WO2014042217A1 - Feuille de protection de cellule solaire et module de cellule solaire flexible - Google Patents

Feuille de protection de cellule solaire et module de cellule solaire flexible Download PDF

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Publication number
WO2014042217A1
WO2014042217A1 PCT/JP2013/074717 JP2013074717W WO2014042217A1 WO 2014042217 A1 WO2014042217 A1 WO 2014042217A1 JP 2013074717 W JP2013074717 W JP 2013074717W WO 2014042217 A1 WO2014042217 A1 WO 2014042217A1
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WO
WIPO (PCT)
Prior art keywords
solar cell
layer
adhesive sealing
sealing layer
protective sheet
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PCT/JP2013/074717
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English (en)
Japanese (ja)
Inventor
嘉謨 郭
平池　宏至
飛鳥　政宏
清巳 上ノ町
一成 八木
石居　正裕
良隆 国広
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積水化学工業株式会社
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Priority to JP2014535590A priority Critical patent/JPWO2014042217A1/ja
Publication of WO2014042217A1 publication Critical patent/WO2014042217A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a highly durable solar cell protective sheet having high adhesion between a protective layer and an adhesive sealing layer, and a flexible solar cell module in which a solar cell element is protected by the solar cell protective sheet.
  • a rigid solar cell module based on glass and a flexible solar cell module based on a polyimide or polyester heat-resistant polymer material or a stainless thin film are known.
  • flexible solar cell modules have been attracting attention because of their ease of transportation and construction due to reduction in thickness and weight, and resistance to impact.
  • Such a flexible solar cell module is a flexible solar cell element in which a photoelectric conversion layer made of a silicon semiconductor or a compound semiconductor having a function of generating a current when irradiated with light is laminated in a thin film on a flexible substrate.
  • the upper and lower surfaces are sealed with an adhesive sealing layer, and a protective layer is provided as the outermost layer.
  • EVA resin ethylene-vinyl acetate (EVA) resin
  • Patent Document 2 ethylene-vinyl acetate (EVA) resin
  • thermoplastic material has often been used for the protective layer because it has high impact resistance and is light.
  • PVDF poly (vinylidene fluoride)
  • PVDF poly (vinylidene fluoride)
  • the adhesion between the adhesive sealing layer and the protective layer is insufficient, and the protective layer may peel off from the adhesive sealing layer when left in the environment for a long time. There was a problem in terms of durability.
  • an attempt is made to improve the adhesion between layers by providing an adhesive layer made of an acrylic resin or a mixture of an acrylic resin and a fluororesin between the adhesive sealing layer and the protective layer. .
  • an adhesive layer made of an acrylic resin or a mixture of an acrylic resin and a fluororesin between the adhesive sealing layer and the protective layer.
  • the present invention provides a highly durable solar cell protective sheet having high adhesion between a protective layer and an adhesive sealing layer, and a flexible solar cell module in which solar cell elements are protected by the solar cell protective sheet. For the purpose.
  • the present invention is a solar cell protective sheet in which a protective layer made of a fluororesin sheet and an adhesive sealing layer are laminated, wherein the protective layer has a nitrogen atom concentration of 0. 0 on the surface in contact with the adhesive sealing layer. It has a surface layer containing 2 mol% or more, and the adhesive sealing layer is a solar cell protective sheet containing a thermal adhesive resin having an acid group or an acid anhydride group.
  • the present invention is described in detail below.
  • the inventors of the present invention form a surface layer containing 0.2 mol% or more of nitrogen atoms on the surface of the protective layer made of a fluororesin sheet in contact with the adhesive sealing layer, and thermally bond the acid group or the acid anhydride group. It has been found that the adhesive strength between layers can be remarkably increased by combining with an adhesive sealing layer containing an adhesive resin. According to the present invention, the adhesiveness between the protective layer and the adhesive sealing layer can be improved without providing an adhesive layer as in the prior art, so there is no deterioration in weather resistance or heat resistance, and roll-to-roll method or the like. Therefore, even when the solar cell elements are continuously sealed, wrinkles and curls are hardly generated.
  • the solar cell protective sheet of the present invention has a structure in which a protective layer and an adhesive sealing layer are laminated.
  • FIG. 1 the longitudinal cross-section schematic diagram of an example of the solar cell protection sheet B which consists of the protective layer 1 and the adhesion sealing layer 2 is shown.
  • a surface layer 12 containing 0.2 mol% or more of nitrogen atoms is formed on the surface of the protective layer 1 in contact with the adhesive sealing layer 2.
  • the protective layer is the outermost layer in the obtained flexible solar cell module, and prevents external impact or corrosion of the solar cell element. It has a role to prevent.
  • the protective layer is made of a fluorine resin sheet.
  • the fluororesin sheet is not particularly limited as long as it is excellent in transparency, heat resistance, and flame retardancy.
  • Tetrafluoroethylene-ethylene copolymer ETFE
  • ECTFE ethylene chlorotrifluoroethylene resin
  • PCTFE Polychlorotrifluoroethylene resin
  • PVDF polyvinylidene fluoride resin
  • FAP polyvinyl fluoride resin
  • PVDF tetrafluoroethylene-hexafluoropropylene
  • the fluororesin is more preferably a polyvinylidene fluoride resin (PVDF), a tetrafluoroethylene-ethylene copolymer (ETFE), or a polyvinyl fluoride resin (PVF) in that it is superior in heat resistance and transparency.
  • PVDF polyvinylidene fluoride resin
  • ETFE tetrafluoroethylene-ethylene copolymer
  • PVF polyvinyl fluoride resin
  • the protective layer has a surface layer containing 0.2 mol% or more of nitrogen atoms on the surface in contact with the adhesive sealing layer.
  • the lower limit of the nitrogen atom content in the surface layer is 0.2 mol%. If it is less than 0.2 mol%, the effect of improving the adhesion between the protective layer and the adhesive sealing layer cannot be obtained.
  • the minimum with preferable content of the nitrogen atom in the surface layer of the said protective layer is 0.5 mol%, and a more preferable minimum is 1.0 mol%.
  • the upper limit of the content of nitrogen atoms in the surface layer of the protective layer is not particularly limited, but technically about 20 mol% is considered to be a substantial upper limit.
  • content of the nitrogen atom in a surface layer means the ratio of content of the nitrogen atom with respect to content of all the atoms contained in the said surface layer.
  • the content of each atom contained in the surface layer can be measured by, for example, X-ray photoelectron spectroscopy (XPS) or Auger electron spectroscopy (AES).
  • a preferable lower limit of the thickness of the surface layer is 0.05 nm. If the thickness of the surface layer is less than 0.05 nm, the effect of improving the adhesion between the protective layer and the adhesive sealing layer may not be obtained. A more preferable lower limit of the thickness of the surface layer is 0.1 nm.
  • the upper limit of the thickness of the surface layer is not particularly limited, but technically about 10 nm is considered to be a substantial upper limit. Note that the thickness of the surface layer is measured from a cross-sectional plot of the surface layer specific element by etching the surface layer using, for example, X-ray photoelectron spectroscopy (XPS) or Auger electron spectroscopy (AES). Can do.
  • Examples of the method for forming the surface layer on the surface of the protective layer in contact with the adhesive sealing layer include a method in which the surface of the protective layer is subjected to plasma treatment and a method in which corona discharge treatment is performed in a nitrogen atmosphere.
  • the adhesive strength with the adhesive sealing layer containing an acid group or an acid anhydride group is remarkably increased, and when left in the environment for a long time. It is possible to prevent the protective layer from being peeled off from the adhesive sealing layer.
  • the method of performing plasma treatment is preferable because the generation of wrinkles is reduced and the adhesive strength after high temperature and high humidity conditions can be maintained high.
  • the plasma treatment to the protective layer can be performed by a conventionally known method.
  • Specific examples include nitrogen gas plasma, nitrogen / methane mixed gas plasma, nitrogen / carbon dioxide mixed gas plasma, and nitrogen / argon mixed gas plasma.
  • nitrogen gas plasma under conditions of a processing speed of 25 m / min or less and a processing intensity of 0.8 kW or more. It is preferable to process.
  • the corona discharge treatment to the protective layer can be performed by a conventionally known method.
  • Specific examples include nitrogen gas corona, nitrogen / hydrogen mixed gas corona, nitrogen / amine mixed gas corona, and nitrogen / methane mixed gas corona.
  • nitrogen gas corona discharge treatment under the condition of a treatment amount of 20 W / m 2 or more.
  • the protective layer preferably has an embossed shape on the surface in contact with the adhesive sealing layer.
  • the adhesive force between the protective layer and the adhesive sealing layer can be further increased.
  • the emboss shape on the surface of the protective layer may be a regular uneven shape or a random uneven shape.
  • the protective layer has an embossed shape on the surface opposite to the surface in contact with the adhesive sealing layer, that is, the surface that seals the solar cell element and becomes the outermost layer of the flexible solar cell module. It is preferable.
  • the outermost layer has an embossed shape, it is possible to reduce the reflection loss of sunlight, prevent glare, and improve the appearance.
  • the embossed shape is a method of performing embossing at the same time when the molten resin is cooled by using an embossed roll as a cooling roll when the fluororesin sheet constituting the protective layer is extruded by a melt extrusion method. Or the like.
  • the embossing may be performed after the plasma treatment or the corona discharge treatment first, but the embossed shape is determined by a method using an embossing roll in the melt extrusion method.
  • a method of performing plasma treatment or corona discharge treatment on the embossed surface of the applied fluororesin sheet by the above method is preferable.
  • the preferable lower limit of the thickness of the protective layer is 10 ⁇ m, and the preferable upper limit is 100 ⁇ m. If the thickness of the protective layer is less than 10 ⁇ m, insulation may not be ensured or flame retardancy may be impaired. If the thickness of the protective layer exceeds 100 ⁇ m, the weight of the flexible solar cell module may be increased, which is economically disadvantageous.
  • the minimum with more preferable thickness of the said protective layer is 15 micrometers, and a more preferable upper limit is 80 micrometers.
  • the solar cell protective sheet of the present invention has an adhesive sealing layer.
  • the said adhesive sealing layer has a role which seals a solar cell element.
  • the adhesive sealing layer contains a heat-adhesive resin having an acid group or an acid anhydride group.
  • a high interlayer adhesion can be achieved by combining such an adhesive sealing layer with a protective layer having a surface layer containing 0.2 mol% or more of the nitrogen atoms.
  • Examples of the acid group include a carboxyl group, an unsaturated carboxylic acid group, a hydroxy acid group, an aromatic carboxylic acid group, and a dicarboxylic acid group.
  • Examples of the acid anhydride group include a maleic anhydride group, an acetic anhydride group, a propionic anhydride group, a succinic anhydride group, a phthalic anhydride group, and a benzoic anhydride group.
  • heat-adhesive resin having an acid group or an acid anhydride group examples include an acid-modified polyolefin, an acid-modified ethylene-glycidyl methacrylate copolymer, an ionomer, and an ethylene-acrylic acid ester-anhydride group copolymer. It is done.
  • thermal adhesive resins having an acid group or an acid anhydride group may be used alone or in combination of two or more.
  • the acid-modified polyolefin can prevent the generation of wrinkles and curls when a solar cell element is sealed using the solar cell protective sheet of the present invention to produce a flexible solar cell module, and the adhesion to the solar cell surface is improved.
  • it is preferably a maleic anhydride-modified polyolefin.
  • the maleic anhydride-modified polyolefin is a resin in which an ⁇ -olefin-ethylene copolymer having an ⁇ -olefin content of 1 to 25% by weight is graft-modified with maleic anhydride, and the total content of maleic anhydride The amount is preferably 0.1 to 3% by weight.
  • the ionomer is preferably one obtained by neutralizing part or all of the unsaturated carboxylic acid group of the ethylene-unsaturated carboxylic acid copolymer with a metal ion.
  • the ethylene-unsaturated carboxylic acid copolymer include a copolymer comprising at least a copolymer component of ethylene and an unsaturated carboxylic acid.
  • the ionomer can be produced by a known method.
  • the unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, maleic acid, phthalic acid, citraconic acid, itaconic acid, and the like, among which acrylic acid and methacrylic acid are preferable.
  • acrylic acid and methacrylic acid are preferable.
  • metal ion a sodium ion and a zinc ion are preferable.
  • the minimum with preferable content of the said unsaturated carboxylic acid component is 15 weight%, and a preferable upper limit is 25 weight%.
  • the ethylene-unsaturated carboxylic acid copolymer may further contain a (meth) acrylic acid ester component as a third component.
  • the (meth) acrylic acid ester is at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate from the viewpoint of cost and polymerizability. Is preferred. Among these, from the viewpoint of the melting point, an acrylate ester is preferable, and specifically, n-butyl acrylate, isobutyl acrylate, and ethyl acrylate are more preferable.
  • the content of the (meth) acrylic acid ester component is preferably 25% by weight or less. If the content of the (meth) acrylic acid ester component exceeds 25% by weight, the melting point may be too low.
  • the upper limit with more preferable content of the said (meth) acrylic acid ester component is 20 weight%.
  • the ethylene- (meth) acrylic acid copolymer is preferably an ethylene-acrylic acid ester-maleic anhydride terpolymer.
  • the ethylene-acrylic acid ester-maleic anhydride terpolymer is a copolymer composed of at least three components of ethylene, acrylic acid ester and maleic anhydride.
  • the acrylic ester is preferably at least one selected from the group consisting of methyl acrylate, ethyl acrylate, and butyl acrylate from the viewpoint of cost and polymerizability.
  • the ethylene- (meth) acrylic acid copolymer has an ethylene component content of 71 to 93% by weight, an acrylic ester component content of 5 to 28% by weight, and a maleic anhydride component content. Is preferably 0.1 to 4% by weight.
  • the ethylene- (meth) acrylic acid copolymer is preferably an ethylene-glycidyl methacrylate copolymer.
  • the ethylene-glycidyl methacrylate copolymer is a copolymer composed of at least two components of ethylene and glycidyl methacrylate.
  • the content of the glycidyl methacrylate component in the ethylene-glycidyl methacrylate copolymer is preferably 7% by weight and preferably 9% by weight from the viewpoint of the melting point.
  • the ethylene-glycidyl methacrylate copolymer can be produced using a conventionally known polymerization method.
  • the ethylene-glycidyl methacrylate copolymer may further contain components derived from other monomers in addition to the ethylene component and the glycidyl methacrylate component.
  • the other monomer is not particularly limited as long as it is a monomer copolymerizable with ethylene and glycidyl methacrylate as long as the physical properties necessary for the present invention are not impaired.
  • (meth) acrylate is preferred from the viewpoint of melting point, polymerizability, and cost.
  • the (meth) acrylate is preferably an acrylate, and methyl acrylate, ethyl acrylate or butyl acrylate is particularly preferable.
  • the preferable upper limit of the content of the (meth) acrylate component is 15% by weight, and the more preferable upper limit is 10% by weight.
  • the lower limit is not particularly limited as long as the copolymer resin can be obtained.
  • the adhesive sealing layer preferably further contains a silane compound having a glycidyl group.
  • a silane compound having a glycidyl group By containing such a silane compound having a glycidyl group, the adhesive force between the protective layer and the adhesive sealing layer can be further improved. Moreover, since almost no foreign substances such as gel are generated when the solar cell protective sheet is manufactured, it can be manufactured continuously. Moreover, when a solar cell element is continuously sealed by a roll-to-roll method or the like, the resin hardly protrudes from the end portion of the protective layer of the obtained flexible solar cell module. Furthermore, the adhesive force between the adhesive sealing layer and the surface of the solar cell element can also be improved.
  • silane compound having a glycidyl group examples include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltriethoxy.
  • 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- Glycidoxypropylmethyldiethoxysilane is preferred.
  • silane compounds having a glycidyl group are Z-6040 (3-glycidoxypropyltrimethoxysilane), Z-6043 (2- (3,4-epoxycyclohexyl) ethyltril) manufactured by Toray Dow Corning. Methoxysilane), KBE-403 (3-glycidoxypropyltriethoxysilane), KBM-402 (3-glycidoxypropylmethyldimethoxysilane), KBE-402 (3-glycidoxypropyl) manufactured by Shin-Etsu Silicone Methyldiethoxysilane) and the like.
  • the content of the silane compound having a glycidyl group in the adhesive sealing layer is 0.05 to 5 parts by weight with respect to 100 parts by weight of the thermoadhesive resin having an acid group or an acid anhydride group. preferable.
  • the adhesive force between the protective layer and the adhesive sealing layer and the adhesive force between the adhesive sealing layer and the solar cell element may be reduced.
  • the content of the silane compound is more preferably 0.07 parts by weight with respect to 100 parts by weight of the thermoadhesive resin having the acid group or acid anhydride group, and the upper limit is 1.5 parts by weight. It is more preferable that
  • the said adhesive sealing layer may further contain the other additive in the range which does not impair the physical property.
  • the other additives include, for example, an ultraviolet stabilizer, an antioxidant, a light resistance stabilizer, a plasticizer, a filler, a colorant, a pigment, an antistatic agent, a surfactant, a toning liquid, and a refractive index matching additive. Agents and dispersion aids.
  • the minimum with the preferable thickness of the said adhesive sealing layer is 80 micrometers, and a preferable upper limit is 700 micrometers. If the thickness of the adhesive sealing layer is less than 80 ⁇ m, the insulating property of the flexible solar cell module may not be maintained. If it exceeds 700 ⁇ m, the flame resistance of the flexible solar cell module may be adversely affected, or the flexible solar cell The module may become heavy.
  • the minimum with more preferable thickness of the said adhesive sealing layer is 150 micrometers, and a more preferable upper limit is 400 micrometers.
  • the method for forming the adhesive sealing layer includes, for example, a predetermined weight ratio of a silane compound having a glycidyl group and an additive added as necessary to the thermal adhesive resin having an acid group or an acid anhydride group. And a method of forming an adhesive sealing layer by feeding into an extruder and melting and kneading, and extruding into a sheet form from the extruder.
  • a single screw extruder or a twin screw extruder may be used as the extruder.
  • the solar cell protective sheet of the present invention is obtained by laminating the protective layer and the adhesive sealing layer.
  • the lamination method for example, a conventionally known method such as a vacuum laminating method, a roll laminating method, or an extrusion laminating method can be used.
  • the solar cell protective sheet of the present invention is for manufacturing a flexible solar cell module by sealing solar cell elements.
  • the flexible solar cell module in which the solar cell protective sheet of the present invention and the solar cell element in which the photoelectric conversion layer is disposed on the flexible base material are laminated and integrated are also one aspect of the present invention.
  • the solar cell element is generally composed of a photoelectric conversion layer in which electrons are generated by receiving light, an electrode layer for taking out the generated electrons, and a flexible substrate.
  • FIG. 3 the longitudinal cross-sectional schematic diagram of an example of the solar cell element C by which the photoelectric converting layer 3 is arrange
  • the flexible substrate is not particularly limited as long as it is flexible and can be used for a flexible solar cell element.
  • heat-resistant resin such as polyimide, polyetheretherketone, polyethersulfone, etc.
  • the base material which consists of can be mentioned.
  • the preferable lower limit of the thickness of the flexible substrate is 10 ⁇ m, and the preferable upper limit is 80 ⁇ m.
  • the photoelectric conversion layer examples include crystal semiconductors such as single crystal silicon, single crystal germanium, polycrystalline silicon, and microcrystalline silicon, amorphous semiconductors such as amorphous silicon, GaAs, InP, AlGaAs, Cds, CdTe, and Cu 2. Examples thereof include compounds formed from compound semiconductors such as S, CuInSe 2 and CuInS 2 , and organic semiconductors such as phthalocyanine and polyacetylene.
  • the photoelectric conversion layer may be a single layer or a multilayer. The minimum with the preferable thickness of the said photoelectric converting layer is 0.5 micrometer, and a preferable upper limit is 10 micrometers.
  • the electrode layer is a layer made of an electrode material.
  • the electrode layer may be on the photoelectric conversion layer, between the photoelectric conversion layer and the flexible base, or on the surface of the flexible base, as necessary.
  • the solar cell element may have a plurality of the electrode layers.
  • the electrode material is preferably a general transparent electrode material such as a metal oxide. Although it does not specifically limit as said transparent electrode material, ITO or ZnO etc. are used suitably.
  • the bus electrode and the finger electrode attached thereto may be patterned with a metal such as silver.
  • the electrode layer on the back side (back side) does not need to be transparent and may be made of a general electrode material, but silver is preferably used as the electrode material.
  • the solar cell element does not specifically limit as a method of manufacturing the said solar cell element, For example, it can manufacture by well-known methods, such as arrange
  • the solar cell element may have a long shape wound in a roll shape or a rectangular sheet shape.
  • the flexible solar cell module of the present invention has an adhesive sealing layer 2 and a protective layer 1 on the side of the photoelectric conversion layer 3 of the solar cell element C.
  • the adhesive sealing layer and the protective layer may also be provided on the side surface of the flexible substrate.
  • FIG. 4 is a schematic longitudinal sectional view of a flexible solar cell module F of the present invention comprising a protective layer 1, an adhesive sealing layer 2, a photoelectric conversion layer 3, a flexible substrate 4, an adhesive sealing layer 2 and a protective layer 1 in this order. Indicates.
  • the solar cell protective sheet comprising the adhesive sealing layer and the protective layer is formed on at least the light receiving surface of the solar cell element by using a pair of heat rolls.
  • a method of constricting and thermocompression bonding can be mentioned.
  • the light receiving surface of the solar cell element is a surface that can receive light and is a surface on which the photoelectric conversion layer of the solar cell element is disposed.
  • the solar cell element and the solar cell element are arranged in a state where the surface on which the photoelectric conversion layer of the solar cell element is disposed and the side surface of the adhesive sealing layer of the solar cell protection sheet are opposed to each other.
  • a method of laminating solar cell protective sheets, constricting them using a pair of heat rolls, and thermocompression bonding is preferable.
  • the preferable lower limit of the temperature of the heat roll when constricting using the pair of heat rolls is 70 ° C., and the preferable upper limit is 160 ° C. If the temperature of the heat roll is less than 70 ° C., adhesion failure may occur. If the temperature of the heat roll exceeds 160 ° C., wrinkles are likely to occur during thermocompression bonding.
  • a more preferable lower limit of the temperature of the heat roll is 80 ° C., and a more preferable upper limit is 110 ° C.
  • a preferable lower limit of the rotation speed of the heat roll is 0.1 m / min, and a preferable upper limit is 10 m / min. If the rotational speed of the heat roll is less than 0.1 m / min, wrinkles may easily occur after thermocompression bonding. When the rotation speed of the heat roll exceeds 10 m / min, there is a possibility that adhesion failure may occur.
  • a more preferable lower limit of the rotation speed of the heat roll is 0.3 m / min, and a more preferable upper limit is 5 m / min.
  • FIG. 5 An example of the method for producing the flexible solar cell module of the present invention will be specifically described with reference to FIG.
  • a long solar cell protective sheet B composed of the protective layer and the adhesive sealing layer and wound in a roll shape, and a solar cell element C are prepared.
  • the roll of the solar cell protection sheet B and the solar cell element C is unwound, and the light receiving surface of the photoelectric conversion layer of the solar cell element C and the adhesive sealing layer surface of the solar cell protection sheet B are arranged to face each other. Both are laminated to obtain a laminated sheet D.
  • the laminated sheet D is supplied between a pair of rolls E and E heated to a predetermined temperature, and the laminated sheet D is heated and thermocompression bonded while pressing in the thickness direction, so that the solar cell element C and the solar cell.
  • the protective sheet B is bonded and integrated. Thereby, a photoelectric converting layer is sealed by the adhesive sealing layer, and the flexible solar cell module A can be obtained.
  • the solar cell protective sheet of the present invention is applied to the side surface of the flexible substrate of the solar cell, and the adhesive sealing layer is a flexible substrate.
  • a method of thermocompression bonding by narrowing them using a pair of heat rolls may be performed on the light receiving surface of the solar cell element described above before the step of thermocompression bonding the solar cell protective sheet, It may be done at the same time or later.
  • the solar cell protective sheet of the present invention for example, an example of a method for producing the flexible solar cell module of the present invention by simultaneously sealing the photoelectric conversion layer side surface and the flexible substrate side surface of the solar cell element, This will be described with reference to FIG. Specifically, while preparing a long solar cell element C wound in a roll shape, two long solar cell protective sheets wound in a roll shape are prepared. And as shown in FIG. 6, while unwinding the elongate solar cell protection sheets B and B, respectively, unwind the elongate solar cell element C, and the adhesive sealing layer of two solar cell protection sheets is In a state of facing each other, the solar cell protective sheets B and B are overlapped with each other through the solar cell element C to obtain a laminated sheet D.
  • the solar cell protective sheets B, B are brought together.
  • the solar cell element C is sealed with the solar cell protective sheets B and B, and the flexible solar cell module F is continuously manufactured.
  • the solar cell protective sheets B and B are overlapped with each other via the solar cell element C to form the laminated sheet D, and at the same time, the laminated sheet D is heated while being pressed in the thickness direction. May be.
  • FIG. 7 an example of the manufacturing point of the flexible solar cell module of this invention at the time of using a rectangular sheet-like thing as the solar cell element C is shown in FIG. Specifically, instead of the long solar cell element C wound in a roll shape, a rectangular sheet-like solar cell element C having a predetermined size is prepared. And as shown in FIG. 7, the solar cell protection sheet which unwinded the elongate solar cell protection sheet B and B currently wound by roll shape, and made each adhesive sealing layer face each other. A solar cell element C is supplied between B and B at predetermined time intervals, and the solar cell protective sheets B and B are overlapped with each other via the solar cell element C to obtain a laminated sheet D.
  • the solar cell protective sheets B, B are brought together.
  • the solar cell element C is sealed with the solar cell protective sheets B and B, and the flexible solar cell module F is continuously manufactured.
  • the laminated sheet D may be heated while being pressed in the thickness direction simultaneously with the formation of the laminated sheet D.
  • the flexible solar cell module of the present invention can be suitably manufactured by applying such a roll-to-roll method.
  • the solar cell protective sheet and the solar cell element of the present invention cut into a desired shape are prepared, and the adhesive sealing layer of the solar cell protective sheet;
  • the solar cell protective sheet and the solar cell element are laminated in a state where the photoelectric conversion layer side surface or both surfaces of the solar cell element are opposed to each other, and the obtained laminate is stationary under reduced pressure.
  • the method may be such that the solar cell element is sealed with the solar cell protective sheet by heating while applying a pressing force in the thickness direction.
  • the step of heating the laminate while applying a pressing force in the thickness direction under reduced pressure can be performed using a conventionally known apparatus such as a vacuum laminator.
  • the flexible solar cell module by which the solar cell element was protected by the solar cell protective sheet excellent in durability with the high adhesiveness of a protective layer and an adhesive sealing layer, and this solar cell protective sheet. can be provided.
  • Example 1 Preparation of PVDF sheet having surface layer Polyvinylidene fluoride (PVDF, manufactured by Arkema Corp., Kyner 720) is used as a fluororesin using a single screw extruder at 250 ° C., 180 rotations / minute, extrusion rate of 12 kg / hour. After melt-kneading under the above conditions, melt extrusion was performed, and an embossing roll was used as a cooling roll, thereby obtaining a PVDF sheet having a thickness of 50 ⁇ m having an embossed shape on one surface.
  • PVDF Polyvinylidene fluoride
  • a plasma processing apparatus (AP / T04-R1540 apparatus and product lineup made by Sekisui Chemical Co., Ltd.) on the surface of the obtained PVDF sheet having an embossed shape, 1 head, sheet processing speed of 5 m / min, processing strength of 1
  • a nitrogen gas plasma treatment was performed under a condition of 3 kW to obtain a PVDF sheet having a surface layer.
  • About the PVDF sheet which has the obtained surface layer when nitrogen atom content of the surface layer was measured by X-ray photoelectron spectroscopy (XPS), it was 2.02 mol%.
  • Modified olefin resin 100 obtained by graft-modifying a butene-ethylene copolymer having an ethylene component content of 75% by weight and a butene component content of 25% by weight with maleic anhydride
  • a composition for an adhesive sealing layer comprising, by weight, 0.5 part by weight of 3-glycidoxypropyltrimethoxysilane (trade name “Z-6040”, manufactured by Dow Corning Toray) as a silane compound having a glycidyl group
  • Z-6040 3-glycidoxypropyltrimethoxysilane
  • the adhesive sealing layer composition is laminated while being extruded on the surface layer of the PVDF sheet having the surface layer obtained above to form an adhesive sealing layer, and contains a modified olefin resin and a silane compound.
  • a solar cell protective sheet having a long and constant width was obtained by laminating and integrating an adhesive sealing layer having a thickness of 300 ⁇ m and a protective layer having a thickness of 50 ⁇ m.
  • the modified olefin resin used had a melt flow rate (MFR) of 3 g / 10 min and a maximum peak temperature (Tm) of an endothermic curve measured by differential scanning calorimetry of 80 ° C.
  • the total content of maleic anhydride in the modified olefin resin was 0.3% by weight.
  • a photoelectric conversion layer made of thin amorphous silicon is formed on a flexible base material made of a flexible polyimide film, and A solar cell element wound in a roll shape and a solar cell protection sheet in which the solar cell protection sheet obtained above was wound in a roll shape were prepared.
  • the solar cell element C and the solar cell protection sheet B are unwound, the solar cell protection sheet B is placed on the photoelectric conversion layer of the solar cell element C, and the adhesive sealing layer is the photoelectric conversion layer.
  • Laminated sheets D were laminated so as to face the layers.
  • the laminated sheet D is supplied between a pair of rolls E and E heated to the temperatures shown in Table 1, and the laminated sheet D is heated while pressing the laminated sheet D in the thickness direction, and the solar cell protective sheet
  • the photoelectric conversion layer was sealed by bonding and integrating B with the solar cell element C, and the flexible solar cell module A was continuously manufactured, and wound around a winding shaft (not shown).
  • (3-2) Manufacture of flexible solar cell module by vacuum laminating method
  • a solar cell element in which a photoelectric conversion layer made of amorphous silicon in the form of a thin film is formed on a flexible base material made of a polyimide film having flexibility.
  • the solar cell protective sheet obtained above was prepared by cutting it into a predetermined shape.
  • the solar cell protective sheet and the solar cell element were laminated in a state where the adhesive sealing layer of the solar cell protective sheet and the photoelectric conversion layer side surface of the solar cell element were opposed to each other.
  • the obtained laminate is heated using a vacuum laminator under a reduced pressure atmosphere of 1000 Pa or less while applying a pressing force in the thickness direction under the conditions shown in Table 1, and the solar cell element is sealed with a solar cell protective sheet. Stopped.
  • Examples 2 to 4, 7 to 9, 13, 15 and Comparative Examples 1 to 4, 6 In the preparation of PVDF sheet, the presence or absence of embossed shape, the plasma treatment conditions were changed as shown in Tables 1 to 4, and the composition of modified olefin resin and the presence or absence of silane compound in the production of solar cell protective sheet A solar cell protective sheet and a flexible solar cell module were obtained in the same manner as in Example 1 except that the values were changed as shown in Tables 1 to 4.
  • Examples 5 and 14 A vinylidene fluoride-hexafluoropropylene copolymer (trade name “Kyner Flex 2800” manufactured by Arkema Co., Ltd.) as a fluororesin is used at 250 ° C., 180 rotations / minute, and an extrusion rate of 12 kg / hour using a single screw extruder. After melt kneading under the conditions, melt extrusion was performed, and an embossing roll was used as a cooling roll to obtain a 50 ⁇ m thick PVDF-HFP copolymer sheet having an embossed shape on one surface.
  • the surface of the obtained PVDF-HFP copolymer sheet having an embossed shape is subjected to plasma surface treatment using a plasma treatment device (AP / T04-R1540 device and product lineup manufactured by Sekisui Chemical Co., Ltd.)
  • a PVDF sheet was obtained. Except for changing the plasma treatment conditions as shown in Tables 1 and 2 or changing the composition of the modified olefin resin and the presence or absence of the silane compound in the production of the solar cell protective sheet as shown in Tables 1 and 2.
  • a solar cell protective sheet and a flexible solar cell module were obtained in the same manner as in Example 1.
  • Tetrafluoroethylene-ethylene copolymer (trade name “Neofluon ETFE”, manufactured by Daikin Industries, Ltd.) is used as a fluororesin under the conditions of 310 ° C., 180 rotations / minute, extrusion rate of 12 kg / hour using a single screw extruder. After melt kneading, melt extrusion was performed, and an embossing roll was used as a cooling roll to obtain an ETFE sheet having an embossed shape on one surface and a thickness of 50 ⁇ m.
  • a nitrogen gas plasma treatment was performed under a condition of .3 kW to obtain an ETFE sheet having a surface layer.
  • a solar cell protective sheet and a flexible solar cell module were obtained in the same manner as in Example 1 except that the ETFE sheet having the obtained surface layer was used.
  • Example 10 Comparative Example 7
  • the plasma treatment conditions were as shown in Tables 2 and 4.
  • a commercial product of ionomer resin (trade name: Himiran 1705, Zn ion type, manufactured by Mitsui DuPont Polychemical Co., Ltd.) was used in place of the modified olefin-based resin.
  • a solar cell protective sheet and a flexible solar cell module were obtained in the same manner as in Example 1.
  • Example 11 Comparative Example 8
  • the plasma treatment conditions were as shown in Tables 2 and 4.
  • an ethylene-acrylic acid ester-maleic anhydride terpolymer containing a predetermined amount of components described in Tables 2 and 4 was used, as described in Tables 2 and 4.
  • a solar cell protective sheet and a flexible solar cell module were obtained in the same manner as in Example 1.
  • Example 12 Comparative Example 9
  • the plasma treatment conditions were as shown in Tables 2 and 4.
  • a resin obtained by modifying an ethylene-glycidyl methacrylate copolymer containing a predetermined amount of ethylene component and glycidyl methacrylate component described in Tables 2 and 4 with maleic anhydride was used.
  • a solar cell protective sheet and a flexible solar cell module were obtained by the same method as in Example 1.
  • PVDF sheet having surface layer Polyvinylidene fluoride (PVDF, manufactured by Arkema Corp., Kyner 720) is used as a fluororesin using a single screw extruder at 250 ° C., 180 rotations / minute, extrusion rate of 12 kg / hour. After melt-kneading under the above conditions, melt extrusion was performed, and an embossing roll was used as a cooling roll, thereby obtaining a PVDF sheet having a thickness of 50 ⁇ m having an embossed shape on one surface.
  • PVDF Polyvinylidene fluoride
  • the surface having the embossed shape of the obtained PVDF sheet is subjected to a nitrogen gas corona discharge treatment using a corona discharge treatment device (manufactured by Kasuga Denki Co., Ltd., high frequency power supply device and treatment station) under conditions of a treatment amount of 20 W / m 2.
  • a PVDF sheet having a surface layer was obtained.
  • a solar cell protective sheet and a flexible solar cell module were obtained in the same manner as in Example 1 except that the obtained PVDF sheet having the surface layer was used.
  • Examples 17 and 18, Comparative Example 5 Except for changing the corona discharge treatment conditions as shown in Tables 2 and 3 in the preparation of the PVDF sheet, and changing the presence or absence of the silane compound as shown in Tables 2 and 3 in the production of the solar cell protective sheet.
  • a solar cell protective sheet and a flexible solar cell module were obtained in the same manner as in Example 16.
  • the initial delamination strength between the protective layer and the adhesive sealing layer is generally required to be 10 N / cm or more, preferably 20 N / cm or more, and more preferably 30 N / cm or more.
  • the flexible solar cell module by which the solar cell element was protected by the solar cell protective sheet excellent in durability with the high adhesiveness of a protective layer and an adhesive sealing layer, and this solar cell protective sheet. can be provided.

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  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photovoltaic Devices (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne la fourniture d'une feuille de protection de cellule solaire, qui présente une forte adhésivité entre une couche de protection et une couche d'étanchéité adhésive, ainsi qu'une excellente durabilité et un module de cellule solaire flexible, dans lequel des éléments de cellule solaire sont protégés par ladite feuille de protection de cellule solaire. Cette feuille de protection de cellule solaire est un stratifié d'une couche de protection, qui comprend une feuille de résine à base de fluor, et d'une couche d'étanchéité adhésive, la couche de protection ayant une couche de surface avec 0,2 % en moles ou plus d'atomes d'azote sur la surface, en contact avec la couche d'étanchéité adhésive et la couche d'étanchéité adhésive contenant une résine adhésive à la chaleur ayant un groupe acide ou un groupe anhydride d'acide.
PCT/JP2013/074717 2012-09-13 2013-09-12 Feuille de protection de cellule solaire et module de cellule solaire flexible WO2014042217A1 (fr)

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Cited By (2)

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JP2019053832A (ja) * 2017-09-12 2019-04-04 トヨタ自動車株式会社 電極の製造方法
JP7535235B2 (ja) 2020-03-19 2024-08-16 大日本印刷株式会社 表面改質フッ素系樹脂フィルム、積層体、及び複合ゴム成形体の製造方法、並びに表面改質フッ素系樹脂フィルム、積層体、及び複合ゴム成形体

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CN114211844B (zh) * 2021-11-26 2023-05-16 常州斯威克光伏新材料有限公司 一种光伏用透明背板及其制备方法

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JP2004031445A (ja) * 2002-06-21 2004-01-29 Du Pont Mitsui Polychem Co Ltd 太陽電池モジュールの表層構造
JP2004055970A (ja) * 2002-07-23 2004-02-19 Fuji Electric Holdings Co Ltd 太陽電池モジュールとその製造方法
JP2012074419A (ja) * 2010-09-27 2012-04-12 Dainippon Printing Co Ltd 太陽電池モジュール用裏面保護シート、太陽電池モジュール用裏面一体化シート及び太陽電池モジュール
WO2012056941A1 (fr) * 2010-10-28 2012-05-03 富士フイルム株式会社 Module de cellules solaires et son procédé de fabrication

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JP2004031445A (ja) * 2002-06-21 2004-01-29 Du Pont Mitsui Polychem Co Ltd 太陽電池モジュールの表層構造
JP2004055970A (ja) * 2002-07-23 2004-02-19 Fuji Electric Holdings Co Ltd 太陽電池モジュールとその製造方法
JP2012074419A (ja) * 2010-09-27 2012-04-12 Dainippon Printing Co Ltd 太陽電池モジュール用裏面保護シート、太陽電池モジュール用裏面一体化シート及び太陽電池モジュール
WO2012056941A1 (fr) * 2010-10-28 2012-05-03 富士フイルム株式会社 Module de cellules solaires et son procédé de fabrication

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019053832A (ja) * 2017-09-12 2019-04-04 トヨタ自動車株式会社 電極の製造方法
JP7535235B2 (ja) 2020-03-19 2024-08-16 大日本印刷株式会社 表面改質フッ素系樹脂フィルム、積層体、及び複合ゴム成形体の製造方法、並びに表面改質フッ素系樹脂フィルム、積層体、及び複合ゴム成形体

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