Graphene quantum dot modified photovoltaic self-cleaning super-infiltration coating system and preparation method thereof

Abstract

The invention discloses a graphene quantum dot modified photovoltaic self-cleaning super-infiltration coating system and a preparation method thereof, nano silicon dioxide is used as a main solid content to form a primer, a porous structure is formed after solvents such as ethanol and water are volatilized and dried, then a finish paint containing a film forming matter is coated on the surface of the nano silicon dioxide porous structure, and the graphene quantum dot modified photovoltaic self-cleaning super-infiltration coating system is obtained. The nano-silica is firmly combined with the nano-silica, so that a coating system shows excellent anti-reflection and anti-static properties and the like. The coating system has the specific advantages that (1) nano silicon dioxide forms a porous structure and then is combined with a film forming matter such as a silane coupling agent, so that the porous structure can be reserved to a certain extent, the refractive index of the coating is reduced, and the coating shows a certain anti-reflection effect; and (2) the graphene oxide quantum dots improve the viscosity of the coating solution to a certain extent, so that the pore ratio of the coating system is improved, and the good anti-reflection performance of the coating is ensured.

Description

Technical Field

[0001] The present invention belongs to the technical field of photovoltaic self-cleaning coatings, and particularly relates to a graphene quantum dot superhydrophilic antistatic self-cleaning coating system and a preparation method thereof. Background Art

[0002] With the improvement of the photoelectric conversion efficiency, photovoltaic power generation, as a renewable energy technology, has developed rapidly in recent years. Especially in the northwestern region of China, there are rich solar energy resources and vast land resources. The photovoltaic power generation technology can not only drive economic development, but also greatly improve the desert control and reduce ecological disasters such as sandstorm erosion under the economic guidance. However, photovoltaic power generation in the northwestern region faces a more serious problem of dust covering, that is, in a sandy environment, particulate matters such as dust are likely to continuously deposit on the solar photovoltaic panel, thereby reducing the light transmittance, reducing the power generation efficiency, and even causing damage to the photovoltaic power generation components. To solve the above problems, people have tried various solutions such as manual dry cleaning, manual water cleaning, engineering vehicle cleaning, cleaning robot cleaning, automatic sprinkler cleaning, and intelligent robotic arm cleaning. However, for large-scale photovoltaic power stations, the above methods all face problems such as large workload, high water resource consumption, and high cost.

[0003] As a new type of functional coating, the transparent self-cleaning coating is applied to the photovoltaic panel. It can not only keep the photovoltaic panel with a high solar irradiance acceptance rate, but also keep the photovoltaic panel clean during the long-term service by reducing the attachment of dust and dirt, and reduce the problem of the reduction of the photoelectric conversion efficiency caused by dust occlusion. However, the current photovoltaic self-cleaning coatings face problems such as immature technology, limited lifespan, and poor light transmittance improvement effect. Therefore, the present invention proposes a preparation method for a photovoltaic self-cleaning coating system. Graphene quantum dots have excellent optical, electrical, and mechanical properties. Adding graphene quantum dots to the photovoltaic self-cleaning coating can improve the antistatic, light transmittance improvement, mechanical, and weather resistance properties of the coating. Summary of the Invention

[0004] The purpose of the present invention is to provide a graphene quantum dot modified photovoltaic self-cleaning superwetting coating system and a preparation method thereof, and an inorganic composite photovoltaic self-cleaning coating system with high light transmittance, high wear resistance, excellent self-cleaning and corrosion resistance is obtained.

[0005] To solve the above technical problems, the following technical solutions are adopted:

[0006] Graphene quantum dot modified photovoltaic self-cleaning superwetting coating system, characterized in that: the system includes a porous nano-silica primer and a graphene oxide quantum dot modified silane topcoat; the mass fraction of the components of the graphene oxide quantum dot modified silane topcoat is: ultraviolet absorber 0.1 - 0.5 parts, ultraviolet stabilizer 0.1 - 0.5 parts, methyl methacrylate 0.5 - 1.5 parts, ethyl methacrylate 0.5 - 1.5 parts, photoinitiator 0.1 - 0.5 parts, dispersant 0.1 - 0.5 parts, graphene oxide quantum dot 0.1 - 0.5 parts, nano-titanium dioxide 0.5 - 1.5 parts, nano-zinc oxide 0.5 - 1 part, nano-tin dioxide 0.5 - 1 part, nano-zirconium dioxide 0.5 - 1 part, silane coupling agent 0.5 - 1.5 parts, water 5 - 10 parts, ethanol 80 - 90 parts.

[0007] The graphene quantum dot modified photovoltaic self-cleaning superwetting coating system according to claim 1, characterized in that: the mass fraction of the components of the porous nano-silica primer is: nano-silica 5 - 15 parts, ethanol 70 - 90 parts, water 5 - 10 parts, tetraethyl orthosilicate 0.5 - 1 part, nano-aluminum trioxide 0.1 - 0.5 part, titanate coupling agent 0.1 - 0.5 part, dispersant 0.1 - 0.5 part.

[0008] After optimization, the dispersant is selected from one or more of polyvinylpyrrolidone, sodium dodecyl sulfate, polyethylene glycol, cetyltrimethylammonium bromide, sodium polyacrylate, polyoxyethylene sorbitan monolaurate, sodium polystyrene sulfonate, ammonium polyacrylate, poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol) triblock copolymer, sodium lignosulfonate;

[0009] After optimization, the ultraviolet stabilizer is selected from one or more of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(2H-benzotriazol-2-yl)-4-methylphenol, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, pentaerythritol tetra(3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 2-hydroxy-4-octyloxybenzophenone, poly(butylene succinate) (tetraethylene glycol ester), 2,2'-thiobis(4-tert-octylphenol)-nickel(II), n-hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, poly(1,2-dihydro-2,2,4-trimethylquinoline), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate;

[0010] After optimization, the ultraviolet light absorber is selected from one or more of 2-hydroxy-4-methoxybenzophenone, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, ethyl 2-cyano-3,3-diphenylacrylate, phenyl salicylate, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, 2,4-dihydroxybenzophenone (BP-1), 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethylhexyloxyphenol, isoamyl p-methoxycinnamate;

[0011] After optimization, the photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-propanone, 2-hydroxy-2-methylpropiophenone, benzophenone (BP), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-isopropylthioxanthone, 4,4'-bis(diethylamino)benzophenone.

[0012] A preparation method of a graphene quantum dot modified photovoltaic self-cleaning superwetting coating system, which is characterized by including the following steps:

[0013] Step 1: Add graphene oxide quantum dots, nano-titanium dioxide, nano-zinc oxide, nano-tin dioxide, nano-zirconium dioxide, dispersant, water and ethanol into a container, and continuously stir at a speed of 300-600 r / min at room temperature for 0.5-1 hour to obtain a suspension solution;

[0014] Step 2: Ultrasonically treat the above coating solution at a power of 200-400 W for 0.5-1 hour to obtain a graphene oxide quantum dot dispersion for use;

[0015] Step 3: Add an ultraviolet light absorber, an ultraviolet light stabilizer, methyl methacrylate, ethyl methacrylate, a photoinitiator, and a silane coupling agent into the above graphene oxide quantum dot dispersion, and continuously stir at a speed of 300-600 r / min at room temperature for 0.5-1 hour to obtain a topcoat paint solution;

[0016] Step 4: Spray the above topcoat paint solution onto the surface of a dry porous nano-silica primer coating, allow the paint solution to level naturally, and ventilate and dry at room temperature for 6-24 hours to obtain a transparent self-cleaning coating.

[0017] After optimization, in the step 1, the carbon-oxygen ratio of the graphene oxide quantum dots is a mixture of 1.5:1 to 3.5:1; the sizes of the nano-titanium dioxide, nano-zinc oxide, nano-tin dioxide, and nano-zirconium dioxide are required to be less than 80 nm.

[0018] After optimization, in the step 3, the silane coupling agent is an organic or inorganic silane coupling agent, such as vinyltriethoxysilane, γ-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, bis-(γ-triethoxysilylpropyl)tetrasulfide, γ-ureidopropyltriethoxysilane.

[0019] After optimization, the porous nano-silica primer is prepared by the following steps:

[0020] (1) Add nano-silica, nano-aluminum oxide, phthalate coupling agent, dispersant, water, and ethanol into a container, and continuously stir at a speed of 300-600 r / min at room temperature for 0.5-1 hour to obtain a suspension solution;

[0021] (2) Then add tetraethyl orthosilicate, and use ammonia water to adjust the pH of the solution to 9-11, and continuously stir at a speed of 300-600 r / min at room temperature for 0.5-2 hours to obtain a primer coating solution;

[0022] (3) Spray the above primer coating solution onto the surface of a clean substrate (the substrate can be glass or other substrates), let the coating solution level off naturally, and dry it in ventilation at room temperature for 1-12 hours.

[0023] After optimization, in the step (1), the nano-silica is one or a combination of several of solid, hollow, or mesoporous nano-silica, and its diameter range is 20-60 nm.

[0024] After optimization, the dispersant is selected from one or several of polyvinylpyrrolidone, sodium dodecyl sulfate, polyethylene glycol, cetyltrimethylammonium bromide, sodium polyacrylate, polyoxyethylene sorbitan monolaurate, sodium polystyrene sulfonate, ammonium polyacrylate, poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol) triblock copolymer, and sodium lignosulfonate.

[0025] After optimization, the ultraviolet light stabilizer is selected from one or more of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(2H-benzotriazol-2-yl)-4-methylphenol, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 2-hydroxy-4-octyloxybenzophenone, polybutylene succinate (tetraethylene glycol ester), 2,2'-thiobis(4-tert-octylphenol)-nickel(II), n-hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, poly(1,2-dihydro-2,2,4-trimethylquinoline), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate;

[0026] After optimization, the ultraviolet light absorber is selected from one or more of 2-hydroxy-4-methoxybenzophenone, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, ethyl 2-cyano-3,3-diphenylacrylate, phenyl salicylate, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, 2,4-dihydroxybenzophenone (BP-1), 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethylhexyloxyphenol, isopentyl p-methoxycinnamate;

[0027] After optimization, the photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-propanone, 2-hydroxy-2-methylpropiophenone, benzophenone (BP), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-isopropylthioxanthone, 4,4'-bis(diethylamino)benzophenone.

[0028] Due to the adoption of the above technical solution, the following beneficial effects are achieved:

[0029] The present invention creatively uses nano-silica as the main solid content to form a primer. After the solvents such as ethanol and water volatilize and dry, a porous structure is formed. Then, a topcoat containing a film-forming substance is coated on the surface of the nano-silica porous structure, forming a firm bond with the nano-silica. Finally, the coating system exhibits excellent light transmittance enhancement, anti-static and other properties. The specific advantages of this coating system are as follows: (1) The nano-silica forms a porous structure and then combines with film-forming substances such as silane coupling agents. To a certain extent, the porous structure can be retained, reducing the refractive index of the coating and making the coating exhibit a certain light transmittance enhancement effect; (2) The graphene oxide quantum dots increase the viscosity of the coating solution to a certain extent, thereby increasing the pore ratio of the coating system, and further ensuring the good light transmittance of the coating; (3) On the other hand, the graphene oxide quantum dots improve the conductivity of the coating system, so that the coating system exhibits anti-static properties; (4) The graphene oxide quantum dots also exhibit ultraviolet light conversion properties, not only improving the weather resistance of the coating, but also improving the light transmittance of the coating; (5) A variety of metal oxides form a synergistic effect with the graphene oxide quantum dots, improving the conductivity and wear resistance of the coating, and also endowing the coating system with photocatalytic properties.

[0030] A graphene oxide quantum dot-modified transparent self-cleaning coating system proposed by the present invention has good light transmittance, solar irradiance light transmittance enhancement, surface self-cleaning property and weather resistance. This coating system includes a silane primer and a graphene oxide quantum dot-modified topcoat, and the thickness of the coating system is about 80 - 150 nm.

[0031] The inventor found through testing that the coating formed by directly adding nano-silica to the coating solution and coating it once hardly has light transmittance enhancement. And as the service time prolongs, dust is likely to accumulate on the coating surface, causing the light transmittance of the coating to continuously decrease, resulting in a continuous decrease in the power generation efficiency of the photovoltaic panel. According to the above steps, a self-cleaning coating system suitable for photovoltaic panels with light transmittance enhancement, anti-static and other properties can be prepared by combining with the graphene oxide quantum dot-modified coating. Brief Description of the Drawings

[0032] The following further illustrates the present invention with reference to the drawings:

[0033] Figure 1 It is a schematic structural diagram of the graphene oxide quantum dot light transmittance enhancement and self-cleaning coating system. Detailed Embodiments

[0034] The present invention aims to provide a graphene quantum dot-modified photovoltaic self-cleaning superhydrophilic coating system and its preparation method, and an inorganic composite photovoltaic self-cleaning coating system with high light transmittance, high wear resistance, excellent self-cleaning and corrosion resistance is obtained.

[0035] The following elaborates on the technical solutions of the present invention in detail with specific embodiments

[0036] Example 1

[0037] The self-cleaning coating formula is as follows:

[0038] Porous nano-silica primer formula: 85 kg of absolute ethanol, 5 kg of water, 10 kg of nano-silica, 0.5 kg of tetraethyl orthosilicate, 0.2 kg of nano-aluminum oxide, 0.2 kg of phthalate coupling agent, 0.2 kg of dispersant polyvinylpyrrolidone.

[0039] Graphene oxide quantum dot modified topcoat formula: 5 kg of water, 85 kg of ethanol, 0.2 kg of UV absorber 2-hydroxy-4-methoxybenzophenone, 0.3 kg of UV stabilizer bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1 kg of methyl methacrylate, 1 kg of ethyl methacrylate, 0.2 kg of photoinitiator 1-hydroxycyclohexyl phenyl ketone, 0.2 kg of polyvinylpyrrolidone, 0.3 kg of graphene oxide quantum dots, 1 kg of nano-titanium dioxide, 0.5 kg of nano-zinc oxide, 0.5 kg of nano-tin dioxide, 0.5 kg of nano-zirconium dioxide, 1 kg of silane coupling agent vinyltriethoxysilane.

[0040] Self-cleaning coating preparation method:

[0041] First, add 85 kg of absolute ethanol and 5 kg of water to a double-layer stirring tank, and then add 10 kg of nano-silica, 0.2 kg of nano-aluminum oxide, 0.2 kg of phthalate coupling agent, and 0.2 kg of polyvinylpyrrolidone to the ethanol solution. Install a shear cutter head on the stirrer, cool the stirring tank by passing water, keep the temperature of the tank wall below 50 °C, and continuously stir the solution at a speed of 360 r / min for 1 hour to obtain a nano-silica dispersion. Add 0.5 kg of tetraethyl orthosilicate and 1 g of 25% concentration ammonia water to the above nano-silica dispersion, and continuously stir at a speed of 300 r / min at room temperature for 1 hour to obtain a primer coating solution. Spray the primer coating solution onto the surface of a clean glass substrate and air dry for more than 1 hour.

[0042] Add 5 kg of water and 85 kg of ethanol into a double-layer stirring tank. Then add 0.3 kg of graphene oxide quantum dots, 1 kg of nano-titanium dioxide, 0.5 kg of nano-zinc oxide, 0.5 kg of nano-tin dioxide, 0.5 kg of nano-zirconium dioxide, and 0.2 kg of dispersant into the above ethanol solution. Stir continuously at a speed of 450 r / min for 0.5 hour at room temperature to obtain a suspension solution. Place the ultrasonic processor in the graphene oxide quantum dot solution and ultrasonically treat it at a power of 300 W for 0.5 hour to obtain a graphene oxide quantum dot dispersion. Add 0.2 kg of 2-hydroxy-4-methoxybenzophenone, 0.3 kg of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1 kg of methyl methacrylate, 1 kg of ethyl methacrylate, 0.2 kg of 1-hydroxycyclohexyl phenyl ketone, and 1 kg of vinyltriethoxysilane into the above graphene oxide dispersion. Stir continuously at a speed of 500 r / min for 1 hour at room temperature to obtain a topcoat paint solution. Spray the topcoat paint solution onto the surface of the above primer and air dry it naturally in a ventilated place for 12 hours to obtain a transparent self-cleaning coating system.

[0043] Example 2

[0044] The self-cleaning coating formulation is as follows:

[0045] Porous nano-silica primer formulation: 80 kg of absolute ethanol, 5 kg of water, 15 kg of nano-silica, 0.5 kg of tetraethyl orthosilicate, 0.2 kg of nano-aluminum oxide, 0.2 kg of phthalate coupling agent, 0.2 kg of dispersant sodium dodecyl sulfate.

[0046] Graphene oxide quantum dot modified topcoat formulation: 5 kg of water, 85 kg of ethanol, 0.2 kg of ultraviolet absorber ethyl-2-cyano-3,3-diphenylacrylate, 0.3 kg of ultraviolet stabilizer bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1 kg of methyl methacrylate, 1 kg of ethyl methacrylate, 0.2 kg of photoinitiator benzophenone, 0.2 kg of dispersant sodium dodecyl sulfate, 0.5 kg of graphene oxide quantum dots, 1 kg of nano-titanium dioxide, 0.5 kg of nano-zinc oxide, 0.5 kg of nano-tin dioxide, 0.5 kg of nano-zirconium dioxide, 0.5 kg of silane coupling agent vinyltriethoxysilane.

[0047] Self-cleaning coating preparation method:

[0048] First, add 80 kg of absolute ethanol and 5 kg of water into a double-layer stirring tank, and then add 15 kg of nano-silica, 0.2 kg of nano-aluminum oxide, 0.2 kg of phthalate coupling agent, and 0.2 kg of dispersant sodium dodecyl sulfate into the ethanol solution. Install a shear cutter head on the stirrer, cool the stirring tank by passing water through it, keep the temperature of the tank wall below 50 °C, and continuously stir the solution at a speed of 360 r / min for 1 hour to obtain a nano-silica dispersion. Add 0.5 kg of tetraethyl orthosilicate and 1 g of 25% ammonia water into the above nano-silica dispersion, and continuously stir at a speed of 300 r / min at room temperature for 1 hour to obtain a primer coating solution. Spray the primer coating solution onto the surface of a clean glass substrate and air dry it for more than 1 hour.

[0049] Add 5 kg of water and 85 kg of ethanol into a double-layer stirring tank, and then add 0.5 kg of graphene oxide quantum dots, 1 kg of nano-titanium dioxide, 0.5 kg of nano-zinc oxide, 0.5 kg of nano-tin dioxide, 0.5 kg of nano-zirconium dioxide, and 0.2 kg of dispersant sodium dodecyl sulfate into the above ethanol solution. Continuously stir at a speed of 450 r / min at room temperature for 0.5 hour to obtain a suspension solution. Place an ultrasonic processor in the graphene oxide quantum dot solution and ultrasonically treat it at a power of 300 W for 0.5 hour to obtain a graphene oxide quantum dot dispersion. Add 0.2 kg of ultraviolet absorber ethyl-2-cyano-3,3-diphenylacrylate, 0.3 kg of ultraviolet stabilizer bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1 kg of methyl methacrylate, 1 kg of ethyl methacrylate, 0.2 kg of photoinitiator benzophenone, and 0.5 kg of silane coupling agent vinyltriethoxysilane into the above graphene oxide dispersion, and continuously stir at a speed of 500 r / min at room temperature for 1 hour to obtain a topcoat coating solution. Spray the topcoat coating solution onto the above primer surface and air dry it in a ventilated place for 12 hours to obtain a transparent self-cleaning coating system.

[0050] Example 3

[0051] The self-cleaning coating formula is as follows:

[0052] Porous nano-silica primer formula: 85 kg of absolute ethanol, 10 kg of nano-silica, 0.5 kg of tetraethyl orthosilicate, 0.2 kg of nano-aluminum oxide, 0.2 kg of phthalate coupling agent, 0.2 kg of dispersant sodium dodecyl sulfate.

[0053] Graphene Oxide Quantum Dot Modified Topcoat Formula: 5 kg of water, 85 kg of ethanol, 0.2 kg of ultraviolet absorber ethyl-2-cyano-3,3-diphenylacrylate, 0.3 kg of ultraviolet stabilizer polybutylene succinate (tetraethylene glycol ester), 1 kg of methyl methacrylate, 1 kg of ethyl methacrylate, 0.2 kg of photoinitiator benzophenone, 0.2 kg of dispersant sodium dodecyl sulfate, 0.3 kg of graphene oxide quantum dots, 1 kg of nano-titanium dioxide, 0.5 kg of nano-zinc oxide, 0.5 kg of nano-tin dioxide, 0.5 kg of nano-zirconium dioxide, 1 kg of silane coupling agent γ-aminopropyltriethoxysilane.

[0054] Preparation Method of Self-Cleaning Coating:

[0055] First, add 85 kg of anhydrous ethanol into a double-layer stirring barrel, and then add 10 kg of nano-silica, 0.2 kg of nano-aluminum oxide, 0.2 kg of phthalate coupling agent, and 0.2 kg of dispersant sodium dodecyl sulfate into the ethanol solution. Install a shear cutter head on the stirrer, cool the stirring barrel by passing water, keep the temperature of the barrel wall below 50 °C, and continuously stir the solution at a speed of 360 r / min for 1 hour to obtain a nano-silica dispersion. Add 0.5 kg of tetraethyl orthosilicate and 1 g of 25% concentration ammonia water into the above nano-silica dispersion, and continuously stir at a speed of 300 r / min at room temperature for 1 hour to obtain a primer coating solution. Spray the primer coating solution onto the surface of a clean glass substrate and air dry it for more than 1 hour.

[0056] Add 5 kg of water and 85 kg of ethanol into a double-layer stirring barrel, and then add 0.3 kg of graphene oxide quantum dots, 1 kg of nano-titanium dioxide, 0.5 kg of nano-zinc oxide, 0.5 kg of nano-tin dioxide, 0.5 kg of nano-zirconium dioxide, and 0.2 kg of dispersant sodium dodecyl sulfate into the above ethanol solution. Continuously stir at a speed of 450 r / min at room temperature for 0.5 hour to obtain a suspension solution. Place the ultrasonic processor in the graphene oxide quantum dot solution and ultrasonically process it at a power of 300 W for 0.5 hour to obtain a graphene oxide quantum dot dispersion. Add 0.2 kg of ultraviolet absorber ethyl-2-cyano-3,3-diphenylacrylate, 0.3 kg of ultraviolet stabilizer polybutylene succinate (tetraethylene glycol ester), 1 kg of methyl methacrylate, 1 kg of ethyl methacrylate, 0.2 kg of photoinitiator benzophenone, and 1 kg of silane coupling agent γ-aminopropyltriethoxysilane into the above graphene oxide dispersion, and continuously stir at a speed of 500 r / min at room temperature for 1 hour to obtain a topcoat coating solution. Spray the topcoat coating solution onto the above primer surface and air dry it in a ventilated place for 12 hours to obtain a transparent self-cleaning coating system.

[0057] Example 4

[0058] The self-cleaning coating formula is as follows:

[0059] Porous nano-silica primer formula: 85 kg of absolute ethanol, 5 kg of water, 10 kg of nano-silica, 1 kg of tetraethyl orthosilicate, 0.5 kg of nano-aluminum oxide, 0.2 kg of phthalate coupling agent, 0.2 kg of dispersant sodium dodecyl sulfate.

[0060] Graphene oxide quantum dot modified topcoat formula: 5 kg of water, 85 kg of ethanol, 0.2 kg of UV absorber 2-hydroxy-4-methoxybenzophenone, 0.3 kg of UV stabilizer 2-hydroxy-4-octoxybenzophenone, 1 kg of methyl methacrylate, 1 kg of ethyl methacrylate, 0.2 kg of photoinitiator 1-hydroxycyclohexyl phenyl ketone, 0.2 kg of dispersant sodium dodecyl sulfate, 0.3 kg of graphene oxide quantum dots, 1 kg of nano-titanium dioxide, 0.5 kg of nano-zinc oxide, 0.5 kg of nano-tin dioxide, 0.5 kg of nano-zirconium dioxide, 1.5 kg of silane coupling agent 3-glycidoxypropyltrimethoxysilane.

[0061] Self-cleaning coating preparation method:

[0062] First, add 85 kg of absolute ethanol and 5 kg of water to a double-layer stirring tank, and then add 10 kg of nano-silica, 0.5 kg of nano-aluminum oxide, 0.2 kg of phthalate coupling agent, and 0.2 kg of dispersant sodium dodecyl sulfate to the ethanol solution. Install a shear cutter head on the stirrer, cool the stirring tank by passing water, keep the temperature of the tank wall below 50 °C, and continuously stir the solution at a speed of 360 r / min for 1 hour to obtain a nano-silica dispersion. Add 1 kg of tetraethyl orthosilicate and 1 g of 25% ammonia water to the above nano-silica dispersion, and continuously stir at a speed of 300 r / min at room temperature for 1 hour to obtain a primer coating solution. Spray the primer coating solution onto the surface of a clean glass substrate and air dry for more than 1 hour.

[0063] Add 5 kg of water and 85 kg of ethanol into a double-layer stirring tank. Then add 0.3 kg of graphene oxide quantum dots, 1 kg of nano-titanium dioxide, 0.5 kg of nano-zinc oxide, 0.5 kg of nano-tin dioxide, 0.5 kg of nano-zirconium dioxide, and 0.2 kg of dispersant sodium dodecyl sulfate into the above ethanol solution. Stir continuously at a speed of 450 r / min at room temperature for 0.5 hours to obtain a suspension solution. Place the ultrasonic processor in the graphene oxide quantum dot solution and ultrasonically process it at a power of 300 W for 0.5 hours to obtain a graphene oxide quantum dot dispersion. Add 0.2 kg of ultraviolet absorber 2-hydroxy-4-methoxybenzophenone, 0.3 kg of ultraviolet stabilizer 2-hydroxy-4-octyloxybenzophenone, 1 kg of methyl methacrylate, 1 kg of ethyl methacrylate, 0.2 kg of photoinitiator 1-hydroxycyclohexyl phenyl ketone, and 1.5 kg of silane coupling agent 3-glycidoxypropyltrimethoxysilane into the above graphene oxide dispersion. Stir continuously at a speed of 500 r / min at room temperature for 1 hour to obtain a topcoat paint solution. Spray the topcoat paint solution onto the surface of the above primer and air dry it naturally in a ventilated place for 12 hours to obtain a transparent self-cleaning coating system.

[0064] The performance of the self-cleaning coatings in Examples 1 to 4 is shown in Table 1 below.

[0065] Table 1 Test results of the performance of the self-cleaning coatings in Examples 1 to 4

[0066]

[0067]

[0068] The above are only specific embodiments of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent replacements, or modifications made based on the present invention to solve substantially the same technical problems and achieve substantially the same technical effects are all covered by the protection scope of the present invention.

Claims

1. Graphene quantum dot modified photovoltaic self-cleaning super-wetting coating system, characterized by: The system comprises a porous nano silicon dioxide primer and a graphene oxide quantum dot modified silane topcoat; the mass fractions of the graphene oxide quantum dot modified silane topcoat components are: 0.1 to 0.5 parts of ultraviolet light absorber, 0.1 to 0.5 parts of ultraviolet light stabilizer, 0.5 to 1.5 parts of methyl methacrylate, 0.5 to 1.5 parts of ethyl methacrylate, 0.1 to 0.5 parts of photoinitiator, 0.1 to 0.5 parts of dispersant, 0.1 to 0.5 parts of graphene oxide quantum dots, 0.5 to 1.5 parts of nano titanium dioxide, 0.5 to 1 parts of nano zinc oxide, 0.5 to 1 parts of nano tin dioxide, 0.5 to 1 parts of nano zirconium dioxide, 0.5 to 1 parts of silane coupling agent, 5 to 10 parts of water and 80 to 90 parts of ethanol.

2. The graphene quantum dot modified photovoltaic self-cleaning super-wetting coating system according to claim 1, characterized in that: The mass fractions of the porous nano-silica primer components are: 5-15 parts of nano-silica, 70-90 parts of ethanol, 5-10 parts of water, 0.5-1 part of ethyl orthosilicate, 0.1-0.5 part of nano-aluminum oxide, 0.1-0.5 part of titanate coupling agent and 0.1-0.5 part of dispersant.

3. A method for preparing a graphene quantum dot modified photovoltaic self-cleaning super-wetting coating system, characterized in that The steps include: Step 1: adding graphene oxide quantum dots, nano titanium dioxide, nano zinc oxide, nano tin dioxide, nano zirconium dioxide, a dispersant, water and ethanol into a container, and continuously stirring at a speed of 300 to 600 r / min for 0.5 to 1 hour at room temperature to obtain a suspension solution; Step 2: ultrasonically treat the coating solution at a power of 200 to 400 W for 0.5 to 1 hour to obtain a graphene oxide quantum dot dispersion for standby use; Step 3: adding an ultraviolet light absorber, an ultraviolet light stabilizer, methyl methacrylate, ethyl methacrylate, a photoinitiator, and a silane coupling agent to the above-mentioned graphene oxide quantum dot dispersion, and continuously stirring at a speed of 300 to 600 r / min for 0.5 to 1 hour at room temperature to obtain a topcoat coating solution; Step 4: Spray the topcoat coating solution onto the dry porous nano-silica primer coating surface, allow the coating solution to level naturally, and ventilate and dry at room temperature for 6 to 24 hours to obtain a transparent self-cleaning coating.

4. The method for preparing the graphene quantum dot modified photovoltaic self-cleaning super-wetting coating system according to claim 3, characterized in that: In the step 1, the graphene oxide quantum dots are a mixture with a carbon-oxygen ratio of 1.5:1 to 3.5:

1.

5. The method for preparing the graphene quantum dot modified photovoltaic self-cleaning super-wetting coating system according to claim 3, characterized in that: In step 1, the size of the nano titanium dioxide, nano zinc oxide, nano tin dioxide, and nano zirconium dioxide is required to be less than 80 nm.

6. The method for preparing the graphene quantum dot modified photovoltaic self-cleaning super-wetting coating system according to claim 3, characterized in that: In the step 3, the silane coupling agent is an organic or inorganic silane coupling agent.

7. The method for preparing the graphene quantum dot modified photovoltaic self-cleaning super-wetting coating system according to claim 3, characterized in that: The porous nano-silica primer is prepared by the following steps: (1) adding nano-silicon dioxide, nano-aluminum oxide, phthalate coupling agent, dispersant, water and ethanol into a container, and stirring at room temperature at a speed of 300 to 600 r / min for 0.5 to 1 hour to obtain a suspension solution; (2) Add ethyl orthosilicate and adjust the solution pH to 9-11 with ammonia water. Stirring continuously at a speed of 300 to 600 r / min for 0.5 to 2 hours to obtain a primer coating solution; (3) Spray the above primer coating solution onto the surface of the substrate, allow the coating solution to flow naturally, and dry it under ventilation at room temperature for 1 to 12 hours.

8. The method for preparing the graphene quantum dot modified photovoltaic self-cleaning super-wetting coating system according to claim 7, characterized in that: In the step (1), the nano-silica is one or a combination of solid, hollow or mesoporous nano-silica, and its diameter ranges from 20 to 60 nm.

9. The method for preparing the graphene quantum dot modified photovoltaic self-cleaning super-wetting coating system according to claim 7, characterized in that: The dispersant is selected from one or more of polyvinyl pyrrolidone, sodium dodecyl sulfate, polyethylene glycol, hexadecyltrimethylammonium bromide, sodium polyacrylate, polyoxyethylene sorbitan monolaurate, sodium polystyrene sulfonate, ammonium polyacrylate, polyethylene glycol-b-polypropylene glycol-b-polyethylene glycol triblock copolymer, and sodium lignin sulfonate.

10. The method for preparing the graphene quantum dot modified photovoltaic self-cleaning super-wetting coating system according to claim 3, characterized in that: The ultraviolet light stabilizer is selected from one or more of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2-(2H-benzotriazole-2-yl)-4-methylphenol, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), pentaerythritol (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 2-hydroxy-4-octyloxybenzophenone, polysuccinic acid (tetraethylene glycol ester), 2,2'-thiobis(4-tert-octylphenol)-nickel(II), 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, poly(1,2-dihydro-2,2,4-trimethylquinoline), and bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate; The ultraviolet light absorber is selected from 2-hydroxy-4-methoxybenzophenone, 2-(2H-benzotriazole-2- One or more of 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2,4-dihydroxybenzophenone (BP-1), 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-ethylhexyloxyphenol, and isoamyl p-methoxycinnamate; The photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2-hydroxy-2-methylpropiophenone, benzophenone (BP), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-isopropylthioxanthone, and 4,4'-bis(diethylamino)benzophenone.

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