WO2013084849A1 - Module de cellule solaire - Google Patents

Module de cellule solaire Download PDF

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Publication number
WO2013084849A1
WO2013084849A1 PCT/JP2012/081300 JP2012081300W WO2013084849A1 WO 2013084849 A1 WO2013084849 A1 WO 2013084849A1 JP 2012081300 W JP2012081300 W JP 2012081300W WO 2013084849 A1 WO2013084849 A1 WO 2013084849A1
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WIPO (PCT)
Prior art keywords
sealing material
solar cell
cell module
sheet
material sheet
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PCT/JP2012/081300
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English (en)
Japanese (ja)
Inventor
吉原　俊夫
石飛　達郎
秀紀 浅井
将 門脇
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大日本印刷株式会社
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Publication of WO2013084849A1 publication Critical patent/WO2013084849A1/fr

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    • 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
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • 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 solar cell module.
  • a solar cell module has a configuration in which a transparent front substrate, a solar cell element, and a back surface protection sheet are laminated via a sealing material sheet.
  • the solar cell module 1 includes a transparent front substrate 2, a front sealing material layer 3, a solar cell element 4, a back sealing material layer 5, and a back surface protection sheet from the light receiving surface side of incident light. 6 are laminated in order, and the front sealing material layer 3 is disposed on the light receiving surface side of the solar cell element 4 and the back sealing material layer 5 is disposed on the back surface side of the solar cell element 4 so as to sandwich the solar cell element 4.
  • a transparent front substrate 2 As illustrated in FIG. 1, the solar cell module 1 includes a transparent front substrate 2, a front sealing material layer 3, a solar cell element 4, a back sealing material layer 5, and a back surface protection sheet from the light receiving surface side of incident light. 6 are laminated in order, and the front sealing material layer 3 is disposed on the light receiving surface side of the solar cell element 4 and the back sealing material layer 5 is disposed on the back surface side of the solar cell element 4 so as to sandwich the solar cell element 4.
  • the front sealing material layer 3 is disposed on the light receiving surface side of the solar cell element 4
  • the encapsulant sheet constituting the encapsulant layer a configuration mainly containing EVA (ethylene-vinyl acetate copolymer) and a crosslinking agent is known from the viewpoint of transparency and fluidity. (See Patent Document 1).
  • EVA ethylene-vinyl acetate copolymer
  • a crosslinking agent is known from the viewpoint of transparency and fluidity.
  • the above composition is molded without being cross-linked, and is cross-linked by heating or the like in a modularization step or a subsequent step.
  • PBR propylene-butene copolymer
  • EBR ethylene-butene copolymer
  • EPR ethylene-butene copolymer
  • a configuration containing (ethylene-propylene copolymer) and the like and a crosslinking agent is known (see Patent Document 2).
  • Patent Document 1 has the advantage of being excellent in transparency and fluidity, but has the basic drawback of poor water vapor barrier properties.
  • Patent Document 2 although the water vapor barrier property is improved by using a low crystalline olefin polymer such as PBR as a base, it has a defect that it is also inferior in transparency compared to EVA.
  • the present invention has been made to solve the above-mentioned problems, and the object thereof is excellent in light transmittance when considered as a module, and also has excellent olefinic characteristics such as water vapor barrier properties and insulating properties.
  • the object is to provide a solar cell module.
  • the present inventors include the front sealing material layer 3 disposed on the light receiving surface side of the solar cell element 4 and the back sealing material layer 5 disposed on the back surface side of the solar cell element 4. Attention was paid to the difference in the required physical properties of the sealing material sheet. Specifically, transparency is important as the front sealing material layer 3 disposed on the light receiving surface side, while the back sealing material layer 5 disposed on the back surface side is more transparent than Rather, water vapor barrier properties and insulation properties are required. In particular, in the so-called back contact method that is often used in recent years, since all or most of the electrodes are disposed on the back surface in order to improve power generation efficiency, high insulation on the back surface side is particularly required.
  • both the front sealing material layer 3 and the back sealing material layer 5 are not necessarily made of the same material.
  • both layers are integrated by vacuum lamination, both layers are required to have high adhesion. From such a point of view, it is found that the above problems can be solved by using a predetermined EVA resin as the front sealing material layer and a predetermined polyethylene resin as the back sealing material layer, and to complete the present invention. It came. More specifically, the present invention provides the following.
  • a solar cell element a first sealing material sheet disposed on the light receiving surface side of the solar cell element, and a second sealing material sheet disposed on the back surface side of the solar cell element
  • the first sealing material sheet is an ethylene-vinyl acetate copolymer resin
  • the second sealing material sheet is a polyethylene resin having a density of 0.940 g / cm 3 or less.
  • the sealing material layer taking advantage of both the transparency of the EVA resin and the water vapor barrier property and insulating property of the polyethylene resin, and the adhesion between the sealing material layers. It is possible to provide an excellent solar cell module.
  • the solar cell module of the present invention is mainly characterized by the material structure of the sealing material layer.
  • the overall configuration of the solar cell module and the manufacturing method thereof will be described, the solar cell module encapsulant sheet constituting the encapsulant layer will be described in detail, and other components will be described.
  • FIG. 1 is a cross-sectional view showing an example of the layer structure of a solar cell module 1 according to an embodiment of the present invention.
  • a transparent front substrate 2 a front sealing material layer 3, a solar cell element 4, a back sealing material layer 5, and a back surface protection sheet 6 are sequentially laminated from the light receiving surface side of incident light.
  • the solar cell element means a minimum structural unit that generates light by receiving light by a photoconductive effect and / or a photovoltaic effect, and has a size of 10 cm ⁇ 10 cm square to 20 cm ⁇ 20 cm square, for example. Things.
  • the solar cell module refers to a configuration in which a plurality of solar cell elements are connected. For example, about 10 to 50 solar cell elements connected to each other have a size of 0.5 m ⁇ 0.5 m square to 2. The thing about 0 m x 2.0 m square can be mentioned.
  • the solar cell module includes a solar cell panel that is an assembly of modules.
  • the solar cell module 1 uses a first sealing material sheet made of an ethylene-vinyl acetate copolymer resin having a gel fraction within a predetermined range as the front sealing material layer 3, and the back surface As the sealing material layer 5, a second sealing material sheet made of a polyethylene resin having a density within a predetermined low density range is used.
  • the first encapsulant sheet is composed mainly of an ethylene-vinyl acetate copolymer resin, and has particularly excellent light transmittance while maintaining necessary flexibility and adhesion.
  • the main resin is a polyethylene resin having a density of 0.940 g / cm 3 or less, and particularly excellent water vapor barrier properties and insulation properties while maintaining necessary flexibility and adhesion.
  • the solar cell module 1 uses the above-described encapsulant sheets having different physical properties in each layer in the solar cell module, and optimally arranges them by taking advantage of their characteristics to transmit light as a solar cell module. Characteristics, water vapor barrier properties, and insulating properties of the encapsulant layer are simultaneously increased to a preferable range. In addition, the detail of each of a 1st sealing material sheet and a 2nd sealing material sheet is mentioned later.
  • the transparent front substrate 2 and the back surface protective sheet 6 which are members other than the front surface sealing material layer 3 and the back surface sealing material layer 5
  • conventionally known materials can be used without particular limitation.
  • the solar cell module 1 of this invention may also contain members other than the said member.
  • the solar cell element 4 is not particularly limited, but is not limited to a crystalline silicon solar cell manufactured using a single crystal silicon substrate or a polycrystalline silicon substrate, and amorphous silicon, microcrystalline silicon, a chalcopyrite compound, or the like is used.
  • the thin-film solar cell (CIGS) is preferably used, and the configuration of the solar cell module is not only the conventional front contact type but also the back contact type in which a plurality of electrodes having different polarities are provided on the non-light-receiving surface side.
  • the solar cell element can be preferably used.
  • a back contact type solar cell element such as a metal wrap through (MWT) method or an emitter wrap through (EWT) method can be used particularly preferably.
  • MTT metal wrap through
  • EWT emitter wrap through
  • the solar cell module 1 uses a second sealing material sheet made of a highly insulating polyethylene-based resin as the back surface sealing material layer 5 in contact with the non-light-receiving surface side of the solar cell element 4, the solar cell element A back contact type solar cell element can be particularly preferably used as 4.
  • a sealing material sheet for solar cell module
  • the sheet is formed into a sheet or film by molding using various molding methods such as injection molding, extrusion molding, hollow molding, compression molding, and rotational molding, which are usually used in plastic resins.
  • the sheet form in this invention means the film form, and there is no difference in both.
  • the first sealing material sheet used as the front sealing material layer 3 contains ethylene-vinyl acetate copolymer resin (EVA) and a crosslinking agent as essential components, and further contains a crosslinking aid and other components as necessary. It consists of the 1st sealing material composition to contain.
  • a 1st sealing material sheet can be obtained by forming this 1st sealing material composition into a film by the above-mentioned shaping
  • the film forming temperature may be 90 ° C. to 120 ° C.
  • the cross-linking may be completed by heating at a high temperature of 150 to 250 ° C. at the time of manufacturing the solar cell module, or the cross-linking may be completed by further performing a curing process by heat treatment after modularization.
  • the first encapsulant sheet has a gel fraction of 60% or more after completion of the crosslinking after being integrated as the solar cell module 1.
  • the gel fraction is preferably 80% or more. By setting the gel fraction to 80% or more, preferable heat resistance at 100 ° C. or more and 150 ° C. or less can be obtained.
  • the gel fraction (%) means that 0.1 g of a sealing material sheet is put in a resin mesh, extracted with 60 ° C. toluene for 4 hours, taken out together with the resin mesh, weighed after drying, and mass before and after extraction. Comparison is made to measure the mass% of the remaining insoluble matter, and this is used as the gel fraction.
  • the thickness of the first sealing material sheet is preferably 100 ⁇ m or more and 600 ⁇ m or less, and more preferably 300 ⁇ m or more and 550 ⁇ m or less. If the thickness is less than 100 ⁇ m, the impact cannot be sufficiently reduced. Moreover, even if it exceeds 600 micrometers, since the effect beyond it is not acquired and it is uneconomical, it is unpreferable.
  • the color of the first encapsulant sheet must be transparent. More specifically, the haze value at a thickness of 400 ⁇ m at the time of integration as the solar cell module 1 is preferably 10% or less, more preferably 5% or less. Thus, by increasing the transparency on the daylighting surface side, it is possible to contribute to the improvement of the power generation efficiency of the solar cell module.
  • EVA used as the main resin of the first encapsulant composition that is the material of the first encapsulant sheet
  • the gel at the time when the solar cell module 1 is integrated is used. What is necessary is just to be able to make the fraction 60% or more, preferably 80% or more.
  • the vinyl acetate content (VA content) is preferably 24% by mass or more and 35% by mass or less.
  • the melt mass flow rate (MFR) of EVA is preferably 1 g / 10 min or more and 40 g / 10 min or less, more preferably 15 g / 10 min or more and 40 g / 10 min or less, at 190 ° C. in JIS K7210 method.
  • the Vicat softening point of JIS K7206 is preferably in the range of 30 ° C to 40 ° C. When the MFR and softening point are within the above ranges, the resin is excellent in the property of being melted by heating, uniformly fluidized with the additive, and deformed to a constant shape until cooling.
  • the first sealing material composition contains a crosslinking agent.
  • a crosslinking agent A well-known thing can be used for a crosslinking agent, It does not specifically limit,
  • a well-known radical polymerization initiator can be used.
  • radical polymerization initiators include hydroperoxides such as diisopropylbenzene hydroperoxide and 2,5-dimethyl-2,5-di (hydroperoxy) hexane; di-t-butyl peroxide, t-butyl Cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-peroxy) hexyne-3, etc.
  • Dialkyl peroxides such as bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide, 2,4-dichlorobenzoyl peroxide; t-butyl peroxyacetate, t-butyl pero Ci-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyoctoate, t-butyl peroxyisopropyl carbonate, t-butyl peroxybenzoate, di-t-butyl peroxyphthalate, 2 , 5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexyne-3, t-butylperoxy-2-ethylhexyl carbonate
  • Oxyesters organic peroxides such as methyl peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, or azo compounds such as azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile), dibutyltin Diacetate, dibutyltin dilaurate It can be mentioned dibutyltin dioctoate, dioctyltin dilaurate, dicumyl peroxide, such a silanol condensation catalyst. These may be used alone or in combination of two or more.
  • the fast curing method in the vacuum heating lamination process of solar cell module fabrication (the sealing material is highly crosslinked only by vacuum heating lamination, and is allowed to stand at about 150 to 160 ° C. for 30 minutes to 1 hour to post-crosslink the sealing material.
  • T-butylperoxy-2-ethylhexyl carbonate (TBEC) is preferably used from the viewpoint of adapting to the method of omitting the curing step.
  • the 10-hour half-life temperature of the crosslinking agent is preferably an organic peroxide of 100 ° C. to 120 ° C. from the upper limit of the resin temperature at which the crosslinking reaction does not start in the extruder.
  • the content of the crosslinking agent is preferably contained in the first sealing material composition by 0.5% by mass or more and 1.0% by mass or less. If it is less than 0.5% by mass, the heat resistance at high temperature is inferior due to insufficient crosslinking, which is not preferable.
  • the first sealing material composition may further contain a crosslinking aid.
  • a polyfunctional monomer having a carbon-carbon double bond and / or an epoxy group can be preferably used, and an allyl group, a (meth) acrylate group or a vinyl group can be preferably used as the functional group of the polyfunctional monomer. This promotes an appropriate crosslinking reaction.
  • crosslinking aids include polyallyl compounds such as triallyl isocyanurate (TAIC), triallyl cyanurate, diallyl phthalate, diallyl fumarate, diallyl maleate, 4-hydroxybutyl acrylate glycidyl ether and two epoxy groups.
  • TAIC triallyl isocyanurate
  • Examples thereof include epoxy compounds such as 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, and trimethylolpropane polyglycidyl ether. These may be used alone or in combination of two or more.
  • triallyl isocyanurate can be preferably used because it has a relatively slow reaction rate and a low shrinkage rate due to the reaction.
  • Trimethylolpropane trimethacrylate (TMPT), trimethylolpropane triacrylate (TMPTA), ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1, Poly (meth) acryloxy compounds such as 9-nonanediol diacrylate, glycidyl methacrylate containing a double bond and an epoxy group, and the like are not preferred because of their high reaction rate.
  • the content of the crosslinking aid is preferably included in the first sealing material composition in the range of 0.5% by mass to 1.0% by mass. If it is less than 0.5% by mass, the heat resistance at high temperature is inferior due to insufficient crosslinking, and the crosslinking time becomes long and cannot be fast cured. If it exceeds 1.0% by mass, crosslinking is promoted by the annealing treatment described later, and the flexibility of the sealing material is lowered, which is not preferable.
  • radical absorbent By using the above-mentioned cross-linking agent as a radical polymerization initiator in combination with the first sealing material composition and the radical absorbent for quenching it, the degree of cross-linking is adjusted to further adjust the gel fraction. May be.
  • radical absorbents include hindered phenol-based antioxidants, hindered amine-based weather resistance stabilization, and the like.
  • a hindered phenol-based radical absorbent having a high radical absorbing ability near the crosslinking temperature is preferred.
  • the content of the radical absorbent is preferably included in the first sealing material composition in the range of 0.01% by mass to 3% by mass, more preferably in the range of 0.05% by mass to 2.0% by mass. It is. If it exists in this range, a crosslinking reaction can be suppressed moderately.
  • the first sealing material composition can further contain other components.
  • components such as a weather resistance masterbatch for imparting weather resistance to the first sealing material sheet, various fillers, a light stabilizer, an ultraviolet absorber, and a heat stabilizer are exemplified. These contents vary depending on the particle shape, density, and the like, but are preferably in the range of 0.001% by mass to 5% by mass in the solar cell module encapsulant composition. By including these additives, it is possible to impart a long-term stable mechanical strength, an effect of preventing yellowing, cracking, and the like to the encapsulant composition for solar cell modules.
  • a weatherproof masterbatch is a dispersion of a light stabilizer, ultraviolet absorber, heat stabilizer, and the above-mentioned antioxidants in a resin such as EVA, and this is added to the first sealing material composition By doing, favorable weather resistance can be provided to a 1st sealing material sheet.
  • the weatherproof masterbatch may be prepared and used as appropriate, or a commercially available product may be used.
  • resin used for a weatherproof masterbatch EVA used for a 1st sealing material sheet may be sufficient, and other resin may be sufficient.
  • These light stabilizers, ultraviolet absorbers, heat stabilizers and antioxidants can be used alone or in combination of two or more.
  • an adhesion improver such as a silane coupling agent, a nucleating agent, a dispersing agent, a leveling agent, a plasticizer, an antifoaming agent, a flame retardant Etc.
  • the second sealing material sheet used as the back sealing material layer 5 includes a low density polyethylene-based resin as a main resin, and further contains a crosslinking agent, a crosslinking aid, and other components as necessary. It consists of a material composition.
  • a 2nd sealing material sheet can be obtained by shape
  • the density of the second sealing material sheet is 0.940 g / cm 3 or less, preferably in the range of 0.900 g / cm 3 or less, more preferably in the range of 0.870 to 0.890 g / cm 3. .
  • the low density polyethylene may be a single type of resin or may be composed of a sealing material composition in which a plurality of polyethylene resins are combined.
  • the second sealing material sheet has preferable flexibility and transparency in addition to high water vapor barrier properties and high insulation properties. Can be.
  • the second encapsulant sheet may be a cross-linked encapsulant sheet by a crosslinking treatment.
  • the molding temperature may be set to a high temperature of 150 to 250 ° C. so that a crosslinked sheet is formed at the end of molding, and the molding temperature is set to a low temperature of, for example, 90 ° C. to 100 ° C. Then, crosslinking may be completed by heating at a high temperature at the time of manufacturing the solar cell module.
  • the uncrosslinked encapsulant sheet may be a cross-linked encapsulant sheet by a crosslinking treatment with ionizing radiation.
  • individual crosslinking conditions are not particularly limited, and may be appropriately set so that the gel fraction is in the following range as a total treatment result.
  • it can be performed by ionizing radiation such as electron beam (EB), ⁇ -ray, ⁇ -ray, ⁇ -ray, neutron beam, etc.
  • EB electron beam
  • the acceleration voltage in electron beam irradiation is determined by the thickness of the sheet that is the object to be irradiated, and the thicker the sheet, the larger the acceleration voltage is required.
  • a 0.5 mm-thick sheet is irradiated with 100 kV or more, preferably 200 kV or more.
  • the irradiation dose is in the range of 1-100 Mrad, preferably 1-30 Mrad. When the irradiation dose is less than 1 Mrad, sufficient crosslinking is not performed, and when it exceeds 50 Mrad, there is a concern about deformation or coloring of the sheet due to generated heat. In addition, you may irradiate from both sides. Irradiation may be in an air atmosphere or a nitrogen atmosphere.
  • the second encapsulant sheet preferably has a gel fraction of 0% or more and 90% or less, more preferably 0% or more and 70% or less, in a state of being integrated as the solar cell module 1.
  • a gel fraction of 0% or more and 90% or less, more preferably 0% or more and 70% or less, in a state of being integrated as the solar cell module 1.
  • the gel fraction is 90% or less, high elasticity can be obtained particularly in a low temperature range from 0 ° C. to 70 ° C.
  • the gel fraction is 70% or more, the fluidity is insufficient at the time of vacuum heating lamination for integration as a solar cell module, and the function of filling an undesired gap space is not sufficiently exhibited.
  • the gel fraction is more preferably 70% or more.
  • the gel fraction of the 2nd sealing material sheet at the time of integrating as the solar cell module 1 is smaller than the gel fraction of the 1st sealing material sheet.
  • the front sealing material layer 3 closer to the light receiving surface side of incident light is more sunlight in the daytime than the back sealing material layer 5 far from the light receiving surface side.
  • the expansion coefficient due to the temperature rise associated with the irradiation is increased.
  • the solar cell element 4 undergoes deformation such as warping due to the difference in stress. May occur.
  • the first sealing material sheet and the first sealing material sheet It can be realized by appropriately adjusting the crosslinking conditions such as the crosslinking temperature of the two encapsulant sheets and the content of the crosslinking agent in the encapsulant composition.
  • the solar cell module 1 in which the gel fraction of each sealing material is adjusted to the above-described preferable relative range can be particularly preferably used as a solar cell module including a thin-film solar cell element.
  • the solar cell module 1 in which the second sealing material sheet is disposed as the back surface sealing material layer 5 can be particularly preferably used as a solar cell module including a back contact type solar cell element in which an electrode is disposed on the back surface side. .
  • the thickness of the second sealing material sheet is preferably not less than 100 ⁇ m and not more than 600 ⁇ m, and if it is less than 100 ⁇ m, the impact cannot be sufficiently mitigated, and the insulating property becomes insufficient, which is not preferable. Further, if the thickness exceeds 600 ⁇ m, no further effect can be obtained, and it becomes difficult to form a pattern of a conductive portion for collecting current from a back contact type solar cell element.
  • the second sealing material sheet preferably has a polystyrene-reduced weight average molecular weight of low density polyethylene as a main resin that is 100,000 g / mol or more and 300,000 g / mol or less.
  • a polystyrene-reduced weight average molecular weight of low density polyethylene as a main resin that is 100,000 g / mol or more and 300,000 g / mol or less.
  • the weight average molecular weight can be measured by a conventionally known GPC method after dissolving in a solvent such as THF.
  • the color of the second sealing material sheet is not particularly limited.
  • the material resin is not particularly colored and may remain colorless and transparent or translucent, or may be colored in any color. For example, by coloring to a color having a high light reflectance such as white, it is possible to reflect incident light and contribute to improving the power generation efficiency of the solar cell module, and by coloring to white or black, The designability of the solar cell module 1 can also be improved.
  • Low density polyethylene As the main resin of the second sealing material composition which is a material of the second sealing material sheet, low density polyethylene (LDPE) having a density of 0.940 or less, preferably linear low density polyethylene (LLDPE) is used.
  • Linear low density polyethylene is a copolymer of ethylene and ⁇ - olefin, in the present invention, within the scope thereof density of 0.940 g / cm 3 or less, preferably 0.900 g / cm 3 within the following ranges More preferably, it is in the range of 0.870 to 0.890 g / cm 3 .
  • metallocene linear low density polyethylene is synthesized using a metallocene catalyst which is a single site catalyst.
  • metallocene catalyst which is a single site catalyst.
  • Such polyethylene has few side chain branches and a uniform comonomer distribution. For this reason, molecular weight distribution is narrow, it is possible to make it the above ultra-low density, and a softness
  • an ⁇ -olefin having no branch is preferably used as the ⁇ -olefin of the linear low density polyethylene.
  • 1-octene is particularly preferably used.
  • the ⁇ -olefin has 6 or more and 8 or less carbon atoms, the second sealing material sheet can be given good flexibility and good strength. As a result, the adhesiveness between the second sealing material sheet and the back surface protective sheet 6 is further increased, and the above problem of moisture intrusion can be further suppressed.
  • the Shore D hardness of the low density polyethylene is preferably 80 degrees or less, preferably 15 degrees or more and 40 degrees or less, and more preferably 15 degrees or more and 35 degrees or less. When the Shore D hardness of the linear low density polyethylene is in the above range, the flexibility of the second sealing material sheet can be maintained.
  • the MFR of the linear low density polyethylene is preferably from 0.5 g / 10 min to 40 g / 10 min at 190 ° C., more preferably from 2 g / 10 min to 40 g / 10 min. When the MFR is in the above range, the processability during film formation is excellent.
  • the second sealing material composition may further contain a silane-modified polyethylene resin.
  • the silane-modified polyethylene resin is obtained by graft-polymerizing an ethylenically unsaturated silane compound as a side chain to linear low-density polyethylene (LLDPE) or the like as a main chain. Since such a graft copolymer has a high degree of freedom of silanol groups that contribute to the adhesive force, the adhesion of the sealing material to other members in the solar cell module can be improved.
  • the silane-modified polyethylene resin can be produced, for example, by the method described in JP-A-2003-46105.
  • the resin By using the resin as a component of a sealing material composition for a solar cell module, strength and durability can be increased.
  • it has excellent weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, yield resistance, and other characteristics, and is also affected by manufacturing conditions such as thermocompression bonding for manufacturing solar cell modules. Therefore, it is possible to manufacture solar cell modules having extremely excellent heat-fusibility, stably and at low cost, and suitable for various applications.
  • Examples of ethylenically unsaturated silane compounds to be graft polymerized with linear low density polyethylene include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltripentyloxysilane , One or more selected from vinyltriphenoxysilane, vinyltribenzyloxysilane, vinyltrimethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, and vinyltricarboxysilane be able to.
  • the graft amount which is the content of the ethylenically unsaturated silane compound, is, for example, 0.001 to 15 mass with respect to a total of 100 mass parts of all resin components in the sealing material composition containing other polyethylene-based resin described later. What is necessary is just to adjust suitably so that it may become a% grade, Preferably, it is 0.01 mass% or more and about 5 mass% grade, Most preferably, it is 0.05 mass% or more and about 2 mass%.
  • the content of the ethylenically unsaturated silane compound is large, the mechanical strength and heat resistance are excellent. However, when the content is excessive, the tensile elongation and heat-fusibility tend to be inferior.
  • the second sealing material composition may further contain an acid-modified polyethylene resin typified by maleic anhydride modification.
  • the acid-modified polyethylene resin is obtained, for example, by graft polymerization using, for example, maleic anhydride or the like as a side chain on linear low density polyethylene (LLDPE) or the like as a main chain.
  • LLDPE linear low density polyethylene
  • Such a graft polymer has a high polarity of the acid part which contributes to adhesive force, and can improve the adhesiveness of the sealing material sheet to the metal member in the solar cell module.
  • the content of the linear low-density polyethylene having a density of 0.940 g / cm 3 or less contained in the second sealing material composition is preferably 10% by mass or more and 99% by mass or less, more preferably in the composition. It is 50 mass% or more and 99 mass% or less, More preferably, it is 90 mass% or more and 99 mass% or less.
  • other resin may be included. These may be used, for example, as an additive resin, and can be used for masterbatching other components described later.
  • the second encapsulant composition may contain a cross-linking agent as necessary, whereby the second encapsulant sheet may be a cross-linked encapsulant sheet.
  • the same crosslinking agent as that of the first sealing material composition can be used and is not particularly limited. Specific examples include various organic peroxides, azo compounds, silanol condensation catalysts, and the like. These may be used alone or in combination of two or more.
  • the content thereof is preferably contained in the second sealing material composition in an amount of 0.01% by mass to 2% by mass, more preferably 0.05% by mass to 1.5% by mass.
  • the range is as follows. If it exists in this range, a crosslinking reaction can be suppressed moderately.
  • the second sealing material composition may contain a crosslinking assistant.
  • a crosslinking aid a polyfunctional vinyl monomer and / or a polyfunctional epoxy monomer can be preferably used. This promotes an appropriate crosslinking reaction so that the gel fraction is 90% or less.
  • the agent reduces the crystallinity of the linear low density polyethylene and maintains transparency. Thereby, a 2nd sealing material sheet can be made into the sealing material sheet which is more excellent in transparency and low temperature flexibility.
  • the crosslinking aid can be the same as the first sealing material composition and is not particularly limited.
  • polyallyl compounds such as triallyl isocyanurate (TAIC) that can be used in the first sealing material composition, trimethylolpropane trimethacrylate (TMPT), trimethylolpropane triacrylate (TMPTA), Poly (meth) acryloxy compounds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, double bonds and epoxy
  • An azo compound such as glycidyl methacrylate containing a group, a silanol condensation catalyst, or the like can also be used. These may be used alone or in combination of two or more.
  • TAIC is preferably used from the viewpoint of good compatibility with low density polyethylene, lowering crystallinity by crosslinking, maintaining transparency, and imparting flexibility at low temperatures.
  • the content thereof is preferably included in the second sealing material composition in an amount of 0.01% by mass to 3% by mass, and more preferably 0.05% by mass to 2.0% by mass. % Or less. Within this range, an appropriate crosslinking reaction can be promoted to make the gel fraction 90% or less.
  • the degree of cross-linking is obtained by using the above-mentioned cross-linking auxiliary agent serving as a radical polymerization initiator and the radical absorbent for quenching it in combination. To adjust the gel fraction more finely.
  • the same thing as what can be used for a 1st sealing material composition can be used in the same content range. If it is in the range, a crosslinking reaction can be moderately suppressed.
  • the second sealing material composition can contain other components such as a weather-resistant masterbatch.
  • a weather-resistant masterbatch about the kind of other component which can be used for a 2nd sealing material composition, content, and the effect by those components, it is the same as that of the case of a 1st sealing material composition.
  • a weatherproof masterbatch it may produce suitably and may use it and a commercial item may be used.
  • the resin used for the weatherproof masterbatch may be a linear low density polyethylene used in the present invention, or other resin.
  • the solar cell module 1 includes, for example, the transparent front substrate 2, the front sealing material layer 3 made of the first sealing material sheet, the solar cell element 4, the back sealing material layer 5 made of the second sealing material sheet, And the member which consists of a back surface protection sheet 6 is laminated
  • the solar cell module 1 is obtained by forming a first encapsulant composition on each of the front surface side and the back surface side of the solar cell element 4 by a molding method usually used in a normal thermoplastic resin, for example, T-die extrusion molding.
  • the second sealing material composition are melt-laminated to sandwich the solar cell element 4 with the front sealing material layer 3 and the back sealing material layer 5, and then the transparent front substrate 2 and the back surface protection sheet 6 are sequentially stacked. Then, they may be manufactured by a method in which these are integrated by vacuum suction or the like and thermocompression bonded.
  • encapsulant sheets having different main vinyl resins as the vinyl acetate content are formed, and the encapsulant sheets are respectively formed.
  • EVA1 Sealing material sheet EVA1 was created using the sealing material composition mix
  • a sealing material sheet EVA2 was prepared using a sealing material composition formulated as follows. For 100 parts by mass of EVA (vinyl acetate content 33%, manufactured by Mitsui DuPont Polychemical, trade name EVAFLEX / EV150 grade) A sealing material composition in which a UV absorber and a weathering stabilizer are blended at the same blending ratio (parts by mass) as the EVA1 sealing material composition is molded under the same conditions as EVA1, and the sealing is 400 ⁇ m in thickness. A material sheet EVA2 was produced. The gel fraction was 0%.
  • an uncrosslinked encapsulant sheet (encapsulant sheets LLDPE 1 and 2) from an encapsulant composition containing a low-density polyethylene resin having a different composition as the main resin as follows.
  • the encapsulant sheet LLDPE2 is subjected to crosslinking treatment by irradiation with ionizing radiation under different crosslinking conditions (described as “EB irradiation” in Table 1), and each crosslinked encapsulant sheet ( Sealing material sheets LLDPE 3 and 4) were prepared and used as sealing material sheets LLDPE 1 to 4.
  • LLDPE1 A sealing material sheet LLDPE1 was prepared using a sealing material composition formulated as follows. Silane modified transparent resin 1: with a density of 0.898 g / cm 3 and with respect to 98 parts by mass of a metallocene linear low density polyethylene having a melt mass flow rate at 190 ° C.
  • a silane-modified transparent resin (hereinafter referred to as “S1”) having a weight of 0.8 g / 10 min was obtained.
  • Weatherproof masterbatch 1 3.8 parts by mass of benzophenol UV absorber and hindered amine light stabilizer with respect to 100 parts by mass of powder obtained by pulverizing Ziegler linear low density polyethylene having a density of 0.920 g / cm 3 5 parts by mass and 0.5 parts by mass of a phosphorous heat stabilizer were mixed and melted and processed to obtain a pelletized master batch.
  • S1 20 parts by mass, weathering master batch 1: 5 parts by mass, metallocene linear low density polyethylene having a density of 0.905 g / cm 3 : 80 parts by mass of a sealing material composition, ⁇ 30 mm extruder, Using a film forming machine having a T die having a width of 200 mm, molding was performed at an extrusion temperature of 210 ° C. and a take-off speed of 1.1 m / min to produce a sealing material sheet LLDPE1 having a thickness of 400 ⁇ m.
  • the encapsulant sheet LLDPE1 had a polystyrene equivalent weight average molecular weight of 101,000 g / mol and a gel fraction of 0%.
  • LLDPE2 A sealing material sheet LLDPE2 was prepared using a sealing material composition formulated as follows.
  • Silane-modified transparent resin 2 98 parts by mass of metallocene linear low density polyethylene (M-LLDPE) having a density of 0.881 g / cm 3 and an MFR of 2 g / 10 min at 190 ° C.
  • M-LLDPE metallocene linear low density polyethylene
  • 2 parts by mass of methoxysilane and 0.1 part by mass of dicumyl peroxide as a radical generator (reaction catalyst) are mixed, melted and kneaded at 200 ° C., density 0.884 g / cm 3 , at 190 ° C.
  • a silane-modified transparent resin (hereinafter referred to as “S2”) having an MFR of 1.8 g / 10 min was obtained.
  • Weatherproof masterbatch 2 3.8 parts by weight of benzophenol UV absorber and hindered amine light stabilizer with respect to 100 parts by weight of powder obtained by pulverizing Ziegler linear low density polyethylene having a density of 0.880 g / cm 3 5 parts by mass and 0.5 parts by mass of a phosphorous heat stabilizer were mixed and melted and processed to obtain a pelletized master batch.
  • Crosslinker compound resin 2,5-dimethyl-2,5-di (t) with respect to 100 parts by mass of M-LLDPE pellets having a density of 0.880 g / cm 3 and MFR at 190 ° C. of 3.1 g / 10 min. -Butylperoxy) hexane was impregnated with 0.1 part by mass to obtain compound pellets.
  • S2 20 parts by mass
  • weather resistant masterbatch 2 5 parts by mass
  • crosslinker compound resin 80 parts by mass of a composition was molded under the same conditions as the sealing material sheet LLDPE1, and sealed with a thickness of 400 ⁇ m Stop material sheet LLDPE2 was produced.
  • the encapsulant sheet LLDPE2 had a polystyrene equivalent weight average molecular weight of 218,000 g / mol and a gel fraction of 0%.
  • LLDPE3 Both sides of the encapsulant sheet LLDPE2 were irradiated at an acceleration voltage of 200 kV and an irradiation intensity of 0.5 Mrad using an electron beam irradiation apparatus (product name EC250 / 15 / 180L, manufactured by Iwasaki Electric Co., Ltd.). A cross-linked encapsulant sheet LLDPE3 was obtained by irradiation with 0 Mrad. The polystyrene-converted weight average molecular weight of the crosslinked sealing material sheet LLDPE3 was 247,000, and the gel fraction was 0%.
  • LLDPE4 Both sides of the sealing material sheet LLDPE2 were irradiated at an acceleration voltage of 200 kV and an irradiation intensity of 4.0 Mrad using an electron beam irradiation apparatus (product name: EC250 / 15 / 180L, manufactured by Iwasaki Electric Co., Ltd.). A cross-linked encapsulant sheet LLDPE4 was obtained by irradiation with 0 Mrad. The polystyrene-converted weight average molecular weight of the crosslinked sealing material sheet LLDPE4 was 293,000, and the gel fraction was 40%.
  • the solar cell module evaluation sample includes a transparent front glass substrate (blue plate glass), a front sealing material layer made of a first sealing material sheet, a solar cell element, a back sealing material layer made of a second sealing material sheet, and The members made of the back surface protection sheet (Dai Nippon Printing Co., Ltd., model number VPEW280 ⁇ m) are sequentially laminated and then manufactured by thermocompression bonding using the above-mentioned members as an integrally formed body by vacuum heating lamination.
  • a solar cell module evaluation sample of a comparative example was used. Regarding the solar cell elements, solar cell elements A to C described below were prepared, and 42 solar cell elements of the same type were electrically connected in series with a connecting member for one solar cell module evaluation sample.
  • the thermal lamination conditions were as follows. ⁇ Heat laminating conditions> (a) Vacuum drawing: 5.0 minutes (b) Pressurization (0 kPa to 100 kPa): 1.5 minutes (c) Pressure holding (100 kPa): 15.0 minutes (d) Temperature 150 ° C. (Solar cell element) A: A crystalline silicon solar cell element produced using a polycrystalline silicon substrate. An electrode for collecting current is arranged on the daylighting side. (Manufactured by Q-CELLS, cell Q6LTT-200 / 1520 156mm) B: Back contact solar cell element.
  • a P-type electrode and an N-type electrode are provided on the back surface.
  • the P-type electrode and the N-type electrode on the back surface are each formed in a comb shape, and each alternately enter between the combs.
  • a P-type electrode and an N-type electrode on the back surface of an adjacent solar battery cell are connected and sealed with a sealing material.
  • C Thin film solar cell element. An n-type transparent conductive film window layer, an n-type high-resistance buffer layer, a p-type CIS-based light absorption layer, a metal back electrode layer, and a thin film power generation element having a device thickness of about 3 ⁇ m excluding a glass substrate made of a glass substrate .
  • EVA1 to 2 and LLDPE1 to 4 encapsulant sheets are sandwiched between ETFE films and heated at 150 ° C. for 13.5 minutes and heated.
  • the samples subjected to the crosslinking treatment were used as samples for evaluating the sealing material layers of the solar cell modules of Examples and Comparative Examples, respectively.
  • Example 1 About the sample for sealing material layer evaluation of an Example and a comparative example, it measured about the molecular weight, the gel fraction, and the haze value (JIS K7136). The results are shown in Table 2. Each test condition is as follows.
  • the sample for evaluation of the sealing material layer was dissolved in o-dichlorobenzene, and the weight average molecular weight in terms of polystyrene of the samples for evaluation of the sealing material layer comprising the sealing material sheets LLDPE1 to 4 was measured under the following conditions.
  • the sample for evaluating the sealing material layer composed of the sealing material sheets EVA1 and EVA2 was not measured because it was not completely dissolved and could not be measured.
  • Gel fraction (%) 0.1 g of the sample for sealing material layer evaluation was put into a resin mesh, extracted with toluene at 60 ° C. for 4 hours, taken out with the resin mesh, weighed after drying treatment, and compared the weight before and after extraction. The mass% of the residual insoluble matter was measured and this was used as the gel fraction.
  • a gel fraction of 0% means that the residual insoluble matter is substantially 0 and that the crosslinking reaction of the encapsulant composition has not substantially started. More specifically, “gel fraction 0%” means that the above-mentioned residual insoluble matter is not present at all, and that the above-mentioned residual insoluble matter mass% measured by a precision balance is less than 0.05% by mass. Shall be said.
  • Haze value (%) Measured with a haze / transmittance system HM150 according to JISK7136 in a state where blue sheet glass was laminated on the upper and lower sides of the sample for evaluation of the sealing material layer.
  • Water vapor barrier property Measured by JIS-K7129 B method. The measurement conditions are as follows. 40 ° C., 90% RH, unit g / m 2 ⁇ d, measuring device: MOCON water vapor permeability measuring device PERMATRAN-W
  • the test for insulation was performed by measuring the volume resistance value of the sample for sealing material layer evaluation according to JIS K6911.
  • a conductive material is attached to the upper and lower sides of a 50 mm sealing material sample sandwiched between 70 mm below and 30 mm above the aluminum foil.
  • a super insulation meter manufactured by Agilent: model number C4156 was used as a measuring instrument.
  • Solar cell element microcrack measurement test For each of the solar cell module evaluation samples of the examples and comparative examples described above, cell microcracks were observed by EL images. The test was performed before and after the cycle test described below. For the cycle test, a method based on the temperature cycle test of JIS C8917 was used. Raise from 25 ° C. to 90 ° C. over 45 minutes, hold at this temperature for 90 minutes, then lower to ⁇ 40 ° C. over 90 minutes, hold at this temperature for 90 minutes, then rise to 25 ° C. over 45 minutes Let This is one cycle (6 hours). This cycle was repeated 400 cycles to perform a cycle test. Observation of the cell microcrack by the EL image was performed as follows.
  • the solar cell module of the present invention is excellent in light transmittance on the light receiving surface side, and excellent in water vapor barrier property and insulating property on the back surface layer side due to its unique sealing material layer configuration. It turns out that it is a thing.
  • the solar cell module of the present invention has a particularly excellent insulating property of the back sealing material layer in a high temperature environment assumed as an actual use environment of the solar cell module. It can be seen that it can be used particularly suitably as a solar cell module including a back contact type solar cell element.
  • the solar cell module of the present invention is also preferably used as a solar cell module having a thin film type solar cell element that has high protection performance of the solar cell element and is easily affected by the deformation of the sealing material. It can be seen that

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  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photovoltaic Devices (AREA)
  • Sealing Material Composition (AREA)

Abstract

La présente invention a trait à un module de cellule solaire qui est doté d'une configuration qui bénéficie des avantages respectifs à la fois de l'EVA et du polyéthylène utilisés en tant que couches de produit d'étanchéité. Le module de cellule solaire (1) selon la présente invention est obtenu en disposant intégralement en couches un substrat de surface avant transparent (2), une couche de produit d'étanchéité de surface avant (3), un élément de cellule solaire (4), une couche de produit d'étanchéité de surface arrière (5) et une feuille de protection de surface inverse (6) suivant la séquence indiquée. Une première feuille de produit d'étanchéité qui forme la couche de produit d'étanchéité de surface avant (3) est une résine de copolymère d'éthylène et d'acétate de vinyle et une seconde feuille de produit d'étanchéité qui forme la couche de produit d'étanchéité de surface arrière (5) est une résine à base de polyéthylène qui est dotée d'une densité non supérieure à 0,940 g/cm3.
PCT/JP2012/081300 2011-12-05 2012-12-03 Module de cellule solaire WO2013084849A1 (fr)

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Cited By (2)

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CN103840036A (zh) * 2014-04-01 2014-06-04 润峰电力有限公司 一种抗pid光伏组件的制备工艺
US20160149063A1 (en) * 2013-06-28 2016-05-26 Dow Global Technologies Llc Backsheets/Frontsheets Having Improved Adhesion to Encapsulants and Photovoltaic Modules Made Therefrom

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JP6034756B2 (ja) * 2013-06-21 2016-11-30 三井化学株式会社 太陽電池封止用シートセットおよびそれを用いた太陽電池モジュール
JP2015012064A (ja) * 2013-06-27 2015-01-19 株式会社ブリヂストン 太陽電池用封止膜用組成物、その製造方法及び太陽電池用封止膜
JP6334871B2 (ja) * 2013-09-11 2018-05-30 株式会社カネカ 太陽電池モジュール
JP2015198096A (ja) * 2014-03-31 2015-11-09 凸版印刷株式会社 太陽電池モジュール
JP6766326B2 (ja) * 2015-07-17 2020-10-14 大日本印刷株式会社 太陽電池モジュールの製造方法
TWI666170B (zh) * 2018-03-28 2019-07-21 鄭光煒 重金屬回收裝置及其用途

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JPH10341030A (ja) * 1997-06-09 1998-12-22 Canon Inc 太陽電池モジュール
JP2006210405A (ja) * 2005-01-25 2006-08-10 Dainippon Printing Co Ltd 太陽電池モジュール
JP2009010277A (ja) * 2007-06-29 2009-01-15 Dainippon Printing Co Ltd 太陽電池モジュール用充填材シートおよび太陽電池モジュール
JP2011176231A (ja) * 2010-02-25 2011-09-08 Sanyo Electric Co Ltd 太陽電池モジュール

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Publication number Priority date Publication date Assignee Title
JPH10341030A (ja) * 1997-06-09 1998-12-22 Canon Inc 太陽電池モジュール
JP2006210405A (ja) * 2005-01-25 2006-08-10 Dainippon Printing Co Ltd 太陽電池モジュール
JP2009010277A (ja) * 2007-06-29 2009-01-15 Dainippon Printing Co Ltd 太陽電池モジュール用充填材シートおよび太陽電池モジュール
JP2011176231A (ja) * 2010-02-25 2011-09-08 Sanyo Electric Co Ltd 太陽電池モジュール

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160149063A1 (en) * 2013-06-28 2016-05-26 Dow Global Technologies Llc Backsheets/Frontsheets Having Improved Adhesion to Encapsulants and Photovoltaic Modules Made Therefrom
CN103840036A (zh) * 2014-04-01 2014-06-04 润峰电力有限公司 一种抗pid光伏组件的制备工艺

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