High-hardness amphiphobic self-cleaning Anti-reflective coating, and preparation method therefor and use thereof

Abstract

A high-hardness amphiphobic self-cleaning anti-reflective coating suitable for a photovoltaic cell. The anti-reflective coating comprises a small-aperture hollow silicon dioxide nanoparticle bottom layer, a large-aperture hollow silicon dioxide nanoparticle top layer, and a low-refractive-index fluoro-silicon multi-block hardening copolymer filled in the particle gaps. By rationally designing and combining the nanoparticle layers and the polymer filler, an anti-reflective coating having a high surface hardness and outstanding amphiphobic self-cleaning performance is obtained. The coating can improve the light transmittance of the glass on the surface of a photovoltaic panel, is hydrophobic and oleophobic, keeps the surface clean, and improves the power generation level; in addition, the coating can also resist external mechanical stress damage, prolong the service life, and reduce a waste of costs caused by manual maintenance and cleaning.

Description

A high-hardness ambiphobic self-cleaning anti-reflection coating and its preparation method and application Technical Field

[0001] The present invention belongs to the technical field of new materials, and in particular relates to a high-hardness ambiphobic self-cleaning anti-reflection coating and a preparation method and application thereof. Background Art

[0002] With the promotion and implementation of my country's "dual carbon" policy, the photovoltaic industry, as a representative of emerging green energy, has seen extensive development in recent years. According to statistics from the National Energy Administration, in the first three quarters of 2023, China added 128.94 million kilowatts of new photovoltaic power generation capacity, a year-on-year increase of 145%. China's total installed photovoltaic power generation capacity also reached 470 million kilowatts, ranking first globally for eight consecutive years. As the primary interface for solar energy intake in power generators, the light transmittance of photovoltaic panels directly affects the unit's power generation efficiency. This drives the development of effective strategies to address the problem of reduced solar energy utilization efficiency caused by low transmittance due to surface contamination and light reflection. On the one hand, the adhesion of contaminants to the photovoltaic panel surface reduces light intake. For example, dust, bird droppings, pollen, and rainwater can cause surface contamination. On the other hand, light is refracted and scattered on the photovoltaic panel surface, reducing the actual light energy absorbed by the photovoltaic module and thus reducing power generation.

[0003] CN202310689178.0 discloses a transmissive hydrophilic coating for photovoltaic panels and a preparation method thereof. The method comprises mixing a silica nanoparticle suspension, a titanium dioxide composite sol, and a non-ionic water-soluble polymer and subjecting them to an aging treatment to prepare a precursor sol. The surface of the photovoltaic panel is treated and a coupling agent is added. The photovoltaic panel is then alternately immersed in a PDDA solution and a precursor solution, and finally rapidly quenched. The prepared coating has super hydrophilicity and a transmittance of up to 99.0%.

[0004] CN202310982606.9 discloses a kind of anti-reflective hydrophilic coating for photovoltaic panels and its preparation method, organic silicate and nano silicon dioxide are added to hydrochloric acid solution for hydrolysis, and after reaction time of 2-5h, magnesium fluoride acidic hydrolyzate is added, and hydrolysis obtains a mixed sol material of nano silicon dioxide and magnesium fluoride. A mixed alcohol solution and nano titanium dioxide sol are added to the mixed sol material to obtain a nano silicon titanium compound complexed magnesium fluoride sol. Finally, the substrate is placed in acetone and deionized water in turn for ultrasonic cleaning, and dried. Finally, the obtained nano silicon titanium compound complexed magnesium fluoride sol is taken, and after coating on the substrate, it is left to dry to obtain a self-cleaning nano coating.

[0005] However, photovoltaic surface coatings reported so far have only achieved one of the following properties: self-cleaning or increased transmittance, and their mechanical durability remains underdeveloped. Therefore, it remains a challenge to prepare a coating that combines amphiphobic surface self-cleaning and anti-reflection properties with excellent resistance to external physical damage.

[0006] Summary of the Invention

[0007] The purpose of this section is to summarize some aspects of the embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the abstract and title of this application to avoid obscuring the purpose of this section, the abstract and the title of the invention, and such simplifications or omissions should not be used to limit the scope of the present invention.

[0008] In view of the above problems and / or the problems existing in the prior art, the present invention is proposed.

[0009] Therefore, the purpose of the present invention is to overcome the deficiencies in the prior art and provide a high-hardness ambiphobic self-cleaning anti-reflection coating.

[0010] In order to solve the above technical problems, the present invention provides the following technical solutions: the high-hardness ambiphobic self-cleaning anti-reflection coating comprises:

[0011] a bottom layer of small-pore hollow silica nanoparticles;

[0012] a top layer of large-pore hollow silica nanoparticles;

[0013] and a low-refractive-index fluorosilicone multi-block hardening copolymer filling the interstices between the particles;

[0014] The particle size of the small-pore hollow silica nanoparticles is 40-45 nm, and the particle size of the large-pore hollow silica nanoparticles is 45-50 nm.

[0015] As a preferred embodiment of the high-hardness amphiphobic self-cleaning anti-reflection coating of the present invention, the formula of the high-hardness amphiphobic self-cleaning anti-reflection coating includes, in terms of mass percentage,

[0016] The bottom layer of the small-pore hollow silica nanoparticles comprises 10-20 wt% hexadecyltrimethylammonium bromide, 5-10 wt% 30 nm particle size 5% monodispersed nano polystyrene sphere-ethanol solvent emulsion, and 10-20 wt% vinyltrimethoxysilane;

[0017] The top layer of the macroporous hollow silica nanoparticles comprises 10-20 wt% of 45 nm particle size, 5% of monodispersed nano polystyrene spheres-ethanol solvent emulsion, and 5-10 wt% of tetraethyl silicate;

[0018] The low-refractive-index fluorosilicone multi-block hardening copolymer comprises 10-20 wt% of perfluorooctyl ethyl acrylate, 1-6 wt% of methacryloyloxypropyltrimethoxysilane, 5-15 wt% of methyl methacrylate, 5-15 wt% of methacryloyloxy-cage polysilsesquioxane, and 0.01-1 wt% of azobisisobutyronitrile.

[0019] Another object of the present invention is to overcome the deficiencies in the prior art and provide a method for preparing a high-hardness ambiphobic self-cleaning anti-reflection and anti-reflection coating.

[0020] [Corrected 16.05.2025 according to Rule 91] To solve the above technical problems, the present invention provides the following technical solution: The preparation method of the high-hardness ambiphobic self-cleaning anti-reflection and anti-reflection coating comprises:

[0021] Hexadecyltrimethylammonium bromide was dissolved in ethanol, the pH was adjusted, and the mixture was stirred evenly. A monodispersed nano-polystyrene sphere emulsion with a particle size of 30 nm was then added and mixed evenly. Vinyltrimethoxysilane was then added dropwise to react to prepare a bottom-layer small-pore hollow silica nanoparticle suspension, designated as suspension A.

[0022] After adjusting the pH with ethanol, a monodisperse nano-polystyrene sphere emulsion with a particle size of 45 nm was added, mixed evenly, and tetraethyl silicate was added in succession to react to prepare a top-layer macroporous hollow silica nanoparticle suspension, which was designated as suspension B.

[0023] Perfluorooctylethyl acrylate, methacryloyloxypropyltrimethoxysilane, methyl methacrylate, and methacryloyloxy-cage polysilsesquioxane were dissolved in tetrahydrofuran, azobisisobutyronitrile was added, and nitrogen was introduced to expel the air. The reaction vessel was sealed and reacted at 25-45°C for 1-3 hours to prepare a low-refractive-index fluorosilicone multi-block hardening copolymer solution, which was designated as solution C.

[0024] Suspension A and suspension B are successively coated onto the surface of a cleaned glass substrate for photovoltaic panels by dip coating and pulling, dried at 70-90°C for 1 hour, and then calcined at 500-600°C for 1-3 hours to pretreat the photovoltaic panel and coat the hollow silica nanoparticle suspension; solution C is applied by spin coating to complete the coating of the low-refractive-index polymer on the photovoltaic panel, and then dried at 70-90°C for 3-5 hours for curing.

[0025] As a preferred solution of the method for preparing the high-hardness ambiphobic self-cleaning anti-reflection coating of the present invention, the pH is adjusted to 10-11 by slowly adding 28%-30% ammonia water.

[0026] As a preferred embodiment of the method for preparing the high-hardness ambiphobic self-cleaning anti-reflection coating of the present invention, wherein: the step of adding tetraethyl silicate in succession includes:

[0027] Tetraethyl silicate was divided into 5 equal parts, and each equal part of tetraethyl silicate was added dropwise to the reaction solution at intervals of 5 min, 10 min, 30 min, 1 h, and 2 h;

[0028] Wherein, the total reaction time of the tetraethyl silicate in the reaction system is 10 hours.

[0029] As a preferred embodiment of the method for preparing the high-hardness ambiphobic self-cleaning anti-reflection and anti-reflection coating of the present invention, the dip coating-pulling process includes:

[0030] The suspension to be coated is placed in a suitable container to ensure that the liquid level can completely cover the vertically placed glass substrate; the dipping-pulling process is completed by a dipping machine. First, the glass substrate is fixed to the fixed fixture of the dipping machine, and the height is manually adjusted until the lower edge of the glass substrate is slightly higher than the surface of the suspension to be coated; then the descent speed is set to 50-650μm / s, the dipping time is 5-30s, and the pulling speed is set to 50-650μm / s.

[0031] As a preferred solution of the method for preparing the high-hardness amphiphobic self-cleaning anti-reflection and anti-reflection coating of the present invention, the mass ratio of the 30nm monodisperse nano-polystyrene sphere emulsion to vinyltrimethoxysilane is 1:1.125-4.5.

[0032] As a preferred solution of the method for preparing the high-hardness amphiphobic self-cleaning anti-reflection and anti-reflection coating of the present invention, the mass ratio of the 45nm monodisperse nano-polystyrene sphere emulsion to tetraethyl silicate is 1-4:2-1.

[0033] As a preferred embodiment of the method for preparing a high-hardness ambiphobic self-cleaning anti-reflection and anti-reflection coating according to the present invention, the mass ratio of the perfluorooctyl ethyl acrylate, methacryloyloxypropyl trimethoxysilane, methyl methacrylate and methacryloyloxy-cage polysilsesquioxane is 2-4:1-3:2-4:1-3; the amount of azobisisobutyronitrile added is 0.2-1 wt% of the total mass of the perfluorooctyl ethyl acrylate, methacryloyloxypropyl trimethoxysilane, methyl methacrylate and methacryloyloxy-cage polysilsesquioxane monomers.

[0034] Another object of the present invention is to overcome the deficiencies in the prior art and provide a high-hardness ambiphobic self-cleaning anti-reflection coating for use on the surface of a photovoltaic cell.

[0035] Beneficial effects of the present invention:

[0036] 1. The high-hardness, dual-repellent, self-cleaning, anti-reflection and anti-reflection coating can reduce the loss of incoming light due to reflection and refraction, increase the amount of light energy that can reach the core components of photovoltaic cells, and thus further improve power generation;

[0037] 2. The high-hardness, dual-repellent, self-cleaning anti-reflection and anti-reflection coating has excellent hydrophobic and oleophobic properties and surface self-cleaning properties, which can keep the surface of the photovoltaic panel clean for a long time, reduce the negative impact of pollutants on the light absorption of the components, and maintain a high level of power generation;

[0038] 3. The high-hardness, dual-repellent, self-cleaning, anti-reflection and anti-reflection coating has high surface hardness and good mechanical durability. The coating can still maintain its inherent performance after being subjected to external stress wear and damage for a certain period of time, thereby improving its service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be derived from these drawings without inventive efforts. Among them:

[0040] FIG1 is a schematic diagram of a high-hardness ambiphobic self-cleaning anti-reflection and anti-reflection coating suitable for photovoltaic cell panels prepared in Example 1 of the present invention.

[0041] Figure 2 shows the particle size distribution curves of two nanoparticles with different hollow pore sizes.

[0042] FIG3 is a comparison curve of the transmittance of the coating-glass prepared in Example 1 of the present invention and the original glass in the visible light region.

[0043] FIG4 is a Vickers hardness measurement of the coating surface obtained in Example 1 of the present invention.

[0044] FIG5 shows the anti-wetting performance of the coating prepared in Example 1 of the present invention.

[0045] FIG6 is a curve showing the change of the water contact angle and sliding angle of the coating surface prepared in Example 1 of the present invention as a function of the wear test.

[0046] FIG7 is a test of the power generation of a photovoltaic panel after coating with the coating prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0047] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.

[0048] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0049] Secondly, the term "one embodiment" or "embodiment" herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in various places throughout this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive of other embodiments.

[0050] Unless otherwise specified, the raw materials used in the present invention are all commercially available.

[0051] The coating prepared in the embodiment of the present invention was tested for performance as follows:

[0052] Vickers Hardness: The coating surface hardness was measured using a FALCON 507 Vickers microhardness tester. Vickers hardness is calculated based on the pressure per unit surface area of ​​the indentation. A diamond regular quadrangular pyramid with a vertex angle of 136° is used to create a square indentation on the test surface of the specimen under a certain pressure. The microscope on the Vickers hardness tester measures the length of the two diagonals of the indentation. The average length of the diagonals is used to determine the Vickers hardness value from the corresponding table. Vickers hardness is typically represented by the symbol HV. The number before HV is the Vickers hardness value, and the number after HV is the load weight during the test.

[0053] Visible light transmittance: The visible light transmittance of the samples (coated glass and pristine glass) was measured using a Shimadzu UV 3600 UV-Visible spectrophotometer. The test sample size was 7.5 cm × 2.5 cm, and a glass slide of the same size was used as a control sample. The transmittance of air was set as the baseline for the test. The test wavelength range was 400 nm to 800 nm.

[0054] Contact Angle: The contact angle of water / oil droplets on the coating surface was measured using a KRüSSDSA25S optical contact angle analysis system. For non-moving contact angle measurements, a motor-controlled syringe was used to apply a water / oil droplet (~5 μL) to the sample surface. When the droplet stabilized, a side view was captured with a camera, and software was used to perform fitting calculations to obtain the static contact angle value of the water / oil droplet on the coating surface.

[0055] Sliding angle: The sliding angle of water droplets / oil droplets on the coating surface was measured using the KRüSSDSA25S optical contact angle analysis system. For sliding angle measurement, a motor-controlled rotatable test platform is used to tilt the sample, and the rotation angle of the platform is displayed in real time on a computer connected to the motor. At the beginning of the test, the initial inclination angle of the platform is maintained at 0°. After a water droplet / oil droplet (~5μL) is added to the coating surface via a syringe, the motor is controlled to rotate the platform. The rotation stops at the moment the droplet begins to roll on the surface, and the rotation angle displayed on the computer is recorded as the rolling angle. Each sample is measured at three different positions to reduce data errors.

[0056] Power generation of the PV panels after coating: Total power generation was cumulatively measured using a WT5000 power analyzer. The photovoltaic power generation performance test used commercial silicon-based PV panels for one month. During the test, the voltage input port was connected in parallel with the PV panel, and the current port was connected in series with the PV panel output port.

[0057] DI: deionized water; EtOH: anhydrous ethanol; THF: tetrahydrofuran; CTAB: cetyltrimethylammonium bromide; TEOS: tetraethyl silicate; PSNS: monodisperse nanopolystyrene sphere emulsion (ethanol solvent, 5%, particle size 30, 45 nm); PFEA: perfluorooctyl ethyl acrylate; KH-570: methacryloxypropyltrimethoxysilane; KH-171: vinyltrimethoxysilane; MMA: methyl methacrylate; M-POSS: methacryloxy-cage polysilsesquioxane; AIBN: azobisisobutyronitrile.

[0058] Example 1

[0059] This embodiment provides a method for preparing a high-hardness ambiphobic self-cleaning anti-reflection and anti-reflection coating, specifically:

[0060] (1) 0.45 g of CTAB was weighed and dissolved in 55 mL of EtOH. 28% to 30% ammonia water was then slowly added to adjust the pH to 10 to 11. The mixture was stirred at 600 rpm for 30 min at room temperature. 0.2 g of a 30 nm monodisperse nanopolystyrene sphere latex was then added to the solution. After stirring for 10 min, 0.45 g of KH-171 was added dropwise. The mixture was stirred for 10 h. The resulting homogeneous suspension was designated as Suspension A.

[0061] (2) 55 mL of EtOH was measured and placed in a round-bottom flask. 28% to 30% ammonia water was then slowly added to adjust the pH to 10 to 11. The mixture was stirred at 600 rpm for 30 min at room temperature. 0.45 g of a monodispersed nano-polystyrene sphere emulsion with a particle size of 45 nm was then weighed and added to the above solution. The mixture was thoroughly mixed and stirred for 10 min to obtain a uniform emulsion. 0.225 g of TEOS was then divided into five equal portions. One portion of TEOS was added dropwise to the above emulsion every 10 min. This was repeated five times for a total of 50 min. Stirring was then continued. After 10 h of reaction, a uniform suspension was obtained, which was designated as Suspension B.

[0062] (3) PFEA, KH-570, MMA, and M-POSS (40 wt%, 10 wt%, 30 wt%, and 20 wt%, respectively) were weighed and dissolved in THF. After stirring at room temperature for 10 min, the initiator AIBN (0.5 wt% of the total monomer mass) was added and nitrogen was introduced to expel the air. The reaction vessel was sealed and reacted at 35°C for 2 h. The resulting polymer solution was recorded as solution C.

[0063] (4) First, the glass substrate used for the photovoltaic panel was rinsed twice with EtOH and DI alternately, and then dried. Then, suspension A was applied to the surface of the glass substrate by dip coating and then dried in an 80°C forced air drying oven for 1 hour. Then, suspension B was applied to the surface of the glass substrate by dip coating and then dried in an 80°C forced air drying oven for 1 hour. PSNS and CTAB were then calcined at 550°C for 2 hours.

[0064] (5) Spin coating the solution C onto the glass substrate prepared in the previous step.

[0065] (6) The glass prepared in the previous step was placed in a blast drying oven and dried at 80°C for 4 hours, thereby obtaining a high-hardness, ambiphobic, self-cleaning, anti-reflection and anti-transmittance coating on the surface of the substrate.

[0066] Figure 1 is a schematic diagram of a high-hardness, ambiphobic, self-cleaning anti-reflection coating suitable for photovoltaic cell panels prepared in Example 1 of the present invention. As shown in the figure, small-aperture hollow nanoparticles with a higher reflectivity serve as the bottom layer, and large-aperture hollow nanoparticles with a lower reflectivity serve as the top layer. An anti-reflection layer with a reflectivity gradient is constructed on the surface of a glass substrate. The pores between the particles are filled with a low-reflectivity fluorinated multi-block copolymer, thereby improving the anti-wetting performance of the coating surface and enhancing the mechanical stability between the particles and the substrate material.

[0067] Figure 2 shows the particle size distribution curves of two types of hollow pore nanoparticles with different diameters. It can be seen that the particle size of small-pore nanoparticles is mainly distributed in the range of 40 to 45 nm, and the particle size of large-pore nanoparticles is mainly distributed in the range of 45 to 50 nm, indicating that the particle size of monodisperse nanopolystyrene spheres will directly affect the hollow inner diameter of hollow nanoparticles, and KH-171 is more likely to form a thicker outer wall than TEOS.

[0068] And after testing, as shown in Figure 3, the high-hardness ambiphobic self-cleaning anti-reflection coating prepared by this invention has an average transmittance of 95.3% in the visible light region, which is about 3% higher than that of the original substrate, indicating that it has the effect of anti-reflection and anti-transmission; the Vickers hardness of the coating surface reaches 414.03 HV0.02 (as shown in Figure 4), indicating that its surface hardness is relatively high; the contact angle of water droplets on the coating surface is 104.7°, and the sliding angle is 13.8°, and the contact angle of oil on the surface is 16.3°, and the sliding angle is 1.12° (as shown in Figure 5), indicating that the coating has excellent repellency to both oil and water; the coating can still maintain the integrity of its performance and structure after Taber wear (as shown in Figure 6); after comparing the phased power generation of the coated-photovoltaic panel and the untreated-photovoltaic panel, it is also confirmed that the coating has an effect of improving the power generation of the photovoltaic module (as shown in Figure 7).

[0069] Example 2

[0070] The difference between this embodiment and Example 1 is that the mass ratio of 30nm monodisperse nano-polystyrene sphere emulsion and KH-171 in the preparation process of the small-pore nanoparticle suspension is adjusted to 1:1.125 (0.4g of monodisperse nano-polystyrene sphere emulsion with a particle size of 30nm and 0.45g of KH-171 are weighed), and the rest of the preparation process is the same as that of Example 1 to obtain a coating.

[0071] Example 3

[0072] The difference between this embodiment and Example 1 is that the mass ratio of 30 nm monodisperse nano-polystyrene sphere emulsion and KH-171 in the preparation process of the small-pore nanoparticle suspension is adjusted to 1:4.5 (0.2 g of monodisperse nano-polystyrene sphere emulsion with a particle size of 30 nm and 0.9 g of KH-171 are weighed). The rest of the preparation process is the same as that of Example 1 to obtain a coating.

[0073] The performance of the materials prepared in the above embodiment was tested, and the comparison results with those in Example 1 are shown in Table 1.

[0074] Table 1

[0075] A slash in the table indicates that the data was not tested.

[0076] The above examples primarily explore the process variables involved in preparing hollow nanoparticles with small pores, primarily in terms of their effect on visible light transmittance. As shown in the table, varying the amounts of monodisperse nanopolystyrene sphere emulsion and KH-171 added affects the pore diameter and wall thickness of the resulting hollow nanoparticles. When only the mass of the monodisperse nano polystyrene sphere emulsion is increased, the hollow pore diameter of the prepared hollow nanoparticles increases. Since the amount and method of addition of KH-171 are not changed, the thickness of the sphere wall does not change much, and the reflection coefficient of the hollow nanoparticles decreases compared with that in Example 1, which will cause the difference in reflection coefficient between the bottom small-pore hollow nanoparticle layer and the glass substrate to increase, resulting in enhanced interface reflection relative to Example 1 and reduced light transmittance; when only the amount of addition of KH-171 is increased, the thickness of the sphere wall of the prepared hollow nanoparticles increases. Since the mass and method of addition of the monodisperse nano polystyrene sphere emulsion are not changed, the inner diameter of the hollow nanoparticles does not change much, and the reflection coefficient of the hollow nanoparticles increases compared with that in Example 1, which will cause the difference in reflection coefficient between the bottom small-pore hollow nanoparticle layer and the top large-pore hollow nanoparticle layer to increase, resulting in enhanced interface reflection relative to Example 1 and reduced light transmittance.

[0077] After testing, the average transmittance of the coatings prepared in Example 2 and Example 3 in the visible light region was approximately 94.7% and 93.6%, respectively. This is considered to be due to the change in the reflectivity gradient caused by the change in the physical properties of the small-pore hollow nanoparticles, but the coating still has the effect of increasing transmittance and reducing reflection.

[0078] According to the results in the above table, in the preparation process of the microporous nanoparticle suspension of the present invention, the best technical effect can be obtained when the mass ratio of 30nm monodisperse nanopolystyrene sphere emulsion to KH-171 is 1:2.25.

[0079] Example 4

[0080] The difference between this embodiment and embodiment 1 is that the mass ratio of 45nm monodisperse nano-polystyrene sphere emulsion to TEOS in the preparation process of the macroporous nanoparticle suspension is adjusted to 1:2 (0.45g of 45nm monodisperse nano-polystyrene sphere emulsion and 0.9g of TEOS are weighed). The rest of the preparation process is the same as that of embodiment 1 to obtain a coating.

[0081] Example 5

[0082] The difference between this embodiment and embodiment 1 is that the mass ratio of 45nm monodisperse nano-polystyrene sphere emulsion to TEOS in the preparation process of the macroporous nanoparticle suspension is adjusted to 4:1 (0.9g of 45nm monodisperse nano-polystyrene sphere emulsion and 0.225g of TEOS are weighed). The rest of the preparation process is the same as that of embodiment 1 to obtain a coating.

[0083] The performance of the materials prepared in the above embodiment was tested, and the comparison results with those in Example 1 are shown in Table 2.

[0084] Table 2

[0085] The above embodiments are mainly the exploration of the condition variables of the preparation process of the top-layer large-aperture hollow nanoparticles, which is mainly reflected in the influence on the transmittance in the visible light region. As can be seen from the above table, the addition amount of 45nm monodisperse nano polystyrene sphere emulsion and TEOS is different, which will affect the hollow pore size and sphere wall thickness of the prepared hollow nanoparticles. In Example 4, when only the mass of TEOS is increased, the hollow pore size of the prepared hollow nanoparticles does not change much, the sphere wall thickness increases, and the reflection coefficient of the large-aperture hollow nanoparticles increases compared to that in Example 1, resulting in an increase in the difference in reflection coefficient between the large-aperture hollow nanoparticle layer on the top layer and the air, causing the interface reflection to be enhanced relative to Example 1 and a decrease in the transmittance of light. Testing showed that the coating prepared in Example 4 had an average transmittance of approximately 93.5% in the visible light region. When only the mass of 45nm monodisperse nanopolystyrene spheres was increased, the hollow pore diameter of the prepared hollow nanoparticles increased, while the sphere wall thickness did not change much. The reflectance coefficient of the large-pore hollow nanoparticles decreased compared to that in Example 1, resulting in an increased difference in reflectance coefficient between the top large-pore hollow nanoparticle layer and the bottom small-pore hollow nanoparticle layer. This resulted in enhanced interfacial reflection relative to Example 1 and reduced light transmittance. Testing showed that the coating prepared in Example 4 had an average transmittance of approximately 94.1% in the visible light region.

[0086] According to the results in the above table, the best technical effect can be obtained when the mass ratio of 45 nm monodisperse nano-polystyrene sphere emulsion to TEOS is 2:1 during the preparation of the microporous nano-particle suspension of the present invention.

[0087] Example 6

[0088] The difference between this embodiment and embodiment 1 is that the mass percentages of PFEA, KH-570, MMA and M-POSS in the preparation process of the fluorinated block copolymer are adjusted to 30wt%, 13wt%, 33wt% and 24wt%, respectively. The rest of the preparation process is the same as that in embodiment 1 to obtain a coating.

[0089] Example 7

[0090] The difference between this embodiment and Example 1 is that the mass percentages of PFEA, KH-570, MMA and M-POSS in the preparation process of the fluorinated block copolymer are adjusted to 40wt%, 10wt%, 40wt% and 10wt%, respectively. The rest of the preparation process is the same as that in Example 1 to obtain a coating.

[0091] The performance of the materials prepared in the above embodiment was tested, and the comparison results with those in Example 1 are shown in Table 3.

[0092] Table 3

[0093] The above embodiment is mainly an exploration of the condition variables of the preparation process of fluorinated multi-block copolymers, which is mainly reflected in the effects on surface hardness and anti-wetting properties. As can be seen from the above table, the different mass percentages of the four components in the fluorinated block copolymer will affect the double-repellent properties and mechanical durability of the coating. In Example 6, the mass proportion of PFEA is reduced. After testing, the coating prepared by Example 6 has a certain degree of decline in hydrophobic and oleophobic properties, such as the contact angle of water on the surface dropped to 98.6°, and the sliding angle was 14.7°; the contact angle of oil on the surface was 15.8°, and the sliding angle was 2.1°. However, the coating still has double-repellent self-cleaning properties.

[0094] The surface hardness of the coating prepared in Example 7 decreased to a certain extent, with a Vickers hardness of about 362.14 HV0.02. However, the coating still had a relatively high surface hardness and could resist damage from external stress to a certain extent.

[0095] In summary, the optimal mass ratio of PFEA, KH-570, MMA and M-POSS is 4:1:3:2.

[0096] Comparative Example 1

[0097] Original glass.

[0098] FIG3 is a comparison curve of the transmittance of the coated glass obtained in Example 1 of the present invention and the original glass in the visible light region. It can be seen that the average transmittance of the original glass in the visible light region is 91.7%, while the average transmittance of Example 1 in the visible light region is 95.3%, indicating that the coating has the effect of increasing transmittance and reducing reflection.

[0099] Comparative Example 2

[0100] The difference between this example and Example 1 is that the dip coating-pulling method in the preparation step (4) of this comparative example is changed to a spray gun spraying method, and the rest of the preparation process is the same as that of Example 1 to obtain a coating.

[0101] The performance of the material obtained in the above comparative example was tested, and the comparison results with those in Example 1 are shown in Table 4.

[0102] Table 4

[0103] Table 4 compares Example 1 with Comparative Examples 1 and 2, primarily focusing on the comparison of the original glass and the exploration of the coating process, primarily focusing on the effects on visible light transmittance and anti-wetting properties. As can be seen from the table above, the coating prepared by our invention exhibits a significant increase in transmittance and anti-reflection compared to the original glass. The coating prepared in Comparative Example 2 is significantly thicker than that in Example 1, while also exhibiting significantly increased surface roughness. This results in a sharp increase in the coating's reflectivity, resulting in a visible light transmittance of only 76.1%.

[0104] The high-surface-hardness, amphiphobic, self-cleaning anti-reflection and anti-reflection coating provided by the present invention comprises a low-refractive-index hollow nanoparticle phase and a low-refractive-index block copolymer phase. By rationally designing and combining the nanoparticle layer with a polymer filler, the resulting anti-reflection and anti-reflection coating exhibits high surface hardness and excellent amphiphobic, self-cleaning properties. The coating improves the light transmittance of photovoltaic panel glass, acts as a hydrophobic and oleophobic barrier, maintains a clean surface, and enhances power generation. It also withstands external mechanical stress damage, extending service life and reducing the cost of manual maintenance and cleaning.

[0105] It should be noted that the above embodiments are only used to illustrate the technical solutions 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 preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. A high-hardness double-hydrophobic and self-cleaning antireflection and antistatic coating, characterized in that: The high-hardness double-hydrophobic self-cleaning antireflection coating comprises a small-aperture hollow silica nanoparticle bottom layer; a large-aperture hollow silica nanoparticle top layer; and a low-refractive-index fluorosilicon multi-block hardening copolymer filled in the particle gaps; wherein, the particle size of the small-aperture hollow silica nanoparticles is 40-45 nm, and the particle size of the large-aperture hollow silica nanoparticles is 45-50 nm.

2. The highly hard double-hydrophobic self-cleaning antireflection and antistatic coating according to claim 1, characterized in that: By mass percentage, the formula of the high-hardness double-hydrophobic self-cleaning antireflection coating comprises the small-aperture hollow silica nanoparticle bottom layer includes 10-20 wt% cetyltrimethylammonium bromide, 5-10 wt% 30-nm particle size 5% monodisperse nanopolystyrene sphere-ethanol solvent emulsion, 10-20 wt% vinyltrimethoxysilane; the large-aperture hollow silica nanoparticle top layer includes 10-20 wt% 45-nm particle size 5% monodisperse nanopolystyrene sphere-ethanol solvent emulsion, 5-10 wt% tetraethyl orthosilicate; the low-refractive-index fluorosilicon multi-block hardening copolymer includes 10-20 wt% perfluorooctylethyl acrylate, 1-6 wt% methacryloxypropyltrimethoxysilane, 5-15 wt% methyl methacrylate, 5-15 wt% methacryloxy-cage polyhedral oligomeric silsesquioxane, 0.01-1 wt% azobisisobutyronitrile.

3. The preparation method of the high-hardness double-hydrophobic and self-cleaning antireflection and antistatic coating according to claim 2, characterized in that: including Cetyltrimethylammonium bromide is dissolved in ethanol, the pH is adjusted and then stirred evenly; then a monodisperse nanopolystyrene sphere emulsion with a particle size of 30 nm is added, mixed evenly, and vinyltrimethoxysilane is added drop by drop for reaction to prepare a bottom-layer small-aperture hollow silica nanoparticle suspension, denoted as suspension A; After the pH is adjusted with ethanol, a monodisperse nanopolystyrene sphere emulsion with a particle size of 45 nm is added, and after mixing evenly, tetraethyl orthosilicate is added successively for reaction to prepare a top-layer large-aperture hollow silica nanoparticle suspension, denoted as suspension B; Perfluorooctylethyl acrylate, methacryloxypropyltrimethoxysilane, methyl methacrylate and methacryloxy-cage polyhedral oligomeric silsesquioxane are dissolved in tetrahydrofuran, azobisisobutyronitrile is added, nitrogen is filled to discharge air, the reaction vessel is sealed and reacted at 25-45 °C for 1-3 h to prepare a low-refractive-index fluorosilicon multi-block hardening copolymer solution, denoted as solution C; Suspension A and suspension B are respectively coated on the surface of the cleaned glass substrate for photovoltaic panels by dip-coating and lifting methods. After drying at 70-90 °C for 1 h, calcination is carried out at 500-600 °C for 1-3 h for the pretreatment of the photovoltaic panel and the coating of the hollow silica nanoparticle suspension; solution C is coated by spin coating. After the coating of the low-refractive-index polymer on the photovoltaic panel is completed, drying is carried out at 70-90 °C for 3-5 h for curing treatment.

4. [Corrected according to Rule 91 on 16.05.2025] The method for preparing a high-hardness double-hydrophobic and self-cleaning antireflection and antistatic coating according to claim 3, characterized in that: The pH adjustment is to adjust the pH to 10-11 by slowly adding 28%-30% ammonia water.

5. [Corrected according to Rule 91 on 16.05.2025] The method for preparing a high-hardness double-hydrophobic and self-cleaning antireflection and antistatic coating according to claim 3, characterized in that: The successive addition of tetraethyl orthosilicate includes Tetraethyl orthosilicate was divided into 5 equal parts, and each equal part of tetraethyl orthosilicate was added dropwise to the reaction solution every 5 min, 10 min, 30 min, 1 h, and 2 h; Among them, the total reaction time of tetraethyl orthosilicate in the reaction system was 10 h.

6. [Corrected according to Rule 91 on 16.05.2025] The method for preparing a high-hardness double-hydrophobic and self-cleaning antireflection and antistatic coating according to claim 3, characterized in that: The dip-coating and pulling includes The suspension to be coated was filled into a suitable container to ensure that the liquid level height could completely submerge the vertically placed glass substrate; the dip-coating and pulling process was completed by a dip-coater. First, the glass substrate was fixed on the fixed fixture of the dip-coater, and the height was manually adjusted so that the lower edge of the glass substrate was slightly higher than the surface of the suspension to be coated; then the descending speed was set to 50 - 650 μm / s, the dip-coating time was 5 - 30 s, and the pulling speed was 50 - 650 μm / s.

7. The preparation method of the high-hardness double-hydrophobic and self-cleaning antireflection and antistatic coating according to claim 2, wherein: The mass ratio of the 30 nm monodisperse polystyrene nanosphere emulsion to vinyltrimethoxysilane was 1∶1.125 - 4.

5.

8. The preparation method of the high-hardness double-hydrophobic and self-cleaning antireflection and antistatic coating according to claim 2, characterized in that: The mass ratio of the 45 nm monodisperse polystyrene nanosphere emulsion to tetraethyl orthosilicate was 1 - 4∶2 - 1.

9. The preparation method of the high-hardness double-hydrophobic and self-cleaning antireflection and antistatic coating according to claim 2, characterized in that: The mass ratio of perfluorooctyl ethyl acrylate, methacryloxypropyltrimethoxysilane, methyl methacrylate, and methacryloxy-cage polyhedral oligomeric silsesquioxane was 2 - 4∶1 - 3∶2 - 4∶1 - 3; the addition amount of azobisisobutyronitrile was 0.2 - 1 wt% of the total mass of perfluorooctyl ethyl acrylate, methacryloxypropyltrimethoxysilane, methyl methacrylate, and methacryloxy-cage polyhedral oligomeric silsesquioxane monomers.

10. Application of the high-hardness double-hydrophobic self-cleaning antireflection and antistatic coating according to claim 1 on the surface of a photovoltaic cell.

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