Antistatic self-cleaning antireflection nano-coating material, and preparation method and application thereof

Abstract

The application relates to an antistatic self-cleaning antireflection nano coating material and a preparation method and application thereof, and belongs to the technical field of photovoltaic module surface coating. The coating material is prepared from modified PEDOT:PSS dispersion solution, photocatalytic material, cosolvent and pH regulator; the volume ratio of the modified PEDOT:PSS dispersion solution, the cosolvent and the pH regulator is 1:20-50:0.001-0.1, and the mass ratio of the modified PEDOT:PSS molecule and the photocatalytic material is 1:0.1-5; the modified PEDOT:PSS dispersion solution is prepared from PEDOT:PSS water dispersion liquid modified by a silanyloxy modifier, and the volume ratio of the PEDOT:PSS water dispersion liquid and the silanyloxy modifier is 1:0.1-10. The antistatic self-cleaning antireflection nano coating material has good adhesion, good antireflection, good antistatic self-cleaning capacity and good weather resistance, and can be applied to photovoltaic module surface coating.

Description

Technical Field

[0001] This invention relates to the field of photovoltaic module surface coating technology, and in particular to an antistatic self-cleaning and antireflective nano-coating material, its preparation method and application. Background Technology

[0002] Currently, the most common problem with photovoltaic (PV) modules is reduced power generation efficiency due to surface dust contamination. This is especially true for many large-scale PV projects located in the vast and remote Northwest region, where the windy and sandy conditions cause severe dust pollution on the PV module surfaces. Existing methods such as manual cleaning, robotic cleaning, and high-pressure water cleaning can quickly damage the light-transmitting coating on the surface of solar PV panels, leading to a rapid decrease in light transmittance. Therefore, applying a dust-proof and self-cleaning coating to the surface of PV panels has become the preferred method for preventing contamination.

[0003] However, existing photovoltaic antifouling coatings suffer from problems such as limited performance, insufficient antistatic ability, and mediocre antireflective effect, failing to meet the stringent requirements of outdoor application scenarios for the dust and dirt resistance of photovoltaic module surfaces.

[0004] In existing technologies, conductive polymers, exemplified by poly(3,4-ethylenedioxythiophene) / poly(styrene sulfonic acid), abbreviated as (PEDOT:PSS), have been successfully commercialized in the field of antistatic applications. For example, Chinese patents CN103627240A, CN108948393A, and CN110484100A primarily focus on high hardness and low sheet resistance, with limited improvement in adhesion, and are not suitable for coatings on photovoltaic module surfaces.

[0005] Therefore, a self-cleaning nano-coating material, its preparation method, and its application are provided, which have excellent anti-reflection and anti-static properties, antistatic properties, photocatalytic self-cleaning properties, good adhesion and mechanical properties, and are suitable for photovoltaic modules. Summary of the Invention

[0006] To address the shortcomings of existing photovoltaic module surface coatings, such as limited functionality and poor adhesion, this invention provides an antistatic, self-cleaning, and antireflective nano-coating material, its preparation method, and its application. By modifying PEDOT:PSS, the organic PEDOT:PSS molecules are uniformly dispersed and grafted onto the surface of the inorganic photovoltaic module substrate. While utilizing the efficient charge transport capability of PEDOT:PSS to impart excellent antistatic properties to the coating, it effectively improves the adhesion of conductive molecules to the substrate surface and the mechanical properties of the coating.

[0007] The present invention provides an antistatic, self-cleaning, and antireflective nano-coating material, the raw material components of which include: modified PEDOT:PSS dispersion solution, photocatalytic material, co-solvent, and pH adjuster; wherein, the volume ratio of modified PEDOT:PSS dispersion solution, co-solvent, and pH adjuster is 1:20-50:0.001-0.1, and the mass ratio of modified PEDOT:PSS molecules to the photocatalytic material is 1:0.1-5; The modified PEDOT:PSS dispersion solution is prepared by modifying the PEDOT:PSS aqueous dispersion with a silane-containing modifier, and the volume ratio of the PEDOT:PSS aqueous dispersion to the silane-containing modifier is 1:0.1-10.

[0008] Furthermore, the solid content of the PEDOT:PSS aqueous dispersion is 0.01-2 wt%.

[0009] Furthermore, the photocatalytic material includes any one of nano-titanium dioxide, carbon nitride, and Mxene.

[0010] Furthermore, the silaneoxy modifier includes any one of dialkoxysilane, trialkoxysilane, and tetraalkoxysilane.

[0011] Furthermore, the co-solvent includes any one of deionized water, ethanol, propylene glycol methyl ether, n-propanol, and n-butanol.

[0012] Furthermore, the pH adjuster includes any one of boric acid, citric acid, lactic acid, phosphoric acid, and oxalic acid.

[0013] This invention also provides a method for preparing the above-mentioned antistatic self-cleaning and antireflective nanocoating material, comprising the following steps: S1. Using PEDOT:PSS aqueous dispersion as the raw material, add silaneoxy-modified material and mix and hydrolyze to obtain modified PEDOT:PSS mixed solution; S2. Add photocatalytic material to the obtained mixed solution, and then hydrolyze the mixture. S3. Add a co-solvent and a pH adjuster to the obtained composite hydrolysate in sequence, and stir the resulting mixed solution for 2-6 hours to obtain an antistatic self-cleaning and anti-reflective nano-coating material.

[0014] Furthermore, in step S3, the stirring temperature is 30-45℃.

[0015] This invention also provides the application of the above-mentioned antistatic self-cleaning and antireflective nano-coating material in the surface coating of photovoltaic modules.

[0016] Furthermore, the coating thickness ranges from 160 to 210 nm.

[0017] Furthermore, the coating application method includes any one of the following: blade coating, sponge coating, solution dip coating, gravity spray coating, or pressure spray coating.

[0018] Compared with the prior art, the present invention has the following beneficial effects: This invention provides an antistatic, self-cleaning, and antireflective nanocoating material. Through modification of PEDOT:PSS, the organic PEDOT:PSS molecules are uniformly dispersed and grafted onto the surface of an inorganic photovoltaic module substrate. While utilizing the efficient charge transport capability of PEDOT:PSS to impart excellent antistatic properties to the coating, it effectively improves the adhesion of conductive molecules to the substrate surface and the mechanical properties of the coating. Furthermore, the introduction of photocatalytic materials promotes the effective removal of organic pollutants from the coating surface. The synergistic effect of these two factors significantly reduces dust accumulation on the photovoltaic module surface, significantly improves the mechanical properties and weather resistance of the antistatic coating, and effectively extends its service life. Simultaneously, the self-cleaning nanocoating obtained by this invention exhibits good antireflective effects. Combined with its superior antistatic and self-cleaning capabilities, it significantly improves the service life and power generation gain of photovoltaic modules in outdoor applications.

[0019] This invention overcomes the shortcomings of traditional photovoltaic functional coatings, such as single performance, easy dust accumulation, and easy wear and tear. It effectively assembles a high-efficiency organic conductive layer with an inorganic photovoltaic module to prepare a multifunctional antistatic self-cleaning coating with high transparency, low sheet resistance, high anti-fouling properties, and strong adhesion. Outdoor construction is simple and easy, and field surveys have shown that it has excellent performance. It can effectively improve the service life and power generation efficiency of photovoltaic modules and reduce maintenance and replacement costs. Attached Figure Description

[0020] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0021] Figure 1 Scanning electron microscope (SEM) images of the coating surface obtained in Example 1 at different magnifications (a, b) and scanning electron microscope (SEM) images of the coating cross-section at different magnifications (c, d). Figure 2 This is a comparison graph of transmittance for Experiment Example 2; Figure 3 This is a comparison graph of the transmittance of Experiment Example 3; Figure 4 A comparison diagram of the water contact angle in Experiment Example 6; Figure 5 This is a comparison graph of the photocatalytic performance of Experiment Example 7. Detailed Implementation

[0022] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following content is merely illustrative and explanatory of the concept of the present invention. Those skilled in the art can make various modifications or additions to the described specific embodiments or use similar methods to replace them, as long as they do not deviate from the inventive concept or exceed the scope defined by the claims, all of which should fall within the protection scope of the present invention.

[0023] Unless otherwise specified, the raw materials and equipment involved in this invention are all commercially available products.

[0024] Example 1: An antistatic, self-cleaning, and antireflective nano-coating material suitable for photovoltaic modules, comprising the following steps: Step 1: Using a PEDOT:PSS aqueous dispersion with a solid content of 1 wt% as the raw material, add a trialkoxysilane and hydrolyze for 2 h. The volume ratio of the two is 1:1 to obtain a modified PEDOT:PSS mixed solution. Step 2: Add carbon nitride material to the obtained mixed solution, wherein the mass ratio of carbon nitride to modified PEDOT:PSS molecules is 1:1, and the two are mixed and hydrolyzed for 2 h; Step 3: Add propylene glycol methyl ether and oxalic acid sequentially to the obtained composite hydrolysate, wherein the volume ratio of the composite hydrolysate, propylene glycol methyl ether and oxalic acid is 1:35:0.01. Stir the resulting mixed solution at 35°C for 4 h to obtain the antistatic self-cleaning and anti-reflective nano-coating material. Step 4: Place the 10 cm × 10 cm photovoltaic glass substrate in ethanol and deionized water for ultrasonic cleaning for 5 min at an ultrasonic power of 300 W, and then dry it; take the antistatic self-cleaning and antireflective nano-coating material obtained in step 3, apply it to the substrate, and let it stand and dry for 9 h to obtain the antistatic self-cleaning nano-coating.

[0025] Example 2: An antistatic, self-cleaning, and antireflective nano-coating material suitable for photovoltaic modules, comprising the following steps: Step 1: Using a PEDOT:PSS aqueous dispersion with a solid content of 0.8 wt% as the raw material, add tetraalkoxysilane and hydrolyze for 1 h. The volume ratio of the two is 1:3 to obtain a modified PEDOT:PSS mixed solution. Step 2: Add nano-titanium dioxide material to the obtained mixed solution, wherein the mass ratio of nano-titanium dioxide to modified PEDOT:PSS molecules is 1:3, and the two are mixed and hydrolyzed for 3 h; Step 3: Add ethanol and oxalic acid sequentially to the obtained composite hydrolysate, wherein the volume ratio of composite hydrolysate, ethanol and oxalic acid is 1:40:0.02. Stir the resulting mixed solution at 30°C for 3 h to obtain the antistatic self-cleaning and anti-reflective nano-coating material. Step 4: Place the 10 cm × 10 cm photovoltaic glass substrate in ethanol and deionized water for ultrasonic cleaning for 10 min at an ultrasonic power of 300 W, and then dry it; take the antistatic self-cleaning and antireflective nano-coating material obtained in step 3, coat it on the substrate, and let it stand and dry for 12 h to obtain the antistatic self-cleaning nano-coating.

[0026] Example 3: An antistatic, self-cleaning, and antireflective nano-coating material suitable for photovoltaic modules, comprising the following steps: Step 1: Using a PEDOT:PSS aqueous dispersion with a solid content of 1.5 wt% as the raw material, add tetraalkoxysilane and hydrolyze for 2 h. The volume ratio of the two is 1:5 to obtain a modified PEDOT:PSS mixed solution. Step 2: Add Mxene material to the obtained mixed solution, wherein the mass ratio of Mxene to modified PEDOT:PSS molecules is 1:2, and the two are mixed and hydrolyzed for 2 h; Step 3: Add deionized water and lactic acid sequentially to the obtained composite hydrolysate, wherein the volume ratio of composite hydrolysate, deionized water and lactic acid is 1:45:0.05. Stir the resulting mixed solution at 40°C for 5 h to obtain the antistatic self-cleaning and anti-reflective nano-coating material. Step 4: Place the 10 cm × 10 cm photovoltaic glass substrate in ethanol and deionized water for ultrasonic cleaning for 10 min at an ultrasonic power of 300 W, and then dry it. Take the antistatic self-cleaning and antireflective nano-coating material obtained in Step 3, coat it on the substrate, and let it stand and dry for 10 h to obtain the antistatic self-cleaning nano-coating.

[0027] Example 4: An antistatic, self-cleaning, and antireflective nano-coating material suitable for photovoltaic modules, comprising the following steps: Step 1: Using a PEDOT:PSS aqueous dispersion with a solid content of 0.01 wt% as the raw material, add a trialkoxysilane and hydrolyze for 2 h. The volume ratio of the two is 1:2 to obtain a modified PEDOT:PSS mixed solution. Step 2: Add nano-titanium dioxide material to the obtained mixed solution, wherein the mass ratio of nano-titanium dioxide to modified PEDOT:PSS molecules is 1:5, and the two are mixed and hydrolyzed for 2 h; Step 3: Add propylene glycol methyl ether and boric acid sequentially to the obtained composite hydrolysate, wherein the volume ratio of the composite hydrolysate, propylene glycol methyl ether and boric acid is 1:30:0.005. Stir the resulting mixed solution at 35°C for 3 h to obtain the antistatic self-cleaning and anti-reflective nano-coating material. Step 4: Place the 10 cm × 10 cm photovoltaic glass substrate in ethanol and deionized water for ultrasonic cleaning for 15 min at an ultrasonic power of 300 W, and then dry it. Take the antistatic self-cleaning and antireflective nano-coating material obtained in Step 3, coat it on the substrate, and let it stand and dry for 8 h to obtain the antistatic self-cleaning nano-coating.

[0028] Control group 1: Take the same 10 cm × 10 cm photovoltaic glass, clean and dry it in the same way as in Example 1, that is, place it in ethanol and deionized water for ultrasonic cleaning and drying, and use it as control group 1.

[0029] Control group 2: Take the same 10 cm × 10 cm photovoltaic glass, clean and dry it in the same way as in Example 1, that is, place it in ethanol and deionized water for ultrasonic cleaning and drying, and then coat it with PEDOT:PSS aqueous dispersion as control group 2.

[0030] Control group 3: Take the same 10 cm × 10 cm photovoltaic glass, clean and dry it in the same way as in Example 1, that is, place it in ethanol and deionized water for ultrasonic cleaning and drying, and then coat it with a common antistatic self-cleaning coating (Haoruijia self-cleaning glass coating, Shenzhen Dexun Technology Co., Ltd.) as control group 3.

[0031] Control group 4: Take the same 10 cm × 10 cm photovoltaic glass, clean and dry it in the same way as in Example 1, that is, place it in ethanol and deionized water for ultrasonic cleaning and drying, and then coat it with a common photovoltaic anti-reflection coating purchased from Guangzhou Biran New Material Technology Co., Ltd. as control group 4.

[0032] Control group 5: Take the same 10 cm × 10 cm photovoltaic glass, clean and dry it in the same way as in Example 1, that is, place it in ethanol and deionized water for ultrasonic cleaning and drying, and then coat it with a nano-coating material that has not been modified by silaneoxymethylene modifier as control group 5.

[0033] Experimental Example 1: The surface resistance of the coating was measured using a 1155TMF multifunctional insulation resistance tester. Surface resistance tests were performed on photovoltaic glass coated with the antistatic self-cleaning antireflective nano-coating prepared in the examples and on photovoltaic glass from the control group under the same conditions. The surface resistance data are recorded and are shown in Table 1.

[0034] Table 1. Coating surface resistance of each example and control group

[0035] As shown in Table 1, the surface resistance of the antistatic self-cleaning and antireflective nano-coatings prepared in Examples 1-3 was significantly improved compared with the blank photovoltaic glass in control group 1. Their antistatic performance was far superior to the commercially available antistatic coatings in control group 3. Furthermore, due to the stable connection established between the modified PEDOT:PSS molecules and the substrate, their antistatic performance was also significantly better than the original PEDOT:PSS coating.

[0036] Experimental Example 2: Using an ultraviolet spectrophotometer with an integrating sphere, the scanning wavelength was set to 400-1100 nm and the scanning interval to 5 nm. The transmittance data curves of the photovoltaic glass coated with the self-cleaning nano-coating prepared in Example 1 and the photovoltaic glasses of control groups 1, 2, and 4 were measured, as shown in the figure. Figure 2 The comparison shows that the transmittance of the photovoltaic glass in Example 1 increased by an average of 3-4% compared to the control group 1, while the transmittance of the control group 4 increased by an average of only 1-2% compared to the control group 1. This proves that the self-cleaning nano-coating prepared in Example 1 can effectively improve the transmittance of photovoltaic glass, and the improvement effect is higher than that of commonly used photovoltaic anti-reflection coatings on the market. At the same time, in the wavelength range of 540 nm-1100 nm, the transmittance of the photovoltaic glass in control group 2 decreased significantly compared to control group 1, proving that the original PEDOT:PSS coating affects the transmittance of photovoltaic glass, while the modified composite self-cleaning nano-coating can effectively improve the transmittance.

[0037] Experimental Example 3: In a xenon lamp weathering test chamber, the blackboard temperature was set to 65℃, the ambient temperature to 40℃, the humidity to 40%, and the irradiance to 100 W / m². 2 After continuous operation for 1.8 h, the sample was moistened with water spray and operated for another 0.2 h as one cycle. After each cycle of 5 times, the sample was removed and aged for 40 h using a UV spectrophotometer with an integrating sphere, with a scanning wavelength of 400-1100 nm and a scanning interval of 5 nm. After each 10 h aging period, the surface resistance of the coating was measured using a 1155TMF multifunctional insulation resistance tester, and the changes in surface resistance were recorded. The results are shown in Table 2. Table 2. Changes in surface resistivity of the coating during aging tests.

[0038] After aging, the transmittance of the coating was measured, and the results are as follows: Figure 3As shown in Table 2, the self-cleaning nano-coating prepared in Example 1 exhibits excellent anti-reflection and anti-aging properties. Under harsh experimental conditions, Example 1 effectively maintained low surface resistance, and its conductivity and anti-aging performance were superior to the coatings in controls 2 and 3. Therefore, the antistatic self-cleaning nano-coating prepared in Example 1, when used as a photovoltaic anti-reflection coating in outdoor applications, can maintain its dust-proof, high anti-reflection, and high hardness capabilities for a long time, helping to improve the lifespan and power generation efficiency of photovoltaic modules.

[0039] Experimental Example 4: According to GB / T 9286-2021, the adhesion of the coating was determined by cross-cut adhesion tester. The results are shown in Table 3. Among them, the antistatic self-cleaning and antireflective coatings described in Examples 1-4 showed excellent adhesion on the glass, which was significantly better than the coating formed on photovoltaic glass by the original PEDOT:PSS described in Control Group 2. This proves that grafting modification of PEDOT:PSS can effectively improve its adhesion on the surface of photovoltaic glass.

[0040] Table 3. Coating adhesion rating evaluation for each example and control group 2

[0041] Experimental Example 5: The hardness of the coating was measured using an electric pencil hardness tester. The measurement showed that the antistatic self-cleaning antireflective coatings described in each embodiment exhibited excellent coating hardness on the glass. The surface hardness of the coatings was measured as shown in Table 4. It can be seen that the hardness of the modified PEDOT:PSS coating is significantly better than that of the original PEDOT:PSS coating, and also higher than that of commonly available antistatic coatings and photovoltaic antireflective coatings.

[0042] Table 4 Surface hardness of each example and control group

[0043] Experimental Example 6: The water contact angle of the photovoltaic glass surface coated with the self-cleaning nano-coating prepared in Example 2 and the water contact angle of the blank photovoltaic glass surface in control group 1 were measured using a contact angle meter. The obtained water contact angles of the photovoltaic glass surfaces are as follows: Figure 4 As shown in (a), the water contact angle of the photovoltaic glass surface coated with the self-cleaning nano-coating prepared in Example 2 is 2-4°, demonstrating its superhydrophilicity; the water contact angle of the photovoltaic glass surface of control group 1 was measured using a contact angle meter, as shown in (a). Figure 4 (b) Its water contact angle is 20-30° and it does not have superhydrophilicity; this comparison proves that, depending on the different needs of outdoor construction, suitable photocatalytic materials can be selectively added to make it have superior superhydrophilicity.

[0044] Experimental Example 7: 30 mL of 0.02 mM methylene blue solution was placed in the experimental reaction tank. Glass coated with the self-cleaning nano-coating prepared in Examples 1-4 was placed in the reaction tank and allowed to adsorb the dye in the dark for 12 h, yielding the following result: Figure 5 (a) shows a glass with adsorbed dye, placed in a xenon lamp weathering test chamber with a black panel temperature of 65°C, a room temperature of 25°C, a humidity of 40%, and an irradiance of 100 W / m². 2 The program runs continuously for 2 hours as one cycle, and is repeated 5 times. After the cycle ends, the result is as follows: Figure 5 (b) shows that the dye on the glass surface has been significantly degraded, which proves that the coating of the embodiment has obvious photocatalytic performance. This can work synergistically with its antistatic performance to achieve effective self-cleaning, dustproof and anti-fouling effect in outdoor environment.

[0045] Finally, 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 it. Any other modifications or equivalent substitutions made by those skilled in the art to the technical solutions of the present invention, as long as they do not depart from the principles and scope of the technical solutions of the present invention, should be covered within the scope of the claims of the present invention.

Claims

1. An antistatic, self-cleaning, and antireflective nano-coating material, characterized in that, Its raw material components include: modified PEDOT:PSS dispersion solution, photocatalytic material, co-solvent, and pH adjuster; wherein, the volume ratio of modified PEDOT:PSS dispersion solution, co-solvent, and pH adjuster is 1:20-50:0.001-0.1, and the mass ratio of modified PEDOT:PSS molecules to the photocatalytic material is 1:0.1-5; The modified PEDOT:PSS dispersion solution is prepared by modifying PEDOT:PSS aqueous dispersion with a silane-containing modifier. Specifically, PEDOT:PSS aqueous dispersion is used as the raw material, and a silane-containing modifier is added and mixed with hydrolysis to obtain a modified PEDOT:PSS mixed solution. The volume ratio of the PEDOT:PSS aqueous dispersion to the silaneoxy-modified material is 1:0.1-10; the silaneoxy-modified agent includes any one of dialkoxysilane, trialkoxysilane, and tetraalkoxysilane; the photocatalytic material includes any one of nano-titanium dioxide, carbon nitride, and Mxene. The solid content of the PEDOT:PSS aqueous dispersion is 0.01-2 wt%; The co-solvent includes any one of deionized water, ethanol, propylene glycol methyl ether, n-propanol, and n-butanol. The pH adjuster includes any one of boric acid, citric acid, lactic acid, phosphoric acid, and oxalic acid.

2. The preparation method of the antistatic self-cleaning and antireflective nano-coating material according to claim 1, characterized in that, Includes the following steps: S1. Using PEDOT:PSS aqueous dispersion as the raw material, add silaneoxy modified material and mix and hydrolyze to obtain modified PEDOT:PSS mixed solution; S2. Add photocatalytic material to the obtained mixed solution, and then hydrolyze the mixture. S3. Add a co-solvent and a pH adjuster to the obtained composite hydrolysate in sequence, and stir the resulting mixed solution for 2-6 h to obtain an antistatic self-cleaning and anti-reflective nano-coating material.

3. The preparation method according to claim 2, characterized in that, In step S3, the stirring temperature is 30-45℃.

4. The application of the antistatic self-cleaning and antireflective nano-coating material as described in claim 1 in the surface coating of photovoltaic modules.

5. The application according to claim 4, characterized in that, The coating thickness ranges from 160 to 210 nm.

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