Anti-reflection coated glass for photovoltaic panel and preparation method of anti-reflection coated glass
By preparing inner and outer nanoporous films on glass substrates for photovoltaic modules, the mechanical strength and wear resistance problems of existing coated glass are solved, achieving a high transmittance and durable anti-reflection effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-14
- Publication Date
- 2026-04-14
AI Technical Summary
Existing anti-reflective coated glass for photovoltaic modules is insufficient in terms of mechanical strength and abrasion resistance, making it prone to damage in outdoor environments and affecting its service life and light transmission performance.
By preparing a nanoporous inner film on a glass substrate, mixing acid-catalyzed silica sol and alkali-catalyzed silica sol, and adding modified composite particles, a porous outer film is formed, which improves adhesion and anti-reflection effect.
It achieves high transmittance and durable anti-reflective effect, improves the mechanical strength and anti-fouling performance of coated glass, and extends its service life.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of coated glass technology, specifically to an anti-reflective coated glass for photovoltaic panels and its preparation method. Background Technology
[0002] Photovoltaic power generation, as an important component of clean energy, directly affects power generation costs and economic benefits through its conversion efficiency and lifespan. Photovoltaic modules typically use ultra-clear glass as a cover to protect the cells from environmental impacts. However, light reflection loss at the glass-air interface significantly reduces the module's power output. To address this issue, anti-reflective coated glass has been developed.
[0003] Currently, existing anti-reflective coating technologies still face some serious challenges when applied to practical applications. For example, although traditional single-layer porous silica anti-reflective films can improve light transmittance, their porous structure leads to low mechanical strength and poor wear resistance. They are easily damaged during long-term outdoor wind, sand, rain, and washing, resulting in performance degradation.
[0004] Therefore, there is an urgent need to find a photovoltaic anti-reflective coated glass with good light transmission performance and long-term environmental durability. Summary of the Invention
[0005] The purpose of this invention is to provide an anti-reflective coated glass for photovoltaic panels and a method for preparing the same, so as to solve the problems raised in the prior art.
[0006] To achieve the above objectives, the present invention provides the following technical solution:
[0007] A method for preparing anti-reflective coated glass for photovoltaic panels includes the following preparation steps:
[0008] Step 1: After ultrasonic cleaning and drying, the glass substrate is placed in an etching solution for etching.
[0009] Step 2: Place the etched glass substrate in the inner pre-prepared sol for immersion and pull coating. After coating, dry and then anneal to obtain a glass substrate with an inner film on the surface.
[0010] Step 3: Place the glass substrate with the inner film on the surface into the outer sol, perform immersion and pull coating, and dry after coating to obtain anti-reflective coated glass;
[0011] Preferably, the preparation steps of the inner layer sol are as follows: tetraethyl orthosilicate, anhydrous ethanol, hydrochloric acid and deionized water are mixed and stirred, and then aged to obtain solution a; tetraethyl orthosilicate, anhydrous ethanol, ammonia and deionized water are mixed and stirred, aged, and refluxed to obtain solution b; triblock copolymer F127, anhydrous ethanol, hydrochloric acid and deionized water are mixed and stirred to obtain solution c; solutions a and b are mixed, hydrochloric acid is added dropwise to adjust the pH of the system to acidic, and then added to solution c, stirred, and aged to obtain the inner layer pre-prepared sol;
[0012] Preferably, the molar ratio of tetraethyl orthosilicate, anhydrous ethanol, hydrochloric acid and deionized water in solution a is 1:6:0.005:2;
[0013] Preferably, the molar ratio of tetraethyl orthosilicate, anhydrous ethanol, ammonia and deionized water in solution b is 1:180:3:16;
[0014] Preferably, the molar ratio of triblock copolymer F127, anhydrous ethanol, hydrochloric acid and deionized water in solution c is 0.003:160:4:1;
[0015] Preferably, the volume ratio of solution a, solution b and solution c in the inner pre-formed sol is 4:1:(0.5-1).
[0016] Preferably, the mixing and stirring time of the raw materials in solution a is 2-3 hours, and the aging process parameters include: temperature of 25-30℃ and time of 5-7 days;
[0017] Preferably, the mixing and stirring time of the raw materials in solution b is 2-3 hours, and the aging process parameters include: temperature of 25-30℃ and time of 5-7 days;
[0018] Preferably, the mixing and stirring time of the raw materials in solution c is 30-50 minutes;
[0019] Preferably, in step 2, the drying temperature is 80-100℃ and the drying time is 4-5 min; the annealing process parameters are: temperature 450-500℃, time 2-3 h; and the inner layer film thickness is 80-100 nm.
[0020] Preferably, the preparation steps of the outer sol are as follows: 1,4-butanediol dimethacrylate and 3-mercaptopropyltrimethoxysilane and catalyst are mixed and stirred for 1 hour under a nitrogen atmosphere to obtain solution d. Anhydrous ethanol, deionized water, acetic acid, modified composite particles and solution a are added, and the mixture is stirred for 20-30 minutes and aged for 10-20 hours to obtain the outer sol.
[0021] Preferably, the raw materials in the outer sol include, by mass percentage: 0.25-0.50% solution d, 60-65% anhydrous ethanol, 6-8% deionized water, 4-6% acetic acid, 1-3% modified composite particles, and the balance being solution a;
[0022] More preferably, the ratio of 1,4-butanediol dimethacrylate and 3-mercaptopropyltrimethoxysilane to catalyst in solution d is 1 g: (2.5-3) mL: 2.5 μL;
[0023] More preferably, the preparation steps of the modified composite particles are as follows: γ-glycidyl etheroxypropyltrimethoxysilane and diethylenetriamine are placed in anhydrous ethanol, sonicated for 20-30 min, then mesoporous silica is added and the mixture is heated to 60°C and stirred for 10-12 h. After filtration, washing, and drying, the mixture is dispersed in tetrahydrofuran, esterified chitin nanofibers are added and stirred for 30-40 min, followed by the addition of dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and then heated to 58-60°C. After being kept at 0℃ for 20-24h, the mixture was washed and dried to obtain composite particles. Under a nitrogen atmosphere, the composite particles were mixed with triethylamine and tetrahydrofuran, and 2-bromoisobutyryl bromide was added. The mixture was reacted at 25-30℃ for 24h. After centrifugation, washing and drying, the mixture was placed in deionized water. Under a nitrogen atmosphere, methacryloylethyl sulfobetaine, 2,2'-bipyridine and CuBr were added sequentially. The mixture was stirred in a water bath at 48-50℃ for 6-8h, and then washed and dried to obtain modified composite particles.
[0024] Preferably, the preparation steps of esterified chitin nanofibers are as follows: chitin and maleic anhydride are mixed at a mass ratio of 1:(4-6), reacted at 120℃ for 2-3 hours, centrifuged and washed, then ultrasonically dispersed in deionized water, sodium hydroxide is added to adjust the pH of the system to alkaline, stirring is continued for 1 hour, centrifuged and washed, then ultrasonically dispersed in deionized water, adjusted to alkaline pH, and ultrasonically broken to obtain esterified chitin nanofibers; the ultrasonic power is 500W, and the ultrasonic time is 30-45 minutes;
[0025] Preferably, the ratio of the composite particles to mesoporous silica, γ-glycidyl etheroxypropyltrimethoxysilane, diethylenetriamine, esterified modified chitin nanofibers, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine is 1g:(0.30-0.28)g:0.12g:(0.1-0.5)g:0.2g:0.05g; and the ratio of the composite particles, 2-bromoisobutyryl bromide, methacryloylethyl sulfobetaine, and 2,2'-bipyridine in the modified composite particles is 1g:3mL:(12-15)g:(2.0-2.5)g.
[0026] An anti-reflective coated glass for photovoltaic panels is prepared by the above-described preparation method.
[0027] Compared with the prior art, the beneficial effects of the present invention are:
[0028] 1. This invention forms a nanoporous structure on the surface of a glass substrate through high-temperature etching, which improves the hydrophilicity of the glass surface and is beneficial to improving the adhesion between the subsequent dip-coating and the glass substrate; then, an inner layer coating is performed by mixing acid-catalyzed silica sol and alkali-catalyzed silica sol, adding a template agent to adjust the pore structure, and calcining to form silica particles with different structures stacked on the surface of the glass substrate, which further improves the refractive index of the inner layer film;
[0029] 2. In this invention, after forming an inner layer film on the surface of a glass substrate, an outer layer sol is designed, in which modified composite particles and organosilicon and other raw materials are added. The modified composite particles are obtained by combining mesoporous silica with chitin nanofibers and then modifying them with zwitterionic polymers. The mesoporous silica and chitin nanofibers are obtained through electrostatic self-assembly of positive and negative charges and amidation bonding. The high aspect ratio of the chitin nanofibers forms a porous structure with the silica when stacked, further increasing the porosity of the outer layer film, thereby reducing the refractive index and improving the anti-reflection effect of the coating. Further modification of the composite particles with zwitterionic polymers improves the anti-fouling performance of the outer coating while improving the dispersion stability of the composite particles in the silica sol. This invention achieves high transmittance and durable anti-reflection effect by precisely controlling the composition between each film layer. Detailed Implementation
[0030] Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0031] In the experiment, the glass substrate was made of quartz glass, which was purchased from Suzhou Zhuoyuan Glass Co., Ltd.
[0032] The preparation method of esterified chitin nanofibers is as follows: chitin and maleic anhydride are mixed at a mass ratio of 1:5, reacted at 120℃ for 3 hours, centrifuged and washed, then placed in deionized water for ultrasonic dispersion, sodium hydroxide is added to adjust the pH of the system to 10.0, stirring is continued for 1 hour, centrifuged and washed, placed in deionized water for ultrasonic dispersion, adjusted to pH 10.0, and ultrasonically broken to obtain esterified chitin nanofibers; the ultrasonic power is 500W, and the ultrasonic time is 40 minutes.
[0033] The preparation method of mesoporous silica is as follows: 1.2g of hexadecylmethylammonium bromide and 80mL of deionized water are mixed and stirred at 45℃ to dissolve. Then, 13.83g of urea and 120mL of deionized water are added and the temperature is raised to 85℃ and kept at 15min. After cooling, 6.02g of tetraethyl orthosilicate is added and stirred for 6h. After centrifugation, washing and drying, the mixture is finally calcined at 500℃ for 5h to obtain mesoporous silica.
[0034] The preparation method of solution a is as follows: tetraethyl orthosilicate, anhydrous ethanol, hydrochloric acid and deionized water are mixed and stirred for 3 hours in a molar ratio of 1:6:0.005:2, and then aged at 25°C for 5 days to obtain solution a;
[0035] The preparation method of solution b is as follows: tetraethyl orthosilicate, anhydrous ethanol, ammonia and deionized water are mixed in a molar ratio of 1:180:3:16 for 2 hours, aged at 25°C for 6 days, and refluxed for 24 hours to obtain solution b;
[0036] Solution c is prepared by mixing triblock copolymer F127, anhydrous ethanol, hydrochloric acid and deionized water in a molar ratio of 0.003:160:4:1 and stirring for 50 min to obtain solution c; the triblock copolymer F127 has an average molecular weight of 12600 and is from the brand Sigma.
[0037] The catalyst is 1,8-diazahexacyclic[5.4.0]undec-7-ene, CAS number: 6674-22-2;
[0038] Example 1: This example provides a method for preparing anti-reflective coated glass for photovoltaic panels. The specific steps are as follows:
[0039] Step 1: Place the glass substrate in a mixed solution of deionized water, anhydrous ethanol and propanol with a volume ratio of 1:1:1, ultrasonically clean for 30 min, dry, and then transfer it to a 0.14 mol / L potassium sodium tartrate tetrahydrate solution and treat it at 180℃ for 2 h.
[0040] Step 2: Mix solutions a and b, add hydrochloric acid to adjust the pH of the system to 3, add to solution c and stir for 22 hours, then age at 25°C for 3 days to obtain the inner layer pre-prepared sol;
[0041] Step 3: Place the etched glass substrate in the inner layer pre-made sol and perform immersion lifting coating. After the coating is completed, dry it at 100°C for 4 minutes, then anneal it and bake it at 500°C for 2 hours; thus forming an inner layer film with a thickness of 85nm on the surface of the glass substrate.
[0042] Step 4: 1,4-Butanediol dimethacrylate, 3-mercaptopropyltrimethoxysilane, and catalyst were mixed at a ratio of 1 g:2.5 mL:2.5 μL and stirred for 1 h under a nitrogen atmosphere to obtain solution d. Anhydrous ethanol, deionized water, acetic acid, modified composite particles, and solution a were added, and the mixture was stirred for 30 min and aged for 20 h to obtain the outer layer sol. The glass substrate with the inner layer film was placed in the outer layer sol and dip-coated. After the coating was completed, it was dried at 100 °C for 4 h to form an outer layer film with a thickness of 100 nm on the surface of the glass substrate.
[0043] The volume ratio of solution a, solution b and solution c in the inner pre-formed sol is 4:1:1.
[0044] The raw materials in the outer sol include, by mass percentage: 0.50% solution d, 62% anhydrous ethanol, 6% deionized water, 5% acetic acid, 3% modified composite particles, and the balance being solution a;
[0045] The preparation steps of the modified composite particles are as follows: 0.30 g γ-glycidyl etheroxypropyltrimethoxysilane and 0.12 g diethylenetriamine are placed in 10 mL of anhydrous ethanol, sonicated for 30 min, then 1 g mesoporous silica is added and the mixture is heated to 60 °C and stirred for 12 h. After filtration, washing, and drying, the mixture is dispersed in 50 mL of tetrahydrofuran. 0.3 g esterified modified chitin nanofibers are added and stirred for 30 min. Then, 0.2 g dicyclohexylcarbodiimide and 0.05 g 4-dimethylaminopyridine are added and stirred at 6 °C. After being kept at 0℃ for 24 h, the mixture was washed and dried to obtain composite particles. Under a nitrogen atmosphere, 1 g of composite particles were mixed with 3 mL of triethylamine and 30 mL of tetrahydrofuran, and 3 mL of 2-bromoisobutyryl bromide was added. The mixture was reacted at 25℃ for 24 h. After centrifugation, washing and drying, the mixture was placed in 50 mL of deionized water. Under a nitrogen atmosphere, 13.4 g of methacryloylethyl sulfobetaine, 2.4 g of 2,2'-bipyridine and 1 g of CuBr were added sequentially. The mixture was stirred in a water bath at 50℃ for 8 h, and then washed and dried to obtain modified composite particles.
[0046] Example 2: This example provides a method for preparing anti-reflective coated glass for photovoltaic panels. The specific steps are as follows:
[0047] Step 1: Place the glass substrate in a mixed solution of deionized water, anhydrous ethanol and propanol with a volume ratio of 1:1:1, ultrasonically clean for 30 min, dry, and then transfer it to a 0.14 mol / L potassium sodium tartrate tetrahydrate solution and treat it at 160℃ for 2 h.
[0048] Step 2: Mix solutions a and b, add hydrochloric acid to adjust the pH of the system to 3, add to solution c and stir for 24 hours, then age at 25°C for 3 days to obtain the inner layer pre-prepared sol;
[0049] Step 3: Place the etched glass substrate in the inner layer pre-made sol and perform immersion lifting coating. After the coating is completed, dry it at 90°C for 5 minutes, then anneal it and bake it at 450°C for 2 hours; thus forming an inner layer film with a thickness of 85nm on the surface of the glass substrate.
[0050] Step 4: 1,4-Butanediol dimethacrylate, 3-mercaptopropyltrimethoxysilane, and catalyst were mixed at a ratio of 1g:2.5mL:2.5μL and stirred for 1h under a nitrogen atmosphere to obtain solution d. Anhydrous ethanol, deionized water, acetic acid, modified composite particles, and solution a were added, and the mixture was stirred for 30min and aged for 20h to obtain the outer layer sol. The glass substrate with the inner layer film was placed in the outer layer sol and dip-coated. After the coating was completed, it was dried at 85℃ for 3h to form an outer layer film with a thickness of 100nm on the surface of the glass substrate.
[0051] The volume ratio of solutions a, b, and c in the inner pre-formed sol is 4:1:0.5.
[0052] The raw materials in the outer sol include, by mass percentage: 0.30% solution d, 60% anhydrous ethanol, 6% deionized water, 4% acetic acid, 1% modified composite particles, and the balance being solution a;
[0053] The preparation steps of the modified composite particles are as follows: 0.30 g γ-glycidyl etheroxypropyltrimethoxysilane and 0.12 g diethylenetriamine are placed in 10 mL of anhydrous ethanol, sonicated for 30 min, then 1 g mesoporous silica is added and the mixture is heated to 60 °C and stirred for 12 h. After filtration, washing, and drying, the mixture is dispersed in 50 mL of tetrahydrofuran. 0.3 g esterified modified chitin nanofibers are added and stirred for 30 min. Then, 0.2 g dicyclohexylcarbodiimide and 0.05 g 4-dimethylaminopyridine are added and stirred at 6 °C. After being kept at 0℃ for 24 h, the mixture was washed and dried to obtain composite particles. Under a nitrogen atmosphere, 1 g of composite particles were mixed with 3 mL of triethylamine and 30 mL of tetrahydrofuran, and 3 mL of 2-bromoisobutyryl bromide was added. The mixture was reacted at 25℃ for 24 h. After centrifugation, washing and drying, the mixture was placed in 50 mL of deionized water. Under a nitrogen atmosphere, 13.4 g of methacryloylethyl sulfobetaine, 2.4 g of 2,2'-bipyridine and 1 g of CuBr were added sequentially. The mixture was stirred in a water bath at 50℃ for 8 h, and then washed and dried to obtain modified composite particles.
[0054] Example 3: This example provides a method for preparing anti-reflective coated glass for photovoltaic panels. The specific steps are as follows:
[0055] Step 1: Place the glass substrate in a mixed solution of deionized water, anhydrous ethanol and propanol with a volume ratio of 1:1:1, ultrasonically clean for 30 min, dry, and then transfer it to a 0.14 mol / L potassium sodium tartrate tetrahydrate solution and treat it at 180℃ for 2 h.
[0056] Step 2: Mix solutions a and b, add hydrochloric acid to adjust the pH of the system to 3, add to solution c and stir for 24 hours, then age at 25°C for 3 days to obtain the inner layer pre-prepared sol;
[0057] Step 3: Place the etched glass substrate in the inner layer pre-made sol and perform immersion lifting coating. After coating, dry at 90°C for 5 minutes, then anneal and bake at 480°C for 3 hours to form an inner layer film with a thickness of 85nm on the surface of the glass substrate.
[0058] Step 4: 1,4-Butanediol dimethacrylate, 3-mercaptopropyltrimethoxysilane, and catalyst were mixed at a ratio of 1g:3mL:2.5μL and stirred for 1h under a nitrogen atmosphere to obtain solution d. Anhydrous ethanol, deionized water, acetic acid, modified composite particles, and solution a were added, and the mixture was stirred for 30min and aged for 20h to obtain the outer layer sol. The glass substrate with the inner layer film was placed in the outer layer sol and dip-coated. After the coating was completed, it was dried at 100℃ for 4h to form an outer layer film with a thickness of 100nm on the surface of the glass substrate.
[0059] The volume ratio of solutions a, b, and c in the inner pre-formed sol is 4:1:0.8.
[0060] The raw materials in the outer sol, by mass percentage, include: 0.40% solution d, 63% anhydrous ethanol, 7% deionized water, 5% acetic acid, 1.6% modified composite particles, and the balance being solution a;
[0061] The preparation steps of the modified composite particles are as follows: 0.30 g γ-glycidyl etheroxypropyltrimethoxysilane and 0.12 g diethylenetriamine are placed in 10 mL of anhydrous ethanol, sonicated for 30 min, then 1 g mesoporous silica is added and the mixture is heated to 60 °C and stirred for 12 h. After filtration, washing, and drying, the mixture is dispersed in 50 mL of tetrahydrofuran. 0.3 g esterified modified chitin nanofibers are added and stirred for 30 min. Then, 0.2 g dicyclohexylcarbodiimide and 0.05 g 4-dimethylaminopyridine are added and stirred at 6 °C. After being kept at 0℃ for 24 h, the mixture was washed and dried to obtain composite particles. Under a nitrogen atmosphere, 1 g of composite particles were mixed with 3 mL of triethylamine and 30 mL of tetrahydrofuran, and 3 mL of 2-bromoisobutyryl bromide was added. The mixture was reacted at 25℃ for 24 h. After centrifugation, washing and drying, the mixture was placed in 50 mL of deionized water. Under a nitrogen atmosphere, 13.4 g of methacryloylethyl sulfobetaine, 2.4 g of 2,2'-bipyridine and 1 g of CuBr were added sequentially. The mixture was stirred in a water bath at 50℃ for 8 h, and then washed and dried to obtain modified composite particles.
[0062] Comparative Example 1: As a control experiment for Example 1, the modified composite particles were replaced with modified mesoporous silica. The specific steps are as follows:
[0063] Step 1: Place the glass substrate in a mixed solution of deionized water, anhydrous ethanol and propanol with a volume ratio of 1:1:1, ultrasonically clean for 30 min, dry, and then transfer it to a 0.14 mol / L potassium sodium tartrate tetrahydrate solution and treat it at 180℃ for 2 h.
[0064] Step 2: Mix solutions a and b, add hydrochloric acid to adjust the pH of the system to 3, add to solution c and stir for 22 hours, then age at 25°C for 3 days to obtain the inner layer pre-prepared sol;
[0065] Step 3: Place the etched glass substrate in the inner layer pre-made sol and perform immersion lifting coating. After the coating is completed, dry it at 100°C for 4 minutes, then anneal it and bake it at 500°C for 2 hours; thus forming an inner layer film with a thickness of 85nm on the surface of the glass substrate.
[0066] Step 4: 1,4-Butanediol dimethacrylate, 3-mercaptopropyltrimethoxysilane, and catalyst were mixed at a ratio of 1 g:2.5 mL:2.5 μL and stirred for 1 h under a nitrogen atmosphere to obtain solution d. Anhydrous ethanol, deionized water, acetic acid, modified mesoporous silica, and solution a were added, and the mixture was stirred for 30 min and aged for 20 h to obtain the outer layer sol. The glass substrate with the inner layer film was placed in the outer layer sol and dip-coated. After the coating was completed, it was dried at 100 °C for 4 h to form an outer layer film with a thickness of 100 nm on the surface of the glass substrate.
[0067] The volume ratio of solution a, solution b and solution c in the inner pre-formed sol is 4:1:1.
[0068] The raw materials in the outer sol include, by mass percentage: 0.50% solution d, 62% anhydrous ethanol, 6% deionized water, 5% acetic acid, 3% modified mesoporous silica, and the balance being solution a;
[0069] The preparation steps of modified mesoporous silica are as follows: 0.30 g γ-glycidyl etheroxypropyltrimethoxysilane and 0.12 g diethylenetriamine are placed in 10 mL anhydrous ethanol, sonicated for 30 min, then 1 g mesoporous silica is added and the mixture is heated to 60 °C and stirred for 12 h. After filtration, washing, and drying, 1 g mesoporous silica is mixed with 3 mL triethylamine and 30 mL tetrahydrofuran under a nitrogen atmosphere, and 3 mL 2-bromoisobutyryl bromide is added. The mixture is reacted at 25 °C for 24 h. After centrifugation, washing, and drying, the mixture is placed in 50 mL deionized water. Under a nitrogen atmosphere, 13.4 g methacryloyl ethyl sulfobetaine, 2.4 g 2,2'-bipyridine, and 1 g CuBr are added sequentially. The mixture is stirred in a water bath at 50 °C for 8 h, then washed and dried to obtain modified mesoporous silica.
[0070] Comparative Example 2: As a control experiment for Example 1, the composite particles were not modified. The specific steps are as follows:
[0071] Step 1: Place the glass substrate in a mixed solution of deionized water, anhydrous ethanol and propanol with a volume ratio of 1:1:1, ultrasonically clean for 30 min, dry, and then transfer it to a 0.14 mol / L potassium sodium tartrate tetrahydrate solution and treat it at 180℃ for 2 h.
[0072] Step 2: Mix solutions a and b, add hydrochloric acid to adjust the pH of the system to 3, add to solution c and stir for 22 hours, then age at 25°C for 3 days to obtain the inner layer pre-prepared sol;
[0073] Step 3: Place the etched glass substrate in the inner layer pre-made sol and perform immersion lifting coating. After the coating is completed, dry it at 100°C for 4 minutes, then anneal it and bake it at 500°C for 2 hours; thus forming an inner layer film with a thickness of 85nm on the surface of the glass substrate.
[0074] Step 4: 1,4-Butanediol dimethacrylate, 3-mercaptopropyltrimethoxysilane, and catalyst were mixed at a ratio of 1 g:2.5 mL:2.5 μL and stirred for 1 h under a nitrogen atmosphere to obtain solution d. Anhydrous ethanol, deionized water, acetic acid, modified composite particles, and solution a were added, and the mixture was stirred for 30 min and aged for 20 h to obtain the outer layer sol. The glass substrate with the inner layer film was placed in the outer layer sol and dip-coated. After the coating was completed, it was dried at 100 °C for 4 h to form an outer layer film with a thickness of 100 nm on the surface of the glass substrate.
[0075] The volume ratio of solution a, solution b and solution c in the inner pre-formed sol is 4:1:1.
[0076] The raw materials in the outer sol include, by mass percentage: 0.50% solution d, 62% anhydrous ethanol, 6% deionized water, 5% acetic acid, 3% composite particles, and the balance being solution a;
[0077] The preparation steps of the composite particles are as follows: 0.30 g γ-glycidyl etheroxypropyltrimethoxysilane and 0.12 g diethylenetriamine are placed in 10 mL of anhydrous ethanol, sonicated for 30 min, 1 g mesoporous silica is added and the mixture is heated to 60 °C and stirred for 12 h. After filtration, washing, and drying, the mixture is dispersed in 50 mL of tetrahydrofuran. 0.3 g esterified modified chitin nanofibers are added and stirred for 30 min. Then, 0.2 g dicyclohexylcarbodiimide and 0.05 g 4-dimethylaminopyridine are added. The mixture is kept at 60 °C for 24 h, washed and dried to obtain the composite particles.
[0078] Comparative Example 3: As a control experiment for Example 1, the glass substrate was not coated with an inner layer film. The specific steps are as follows:
[0079] Step 1: Place the glass substrate in a mixed solution of deionized water, anhydrous ethanol and propanol with a volume ratio of 1:1:1, ultrasonically clean for 30 min, dry, and then transfer it to a 0.14 mol / L potassium sodium tartrate tetrahydrate solution and treat it at 180℃ for 2 h.
[0080] Step 3: 1,4-Butanediol dimethacrylate, 3-mercaptopropyltrimethoxysilane, and catalyst were mixed at a ratio of 1g:2.5mL:2.5μL and stirred for 1h under a nitrogen atmosphere to obtain solution d. Anhydrous ethanol, deionized water, acetic acid, modified composite particles, and solution a were added, and the mixture was stirred for 30min and aged for 20h to obtain the outer layer sol. The etched glass substrate was placed in the outer layer sol and dip-coating was performed. After coating, the substrate was dried at 100℃ for 4h to form an outer layer film with a thickness of 100nm on the surface of the glass substrate.
[0081] The outer sol contains the following raw materials by mass percentage: 0.50% solution d, 62% anhydrous ethanol, 6% deionized water, 5% acetic acid, 3% modified composite particles, and the remainder is solution a;
[0082] The preparation steps of the modified composite particles are as follows: 0.30 g γ-glycidyl etheroxypropyltrimethoxysilane and 0.12 g diethylenetriamine are placed in 10 mL of anhydrous ethanol, sonicated for 30 min, then 1 g mesoporous silica is added and the mixture is heated to 60 °C and stirred for 12 h. After filtration, washing, and drying, the mixture is dispersed in 50 mL of tetrahydrofuran. 0.3 g esterified modified chitin nanofibers are added and stirred for 30 min. Then, 0.2 g dicyclohexylcarbodiimide and 0.05 g 4-dimethylaminopyridine are added and stirred at 6 °C. After being kept at 0℃ for 24 h, the mixture was washed and dried to obtain composite particles. Under a nitrogen atmosphere, 1 g of composite particles were mixed with 3 mL of triethylamine and 30 mL of tetrahydrofuran, and 3 mL of 2-bromoisobutyryl bromide was added. The mixture was reacted at 25℃ for 24 h. After centrifugation, washing and drying, the mixture was placed in 50 mL of deionized water. Under a nitrogen atmosphere, 13.4 g of methacryloylethyl sulfobetaine, 2.4 g of 2,2'-bipyridine and 1 g of CuBr were added sequentially. The mixture was stirred in a water bath at 50℃ for 8 h, and then washed and dried to obtain modified composite particles.
[0083] Testing and Experiment
[0084] 1. Antireflection performance: The transmittance of the coated glass prepared in Examples 1-3 and Comparative Examples 1-3 was tested using a U-4100 UV-Vis-NIR spectrophotometer, and the data were recorded in Table 1. Then, a spectacle cloth was used to cover the surface of the coated glass, a 50g weight was placed on the spectacle cloth, and the glass was wiped 500 times in the same direction. The transmittance after wiping was tested, and the data were recorded in Table 1.
[0085] 2. Adhesion test: Refer to GB / T9286, use a cross-cutting knife to make cuts, then rotate the blade 90° to make vertical cuts, then stick pressure-sensitive tape to the cuts, and finally tear the tape at a 90° angle to the direction of the coating film on the glass surface, observe the coating peeling, and evaluate the adhesion according to the specified grade.
[0086] 3. Stain resistance test: The static contact angle of water droplets falling on the glass surface was measured using an SDC-350H contact angle meter, and the data were recorded in Table 1.
[0087] Table 1
[0088]
[0089] In conclusion, the test data above show that Example 1 achieves better technical results than the other examples in terms of antireflection performance, antifouling performance, and interfacial bonding performance. Comparative experiments were conducted on Example 1. In Comparative Example 1, the absence of chitin nanofibers in the preparation of the modified composite particles resulted in a decrease in transmittance and contact angle. In Comparative Example 2, the absence of polymers in the preparation of the modified composite particles resulted in a decrease in hydrophilicity, which affected transmittance. In Comparative Example 3, the absence of inner layer film deposition resulted in a significant decrease in transmittance and adhesion.
[0090] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A method for preparing anti-reflective coated glass for photovoltaic panels, characterized in that, The preparation steps include the following: Step 1: After ultrasonic cleaning and drying, the glass substrate is placed in an etching solution for etching. Step 2: Place the etched glass substrate in the inner pre-prepared sol for immersion and pull coating. After coating, dry and then anneal to obtain a glass substrate with an inner film on the surface. Step 3: Place the glass substrate with the inner film on the surface into the outer sol, perform immersion and pull coating, and dry after coating to obtain anti-reflective coated glass; The preparation steps of the inner layer pre-formed sol are as follows: tetraethyl orthosilicate, anhydrous ethanol, hydrochloric acid and deionized water are mixed and stirred, and then aged to obtain solution a; tetraethyl orthosilicate, anhydrous ethanol, ammonia and deionized water are mixed and stirred, aged and refluxed to obtain solution b; triblock copolymer F127, anhydrous ethanol, hydrochloric acid and deionized water are mixed and stirred to obtain solution c; solutions a and b are mixed, hydrochloric acid is added dropwise to adjust the pH of the system to acidic, and then added to solution c and stirred, and aged to obtain the inner layer pre-formed sol.
2. The method for preparing anti-reflective coated glass for photovoltaic panels according to claim 1, characterized in that, The molar ratio of tetraethyl orthosilicate, anhydrous ethanol, hydrochloric acid, and deionized water in solution a is 1:6:0.005:2; the molar ratio of tetraethyl orthosilicate, anhydrous ethanol, ammonia, and deionized water in solution b is 1:180:3:16; the molar ratio of triblock copolymer F127, anhydrous ethanol, hydrochloric acid, and deionized water in solution c is 0.003:160:4:1; and the volume ratio of solutions a, b, and c in the inner pre-formed sol is 4:1:(0.5-1).
3. The method for preparing anti-reflective coated glass for photovoltaic panels according to claim 1, characterized in that, The raw materials in solution a are mixed and stirred for 2-3 hours, and the aging process parameters include: temperature 25-30℃ and time 5-7 days; the raw materials in solution b are mixed and stirred for 2-3 hours, and the aging process parameters include: temperature 25-30℃ and time 5-7 days; the raw materials in solution c are mixed and stirred for 30-50 minutes.
4. The method for preparing anti-reflective coated glass for photovoltaic panels according to claim 1, characterized in that, In step 2, the drying temperature is 80-100℃ and the drying time is 4-5 min; the annealing process parameters are: temperature 450-500℃ and time 2-3 h; the inner layer film thickness is 80-100 nm.
5. The method for preparing anti-reflective coated glass for photovoltaic panels according to claim 1, characterized in that, The preparation steps of the outer sol are as follows: 1,4-butanediol dimethacrylate, 3-mercaptopropyltrimethoxysilane, and catalyst are mixed and stirred for 1 hour under a nitrogen atmosphere to obtain solution d. Anhydrous ethanol, deionized water, acetic acid, modified composite particles, and solution a are added, and the mixture is stirred for 20-30 minutes and then aged for 10-20 hours to obtain the outer sol.
6. The method for preparing anti-reflective coated glass for photovoltaic panels according to claim 5, characterized in that, The raw materials in the outer sol include, by mass percentage: 0.25-0.50% solution d, 60-65% anhydrous ethanol, 6-8% deionized water, 4-6% acetic acid, 1-3% modified composite particles, and the balance being solution a.
7. The method for preparing anti-reflective coated glass for photovoltaic panels according to claim 5, characterized in that, The ratio of 1,4-butanediol dimethacrylate and 3-mercaptopropyltrimethoxysilane to catalyst in solution d is 1 g:(2.5-3) mL:2.5 μL. The preparation steps of the modified composite particles are as follows: γ-glycidyl etheroxypropyltrimethoxysilane and diethylenetriamine are placed in anhydrous ethanol, sonicated for 20-30 min, then mesoporous silica is added and the temperature is raised to 58-60℃ and stirred for 10-12 h. After filtration, washing, drying, and dispersion in tetrahydrofuran, esterified chitin nanofibers are added and stirred for 30-40 min. Then, dicyclohexylcarbodiimide and 4-dimethylaminopyridine are added, and the mixture is kept at 55-60℃ for 20-24h. After washing and drying, composite particles are obtained. Under a nitrogen atmosphere, the composite particles are mixed with triethylamine and tetrahydrofuran, and 2-bromoisobutyryl bromide is added. The mixture is reacted at 25-30℃ for 24h. After centrifugation, washing and drying, the mixture is placed in deionized water. Under a nitrogen atmosphere, methacryloylethyl sulfobetaine, 2,2'-bipyridine and CuBr are added sequentially. The mixture is stirred in a water bath at 48-50℃ for 6-8h, and then washed and dried to obtain modified composite particles.
8. The method for preparing anti-reflective coated glass for photovoltaic panels according to claim 7, characterized in that, The preparation steps of the esterified chitin nanofibers are as follows: chitin and maleic anhydride are mixed at a mass ratio of 1:(4-6), reacted at 120℃ for 2-3 hours, centrifuged and washed, then placed in deionized water for ultrasonic dispersion, sodium hydroxide is added to adjust the pH of the system to alkaline, stirring is continued for 1 hour, centrifuged and washed, placed in deionized water for ultrasonic dispersion, adjusted to alkaline pH, and ultrasonically broken to obtain esterified chitin nanofibers; the ultrasonic power is 500W, and the ultrasonic time is 30-45 minutes.
9. The method for preparing anti-reflective coated glass for photovoltaic panels according to claim 7, characterized in that, The ratio of the composite particles to mesoporous silica, γ-glycidyl etheroxypropyltrimethoxysilane, diethylenetriamine, esterified chitin nanofibers, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine is 1g:(0.30-0.28)g:0.12g:(0.1-0.5)g:0.2g:0.05g; the ratio of the composite particles, 2-bromoisobutyryl bromide, methacryloylethyl sulfobetaine, and 2,2'-bipyridine in the modified composite particles is 1g:3mL:(12-15)g:(2.0-2.5)g.
10. An anti-reflective coated glass for photovoltaic panels, characterized in that, It is prepared by the preparation method according to any one of claims 1-9.