CN115772004A - Photovoltaic glaze, photovoltaic back plate glass, preparation method of photovoltaic back plate glass and double-glass photovoltaic module - Google Patents
Photovoltaic glaze, photovoltaic back plate glass, preparation method of photovoltaic back plate glass and double-glass photovoltaic module Download PDFInfo
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- CN115772004A CN115772004A CN202211632964.9A CN202211632964A CN115772004A CN 115772004 A CN115772004 A CN 115772004A CN 202211632964 A CN202211632964 A CN 202211632964A CN 115772004 A CN115772004 A CN 115772004A
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- photovoltaic
- glass
- glaze
- back plate
- titanium dioxide
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- 239000011521 glass Substances 0.000 title claims abstract description 104
- 239000005357 flat glass Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 230000004907 flux Effects 0.000 claims abstract description 52
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 235000019832 sodium triphosphate Nutrition 0.000 claims abstract description 22
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- 230000009974 thixotropic effect Effects 0.000 claims abstract description 16
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- -1 modified aluminum tripolyphosphate Chemical class 0.000 claims abstract description 7
- 239000003921 oil Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 36
- 239000006185 dispersion Substances 0.000 claims description 21
- 239000002966 varnish Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 8
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 7
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 230000009977 dual effect Effects 0.000 claims 1
- 238000002310 reflectometry Methods 0.000 abstract description 8
- 238000010411 cooking Methods 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- 238000003756 stirring Methods 0.000 description 17
- 239000000377 silicon dioxide Substances 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000004952 Polyamide Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 7
- 229920002647 polyamide Polymers 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 238000005496 tempering Methods 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 238000007499 fusion processing Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 3
- 229910001950 potassium oxide Inorganic materials 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- XLUBVTJUEUUZMR-UHFFFAOYSA-B silicon(4+);tetraphosphate Chemical compound [Si+4].[Si+4].[Si+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XLUBVTJUEUUZMR-UHFFFAOYSA-B 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241000212376 Ammi Species 0.000 description 1
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 1
- 235000007034 Carum copticum Nutrition 0.000 description 1
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 1
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RNFAKTRFMQEEQE-UHFFFAOYSA-N Tripropylene glycol butyl ether Chemical compound CCCCOC(CC)OC(C)COC(O)CC RNFAKTRFMQEEQE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- LGERWORIZMAZTA-UHFFFAOYSA-N silicon zinc Chemical compound [Si].[Zn] LGERWORIZMAZTA-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Glass Compositions (AREA)
Abstract
The invention discloses a photovoltaic glaze, photovoltaic back plate glass, a preparation method of the photovoltaic back plate glass and a double-glass photovoltaic module, wherein the preparation raw materials of the photovoltaic glaze comprise: mixing ink oil, titanium dioxide, glass flux, auxiliary agent and additive; the auxiliary agent comprises at least one of a dispersant and a thixotropic anti-settling agent; the additive is at least one of aluminum tripolyphosphate, aluminum dihydrogen tripolyphosphate and modified aluminum tripolyphosphate. Through the introduction of the additive, the reflectivity of a reflecting layer formed by glaze can be improved, the adhesive force of the glaze layer is better, and the high-pressure cooking resistance is obviously improved.
Description
Technical Field
The invention relates to the technical field of photovoltaic glass, in particular to a photovoltaic glaze, photovoltaic back plate glass, a preparation method of the photovoltaic back plate glass and a double-glass photovoltaic assembly.
Background
With the progress of technology, double-glass photovoltaic module gradually gets into people's field of vision. Double-glass photovoltaic module adopts high reflection to plate glaze backplate glass and replaces traditional backplate, and high reflection plates glaze glass backplate and utilizes the space between battery piece and the battery piece to plate the glaze and scribble whitely, will see through the sunlight reflection in solar wafer clearance to the surface of solar wafer, makes sunlight can reutilization, promotes the absorptive capacity that double-glass photovoltaic module set a light, reaches the effect that hinders light reflection promotion subassembly power. By combining the technology of double-sided batteries such as PERC, HJT, PERT, topcon and the like, the glazed double-glass photovoltaic module can realize double-sided power generation without obviously increasing the cost, and meanwhile, the power generation gain of 10-30% is realized at the system end. Therefore, each component manufacturer has introduced the grid-type high-reflection glazed glass on a large scale.
The photovoltaic back plate glazing technology is only five or six years old in development, the performance standard of the glazing back plate glass for the photovoltaic module does not form a national standard, and the performance requirements of the current market on the glazing glass mainly comprise reflectivity, adhesive force, weather resistance, EVA (ethylene vinyl acetate) bonding strength and PID (proportion integration differentiation) resistance. The white high-reflection glaze for the photovoltaic back plate has few research manufacturers in China, the reflectivity of most of the currently applied photovoltaic high-reflection glaze can be more than 75%, the adhesive force is 0-1 grade, and the basic requirements of customers are met. However, with the widespread use of the back plate glazing glass, some problems exist in the application process of the feedback glazing back plate glass in a component factory, for example, the reflectivity of the glazing back plate glass is attenuated by more than 3% when a high-pressure cooking test is carried out, and even the stripping phenomenon occurs, so that the stability of the high-reflection glazing layer on the long-term outdoor use gain of the photovoltaic component is greatly influenced.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a photovoltaic glaze, photovoltaic back plate glass, a preparation method of the photovoltaic back plate glass and a double-glass photovoltaic module.
In a first aspect of the present invention, a photovoltaic glaze is provided, which is prepared from the following raw materials: mixing ink oil, titanium dioxide, glass flux, auxiliary agent and additive; the auxiliary agent comprises at least one of a dispersing agent and a thixotropic anti-settling agent; the additive is selected from at least one of aluminum tripolyphosphate, aluminum dihydrogen tripolyphosphate and modified aluminum tripolyphosphate.
According to the photovoltaic glaze disclosed by the embodiment of the invention, at least the following beneficial effects are achieved: the photovoltaic glaze is prepared by further adding at least one additive of aluminum tripolyphosphate, aluminum dihydrogen tripolyphosphate and modified aluminum tripolyphosphate on the basis of preparation raw materials comprising ink adjusting oil, titanium dioxide, a glass flux and at least one additive of a dispersing agent and a thixotropic anti-settling agent, wherein the additive is high in phosphorus content and good in thermal stability, and can improve whiteness and opacity in the glaze, so that a formed glaze layer is opaque and the light reflectivity of the glaze layer can be improved; in addition, the addition of the additive can promote the sintering of ceramics, when the glass is tempered at high temperature, the additive can react with silicon dioxide in the glass flux to generate compact silicon phosphate and alumina ceramics, so that the anisotropy of lattice expansion is minimized, the generation of microcracks in the cooling process is reduced, the thermal shock resistance of the material is improved, and meanwhile, the silicon phosphate is solid acid, and the hydrolysis can make the surface of the glass acidic under the damp and hot conditions, so that the alkaline hydrolysis of the glass melt is effectively retarded, and the weather resistance, especially the high-pressure cooking resistance, of a glaze layer can be improved. Therefore, by introducing the additive, the reflectivity of a reflecting layer formed by glaze can be improved, the adhesive force of the glaze layer is better, and the high-pressure cooking resistance is obviously improved.
In some embodiments of the present invention, the mass ratio of the titanium dioxide powder to the glass flux is 3:7 to 1:1; the dosage of the additive is 1 to 20 percent of the total mass of the titanium dioxide and the glass flux; the amount of the ink mixing oil is 20-30% of the total mass of the titanium dioxide, the glass flux and the additive. Wherein, the dosage of the additive is preferably 5 to 10 percent of the total mass of the titanium dioxide and the glass flux; the amount of the varnish is preferably 20-25% of the total mass of the titanium dioxide, the glass flux and the additive.
In some embodiments of the invention, the amount of the auxiliary agent is 1.5-4% of the total mass of the titanium dioxide, the glass flux and the additive.
In some embodiments of the invention, the adjuvant comprises a dispersant and a thixotropic anti-settling agent. The dosage of the dispersant can be controlled to be 0.5 to 2 percent of the total mass of the powder preparation raw materials; the dosage of the thixotropic dustproof agent can be controlled to be 1-2% of the total mass of the powder preparation raw materials. For example, the amount of the dispersing agent can be 0.5-2% of the total mass of the titanium dioxide, the glass flux and the additive, and the amount of the thixotropic dustproof agent can be 1-2% of the total mass of the titanium dioxide, the glass flux and the additive.
In some embodiments of the present invention, the titanium dioxide is rutile titanium dioxide.
In some embodiments of the present invention, titanium dioxide is rutile titanium dioxide prepared by a chlorination process; the titanium dioxide prepared by the method has extremely low impurity content.
In some embodiments of the invention, the titanium dioxide is rutile titanium dioxide prepared by chlorination process, and silica and alumina are used for inorganic coating treatment; wherein, the coating treatment by using silicon oxide and aluminum oxide can block the lattice defect of titanium dioxide caused under the condition of ultraviolet irradiation, shield the photoactivation point on the surface of the titanium dioxide, and improve the PID resistance.
In some embodiments of the invention, the dispersant is a wetting dispersant, and specifically one of TEGO Dispers 735W and TEGO Surten 404E may be used.
In some embodiments of the invention, the thixotropic anti-settling agent is selected from at least one of a polyamide wax, an organobentonite, a fumed silica. Fumed silica specifically can use fumed silica A200, and the thixotropic anti-settling agent preferably uses polyamide wax.
In some embodiments of the invention, the varnish is an aqueous varnish. The components of the aqueous varnish comprise water-soluble resin, polyvinyl alcohol and solvent. Preferably, the components of the aqueous varnish comprise, by mass percent: 5 to 25 percent of water-soluble acrylic resin, 1 to 5 percent of polyvinyl alcohol, 10 to 18 percent of ethanol, 5 to 20 percent of ethylene glycol, 15 to 30 percent of diethylene glycol monobutyl ether, and the balance of water.
In some embodiments of the invention, the glass fluxing agent is a lead-free, cadmium-free, low melting point glass fluxing agent.
In some embodiments of the invention, the glass fluxing agent comprises 36 to 45wt% SiO 2 . By mixing SiO 2 The content of the components is controlled to be more than 36 percent, the grid structure of the glass has stronger stability, better chemical stability, better water resistance, acid and alkali resistance and electrical insulation performance, and higher mechanical strength; simultaneously adding SiO 2 The content of the component is controlled below 45 percent so as to avoid excessive SiO 2 The content of the inorganic filler causes the softening temperature and the complete melting temperature to be higher, thereby affecting the adhesion and the weather resistance of the glaze layer.
In some embodiments of the invention, the glass fluxing agent has a softening temperature of 450 to 550 ℃. If the softening point of the glass flux is too low, the ink-adjusting oil cannot be completely gasified, so that the glaze layer is yellow and black, and the weather resistance of the glaze layer is influenced; by controlling the softening temperature of the glass flux within the range, the whiteness of a glaze layer formed by the glaze material can be ensured, and the weather resistance of the glaze layer is ensured.
In some embodiments of the invention, the glass fluxing agent has a total melting temperature of between 600 and 670 ℃. By controlling the full-melting temperature of the glass flux within the range, the white high-reflection glaze can be completely melted in a short time within the tempering temperature range of 680-720 ℃, the melting fluidity is better, so that better coating performance on titanium dioxide is ensured, and high adhesion and weather resistance of a glaze layer are further ensured.
The glass flux can be a lead-free cadmium-free low-melting-point glass flux with a component system of silicon-aluminum-boron-zinc-zirconium-titanium system. In some embodiments of the invention, the components of the glass fluxing agent comprise, in mass percent: 36 to 45 percent of SiO 2 、18～20％ B 2 O 3 、1～5％ Al 2 O 3 、8～10％Na 2 O、1～5％K 2 O、12～15％ZnO、3～5％ TiO 2 、1～3％ ZrO 2 . The preparation method comprises the following steps: uniformly mixing the components to obtain a mixture; then, preheating the mixture, and then smelting to obtain molten glass; and performing water quenching on the glass liquid to obtain glass frit, and performing ball milling to obtain the glass fusing agent. Wherein the temperature of the preheating treatment can be controlled between 500 and 600 ℃, and the time of the preheating treatment can be 10 to 30min; the smelting temperature can be 1000-1100 ℃, and the smelting time can be 30-90 min.
In some embodiments of the invention, the glass flux has a particle size of 10 μm or less.
In some embodiments of the invention, the modified aluminum tripolyphosphate is selected from at least one of a zinc modified aluminum tripolyphosphate, a zinc silicon modified aluminum tripolyphosphate.
In a second aspect of the present invention, a method for preparing more than one photovoltaic glaze is provided, which comprises the following steps:
s1, uniformly mixing varnish and a dispersing agent to obtain a first mixed material;
s2, adding titanium dioxide, a glass flux, an additive and the rest of auxiliary agents into the first mixed material, and performing dispersion treatment; obtaining a second mixed material;
and S3, pouring the second mixed material into a three-roll grinding machine for ink rolling to obtain the photovoltaic glaze.
The step S1 may specifically include: adding a dispersing agent into the varnish under a stirring state, and uniformly dispersing and mixing to obtain a first mixed material; wherein the stirring speed can be controlled at 500-1500 rpm, and the dispersion time can be controlled at 10-90 min.
In step S2, the dispersion treatment can be high-speed dispersion at 500-1500 rpm, and the dispersion time can be controlled to be 10-90 min.
In some embodiments of the invention, in step S3, a diluent is added to the second blend before the rolling is performed, and the viscosity of the second blend is adjusted to 60000 to 1000000mpas. Wherein the diluent can be one or more of diethylene glycol methyl ether, diethylene glycol butyl ether, tripropylene glycol methyl ether, tripropylene glycol butyl ether, dipropylene glycol butyl ether and dipropylene glycol methyl ether. By controlling the viscosity of the second mixed material in the range, the processing performance of the glaze can be improved, and the stability of the glaze can be improved.
In some embodiments of the invention, the second blend is padded in step S3 to a fineness of less than 10 μm.
In a third aspect of the present invention, a photovoltaic back plate glass is provided, including a back plate glass and a glaze layer provided on a surface of the back plate glass, where a forming material of the glaze layer includes any one of the photovoltaic glazes provided in the first aspect of the present invention.
In a fourth aspect of the present invention, a method for preparing more than one photovoltaic back panel glass is provided, comprising: and covering the photovoltaic glaze on the surface of the back plate glass, and curing and sintering to obtain the photovoltaic back plate glass. Wherein, the follow-up of a wet film formed by covering the photovoltaic glaze on the surface of the back plate glass can be controlled to be 15-25 μm; the curing temperature can be controlled between 180 and 250 ℃, and the curing time can be controlled between 2 and 5min; the sintering temperature can be controlled at 680-720 ℃.
In a fifth aspect of the invention, a dual-glass photovoltaic module is provided, which comprises any one of the photovoltaic back plate glasses provided by the third aspect of the invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
The components of the glass flux used in each of the following examples 1 to 3 and comparative example 1 were comprised by mass percent: 42% of silicon dioxide, 18.3% of boron oxide, 4.7% of aluminum oxide, 8.8% of sodium oxide, 2.2% of potassium oxide, 14.6% of zinc oxide, 4.1% of titanium oxide, 3% of zirconium oxide and 2.3% of the rest (lead-free and cadmium-free); the preparation method specifically comprises the following steps:
s1, adding the components into a mixer to be uniformly mixed to obtain a mixture;
s2, placing the mixture obtained in the step S1 into an electric furnace, preheating at 570 ℃ for 20min, and then heating to 1050 ℃ for smelting for 60min to obtain molten glass;
s3, performing water quenching on the glass liquid obtained in the step S2 to obtain a glass frit; and then putting the glass frit into a ball mill for ball milling for 3 hours to ensure that the particle size of the powder is less than or equal to 5 mu m, thus obtaining the low-melting-point glass fusing agent, wherein the softening temperature is 530 ℃ and the full-melting temperature is 620 ℃.
The aqueous varnish used in each of examples 1 to 3 and comparative examples 1 to 4 described below was prepared by mixing 10wt% of a water-soluble acrylic resin, 2wt% of polyvinyl alcohol, 15wt% of ethanol, 15wt% of ethylene glycol, 30wt% of diethylene glycol monobutyl ether, and 28wt% of water.
Example 1
The embodiment prepares the photovoltaic glaze, and the preparation method comprises the following steps:
s1, adding 80g of water-based varnish into a dispersion cylinder, starting a mechanical stirrer, adding 4g of TEGO Dispers 735W dispersant into the dispersion cylinder while stirring at a stirring speed of 500rpm, and stirring and dispersing for 10min to obtain a first mixed material;
s2, adding 104g of titanium dioxide, 216g of glass flux, 24g of aluminum tripolyphosphate and 4g of thixotropic anti-settling agent polyamide wax into a dispersion cylinder in sequence, and continuing to disperse at a high speed of 1500rpm for 50min to obtain a second mixed material; wherein, the titanium dioxide is rutile titanium dioxide prepared by a chlorination method, and silica and alumina are used for inorganic coating treatment;
s3, adjusting the viscosity of the second mixed material to about 60000-100000 mpas by using diethylene glycol butyl ether serving as a diluent according to needs;
and S4, pouring the mixed material obtained by the treatment in the step S3 into a three-roll grinder to prick ink, and detecting the fineness of the ink to enable the fineness to be less than 10 mu m to obtain the photovoltaic glaze.
Example 2
The embodiment prepares the photovoltaic glaze, and the preparation method comprises the following steps:
s1, adding 80g of water-based varnish into a dispersion cylinder, starting a mechanical stirrer, adding 3g of TEGO Dispers 735W dispersant into the dispersion cylinder while stirring at a stirring speed of 500rpm, and stirring and dispersing for 10min to obtain a first mixed material;
s2, sequentially adding 96g of titanium dioxide, 224g of glass flux, 32g of aluminium dihydrogen tripolyphosphate and 5g of thixotropic anti-settling agent polyamide wax into a dispersion cylinder, and continuously dispersing at a high speed of 1500rpm for 50min to obtain a second mixed material; wherein, the titanium dioxide is rutile titanium dioxide prepared by a chlorination method, and silica and alumina are used for inorganic coating treatment;
s3, adjusting the viscosity of the second mixed material to about 60000-100000 mpas by using diethylene glycol monobutyl ether serving as a diluent according to needs;
and S4, pouring the mixed material obtained by the treatment in the step S3 into a three-roll grinder to prick ink, and detecting the fineness of the ink to enable the fineness to be less than 10 mu m to obtain the photovoltaic glaze.
Example 3
The embodiment prepares the photovoltaic glaze, and the preparation method comprises the following steps:
s1, adding 80g of water-based varnish into a dispersion cylinder, starting a mechanical stirrer, adding 5g of TEGO Dispers 735W dispersant into the dispersion cylinder while stirring at a stirring speed of 500rpm, and stirring and dispersing for 10min to obtain a first mixed material;
s2, adding 112g of titanium dioxide, 208g of glass flux, 16g of modified aluminum tripolyphosphate and 5g of thixotropic anti-settling agent polyamide wax into a dispersion cylinder in sequence, and continuing to disperse at a high speed of 1500rpm for 50min to obtain a second mixed material; wherein, the titanium dioxide is rutile titanium dioxide prepared by a chlorination method, and silica and alumina are used for inorganic coating treatment;
s3, adjusting the viscosity of the second mixed material to about 60000-100000 mpas by using diethylene glycol monobutyl ether serving as a diluent according to needs;
and S4, pouring the mixed material obtained by the treatment in the step S3 into a three-roll grinder to prick ink, and detecting the fineness of the ink to enable the fineness to be less than 10 mu m to obtain the photovoltaic glaze.
Comparative example 1
This comparative example, which differs from example 1 in that a photovoltaic glazing was prepared: in this comparative example, the addition of aluminum tripolyphosphate was eliminated, and the other operations were substantially the same as in example 1. The preparation method specifically comprises the following steps:
s1, adding 80g of water-based varnish into a dispersion cylinder, starting a mechanical stirrer, adding 3g of TEGO Dispers 735W dispersant into the dispersion cylinder while stirring at a stirring speed of 500rpm, and stirring and dispersing for 10min to obtain a first mixed material;
s2, adding 104g of titanium dioxide, 216g of glass flux and 5g of thixotropic anti-settling agent polyamide wax into a dispersion cylinder in sequence, and continuing to disperse at a high speed of 1500rpm for 50min to obtain a second mixed material; wherein, the titanium dioxide is rutile titanium dioxide prepared by a chlorination method, and silica and alumina are used for inorganic coating treatment;
s3, adjusting the viscosity of the second mixed material to about 60000-100000 mpas by using diethylene glycol monobutyl ether serving as a diluent according to needs;
and S4, pouring the mixed material obtained by the treatment in the step S3 into a three-roll grinder to prick ink, and detecting the fineness of the ink to enable the fineness to be less than 10 mu m to obtain the photovoltaic glaze.
Comparative example 2
The comparative example, which is different from comparative example 1 in that: the glass flux D250 was used instead of the glass flux in comparative example 1, and the other operations were substantially the same as in comparative example 1. Wherein the glass flux D250 is a commercially available product of Ammi micro-nano new material Co., ltd, and the content of silicon dioxide is lower than that of the glass flux adopted in comparative example 1. The preparation method of the photovoltaic glaze material of the comparative example specifically comprises the following steps:
s1, adding 80g of water-based varnish into a dispersion cylinder, starting a mechanical stirrer, adding 3g of TEGO Dispers 735W dispersant into the dispersion cylinder while stirring at a stirring speed of 500rpm, and stirring and dispersing for 10min to obtain a first mixed material;
s2, adding 104g of titanium dioxide, 216g of glass flux D250 and 5g of thixotropic anti-settling agent polyamide wax into a dispersion cylinder in sequence, and continuing to disperse at a high speed of 1500rpm for 50min to obtain a second mixed material; wherein, the titanium dioxide is rutile titanium dioxide prepared by a chlorination method, and silica and alumina are used for inorganic coating treatment;
s3, adjusting the viscosity of the second mixed material to about 60000-100000 mpas by using diethylene glycol monobutyl ether serving as a diluent according to needs;
and S4, pouring the mixed material obtained by the treatment in the step S3 into a three-roll grinder to prick ink, and detecting the fineness of the ink to enable the fineness to be less than 10 mu m to obtain the photovoltaic glaze.
Comparative example 3
This comparative example, which differs from example 1 in that a photovoltaic glazing was prepared: the component amount configuration of the glass flux is different from that of the glass flux used in example 1, and other operations (including the preparation method of the glass flux and the preparation method of the photovoltaic glaze) are basically the same as those of example 1.
The components of the glass flux adopted in the comparative example comprise, by mass: 32% of silicon dioxide, 20.3% of boron oxide, 4.7% of aluminum oxide, 13% of sodium oxide, 6% of potassium oxide, 14.6% of zinc oxide, 4.1% of titanium oxide, 3% of zirconium oxide and the balance of 2.3% (lead-free and cadmium-free); according to the same production method as that of the glass flux used in example 1, a low melting point glass flux was obtained, the softening temperature of which was 450 ℃ and the total melting temperature of which was 580 ℃.
Comparative example 4
A photovoltaic glazing was prepared in this comparative example, which differs from example 1 in that: the component amount configuration of the glass flux is different from that of the glass flux used in example 1, and other operations (including the preparation method of the glass flux and the preparation method of the photovoltaic glaze) are basically the same as those of example 1.
The components of the glass flux adopted in the comparative example comprise, by mass: 52% of silicon dioxide, 13.3% of boron oxide, 4.7% of aluminum oxide, 4% of sodium oxide, 2% of potassium oxide, 14.6% of zinc oxide, 4.1% of titanium oxide, 3% of zirconium oxide and the balance of 2.3% (lead-free and cadmium-free); according to the same production method as that of the glass flux used in example 1, a low melting point glass flux was obtained, the softening temperature of which was 610 ℃ and the total melting temperature of which was 740 ℃.
Example 4
The embodiment prepares the photovoltaic back plate glass, and the preparation method comprises the following steps: and (3) screen-printing the photovoltaic glaze prepared in the embodiment 1 on the surface of the photovoltaic back plate glass by using a 200-mesh screen to form a wet film, controlling the thickness of the wet film to be 22 mu m, curing for 3min at 250 ℃, and sintering and toughening at 695-700 ℃ to obtain the photovoltaic back plate glass.
Example 5
This example prepared a photovoltaic back sheet glass, and differs from example 4 in that: the photovoltaic glazing obtained in example 2 was used in this example instead of the photovoltaic glazing used in example 4, the procedure being otherwise the same as in example 4.
Example 6
This example prepared a photovoltaic back sheet glass, and differs from example 4 in that: the photovoltaic glazing obtained in example 3 was used in this example instead of the photovoltaic glazing used in example 4, the procedure being otherwise the same as in example 4.
Comparative example 5
This comparative example prepared a photovoltaic backsheet glass, which differs from example 4 in that: this example uses the photovoltaic glaze obtained in comparative example 1 in place of the photovoltaic glaze used in example 4, and adjusts the sintering tempering temperature to 695 to 700 ℃, and the other operations are the same as example 4.
Comparative example 6
This comparative example prepared a photovoltaic backsheet glass, which differs from example 4 in that: in this example, the photovoltaic glaze obtained in comparative example 2 was used in place of the photovoltaic glaze used in example 4, and the sintering tempering temperature was adjusted to 695 to 700 ℃, and the other operations were the same as in example 4.
Comparative example 7
This comparative example prepared a photovoltaic backsheet glass, which differs from example 4 in that: the photovoltaic glaze prepared in comparative example 3 was used in this example in place of the photovoltaic glaze used in example 4, and the sintering tempering temperature was adjusted to 695 to 700 ℃, and the other operations were the same as in example 4.
Comparative example 8
This comparative example prepared a photovoltaic backsheet glass, which differs from example 4 in that: this example uses the photovoltaic glaze obtained in comparative example 4 in place of the photovoltaic glaze used in example 4, and adjusts the sintering tempering temperature to 695 to 700 ℃, and the other operations are the same as example 4.
Performance testing
The appearance, reflectivity, adhesion and autoclaving resistance of the photovoltaic back plate glass prepared in the above examples 4 to 6 and comparative examples 5 to 8 were respectively tested, and the specific test method was as follows:
(1) Appearance: visual inspection;
(2) Reflectance ratio: testing by a CM-26dG/26d/25d spectrocolorimeter of Konika Mentada;
(3) Adhesion force: detecting by adopting a hundred-grid knife grid cutting method;
(4) High Pressure Cooking (PCT) test: referring to T/CPIA 0028.2-2021 part 2 of glass for photovoltaic modules: according to the standard of double-glass assembly backboard reflection-enhanced coated glass, a glass sample and a laminating piece sample are placed in a test box, the test temperature is 121 +/-0.5 ℃, the relative humidity is 99-100%, the test time is 48h, all samples are subjected to appearance inspection after the test, the existence of delamination, bubbling, cracking, powdering and shedding of a glaze layer is observed, the photovoltaic reflectance R of the aged glass sample is tested, and the photovoltaic reflectance attenuation value delta R is calculated;
the performance of the photovoltaic back sheet glass of examples 4 to 6 and comparative examples 5 to 8 was tested according to the above test methods, and the results are shown in table 1:
TABLE 1
As can be seen from the above Table 1, the photovoltaic back sheet glasses of examples 4 to 6 correspond to the glasses of examples 1 to 3The photovoltaic glaze is added with aluminum tripolyphosphate, the glaze layer has good adhesion, is uniform and white, has high reflectivity and excellent weather resistance, does not have layering, bubbling, cracking, powdering and shedding after being steamed and boiled for 192 hours under high pressure, and has reflectivity attenuation delta R less than 3%. Specifically comparing example 4 with comparative example 5, example 4 using the photovoltaic glaze containing aluminum tripolyphosphate of example 1, the adhesion and weather resistance were significantly improved and the reflectance decay was significantly reduced after autoclaving for 192 hours, compared to using the photovoltaic glaze containing no aluminum tripolyphosphate of comparative example 1 for the photovoltaic backsheet glass of comparative example 5. In addition, the photovoltaic back panel glass of comparative example 6 was prepared by using the glass flux of the photovoltaic glaze of comparative example 2 as the commercially available glass flux D250, while the photovoltaic glazes of examples 4 to 6 and comparative example 5 were prepared by using SiO 2 The lead-free cadmium-free low-melting-point glass fusing agent with the content of 42 percent obviously improves the weather resistance of the photovoltaic glass back plate. Comparative example 7 photovoltaic backsheet glass comparative example 3 photovoltaic glaze SiO used in photovoltaic glaze, in comparison with examples 4-6 and comparative example 5 2 The content is lower than 36%, and the weather resistance of the photovoltaic glass back plate is obviously reduced; comparative example 8 photovoltaic backsheet glass comparative example 4 photovoltaic glaze SiO 2 The content is more than 45%, and the caking property and the weather resistance of the photovoltaic glass back plate are obviously reduced.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the present invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention.
Claims (10)
1. The photovoltaic glaze is characterized by comprising the following preparation raw materials: mixing ink oil, titanium dioxide, glass flux, auxiliary agent and additive; the auxiliary agent comprises at least one of a dispersing agent and a thixotropic anti-settling agent; the additive is selected from at least one of aluminum tripolyphosphate, aluminum dihydrogen tripolyphosphate and modified aluminum tripolyphosphate.
2. The photovoltaic glaze according to claim 1, wherein the mass ratio of the titanium dioxide to the glass flux is 3:7 to 1:1; the dosage of the additive is 1 to 20 percent of the total mass of the titanium dioxide and the glass flux; the amount of the ink mixing oil is 20-30% of the total mass of the titanium dioxide, the glass flux and the additive.
3. The photovoltaic glazing as claimed in claim 2, characterized in that the auxiliaries comprise a dispersant and a thixotropic anti-settling agent; the dosage of the dispersing agent is 0.5-2% of the total mass of the titanium dioxide, the glass flux and the additive, and the dosage of the thixotropic dustproof agent is 1-2% of the total mass of the titanium dioxide, the glass flux and the additive.
4. The photovoltaic glazing as claimed in claim 1, characterized in that the varnish is an aqueous varnish; preferably, the components of the aqueous varnish comprise, by mass percent: 5 to 25 percent of water-soluble acrylic resin, 1 to 5 percent of polyvinyl alcohol, 10 to 18 percent of ethanol, 5 to 20 percent of ethylene glycol, 15 to 30 percent of diethylene glycol monobutyl ether, and the balance of water.
5. The photovoltaic glazing as claimed in any one of claims 1 to 4 wherein the glass flux is a lead-free and cadmium-free low melting point glass flux; preferably, the glass fluxing agent contains 36-45 wt% of SiO 2 。
6. The process for preparing a photovoltaic glazing as claimed in any one of claims 1 to 5, characterized in that it comprises the following steps:
s1, uniformly mixing varnish and a dispersing agent to obtain a first mixed material;
s2, adding titanium dioxide, a glass flux, an additive and the rest of auxiliaries into the first mixed material, and performing dispersion treatment; obtaining a second mixed material;
and S3, pouring the second mixed material into a three-roll grinding machine for ink rolling to obtain the photovoltaic glaze.
7. The method for preparing photovoltaic glazing as claimed in claim 6, characterized in that in step S3, before the ink rolling, a diluent is added to the second mixture, so as to adjust the viscosity of the second mixture to 60000 to 1000000mPas.
8. A photovoltaic back plate glass, comprising a back plate glass and a glaze layer provided on the surface of the back plate glass, wherein the material forming the glaze layer comprises the photovoltaic glaze material according to any one of claims 1 to 7.
9. The method of making a photovoltaic backsheet glass of claim 8, comprising: and covering the photovoltaic glaze on the surface of the back plate glass, and curing and sintering to obtain the photovoltaic back plate glass.
10. A dual glass photovoltaic module comprising the photovoltaic backsheet glass of claim 8.
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