A phase change energy storage composite coating with photo-thermal and electric-thermal functions, a preparation method thereof and all-weather anti-icing and deicing applications

Abstract

The present application relates to the technical field of phase change functional materials, in particular to a phase change energy storage composite coating with photothermal and electrothermal properties, a preparation method thereof and all-weather anti-icing and deicing applications. The preparation method is to sequentially coat and form a phase change energy storage layer, paste a copper foil, coat and form a conductive energy storage layer, and coat and form a photothermal super-hydrophobic energy storage coating. The coating can effectively delay icing by combining photothermal, electrothermal, super-hydrophobic properties and the heat storage properties of phase change microcapsules. The coating has the advantages of simple preparation method, low preparation cost, high anti-icing and deicing efficiency, good photothermal conversion performance, good super-hydrophobic performance, and can cope with the anti-icing and deicing of the surface under extreme weather conditions, ensuring that the coating maintains effective anti-icing and deicing function during night, overcast days and other time periods. The phase change energy storage composite coating with photothermal and electrothermal properties can be applied to the surface of outdoor equipment, and the raw materials are low in price and can be mass-produced, having the advantages of high efficiency and energy saving, and being suitable for a wide range of industrial and civil fields.

Description

Technical Field

[0001] The present invention relates to the technical field of phase change functional materials, and in particular to a phase change energy storage composite coating with both photothermal and electrothermal properties, a preparation method thereof, and all-weather anti-icing and de-icing applications. Background Art

[0002] Traditional anti-icing and de-icing technologies mainly rely on mechanical or chemical methods, such as the use of de-icing agents or mechanical scraping to remove ice and snow, but these methods have problems such as low efficiency, high energy consumption, and environmental pollution. In recent years, with the development of new materials technology, super-hydrophobic coating materials based on photothermal or electrothermal conversion technology have gradually become a green, environmentally friendly, and low-energy anti-icing and de-icing solution. These materials combine the principles of photothermal or electrothermal conversion to use light energy or electrical energy to increase the surface temperature of the material, thereby preventing the formation of ice or quickly melting the ice layer that has formed. At the same time, the super-hydrophobic property can reduce the chance of water droplets adhering to the surface, further enhancing the anti-icing effect. This multifunctional coating material can self-regulate the surface temperature, reduce energy consumption, and has broad application prospects.

[0003] Combining photothermal and superhydrophobic surfaces is a new approach to improving ice resistance and deicing. Chinese patent application CN114058224A discloses a photothermally responsive superhydrophobic anti-icing composite coating and its preparation method. This method involves applying silicone rubber to a substrate surface, dispersing micron- and nanoparticles in a solvent to create a uniform dispersion, spraying the coating onto the substrate, and finally subjecting the coating to heat treatment and fluorination. Chinese patent CN 116790186 B ​​discloses an environmentally friendly, super-hydrophobic anti-icing and de-icing material with efficient photothermal conversion and its preparation method. The method first combines a two-dimensional sheet material with photothermal response and photothermal-responsive nanoparticles through an in-situ gradient reduction process. The composite photothermal conversion material is then coated on a substrate surface with a three-dimensional columnar array structure along with a hydrophobic modifier. The hydrophobicity of the coating and the multiple reflections of the columnar array microstructure promote light absorption followed by photothermal conversion, achieving an excellent photothermal response temperature for the material and enhancing the de-icing effect, capable of simultaneously meeting the requirements of passive anti-icing and anti-frost and active de-icing and defrosting. While environmentally friendly photothermal materials utilize solar energy to enhance both anti-icing and active de-icing and defrosting, the coatings are not effective at night or on cloudy days, meaning they cannot achieve all-weather anti-icing and de-icing. Furthermore, current methods combining photothermal properties with super-hydrophobic surfaces have limited effectiveness in delaying ice formation. The energy converted from photothermal energy is easily dissipated into the environment, affecting the ice-delaying effect, resulting in low overall energy utilization. Summary of the Invention

[0004] In order to overcome the deficiencies of the prior art, the first object of the present invention is to provide a method for preparing a phase-change energy storage composite coating having both photothermal and electrothermal properties.

[0005] The present invention first prepares a photothermal phase change energy storage material by integrating phase change materials (PCMs) and photothermal conversion carriers; using the simple phase change thermal energy storage and release principle, the photothermal conversion carrier is combined with the phase change material to absorb and store heat when there is sufficient light, and release the stored energy when the light is weakened or there is no light. This characteristic gives them unique advantages in improving the efficiency of solar energy utilization and solving the problem of intermittent solar energy, effectively improving the energy utilization efficiency. Specifically, by combining microencapsulation technology, a phase change microcapsule energy storage material with high heat capacity and stable phase change characteristics was successfully prepared. Then, Cu micro-nanoparticles with photothermal effects are in situ reduced on the surface of the phase change microcapsule energy storage material, and the characteristics of photothermal and phase change energy storage are realized at the same time; finally, superhydrophobicity is achieved by combining surface modification and the micro-nanostructure of the material. The specific material preparation method is to coat a formed phase change energy storage layer, apply copper foil, coat an electric thermal energy storage layer, and coat a formed photothermal superhydrophobic energy storage coating in sequence, so as to simultaneously combine photothermal, electric thermal, superhydrophobic properties and phase change microcapsule energy storage. The utilization efficiency of solar energy is improved by combining photothermal and phase change microcapsule energy storage, and the efficiency of electricity consumption is also improved by combining electric thermal and phase change microcapsule energy storage. The phase change energy storage of the three coating layers effectively improves the effect of delaying icing and can achieve all-weather active deicing, to cope with surface anti-icing and deicing under extreme climatic conditions, and ensure that the coating maintains effective anti-icing and deicing functions at night, on cloudy days and other time periods.

[0006] In order to overcome the shortcomings of the prior art, the second purpose of the present invention is to provide a phase-change energy storage composite coating that combines photothermal and electrothermal properties. The phase-change energy storage composite coating that combines photothermal and electrothermal properties has the advantages of low preparation cost, high anti-icing and deicing efficiency, high energy utilization rate, and good superhydrophobic performance.

[0007] The third object of the present invention is to provide a phase-change energy storage composite coating with both photothermal and electrothermal properties for use in all-weather anti-icing and deicing.

[0008] In order to achieve the first object of the above invention, the technical solution adopted by the present invention is as follows:

[0009] The present invention provides a method for preparing a phase-change energy storage composite coating having both photothermal and electrothermal properties, comprising the following steps:

[0010] S1. Coating and forming a phase change energy storage layer: coating a slurry containing silicon dioxide-coated n-hexadecane phase change microcapsules on a substrate, and then curing and forming the phase change energy storage layer;

[0011] S2. Copper foil pasting and coating an electric thermal energy storage layer: Copper foil electrodes are pasted on two opposite edges of the surface of the phase change energy storage layer formed in step S1 and extended to the outside of the phase change energy storage layer, and then a slurry containing silicon dioxide-copper double-shelled n-hexadecane phase change microcapsules and graphite is coated on the surface of the phase change energy storage layer to form an electric thermal energy storage layer;

[0012] S3. Coating and forming a photothermal super-hydrophobic energy storage coating: coating the surface of the electrothermal energy storage layer formed in step S2 with a slurry containing fluorinated silica-copper double-shell-coated n-hexadecane phase change microcapsules, and then curing and forming the photothermal super-hydrophobic energy storage coating, thereby obtaining the phase change energy storage composite coating with both photothermal and electrothermal properties.

[0013] Furthermore, in step S1, a slurry containing silica-coated n-hexadecane phase change microcapsules is coated on an aluminum plate that has been polished with sandpaper and cleaned with isopropyl alcohol, and then cured to form a phase change energy storage layer; the synthesis method of the silica-coated n-hexadecane phase change microcapsules comprises the following steps:

[0014] 1) Emulsification: After heating a mixed solution of anhydrous ethanol and water, n-hexadecane, hexadecyltrimethylammonium bromide and tetraethyl orthosilicate are added to disperse the mixture to form an oil-in-water emulsion;

[0015] 2) Polycondensation reaction: adding a base to the oil-in-water emulsion obtained in step 1) to carry out polycondensation reaction, and then filtering, washing and drying to obtain the silica-coated n-hexadecane phase change microcapsules.

[0016] The mechanisms of the emulsification step and the polycondensation step are as follows:

[0017] Cetyltrimethylammonium bromide is used as an emulsifier. Cetyltrimethylammonium bromide can ionize in water to generate hydrophilic NH4 + , can form a strong positive electric field on the surface of n-hexadecane droplets, thereby improving the dispersion stability of the emulsification system and the enrichment ability of small molecules of the wall material, so that the obtained water-in-oil emulsion is stable and does not stratify. In addition, during the polycondensation reaction, under alkaline conditions, OH - Directly nucleophilically attack the central silicon atom, negatively charged OH - The electron cloud of tetraethyl orthosilicate is shifted to the side of -OR, resulting in the breaking of the silicon-oxygen bond and the occurrence of a hydrolysis reaction. When one -OR is hydrolyzed, the Si atom becomes positively charged, making the hydrolysis reaction more likely to occur, making the hydrolysis rate of tetraethyl orthosilicate faster and more complete. After hydrolysis, silicic acid and silicic acid, and silicic acid and tetraethyl orthosilicate, will undergo polycondensation to form tiny crystal nuclei. The subsequent hydrolysis products continue to grow and deposit on the surface of the crystal nuclei, eventually forming a SiO2 shell to coat the n-hexadecane. The reaction principle of the hydrolysis and polycondensation of tetraethyl orthosilicate to SiO2 is shown in Formula I:

[0018]

[0019] Furthermore, in the emulsification step, the volume ratio of the anhydrous ethanol to water is 1:(1.5-3); the mass ratio of n-hexadecane, hexadecyltrimethylammonium bromide, and tetraethyl orthosilicate is (8-12):(1-2.5):(10-15); the mass volume ratio of n-hexadecane to the mixed solution is (8-12) g:(250-300) mL; the heating is performed by heating to 30° C.-40° C. in a water bath; and the dispersion is performed by stirring at a speed of 2000 rpm-3000 rpm in a high-speed disperser for 5 min-15 min; and / or

[0020] In the polycondensation reaction step, ammonia water with a mass concentration of 25%-28% is added to the oil-in-water emulsion obtained in the emulsification step at 30°C-40°C for a polycondensation reaction for 22h-26h, followed by filtration, washing with petroleum ether and anhydrous ethanol 2-4 times, respectively, and then washing with clean water 1-3 times, and then freeze-drying for 22h-26h to obtain a white powder product, namely the silica-coated n-hexadecane phase change microcapsules; the volume ratio of the alkali to the oil-in-water emulsion is (1-5):(250-350).

[0021] Furthermore, in step S2, the synthesis method of the silicon dioxide-copper double-shell coated n-hexadecane phase change microcapsules comprises the following steps:

[0022] 1) Sensitization: adding hydrochloric acid to the SnCl2 solution and mixing, adding the silica-coated n-hexadecane phase change microcapsules prepared in step S1 to react to obtain sensitized phase change microcapsules;

[0023] 2) Activation: adding the sensitized phase change microcapsules into a PdCl2 solution for activation reaction, filtering and washing to obtain activated phase change microcapsules;

[0024] 3) Chemical copper plating: adding the activated phase change microcapsules, copper sulfate pentahydrate, and EDTA into water, and then adding sodium hypophosphite under stirring to carry out chemical copper plating reaction, thereby preparing the silicon dioxide-copper double-shell n-hexadecane-coated phase change microcapsules.

[0025] Among them, the mechanism of SnCl2 sensitization is as follows: In SnCl2 solution, Sn 2+ (Stannic ions) react with the hydroxyl (-OH) adsorption sites of the silica shell to form a Sn(OH)2 film. At the same time, some Sn 2+ It will be oxidized to Sn in the air 4+ , thereby generating Sn on the substrate surface 2+ / Sn 4+Mixed state. This mixed state film has strong adsorption and can well adsorb the subsequent activator Pd 2+ .

[0026] The activation mechanism of PdCl2 is as follows: In PdCl2 solution, Pd 2+ It will undergo redox reaction with the sensitized Sn layer. 2+ Pd 2+ Reduced to metal Pd with catalytic activity. The ionic reaction equation is shown in Formula II:

[0027] Sn 2+ +Pd 2+ =Pd+Sn 4+

[0028] Formula II.

[0029] Then, metallic Pd is deposited on the surface of the SiO2 shell substrate in the form of very fine nanoparticles. These nano Pd particles act as active catalytic centers, providing the required active sites for the subsequent autocatalytic electroless copper plating. Under the catalysis of the nano Pd particles, sodium hypophosphite reduces the copper ions in the plating reaction equation as shown in Equation III:

[0030]

[0031] Furthermore, in the sensitization step, hydrochloric acid with a concentration of 9 mol / L-12 mol / L is added to a SnCl2 solution with a mass concentration of 0.5%-1.5%, and after stirring at 250 rpm-350 rpm for 3 min-8 min, the silica-coated n-hexadecane phase change microcapsules in step S1 are added, and the mixture is stirred for 5 min-15 min, and then filtered and washed 2-4 times to obtain sensitized phase change microcapsules; the mass volume ratio of the silica-coated n-hexadecane phase change microcapsules, SnCl2 solution and hydrochloric acid is (3-8) g: (90-110) mL: (3-5) mL; and / or

[0032] In the activation step, the mass volume ratio of the sensitized phase change microcapsules to the PdCl2 solution is (0.5-1.5) g: (40-60) mL; the concentration of the PdCl2 solution is 40 mg / L-60 mg / L, and the activation time is 3 min-8 min; and / or

[0033] In the chemical copper plating step, the mass volume ratio of the copper sulfate pentahydrate, EDTA, activated phase change microcapsules, sodium hypophosphite and water is (1-3) g: (0.5-2) g: (1-3) g: (2-4) g: (90-110) mL; the stirring speed is 150 rpm-250 rpm; and the chemical copper plating reaction time is 50 min-70 min.

[0034] Furthermore, in step S3, the synthesis method of the fluorinated silica-copper double-shell n-hexadecane phase change microcapsules is as follows: using a micro-etching solution to micro-etch the surface of the silica-copper double-shell n-hexadecane phase change microcapsules, dissolving tridecafluorooctyltriethoxysilane in anhydrous ethanol, then adding the micro-etched silica-copper double-shell n-hexadecane phase change microcapsules and stirring and dispersing them, then adding deionized water and stirring and hydrolyzing them for 1.5h-2.5h, filtering and washing with ethanol, and then placing in a vacuum drying oven at 75°C-85°C for 3h-5h; and / or

[0035] The mass volume ratio of the tridecafluorooctyltriethoxysilane, ethanol, silicon dioxide-copper double-shell coated n-hexadecane phase change microcapsules, and water is (3-5) mL: (180-220) mL: (3-5) g: (0.3-0.8) mL; and / or

[0036] The micro-etching solution comprises sulfuric acid, hydrogen peroxide, sodium silicate and water, and the mass ratio of the sulfuric acid, hydrogen peroxide, sodium silicate and water is (5-6) g: (2-3) g: (0.05-0.1) g: (100-200) mL.

[0037] Among them, tridecafluorooctyl triethoxysilane was hydrolyzed and coated with n-hexadecane phase change microcapsules (denoted as nC 16 @SiO2-Cu) surface to form Cu-O-Si bonds, and then the tridecafluorooctyl group is modified to nC 16 @SiO2-Cu surface. 16 @SiO2-Cu surface modification can increase nC 16 @Surface hydrophobic properties of SiO2-Cu.

[0038] Furthermore, in step S1, a phase change energy storage layer is formed by coating: hydroxy-terminated polydimethylsiloxane and a curing agent are added to n-hexane and stirred and mixed, and then silicon dioxide-coated n-hexadecane phase change microcapsules are added and mixed to form the slurry, and then the slurry is sprayed and cured at 90° C.-110° C. for 1.5 h-2.5 h to form the phase change energy storage layer;

[0039] In the step S2, copper foil is applied and an electric thermal energy storage layer is coated: copper foil electrodes are applied to two opposite edges of the surface of the phase change energy storage layer formed in step S1 and extend to the outside of the phase change energy storage layer; hydroxy-terminated polydimethylsiloxane and a curing agent are added to n-hexane and stirred and mixed, and then silicon dioxide-copper double-shell coated n-hexadecane phase change microcapsules and graphite are added to form the slurry, and then the slurry is sprayed on the surface of the phase change energy storage layer to form the electric thermal energy storage layer;

[0040] In this step S2, the n-hexadecane phase change microcapsules are coated with a silicon dioxide-copper double shell layer and combined with a small amount of graphite to play the role of connecting the conductive network, thereby obtaining an electrothermal energy storage coating with good electrothermal performance.

[0041] In the step S3, a photothermal super-hydrophobic energy storage coating is coated and formed: terminal hydroxyl polydimethylsiloxane and a curing agent are added to n-hexane and stirred and mixed, and then fluorinated silica-copper double-shell coated n-hexadecane phase change microcapsules are added and mixed to form the slurry, and then the slurry is sprayed on the surface of the electrothermal energy storage layer, and then cured at 90°C-110°C for 5h-7h to form the photothermal super-hydrophobic energy storage coating, thereby obtaining the phase change energy storage composite coating with both photothermal and electrothermal properties.

[0042] Furthermore, the curing agent in steps S1, S2 and S3 is component B of Dow Corning 184;

[0043] In step S1, the mass volume ratio of the hydroxy-terminated polydimethylsiloxane, the curing agent, the silica-coated n-hexadecane phase change microcapsules and n-hexane is (3-4) g: (0.2-0.5) g: (0.5-1.5) g: (15-25) mL;

[0044] In step S2, the mass volume ratio of the hydroxy-terminated polydimethylsiloxane, curing agent, silica-copper double-shell coated n-hexadecane phase change microcapsules, graphite and n-hexane is (1.5-2.5) g: (0.1-0.3) g: (0.3-0.8) g: (0.1-0.3) g: (10-20) mL;

[0045] In step S3, the mass volume ratio of the hydroxy-terminated polydimethylsiloxane, the curing agent, the fluorinated silica-copper double-shell coated n-hexadecane phase change microcapsules and n-hexane is (0.5-1.5) g: (0.1-0.2) g: (0.5-1.2) g: (5-15) mL;

[0046] In the step S2, the particle size of the graphite is 1 μm-5 μm.

[0047] In order to achieve the second purpose of the above invention, the technical solution adopted by the present invention is as follows:

[0048] The present invention provides a phase-change energy storage composite coating with both photothermal and electrothermal properties, which is prepared by the above-mentioned method for preparing a phase-change energy storage composite coating with both photothermal and electrothermal properties.

[0049] In order to achieve the third purpose of the above invention, the technical solution adopted by the present invention is as follows:

[0050] The present invention provides a method for preparing a phase-change energy storage composite coating with both photothermal and electrothermal properties, and application of the prepared phase-change energy storage composite coating with both photothermal and electrothermal properties in all-weather anti-icing and de-icing.

[0051] The phase-change energy storage composite coating with both photothermal and electric heating properties prepared by the present invention is a super-hydrophobic anti-icing and de-icing coating. Due to its efficient photothermal and electric heating conversion and energy storage functions, it can be applied to the surface of outdoor equipment. The photothermal or electric heating conversion performance of the phase-change energy storage composite coating with both photothermal and electric heating properties is used to increase the surface temperature of the equipment and prevent icing. In addition, its hydrophobic property can prevent the adhesion of water and ice, thereby extending the service life of the equipment. It is especially capable of coping with the problem of surface icing under extreme climatic conditions, and ensures that the coating maintains effective anti-icing and de-icing functions at night, on cloudy days, and other time periods.

[0052] Compared with the prior art, the present invention has the following beneficial effects:

[0053] (1) The present invention provides a method for preparing a phase-change energy storage composite coating having both photothermal and electrothermal properties. The method comprises the following steps: sequentially coating a formed phase-change energy storage layer, pasting a copper foil, coating an electrothermal energy storage layer, and coating a formed photothermal super-hydrophobic energy storage coating. The method combines the photothermal, electrothermal, and super-hydrophobic properties with the energy storage function of phase-change microcapsules to effectively delay icing. The method has the advantages of simple preparation method, high anti-icing and deicing efficiency, good photothermal conversion performance, and good super-hydrophobic performance. The method can also cope with surface anti-icing and deicing under extreme climatic conditions, ensuring that the coating maintains effective anti-icing and deicing functions at night, on cloudy days, and other time periods.

[0054] (2) The present invention provides a method for preparing a phase-change energy storage composite coating with both photothermal and electrothermal properties. The method utilizes an interfacial polymerization method to prepare silica-coated n-hexadecane phase-change microcapsules with a phase-change enthalpy of 170 J / g. The microcapsules are nano-scale. On the one hand, the problem of n-hexadecane leaking during the phase change process can be avoided. On the other hand, a phase-change energy storage layer is formed by combining silica-coated n-hexadecane phase-change microcapsules with end-hydroxyl polydimethylsiloxane. When the ambient temperature is lower than the phase-change temperature of the phase-change material, the silica-coated n-hexadecane phase-change microcapsules begin to solidify and release a large amount of latent heat, thereby providing heat, maintaining a high surface temperature, and preventing freezing caused by excessively low temperature.

[0055] Furthermore, by electrolessly plating copper onto silica-coated n-hexadecane phase-change microcapsules, a controlled process achieves two goals with one stone: conductivity and photothermal conversion, effectively converting sunlight into heat. A silica-copper double-shell coating of n-hexadecane phase-change microcapsules, combined with graphite and hydroxyl-terminated polydimethylsiloxane, forms an electrothermal energy storage layer. Copper foil serves as both the electrodes and the conductor for connecting to the external current. This enables the phase-change energy storage composite coating to possess excellent electrical conductivity and electrothermal properties, addressing all-weather requirements and ensuring effective anti-icing and de-icing capabilities at night and on cloudy days. Furthermore, the n-hexadecane within the phase-change microcapsules possesses a suitable phase-change temperature of 18°C ​​and a high latent heat of 230 J / g. Furthermore, it exhibits excellent chemical stability and resists decomposition at high temperatures. This allows for the storage of electrical heat through phase change, preventing rapid heat loss and improving energy efficiency, thereby enhancing active de-icing efficiency.

[0056] The use of silica-copper double-shelled n-hexadecane phase-change microcapsules as photothermal responsive particles can effectively delay ice formation and actively remove ice during the day. Furthermore, a photothermal super-hydrophobic coating is formed by combining fluorinated silica-copper double-shelled n-hexadecane phase-change microcapsules with hydroxyl-terminated polydimethylsiloxane. The resulting composite coating not only possesses photothermal, electrothermal, and phase-change energy storage properties, but also possesses super-hydrophobic properties, making the surface less susceptible to contaminants and exhibiting self-cleaning properties. This property, in turn, enhances the photothermal conversion effect, thereby improving the overall performance and application potential of the composite coating.

[0057] (3) A phase-change energy storage composite coating having both photothermal and electrothermal properties according to the present invention,

[0058] The silica-coated n-hexadecane phase change microcapsules, silica-copper double-shelled n-hexadecane phase change microcapsules, and fluorinated silica-copper double-shelled n-hexadecane phase change microcapsules contained in the coating can all utilize phase change to absorb or release heat. Among them, the photothermal layer prepared by fluorinated silica-copper double-shelled n-hexadecane phase change microcapsules improves the utilization efficiency of solar energy by combining photothermal energy with phase change microcapsule energy storage. Among them, the conductive layer prepared by silica-copper double-shelled n-hexadecane phase change microcapsules and graphite also improves the efficiency of electricity consumption by combining electric heating with phase change microcapsule energy storage. In addition, close to the substrate is the phase change energy storage layer prepared by silica-coated n-hexadecane phase change microcapsules, which further maintains energy storage.

[0059] In summary, the phase-change microcapsules contained in the three coating layers enable the coating to retain heat during hot and cold cycles, reducing heat loss and improving energy efficiency, thereby regulating surface temperature. This characteristic effectively prolongs the accumulation of ice and frost on surfaces in low-temperature, high-humidity environments, effectively enhancing the effectiveness of delaying ice and frost formation.

[0060] (4) The present invention provides a phase-change energy storage composite coating with both photothermal and electric heating for all-weather anti-icing and de-icing. Since the phase-change energy storage composite coating with both photothermal and electric heating is a super-hydrophobic anti-icing and de-icing coating, it has high-efficiency photothermal and electric heating conversion and energy storage functions and can be applied to the surface of outdoor equipment. The photothermal or electric heating conversion performance of the phase-change energy storage composite coating with both photothermal and electric heating can increase the surface temperature of the equipment and prevent icing. In addition, its hydrophobic property can prevent the adhesion of water and ice, thereby extending the service life of the equipment. In particular, it can cope with the problem of surface icing under extreme climatic conditions and ensure that the coating maintains effective anti-icing and de-icing functions at night, on cloudy days, and other time periods. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0062] Figure 1 The present invention is a schematic diagram of the synthesis route of the silicon dioxide-coated n-hexadecane phase change microcapsules and the silicon dioxide-copper double-shell-coated n-hexadecane phase change microcapsules.

[0063] Figure 2 This is an SEM image of the silicon dioxide-coated n-hexadecane phase change microcapsules prepared in Example 1.

[0064] Figure 3 This is an SEM image of the silicon dioxide-copper double-shell coated n-hexadecane phase change microcapsules prepared in Example 1.

[0065] Figure 4 This is an SEM image of the surface structure of a phase-change energy storage composite coating with both photothermal and electrothermal properties obtained in Example 1.

[0066] Figure 5 1 is an infrared spectrum of SiO2, n-hexadecane and the silicon dioxide-coated n-hexadecane phase change microcapsules prepared in Example 1.

[0067] Figure 6 These are X-ray powder diffraction patterns of SiO2, the silicon dioxide-coated n-hexadecane phase change microcapsules prepared in Example 1, and the silicon dioxide-copper double-shell-coated n-hexadecane phase change microcapsules.

[0068] Figure 7 This is an EDS spectrum analysis diagram of the silicon dioxide-copper double-shell n-hexadecane phase change microcapsules prepared in Example 1.

[0069] Figure 8 This is a surface vertical motion adhesion test diagram of a phase-change energy storage composite coating with both photothermal and electrothermal properties obtained in Example 1.

[0070] Figure 9 This is a surface water drop elasticity test diagram of a phase change energy storage composite coating with both photothermal and electrothermal properties prepared in Example 1.

[0071] Figure 10 This is an electrothermal cycle test diagram of a phase-change energy storage composite coating with both photothermal and electrothermal properties obtained in Example 1.

[0072] Figure 11 This is a photothermal cycle test diagram of a phase-change energy storage composite coating with both photothermal and electrothermal properties prepared in Example 1.

[0073] Figure 12 This is a static freezing delay test diagram of the photothermal super-hydrophobic energy storage coating prepared in Example 1 and a phase-change energy storage composite coating with both photothermal and electrothermal properties at low temperatures.

[0074] Figure 13 This is a test chart of the photothermal deicing speed of a phase-change energy storage composite coating with both photothermal and electrothermal properties prepared in Example 1 under light.

[0075] Figure 14 This is a test chart of the electric heating deicing speed of a phase change energy storage composite coating with both photothermal and electric heating properties prepared in Example 1 under a DC power supply. DETAILED DESCRIPTION

[0076] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0077] The terms used in the embodiments of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. In the present invention, the singular forms "a", "an", "the" and "the" used in the embodiments and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0078] The following describes the details in conjunction with specific embodiments.

[0079] Example 1

[0080] A method for preparing a phase-change energy storage composite coating having both photothermal and electrothermal properties, characterized by comprising the following steps:

[0081] S1. Coating and forming phase change energy storage layer: Add hydroxyl-terminated polydimethylsiloxane and curing agent into n-hexane and stir to mix, then add silicon dioxide-coated n-hexadecane phase change microcapsules (recorded as nC 16 @SiO2), mixed to form a slurry, which was then sprayed onto an aluminum plate polished with sandpaper and cleaned with isopropyl alcohol, and cured at 100°C for 2 hours to form a phase change energy storage layer; in this embodiment, the mass volume ratio of hydroxyl-terminated polydimethylsiloxane, curing agent, silica-coated n-hexadecane phase change microcapsules and n-hexane was 3.5g:0.3g:1g:20mL;

[0082] Among them, nC 16 The synthesis method of @SiO2 includes the following steps:

[0083] 1) Emulsification: After heating a mixed solution of anhydrous ethanol and deionized water to 35° C. in a water bath, n-hexadecane, hexadecyltrimethylammonium bromide, and tetraethyl orthosilicate were added and stirred and dispersed at 2500 rpm in a high-speed disperser for 10 minutes to form an oil-in-water emulsion. In this embodiment, the volume ratio of anhydrous ethanol to deionized water is 1:2; the mass ratio of n-hexadecane, hexadecyltrimethylammonium bromide, and tetraethyl orthosilicate is 10:2:12; and the mass-to-volume ratio of n-hexadecane to the mixed solution is 10 g:280 mL.

[0084] 2) Polycondensation reaction: 2.5 mL of 25%-28% aqueous ammonia was added to the oil-in-water emulsion obtained in the emulsification step at 35°C for 24 hours for polycondensation reaction. The mixture was then filtered, washed with petroleum ether and anhydrous ethanol three times, and then washed with deionized water twice. The mixture was then freeze-dried for 24 hours to obtain a white powder product, namely nC 16 @SiO2; In this embodiment, the volume ratio of alkali to oil-in-water emulsion is 3:300.

[0085] S2, pasting copper foil and coating the electric heat storage layer: Paste copper foil electrodes on the two opposite edges of the phase change storage layer formed in step S1 and extend them to the outside of the phase change storage layer; add hydroxyl-terminated polydimethylsiloxane and curing agent into n-hexane and stir to mix, and then add silicon dioxide-copper double shell coated n-hexadecane phase change microcapsules (recorded as nC 16 @SiO 2- Cu) and graphite are mixed to form a slurry, and then the slurry is sprayed on the surface of the phase change energy storage layer to form an electric thermal energy storage layer; In this embodiment, the terminal hydroxyl polydimethylsiloxane, curing agent, nC 16 @SiO 2-The mass volume ratio of Cu, graphite and n-hexane is 2g:0.2g:0.5g:0.2g:15mL;

[0086] Among them, nC 16 @SiO 2- The synthesis method of Cu comprises the following steps:

[0087] 1) Sensitization: Add 12 mol / L hydrochloric acid to a 1% SnCl2 solution, stir at 300 rpm for 5 min, add the silica-coated n-hexadecane phase change microcapsules prepared in step S1, stir and react for 10 min, and then filter and wash three times to obtain sensitized phase change microcapsules; nC 16 @The mass volume ratio of SiO2, SnCl2 solution and hydrochloric acid is 5g:100mL:4mL;

[0088] 2) Activation: The sensitized phase change microcapsules were added to a 50 mg / L PdCl2 solution for activation reaction for 5 minutes. After filtration and washing, the activated phase change microcapsules were obtained. In this embodiment, the mass volume ratio of the sensitized phase change microcapsules to the PdCl2 solution was 1 g:50 mL.

[0089] 3) Chemical copper plating: The activated phase change microcapsules, copper sulfate pentahydrate, and EDTA were added to deionized water, and then sodium hypophosphite was added under stirring at a speed of 200 rpm to carry out chemical copper plating reaction for 60 minutes to obtain the nC 16 @SiO 2- In this embodiment, the mass volume ratio of copper sulfate pentahydrate, EDTA, activated phase change microcapsules, sodium hypophosphite and deionized water is 2g:1g:2g:3g:100mL.

[0090] S3. Coating to form a photothermal super-hydrophobic energy storage coating: Add hydroxyl-terminated polydimethylsiloxane and a curing agent to n-hexane and stir to mix, then add fluorinated silica-copper double-shell coated n-hexadecane phase change microcapsules, mix to form a slurry, and then spray the slurry on the surface of the electrothermal energy storage layer, and then cure it at 100°C for 6 hours to form a photothermal super-hydrophobic energy storage coating, that is, to obtain a phase change energy storage composite coating with both photothermal and electrothermal properties. In this embodiment, the particle size of graphite is 2μm-5μm. In this embodiment, the mass volume ratio of hydroxyl-terminated polydimethylsiloxane, curing agent, fluorinated silica-copper double-shell coated n-hexadecane phase change microcapsules and n-hexane is 1g:0.15g:0.8g:10mL;

[0091] Among them, the fluorinated nC 16 @SiO 2-The synthesis method of Cu is as follows: micro-etching the surface of the silicon dioxide-copper double-shell n-hexadecane phase change microcapsules with a micro-etching solution, dissolving tridecafluorooctyl triethoxysilane in anhydrous ethanol, then adding the micro-etched silicon dioxide-copper double-shell n-hexadecane phase change microcapsules, stirring and dispersing, then adding water, stirring and hydrolyzing for 2 hours, filtering and washing with ethanol, and then placing in a vacuum drying oven at 80°C for 4 hours; in this embodiment, tridecafluorooctyl triethoxysilane, ethanol, nC 16 @SiO 2- The mass volume ratio of Cu and deionized water is 4 mL:200 mL:4 g:0.5 mL.

[0092] In this embodiment, the micro-etching solution includes sulfuric acid, hydrogen peroxide, sodium silicate and deionized water, and the mass ratio of sulfuric acid, hydrogen peroxide, sodium silicate and water is 5.5g:2.5g:0.08g:150mL.

[0093] In this embodiment, the curing agent in steps S1, S2 and S3 is component B of Dow Corning 184.

[0094] Among them, the schematic diagram of the synthesis route of silica-coated n-hexadecane phase change microcapsules and silica-copper double shell-coated n-hexadecane phase change microcapsules is as follows: Figure 1 shown. Figure 1 In the formula, CATB stands for the emulsifier cetyltrimethylammonium bromide, and TEOS stands for tetraethyl orthosilicate.

[0095] Example 2

[0096] A method for preparing a phase-change energy storage composite coating having both photothermal and electrothermal properties, characterized by comprising the following steps:

[0097] S1. Coating and forming phase change energy storage layer: Add hydroxyl-terminated polydimethylsiloxane and curing agent into n-hexane and stir to mix, then add silicon dioxide-coated n-hexadecane phase change microcapsules (recorded as nC 16 @SiO2), mixed to form a slurry, which was then sprayed onto an aluminum plate polished with sandpaper and cleaned with isopropyl alcohol, and cured at 90°C for 2.5 hours to form a phase change energy storage layer; in this embodiment, the mass volume ratio of hydroxyl-terminated polydimethylsiloxane, curing agent, silica-coated n-hexadecane phase change microcapsules, and n-hexane was 3g:0.2g:0.5g:15mL;

[0098] Among them, nC 16 The synthesis method of @SiO2 includes the following steps:

[0099] 1) Emulsification: After heating a mixed solution of anhydrous ethanol and water to 30° C. in a water bath, n-hexadecane, hexadecyltrimethylammonium bromide, and tetraethyl orthosilicate were added and stirred and dispersed at 2000 rpm in a high-speed disperser for 15 minutes to form an oil-in-water emulsion. In this embodiment, the volume ratio of anhydrous ethanol to water is 1:1.5; the mass ratio of n-hexadecane, hexadecyltrimethylammonium bromide, and tetraethyl orthosilicate is 8:1:10; and the mass-to-volume ratio of n-hexadecane to the mixed solution is 8 g:250 mL.

[0100] 2) Polycondensation reaction: 2 mL of 25%-28% aqueous ammonia was added to the oil-in-water emulsion obtained in the emulsification step at 30°C for 26 hours for polycondensation reaction. The mixture was then filtered, washed twice with petroleum ether and anhydrous ethanol, and once with deionized water. The mixture was then freeze-dried for 22 hours to obtain a white powder product, namely nC 16 @SiO2; In this embodiment, the volume ratio of alkali to oil-in-water emulsion is 1:250.

[0101] S2, pasting copper foil and coating the electric heat storage layer: Paste copper foil electrodes on the two opposite edges of the phase change storage layer formed in step S1 and extend them to the outside of the phase change storage layer; add hydroxyl-terminated polydimethylsiloxane and curing agent into n-hexane and stir to mix, and then add silicon dioxide-copper double shell coated n-hexadecane phase change microcapsules (recorded as nC 16 @SiO 2- Cu) and graphite are mixed to form a slurry, and then the slurry is sprayed on the surface of the phase change energy storage layer to form an electric thermal energy storage layer; In this embodiment, the terminal hydroxyl polydimethylsiloxane, curing agent, nC 16 @SiO 2- The mass volume ratio of Cu, graphite and n-hexane is 1.5 g: 0.1 g: 0.3 g: 0.1 g: 10 mL;

[0102] Among them, nC 16 @SiO 2- The synthesis method of Cu comprises the following steps:

[0103] 1) Sensitization: 10 mol / L hydrochloric acid was added to a 0.5% SnCl2 solution, and the mixture was stirred at 250 rpm for 8 min. Then, the silica-coated n-hexadecane phase change microcapsules prepared in step S1 were added and stirred for 5 min. The mixture was then filtered and washed twice to obtain sensitized phase change microcapsules. The mass volume ratio of the silica-coated n-hexadecane phase change microcapsules, SnCl2 solution, and hydrochloric acid was 3 g:90 mL:3 mL.

[0104] 2) Activation: The sensitized phase change microcapsules were added to a 40 mg / L PdCl2 solution for activation reaction for 3 minutes. After filtration and washing, the activated phase change microcapsules were obtained. In this embodiment, the mass volume ratio of the sensitized phase change microcapsules to the PdCl2 solution was 0.5 g:40 mL.

[0105] 3) Chemical copper plating: The activated phase change microcapsules, copper sulfate pentahydrate, and EDTA were added to deionized water, and then sodium hypophosphite was added under stirring with a magnetic stirrer at a speed of 150 rpm to carry out chemical copper plating for 70 minutes to obtain the nC 16 @SiO 2- In this embodiment, the mass volume ratio of copper sulfate pentahydrate, EDTA, activated phase change microcapsules, sodium hypophosphite and deionized water is 1g:0.5g:1g:2g:90mL.

[0106] S3, coating to form a photothermal super-hydrophobic energy storage coating: add hydroxyl-terminated polydimethylsiloxane and a curing agent to n-hexane and stir to mix, then add fluorinated silica-copper double-shell coated n-hexadecane phase change microcapsules, mix to form a slurry, and then spray the slurry on the surface of the electrothermal energy storage layer, and then cure it at 90°C for 7h to form a photothermal super-hydrophobic energy storage coating, that is, to obtain a phase change energy storage composite coating with both photothermal and electrothermal properties. In this embodiment, the particle size of graphite is 2μm-5μm. In this embodiment, the mass volume ratio of hydroxyl-terminated polydimethylsiloxane, curing agent, fluorinated silica-copper double-shell coated n-hexadecane phase change microcapsules and n-hexane is 0.5g:0.1g:0.5g:5mL;

[0107] Among them, the fluorinated nC 16 @SiO 2- The synthesis method of Cu is as follows: micro-etching the surface of the silicon dioxide-copper double-shell n-hexadecane phase change microcapsules with a micro-etching solution, dissolving tridecafluorooctyl triethoxysilane in anhydrous ethanol, then adding the micro-etched silicon dioxide-copper double-shell n-hexadecane phase change microcapsules and stirring to disperse, then adding 0.5 mL of deionized water, stirring and hydrolyzing for 1.5 hours, filtering and washing with ethanol, and then placing in a vacuum drying oven at 75° C. for 5 hours; in this embodiment, tridecafluorooctyl triethoxysilane, ethanol, nC 16 @SiO 2- The mass volume ratio of Cu and deionized water is 3 mL:180 mL:3 g:0.3 mL.

[0108] In this embodiment, the micro-etching solution includes sulfuric acid, hydrogen peroxide, sodium silicate and deionized water, and the mass ratio of sulfuric acid, hydrogen peroxide, sodium silicate and water is 5g:2g:0.05g:100mL.

[0109] In this embodiment, the curing agent in steps S1, S2 and S3 is component B of Dow Corning 184.

[0110] Example 3

[0111] A method for preparing a phase-change energy storage composite coating having both photothermal and electrothermal properties, characterized by comprising the following steps:

[0112] S1. Coating and forming phase change energy storage layer: Add hydroxyl-terminated polydimethylsiloxane and curing agent into n-hexane and stir to mix, then add silicon dioxide-coated n-hexadecane phase change microcapsules (recorded as nC 16 @SiO2), mixed to form a slurry, which was then sprayed onto an aluminum plate polished with sandpaper and cleaned with isopropyl alcohol, and cured at 110°C for 1.5 hours to form a phase change energy storage layer; in this embodiment, the mass volume ratio of hydroxyl-terminated polydimethylsiloxane, curing agent, silica-coated n-hexadecane phase change microcapsules, and n-hexane was 4g:0.5g:1.5g:25mL;

[0113] Among them, nC 16 The synthesis method of @SiO2 includes the following steps:

[0114] 1) Emulsification: After heating a mixed solution of anhydrous ethanol and water to 40° C. in a water bath, n-hexadecane, hexadecyltrimethylammonium bromide, and tetraethyl orthosilicate were added and stirred and dispersed at 3000 rpm in a high-speed disperser for 5 minutes to form an oil-in-water emulsion. In this embodiment, the volume ratio of anhydrous ethanol to water is 1:3; the mass ratio of n-hexadecane, hexadecyltrimethylammonium bromide, and tetraethyl orthosilicate is 12:2.5:15; and the mass-to-volume ratio of n-hexadecane to the mixed solution is 12 g:300 mL.

[0115] 2) Polycondensation reaction: 3 mL of 25%-28% aqueous ammonia was added to the oil-in-water emulsion obtained in the emulsification step at 40°C for 26 hours for polycondensation reaction. The mixture was then filtered, washed with petroleum ether and anhydrous ethanol four times, and then washed with deionized water three times. The mixture was then freeze-dried for 26 hours to obtain a white powder product, namely nC 16 @SiO2; In this embodiment, the volume ratio of alkali to oil-in-water emulsion is 5:350.

[0116] S2, pasting copper foil and coating the electric heat storage layer: Paste copper foil electrodes on the two opposite edges of the phase change storage layer formed in step S1 and extend them to the outside of the phase change storage layer; add hydroxyl-terminated polydimethylsiloxane and curing agent into n-hexane and stir to mix, and then add silicon dioxide-copper double shell coated n-hexadecane phase change microcapsules (recorded as nC 16 @SiO 2-Cu) and graphite are mixed to form a slurry, and then the slurry is sprayed on the surface of the phase change energy storage layer to form an electric thermal energy storage layer; In this embodiment, the terminal hydroxyl polydimethylsiloxane, curing agent, nC 16 @SiO 2- The mass volume ratio of Cu, graphite and n-hexane is 2.5 g: 0.3 g: 0.8 g: 0.3 g: 20 mL;

[0117] Among them, nC 16 @SiO 2- The synthesis method of Cu comprises the following steps:

[0118] 1) Sensitization: Add 9 mol / L hydrochloric acid to a 1.5% SnCl2 solution, stir at 350 rpm for 3 min, add the silica-coated n-hexadecane phase change microcapsules prepared in step S1, stir and react for 15 min, and then filter and wash 4 times to obtain sensitized phase change microcapsules; nC 16 @The mass volume ratio of SiO2, SnCl2 solution and hydrochloric acid is 8g:110mL:5mL;

[0119] 2) Activation: The sensitized phase change microcapsules were added to a 60 mg / L PdCl2 solution for an activation reaction for 8 minutes. After filtration and washing, the activated phase change microcapsules were obtained. In this embodiment, the mass volume ratio of the sensitized phase change microcapsules to the PdCl2 solution was 1.5 g:60 mL.

[0120] 3) Chemical copper plating: The activated phase change microcapsules, copper sulfate pentahydrate, and EDTA were added to deionized water, and then sodium hypophosphite was added under stirring at a speed of 250 rpm to carry out chemical copper plating reaction for 50 minutes to obtain the nC 16 @SiO 2- In this embodiment, the mass volume ratio of copper sulfate pentahydrate, EDTA, activated phase change microcapsules, sodium hypophosphite and water is 3g:2g:3g:4g:110mL.

[0121] S3. Coating and forming a photothermal super-hydrophobic energy storage coating: Add hydroxyl-terminated polydimethylsiloxane and a curing agent to n-hexane and stir to mix, then add fluorinated silica-copper double-shell coated n-hexadecane phase change microcapsules, mix to form a slurry, and then spray the slurry on the surface of the electrothermal energy storage layer, and then cure it at 110°C for 5h to form a photothermal super-hydrophobic energy storage coating, that is, to obtain a phase change energy storage composite coating with both photothermal and electrothermal properties. In this embodiment, the particle size of graphite is 2μm-5μm. In this embodiment, the mass volume ratio of hydroxyl-terminated polydimethylsiloxane, curing agent, fluorinated silica-copper double-shell coated n-hexadecane phase change microcapsules and n-hexane is 1.5g:0.2g:1.2g:15mL;

[0122] Among them, the fluorinated nC 16 @SiO 2- The synthesis method of Cu is as follows: micro-etching the surface of the silicon dioxide-copper double-shell n-hexadecane phase change microcapsules with a micro-etching solution, dissolving tridecafluorooctyl triethoxysilane in anhydrous ethanol, then adding the micro-etched silicon dioxide-copper double-shell n-hexadecane phase change microcapsules, stirring and dispersing, then adding water, stirring and hydrolyzing for 2.5 hours, filtering and washing with ethanol, and then placing in a vacuum drying oven at 85°C for 3 hours; in this embodiment, tridecafluorooctyl triethoxysilane, ethanol, nC 16 @SiO 2- The mass volume ratio of Cu and deionized water is 5 mL:220 mL:5 g:0.8 mL.

[0123] In this embodiment, the micro-etching solution includes sulfuric acid, hydrogen peroxide, sodium silicate and deionized water, and the mass ratio of sulfuric acid, hydrogen peroxide, sodium silicate and water is 6g:3g:0.1g:200mL.

[0124] In this embodiment, the curing agent in steps S1, S2 and S3 is component B of Dow Corning 184.

[0125] Example 4

[0126] A method for preparing a phase-change energy storage composite coating having both photothermal and electrothermal properties, characterized by comprising the following steps:

[0127] S1. Coating and forming phase change energy storage layer: Add hydroxyl-terminated polydimethylsiloxane and curing agent into n-hexane and stir to mix, then add silicon dioxide-coated n-hexadecane phase change microcapsules (recorded as nC 16 @SiO2), mixed to form a slurry, which was then sprayed onto an aluminum plate polished with sandpaper and cleaned with isopropyl alcohol, and cured at 95°C for 2.2 hours to form a phase change energy storage layer; in this embodiment, the mass volume ratio of hydroxyl-terminated polydimethylsiloxane, curing agent, silica-coated n-hexadecane phase change microcapsules, and n-hexane was 3.3 g: 0.3 g: 0.8 g: 18 mL;

[0128] Among them, nC 16 The synthesis method of @SiO2 includes the following steps:

[0129] 1) Emulsification: After heating a mixed solution of anhydrous ethanol and water to 32° C. in a water bath, n-hexadecane, hexadecyltrimethylammonium bromide, and tetraethyl orthosilicate were added and stirred and dispersed at 2400 rpm in a high-speed disperser for 7 minutes to form an oil-in-water emulsion. In this embodiment, the volume ratio of anhydrous ethanol to deionized water is 1:1.8; the mass ratio of n-hexadecane, hexadecyltrimethylammonium bromide, and tetraethyl orthosilicate is 9:1.9:11; and the mass-to-volume ratio of n-hexadecane to the mixed solution is 9 g:260 mL.

[0130] 2) Polycondensation reaction: 2.2 mL of 25%-28% aqueous ammonia was added to the oil-in-water emulsion obtained in the emulsification step at 32°C for 23 hours for polycondensation reaction. The mixture was then filtered, washed with petroleum ether and anhydrous ethanol three times, and then washed with deionized water twice. The mixture was then freeze-dried for 23 hours to obtain a white powder product, namely nC 16 @SiO2; In this embodiment, the volume ratio of alkali to oil-in-water emulsion is 2:280.

[0131] S2, pasting copper foil and coating the electric heat storage layer: Paste copper foil electrodes on the two opposite edges of the phase change storage layer formed in step S1 and extend them to the outside of the phase change storage layer; add hydroxyl-terminated polydimethylsiloxane and curing agent into n-hexane and stir to mix, and then add silicon dioxide-copper double shell coated n-hexadecane phase change microcapsules (recorded as nC 16 @SiO 2- Cu) and graphite are mixed to form a slurry, and then the slurry is sprayed on the surface of the phase change energy storage layer to form an electric thermal energy storage layer; In this embodiment, the terminal hydroxyl polydimethylsiloxane, curing agent, nC 16 @SiO 2- The mass volume ratio of Cu, graphite and n-hexane is 1.7 g: 0.1 g: 0.4 g: 0.2 g: 13 mL;

[0132] Among them, nC 16 @SiO 2- The synthesis method of Cu comprises the following steps:

[0133] 1) Sensitization: 12 mol / L hydrochloric acid was added to a 0.8% SnCl2 solution, and the mixture was stirred at 280 rpm for 7 min. Then, the silica-coated n-hexadecane phase change microcapsules prepared in step S1 were added and stirred for 8 min. The mixture was then filtered and washed three times to obtain sensitized phase change microcapsules. 16 @The mass volume ratio of SiO2, SnCl2 solution and hydrochloric acid is 4g:95mL:4mL;

[0134] 2) Activation: The sensitized phase change microcapsules were added to a 45 mg / L PdCl2 solution for activation reaction for 4 minutes. After filtration and washing, the activated phase change microcapsules were obtained. In this embodiment, the mass volume ratio of the sensitized phase change microcapsules to the PdCl2 solution was 0.8 g:45 mL.

[0135] 3) Chemical copper plating: The activated phase change microcapsules, copper sulfate pentahydrate, and EDTA were added to deionized water, and then sodium hypophosphite was added under stirring at a speed of 180 rpm to carry out chemical copper plating reaction for 65 minutes to obtain the nC 16 @SiO 2- In this embodiment, the mass volume ratio of copper sulfate pentahydrate, EDTA, activated phase change microcapsules, sodium hypophosphite and water is 1.5g:0.8g:1.5g:3g:95mL.

[0136] S3, coating to form a photothermal super-hydrophobic energy storage coating: add hydroxyl-terminated polydimethylsiloxane and a curing agent to n-hexane and stir to mix, then add fluorinated silica-copper double-shell coated n-hexadecane phase change microcapsules, mix to form a slurry, and then spray the slurry on the surface of the electrothermal energy storage layer, and then cure it at 95°C for 6.5h to form a photothermal super-hydrophobic energy storage coating, that is, to obtain a phase change energy storage composite coating with both photothermal and electrothermal properties. In this embodiment, the particle size of graphite is 2μm-5μm. In this embodiment, the mass volume ratio of hydroxyl-terminated polydimethylsiloxane, curing agent, fluorinated silica-copper double-shell coated n-hexadecane phase change microcapsules and n-hexane is 0.8g:0.13g:0.7g:8mL;

[0137] Among them, the fluorinated nC 16 @SiO 2- The synthesis method of Cu is as follows: micro-etching the surface of the silicon dioxide-copper double-shell n-hexadecane phase change microcapsules with a micro-etching solution, dissolving tridecafluorooctyl triethoxysilane in anhydrous ethanol, then adding the micro-etched silicon dioxide-copper double-shell n-hexadecane phase change microcapsules, stirring and dispersing, then adding deionized water, stirring and hydrolyzing for 1.8 hours, filtering and washing with ethanol, and then placing in a vacuum drying oven at 78°C for 4.5 hours; in this embodiment, tridecafluorooctyl triethoxysilane, ethanol, nC 16 @SiO 2- The mass volume ratio of Cu and deionized water is 3.5 mL:190 mL:3.5 g:0.4 mL.

[0138] In this embodiment, the micro-etching solution includes sulfuric acid, hydrogen peroxide, sodium silicate and deionized water, and the mass ratio of sulfuric acid, hydrogen peroxide, sodium silicate and water is 5.3g:2.2g:0.06g:120mL.

[0139] In this embodiment, the curing agent in steps S1, S2 and S3 is component B of Dow Corning 184.

[0140] Example 5

[0141] A method for preparing a phase-change energy storage composite coating having both photothermal and electrothermal properties, characterized by comprising the following steps:

[0142] S1. Coating and forming phase change energy storage layer: Add hydroxyl-terminated polydimethylsiloxane and curing agent into n-hexane and stir to mix, then add silicon dioxide-coated n-hexadecane phase change microcapsules (recorded as nC 16 @SiO2), mixed to form a slurry, which was then sprayed onto an aluminum plate polished with sandpaper and cleaned with isopropyl alcohol, and cured at 105°C for 1.8 hours to form a phase change energy storage layer; in this embodiment, the mass volume ratio of hydroxyl-terminated polydimethylsiloxane, curing agent, silica-coated n-hexadecane phase change microcapsules, and n-hexane was 3.8g:0.4g:1.2g:22mL;

[0143] Among them, nC 16 The synthesis method of @SiO2 includes the following steps:

[0144] 1) Emulsification: After heating a mixed solution of anhydrous ethanol and deionized water to 38° C. in a water bath, n-hexadecane, hexadecyltrimethylammonium bromide, and tetraethyl orthosilicate were added and stirred and dispersed at 2800 rpm in a high-speed disperser for 12 minutes to form an oil-in-water emulsion. In this embodiment, the volume ratio of anhydrous ethanol to deionized water is 1:2.5; the mass ratio of n-hexadecane, hexadecyltrimethylammonium bromide, and tetraethyl orthosilicate is 11:2.2:14; and the mass-to-volume ratio of n-hexadecane to the mixed solution is 11 g:290 mL.

[0145] 2) Polycondensation reaction: 2.7 mL of 25%-28% aqueous ammonia was added to the oil-in-water emulsion obtained in the emulsification step at 38°C for 25 h of polycondensation reaction. The mixture was then filtered, washed twice with petroleum ether and anhydrous ethanol, and then washed twice with deionized water. The mixture was then freeze-dried for 25 h to obtain a white powder product, namely nC 16 @SiO2; In this embodiment, the volume ratio of alkali to oil-in-water emulsion is 4:320.

[0146] S2, pasting copper foil and coating the electric heat storage layer: Paste copper foil electrodes on the two opposite edges of the phase change storage layer formed in step S1 and extend them to the outside of the phase change storage layer; add hydroxyl-terminated polydimethylsiloxane and curing agent into n-hexane and stir to mix, and then add silicon dioxide-copper double shell coated n-hexadecane phase change microcapsules (recorded as nC 16 @SiO 2-Cu) and graphite are mixed to form a slurry, and then the slurry is sprayed on the surface of the phase change energy storage layer to form an electric thermal energy storage layer; In this embodiment, the terminal hydroxyl polydimethylsiloxane, curing agent, nC 16 @SiO 2- The mass volume ratio of Cu, graphite and n-hexane is 2.2 g: 0.2 g: 0.7 g: 0.3 g: 18 mL;

[0147] Among them, nC 16 @SiO 2- The synthesis method of Cu comprises the following steps:

[0148] 1) Sensitization: 12 mol / L hydrochloric acid was added to a 1.3% SnCl2 solution, stirred at 330 rpm for 4 min, and then the silica-coated n-hexadecane phase change microcapsules prepared in step S1 were added. The mixture was stirred for 12 min, and then filtered and washed three times to obtain sensitized phase change microcapsules. 16 @The mass volume ratio of SiO2, SnCl2 solution and hydrochloric acid is 7g:105mL:4mL;

[0149] 2) Activation: The sensitized phase change microcapsules were added to a 55 mg / L PdCl2 solution for activation reaction for 7 minutes. After filtration and washing, the activated phase change microcapsules were obtained. In this embodiment, the mass volume ratio of the sensitized phase change microcapsules to the PdCl2 solution was 1.2 g:55 mL.

[0150] 3) Chemical copper plating: The activated phase change microcapsules, copper sulfate pentahydrate, and EDTA were added to deionized water, and then sodium hypophosphite was added under stirring at a speed of 230 rpm to carry out chemical copper plating reaction for 55 minutes to obtain the nC 16 @SiO 2- In this embodiment, the mass volume ratio of copper sulfate pentahydrate, EDTA, activated phase change microcapsules, sodium hypophosphite and water is 2g:1.6g:2.5g:3.5g:105mL.

[0151] S3. Coating to form a photothermal super-hydrophobic energy storage coating: Add hydroxyl-terminated polydimethylsiloxane and a curing agent to n-hexane and stir to mix, then add fluorinated silica-copper double-shell coated n-hexadecane phase change microcapsules, mix to form a slurry, and then spray the slurry on the surface of the electrothermal energy storage layer, and then cure it at 105°C for 5.5h to form a photothermal super-hydrophobic energy storage coating, that is, to obtain a phase change energy storage composite coating with both photothermal and electrothermal properties. In this embodiment, the particle size of graphite is 4μm. In this embodiment, the mass volume ratio of hydroxyl-terminated polydimethylsiloxane, curing agent, fluorinated silica-copper double-shell coated n-hexadecane phase change microcapsules and n-hexane is 1.2g:0.18g:1.1g:13mL;

[0152] Among them, the fluorinated nC 16 @SiO 2- The synthesis method of Cu is as follows: micro-etching the surface of the silicon dioxide-copper double-shell n-hexadecane phase change microcapsules with a micro-etching solution, dissolving tridecafluorooctyl triethoxysilane in anhydrous ethanol, then adding the micro-etched silicon dioxide-copper double-shell n-hexadecane phase change microcapsules and stirring to disperse, then adding 0.5 mL of deionized water, stirring and hydrolyzing for 2.2 hours, filtering and washing with ethanol, and then placing in a vacuum drying oven at 83° C. for 3.5 hours; in this embodiment, tridecafluorooctyl triethoxysilane, ethanol, nC 16 @SiO 2- The mass volume ratio of Cu and deionized water is 4.5 mL:210 mL:4.5 g:0.7 mL.

[0153] In this embodiment, the micro-etching solution includes sulfuric acid, hydrogen peroxide, sodium silicate and water, and the mass ratio of sulfuric acid, hydrogen peroxide, sodium silicate and deionized water is 5.8g:2.7g:0.09g:180mL.

[0154] In this embodiment, the curing agent in steps S1, S2 and S3 is component B of Dow Corning 184.

[0155] Example 6

[0156] The application of a phase-change energy storage composite coating with both photothermal and electric heating, prepared by the method for preparing any one of the phase-change energy storage composite coatings with both photothermal and electric heating described in Examples 1 to 5, in all-weather anti-icing and de-icing. Applied to the surface of outdoor equipment, the photothermal or electric heating conversion properties of the phase-change energy storage composite coating with both photothermal and electric heating increase the surface temperature of the equipment, preventing icing. Furthermore, its hydrophobic properties prevent the adhesion of water and ice, extending the service life of the equipment. This coating is particularly effective in addressing surface icing in extreme weather conditions and ensuring that the coating maintains effective anti-icing and de-icing capabilities at night and on cloudy days.

[0157] Structural morphology characterization

[0158] (1) Morphological characterization by scanning electron microscopy

[0159] The silica-coated n-hexadecane phase change microcapsules and silica-copper double-shelled n-hexadecane phase change microcapsules prepared by the method for preparing a phase change energy storage composite coating with both photothermal and electrothermal properties in Example 1 were characterized by scanning electron microscopy (SEM). The SEM images of the silica-coated n-hexadecane phase change microcapsules are shown in FIG. Figure 2 As shown in the SEM image of the silicon dioxide-copper double shell coated hexadecane phase change microcapsules Figure 3 shown.

[0160] Depend on Figure 2 It can be seen that the silica-coated n-hexadecane phase change microcapsules are spherical in structure and have good coating uniformity. Figure 3 It can be seen that the silica-copper double-shell coated n-hexadecane phase change microcapsules are spherical structures, and the copper particles are evenly distributed on the surface of the microcapsules.

[0161] The phase-change energy storage composite coating with both photothermal and electrothermal properties prepared in Example 1 was characterized by scanning electron microscopy (SEM). The microstructure of the surface of the phase-change energy storage composite coating is as follows: Figure 4 shown.

[0162] Figure 4 From the SEM image of the phase change energy storage composite coating, it can be seen that its surface microstructure is a nano-level microstructure. Therefore, the phase change energy storage composite coating can significantly change the surface contact angle and water wetting behavior, thereby achieving superhydrophobic behavior.

[0163] (2) Structural characterization by infrared spectroscopy

[0164] The structures of SiO2, n-hexadecane and the silicon dioxide-coated n-hexadecane phase change microcapsules prepared in Example 1 were characterized by infrared spectroscopy. Figure 5 shown. Figure 5 In the figure, n-hexadecane@SiO2 refers to silica-coated n-hexadecane phase change microcapsules.

[0165] Depend on Figure 5 It can be seen from the infrared spectrum that the spectrum of the prepared silica-coated n-hexadecane phase change microcapsules contains all the absorption peaks of both SiO2 and the core material n-hexadecane, indicating that the core material n-hexadecane is successfully encapsulated by the shell SiO2 and the preparation process does not destroy the chemical properties of n-hexadecane.

[0166] (3) Structural characterization by X-ray powder diffraction

[0167] The SiO2, the silicon dioxide-coated n-hexadecane phase change microcapsules and the silicon dioxide-copper double-shell-coated n-hexadecane phase change microcapsules prepared in Example 1 were characterized by X-ray powder diffraction. Figure 6 shown. Figure 6 In the figure, n-hexadecane@SiO2 refers to n-hexadecane phase change microcapsules coated with silica, and n-hexadecane@SiO2@Cu refers to n-hexadecane phase change microcapsules coated with silica-copper double shells.

[0168] Depend on Figure 6 X-ray powder diffraction results show that diffraction peaks of n-hexadecane were observed in both the silica-coated n-hexadecane phase-change microcapsules and the silica-copper double-shelled n-hexadecane phase-change microcapsules, indicating that the crystalline structure of n-hexadecane was retained after the composite shell formation process. The X-ray powder diffraction pattern of the silica-coated n-hexadecane phase-change microcapsules exhibited a broad, low diffraction peak at 2θ = 22°, indicating that the silica shell had an amorphous structure. The X-ray powder diffraction pattern of the silica-copper double-shelled n-hexadecane phase-change microcapsules exhibited three peaks of elemental copper, indicating that the surface of the shell was successfully plated with copper.

[0169] (IV) Structural characterization by EDS spectrum analysis

[0170] The silicon dioxide-copper double-shell n-hexadecane phase change microcapsules prepared in Example 1 were subjected to EDS spectrum analysis to obtain elemental mapping spectra of O, Si and Cu, as shown in FIG. Figure 7 As shown. Figure 7 It can be seen that the silica-copper double-shell coated n-hexadecane phase change microcapsules prepared in Example 1 successfully completed the double-shell coating of the silica shell and the copper shell.

[0171] Performance Testing

[0172] (1) Vertical movement adhesion test of coating surface

[0173] The phase change energy storage composite coating with both photothermal and electrothermal properties prepared in Example 1 was subjected to a vertical motion adhesion test on the coating surface. Figure 8 shown.

[0174] Depend on Figure 8 It can be seen that the vertical manipulation behavior of water droplets on the phase-change energy storage composite coating with both photothermal and electrothermal properties prepared by the present invention can be successfully separated in the end, indicating that the adhesion between the water droplets and the surface of the phase-change energy storage composite coating is relatively small.

[0175] (2) Water drop elasticity test on coating surface

[0176] The phase change energy storage composite coating with both photothermal and electrothermal properties prepared in Example 1 was subjected to a water drop drop elasticity test on the coating surface. Figure 9 shown.

[0177] Depend on Figure 9 It can be seen that the low adhesion and excellent repellent properties of the surface of the phase-change energy storage composite coating with both photothermal and electrothermal properties prepared by the present invention enable a 10 μL water droplet to bounce continuously for more than 2 times from a height of 20 mm.

[0178] (3) Electrothermal cycle test of coating

[0179] The phase-change energy storage composite coating with both photothermal and electrothermal properties prepared in Example 1 was subjected to an electrothermal cycle test under the conditions of a DC power supply of 24 V and 0.2 A. Figure 10 shown.

[0180] Depend on Figure 10 It can be seen that the phase-change energy storage composite coating with both photothermal and electrothermal properties prepared by the present invention has high photothermal cycle stability.

[0181] (IV) Photothermal cycle test of coating

[0182] The phase-change energy storage composite coating with both photothermal and electrothermal properties prepared in Example 1 was heated to 100 mW / cm 2 The light-heat cycle test was carried out under the conditions of Figure 11 shown.

[0183] Depend on Figure 11 It can be seen that the phase-change energy storage composite coating with both photothermal and electrothermal properties prepared by the present invention has very high electrothermal cycle stability.

[0184] (V) Static icing delay test of coating at low temperature

[0185] The photothermal super-hydrophobic energy storage coating prepared in Example 1 and a phase-change energy storage composite coating with both photothermal and electrothermal properties were subjected to static freezing delay tests at -22 degrees Celsius. Figure 12 shown. Figure 12 In the embodiment, the “phase-change energy storage composite coating with both photothermal and electric heating properties” is a phase-change energy storage composite coating with both photothermal and electric heating properties obtained in Example 1.

[0186] Depend on Figure 12 It can be seen that the photothermal super-hydrophobic energy storage coating prepared in Example 1 delays freezing for 37 seconds at -22 degrees Celsius, while the phase-change energy storage composite coating with both photothermal and electric heating prepared in Example 1 delays freezing for 702 seconds at -22 degrees Celsius. Therefore, the phase-change energy storage composite coating with both photothermal and electric heating prepared in the present invention has a significant effect on delaying the freezing process of surface water droplets and can effectively delay freezing under extreme climate conditions.

[0187] (6) Photothermal deicing speed test of coating

[0188] The phase-change energy storage composite coating with both photothermal and electrothermal properties prepared in Example 1 was heated to 100 mW / cm 2 The light-heat deicing speed test is carried out under illumination, such as Figure 13 shown.

[0189] Depend on Figure 13 It can be seen that the phase change energy storage composite coating with both photothermal and electrothermal properties prepared by the present invention has a thermal conductivity of 100mW / cm 2 The ice droplets can melt quickly after 120 seconds under light.

[0190] (VII) Electric heating deicing speed test of coating

[0191] The phase change energy storage composite coating with both photothermal and electrothermal properties prepared in Example 1 was subjected to an electrothermal deicing speed test under a 24V, 0.02A DC power supply. Figure 14 shown.

[0192] Depend on Figure 14 It can be seen that the phase-change energy storage composite coating with both photothermal and electric heating prepared by the present invention can quickly melt ice droplets within 95 seconds under a DC power supply of 24V and 0.02A. Therefore, the phase-change energy storage composite coating with both photothermal and electric heating of the present invention has a high efficiency in deicing rate.

[0193] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. A method for preparing a phase-change energy storage composite coating with both photothermal and electrothermal properties, characterized in that: The following steps are involved: S1. Coating and forming a phase change energy storage layer: coating a slurry containing silicon dioxide-coated n-hexadecane phase change microcapsules on a substrate, and then curing and forming the phase change energy storage layer; S2. Copper foil pasting and coating an electric thermal energy storage layer: Copper foil electrodes are pasted on two opposite edges of the surface of the phase change energy storage layer formed in step S1 and extended to the outside of the phase change energy storage layer, and then a slurry containing silicon dioxide-copper double-shelled n-hexadecane phase change microcapsules and graphite is coated on the surface of the phase change energy storage layer to form an electric thermal energy storage layer; S3. Coating and forming a photothermal super-hydrophobic energy storage coating: coating the surface of the electrothermal energy storage layer formed in step S2 with a slurry containing fluorinated silica-copper double-shell-coated n-hexadecane phase change microcapsules, and then curing and forming the photothermal super-hydrophobic energy storage coating, thereby obtaining the phase change energy storage composite coating with both photothermal and electrothermal properties.

2. The method for preparing a phase-change energy storage composite coating with both photothermal and electrothermal properties according to claim 1, wherein: In step S1, a slurry containing silica-coated n-hexadecane phase change microcapsules is coated on an aluminum plate that has been polished with sandpaper and cleaned with isopropyl alcohol, and then cured to form a phase change energy storage layer. The synthesis method of the silica-coated n-hexadecane phase change microcapsules comprises the following steps: 1) Emulsification: After heating the mixture of anhydrous ethanol and water, n-hexadecane, hexadecyltrimethylammonium bromide and tetraethyl orthosilicate are added to disperse and form an oil-in-water emulsion; 2) Polycondensation reaction: adding alkali to the oil-in-water emulsion obtained in step 1) to carry out polycondensation reaction, and then filtering, washing and drying to obtain the silica-coated n-hexadecane phase change microcapsules.

3. The method for preparing a phase-change energy storage composite coating with both photothermal and electrothermal properties according to claim 2, wherein: In the emulsification step, the volume ratio of anhydrous ethanol to water is 1:(1.5-3); the mass ratio of n-hexadecane, hexadecyltrimethylammonium bromide, and tetraethyl orthosilicate is (8-12):(1-2.5):(10-15); the mass volume ratio of n-hexadecane to the mixture is (8-12) g:(250-300) mL; the heating is performed by heating to 30°C-40°C in a water bath; the dispersion is performed by stirring at a speed of 2000 rpm-3000 rpm in a high-speed disperser for 5 min-15 min; and / or In the polycondensation reaction step, ammonia water with a mass concentration of 25%-28% is added to the oil-in-water emulsion obtained in the emulsification step at 30°C-40°C, and the polycondensation reaction is carried out for 22h-26h. The product is then filtered, washed with petroleum ether and anhydrous ethanol 2-4 times, respectively, and then washed with deionized water 1-3 times. The product is then freeze-dried for 22h-26h to obtain a white powder product, which is the silica-coated n-hexadecane phase change microcapsule. The volume ratio of the base to the oil-in-water emulsion is (1-5): (250-350).

4. The method for preparing a phase-change energy storage composite coating with both photothermal and electrothermal properties according to claim 1, wherein: In step S2, the synthesis method of silicon dioxide-copper double-shell coated n-hexadecane phase change microcapsules comprises the following steps: 1) Sensitization: After adding hydrochloric acid to the SnCl2 solution and mixing, the silica-coated n-hexadecane phase change microcapsules prepared in step S1 are added to react to obtain sensitized phase change microcapsules; 2) Activation: The sensitized phase change microcapsules are added to a PdCl2 solution for activation reaction. After filtration and washing with deionized water, the activated phase change microcapsules are obtained. 3) Chemical copper plating: The activated phase change microcapsules, copper sulfate pentahydrate, and EDTA are added to water, and then sodium hypophosphite is added under stirring to carry out a chemical copper plating reaction, thereby preparing the silica-copper double-shell n-hexadecane-coated phase change microcapsules.

5. The method for preparing a phase-change energy storage composite coating with both photothermal and electrothermal properties according to claim 4, characterized in that: In the sensitization step, hydrochloric acid with a concentration of 9 mol / L-12 mol / L is added to a SnCl2 solution with a mass concentration of 0.5%-1.5%, and after stirring at 250 rpm-350 rpm for 3 min-8 min, the silica-coated n-hexadecane phase change microcapsules in step S1 are added, and the mixture is stirred for reaction for 5 min-15 min, and then filtered and washed 2-4 times to obtain sensitized phase change microcapsules; the mass volume ratio of the silica-coated n-hexadecane phase change microcapsules, SnCl2 solution and hydrochloric acid is (3-8) g: (90-110) mL: (3-5) mL; and / or In the activation step, the mass volume ratio of the sensitized phase change microcapsules to the PdCl2 solution is (0.5-1.5) g: (40-60) mL; the concentration of the PdCl2 solution is 40 mg / L-60 mg / L, and the activation reaction time is 3 min-8 min; and / or In the chemical copper plating step, the mass volume ratio of the copper sulfate pentahydrate, EDTA, activated phase change microcapsules, sodium hypophosphite and water is (1-3) g: (0.5-2) g: (1-3) g: (2-4) g: (90-110) mL; the stirring speed is 150 rpm-250 rpm; and the chemical copper plating reaction time is 50 min-70 min.

6. The method for preparing a phase-change energy storage composite coating with both photothermal and electrothermal properties according to claim 1, wherein: In step S3, the synthesis method of the fluorinated silica-copper double-shell n-hexadecane phase change microcapsules is as follows: micro-etching the surface of the silica-copper double-shell n-hexadecane phase change microcapsules with a micro-etching solution, dissolving tridecafluorooctyltriethoxysilane in anhydrous ethanol, then adding the micro-etched silica-copper double-shell n-hexadecane phase change microcapsules and stirring to disperse them, then adding water and stirring to hydrolyze the microcapsules for 1.5 hours to 2.5 hours, filtering and washing with ethanol, and then drying in a vacuum drying oven at 75° C. to 85° C. for 3 hours to 5 hours; and / or The mass volume ratio of the tridecafluorooctyltriethoxysilane, ethanol, silicon dioxide-copper double-shell coated n-hexadecane phase change microcapsules, and water is (3-5) mL: (180-220) mL: (3-5) g: (0.3-0.8) mL; and / or The micro-etching solution includes sulfuric acid, hydrogen peroxide, sodium silicate and water, and the mass volume ratio of the sulfuric acid, hydrogen peroxide, sodium silicate and water is (5-6) g: (2-3) g: (0.05-0.1) g: (100-200) mL.

7. The method for preparing a phase-change energy storage composite coating with both photothermal and electrothermal properties according to claim 1, wherein: In the step S1, coating and forming a phase change energy storage layer: adding hydroxyl-terminated polydimethylsiloxane and a curing agent to n-hexane and stirring and mixing, then adding silica-coated n-hexadecane phase change microcapsules, mixing to form the slurry, and then spraying the slurry and curing it at 90° C.-110° C. for 1.5 h-2.5 h to form the phase change energy storage layer; In the step S2, copper foil is applied and an electric thermal energy storage layer is coated: copper foil electrodes are applied to two opposite edges of the surface of the phase change energy storage layer formed in step S1 and extend to the outside of the phase change energy storage layer; hydroxy-terminated polydimethylsiloxane and a curing agent are added to n-hexane and stirred and mixed, and then silicon dioxide-copper double-shell coated n-hexadecane phase change microcapsules and graphite are added to form the slurry, and then the slurry is sprayed on the surface of the phase change energy storage layer to form the electric thermal energy storage layer; In the step S3, a photothermal super-hydrophobic energy storage coating is coated and formed: terminal hydroxyl polydimethylsiloxane and a curing agent are added to n-hexane and stirred and mixed, and then fluorinated silica-copper double-shell coated n-hexadecane phase change microcapsules are added and mixed to form the slurry, and then the slurry is sprayed on the surface of the electrothermal energy storage layer, and then cured at 90°C-110°C for 5h-7h to form the photothermal super-hydrophobic energy storage coating, thereby obtaining the phase change energy storage composite coating with both photothermal and electrothermal properties.

8. The method for preparing a phase-change energy storage composite coating with both photothermal and electrothermal properties according to claim 7, wherein: The curing agent in steps S1, S2 and S3 is component B of Dow Corning 184; In step S1, the mass volume ratio of the hydroxy-terminated polydimethylsiloxane, curing agent, silica-coated n-hexadecane phase change microcapsules and n-hexane is (3-4) g: (0.2-0.5) g: (0.5-1.5) g: (15-25) mL; In step S2, the mass volume ratio of the hydroxy-terminated polydimethylsiloxane, curing agent, silica-copper double-shell coated n-hexadecane phase change microcapsules, graphite and n-hexane is (1.5-2.5) g: (0.1-0.3) g: (0.3-0.8) g: (0.1-0.3) g: (10-20) mL; In step S3, the mass volume ratio of the hydroxy-terminated polydimethylsiloxane, the curing agent, the fluorinated silica-copper double-shell coated n-hexadecane phase change microcapsules, and n-hexane is (0.5-1.5) g: (0.1-0.2) g: (0.5-1.2) g: (5-15) mL; In the step S2, the particle size of the graphite is 1µm-5µm.

9. A phase-change energy storage composite coating with both photothermal and electrothermal properties, characterized in that: It is prepared by the preparation method of a phase-change energy storage composite coating with both photothermal and electrothermal properties as described in any one of claims 1 to 8.

10. Application of the phase-change energy storage composite coating with both photothermal and electrothermal properties obtained by the method for preparing the phase-change energy storage composite coating with both photothermal and electrothermal properties as described in any one of claims 1 to 8 in all-weather anti-icing and de-icing.

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