Photovoltaic coated glass, preparation method thereof and photovoltaic module

Abstract

The invention discloses photovoltaic coated glass, a preparation method thereof and a photovoltaic module, and belongs to the technical field of glass manufacturing. The preparation method comprises the following steps: mixing a matrix material, a main sensitizer, an intermediate sensitizer, an exciting agent, a first chelating agent, deionized water and a nitric acid solution, and reacting to obtain a solution A; tetraethoxysilane, deionized water, an organic solvent and a second metal chelating agent are mixed and subjected to a hydrolysis reaction, and a solution B is obtained; mixing the solution A and the solution B, and preparing a first sol solution through a sol-gel method; coating the surface of a glass substrate with the first sol solution, and drying to obtain a light conversion antireflection film layer; preparing a protective film layer on the surface, far away from the glass substrate, of the light conversion antireflection film layer; the photovoltaic coated glass is obtained by carrying out toughening treatment on the glass substrate containing the light conversion antireflection film layer and the protective film layer, and the photovoltaic coated glass is applied to the photovoltaic module, so that the sunlight capture and utilization efficiency of the photovoltaic module can be improved, and the wear resistance can be enhanced.

Description

Technical Field

[0001] This invention relates to the field of glass manufacturing technology, and in particular to a photovoltaic coated glass, its preparation method, and a photovoltaic module. Background Technology

[0002] In recent years, with the global consensus on addressing climate change, major economies have set carbon emission reduction targets. This necessitates more clean energy, especially more cost-effective green energy. Improving the cost-effectiveness of photovoltaic (PV) modules to enhance their competitiveness with other green energy sources is of great practical significance for the healthy and sustainable development of the PV market and the achievement of carbon reduction goals. This can be achieved by reducing material costs and optimizing production processes to lower module costs; or by improving the photoelectric conversion efficiency of the modules. Compared to the former, which already has sufficiently low raw material costs and mature processes, the latter offers greater potential and opportunities, such as new PV cell technologies. Module encapsulation for new PV cells will be a crucial step, with the light transmittance of PV glass being a key factor affecting module conversion efficiency.

[0003] Currently, many methods exist for achieving anti-reflection in glass, with surface coating being the most common approach. Furthermore, for novel photovoltaic cells, their response to sunlight is generally concentrated in the visible light range, while the high-energy ultraviolet light remains unusable, resulting in significant losses. In recent years, rare-earth-doped light conversion materials have begun to be used in solar cell modules, such as encapsulating films for light conversion and coated glasses for light conversion. However, despite significant progress in laboratory studies of rare-earth-doped downconversion materials, industrial production still faces challenges, including the absorption range, cost, and preparation process of these materials. Existing technology discloses an anti-reflection glass film and its preparation method. By using a coating solution as a carrier, combining it with a precursor of a downconversion material, and uniformly coating it onto the glass surface, an anti-reflection glass film is prepared in situ through co-firing. Compared to traditional coated glass, this method significantly improves light transmittance. However, the light-converting glass coating prepared by this method has poor UV resistance and a narrow absorption wavelength range. Furthermore, the surface hardness of the coated glass is low, resulting in poor abrasion resistance, easy scratching and peeling, and the formation of belt marks during component production. In summary, solving these problems and preparing a high-hardness light-converting anti-reflective coated glass with superior performance is of great value. Summary of the Invention

[0004] The main objective of this invention is to provide a photovoltaic coated glass, its preparation method, and a photovoltaic module, thereby solving the technical problems of low utilization rate of sunlight and poor mechanical properties of photovoltaic coated glass.

[0005] To achieve the above objectives, the present invention provides a method for preparing photovoltaic coated glass, comprising the following steps: Solution A is obtained by mixing and reacting matrix material, main sensitizer and intermediate sensitizer, activator, first chelating agent, deionized water and nitric acid solution. Solution B is obtained by mixing tetraethyl orthosilicate, deionized water, organic solvent, and a second metal chelating agent and then hydrolyzing the mixture. The first sol solution was prepared by mixing the solutions A and B using the sol-gel method. The first sol solution is coated onto the surface of a glass substrate and dried to obtain a light conversion antireflection film layer; A protective film layer is prepared on the surface of the light conversion antireflection film layer away from the glass substrate; The photovoltaic coated glass is obtained by tempering a glass substrate containing the light conversion antireflection film and the protective film.

[0006] In some embodiments of the present invention, the activator includes at least one selected from europium oxide (Eu2O3), thulium oxide (Tm2O3), ytterbium oxide (Yb2O3), and chromium oxide (Cr2O3); And / or, the primary sensitizer includes at least one of bismuth oxide (Bi2O3), cerium oxide (Ce2O3), antimony oxide (Sb2O3), and praseodymium oxide (Pr2O3); And / or, the intermediate sensitizer includes at least one of terbium oxide (Tb2O3), cerium oxide (Ce2O3), gadolinium oxide (Gd2O3), and manganese oxide (Mn2O3).

[0007] In some embodiments of the present invention, the matrix material includes a first matrix material and a second matrix material, wherein the first matrix material includes yttrium oxide (Y2O3) and the second matrix material includes ammonium metavanadate.

[0008] In some embodiments of the present invention, the first matrix is ​​yttrium oxide (Y₂O₃), the second matrix is ​​ammonium metavanadate, the main sensitizer is bismuth oxide, the intermediate sensitizer is terbium oxide, the activator is europium oxide, and the first sol solution is SiO₂@YVO₄:Eu 3+ ,Tb 3+ ,Bi 3+ Solution.

[0009] In some embodiments of the present invention, the SiO2@YVO4:Eu 3+ ,Tb 3+ ,Bi 3+ Y in solution 3+ Eu 3+ 、Tb 3 +Bi 3+ Based on a total molar content of 100%, Bi 3+ The molar content is 0.5%~2%, Tb 3+ The molar content is 3% to 7%, Eu 3+ The molar content is 1%~4%, with the balance being Y. 3+ .

[0010] In some embodiments of the present invention, the molar ratio of tetraethyl orthosilicate, deionized water, organic solvent, and second chelating agent in solution B is 1:(3~9):(4~12):(0.01~0.1); And / or, the drying temperature is 50℃~200℃; And / or, the drying time is 10s to 80s; And / or, the tempering temperature is 600℃~900℃; And / or, the tempering time is 80s~300s.

[0011] In some embodiments of the present invention, the preparation of the protective film layer includes the following steps: The reactant is obtained by hydrolyzing aminosilane and then reacting it with acrylate via a Michael addition reaction. The reactants, amino-terminated polydimethylsiloxane, and organic solvent are mixed to obtain a second sol solution. The second sol solution is coated onto the surface of the light conversion antireflection film layer away from the glass substrate, and dried to obtain the protective film layer.

[0012] In some embodiments of the present invention, the thickness of the light conversion antireflection film is 150nm~300nm; and / or, the thickness of the protective film is 5nm~100nm.

[0013] The present invention also provides a photovoltaic coated glass, which is prepared by the photovoltaic coated glass preparation method described above.

[0014] The present invention also provides a photovoltaic module, the photovoltaic module comprising the photovoltaic coated glass as described above.

[0015] The beneficial effects that this invention can achieve are: This invention prepares a light-conversion antireflective film by combining light-conversion materials with porous SiO2 nanostructures in a sol-gel process. This film can effectively adjust the solar spectrum range and convert the solar spectrum in the 250nm~360nm wavelength range into visible light in the 400~650nm wavelength range, especially visible light in the 530nm~630nm wavelength range, thereby effectively improving the light conversion efficiency of photovoltaic modules.

[0016] Moreover, the light conversion antireflection film is a triple co-doped system consisting of a main sensitizer, an intermediate sensitizer, and an exciter. The main sensitizer can transfer energy to the intermediate sensitizer, which acts as a bridge to transfer energy to the exciter. This can compensate for the low efficiency problem of direct energy transfer between the main sensitizer and the exciter.

[0017] Meanwhile, the light-conversion antireflection film layer formed by the sol-gel process has a porous SiO2 nanostructure, resulting in a refractive index lower than that of the substrate glass. This significantly reduces sunlight reflection loss and enhances light transmittance. Ultimately, this synergistic effect of "light conversion" and "antireflection" improves the photovoltaic module's efficiency in capturing and utilizing sunlight, thereby increasing the module's light conversion efficiency and power output.

[0018] This invention also prepares a protective film layer on the surface of the light conversion antireflection film layer, which can obtain high-hardness photovoltaic coated glass while ensuring light transmittance, enhance the mechanical properties of photovoltaic coated glass, and make the surface hardness of coated glass reach 5H or above. Compared with the existing coated glass with a hardness of 3H to 4H, the photovoltaic coated glass of this invention is better suited to the production requirements of photovoltaic modules and is less prone to problems such as belt marks and scratches.

[0019] Furthermore, the photovoltaic coated glass of the present invention has a simple preparation process, low cost, and is convenient for coating processing of photovoltaic glass, thus having good practical value. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art are briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0021] Figure 1 This is a schematic diagram of the structure of a photovoltaic coated glass according to the present invention.

[0022] Explanation of icon numbers: 1. Glass substrate; 2. Light conversion antireflective coating; 3. Protective coating.

[0023] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0024] It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0025] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0026] In this invention, descriptions involving "first," "second," etc., are for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. Furthermore, the technical solutions of the various embodiments can be combined with each other, but only on the basis of being achievable by those skilled in the art. If the combination of technical solutions is contradictory or impossible to implement, such a combination should be considered non-existent and not within the scope of protection claimed by this invention.

[0027] This invention provides a photovoltaic coated glass and a method for preparing the photovoltaic coated glass. The method for preparing the photovoltaic coated glass includes the following steps: S10. Mix the matrix material, main sensitizer, intermediate sensitizer, activator, first chelating agent, deionized water, and nitric acid solution to obtain solution A. S20. Mix tetraethyl orthosilicate, deionized water, organic solvent, and second metal chelating agent and hydrolyze to obtain solution B; S30. Mix solution A and solution B, and prepare the first sol solution by the sol-gel method; S40. The first sol solution is coated onto the surface of the glass substrate and dried to obtain a light conversion antireflection film layer; S50. Prepare a protective film layer on the surface of the light conversion antireflection film layer away from the glass substrate; S60. A glass substrate containing a light conversion antireflective coating and a protective coating is tempered to obtain photovoltaic coated glass.

[0028] refer to Figure 1 The photovoltaic coated glass prepared includes a glass substrate 1, a light conversion antireflective film layer 2, and a protective film layer 3.

[0029] In this invention, the sensitizer captures the energy of external excitation light, causing itself to transition from the ground state to the excited state. Once in the excited state, the energy is transferred to the exciter, which then emits visible light, thereby realizing the conversion of invisible ultraviolet light into visible light for use by photovoltaic modules.

[0030] It is understandable that both the primary sensitizer and the intermediate sensitizer are sensitizers, and the primary sensitizer and the intermediate sensitizer have the following relationship: the energy generated by the primary sensitizer from the transition from the ground state to the excited state can be transferred to the intermediate sensitizer, and the energy can be transferred to the exciter through the intermediate sensitizer.

[0031] This invention utilizes a sol-gel process to prepare a light-conversion antireflection film, combining light-conversion materials with a porous SiO2 nanostructure. This process effectively modulates the solar spectrum, converting the 250nm–360nm wavelength range of solar light into visible light in the 400–650nm wavelength range, particularly the 400nm–630nm range, thus significantly improving the light conversion efficiency of photovoltaic modules. Furthermore, the antireflection film is a triple-doped system consisting of a main sensitizer, an intermediate sensitizer, and an exciter. The main sensitizer transfers energy to the intermediate sensitizer, which acts as a bridge, transferring energy to the exciter. This overcomes the low efficiency problem of direct energy transfer between the main sensitizer and the exciter. Simultaneously, the antireflection film formed by the sol-gel process possesses a porous SiO2 nanostructure, resulting in a refractive index lower than that of the substrate glass. This significantly reduces solar light reflection loss and enhances light transmittance. Ultimately, the synergistic effect of "light conversion" and "anti-reflection" improves the efficiency of photovoltaic modules in capturing and utilizing sunlight, thereby increasing the light conversion efficiency and power output of the photovoltaic modules.

[0032] This invention also prepares a protective film layer on the surface of the light conversion antireflection film layer, which can obtain high-hardness photovoltaic coated glass while ensuring light transmittance, enhance the mechanical properties of photovoltaic coated glass, and make the surface hardness of coated glass reach 5H or above. Compared with the existing coated glass with a hardness of 3H to 4H, the photovoltaic coated glass of this invention is better suited to the production requirements of photovoltaic modules and is less prone to problems such as belt marks and scratches.

[0033] Furthermore, the photovoltaic coated glass of the present invention has a simple preparation process, low cost, and is convenient for coating processing of photovoltaic glass, thus having good practical value.

[0034] In some embodiments, the primary sensitizer includes at least one selected from bismuth oxide (Bi₂O₃), cerium oxide (Ce₂O₃), antimony oxide (Sb₂O₃), and praseodymium oxide (Pr₂O₃), while the intermediate sensitizer includes at least one selected from terbium oxide (Tb₂O₃), cerium oxide (Ce₂O₃), gadolinium oxide (Gd₂O₃), and manganese oxide (Mn₂O₃). The primary sensitizer can transfer the energy generated from the transition from the ground state to the excited state to the intermediate sensitizer, and then transfer the energy to the exciter through the intermediate sensitizer, thus overcoming the low efficiency problem of direct energy transfer between the primary sensitizer and the exciter.

[0035] For example, the primary sensitizer includes bismuth oxide (Bi₂O₃), and the intermediate sensitizer includes terbium oxide (Tb₂O₃). The Bi₂O₃ in the bismuth oxide... 3+ It exhibits broadband blue-green light emission in the 400nm~500nm range, by 3 P1 direction 1 The energy generated by the S0 transition can be transferred to Tb in the intermediate sensitizer terbium oxide. 3+ And Tb 3+ Not only can it receive from Bi 3+ The energy can be efficiently transferred to activators such as europium oxide, which can solve the problem of Bi 3+ The problem of low efficiency and poor effect in directly transferring energy to the activator.

[0036] In some embodiments, the activator includes at least one of europium oxide (Eu2O3), chromium oxide (Cr2O3), thulium oxide (Tm2O3), and ytterbium oxide (Yb2O3).

[0037] In some embodiments, the matrix material includes a first matrix material and a second matrix material. The first matrix material includes yttrium oxide (Y₂O₃), and the second matrix material includes ammonium metavanadate. Yttrium oxide and ammonium metavanadate are mixed and reacted to obtain a matrix primarily composed of YVO₄, wherein VO₄… 3- The group has strong absorption in the ultraviolet region of 250 nm to 350 nm, which can transfer energy to the doped exciter ions and sensitizer ions.

[0038] In some embodiments, the molar ratio of the primary sensitizer, intermediate sensitizer, activator, and first matrix material is (0.5~2):(3~7):(1~4):(87~95.5).

[0039] In some embodiments, the molar ratio of the first matrix material to the second matrix material is 4:1 to 9:1.

[0040] In some embodiments, the molar ratio of the first matrix material to the first chelating agent is 1:(2~3).

[0041] In some embodiments, the first matrix material is yttrium oxide, the second matrix material is ammonium metavanadate, the main sensitizer is bismuth oxide (Bi₂O₃), the intermediate sensitizer is terbium oxide (Tb₂O₃), the activator is europium oxide (Eu₂O₃), and the prepared solution A is YVO₄:Eu 3+ ,Tb 3+ ,Bi 3+ The first sol solution, obtained by mixing solutions A and B via the sol-gel method, is SiO2@YVO4:Eu 3+ ,Tb 3+ ,Bi 3+The prepared light conversion antireflection film contains SiO2@YVO4:Eu 3+ ,Tb 3+ ,Bi 3+ .

[0042] In the above embodiments, the light conversion antireflection film layer is made of YVO4:Eu wrapped with SiO2. 3+ , Tb 3+ Bi 3+ The resulting core-shell nanostructure, with SiO2 as the shell, can reduce surface quenching and enhance material stability, and YVO4 as the matrix, YVO4... 3- The group can absorb ultraviolet light in the 250nm~360nm range and activate the doped ions Eu through energy transfer. 3+ 、Tb 3+ Bi 3+ Bi 3+ It exhibits broadband blue-green light emission of 400-500 nm in the YVO4 matrix, which is caused by... 3 P1 direction 1 The energy generated by the S0 transition can be transferred to Tb in the intermediate sensitizer terbium oxide. 3+ , and Tb 3+ Not only can it receive from Bi 3+ The energy, and can be effectively transferred to the activator Eu. 3+ The dual sensitizer in this embodiment solves the Bi problem. 3+ To Eu 3+ The problem of low efficiency and poor effect of direct energy transfer can be significantly enhanced by Bi. 3+ This significantly improves the energy transfer efficiency of photovoltaic modules, thereby greatly enhancing their utilization of sunlight.

[0043] In some embodiments, SiO2@YVO4:Eu 3+ ,Tb 3+ ,Bi 3+ Y in 3+ Eu 3+ Ce 3+ Bi 3+的 Based on a total molar content of 100%, Bi 3+ The molar content is 0.5%~2%, Tb 3+ The molar content is 3% to 7%, Eu 3+ The molar content is 1%~4%, with the balance being Y. 3+ Eu was implemented. 3+ 、Tb 3+ Bi 3+ and matrix ion Y 3+ The synergistic effect between them allows this ratio to effectively absorb a wide range of ultraviolet light while enhancing Bi3+ The improved luminous efficiency and thermal stability greatly enhance the quantum efficiency of the light conversion antireflective film and the utilization rate of the ultraviolet spectrum in photovoltaic modules.

[0044] In some embodiments, the first metal chelating agent includes at least one selected from citric acid, tartaric acid, malic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and acetylacetone.

[0045] In some embodiments, the second metal chelating agent includes at least one selected from citric acid, tartaric acid, malic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and acetylacetone.

[0046] In some embodiments, after the first sol solution is coated onto the surface of the glass substrate, the drying temperature is 50°C to 200°C, which can be 50°C, 100°C, 150°C, 200°C, etc., and the drying time is 10s to 80s, which can be 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, etc. This helps to form the film layer, ensures a firm bond between the film layer and the glass substrate, and at the same time avoids cracking or peeling of the film layer, thereby improving the durability and optical performance of the product.

[0047] In some embodiments, the reaction time for mixing the matrix material, sensitizer, activator, first chelating agent, deionized water, and nitric acid solution is 3.5 h to 4.5 h, and the reaction temperature is 70 °C to 90 °C.

[0048] In some embodiments, the pH of the matrix material, sensitizer, activator, first chelating agent, deionized water, and nitric acid solution before the reaction is 4.5 to 5.5, and the pH can be adjusted to 4.5 to 5.5 by adding ammonia.

[0049] The matrix material, sensitizer, activator, first chelating agent, deionized water, and nitric acid solution are mixed, and the pH value is adjusted to 4.5-5.5 by adding ammonia. The mixture is then reacted at 70℃-90℃ for 3.5-4.5 hours (or 4 hours) to obtain solution A. This embodiment, by precisely controlling the pH value and reaction temperature of solution A, ensures that the activator, sensitizer, and matrix material can undergo a sufficient and uniform co-precipitation reaction to form a precursor. This lays the foundation for the subsequent formation of nanocrystals with good crystallinity and high luminescence efficiency, thereby ensuring the high efficiency and stability of the light conversion antireflection film.

[0050] In some embodiments, the matrix material, sensitizer, and activator can be dissolved in nitric acid solution to obtain matrix material nitric acid solution, sensitizer nitric acid solution, and activator nitric acid solution, respectively. Then, the matrix material nitric acid solution, sensitizer nitric acid solution, activator nitric acid solution, first chelating agent, and deionized water are mixed and reacted to obtain solution A.

[0051] In some embodiments, the molar ratio of tetraethyl orthosilicate:deionized water:organic solvent:second chelating agent in solution B is 1:(3~9):(4~12):(0.01~0.1), and more specifically 1:5:7:0.02. This embodiment optimizes the ratio to ensure a moderate rate of hydrolysis and polycondensation of the silica sol, resulting in a sol with good stability and film-forming properties. Furthermore, the chelating agent effectively controls the reaction process, ultimately forming a dense and uniform SiO2 shell that provides optimal protection for the core luminescent material while ensuring high light transmittance of the film.

[0052] In some embodiments, the pH of the mixture of tetraethyl orthosilicate, deionized water, organic solvent, and second metal chelating agent before the reaction is 3.5 to 4.5, which can be adjusted by adding ammonia.

[0053] In some embodiments, tetraethyl orthosilicate, deionized water, an organic solvent, and a second metal chelating agent are mixed, and the pH of the reaction system is adjusted to 3.5-4.5 by adding ammonia. The reaction is then hydrolyzed at 50-70°C for 23-25 ​​hours (or 24 hours) to obtain solution B. In this embodiment, the slow hydrolysis of tetraethyl orthosilicate under weakly acidic conditions facilitates the formation of a uniformly sized and structurally stable silica sol. This sol, when mixed with solution A, effectively coats the luminescent material, forming a core-shell structure, preventing quenching of the luminescent centers, improving the dispersibility and chemical stability of the material, and extending the film's lifespan.

[0054] In some embodiments, the preparation of the first sol solution by the sol-gel method includes: mixing solution A and solution B, stirring until homogeneous and clear to obtain the first sol solution.

[0055] In some embodiments, the volume ratio of solution A to solution B is 1:4 to 1:5, which can be 1:4, 1:4.5, 1:5, etc.

[0056] In some embodiments, the ambient humidity when coating the first sol solution onto the surface of the glass substrate is 30%~60% and the temperature is 20℃~25℃. Strictly controlling the temperature and humidity of the coating environment can effectively control the evaporation rate of the sol and the hydrolysis-condensation reaction rate, avoid the film layer from cracking due to excessive dryness, or the film layer from fogging or whitening due to excessive humidity, and ensure the uniformity of the film layer.

[0057] In some embodiments, preparing the protective film layer includes the following steps: Step 1: Hydrolyze aminosilane and then react it with acrylate to obtain the reactant; Step 2: The reactants, amino-terminated polydimethylsiloxane, and organic solvent are mixed to obtain the second sol solution; Step 3: Coat the second sol solution onto the surface of the light conversion antireflection film layer away from the glass substrate, and dry to obtain the protective film layer.

[0058] The process in this embodiment can effectively improve the hardness of the high protective film layer, thereby effectively resisting scratches and wear, adapting to the high-intensity processing environment of photovoltaic modules, and at the same time, ensuring sufficient light transmittance to ensure the efficiency of photovoltaic modules in capturing and utilizing sunlight.

[0059] In some embodiments, aminosilanes include one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropyltris(2-ethylhexyloxy)silane.

[0060] In some embodiments, the acrylate includes one or more of pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ethoxylated / propoxylated pentaerythritol tetraacrylate, and trimethylolpropane trimethacrylate.

[0061] In step 1, the mass ratio of aminosilane to pentaerythritol triacrylate is (10~15):5.

[0062] In step 1, the Michael addition reaction is carried out at a temperature of 35°C to 40°C for 1.5 h to 2 h.

[0063] In some embodiments, the mass ratio of aminosilane to amino-terminated polydimethylsiloxane is (10~15):2.

[0064] In some embodiments, the mass ratio of aminosilane to organic solvent in step 2 is (10~15):(5~10).

[0065] In some embodiments, the ambient humidity is 30%~60% and the temperature is 20℃~25℃ when the second sol solution is coated onto the surface of the light conversion antireflection film away from the glass substrate. Strict control of the temperature and humidity of the coating environment can effectively control the evaporation rate of the sol and the hydrolysis and condensation reaction rate, avoid the film layer from cracking due to excessive dryness, or the film layer from fogging or whitening due to excessive humidity, and ensure the uniformity of the film layer.

[0066] In some embodiments, the protective film formed by coating the second sol solution onto the surface of the light conversion antireflection film away from the glass substrate and drying it contains SiO2. The shell structure size of the SiO2 is 1nm~20nm, and can be 1nm, 2nm, 3nm, 4nm, 5nm, 8nm, 10nm, 12nm, 15nm, 18nm, 20nm, etc., so that it can be well dispersed in the organosilicon-acrylate hybrid system, acting as a nano-reinforcement. These small-sized rigid particles can effectively improve the hardness, wear resistance and density of the composite film, thereby achieving a hardness of up to 5H with an extremely thin film thickness, while not affecting visible light transmittance.

[0067] In this invention, the glass substrate with light conversion antireflection film and protective film is tempered, which not only physically strengthens the glass substrate in one step, but also densifies the double film layer through high-temperature sintering, ultimately further improving the strength of the glass, the hardness of the film layer and optimizing the weather resistance of the glass.

[0068] In some embodiments, the tempering temperature is 600℃~900℃ and the tempering time is 80s~300s.

[0069] In some embodiments, the thickness of the light conversion antireflection film is 150nm~300nm, which can be 150nm, 160nm, 170nm, 180nm, 190nm, 200nm, 230nm, 250nm, 280nm, 290nm, 300nm, etc., to ensure good antireflection and light conversion functions.

[0070] In some embodiments, the thickness of the protective film layer is 5nm~100nm, which can be 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, etc., which can ensure that the surface layer has sufficient mechanical strength and weather resistance, and can be used in photovoltaic modules to achieve long-term outdoor use.

[0071] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following specific embodiments are only used to explain the present invention and are not intended to limit the present invention.

[0072] Example 1 The method for preparing photovoltaic coated glass in this embodiment is as follows: S10. Preparation of solution A The first sol solution SiO2@YVO4:Eu 3+ ,Tb 3+ ,Bi 3+ Y in solution 3+ Eu 3+ 、Tb3+ Bi 3+ Based on a total molar content of 100%, Bi was designed. 3+ The molar content is 2%, Tb 3+ The molar content is 5%, Eu 3+ The molar content is 3%, and the balance is 90% Y. 3+ Based on the Y in the first sol solution above 3+ Eu 3+ 、Tb 3+ Bi 3+ According to the molar ratio, the first matrix yttrium oxide (Y2O3), europium oxide (Eu2O3), terbium oxide (Tb2O3), and bismuth oxide (Bi2O3) were weighed out, dissolved in an appropriate amount of dilute nitric acid, and heated and stirred until completely clear to obtain Y(NO3)3, Eu(NO3)3, Tb(NO3)3, and Bi(NO3)3.

[0073] The four nitrate solutions were mixed in a beaker, and 200 ml of deionized water was added. Then, ammonium metavanadate (NH4VO3) and citric acid (as the first metal chelating agent) were added according to a molar ratio of yttrium oxide (Y2O3) to the second matrix of 4:9 and a molar ratio of yttrium oxide (Y2O3) to the first chelating agent of 1:2. The mixture was stirred until completely dissolved. While continuously stirring, ammonia was added dropwise to adjust the pH of the solution to 5.0. The solution was then placed in an 80°C water bath and reacted at this temperature for 4 hours to obtain a pale yellow, transparent solution A.

[0074] S20, Preparation of solution B Tetraethyl orthosilicate (TEOS), deionized water, isopropanol (IPA), and citric acid (a second metal chelating agent) were mixed in a molar ratio of 1:5:7:0.02 and stirred to dissolve. Then, a few drops of ammonia were added to adjust the pH of the mixed solution to 4.0. The solution was then placed in a 60°C water bath and stirred for 24 hours to obtain a clear SiO2 sol, i.e., solution B.

[0075] S30. Preparation of the first sol solution: While stirring, solution A was slowly added dropwise to solution B prepared in step S20 at a volume ratio of 1:4 (A:B). After the addition was complete, stirring was continued for 2 hours to ensure thorough mixing. The mixture was then allowed to stand for 12 hours to age, resulting in a homogeneous, clear SiO2@YVO4:Eu coating. 3+ ,Tb 3+ ,Bi 3+ The first sol solution, wherein SiO2@YVO4:Eu 3+ ,Tb 3+ ,Bi 3+ Y in solution 3+ Eu3+ 、Tb 3+ Bi 3+ Based on a total molar content of 100%, Bi 3+ The molar content is 2%, Tb 3+ The molar content is 5%, Eu 3+ The molar content is 3%, and the balance is 90% Y. 3+ .

[0076] S40, Preparation of light conversion antireflection coating layer A 1000mm × 2000mm sheet of ultra-clear float glass was cleaned with deionized water and dried before being placed on the conveyor belt of a roller coater. The first sol solution was uniformly coated onto the surface of the ultra-clear float glass using a roller coating method. The coated ultra-clear float glass was immediately passed through a drying channel set at 120℃ for 40 seconds, thereby forming a dry light conversion antireflection film layer with a thickness of approximately 180nm on the glass surface.

[0077] S50, Preparation of protective film layer Weigh 10 g of 3-aminopropyltriethoxysilane (APTES) and add it to a mixed solvent of 10 g of deionized water and 50 g of isopropanol. Use 0.1 mol·L⁻¹ -1 The pH was adjusted to 2.5 with HCl, and the mixture was stirred at room temperature for 30 min to obtain a clear hydrolysate. Then, 5 g of pentaerythritol triacrylate (PETA) was added, and the mixture was reacted at 40 °C for 2 h to induce a Michael addition reaction. Finally, 2 g of amino-terminated polydimethylsiloxane (PDMS) and 10 g of the organic solvent isopropanol were added to adjust the solid content, and the mixture was stirred evenly to obtain the second sol solution.

[0078] The second sol solution is coated onto the surface of the light conversion antireflection film obtained by S40 away from the ultra-white float glass by roller coating. Then, it is dried for 30 seconds through a 100°C drying channel to form a dense and high-hardness film with a thickness of about 20nm.

[0079] S60, tempered steel The glass coated with the double-layer film is sent into a tempering furnace and tempered at 700°C for 120 seconds. It is then taken out and cooled to obtain photovoltaic coated glass with a high-hardness light conversion anti-reflection coating.

[0080] Example 2 Example 2: Photovoltaic coated glass was prepared using the same method as in Example 1, except that Bi... 3+ The molar content of Tb is 1%. 3+ The molar content is 3%, Eu 3+ The molar content is 3%, and the balance is 93% Y. 3+.

[0081] Example 3 Example 3 describes the preparation of photovoltaic coated glass using the same method as in Example 1, except that the intermediate sensitizer terbium oxide (Tb2O3) is replaced with cerium oxide (Ce2O3).

[0082] Example 4 Example 4 describes the preparation of photovoltaic coated glass using the same method as in Example 1, except that the molar ratio of tetraethyl orthosilicate, deionized water, organic solvent, and second chelating agent in Example 4 is 1:3:8:0.1.

[0083] Example 5 Example 5 describes the preparation of photovoltaic coated glass using the same method as in Example 1, except that the activator europium oxide is replaced with thulium oxide (Tm2O3).

[0084] Comparative Example 1 Comparative Example 1 prepared photovoltaic coated glass according to the method of Example 1, except that Comparative Example 1 only had the main sensitizer (Bi2O3).

[0085] Comparative Example 2 Comparative Example 2 prepared photovoltaic coated glass according to the method of Example 1, except that Comparative Example 2 only had terbium oxide (Tb2O3) as an intermediate sensitizer.

[0086] Comparative Example 3 Comparative Example 3 prepared photovoltaic coated glass according to the method of Example 1, except that Comparative Example 3 did not prepare a protective film layer.

[0087] Performance testing 1. Hardness test shall be conducted in accordance with GB / T 6739-1996 "Determination of Hardness of Coatings by Pencil Test"; 2. Light transmittance, in accordance with the national standard GB / T 18915.2-2013 for coated glass; 3. Apply the photovoltaic coated glass prepared in the examples and comparative examples to photovoltaic modules, and calculate the power change of photovoltaic modules using photovoltaic coated glass from the examples and comparative examples versus those using ordinary photovoltaic coated glass.

[0088] The test results are shown in Table 1.

[0089] Table 1

[0090] As shown in Table 1, this invention uses a sol-gel process combining light conversion materials with porous SiO2 nanostructures to prepare a light conversion antireflection coating. The antireflection coating is a triple-doped system consisting of a main sensitizer, an intermediate sensitizer, and an exciter. This system can effectively adjust the solar spectral range of the antireflection coating, improve energy transfer efficiency, and achieve a refractive index lower than the substrate glass. This significantly reduces solar reflection loss and enhances light transmittance, thereby improving the efficiency of sunlight capture and utilization. This effectively increases the light conversion efficiency and power of photovoltaic modules. Furthermore, this invention also prepares a protective film on the surface of the antireflection coating, which allows for the production of high-hardness photovoltaic coated glass while maintaining light transmittance. This enhances the mechanical properties of the photovoltaic coated glass, achieving a surface hardness of 5H or higher.

[0091] The above are merely preferred embodiments of the present invention and do not limit the scope of the patent. Any equivalent structural or procedural transformations made based on the description and drawings of the present invention, or direct or indirect applications in other related technical fields, are similarly included within the scope of patent protection of the present invention.

Claims

1. A method for preparing photovoltaic coated glass, characterized in that, Includes the following steps: Solution A is obtained by mixing and reacting matrix material, main sensitizer and intermediate sensitizer, activator, first chelating agent, deionized water and nitric acid solution. Solution B is obtained by mixing tetraethyl orthosilicate, deionized water, organic solvent, and a second metal chelating agent and then hydrolyzing the mixture. The first sol solution was prepared by mixing the solutions A and B using the sol-gel method. The first sol solution is coated onto the surface of a glass substrate and dried to obtain a light conversion antireflection film layer; A protective film layer is prepared on the surface of the light conversion antireflection film layer away from the glass substrate; The photovoltaic coated glass is obtained by tempering a glass substrate containing the light conversion antireflection film and the protective film.

2. The method for preparing photovoltaic coated glass according to claim 1, characterized in that, The activator includes at least one of europium oxide (Eu2O3), thulium oxide (Tm2O3), ytterbium oxide (Yb2O3), and chromium oxide (Cr2O3); And / or, the primary sensitizer includes at least one of bismuth oxide (Bi2O3), cerium oxide (Ce2O3), antimony oxide (Sb2O3), and praseodymium oxide (Pr2O3); And / or, the intermediate sensitizer includes at least one of terbium oxide (Tb2O3), cerium oxide (Ce2O3), gadolinium oxide (Gd2O3), and manganese oxide (Mn2O3).

3. The method for preparing photovoltaic coated glass according to claim 1 or 2, characterized in that, The matrix material includes a first matrix material and a second matrix material, wherein the first matrix material includes yttrium oxide (Y2O3) and the second matrix material includes ammonium metavanadate.

4. The method for preparing photovoltaic coated glass according to claim 3, characterized in that, The first matrix is ​​yttrium oxide (Y₂O₃), the second matrix is ​​ammonium metavanadate, the main sensitizer is bismuth oxide, the intermediate sensitizer is terbium oxide, the activator is europium oxide, and the first sol solution is SiO₂@YVO₄:Eu 3+ ,Tb 3+ ,Bi 3+ Solution.

5. The method for preparing photovoltaic coated glass according to claim 4, characterized in that, With the SiO2@YVO4:Eu 3+ ,Tb 3+ ,Bi 3+ Y in solution 3+ Eu 3+ 、Tb 3+ Bi 3+ Based on a total molar content of 100%, Bi 3+ The molar content is 0.5%~2%, Tb 3+ The molar content is 3%~7%, Eu 3+ The molar content is 1%~4%, with the balance being Y. 3+ .

6. The method for preparing photovoltaic coated glass according to claim 1, characterized in that, The molar ratio of tetraethyl orthosilicate, deionized water, organic solvent, and second chelating agent in solution B is 1:(3~9):(4~12):(0.01~0.1). And / or, the drying temperature is 50℃~200℃; And / or, the drying time is 10s to 80s; And / or, the tempering temperature is 600℃~900℃; And / or, the tempering time is 80s~300s.

7. The method for preparing photovoltaic coated glass according to claim 1, characterized in that, The preparation of the protective film includes the following steps: The reactant is obtained by hydrolyzing aminosilane and then reacting it with acrylate via a Michael addition reaction. The reactants, amino-terminated polydimethylsiloxane, and organic solvent are mixed to obtain a second sol solution. The second sol solution is coated onto the surface of the light conversion antireflection film layer away from the glass substrate, and dried to obtain the protective film layer.

8. The method for preparing photovoltaic coated glass according to claim 1, characterized in that, The thickness of the light conversion antireflection film is 150nm~300nm; and / or, the thickness of the protective film is 5nm~100nm.

9. A photovoltaic coated glass, characterized in that, The photovoltaic coated glass is prepared by the photovoltaic coated glass preparation method according to any one of claims 1 to 8.

10. A photovoltaic module, characterized in that, The photovoltaic module includes the photovoltaic coated glass as described in claim 9.

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