CN115010382B - Combined material suitable for photovoltaic glass and preparation method and application thereof - Google Patents

Combined material suitable for photovoltaic glass and preparation method and application thereof Download PDF

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Publication number
CN115010382B
CN115010382B CN202210817453.8A CN202210817453A CN115010382B CN 115010382 B CN115010382 B CN 115010382B CN 202210817453 A CN202210817453 A CN 202210817453A CN 115010382 B CN115010382 B CN 115010382B
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parts
layer
coating liquid
photovoltaic
glass
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CN115010382A (en
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乔仁静
何蒙
柳生
刘明刚
何进
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CSG Holding Co Ltd
Wujiang CSG Glass Co Ltd
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CSG Holding Co Ltd
Wujiang CSG Glass Co Ltd
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    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0488—Double glass encapsulation, e.g. photovoltaic cells arranged between front and rear glass sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • 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
    • C03C2217/70—Properties of coatings
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/112—Deposition methods from solutions or suspensions by spraying
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • 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
    • Y02E10/52—PV systems with concentrators

Abstract

The invention discloses a combined material suitable for photovoltaic glass, which comprises a bottom coating liquid for forming an adhesive layer on the photovoltaic glass and a surface glaze for forming a reflecting layer, wherein the adhesive layer is used for adhering the reflecting layer on the photovoltaic glass; the bottom coating liquid and the surface glaze both contain propylene glycol methyl ether acetate and silicone resin; the mass ratio of the silicon resin in the bottom layer coating liquid is larger than that of the silicon resin in the surface layer glaze; the content of hydroxyl contained in the silicone resin in the bottom coating liquid is larger than that in the surface glaze according to mass percent. According to the composite material suitable for the photovoltaic glass, the bottom coating liquid and the surface glaze are sequentially coated and glazed at the joint light transmission part of the battery piece on the surface of the photovoltaic backboard glass to form a multi-layer structure consisting of the bonding layer and the reflecting layer, and the composite material has high photovoltaic reflectance and excellent high-pressure steaming resistance (PCT) in the spectrum range of 380-1100 nm.

Description

Combined material suitable for photovoltaic glass and preparation method and application thereof
Technical Field
The invention relates to the technical field of semi-tempered glass and photovoltaic modules, in particular to a combined material suitable for photovoltaic glass, a preparation method of the combined material and application of the combined material in semi-tempered glass of a photovoltaic backboard.
Background
In order to effectively improve the power generation efficiency of the double-glass assembly, the photovoltaic backboard glass is taken as a base, the high-reflection glaze is coated on the surface of the photovoltaic backboard glass at the position where the battery piece is connected with the light transmission part in a screen printing way, the high-reflection glaze coating layer is formed through solidification and tempering treatment, and sunlight at the position can be reflected to the battery piece again for utilization, so that the photovoltaic assembly obtains the gain output power.
The high Pressure Cooking (PCT) test is an evaluation method for rapidly testing the weather resistance of high-reflection glazed glass, and is characterized in the section 2 of the glass for photovoltaic modules of T/CPIA 0028.2-2021: the test conditions are specified in the standard of the dual-glass assembly backboard reflection-increasing coating glass: placing the glass sample and the laminate sample in a test box, wherein the test temperature is 121+/-0.5 ℃, the relative humidity is 99% -100%, the test time is 48 hours, performing appearance inspection on all the samples after the test, observing whether layering, foaming, cracking, chalking and falling off of a glaze layer exist, testing the photovoltaic reflectance R of the aged glass sample, and calculating the photovoltaic reflectance attenuation value DeltaR which is less than or equal to 2%.
At present, the high-reflection glaze layer of the semi-toughened glaze-coated glass of the photovoltaic backboard prepared by partial high-reflection glaze materials in the domestic market has a photovoltaic reflectance R of more than 80 percent in a 380-1100nm spectral range, but the attenuation value delta R of the photovoltaic reflectance after a high-Pressure Cooking (PCT) test reaches 3-4 percent, and even the drop phenomenon occurs, which greatly influences the stability of the high-reflection glaze layer on the long-term outdoor use gain of the photovoltaic module and even the functional deficiency in the aspect of the output power gain of the photovoltaic module.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a composite material suitable for photovoltaic glass, which comprises a bottom coating liquid and a surface glaze, and meanwhile, the invention provides the photovoltaic glass, which is provided with an adhesive layer formed by the bottom coating liquid and a reflecting layer formed by the surface glaze, wherein the adhesive layer and the reflecting layer form a multi-layer structure; by arranging the adhesive layer between the reflecting layer and the glass, firm connection between the multi-layer structure layer and the glass is realizedCombining; forming SiO after tempering and calcining the hydroxyl-containing silicone resin in the surface glaze 2 The network structure ensures the high pressure resistant steaming (PCT) performance of the reflecting layer in the multi-layer structure.
In order to achieve the above object, the present invention adopts the following technical scheme:
a composite material suitable for photovoltaic glass, the composite material comprising a bottom layer coating liquid for forming an adhesive layer on the photovoltaic glass and a surface layer glaze for forming a reflecting layer, wherein the adhesive layer is used for adhering the reflecting layer on the photovoltaic glass; the bottom coating liquid and the surface glaze both contain propylene glycol methyl ether acetate and silicone resin; the mass ratio of the silicon resin in the bottom layer coating liquid is larger than that of the silicon resin in the surface layer glaze; the content of hydroxyl contained in the silicone resin in the bottom coating liquid is larger than that in the surface glaze according to mass percent.
The bottom coating liquid is used as a low-temperature adhesive by using low-temperature baking acrylic resin, the adhesive layer is formed by spraying coating film on the connection light transmission part of the battery piece on the surface of the photovoltaic backboard glass by using the bottom coating liquid, and the adhesive layer is obtained by low-temperature baking film forming, cooling and cooling; the reflecting layer is formed by silk-screen coating glaze on the surface of the bonding layer, curing to form a film, and then integrally tempering to form a multi-layer structure.
In some embodiments, the silicon-containing hydroxy silicone resin in both the primer coating solution and the topcoat glaze may be selected from one or more of the group consisting of Dow RSN-0217, dow RSN-0220, and Dow RSN-0255.
The bottom coating liquid contains silicon-containing hydroxyl silicone resin, hydroxyl groups of the formed bonding layer are condensed with hydroxyl groups at the interface of the photovoltaic backboard glass substrate to form-Si-O-Si-bonds, the surface glaze also contains a certain amount of silicon-containing hydroxyl silicone resin, the bonding layer is condensed with hydroxyl groups at the interface of the reflecting layer to form-Si-O-Si-bonds, namely the bonding layer firmly bonds the photovoltaic backboard glass substrate and the reflecting layer, and firm bonding among the multi-layer structure layers and between the multi-layer structure and glass is realized; forming SiO after tempering and calcining the hydroxyl-containing silicone resin in the surface glaze 2 The network structure ensures the high pressure resistant steaming (PCT) performance of the reflecting layer in the multi-layer structure.
The multilayer structure composed of the bonding layer and the reflecting layer has a photovoltaic reflectance R of more than or equal to 82% in the spectrum range of 380-1100 nm; after a high-Pressure Cooking (PCT) test, the surface glaze layer is free from layering, foaming, cracking, pulverization and falling, and the attenuation value DeltaR of the photovoltaic reflectance is less than or equal to 1 percent.
According to some preferred implementation aspects of the invention, the mass ratio of the silicon resin in the bottom layer coating liquid is 35-60%; the content of hydroxyl contained in the silicon resin in the bottom coating liquid is 2-3% by mass, and the effect of the formed adhesive layer is to firmly bond the photovoltaic backboard glass substrate and the reflecting layer; the silicon resin in the surface glaze contains hydroxyl groups with the content of not less than 0.25 percent by mass, and the silicon resin acts on the silicon resin containing the hydroxyl groups in the surface glaze to form SiO after tempering and calcining 2 The network structure ensures the high pressure resistant steaming (PCT) performance of the reflecting layer in the multi-layer structure.
According to some preferred embodiments of the present invention, the bottom coating liquid comprises, by mass, 40-50 parts of propylene glycol methyl ether acetate, 40-50 parts of silicone resin and 5-10 parts of acrylic resin; the acrylic resin is selected from low-temperature baking acrylic resin which can be heated to self-drying at 50-60 ℃ to form a film.
In some embodiments, the bottom layer coating solution is prepared by the following method: according to the parts by mass, 40-50 parts of propylene glycol methyl ether acetate and 40-50 parts of silicon-containing hydroxyl silicone resin are mixed and stirred, heated to 50-60 ℃, kept warm for dissolution for 2-4 hours, added with 5-10 parts of low-temperature baking acrylic resin, uniformly mixed, cooled to room temperature, and the bottom coating liquid is obtained.
According to some preferred embodiments of the present invention, the surface glaze component comprises, by mass, 5-10 parts of propylene glycol methyl ether acetate, 5-10 parts of silicone resin, 10-15 parts of water-soluble varnish, 30-40 parts of low-expansion glass powder and 35-45 parts of titanium pigment.
In some embodiments, the skin glaze is prepared by the following method: according to the parts by mass, 5-10 parts of propylene glycol methyl ether acetate and 5-10 parts of silicon-containing hydroxyl silicone resin are mixed and stirred and heated to 50-60 ℃, the temperature is kept for dissolution, the time of heat preservation is 2-4 hours, 10-15 parts of water-soluble ink-transfer oil, 30-40 parts of low-expansion glass powder and 35-45 parts of titanium dioxide are added, mixed and dispersed at a high speed until uniform, and the surface glaze is obtained by a three-roller grinding machine with the grinding fineness value of less than 20 mu m and vibration filtration. Wherein the titanium dioxide is selected from one or more of Long Mang Bai Libian R-996, kemu R-902+ and Kemu R-706.
The low-expansion glass powder in the surface glaze can be melted and sintered at the tempering temperature of 600-720 ℃, and the low-expansion glass powder is used as a high-temperature binder to coat titanium pigment and is adhered to the adhesive layer, so that the reflecting layer is obtained.
According to some preferred embodiments of the present invention, the water-soluble varnish component comprises, in parts by mass: 20-30 parts of dipropylene glycol methyl ether, 15-25 parts of tripropylene glycol methyl ether, 15-25 parts of diethylene glycol butyl ether, 20-40 parts of water-soluble acrylic resin, 1-5 parts of ethyl cellulose and 1-5 parts of water-based dispersing agent.
In some embodiments, the water-soluble varnish is prepared by the following method: according to the mass parts, 20-30 parts of dipropylene glycol methyl ether, 15-25 parts of tripropylene glycol methyl ether, 15-25 parts of diethylene glycol butyl ether, 20-40 parts of water-soluble acrylic resin and 1-5 parts of ethyl cellulose are mixed, stirred, heated to 50-60 ℃, dissolved in a heat preservation way for 2-4 hours, added with 1-5 parts of water-based dispersing agent, uniformly mixed and cooled to room temperature to obtain the water-soluble varnish.
According to some preferred embodiments of the present invention, the low expansion glass frit component comprises, in parts by mass: 30-40 parts of zinc oxide, 25-35 parts of silicon dioxide, 10-20 parts of boron oxide, 5-10 parts of aluminum oxide, 5-10 parts of titanium dioxide, 3-6 parts of bismuth oxide, 2-3 parts of lithium carbonate and 1-2 parts of potassium carbonate.
In some embodiments, the low expansion glass frit is prepared by the following method: mixing the ingredients, melting, quenching, grinding and homogenizing; the melting and smelting temperature is 1150-1300 ℃; the homogenized and sieved particle size D 50 Has a value of 1-2 μm and D 97 A value of 3-4 μm; the softening temperature of the low-expansion glass powder is 510-530 ℃; the average linear expansion coefficient of the low expansion glass powder is (80+/-5) multiplied by 10 -7 /K(50-300℃)。
The invention also provides a preparation method of the composite material, which comprises the following preparation steps:
1) Preparing a bottom layer coating liquid: mixing propylene glycol methyl ether acetate with silicone resin, heating, preserving heat and dissolving, adding acrylic resin, uniformly mixing, and cooling to room temperature to obtain a bottom coating liquid;
2.1 Preparation of water-soluble varnish: mixing dipropylene glycol methyl ether, tripropylene glycol methyl ether, diethylene glycol butyl ether, water-soluble acrylic resin and ethyl cellulose, stirring, heating, preserving heat and dissolving, adding a water-based dispersing agent, uniformly mixing, and cooling to room temperature to obtain water-soluble varnish;
2.2 Preparation of low expansion glass frit: the low-expansion glass powder is obtained after the materials are evenly mixed, melted, quenched, ground and homogenized in sequence; the method comprises the following steps:
2.2.1 Mixing the ingredients: mixing materials according to the parts by mass, adding the materials into a container, and uniformly mixing the materials in an oscillating mixer to obtain a premix;
2.2.2 Melting): filling the premix into a corundum crucible, putting the corundum crucible into a muffle furnace, heating to a smelting temperature and preserving heat to finish smelting, and obtaining glass liquid;
2.2.3 Quenching: taking out the corundum crucible, pouring the glass liquid into cold water for water quenching to obtain glass frit;
2.2.4 Grinding: placing the glass frit blocks in a ball mill, adding pure water medium and zirconium balls, and carrying out wet grinding to obtain glass slurry;
2.2.5 Homogenization): sieving the glass slurry by vibration, and drying; and (3) uniformly crushing by high-pressure air flow, detecting and screening the particle size, and obtaining the glass powder.
2.3 Surface glaze preparation: mixing propylene glycol methyl ether acetate and silicone resin, stirring, heating, preserving heat, dissolving, adding water-soluble varnish, low-expansion glass powder and titanium pigment, mixing, dispersing to uniformity, grinding to fineness of below 20 μm by a grinder, and vibration filtering to obtain surface glaze.
The invention also provides the photovoltaic glass, wherein the photovoltaic glass is provided with a multi-layer structure consisting of an adhesive layer and a reflecting layer, the adhesive layer is formed by curing and tempering the bottom coating liquid, and the reflecting layer is formed by curing and tempering the surface layer glaze.
The method is characterized in that photovoltaic backboard glass is used as a base, a bottom coating liquid spray coating is carried out at a light transmission part of a cell piece connection gap on the surface of the photovoltaic backboard glass, film forming, cooling and cooling are carried out through low-temperature baking (50-60 ℃) to form a film, the surface glaze silk screen printing glaze plating and solidifying (180-200 ℃) to form a film, the whole body is tempered (600-720 ℃) to form a multi-layer structure formed by an adhesive layer and a reflecting layer, the multi-layer structure has high photovoltaic reflectance and excellent high-pressure steaming (PCT) resistance in a 380-1100nm spectral range, and after a high-pressure steaming (PCT) test, the surface glaze layer is free of layering, foaming, cracking, powdering and falling, and the attenuation value DeltaR of the photovoltaic reflectance is less than or equal to 1%.
According to some preferred embodiments of the invention, the multilayer structure has a photovoltaic reflectance R > 82% in the spectral range 380-1100 nm; after the test by high-Pressure Cooking (PCT), the surface glaze layer has no layering, no foaming, no cracking, no pulverization and no falling, and the attenuation value DeltaR of the photovoltaic reflectance is less than or equal to 1 percent.
The invention also provides a photovoltaic module, which comprises front plate glass, a front packaging material layer, a battery layer, a rear packaging material layer and back plate glass which are sequentially arranged from top to bottom, wherein the back plate glass is the photovoltaic glass.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages: according to the composite material suitable for the photovoltaic glass, a bottom coating liquid and a surface glaze are sequentially coated and glazed at a light transmission part where a battery piece on the surface of the photovoltaic backboard glass is connected, and an adhesive layer and a reflecting layer are respectively formed to obtain a multi-layer structure; the bottom coating liquid contains silicon-containing hydroxyl silicone resin, hydroxyl groups of the formed bonding layer are condensed with hydroxyl groups at the interface of the photovoltaic backboard glass substrate to form-Si-O-Si-bonds, the surface glaze also contains a certain amount of silicon-containing hydroxyl silicone resin, the bonding layer is condensed with hydroxyl groups at the interface of the reflecting layer to form-Si-O-Si-bonds, namely the bonding layer firmly bonds the photovoltaic backboard glass substrate and the reflecting layer, and firm bonding among the multi-layer structure layers and between the multi-layer structure and glass is realized; hydroxyl group-containing in surface layer glazeForming SiO after tempering and calcining the silicon resin 2 The network structure ensures the high pressure resistant steaming (PCT) performance of the reflecting layer in the multi-layer structure.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution will be clearly and completely described in connection with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
The preparation steps of the composite material suitable for the photovoltaic glass of the embodiment are as follows:
1) Preparation of bottom coating liquid
According to the mass parts, 45 parts of propylene glycol methyl ether acetate and 50 parts of ceramic RSN-0220 silicon resin are mixed and stirred, heated to 60 ℃, kept warm for dissolution for 2 hours, added with 5 parts of low-temperature baking type acrylic resin, uniformly mixed, and cooled to room temperature, so as to obtain the bottom coating liquid. In the bottom layer coating liquid of the embodiment, the mass ratio of the silicon resin is 50%, and the content of silicon hydroxyl in the silicon resin is 3%.
2.1 Preparation of Water-soluble varnish
According to the mass parts, 25 parts of dipropylene glycol methyl ether, 15 parts of tripropylene glycol methyl ether, 20 parts of diethylene glycol butyl ether, 30 parts of water-soluble acrylic resin and 5 parts of ethyl cellulose are mixed, stirred and heated to 50 ℃, the temperature is kept for dissolution for 2 hours, 5 parts of water-based dispersing agent is added, the mixture is uniformly mixed, and the mixture is cooled to room temperature, so that the water-soluble varnish is obtained.
2.2 Preparation of low expansion glass frit:
2.2.1 Mixing the ingredients
According to the parts by mass, 35 parts of zinc oxide, 25 parts of silicon dioxide, 18 parts of boron oxide, 8 parts of aluminum oxide, 7 parts of titanium dioxide, 4 parts of bismuth oxide, 2 parts of lithium carbonate and 1 part of potassium carbonate are added into a container, and are placed into an oscillating mixer for uniform mixing, so as to obtain a premix;
2.2.2 Melting)
Filling the premix into a corundum crucible, putting the corundum crucible into a muffle furnace, heating to a smelting temperature of 1200 ℃ and preserving heat for 2 hours to finish smelting, and obtaining glass liquid;
2.2.3 Quenching)
Taking out the corundum crucible, pouring the glass liquid into cold water for water quenching to obtain glass frit;
2.2.4 Grinding (d)
Placing the glass frit blocks in a ball mill, adding pure water medium and zirconium balls, and carrying out wet grinding to obtain glass slurry;
2.2.5 Homogenization)
Sieving the glass slurry by vibration, and drying; the screening particle diameter D is detected through uniform high-pressure air flow crushing 50 Has a value of 1-2 μm and D 97 The value is 3-4 mu m, and the low-expansion glass powder is obtained.
2.3 Surface glaze preparation)
According to the mass parts, 5 parts of propylene glycol methyl ether acetate and 6 parts of ceramic RSN-0220 silicone resin are mixed and stirred, heated to 60 ℃, kept warm and dissolved, kept warm for 2 hours, added with 12 parts of water-soluble varnish, 35 parts of low-expansion glass powder and 42 parts of Kemu R-902+titanium dioxide, mixed and dispersed at a high speed until uniform, ground to a fineness value below 20 mu m by a three-roller grinder, and subjected to vibration filtration to obtain the surface glaze. In this example, the mass ratio of the silicone resin in the surface layer glaze is 6%, and the content of the silicon hydroxyl groups in the silicone resin is 0.36%.
The method comprises the steps of taking photovoltaic backboard glass as a base, spraying a bottom coating liquid at a light transmission part of a connecting gap between adjacent battery pieces, baking at a low temperature to form a film, cooling, performing surface glaze silk-screen coating, solidifying to form a film in the area, and performing tempering treatment integrally to form a multi-layer structure consisting of an adhesive layer and a reflecting layer.
Example 2
The preparation steps of the composite material suitable for the photovoltaic glass of the embodiment are as follows:
1.1 Preparation of bottom coating liquid
According to the parts by mass, 45 parts of propylene glycol methyl ether acetate and 45 parts of Tao Shitao RSN-0217 silicone resin are mixed and stirred, heated to 60 ℃, kept warm for dissolution for 2 hours, added with 10 parts of low-temperature baking acrylic resin, uniformly mixed, and cooled to room temperature, thus obtaining the bottom coating liquid. In the bottom layer coating liquid of the embodiment, the mass ratio of the silicon resin is 45%, and the content of the silicon hydroxyl in the silicon resin is 2.7%.
2.1 Preparation of Water-soluble varnish
According to the mass parts, 30 parts of dipropylene glycol methyl ether, 20 parts of tripropylene glycol methyl ether, 15 parts of diethylene glycol butyl ether, 25 parts of water-soluble acrylic resin and 5 parts of ethyl cellulose are mixed, stirred and heated to 50 ℃, the temperature is kept for dissolution for 2 hours, 5 parts of water-based dispersing agent is added, the mixture is uniformly mixed, and the mixture is cooled to room temperature, so that the water-soluble varnish is obtained.
2.2 Low expansion glass frit the same as in example 1.
2.3 Surface glaze preparation)
According to the mass parts, 5 parts of propylene glycol methyl ether acetate and 6 parts of ceramic RSN-0220 silicone resin are mixed and stirred, heated to 60 ℃, kept warm and dissolved, kept warm for 2 hours, added with 12 parts of water-soluble varnish, 35 parts of low-expansion glass powder and 42 parts of Kemu R-902+titanium dioxide, mixed and dispersed at a high speed until uniform, ground to a fineness value below 20 mu m by a three-roller grinder, and subjected to vibration filtration to obtain the surface glaze. In this example, the mass ratio of the silicone resin in the surface layer glaze is 6%, and the content of the silicon hydroxyl groups in the silicone resin is 0.36%.
The method comprises the steps of taking photovoltaic backboard glass as a base, spraying a bottom coating liquid at a light transmission part of a connecting gap between adjacent battery pieces, baking at a low temperature to form a film, cooling, performing surface glaze silk-screen coating, solidifying to form a film in the area, and performing tempering treatment integrally to form a multi-layer structure consisting of an adhesive layer and a reflecting layer.
Comparative example 1
The difference between this comparative example and example 1 is that: in the comparative example, the photovoltaic backboard glass is used as a base, the light transmission part of the connecting gap of the adjacent battery pieces is only provided with a reflecting layer formed by surface glaze, and no bonding layer formed by bottom coating liquid is arranged. The preparation of the water-soluble varnish, the low-expansion glass frit and the surface glaze was the same as in example 1, and the reflective layer was provided as in example 1.
Comparative example 2
The surface glaze in this comparative example was prepared by the following steps: according to the mass parts, 5 parts of propylene glycol methyl ether acetate and 3 parts of ceramic RSN-0220 silicone resin are mixed and stirred, heated to 60 ℃, kept warm and dissolved, kept warm for 2 hours, added with 15 parts of water-soluble varnish, 35 parts of low-expansion glass powder and 42 parts of Kemu R-902+titanium dioxide, mixed and dispersed at a high speed until uniform, ground to a fineness value below 20 mu m by a three-roller grinder, and subjected to vibration filtration to obtain the surface glaze. In the comparative example, the mass ratio of the silicon resin of the surface glaze is 3%, the hydroxyl content of the silicon resin is 0.18% and is lower than 0.25%. The primer coating liquid, the water-soluble varnish and the low-expansion glass powder are the same as in example 1, and the adhesive layer and the reflective layer are arranged as in example 1.
Example 3
Sieving particle diameter D of Low expansion glass powder used in examples 1-2 and comparative examples 1-2 50 Value 1.765 μm, D 97 The value of 3.961 μm, the softening temperature of 525℃and the average linear expansion coefficient of 82X 10 -7 /K(50-300℃)。
The photovoltaic backsheet semi-tempered coated glass prepared in examples 1-2 and comparative examples 1-2, on which the multi-layer structure was in the 380-1100nm spectral range, was tested for photovoltaic reflectance R, appearance of glazing after autoclaving (PCT) test, photovoltaic reflectance R x and photovoltaic reflectance attenuation value Δr, and the test results are shown in table 1 below.
Table 1 test results
The results in Table 1 show that the composite material suitable for the photovoltaic glass is prepared by adopting the method in the embodiment, the bottom coating liquid and the surface glaze are sequentially coated and glazed at the joint light transmission part of the battery piece on the surface of the photovoltaic backboard glass to form a multi-layer structure, the photovoltaic reflectance R of the composite material in the spectral range of 380-1100nm is more than or equal to 82%, and after a high-Pressure Cooking (PCT) test, the surface glaze layer is free from layering, foaming, cracking, powdering and falling, and the photovoltaic reflectance attenuation value DeltaR is less than or equal to 1%.
The invention provides a composite material suitable for photovoltaic glass, which comprises the following components: 1. coating a film and glazing the battery piece connection light transmission part of the surface of the photovoltaic backboard glass with the bottom layer coating liquid and the surface glaze sequentially to form an adhesive layer and a reflecting layer respectively, so as to obtain a multi-layer structure; 2. the bottom coating liquid contains silicon-containing hydroxyl silicone resin, hydroxyl groups of the formed bonding layer are condensed with hydroxyl groups at the interface of the photovoltaic backboard glass substrate to form-Si-O-Si-bonds, the surface glaze also contains a certain amount of silicon-containing hydroxyl silicone resin, the bonding layer is condensed with hydroxyl groups at the interface of the reflecting layer to form-Si-O-Si-bonds, namely the bonding layer firmly bonds the photovoltaic backboard glass substrate and the reflecting layer, and firm bonding among the multi-layer structure layers and between the multi-layer structure and glass is realized; forming SiO after tempering and calcining the hydroxyl-containing silicone resin in the surface glaze 2 A network structure for ensuring high pressure cooking resistance (PCT) of the reflective layer in the multilayer structure; 3. the multi-layer structure has high photovoltaic reflectance and excellent high-pressure steaming (PCT) resistance in the 380-1100nm spectral range, and after a high-pressure steaming (PCT) test, the surface glaze layer is free of layering, foaming, cracking, pulverization and falling, the attenuation value DeltaR of the photovoltaic reflectance is less than or equal to 1%, and the high efficiency and the continuous stability of the output power gain of the photovoltaic module in long-term outdoor use are effectively ensured.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, but are not intended to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.

Claims (7)

1. The composite material is characterized by comprising a bottom coating liquid for forming an adhesive layer on the photovoltaic glass and a surface glaze for forming a reflecting layer, wherein the adhesive layer is used for adhering the reflecting layer on the photovoltaic glass; the bottom coating liquid and the surface glaze both contain propylene glycol methyl ether acetate and silicone resin; the mass ratio of the silicon resin in the bottom layer coating liquid is larger than that of the silicon resin in the surface layer glaze; the content of hydroxyl contained in the silicone resin in the bottom coating liquid is larger than that in the surface glaze according to the mass percentage;
the mass ratio of the silicon resin in the bottom layer coating liquid is 35-60%; the content of hydroxyl contained in the silicon resin in the bottom coating liquid is 2-3% by mass percent; the content of hydroxyl contained in the silicone resin in the surface glaze is not less than 0.25 percent by mass;
the bottom layer coating liquid comprises 40-50 parts of propylene glycol methyl ether acetate, 40-50 parts of silicone resin and 5-10 parts of acrylic resin; the surface glaze comprises 5-10 parts of propylene glycol methyl ether acetate, 5-10 parts of silicone resin, 10-15 parts of water-soluble varnish, 30-40 parts of low-expansion glass powder and 35-45 parts of titanium dioxide.
2. The composition according to claim 1, wherein the water-soluble varnish component comprises, in parts by mass: 20-30 parts of dipropylene glycol methyl ether, 15-25 parts of tripropylene glycol methyl ether, 15-25 parts of diethylene glycol butyl ether, 20-40 parts of water-soluble acrylic resin, 1-5 parts of ethyl cellulose and 1-5 parts of water-based dispersing agent.
3. The composition according to claim 1, wherein the low-expansion glass frit component comprises, in parts by mass: 30-40 parts of zinc oxide, 25-35 parts of silicon dioxide, 10-20 parts of boron oxide, 5-10 parts of aluminum oxide, 5-10 parts of titanium dioxide, 3-6 parts of bismuth oxide, 2-3 parts of lithium carbonate and 1-2 parts of potassium carbonate.
4. A method of preparing a composite according to any one of claims 1 to 3, comprising the steps of:
1) Preparing a bottom layer coating liquid: mixing propylene glycol methyl ether acetate with silicone resin, heating, preserving heat and dissolving, adding acrylic resin, uniformly mixing, and cooling to room temperature to obtain a bottom coating liquid;
2.1 Preparation of water-soluble varnish: mixing dipropylene glycol methyl ether, tripropylene glycol methyl ether, diethylene glycol butyl ether, water-soluble acrylic resin and ethyl cellulose, stirring, heating, preserving heat and dissolving, adding a water-based dispersing agent, uniformly mixing, and cooling to room temperature to obtain water-soluble varnish;
2.2 Preparation of low expansion glass frit: sequentially carrying out batch mixing, melting, quenching, grinding and homogenization to obtain low-expansion glass powder;
2.3 Surface glaze preparation: mixing propylene glycol methyl ether acetate and silicone resin, stirring, heating, preserving heat, dissolving, adding water-soluble varnish, low-expansion glass powder and titanium pigment, mixing, dispersing to uniformity, grinding to fineness of below 20 μm by a grinder, and vibration filtering to obtain surface glaze.
5. The photovoltaic glass is characterized by comprising a multi-layer structure composed of an adhesive layer and a reflecting layer, wherein the adhesive layer is formed by curing and toughening the bottom coating liquid according to any one of claims 1-3, and the reflecting layer is formed by curing and toughening the surface layer glaze according to any one of claims 1-3.
6. The photovoltaic glass according to claim 5, wherein the photovoltaic reflectance R of the multilayer structure is greater than or equal to 82% in the spectral range of 380-1100 nm; after being tested by a high-pressure cooking PCT, the attenuation value DeltaR of the photovoltaic reflectance is less than or equal to 1%.
7. A photovoltaic module comprising front plate glass, a front packaging material layer, a battery layer, a rear packaging material layer and back plate glass which are sequentially arranged from top to bottom, wherein the back plate glass is the photovoltaic glass as claimed in claim 5 or 6.
CN202210817453.8A 2022-07-12 2022-07-12 Combined material suitable for photovoltaic glass and preparation method and application thereof Active CN115010382B (en)

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