High-light-transmittance antifouling radiation refrigeration glass, preparation method thereof and application of high-light-transmittance antifouling radiation refrigeration glass in field of ocean photovoltaic equipment

Abstract

The invention relates to high-light-transmittance antifouling radiation refrigeration glass, a preparation method thereof and application of the high-light-transmittance antifouling radiation refrigeration glass in the field of ocean photovoltaic equipment, the high-light-transmittance antifouling radiation refrigeration glass is composed of a transparent glass substrate and a coating covering the transparent glass substrate, and the coating is obtained by arranging nanoparticles with high surface roughness. The nano-particles have a spongy ordered porous structure, and are obtained by coating inorganic nano-particles with transparent resin. The high-light-transmittance antifouling radiation refrigeration glass provided by the invention has good surface hydrophobicity and high light transmittance, also has relatively high atmospheric window emissivity, can effectively repel water drops, avoid pollutant adhesion and improve the power generation efficiency of photovoltaic power generation equipment, and meanwhile, the super-hydrophobic coating also has the characteristics of salt spray corrosion resistance and mechanical wear resistance, so that the glass can be widely applied to the field of photovoltaic power generation equipment. The service life of the ocean photovoltaic power generation equipment is greatly prolonged, and the problem that the power is reduced due to the fact that the light transmission of the cover plate glass in the existing ocean photovoltaic power generation equipment is damaged in salt mist, strong storm waves, high humidity and high temperature environments is solved.

Description

Technical Field

[0001] The present invention belongs to the technical field of glass surface treatment, and particularly relates to a high light transmittance anti-fouling radiative cooling glass, its preparation method and application in the field of marine photovoltaic equipment. Background Art

[0002] With the increase in global greenhouse gas emissions, climate problems have become increasingly serious, and there is an urgent need to accelerate the transformation from conventional energy to sustainable low-carbon energy. As an important sustainable energy source, solar energy plays an important role in the low-carbon transformation of energy. Photovoltaic equipment can achieve high-quality energy conversion from solar heat energy to electrical energy. Compared with traditional terrestrial photovoltaic systems, marine photovoltaics can significantly improve their space utilization rate and enhance power generation efficiency. However, marine photovoltaic equipment faces harsh marine environments, such as high temperature, high humidity, and high salinity. These environmental factors cause problems such as corrosion and ultraviolet radiation to the equipment, seriously affecting the photovoltaic efficiency of marine photovoltaic equipment and shortening the service life of the equipment. In addition, dust accumulation and salt deposition on the equipment surface are inevitable, as well as the attachment of bird droppings and marine organisms, causing blockage and corrosion, further damaging and reducing the equipment performance. The crystalline silicon material used in photovoltaic equipment is also vulnerable to typhoons and waves in the marine environment, resulting in the phenomenon of hidden cracks. At the same time, the ultraviolet intensity is higher at sea, and long-term exposure will cause the aging of photovoltaic module materials.

[0003] Setting a self-cleaning superhydrophobic coating on the cover glass of photovoltaic equipment is regarded as one of the solutions to prevent dust, biological fouling, and salt accumulation, and thus maintain the power generation efficiency of the photovoltaic system. The superhydrophobic coating has a surface with a water contact angle greater than 150° and a sliding angle less than 10°. The superhydrophobic property of the coating surface can be achieved by increasing its surface roughness or reducing the surface energy. However, there is usually a competitive relationship between the superhydrophobicity and high light transmittance of the glass surface. High roughness is likely to cause Mie scattering, resulting in a decrease in the light transmittance of the glass. In addition, high salinity and strong ultraviolet radiation in the marine environment will accelerate the degradation of the coating, reducing its hydrophobicity and light transmittance. Therefore, the coating on the cover glass of marine photovoltaic equipment needs to optimize the surface roughness, balance the light transmittance and self-cleaning function, and use materials resistant to salt spray and high temperature to ensure the long-term effective operation stability of the photovoltaic equipment.

[0004] Most of the transparent cover glasses with superhydrophobic properties in existing research focus on terrestrial photovoltaic self-cleaning applications (such as CN202111535522.8). The bonding layer, polyvinyl alcohol (PVA), has a risk of hydrolysis failure in high-humidity / salt spray environments, and the coating does not integrate radiation cooling functions and long-term anti-ultraviolet structures, resulting in insufficient cooling and weather resistance in marine scenarios. The solution proposed in CN202410548677.2 constructs a hydrophobic layer based on polydimethylsiloxane (PDMS). Although it improves the interfacial bonding force, PDMS has weak anti-ultraviolet aging performance and lacks anti-salt spray components, making it prone to hydrophobicity and light transmittance attenuation when exposed to the marine environment for a long time. CN202210033583.2 prepares a superhydrophobic surface by depositing silicon carbide thin film through hydrofluoric acid corrosion and plasma-enhanced chemical vapor deposition technology. However, the large-scale production cost is high, and the process relies on chemical etching of rigid glass substrates and cannot be compatible with flexible photovoltaic modules. The silicon carbide thin film does not design radiation cooling spectral regulation and anti-mechanical wear strengthening layers. The defects of existing products are that the glass performance cannot meet the usage requirements of marine photovoltaic devices. Therefore, there is an urgent need to research a glass for marine photovoltaic devices with a transparent superhydrophobic radiation cooling coating on its surface, which integrates self-cleaning - cooling - anti-corrosion functions to break through the bottleneck of existing technologies. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide, in view of the deficiencies in the prior art, a high light transmittance anti-fouling radiation cooling glass, its preparation method, and its application in the field of marine photovoltaic devices. The glass surface has a coating composed of orderly arranged nanoparticles, enabling the glass to have superhydrophobic, high light transmittance, and radiation cooling characteristics. Moreover, the coating is resistant to high temperatures and high-salt high-humidity environments, with excellent durability and good application prospects in the field of marine photovoltaic devices.

[0006] The present invention provides a high light transmittance anti-fouling radiation cooling glass, which is composed of a transparent glass substrate and a coating covering thereon. The coating is obtained by arranging nanoparticles with high surface roughness and has a sponge-like orderly porous structure. The nanoparticles are obtained by coating inorganic nanoparticles with a transparent resin.

[0007] According to the above solution, the thickness of the coating is 500nm - 1μm.

[0008] According to the above solution, the transparent resin is obtained by curing one of polydimethylsiloxane (PDMS), polymethyl methacrylate (PMMA), and bisphenol A diglycidyl ether.

[0009] According to the above solution, the particle size of the nanoparticles is 10 - 30nm.

[0010] According to the above scheme, the inorganic nanoparticles are one of SiO2, Al2O3, and TiO2, and the particle size of the inorganic nanoparticles is 12 - 30 nm.

[0011] According to the above scheme, the water contact angle of the surface of the high light transmittance anti-fouling and radiative cooling glass is 160 - 164°, the sliding angle is 2 - 5°, the light transmittance is 85 - 90%, and the average emissivity in the wavelength range of 8 - 13 μm is 95 - 97%.

[0012] The present invention also provides a preparation method of the above high light transmittance anti-fouling and radiative cooling glass, and the specific steps are as follows:

[0013] 1) Modification treatment of inorganic nanoparticles: Ultrasonically disperse the inorganic nanoparticles or the precursor for preparing the inorganic nanoparticles in ethanol, then add an ammonia aqueous solution, add a surface modifier after the second ultrasonic dispersion, ultrasonically disperse again, and finally stir and react to obtain a modified nanoparticle suspension;

[0014] 2) Filter the modified nanoparticle suspension obtained in step 1) by suction filtration, dry the obtained solid to obtain modified nanoparticles, add the high transparency and high emissivity resin into cyclohexane, add a curing agent applicable to the high transparency and high emissivity resin as needed, mix evenly to obtain a suspension, and then add the modified nanoparticles and stir evenly to obtain a superhydrophobic coating;

[0015] 3) Pretreat the transparent glass substrate with a piranha solution (a mixture of concentrated sulfuric acid and 30 wt% hydrogen peroxide in a volume ratio of 7:3), clean it, then spray the superhydrophobic coating obtained in step 2) onto the glass substrate through a spray gun, then perform a curing treatment to obtain a precursor, and then calcine the obtained precursor to obtain the high light transmittance anti-fouling and radiative cooling glass.

[0016] According to the above scheme, the inorganic nanoparticles in step 1) are one of SiO2, Al2O3, and TiO2, and the particle size is 10 - 30 nm. The selected low surface energy nanoparticles have good stability, are difficult to decompose, and there are phonon polarization vibrations corresponding to the atmospheric window, which can improve the radiative cooling effect of the glass. Selecting nanoparticles in this particle size range can reduce their influence on the light transmittance of the glass based on Rayleigh scattering.

[0017] According to the above scheme, the precursor for preparing the inorganic nanoparticles in step 1) is tetraethoxysilane.

[0018] According to the above scheme, the mass ratio of the inorganic nanoparticles to ethanol in step 1) is 0.1 - 0.125:1; the mass ratio of the precursor for preparing the inorganic nanoparticles to ethanol is 0.5 - 0.75:1.

[0019] According to the above scheme, in step 1), the ultrasonic dispersion time is 30 - 60 min each time, and the stirring reaction time is 2 - 3 h.

[0020] According to the above scheme, in step 1), the concentration of the ammonia aqueous solution is 1 - 5 wt%, and the mass - volume ratio of ethanol to the ammonia aqueous solution is 20 - 25 g / mL.

[0021] According to the above scheme, the surface modifier in step 1) is one of 1H,1H,2H,2H - perfluorooctyltriethoxysilane (PTES), methyltrimethoxysilane (MTMS), or trichloro(1H,1H,2H,2H - perfluorooctyl)silane (PFOTS), and the mass ratio of ethanol to the surface modifier is 20 - 25:1. Such surface modifiers can reduce the surface energy of particles and improve hydrophobicity.

[0022] According to the above scheme, in step 2), the drying temperature is 80 - 85 °C, and the drying time is 12 - 15 h.

[0023] According to the above scheme, the high - transparency and high - emissivity resin in step 2) is one of polydimethylsiloxane (PDMS), polymethylmethacrylate (PMMA), and bisphenol A epoxy resin, and the molecular weight of the high - transparency and high - emissivity resin is 50 - 70W. These resins are in a high - transparency state after curing, with a light transmittance as high as 90 - 98% itself, and there are various functional group vibrations corresponding to the atmospheric window in the resin, having excellent radiative cooling effect.

[0024] According to the above scheme, the ratio of the high - transparency and high - emissivity resin to cyclohexane in step 2) is 1:10 - 15.

[0025] According to the above scheme, when the high - transparency and high - emissivity resin in step 2) is polydimethylsiloxane, the curing agent is Sylgard 184 B component, and the mass ratio of polydimethylsiloxane to the curing agent is 10 - 12:1; when the high - transparency and high - emissivity resin is polymethylmethacrylate, no curing agent is added; when the high - transparency and high - emissivity resin is bisphenol A epoxy resin, the curing agent is polyetheramine D - 230, and the mass ratio of bisphenol A epoxy resin to the curing agent is 3 - 5:1.

[0026] According to the above scheme, the concentration of the modified nanoparticles in the super - hydrophobic coating in step 2) is 10 - 12 wt%.

[0027] According to the above scheme, the method for pretreating the transparent glass substrate in step 3) with piranha solution is as follows: Immerse the transparent glass substrate in the piranha solution for 1 - 1.5 h. The piranha solution pretreatment removes organic pollutants, grease, and dust on the glass surface, exposes the active silicon-based surface, roughens the glass surface, and improves the adhesion firmness of the coating. The pretreatment can also activate the glass surface to generate silanol groups, which chemically react with silane compounds in the coating, enhancing the adhesion and stability of the coating.

[0028] According to the above scheme, in step 3), the superhydrophobic coating is sprayed onto the glass substrate through a spray gun. The nozzle pressure is 0.28 - 0.30 MPa, the spraying distance is 10 - 20 cm, and the spraying time is 20 - 30 s.

[0029] According to the above scheme, in step 3), when the highly transparent and high emissivity resin in the superhydrophobic coating is polydimethylsiloxane, the curing temperature is 70 - 90 °C and the curing time is 2 - 4 h; when the highly transparent and high emissivity resin is polymethyl methacrylate, the curing temperature is room temperature (15 - 35 °C) and the curing time is 12 - 36 h; when the highly transparent and high emissivity resin is bisphenol A diglycidyl ether, the curing temperature is 70 - 90 °C and the curing time is 2 - 4 h.

[0030] According to the above scheme, the calcination process conditions in step 3) are as follows: Heat up to 380 - 410 °C at a heating rate of 10 - 15 °C / min, hold for 1 - 2 hours, and then cool to room temperature with the furnace.

[0031] During the calcination process, the resin matrix used in the superhydrophobic coating of the present invention undergoes thermal decomposition, mainly including a multi-stage degradation mechanism of main chain scission and oxidative crosslinking. Taking PDMS as an example, under these temperature conditions, the Si-O-Si main chain undergoes cleavage, releasing volatile cyclic siloxane by-products (such as low molecular weight cyclic siloxanes D3 and D4). At the same time, the methyl side chains are oxidized to CO2 and H2O, forming a brittle silica network structure. The remaining silanol groups (Si-OH) form additional Si-O-Si bonds through condensation reactions, further enhancing the crosslinking density, but sacrificing flexibility at the same time. The thermally stable nanoparticles added to the system, such as silica, alumina, or titanium dioxide, not only improve the thermal stability of the coating but also act as free radical scavengers, delaying the main chain degradation of the PDMS matrix, thereby enhancing the overall performance of the coating. Additionally, during the calcination process, the organic components in the resin and the surface modifier gradually volatilize, forming Si-OH groups, which promote surface diffusion and contact between the nanoparticles, forming sintering necks. As the temperature increases, the particles condense through Si-O-Si bonds, and the network structure gradually densifies, reducing the pores between the particles and lowering the light scattering effect, thereby enhancing the transparency of the coating. In addition, the aggregation and surface modification of the particles make the structure of the coating more stable.

[0032] The present invention also includes a superhydrophobic coating, and its preparation method is as follows:

[0033] 1) Modification treatment of inorganic nanoparticles: Ultrasonically disperse inorganic nanoparticles or the precursors for preparing inorganic nanoparticles in ethanol, then add an ammonia aqueous solution. After the second ultrasonic dispersion, add a surface modifier, and ultrasonically disperse again. Finally, stir and react to obtain a suspension of modified nanoparticles;

[0034] 2) Filter the suspension of modified nanoparticles obtained in step 1) by suction filtration. After drying the obtained solid, modified nanoparticles are obtained. Add a high-transparency and high-emissivity resin to cyclohexane, add a curing agent suitable for the high-transparency and high-emissivity resin as needed, mix evenly to obtain a suspension, and then add the modified nanoparticles and stir evenly to obtain a superhydrophobic coating.

[0035] The present invention also includes the application of the above high light transmittance anti-fouling and radiative cooling glass and superhydrophobic coating in the field of marine photovoltaic equipment.

[0036] The present invention prepares glass with superhydrophobic surface and good light transmittance using inorganic nanoparticles with good stability and low surface energy as raw materials. In order to improve the hydrophobicity of the glass surface, the present invention first modifies the inorganic nanoparticles with a surface modifier to increase their surface roughness. After the inorganic nanoparticles are modified, the hydrophobicity of the obtained glass coating is significantly improved, but at the same time, the light transmittance of the glass decreases. Experiments have found that by performing a post-treatment on the glass coating using a specific calcination process, the inorganic nanoparticles in the coating can be rearranged, and the refractive index is optimized, so that while maintaining the superhydrophobicity of the coating, the light transmittance of the coating is significantly improved.

[0037] The beneficial effects of the present invention are as follows: 1. The water contact angle of the high light transmittance anti-fouling and radiative cooling glass provided by the present invention can reach 164°, the sliding angle is small, and the light transmittance is high. At the same time, it has a high emissivity in the atmospheric window, can effectively repel water droplets, avoid salt mist attachment, thereby maintaining the stable light transmittance of the cover glass, and reducing the surface temperature of the photovoltaic glass through radiative cooling, improving the power generation efficiency of the photovoltaic power generation device. At the same time, the glass coating also has the characteristics of salt mist corrosion resistance, anti-ultraviolet aging and mechanical wear resistance, greatly extending the service life of the marine photovoltaic power generation device, and solving the problems of impaired light transmittance and power decline of the cover glass in the current marine photovoltaic power generation device under the conditions of salt mist, strong wind and waves, high humidity and high temperature; 2. The preparation method provided by the present invention is prepared by spraying method, and the steps are relatively simple, providing a low-cost, effective and practical solution for its large-scale application. Description of the Drawings

[0038] Figure 1 It is the TEM image of the titanium dioxide nanoparticles used in Example 2 of the present invention before and after modification;

[0039] Figure 2 It is the contact angle test image of the surface of the high light transmittance anti-fouling and radiative cooling glass prepared in Example 2 with water;

[0040] Figure 3 It is the sliding angle test image of the surface of the high light transmittance anti-fouling and radiative cooling glass prepared in Example 2 with water;

[0041] Figure 4 It is the light transmittance test image of the glass slide used in Example 2, the glass slide after spraying the superhydrophobic coating and after calcination;

[0042] Figure 5 It is the scanning electron microscope (SEM) image of the surface of the precursor prepared in step 3) of Example 2;

[0043] Figure 6 It is the scanning electron microscope image of the surface of the high light transmittance anti-fouling and radiative cooling glass obtained after calcining the precursor prepared in step 3) of Example 2;

[0044] Figure 7 Emissivity test chart of the high light transmittance anti-fouling radiative cooling glass prepared in Example 2;

[0045] Figure 8 Radiative cooling test chart of the glass slide used in Example 2 and the prepared high light transmittance anti-fouling radiative cooling glass;

[0046] Figure 9 Appearance change comparison chart of the high light transmittance anti-fouling radiative cooling glass prepared in Example 2 after 720h of salt spray corrosion;

[0047] Figure 10 Contact angle and sliding angle change comparison chart during the salt spray test of the high light transmittance anti-fouling radiative cooling glass prepared in Example 2;

[0048] Figure 11 Contact angle and sliding angle change comparison chart during the sandpaper abrasion test of the high light transmittance anti-fouling radiative cooling glass prepared in Example 2;

[0049] Figure 12 Contact angle and sliding angle change comparison chart of the high light transmittance anti-fouling radiative cooling glass prepared in Example 2 during the water flow impact test. Detailed implementation method

[0050] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below using examples in conjunction with the accompanying drawings.

[0051] Example 1

[0052] A high light transmittance anti-fouling radiative cooling glass, and its preparation method is as follows:

[0053] 1) Nano-titanium dioxide modification treatment: Add 2g of titanium dioxide nanoparticles (average particle size 20nm) to 20g of ethanol, ultrasonically disperse for 30min, then add 1mL of ammonia water solution (2wt%), then ultrasonically disperse for 30min, then add 1g of MTMS, ultrasonically disperse again for 30min, and finally stir and react at room temperature for 2h to obtain a modified nano-titanium dioxide suspension;

[0054] 2) Preparation of superhydrophobic coating: Vacuum filter the obtained modified nano-titanium dioxide suspension, and dry the obtained solid at 80°C for 12h to obtain 1.9g of modified titanium dioxide nanoparticles. Add 2g of PMMA (molecular weight 600,000) to 20g of cyclohexane, magnetically stir and mix for 30min to obtain a PMMA suspension, and then add the above-obtained modified titanium dioxide nanoparticles to the PMMA suspension, magnetically stir and mix for 30min to obtain a superhydrophobic coating;

[0055] 3) After cleaning the glass slide (75 mm × 25 mm), soak it in piranha solution at 70 °C for 1 h for etching pretreatment of the glass slide. Subsequently, wash the glass slide repeatedly with ethanol and deionized water, then dry the glass slide. Then, use a spray gun (nozzle diameter is 1.3 mm) to spray the superhydrophobic coating obtained in step 2) onto the glass slide, with a spraying distance of 15 cm, a spraying pressure of 0.29 MPa, a spraying time of 30 s, and a spraying thickness of 500 nm - 1 μm. Then, place the glass slide at room temperature for 24 h for curing to obtain a precursor. Then, place the precursor in a muffle furnace and heat it to 400 °C at a heating rate of 10 °C / min in an air atmosphere and calcine for 1 h, and then cool it to room temperature with the furnace to obtain a high light transmittance anti-fouling radiative cooling glass (coating thickness 500 nm - 1 μm).

[0056] Example 2

[0057] A high light transmittance anti-fouling radiative cooling glass, and its preparation method is as follows:

[0058] 1) Modification treatment of nano-silica: Add 12 g of tetraethoxysilane (TEOS) to 20 g of ethanol, ultrasonically disperse for 30 min, then add 1 mL of ammonia water solution (concentration 2 wt%), then ultrasonically disperse for 30 min, then add 1 g of MTMS, ultrasonically disperse again for 30 min, and finally magnetically stir and react at room temperature for 2 h to obtain a modified nano-silica suspension;

[0059] 2) Preparation of superhydrophobic coating: Perform vacuum filtration on the above-obtained modified nano-titanium dioxide suspension, and dry the obtained solid at 80 °C for 12 h to obtain 1.9 g of modified silica nanoparticles (particle size about 20 nm). Add 2 g of PDMS (molecular weight 60W) and 0.2 g of Sylgard 184 B component to 20 g of cyclohexane, magnetically stir and mix for 30 min to obtain a PDMS suspension, and then add the above-obtained modified silica nanoparticles to the PDMS suspension, magnetically stir and mix for 30 min to obtain a superhydrophobic coating;

[0060] 3) After cleaning the glass slide (75 mm × 25 mm), soak it in piranha solution at 70 °C for 1 h for etching pretreatment of the glass slide. Subsequently, wash the glass slide repeatedly with ethanol and deionized water, then dry the glass slide. Then, use a spray gun (with a nozzle diameter of 1.3 mm) to spray the superhydrophobic coating obtained in step 2) onto the glass slide, with a spraying distance of 15 cm, a spraying pressure of 0.29 MPa, a spraying time of 30 s, and a spraying thickness of 500 nm - 1 μm. Then, place the glass slide in an oven at 80 °C for 2 h for curing to obtain a precursor. Then, place the precursor in a muffle furnace and heat it to 400 °C at a heating rate of 10 °C / min in an air atmosphere and calcine for 1 h, and then cool it to room temperature with the furnace to obtain a high light transmittance anti-fouling radiative cooling glass (coating thickness 500 nm - 1 μm).

[0061] As Figure 1 shown are the TEM images of the titanium dioxide nanoparticles before and after modification used in this example. Figure (i) shows the titanium dioxide nanoparticles, and Figure (ii) shows the modified titanium dioxide nanoparticles obtained in step 2). By comparison, it can be seen that the particle size of the nanoparticles remains basically unchanged after modification, but the contour is clearer.

[0062] Hydrophobic angle and sliding angle test: Use a German Dataphysics OCA 20 contact angle tester to measure the hydrophobic angle of the product prepared in this example using the goniometry method. The test temperature is room temperature, the water droplet volume is 5 μL, and the contact angle and sliding angle are measured continuously twice and the average value is calculated. Figure 2 This is the contact angle test diagram of the surface of the high light transmittance anti-fouling radiative cooling glass prepared in this example with water, and its surface contact angle with water is 163°. Figure 3 This is the sliding angle test diagram of the surface of the high light transmittance anti-fouling radiative cooling glass prepared in this example with water, and its surface sliding angle is 3.4°.

[0063] Light transmittance test: Use a UV-Vis spectrometer with an integrating sphere to measure the UV-VIS-NIR light transmittance of the product prepared in this example at a wavelength of 300 - 2500 nm. Figure 4 This is the light transmittance test diagram of the glass slide used in this example, the glass slide after spraying the superhydrophobic coating, and after calcination. The light transmittance of the glass slide is 91%, the light transmittance after spraying the superhydrophobic coating is 79%, and the light transmittance after calcination is 88.8%.

[0064] Figure 5 This is the scanning electron microscope image of the surface of the precursor prepared in step 3) of this example. It can be seen that the coating is formed by the agglomeration of particles with a particle size of 30 - 45 nm, and the particle size and position distribution are disordered, which may be caused by severe agglomeration between particles.

[0065] Figure 6This is a scanning electron microscope image of the surface of the high-transmittance anti-fouling radiative cooling glass obtained after calcining the precursor prepared in step 3) of this example. Compared with Figure 2 It can be seen that after calcination, the particle size of the coating surface is more uniform, the distribution is more uniform and orderly, a uniform porous sponge structure is formed, and the particle agglomeration phenomenon is weakened after calcination. The possible reason is that high temperature promotes the volatilization and decomposition of part of the organic solvent, which overflows from the pores. At this time, the nanoparticles fill the voids, thus completing rearrangement, and finally the particle distribution is more uniform and orderly.

[0066] Emissivity test: Use an ultraviolet-visible spectrometer with an integrating sphere to measure the UV-VIS-NIR transmittance of the product prepared in this example at wavelengths from 300 to 2500 nm, and use a Fourier transform infrared spectrometer with an integrating sphere to measure the infrared light transmittance and reflectance in the wavelength range of 2.5 - 25 μm to obtain the emissivity (emissivity = 1 - transmittance - reflectance). Use a Fourier transform infrared spectrometer to measure the vibration of the functional groups of the sample at 400 - 4000 cm -1 -1. Figure 7 This is the emissivity test chart of the high-transmittance anti-fouling radiative cooling glass prepared in this example. It can be seen that its average emissivity in the wavelength range of 8 - 13 μm (atmospheric window) is 95.5%.

[0067] Radiative cooling test: Place the glass slide used in this example and the prepared high-transmittance anti-fouling radiative cooling glass above the photovoltaic cell, use a pyranometer to monitor the solar irradiance, and use a thermocouple to measure the temperature change on the back of the photovoltaic cell. Figure 8 This is the radiative cooling effect test chart of the glass slide used in this example and the prepared high-transmittance anti-fouling radiative cooling glass. During the daytime, the temperature on the back of the photovoltaic cell under the high-transmittance anti-fouling radiative cooling glass is significantly lower than that on the back of the photovoltaic cell under the glass slide, with a maximum temperature drop of 7.98 °C.

[0068] Corrosion resistance test: According to ASTM B117, the long-term stability of the surface coating of the high-transmittance anti-fouling radiative cooling glass prepared in this example in neutral salt spray is tested according to the ASTM B117 salt spray test method. Fix the sample at an inclination angle of 70° in the salt spray chamber, where the ambient temperature is 35 °C, the concentration of the sprayed salt solution is 5 wt.%, and the pH value is 6.80. Record the surface morphology and superhydrophobicity of the coating during the salt spray test to evaluate its anti-corrosion ability. Figure 9 This is the comparison chart of the appearance change of the high-transmittance anti-fouling radiative cooling glass prepared in this example after 720 h of salt spray corrosion. It can be observed that there is almost no change in the appearance of the glass after 720 h. Figure 10The comparative chart of the changes in the contact angle and sliding angle of the high light transmittance anti-fouling and radiative cooling glass prepared in this example during the salt spray test. It can be observed that after 720h, the water contact angle on the glass surface hardly changes, and the water sliding angle increases slightly, indicating its excellent salt spray corrosion resistance.

[0069] The abrasion resistance of the high light transmittance anti-fouling and radiative cooling glass prepared in this example was tested by the sandpaper abrasion test: the sample was inverted on 600-mesh sandpaper, and a 200g weight was loaded on the sample. The sandpaper abrasion test was carried out by moving the sample parallel on the sandpaper. The water contact angle and sliding angle after each 20cm movement of the sample were measured. Figure 11 The comparative chart of the changes in the contact angle and sliding angle of the high light transmittance anti-fouling and radiative cooling glass prepared in this example after 200cm of sandpaper abrasion test on the glass surface. It can be seen from the figure that during the test, the changes in the water contact angle and sliding angle on the glass surface are small.

[0070] Water flow impact resistance test: The high light transmittance anti-fouling and radiative cooling glass sample prepared in this example was tilted at 45°, and was impacted by a 300mL water column downward from a height of 50cm above the glass for 200 times. The water contact angle and sliding angle values on the surface were measured every 20 water column impacts. Figure 12 The comparative chart of the changes in the contact angle and sliding angle of the high light transmittance anti-fouling and radiative cooling glass prepared in this example during 200 water flow impact tests. It can be seen that the water flow impact has little effect on the water contact angle and sliding angle on the glass surface.

[0071] Example 3

[0072] A high light transmittance anti-fouling and radiative cooling glass, and its preparation method is as follows:

[0073] 1) Nano-aluminum oxide modification treatment: Add 2g of aluminum oxide nanoparticles (particle size 20nm) to 20g of ethanol, ultrasonically disperse for 30min, then add 1mL of ammonia water solution (concentration 2wt%), then ultrasonically disperse for 30min, then add 1g of MTMS, ultrasonically disperse again for 30min, and then magnetically stir and react at room temperature for 2h to obtain a modified nano-aluminum oxide suspension;

[0074] 2) Preparation of superhydrophobic coating: Vacuum filter the above-mentioned obtained modified nano-aluminum oxide suspension, and dry the obtained solid at 80°C for 12h to obtain 1.9g of modified aluminum oxide nanoparticles (particle size about 20nm). Add 2g of bisphenol A epoxy resin (molecular weight 60W) and 0.67g of polyetheramine D-230 to 20g of cyclohexane, magnetically stir and mix for 30min to obtain an epoxy resin suspension, and then add the above-mentioned obtained modified aluminum oxide nanoparticles to the epoxy resin suspension, magnetically stir and mix for 30min to obtain a superhydrophobic coating;

[0075] 3) After cleaning the glass slide (75 mm × 25 mm), soak it in piranha solution at 70 °C for 1 h for etching pretreatment of the glass slide. Subsequently, wash the glass slide repeatedly with ethanol and deionized water, then dry the glass slide. Then, use a spray gun (nozzle diameter is 1.3 mm) to spray the superhydrophobic coating obtained in step 2) onto the glass slide, with a spraying distance of 15 cm, a spraying pressure of 0.29 MPa, a spraying time of 30 s, and a spraying thickness of 500 nm - 1 μm. Then, place the glass slide at 80 °C for 2 h for curing to obtain a precursor. Then, place the precursor in a muffle furnace and heat it to 400 °C at a heating rate of 10 °C / min in an air atmosphere and calcine for 1 h, and then cool it to room temperature with the furnace to obtain a high light transmittance anti-fouling radiative cooling glass.

Claims

1. A high light transmittance anti-fouling radiative cooling glass, characterized in that, The high light transmittance anti-fouling radiative cooling glass is composed of a transparent glass substrate and a coating covered thereon. The coating is formed by arranging nanoparticles with a high surface roughness and has a sponge-like ordered porous structure. The nanoparticles are obtained by coating inorganic nanoparticles with a transparent resin.

2. The high light transmittance anti-fouling radiative cooling glass according to claim 1, wherein The thickness of the coating is 500 nm - 1 μm, and the transparent resin is obtained by curing one of polydimethylsiloxane, polymethyl methacrylate, and bisphenol A diglycidyl ether.

3. The high light transmittance anti-fouling radiation cooling glass according to claim 1, wherein The inorganic nanoparticles are one of SiO2, Al2O3, and TiO2, and the particle size of the inorganic nanoparticles is 10 - 30 nm.

4. The high light transmittance anti-fouling radiative cooling glass according to claim 1, wherein, The water contact angle of the surface of the high light transmittance anti-fouling radiative cooling glass is 160 - 164°, the sliding angle is 2 - 5°, the light transmittance is 85 - 90%, and the average emissivity in the wavelength range of 8 - 13 μm is 95 - 97%.

5. A method for preparing the high light transmittance anti-fouling radiative cooling glass according to any one of claims 1-4, characterized in that, The specific steps are as follows: 1) Modification treatment of inorganic nanoparticles: Ultrasonically disperse the inorganic nanoparticles or the precursor for preparing the inorganic nanoparticles in ethanol, then add an ammonia water solution. After ultrasonic dispersion for the second time, add a surface modifier and ultrasonic disperse again. Finally, stir and react to obtain a suspension of modified nanoparticles; 2) Filter the suspension of modified nanoparticles obtained in step 1) by suction filtration. After drying the obtained solid, modified nanoparticles are obtained. Add a high-transparency and high-emissivity resin into cyclohexane, add a curing agent suitable for the high-transparency and high-emissivity resin as needed, mix evenly to obtain a suspension, and then add the modified nanoparticles and stir evenly to obtain a superhydrophobic coating; 3) Pretreat the transparent glass substrate with piranha solution, clean it, then spray the superhydrophobic coating obtained in step 2) onto the glass substrate through a spray gun, then perform a curing treatment to obtain a precursor, and then calcine the obtained precursor to obtain the high light transmittance anti-fouling radiative cooling glass.

6. The preparation method of the high light transmittance anti-fouling radiation cooling glass according to claim 5, characterized in that, In step 1), the inorganic nanoparticles are one of SiO2, Al2O3, and TiO2, and the particle size is 10 - 30 nm; in step 1), the mass ratio of the inorganic nanoparticles to ethanol is 0.1 - 0.125:1; the mass ratio of the precursor for preparing the inorganic nanoparticles to ethanol is 0.5 - 0.75:1; the ultrasonic dispersion time in step 1) is 30 - 60 min each time, and the stirring reaction time is 2 - 3 h; the concentration of the ammonia water solution in step 1) is 1 - 5 wt%, and the mass volume ratio of ethanol to the ammonia water solution is 20 - 25 g / mL; in step 1), the surface modifier is one of 1H,1H,2H,2H-perfluorooctyltriethoxysilane, methyltrimethoxysilane, or trichloro(1H,1H,2H,2H-perfluorooctyl)silane, and the mass ratio of ethanol to the surface modifier is 20 - 25:

1.

7. The preparation method of the high light transmittance anti-fouling radiative cooling glass according to claim 5, characterized in that, Step 2) The drying temperature is 80 - 85 °C, and the drying time is 12 - 15 h; in step 2), the high-transparency and high-emissivity resin is one of polydimethylsiloxane, polymethyl methacrylate, and bisphenol A epoxy resin, and the molecular weight of the high-transparency and high-emissivity resin is 500,000 - 700,000; the ratio of the high-transparency and high-emissivity resin to cyclohexane in step 2) is 1:10 - 15; when the high-transparency and high-emissivity resin in step 2) is polydimethylsiloxane, the curing agent is Sylgard 184 B component, and the mass ratio of polydimethylsiloxane to the curing agent is 10 - 12:1; when the high-transparency and high-emissivity resin is polymethyl methacrylate, no curing agent is added; when the high-transparency and high-emissivity resin is bisphenol A epoxy resin, the curing agent is polyetheramine D-230, and the mass ratio of bisphenol A epoxy resin to the curing agent is 3 - 5:1; the concentration of the modified nanoparticles in the superhydrophobic coating in step 2) is 10 - 12 wt%.

8. The preparation method of the high light transmittance anti-fouling and radiation cooling glass according to claim 5, characterized in that, Step 3) The method for pretreating the transparent glass substrate with piranha solution is: immersing the transparent glass substrate in the piranha solution for 1 - 1.5 h; in step 3), spraying the superhydrophobic coating onto the glass substrate with a spray gun, the nozzle pressure is 0.28 - 0.30 MPa, the spraying distance is 10 - 20 cm, and the spraying time is 20 - 30 s; when the high-transparency and high-emissivity resin in the superhydrophobic coating in step 3) is polydimethylsiloxane, the curing treatment temperature is 70 - 90 °C, and the curing time is 2 - 4 h; when the high-transparency and high-emissivity resin is polymethyl methacrylate, the curing treatment temperature is room temperature, and the curing time is 12 - 36 h; when the high-transparency and high-emissivity resin is bisphenol A diglycidyl ether, the curing treatment temperature is 70 - 90 °C, and the curing time is 2 - 4 h; the calcination process conditions in step 3) are: heating to 380 - 410 °C at a heating rate of 10 - 15 °C / min, holding for 1 - 2 hours, and then cooling to room temperature with the furnace.

9. A superhydrophobic coating, characterized in that, The preparation method is as follows: 1) Modification treatment of inorganic nanoparticles: Ultrasonically disperse inorganic nanoparticles or precursors for preparing inorganic nanoparticles in ethanol, then add ammonia water solution, ultrasonically disperse for the second time, add a surface modifier, ultrasonically disperse again, and finally stir and react to obtain a suspension of modified nanoparticles; 2) Filter the suspension of modified nanoparticles obtained in step 1) by suction filtration, dry the obtained solid to obtain modified nanoparticles, add the high-transparency and high-emissivity resin to cyclohexane, add a curing agent suitable for the high-transparency and high-emissivity resin as needed, mix evenly to obtain a suspension, and then add the modified nanoparticles and stir evenly to obtain a superhydrophobic coating.

10. Application of the high light transmittance anti-fouling and radiation cooling glass according to any one of claims 1 - 4 and the superhydrophobic coating according to claim 9 in the field of marine photovoltaic equipment.

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