Salt-fog-resistant offshore photovoltaic glass and preparation method thereof
By designing a composite structure of a dense passivation layer and a surface hydrophobic layer on marine photovoltaic glass, the problems of corrosion and reduced light transmittance of marine photovoltaic glass in high salt spray and high humidity environments have been solved, achieving high light transmittance and mechanical strength stability, and extending service life.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- FLAT GLASS GROUP CO LTD
- Filing Date
- 2026-03-09
- Publication Date
- 2026-06-05
AI Technical Summary
Marine photovoltaic glass is prone to corrosion in high salt spray and high humidity environments, leading to decreased light transmittance and the propagation of microcracks. Existing anti-reflective coatings are also prone to degradation and cannot maintain high light transmittance and mechanical strength for a long time.
The composite structure of a dense passivation layer and a surface hydrophobic layer is adopted. The dense passivation layer is composed of silicon dioxide, zirconium dioxide, rare metal oxides and nanoparticles, forming a three-dimensional network structure through Zr-O-Si covalent bonds. The refractive index is adjusted by combining rare earth oxides. The surface hydrophobic layer is composed of fluorosilane-modified silicon dioxide to enhance the protective performance.
The light transmittance remains stable in salt spray, seawater immersion, and humid and hot environments, with an attenuation rate of less than 0.8%, improved mechanical strength and wear resistance, and extended service life of photovoltaic glass.
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Figure CN122145048A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the technical field of solar energy devices, and in particular to a salt spray resistant marine photovoltaic glass and its preparation method. Background Technology
[0002] Offshore photovoltaic power plants are typically exposed to environments with high salt spray, high humidity and heat, and strong ultraviolet radiation. Long-term exposure to these factors significantly reduces the light transmittance of photovoltaic glass. The main reasons are: Glass surface corrosion: Sodium and calcium ions in ordinary ultra-clear patterned glass migrate and precipitate to the glass surface under high humidity and high salt conditions, forming white alkali spots or corrosion pits. This not only reduces light transmittance and affects power generation efficiency, but also damages the surface structure.
[0003] Microcrack initiation and propagation: Salt crystallizes at microcracks or defects on the glass surface, generating crystallization pressure. The stress caused by wet-dry cycles also accelerates the propagation of microcracks and reduces the mechanical strength of the glass.
[0004] Antireflective coating degradation: Conventional antireflective films (such as SiO2 porous films prepared by sol-gel method) are prone to hydrolysis and peeling under long-term salt spray and moisture penetration, losing their antireflective effect and reducing light transmittance.
[0005] Therefore, this application provides a salt spray resistant marine photovoltaic glass, which aims to solve the problems of surface corrosion, microcracks, and reduced light transmittance of the aforementioned glass. Summary of the Invention
[0006] The purpose of this application is to provide a salt spray resistant marine photovoltaic glass to improve the problems in the prior art where marine photovoltaic glass is easily corroded on the surface due to long-term exposure to high salt spray and high humidity and heat, resulting in a decrease in light transmittance, and the difficulty in self-repairing of capillaries and microcracks.
[0007] For the purposes mentioned above, this application provides the following technical solution: This application provides a salt spray resistant marine photovoltaic glass, comprising a glass substrate, a dense passivation layer, and a surface hydrophobic layer. The thickness of the dense passivation layer is 20-40 nm; the thickness of the surface hydrophobic layer is 110-150 nm; the dense passivation layer comprises silicon dioxide, zirconium dioxide, rare metal oxides, and nanoparticles; the surface hydrophobic layer comprises fluorosilane-modified silicon dioxide.
[0008] Furthermore, based on 100 parts by mass of the dense passivation layer, the content of zirconium dioxide in the dense passivation layer is 1 to 10 parts by mass, the content of rare earth metal oxide is 1 to 10 parts by mass, and the content of nanoparticles is 1 to 5 parts by mass.
[0009] Furthermore, the refractive index of the dense passivation layer is 1.6 to 1.8.
[0010] Furthermore, the light transmittance of the salt spray resistant marine photovoltaic glass is 94.4%~94.8%, and after being immersed in seawater for 3~90 days, the light transmittance decay rate is 0~0.3%; after being tested in a salt spray environment for 4~36 days, the light transmittance decay rate is 0%~0.8%; and after being tested in a damp heat environment for 0~7 days, the light transmittance decay rate is 0~0.6%.
[0011] Furthermore, the rare metal oxide is CeO. x MoO x EuO x 、YO x TbO x ErO x One or more of the following, where x is 1 to 10.
[0012] Furthermore, the nanoparticles are one or more of TiO2, Al2O3, IrO2, MgO, ZnO and CeO2, and the particle size of the nanoparticles is 10~50nm.
[0013] Furthermore, the mass ratio of silicon dioxide to fluorosilane in the surface hydrophobic layer is 20~40:1~5.
[0014] Furthermore, the mesopores of the surface hydrophobic layer are 2~50nm.
[0015] This application also provides a method for preparing salt spray resistant marine photovoltaic glass, wherein the method for preparing the dense passivation layer sol includes the following steps: Step 1: Mix silane compounds, silane coupling agents and alcohol solvents, and stir at 1000~2000 r / min for 30~60 min under nitrogen protection; Step 2: Add water and acid solvent to the solution from Step 1, stir at 1000-2000 r / min for 4.5-5 h at 25-30℃, sonicate for 20-40 min at an ultrasonic frequency of 30-50 kHz, and age for 24-48 h to obtain silica sol. Step 3: Add zirconium silicate sol to silica sol, stir at a low speed of 300~500 r / min for 20~40 min for preliminary mixing, and then sonicate for 20~40 min at a sonic frequency of 30~50 kHz to obtain solution A; Step 4: Mix nanoparticles, rare metal salts and silane coupling agent at 30-40℃ and stir at 1000-2000 r / min for 4.5-5 h, then sonicate for 20 min to obtain solution B; Step 6: Add solution B to solution A, and stir at 450-500 r / min for 9-10 h at 50-80℃ to obtain a dense passivation layer sol; Furthermore, the preparation method of the surface hydrophobic layer sol includes the following steps: mixing silica sol, silane coupling agent and alcohol solvent, stirring at 1000~2000 r / min for 30~60 min under nitrogen protection to obtain solution C; adding fluorosilane to solution C and homogenizing under high pressure in alcohol solvent at a pressure of 100~200 MPa, stirring at 300~500 r / min for 7.5~8 h at 25~30℃ to obtain surface hydrophobic layer sol; Furthermore, the dense passivation layer sol is coated onto the upper surface of the glass substrate; after gradient curing, a dense passivation layer is obtained. Furthermore, the surface hydrophobic sol is coated onto the upper surface of the dense passivation layer to obtain a surface hydrophobic layer; the temperature is increased to 595~705℃ at 10~15℃ / s and held for 2.5~3min to obtain salt spray resistant photovoltaic glass.
[0016] Furthermore, the film-forming agent is zirconium silicate sol with a particle size ≤100nm and pH=3~5; Furthermore, the mass ratio of the silica sol to the film-forming agent is 122~200:1~10.
[0017] Furthermore, the fluorosilane is CF3 (CF2). n SiF3, where n is 1~10.
[0018] Furthermore, the silane compound is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, and butyl orthosilicate; Furthermore, the silane coupling agent is one or more selected from methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, vinyltriethoxysilane, vinylmethyldichlorosilane, vinyltriacetoxysilane, γ-ureidopropyltriethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltrichlorosilane, γ-methacryloyloxypropyltrichlorosilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and γ-aminopropyltriethoxysilane. Furthermore, the alcohol solvent is one or more selected from methanol, ethanol, isopropanol, n-propanol, and n-butanol; Furthermore, the acid solvent is one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, and acrylic acid.
[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: The salt spray resistant marine photovoltaic glass provided in this application utilizes the interaction between the silanol groups (-Si-OH) in the silica sol and the Zr in the film-forming agent (zirconium silicate sol) in the dense passivation layer. 4+Through coordination bonds, a condensation reaction occurs, forming Zr-O-Si covalent bonds and a three-dimensional network structure. The zirconium dioxide and nanoparticles generated after the calcination of zirconium silicate sol fill the capillaries or cracks on the surface of this three-dimensional network structure or passivation layer, reducing the porosity of the film and preventing salt crystallization in the capillaries or cracks (thus solving the problem of self-repairing capillaries and microcracks in salt spray resistant marine glass). The high refractive index of rare earth oxides can fine-tune the refractive index of the dense passivation layer; and zirconium dioxide has high chemical inertness, i.e., it is inert to Cl... - It has excellent stability and can effectively block Cl. - The penetration into the glass substrate avoids the formation of capillaries and microcracks, thereby improving the light transmittance of the salt spray resistant marine photovoltaic glass. The light transmittance of the salt spray resistant marine photovoltaic glass of this application is 94.4%~94.8%. Furthermore, the strong structural stability of this three-dimensional network structure enhances the mechanical strength, wear resistance, and environmental stress resistance of the dense passivation layer. After immersion in seawater for 3~90 days, the light transmittance of the salt spray resistant marine photovoltaic glass of this application decreases by 0~0.3%; after 4~36 days of salt spray environment testing, the light transmittance decreases by 0%~0.8%; and after 0~7 days of damp heat testing, the light transmittance decreases by 0~0.6%.
[0020] In addition, the dense passivation layer, the surface hydrophobic layer, and the glass substrate are connected by a Si-O-Si structure, which can improve the overall mechanical strength and light transmittance of the salt spray resistant glass. Attached Figure Description
[0021] To more clearly illustrate the technical solutions in the specific embodiments of this application or the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0022] Figure 1 This is a schematic diagram of the structure of the marine salt spray resistant photovoltaic glass provided in Embodiment 1 of this application.
[0023] Figure 2 This is a SEM characterization image of the marine salt spray resistant photovoltaic glass provided in Embodiment 1 of this application.
[0024] Figure 3 The image shows the SEM characterization of the marine salt spray resistant photovoltaic glass provided in Comparative Example 1 of this application.
[0025] Figure 4 The transmittance attenuation diagrams for the marine salt spray resistant photovoltaic glass provided in Embodiment 1 and Comparative Example 1 of this application are shown in the salt spray test.
[0026] Figure 5The transmittance attenuation diagrams for marine salt spray resistant photovoltaic glass provided in Embodiment 1 and Comparative Example 1 of this application are shown in the damp heat test.
[0027] Figure 6 The transmittance attenuation diagrams for the marine salt spray resistant photovoltaic glass provided in Embodiment 1 and Comparative Example 1 of this application are obtained from seawater immersion tests.
[0028] See Figure 1 In the middle, there is a glass substrate 1, a dense passivation layer 2, and a surface hydrophobic layer 3. Detailed Implementation
[0029] The technical solutions of this application will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.
[0030] On one hand, embodiments of this application provide a salt spray resistant marine photovoltaic glass comprising: a glass substrate, a dense passivation layer, and a surface hydrophobic layer, wherein the thickness of the dense passivation layer is 20-40 nm; the thickness of the surface hydrophobic layer is 110-150 nm; the dense passivation layer comprises: silicon dioxide, zirconium dioxide, rare metal oxides, and nanoparticles; and the surface hydrophobic layer comprises fluorosilane-modified silicon dioxide.
[0031] Understandably, the glass substrate of salt spray resistant marine photovoltaic glass serves as the front cover of photovoltaic modules. Its most fundamental function is to maximize the transmission of sunlight (especially visible and near-infrared light, which are effective for power generation) and protect the fragile internal solar cells from mechanical damage and direct contact with the external environment. The dense passivation layer is located between the glass substrate and the surface hydrophobic layer, acting as a physical barrier and providing chemical passivation. The surface hydrophobic layer is the outermost functional coating of the salt spray resistant photovoltaic glass, which has functions such as hydrophobic anti-adhesion (seawater droplets and fog are difficult to wet and spread, but instead form water droplets and roll off) and self-cleaning.
[0032] Preferably, the thickness of the dense passivation layer is 25~35nm.
[0033] Understandably, a dense passivation layer with a thickness of less than 20 nm will have pinholes or uneven coverage, affecting the Cl in the salt spray. - Na + H2O can easily penetrate, causing the dense passivation layer to lose its core protective function. If the thickness is greater than 40nm, it will lead to the accumulation of internal stress, easy cracking, peeling, or even peeling off from the glass substrate, and will also cause unnecessary optical loss.
[0034] Preferably, the thickness of the surface hydrophobic layer is 120~140nm.
[0035] Understandably, a surface hydrophobic layer thickness of less than 110 nm cannot cover a dense passivation layer, and the hydrophobic effect is not obvious or durable. If the thickness is greater than 150 nm, the refractive index of the hydrophobic layer (especially one containing organic components) differs significantly from that of glass, and light absorption may occur. Excessive thickness will also significantly increase light reflection and absorption losses, seriously affecting the power generation efficiency of the module.
[0036] The dense passivation layer comprises silicon dioxide, zirconium dioxide, rare metal oxides, and nanoparticles. This is the composition of the dense passivation layer after tempering. The presence of zirconium silicate sol plays two main roles in the preparation of the dense passivation layer: firstly, the Zr in the zirconium silicate sol... 4+ The zirconium dioxide sol undergoes a condensation reaction with the silanol groups (-Si-OH) in the silica sol through coordination bonds to form Zr-O-Si covalent bonds, creating a three-dimensional network structure that enhances the mechanical strength within the layer. Secondly, the zirconium dioxide generated after calcining the zirconium silicate sol, along with nanoparticles, fills the capillaries or cracks on the surface of the aforementioned three-dimensional network structure or passivation layer. This reduces the porosity of the film, prevents salt crystallization in the capillaries or cracks, and thus improves the light transmittance of marine photovoltaic glass. Furthermore, zirconium dioxide exhibits high chemical inertness, meaning it is inert to Cl-. - It exhibits excellent stability (the essence of salt spray corrosion is Cl). - It penetrates the film layer and combines with sodium and calcium ions in the glass to form soluble salts and disrupt the glass network structure, effectively blocking Cl. - Penetration into the glass matrix.
[0037] At the same time, nanoparticles can also improve the barrier properties against corrosive media and enhance the density of the film.
[0038] The presence of rare metal oxides can further improve the light transmittance and weather resistance of marine salt spray resistant photovoltaic glass. The core of the double-layer film design lies in achieving broad-spectrum anti-reflection through the combination of high and low refractive indices. Rare earth oxides typically have high refractive indices. By precisely controlling their doping amount in the dense passivation layer, the refractive index of the dense passivation layer can be fine-tuned to better match the glass substrate and the surface hydrophobic layer, achieving a superior anti-reflection effect. Simultaneously, cerium oxide strongly absorbs ultraviolet light, inhibiting film aging and significantly improving the reliability of photovoltaic glass during long-term outdoor operation (e.g., over 25 years).
[0039] In some embodiments, based on 100 parts by mass of the dense passivation layer, the content of zirconium dioxide in the dense passivation layer is 1 to 10 parts by mass, the content of rare earth metal oxide is 1 to 10 parts by mass, and the content of nanoparticles is 1 to 5 parts by mass.
[0040] Preferably, the dense passivation layer contains 3 to 8 parts by mass of zirconium dioxide, 3 to 8 parts by mass of rare earth metal oxides, and 2 to 5 parts by mass of nanoparticles.
[0041] In some embodiments, the refractive index of the dense passivation layer is 1.6 to 1.8.
[0042] Preferably, the refractive index of the dense passivation layer is 1.65 to 1.75.
[0043] Understandably, the refractive index of the dense passivation layer is mainly determined by the ZrO2 / SiO2 ratio. This is because ZrO2 exhibits low absorption and weak dispersion in the visible and near-infrared regions, and possesses a high laser damage threshold as well as good chemical and thermal stability, making it suitable for use as a high-refractive-index material. SiO2, on the other hand, is a low-refractive-index material. Therefore, the higher the proportion of Zr content, the higher the refractive index of the film. When a film with a refractive index gradient (dense passivation layer and surface hydrophobic layer) is deposited on a glass substrate, optimal light transmittance can be achieved when the refractive index and thickness of the film are properly controlled.
[0044] In some embodiments, the transmittance of the salt spray resistant marine photovoltaic glass is 94.4%~94.8%, and the transmittance decay rate is 0~0.3% after immersion in seawater for 3~90 days; the transmittance decay rate is 0%~0.8% after 4~36 days of salt spray environment testing; and the transmittance decay rate is 0~0.6% after 0~7 days of damp heat testing.
[0045] Understandably, the transmittance attenuation rate = transmittance of salt spray resistant marine photovoltaic glass - transmittance of salt spray resistant marine photovoltaic glass after passing the weather resistance test.
[0046] In some embodiments, the rare metal oxide is CeO. x MoO x EuO x 、YO x TbO x ErO x One or more of the following, where x is 1 to 10.
[0047] Preferably, the rare metal oxide is CeO. x MoO x One or more of the following, where x is 1 to 7.
[0048] In some embodiments, the nanoparticles are one or more of TiO2, Al2O3, IrO2, MgO, ZnO and CeO2, and the particle size of the nanoparticles is 10~50 nm.
[0049] Preferably, the nanoparticles are one or more of ZnO, TiO2 and CeO2, and the particle size of the nanoparticles is 20~40nm.
[0050] Understandably, when the particle size of nanoparticles is too small, they are prone to uncontrolled aggregation, forming larger particles that disrupt optical uniformity. When the particle size of nanoparticles is too large, it leads to decreased light transmittance, increased haze, and a whitish or foggy appearance.
[0051] In some embodiments, the mass ratio of silicon dioxide to fluorosilane in the surface hydrophobic layer is 20~40:1~5.
[0052] Preferably, the mass ratio of silicon dioxide to fluorosilane in the surface hydrophobic layer is 25~35:1~3.
[0053] Understandably, in the hydrophobic layer, fluorosilanes with a mass ratio of fluorosilane to silica at the above-mentioned ratio help to form more hydrophobic crosslinks between silica particles, thereby improving the water resistance and mechanical strength of the film.
[0054] In some embodiments, the mesopores of the surface hydrophobic layer are 2-50 nm.
[0055] Preferably, the mesopores of the surface hydrophobic layer are 2~30nm.
[0056] Understandably, when the mesopores of the surface hydrophobic layer are 2~50nm, a continuous and robust three-dimensional network framework can be formed at the nanoscale. The molecular size of fluorosilane is usually less than 2nm, and the pore size greater than 2nm ensures that it can freely enter and modify the inner surface of the pores, thus achieving hydrophobicity of the film.
[0057] On the other hand, this application also provides a method for preparing salt spray resistant marine photovoltaic glass, wherein the method for preparing the dense passivation layer sol includes the following steps: Step 1: Mix silane compounds, silane coupling agents and alcohol solvents, and stir at 1000~2000 r / min for 30~60 min under nitrogen protection; Step 2: Add water and acid solvent to the solution from Step 1, stir at 1000-2000 r / min for 4.5-5 h at 25-30℃, sonicate for 20-40 min at an ultrasonic frequency of 30-50 kHz, and age for 24-48 h to obtain silica sol. Step 3: Add zirconium silicate sol to silica sol, stir at a low speed of 300~500 r / min for 20~40 min for preliminary mixing, and then sonicate for 20~40 min at a sonic frequency of 30~50 kHz to obtain solution A; Understandably, Zr-O-Si covalent bonds are formed in step 3, that is, Zr in the zirconium silicate sol... 4+Through coordination bonds, Zr-O-Si covalent bonds are formed by condensation reaction with -Si-OH in silica sol, thus constructing a three-dimensional cross-linked network.
[0058] Step 4: Mix nanoparticles, rare metal salts and silane coupling agent at 30-40℃ and stir at 1000-2000 r / min for 4.5-5 h, then sonicate for 20 min to obtain solution B; Step 6: Add solution B to solution A, and stir at 450-500 r / min for 9-10 h at 50-80℃ to obtain a dense passivation layer sol; In some embodiments, the preparation method of the surface hydrophobic sol includes the following steps: mixing silica sol, silane coupling agent and alcohol solvent, stirring at 1000~2000 r / min for 30~60 min under nitrogen protection to obtain solution C; adding fluorosilane to solution C and homogenizing under high pressure in alcohol solvent at a pressure of 100~200 MPa, stirring at 300~500 r / min for 7.5~8 h at 25~30℃ to obtain surface hydrophobic sol; In some embodiments, the dense passivation layer sol is coated onto the upper surface of the glass substrate; a dense passivation layer is obtained after gradient curing. In some embodiments, the surface hydrophobic sol is coated onto the upper surface of the dense passivation layer to obtain a surface hydrophobic layer; In some embodiments, salt spray resistant photovoltaic glass is obtained by heating to 595-705°C at a rate of 10-15°C / s and holding the temperature for 2.5-3 minutes.
[0059] In some embodiments, the film-forming agent is zirconium silicate sol with a particle size ≤100nm and pH=3~5; Preferably, the film-forming agent is zirconium silicate sol with a particle size ≤80nm and pH=4~5.
[0060] Understandably, zirconium silicate sol exhibits good dispersibility and stability when the particle size is ≤100nm and the pH is 3~5, avoiding agglomeration and forming a uniform and stable film in the coating solution. Under alkaline conditions, zirconium silicate sol may agglomerate, and silica sol easily dissolves to form sodium silicate, leading to system instability.
[0061] In some embodiments, the mass ratio of the silica sol to the film-forming agent is 122~200 : 1~10.
[0062] Preferably, the mass ratio of the silica sol to the film-forming agent is 130~180:3~6.
[0063] In some embodiments, the fluorosilane is CF3 (CF2). n SiF3, where n is 1~10.
[0064] Preferably, the fluorosilane is CF3 (CF2). n SiF3, where n is 1 to 6.
[0065] In some embodiments, the silane compound is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, and butyl orthosilicate; In some embodiments, the silane coupling agent is one or more selected from methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, vinyltriethoxysilane, vinylmethyldichlorosilane, vinyltriacetoxysilane, γ-ureidopropyltriethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltrichlorosilane, γ-methacryloyloxypropyltrichlorosilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and γ-aminopropyltriethoxysilane. In some embodiments, the alcohol solvent is one or more selected from methanol, ethanol, isopropanol, n-propanol, and n-butanol; In some embodiments, the acid solvent is one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, and acrylic acid.
[0066] In order to enable those skilled in the art to clearly understand the above-described implementation details and operations of this application, and to demonstrate the significant improvement in the performance of the salt spray marine photovoltaic glass and its preparation method provided by the embodiments of this application, the above technical solutions are illustrated below through examples.
[0067] Example 1 A method for preparing salt spray resistant marine photovoltaic glass includes the following steps: The method for preparing the dense passivation layer sol is as follows: Step 1: Mix 30 parts by mass of tetraethyl orthosilicate, 3 parts by mass of methyltriethoxysilane, 90 parts by mass of ethanol and 10 parts by mass of isopropanol, and stir at 1500 r / min for 30 min under nitrogen protection.
[0068] Step 2: Add 15 parts by weight of pure water and 1 part by weight of hydrochloric acid, stir at 1000 r / min for 4.5 h at 25 °C, sonicate for 30 min at 30 kHz, and age for 24 h to obtain silica sol. Step 3: Add 5 parts by mass of zirconium silicate sol with a particle size of 50 nm and pH=4 to silica sol. First, stir at a low speed of 300 r / min for 30 min for preliminary mixing, and then sonicate for 30 min at a frequency of 50 kHz to obtain solution A. Step 4: Mix 3 parts by mass of zinc oxide with a particle size of 30 nm, 6 parts by mass of cerium nitrate, and 3 parts by mass of methyltriethoxysilane, stir at 1000 r / min for 4.5 h, and sonicate for 20 min to obtain solution B; Step 5: Add solution B to solution A and stir at 450 r / min for 10 h at 50 °C to obtain a dense passivation layer sol.
[0069] The preparation method of the surface hydrophobic layer sol is as follows: Step 1: Mix 30 parts by mass of silica sol, 3 parts by mass of methyltriethoxysilane, 90 parts by mass of ethanol and 10 parts by mass of isopropanol, and stir at 1000 r / min for 60 min under nitrogen protection to obtain solution C.
[0070] Step 2: Add 3 parts by mass of fluorosilane to solution C in an alcohol solvent, homogenize under high pressure at 150 MPa, and stir at 400 r / min for 8 h at 25 °C to obtain a hydrophobic sol layer on the surface.
[0071] A method for preparing salt spray resistant marine photovoltaic glass is as follows: Step 1: Rinse the ultra-clear patterned glass with deionized water and then air dry; Step 2: Apply the dense passivation layer sol to the surface of the ultra-white patterned glass (glass substrate) by roller coating, with an undercoat thickness of 30nm; Step 3: Gradient curing: cure at 30℃ for 30s, then at 40℃ for 30s, and finally at 50℃ for 1min; Step 4: Apply the surface hydrophobic sol to the surface of the cured dense passivation layer sol by roller coating; Step 5: Temperature-controlled tempering: Increase the temperature to 650℃ at a rate of 10℃ / s and hold for 3 minutes.
[0072] Based on a density passivation layer of 100 parts by mass, the density passivation layer contains 5 parts by mass of zirconium dioxide, 6 parts by mass of cerium nitrate, 3 parts by mass of zinc oxide, a thickness of 30 nm, and a thickness of 130 nm for the surface hydrophobic layer.
[0073] The structure of the marine salt spray resistant photovoltaic glass prepared in Example 1 is as follows: Figure 1 As shown, a dense passivation layer 2 is formed on one surface of the glass substrate 1, and a surface hydrophobic layer 3 is formed on the surface of the dense passivation layer 2.
[0074] SEM characterization image of the marine salt spray resistant photovoltaic glass prepared in Example 1 is shown below. Figure 2As shown, the lower substrate (glass substrate and dense passivation layer) of the salt spray resistant marine photovoltaic glass exhibits a smooth and uniform microstructure without obvious ripples, depressions, or interface defects. This smooth interface means stronger adhesion between the film layer and the substrate, effectively preventing corrosive media from penetrating through interface defects in a salt spray environment (containing corrosive media such as chloride ions), reducing the risk of interlayer delamination or substrate corrosion. Furthermore, the mesopores in the surface hydrophobic layer are uniformly distributed and relatively consistent in size. This uniform mesopore structure blocks the penetration path of corrosive media in the salt spray environment, reducing the diffusion rate of corrosive media within the film layer, thereby improving salt spray corrosion resistance. The transmittance attenuation of the marine salt spray resistant photovoltaic glass prepared in Example 1 during salt spray testing is as follows: Figure 4 As shown, the transmittance attenuation during the salt spray test (36 days) was 0.46%; the transmittance attenuation during the damp heat test was as follows. Figure 5 As shown, the transmittance decreased by 0.28% after the damp heat test (7 days); the transmittance decreased as shown in the seawater immersion test. Figure 6 As shown, the light transmittance decreased by 0.11% after immersion in seawater (90 days).
[0075] Example 2 The preparation method of Example 2 is the same as that of Example 1, except that 10 parts by mass of film-forming agent zirconium silicate sol are added in step 3 of the dense passivation layer preparation method.
[0076] Example 3 The preparation method of Example 3 is the same as that of Example 1, except that 1 part by mass of film-forming agent zirconium silicate sol is added in step 3 of the dense passivation layer preparation method.
[0077] Example 4 The preparation method of Example 4 is the same as that of Example 1, except that 1 part by mass of rare metal salt cerium nitrate is added in step 4 of the dense passivation layer preparation method.
[0078] Example 5 The preparation method of Example 5 is the same as that of Example 1, except that 10 parts by mass of rare metal salt cerium nitrate are added in step 4 of the dense passivation layer preparation method.
[0079] Example 6 The preparation method of Example 6 is the same as that of Example 1, except that 5 parts by mass of zinc oxide nanoparticles are added in step 4 of the dense passivation layer preparation method.
[0080] Example 7 The preparation method of Example 7 is the same as that of Example 1, except that 1 part by mass of zinc oxide nanoparticles is added in step 4 of the dense passivation layer preparation method.
[0081] Example 8 The preparation method of Example 8 is the same as that of Example 1, except that the thickness of the dense passivation layer is 20 nm.
[0082] Example 9 The preparation method of Example 9 is the same as that of Example 1, except that the thickness of the dense passivation layer is 40 nm.
[0083] Example 10 The preparation method of Example 10 is the same as that of Example 1, except that the thickness of the surface hydrophobic layer is 110 nm.
[0084] Example 11 The preparation method of Example 11 is the same as that of Example 1, except that the thickness of the surface hydrophobic layer is 150 nm.
[0085] Comparative Example 1 The preparation method of Comparative Example 1 is the same as that of Example 1, except that step 3 of the dense passivation layer preparation method does not include the film-forming agent zirconium silicate sol.
[0086] SEM characterization image of the marine salt spray resistant photovoltaic glass prepared in Comparative Example 1 is shown below. Figure 3 The underlying substrate (glass substrate and dense passivation layer) of the salt spray resistant marine photovoltaic glass exhibits obvious cracks and uneven microstructure. The mesopore distribution and size of the surface hydrophobic layer are also uneven. The transmittance attenuation in the salt spray resistance test of the marine salt spray resistant photovoltaic glass prepared in Comparative Example 1 is as follows: Figure 4 As shown, the transmittance attenuation during the salt spray test (36 days) was 1.23%; the transmittance attenuation during the damp heat test was as follows: Figure 5 As shown, the transmittance decreased by 0.82% after the damp heat test (7 days); the transmittance decreased as shown in the seawater immersion test. Figure 6 As shown, the light transmittance decreased by 0.68% after immersion in seawater (90 days).
[0087] Comparative Example 2 The preparation method of Comparative Example 2 is the same as that of Example 1, except that the rare metal salt cerium nitrate was not added in step 4 of the dense passivation layer preparation method.
[0088] Comparative Example 3 The preparation method of Comparative Example 3 is the same as that of Example 1, except that 20 parts by mass of film-forming agent zirconium silicate are added in step 3 of the dense passivation layer preparation method.
[0089] Comparative Example 4 The preparation method of Comparative Example 4 is the same as that of Example 1, except that 0.5 parts by mass of film-forming agent zirconium silicate are added in step 3 of the dense passivation layer preparation method.
[0090] Comparative Example 5 The preparation method of Comparative Example 5 is the same as that of Example 1, except that 0.5 parts by mass of rare metal salt cerium nitrate are added in step 4 of the dense passivation layer preparation method.
[0091] Comparative Example 6 The preparation method of Comparative Example 6 is the same as that of Example 1, except that 20 parts by mass of rare metal salt cerium nitrate are added in step 4 of the dense passivation layer preparation method.
[0092] Comparative Example 7 The preparation method of Comparative Example 7 is the same as that of Example 1, except that the thickness of the dense passivation layer is 60 nm.
[0093] Comparative Example 8 The preparation method of Comparative Example 8 is the same as that of Example 1, except that the thickness of the dense passivation layer is 10 nm.
[0094] Comparative Example 9 The preparation method of Comparative Example 9 is the same as that of Example 1, except that the thickness of the surface hydrophobic layer is 180 nm.
[0095] Comparative Example 10 The preparation method of Comparative Example 10 is the same as that of Example 1, except that the thickness of the surface hydrophobic layer is 90 nm.
[0096] The physical parameters of the dense passivation layer, glass substrate, and surface hydrophobic layer in the salt spray resistant marine photovoltaic glass of each embodiment and comparative example are summarized in Table 1 below.
[0097]
[0098] The performance of the salt spray-resistant marine photovoltaic glass prepared in each embodiment and comparative example was tested. The results are shown in Table 2.
[0099] Light transmittance test: The transmittance of the salt spray resistant marine photovoltaic glass at four points on the edge and at the center was measured using the Filmeasure 2100 air-floating tabletop spectral transmittance measurement system, ranging from 380 to 1100 nm. The average value of the five points was taken as the result.
[0100] Salt spray resistance test: Refer to GB / T 2423.17-2024.
[0101] Seawater immersion test: Referring to CN220231418U (Seawater Immersion Test Apparatus for Photovoltaic Coated Glass), salt spray resistant marine photovoltaic glass was placed on a shelf and immersed in immersion liquid for periodic testing.
[0102] Damp heat test: 1) Pretreatment stage: The sample is equilibrated in an environment of 23±2℃ / 50±5%RH for 48 hours; 2) Initial parameter determination: The baseline data of all test items is collected; 3) Test chamber parameter setting: The temperature is controlled with precision at 85±0.5℃ and the humidity at 85±2%RH; 4) Periodic monitoring: Intermediate tests are conducted and the dew point temperature fluctuation value inside the chamber is recorded; 5) Recovery treatment: The sample is subjected to final testing after being warmed to standard environment for 4 hours.
[0103]
[0104] As can be seen from Table 1, in Examples 1 to 11, based on 100 parts by mass of the dense passivation layer, the content of zirconium dioxide in the dense passivation layer is 1 to 10 parts by mass, the content of rare earth metal oxide is 1 to 10 parts by mass, and the content of nanoparticles is 1 to 5 parts by mass. The light transmittance of the marine salt spray resistant glass is 94.4% to 94.8%, and the light transmittance attenuation rate after salt spray resistance, seawater immersion, and damp heat test is 0.34 to 0.72%, 0.08 to 0.21%, and 0.18 to 0.51%, respectively. That is, by controlling the composition of the dense passivation layer, the photovoltaic glass can maintain good light transmittance in salt spray, seawater immersion, and damp heat environments. Compared to Comparative Example 1, Example 1 did not contain zirconium silicate sol, thus failing to form a Zr-O-Si three-dimensional network structure or zirconium oxide. Therefore, the light transmittance of the marine salt spray resistant glass significantly decreased after salt spray resistance testing, marine immersion testing, and damp heat testing. Comparing Example 1 and Comparative Example 2, the photovoltaic glass in Comparative Example 2, lacking rare metal oxides, exhibited reduced light transmittance and poorer weather resistance. Comparative Examples 3 to 6 demonstrate that excessive or insufficient content of zirconium oxide and rare metal oxides in the salt spray resistant photovoltaic glass reduces its light transmittance and reduces its weather resistance. Comparative Examples 7 to 10 illustrate that the thickness of the dense passivation layer and the surface hydrophobic layer needs to be controlled within a reasonable range to achieve strong light transmittance and good weather resistance in marine salt spray resistant photovoltaic glass.
[0105] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.
Claims
1. A salt spray resistant marine photovoltaic glass, characterized in that, The material includes a glass substrate, a dense passivation layer, and a surface hydrophobic layer. The thickness of the dense passivation layer is 20-40 nm. The thickness of the surface hydrophobic layer is 110-150 nm. The dense passivation layer includes silicon dioxide, zirconium dioxide, rare metal oxides, and nanoparticles. The surface hydrophobic layer includes fluorosilane-modified silicon dioxide.
2. The salt spray resistant marine photovoltaic glass according to claim 1, characterized in that, Based on 100 parts by mass of the dense passivation layer, the content of zirconium dioxide in the dense passivation layer is 1 to 10 parts by mass, the content of rare earth metal oxide is 1 to 10 parts by mass, and the content of nanoparticles is 1 to 5 parts by mass.
3. The salt spray resistant marine photovoltaic glass according to claim 1, characterized in that, The refractive index of the dense passivation layer is 1.6 to 1.
8.
4. The salt spray resistant marine photovoltaic glass according to claim 1, characterized in that, The light transmittance of the salt spray resistant marine photovoltaic glass is 94.4%~94.8%. After being immersed in seawater for 3~90 days, the light transmittance decay rate is 0~0.3%. After being tested in a salt spray environment for 4~36 days, the light transmittance decay rate is 0%~0.8%. After being tested in a damp heat environment for 0~7 days, the light transmittance decay rate is 0~0.6%.
5. The salt spray resistant marine photovoltaic glass according to claim 1, characterized in that, The rare metal oxide is CeO. x MoO x EuO x 、YO x TbO x ErO x One or more of the following, where x is 1 to 10.
6. The salt spray resistant marine photovoltaic glass according to claim 1, characterized in that, The nanoparticles are one or more of TiO2, Al2O3, IrO2, MgO, ZnO and CeO2, and the particle size of the nanoparticles is 10~50nm.
7. The salt spray resistant marine photovoltaic glass according to claim 1, characterized in that, The mass ratio of silicon dioxide to fluorosilane in the surface hydrophobic layer is 20~40:1~5.
8. The salt spray resistant marine photovoltaic glass according to claim 1, characterized in that, The mesopores of the surface hydrophobic layer are 2~50nm.
9. A method for preparing salt spray resistant marine photovoltaic glass, characterized in that, The method for preparing the dense passivation layer sol includes the following steps: Step 1: Mix silane compounds, silane coupling agents and alcohol solvents, and stir at 1000~2000 r / min for 30~60 min under nitrogen protection; Step 2: Add water and acid solvent to the solution from Step 1, stir at 1000-2000 r / min for 4.5-5 h at 25-30℃, sonicate for 20-40 min at an ultrasonic frequency of 30-50 kHz, and age for 24-48 h to obtain silica sol. Step 3: Add zirconium silicate sol to silica sol, stir at a low speed of 300~500 r / min for 20~40 min for preliminary mixing, and then sonicate for 20~40 min at a sonic frequency of 30~50 kHz to obtain solution A; Step 4: Mix nanoparticles, rare metal salts and silane coupling agent at 30-40℃ and stir at 1000-2000 r / min for 4.5-5 h, then sonicate for 20 min to obtain solution B; Step 5: Add solution B to solution A and stir at 450-500 r / min at 50-80℃ for 9-10 h to obtain a dense passivation layer sol; And / or, The preparation method of the surface hydrophobic layer sol includes the following steps: mixing silica sol, silane coupling agent and alcohol solvent, and stirring at 1000~2000 r / min for 30~60 min under nitrogen protection to obtain solution C; adding fluorosilane to solution C and homogenizing under high pressure in alcohol solvent at a pressure of 100~200 MPa, stirring at 300~500 r / min for 7.5~8 h at 25~30℃ to obtain surface hydrophobic layer sol; The dense passivation layer sol is coated onto the upper surface of the glass substrate; after gradient curing, a dense passivation layer is obtained. The surface hydrophobic sol is coated onto the upper surface of the dense passivation layer to obtain a surface hydrophobic layer. Salt spray resistant photovoltaic glass is obtained by heating to 595-705℃ at a rate of 10-15℃ / s and holding for 2.5-3 minutes.
10. The method for preparing salt spray resistant marine photovoltaic glass according to claim 9, characterized in that, The film-forming agent is zirconium silicate sol with a particle size ≤100nm and pH=3~5; And / or, The mass ratio of the silica sol to the film-forming agent is 122~200 : 1~10.
11. The method for preparing salt spray resistant marine photovoltaic glass according to claim 9, characterized in that, The fluorosilane is CF3 (CF2). n SiF3, where n is 1~10.
12. The method for preparing salt spray resistant marine photovoltaic glass according to claim 9, characterized in that, The silane compounds are one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, and butyl orthosilicate. And / or, The silane coupling agent is one or more of the following: methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, vinyltriethoxysilane, vinylmethyldichlorosilane, vinyltriacetoxysilane, γ-ureidopropyltriethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltrichlorosilane, γ-methacryloyloxypropyltrichlorosilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and γ-aminopropyltriethoxysilane. And / or, the alcohol solvent is one or more selected from methanol, ethanol, isopropanol, n-propanol, and n-butanol; And / or, The acid solvent is one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, and acrylic acid.