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WO2012046565A1 - Procédé pour produire un module de photopile souple - Google Patents

Procédé pour produire un module de photopile souple Download PDF

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Publication number
WO2012046565A1
WO2012046565A1 PCT/JP2011/071274 JP2011071274W WO2012046565A1 WO 2012046565 A1 WO2012046565 A1 WO 2012046565A1 JP 2011071274 W JP2011071274 W JP 2011071274W WO 2012046565 A1 WO2012046565 A1 WO 2012046565A1
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WO
WIPO (PCT)
Prior art keywords
solar cell
sheet
flexible
resin
cell module
Prior art date
Application number
PCT/JP2011/071274
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English (en)
Japanese (ja)
Inventor
平池　宏至
飛鳥　政宏
清巳 上ノ町
嘉謨 郭
高弘 野村
澤田　貴彦
石居　正裕
Original Assignee
積水化学工業株式会社
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 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to JP2011539835A priority Critical patent/JPWO2012046565A1/ja
Publication of WO2012046565A1 publication Critical patent/WO2012046565A1/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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
    • H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
    • H02S40/30—Electrical components
    • H02S40/32—Electrical components comprising DC/AC inverter means associated with the PV module itself, e.g. AC modules
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • 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 continuously seals solar cell elements without requiring a crosslinking step, does not generate wrinkles or curls, and is a flexible solar cell excellent in adhesiveness between the solar cell elements and the solar cell sealing sheet.
  • the present invention relates to a method for manufacturing a flexible solar cell module, which can manufacture a module with high efficiency.
  • 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 by laminating solar cell encapsulating sheets.
  • the said solar cell sealing sheet is for preventing the impact from the outside, or preventing corrosion of a solar cell element.
  • the solar cell encapsulating sheet has an adhesive layer formed on a transparent sheet, and an ethylene-vinyl acetate (EVA) resin has been conventionally used for the adhesive layer for encapsulating the solar cell element.
  • EVA ethylene-vinyl acetate
  • Patent Document 1 ethylene-vinyl acetate
  • non-EVA-based resins such as silane-modified olefin resins has been studied as the adhesive layer of the solar cell encapsulating sheet (see, for example, Patent Document 2).
  • the method for producing the flexible solar cell module is a method of laminating a flexible solar cell element and a solar cell encapsulating sheet in advance after cutting them into a desired shape, and laminating and integrating them by vacuum lamination in a stationary state. It has been done from the past. In such a vacuum laminating method, there has been a problem that the bonding process takes time and the manufacturing efficiency of the solar cell module is low.
  • a roll-to-roll method As a method for producing the flexible solar cell module, a roll-to-roll method has been studied in terms of being excellent in mass production (for example, see Patent Document 3).
  • the roll-to-roll method uses a roll in which a film-like solar cell encapsulating sheet is wound, and the solar cell encapsulating sheet unwound from the roll is narrowed by using a pair of rolls, thereby obtaining a solar cell.
  • This is a method for continuously manufacturing flexible solar cell modules by performing thermocompression bonding to the element and sealing. According to such a roll-to-roll method, it can be expected to continuously manufacture flexible solar cell modules with extremely high efficiency.
  • the present invention continuously seals solar cell elements without the need for a crosslinking step, does not cause wrinkles or curls, and adheres between the solar cell elements and the solar cell sealing sheet. It aims at providing the manufacturing method of a flexible solar cell module which can manufacture the flexible solar cell module excellent in in high efficiency.
  • the present invention includes a step of thermocompression bonding a solar cell encapsulating sheet by constricting it using at least a light receiving surface of a solar cell element having a photoelectric conversion layer disposed on a flexible substrate using a pair of heat rolls.
  • the solar cell encapsulating sheet is a resin obtained by graft-modifying an ⁇ -olefin-ethylene copolymer having an ⁇ -olefin content of 1 to 25% by weight with maleic anhydride on a fluororesin sheet.
  • a method for producing a flexible solar cell module comprising an adhesive layer made of a maleic anhydride-modified olefin resin having a total maleic anhydride content of 0.1 to 3% by weight.
  • the present invention seals a solar cell element using a solar cell encapsulating sheet having an adhesive layer made of a specific component and a fluororesin sheet, thereby preventing wrinkles and curling from occurring.
  • a flexible solar cell module having excellent adhesion between the stop sheet and the solar cell element is continuously produced by a roll-to-roll method. That is, the present inventors seal a solar cell element with a solar cell sealing sheet in which an adhesive layer made of an olefin resin graft-modified with a specific maleic anhydride is formed on a fluorine-based resin sheet.
  • thermocompression bonding can be performed in a short time at a relatively low temperature, and solar cell elements can be continuously sealed by a roll-to-roll method, thereby completing the present invention.
  • a solar cell encapsulating sheet is narrowed by using a pair of heat rolls on at least a light receiving surface of a solar cell element in which a photoelectric conversion layer is disposed on a flexible substrate.
  • the solar cell encapsulating sheet has an adhesive layer made of maleic anhydride-modified olefin resin on a fluorine resin sheet.
  • the maleic anhydride-modified olefin resin is a resin obtained by graft-modifying an ⁇ -olefin-ethylene copolymer having an ⁇ -olefin content of 1 to 25% by weight with maleic anhydride, and maleic anhydride.
  • the total content of is 0.1 to 3% by weight.
  • a flexible solar cell module can be suitably manufactured by a roll-to-roll method by using the solar cell sealing sheet which has the contact bonding layer which consists of such specific resin.
  • the ⁇ -olefin-ethylene copolymer is a copolymer of an ⁇ -olefin and ethylene.
  • the ⁇ -olefin preferably has 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms, in order to lower the melting point and improve flexibility by improving the amorphous nature of the resin.
  • Specific examples of the ⁇ -olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. Of these, 1-butene, 1-hexene and 1-octene are preferable.
  • the ⁇ -olefin-ethylene copolymer is preferably a butene-ethylene copolymer, a hexene-ethylene copolymer, or an octene-ethylene copolymer.
  • the ⁇ -olefin-ethylene copolymer has an ⁇ -olefin content of 1 to 25% by weight.
  • the ⁇ -olefin content is less than 1% by weight, the flexibility of the solar cell encapsulating sheet is lowered, and the melting point of the solar cell encapsulating sheet is increased. Heating is required, and wrinkles and curls are likely to occur.
  • the ⁇ -olefin content exceeds 25% by weight, the crystallinity or fluidity of the solar cell encapsulating sheet becomes non-uniform and distortion occurs, or the melting point of the solar cell encapsulating sheet itself becomes too low.
  • the preferable lower limit of the ⁇ -olefin content is 10% by weight, and the preferable upper limit is 20% by weight.
  • the content of the ⁇ -olefin in the ⁇ -olefin-ethylene copolymer can be determined from the spectrum integrated value of 13 C-NMR. Specifically, for example, when 1-butene is used, a spectral integral value derived from the 1-butene structure obtained in deuterated chloroform at around 10.9 ppm, 26.1 ppm, or 39.1 ppm, and around 26.9 ppm. , 29.7 ppm vicinity, 30.2 ppm vicinity, 33.4 ppm vicinity, it calculates using the spectrum integral value derived from the ethylene structure. For spectral attribution, known data such as a polymer analysis handbook (edited by the Analytical Society of Japan, published by Asakura Shoten, 2008) may be used.
  • a known method is used as a method of graft-modifying the ⁇ -olefin-ethylene copolymer with maleic anhydride.
  • a composition containing the ⁇ -olefin-ethylene copolymer, maleic anhydride, and a radical polymerization initiator is supplied to an extruder and melt-kneaded, and then the maleic anhydride is added to the copolymer.
  • a melt modification method in which an acid is graft-polymerized or a solution is prepared by dissolving the ⁇ -olefin-ethylene copolymer in a solvent, and maleic anhydride and a radical polymerization initiator are added to the solution to add the copolymer.
  • examples thereof include a solution modification method in which maleic anhydride is graft-polymerized to the polymer.
  • the melt modification method is preferable because it can be mixed in an extruder and has excellent productivity.
  • the radical polymerization initiator used in the graft modification method is not particularly limited as long as it is conventionally used for radical polymerization. Specific examples include benzoyl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, cumyl peroxyneodecanoate, cumyl peroxy octoate, azobisisobutyronitrile and the like.
  • the maleic anhydride-modified olefin resin has a total maleic anhydride content of 0.1 to 3% by weight.
  • the adhesiveness with respect to the solar cell element of the said solar cell sealing sheet falls that the total content of the said maleic anhydride is less than 0.1 weight%. If the total maleic anhydride content exceeds 3% by weight, the maleic anhydride-modified olefin resin is cross-linked and a gel is generated during the production of the solar cell encapsulating sheet, making it impossible to produce the encapsulating sheet. Or the extrusion moldability of the solar cell encapsulating sheet may be reduced.
  • the minimum with preferable total content of the said maleic anhydride is 0.2 weight%, and a preferable upper limit is 1.5 weight%, and it is more preferable that it is less than 1.0 weight%.
  • the total maleic anhydride content was determined from the absorption intensity around 1790 cm ⁇ 1 by preparing a test film using the maleic anhydride-modified olefin resin and measuring the infrared absorption spectrum of the test film. Can be calculated.
  • the total content of maleic anhydride in the maleic anhydride-modified olefin resin is, for example, FT-IR (Fourier Transform Infrared Spectrometer Nicolet 6700 FT-IR) Polymer Analysis Handbook ( It can be measured by a known measurement method described in the Japan Analytical Chemical Society, published by Asakura Shoten, 2008).
  • FT-IR Fastier Transform Infrared Spectrometer Nicolet 6700 FT-IR
  • the maleic anhydride-modified olefin resin preferably has a maximum peak temperature (Tm) of an endothermic curve measured by differential scanning calorimetry of 80 to 125 ° C. If the maximum peak temperature (Tm) of the endothermic curve is lower than 80 ° C, the heat resistance of the solar cell encapsulating sheet may be reduced. When the maximum peak temperature (Tm) of the endothermic curve is higher than 125 ° C., the heating time of the solar cell encapsulating sheet in the encapsulating process becomes long, and the productivity of the solar cell module is reduced, or the solar cell element There is a risk that the sealing of the resin becomes insufficient.
  • Tm maximum peak temperature
  • the maximum peak temperature (Tm) of the endothermic curve is more preferably 83 to 110 ° C.
  • the maximum peak temperature (Tm) of the endothermic curve measured by the differential scanning calorimetry can be measured according to the measurement method defined in JIS K7121.
  • the maleic anhydride-modified olefin resin preferably has a melt flow rate (MFR) of 0.5 g / 10 min to 29 g / 10 min.
  • MFR melt flow rate
  • the melt flow rate is less than 0.5 g / 10 minutes, strain remains in the sealing sheet during the production of the solar cell encapsulating sheet, and the module may be curled after the solar cell module is produced. If it exceeds 29 g / 10 minutes, it is easy to draw down during the production of the solar cell encapsulating sheet, and it is difficult to produce a sheet having a uniform thickness. It becomes easy to produce a pinhole etc. in a sheet
  • the melt flow rate is more preferably 2 g / 10 min to 10 g / 10 min.
  • the melt flow rate of the maleic anhydride-modified olefin resin is a value measured at a load of 2.16 kg in accordance with ASTM D1238, which is a method for measuring the melt flow rate of a polyethylene resin.
  • the maleic anhydride-modified olefin resin preferably has a viscoelastic storage elastic modulus at 30 ° C. of 2 ⁇ 10 8 Pa or less.
  • a viscoelastic storage elastic modulus at 30 ° C. exceeds 2 ⁇ 10 8 Pa, the flexibility of the solar cell encapsulating sheet is lowered and the handleability is lowered, or the solar cell element is replaced by the solar cell encapsulating sheet.
  • the upper limit is more preferably 1.5 ⁇ 10 8 Pa.
  • the maleic anhydride-modified olefin resin preferably has a viscoelastic storage elastic modulus at 100 ° C. of 5 ⁇ 10 6 Pa or less.
  • the viscoelastic storage elastic modulus at 100 ° C. exceeds 5 ⁇ 10 6 Pa, the adhesion of the solar cell encapsulating sheet to the solar cell element may be reduced.
  • the viscoelastic storage elastic modulus at 100 ° C. is too low, the solar cell encapsulating sheet is pressed by a pressing force when the solar cell element is encapsulated by the solar cell encapsulating sheet to produce a solar cell module.
  • the lower limit is preferably 1 ⁇ 10 4 Pa because there is a risk that the solar cell encapsulating sheet will be greatly fluidized and the thickness of the solar cell encapsulating sheet may become uneven.
  • the upper limit is more preferably 4 ⁇ 10 6 Pa.
  • the viscoelastic storage elastic modulus of the maleic anhydride-modified olefin resin refers to a value measured by a dynamic property test method based on JIS K6394.
  • the adhesive layer further contains a silane compound.
  • the silane compound By containing the silane compound, the adhesiveness between the adhesive layer and the solar cell element surface can be further improved.
  • the said contact bonding layer contains the silane compound which has an epoxy group.
  • the silane compound having an epoxy group particularly high heat resistance can be imparted to the obtained flexible solar cell module while sufficiently exhibiting high mass productivity of the roll-to-roll method.
  • the solar cell encapsulating sheet whose surface has an embossed shape previously formed is thermocompression bonded to the solar cell element, the embossed shape is easily maintained.
  • the maleic anhydride group in the maleic anhydride-modified olefin resin reacts with the epoxy group of the silane compound having an epoxy group, and the silane compound is taken into the side chain of the resin. .
  • the silane compounds in the side chains form siloxane bonds by hydrolysis condensation, and a crosslinked structure is formed between the resins. That is, the silane compound having an epoxy group also serves as a crosslinking agent for the maleic anhydride-modified olefin resin. By forming a crosslinked structure between the resins, it is considered that the elastic modulus at high temperature is improved and the heat resistance is increased.
  • the silane compound having an epoxy group may have at least one epoxy group such as an aliphatic epoxy group or an alicyclic epoxy group in the molecule.
  • the silane compound having an epoxy group is preferably a silane compound represented by the following general formula (I).
  • R 1 represents a 3-glycidoxypropyl group or 2- (3,4-epoxycyclohexyl) ethyl group
  • R 2 represents an alkyl group having 1 to 3 carbon atoms
  • R 3 represents Represents an alkyl group having 1 to 3 carbon atoms
  • n is 0 or 1.
  • R 1 represents a 3-glycidoxypropyl group represented by the following formula (II) or a 2- (3,4-epoxycyclohexyl) ethyl group represented by the following formula (III).
  • R 2 is not particularly limited as long as it is an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • a methyl group and an ethyl group are preferable, and a methyl group is more preferable. preferable.
  • R 3 is not particularly limited as long as it is an alkyl group having 1 to 3 carbon atoms. Examples thereof include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable.
  • n is 0 or 1, and it is preferable that it is 0.
  • Examples of the silane compound represented by the general formula (I) include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidide.
  • 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane), 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane is preferred.
  • silane compounds represented by the above general formula (I) are Z-6040 (3-glycidoxypropyltrimethoxysilane) and Z6043 (2- (3,4-epoxycyclohexyl) manufactured by Toray Dow Corning. Ethyltrimethoxysilane), Shin-Etsu Silicone KBE-403 (3-glycidoxypropyltriethoxysilane), KBM-402 (3-glycidoxypropylmethyldimethoxysilane), KBE-402 (3-glycidide) Xylpropylmethyldiethoxysilane) and the like.
  • the content of the silane compound in the adhesive layer is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the maleic anhydride-modified olefin resin.
  • the adhesiveness of a solar cell sealing sheet may fall that content of the said silane compound is less than 0.05 weight part.
  • the solar cell encapsulating sheet is strongly contracted, which may cause wrinkles or generate a gel to impair the appearance of the sheet.
  • the minimum with more preferable content of the said silane compound is 0.1 weight part, and a more preferable upper limit is 1.5 weight part.
  • the viscosity of the adhesive layer resin is increased by the crosslinking reaction of the maleic anhydride-modified olefin resin, and the handleability during extrusion molding is reduced.
  • the low density polyethylene may be a linear low density polyethylene, specifically, a copolymer of ethylene and ⁇ -olefin.
  • the said adhesive layer may further contain additives, such as a light stabilizer, a ultraviolet absorber, and a heat stabilizer, in the range which does not impair the physical property.
  • additives such as a light stabilizer, a ultraviolet absorber, and a heat stabilizer, in the range which does not impair the physical property.
  • the method for producing the adhesive layer includes melting and kneading the maleic anhydride-modified olefin resin, the silane compound, and an additive that is added as necessary to an extruder at a predetermined weight ratio. And a method of producing an adhesive layer by extruding into a sheet form from an extruder.
  • the adhesive layer preferably has a thickness of 80 to 700 ⁇ m. There exists a possibility that the insulation of a flexible solar cell module cannot be hold
  • the preferable lower limit of the thickness of the adhesive layer is 150 ⁇ m, and the preferable upper limit is 400 ⁇ m.
  • the solar cell encapsulating sheet is obtained by forming the adhesive layer on a fluororesin 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 polyvinylidene fluoride resin
  • FAP polyvinylidene fluoride resin
  • PVDF tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
  • FAP polyvinyl fluoride resin
  • PVDF tetrafluoroethylene-hexafluoropropylene
  • FEP tetrafluoroethylene-hexafluoropropylene
  • PVDF polyvinylidene fluoride resin
  • ETFE tetrafluoroethylene-ethylene copolymer
  • PVF polyvinyl fluoride resin
  • the fluororesin sheet preferably has a thickness of 10 to 100 ⁇ m. If the thickness of the fluororesin sheet is less than 10 ⁇ m, insulation may not be ensured or flame retardancy may be impaired. If the thickness of the fluororesin sheet exceeds 100 ⁇ m, the weight of the flexible solar cell module may increase, which is economically disadvantageous. A more preferable lower limit of the thickness of the fluororesin sheet is 15 ⁇ m, and a more preferable upper limit is 80 ⁇ m.
  • the solar cell encapsulating sheet can be produced by laminating and integrating the fluororesin sheet and the adhesive layer.
  • the method of laminating and integrating is not particularly limited, for example, a method of forming by extrusion laminating the fluororesin sheet on one surface of the adhesive layer, or a coextrusion of the adhesive layer and the fluororesin sheet. And the like.
  • the extrusion setting temperature is preferably 30 ° C. or more from the melting point of the fluorine resin and the maleic anhydride-modified olefin resin and less than 30 ° C. from the decomposition temperature.
  • the solar cell encapsulating sheet is preferably an integral laminate in which the adhesive layer and the fluororesin sheet are simultaneously formed and laminated by a co-extrusion process.
  • the solar cell encapsulating sheet preferably has an embossed shape on the surface.
  • the solar cell encapsulating sheet preferably has an embossed shape on the surface that becomes the light receiving surface when applied. More specifically, when the flexible solar cell module is manufactured, it is preferable that the fluororesin sheet surface of the solar cell sealing sheet on the light receiving surface side has an embossed shape.
  • the embossed shape may be a regular uneven shape or a random uneven shape.
  • the embossed shape may be embossed before being bonded to the solar cell element, embossed after being bonded to the solar cell element, or simultaneously molded in the step of bonding to the solar cell element. May be. Among them, it is preferable to form by embossing before bonding to the solar cell element because there is no unevenness of emboss transfer and a uniform emboss shape can be obtained.
  • a flexible solar cell element is sealed by a roll-to-roll method using a solar cell encapsulating sheet having an embossed shape on the surface in advance, a part of the embossed shape disappears in the thermocompression bonding process at the time of sealing. There was a case.
  • the method for imparting an embossed shape to the surface of the solar cell encapsulating sheet is not particularly limited.
  • An embossing roll is used as the cooling roll, and a method of embossing the surface simultaneously with cooling the molten resin is suitable.
  • 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.
  • the photoelectric conversion layer includes, for example, a crystalline semiconductor such as single crystal silicon, single crystal germanium, polycrystalline silicon, and microcrystalline silicon, an amorphous semiconductor such as amorphous silicon, GaAs, InP, AlGaAs, Cds, CdTe, and Cu 2 S. , CuInSe 2 , CuInS 2 and other compound semiconductors, and organic semiconductors such as phthalocyanine and polyacetylene.
  • the photoelectric conversion layer may be a single layer or a multilayer.
  • the thickness of the photoelectric conversion layer is preferably 0.5 to 10 ⁇ m.
  • the flexible base material is not particularly limited as long as it is flexible and can be used for a flexible solar cell.
  • the flexible base material is made of a heat-resistant resin such as polyimide, polyether ether ketone, or polyether sulfone.
  • a substrate can be mentioned.
  • the thickness of the flexible substrate is preferably 10 to 80 ⁇ m.
  • 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 layer on the light receiving surface side is preferably a transparent electrode because it needs to transmit light.
  • the said electrode material will not be specifically limited if it is common transparent electrode materials, such as a metal oxide, 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. Since the electrode layer on the back side does not need to be transparent, it may be formed of a general electrode material, but silver is preferably used as the electrode material.
  • the method for producing the solar cell element is not particularly limited as long as it is a known method.
  • it may be formed by a known method in which the photoelectric conversion layer or the electrode layer is disposed on the flexible substrate.
  • the solar cell element may have a long shape wound in a roll shape or a rectangular sheet shape.
  • the manufacturing method of the flexible solar cell module of this invention thermocompression-bonds by narrowing the said solar cell sealing sheet using a pair of heat roll on the light-receiving surface of the said solar cell element at least.
  • the light receiving surface of the solar cell element is a surface on which power can be generated by receiving light, and is a surface on which the photoelectric conversion layer is disposed with respect to the flexible base material.
  • the solar cell element and the solar cell 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 layer of the solar cell sealing sheet face each other.
  • a method of laminating a battery sealing sheet, constricting them with a pair of heat rolls, and thermocompression bonding is preferable.
  • the temperature of the heat roll when narrowing using the pair of heat rolls is preferably 70 to 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.
  • the temperature of the hot roll is more preferably 80 to 150 ° C.
  • the rotational speed of the hot roll is preferably 0.1 to 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.
  • the rotational speed of the hot roll is more preferably 0.3 to 5 m / min.
  • the manufacturing method of the flexible solar cell module of the present invention can perform thermocompression bonding in a short time because the adhesive layer of the solar cell encapsulating sheet is made of a specific resin and thus does not require a crosslinking step. it can. Moreover, thermocompression bonding at a low temperature is also possible. For this reason, sufficient adhesion
  • the manufacturing method of the flexible solar cell module of this invention is demonstrated concretely using FIG.
  • the solar cell element A and the solar cell encapsulating sheet B are long and wound in a roll shape.
  • the roll of the solar cell element A and the solar cell encapsulating sheet B is unwound, and the light receiving surface of the solar cell element A and the adhesive layer surface of the solar cell encapsulating sheet B are arranged to face each other.
  • the laminated sheet C is supplied between a pair of rolls D and D heated to a predetermined temperature, and heated and thermocompression bonded while pressing the laminated sheet C in the thickness direction, so that the solar cell element A and the sun
  • the battery sealing sheet B is bonded and integrated. Thereby, the said solar cell element A is sealed with the said solar cell sealing sheet B, and the flexible solar cell module E can be obtained.
  • FIG. 2 the longitudinal cross-sectional schematic diagram of an example of the solar cell element A used in the manufacturing method of the flexible solar cell module of this invention is shown, and the longitudinal cross-sectional schematic diagram of an example of the solar cell sealing sheet B is shown in FIG. .
  • the solar cell element A has a photoelectric conversion layer 2 disposed on a flexible substrate 1.
  • the electrode layer can be arranged in various ways and is omitted here.
  • the solar cell encapsulating sheet B has a fluorine resin sheet 4 and an adhesive layer 3.
  • the adhesive layer 3 may be inside or outside.
  • FIG. 4 the longitudinal cross-sectional schematic diagram of an example of the flexible solar cell module obtained by the manufacturing method of this invention is shown in FIG.
  • the side of the photoelectric conversion layer 2 of the solar cell element A is sealed by the adhesive layer 3 of the solar cell sealing sheet B, so that the solar cell element A and the solar cell sealing sheet B are laminated. It is integrated and the flexible solar cell module E is obtained.
  • the method for producing a flexible solar cell module of the present invention also includes a step of thermocompression bonding the solar cell sealing sheet on the upper surface of the flexible base material of the solar cell element by constricting the solar cell sealing sheet using a pair of heat rolls. It may be.
  • the solar cell element is sealed better and stably over a long period of time. It can be set as the flexible solar cell module which can generate electric power.
  • thermocompression bonding the solar cell sealing sheet to the side surface (back surface) of the flexible substrate is, for example, in the same manner as described above, on the side surface (back surface) of the flexible substrate of the solar cell element. May be arranged such that the adhesive layer faces the flexible substrate and is subjected to thermocompression bonding by narrowing using a pair of heat rolls.
  • the solar cell sealing sheet which consists of an contact bonding layer and a metal plate.
  • the adhesive layer include the same adhesive layer as that of the solar cell encapsulating sheet.
  • the metal plate include a plate made of stainless steel, aluminum or the like. The thickness of the metal plate is preferably 25 to 800 ⁇ m.
  • the flexible substrate side surface (back surface) of the solar cell element is sealed with the adhesive layer and the metal plate, for example, a sheet made of the adhesive layer and the metal plate is formed first, and the same as described above.
  • the flexible substrate and the adhesive layer may be thermocompression bonded to the side surface (back surface) of the flexible substrate of the solar cell element using a sheet made of an adhesive layer and a metal plate.
  • the step of thermocompression bonding the solar cell sealing sheet or the sheet made of the adhesive layer and the metal plate to the flexible substrate side surface (back surface) of the solar cell element includes the step of forming the solar cell on the light receiving surface of the solar cell element. It may be performed before the step of thermocompression bonding the battery sealing sheet, may be performed simultaneously, or may be performed after.
  • FIG. 1 As an example of the method for producing a flexible solar cell of the present invention, an example of a method for simultaneously sealing the photoelectric conversion layer side surface (front surface) and the flexible substrate side surface (back surface) of a solar cell element will be described with reference to FIG. . Specifically, while preparing the elongate solar cell element A wound in roll shape, two elongate solar cell sealing sheets wound in roll shape are prepared. And as shown in FIG.
  • the solar cell encapsulating sheets B and B are overlapped with each other via the solar cell element A to obtain a laminated sheet C.
  • the laminated sheet C is supplied between a pair of rolls D and D heated to a predetermined temperature, and heated while pressing the laminated sheet C in the thickness direction thereof, thereby sealing the solar cell encapsulating sheets B and B.
  • the solar cell elements A are sealed by the solar cell sealing sheets B and B, and the flexible solar cell module F is continuously manufactured.
  • the solar cell encapsulating sheets B and B are overlapped with each other via the solar cell element A to form the laminated sheet C, while simultaneously pressing the laminated sheet C in the thickness direction. You may heat.
  • FIG. 6 an example of the manufacturing point of the flexible solar cell module at the time of using a rectangular thing as a solar cell element is shown in FIG. Specifically, a rectangular sheet-like solar cell element A having a predetermined size is prepared instead of the long solar cell element wound in a roll shape. And as shown in FIG. 6, the long solar cell sealing sheet
  • the laminated sheet C is supplied between a pair of rolls D and D heated to a predetermined temperature, and heated while pressing the laminated sheet C in the thickness direction thereof, thereby sealing the solar cell encapsulating sheets B and B.
  • the solar cell elements A are sealed by the solar cell sealing sheets B and B, and the flexible solar cell module F is continuously manufactured.
  • FIG. 7 is a schematic vertical cross-sectional view of an example of a flexible solar cell module F in which the photoelectric conversion layer 2 side surface and the flexible base material 1 side surface of the solar cell element A are both sealed with the adhesive layer 3 of the solar cell sealing sheet B. It is.
  • the side surface of the photoelectric conversion layer 2 of the solar cell element A is sealed with the adhesive layer 3 of the solar cell encapsulating sheet B, and the flexible substrate side 1 surface is composed of the adhesive layer 3 and the metal plate 5.
  • the manufacturing method of the flexible solar cell module of this invention is characterized by sealing a solar cell element using the solar cell sealing sheet which consists of a specific structure. For this reason, a wrinkle and a curl do not generate
  • the manufacturing method of the flexible solar cell module of this invention consists of the above-mentioned structure, in manufacturing a solar cell module, a solar cell element is continuously sealed and a wrinkle is not required, without requiring a bridge
  • a flexible solar cell module excellent in adhesiveness between the solar cell element and the solar cell encapsulating sheet can be suitably produced by a roll-to-roll method.
  • Examples 1 to 29, Comparative Examples 4, 6, and 7 100 parts by weight of a modified butene resin obtained by graft-modifying a butene-ethylene copolymer having a predetermined amount of butene component content and ethylene component content shown in Tables 1 to 5 with maleic anhydride, and a silane compound Predetermined amounts of 3-glycidoxypropyltrimethoxysilane (made by Toray Dow Corning, trade name “Z-6040”) or 3-acryloxypropyltrimethoxysilane (made by Shin-Etsu Chemical Co., Ltd.) shown in Tables 1 to 5
  • the composition for the adhesive layer having the trade name “KBM-5103”) was supplied to the first extruder and melt-kneaded at 250 ° C.
  • predetermined fluorine-based resins shown in Tables 1 to 5 polyvinylidene fluoride (trade name “Kyner 720” manufactured by Arkema Co., Ltd.)), tetrafluoroethylene-ethylene copolymer (trade name “Neofuron” manufactured by Daikin Industries, Ltd.) ETFE ”), polyvinyl fluoride resin (trade name“ Tedlar ”manufactured by DuPont), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (trade name“ Neofuron PFA ”manufactured by Daikin Industries, Ltd.), ethylene chlorotrifluoro Ethylene resin (made by Solvay, trade name “halar ECTFE”), polychlorotrifluoroethylene resin (made by Daikin Industries, trade name “neoflon PCTFE”), vinylidene fluoride-hexafluoropropylene copolymer (made by Ark
  • the joining layer composition and the fluororesin are supplied and joined to a joining die that connects the first extruder and the second extruder together, and T is connected to the joining die. From the die, it was extruded into a sheet shape so that the thickness of the adhesive layer was 0.3 mm and the thickness of the fluororesin layer was 0.03 mm. In addition, when extruding from a T-die into a sheet shape, the regular uneven shape shown in FIG. 10 is formed on the surface of the fluororesin layer using a cooling roll having the regular uneven surface shown in FIG. did.
  • a solar cell encapsulating sheet having a long, constant width and having an embossed shape on the surface was obtained by laminating and integrating the fluororesin layer on one surface of the adhesive layer made of the above adhesive layer composition.
  • the sheet roll of the solar cell encapsulating sheet may be either on the inner side or on the outer side.
  • FIG. 11 the arrangement
  • Tables 1 to 5 show the melt flow rate (MFR) of the modified butene resin used and the maximum peak temperature (Tm) of the endothermic curve measured by differential scanning calorimetry. The total maleic anhydride content in the modified butene resin is shown in Tables 1-5.
  • the flexible solar cell module was produced in the following ways using the solar cell sealing sheet obtained above.
  • a solar cell in the form of a rectangular sheet, in which a photoelectric conversion layer made of thin amorphous silicon is formed on a flexible base material made of a flexible polyimide film.
  • the long solar cell encapsulating sheets B and B wound in a roll shape are unwound and the solar cell encapsulated with the respective adhesive layers facing each other.
  • the solar cell element A was supplied between the stop sheets B and B, and the solar cell sealing sheets B and B were overlapped with each other through the solar cell element A to obtain a laminated sheet C.
  • the laminated sheet C is supplied between a pair of rolls D and D heated to the temperatures shown in Tables 1 to 5, and heated while pressing the laminated sheet C in the thickness direction thereof. Sealing sheets B and B were bonded and integrated to seal solar cell element A, and flexible solar cell module F was manufactured.
  • a low density polyethylene (Comparative Example 1) or a modified polyethylene graft modified with maleic anhydride (Comparative Example 2) is used, and the silane compound and the fluorine resin shown in Table 5 are used.
  • a flexible solar cell module was obtained in the same manner as in Example 1 except that the obtained solar cell encapsulating sheet was used and encapsulated at the roll temperature shown in Table 5.
  • Example 3 A flexible solar cell in the same manner as in Example 1 except that EVA was used in place of the modified butene-based resin and the solar cell encapsulating sheet obtained using the silane compound and fluorine-based resin shown in Table 5 was used. Got a module.
  • the resulting flexible solar cell module was evaluated for wrinkle generation, curl generation, peel strength, high temperature and high humidity durability, and emboss shape retention in the following manner, and the results are shown in Tables 1-5. It was. In Comparative Examples 1 to 3, evaluation of high temperature and high humidity durability and emboss shape retention was not performed because the requirements as a solar cell element were not satisfied. Further, in Comparative Examples 4 and 5, the peel strength was not sufficiently obtained and the requirements as a solar cell element were not satisfied, so the high temperature and high humidity durability evaluation was not performed.
  • the flexible solar cell module having a size of 500 mm ⁇ 500 mm was placed on a flat plane, and the height of lifting from the horizontal plane at the end was measured.
  • Examples 30 to 34 100 parts by weight of a modified butene resin obtained by graft-modifying a butene-ethylene copolymer having a predetermined amount of butene component content and ethylene component content shown in Table 6 with maleic anhydride; 3-glycidoxypropyltrimethoxysilane (trade name “Z-6040” manufactured by Toray Dow Corning Co., Ltd.), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (Toray Dow Corning, trade name “Z6043”), 3-glycidoxypropyltriethoxysilane (Shin-Etsu Silicone, trade name “KBE-403”), 3-glycidoxypropylmethyldimethoxysilane (Shin-Etsu Silicone, Trade name “KBM-402”) or 3-glycidoxypropylmethyldiethoxysilane (Shin-Etsu Silicone) Ltd., except for using the adhesive layer composition comprising the
  • Examples 35 to 39, Comparative Examples 9 to 11 100 parts by weight of a modified ⁇ -olefin resin obtained by graft-modifying an ⁇ -olefin-ethylene copolymer having a predetermined amount of ⁇ -olefin component content and ethylene component content shown in Table 7 with maleic anhydride; Except that a composition for an adhesive layer composed of a predetermined amount of 3-glycidoxypropyltrimethoxysilane (trade name “Z-6040” manufactured by Toray Dow Corning Co., Ltd.) shown in Table 7 as a silane compound was used. In the same manner as in Example 1, a flexible solar cell module was obtained and evaluated. The results are shown in Table 7.
  • Examples 40 and 41 90 parts by weight of a modified butene resin obtained by graft-modifying a butene-ethylene copolymer having a predetermined amount of butene component content and ethylene component content shown in Table 8 with maleic anhydride, and low-density polyethylene (Asahi Kasei) Chemicals, trade name “L1780”) or linear low-density polyethylene copolymer (ethylene-1-butene copolymer having an ethylene component amount of 84 wt% and a 1-butene component amount of 16 wt%), Example 1 except that a composition for an adhesive layer comprising 0.5 part by weight of 3-glycidoxypropyltrimethoxysilane (trade name “Z-6040” manufactured by Toray Dow Corning Co., Ltd.) was used as the silane compound. In the same manner as above, a flexible solar cell module was obtained and evaluated. The results are shown in Table 8.
  • a flexible solar cell module excellent in adhesion between the solar cell element and the solar cell encapsulating sheet is suitably formed by a roll-to-roll method without causing wrinkles or curling. Can be manufactured.

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  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
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Abstract

L'invention concerne un procédé pour produire un module de photopile souple permettant d'étanchéifier de manière continue un élément photopile sans qu'une étape de réticulation soit nécessaire et de produire de manière avantageuse au moyen d'un processus d'impression par rotative "roll-to-roll" un module de photopile souple sans pli, ni frisure qui présente de meilleures propriétés adhésives entre l'élément photopile et une feuille d'étanchéité de photopile. Le procédé de production d'un module de photopile souple comprend une étape faisant intervenir une paire de cylindres chauds en tant que moyens de constriction pour le soudage par thermocompression d'une feuille d'étanchéité de photopile sur au moins une surface de réception de lumière de l'élément photopile, une couche de conversion photoélectrique étant déposée sur un substrat souple. La feuille d'étanchéité de photopile comporte une couche d'adhérence comprenant une résine d'oléfine modifiée par un anhydride maléique. Un copolymère α-oléfine-éthylène dont la quantité d'α-oléfine est comprise entre 1 et 25 % en poids est modifié par greffe par l'anhydride maléique, et la quantité totale d'anhydride maléique est comprise entre 0.1 et 3 % en poids.
PCT/JP2011/071274 2010-10-06 2011-09-16 Procédé pour produire un module de photopile souple WO2012046565A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015001951A1 (fr) * 2013-07-05 2015-01-08 東レ株式会社 Substrat protecteur côté inférieur, module de photopile et procédé de production d'un module de photopile

Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2001326374A (ja) * 2000-05-16 2001-11-22 Dainippon Printing Co Ltd 太陽電池モジュ−ル
WO2004055908A1 (fr) * 2002-12-16 2004-07-01 Dai Nippon Printing Co., Ltd. Couche de remplissage pour module solaire et module solaire comprenant celle-ci
WO2007088892A1 (fr) * 2006-02-02 2007-08-09 Mitsui Chemicals, Inc. Substrat protecteur arriere destine a un module de cellules solaires, module de cellules solaires et generateur d'electricite

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001326374A (ja) * 2000-05-16 2001-11-22 Dainippon Printing Co Ltd 太陽電池モジュ−ル
WO2004055908A1 (fr) * 2002-12-16 2004-07-01 Dai Nippon Printing Co., Ltd. Couche de remplissage pour module solaire et module solaire comprenant celle-ci
WO2007088892A1 (fr) * 2006-02-02 2007-08-09 Mitsui Chemicals, Inc. Substrat protecteur arriere destine a un module de cellules solaires, module de cellules solaires et generateur d'electricite

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015001951A1 (fr) * 2013-07-05 2015-01-08 東レ株式会社 Substrat protecteur côté inférieur, module de photopile et procédé de production d'un module de photopile

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