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WO2012090674A1 - Matériau de surface pour batterie solaire, matériau de recouvrement pour batterie solaire, et module de batterie solaire - Google Patents

Matériau de surface pour batterie solaire, matériau de recouvrement pour batterie solaire, et module de batterie solaire Download PDF

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Publication number
WO2012090674A1
WO2012090674A1 PCT/JP2011/078490 JP2011078490W WO2012090674A1 WO 2012090674 A1 WO2012090674 A1 WO 2012090674A1 JP 2011078490 W JP2011078490 W JP 2011078490W WO 2012090674 A1 WO2012090674 A1 WO 2012090674A1
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Prior art keywords
solar cell
surface material
cerium oxide
fluororesin
solar battery
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Japanese (ja)
Inventor
有賀　広志
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AGC Inc
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Asahi Glass Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/804—Materials of encapsulations
    • 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 surface material, a solar cell coating material, and a solar cell module.
  • Fluororesin especially ethylene-tetrafluoroethylene copolymer (ETFE) has been noted for its weather resistance and is used as a surface material instead of glass in flexible solar cells.
  • the ETFE film used as the surface material of the solar cell is made of a material such as an ethylene-vinyl acetate copolymer (EVA), a modified polyethylene, or polybutyl vinyl (PVB) that serves as a filler for enclosing the solar cell.
  • EVA ethylene-vinyl acetate copolymer
  • PVB polybutyl vinyl
  • the film is heat laminated at 135 to 160 ° C. without using an adhesive.
  • a fluororesin film such as an ETFE film does not have sufficient adhesion to a filler such as EVA as it is.
  • Patent Document 1 describes that a fluorine resin attached to a transparent electrode of a solar cell is subjected to corona discharge treatment and oxygen atoms and nitrogen atoms are introduced into the surface of the fluorine resin.
  • Patent Document 2 describes that a fluororesin is subjected to a discharge treatment in an atmosphere containing methane gas and carbon dioxide in a rare gas.
  • Patent Document 3 describes that a fluororesin is subjected to a discharge treatment in an atmosphere containing a polymerizable unsaturated compound gas and carbon dioxide in an inert gas.
  • Patent Document 4 describes that a fluororesin is subjected to a discharge treatment in an inert gas atmosphere containing an organic compound having a functional group.
  • a discharge treatment in an inert gas atmosphere containing an organic compound having a functional group.
  • Patent Document 5 describes that a high-molecular ultraviolet absorber having a molecular weight of 300 or more is added to a fluororesin film. This high molecular weight UV absorber is inferior in heat resistance and cannot withstand the temperature (200 ° C. or more) at the time of molding the fluororesin.
  • the fluororesin film is immersed in an organic solvent in which a high-molecular UV absorber is dissolved, and the UV absorber is vaporized by a dyeing method in which the UV absorber is contained.
  • a method is described in which a high-molecular ultraviolet absorber is added to the fluororesin film by a thermal diffusion method in which the fluororesin film is exposed and impregnated with the ultraviolet absorber.
  • Patent Document 6 describes an invention in which an ultraviolet absorber is added to a surface coating material composed of a laminate of a fluororesin film and EVA, and in the examples, it is described that an ultraviolet absorber is added to EVA.
  • examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as titanium oxide, zinc oxide and tin oxide, and high molecular weight ultraviolet absorbers.
  • Patent Document 7 describes that a fluorine resin laminated with EVA contains titanium oxide particles for the purpose of preventing EVA deterioration and surface contamination.
  • the present invention has been made in view of the above problems, and although it is excellent in weather resistance, as it is, it is composed of a fluororesin film having poor adhesion to a filler such as EVA, but the filler and It is an object of the present invention to provide a surface material for a solar cell that is excellent in the adhesion of the solar cell, can maintain the adhesion for a long period of time, and does not adversely affect the power generation efficiency of the solar cell.
  • Another object of the present invention is to provide a solar cell module that has excellent durability and does not impair power generation efficiency by having a solar cell coating material that can be used stably for a long period of time.
  • the present invention employs the following configuration.
  • a solar cell surface material comprising a fluororesin film having a surface subjected to glow discharge treatment and containing an ultraviolet absorber containing cerium oxide.
  • the ultraviolet absorber includes cerium oxide particles and a coating layer that covers a surface of the cerium oxide particles, and the coating layer includes silicon oxide.
  • a solar cell coating material wherein the surface material for a solar cell according to any one of [1] to [9] and a filler made of an organic resin are laminated.
  • the solar cell coating material according to [10] wherein the surface side of the solar cell surface material that has been subjected to the glow discharge treatment is laminated so as to be in contact with the filler.
  • a solar cell having one or more thin-film photoelectric conversion layers is provided inside, and at least one surface side of the solar cell is for the solar cell according to any one of [10] to [12].
  • the solar cell surface material of the present invention is excellent in adhesiveness with a filler encapsulating solar cells, can maintain the adhesiveness for a long time, and does not adversely affect the power generation efficiency of the solar cell.
  • the covering material for solar cells of the present invention is constituted by laminating the surface material for solar cells and the filler of the present invention, it can be used stably for a long period of time, and the power generation efficiency of the solar cells is adversely affected. Don't give.
  • the solar cell module of the present invention has excellent durability and high power generation efficiency by having a solar cell coating material that can be used stably for a long period of time.
  • FIG. 1 It is a schematic sectional drawing which shows one Embodiment of the solar cell module of this invention. It is an example of the relationship between the wavelength of the solar cell module of this invention, and collection efficiency. It is a figure which shows the light transmittance of the surface material for solar cells of Example 1.
  • FIG. 2 It is a figure which shows the light transmittance of the surface material for solar cells of Example 2.
  • FIG. 2 It is a figure which shows the light transmittance of the surface material for solar cells of Example 3.
  • FIG. It is a figure which shows the light transmittance of the surface material for solar cells of the comparative example 1.
  • FIG. 1 shows the light transmittance of the surface material for solar cells of Example 1.
  • the surface material for a solar cell of the present invention is made of a fluororesin film whose surface is modified by glow discharge treatment, and contains an ultraviolet absorber containing cerium oxide in a dispersed manner.
  • the ultraviolet absorber preferably has cerium oxide particles and a coating layer that covers the surface of the cerium oxide particles, and the coating layer preferably contains silicon oxide.
  • the surface material for solar cells of the present invention preferably has a light transmittance of 80% or more at 400 nm and a light transmittance of 70% or less at 300 nm as the surface material itself.
  • fluororesin examples of the fluororesin constituting the surface material for solar cells include ethylene-tetrafluoroethylene copolymer (hereinafter also referred to as “ETFE”), polytrifluoroethylene chloride (PCTFE), ethylene-trifluorochloride.
  • ETFE ethylene-tetrafluoroethylene copolymer
  • PCTFE polytrifluoroethylene chloride
  • Highly transparent fluororesin such as ethylene copolymer (ECTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), or these A mixture is mentioned.
  • ECTFE ethylene copolymer
  • PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • ETFE a fluororesin mainly composed of ETFE having a ratio of ETFE in the resin component of 80% by mass or more, preferably 90% by mass or more, and particularly preferably 100% by mass.
  • ETFE is a copolymer of ethylene (hereinafter referred to as “E”) and tetrafluoroethylene (hereinafter referred to as “TFE”), or a copolymerizable in addition to a repeating unit based on E and TFE. It is a copolymer containing repeating units based on these monomers.
  • the ratio (molar ratio) between the repeating unit based on TFE and the repeating unit based on E in ETFE is preferably 70/30 to 30/70, more preferably 65/35 to 40/60, and 60/40 to 40/60. Is particularly preferred. Unless otherwise specified, “to” indicating the numerical range described above is used to mean that the numerical values described before and after it are used as a lower limit value and an upper limit value, and hereinafter “to” Used with meaning. In addition to the repeating units based on E and TFE, when containing repeating units based on other monomers that are copolymerizable, the content of the repeating units based on other monomers is in the total repeating units of ETFE.
  • it is preferably 0.1 mol% or more, more preferably 0.5 to 30 mol%, particularly preferably 0.5 to 20 mol%.
  • functions such as high solubility, water repellency, oil repellency, and adhesion to the substrate are imparted without impairing the physical properties of ETFE. Is possible.
  • Examples of other monomers include other fluoroolefins other than TFE, other olefins other than E, and vinyl monomers.
  • Examples of other fluoroolefins include C2-C3 fluoroolefins such as chlorotrifluoroethylene, hexafluoropropylene, vinylidene fluoride, and vinyl fluoride.
  • fluorovinyl monomers such as (perfluoroalkyl) ethylene, are mentioned.
  • Examples of other olefins include propylene and isobutylene.
  • Examples of vinyl monomers include vinyl ether, allyl ether, carboxylic acid vinyl ester, carboxylic acid allyl ester, and the like.
  • Examples of the vinyl ether include cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; alkyl vinyl ethers such as nonyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, and t-butyl vinyl ether.
  • Examples of allyl ethers include alkyl allyl ethers such as ethyl allyl ether and hexyl allyl ether.
  • Examples of the carboxylic acid vinyl ester include vinyl esters of carboxylic acids such as acetic acid, butyric acid, pivalic acid, benzoic acid, and propionic acid.
  • carboxylic acid allyl ester examples include allyl esters of the above carboxylic acids.
  • a vinyl ester of a carboxylic acid having a branched alkyl group may be used.
  • Specific examples include “Beoba-9” and “Beoba-10” (both manufactured by Shell Chemical Co., Ltd.).
  • the other copolymer monomers may be used alone or in combination of two or more.
  • Examples of the resin other than ETFE in the fluororesin mainly composed of ETFE include, for example, hexafluoropropylene-tetrafluoroethylene copolymer, perfluoro (alkyl vinyl ether) -tetrafluoroethylene copolymer, and tetrafluoroethylene.
  • -Fluororesin such as hexafluoropropylene-vinylidene fluoride copolymer and chlorotrifluoroethylene-ethylene copolymer.
  • the fluororesin mainly composed of ETFE may contain a resin other than the fluororesin.
  • the other resins may be used alone or in combination of two or more.
  • the surface material for a solar cell of the present invention comprises a fluororesin film whose surface is modified by glow discharge treatment.
  • a glow discharge treatment by polymerizing a polymerizable gas, a plasma polymerization treatment for introducing a polymer containing oxygen atoms and nitrogen atoms and not containing fluorine onto the fluororesin film; Non-polymerizable plasma treatment in which nitrogen atoms are introduced may be mentioned.
  • the introduced oxygen atom or nitrogen atom provides adhesion to the filler.
  • Both the plasma polymerization treatment and the non-polymerization plasma treatment are plasma treatments using glow discharge caused by ionized plasma.
  • a high-frequency electromagnetic field composed of a high frequency, a pulse wave, a microwave, or the like is formed between the discharge electrode and the counter electrode in an atmosphere where a predetermined gas exists, and is disposed between the discharge electrode and the counter electrode.
  • Glow discharge treatment is performed on the surface of the fluororesin film.
  • a nitrogen atmosphere is preferable in terms of running cost.
  • the oxygen concentration in the nitrogen atmosphere is preferably 100 ppm or less, more preferably 90 ppm or less, and further preferably 60 ppm or less. The lower the oxygen concentration, the easier it is to obtain a fluororesin film that can maintain adhesion for a long period of time by surface treatment.
  • carbon dioxide gas and / or hydrogen gas may be introduced in addition to nitrogen gas.
  • Carbon dioxide gas serves as an oxygen supply source for introducing oxygen functional groups such as hydroxy groups on the surface of the fluororesin.
  • the hydrogen gas functions as a hydrogen supply source for introducing amino groups on the surface of the fluororesin.
  • the total introduction amount of carbon dioxide gas and / or hydrogen gas is preferably 10 mol% or less when the total amount of both is 100 mol%. If the total introduction amount of carbon dioxide gas and hydrogen gas is 10 mol% or less with respect to 100 mol% of nitrogen gas, fluorine oligomers and fluorine low molecular weight substances, which are specific actions of nitrogen plasma gas, are introduced from the surface. Easy to get rid of effect. Helium gas and argon gas can also be turned into plasma and glow discharge is possible, and the above-described discharge effect is easily obtained. However, these gases are expensive.
  • a mixed gas atmosphere composed of a polymerizable unsaturated compound gas and a carbon oxide gas is preferable.
  • methane gas and ethane gas classified as saturated hydrocarbons represented by C 4 H 2n + 2 are also preferable because plasma polymerization is performed in a mixed gas with a carbon oxide gas.
  • the polymerizable unsaturated compound gas include a compound gas having a double bond such as ethylene gas and propylene gas.
  • the carbon oxide gas include carbon dioxide gas and carbon monoxide gas. In the saturated hydrocarbon represented by C 4 H 2n + 2 , methane and ethane are preferable, and methane is more preferable.
  • the atmospheric pressure when performing the glow discharge treatment is preferably near atmospheric pressure. That is, 500 to 800 Torr is preferable, and 700 to 780 Torr is more preferable. If the pressure is 500 Torr or more, it is easy to suppress mixing of gases other than the introduced gas into the discharge part. If the pressure is 800 Torr or less, it is easy to suppress the plasma-treated gases from colliding with each other and reducing the surface treatment effect of the film.
  • the atmosphere temperature during the glow discharge treatment is not particularly limited and is preferably 0 to 60 ° C, more preferably 10 to 40 ° C.
  • the electric field applied to the discharge electrode and the counter electrode is preferably a pulsed electric field (hereinafter referred to as “pulse electric field”) having a voltage rise time of 10 ⁇ sec or less. If the voltage rise time is 10 ⁇ sec or less, the discharge state can be prevented from shifting to arc discharge, and the glow discharge treatment can be performed stably.
  • the voltage rise time of the pulse voltage is more preferably 5 ⁇ sec or less. As the voltage rise time is shorter, the gas is more easily ionized and becomes plasma, and glow discharge is more likely to occur. However, the voltage rise time is a time during which the voltage change is continuously positive.
  • the voltage fall time of the applied electric field is preferably as short as the voltage rise time, and the rise time and the fall time are preferably set to the same time.
  • the voltage fall time is a time during which the voltage change is continuously negative.
  • the waveform of the pulse electric field is not particularly limited, and examples thereof include an impulse waveform, a square waveform, and a modulation waveform. Further, when the frequency exceeds 20 kHz, a sine wave is likely to be formed.
  • the pulse duration in the pulse electric field is preferably 0.5 to 200 ⁇ sec, more preferably 1 to 10 ⁇ sec. If the pulse duration is 0.5 ⁇ sec or more, the discharge becomes more stable. If the pulse duration is 200 ⁇ s or less, it is easy to suppress the transition of glow discharge to arc discharge.
  • the pulse duration can be adjusted by the frequency of the electric field pulse. However, the pulse duration is the time during which the pulses are continuous. For example, if each pulse is an intermittent pulse that is separated, the pulse duration is the same as the pulse width time. When a plurality of pulses are continuous, the pulse duration is the same as the sum of the pulse width times of the series of continuous pulses.
  • the electric field strength of the applied electric field is preferably 10 to 1,000 kV / cm, more preferably 100 to 300 kV / cm. If the electric field strength is 10 kV / cm or more, the gas is easily turned into plasma by glow discharge. If the electric field strength is 1000 kV / cm or less, it is easy to suppress the occurrence of arc discharge.
  • the frequency of the pulse voltage is preferably 0.5 to 100 kHz, more preferably 5 to 50 kHz. When the frequency of the pulse voltage is 0.5 kHz or more, the discharge density of the glow discharge is improved and the time required for the surface treatment is shortened. If the frequency of the pulse voltage is 100 kHz or less, the discharge state can be prevented from shifting to arc discharge, and the glow discharge treatment can be performed stably.
  • the glow discharge treatment using a pulsed electric field is preferably performed a plurality of times with an interval of 0.01 seconds or more.
  • the discharge density of each glow discharge treatment that is, the discharge density between each discharge electrode and the counter electrode is preferably 40 to 200 W ⁇ min / m 2 , and preferably 60 to 180 W ⁇ min / m 2. More preferred. If the discharge density of each glow discharge treatment is 40 W ⁇ min / m 2 or more, nitrogen functional groups and oxygen functional groups are easily introduced. Further, when the discharge density is less than that, the number of functional groups to be introduced is extremely small. If the discharge density of each glow discharge treatment is 200 W ⁇ min / m 2 or less, the adhesion obtained by the surface treatment can be easily maintained for a long period of time.
  • the increase in the temperature of the fluororesin film to be treated is reduced, and the temperature once increased between each discharge treatment is reduced. Therefore, the movement of the oligomer component to the surface layer due to heat is suppressed.
  • the amount of oligomer components generated due to the breakage of the carbon-carbon bond of the fluororesin on the surface layer is reduced. Therefore, the oligomer component is reduced on the surface layer of the fluororesin film, and oxygen atoms and nitrogen atoms are easily introduced into the fluororesin itself, not into the oligomer component having a weak binding force.
  • a known electrode structure can be freely adopted as the structure of the discharge electrode and the counter electrode used for the glow discharge.
  • a curved electrode or a flat electrode is used as the counter electrode.
  • the distance between both electrodes is preferably 0.5 to 10 mm.
  • By setting the thickness to 0.5 mm or more it is easy to dispose a fluororesin film between both electrodes.
  • by setting it as 10 mm or less it is easy to obtain discharge with stable discharge and high discharge density.
  • a single metal such as copper or aluminum, an alloy such as stainless steel or brass, or the like can be used.
  • a solid dielectric In order to prevent the occurrence of arc discharge, it is preferable to coat a solid dielectric on at least one opposing surface side of both electrodes. In order to create a better plasma state, a solid dielectric should be placed on both electrodes.
  • a metal oxide such as silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide. Synthetic resins such as polytetrafluoroethylene and polyethylene terephthalate, and glass can also be used.
  • a solid dielectric having a relative dielectric constant of 10 or more (relative dielectric constant in an environment at 25 ° C., the same shall apply hereinafter). Examples of the solid dielectric having a relative dielectric constant of 10 or more include metal oxides such as zirconium dioxide and titanium dioxide, and double oxides such as barium titanate.
  • Titanium dioxide is known as a ferroelectric, and in the case of a titanium dioxide single composition, the relative dielectric constant differs depending on the crystal structure, and the relative dielectric constant is about 80 for the rutile crystal structure. Further, a dielectric composition having a relative dielectric constant of about 2000 to 18500 is obtained by using a mixed composition of at least one selected from metal oxides such as Ba, Sr, Pb, Ca, Mg, and Zr and titanium dioxide. The body is obtained. That is, the relative dielectric constant can be changed depending on the type and ratio of other oxides to be mixed and the crystallinity. Titanium dioxide alone has a drastic compositional change in a heating environment, restricts the use environment, and is difficult to handle when formed as a film on an electrode. Therefore, it is preferable to use a mixed composition composed of 5 to 50% by mass of titanium dioxide and 50 to 95% by mass of aluminum oxide with improved thermal stability.
  • Zirconium dioxide when used alone, has a relative dielectric constant of about 12 and is advantageous for generating a discharge plasma at a low voltage. Moreover, it is good also as a mixed composition with another metal oxide.
  • the relative dielectric constant can be changed depending on the type and ratio of other oxides to be mixed and the crystallinity.
  • Zirconium oxide is preferably mixed with yttrium oxide (Y 2 O 3 ), calcium carbonate (CaCO 3 ), magnesium oxide (MgO), or the like because it is stabilized by preventing expansion and contraction due to crystal transformation.
  • Y 2 O 3 yttrium oxide
  • CaCO 3 calcium carbonate
  • MgO magnesium oxide
  • at least 70% by mass is zirconium oxide, and the proportion of the other oxides is preferably within 30% by mass.
  • a zirconium oxide film to which 4 to 20% by mass of yttrium oxide is added is preferable because the relative dielectric constant is about 8 to 16.
  • the thickness of the solid dielectric on the discharge electrode side is appropriately determined depending on the thickness of the substrate to be processed and the applied voltage, but is preferably 0.01 to 4 mm. If it is too thick, a high voltage is required to generate plasma discharge. If it is too thin, dielectric breakdown occurs when voltage is applied, and arc discharge occurs.
  • the solid dielectric on the counter electrode side supports the fluororesin film, it is familiar with the fluororesin film and is preferably a soft material.
  • silicon rubber is effective.
  • the surface material for a solar cell of the present invention contains an ultraviolet absorber.
  • an ultraviolet absorber is contained in the surface material, not in the filler.
  • the ultraviolet absorbent in the present invention is characterized by containing cerium oxide. If it is cerium oxide, it does not have a photocatalytic action like titanium oxide, so even if it is contained in the fluororesin film, the fluororesin film is discolored to reduce the light transmittance or reduce the mechanical strength. Does not cause such problems. Further, as will be apparent from the examples described later, cerium oxide absorbs less light in a wavelength region of 350 nm or more, which has high collection efficiency in power generation by a solar cell. On the other hand, ultraviolet rays on the low wavelength side (especially less than 350 nm) that have a large influence on the functional group have sufficient absorbency.
  • the functional group in the discharge-treated fluororesin can be protected from ultraviolet rays without substantially impairing the power generation efficiency.
  • zinc oxide and the like are also known as ultraviolet absorbers that do not have a photocatalytic action.
  • zinc oxide has a large absorption with respect to light of 350 to 360 nm that can obtain a certain degree of collection efficiency in power generation of a solar cell. For this reason, if zinc oxide is used as a UV absorber for a solar cell surface material, sufficient power generation efficiency cannot be obtained.
  • Cerium oxide is easily dissolved by hydrogen fluoride generated by the decomposition of the fluororesin. Therefore, in order to obtain higher weather resistance, it is preferable to use composite particles in which the surface of the cerium oxide particles is covered with a coating layer for protecting from hydrogen fluoride.
  • a coating layer containing silicon oxide is preferable, and a silicon oxide having a silicon oxide ratio of 60% by mass or more, preferably 80% by mass or more, particularly preferably 100% by mass in the coating layer as a main component.
  • a coating layer is preferred.
  • other components contained in the coating layer include aluminum oxide remaining on the surface of the coating layer derived from aluminum sulfate (aggregating agent) used during the production of the composite particles.
  • the composite particle in which the surface of the cerium oxide particle is covered with a coating layer for protecting from hydrogen fluoride is a cerium oxide-silica composite in which the surface of the cerium oxide particle is covered with silicon oxide (ie, silica).
  • silicon oxide ie, silica
  • the CeO 2 : SiO 2 mass ratio of the cerium oxide-silica composite particles in which the surface of the cerium oxide particles is covered with silica is preferably 30:70 to 80:20, and 40:60 to 70: 30 is more preferable.
  • the mass ratio of the CeO 2 and SiO 2 is cerium oxide - a ratio between CeO 2 and SiO 2 in the entire particles of the silica complex. When the ratio of silica is increased, the weather resistance is improved.
  • a silicon oxide is an amorphous silica (namely, amorphous silica) which does not have crystallinity.
  • amorphous silica include amorphous silica obtained by hydrolyzing sodium silicate. That is, the composite particle in which the surface of the cerium oxide particle is covered with a coating layer for protecting from hydrogen fluoride is preferably a cerium oxide-amorphous silica composite in which the surface of the cerium oxide particle is covered with amorphous silica.
  • the particles of the cerium oxide-amorphous silica composite are preferably secondary particles in which a plurality of particles in which primary particles of cerium oxide are coated with amorphous silica are aggregated and the amorphous silica is fused together.
  • the distribution of the secondary particle diameter of the cerium oxide-amorphous silica composite particles measured by a laser diffraction particle size distribution analyzer is preferably 95% by mass or more in the range of 1 to 30 ⁇ m. More preferably, it is in the range of 10 ⁇ m.
  • the average secondary particle diameter of the cerium oxide-amorphous silica composite particles measured by a laser diffraction particle size distribution analyzer is preferably 2 to 8 ⁇ m, and particularly preferably 1 to 5 ⁇ m.
  • the average particle diameter (average primary particle diameter) measured by SEM (scanning electron microscope) of the cerium oxide particles in the cerium oxide-amorphous silica composite is such that the necessary ultraviolet absorbing ability is obtained and the solar cell In power generation, the thickness is preferably 10 to 250 nm from the viewpoint of obtaining high transparency with respect to light of 400 nm or more, which can obtain a certain degree of high collection efficiency.
  • the average primary particle size here is the particle size of the cerium oxide particles.
  • the method for producing particles of the cerium oxide-amorphous silica composite in which the surface of the cerium oxide particles is covered with amorphous silica is not limited to the above method.
  • cerium oxide particles are synthesized, and water glass or ethyl silicate is synthesized therewith.
  • a method of performing silica coating using as a material may be used.
  • a flocculant such as aluminum sulfate is used to facilitate filtration of the silica-coated insoluble cerium compound dispersed in water.
  • aluminum sulfate aluminum oxide derived from aluminum ions attached to the surface remains on the surface of the coating layer, but there is no particular problem in performance.
  • the surface of the ultraviolet absorber containing cerium oxide (that is, cerium oxide particles or cerium oxide particles having a coating layer containing silica) is subjected to a hydrophobic treatment.
  • a hydrophobic treatment thereby, the dispersibility in a fluororesin film improves.
  • the fluororesin comes into contact with the screw and the cylinder many times, but the shearing at that time can be kept low by hydrophobization, Resin coloring is suppressed.
  • the degree of hydrophobicity is preferably 40 to 75% of the degree of methanol hydrophobicity.
  • Methanol hydrophobicity is an index indicating the hydrophobicity of particles.
  • the measurement method is as follows. That is, 50 cc of distilled water is put into a 300 cc beaker, and 5 g of particles are added while stirring well. If the particles are evenly dispersed, the particles are very familiar with distilled water and the degree of methanol hydrophobization is 0%. If the particles are not uniformly dispersed, methanol is gradually added dropwise until the particles are uniformly dispersed in the aqueous solution.
  • the preferred degree of methanol hydrophobicity required differs depending on the type of fluororesin, and in the case of ETFE, it is preferably 40 to 70%.
  • reactive organosilicon compounds include tetraalkoxysilanes such as tetraethoxysilane and tetramethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, and (3,3,3-trifluoropropyl) trimethoxysilane.
  • silicone oils such as trialkoxysilanes, dimethyl silicone oil, methyl hydrogen silicone oil, and phenylmethyl silicone oil. Of these, isobutyltrimethoxysilane, hexyltrimethoxysilane, dimethyl silicone oil, and phenylmethyl silicone oil are preferable. .
  • the required amount of the reactive organosilicon compound used for the hydrophobization treatment is the size of the specific surface area of the cerium oxide-amorphous silica composite. Is proportional to When the amount of the reactive organosilicon compound is small, the cerium oxide-amorphous silica composite particles may turn black or brown when kneaded with the fluororesin. When there are many reactive organosilicon compounds, the aggregate which consists of a reactive organosilicon compound appears as a lump, and the film external appearance may worsen.
  • the reactive organosilicon compound is silicone oil
  • alkoxysilane such as isobutyltrimethoxysilane.
  • the content of the UV absorber containing cerium oxide in the surface material is determined in consideration of the balance between the UV absorbing ability required from the viewpoint of maintaining adhesion and the transmittance of light having a wavelength that contributes to power generation.
  • the transmittance of 300 nm of the surface material is preferably as low as possible from the viewpoint of improving adhesion, and therefore it is necessary to contain a sufficient amount of the ultraviolet absorber.
  • the content is too large, the absorption characteristic of cerium oxide becomes remarkable, and the transmittance around 400 nm, which particularly affects the power generation efficiency, is lowered.
  • the ultraviolet absorber containing cerium oxide is preferably contained so that the transmittance at 400 nm of the surface material is 80% or more and the transmittance at 300 nm is 20 to 70%. Further, it is more preferable that the surface material be contained so that the transmittance at 400 nm is 85% or more and the transmittance at 300 nm is 20 to 50%.
  • the surface material having the preferable light transmission characteristics can be easily obtained. Specifically, it is preferable to contain an ultraviolet absorber so that the amount of cerium oxide per unit area in the surface material is 0.1 to 2 g / m 2 . Further, although depending on the thickness of the film and the amount of the coating layer, the ratio of the amount of cerium oxide to the whole surface material is preferably in the range of 0.1 to 2% by mass.
  • the surface material contains other UV absorbers, pigments, carbon black, carbon fibers, silicon carbide, glass fibers, mica, cross-linking agents, and fillers. May be.
  • the thickness of the surface material is preferably 10 to 300 ⁇ m, more preferably 20 to 250 ⁇ m, and particularly preferably 25 to 200 ⁇ m. If it exists in this range, the handling of the film at the time of discharge processing will be easy, and the wrinkle by discharge will not generate
  • the covering material for solar cells of the present invention is a laminate of the surface material of the present invention and a filler made of an organic resin.
  • the surface material and the filler are laminated so that the surface of the surface material subjected to the discharge treatment is in contact with the filler.
  • the filler for the solar battery covers at least the unevenness of the internal element having the solar battery cell, and functions as an adhesive between the internal element and the surface material. Therefore, light resistance, adhesiveness, and heat resistance are required.
  • an ethylene copolymer is preferable, and an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA), an ethylene-ethyl acrylate copolymer (EEA), and an ethylene-methyl acrylate (EMA) and polybutyl vinylal (PVB).
  • EVA ethylene-vinyl acetate copolymer
  • EAA ethylene-ethyl acrylate copolymer
  • EMA ethylene-methyl acrylate
  • PVB polybutyl vinylal
  • blended the crosslinking material with polyethylene (henceforth PE) is also mentioned.
  • the filler in the solar cell of the present invention preferably contains one or more of EVA, EEA, EMA and PVB.
  • the filler is preferably cross-linked so as to be resistant to high temperature use environments. When the filler is EVA, crosslinking with an organic peroxide is preferred.
  • crosslinking treatment is preferably performed in a state “after hot pressing” in the step of joining the solar battery cell to the solar battery covering material when the solar battery module is manufactured.
  • Crosslinking may be performed using a crosslinking agent such as isocyanate or melamine.
  • ⁇ Solar cell module> An embodiment of the solar cell module of the present invention will be described with reference to FIG.
  • a filler 2a and a surface material 3a are sequentially laminated on the light incident side of the solar battery cell 1, and a covering material 4a is constituted by the filler 2a and the surface material 3a.
  • the filler 2b and the surface material 3b are sequentially laminated on the side opposite to the light incident side of the solar battery cell, and the covering material 4b is configured by the filler 2b and the surface material 3b.
  • At least one of the surface material 3a and the surface material 3b is the surface material for solar cells of the present invention.
  • the coating material 4a and the coating material 4b is the solar cell coating material of the present invention.
  • the surface material 3a disposed on the light incident side is the surface material for solar cells of the present invention, that is, the coating material 4a is the coating material for solar cells of the present invention.
  • both the surface material 3a and the surface material 3b are the solar cell surface material of the present invention, that is, both the coating material 4a and the coating material 4b are the solar cell coating material of the present invention.
  • Solar cell 1 has one or more thin film photoelectric conversion layers between a pair of conductive layers.
  • a cell in which a plurality of thin film photoelectric conversion layers having different wavelength regions from which high collection efficiency is obtained is widely used.
  • FIG. 2 shows an amorphous silicon-germanium (a-Si) thin film photoelectric conversion layer with high collection efficiency for light on the short wavelength side as a top cell and amorphous silicon-germanium (with high collection efficiency for light on the long wavelength side).
  • the collection efficiency obtained in a cell in which a thin film photoelectric conversion layer of (a-SiGe) is a bottom cell and a laminate of a top cell and a bottom cell is disposed between a pair of conductive layers is shown.
  • the overall collection efficiency is a value obtained by combining the collection efficiencies of the top cell and the bottom cell.
  • the collection efficiency at a wavelength of 300 to 400 nm is almost equal to the collection efficiency of the top cell alone.
  • the transmittance curve of the surface material of the present invention decreases very closely with the collection efficiency curve of the amorphous silicon (a-Si) thin film photoelectric conversion layer of FIG. Show the trend. Therefore, the solar cell module of the present invention easily maintains high power generation efficiency particularly when it has a thin film photoelectric conversion layer of amorphous silicon (a-Si). Similarly, in other solar cells that generate power in a wide wavelength range of 350 to 1500 nm, for example, called CIGS, it is easy to maintain high power generation efficiency.
  • permeability curve of the surface material of this invention has low transmittance
  • hydrophobized silica-coated cerium oxide particles 100 g was added to 1900 g of ETFE resin (manufactured by Asahi Glass Co., Ltd., Full-on ETFE: 88AX), and after stirring well, hydrophobized silica with a biaxial extruder Master batch pellets containing 5% coated cerium oxide particles (2.95% cerium oxide) were prepared.
  • the extrusion conditions were a cylinder temperature of 310 ° C and a head temperature of 320 ° C.
  • the pellets and ETFE resin pellets containing no silica-coated cerium oxide particles are put in a polypropylene bag at a ratio of 1: 9 and shaken vigorously by hand 10 times. Mixed. This was molded with a T die having a cylinder temperature and a die temperature of 320 ° C. to obtain an ETFE film having a width of 550 mm and a thickness of 50 ⁇ m.
  • the surface of the ETFE film was discharged.
  • a plasma processing apparatus RD550 manufactured by Sekisui Chemical Co., Ltd. was used.
  • the discharge electrode a ceramic dielectric (solid dielectric) layer having a thickness of 1 mm on a carbon steel plate having a length of 100 mm in the transport direction of the ETFE film and a length of 650 mm in the width direction of the ETFE film and a thickness of 20 mm. The one provided with was used.
  • covered the silicon rubber of thickness 2mm was used for the metal roll surface with a diameter of 30 cm, and roll temperature was hold
  • the flow rate of nitrogen gas to be introduced was 50 L / min, and the gas was introduced for 2 minutes, and it was confirmed that the oxygen concentration was 100 ppm. Thereafter, while introducing nitrogen gas, the output voltage of the high frequency power source is 450 V, the output current is 5.4 A, the processing power is 2.43 kW, and the ETFE film is transported at 6 m / min, so that the discharge density is 623 W ⁇ min / A glow discharge treatment of m 2 was performed. The frequency was 40 kHz. Therefore, the waveform of the pulse electric field is close to a sine wave.
  • the discharge density was calculated by the following formula (1).
  • Example 2 An ETFE film was obtained in the same manner as in Example 1 except that the mixing ratio of the masterbatch pellets and ETFE resin containing no silica-coated cerium oxide particles (Asahi Glass Co., Ltd., Fullon ETFE: 88AX) was 1: 4. Further, the surface was discharged in the same manner as in Example 1 to obtain the surface material of Example 2.
  • Example 3 An ETFE film was obtained in the same manner as in Example 1 except that the mixing ratio of the masterbatch pellets and the ETFE resin containing no silica-coated cerium oxide particles (Asahi Glass Co., Ltd., Fullon ETFE: 88AX) was 1:19. Further, the surface was discharged in the same manner as in Example 1 to obtain the surface material of Example 3.
  • Example 4 An ETFE film was molded in the same manner as in Example 1, and the gas composition introduced from the gas inlet was 99 vol% argon, 0.3 vol% carbon dioxide, 0.7 vol% methane, and a gas flow rate of 20 l / Example 1 except that the output voltage of the high-frequency power source was 110 V, the output current was 2.2 A, the processing power was 2.42 W, the transport speed of the ETFE film was 1 m / min, and the discharge density was 372 W ⁇ min / m 2.
  • the surface material of Example 4 was obtained in the same manner as described above.
  • Example 5 An ETFE film was obtained in the same manner as in Example 2, and the surface was discharged in the same manner as in Example 4 to obtain the surface material of Example 5.
  • Example 6 An ETFE film was obtained in the same manner as in Example 3, and the surface was discharged in the same manner as in Example 4 to obtain the surface material of Example 6.
  • the transmittance of the surface material of each example is very close to the collection efficiency curve of the amorphous silicon (a-Si) thin film photoelectric conversion layer of FIG. 2 from the wavelength of 400 nm to 300 nm. Showed a decreasing trend.
  • the surface material of Comparative Example 2 had a transmittance of about 360 nm or less, which was a characteristic that had to substantially affect the power generation efficiency of the solar cell.
  • Tables 2 to 5 in Examples 1 to 6, the adhesion after the weathering test was maintained well compared to any of Comparative Examples 1 to 4.
  • the surface material for solar cell of the present invention has excellent adhesion to the filler used for the coating material for solar cell, can maintain the adhesion for a long time, and adversely affects the power generation efficiency of the solar cell. Therefore, it is useful for a solar cell coating material and for a solar cell module.

Landscapes

  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne un matériau de surface pour batterie solaire, qui présente une excellente adhésion à une charge technique, qui peut maintenir cette adhésion pendant une longue période, et qui n'affecte pas le rendement de génération de puissance de la batterie solaire. L'invention concerne également un matériau de recouvrement, formé en recouvrant le matériau de surface et la charge technique, ainsi qu'un module de batterie solaire utilisant le matériau de recouvrement. Un absorbant d'ultraviolet comprenant de l'oxyde de cérium est contenu dans un film de fluoro-résine dont la surface est traitée au moyen d'un traitement par décharge luminescente.
PCT/JP2011/078490 2010-12-27 2011-12-08 Matériau de surface pour batterie solaire, matériau de recouvrement pour batterie solaire, et module de batterie solaire Ceased WO2012090674A1 (fr)

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JP5532182B1 (ja) * 2012-12-25 2014-06-25 ダイキン工業株式会社 透明性に優れたフッ素樹脂フィルム
CN111511814A (zh) * 2018-01-18 2020-08-07 株式会社表面·界面工房 有机无机杂化膜
JP2020161825A (ja) * 2015-02-06 2020-10-01 三井・ダウポリケミカル株式会社 配線シート、構造体および光発電モジュール

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JP2000103888A (ja) * 1998-09-25 2000-04-11 Asahi Glass Co Ltd 含フッ素樹脂フィルムおよび積層体
JP2000150936A (ja) * 1998-11-17 2000-05-30 Canon Inc 半導体装置及び太陽光発電装置
WO2008129901A1 (fr) * 2007-04-13 2008-10-30 Asahi Glass Company, Limited Procédé de fabrication de particules d'oxyde métallique enrobées d'oxyde de silicium rendu hydrophobe

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JPH0867867A (ja) * 1994-06-23 1996-03-12 Suzuki Yushi Kogyo Kk 紫外線遮蔽材及びそれを用いた紫外線遮蔽合成樹脂、紫外線遮蔽化粧品、紫外線遮蔽塗膜
JP3785731B2 (ja) * 1997-04-11 2006-06-14 旭硝子株式会社 フッ素樹脂フィルム
JP5266100B2 (ja) * 2009-03-05 2013-08-21 ケイミュー株式会社 着色基材

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JP2000103888A (ja) * 1998-09-25 2000-04-11 Asahi Glass Co Ltd 含フッ素樹脂フィルムおよび積層体
JP2000150936A (ja) * 1998-11-17 2000-05-30 Canon Inc 半導体装置及び太陽光発電装置
WO2008129901A1 (fr) * 2007-04-13 2008-10-30 Asahi Glass Company, Limited Procédé de fabrication de particules d'oxyde métallique enrobées d'oxyde de silicium rendu hydrophobe

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Publication number Priority date Publication date Assignee Title
JP5532182B1 (ja) * 2012-12-25 2014-06-25 ダイキン工業株式会社 透明性に優れたフッ素樹脂フィルム
WO2014103845A1 (fr) * 2012-12-25 2014-07-03 ダイキン工業株式会社 Film en fluororésine présentant une excellente transparence
US20150252156A1 (en) * 2012-12-25 2015-09-10 Daikin Industries, Ltd. Fluororesin film having excellent transparency
US9822225B2 (en) 2012-12-25 2017-11-21 Daikin Industries, Ltd. Fluororesin film having excellent transparency
JP2020161825A (ja) * 2015-02-06 2020-10-01 三井・ダウポリケミカル株式会社 配線シート、構造体および光発電モジュール
CN111511814A (zh) * 2018-01-18 2020-08-07 株式会社表面·界面工房 有机无机杂化膜
EP3741797A4 (fr) * 2018-01-18 2021-09-22 Hyomen Kaimen Kobo Corporation Film hybride organique et inorganique
US11655347B2 (en) 2018-01-18 2023-05-23 Hyomen Kaimen Kobo Corporation Organic-inorganic hybrid membrane

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