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WO2026004389A1 - Flexible solar cell - Google Patents

Flexible solar cell

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Publication number
WO2026004389A1
WO2026004389A1 PCT/JP2025/017906 JP2025017906W WO2026004389A1 WO 2026004389 A1 WO2026004389 A1 WO 2026004389A1 JP 2025017906 W JP2025017906 W JP 2025017906W WO 2026004389 A1 WO2026004389 A1 WO 2026004389A1
Authority
WO
WIPO (PCT)
Prior art keywords
flame
power generation
layer
solar cell
retardant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/017906
Other languages
French (fr)
Japanese (ja)
Inventor
悠介 富田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sekisui Chemical Co Ltd
Original Assignee
Sekisui Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Publication of WO2026004389A1 publication Critical patent/WO2026004389A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Definitions

  • the present invention relates to flexible solar cells.
  • Flexible solar cells using heat-resistant polymer materials such as polyimide and polyester, or metal foil as a substrate have been attracting attention.
  • Flexible solar cells have advantages such as ease of transportation and installation due to their thinness and light weight, and are impact resistant. For example, they are manufactured by laminating multiple layers, such as a photoelectric conversion layer that generates current when irradiated with light, in a thin film form on a flexible substrate.
  • an encapsulating sheet is laminated on the top and bottom surfaces of the flexible solar cell for encapsulation.
  • Patent Document 2 describes a substrate for a semiconductor device including a sheet-like aluminum base material, and an organic thin-film solar cell including this substrate for a semiconductor device.
  • JP 2014-72327 A Japanese Patent Application Laid-Open No. 2013-253317
  • Such flexible solar cells often use organic materials to give them transparency and flexibility. Because organic materials are more flammable than inorganic materials, flexible solar cells require more fire prevention measures than conventional solar cells.
  • conventional solar cells have been proposed that are flame retardant in the thickness direction of the solar cell, flame retardancy in the planar direction (the surface direction perpendicular to the thickness direction) has not been sufficiently studied.
  • advances in manufacturing technology have resulted in larger areas per flexible solar cell unit, and as poor flame retardancy in the planar direction not only could result in the burning of a large number of solar cells, but also increases the risk of the fire spreading to other areas, flame retardancy in the planar direction is becoming even more important.
  • one proposed method for improving the flame retardancy of flexible solar cells is to add a flame-retardant material to the encapsulant that protects the power generation section of the flexible solar cell.
  • Hydrocarbon-based resins are preferably used as encapsulants due to their low moisture permeability, but they are highly flammable. Therefore, adding a flame-retardant material to a highly flammable encapsulant can significantly improve flame retardancy, and can also improve flame retardancy in the planar direction.
  • some flexible solar cells that have had a flame-retardant material added to the encapsulant have experienced a deterioration in power generation performance.
  • the objective of the present invention is to provide a flexible solar cell that has excellent flame retardancy in the planar direction while minimizing degradation of power generation performance.
  • a flexible solar cell having a power generation unit, a flame-retardant layer, a blocking layer disposed between the power generation unit and the flame-retardant layer, and a sealing material that seals the power generation unit
  • the power generation unit has an electrode, a photoelectric conversion layer, and a counter electrode
  • the photoelectric conversion layer contains an organic-inorganic perovskite compound
  • the flame-retardant layer contains a resin material and a flame-retardant material
  • the flexible solar cell is characterized in that the blocking layer contains a resin having at least one of a degree of crystallinity and a glass transition temperature higher than those of the resin material.
  • the flexible solar cell of the present invention has a power generation section, and the power generation section has an electrode, a photoelectric conversion layer, and a counter electrode.
  • the power generating section is a section that converts sunlight into electricity, and is composed of an electrode, a counter electrode, a photoelectric conversion layer, an electron transport layer, a hole transport layer, etc., and has at least an electrode, a photoelectric conversion layer, and a counter electrode.
  • the term "layer” refers not only to a layer having a clear boundary, but also to a layer having a concentration gradient in which the contained elements gradually change.
  • Elemental analysis of a layer can be performed, for example, by performing FE-TEM/EDS line analysis of a cross section of a solar cell to confirm the element distribution of a specific element.
  • layer refers not only to a flat thin-film layer, but also to a layer that can form a complex, intricate structure together with other layers.
  • upper refers to the direction toward the light incident surface in the thickness direction of the flexible solar cell, and “lower” refers to the opposite direction of "upper,” i.e., the direction toward the installation surface.
  • the materials for the electrodes and counter electrodes are not particularly limited, and examples thereof include FTO (fluorine-doped tin oxide), ITO (tin-doped indium oxide), AZO (aluminum zinc oxide), IZO (indium zinc oxide), GZO (gallium zinc oxide), sodium, sodium-potassium alloy, lithium, magnesium, aluminum, magnesium-silver mixture, magnesium-indium mixture, aluminum-lithium alloy, Al/Al 2 O 3 mixture, and Al/LiF mixture.
  • Other examples include gold, silver, titanium, molybdenum, tantalum, tungsten, carbon, nickel, and chromium. These materials may be used alone, or two or more may be used in combination.
  • the thickness of the electrode and counter electrode is not particularly limited, but a preferred lower limit is 10 nm and a preferred upper limit is 1000 nm. If the thickness is 10 nm or more, the resistance can be reduced while still functioning as an electrode. If the thickness is 1000 nm or less, the light transmittance can be further improved. A more preferred lower limit for the thickness of the electrode and counter electrode is 50 nm and a more preferred upper limit is 500 nm.
  • the photoelectric conversion layer contains an organic-inorganic perovskite compound.
  • the organic-inorganic perovskite compound is represented by the general formula AMX (wherein A is an organic base compound and/or an alkali metal, M is a lead or tin atom, and X is a halogen atom), and a solar cell containing the organic-inorganic perovskite compound is also called an organic-inorganic hybrid solar cell.
  • the above A is an organic base compound and/or an alkali metal.
  • the organic base compound include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, ethylmethylamine, methylpropylamine, butylmethylamine, methylpentylamine, hexylmethylamine, ethylpropylamine, ethylbutylamine, formamidine, acetamidine, guanidine, imidazole, azole, pyrrole, aziridine, azirine, azetidine, azeto, azole, imidazoline, carbazole, and ions thereof (e.
  • methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, formamidine, acetamidine, ions thereof, and phenethylammonium are preferred, and methylamine, ethylamine, propylamine, formamidine, and ions thereof are more preferred.
  • alkali metal include lithium, sodium, potassium, rubidium, and cesium.
  • the above-mentioned M is a metal atom and is a lead or tin atom. These metal atoms may be used alone or in combination of two or more types.
  • X is a halogen atom
  • examples of halogen atoms include chlorine, bromine, iodine, sulfur, and selenium. These halogen atoms may be used alone or in combination of two or more.
  • halogen atoms may be used alone or in combination of two or more.
  • X is preferably iodine, as this narrows the energy band gap of the organic-inorganic perovskite compound.
  • the organic-inorganic perovskite compound preferably has a cubic structure in which a metal atom M is located at the body center, an organic base compound or alkali metal A is located at each vertex, and a halogen atom X is located at the face center.
  • the organic-inorganic perovskite compound is preferably a crystalline semiconductor.
  • a crystalline semiconductor refers to a semiconductor in which a scattering peak can be detected by measuring the X-ray scattering intensity distribution.
  • the organic-inorganic perovskite compound is a crystalline semiconductor, the mobility of electrons in the organic-inorganic perovskite compound increases, improving the photoelectric conversion efficiency of the flexible solar cell.
  • the degree of crystallinity can also be evaluated as an index of crystallization by separating the scattering peaks derived from crystalline materials and the halo derived from amorphous parts detected by X-ray scattering intensity distribution measurement by fitting, determining the respective intensity integrals, and calculating the ratio of the crystalline parts to the whole.
  • the preferred lower limit of the crystallinity of the organic-inorganic perovskite compound is 30%.
  • a crystallinity of 30% or more increases the mobility of electrons in the organic-inorganic perovskite compound, improving the photoelectric conversion efficiency of the solar cell.
  • a more preferred lower limit of the crystallinity is 50%, and an even more preferred lower limit is 70%.
  • Methods for increasing the crystallinity of the organic-inorganic perovskite compound include, for example, thermal annealing, irradiation with high-intensity light such as laser, and plasma irradiation.
  • the photoelectric conversion layer may further contain an organic or inorganic semiconductor in addition to the organic-inorganic perovskite compound, as long as the effects of the present invention are not impaired.
  • the organic or inorganic semiconductor may function as a hole transport layer or an electron transport layer.
  • Examples of the organic semiconductor include compounds having a thiophene skeleton such as poly(3-alkylthiophene).
  • Other examples include conductive polymers having a polyparaphenylene vinylene skeleton, a polyvinyl carbazole skeleton, a polyaniline skeleton, a polyacetylene skeleton, or the like.
  • the inorganic semiconductor examples include titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, zinc sulfide, CuSCN, Cu2O , CuI, MoO3 , V2O5 , WO3 , MoS2 , MoSe2 , and Cu2S .
  • the photoelectric conversion layer contains the organic-inorganic perovskite compound and the organic semiconductor or inorganic semiconductor
  • it may be a laminate in which a thin-film organic semiconductor or inorganic semiconductor portion is laminated with a thin-film organic-inorganic perovskite compound portion, or it may be a composite film in which an organic semiconductor or inorganic semiconductor portion is composited with an organic-inorganic perovskite compound portion.
  • a laminate is preferred in that it can be produced easily, and a composite film is preferred in that it can improve the charge separation efficiency in the organic semiconductor or inorganic semiconductor.
  • the preferred lower limit of the thickness of the composite film is 30 nm, and the preferred upper limit is 3000 nm. If the thickness is 30 nm or more, sufficient light absorption is achieved, resulting in high photoelectric conversion efficiency. If the thickness is 3000 nm or less, charges can more easily reach the electrode, resulting in high photoelectric conversion efficiency.
  • a more preferred lower limit of the thickness is 40 nm, and a more preferred upper limit is 2000 nm, with an even more preferred lower limit being 50 nm and an even more preferred upper limit being 1000 nm.
  • the power generating section may have an electron transport layer between the cathode electrode or the counter electrode and the photoelectric conversion layer.
  • the material for the electron transport layer is not particularly limited, and examples thereof include N-type conductive polymers, N-type low-molecular-weight organic semiconductors, N-type metal oxides, N-type metal sulfides, alkali metal halides, alkali metals, surfactants, and the like.
  • Specific examples thereof include cyano group-containing polyphenylene vinylene, boron-containing polymers, bathocuproine, bathophenanthrene, hydroxyquinolinatoaluminum, oxadiazole compounds, benzimidazole compounds, naphthalene tetracarboxylic acid compounds, perylene derivatives, phosphine oxide compounds, phosphine sulfide compounds, fluoro group-containing phthalocyanines, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, and zinc sulfide.
  • the electron transport layer may consist solely of a thin-film electron transport layer, but preferably includes a porous electron transport layer.
  • the photoelectric conversion layer is a composite film combining an organic semiconductor or inorganic semiconductor portion with an organic-inorganic perovskite compound portion, it is preferable that the composite film be formed on a porous electron transport layer, as this results in a more complex composite film (a more intricate and intricate structure) and higher photoelectric conversion efficiency.
  • the preferred lower limit of the thickness of the electron transport layer is 1 nm, and the preferred upper limit is 2000 nm. If the thickness is 1 nm or more, holes can be sufficiently blocked. If the thickness is 2000 nm or less, resistance during electron transport is unlikely to occur, resulting in high photoelectric conversion efficiency.
  • a more preferred lower limit of the thickness of the electron transport layer is 3 nm, and a more preferred upper limit is 1000 nm, and an even more preferred lower limit is 5 nm, and an even more preferred upper limit is 500 nm.
  • the power generating section may have a hole transport layer between the electrode serving as the anode or the counter electrode and the photoelectric conversion layer.
  • the material of the hole transport layer is not particularly limited, and the hole transport layer may be made of an organic material.
  • Examples of materials for the hole transport layer include p-type conductive polymers, p-type low-molecular-weight organic semiconductors, p-type metal oxides, p-type metal sulfides, surfactants, etc. Specific examples include compounds having a thiophene skeleton such as poly(3-alkylthiophene).
  • Further examples include compounds having a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene skeleton, or a benzoporphyrin skeleton, a spirobifluorene skeleton, etc. Molybdenum sulfide, tungsten sulfide, copper sulfide, tin sulfide, etc. Fluoro-containing phosphonic acid, carbonyl-containing phosphonic acid, and copper compounds such as CuSCN and CuI.
  • the power generation unit may be formed on a substrate.
  • the substrate include a resin film made of a heat-resistant polymer such as polyimide or polyester, a metal foil, or thin glass. From the standpoint of flexibility and transparency, it is preferable that the substrate contain polyethylene terephthalate, polyethylene, polypropylene, polyethylene naphthalate, polymethyl methacrylate, polystyrene, or polycarbonate. Note that, in this specification, the substrate is not included in the power generation unit.
  • the substrate preferably has a thickness of 30 ⁇ m or more and 200 ⁇ m or less.
  • the thickness of the substrate is within the above range, even when the substrate is in contact with the flame-retardant layer described below, the flame-retardant layer is less likely to come into contact with the power generation section by wrapping around the side surface of the substrate, and flexibility can be further improved.
  • the thickness of the substrate is more preferably 50 ⁇ m or more, and even more preferably 70 ⁇ m or more.
  • the thickness of the substrate is more preferably 150 ⁇ m or less, and even more preferably 100 ⁇ m or less.
  • the flexible solar cell of the present invention has a sealing material that seals the power generation section.
  • a sealing material that seals the power generation section.
  • sealing materials that make up the sealing material include thermosetting resins, thermoplastic resins, and inorganic materials.
  • thermosetting resins and thermoplastic resins include epoxy resins, acrylic resins, silicone resins, phenolic resins, melamine resins, and urea resins.
  • Other examples include butyl rubber, polyester, polyurethane, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl alcohol, polyvinyl acetate, ABS resin, polybutadiene, polyamide, polycarbonate, polyimide, and polyisobutylene.
  • polyisobutylene is preferred due to its excellent sealing performance.
  • the flexible solar cell of the present invention has a flame-retardant layer.
  • the flame retardancy particularly the flame retardancy in the planar direction, can also be improved.
  • flame retardancy in the planar direction means the property of making it difficult for fire to spread in the planar direction when the flexible solar cell is brought into contact with a flame and then released.
  • the flame-retardant layer contains a resin material.
  • the resin material is the main component (the component with the highest content) of the flame-retardant layer, and is not particularly limited as long as it has flexibility, but is preferably a sealing material because it can also impart sealing performance.
  • the sealing material can be the same as the sealing material of the sealing material.
  • the resin material that is the main component of the flame-retardant layer preferably has a crystallinity of 10% or more and 50% or less.
  • the crystallinity of the resin material that is the main component of the flame-retardant layer is 10% or more, flexibility can be further increased while maintaining the layer structure, and when it is 50% or less, the balance between adhesion and water vapor permeability can be further improved.
  • the crystallinity of the resin material that is the main component of the flame-retardant layer is more preferably 20% or more, and from the viewpoint of further improving the balance between adhesion and water vapor permeability, it is more preferably 40% or less, and even more preferably 30% or less.
  • the thickness of the front sheet is not particularly limited, but from the viewpoint of the balance between light transmittance and the functionality of the front sheet, it is preferably 25 ⁇ m or more, more preferably 50 ⁇ m or more, and is preferably 1000 ⁇ m or less, more preferably 300 ⁇ m or less.
  • the flexible solar cell of the present invention may have a backsheet at the bottom.
  • the back sheet has the role of preventing the penetration of substances such as moisture that cannot be prevented by the sealing layer alone, thereby improving the weather resistance of the flexible solar cell.
  • materials for the back sheet include polyethylene terephthalate.
  • the method for manufacturing the flexible solar cell of the present invention is not particularly limited, but a method in which the power generating unit 1 is sandwiched between a sheet (sheet A) having a flame-retardant layer 3 and, if necessary, a sealant 4 and a front sheet 5, and a sheet (sheet B) having a sealant 4 and, if necessary, a flame-retardant layer 3 and a back sheet 6, and then laminated, as shown in Figure 7, is preferred because it allows for easy manufacturing over a large area.
  • the power generation unit can be obtained by sequentially stacking layers such as an electrode, electron transport layer, photoelectric conversion layer, hole transport layer, and counter electrode on a substrate (blocking layer). It can also be obtained by stacking each layer on an electrode instead of a substrate. Conventional methods can be used to stack each layer, with no particular restrictions.
  • the above-mentioned sheet B can be obtained by laminating an encapsulant onto a backsheet. Furthermore, when there is no backsheet, it can be obtained by laminating an encapsulant by coating or the like.
  • One example of a method for laminating sheet A, the power generation unit, and sheet B is the roll-to-roll method. Using the roll-to-roll method, large-area flexible solar cells can be continuously manufactured.
  • the present invention makes it possible to provide a flexible solar cell that exhibits excellent flame retardancy in the planar direction while minimizing degradation of power generation performance.
  • 1 is a schematic diagram showing an example of the structure of a flexible solar cell of the present invention.
  • 1 is a schematic diagram showing an example of the structure of a flexible solar cell of the present invention.
  • 1 is a schematic diagram showing an example of the structure of a flexible solar cell of the present invention.
  • 1 is a schematic diagram showing an example of the structure of a flexible solar cell of the present invention.
  • 1 is a schematic diagram showing an example of the structure of a flexible solar cell in which the shortest interfacial distance to the flame-retardant layer is equal to or greater than a certain distance.
  • 1 is a schematic diagram showing an example of the structure of a flexible solar cell in which the shortest interfacial distance to the flame-retardant layer is equal to or greater than a certain distance.
  • 1A to 1C are schematic diagrams illustrating an example of the production of a flexible solar cell of the present invention.
  • Example 1 ⁇ Manufacturing flexible solar cells> A 100 ⁇ m-thick polyethylene terephthalate (PET) film (crystallinity: 60%, glass transition temperature: 70°C) was prepared as a blocking layer. A 200 nm-thick ITO film was formed on the blocking layer by sputtering as a counter electrode. A 20 nm-thick thin-film electron transport layer was formed on the formed counter electrode by sputtering. Furthermore, a titanium oxide paste containing titanium oxide was applied to the thin-film electron transport layer by spin coating and then dried to form a 100 nm-thick porous electron transport layer.
  • PET polyethylene terephthalate
  • lead iodide as a metal halide compound, was dissolved in a mixed solvent of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) to prepare a 1 M solution, and this was then spin-coated onto the porous electron transport layer. Furthermore, methylammonium iodide, as an amine compound, was dissolved in 2-propanol to prepare an 8 wt % solution. This solution was applied to the lead iodide substrate by spin coating, followed by annealing at 150°C for 10 minutes to form a 700 nm thick photoelectric conversion layer containing the organic-inorganic perovskite compound CH3NH3PbI3 .
  • DMF N,N-dimethylformamide
  • DMSO dimethyl sulfoxide
  • a chlorobenzene solution containing 2 wt % Spiro-OMETAD (manufactured by Merck) was applied to the photoelectric conversion layer by spin coating, followed by drying to form an 80 nm thick hole transport layer.
  • a 100 nm thick Al film was then formed as an electrode on the photoelectric conversion layer by sputtering, yielding a laminate in which a power generation unit consisting of a counter electrode, electron transport layer, photoelectric conversion layer, hole transport layer, and electrode was formed on the blocking layer.
  • a 50 ⁇ m-thick PET sheet was prepared as the front sheet.
  • 10 wt% of the flame-retardant material Enpara 40 (chlorinated paraffin, chlorine content 40-42%, manufactured by Ajinomoto Fine-Techno Co., Inc.), was added to the main component, polyisobutylene (crystallinity: 40%, glass transition temperature: -70°C), to prepare a flame-retardant-containing resin. This resin was then applied to the front sheet to a thickness of 100 ⁇ m, yielding Sheet A with a flame-retardant layer.
  • Enpara 40 chlorinated paraffin, chlorine content 40-42%, manufactured by Ajinomoto Fine-Techno Co., Inc.
  • Examples 2 to 5 A flexible solar cell was obtained in the same manner as in Example 1, except that the following flame-retardant material was used.
  • Empara K-50 Chlorinated paraffin, chlorine content 50-52%, manufactured by Ajinomoto Fine-Techno Co., Ltd.
  • Empara A-1 Chlorinated fatty acid ester, chlorine content 35-36.5%, manufactured by Ajinomoto Fine-Techno Co., Ltd.
  • Empara A-3 Chlorinated fatty acid ester, chlorine content 31-33%, manufactured by Ajinomoto Fine-Techno Co., Ltd.
  • Empara M-3 Chlorinated fatty acid ester, chlorine content 32-34%, manufactured by Ajinomoto Fine-Techno Co., Ltd.
  • a laminate was obtained in the same manner as in Example 1. Next, a 360 ⁇ m thick aluminum-containing back sheet (manufactured by Toyo Aluminum Co., Ltd., FAPL) was prepared as the back sheet. A flame-retardant material-containing resin was prepared on the back sheet by adding 10 wt% of the flame-retardant material, Enpara A-1, to the main component, polyisobutylene (crystallinity: 40%, glass transition temperature: -70°C). This resin was then applied to the front sheet to a thickness of 100 ⁇ m to form a flame-retardant layer.
  • Sheet A which had a flame-retardant layer, was then applied to the formed flame-retardant layer with an encapsulant consisting solely of polyisobutylene to a thickness of 100 ⁇ m. Meanwhile, a 50 ⁇ m thick PET sheet was prepared as the front sheet, and a 70 ⁇ m encapsulant was applied to obtain Sheet B. The laminate was then sandwiched between Sheet A and Sheet B and laminated so that the flame-retardant layer of Sheet A faced the power generation section, and the encapsulant of Sheet B faced the block layer. This produced a flexible solar cell having the structure shown in FIG. 6. In addition, since the blocking layer of the obtained flexible solar cell was on the sheet B side, it was not necessary to consider changes in thickness due to the sealing material wrapping around the side of the blocking layer, and therefore the thickness of the sealing material of sheet A was used as the shortest interface distance.
  • the photoelectric conversion efficiency of the flexible solar cell after the durability test was measured in the same manner as the initial conversion efficiency, and the maintenance rate from the initial conversion efficiency was calculated.
  • Durability was evaluated as follows: a maintenance rate of 90% or more was evaluated as " ⁇ ”, a maintenance rate of 80% or more but less than 90% was evaluated as “ ⁇ ”, a maintenance rate of 70% or more but less than 80% was evaluated as “ ⁇ ”, and a maintenance rate of less than 70% was evaluated as " ⁇ ".
  • the present invention makes it possible to provide a flexible solar cell that exhibits excellent flame retardancy in the planar direction while minimizing degradation of power generation performance.

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Abstract

The purpose of the present invention is to provide a flexible solar cell that has excellent flame retardancy in the planar direction while also suppressing a reduction in power generation performance. The present invention is a flexible solar cell comprising a power generation part (1), a flame retardant layer (3), a blocking layer (2) that is disposed between the power generation part (1) and the flame retardant layer (3), and a sealing material (4) that seals the power generation part (1), wherein: the power generation part (1) has an electrode (13), a photoelectric conversion layer (12), and a counter electrode (11); the photoelectric conversion layer (12) contains an organic inorganic perovskite compound; the flame retardant layer (3) contains a resin material and a flame retardant material; and the blocking layer (2) contains a resin which has a higher crystallinity and/or glass transition temperature than the resin material.

Description

フレキシブル太陽電池flexible solar cells

本発明は、フレキシブル太陽電池に関する。 The present invention relates to flexible solar cells.

従来、太陽電池として、対向する電極間にN型半導体層とP型半導体層とを配置した積層体が盛んに開発されており、上記N型、P型半導体として主にシリコン等の無機半導体が用いられている。しかしながら、このような無機太陽電池は、製造にコストがかかるうえ大型化が困難であり、利用範囲が限られてしまうという問題があった。
そこで、近年、中心金属に鉛、スズ等を用いたペロブスカイト構造を有する有機無機ペロブスカイト化合物を光電変換層に用いた、ペロブスカイト太陽電池が注目されている(例えば、特許文献1、非特許文献1)。ペロブスカイト太陽電池は、高い光電変換効率が期待できるうえに、印刷法によって製造できることから製造コストを大幅に削減することができる。
Conventionally, solar cells have been actively developed using laminates in which an N-type semiconductor layer and a P-type semiconductor layer are disposed between opposing electrodes, and inorganic semiconductors such as silicon are mainly used as the N-type and P-type semiconductors. However, such inorganic solar cells have problems in that they are costly to manufacture and difficult to enlarge, limiting the range of their use.
Therefore, in recent years, perovskite solar cells have been attracting attention, which use organic-inorganic perovskite compounds with a perovskite structure using lead, tin, or the like as the central metal in their photoelectric conversion layers (see, for example, Patent Document 1 and Non-Patent Document 1). Perovskite solar cells are expected to have high photoelectric conversion efficiency, and can be manufactured by printing, which significantly reduces manufacturing costs.

一方、近年、ポリイミド、ポリエステル系の耐熱高分子材料や金属箔を基材とするフレキシブルな太陽電池が注目されるようになってきている。フレキシブル太陽電池は、薄型化や軽量化による運搬、施工の容易さや、衝撃に強い等の利点があり、例えば、フレキシブル基材上に、光が照射されると電流を生じる機能を有する光電変換層等の複数の層を薄膜状に積層することにより製造される。更に、必要に応じてフレキシブル太陽電池の上下面に封止シートを積層して封止する。
例えば、特許文献2には、シート状のアルミニウム基材を含む半導体装置用基板、及び、この半導体装置用基板を含む有機薄膜太陽電池が記載されている。
On the other hand, in recent years, flexible solar cells using heat-resistant polymer materials such as polyimide and polyester, or metal foil as a substrate have been attracting attention. Flexible solar cells have advantages such as ease of transportation and installation due to their thinness and light weight, and are impact resistant. For example, they are manufactured by laminating multiple layers, such as a photoelectric conversion layer that generates current when irradiated with light, in a thin film form on a flexible substrate. Furthermore, if necessary, an encapsulating sheet is laminated on the top and bottom surfaces of the flexible solar cell for encapsulation.
For example, Patent Document 2 describes a substrate for a semiconductor device including a sheet-like aluminum base material, and an organic thin-film solar cell including this substrate for a semiconductor device.

特開2014-72327号公報JP 2014-72327 A 特開2013-253317号公報Japanese Patent Application Laid-Open No. 2013-253317

M.M.Lee,et al,Science,2012,338,643M. M. Lee, et al., Science, 2012, 338, 643

このようなフレキシブル太陽電池は、透明性と柔軟性を付与するために有機材料が多く用いられている。有機材料は無機材料に比べて燃えやすいため、フレキシブル太陽電池は従来の太陽電池よりも火災に対する対策が要求される。しかしながら、従来の太陽電池では太陽電池の厚み方向に対する難燃性を有するものは提案されているものの、平面方向(厚み方向に対して垂直な面方向)に対する難燃性は充分に検討がなされていなかった。特に近年は製造技術の進歩によってフレキシブル太陽電池1ユニット当たりの面積が大型化していることから、平面方向への難燃性が低いと大量の太陽電池が焼失するばかりか他に延焼する危険性も高まるため、より平面方向への難燃性が重要になってきている。 Such flexible solar cells often use organic materials to give them transparency and flexibility. Because organic materials are more flammable than inorganic materials, flexible solar cells require more fire prevention measures than conventional solar cells. However, while conventional solar cells have been proposed that are flame retardant in the thickness direction of the solar cell, flame retardancy in the planar direction (the surface direction perpendicular to the thickness direction) has not been sufficiently studied. In particular, in recent years, advances in manufacturing technology have resulted in larger areas per flexible solar cell unit, and as poor flame retardancy in the planar direction not only could result in the burning of a large number of solar cells, but also increases the risk of the fire spreading to other areas, flame retardancy in the planar direction is becoming even more important.

この問題に対して、フレキシブル太陽電池の難燃性を高める方法として、フレキシブル太陽電池の発電部を保護する封止材に難燃性材料を添加する方法が提案されている。封止材は低透湿性の観点から炭化水素系樹脂が好ましく用いられているが、可燃性が非常に高いという性質がある。そのため、可燃性が高い封止材に難燃性材料を添加することで、難燃性を各段に向上させることができ、平面方向の難燃性も高めることができる。しかしながら、封止材に難燃性材料を添加したフレキシブル太陽電池の中には発電性能が劣化するものがあった。 In response to this issue, one proposed method for improving the flame retardancy of flexible solar cells is to add a flame-retardant material to the encapsulant that protects the power generation section of the flexible solar cell. Hydrocarbon-based resins are preferably used as encapsulants due to their low moisture permeability, but they are highly flammable. Therefore, adding a flame-retardant material to a highly flammable encapsulant can significantly improve flame retardancy, and can also improve flame retardancy in the planar direction. However, some flexible solar cells that have had a flame-retardant material added to the encapsulant have experienced a deterioration in power generation performance.

本発明は、発電性能の低下を抑えつつ平面方向への難燃性に優れるフレキシブル太陽電池を提供することを目的とする。 The objective of the present invention is to provide a flexible solar cell that has excellent flame retardancy in the planar direction while minimizing degradation of power generation performance.

本発明は以下の開示1~7を含む。以下、本発明について詳述する。
[開示1]
発電部と、難燃性層と、前記発電部と前記難燃性層との間に配置されるブロック層と、前記発電部を封止する封止材とを有するフレキシブル太陽電池であって、
前記発電部は、電極と光電変換層及び対向電極を有し、
前記光電変換層は有機無機ペロブスカイト化合物を含有し、
前記難燃性層は、樹脂材料と難燃性材料を含有し、
前記ブロック層は、前記樹脂材料よりも結晶化度又はガラス転移温度の少なくともいずれかが高い樹脂を含有する
ことを特徴とするフレキシブル太陽電池。
[開示2]
前記発電部及び前記ブロック層の界面が前記封止材のみと接触することを特徴とする開示1記載のフレキシブル太陽電池。
[開示3]
前記ブロック層は、前記難燃性層と接触することを特徴とする開示1記載のフレキシブル太陽電池。
[開示4]
前記発電部から前記難燃性層と前記封止材との界面までの平均距離が10μm以上100μm以下であることを特徴とする開示1~3のいずれかに記載のフレキシブル太陽電池。
[開示5]
前記難燃性層は、前記発電部の上面側に配置されることを特徴とする開示1~4のいずれかに記載のフレキシブル太陽電池。
[開示6]
前記難燃性材料は、塩素原子を含有することを特徴とする開示1~5のいずれかに記載のフレキシブル太陽電池。
[開示7]
前記発電部の上面及び/又は下面に積層される前記封止材は、それぞれの厚みと前記発電部の厚みとの比(封止材の厚み:発電部の厚み)が1:2以上6:1以下であることを特徴とする開示1~6のいずれかに記載のフレキシブル太陽電池。
The present invention includes the following Disclosures 1 to 7. The present invention will be described in detail below.
[Disclosure 1]
A flexible solar cell having a power generation unit, a flame-retardant layer, a blocking layer disposed between the power generation unit and the flame-retardant layer, and a sealing material that seals the power generation unit,
the power generation unit has an electrode, a photoelectric conversion layer, and a counter electrode,
the photoelectric conversion layer contains an organic-inorganic perovskite compound,
the flame-retardant layer contains a resin material and a flame-retardant material,
The flexible solar cell is characterized in that the blocking layer contains a resin having at least one of a degree of crystallinity and a glass transition temperature higher than those of the resin material.
[Disclosure 2]
The flexible solar cell according to Disclosure 1, wherein the interface between the power generating section and the blocking layer is in contact with only the encapsulant.
[Disclosure 3]
The flexible solar cell according to Disclosure 1, wherein the blocking layer is in contact with the flame-retardant layer.
[Disclosure 4]
The flexible solar cell according to any one of Disclosures 1 to 3, wherein the average distance from the power generation section to the interface between the flame-retardant layer and the sealing material is 10 μm or more and 100 μm or less.
[Disclosure 5]
The flexible solar cell according to any one of Disclosures 1 to 4, wherein the flame-retardant layer is disposed on the upper surface side of the power generating section.
[Disclosure 6]
The flexible solar cell according to any one of Disclosures 1 to 5, wherein the flame-retardant material contains chlorine atoms.
[Disclosure 7]
The flexible solar cell described in any one of Disclosures 1 to 6, wherein the ratio of the thickness of the sealing material laminated on the upper and/or lower surfaces of the power generation unit to the thickness of the power generation unit (thickness of sealing material:thickness of power generation unit) is 1:2 or more and 6:1 or less.

本発明のフレキシブル太陽電池は、発電部を有し、上記発電部は、電極、光電変換層及び対向電極を有する。
上記発電部は太陽光を電力に変換する部位であり、電極、対向電極、光電変換層、電子輸送層、ホール輸送層等から構成され、少なくとも電極、光電変換層及び対向電極を有する。
本明細書中、層とは、明確な境界を有する層だけではなく、含有元素が徐々に変化する濃度勾配のある層をも意味する。なお、層の元素分析は、例えば、太陽電池の断面のFE-TEM/EDS線分析測定を行い、特定元素の元素分布を確認する等によって行うことができる。また、本明細書中、層とは、平坦な薄膜状の層だけではなく、他の層と一緒になって複雑に入り組んだ構造を形成しうる層をも意味する。また、本明細書中において「上」とはフレキシブル太陽電池の厚み方向のうち光の入射面側の方向を指し、「下」とは上の反対方向、即ち、設置面側の方向を指す。
The flexible solar cell of the present invention has a power generation section, and the power generation section has an electrode, a photoelectric conversion layer, and a counter electrode.
The power generating section is a section that converts sunlight into electricity, and is composed of an electrode, a counter electrode, a photoelectric conversion layer, an electron transport layer, a hole transport layer, etc., and has at least an electrode, a photoelectric conversion layer, and a counter electrode.
In this specification, the term "layer" refers not only to a layer having a clear boundary, but also to a layer having a concentration gradient in which the contained elements gradually change. Elemental analysis of a layer can be performed, for example, by performing FE-TEM/EDS line analysis of a cross section of a solar cell to confirm the element distribution of a specific element. Furthermore, in this specification, the term "layer" refers not only to a flat thin-film layer, but also to a layer that can form a complex, intricate structure together with other layers. Furthermore, in this specification, "upper" refers to the direction toward the light incident surface in the thickness direction of the flexible solar cell, and "lower" refers to the opposite direction of "upper," i.e., the direction toward the installation surface.

上記電極及び対向電極の材料は特に限定されず、例えば、FTO(フッ素ドープ酸化スズ)、ITO(スズドープ酸化インジウム)、AZO(アルミニウム亜鉛酸化物)、IZO(インジウム亜鉛酸化物)、GZO(ガリウム亜鉛酸化物)、ナトリウム、ナトリウム-カリウム合金、リチウム、マグネシウム、アルミニウム、マグネシウム-銀混合物、マグネシウム-インジウム混合物、アルミニウム-リチウム合金、Al/Al混合物、Al/LiF混合物等が挙げられる。また、金、銀、チタン、モリブデン、タンタル、タングステン、カーボン、ニッケル、クロム等も挙げられる。これらの材料は単独で用いられてもよく、2種以上が併用されてもよい。 The materials for the electrodes and counter electrodes are not particularly limited, and examples thereof include FTO (fluorine-doped tin oxide), ITO (tin-doped indium oxide), AZO (aluminum zinc oxide), IZO (indium zinc oxide), GZO (gallium zinc oxide), sodium, sodium-potassium alloy, lithium, magnesium, aluminum, magnesium-silver mixture, magnesium-indium mixture, aluminum-lithium alloy, Al/Al 2 O 3 mixture, and Al/LiF mixture. Other examples include gold, silver, titanium, molybdenum, tantalum, tungsten, carbon, nickel, and chromium. These materials may be used alone, or two or more may be used in combination.

上記電極及び対向電極の厚みは特に限定されないが、好ましい下限は10nm、好ましい上限は1000nmである。上記厚みが10nm以上であれば、電極としての機能を発揮したうえで抵抗を抑えることができる。上記厚みが1000nm以下であれば、光の透過性をより向上させることができる。上記電極及び対向電極の厚みのより好ましい下限は50nm、より好ましい上限は500nmである。 The thickness of the electrode and counter electrode is not particularly limited, but a preferred lower limit is 10 nm and a preferred upper limit is 1000 nm. If the thickness is 10 nm or more, the resistance can be reduced while still functioning as an electrode. If the thickness is 1000 nm or less, the light transmittance can be further improved. A more preferred lower limit for the thickness of the electrode and counter electrode is 50 nm and a more preferred upper limit is 500 nm.

上記光電変換層は、有機無機ペロブスカイト化合物を含有する。
上記有機無機ペロブスカイト化合物は、一般式AMX(但し、Aは有機塩基化合物及び/又はアルカリ金属、Mは鉛又はスズ原子、Xはハロゲン原子である。)で表され、上記有機無機ペロブスカイト化合物を含む太陽電池は、有機無機ハイブリッド型太陽電池とも呼ばれる。
上記光電変換層に上記有機無機ペロブスカイト化合物を用いることにより、フレキシブル太陽電池の光電変換効率を向上させることができる。
The photoelectric conversion layer contains an organic-inorganic perovskite compound.
The organic-inorganic perovskite compound is represented by the general formula AMX (wherein A is an organic base compound and/or an alkali metal, M is a lead or tin atom, and X is a halogen atom), and a solar cell containing the organic-inorganic perovskite compound is also called an organic-inorganic hybrid solar cell.
By using the organic-inorganic perovskite compound in the photoelectric conversion layer, the photoelectric conversion efficiency of the flexible solar cell can be improved.

上記Aは有機塩基化合物及び/又はアルカリ金属である。
上記有機塩基化合物は、具体的には例えば、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ペンチルアミン、ヘキシルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、ジペンチルアミン、ジヘキシルアミン、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリペンチルアミン、トリヘキシルアミン、エチルメチルアミン、メチルプロピルアミン、ブチルメチルアミン、メチルペンチルアミン、ヘキシルメチルアミン、エチルプロピルアミン、エチルブチルアミン、ホルムアミジン、アセトアミジン、グアニジン、イミダゾール、アゾール、ピロール、アジリジン、アジリン、アゼチジン、アゼト、アゾール、イミダゾリン、カルバゾール及びこれらのイオン(例えば、メチルアンモニウム(CHNH)等)やフェネチルアンモニウム等が挙げられる。なかでも、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ペンチルアミン、ヘキシルアミン、ホルムアミジン、アセトアミジン及びこれらのイオンやフェネチルアンモニウムが好ましく、メチルアミン、エチルアミン、プロピルアミン、ホルムアミジン及びこれらのイオンがより好ましい。
上記アルカリ金属としては、例えば、リチウム、ナトリウム、カリウム、ルビジウム、セシウム等が挙げられる。
The above A is an organic base compound and/or an alkali metal.
Specific examples of the organic base compound include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, ethylmethylamine, methylpropylamine, butylmethylamine, methylpentylamine, hexylmethylamine, ethylpropylamine, ethylbutylamine, formamidine, acetamidine, guanidine, imidazole, azole, pyrrole, aziridine, azirine, azetidine, azeto, azole, imidazoline, carbazole, and ions thereof (e.g., methylammonium ( CH3NH3 )), phenethylammonium, and the like . Of these, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, formamidine, acetamidine, ions thereof, and phenethylammonium are preferred, and methylamine, ethylamine, propylamine, formamidine, and ions thereof are more preferred.
Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium.

上記Mは金属原子であり鉛又はスズ原子である。これらの金属原子は単独で用いられてもよく、2種以上が併用されてもよい。 The above-mentioned M is a metal atom and is a lead or tin atom. These metal atoms may be used alone or in combination of two or more types.

上記Xはハロゲン原子であり、ハロゲン原子としては、例えば、塩素、臭素、ヨウ素、硫黄、セレン等が挙げられる。これらのハロゲン原子は単独で用いられてもよく、2種以上が併用されてもよい。構造中にハロゲンを含有することで、上記有機無機ペロブスカイト化合物が有機溶媒に可溶になり、安価な印刷法等への適用が可能になる。なかでも、上記有機無機ペロブスカイト化合物のエネルギーバンドギャップが狭くなることから、Xはヨウ素であることが好ましい。 The above-mentioned X is a halogen atom, and examples of halogen atoms include chlorine, bromine, iodine, sulfur, and selenium. These halogen atoms may be used alone or in combination of two or more. By containing a halogen in the structure, the organic-inorganic perovskite compound becomes soluble in organic solvents, enabling application to inexpensive printing methods, etc. In particular, X is preferably iodine, as this narrows the energy band gap of the organic-inorganic perovskite compound.

上記有機無機ペロブスカイト化合物は、体心に金属原子M、各頂点に有機塩基化合物又はアルカリ金属A、面心にハロゲン原子Xが配置された立方晶系の構造を有することが好ましい。
詳細は明らかではないが、上記構造を有することにより、結晶格子内の八面体の向きが容易に変わることができるため、上記有機無機ペロブスカイト化合物中の電子の移動度が高くなり、太陽電池の光電変換効率が向上すると推定される。
The organic-inorganic perovskite compound preferably has a cubic structure in which a metal atom M is located at the body center, an organic base compound or alkali metal A is located at each vertex, and a halogen atom X is located at the face center.
Although the details are not clear, it is presumed that the above structure allows the orientation of the octahedra within the crystal lattice to be easily changed, thereby increasing the mobility of electrons in the organic-inorganic perovskite compound and improving the photoelectric conversion efficiency of solar cells.

上記有機無機ペロブスカイト化合物は、結晶性半導体であることが好ましい。結晶性半導体とは、X線散乱強度分布を測定し、散乱ピークが検出できる半導体を意味している。上記有機無機ペロブスカイト化合物が結晶性半導体であることにより、上記有機無機ペロブスカイト化合物中の電子の移動度が高くなり、フレキシブル太陽電池の光電変換効率が向上する。 The organic-inorganic perovskite compound is preferably a crystalline semiconductor. A crystalline semiconductor refers to a semiconductor in which a scattering peak can be detected by measuring the X-ray scattering intensity distribution. When the organic-inorganic perovskite compound is a crystalline semiconductor, the mobility of electrons in the organic-inorganic perovskite compound increases, improving the photoelectric conversion efficiency of the flexible solar cell.

また、結晶化の指標として結晶化度を評価することもできる。結晶化度は、X線散乱強度分布測定により検出された結晶質由来の散乱ピークと非晶質部由来のハローとをフィッティングにより分離し、それぞれの強度積分を求めて、全体のうちの結晶部分の比を算出することにより求めることができる。
上記有機無機ペロブスカイト化合物の結晶化度の好ましい下限は30%である。結晶化度が30%以上であると、上記有機無機ペロブスカイト化合物中の電子の移動度が高くなり、太陽電池の光電変換効率が向上する。結晶化度のより好ましい下限は50%、更に好ましい下限は70%である。
また、上記有機無機ペロブスカイト化合物の結晶化度を上げる方法として、例えば、熱アニール、レーザー等の強度の強い光の照射、プラズマ照射等が挙げられる。
The degree of crystallinity can also be evaluated as an index of crystallization by separating the scattering peaks derived from crystalline materials and the halo derived from amorphous parts detected by X-ray scattering intensity distribution measurement by fitting, determining the respective intensity integrals, and calculating the ratio of the crystalline parts to the whole.
The preferred lower limit of the crystallinity of the organic-inorganic perovskite compound is 30%. A crystallinity of 30% or more increases the mobility of electrons in the organic-inorganic perovskite compound, improving the photoelectric conversion efficiency of the solar cell. A more preferred lower limit of the crystallinity is 50%, and an even more preferred lower limit is 70%.
Methods for increasing the crystallinity of the organic-inorganic perovskite compound include, for example, thermal annealing, irradiation with high-intensity light such as laser, and plasma irradiation.

上記光電変換層は、本発明の効果を損なわない範囲内であれば、上記有機無機ペロブスカイト化合物に加えて、更に、有機半導体又は無機半導体を含んでいてもよい。なお、ここでいう有機半導体又は無機半導体は、ホール輸送層、又は、電子輸送層としての役割を果たしてもよい。
上記有機半導体として、例えば、ポリ(3-アルキルチオフェン)等のチオフェン骨格を有する化合物等が挙げられる。また、例えば、ポリパラフェニレンビニレン骨格、ポリビニルカルバゾール骨格、ポリアニリン骨格、ポリアセチレン骨格等を有する導電性高分子等も挙げられる。更に、例えば、フタロシアニン骨格、ナフタロシアニン骨格、ペンタセン骨格、ベンゾポルフィリン骨格等のポルフィリン骨格、スピロビフルオレン骨格等を有する化合物や、表面修飾されていてもよいカーボンナノチューブ、グラフェン、フラーレン等のカーボン含有材料も挙げられる。
The photoelectric conversion layer may further contain an organic or inorganic semiconductor in addition to the organic-inorganic perovskite compound, as long as the effects of the present invention are not impaired. The organic or inorganic semiconductor may function as a hole transport layer or an electron transport layer.
Examples of the organic semiconductor include compounds having a thiophene skeleton such as poly(3-alkylthiophene). Other examples include conductive polymers having a polyparaphenylene vinylene skeleton, a polyvinyl carbazole skeleton, a polyaniline skeleton, a polyacetylene skeleton, or the like. Further examples include compounds having a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene skeleton, or a benzoporphyrin skeleton, or a spirobifluorene skeleton, as well as carbon-containing materials such as carbon nanotubes, graphene, and fullerene, which may be surface-modified.

上記無機半導体として、例えば、酸化チタン、酸化亜鉛、酸化インジウム、酸化スズ、酸化ガリウム、硫化スズ、硫化インジウム、硫化亜鉛、CuSCN、CuO、CuI、MoO、V、WO、MoS、MoSe、CuS等が挙げられる。 Examples of the inorganic semiconductor include titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, zinc sulfide, CuSCN, Cu2O , CuI, MoO3 , V2O5 , WO3 , MoS2 , MoSe2 , and Cu2S .

上記光電変換層は、上記有機無機ペロブスカイト化合物と上記有機半導体又は上記無機半導体とを含む場合、薄膜状の有機半導体又は無機半導体部位と薄膜状の有機無機ペロブスカイト化合物部位とを積層した積層体であってもよいし、有機半導体又は無機半導体部位と有機無機ペロブスカイト化合物部位とを複合化した複合膜であってもよい。製法が簡便である点では積層体が好ましく、上記有機半導体又は上記無機半導体中の電荷分離効率を向上させることができる点では複合膜が好ましい。 When the photoelectric conversion layer contains the organic-inorganic perovskite compound and the organic semiconductor or inorganic semiconductor, it may be a laminate in which a thin-film organic semiconductor or inorganic semiconductor portion is laminated with a thin-film organic-inorganic perovskite compound portion, or it may be a composite film in which an organic semiconductor or inorganic semiconductor portion is composited with an organic-inorganic perovskite compound portion. A laminate is preferred in that it can be produced easily, and a composite film is preferred in that it can improve the charge separation efficiency in the organic semiconductor or inorganic semiconductor.

上記光電変換層の厚みは、好ましい下限が5nm、好ましい上限が5000nmである。上記厚みが5nm以上であれば、充分に光を吸収することができるようになり、光電変換効率が高くなる。上記厚みが5000nm以下であれば、電荷分離できない領域が発生することを抑制できるため、光電変換効率の向上につながる。上記厚みのより好ましい下限は10nm、より好ましい上限は1000nmであり、更に好ましい下限は20nm、更に好ましい上限は500nmである。 The preferred lower limit of the thickness of the photoelectric conversion layer is 5 nm, and the preferred upper limit is 5,000 nm. If the thickness is 5 nm or more, sufficient light absorption is possible, resulting in high photoelectric conversion efficiency. If the thickness is 5,000 nm or less, the occurrence of regions where charge separation is not possible can be suppressed, leading to improved photoelectric conversion efficiency. A more preferred lower limit of the thickness is 10 nm, a more preferred upper limit is 1,000 nm, an even more preferred lower limit is 20 nm, and an even more preferred upper limit is 500 nm.

上記光電変換層が、有機半導体又は無機半導体部位と有機無機ペロブスカイト化合物部位とを複合化した複合膜である場合、上記複合膜の厚みの好ましい下限は30nm、好ましい上限は3000nmである。上記厚みが30nm以上であれば、充分に光を吸収することができるようになり、光電変換効率が高くなる。上記厚みが3000nm以下であれば、電荷が電極に到達しやすくなるため、光電変換効率が高くなる。上記厚みのより好ましい下限は40nm、より好ましい上限は2000nmであり、更に好ましい下限は50nm、更に好ましい上限は1000nmである。 When the photoelectric conversion layer is a composite film formed by combining an organic semiconductor or inorganic semiconductor portion with an organic-inorganic perovskite compound portion, the preferred lower limit of the thickness of the composite film is 30 nm, and the preferred upper limit is 3000 nm. If the thickness is 30 nm or more, sufficient light absorption is achieved, resulting in high photoelectric conversion efficiency. If the thickness is 3000 nm or less, charges can more easily reach the electrode, resulting in high photoelectric conversion efficiency. A more preferred lower limit of the thickness is 40 nm, and a more preferred upper limit is 2000 nm, with an even more preferred lower limit being 50 nm and an even more preferred upper limit being 1000 nm.

上記光電変換層を形成する方法は特に限定されず、真空蒸着法、スパッタリング法、気相反応法(CVD)、電気化学沈積法、印刷法等が挙げられる。なかでも、印刷法を採用することで、高い光電変換効率を発揮できる太陽電池を大面積で簡易に形成することができる。印刷法として、例えば、スピンコート法、キャスト法等が挙げられ、印刷法を用いた方法としてロールtoロール法等が挙げられる。 The method for forming the photoelectric conversion layer is not particularly limited, and examples include vacuum deposition, sputtering, chemical vapor deposition (CVD), electrochemical deposition, and printing. Among these, the use of printing allows for the easy formation of large-area solar cells that can achieve high photoelectric conversion efficiency. Examples of printing methods include spin coating and casting, and examples of methods using printing include roll-to-roll methods.

上記発電部は、陰極に当たる電極又は対向電極と上記光電変換層との間に、電子輸送層を有していてもよい。
上記電子輸送層の材料は特に限定されず、例えば、N型導電性高分子、N型低分子有機半導体、N型金属酸化物、N型金属硫化物、ハロゲン化アルカリ金属、アルカリ金属、界面活性剤等が挙げられ、具体的には例えば、シアノ基含有ポリフェニレンビニレン、ホウ素含有ポリマー、バソキュプロイン、バソフェナントレン、ヒドロキシキノリナトアルミニウム、オキサジアゾール化合物、ベンゾイミダゾール化合物、ナフタレンテトラカルボン酸化合物、ペリレン誘導体、ホスフィンオキサイド化合物、ホスフィンスルフィド化合物、フルオロ基含有フタロシアニン、酸化チタン、酸化亜鉛、酸化インジウム、酸化スズ、酸化ガリウム、硫化スズ、硫化インジウム、硫化亜鉛等が挙げられる。
The power generating section may have an electron transport layer between the cathode electrode or the counter electrode and the photoelectric conversion layer.
The material for the electron transport layer is not particularly limited, and examples thereof include N-type conductive polymers, N-type low-molecular-weight organic semiconductors, N-type metal oxides, N-type metal sulfides, alkali metal halides, alkali metals, surfactants, and the like. Specific examples thereof include cyano group-containing polyphenylene vinylene, boron-containing polymers, bathocuproine, bathophenanthrene, hydroxyquinolinatoaluminum, oxadiazole compounds, benzimidazole compounds, naphthalene tetracarboxylic acid compounds, perylene derivatives, phosphine oxide compounds, phosphine sulfide compounds, fluoro group-containing phthalocyanines, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, and zinc sulfide.

上記電子輸送層は、薄膜状の電子輸送層のみからなっていてもよいが、多孔質状の電子輸送層を含むことが好ましい。特に、光電変換層が、有機半導体又は無機半導体部位と有機無機ペロブスカイト化合物部位とを複合化した複合膜である場合、より複雑な複合膜(より複雑に入り組んだ構造)が得られ、光電変換効率が高くなることから、多孔質状の電子輸送層上に複合膜が製膜されていることが好ましい。 The electron transport layer may consist solely of a thin-film electron transport layer, but preferably includes a porous electron transport layer. In particular, when the photoelectric conversion layer is a composite film combining an organic semiconductor or inorganic semiconductor portion with an organic-inorganic perovskite compound portion, it is preferable that the composite film be formed on a porous electron transport layer, as this results in a more complex composite film (a more intricate and intricate structure) and higher photoelectric conversion efficiency.

上記電子輸送層の厚みは、好ましい下限が1nm、好ましい上限が2000nmである。上記厚みが1nm以上であれば、充分にホールをブロックできるようになる。上記厚みが2000nm以下であれば、電子輸送の際の抵抗になり難く、光電変換効率が高くなる。上記電子輸送層の厚みのより好ましい下限は3nm、より好ましい上限は1000nmであり、更に好ましい下限は5nm、更に好ましい上限は500nmである。 The preferred lower limit of the thickness of the electron transport layer is 1 nm, and the preferred upper limit is 2000 nm. If the thickness is 1 nm or more, holes can be sufficiently blocked. If the thickness is 2000 nm or less, resistance during electron transport is unlikely to occur, resulting in high photoelectric conversion efficiency. A more preferred lower limit of the thickness of the electron transport layer is 3 nm, and a more preferred upper limit is 1000 nm, and an even more preferred lower limit is 5 nm, and an even more preferred upper limit is 500 nm.

上記発電部は、陽極に当たる電極又は対向電極と上記光電変換層との間に、ホール輸送層を有していてもよい。
上記ホール輸送層の材料は特に限定されず、上記ホール輸送層が有機材料からなっていてもよい。上記ホール輸送層の材料として、例えば、P型導電性高分子、P型低分子有機半導体、P型金属酸化物、P型金属硫化物、界面活性剤等が挙げられ、具体的には例えば、ポリ(3-アルキルチオフェン)等のチオフェン骨格を有する化合物等が挙げられる。また、例えば、トリフェニルアミン骨格、ポリパラフェニレンビニレン骨格、ポリビニルカルバゾール骨格、ポリアニリン骨格、ポリアセチレン骨格等を有する導電性高分子等も挙げられる。更に、例えば、フタロシアニン骨格、ナフタロシアニン骨格、ペンタセン骨格、ベンゾポルフィリン骨格等のポルフィリン骨格、スピロビフルオレン骨格等を有する化合物、硫化モリブデン、硫化タングステン、硫化銅、硫化スズ等、フルオロ基含有ホスホン酸、カルボニル基含有ホスホン酸、CuSCN、CuI等の銅化合物等が挙げられる。
The power generating section may have a hole transport layer between the electrode serving as the anode or the counter electrode and the photoelectric conversion layer.
The material of the hole transport layer is not particularly limited, and the hole transport layer may be made of an organic material. Examples of materials for the hole transport layer include p-type conductive polymers, p-type low-molecular-weight organic semiconductors, p-type metal oxides, p-type metal sulfides, surfactants, etc. Specific examples include compounds having a thiophene skeleton such as poly(3-alkylthiophene). Other examples include conductive polymers having a triphenylamine skeleton, polyparaphenylenevinylene skeleton, polyvinylcarbazole skeleton, polyaniline skeleton, polyacetylene skeleton, etc. Further examples include compounds having a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene skeleton, or a benzoporphyrin skeleton, a spirobifluorene skeleton, etc. Molybdenum sulfide, tungsten sulfide, copper sulfide, tin sulfide, etc. Fluoro-containing phosphonic acid, carbonyl-containing phosphonic acid, and copper compounds such as CuSCN and CuI.

上記発電部は、基材上に形成されていてもよい。上記基材としては、例えば、ポリイミド、ポリエステル系の耐熱性高分子からなる樹脂フィルム、金属箔、薄板ガラス等を有するものが挙げられる。なかでも柔軟性と透明性の観点から、上記基材はポリエチレンテレフタレート、ポリエチレン、ポリプロピレン、ポリエチレンナフタレート、ポリメタクリル酸メチル、ポリスチレン又はポリカーボネートを含有することが好ましい。なお、本明細書において上記基材は上記発電部に含まれない。 The power generation unit may be formed on a substrate. Examples of the substrate include a resin film made of a heat-resistant polymer such as polyimide or polyester, a metal foil, or thin glass. From the standpoint of flexibility and transparency, it is preferable that the substrate contain polyethylene terephthalate, polyethylene, polypropylene, polyethylene naphthalate, polymethyl methacrylate, polystyrene, or polycarbonate. Note that, in this specification, the substrate is not included in the power generation unit.

上記基材は厚みが30μm以上200μm以下であることが好ましい。
基材の厚みが上記範囲であることで、基材が後述する難燃性層と接触している場合であっても難燃性層が基材の側面を回り込んで発電部と接触し難くなるとともに、柔軟性をより高めることができる。難燃性層を発電部により到達し難くする観点から、上記基材の厚みは50μm以上がより好ましく、70μm以上が更に好ましい。柔軟性をより高める観点から上記基材の厚みは150μm以下であることがより好ましく、100μm以下であることがより好ましい。
The substrate preferably has a thickness of 30 μm or more and 200 μm or less.
When the thickness of the substrate is within the above range, even when the substrate is in contact with the flame-retardant layer described below, the flame-retardant layer is less likely to come into contact with the power generation section by wrapping around the side surface of the substrate, and flexibility can be further improved. From the viewpoint of making it more difficult for the flame-retardant layer to reach the power generation section, the thickness of the substrate is more preferably 50 μm or more, and even more preferably 70 μm or more. From the viewpoint of further improving flexibility, the thickness of the substrate is more preferably 150 μm or less, and even more preferably 100 μm or less.

本発明のフレキシブル太陽電池は、上記発電部を封止する封止材を有する。
発電部を封止材で包み、封止することで、大気中の成分による発電部の劣化を抑えることができる。
The flexible solar cell of the present invention has a sealing material that seals the power generation section.
By encasing and sealing the power generation section in a sealing material, deterioration of the power generation section due to components in the atmosphere can be suppressed.

上記封止材を構成する封止材料としては、例えば、熱硬化性樹脂、熱可塑性樹脂又は無機材料等が挙げられる。上記熱硬化性樹脂又は熱可塑性樹脂としては、エポキシ樹脂、アクリル樹脂、シリコーン樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂等が挙げられる。また、ブチルゴム、ポリエステル、ポリウレタン、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、ポリビニルアルコール、ポリ酢酸ビニル、ABS樹脂、ポリブタジエン、ポリアミド、ポリカーボネート、ポリイミド、ポリイソブチレン等が挙げられる。なかでも、封止性能に優れることからポリイソブチレンが好ましい。 Examples of sealing materials that make up the sealing material include thermosetting resins, thermoplastic resins, and inorganic materials. Examples of thermosetting resins and thermoplastic resins include epoxy resins, acrylic resins, silicone resins, phenolic resins, melamine resins, and urea resins. Other examples include butyl rubber, polyester, polyurethane, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl alcohol, polyvinyl acetate, ABS resin, polybutadiene, polyamide, polycarbonate, polyimide, and polyisobutylene. Among these, polyisobutylene is preferred due to its excellent sealing performance.

本発明のフレキシブル太陽電池は、難燃性層を有する。フレキシブル太陽電池が難燃性層を有することにより、難燃性、特に平面方向の難燃性も高めることができる。
なお、本明細書において平面方向の難燃性とは、フレキシブル太陽電池を火炎と接触させて離したときに平面方向へ延焼し難い性質を意味する。
The flexible solar cell of the present invention has a flame-retardant layer. By having the flame-retardant layer in the flexible solar cell, the flame retardancy, particularly the flame retardancy in the planar direction, can also be improved.
In this specification, flame retardancy in the planar direction means the property of making it difficult for fire to spread in the planar direction when the flexible solar cell is brought into contact with a flame and then released.

上記難燃性層は、樹脂材料を含有する。
上記樹脂材料は、難燃性層の主成分(含有量の最も多い成分)であり、柔軟性を有していれば特に限定されないが、封止性能も同時に付与できることから封止材料であることが好ましい。上記封止材料は、上記封止材の封止材料と同様のものを用いることができる。
The flame-retardant layer contains a resin material.
The resin material is the main component (the component with the highest content) of the flame-retardant layer, and is not particularly limited as long as it has flexibility, but is preferably a sealing material because it can also impart sealing performance. The sealing material can be the same as the sealing material of the sealing material.

上記難燃性層中における上記樹脂材料の含有量は特に限定されないが、50重量%以上であることが好ましく、60重量%以上であることがより好ましく、99重量%以下であることが好ましく、90重量%以下であることがより好ましい。 The content of the resin material in the flame-retardant layer is not particularly limited, but is preferably 50% by weight or more, more preferably 60% by weight or more, and is preferably 99% by weight or less, more preferably 90% by weight or less.

上記難燃性層の主成分となる樹脂材料は、結晶化度が10%以上50%以下であることが好ましい。
上記難燃性層の主成分となる樹脂材料の結晶化度が10%以上であることで、層構造を維持しつつより柔軟性を高めることができ、50%以下であることで、接着性と水蒸気透過性のバランスをより向上させることができる。層構造を維持しつつより柔軟性を高める観点からは、上記難燃性層の主成分となる樹脂材料の結晶化度は20%以上であることがより好ましく、接着性と水蒸気透過性のバランスをより向上させる観点からは、40%以下であることがより好ましく、30%以下であることが更に好ましい。
The resin material that is the main component of the flame-retardant layer preferably has a crystallinity of 10% or more and 50% or less.
When the crystallinity of the resin material that is the main component of the flame-retardant layer is 10% or more, flexibility can be further increased while maintaining the layer structure, and when it is 50% or less, the balance between adhesion and water vapor permeability can be further improved. From the viewpoint of further increasing flexibility while maintaining the layer structure, the crystallinity of the resin material that is the main component of the flame-retardant layer is more preferably 20% or more, and from the viewpoint of further improving the balance between adhesion and water vapor permeability, it is more preferably 40% or less, and even more preferably 30% or less.

上記難燃性層は難燃性材料を含有する。
難燃性層が難燃性材料を含有することで、難燃性が付与される。上記難燃性材料は、難燃性を有していれば特に限定されない。上記難燃性材料の具体例としては、金属水酸化物系難燃剤、窒素化合物系難燃剤、ハロゲン系難燃剤が挙げられる。なかでも、高い難燃性を有しながらも透明性が高く封止材との相溶性も良好であり、発電部の上面側に難燃性層を形成しても発電量の低下が起き難いことからハロゲン系難燃剤が好ましい。ハロゲン系難燃剤としては、例えば、塩素化パラフィン、塩素化脂肪酸エステル、臭化物系難燃剤等が挙げられる。なかでも、上記樹脂材料に添加した場合により高い透明性を有することから、上記難燃性材料は塩素原子を含有することが好ましい。
The flame-retardant layer contains a flame-retardant material.
The flame-retardant layer contains a flame-retardant material, which provides flame retardancy. The flame-retardant material is not particularly limited as long as it has flame retardancy. Specific examples of the flame-retardant material include metal hydroxide-based flame retardants, nitrogen compound-based flame retardants, and halogen-based flame retardants. Among these, halogen-based flame retardants are preferred because they have high flame retardancy, high transparency, good compatibility with the sealing material, and are less likely to cause a decrease in power generation even when a flame-retardant layer is formed on the upper surface of the power generation section. Examples of halogen-based flame retardants include chlorinated paraffin, chlorinated fatty acid ester, and bromide-based flame retardants. Among these, it is preferable that the flame-retardant material contains chlorine atoms, as this provides higher transparency when added to the resin material.

上記難燃性材料は、23℃において液体であることが好ましい。
難燃性材料が常温で液体であることで、上記樹脂材料とより相溶しやすくなるため、難燃性を高めながらも難燃性層の透明性の低下をより抑えることができる。上記23℃において液体である難燃性材料としては、上記ハロゲン系難燃剤等が挙げられる。
The flame-retardant material is preferably liquid at 23°C.
When the flame-retardant material is liquid at room temperature, it is more compatible with the resin material, and therefore the flame retardancy can be improved while further suppressing a decrease in the transparency of the flame-retardant layer. Examples of the flame-retardant material that is liquid at 23°C include the halogen-based flame retardants described above.

上記難燃性材料がハロゲン系難燃剤である場合、上記ハロゲン系難燃剤はハロゲン原子の含有率(組成比)が30%以上60%以下であることが好ましい。
ハロゲン系難燃剤におけるハロゲン原子の含有率が上記範囲であることで、上記樹脂材料に添加した場合でも十分な難燃性を付与することができる。上記ハロゲン系難燃剤におけるハロゲン原子の含有率は、40%以上であることがより好ましく、50%以下であることがより好ましい。なお、上記ハロゲン原子の含有率は元素分析によって測定することができる。
When the flame-retardant material is a halogen-based flame retardant, the halogen-based flame retardant preferably has a halogen atom content (composition ratio) of 30% or more and 60% or less.
When the halogen atom content of the halogen-based flame retardant is within the above range, sufficient flame retardancy can be imparted even when added to the resin material. The halogen atom content of the halogen-based flame retardant is more preferably 40% or more, and more preferably 50% or less. The halogen atom content can be measured by elemental analysis.

上記難燃性層中における上記難燃性材料の含有量は1重量%以上50重量%以下であることが好ましい。
難燃性材料の含有量が上記範囲であることで、難燃性をより向上できるとともに難燃性層の透明性の低下をより抑えることができる。上記難燃性層中における上記難燃性材料の含有量は5重量%以上であることがより好ましく、10重量%以上であることが更に好ましく、30重量%以下であることがより好ましく、20重量%以下であることが更に好ましく、15重量%以下であることが更により好ましい。
The content of the flame-retardant material in the flame-retardant layer is preferably 1% by weight or more and 50% by weight or less.
When the content of the flame-retardant material is within the above range, the flame retardancy can be further improved and the decrease in the transparency of the flame-retardant layer can be further suppressed. The content of the flame-retardant material in the flame-retardant layer is more preferably 5% by weight or more, even more preferably 10% by weight or more, more preferably 30% by weight or less, even more preferably 20% by weight or less, and even more preferably 15% by weight or less.

上記難燃性層は、上記発電部の上面側に配置されていることが好ましい。
本明細書において「上面」とは、フレキシブル太陽電池を設置した際に受光面側となる面を意味し、「下面」とは、設置面側となる面を意味する。
フレキシブル太陽電池は、発電部より下面側は透光性を考慮する必要がないため金属等の不燃性材料を用いやすい。一方、発電部よりも上面側は透光性の高い材料を用いる必要があるが、フレキシブル太陽電池としての柔軟性も必要であることから、硬く割れやすいガラス等を用いることができず、燃えやすい有機材料を多く用いざるを得ない。そのため、上記難燃性層が発電部よりも上面側に配置されていることで、難燃性をより高めることができる。また、一般に流通している難燃剤は固体のものが多く、これを用いた難燃性層を上面に用いると透光性が低下し、太陽電池の発電効率の低下に繋がる。一方、透光性の高い難燃剤を用いるとフレキシブル太陽電池の上面、下面の両方を難燃化することができ、より高い難燃性を実現することができる。なお、上記難燃性層を発電部の上面に配置する場合は、発電への影響を抑えるために透明性の高い難燃性材料を選択する必要がある。
The flame-retardant layer is preferably disposed on the upper surface of the power generation section.
In this specification, the "upper surface" refers to the surface that will be the light-receiving surface when the flexible solar cell is installed, and the "lower surface" refers to the surface that will be the installation surface.
Flexible solar cells do not require consideration of translucency below the power generation section, making it easy to use non-flammable materials such as metals. On the other hand, highly translucent materials must be used above the power generation section. However, because flexibility is also required for flexible solar cells, materials such as hard, easily broken glass cannot be used, and flammable organic materials must be used. Therefore, by placing the flame-retardant layer above the power generation section, flame retardancy can be further improved. Furthermore, many commonly available flame retardants are solid, and using a flame-retardant layer containing such a material on the top surface reduces translucency, leading to a decrease in the power generation efficiency of the solar cell. On the other hand, using a highly translucent flame retardant can make both the top and bottom surfaces of the flexible solar cell flame-retardant, achieving even higher flame retardancy. When placing the flame-retardant layer on the top surface of the power generation section, a highly transparent flame-retardant material must be selected to minimize its impact on power generation.

上記難燃性層が上記発電部の上面側に配置されている場合、上記難燃性層は、波長500nm~1000nmにおける光の透過率が85%以上100%以下であることが好ましい。
難燃性層の光の透過率が上記範囲であることで、難燃性材料の存在による発電性能の低下をより抑えることができる。上記難燃性材料の波長500nm~1000nmにおける光の透過率は90%以上であることがより好ましく、95%以上であることが更に好ましい。上記難燃性層の光の透過率を上記範囲とする方法としては、光透過率の高い難燃剤を用いることが挙げられる。しかしながら、たとえ光透過率の高い難燃剤を用いたとしても、上記樹脂材料への相溶性が低ければ難燃剤が一部に遍在することとなり、結果として光の透過率が低下するため、上記樹脂材料との相溶性も考慮して難燃剤を選択する必要がある。
When the flame-retardant layer is disposed on the upper surface of the power generation section, the flame-retardant layer preferably has a transmittance of 85% or more and 100% or less for light in the wavelength range of 500 nm to 1000 nm.
By ensuring that the light transmittance of the flame-retardant layer is within the above range, the degradation of power generation performance due to the presence of the flame-retardant material can be further suppressed. The flame-retardant material preferably has a light transmittance of 90% or more at wavelengths of 500 nm to 1000 nm, and more preferably 95% or more. One method for achieving the light transmittance of the flame-retardant layer within the above range is to use a flame retardant with high light transmittance. However, even if a flame retardant with high light transmittance is used, if its compatibility with the resin material is low, the flame retardant will be omnipresent in some areas, resulting in a decrease in light transmittance. Therefore, it is necessary to select a flame retardant taking into consideration its compatibility with the resin material.

上記難燃性層の厚みは20μm以上180μm以下であることが好ましい。
難燃性層の厚みを上記範囲とすることで、平面方向の難燃性と発電部の保護性能をより高めることができるとともに、柔軟性をより高めることができる。上記難燃性層の厚みは50μm以上であることがより好ましく、70μm以上であることが更に好ましく、150μm以下であることがより好ましく、100μm以下であることが更に好ましい。なお、上記難燃性層が複数存在する場合、上記難燃性層の厚みは、個々の難燃性層の厚みを指す。
The thickness of the flame-retardant layer is preferably 20 μm or more and 180 μm or less.
By setting the thickness of the flame-retardant layer within the above range, it is possible to further improve the flame retardancy in the planar direction and the protection performance of the power generation section, as well as to further improve flexibility. The thickness of the flame-retardant layer is more preferably 50 μm or more, even more preferably 70 μm or more, more preferably 150 μm or less, and even more preferably 100 μm or less. Note that when multiple flame-retardant layers are present, the thickness of the flame-retardant layer refers to the thickness of each individual flame-retardant layer.

前記発電部の上面及び/又は下面に積層される前記封止材は、それぞれの厚みと前記発電部の厚みとの比(封止材の厚み:発電部の厚み)が1:2以上6:1以下であることが好ましい(以下、発電部と封止材の厚み比率ともいう)。
発電部の上面側及び/又は下面側に積層される封止材のそれぞれの厚みが発電部の厚みに対して上記範囲の比率である、つまり、封止材が発電部の周囲を一定以上の厚みで封止していることで、難燃性層中の難燃性材料が発電部により到達し難くなり、発電性能の低下をより抑えることができる。上記発電部と封止材の厚み比率は、1:1以上であることがより好ましく、4:1以下であることがより好ましい。
It is preferable that the ratio of the thickness of the sealing material laminated on the upper and/or lower surfaces of the power generation unit to the thickness of the power generation unit (thickness of sealing material: thickness of power generation unit) is 1:2 or more and 6:1 or less (hereinafter also referred to as the thickness ratio of the power generation unit to sealing material).
The thickness of each of the sealing materials laminated on the upper and/or lower sides of the power generation unit is within the above-mentioned range relative to the thickness of the power generation unit, i.e., the sealing material seals the periphery of the power generation unit to a certain thickness or more, making it more difficult for the flame-retardant material in the flame-retardant layer to reach the power generation unit, thereby further suppressing deterioration in power generation performance. The thickness ratio of the power generation unit to the sealing material is more preferably 1:1 or more, and more preferably 4:1 or less.

上記封止材は難燃性層と封止材の厚みの比(難燃性層:封止材)が10:90以上50:50以下であることが好ましい(以下、難燃性層-封止材厚み比率ともいう)。
難燃性層と封止材の厚みの比が上記範囲であることで、発電性能の低下をより抑えつつ平面方向の難燃性をより向上させることができる。上記難燃性層-封止材厚み比率は、30:70以上であることがより好ましく、40:60以下であることがより好ましい。
The thickness ratio of the flame-retardant layer to the sealing material (flame-retardant layer:sealant) is preferably 10:90 or more and 50:50 or less (hereinafter also referred to as the flame-retardant layer-sealant thickness ratio).
By setting the thickness ratio of the flame-retardant layer to the sealing material within the above range, it is possible to further improve the flame retardancy in the planar direction while further suppressing the deterioration of power generation performance. The thickness ratio of the flame-retardant layer to the sealing material is more preferably 30:70 or more and more preferably 40:60 or less.

上記封止材及び上記難燃性層の合計厚みは上記発電部の保護性能とフレキシブル性とのバランスの観点から10μm以上であることが好ましく、50μm以上であることがより好ましく、100μm以上であることが更に好ましく、200μm以上であることが更により好ましく、1000μm以下であることが好ましく、700μm以下であることがより好ましい。なお、上記封止材及び上記難燃性の合計厚みは上記発電部及び後述するブロック層が配置された領域では、上記発電部及び上記ブロック層の厚みを加えた厚みを指す。 From the viewpoint of balancing the protection performance of the power generation unit with flexibility, the total thickness of the sealing material and the flame-retardant layer is preferably 10 μm or more, more preferably 50 μm or more, even more preferably 100 μm or more, and even more preferably 200 μm or more, and is preferably 1000 μm or less, and more preferably 700 μm or less. Note that the total thickness of the sealing material and the flame-retardant layer refers to the sum of the thicknesses of the power generation unit and the blocking layer, as will be described later, in the region where the power generation unit and the blocking layer are disposed.

本発明のフレキシブル太陽電池は、前記発電部と前記難燃性層との間に配置されるブロック層を有する。
光電変換層に有機無機ペロブスカイト化合物を用いた従来のフレキシブル太陽電池は、封止材に難燃性材料を添加した場合、難燃性材料と発電部が接触することで発電性能が低下することがあった。本発明では、難燃性材料を含む難燃性層と発電部の間にブロック層を配置することで、難燃性材料と発電部の接触が抑えられ、発電性能の低下を抑えることができる。
The flexible solar cell of the present invention has a blocking layer disposed between the power generation section and the flame-retardant layer.
In conventional flexible solar cells that use an organic-inorganic perovskite compound in the photoelectric conversion layer, when a flame-retardant material is added to the encapsulant, contact between the flame-retardant material and the power generation section can result in a decrease in power generation performance. In the present invention, by disposing a blocking layer between the flame-retardant layer containing the flame-retardant material and the power generation section, contact between the flame-retardant material and the power generation section can be prevented, thereby preventing a decrease in power generation performance.

上記ブロック層は、上記樹脂材料よりも結晶化度又はガラス転移温度の少なくともいずれかが高い樹脂を含有する。
上記ブロック層の主成分となる樹脂が上記難燃性層の主成分である上記樹脂材料よりも結晶化度又はガラス転移温度の少なくともいずれかが高いことで、難燃性材料がブロック層を通過し難くなり、発電性能の低下を抑えることができる。
なお、上記結晶化度及びガラス転移温度はJIS K 7121-1987に準拠し、示差走査熱量計(DSC-60、島津製作所社製又は同等品)を用いて、昇温速度10℃/分の条件で測定することができる。
The blocking layer contains a resin having at least one of a crystallinity and a glass transition temperature higher than those of the resin material.
When the resin that is the main component of the block layer has at least one of a degree of crystallinity or a glass transition temperature higher than that of the resin material that is the main component of the flame-retardant layer, it becomes difficult for the flame-retardant material to pass through the block layer, thereby suppressing a decrease in power generation performance.
The crystallinity and glass transition temperature can be measured in accordance with JIS K 7121-1987 using a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation or an equivalent product) at a temperature rise rate of 10° C./min.

上記ブロック層の上記樹脂は、上記樹脂材料よりも結晶化度又はガラス転移温度の少なくともいずれかが高く、柔軟性を有しており、発電部の上面側に配置される場合は更に透明性を有していれば特に限定されない。具体的には、例えば、ポリイミド、ポリエステル系の耐熱性高分子からなる樹脂フィルム、金属箔、薄板ガラス等を有するものが挙げられる。なかでも柔軟性と透明性の観点から、上記ブロック層はポリエチレンテレフタレート、ポリエチレン、ポリプロピレン、ポリエチレンナフタレート、ポリメタクリル酸メチル、ポリスチレン又はポリカーボネートを含有することが好ましい。 The resin of the block layer is not particularly limited as long as it has at least one of a higher crystallinity or a higher glass transition temperature than the resin material, is flexible, and, when placed on the upper surface of the power generation section, is transparent. Specific examples include resin films made of heat-resistant polymers such as polyimide and polyester, metal foil, and thin glass sheets. From the standpoints of flexibility and transparency, it is preferable that the block layer contain polyethylene terephthalate, polyethylene, polypropylene, polyethylene naphthalate, polymethyl methacrylate, polystyrene, or polycarbonate.

上記ブロック層中の上記樹脂の含有量は50重量%を超えていればよく、70重量%以上であることが好ましく、80重量%以上であることがより好ましい。上記ブロック層中の上記樹脂の含有量は100重量%であってもよい。 The content of the resin in the block layer may be greater than 50% by weight, preferably greater than 70% by weight, and more preferably greater than 80% by weight. The content of the resin in the block layer may be 100% by weight.

上記ブロック層は、上記基材をブロック層としてもよく、別のブロック層を用意してもよい。また、上記ブロック層は、発電部の上面と接触するように配置されていてもよく、下面と接触するように配置されていてもよく、上面及び下面と接触するように配置されていてもよい。また、上記ブロック層は、発電部の上面又は下面に加えて側面を覆っていてもよい。更に、上記ブロック層と上記発電部は必ずしも直接接触している必要はなく、上記ブロック層と上記発電部の間に上記封止材が配置されていてもよい。 The blocking layer may be the base material, or a separate blocking layer may be provided. The blocking layer may be arranged so as to contact the top surface of the power generation unit, the bottom surface, or both the top and bottom surfaces. The blocking layer may also cover the side surfaces of the power generation unit in addition to the top or bottom surface. Furthermore, the blocking layer and the power generation unit do not necessarily need to be in direct contact; the sealing material may be arranged between the blocking layer and the power generation unit.

上記ブロック層を構成する上記樹脂は、結晶化度が30%以上80%以下であることが好ましい。
上記ブロック層を構成する樹脂の結晶化度が30%以上であることで、ブロック層の機械的強度をより高めることができ、80%以下であることで、他の層との接着性をより高めることができる。更に機械的強度を高める観点から、上記ブロック層を構成する樹脂の結晶化度は40%以上であることがより好ましく、50%以上であることが更に好ましい。また、更に他の層との接着性を高める観点から、上記ブロック層を構成する樹脂の結晶化度は70%以下であることがより好ましく、60%以下であることが更に好ましい。
The resin constituting the blocking layer preferably has a crystallinity of 30% or more and 80% or less.
When the crystallinity of the resin constituting the block layer is 30% or more, the mechanical strength of the block layer can be further increased, and when it is 80% or less, the adhesion to other layers can be further increased. From the viewpoint of further increasing the mechanical strength, the crystallinity of the resin constituting the block layer is more preferably 40% or more, and even more preferably 50% or more. Furthermore, from the viewpoint of further increasing the adhesion to other layers, the crystallinity of the resin constituting the block layer is more preferably 70% or less, and even more preferably 60% or less.

上記ブロック層を構成する上記樹脂は、上記難燃性層の主成分である上記樹脂材料よりもガラス転移温度の差(以下、ブロック層と難燃性層のガラス転移温度差という)が20℃以上であることが好ましい。
上記ブロック層と上記難燃性層の主成分のガラス転移温度差が上記下限以上であることで、ブロック層の分子鎖間の隙間が封止材の分子鎖間の隙間より狭くなるため、難燃性材料をより通過させ難くすることができる。上記ブロック層と難燃性層のガラス転移温度差は、30℃以上であることがより好ましく、40℃以上であることが更に好ましい。
The resin constituting the block layer preferably has a glass transition temperature difference of 20° C. or more than that of the resin material that is the main component of the flame-retardant layer (hereinafter referred to as the glass transition temperature difference between the block layer and the flame-retardant layer).
When the difference in glass transition temperature between the main components of the blocking layer and the flame-retardant layer is equal to or greater than the lower limit, the gaps between the molecular chains of the blocking layer become narrower than the gaps between the molecular chains of the sealing material, making it more difficult for the flame-retardant material to pass through. The difference in glass transition temperature between the blocking layer and the flame-retardant layer is more preferably 30°C or more, and even more preferably 40°C or more.

上記ブロック層は、厚みが30μm以上200μm以下であることが好ましい。
ブロック層の厚みが上記範囲であることで、上記難燃性層がブロック層の側面を回り込んで発電部までより到達し難くなるとともに、柔軟性をより高めることができる。難燃性層を発電部により到達し難くする観点から、上記ブロック層の厚みは50μm以上がより好ましく、70μm以上が更に好ましい。柔軟性をより高める観点から上記ブロック層の厚みは150μm以下であることがより好ましく、100μm以下であることが更に好ましい。
The blocking layer preferably has a thickness of 30 μm or more and 200 μm or less.
When the thickness of the blocking layer is within the above range, it becomes more difficult for the flame-retardant layer to reach the power generation section by wrapping around the side surface of the blocking layer, and flexibility can be further improved. From the viewpoint of making it more difficult for the flame-retardant layer to reach the power generation section, the thickness of the blocking layer is more preferably 50 μm or more, and even more preferably 70 μm or more. From the viewpoint of further improving flexibility, the thickness of the blocking layer is more preferably 150 μm or less, and even more preferably 100 μm or less.

より発電性能の低下を抑える観点から、上記発電部及び上記ブロック層の界面は上記封止材のみと接触する、つまり、上記発電部及び上記ブロック層は上記難燃性層と接触していないことが好ましい。一方、フレキシブル太陽電池をより薄くする観点からは、上記ブロック層は、上記難燃性層と接触することが好ましい。 From the perspective of further preventing a decrease in power generation performance, it is preferable that the interface between the power generation unit and the blocking layer be in contact only with the sealing material; that is, the power generation unit and the blocking layer are not in contact with the flame-retardant layer. On the other hand, from the perspective of making the flexible solar cell thinner, it is preferable that the blocking layer be in contact with the flame-retardant layer.

本発明のフレキシブル太陽電池は、上記発電部から上記難燃性層と上記封止材との界面までの平均距離が10μm以上100μm以下であることが好ましい(以下、界面距離ともいう)。
発電部から難燃性層と封止材との界面までの平均距離が上記範囲であることで、難燃性層中の難燃性材料が発電部により到達し難くなり、発電性能の低下をより抑えることができる。上記界面距離は、30μm以上であることがより好ましく、50μm以上であることが更に好ましく、80μm以下であることがより好ましく、60μm以下であることが更に好ましい。なお、上記界面距離は、発電部の界面に近い側の電極から界面までの平均距離を指す。また、上記界面距離は発電部と難燃性層が接触していない場合の界面距離であり、発電部と難燃性層が接触している場合(界面が発電部の側面上に存在する場合)、界面距離は存在しない。
In the flexible solar cell of the present invention, the average distance from the power generation section to the interface between the flame-retardant layer and the sealing material is preferably 10 μm or more and 100 μm or less (hereinafter also referred to as interface distance).
When the average distance from the power generation section to the interface between the flame-retardant layer and the sealing material is within the above range, the flame-retardant material in the flame-retardant layer is less likely to reach the power generation section, thereby further suppressing deterioration in power generation performance. The above interfacial distance is more preferably 30 μm or more, even more preferably 50 μm or more, more preferably 80 μm or less, and even more preferably 60 μm or less. Note that the above interfacial distance refers to the average distance from the electrode closest to the interface of the power generation section to the interface. Furthermore, the above interfacial distance is the interfacial distance when the power generation section and the flame-retardant layer are not in contact; when the power generation section and the flame-retardant layer are in contact (when the interface is on the side of the power generation section), there is no interfacial distance.

本発明のフレキシブル太陽電池は、上記発電部から上記難燃性層までの最短距離が100μm以上であることが好ましい。
上記難燃性層までの界面最短距離が100μm以上であることで、難燃性層中の難燃性材料が封止材中に拡散した場合であっても発電部まで到達し難くなるため発電性能の低下を抑えることができる。また、フレキシブル太陽電池全体の厚みが大きくなるものの、上記難燃性層までの最短距離を満たしていれば、難燃性層と発電部の間にブロック層を設けなくても難燃性材料と発電部の接触を起こり難くでき、発電性能の低下を抑えることができる。
即ち、発電部と、前記発電部全体を封止する封止材と、前記封止材と接触する難燃性層を有するフレキシブル太陽電池であって、前記発電部は、電極、光電変換層及び対向電極を有し、前記光電変換層は有機無機ペロブスカイト化合物を含有し、前記難燃性層は、難燃性材料を含有し、前記発電部から前記難燃性層までの最短距離が100μm以上であるフレキシブル太陽電池であっても本発明の効果を発揮できる。
In the flexible solar cell of the present invention, the shortest distance from the power generation section to the flame-retardant layer is preferably 100 μm or more.
By ensuring that the shortest interfacial distance to the flame-retardant layer is 100 μm or more, even if the flame-retardant material in the flame-retardant layer diffuses into the encapsulant, it is difficult for the flame-retardant material to reach the power generation section, thereby preventing a decrease in power generation performance. Furthermore, although the overall thickness of the flexible solar cell increases, as long as the shortest distance to the flame-retardant layer is met, contact between the flame-retardant material and the power generation section is unlikely to occur, even without providing a blocking layer between the flame-retardant layer and the power generation section, thereby preventing a decrease in power generation performance.
That is, the effects of the present invention can be achieved even with a flexible solar cell having a power generation unit, a sealing material that seals the entire power generation unit, and a flame-retardant layer that is in contact with the sealing material, wherein the power generation unit has an electrode, a photoelectric conversion layer, and a counter electrode, the photoelectric conversion layer contains an organic-inorganic perovskite compound, and the flame-retardant layer contains a flame-retardant material, and the shortest distance from the power generation unit to the flame-retardant layer is 100 μm or more.

上記難燃性層までの最短距離は140μm以上であることが好ましく、200μm以上であることがより好ましく、300μm以上であることが更に好ましい。上記難燃性層までの最短距離の上限は特に限定されず、大きいほど難燃性材料による発電性能の低下を抑えられるが、フレキシブル太陽電池をより薄くする観点から1000μm以下であることが好ましい。 The shortest distance to the flame-retardant layer is preferably 140 μm or more, more preferably 200 μm or more, and even more preferably 300 μm or more. There is no particular upper limit to the shortest distance to the flame-retardant layer; the longer the distance, the more likely it is to prevent a decrease in power generation performance due to the flame-retardant material. However, from the perspective of making flexible solar cells thinner, it is preferably 1000 μm or less.

本発明のフレキシブル太陽電池は、最上部にフロントシートを有していてもよい。
フロントシートは、表面に凹凸、円弧等のパターンを形成することで、光の反射を抑制したり、フレキシブル太陽電池表面の排水性能を高める役割を有する。例えば、フレキシブル太陽電池中心部に頂点を有する凸型の円弧を有するフロントシートを設けると、太陽電池の中心部から端部に向かう排水勾配を設けることができ、フレキシブル太陽電池中心部に最低部を有する凹型の円弧を有するフロントシートを設けると、太陽電池の端部から中心部に向かう集水部を設けることができる。このような排水勾配や集水部を設けることで、汚れ等の堆積を特定の個所に集中させることができる。また、フロントシートにランダムに凹凸を形成することで意匠性を向上させることもできる。
The flexible solar cell of the present invention may have a front sheet on top.
The front sheet can suppress light reflection and improve the drainage performance of the flexible solar cell surface by forming a pattern of irregularities, arcs, etc. on its surface. For example, providing a front sheet with a convex arc with a peak at the center of the flexible solar cell can provide a drainage gradient from the center to the edge of the solar cell, while providing a front sheet with a concave arc with a bottom at the center of the flexible solar cell can provide a water collection area from the edge to the center of the solar cell. By providing such a drainage gradient or water collection area, the accumulation of dirt and other contaminants can be concentrated in specific areas. Furthermore, randomly forming irregularities on the front sheet can improve the design.

上記フロントシートの材料は、透明性を有するものであれば特に限定されず、例えば、フッ素含有樹脂、塩化ビニル系樹脂、ポリエチレン系樹脂、ポリカーボネート系樹脂等が挙げられる。具体的には、ポリカーボネート、ポリ塩化ビニル、四フッ化エチレン樹脂、ポリフッ化ビニリデン、ポリクロロトリフルオロエチレン等が挙げられる。中でも、耐候性に優れていることから、フッ素含有樹脂が好ましい。 The material for the front sheet is not particularly limited as long as it is transparent, and examples include fluorine-containing resins, vinyl chloride resins, polyethylene resins, polycarbonate resins, etc. Specific examples include polycarbonate, polyvinyl chloride, tetrafluoroethylene resin, polyvinylidene fluoride, polychlorotrifluoroethylene, etc. Among these, fluorine-containing resins are preferred due to their excellent weather resistance.

上記フロントシートの厚みは特に限定されないが、光の透過性とフロントシートの機能性とのバランスの観点から25μm以上であることが好ましく、50μm以上であることがより好ましく、1000μm以下であることが好ましく、300μm以下であることがより好ましい。 The thickness of the front sheet is not particularly limited, but from the viewpoint of the balance between light transmittance and the functionality of the front sheet, it is preferably 25 μm or more, more preferably 50 μm or more, and is preferably 1000 μm or less, more preferably 300 μm or less.

本発明のフレキシブル太陽電池は最下部にバックシートを有していてもよい。
バックシートは水分等の封止層だけでは侵入を防止しきれない物質の侵入を防いでフレキシブル太陽電池の耐候性を高める役割を有する。上記バックシートの材料としては、例えば、ポリエチレンテレフタレート等が挙げられる。
The flexible solar cell of the present invention may have a backsheet at the bottom.
The back sheet has the role of preventing the penetration of substances such as moisture that cannot be prevented by the sealing layer alone, thereby improving the weather resistance of the flexible solar cell. Examples of materials for the back sheet include polyethylene terephthalate.

上記バックシートの厚みは特に限定されないが、フレキシブル性とバックシートの機能性とのバランスの観点から50μm以上であることが好ましく、100μm以上であることがより好ましく、1000μm以下であることが好ましく、500μm以下であることがより好ましい。 The thickness of the back sheet is not particularly limited, but from the viewpoint of balancing flexibility with the functionality of the back sheet, it is preferably 50 μm or more, more preferably 100 μm or more, and preferably 1000 μm or less, more preferably 500 μm or less.

ここで、本発明のフレキシブル太陽電池の構造の一例を表した模式図を図1~4に、難燃性層までの界面最短距離が一定以上であるフレキシブル太陽電池の構造の一例を表した模式図を図5、6に示す。図1に示すフレキシブル太陽電池は、電極13、光電変換層12、対向電極11を有する発電部1と、難燃性層3と、発電部1と難燃性層3との間に配置されるブロック層2と、発電部1を封止する封止材4とを有し、最上部及び最下部にフロントシート5とバックシート6が配置された構造になっている。発電部1は封止材4のみと接触し、難燃性層3と接触しておらず、ブロック層2によって難燃性層3が発電部1と直接接触しない配置となっている。各層をこのような配置とし、かつ、ブロック層2を構成する樹脂の結晶化度又はガラス転移温度の少なくともいずれかが難燃性層3を構成する樹脂材料よりも高いことで、難燃性材料が発電部1と接触し難くなるため、発電部1の劣化を抑えつつ平面方向の難燃性を高めることができる。 Here, Figures 1 to 4 show schematic diagrams illustrating an example of the structure of a flexible solar cell of the present invention, and Figures 5 and 6 show schematic diagrams illustrating an example of the structure of a flexible solar cell having a minimum interfacial distance to the flame-retardant layer. The flexible solar cell shown in Figure 1 has a power generation unit 1 including an electrode 13, a photoelectric conversion layer 12, and a counter electrode 11; a flame-retardant layer 3; a blocking layer 2 disposed between the power generation unit 1 and the flame-retardant layer 3; and a sealing material 4 that seals the power generation unit 1. A front sheet 5 and a back sheet 6 are disposed at the top and bottom. The power generation unit 1 is in contact only with the sealing material 4, not with the flame-retardant layer 3. The blocking layer 2 prevents the flame-retardant layer 3 from coming into direct contact with the power generation unit 1. By arranging the layers in this way and by ensuring that at least one of the crystallinity or glass transition temperature of the resin constituting the blocking layer 2 is higher than that of the resin material constituting the flame-retardant layer 3, the flame-retardant material is less likely to come into contact with the power generation unit 1, thereby enhancing flame retardancy in the planar direction while suppressing deterioration of the power generation unit 1.

図2に示すフレキシブル太陽電池は、ブロック層2が発電部1の電極13側の面に配置されている。また、ブロック層2が発電部1の下側に配置されているため、難燃性層3も下側に配置されている。図3に示すフレキシブル太陽電池は、ブロック層2が発電部1の両面に配置されている。このような配置とすることで、発電部1の劣化を更に抑えることができる。図4のフレキシブル太陽電池は、ブロック層2が発電部1の電極13側の面と発電部1の側面を覆う構造となっている。発電部1の側面までブロック層2で覆うことにより、ブロック層2側面へ回り込んだ難燃性層3がより発電部1まで到達し難くなり、発電部1の劣化を抑えることができる。 In the flexible solar cell shown in Figure 2, the blocking layer 2 is arranged on the electrode 13 side of the power generation unit 1. Furthermore, because the blocking layer 2 is arranged below the power generation unit 1, the flame-retardant layer 3 is also arranged below. In the flexible solar cell shown in Figure 3, the blocking layer 2 is arranged on both sides of the power generation unit 1. This arrangement can further prevent deterioration of the power generation unit 1. In the flexible solar cell shown in Figure 4, the blocking layer 2 covers the electrode 13 side of the power generation unit 1 and the side surfaces of the power generation unit 1. By covering the side surfaces of the power generation unit 1 with the blocking layer 2, it becomes more difficult for the flame-retardant layer 3 that has wrapped around to the side surfaces of the blocking layer 2 to reach the power generation unit 1, thereby preventing deterioration of the power generation unit 1.

図5に示すフレキシブル太陽電池は、難燃性層までの界面最短距離が一定以上であるフレキシブル太陽電池であり、封止材4の上下に難燃性層3が積層された構造となっている。また、電極13及び対向電極11から難燃性層3までの最短距離が100μm以上となっており、このような構造とすることにより、平面方向への難燃性をより高めることができるとともに、難燃性層3中の難燃性材料が封止材4へ拡散したとしても発電部1へ到達し難くなるため発電性能の低下を抑えることができる。図6に示すフレキシブル太陽電池は、難燃性層3と発電部1の間にブロック層が配置されておらず、難燃性層3と発電部1の間が封止材4で隔てられた構造となっている。図6のフレキシブル太陽電池は、図5のフレキシブル太陽電池と同様に、難燃性層までの最短距離が100μm以上となっているため、高い平面方向の難燃性を発揮しながらも発電性能の低下を抑えることができる。なお、図6のフレキシブル太陽電池においてブロック層2は難燃性層3側に積層されていないため、本発明の効果に対する寄与はない。 The flexible solar cell shown in Figure 5 is a flexible solar cell with a minimum interfacial distance to the flame-retardant layer of at least a certain level, and has a structure in which flame-retardant layers 3 are laminated above and below the encapsulant 4. Furthermore, the minimum distance from the electrode 13 and counter electrode 11 to the flame-retardant layer 3 is at least 100 μm. This structure further enhances flame retardancy in the planar direction and makes it difficult for the flame-retardant material in the flame-retardant layer 3 to reach the power generation unit 1 even if it diffuses into the encapsulant 4, thereby suppressing a decrease in power generation performance. The flexible solar cell shown in Figure 6 does not have a blocking layer disposed between the flame-retardant layer 3 and the power generation unit 1, and instead has a structure in which the flame-retardant layer 3 and the power generation unit 1 are separated by the encapsulant 4. Like the flexible solar cell of Figure 5, the flexible solar cell of Figure 6 has a minimum interfacial distance to the flame-retardant layer of at least 100 μm, thereby suppressing a decrease in power generation performance while exhibiting high flame retardancy in the planar direction. Note that in the flexible solar cell of Figure 6, the blocking layer 2 is not laminated on the flame-retardant layer 3 side, and therefore does not contribute to the effects of the present invention.

本発明のフレキシブル太陽電池の製造方法は特に限定されないが、大面積での製造が容易であることから、図7に示すように難燃性層3及び必要に応じて封止材4とフロントシート5を有するシート(シートA)と、封止材4及び必要に応じて難燃性層3とバックシート6を有するシート(シートB)の間に発電部1を挟んでラミネートする方法が好ましい。 The method for manufacturing the flexible solar cell of the present invention is not particularly limited, but a method in which the power generating unit 1 is sandwiched between a sheet (sheet A) having a flame-retardant layer 3 and, if necessary, a sealant 4 and a front sheet 5, and a sheet (sheet B) having a sealant 4 and, if necessary, a flame-retardant layer 3 and a back sheet 6, and then laminated, as shown in Figure 7, is preferred because it allows for easy manufacturing over a large area.

上記シートAは、フレキシブル太陽電池が図1のような構造である場合、フロントシート上に難燃性層を積層する工程を行うことでシートAを得ることができる。また、フレキシブル太陽電池が図5のような構造である場合、フロントシート上に難燃性層を積層し、更に封止材4を積層することでシートAを得ることができる。なお、フレキシブル太陽電池が封止材とフロントシートを接着する接着剤層を有する場合は、難燃性層の積層前に接着剤層をフロントシート上に積層する。 When the flexible solar cell has a structure as shown in Figure 1, the above-mentioned sheet A can be obtained by laminating a flame-retardant layer on the front sheet. Also, when the flexible solar cell has a structure as shown in Figure 5, the sheet A can be obtained by laminating a flame-retardant layer on the front sheet and then laminating an encapsulant 4 on it. Furthermore, when the flexible solar cell has an adhesive layer that bonds the encapsulant and front sheet, the adhesive layer is laminated on the front sheet before laminating the flame-retardant layer.

上記発電部は、基材(ブロック層)上に電極、電子輸送層、光電変換層、ホール輸送層、対向電極等の各層を順次積層させることで得ることができる。また、電極を基材の代わりとして電極上に各層を積層することでも得ることができる。各層の積層方法については従来の方法を特に限定なく用いることができる。 The power generation unit can be obtained by sequentially stacking layers such as an electrode, electron transport layer, photoelectric conversion layer, hole transport layer, and counter electrode on a substrate (blocking layer). It can also be obtained by stacking each layer on an electrode instead of a substrate. Conventional methods can be used to stack each layer, with no particular restrictions.

上記シートBは、フレキシブル太陽電池が図1に示すような構造である場合、バックシート上に封止材を積層する工程を行うことによって得ることができる。また、バックシートを有さない場合は、塗布等によって封止材を積層することで得ることができる。 When the flexible solar cell has the structure shown in Figure 1, the above-mentioned sheet B can be obtained by laminating an encapsulant onto a backsheet. Furthermore, when there is no backsheet, it can be obtained by laminating an encapsulant by coating or the like.

上記シートA、上記発電部及び上記シートBをラミネートする方法は例えば、ロールtoロール法が挙げられる。ロールtoロール法を用いることで、大面積のフレキシブル太陽電池を連続的に製造することができる。 One example of a method for laminating sheet A, the power generation unit, and sheet B is the roll-to-roll method. Using the roll-to-roll method, large-area flexible solar cells can be continuously manufactured.

本発明によれば、発電性能の低下を抑えつつ平面方向への難燃性に優れるフレキシブル太陽電池を提供することができる。 The present invention makes it possible to provide a flexible solar cell that exhibits excellent flame retardancy in the planar direction while minimizing degradation of power generation performance.

本発明のフレキシブル太陽電池の構造の一例を表した模式図である。1 is a schematic diagram showing an example of the structure of a flexible solar cell of the present invention. 本発明のフレキシブル太陽電池の構造の一例を表した模式図である。1 is a schematic diagram showing an example of the structure of a flexible solar cell of the present invention. 本発明のフレキシブル太陽電池の構造の一例を表した模式図である。1 is a schematic diagram showing an example of the structure of a flexible solar cell of the present invention. 本発明のフレキシブル太陽電池の構造の一例を表した模式図である。1 is a schematic diagram showing an example of the structure of a flexible solar cell of the present invention. 難燃性層までの界面最短距離が一定以上であるフレキシブル太陽電池の構造の一例を表した模式図である。1 is a schematic diagram showing an example of the structure of a flexible solar cell in which the shortest interfacial distance to the flame-retardant layer is equal to or greater than a certain distance. 難燃性層までの界面最短距離が一定以上であるフレキシブル太陽電池の構造の一例を表した模式図である。1 is a schematic diagram showing an example of the structure of a flexible solar cell in which the shortest interfacial distance to the flame-retardant layer is equal to or greater than a certain distance. 本発明のフレキシブル太陽電池の製造の一例を表した模式図である。1A to 1C are schematic diagrams illustrating an example of the production of a flexible solar cell of the present invention.

以下に実施例を挙げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 The present invention will be explained in more detail below using examples, but the present invention is not limited to these examples.

(実施例1)
<フレキシブル太陽電池の製造>
ブロック層として厚み100μmのポリエチレンテレフタレート(PET)フィルム(結晶化度:60%、ガラス転移温度70℃)を用意した。ブロック層上にスパッタリングによって対向電極として厚み200nmのITO膜を形成した。形成した対向電極上にスパッタリングにより厚み20nmの薄膜状の電子輸送層を形成した。更に、薄膜状の電子輸送層上に、酸化チタンを含有する酸化チタンペーストをスピンコート法により塗布後、乾燥し、厚み100nmの多孔質状の電子輸送層を形成した。次いで、ハロゲン化金属化合物としてヨウ化鉛をN,N-ジメチルホルムアミド(DMF)とジメチルスルホキシド(DMSO)の混合溶媒に溶解させて1Mの溶液を調製し、多孔質状の電子輸送層上にスピンコート法によって製膜した。更に、アミン化合物としてヨウ化メチルアンモニウムを2-プロパノールに溶解させて8重量%の溶液を調製した。この溶液を上記のヨウ化鉛上にスピンコート法により塗布し、150℃で10分間アニール処理をすることよって、厚み700nmの有機無機ペロブスカイト化合物であるCHNHPbIを含む光電変換層を形成した。次いで、光電変換層上にSpiro-OMETAD(メルク社製)2重量%を含有するクロロベンゼン溶液をスピンコート法により塗布後、乾燥させることにより、厚み80nmのホール輸送層を形成した。その後光電変換層上に、スパッタリングにより電極として厚み100nmのAl膜を形成し、ブロック層上に対向電極、電子輸送層、光電変換層、ホール輸送層、電極からなる発電部が形成された積層体を得た。
Example 1
<Manufacturing flexible solar cells>
A 100 μm-thick polyethylene terephthalate (PET) film (crystallinity: 60%, glass transition temperature: 70°C) was prepared as a blocking layer. A 200 nm-thick ITO film was formed on the blocking layer by sputtering as a counter electrode. A 20 nm-thick thin-film electron transport layer was formed on the formed counter electrode by sputtering. Furthermore, a titanium oxide paste containing titanium oxide was applied to the thin-film electron transport layer by spin coating and then dried to form a 100 nm-thick porous electron transport layer. Next, lead iodide, as a metal halide compound, was dissolved in a mixed solvent of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) to prepare a 1 M solution, and this was then spin-coated onto the porous electron transport layer. Furthermore, methylammonium iodide, as an amine compound, was dissolved in 2-propanol to prepare an 8 wt % solution. This solution was applied to the lead iodide substrate by spin coating, followed by annealing at 150°C for 10 minutes to form a 700 nm thick photoelectric conversion layer containing the organic-inorganic perovskite compound CH3NH3PbI3 . Next, a chlorobenzene solution containing 2 wt % Spiro-OMETAD (manufactured by Merck) was applied to the photoelectric conversion layer by spin coating, followed by drying to form an 80 nm thick hole transport layer. A 100 nm thick Al film was then formed as an electrode on the photoelectric conversion layer by sputtering, yielding a laminate in which a power generation unit consisting of a counter electrode, electron transport layer, photoelectric conversion layer, hole transport layer, and electrode was formed on the blocking layer.

続いて、フロントシートとして厚み50μmのPETを用意した。次いで、主成分であるポリイソブチレン(結晶化度:40%、ガラス転移温度:-70℃)に難燃性材料であるエンパラ40(塩素化パラフィン、塩素含有量40~42%、味の素ファインテクノ社製)を10重量%となるように添加することで難燃性材料含有樹脂を調製し、フロントシート上に厚み100μmとなるように塗布することで難燃性層を有するシートAを得た。一方で、バックシートとして厚み360μmのアルミ入りバックシート(東洋アルミ社製、FAPL)を用意し、ポリイソブチレンのみからなる封止材を70μmの厚みとなるように塗布することでシートBを得た。その後、シートAの難燃性層とブロック層が対向し、シートBの封止材と発電部が対向するように、積層体をシートA、シートBに挟んでラミネートすることで、ブロック層側に難燃性層が積層された図1に示す構造を有するフレキシブル太陽電池を得た。得られたフレキシブル太陽電池について電子顕微鏡を用いて断面を観察し、難燃性層までの最短距離を測定した。 Next, a 50 μm-thick PET sheet was prepared as the front sheet. Next, 10 wt% of the flame-retardant material, Enpara 40 (chlorinated paraffin, chlorine content 40-42%, manufactured by Ajinomoto Fine-Techno Co., Inc.), was added to the main component, polyisobutylene (crystallinity: 40%, glass transition temperature: -70°C), to prepare a flame-retardant-containing resin. This resin was then applied to the front sheet to a thickness of 100 μm, yielding Sheet A with a flame-retardant layer. Meanwhile, a 360 μm-thick aluminum-containing back sheet (manufactured by Toyo Aluminum Co., Ltd., FAPL) was prepared as the back sheet, and a 70 μm-thick encapsulant consisting solely of polyisobutylene was applied to obtain Sheet B. The laminate was then sandwiched between Sheets A and B and laminated so that the flame-retardant layer of Sheet A faced the block layer, and the encapsulant of Sheet B faced the power generation section. This resulted in a flexible solar cell with the structure shown in Figure 1, in which the flame-retardant layer was laminated on the block layer side. The cross section of the resulting flexible solar cell was observed using an electron microscope, and the shortest distance to the flame-retardant layer was measured.

(実施例2~5)
難燃性材料として以下のものを用いた以外は実施例1と同様にしてフレキシブル太陽電池を得た。
エンパラK-50:塩素化パラフィン、塩素含有量50~52%、味の素ファインテクノ社製
エンパラA-1:塩素化脂肪酸エステル、塩素含有量35~36.5%、味の素ファインテクノ社製
エンパラA-3:塩素化脂肪酸エステル、塩素含有量31~33%、味の素ファインテクノ社製
エンパラM-3:塩素化脂肪酸エステル、塩素含有量32~34%、味の素ファインテクノ社製
Examples 2 to 5
A flexible solar cell was obtained in the same manner as in Example 1, except that the following flame-retardant material was used.
Empara K-50: Chlorinated paraffin, chlorine content 50-52%, manufactured by Ajinomoto Fine-Techno Co., Ltd. Empara A-1: Chlorinated fatty acid ester, chlorine content 35-36.5%, manufactured by Ajinomoto Fine-Techno Co., Ltd. Empara A-3: Chlorinated fatty acid ester, chlorine content 31-33%, manufactured by Ajinomoto Fine-Techno Co., Ltd. Empara M-3: Chlorinated fatty acid ester, chlorine content 32-34%, manufactured by Ajinomoto Fine-Techno Co., Ltd.

(参考例1)
実施例1と同様にして積層体を得た。続いて、バックシートとして厚み360μmのアルミ入りバックシート(東洋アルミ社製、FAPL)を用意した。バックシート上に主成分であるポリイソブチレン(結晶化度:40%、ガラス転移温度:-70℃)に難燃性材料であるエンパラA-1を10重量%となるように添加することで難燃性材料含有樹脂を調製し、フロントシート上に厚み100μmとなるように塗布することで難燃性層を形成した。その後、形成した難燃性層上にポリイソブチレンのみからなる封止材を100μmの厚みとなるように塗布することで難燃性層を有するシートAを得た。一方で、フロントシートとして厚み50μmのPETを用意し、封止材を70μmの厚みとなるように塗布することでシートBを得た。その後、シートAの難燃性層と発電部が対向し、シートBの封止材とブロック層が対向するように、積層体をシートA、シートBに挟んでラミネートすることで、図6に示す構造を有するフレキシブル太陽電池を得た。なお、得られたフレキシブル太陽電池はブロック層がシートB側にあるため、封止材がブロック層の側面に回り込むことによる厚みの変化を考慮しなくてもよいことから、界面最短距離はシートAの封止材の厚みをそのまま用いた。
(Reference example 1)
A laminate was obtained in the same manner as in Example 1. Next, a 360 μm thick aluminum-containing back sheet (manufactured by Toyo Aluminum Co., Ltd., FAPL) was prepared as the back sheet. A flame-retardant material-containing resin was prepared on the back sheet by adding 10 wt% of the flame-retardant material, Enpara A-1, to the main component, polyisobutylene (crystallinity: 40%, glass transition temperature: -70°C). This resin was then applied to the front sheet to a thickness of 100 μm to form a flame-retardant layer. Sheet A, which had a flame-retardant layer, was then applied to the formed flame-retardant layer with an encapsulant consisting solely of polyisobutylene to a thickness of 100 μm. Meanwhile, a 50 μm thick PET sheet was prepared as the front sheet, and a 70 μm encapsulant was applied to obtain Sheet B. The laminate was then sandwiched between Sheet A and Sheet B and laminated so that the flame-retardant layer of Sheet A faced the power generation section, and the encapsulant of Sheet B faced the block layer. This produced a flexible solar cell having the structure shown in FIG. 6. In addition, since the blocking layer of the obtained flexible solar cell was on the sheet B side, it was not necessary to consider changes in thickness due to the sealing material wrapping around the side of the blocking layer, and therefore the thickness of the sealing material of sheet A was used as the shortest interface distance.

(参考例2~6、比較例7、8)
シートAの作製の際に塗布する封止材の厚みを調節して難燃性層までの最短距離を表1の通りとしたこと、用いる難燃性材料を表1の通りとしたこと以外は参考例1と同様にしてフレキシブル太陽電池を得た。
(Reference Examples 2 to 6, Comparative Examples 7 and 8)
A flexible solar cell was obtained in the same manner as in Reference Example 1, except that the thickness of the encapsulant applied during the production of Sheet A was adjusted to set the shortest distance to the flame-retardant layer as shown in Table 1, and the flame-retardant material used was as shown in Table 1.

(比較例1~5)
用いる難燃性材料を表1の通りとし、バックシートに塗布する封止材を難燃性材料含有樹脂とした以外は実施例1と同様にして積層体が難燃性層のみで封止されたフレキシブル太陽電池を作製した。
(Comparative Examples 1 to 5)
A flexible solar cell in which the laminate was sealed only with a flame-retardant layer was produced in the same manner as in Example 1, except that the flame-retardant materials used were as shown in Table 1 and the sealing material applied to the backsheet was a resin containing a flame-retardant material.

(比較例6)
フロントシートに封止材(ポリイソブチレン)のみを塗布した以外は実施例1と同様にして積層体が封止材のみで封止されたフレキシブル太陽電池を得た。
(Comparative Example 6)
A flexible solar cell in which the laminate was sealed only with the sealing material was obtained in the same manner as in Example 1, except that only the sealing material (polyisobutylene) was applied to the front sheet.

<評価>
実施例及び比較例で得られたフレキシブル太陽電池について、以下の評価を行った。結果を表1に示した。
<Evaluation>
The flexible solar cells obtained in the examples and comparative examples were evaluated as follows. The results are shown in Table 1.

(1)難燃性の評価
各実施例及び比較例と同様の難燃性材料含有樹脂を調製し、厚さ0.3mmのアルミ薄板に上記難燃性材料含有樹脂を厚さ100μmとなるように塗布することで評価サンプルを得た。得られた評価サンプルを垂直に固定し、下端から炎を10秒間接炎して離した後の難燃性材料含有樹脂の燃焼を確認した。鎮火した又は延焼距離が15cm以下であった場合を「〇」、延焼距離が15cmを超えた場合を「×」として難燃性を評価した。なお、比較例6は難燃性層を有さないため、封止材を用いて評価した。
(1) Evaluation of Flame Retardancy: A flame-retardant resin similar to that used in each Example and Comparative Example was prepared and applied to a 0.3 mm thick aluminum plate to a thickness of 100 μm to obtain an evaluation sample. The obtained evaluation sample was fixed vertically, and a flame was applied from the bottom edge for 10 seconds, and the combustion of the flame-retardant resin was confirmed after removal. Flame retardancy was evaluated as "Good" if the fire was extinguished or the fire spread distance was 15 cm or less, and as "Poor" if the fire spread distance exceeded 15 cm. Comparative Example 6 did not have a flame-retardant layer, so it was evaluated using an encapsulant.

(2)透光性の評価
上記方法でシートA、Bのうち難燃性層を含む方のシートを作成し、測定サンプルとした。得られた測定サンプルについて、分光光度計(U-4100、日立社製)を用いて200nm~1000nmの範囲で紫外可視吸収スペクトルを測定した。得られた吸収スペクトルのうち、400~1000nmの透過率が85%以上であった場合を「○」、85%未満であった場合を「×」として発電部より上面側に積層する層の透光性を評価した。なお、比較例6についてはシートAを用いて評価を行った。
(2) Evaluation of Light Transmittance One of the sheets A and B, which included a flame-retardant layer, was prepared using the method described above and used as a measurement sample. The ultraviolet-visible absorption spectrum of the obtained measurement sample was measured in the range of 200 nm to 1000 nm using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.). The light transmittance of the layer laminated above the power generation section was evaluated by marking it as "○" if the transmittance in the 400-1000 nm range of the obtained absorption spectrum was 85% or higher, and "×" if it was less than 85%. Note that evaluation was performed using Sheet A for Comparative Example 6.

(3)耐久性の評価
フレキシブル太陽電池の製造直後、フレキシブル太陽電池の電極間に電源(KEITHLEY社製、236モデル)を接続し、強度100mW/cmのソーラーシミュレーション(山下電装社製)を用いて光電変換効率を測定した。得られた光電変換効率について比較例6を1としたときの相対値を算出し、これを初期変換効率とした。初期変換効率が0.8以上の場合を「○」、0.8未満の場合を「×」として評価した。次いで、温度85℃、湿度85%で500時間の耐湿熱試験を行うことで耐久性試験を行った。耐久性試験後のフレキシブル太陽電池について初期変換効率と同様にして光電変換効率を測定し、初期変換効率からの維持率を算出した。維持率が90%以上である場合を「◎」、80%以上90%未満である場合を「○」、70%以上80%未満である場合を「△」、70%未満である場合を「×」として耐久性を評価した。
(3) Evaluation of Durability Immediately after manufacturing the flexible solar cell, a power supply (KEITHLEY, Model 236) was connected between the electrodes of the flexible solar cell, and the photoelectric conversion efficiency was measured using a solar simulator (Yamashita Denso Co., Ltd.) with an intensity of 100 mW/cm 2. The obtained photoelectric conversion efficiency was calculated relative to Comparative Example 6, which was set to 1, and this was defined as the initial conversion efficiency. An initial conversion efficiency of 0.8 or more was evaluated as "○", and an initial conversion efficiency of less than 0.8 was evaluated as "×". Next, a durability test was performed by conducting a 500-hour moist heat resistance test at a temperature of 85°C and a humidity of 85%. The photoelectric conversion efficiency of the flexible solar cell after the durability test was measured in the same manner as the initial conversion efficiency, and the maintenance rate from the initial conversion efficiency was calculated. Durability was evaluated as follows: a maintenance rate of 90% or more was evaluated as "◎", a maintenance rate of 80% or more but less than 90% was evaluated as "○", a maintenance rate of 70% or more but less than 80% was evaluated as "△", and a maintenance rate of less than 70% was evaluated as "×".

本発明によれば、発電性能の低下を抑えつつ平面方向への難燃性に優れるフレキシブル太陽電池を提供することができる。 The present invention makes it possible to provide a flexible solar cell that exhibits excellent flame retardancy in the planar direction while minimizing degradation of power generation performance.

1  発電部
11 対向電極
12 光電変換層
13 電極
2  基材
3 難燃性層
4 封止材
5  フロントシート
6  バックシート
REFERENCE SIGNS LIST 1 power generation section 11 counter electrode 12 photoelectric conversion layer 13 electrode 2 substrate 3 flame retardant layer 4 sealing material 5 front sheet 6 back sheet

Claims (7)

発電部と、難燃性層と、前記発電部と前記難燃性層との間に配置されるブロック層と、前記発電部を封止する封止材とを有するフレキシブル太陽電池であって、
前記発電部は、電極と光電変換層及び対向電極を有し、
前記光電変換層は有機無機ペロブスカイト化合物を含有し、
前記難燃性層は、樹脂材料と難燃性材料を含有し、
前記ブロック層は、前記樹脂材料よりも結晶化度又はガラス転移温度の少なくともいずれかが高い樹脂を含有する
ことを特徴とするフレキシブル太陽電池。
A flexible solar cell having a power generation unit, a flame-retardant layer, a blocking layer disposed between the power generation unit and the flame-retardant layer, and a sealing material that seals the power generation unit,
the power generation unit has an electrode, a photoelectric conversion layer, and a counter electrode,
the photoelectric conversion layer contains an organic-inorganic perovskite compound,
the flame-retardant layer contains a resin material and a flame-retardant material,
The flexible solar cell is characterized in that the blocking layer contains a resin having at least one of a crystallinity and a glass transition temperature higher than those of the resin material.
前記発電部及び前記ブロック層の界面が前記封止材のみと接触することを特徴とする請求項1記載のフレキシブル太陽電池。 The flexible solar cell described in claim 1, characterized in that the interface between the power generation section and the blocking layer is in contact only with the sealing material. 前記ブロック層は、前記難燃性層と接触することを特徴とする請求項1記載のフレキシブル太陽電池。 The flexible solar cell of claim 1, wherein the blocking layer is in contact with the flame-retardant layer. 前記発電部から前記難燃性層と前記封止材との界面までの平均距離が10μm以上100μm以下であることを特徴とする請求項1~3のいずれかに記載のフレキシブル太陽電池。 A flexible solar cell according to any one of claims 1 to 3, characterized in that the average distance from the power generation section to the interface between the flame-retardant layer and the sealing material is 10 μm or more and 100 μm or less. 前記難燃性層は、前記発電部の上面側に配置されることを特徴とする請求項1~4のいずれかに記載のフレキシブル太陽電池。 A flexible solar cell as described in any one of claims 1 to 4, characterized in that the flame-retardant layer is arranged on the upper surface side of the power generation section. 前記難燃性材料は、塩素原子を含有することを特徴とする請求項1~5のいずれかに記載のフレキシブル太陽電池。 A flexible solar cell according to any one of claims 1 to 5, characterized in that the flame-retardant material contains chlorine atoms. 前記発電部の上面及び/又は下面に積層される前記封止材は、それぞれの厚みと前記発電部の厚みとの比(封止材の厚み:発電部の厚み)が1:2以上6:1以下であることを特徴とする請求項1~6のいずれかに記載のフレキシブル太陽電池。 A flexible solar cell as described in any one of claims 1 to 6, characterized in that the ratio of the thickness of the sealing material laminated on the upper and/or lower surfaces of the power generation unit to the thickness of the power generation unit (thickness of sealing material:thickness of power generation unit) is 1:2 or more and 6:1 or less.
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JPH0927633A (en) * 1995-05-08 1997-01-28 Bridgestone Corp Solar cell encapsulant film and solar cell module
JP2000315810A (en) * 1999-04-28 2000-11-14 Kyocera Corp Solar cell module
JP2013191673A (en) * 2012-03-13 2013-09-26 Fuji Electric Co Ltd Flexible solar battery module
JP2014038925A (en) * 2012-08-15 2014-02-27 Mitsubishi Chemicals Corp Antiflaming solar cell module
JP2017135377A (en) * 2016-01-22 2017-08-03 三菱ケミカル株式会社 Organic thin film solar cell module
JP2018125381A (en) * 2017-01-31 2018-08-09 三菱ケミカル株式会社 Solar cell module
JP2018137408A (en) * 2017-02-23 2018-08-30 三菱ケミカル株式会社 Thin film solar battery module
WO2024204490A1 (en) * 2023-03-28 2024-10-03 積水化学工業株式会社 Flexible solar cell

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0927633A (en) * 1995-05-08 1997-01-28 Bridgestone Corp Solar cell encapsulant film and solar cell module
JP2000315810A (en) * 1999-04-28 2000-11-14 Kyocera Corp Solar cell module
JP2013191673A (en) * 2012-03-13 2013-09-26 Fuji Electric Co Ltd Flexible solar battery module
JP2014038925A (en) * 2012-08-15 2014-02-27 Mitsubishi Chemicals Corp Antiflaming solar cell module
JP2017135377A (en) * 2016-01-22 2017-08-03 三菱ケミカル株式会社 Organic thin film solar cell module
JP2018125381A (en) * 2017-01-31 2018-08-09 三菱ケミカル株式会社 Solar cell module
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