorbed to the oxide semiconductor layer 50 by applying a solution containing the dye to the oxide semiconductor layer 50 and then drying the solution. .
  • the sealing part forming body can be obtained, for example, by preparing a sealing resin film and forming one rectangular opening in the sealing resin film.
  • this sealing part formation body is arrange
  • adhesion of the sealing portion forming body to the electrode substrate 10 can be performed, for example, by heating and melting the sealing portion forming body.
  • an electrolyte 40 is prepared. And the electrolyte 40 is arrange
  • the counter substrate 20 is prepared.
  • the counter substrate 20 includes the conductive substrate 21 and the conductive catalyst layer 22 that is provided on the electrode substrate 10 side of the conductive substrate 21 and promotes the reduction reaction on the surface of the counter substrate 20. Is.
  • the sealing portion 30 is formed between the electrode substrate 10 and the counter substrate 20.
  • Lamination of the counter substrate 20 to the sealing portion forming body may be performed under atmospheric pressure or under reduced pressure, but is preferably performed under reduced pressure.
  • the oxygen barrier part forming body can be obtained, for example, by preparing a resin film having a hydroxyl group and forming one rectangular opening in the resin film.
  • this oxygen barrier part formation body is extended from the main body part 61 covering the exposed surface of the sealing part 30 to the opposite side of the electrode substrate 10 from the main body part 61 to the counter substrate 20.
  • the extension part 62 to be bonded is bonded to form.
  • adhesion of the oxygen barrier portion forming body to the sealing portion 30 and the counter substrate 20 can be performed, for example, by heating and melting the oxygen barrier portion forming body.
  • the oxygen barrier part 60 is formed outside the sealing part 30.
  • an adhesive portion 80 is formed so as to cover the exposed portion of the oxygen barrier portion 60 and the surface of the counter substrate 20 opposite to the electrode substrate 10.
  • the adhesive part 80 can be formed, for example, by applying an adhesive to the exposed part of the oxygen barrier part 60 and the surface of the counter substrate 20 opposite to the electrode substrate 10 and then drying the adhesive.
  • the water shielding part 70 is formed on the adhesive part 80 so as to cover the exposed part of the adhesive part 80.
  • the water shielding part 70 can be formed by applying a water shielding part forming body containing a resin such as an epoxy resin on the adhesive part 80 and curing it by heating.
  • the photoelectric conversion element 100 including one photoelectric conversion cell 90 is obtained.
  • the present invention is not limited to the above embodiment.
  • the oxide semiconductor layer 50 is provided on the surface of the electrode substrate 10 on the counter substrate 20 side.
  • the oxide semiconductor layer 50 may be provided on the counter substrate 20.
  • the catalyst layer 22 of the counter substrate 20 is provided on the electrode substrate 10.
  • the photoelectric conversion element 100 is configured by one photoelectric conversion cell 90, but the photoelectric conversion element 100 may include a plurality of photoelectric conversion cells 90.
  • the photoelectric conversion element 100 has the adhesion part 80 between the oxygen barrier part 60 and the water-impervious part 70, the adhesion part 80 may be abbreviate
  • the oxygen barrier part 60 has the main-body part 61 and the extension part 62 in the photoelectric conversion cell 90, the sealing part 30 should just be covered with the oxygen barrier part 60 at least. Therefore, the oxygen barrier part 60 does not necessarily have the extending part 62.
  • the water shielding part 70 has covered the surface on the opposite side to the electrode substrate 10 among the oxygen barrier part 60 and the opposing board
  • the surface outside the oxygen barrier part 60 is water shielding. Since the water shielding portion 70 may be covered with the portion 70, the water shielding portion 70 may not cover the surface of the counter substrate 20 opposite to the electrode substrate 10.
  • substrate 21 and the catalyst layer 22 comprise the opposing board
  • an insulating substrate 220 may be used.
  • the structure 202 is disposed in the space between the insulating substrate 220, the sealing portion 30, and the electrode substrate 10.
  • the structure 202 is provided on the surface of the electrode substrate 10 on the insulating substrate 220 side.
  • the structure 202 includes an oxide semiconductor layer 50, a porous insulating layer 203, and a counter electrode 201 in order from the electrode substrate 10 side.
  • An electrolyte 40 is disposed in the space.
  • the electrolyte 40 is impregnated into the oxide semiconductor layer 50 and the porous insulating layer 203.
  • the insulating substrate 220 for example, a glass substrate or a resin film can be used.
  • the counter electrode 201 the same electrode as the counter substrate 20 can be used.
  • the counter electrode 201 may be composed of a porous single layer including, for example, carbon.
  • the porous insulating layer 203 is mainly for preventing physical contact between the oxide semiconductor layer 50 and the counter substrate 220 and impregnating the electrolyte 40 therein.
  • a porous insulating layer 203 for example, a fired body of an oxide can be used. Note that in the photoelectric conversion element 200 illustrated in FIG.
  • only one structure 202 is provided in the space between the sealing unit 30, the electrode substrate 10, and the insulating substrate 220. It may be provided.
  • the porous insulating layer 203 is provided between the oxide semiconductor layer 50 and the counter electrode 201, but may be provided between the electrode substrate 10 and the counter electrode 201 so as to surround the oxide semiconductor layer 50. Good. Even in this configuration, physical contact between the oxide semiconductor layer 50 and the counter electrode 201 can be prevented.
  • Example 1 First, a laminate was prepared by forming a transparent conductive layer made of FTO having a thickness of 0.6 ⁇ m on a transparent substrate made of glass having a thickness of 2.2 mm. And after printing glass paste so that the thickness after sintering may become 10 micrometers in the edge part except the part used as a terminal among the surfaces in which the transparent conductive layer of the laminated body was formed, it baked at 500 degreeC for 0.5 hour. As a result, a short-circuit prevention layer for preventing contact between the electrode substrate and the counter substrate was produced. Thus, an electrode substrate was obtained.
  • an oxide semiconductor layer forming paste containing titania was applied onto the transparent conductive layer of the electrode substrate and dried, followed by baking at 500 ° C. for 0.5 hour. Thus, an oxide semiconductor layer was formed over the electrode substrate.
  • the electrode substrate is converted into cis-di (thiocyanate)-(2,2′-bipyridyl-4,4′-dicarboxylic acid) (4,4′-dinonyl-2,2′-bipyridyl) -ruthenium (II). It was immersed in a dye solution containing 0.2 mM of a photosensitizing dye consisting of (Z907) and mixed with acetonitrile and t-butanol mixed at a volume ratio of 1: 1 as a solvent, and then taken out and dried. The photosensitizing dye was supported on the oxide semiconductor layer.
  • a 55 mm ⁇ 55 mm ⁇ 50 ⁇ m sealing resin film (trade name “Binell 4164”, manufactured by DuPont) made of the composition is prepared, and an opening of 50 mm ⁇ 50 mm ⁇ 50 ⁇ m is formed on the sealing resin film.
  • the sealing part formation body was prepared by forming one.
  • the sealing part forming body was placed on the electrode substrate, the sealing part forming body was bonded to the electrode substrate by heating and melting.
  • the counter substrate was prepared by forming a catalyst layer made of platinum having a thickness of 5 nm on a titanium foil having a thickness of 40 ⁇ m by sputtering.
  • the sealing portion forming body was heated at 190 ° C. while being pressurized at 0.1 MPa, and the sealing portion forming body was heated and melted. Thus, a sealing portion was formed between the electrode substrate and the counter substrate.
  • the oxygen barrier portion forming body is a resin film having a thickness of 30 ⁇ m (ethylene-vinyl alcohol copolymer, vinyl alcohol unit content: 56 mol%, water vapor transmission coefficient: 0.81 g ⁇ mm / m 2 ⁇ 24 h (40 ° C., 90 % RH))) to form one opening of 45 mm ⁇ 45 mm ⁇ 30 ⁇ m.
  • the oxygen barrier portion forming body is disposed so as to cover the entire exposed outer surface of the sealing portion, and then heated at 210 ° C. to heat and melt the oxygen barrier portion forming body to the sealing portion. I wore it. Thus, an oxygen barrier layer was formed.
  • an adhesive (trade name “Hi-Touch Verde”, manufactured by Daido Paint Co., Ltd.) covers the outer surface of the oxygen barrier that is exposed to the atmosphere and the entire surface of the counter substrate opposite to the electrode substrate. was applied so that the thickness after drying was 20 ⁇ m and dried to form an adhesive portion.
  • the water shielding portion forming body is applied so as to cover the entire adhesive portion and have a thickness after curing of 100 ⁇ m, and in an oven (product name “HISPEC horizontal type HT210S”, manufactured by ETAC) at room temperature. The temperature was raised from 10 to 80 ° C. at 10 ° C./h and held at 80 ° C. for 1 hour to form a water shielding portion.
  • an epoxy resin trade name “Maxive”, manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • a clay mineral trade name “Esven NZ”, manufactured by Hojun Co.
  • the content rate of the clay mineral in a water-impervious part formation body was made to be 2 mass%.
  • a film for measuring a water vapor transmission coefficient having a thickness of 50 ⁇ m was prepared.
  • the water vapor transmission coefficient at 40 ° C. and 90% RH (relative humidity) was measured using a moisture permeable cup (product name “moisture permeable cup (screw tightening type) JIS Z 0208”, manufactured by Imoto Seisakusho).
  • the water vapor transmission coefficient ratio R 1 represented by the following formula (1) was determined. The results are shown in Table 1.
  • the unit of the water vapor transmission coefficient in Table 1 is “g ⁇ mm / m 2 ⁇ 24h”.
  • R 1 A / B (1) (In the above formula (1), A represents the water vapor transmission coefficient (g ⁇ mm / m 2 ⁇ 24h) at 40 ° C. and 90% RH of the water shielding portion, and B represents 40 ° C. and 90% RH of the oxygen barrier portion. Water vapor transmission coefficient (g ⁇ mm / m 2 ⁇ 24 h)
  • an oxygen permeability coefficient measurement film having a thickness of 50 ⁇ m is prepared,
  • the oxygen permeation coefficient at 22 ° C. and 90% relative humidity was measured according to JIS K7126-2 using an oxygen permeation measuring device (product name “OXTRAN”, manufactured by MOCON), and represented by the following formula (2). It was determined coefficient ratio R 2.
  • the results are shown in Table 1.
  • the unit of the oxygen transmission coefficient in Table 1 is “cc ⁇ mm / m 2 ⁇ 24 h / atm”.
  • R 2 C / D (2)
  • C represents an oxygen transmission coefficient (cc ⁇ mm / m 2 ⁇ 24 h / atm) at 22 ° C. and 90% RH of the oxygen barrier portion
  • D represents 22 ° C. and 90% of the sealing portion.
  • Oxygen permeability coefficient in RH (cc ⁇ mm / m 2 ⁇ 24 h / atm).
  • Example 2 Instead of clay mineral, zeolite as a desiccant is used as the inorganic substance in the water-impervious part forming body, and the water vapor transmission coefficient of the oxygen barrier part, the water vapor transmission coefficient of the water-impervious part, the water vapor transmission coefficient ratio R 1 , the sealing part oxygen permeability, an oxygen permeability coefficient of oxygen barrier section, as well as to prepare a photoelectric conversion element oxygen permeability coefficient ratio R 2 in the same manner as in example 1 except that were as shown in Table 1.
  • Example 3 Clay mineral is not included in the water-impervious part forming body, the water vapor transmission coefficient of the oxygen barrier part, the water vapor transmission coefficient of the water shielding part, the water vapor transmission coefficient ratio R 1 , the oxygen transmission coefficient of the sealing part, the oxygen transmission coefficient of the oxygen barrier part , as well as to prepare a photoelectric conversion element oxygen permeability coefficient ratio R 2 in the same manner as in example 1 except that it was as shown in Table 1.
  • Example 4 Without forming an adhesive part, the water vapor transmission coefficient of the oxygen barrier part, the water vapor transmission coefficient of the water shielding part, the water vapor transmission coefficient ratio R 1 , the oxygen transmission coefficient of the sealing part, the oxygen transmission coefficient of the oxygen barrier part, and the oxygen transmission coefficient to prepare a photoelectric conversion element the ratio R 2 in the same manner as in example 1 except that it was as shown in Table 1.
  • Example 5 No adhesion part is formed, no clay mineral is included in the water shielding part forming body, the water vapor transmission coefficient of the oxygen barrier part, the water vapor transmission coefficient of the water shielding part, the water vapor transmission coefficient ratio R 1 , the oxygen transmission coefficient of the sealing part, oxygen permeability coefficient of oxygen barrier section, as well as to prepare a photoelectric conversion element oxygen permeability coefficient ratio R 2 in the same manner as in example 1 except that were as shown in Table 1.
  • Table 1 shows the water vapor transmission coefficient of the oxygen barrier part, the water vapor transmission coefficient of the impermeable part, the water vapor transmission coefficient ratio R 1 , the oxygen transmission coefficient of the sealing part, the oxygen transmission coefficient of the oxygen barrier part, and the oxygen transmission coefficient ratio R 2.
  • a photoelectric conversion element was produced in the same manner as in Example 1 except that it was as shown.
  • Example 6 An adhesive portion is not formed, but a water-blocking portion is formed by using butyl rubber instead of epoxy resin and clay mineral as a water-blocking portion forming body and heat-sealing the water-blocking portion forming body at 200 ° C.
  • Table 2 shows the water vapor transmission coefficient of the part, the water vapor transmission coefficient of the impermeable part, the water vapor transmission coefficient ratio R 1 , the oxygen transmission coefficient of the sealing part, the oxygen transmission coefficient of the oxygen barrier part, and the oxygen transmission coefficient ratio R 2.
  • a photoelectric conversion element was produced in the same manner as in Example 1 except that.
  • Example 7 Without forming an adhesive part, using a low density polyethylene instead of an epoxy resin and clay mineral as a water shielding part forming body, forming a water shielding part by heat-sealing the water shielding part forming body at 200 ° C., Table 2 shows the water vapor transmission coefficient of the oxygen barrier part, the water vapor transmission coefficient of the impermeable part, the water vapor transmission coefficient ratio R 1 , the oxygen transmission coefficient of the sealing part, the oxygen transmission coefficient of the oxygen barrier part, and the oxygen transmission coefficient ratio R 2 A photoelectric conversion element was produced in the same manner as in Example 1 except that it was as shown.
  • Nylon 6 is used instead of epoxy resin and clay mineral as a water shielding part forming body without forming an adhesive part, and a nylon 6 solution using hexafluoro-2-propanol as a solvent is applied and dried.
  • a water vapor transmission coefficient of the oxygen barrier part, a water vapor transmission coefficient of the water shielding part, a water vapor transmission coefficient ratio R 1 , an oxygen transmission coefficient of the sealing part, an oxygen transmission coefficient of the oxygen barrier part, and an oxygen transmission coefficient ratio R A photoelectric conversion element was produced in the same manner as in Example 1 except that 2 was set as shown in Table 2.
  • Light source White LED (product name “LEL-SL5N-F”, manufactured by Toshiba Lighting & Technology Corp.)
  • Illuminance meter Product name “Digital Illuminance Meter 51013”, Yokogawa Meter & Instruments Power Supply: Voltage / Current Generator (Product name “R6246I”, ADVANTEST)
  • the photoelectric conversion element is placed in a constant temperature and humidity chamber (product name “PL-3KPH-E”, manufactured by ESPEC) at 85 ° C. and a relative humidity of 85% for 200 hours, and then 1 sun pseudo-sunlight in the atmosphere.
  • the IV curve was measured after being irradiated for 300 hours under irradiation and again irradiated with the above-described white light of 200 lux, and the maximum output operating power PW ( ⁇ W) calculated from this IV curve was calculated as “output 3”.
  • the output maintenance factor high humidity conditions
  • the photoelectric conversion element of the present invention has excellent durability even in a high humidity environment.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Photovoltaic Devices (AREA)
  • Hybrid Cells (AREA)

Abstract

La présente invention concerne un élément de conversion photoélectrique qui comprend au moins une cellule de conversion photoélectrique. La cellule de conversion photoélectrique comporte : un substrat d'électrode ; un contre-substrat qui fait face au substrat d'électrode ; une partie de scellement en forme d'anneau qui colle le substrat d'électrode et le contre-substrat l'un à l'autre ; un électrolyte qui est disposé à l'intérieur de la partie de scellement ; une partie de barrière à l'oxygène qui est disposée à l'extérieur de la partie de scellement de sorte à recouvrir la partie de scellement ; et une partie de blocage de l'eau qui est disposée à l'extérieur de la partie de barrière à l'oxygène de sorte à recouvrir la partie de barrière à l'oxygène. La partie de barrière à l'oxygène contient une résine ayant un groupe hydroxyle ; le coefficient de perméabilité à l'oxygène de la partie de barrière à l'oxygène à 22 °C à 90 % d'humidité relative est inférieur au coefficient de perméabilité à l'oxygène de la partie de scellement à 22 °C à 90 % d'humidité relative ; et le coefficient de perméabilité à la vapeur d'eau de la partie de blocage de l'eau à 40 °C à 90 % d'humidité relative est inférieur au coefficient de perméabilité à la vapeur d'eau de la partie de barrière à l'oxygène à 40 °C à 90 % d'humidité relative.
PCT/JP2017/024784 2016-07-12 2017-07-06 Élément de conversion photoélectrique WO2018012392A1 (fr)

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Publication number Priority date Publication date Assignee Title
JP2019169628A (ja) * 2018-03-23 2019-10-03 株式会社フジクラ 光電変換素子
WO2023132136A1 (fr) * 2022-01-07 2023-07-13 パナソニックホールディングス株式会社 Module de conversion photoélectrique

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JP2006236788A (ja) * 2005-02-25 2006-09-07 Sony Corp 光電変換装置
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JP2012099449A (ja) * 2010-10-06 2012-05-24 Fujikura Ltd 色素増感太陽電池
JP2013203987A (ja) * 2012-03-29 2013-10-07 Sekisui Plastics Co Ltd ポリ乳酸系樹脂発泡成形体およびその製造方法
JP2013227073A (ja) * 2012-03-30 2013-11-07 Kuraray Co Ltd フィルムロールの包装体

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JPH07251871A (ja) * 1994-01-26 1995-10-03 Sumitomo Chem Co Ltd 積層フィルム
JP2011026012A (ja) * 1997-11-12 2011-02-10 B Braun Medical Inc 可撓容器を充填する充填方法および可撓容器
JP2006100069A (ja) * 2004-09-29 2006-04-13 Kyocera Corp 光電変換装置およびそれを用いた光発電装置
JP2006236788A (ja) * 2005-02-25 2006-09-07 Sony Corp 光電変換装置
JP2012099449A (ja) * 2010-10-06 2012-05-24 Fujikura Ltd 色素増感太陽電池
JP2013203987A (ja) * 2012-03-29 2013-10-07 Sekisui Plastics Co Ltd ポリ乳酸系樹脂発泡成形体およびその製造方法
JP2013227073A (ja) * 2012-03-30 2013-11-07 Kuraray Co Ltd フィルムロールの包装体

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019169628A (ja) * 2018-03-23 2019-10-03 株式会社フジクラ 光電変換素子
JP7014656B2 (ja) 2018-03-23 2022-02-01 株式会社フジクラ 光電変換素子
WO2023132136A1 (fr) * 2022-01-07 2023-07-13 パナソニックホールディングス株式会社 Module de conversion photoélectrique

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