WO2014199798A1 - 太陽電池劣化抑制用の塗工液及びその薄膜、並びに太陽電池劣化抑制方法 - Google Patents
太陽電池劣化抑制用の塗工液及びその薄膜、並びに太陽電池劣化抑制方法 Download PDFInfo
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- WO2014199798A1 WO2014199798A1 PCT/JP2014/063644 JP2014063644W WO2014199798A1 WO 2014199798 A1 WO2014199798 A1 WO 2014199798A1 JP 2014063644 W JP2014063644 W JP 2014063644W WO 2014199798 A1 WO2014199798 A1 WO 2014199798A1
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- WO
- WIPO (PCT)
- Prior art keywords
- solar cell
- thin film
- deterioration
- coating liquid
- metal
- Prior art date
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- 239000010409 thin film Substances 0.000 title claims abstract description 40
- 238000000576 coating method Methods 0.000 title claims abstract description 36
- 239000011248 coating agent Substances 0.000 title claims abstract description 34
- 230000006866 deterioration Effects 0.000 title claims abstract description 21
- 239000007788 liquid Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 239000006059 cover glass Substances 0.000 claims abstract description 26
- 239000010419 fine particle Substances 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000011164 primary particle Substances 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 12
- 239000010408 film Substances 0.000 claims description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 230000001629 suppression Effects 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- VJMAITQRABEEKP-UHFFFAOYSA-N [6-(phenylmethoxymethyl)-1,4-dioxan-2-yl]methyl acetate Chemical compound O1C(COC(=O)C)COCC1COCC1=CC=CC=C1 VJMAITQRABEEKP-UHFFFAOYSA-N 0.000 claims 1
- 238000010248 power generation Methods 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008213 purified water Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- AEVBYEFXMFLHPX-UHFFFAOYSA-N C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.O Chemical group C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.O AEVBYEFXMFLHPX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
- C03C17/253—Coating containing SnO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/27—Oxides by oxidation of a coating previously applied
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- 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
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/211—SnO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/213—SiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/214—Al2O3
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/22—ZrO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
-
- 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 protection of solar cells. More specifically, it is an easy and inexpensive method of coating various solar cell cover glasses, in particular a method for preventing performance degradation called PID, a coating solution used therefor, and a thin film formed from the coating solution About.
- Non-Patent Document 1 a mechanism has been proposed in which Na ions in the cover glass diffuse to the inside and block the charge transfer of the cell (battery) (Non-Patent Document 1).
- the present invention has been made in view of the above-described problems, and an object thereof is to prevent a decrease in power generation capability of a solar cell without changing the solar cell member itself.
- the inventors of the present invention have formed a metal oxide thin film that easily cures at room temperature to about 120 ° C. on the surface or back surface of the cover glass of the solar cell, thereby insulating the cover glass surface. It was found that the leakage current can be suppressed and the power generation efficiency can be prevented from being lowered by PID. In particular, even when applied to the surface of the solar cell itself, it has become clear that some effects of suppressing the performance degradation of the battery can be seen, and this may be possible even for already installed solar cells. This discovery is significant and has great significance in terms of protecting existing solar cells.
- the present invention provides the following inventions.
- the present invention firstly comprises an aqueous solution of a compound of at least one metal selected from silicon, aluminum, zirconium, tin, and zinc, or a fine particle dispersion of the metal oxide, and the aqueous solution and the fine particle dispersion are Each of the compound and the oxide contains 0.01 to 10% by mass in terms of metal oxide, and the fine particle dispersion has fine particles having an average primary particle size of 50 nm or less and a dispersed particle size (D50) of less than 100 nm.
- Dispersing coating liquid for suppressing solar cell deterioration is provided.
- the present invention secondly suppresses deterioration of a solar cell having a thickness of 10 to 700 nm made of an oxide of at least one metal selected from silicon, aluminum, zirconium, tin and zinc formed from the coating solution.
- a thin film is provided.
- the present invention is characterized in that a thin film is formed by drying and curing a coating film formed by applying the coating liquid on the front or back surface of a cover glass of a solar cell at a temperature of room temperature to 200 ° C.
- a solar cell deterioration suppressing method is provided.
- the present invention provides a solar cell in which deterioration is suppressed, having a thin film having a thickness of 10 to 700 nm formed by applying the coating liquid on the front or back surface of a cover glass of the solar cell. .
- the present invention it is possible to prevent performance degradation due to PID of various solar cell panels by an easy and inexpensive method of forming a metal inorganic oxide thin film on a solar cell cover glass.
- the type of solar cell to which this method can be applied is not particularly limited as long as it has a cover glass on the surface, and in particular, in the order of cover glass / sealing sheet / cell / sealing sheet / back sheet.
- a stacked solar cell is preferred.
- metal oxide coating solution that can be used for forming the thin film
- a coating solution that satisfies the following conditions can be suitably used. That is, an aqueous solution of a water-soluble metal compound or a metal oxide fine particle dispersion capable of forming a metal inorganic oxide thin film after coating. Silicon, aluminum, zirconium, tin, zinc or the like is selected as the metal species.
- aqueous solution of the metal compound examples include an aqueous solution of a water-soluble compound of the metal species.
- a water-soluble silicate liquid aqueous solution of water-soluble silicate
- a SiO 2 precursor an aluminum chloride aqueous solution as an Al 2 O 3 precursor
- a (NH 4 ) 2 ZrO (CO that is a ZrO 2 precursor 3 ) 2 aqueous solution
- zinc acetate precursor zinc acetate acetate hydrate.
- the metal oxide fine particle dispersion is a dispersion in which fine particles of the above metal species having an average primary particle size of 50 nm or less, preferably 30 nm or less, are dispersed in a solvent, preferably water.
- D50 in the dispersed particle size means, for example, a volume-based 50% cumulative distribution diameter measured by a dynamic light scattering method using laser light using Nanotrac UPA-UZ152 manufactured by Nikkiso Co., Ltd. I mean.
- the average primary particle size is a particle size that can be confirmed by a transmission electron microscope (for example, H-9500 manufactured by Hitachi High-Technologies Corporation) at a magnification of about 150,000. This is the average value for 20 arbitrary visual fields.
- colloidal silica having a dispersed particle size of 1 to 50 nm as SiO 2 fine particles, an alumina fine particle dispersion having particle properties in which particles having an average primary particle size of 50 nm or less are dispersed with a dispersed particle size of less than 100 nm, zirconium oxide Examples thereof include fine particle dispersion, tin oxide fine particle dispersion, and zinc oxide fine particle dispersion.
- the coating liquid is a liquid containing the above metal compound or metal oxide fine particles, and the metal compound or metal oxide is about 0.01% by mass to 10% by mass in terms of metal oxide, preferably 0.1% by mass to Those containing 5% by mass are preferably used. If the concentration is too low, the resulting thin film will be too thin, and if the concentration is too high, the film will be too thick and the film will be cracked, preventing the insulation effect.
- any conventionally known method can be used to apply the coating solution to the solar cell cover glass. Specifically, dip coating method, spin coating method, spray coating method, flow coating method, brush coating method, impregnation method, roll method, wire bar method, die coating method, screen printing method, gravure printing method, ink jet method, etc. Can be used to form a coating film on the cover glass.
- the said coating liquid can be apply
- the coating film on the cover glass to form a thin film is preferably treated at a temperature range of room temperature to 200 ° C. for 1 to 120 minutes, particularly 5 to 5 ° C. at a temperature range of room temperature to 120 ° C. It is preferable to treat for 60 minutes. If the drying / curing temperature is too low or the drying / curing time is too short, there is a risk of curing failure, and if the drying / curing temperature is too high or the drying / curing time is too long, Na ions will leach out due to thermal diffusion, Insulation function may be reduced.
- the thickness of the thin film to be formed is preferably between 10 and 700 nm, more preferably between 20 and 500 nm, and particularly preferably between 50 and 300 nm. If the thin film is too thin, the insulating effect may not be exhibited, and if it is too thick, cracks may occur and the insulating effect may not be exhibited.
- the decrease ( ⁇ ) in the total light transmittance of the cover glass before and after the formation of the thin film is preferably 5% or less, and the increase ( ⁇ ) in the haze ratio is preferably 2% or less. If the change in total light transmittance ( ⁇ ) is reduced by more than 10% after the thin film is formed, the transparency is lowered, and the light reaching the solar cell is reduced, so that the power generation efficiency may be lowered. If the haze rate rises beyond 2% after the thin film is formed, the film becomes turbid, and the light reaching the solar cell is reduced by light scattering, which may reduce the power generation efficiency.
- Examples 1-37, Comparative Examples 1-2 In any example, an aqueous solution or an aqueous dispersion prepared by adjusting a coating material for forming the following thin film to a total solid content (converted to metal oxide) concentration of 1% by mass was used as the coating solution.
- Each coating solution is applied to the front or back surface of the following solar cell test module cover glass by the dip coating method, dried and cured at 80 ° C. for 15 minutes, and the thin films having the thicknesses shown in Tables 1 and 2 are formed on the cover glass. Formed on top.
- silicate molecule with clear structure> (Examples 7 to 12) PSS hydrate-octakis (tetramethylammonium) substitution product (cage silsesquioxane with Q 3 8 TMA structure, handled by Sigma-Aldrich) dissolved in water as a water-soluble SiO 2 forming component, strongly acidic Na ions were removed with an ion exchange resin, diluted with purified water, and used after solid content adjustment (1% by mass in terms of SiO 2 ).
- PSS hydrate-octakis (tetramethylammonium) substitution product (cage silsesquioxane with Q 3 8 TMA structure, handled by Sigma-Aldrich) dissolved in water as a water-soluble SiO 2 forming component, strongly acidic Na ions were removed with an ion exchange resin, diluted with purified water, and used after solid content adjustment (1% by mass in terms of SiO 2 ).
- alpha-in 83 product name, 23% highly basic aluminum chloride salt aqueous solution, manufactured by Daimei Chemical
- purified water is diluted with purified water to adjust the solid content (1% by mass in terms of Al 2 O 3 ) Used after.
- ⁇ ZrO 2 precursor> (Examples 19 to 24) Zircozol AC-20 (product name, (NH 4 ) 2 ZrO (CO 3 ) 2 , aqueous solution of zirconium compound, manufactured by Daiichi Rare Elemental Science) is diluted with purified water as a water-soluble zirconium salt aqueous solution to adjust the solid content It was used after (1% by mass in terms of ZrO 2 ).
- ⁇ Aqueous dispersion of SnO 2 ultrafine particles> (Examples 25 to 30) As fine particles of SnO 2 , ultrafine stannic oxide sol (average primary particle size 5 nm, manufactured by Yamanaka Sangyo Co., Ltd.) was used after adjusting the concentration with purified water (1% by mass in terms of SnO 2 ). The obtained aqueous dispersion had a dispersed particle diameter D50 of 50 nm.
- ⁇ ZnO precursor> (Examples 31 to 36) A commercially available zinc acetate dihydrate hydrolyzed with water / ethanol + triethanolamine aqueous solution so as to be 1% by mass in terms of zinc oxide was immediately used.
- ⁇ SiO 2 fine particle (large) aqueous dispersion> (Comparative Example 1) As an aqueous dispersion of SiO 2 fine particles, Snowtex ST-OUP (product name, colloidal silica with an average primary particle size of 100 nm, manufactured by Nissan Chemical) is diluted with purified water and the concentration is adjusted (1% by mass in terms of SiO 2 ). Used. The dispersion particle diameter D50 of the aqueous dispersion was 100 nm.
- ⁇ SiO 2 fine particle (small) aqueous dispersion> (Example 37) As an aqueous dispersion of fine SiO 2 particles, Snowtex ST-NXS (product name, colloidal silica with an average primary particle size of 5 nm, manufactured by Nissan Chemical Co., Ltd., with an average primary particle size of 5 nm) is diluted with purified water to adjust the concentration (SiO 2 equivalent) 1% by mass).
- the dispersion particle diameter D50 of the aqueous dispersion was 5 nm.
- the film thickness of the thin film was measured using a thin film measuring apparatus F-20 (product name, manufactured by FILMETRICS) and a scanning electron microscope S-3400 nm (product name, manufactured by Hitachi High-Technologies).
- the total light transmittance and haze ratio of the thin film were measured using a digital haze meter NDH-20D (manufactured by Nippon Denshoku Industries Co., Ltd.).
- the PID-promoting environment for solar cells was exposed to a temperature of 60 ° C / humidity 85% RH / surface-water-filled, and a test voltage of -1,000Vdc applied [-1,000Vdc on the internal circuit based on the frame potential] for 96 hours.
- the characteristics of the solar cell were measured using a specified apparatus (IV curve tracer MP160, Eihiro Seiki Co., Ltd.) and an EL image inspection apparatus (PVX-300, ITES Co., Ltd.).
- the EL image determination shows that the light emission capability still remains and suppresses the decrease in conversion efficiency It had been. This indicates that PID can be attenuated even if it is applied to the surface of a cover panel of a solar cell that has already been applied, which is significant.
- the leakage current was less than half, and many cells in which the light emission performance remained were observed even in the EL image inspection, and obvious deterioration suppression was recognized.
- the thin film of Example 37 using a fine particle dispersion having small particles has an insulating effect and an effect of suppressing deterioration.
- the thin film of Comparative Example 1 does not have the expected effect due to the large particles. It is considered that since the used particles were large, the density of the thin film was low, and a sufficient deterioration suppressing effect could not be obtained.
- Comparative Example 2 the SiO 2 thin film was applied to a thickness of 1 micron (1000 nm) and tested, but the 1 micron thick inorganic film is very hard and easily cracks in normal handling environments. appear. The occurrence of this crack can be judged from a significant decrease in optical properties. It is considered that due to this crack, a sufficient density cannot be obtained in the inorganic film, and a sufficient deterioration suppressing effect cannot be obtained.
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Abstract
Description
また、特に、太陽電池自体の表面に塗布した際にも一部、電池の性能低下を抑制する効果が見られる事も明らかになり、これは既に施工済みの太陽電池においても対策できる可能性を示す発見であり、既存太陽電池の保護という観点から大きな意義がある。
本方法が適用可能な太陽電池の種類は、表面にカバーガラスを備えている形態のものであれば特に制限されないが、特に、カバーガラス/封止シート/セル/封止シート/バックシートの順に積層された太陽電池であるのが好適である。
薄膜の形成に使用しうる金属酸化物の塗工液は、下記条件を満たすものが好適に使用できる。
即ち、塗布後に金属無機酸化物薄膜を形成しうる、水溶性金属化合物の水溶液、または金属酸化物の微粒子分散液である。
上記金属種として、ケイ素、アルミニウム、ジルコニウム、スズ、亜鉛などが選択される。
ここで分散粒径における「D50」とは、例えば日機装(株)製ナノトラックUPA-UZ152等を用いて、レーザー光を用いた動的光散乱法により測定される体積基準の50%累積分布径のことをいう。D50が100nmより大きな粒子であると形成後の薄膜に空隙が多く、薄膜の密度が低いために、先述のNaイオンの拡散を止める力が弱く、発電能力低下抑制の効果が得られない。
上記平均一次粒径とは、透過型電子顕微鏡(例えば(株)日立ハイテクノロジーズ製H-9500)にて、倍率150,000程度にて一粒を確認し得る粒子サイズを測定し、これを他の任意の視野20か所に対して行った平均値である。
具体的には、SiO2微粒子として分散粒径1~50nmのコロイダルシリカ、平均一次粒径50nm以下の粒子が、分散粒径100nm未満で分散している粒子物性を持つアルミナ微粒子分散液、酸化ジルコニウム微粒子分散液、酸化スズ微粒子分散液、および酸化亜鉛微粒子分散液が挙げられる。
前記塗工液としては、上記金属化合物若しくは金属酸化物微粒子を含む液であって、該金属化合物若しくは金属酸化物を金属酸化物換算で0.01質量%~10質量%程度、好ましくは0.1質量%~5質量%の質量で含むものが好適に用いられる。濃度が低すぎると得られる薄膜が薄くなりすぎ、濃度が高すぎると膜が厚くなり、膜が割れて絶縁効果が得られない。
上記塗工液を太陽電池カバーガラスに塗布するには、従来公知のいずれの方法も用いることができる。具体的には、ディップコーティング法、スピンコーティング法、スプレーコーティング法、フローコーティング法、ハケ塗り法、含浸法、ロール法、ワイヤーバー法、ダイコーティング法、スクリーン印刷法、グラビア印刷法、インクジェット法等を利用して、塗膜をカバーガラス上に形成させることができる。上記塗工液は太陽電池カバーガラスの表(オモテ)面及び/又は裏面に塗布することができるが、カバーガラスの裏面の塗布がより効果的である。また、太陽電池の表面に直接塗布することもできる。
薄膜形成後に全光線透過率変化(△)が10%を越えて低下すると透明性が低下し、太陽電池に届く光が減少するために、発電効率が低下してしまうことがある。薄膜形成後にヘイズ率が2%を越えて上昇すると膜に濁りが生じ、光の散乱によって太陽電池に届く光が減少するために、発電効率が低下してしまうことがある。
いずれの例でも、塗工液として、下記薄膜形成用のコーティング材料を総固形分(金属酸化物換算)濃度1質量%に調整した水溶液又は水分散液を用いた。ディップコーティング法により各塗工液を下記太陽電池試験モジュールのカバーガラスの表面又は裏面に塗布し、80℃で15分間乾燥硬化して、表1及び表2に示す厚さの薄膜を該カバーガラス上に形成した。
テストモジュールとして、6インチ多結晶シリコン4直列のセルを、カバーガラス/EVA(エチレン・酢酸ビニルコポリマー)封止シート/セル/EVA封止シート/バックシートの順に積層し、熱ラミネートして作成したものを用いた。
<SiO2前駆体、不定形シリケート>(実施例1~6、比較例2)
水溶性のシリケート液として、Shield-S(製品名、シリケート水溶液、信越化学塩ビ研開発製品)を使用した。
水溶性のSiO2形成成分として、PSS水和物‐オクタキス(テトラメチルアンモニウム)置換体(Q3 8TMA構造を有するカゴ型シルセスキオキサン、シグマアルドリッチ社取扱)を水に溶解し、強酸性イオン交換樹脂にてNaイオンを除去し、精製水で希釈して固形分調整(SiO2換算で1質量%)の後に使用した。
水溶性のアルミニウム塩水溶液として、アルファイン83(製品名、23%高塩基性塩化アルミニウム塩水溶液、大明化学製)を精製水で希釈して固形分調整(Al2O3換算で1質量%)の後に使用した。
水溶性のジルコニウム塩水溶液として、ジルコゾールAC-20(製品名、(NH4)2ZrO(CO3)2、ジルコニウム化合物の水溶液、第一稀元素科学製)を精製水で希釈して固形分調整(ZrO2換算で1質量%)の後に使用した。
SnO2の微粒子として、超微粒子酸化第二錫ゾル(平均一次粒径5nm、山中産業株式会社製)を精製水で濃度調整(SnO2換算で1質量%)して用いた。得られた水分散液の分散粒径D50は50nmであった。
市販の酢酸亜鉛二水和物を、酸化亜鉛換算で1質量%となるように水/エタノール+トリエタノールアミン水溶液にて加水分解したものを直ちに用いた。
SiO2微粒子の水分散液として、スノーテックスST-OUP(製品名、平均一次粒径100nmのコロイダルシリカ、日産化学製)を精製水にて希釈し濃度調整(SiO2換算で1質量%)して使用した。該水分散液の分散粒径D50は100nmであった。
SiO2微粒子の水分散液として、スノーテックスST-NXS(製品名、粒径4~6nm、平均一次粒径5nmのコロイダルシリカ、日産化学製)を精製水にて希釈し濃度調整(SiO2換算で1質量%)して使用した。該水分散液の分散粒径D50は5nmであった。
薄膜の膜厚は、薄膜測定装置F-20(製品名、FILMETRICS社製)及び走査型電子顕微鏡S-3400nm(製品名、日立ハイテクノロジーズ製)を用いて測定した。
薄膜の全光線透過率およびヘイズ率は、デジタルヘイズメーターNDH-20D(日本電色工業製)を用いて測定した。
太陽電池のPID促進環境は、温度60℃/湿度85%RH/表面水張り、試験電圧-1,000Vdc印加[フレーム電位を基準として、内部回路に-1,000Vdc]の環境下に96時間暴露した。
太陽電池の特性は、規定の装置(I-Vカーブトレーサー MP160,英弘精機(株))によるI-V特性の測定、およびEL画像検査装置(PVX-300、(株)アイテス)を用いて測定した。
実施例でカバーガラスの裏面に塗布した場合、漏れ電流が半分以下となり、EL画像検査でも発光性能が残存しているセルが多数認められ、明らかな劣化抑制が認められた。
Claims (8)
- ケイ素、アルミニウム、ジルコニウム、スズ及び亜鉛から選ばれる少なくとも1種の金属の、水溶性化合物の水溶液又は該金属の酸化物の微粒子分散液からなり、該水溶液および該微粒子分散液はそれぞれ、該化合物又は該酸化物を金属酸化物に換算して0.01~10質量%含み、該微粒子分散液は平均一次粒径が50nm以下の微粒子が、分散粒径(D50)100nm未満で分散している、太陽電池劣化抑制用塗工液。
- 前記水溶性金属化合物が、水溶性シリケート、塩化アルミニウム、(NH4)2ZrO(CO3)2、及び酢酸亜鉛から選ばれる、請求項1記載の太陽電池劣化抑制用塗工液。
- 前記金属酸化物の微粒子分散液が、分散粒径D50が50nm以下の微粒子の水分散液である、請求項1記載の太陽電池劣化抑制用塗工液。
- 請求項1~3のいずれか1項記載の塗工液から形成された、ケイ素、アルミニウム、ジルコニウム、スズ及び亜鉛から選ばれる少なくとも1種の金属の酸化物からなる、厚さ10~700nmの太陽電池劣化抑制用薄膜。
- 太陽電池のカバーガラス面上に形成される、請求項4記載の太陽電池劣化抑制用薄膜。
- 太陽電池のカバーガラスの裏面上に形成される、請求項4記載の太陽電池劣化抑制用薄膜。
- 請求項1~3のいずれか1項記載の塗工液を太陽電池のカバーガラスの表面又は裏面上に塗布し、形成された塗膜を常温~200℃の温度で乾燥硬化させて、ケイ素、アルミニウム、ジルコニウム、スズ及び亜鉛から選ばれる少なくとも1種の金属の酸化物から成る厚さ10~700nmの薄膜を形成することを特徴とする、太陽電池劣化抑制方法。
- 太陽電池のカバーガラスの表面又は裏面上に、請求項1~3のいずれか1項記載の塗工液を塗布して形成された、ケイ素、アルミニウム、ジルコニウム、スズ及び亜鉛から選ばれる少なくとも1種の金属の酸化物からなる厚さ10~700nmの薄膜を有する、劣化が抑制された太陽電池。
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CN105990468A (zh) * | 2015-02-11 | 2016-10-05 | 英利集团有限公司 | 硅片生产系统 |
CN105990468B (zh) * | 2015-02-11 | 2018-09-07 | 英利集团有限公司 | 硅片生产系统 |
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EP3010047A1 (en) | 2016-04-20 |
US20160111559A1 (en) | 2016-04-21 |
JP6107950B2 (ja) | 2017-04-05 |
AU2014279389A1 (en) | 2016-01-07 |
KR20160018700A (ko) | 2016-02-17 |
JPWO2014199798A1 (ja) | 2017-02-23 |
CN105518873A (zh) | 2016-04-20 |
EP3010047B1 (en) | 2021-01-20 |
AU2014279389B2 (en) | 2018-06-14 |
EP3010047A4 (en) | 2017-01-18 |
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