High-transmittance glass with synergistic effect of thin film diffraction and microstructure scattering
By stacking a bottom alkaline film, a middle particle film, and a surface acidic fixing layer on photovoltaic glass, the problem of poor adhesion of the particle film layers was solved, resulting in high transmittance and improved photovoltaic cell efficiency, thus enhancing the optical gain effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CNBM RESEARCH INSTITUTE FOR ADVANCED GLASS MATERIALS GROUP CO LTD
- Filing Date
- 2026-02-06
- Publication Date
- 2026-05-29
AI Technical Summary
The bonding strength of the particle film layers in existing high-transmittance glass is generally weak, making it difficult to achieve stable particle encapsulation and gap filling through the surface sol layer. This results in a significant reduction in the optical gain effect of the multilayer film structure, limiting the improvement of the light transmittance of photovoltaic glass.
Using an ultra-white photovoltaic glass substrate, a bottom alkaline film, a middle particle film, and a surface acidic fixing layer are sequentially stacked. Through the preparation of alkaline sol, microsphere emulsion, and acidic sol, a stable protrusion structure is formed on the surface of the film, which generates a light trapping effect. The optical transmittance is enhanced by the light interference of the bottom optical film.
High transmittance of photovoltaic glass was achieved, improving the power generation efficiency of photovoltaic cells and enhancing product competitiveness. Through the synergistic effect of thin film diffraction and microstructure scattering, optical transmittance and film adhesion were improved.
Smart Images
Figure CN122102531A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of photovoltaic glass technology, and in particular to a high-transmittance glass with the synergistic effect of thin-film diffraction and microstructure scattering. Background Technology
[0002] In the solar photovoltaic industry, anti-reflective glass is a crucial component, widely used in solar cell modules. Solar modules require high optical transmittance to improve cell power generation efficiency, and currently, ultra-white glass is being widely adopted. Anti-reflective coated glass, when used as a battery cover, can increase the transmittance of sunlight in the visible light region, thereby improving the power generation efficiency of solar cells.
[0003] In existing high-transmittance glass, the bonding force of the particle film layer is generally weak, making it difficult to achieve stable particle encapsulation and gap filling through the surface sol layer. Ultimately, this significantly reduces the optical gain effect of the multilayer film structure, limiting the improvement of the light transmittance of photovoltaic glass.
[0004] Therefore, it is necessary to propose a high-transmittance glass that combines thin-film diffraction and microstructure scattering to solve the above problems. Summary of the Invention
[0005] The purpose of this invention is to provide a high-transmittance glass that combines thin-film diffraction and microstructure scattering, in order to solve the problem that in existing high-transmittance glasses, the bonding force of the particle film layer is generally weak, making it difficult to achieve stable particle encapsulation and gap filling through the surface sol layer. Ultimately, this results in a significant reduction in the optical gain effect of the multilayer film structure and a limited increase in the light transmittance of photovoltaic glass.
[0006] To achieve the above objectives, the present invention provides the following technical solution: a high-transmittance glass with synergistic effects of thin-film diffraction and microstructure scattering, comprising an ultra-white photovoltaic glass substrate and a bottom alkaline layer sequentially stacked on the surface of the ultra-white photovoltaic glass substrate. Thin film, intermediate layer Particle film and surface acidity Fixed layer; The underlying alkalinity The film is alkaline It is prepared by sol; The middle layer The particle membrane consists of It is prepared by microsphere emulsion; The surface acidity The fixed layer is acidic It is prepared by sol, and the surface layer is acidic. The fixed layer permeates and fills the middle layer The particle film intersects the particle surface and encapsulates the particle surface.
[0007] Preferably, the alkalinity The sol used tetraethyl orthosilicate as a precursor and ethanol as a solvent.
[0008] Preferably, the The raw materials for microsphere emulsions include tetraethyl orthosilicate, carboxylates, and cationic surfactants.
[0009] Preferably, the acidic The sol used tetraethyl orthosilicate as a precursor and ethanol as a solvent.
[0010] This invention also discloses a method for preparing high-transmittance glass with the synergistic effect of thin-film diffraction and microstructure scattering, applicable to the preparation of the aforementioned high-transmittance glass with the synergistic effect of thin-film diffraction and microstructure scattering, and further includes the following steps: S1: Sol preparation, separately preparing acidic solutions for forming the surface fixation layer. Sol and alkaline solution used to form the underlying film Sol; S2: Microsphere emulsion preparation: The Stobber method was used to prepare microspheres for forming a mesosphere scattering structure. Microsphere emulsion; S3: Alkaline bottom layer Thin film preparation, using the alkaline solution prepared in S1 Sol is used as a coating solution to prepare an alkaline underlayer on the surface of an ultra-white photovoltaic glass substrate that has been ultrasonically cleaned and dried. film; S4: Middle Layer Particle film preparation, using the material prepared in S2 Using microsphere emulsion as raw material, a wire rod coating method is used to coat the alkaline substrate. Preparation of intermediate layer on thin film surface Particle film, forming a microstructured scattering layer; S5: Surface acidity Preparation of the immobilized layer, using the acidic material prepared in S1 The sol is a coating solution, and a preparation method compatible with S3 is used in the middle layer. Prepare an extremely thin surface layer of acidic material on the particle film surface. Fixed layer, the surface layer is acidic The fixed layer permeates and fills the middle layer The particle film intersects the particle surface and encapsulates the particle surface.
[0011] Preferably, in step S2, the Stobber method is used to prepare... Microsphere emulsions include the preparation of reaction media, The process involves three steps: microsphere synthesis, washing, and dispersion.
[0012] Preferably, the preparation of the reaction medium includes the following steps: selecting sodium acetate or sodium propionate as the carboxylate raw material, and preparing a carboxylate solution with a concentration of 0.01 mol / L to 0.10 mol / L; The carboxylate solution was heated and stirred in a constant temperature oil bath or water bath to stabilize the temperature of the mixture at 50℃~90℃. The cationic surfactant is slowly added during stirring, and the mixture is continuously stirred and homogenized for 0.5 to 3 hours to ensure that the surfactant is completely dissolved and uniformly dispersed in the carboxylate solution, forming a stable reaction medium. The cationic surfactant is hexadecyltrimethylammonium bromide.
[0013] Preferably, the The synthesis of the microspheres includes the following steps: Tetraethyl orthosilicate is added dropwise to a stable reaction medium at a molar ratio of carboxylate, cationic surfactant, and tetraethyl orthosilicate of 0.01~0.10:0.02~0.20:0.1~2.0. Under constant temperature conditions of 50℃~90℃, the mixture is continuously heated and stirred for 16~24 hours to allow tetraethyl orthosilicate to fully hydrolyze and condense to form... Nanospheres.
[0014] Preferably, in S4, the middle layer The preparation of the particle film includes the following steps: selecting wire rods with a gap size of 2μm~20μm, and pressing the wire rods steadily onto the substrate that has been coated with an alkaline substrate. At the edge of the glass substrate of the thin film, the wire rod is made to fit tightly against the substrate surface; Prepared by S2 The microsphere emulsion was dropped onto the contact line between the rod and the substrate; The emulsion is uniformly coated along the substrate surface using a wire-bar coating machine at a speed of 1-5 m / min. After the ethanol in the emulsion evaporates... Microspheres spread evenly to form Particle colloidal crystal thin films.
[0015] Preferably, in S5, the surface layer is acidic. The structure of the fixed layer and the middle layer The particle membranes have a consistent structure and an acidic surface. The anchoring layer fills the middle layer through molecular-level permeation. The particle film intersects the particle surface and encapsulates the particle surface.
[0016] Technical effects and advantages of the present invention: 1. The upper continuous or discontinuous particle film and the surface acidic layer The sol film forms a stable surface protrusion structure, producing a light-trapping effect that reduces light reflection by scattering light. Simultaneously, the surface is covered with an extremely thin layer of acidic sol. This layer solves the problem of poor film adhesion that is common with particle film layers. Finally, by enhancing the optical interference of the underlying optical thin film, the optical transmittance of the coated glass is further enhanced, thereby further improving the power generation efficiency of photovoltaic cells and enhancing product competitiveness. 2. The prepared composite film has a regular protruding structure on its surface. Particles are affected by surface acidity The membrane tightly wraps around the protrusions, achieving a stable fixation effect, and the protrusions naturally form a concave structure. This special "protrusion-concave" composite structure can generate a strong light-trapping effect, reducing the amount of light reflection by changing the direction of incident light reflection; at the same time, the underlying alkaline layer... The loose structure of the thin film can form an ordered diffraction grating, which modulates the phase of the incident light and produces reflected light diffraction. This works in conjunction with the light trapping effect of the surface layer, and is further enhanced by the interface interference between the surface and middle layers, thus achieving triple optical effect coupling. Attached Figure Description
[0017] Figure 1 This is a cross-sectional morphology diagram of the high-transmittance glass structure resulting from the synergistic effect of thin-film diffraction and microstructure scattering in this invention.
[0018] Figure 2 This is a surface morphology diagram of the high-transmittance glass that exhibits the synergistic effect of thin-film diffraction and microstructure scattering according to the present invention.
[0019] Figure 3 This is the transmittance spectrum of the high-transmittance glass produced by the synergistic effect of thin-film diffraction and microstructure scattering in this invention. Detailed Implementation
[0020] This invention provides, for example Figures 1-3 The high-transmittance glass shown is a product of the synergistic effect of thin-film diffraction and microstructure scattering, comprising an ultra-white photovoltaic glass substrate and an underlying alkaline layer sequentially stacked on the surface of the ultra-white photovoltaic glass substrate. Thin film, intermediate layer Particle film and surface acidity Fixed layer, in which the bottom layer is alkaline The film is alkaline Prepared from sol; middle layer The particle membrane consists of Prepared from microsphere emulsion; surface acidic The fixed layer is acidic Prepared from sol, with an acidic surface. The fixed layer permeates and fills the middle layer The particle film intersects the particle surface and encapsulates the particle surface.
[0021] The upper continuous or discontinuous particle film and the surface acidic The sol film forms a stable surface protrusion structure, producing a light-trapping effect that reduces light reflection by scattering light. Simultaneously, the surface is covered with an extremely thin layer of acidic sol. This layer solves the problem of poor film adhesion caused by typical particle film layers. Finally, by enhancing the optical interference of the underlying optical thin film, the optical transmittance of the coated glass is further enhanced, thereby further improving the power generation efficiency of photovoltaic cells and enhancing product competitiveness.
[0022] Based on the technical principle of synergistic effect of thin film diffraction and microstructure scattering, high-transparency glass is prepared through a stepwise process of sol preparation, microsphere emulsion synthesis, multilayer coating and particle film fixation.
[0023] S1. Sol preparation: S11, acidic Sol preparation First, a measured amount of ethanol was added to a beaker, followed by slow injection of tetraethyl orthosilicate and stirring until homogeneous, forming a uniform mixed dispersion system with ethanol as the dispersant and tetraethyl orthosilicate as the dispersed phase. Then, concentrated hydrochloric acid was added dropwise to adjust the pH of the mixed dispersion system, maintaining it stably within the range of 2.0–6.5. Simultaneously, a magnetic stirrer was used for constant-temperature stirring at a rate of 300–500 rpm and an ambient temperature of 25–30°C for 30 minutes. During this process, tetraethyl orthosilicate gradually underwent hydrolysis-condensation under acidic conditions, generating silicic acid oligomers which gradually aggregated to form… Sol.
[0024] After stirring, the concentration of the mixed dispersion system is adjusted by precise metering to control the resulting concentration. In sol The solid content is 0.1~0.3%. After sealing, it should be left to stand at room temperature for later use. The standing process can further stabilize the dispersed phase in the sol and improve the consistency of subsequent film formation.
[0025] S12, alkaline Sol preparation Used with acid A precursor (tetraethyl orthosilicate) with identical sol ratio and solvent (ethanol) was prepared. A measured amount of ethanol was first added to a beaker, followed by a slow addition of the corresponding proportion of tetraethyl orthosilicate. After stirring until homogeneous, a uniform dispersion was formed. The pH of this dispersion was then adjusted dropwise with ammonia water until it stabilized within the range of 7.0–10.0. Simultaneously, a magnetic stirrer was used to maintain a constant temperature (stirring speed 300–500 rpm, temperature 25–30°C) for 30 minutes, allowing the tetraethyl orthosilicate to undergo a gentle hydrolysis-condensation reaction in an alkaline environment, gradually forming… Sol.
[0026] After stirring, the concentration is controlled by calibration. In sol With a solid content of 0.1~0.3%, continue stirring for 5 minutes to ensure the system is homogeneous, then seal and let it stand at room temperature for later use to ensure the stability of the sol and its applicability to subsequent coatings.
[0027] S2: Microsphere emulsion preparation Using tetraethyl orthosilicate as a precursor, electrons with diameters of 80–250 nm were prepared by the Stober method. The specific steps for making microsphere emulsions are as follows: S21. Preparation of reaction medium First, sodium acetate or sodium propionate is selected as the carboxylate raw material, and a carboxylate solution with a concentration of 0.01 mol / L to 0.10 mol / L is prepared. The solution is placed in a constant temperature oil bath or water bath for heating and stirring to form a mixed system. The temperature of the mixed system is stabilized at 50℃ to 90℃. During the stirring process, a cationic surfactant (such as hexadecyltrimethylammonium bromide) is slowly added, and the mixture is continuously stirred and homogenized for 0.5 to 3 hours to ensure that the surfactant is completely dissolved and uniformly dispersed in the carboxylate solution to form a stable reaction medium.
[0028] S22, Small ball synthesis According to the molar ratio of carboxylate, cationic surfactant, and tetraethyl orthosilicate of 0.01~0.10:0.02~0.20:0.1~2.0, tetraethyl orthosilicate is added dropwise to the above mixture. The mixture is then heated and stirred at a constant temperature of 50℃~90℃ for 16~24 hours to allow the tetraethyl orthosilicate to fully hydrolyze and condense, gradually forming… Nanospheres were used to obtain the sample.
[0029] S23, Washing and Dispersion Treatment After the reaction was completed, the obtained sample was subjected to centrifugal ultrasonic washing: the product was separated by high-speed centrifugation. The precipitate is washed 3-5 times with anhydrous ethanol to remove unreacted organic impurities, and then washed 2-4 times with deionized water to remove residual salts. No drying is required throughout the process, and the product is directly obtained in an aqueous dispersion state. Microsphere emulsion, tested in the original emulsion The solid content of the pellets is 5.8%.
[0030] Depending on the requirements of subsequent coating processes, add an appropriate amount of ethanol or deionized water to the original emulsion. The solid content of the microspheres is precisely adjusted to 1%~5%, then a small amount of cationic surfactant (such as hexadecyltrimethylammonium bromide) is added, and the mixture is dispersed in an ultrasonic disperser for 20~80 minutes to ensure... The small balls are evenly dispersed without clumping, resulting in a stable distribution. Microsphere emulsion is ready for use.
[0031] S3: Alkaline bottom layer Thin film preparation Select an ultra-white photovoltaic glass substrate that has been ultrasonically cleaned, dried, and had its surface impurities removed, and use the alkaline solution prepared in S1. Sol is used as a coating solution to prepare a coating on the surface of a treated ultra-white photovoltaic glass substrate. film.
[0032] The preparation method can be selected according to production needs, such as dip-coating, spin coating, or roll coating: when using dip-coating, the dipping rate is controlled at 5~10mm / s; when using spin coating, the rotation speed is set at 2000~4000r / min; when using roll coating, the roller pressure and rotation speed are adjusted to match, and the film thickness is monitored in real time by a film thickness measuring instrument. Finally, the film thickness is controlled within the range of 50~200nm. This film serves as the underlying optical film, providing a foundation for subsequent microstructure scattering and optical interference.
[0033] S4: Middle Layer Particle film preparation Single-layer continuous or discontinuous particle films are prepared by wire rod coating: First, wire rods with a gap size of 2μm~20μm are selected and pressed stably onto a substrate coated with alkaline solution. At one edge of the glass substrate of the thin film, ensure that the wire rod is in close contact with the substrate surface and is not tilted. (The text then abruptly shifts to a seemingly unrelated topic: "Using S2 after ultrasonic dispersion...") Using microsphere emulsion as the raw material, an appropriate amount of emulsion is added dropwise to the contact line between the microsphere and the substrate using a pipette or dropper, ensuring that the emulsion evenly covers the contact area without overflowing. Subsequently, a microsphere coating machine is used for scraping, with the scraping speed set to 1-5 m / min, allowing the microsphere to scrape uniformly across the substrate surface. During this process, the ethanol in the emulsion evaporates rapidly upon contact with air. Microspheres spread evenly on the surface of the underlying film as the emulsion flows, eventually forming a film composed of... Colloidal crystalline thin films composed of particles can be flexibly controlled to present a continuous or discontinuous state by adjusting the gap between the wire rods and the coating rate.
[0034] S5: Surface acidity Preparation of fixed layer acidic The sol is a coating solution, prepared using a method compatible with the underlying thin film in S3, and has already formed in S4. Prepare extremely thin acidic films on particle film surfaces layer.
[0035] If the bottom film is prepared by spin coating, the top layer can also be prepared using spin coating, with the rotation speed set to 3000~5000 r / min to control the ultrathin film characteristics; if the bottom layer is prepared by dip-coating, the top layer can be prepared using dip-coating, with the dipping rate adjusted to 8~12 mm / s to ensure uniform film coverage. This acidic... The layer can be designed as a continuous or discontinuous structure according to the continuous state of the particle membrane. Its core function is to partially fill the membrane through molecular-level permeation. The gaps between particles and the tight wrapping of the particle surface form a fixed structure of "point-to-surface combination". This not only solves the industry pain point of poor bonding force of traditional particle film layers, but also does not destroy the loose scattering characteristics of the middle particle film, while ensuring that the entire composite film layer has both high permeability and high hardness.
[0036] Reference Figure 1 , Figure 2 As shown, scanning electron microscopy revealed that the surface of the prepared composite film exhibited a regular protruding structure. Particles are affected by surface acidity The membrane tightly wraps around the protrusions, achieving a stable fixation effect, and the protrusions naturally form a concave structure. This special "protrusion-concave" composite structure can generate a strong light-trapping effect, reducing the amount of light reflection by changing the direction of incident light reflection; at the same time, the underlying alkaline layer... The loose structure of the thin film can form an ordered diffraction grating, which modulates the phase of the incident light and produces reflected light diffraction. This works in conjunction with the light trapping effect of the surface layer, and is further enhanced by the interface interference between the surface and middle layers, thus achieving triple optical effect coupling.
[0037] Reference Figure 3 As shown, according to the ultraviolet-visible-near-infrared spectrophotometer, the high-transmittance glass has an average transmittance (91.2%) that is more than 2.5% higher than that of ordinary ultra-white glass (88.6%) in a wide spectral range of 380~1100nm. This can effectively improve the light absorption efficiency of photovoltaic cells, thereby increasing power generation and significantly enhancing the core competitiveness of the product in the fierce competition of the photovoltaic industry.
[0038] Furthermore, the method for preparing high-transmittance glass through the synergistic effect of thin-film diffraction and microstructure scattering includes the following examples: Example 1: S1, Sol Preparation S11, acidic Sol preparation A measured amount of ethanol was added to a beaker, followed by slow injection of tetraethyl orthosilicate and stirring until a homogeneous dispersion was formed. The pH of the system was adjusted to a stable 2.0 by adding concentrated hydrochloric acid dropwise. The system was then stirred at a constant temperature of 300 rpm and 25°C on a magnetic stirrer for 30 minutes to allow the tetraethyl orthosilicate to undergo a hydrolysis-condensation reaction to form… Sol. After stirring, calibrate the system concentration and control the resulting solution. In sol The solid content is 0.1%. After sealing, it should be left to stand at room temperature for later use.
[0039] S12, alkaline Sol preparation Used with acid To prepare a sol-gel mixture with the same ratio of tetraethyl orthosilicate to ethanol, add a measured amount of ethanol to a beaker, then slowly pour in the corresponding proportion of tetraethyl orthosilicate and stir until homogeneous. Gradually add ammonia to adjust the pH of the system to 7.0. Stir the mixture on a magnetic stirrer at a constant temperature of 300 rpm and 25°C for 30 minutes. After stirring, calibrate the concentration. In sol The solid content is 0.1%. After stirring for another 5 minutes, seal and let stand at room temperature for later use.
[0040] S2, Microsphere emulsion preparation S21. Preparation of reaction medium Sodium acetate was selected as the carboxylate raw material, and a sodium acetate solution with a concentration of 0.01 mol / L was prepared. The solution was placed in a water bath and heated and stirred until the system temperature stabilized at 50℃. During the stirring process, the cationic surfactant hexadecyltrimethylammonium bromide was slowly added, and the mixture was continuously stirred and homogenized for 0.5 h to form a stable reaction medium.
[0041] S22, Small ball synthesis According to the molar ratio of sodium acetate: hexadecyltrimethylammonium bromide: tetraethyl orthosilicate of 0.01:0.02:0.1, tetraethyl orthosilicate was added dropwise to the above mixture, and the mixture was heated and stirred at a constant temperature of 50°C for 16 hours to complete the process. Synthesis of nanospheres.
[0042] S23, Washing and Dispersion Treatment After the reaction is complete, the sample is subjected to centrifugal ultrasonic washing and high-speed centrifugation separation. The precipitate was washed three times with anhydrous ethanol to remove organic impurities, and then washed twice with deionized water to remove residual salts, resulting in an aqueous dispersion. Small ball original emulsion (solid content 5.8%). Add an appropriate amount of deionized water to the original emulsion, and... The solid content of the pellets was precisely adjusted to 1%, a small amount of hexadecyltrimethylammonium bromide was added, and the pellets were dispersed in an ultrasonic disperser for 20 minutes to obtain a stable product. Microsphere emulsion is ready for use.
[0043] S3, bottom alkaline Thin film preparation Ultra-white photovoltaic glass substrates that have undergone ultrasonic cleaning and drying to remove impurities were selected to prepare the alkaline... The sol was used as the coating solution. The bottom film was prepared by dip-coating method, and the coating rate was controlled at 5 mm / s. Finally, the film thickness was precisely controlled at 50 nm.
[0044] S4, Middle Layer Particle film preparation Particle films were prepared using a bar-and-wire coating method. A bar with a gap size of 2 μm was selected and smoothly pressed onto the edge of a glass substrate coated with the underlying film, ensuring tight adhesion without tilting. The film was then coated using a dropper. The microsphere emulsion was drop-added to the contact line between the wire rod and the substrate, and then uniformly coated using a wire rod coater at a speed of 1 m / min. After the ethanol in the emulsion evaporated rapidly... Microspheres spread evenly to form Particle colloidal crystal thin films.
[0045] S5, surface acidity Preparation of fixed layer acidic The sol is used as the coating solution, and the surface acidic layer is prepared on the surface of the intermediate particle film using the dip-coating method. A fixed layer was formed by adjusting the lifting rate to 8 mm / s, creating an ultrathin acidic layer compatible with the particle film. Layer, this layer is filled with molecular-level permeation The particles intersect and coat the particle surface, forming a stable composite film structure.
[0046] The resulting composite film exhibits a 3.0% increase in average transmittance over a broad spectral range of 380–1100 nm compared to the ultra-white photovoltaic glass substrate. No particles detached, film hardness met standards, and the triple optical effect of light trapping and diffraction interference was well coupled.
[0047] Example 2: S1, Sol Preparation S11, acidic Sol preparation Add a measured amount of ethanol to a beaker, then slowly inject tetraethyl orthosilicate and stir until a homogeneous mixture is formed. Add concentrated hydrochloric acid dropwise to adjust the pH of the system to 4.2. Stir on a magnetic stirrer at a constant temperature of 400 rpm and 27°C for 30 minutes to complete the hydrolysis-condensation reaction. After stirring, calibrate the concentration to... In sol The solid content is 0.2%, and it should be sealed and left to stand at room temperature for later use.
[0048] S12, alkaline Sol preparation Used with acid Ethyl orthosilicate and ethanol of the same sol ratio were mixed thoroughly by stirring. Ammonia was then added dropwise to adjust the pH of the system to 8.5. The mixture was then stirred using a magnetic stirrer at a constant temperature of 400 rpm and 27°C for 30 minutes. After stirring, the concentration was calibrated. In sol The solid content is 0.2%. After stirring for another 5 minutes, seal and let stand at room temperature for later use.
[0049] S2, Microsphere emulsion preparation S21. Preparation of reaction medium Sodium propionate was selected as the carboxylate raw material, and a sodium propionate solution with a concentration of 0.055 mol / L was prepared. The solution was heated and stirred in an oil bath until the system temperature stabilized at 70℃. The cationic surfactant hexadecyltrimethylammonium bromide was slowly added, and the mixture was stirred and homogenized for 1.75 h to form a stable reaction medium.
[0050] S22, Small ball synthesis According to the molar ratio of sodium propionate: hexadecyltrimethylammonium bromide: tetraethyl orthosilicate of 0.055:0.11:1.05, tetraethyl orthosilicate was added dropwise to the mixture, and the mixture was heated and stirred at a constant temperature of 70°C for 20 hours to complete the process. Synthesis of nanospheres.
[0051] S23, Washing and Dispersion Treatment After the reaction is complete, high-speed centrifugation is performed. The precipitate of small spheres was washed four times with anhydrous ethanol and three times with deionized water to obtain an aqueous dispersion. Small-sphere primary emulsion. Add an equal proportion of ethanol and deionized water to the primary emulsion. The solid content of the pellets was adjusted to 3%, a small amount of hexadecyltrimethylammonium bromide was added, and the mixture was dispersed in an ultrasonic disperser for 50 minutes to obtain a stable pellet. Microsphere emulsion is ready for use.
[0052] S3, bottom alkaline Thin film preparation Ultra-white photovoltaic glass substrates that have undergone ultrasonic cleaning and drying are selected and then subjected to alkaline treatment. The sol was used as the coating solution, and the bottom film was prepared by spin coating. The rotation speed was set to 3000 r / min, and the final film thickness was controlled at 125 nm.
[0053] S4, Middle Layer Particle film preparation A wire bar with a gap size of 11 μm was selected and pressed onto the edge of the glass substrate of the underlying thin film, and then droplets were added. The microsphere emulsion is applied to the contact line using a wire-bar coater at a uniform speed of 3 m / min to form a uniform coating. Particle colloidal crystal thin films.
[0054] S5, surface acidity Preparation of fixed layer acidic The sol is used as the coating solution, and an acidic surface layer is prepared on the surface of the intermediate particle film using the spin coating method. A fixed layer is formed by setting the rotation speed to 4000 r / min, resulting in an ultra-thin and suitable acidic layer. Fixed layer.
[0055] The resulting composite film exhibits an average transmittance 3.6% higher than that of the ultra-white photovoltaic glass substrate within a wide spectral range of 380–1100 nm, representing the best performance among the three embodiments. It also demonstrates excellent film adhesion, no particle aggregation, the highest degree of synergistic coupling of the triple optical effects, and a significant improvement in photovoltaic light absorption efficiency.
[0056] Example 3: S1, Sol Preparation S11, acidic Sol preparation Add a measured amount of ethanol to a beaker, then slowly inject tetraethyl orthosilicate and stir until a homogeneous mixture is formed. Add concentrated hydrochloric acid dropwise to adjust the pH of the system to 6.5. Stir on a magnetic stirrer at a constant temperature of 500 rpm and 30°C for 30 minutes to complete the hydrolysis-condensation reaction. After stirring, calibrate the concentration to... In sol The solid content is 0.3%, and it should be sealed and left to stand at room temperature for later use.
[0057] S12, alkaline Sol preparation Used with acid Tetraethyl orthosilicate and ethanol were mixed in the same sol ratio. After thorough mixing, ammonia was added dropwise to adjust the pH of the system to 10.0. The mixture was then stirred at a constant temperature of 30°C and 500 rpm for 30 minutes using a magnetic stirrer. After stirring, the concentration was calibrated. In sol The solid content is 0.3%. After stirring for another 5 minutes, seal and let stand at room temperature for later use.
[0058] S2, Microsphere emulsion preparation S21. Preparation of reaction medium Sodium acetate was selected as the carboxylate raw material, and a sodium acetate solution with a concentration of 0.10 mol / L was prepared. The solution was heated and stirred in an oil bath until the system temperature stabilized at 90℃. The cationic surfactant hexadecyltrimethylammonium bromide was slowly added, and the mixture was stirred and homogenized for 3 hours to form a stable reaction medium.
[0059] S22, Small ball synthesis According to the molar ratio of sodium acetate: hexadecyltrimethylammonium bromide: tetraethyl orthosilicate of 0.10:0.20:2.0, tetraethyl orthosilicate was added dropwise to the mixture, and the mixture was heated and stirred at a constant temperature of 90°C for 24 hours to complete the process. Synthesis of nanospheres.
[0060] S23, Washing and Dispersion Treatment After the reaction is complete, high-speed centrifugation is performed. The precipitate of small spheres was washed five times with anhydrous ethanol and four times with deionized water to obtain an aqueous dispersion. Microsphere primary emulsion. Add an appropriate amount of ethanol to the primary emulsion, and... The solid content of the pellets was adjusted to 5%, a small amount of hexadecyltrimethylammonium bromide was added, and the mixture was dispersed in an ultrasonic disperser for 80 minutes to obtain a stable product. Microsphere emulsion is ready for use.
[0061] S3, bottom alkaline Thin film preparation Ultra-white photovoltaic glass substrates that have undergone ultrasonic cleaning and drying are selected and then subjected to alkaline treatment. The sol is used as the coating solution. The bottom film is prepared by roller coating. The roller pressure and speed are adjusted to match. The film thickness is monitored in real time by a film thickness measuring instrument. Finally, the film thickness is controlled at 200nm.
[0062] S4, Middle Layer Particle film preparation Select a wire bar with a gap size of 20 μm, press it onto the edge of the glass substrate of the underlying thin film, and drop it onto the substrate. The microsphere emulsion is applied to the contact line using a wire-bar coating machine at a uniform speed of 5 m / min to form... Particle colloidal crystal thin films.
[0063] S5, surface acidity Preparation of fixed layer acidic The sol is a coating solution, and the surface acidic coating is prepared using the roller coating method. A fixation layer is formed, creating an ultrathin fixation layer that matches the particle film structure, thereby achieving... The tight encapsulation and fixation of particles.
[0064] The resulting composite film exhibits an average transmittance 3.1% higher than that of the ultra-white photovoltaic glass substrate within a wide spectral range of 380–1100 nm. It also demonstrates high film hardness, strong particle adhesion, and stable coupling of the triple optical effects, thus meeting the practical application requirements of photovoltaic glass.
Claims
1. A high-transmittance glass with synergistic effect of thin-film diffraction and microstructure scattering, characterized in that... It includes an ultra-white photovoltaic glass substrate and an underlying alkaline layer sequentially stacked on the surface of the ultra-white photovoltaic glass substrate. Thin film, intermediate layer Particle film and surface acidity Fixed layer; The underlying alkalinity The film is alkaline It is prepared by sol; The middle layer The particle membrane consists of It is prepared by microsphere emulsion; The surface acidity The fixed layer is acidic It is prepared by sol, and the surface layer is acidic. The fixed layer permeates and fills the middle layer The particle film intersects the particle surface and encapsulates the particle surface.
2. The high-transmittance glass with synergistic effect of thin-film diffraction and microstructure scattering according to claim 1, characterized in that... The alkaline The sol used tetraethyl orthosilicate as a precursor and ethanol as a solvent.
3. The high-transmittance glass with synergistic effect of thin-film diffraction and microstructure scattering according to claim 1, characterized in that... The The raw materials for microsphere emulsions include tetraethyl orthosilicate, carboxylates, and cationic surfactants.
4. The high-transmittance glass with synergistic effect of thin-film diffraction and microstructure scattering according to claim 1, characterized in that... The acidity The sol used tetraethyl orthosilicate as a precursor and ethanol as a solvent.
5. A method for preparing high-transmittance glass through the synergistic effect of thin-film diffraction and microstructure scattering, characterized in that... The method, applied to the preparation of high-transmittance glass with synergistic effect of thin-film diffraction and microstructure scattering as described in any one of claims 1 to 4, further includes the following steps: S1: Sol preparation, separately preparing acidic solutions for forming the surface fixation layer. Sol and alkaline solution used to form the underlying film Sol; S2: Microsphere emulsion preparation: The Stobber method was used to prepare microspheres for forming a mesosphere scattering structure. Microsphere emulsion; S3: Alkaline bottom layer Thin film preparation, using the alkaline solution prepared in S1 Sol is used as a coating solution to prepare an alkaline underlayer on the surface of an ultra-white photovoltaic glass substrate that has been ultrasonically cleaned and dried. film; S4: Middle Layer Particle film preparation, using the material prepared in S2 Using microsphere emulsion as raw material, a wire rod coating method is used to coat the alkaline substrate. Preparation of intermediate layer on thin film surface Particle film, forming a microstructured scattering layer; S5: Surface acidity Preparation of the immobilized layer, using the acidic material prepared in S1 The sol is a coating solution, and a preparation method compatible with S3 is used in the middle layer. Prepare an extremely thin surface layer of acidic material on the particle film surface. Fixed layer, the surface layer is acidic The fixed layer permeates and fills the middle layer The particle film intersects the particle surface and encapsulates the particle surface.
6. The method for preparing high-transmittance glass with synergistic effect of thin-film diffraction and microstructure scattering according to claim 5, characterized in that... In S2, the Stobber method is used to prepare... Microsphere emulsions include the preparation of reaction media, The process involves three steps: microsphere synthesis, washing, and dispersion.
7. The method for preparing high-transmittance glass with synergistic effect of thin-film diffraction and microstructure scattering according to claim 6, characterized in that... The preparation of the reaction medium includes the following steps: selecting sodium acetate or sodium propionate as the carboxylate raw material, and preparing a carboxylate solution with a concentration of 0.01 mol / L to 0.10 mol / L; The carboxylate solution was heated and stirred in a constant temperature oil bath or water bath to stabilize the temperature of the mixture at 50℃~90℃. The cationic surfactant is slowly added during stirring, and the mixture is continuously stirred and homogenized for 0.5 to 3 hours to ensure that the surfactant is completely dissolved and uniformly dispersed in the carboxylate solution, forming a stable reaction medium. The cationic surfactant is hexadecyltrimethylammonium bromide.
8. The method for preparing high-transmittance glass with synergistic effect of thin-film diffraction and microstructure scattering according to claim 7, characterized in that... The The synthesis of the microspheres includes the following steps: Tetraethyl orthosilicate is added dropwise to a stable reaction medium at a molar ratio of carboxylate, cationic surfactant, and tetraethyl orthosilicate of 0.01~0.10:0.02~0.20:0.1~2.
0. Under constant temperature conditions of 50℃~90℃, the mixture is continuously heated and stirred for 16~24 hours to allow tetraethyl orthosilicate to fully hydrolyze and condense to form... Nanospheres.
9. The method for preparing high-transmittance glass with synergistic effect of thin-film diffraction and microstructure scattering according to claim 5, characterized in that... In S4, the middle layer The preparation of the particle film includes the following steps: selecting wire rods with a gap size of 2μm~20μm, and pressing the wire rods steadily onto the substrate that has been coated with an alkaline substrate. At the edge of the glass substrate of the thin film, the wire rod is made to fit tightly against the substrate surface; Prepared by S2 The microsphere emulsion was dropped onto the contact line between the rod and the substrate; The emulsion is uniformly coated along the substrate surface using a wire-bar coating machine at a speed of 1-5 m / min. After the ethanol in the emulsion evaporates... Microspheres spread evenly to form Particle colloidal crystal thin films.
10. The method for preparing high-transmittance glass with synergistic effect of thin-film diffraction and microstructure scattering according to claim 5, characterized in that... In S5, the surface is acidic. The structure of the fixed layer and the middle layer The particle membranes have a consistent structure and an acidic surface. The anchoring layer fills the middle layer through molecular-level permeation. The particle film intersects the particle surface and encapsulates the particle surface.