A color photovoltaic module based on photonic crystal coating technology and its preparation method

Abstract

The present invention discloses a color photovoltaic module based on a photonic crystal coating technology and a preparation method thereof. The present invention creatively prepares nano-monodisperse spheres with an inorganic structure coating an organic structure, and at the same time adopts an organic-inorganic hybrid primer that is heat-resistant and has a short-chain anchoring entanglement structure. The perfect cooperation of the two structures results in a photonic crystal structure that can withstand high temperatures and strong light for a long time, and at the same time has strong mechanical properties, which is particularly suitable for the use of color photovoltaics in harsh environments. The color photovoltaic module obtained by the present invention has a gorgeous metallic luster texture and can achieve the characteristic of color change with the angle. Compared with traditional color photovoltaic modules, the power generation efficiency of its power generation module is higher, and it can meet the needs of personalized building color photovoltaic integration.

Description

Technical Field

[0001] The invention belongs to the technical field of photovoltaics, and in particular relates to a color photovoltaic component based on photonic crystal coating technology and a preparation method thereof. Background Art

[0002] With the rapid development of my country's photovoltaic technology and industry, the demand for color photovoltaics is also increasing, becoming an important part of building photovoltaic integration. Building photovoltaic integration refers to the use of photovoltaic power generation products as building materials or components, that is, photovoltaic building materials, in buildings.

[0003] Traditional color photovoltaics are mainly prepared through multi-layer composites of colored glass, colored encapsulation glue, colored textured film, etc., and their single color characteristics cannot meet the increasingly personalized architectural design needs. Photonic crystal technology is a technology derived from nature. For example, photonic crystal structures can be observed on the surfaces of opals, peacock feathers, butterfly wings, etc. in nature. This periodic arrangement of nanostructures can achieve the regulation of photon propagation. The three-dimensional photonic crystal structure can better show the optical characteristics of changing color with angles, and the colors are bright and have a unique metallic texture. Therefore, introducing photonic crystal technology into the color photovoltaic industry can greatly expand the color characteristics of color photovoltaic products, so that this technology derived from nature can be redefined and return to nature again. Summary of the invention

[0004] The purpose of the present invention is to provide a color photovoltaic module based on photonic crystal coating technology and a preparation method thereof. The present invention innovatively prepares nano monodisperse spheres with inorganic structures encapsulating organic structures, and at the same time adopts an organic-inorganic hybrid primer that is resistant to high temperatures and has a short-chain anchored entanglement structure. The two structures are perfectly matched to obtain a photonic crystal structure that can withstand high temperatures and strong light for a long time and has strong mechanical properties, which is particularly suitable for color photovoltaic use in harsh environments. The color photovoltaic module obtained by the present invention has a gorgeous metallic luster and texture, and can achieve the characteristic of changing color with angles. Compared with traditional color photovoltaic modules, its power generation components have higher electrical efficiency and can meet the needs of personalized architectural color photovoltaic integration.

[0005] The preparation method of the color photovoltaic module based on the photonic crystal coating technology is as follows: the photonic crystal plate, the encapsulation film, the power generation component, the encapsulation film, and the bottom plate are sequentially stacked and then hot pressed; the photonic crystal plate is sequentially coated with a base coating, a photonic crystal coating, and a photonic crystal protective coating on a colorless and transparent tempered glass panel or a plastic plate. The thickness of the photonic crystal coating is 1-20 μm. The thicker the photonic crystal coating, the brighter the color of the obtained color photovoltaic module, and vice versa.

[0006] The preparation method of the bottom coating is as follows: perform degreasing and dust removal cleaning operations on a colorless and transparent tempered glass panel or plastic plate, then coat the bottom coating liquid, and obtain the bottom coating after drying; the bottom coating liquid contains 2-20 wt% of a silicon hybrid resin with active groups based on aromatic hydrocarbons. The active groups are one or more of alkynyl, vinyl, silicon-chlorine bond, and silicon hydroxyl group. The solvents selected for formulating the bottom coating liquid are one or more of ethyl acetate, tetrahydrofuran, toluene, dichloromethane, n-hexane, n-butyl ether, petroleum ether, and phenyl ether.

[0007] The preparation method of the photonic crystal coating is as follows: coat the photonic crystal coating liquid on the bottom coating, and obtain the photonic crystal coating after drying; the photonic crystal coating liquid contains 10-50 wt% of monodisperse photonic crystal microspheres.

[0008] The solvents in the photonic crystal coating liquid are selected from one or more of water, ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, pentaerythritol, diethylene glycol, triethylene glycol, polyethylene glycol 200, tetrahydrofuran, formamide, and N,N-dimethylformamide.

[0009] The monodisperse photonic crystal microspheres have a core-shell structure with a polymer microsphere as the core and an inorganic material as the shell, and the ratio of the radius of the core to the thickness of the shell is 1:0.5-1. The particle size of the monodisperse photonic crystal microspheres is 150-350 nm, and the monodispersity index PDI is less than 0.05. As the particle size of the monodisperse photonic crystal microspheres gradually increases, the color of the obtained photonic crystal coating gradually redshifts, and vice versa, the color blueshifts.

[0010] The preparation method of the monodisperse photonic crystal microspheres is as follows:

[0011] (1) Add an initiator, a monomer, an emulsifier, and deionized water to a reaction kettle. The mass concentration of the monomer is 2-50%, the addition amount of the initiator is 0.2-5% of the mass of the monomer, and the addition amount of the emulsifier is 0.1-5% of the mass of the monomer; heat up to 75-90 °C, stir and react for 1-2 hours, then dropwise add a silane coupling agent to the reaction kettle, with an addition amount of 1-10% of the mass of the monomer, and the dropping time is 2-4 hours; after the dropping is completed, continue to keep the temperature for reaction for 1-2 hours, cool down, filter to remove impurities, and obtain a polymer microsphere emulsion;

[0012] (2) Dissolve a silane ester in an alcohol solvent to prepare a silane ester solution with a mass content of 20-50%;

[0013] (3) At room temperature, dropwise add the silane ester solution and a catalyst to the polymer microsphere emulsion within 1-3 hours, and the mass ratio of the silane ester to the polymer microspheres is 4-25:1; after the dropping is completed, continue to stir and react for 5-8 hours, filter, and wash to obtain the monodisperse photonic crystal microspheres.

[0014] The initiator is one or more of ammonium persulfate, potassium persulfate, and sodium persulfate.

[0015] The monomer is one or more of methyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, styrene, acrylic acid, acrylonitrile, and vinyl acetate.

[0016] The emulsifier is one or more of ammonium allyloxynonylphenol polyoxyethylene (10) ether sulfate, ammonium allyloxydecyl polyoxyethylene (10) ether sulfate, sodium 2-acrylamido-2-methylpropanesulfonate, sodium allyloxyhydroxypropylsulfonate, and sodium vinylsulfonate.

[0017] The silane coupling agent is one or more of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriisopropoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, and methacryloxypropyltriethoxysilane.

[0018] The catalyst is one or more of ammonia water, triethylamine, and sodium hydroxide; the silicate ester is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, and butyl orthosilicate; the alcohol solvent is one or more of methanol, ethanol, n-propanol, isopropanol, and n-butanol.

[0019] The preparation method of the photonic crystal protective coating is as follows: coat the photonic crystal protective layer coating solution on the photonic crystal coating, and obtain a transparent and firm photonic crystal protective coating after curing; the photonic crystal protective layer coating solution is a 5-40 wt% organic film-forming resin solution, and the solvents used are one or more of water, ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, pentaerythritol, diethylene glycol, triethylene glycol, formamide, N,N-dimethylformamide, acetone, butanone, methyl isobutyl ketone, cyclohexanone, n-pentane, n-hexane, n-octane, ethyl acetate, and butyl acetate.

[0020] The organic film-forming resin is polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl butyral, epoxy resin system, phenolic resin system, polyurethane resin system, polyester resin system, acrylic resin system, epoxy acrylate resin system, or polyurethane acrylate system.

[0021] The coating method is spin coating, slot coating, roll coating, inkjet printing, spraying, or curtain coating.

[0022] The inkjet printing is piezoelectric inkjet printing.

[0023] The spraying is low-pressure and low-flow spraying; the atomization pressure is 5-30 Kpa, and the flow rate is 1-20 mL / min.

[0024] The encapsulation film is a polyvinyl butyral (PVB), ethylene-vinyl acetate copolymer (EVA), or polyolefin elastomer (POE) film.

[0025] The power generation component is a monocrystalline silicon or polycrystalline silicon solar component.

[0026] The bottom plate is tempered glass or an organic composite film, and the organic composite film is a polyvinyl fluoride composite film (TPT), thermoplastic elastomer (TPE) film, fluoropolymer composite film (BBF), polyamide composite film (APE), or ethylene-vinyl acetate (EVA) film.

[0027] The present invention has the following beneficial effects:

[0028] (1) The main structure of the bottom coating of the present invention is an aromatic cross-linked structure. After curing, it is heat-resistant and solvent-resistant (can withstand high temperatures above 300 °C). At the same time, the resin adopts an addition curing method with small shrinkage and good mechanical properties. There are also a large number of groups that can be well bridged, ensuring a good mechanical property basis for the photonic crystal structure on the bottom coating.

[0029] (2) The photonic crystal coating of the present invention is a three-dimensional photonic crystal structure. The present invention introduces this "physical" structural color of the photonic crystal into the photovoltaic structural component, making the originally monotonous-colored photovoltaic component have rich and diverse colors. Different from the chemical color principle of "selective absorption", the photonic crystal structure is based on the principle of "selective reflection", that is, the corresponding color is reflected through the photonic bandgap effect. Therefore, most natural light can be absorbed by the photovoltaic device. As a result, for visually identical-colored colored photovoltaic components, the photovoltaic components using photonic crystal color production will have a higher photoelectric conversion efficiency than the photovoltaic components with traditional chemical colors. The color generation mechanism of chemical color lies in the chromogenic groups or structures of different chemical substances, which are easily bleached by light and fade under light. While the photonic crystal is a physical structural color, as long as the structure is not damaged, its color presentation will be stable and will not fade.

[0030] (3) The photonic crystal coating solution of the present invention has monodispersity, and the particle size distribution D 100 is less than 500 nm, meeting the strict requirements for particle size in printing methods such as inkjet printing and spraying. The material utilization rates of both inkjet printing and spraying methods for raw materials can reach more than 80%. For special photonic crystal raw materials, high material utilization efficiency is the key concern in its industrialization.

[0031] (4)Coating the photonic crystal protective coating is to quantitatively deposit an organic film-forming resin on the surface of the three-dimensional photonic crystal coating. Through the dissolution of the film-forming resin by the solvent in the coating solution of the photonic crystal protective coating, after the film-forming resin protective solution is quantitatively processed and coated on the surface of the three-dimensional photonic crystal coating, the coating solution of the photonic crystal protective coating can fill the three-dimensional photonic crystal structure through the microsphere gaps in the face-centered cubic structure of the photonic crystal. During the filling process, the coating solution of the photonic crystal protective coating discharges air. As the solvent in the coating solution volatilizes, a uniform and dense colored transparent film is gradually formed, realizing the bonding and protection of the nanospheres in the three-dimensional photonic crystal structure. Description of the Drawings

[0032] Figure 1 It is an SEM photograph of the cross-section of a photonic crystal glass sample.

[0033] Figure 2 It is the reflection spectrum diagram of a red photonic crystal glass sample made of 300-nm photonic crystal microspheres. The curves from right to left correspond to the reflection spectrum curves at test angles of 180°, 170°, 160°, 150°, 140°, 130°, and 120° respectively.

[0034] Figure 3 It is the light transmittance curve diagram of a green photonic crystal glass plate. Four test points were randomly selected during the test.

[0035] Figure 4 It is a digital photo of a photonic crystal color photovoltaic module sample obtained by hot pressing a green photonic crystal tempered glass plate, an EVA film, a monocrystalline silicon photovoltaic module, an EVA film, and a TPT black bottom plate.

[0036] Figure 5 It is a digital photo of a color photovoltaic module sample with the color effects of red, green, and blue. From left to right, they are photonic crystal glass plates made using red, green, and blue photonic crystal microspheres, and then the three-color photonic crystal color photovoltaic module samples obtained by hot pressing the photonic crystal glass plates, EVA films, monocrystalline silicon photovoltaic modules, EVA films, and TPT black bottom plates. Detailed Description of the Invention

[0037] Example 1

[0038] Bottom coating resin: A 100 mL three-necked flask equipped with electromagnetic stirring, reflux condenser, joint with piston, nitrogen balloon and septum. Evacuate and fill with nitrogen three times to remove oxygen. Add triethynylphenylbenzene (0.945 g, 2.5 mmol), 15 mL of dried tetrahydrofuran, cool to -30 °C, and slowly add n-butyllithium (5 mmol, 2.5 mol / L n-hexane solution). The solution gradually turns green and turbid as n-butyllithium is added. The mixture is stirred for another 3 hours, then diethoxydichlorosilane (0.47 g, 2.5 mmol, Hubei Chengfeng Chemical Co., Ltd.) is slowly added dropwise. After addition, it gradually becomes a yellow transparent solution. The reaction is heated to room temperature and continued for 12 hours. After the reaction, it is extracted with a toluene-water system, and after liquid separation, the toluene layer is dried with anhydrous magnesium sulfate and dried under vacuum at 60 °C to obtain 1.2 g of yellow solid (yield 84%). Labeled as bottom coating resin A.

[0039]

[0040] The nano-microspheres in this example are 300 nm photonic crystal microspheres with a PDI of 0.035, and the preparation method is as follows:

[0041] (1) Add 0.2 g of ammonium persulfate, 20 g of methyl methacrylate, 0.3 g of allyloxy nonylphenol polyoxyethylene (10) ether ammonium sulfate and 70 g of deionized water to the reaction kettle, heat to 80 °C, stir and react for 2 hours, then add 1.5 g of vinyltrimethoxysilane dropwise to the reaction kettle over 2 hours. After the dropwise addition is completed, continue to keep the temperature and react for 2 hours, cool down, and filter to obtain a polymethyl methacrylate microsphere emulsion.

[0042] (2) Dissolve 50 g of tetraethyl orthosilicate in 100 g of absolute ethanol to prepare a tetraethyl orthosilicate solution.

[0043] (3) At room temperature, the tetraethyl orthosilicate solution and 1 g of ammonia water (mass fraction 25%) are added dropwise to the above polymethyl methacrylate microsphere emulsion within 2 hours. After the dropwise addition is completed, continue to stir and react for 5 hours, then filter and wash to obtain photonic crystal microspheres.

[0044] The bottom coating spraying liquid is: 5% (all are mass fractions in this invention) of bottom coating resin A, 0.5% of polyacrylate surface additive, and the rest is ethyl acetate solvent; the photonic crystal coating liquid is 40% of photonic crystal microspheres, 20% of diethylene glycol, and the rest is water; the film-forming resin protective liquid is 20% of polyvinyl alcohol, and the rest is water.

[0045] A colorless and transparent tempered glass with dimensions of 1000 * 600 * 5 mm is degreased and dusted to obtain a clean glass processing surface.

[0046] First, thinly spray the primer coating solution on the clean glass processing surface. After spraying, dry it at 50 °C for 2 min. Use a Yantian micro-mist spray gun with a spray hole of 0.5 mm to spray the photonic crystal coating solution. After spraying, let it dry naturally to obtain a three-dimensional photonic crystal coating. Then, use the same type of spraying equipment to spray the film-forming resin protective solution again. After spraying, let it dry naturally and put it into a baking equipment for curing at 150 °C for 10 min to obtain a red photonic crystal glass plate. The microscopic structure of the photonic crystal glass plate is as Figure 1 shown. The reflection spectrum diagram of the sample is as Figure 2 shown. At a vertical viewing angle of 180°, its color is red with a wavelength of 650 nm. As the viewing angle decreases, its color gradually blueshifts. At a side viewing angle of 150°, its color is yellow with a wavelength of 610 nm. At a small viewing angle of 130°, its color is green with a wavelength of 560 nm. Example 2

[0047] Base coating resin: A 100 mL three-necked flask equipped with an electromagnetic stirrer, a reflux condenser, a joint with a piston, a nitrogen balloon, and a septum. Evacuate and fill with nitrogen three times to remove oxygen. Add 1,4-diethynylbenzene (0.756 g, 6 mmol, TCI (Shanghai) Chemical Industry Development Co., Ltd.), 30 mL of dried tetrahydrofuran, cool to -30 °C, and slowly add n-butyllithium (12 mmol, 2.5 mol / L n-hexane solution). The solution gradually becomes green and turbid as n-butyllithium is added. The mixture is stirred for another 3 hours, and then 2-acetoxyethylmethyldichlorosilane (1.2 g, 6 mmol, Shanghai Macklin Biochemical Co., Ltd.) is slowly added dropwise. After adding, it gradually becomes a light red transparent solution. The reaction is heated to room temperature and continued for 12 hours. After the reaction is completed, extract with a toluene-water system. After liquid separation, the toluene layer is dried with anhydrous magnesium sulfate and vacuum dried at 60 °C to obtain 1.56 g of a red viscous substance (yield 80%). Marked as base coating resin B.

[0048]

[0049] The photonic crystal microspheres in this example are 260 nm core-shell structure photonic crystal microspheres with a PDI of 0.003. The preparation method is as follows:

[0050] (1) Add 0.1 g of ammonium persulfate, 10 g of acrylonitrile, 0.3 g of allyloxydecyl polyoxyethylene (10) ether ammonium sulfate, and 30 g of deionized water to the reaction kettle, heat to 75 °C, stir and react for 2 hours. Then, add 0.7 g of vinyltriethoxysilane dropwise to the reaction kettle over 3 hours. After the dropwise addition is completed, continue to keep the temperature for reaction for 1 hour, cool down, and filter to obtain a polyacrylonitrile microsphere emulsion.

[0051] (2) Dissolve 40 g of methyl orthosilicate in 94 g of n-butanol to prepare a methyl orthosilicate solution.

[0052] (3) At room temperature, drop the methyl orthosilicate solution and 1 g of triethylamine into the above polyacrylonitrile microsphere emulsion within 2 hours. After the dropping is completed, continue stirring and reacting for 7 hours, then filter and wash to obtain the photonic crystal microspheres.

[0053] The primer spray solution is 12% (all mass fractions in this invention) of primer resin B, and the rest is toluene solution; the photonic crystal coating solution is 30% photonic crystal microspheres, 10% ethylene glycol, 5% formamide, 1% polyether-modified polysiloxane leveling agent, and the rest is water; the film-forming resin protective solution is 10% thermosetting polyester resin, 1% isocyanate curing agent, and the rest is butyl acetate and methyl isobutyl ketone in a 1:1 ratio.

[0054] Perform degreasing and dust removal treatments on a colorless and transparent tempered glass with dimensions of 360*360*5 mm to obtain a clean glass processing surface. First, thinly spray the primer spray solution on the clean glass processing surface, and after spraying, dry it at 40 °C for 10 min. Use a slit coater to coat the photonic crystal coating solution, and after coating, let it dry naturally to obtain a three-dimensional photonic crystal coating; then use a wire bar coater to coat the film-forming resin protective solution, and after coating, let it dry naturally or dry it with hot air, put it into an oven for heat treatment at 80 °C for 10 min, and after completely volatilizing the solvent, raise the temperature to 150 °C for thermal curing to obtain a green photonic crystal glass plate. The light transmittance curve of this photonic crystal glass plate is as Figure 3 shown, and four test points are taken in the figure.

[0055] Use the above green photonic crystal glass plate to fabricate a colored photovoltaic module. Stack the green photonic crystal tempered glass plate (with the photonic crystal coating surface facing up), EVA film, monocrystalline silicon photovoltaic module, EVA film, and polyvinyl fluoride composite film (TPT) black bottom plate in sequence. After overall alignment, put them into a vacuum hot press, with a hot pressing temperature of 140 °C and a hot pressing time of 500 s. Finally, obtain Figure 4 the green photonic crystal colored photovoltaic module as shown.

[0056] Conduct an aging performance test on this group of samples. The test item content is shown in Table 1. The high-temperature and high-humidity aging performance and high-low temperature cycle aging performance can meet the standard requirements within 600 h. Since there is no sign of delamination in the samples after 600 h of testing, the experiment did not continue the test.

[0057] Table 1

[0058]

[0059] Finally, the photonic crystal color component and the junction box are installed to obtain a complete color solar panel. Comparative tests on the power generation efficiency of this group of samples are carried out, and the test results are shown in Table 2. The normal power of the cell is 22.96W; the test power of the conventional lightweight component is 19.69W, and the efficiency of the conventional lightweight component is 85.75%; the test power of the color glass component sample is 18.25W, and the efficiency of the color glass component is 79.48%. The efficiency of the color glass component is about 6% lower than that of the conventional lightweight component, which can well meet the usage requirements of color photovoltaic building integration.

[0060] Table 2

[0061]

[0062] Example 3

[0063] Base coating resin: Polyarylacetylene resin (1g, 10mmol, The First Research Institute of China National Space Administration), triethoxysilane (1.64g, 10mmol, purchased from The First Research Institute of China National Space Administration), 80 mL of toluene and 3g of magnesium oxide are injected into a 250 mL single-necked round-bottom flask, and the reaction can be completed by stirring at room temperature (30°C) for 8h under nitrogen protection. After the reaction is completed, MgO is removed by filtration, and the toluene is rotary evaporated to obtain a copolymer resin of polyarylacetylene resin and triethoxysilane, which is a black-red viscous fluid at room temperature with almost no loss. It is labeled as base coating resin C.

[0064]

[0065] The nanospheres in this example are 260nm core-shell structure photonic crystal microspheres, and the PDI is 0.045. The preparation method is as follows:

[0066] (1) Add 0.2 g of sodium persulfate, 15 g of cyclohexyl methacrylate, 0.2 g of sodium vinyl sulfonate and 60 g of deionized water into the reaction kettle, heat up to 80°C, stir and react for 2 hours, then add 0.5 g of vinyltris(2-methoxyethoxy)silane dropwise into the reaction kettle over 4 hours. After the dropping is completed, continue to keep the temperature and react for 1 hour, cool down, and filter to obtain a polycyclohexyl methacrylate microsphere emulsion.

[0067] (2) Dissolve 90 g of tetrabutyl orthosilicate in 135 g of isopropanol to prepare a tetrabutyl orthosilicate solution.

[0068] (3) At room temperature, the tetrabutyl orthosilicate solution and 0.8 g of sodium hydroxide are added dropwise to the above polycyclohexyl methacrylate microsphere emulsion within 3 hours. After the dropping is completed, continue to stir and react for 8 hours, then filter and wash to obtain photonic crystal microspheres.

[0069] The primer spraying solution is 10% primer resin C (all mass fractions in the present invention), and the rest is toluene solution; the photonic crystal coating solution is 20% photonic crystal microspheres, 10% ethylene glycol, 0.5% polyether-modified polysiloxane leveling agent, and the rest is water; the film-forming resin protective solution is 20% polyester-modified acrylate resin, 2% photoinitiator TPO, and the rest is 28% methyl ethyl ketone and 50% butyl acetate.

[0070] The colorless transparent tempered glass of 360*360*5 mm is degreased and dust-removed to obtain a clean glass processing surface. First, the primer spraying solution is thinly sprayed on the clean glass processing surface, and after spraying, it is dried at 50°C for 2 min. The photonic crystal coating solution is coated using a slit coater, and after coating, it is naturally air-dried to obtain a three-dimensional photonic crystal coating; then, the film-forming resin protective solution is sprayed using a hand spray gun from Yantian, and after spraying, it is naturally air-dried or dried with hot air, and the coating is cured using a 395 nm UV-LED lamp to obtain a green photonic crystal glass plate. Example 4

[0071] Primer resin: A 100 mL three-necked flask is equipped with an electromagnetic stirrer, a reflux condenser, a joint with a piston, a nitrogen balloon, and a septum. The air in the flask is removed by evacuation and refilling with nitrogen three times. 1,3,5-Triethynylbenzene (0.9 g, 6 mmol, TCI Shanghai Chemical Industry Development Co., Ltd.) and 15 mL of dried tetrahydrofuran are added, and the temperature is lowered to -30°C. n-Butyllithium (12 mmol, 2.5 mol / L n-hexane solution) is slowly added, and the solution gradually turns green and turbid as the butyllithium is added. The mixture is stirred for another 3 hours, and then diphenyldichlorosilane (1.512 g, 6 mmol) is slowly added dropwise, and the solution gradually turns yellow and transparent after addition. The reaction is heated to room temperature and continued for 12 hours. After the reaction is completed, it is extracted with a toluene-water system, and after liquid separation, the toluene layer is dried with anhydrous magnesium sulfate and vacuum-dried at 60°C to obtain 1.9 g of a yellow viscous substance (yield 79%). It is labeled as primer resin D.

[0072]

[0073] The nano-microspheres in this example are 220 nm core-shell structure photonic crystal microspheres with a PDI of 0.02. The preparation method is as follows:

[0074] (1) 0.1 g of potassium persulfate, 10 g of isobornyl methacrylate, 0.3 g of allyloxyhydroxypropylsulfonic acid sodium, and 40 g of deionized water are added to a reaction kettle, heated to 85°C, and stirred for 2 hours. Then, 0.4 g of methylvinyldimethoxysilane is added dropwise to the reaction kettle over 3 hours. After the dropwise addition is completed, the reaction is continued under insulation for 1 hour, cooled, and filtered to obtain a polyisobornyl methacrylate microsphere emulsion.

[0075] (2) Dissolve 30 g of propyl orthosilicate in 30 g of n-propanol to prepare a propyl orthosilicate solution.

[0076] (3) At room temperature, drop the propyl orthosilicate solution and 0.6 g of ammonia water into the above-mentioned polyisobornyl methacrylate microsphere emulsion within 2 hours. After the dropping is completed, continue to stir and react for 6 hours, then filter and wash to obtain the photonic crystal microspheres.

[0077] The primer spraying solution is 15% (all are mass fractions in the present invention) of primer resin D, 1% of polyether-modified polydimethylsiloxane additive, and the rest is tetrahydrofuran solution; the photonic crystal coating solution is 10% of photonic crystal microspheres, 80% of ethanol, and 10% of ethylene glycol; the film-forming resin protective solution is 20% of polyvinyl butyral resin, and the rest is 5% of ethylene glycol and 75% of ethanol.

[0078] Perform degreasing and dust removal on the colorless and transparent tempered glass of 300*300*10 mm to obtain a clean glass processing surface. First, thinly spray the primer spraying solution on the clean glass processing surface, and after the spraying is completed, dry it at 50 °C for 2 min. Use a RDS No. 22 wire bar to coat the photonic crystal coating solution on the coater. After the coating is completed, air dry it naturally until the complete photonic crystal color appears, and then put it into an oven at 100 °C for 10 min for thorough drying to obtain a three-dimensional photonic crystal coating; then use an automatic spray gun of Yantian to spray the film-forming resin protective solution, and after spraying, air dry it naturally or dry it with hot air, and put it into an oven at 150 °C for 20 min for curing to obtain a blue photonic crystal glass plate.

[0079] The above has described in detail the implementable methods of the present invention. However, the present invention is not limited thereto. Simple deformations within the technical concept of the present invention or combinations suitable for this method should be regarded as the content disclosed by the present invention and all fall within the protection scope of the present invention.

[0080] In addition, various embodiments of the present invention can be arbitrarily combined on the premise of no contradiction. As long as it does not violate the idea of the present invention, it should be regarded as the content disclosed by the present invention.

Claims

1. A preparation method of a color photovoltaic module based on a photonic crystal coating technology, characterized in that, The specific operation of the preparation method is as follows: stack a photonic crystal plate, a packaging adhesive film, a power generation component, a packaging adhesive film, and a bottom plate in sequence and then perform hot pressing to obtain; the photonic crystal plate is obtained by sequentially coating a bottom coating layer, a photonic crystal coating layer, and a photonic crystal protection coating layer on a colorless and transparent tempered glass panel or plastic plate; The preparation method of the bottom coating layer is as follows: perform degreasing and dust removal cleaning operations on a colorless and transparent tempered glass panel or plastic plate, and then coat the bottom coating liquid and dry to obtain the bottom coating layer; the bottom coating liquid contains 2-20wt% of a silicon hybrid resin with an aromatic hydrocarbon as the main body and containing active groups; the active groups are one or more of alkynyl, vinyl, silicon-chlorine bond, and silicon hydroxyl group; the solvents selected for preparing the bottom coating liquid are one or more of ethyl acetate, tetrahydrofuran, toluene, dichloromethane, n-hexane, n-butyl ether, petroleum ether, and phenyl ether; The preparation method of the photonic crystal coating layer is as follows: coat the photonic crystal coating liquid on the bottom coating layer and dry to obtain the photonic crystal coating layer; the photonic crystal coating liquid contains 10-50wt% of monodisperse photonic crystal microspheres; the solvents in the photonic crystal coating liquid are selected from one or more of water, ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, pentaerythritol, diethylene glycol, triethylene glycol, polyethylene glycol 200, tetrahydrofuran, formamide, and N,N-dimethylformamide; The monodisperse photonic crystal microspheres have a core-shell structure with a polymer microsphere as the core and an inorganic material as the shell, and the ratio of the radius of the core to the thickness of the shell is 1:0.5-1; the particle size of the monodisperse photonic crystal microspheres is 150-350nm, and the monodispersity index PDI is less than 0.05; The preparation method of the monodisperse photonic crystal microspheres is as follows: (1) Add an initiator, a monomer, an emulsifier, and deionized water into a reaction kettle, the mass concentration of the monomer is 2-50%, the addition amount of the initiator is 0.2-5% of the mass of the monomer, and the addition amount of the emulsifier is 0.1-5% of the mass of the monomer; Heat up to 75-90°C, stir and react for 1-2 hours, then dropwise add a silane coupling agent into the reaction kettle, the addition amount is 1-10% of the mass of the monomer, and the dropping time is 2-4 hours; after the dropping is completed, continue to keep warm and react for 1-2 hours, cool down, filter to remove impurities, and obtain a polymer microsphere emulsion; (2) Dissolve a silane ester in an alcohol solvent to prepare a silane ester solution with a mass content of 20-50%; (3) At room temperature, dropwise add the silane ester solution and a catalyst into the polymer microsphere emulsion within 1-3 hours, and the mass ratio of the silane ester to the polymer microspheres is 4-25:1; after the dropping is completed, continue to stir and react for 5-8 hours, filter, and wash to obtain monodisperse photonic crystal microspheres.

2. The preparation method according to claim 1, characterized in that, The initiator is one or more of ammonium persulfate, potassium persulfate, and sodium persulfate; the monomer is one or more of methyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, styrene, acrylic acid, acrylonitrile, and vinyl acetate; the emulsifier is one or more of ammonium allyloxynonylphenol polyoxyethylene (10) ether sulfate, ammonium allyloxydecyl polyoxyethylene (10) ether sulfate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt, allyloxyhydroxypropylsulfonic acid sodium salt, and sodium vinylsulfonate; the silane coupling agent is one or more of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriisopropoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, and methacryloxypropyltriethoxysilane. The catalyst is one or more of ammonia water, triethylamine, and sodium hydroxide; the silicate ester is one or more of methyl silicate, ethyl silicate, propyl silicate, and butyl silicate; the alcohol solvent is one or more of methanol, ethanol, n-propanol, isopropanol, and n-butanol.

3. The preparation method according to claim 1, wherein The preparation method of the photonic crystal protective coating is as follows: coat the photonic crystal protective layer coating solution on the photonic crystal coating, and a transparent and firm photonic crystal protective coating is obtained after curing; the photonic crystal protective layer coating solution is a 5-40wt% organic film-forming resin solution, and the solvents used are one or more of water, ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, pentaerythritol, diethylene glycol, triethylene glycol, formamide, N,N-dimethylformamide, acetone, butanone, methyl isobutyl ketone, cyclohexanone, n-pentane, n-hexane, n-octane, ethyl acetate, and butyl acetate.

4. The preparation method according to claim 3, characterized in that, The organic film-forming resin is polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl butyral, epoxy resin system, phenolic resin system, polyurethane resin system, polyester resin system, acrylic resin system, epoxy acrylate resin system, or polyurethane acrylate system.

5. The preparation method according to any one of claims 1-4, characterized in that The coating method is spin coating, slot coating, roll coating, inkjet printing, spraying, or curtain coating; the inkjet printing is piezoelectric inkjet printing; the spraying is low-pressure and low-flow spraying; the atomization pressure is 5-30 Kpa, and the flow rate is 1-20 mL / min.

6. The preparation method according to claim 1, wherein The encapsulation adhesive film is polyvinyl butyral, ethylene-vinyl acetate copolymer, or polyolefin elastomer film; the power generation component is a monocrystalline silicon or polycrystalline silicon solar module; the bottom plate is tempered glass or an organic composite film, and the organic composite film is a polyvinyl fluoride composite film, thermoplastic elastomer film, fluoropolymer composite film, polyamide composite film, or ethylene-vinyl acetate film.

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