CN111073413B - Water-based electrothermal energy storage coating, preparation method and application - Google Patents
Water-based electrothermal energy storage coating, preparation method and application Download PDFInfo
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Abstract
The invention discloses a water-based electrothermal energy storage coating, a preparation method and application thereof, wherein the water-based electrothermal energy storage material comprises the following components in parts by weight: aqueous resin emulsion: 10-15 parts; auxiliary agent: 3-5 parts; conductive filler: 35-45 parts of a solvent; energy storage filler: 35-45 parts of an aqueous electrothermal energy storage coating with more excellent and stable performance can be obtained according to the disclosed formula and correspondingly set parameters in the preparation method. The water-based electric heating energy storage coating has the characteristics of heating and energy storage, and can be used for peak clipping and valley filling of a power grid.
Description
Technical Field
The invention belongs to the field of special coatings, and particularly provides a water-based electrothermal energy storage coating, a preparation method and application thereof.
Background
The water-based electrothermal energy storage coating is a water-based special coating, a formed coating has smaller impedance under the action of an external electric field, electric energy can be effectively converted into infrared radiation to be directly applied to a heated object, and the coating does not have light pollution and noise during working because a heating system does not comprise a motion component, so that the water-based electrothermal energy storage coating is a novel high-efficiency infrared radiation heating material.
The thickness of the electric heating coating is generally thin, although the electric heating coating is heated quickly, the electric heating coating mainly depends on infrared radiation as a main heating mode, and the heat capacities of the electric heating coating and a base material are limited, so that the electric heating coating loses heat quickly after power failure and basically has no energy storage capacity. Conventional electrocaloric coatings require a continuous supply of electricity in order to maintain the temperature of the heated environment.
The electrothermal paint disclosed in chinese patents CN102086330A and CN1068582A mostly uses oily polymer resin as a film forming material, and volatile organic compound as a paint solvent, inevitably generates small molecular VOCs during construction and use, is not suitable for indoor heating, and limits the application range of the paint.
In the electrothermal coating disclosed in Chinese patent CN106349876A and other patents, the conductive particles are metal particles, especially copper particles. The metal particles are used as good electric conductors, can obviously improve the electric heating performance of the coating, but have poor corrosion resistance and oxidation resistance, and the performance and the service life of the coating are greatly influenced by the service environment.
The water-based electric heating paint disclosed in Chinese patents CN101892008A, CN107236382A, CN108084823A and the like adopts a water-based resin system, so that the pollution in the paint construction and use process is reduced; carbon-based particles are mainly used as conductive particles, so that the service life of the coating is prolonged. But the particle size of the adopted carbon-based particles is generally lower, and the particle size is further reduced by the preparation process. In a coating formed by curing the coating, although the smaller particle size has better film-forming property, the conductivity is affected. In addition, the graphitized carbon particles are adopted in the patents, so that the cost can be reduced, but the emissivity is low at the use temperature, and the emissivity of a thermal band of 8-14 microns is only 0.7-0.8. As an electrothermal coating using infrared radiation as a main working mode, the graphitized carbon particles can obviously influence the electric-radiation conversion efficiency of the coating. Meanwhile, the temperature of the coating disclosed by the patent is rapidly reduced after power failure, the coating basically does not have energy storage capacity, the requirements of energy conservation and emission reduction of buildings are not met, the use cost is increased, and the practicability is low.
Disclosure of Invention
In view of the above, the present invention provides an aqueous electrothermal energy storage coating, a preparation method and an application thereof, so as to solve the problem that the existing aqueous electrothermal energy storage coating has no energy storage capability due to the limited heat capacities of the coating and a substrate, and the coating loses heat rapidly after power failure.
The invention provides a water-based electrothermal energy storage coating which comprises the following components in parts by weight: aqueous resin emulsion: 10-15 parts; auxiliary agent: 3-5 parts; conductive filler: 35-45 parts of a solvent; energy storage filler: 35-45 parts.
Preferably, the aqueous resin emulsion is one or more of aqueous acrylic emulsion, aqueous polyurethane emulsion and aqueous epoxy resin emulsion, and the solid content in the aqueous resin emulsion is 40-60%.
Further preferably, the auxiliary agent is one or more of a defoaming agent, a wetting agent and a film-forming auxiliary agent.
Further preferably, the auxiliary agent comprises the following components in percentage by weight: defoaming agent: 5-8 parts; wetting agent: 50-65 parts; film-forming auxiliary agent: 30-45 parts.
Preferably, the conductive filler is one or more of a multiwall carbon nanotube, superconducting carbon black and short carbon fiber, wherein the multiwall carbon nanotube is carbon nanotube black powder, the length-diameter ratio is 500-2000, the tube length is 5-10 μm, the superconducting carbon black is one or more of superconducting acetylene carbon black, superconducting furnace carbon black and superconducting pigment carbon black, the resistivity of the superconducting carbon black is 0.2-1.0 Ω · m, the average particle size is 10-25 nm, the short carbon fiber is non-glue polyacrylonitrile carbonized carbon fiber, the diameter of a monofilament fiber is 5-10 μm, the resistivity is 1.0-2.5 Ω · m, and the short length is 1.0-5.0 mm.
Further preferably, the conductive filler comprises, by weight: multi-walled carbon nanotubes: 1-5 parts; superconducting carbon black: 40-50 parts; short carbon fiber: 55-60 parts.
Further preferably, the energy storage filler is one or two of a microencapsulated phase change material and an adsorption type phase change material.
The invention also provides a preparation method of the water-based electrothermal energy storage coating, which comprises the following steps:
(1) mixing the aqueous resin emulsion and the auxiliary agent according to the weight ratio, and dispersing by adopting a stirring paddle, wherein the dispersing speed of the stirring paddle is 500-1000 r/min, and the stirring time is 5-10 min;
(2) adding a conductive filler into the dispersed emulsion in the step (1), stirring the mixture into paste, and adding zirconia balls with the weight being 1.5-5 times that of the dispersed emulsion and the particle size being 1-10 mm into the paste for ball milling dispersion, wherein the dispersion time is 5-8 hours;
(3) and (3) adding the energy storage filler into the slurry dispersed in the step (2), and dispersing by adopting a stirring paddle, wherein the dispersing speed of the stirring paddle is lower than 200-400 r/min, and the stirring time is 1-2 h.
The invention also provides an application of the water-based electrothermal energy storage coating, which comprises the following steps:
(1) selecting an insulating and drying plane or a surface with a certain curvature, calculating according to an input voltage of 24-36V and a surface power of 100-300W/m 2 to obtain a construction area of the water-based electric heating energy storage coating, and constructing a coating electrode according to a use area in a bonding mode;
(2) performing construction of the water-based electric heating energy storage coating between the electrodes laid in the step (1) by adopting a roll coating and silk screen printing mode;
(3) and after the coating is dried, testing the resistance of the coating between two electrodes, and electrifying and heating to check the electric heating performance until the electric heating performance of the coating meets the design requirement.
Preferably, step (1) is preceded by the step of pre-embedding a container containing a phase change material in an insulating, dry plane or surface having a curvature.
The invention provides a water-based electrothermal energy storage coating, which is a paste-like slurry with slight viscosity. On one hand, the stability of the coating can be ensured on the basis of ensuring the higher solid content of the filler of the coating, and on the other hand, the short carbon fibers and the carbon nanotube powder which are dispersed by ball milling can also play a certain role in tackifying in a coating system. The paste slurry is more suitable for the construction processes of roller coating, silk screen printing and the like, and the solvent water in the coating is completely from water-based emulsion. The coating formula diluted by water is adopted, and although the preparation process is simple, the storage property and the construction performance of the coating are obviously reduced. Therefore, on the basis of the water-based resin, a large amount of auxiliary agents of the coating are needed, cracking of the surface of the coating after construction is avoided, loss of the construction coating is reduced, and the construction performance of the coating is improved.
The conductive particles adopted by the invention are all carbon-based conductive particles with high emissivity and good stability. The particles and the length-diameter ratio are graded to form reasonable preparation from small carbon nanotubes to short carbon fibers, a good conduction path with short and long paths is formed in the coating, the surface resistance of the coating is effectively reduced, and the coating can have high surface power under low safe voltage.
Wherein, the carbon nano tube powder is a carbon nano tube product with low impurity content and low water content. Compared with the carbon nano tube dispersion liquid, the carbon nano tube powder has lower cost, does not contain organic solvent with high boiling point in the dispersion liquid, and does not contain a large amount of surfactant in the dispersion liquid. During production, the carbon nano tube powder can be effectively dispersed by a ball milling process to form the water-based electric heating energy storage coating with low volatilization amount and good film forming and binding force.
The length of the chopped carbon fibers in the final coating is also one of the important factors affecting the coating performance. When the length of the chopped fiber is longer, the conductive heating performance of the coating is better, but the preparation and application processes are limited. When the length of the chopped fiber is insufficient, the conductive heating performance of the coating is poor. During the ball milling and mixing process, the chopped carbon fibers are impacted by zirconia balls to reduce the length, and the surface of the fibers can also generate defects. It is therefore desirable to simultaneously control the chopped fiber feedstock length and the manufacturing process to adjust the fiber length distribution in the final coating. The surface defects of the fiber are beneficial to reducing the resistance of the coating. For the chopped carbon fiber raw material containing the rubber, the raw material needs to be preheated to 600 ℃ in a tube furnace filled with nitrogen and kept for 2 hours to remove the rubber on the surface of the fiber.
The surface emissivity has a great influence on the performance of the coating of the invention. The water-based electrothermal energy storage coating mainly heats the surrounding environment in the form of infrared radiation, and the infrared radiation energy of the coating is in direct proportion to the emissivity of the coating on the premise that the temperature of the coating is the same. The conductive particles disclosed by the invention can obviously improve the surface emissivity of the coating by preference.
The energy storage filler adopted by the invention is mainly based on two types of phase change materials of solid-liquid and solid-solid phase change within the working temperature range of the coating, and the phase change materials are processed by microencapsulation or adsorption means, and the energy storage filler brings an obvious energy storage function for the coating by a mixing means. A part of heat in the heating process of the coating is absorbed by the phase-change material, and besides the heat capacity of the phase-change material, when the temperature of the phase-change material is raised to be close to the phase-change temperature, the phase-change material can further absorb a large amount of heat with the phase-change enthalpy of 100-300 kJ/kg and undergoes phase change. After the coating is powered off, the phase-change material in the coating gradually releases the stored heat energy, so that the effects of peak clipping, valley filling, energy saving and emission reduction are achieved.
When the water-based electrothermal energy storage coating provided by the invention is applied indoors, the main working temperature is about 30-70 ℃, so that the phase change temperature of the selected phase change material is within the temperature range, and the coating has the maximum effect. Most phase change materials are dominated by solid-liquid phase changes over this temperature range. In order to avoid the energy storage filler from seeping out of the coating after phase change, the invention adopts microcapsules or adsorption means for fixation. After fixing, on the one hand, processing such as mixing can be carried out in a certain degree, and on the other hand, phase change material is prevented from seeping out.
The water-based electrothermal energy storage coating provided by the invention can effectively store the residual heat of the electrothermal coating, can continuously release heat for several hours after power failure, and can be used for peak clipping and valley filling of a power grid, energy conservation and emission reduction.
Drawings
The invention is described in further detail below with reference to the following figures and embodiments:
FIG. 1 is a temperature rise and temperature drop curve diagram of the aqueous electrothermal energy storage coating obtained in example 1.
Detailed Description
In order to solve the problems that the existing electrothermal coating possibly generates VOC pollution, has short service life of a coating and low electric-radiation conversion efficiency of the coating and cannot store energy in the construction and use processes, the invention provides a water-based electrothermal energy storage coating with heating and energy storage performances, which comprises the following components in percentage by weight: aqueous resin emulsion: 10-15 parts; auxiliary agent: 3-5 parts; conductive filler: 35-45 parts of a solvent; energy storage filler: 35-45 parts.
Preferably, the aqueous resin emulsion is one or more of aqueous acrylic emulsion, aqueous polyurethane emulsion and aqueous epoxy resin emulsion; the solid content of the aqueous resin emulsion is 40-60%, if the solid content is reduced, the dosage of the emulsion needs to be increased properly, preferably, the aqueous resin emulsion is acrylate high-molecular copolymer emulsion with the solid content of 35-55%, and a commercially available aqueous emulsion product can be adopted.
Preferably, the auxiliary agent is one or more of a defoaming agent, a wetting agent and a film-forming auxiliary agent, the defoaming agent can be an industrially common defoaming agent, preferably a nonionic aqueous emulsion defoaming agent, the wetting agent can be an industrially common wetting auxiliary agent with a surface activity effect, preferably a nonionic surfactant, and the film-forming auxiliary agent can be an industrially common film-forming auxiliary agent such as alcohol, ether, alcohol ether acetate, alcohol ester and the like, preferably an alcohol ester film-forming auxiliary agent.
Further preferably, the auxiliary agent comprises the following components in percentage by weight: defoaming agent: 5-8 parts; wetting agent: 50-65 parts; film-forming auxiliary agent: 30-45 parts.
Preferably, the conductive filler is one or more of multi-wall carbon nanotubes, superconducting carbon black and short carbon fibers; the multi-walled carbon nanotube is black carbon nanotube powder, the length-diameter ratio is 500-2000, the length of the multi-walled carbon nanotube is 5-10 mu m, and further preferably, the length of the multi-walled carbon nanotube is 8-10 mu m, and the pipe diameter is 8-10 nm; the superconducting carbon black is one or more of superconducting acetylene carbon black, superconducting furnace carbon black and superconducting pigment carbon black, the resistivity of the superconducting carbon black is 0.2-1.0 omega.m, the average particle size is 10-25 nm, and further the preferable superconducting carbon black is 0.5-0.8 omega.m and the average particle size is 15-18 nm; the chopped carbon fibers are non-adhesive polyacrylonitrile carbonized carbon fibers, the diameters of the single fibers are 5-10 mu m, the resistivity is 1.0-2.5 omega.m, the chopped length is 1.0-5.0 mm, and the chopped carbon fibers are further preferably non-adhesive polyacrylonitrile carbonized chopped carbon fibers with the diameters of the single fibers of 6-7 mu m, the resistivity is 1.2-1.6 omega.m, and the chopped length is 1.5-2.5 mm.
Further preferably, the conductive filler comprises, by weight: multi-walled carbon nanotubes: 1-5 parts; superconducting carbon black: 40-50 parts; short carbon fiber: 55-60 parts.
Preferably, the energy storage filler is one or two of a microencapsulated phase change material and an adsorption type phase change material, and further preferably, the phase change material is one or more of n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-eicosane, n-heneicosane, n-tricosane, paraffin, glycerol, lithium chloride ethoxide, polyethylene glycol 600, lactic acid, methyl palmitate, cyanamide, palmitic acid, glyceryl stearate, calcium chloride hexahydrate, sodium sulfate decahydrate, sodium carbonate decahydrate, ferric trichloride hexahydrate, ferric nitrate nonahydrate, magnesium sulfate heptahydrate, magnesium chloride tetrahydrate, a neopentyl glycol/pentaerythritol/trimethylolethane mixture, calcium chloride/sodium chloride/potassium chloride/water mixture. Preferably, the energy storage filler is one or more of n-eicosane, n-heneicosane, n-docosane, n-tricosane, paraffin, palmitic acid and glyceryl stearate, wherein the microencapsulated phase change material is a phase change material which is emulsified and then coated with the phase change material through an in-situ polymerization method or an interface polymerization method, and the mass ratio of a shell to a core is 5-30%, wherein the adsorption type phase change material is a phase change material which is melted and then adsorbed by porous materials such as diatomite, zeolite and expanded perlite, and the mass ratio of the phase change material is 30-80%, wherein the adsorption type phase change material can also be subjected to microencapsulation treatment, and further preferably, the energy storage filler is an adsorption type phase change material, and the mass ratio of the phase change material is 50-65%.
The invention also discloses a preparation method of the water-based electrothermal energy storage coating, which comprises the following steps:
(1) mixing the aqueous resin emulsion and the auxiliary agent according to the weight ratio, and dispersing by adopting a stirring paddle, wherein the dispersing speed of the stirring paddle is 500-1000 r/min, and the stirring time is 5-10 min;
(2) adding a conductive filler into the dispersed emulsion in the step (1), stirring the mixture into paste, and adding zirconia balls with the weight being 1.5-5 times that of the dispersed emulsion and the particle size being 1-10 mm into the paste for ball milling dispersion, wherein the dispersion time is 5-8 hours;
(3) and (3) adding the energy storage filler into the slurry dispersed in the step (2), and dispersing by adopting a stirring paddle, wherein the dispersing speed of the stirring paddle is lower than 200-400 r/min, and the stirring time is 1-2 h.
According to the preparation method provided by the invention, the water-based electrothermal energy storage coating with more excellent and more stable performance can be obtained according to the disclosed formula and the parameters set correspondingly, and the parameters are set and added to form a complete preparation system, and the water-based electrothermal energy storage coating with the most excellent and stable performance can be obtained by matching with the formula disclosed by the invention.
The invention also provides an application of the water-based electrothermal energy storage coating, which comprises the following steps:
(1) selecting an insulating and drying plane or a surface with a certain curvature, calculating according to an input voltage of 24-36V and a surface power of 100-300W/m 2 to obtain a construction area of the water-based electric heating energy storage coating, and constructing a coating electrode according to a use area in a bonding mode;
(2) performing construction of the water-based electric heating energy storage coating between the electrodes laid in the step (1) by adopting a roll coating and silk screen printing mode;
(3) and after the coating is dried, testing the resistance of the coating between two electrodes, and electrifying and heating to check the electric heating performance until the electric heating performance of the coating meets the design requirement.
After the electric heating performance of the coating meets the design requirement, the surface of the coating can be constructed by other decorative or functional coatings or workpieces, the decorative coatings or workpieces can be veneer coatings, facing materials and facing bricks, and the functional coatings or workpieces can be hydrophobic coatings, heat dissipation coatings, high-emissivity coatings, heat preservation coatings, phase change coatings, temperature measurement workpieces, heat flow density test workpieces, heat dissipation workpieces and heat preservation workpieces.
Before the step (1), an isolation layer can be constructed on an insulating and drying plane or a surface with a certain curvature in advance, and the step (1) is executed after the isolation layer is dried, wherein the isolation layer can be a functional coating with heat insulation and heat reflection.
Preferably, step (1) is preceded by the step of pre-embedding a container containing a phase change material in an insulating, dry plane or surface having a curvature. The phase change material can be one or more of n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-eicosane, n-heneicosane, n-docosane, n-tricosane, paraffin, glycerol, lithium chloride ethoxide, polyethylene glycol 600, lactic acid, methyl palmitate, cyanamide, palmitic acid, glyceryl stearate, calcium chloride hexahydrate, sodium sulfate decahydrate, sodium carbonate decahydrate, ferric chloride hexahydrate, ferric nitrate nonahydrate, magnesium sulfate heptahydrate, magnesium chloride tetrahydrate, a neopentyl glycol/pentaerythritol/trimethylolethane mixture, a calcium chloride/sodium chloride/potassium chloride/water mixture, a container packaged with the phase change material can be a metal or plastic sealed shell, and the thickness of the shell is preferably 0.1-1 mm.
The application mode is only one application mode of the water-based electric heating energy storage coating, and is not any limitation on other forms of the water-based electric heating energy storage coating.
The present invention will be further explained with reference to specific examples, but the present invention is not limited thereto.
Example 1
Adding 12.5 kg of acrylic emulsion (TRC-4369, 50 +/-1% of solid content) into a container, adding 0.2 kg of defoaming agent (Karano CN-103, Germany), 2.0 kg of wetting agent (PE 100, Kening, Germany) and 1.2 kg of film-forming aid dodecyl alcohol ester (Runtai chemical, Jiangsu), stirring at a stirring speed of 600r/min by using a paddle stirrer, and stirring and dispersing for 10 min; adding 1 kg of carbon nanotube powder (LG chemical, LUCAN CP1002M), 15 kg of superconducting carbon black (PRINTex L6, Germany), 22 kg of chopped carbon fiber (Haaining Anjie CC3-12, the chopped length is 5mm) again, stirring at 500r/min by using a paddle stirrer, and stirring and dispersing for 20 min; transferring the obtained paste into a ball milling tank, adding 85 kg of zirconia balls (the mass ratio of the zirconia balls with the diameters of 2mm, 3mm and 5mm is 1:2:2), ball milling for 6 hours, and filtering; 40.0 kg of diatomite is added into the obtained slurry to adsorb paraffin (the phase transition temperature of the paraffin is 55 ℃, the mass of the phase transition material accounts for 55 percent), the paddle type stirrer is used again, the stirring speed is 200r/min, and the stirring and the dispersion are carried out for 2 hours, so that the water-based electric heating energy storage coating is obtained.
Two pure copper electrodes are bonded on the surface of a gypsum board with the thickness of 18mm, the prepared coating is constructed in a rolling coating mode between the electrodes, the rolling coating is carried out for 2-4 times, the time interval is 2 hours, and the final wet film thickness is 4.5 mm. After 24h, the resistance between the two electrodes of the coating was tested to be stable. After the direct current 24V is used for supplying power, the heating power of the coating is 238W, and the water-based electric heating energy storage coating is obtained. The temperature rising and reducing curve of the water-based electrothermal energy storage coating is shown in figure 1 when the room temperature is 26 ℃.
As can be seen from FIG. 1, in the processes of temperature rise and temperature reduction, obvious phase change energy storage areas are observed, after the coating is powered off, the energy storage begins to be released, and the time of the coating cooled to 30 ℃ is extrapolated to be at least prolonged by 2 hours according to a temperature curve.
Example 2
13.0 kg of acrylic emulsion (SAE 1318VAE, USA, 48 +/-3% of solid content) was added to a vessel, 0.25 kg of defoamer (BYK-025, Germany), 2.5kg of wetting agent (Kaiyue KX-F325) and 1.0 kg of film-forming aid (Texanol) were added, and a paddle mixer was used with a mixing speed of 500r/min and a mixing dispersion time of 8min was employed. 1 kg of carbon nanotube powder (LG chemical, LUCAN BT1003M), 13 kg of superconducting carbon black (Dutch Aksu 600JD) and 22.5 kg of chopped carbon fibers (Shanghai long-standing and chopped length of 4mm) are added again, a paddle stirrer is used, the stirring speed is 500r/min, and the stirring and dispersion are carried out for 15 min. Transferring the obtained paste into a ball milling tank, adding 90 kg of zirconia balls (the mass ratio of the zirconia balls with the diameters of 2mm, 3mm and 5mm to 8mm is 1:2:2:0.5), carrying out ball milling for 8h, and filtering. 38.5 kilograms of diatomite is added into the obtained slurry to adsorb n-tricosane (the mass of the phase change material accounts for 60 percent), a paddle type stirrer is used again, the stirring speed is 200r/min, and the stirring and the dispersion are carried out for 1.5 hours, so that the water-based electric heating energy storage coating is obtained.
The method comprises the steps of firstly brushing a layer of heat-reflecting closed coating (Asia-Shi BE reflecting heat-insulating water-based coating) on the surface of a cement wall, bonding two pure aluminum electrodes after curing, and constructing the prepared coating in a rolling coating mode between the electrodes for 3-5 times at intervals of 2 hours, wherein the thickness of a final wet film is 5.0 mm. After 24h, the resistance between the two electrodes of the coating was tested to be stable. After the direct current 24V is used for supplying power, the heating power of the coating is 245W, and the water-based electric heating energy storage coating is obtained.
Example 3
12.0 kg of acrylic emulsion Jiangsu sunrise chemical TL-615D with 50 percent of solid content is added into a container, 0.2 kg of defoaming agent (Elite YX-502C), 2.8 kg of wetting agent (Dow chemical CF-10) and 1.2 kg of film-forming additive (Istmann Texanol) are added, a paddle type stirrer is used, the stirring speed is 500r/min, and the stirring and the dispersion are carried out for 5 min. And adding 1 kg of carbon nanotube powder (Shenzhen German square CNT-F), 12.5 kg of superconducting carbon black (American cabot BP2000) and 21.5 kg of chopped carbon fibers (Guangwei composite material, the chopped length is 5mm) again, stirring and dispersing for 10min at the stirring speed of 500r/min by using a paddle stirrer. Transferring the obtained paste into a ball milling tank, adding 90 kg of zirconia balls (the mass ratio of zirconia balls with the diameter of 3mm to 5mm to 8mm is 0.5:2:2), ball milling for 6h, and filtering. 40.0 kg of diatomite is added into the obtained slurry to adsorb a neopentyl glycol/pentaerythritol/trimethylolethane mixture (the mass ratio of the neopentyl glycol/pentaerythritol/trimethylolethane mixture is 1:0.5:0.8, the mass ratio of the phase change material is 50%), a paddle type stirrer is used again, the stirring speed is 200r/min, and the stirring and the dispersion are carried out for 2 hours, so that the water-based electrothermal energy storage coating is obtained.
On the surface of the cement wall, firstly, a plurality of deep grooves are arranged, copper pipes filled with sealing paraffin are filled in the grooves, and the filling amount of the paraffin is 2.5kg/m3And then brushing a layer of water-based sealing coating (Bombuke YBW1800A), bonding two pure copper electrodes after curing, constructing the prepared coating in a rolling coating mode between the electrodes for 1-3 times at intervals of 2 hours, and finally obtaining a wet film thickness of 3.0 mm. After 24h, the resistance between the two electrodes of the coating was tested to be stable. After the power supply of the alternating current 24V is used, the heating power of the coating is 205W, and the water-based electric heating energy storage coating is obtained.
The coatings obtained in examples 1 to 3 were subjected to performance tests, and the test results are shown in table 1.
Coating Performance index in the examples of Table 1
The aqueous electrothermal energy storage coatings obtained in examples 1 to 3 were tested under the following test conditions: the temperature is 20 ℃ at room temperature, the temperature is naturally reduced to 30 ℃ after the power is cut off when the temperature is heated to the same temperature (70 ℃) in the environment without strong convection, and the required time is shown in Table 2.
Table 2: coating energy storage performance test result
| Item | Examples 1 | EXAMPLES example 2 | EXAMPLE 3 |
| Time of temperature reduction | 2.0h | 2.5h | 4.5h |
In example 3, before the coating is applied, the pre-packaged phase change energy storage material is embedded in the construction plane, so that the cooling time is obviously prolonged on the basis of the first two examples.
Example 4
The difference from example 1 is that: the water-based electrothermal energy storage coating comprises the following components in percentage by weight: aqueous resin emulsion: 10 parts of (A); auxiliary agent: 3 parts of a mixture; conductive filler: 35 parts of (B); energy storage filler: 45 parts of aqueous resin emulsion, namely aqueous acrylic emulsion and aqueous polyurethane emulsion, wherein the solid content of the aqueous resin emulsion is 60%, and the auxiliary defoamer: 8 parts of a mixture; wetting agent: 50 parts of a mixture; film-forming auxiliary agent: 30 parts of conductive filler, which comprises the following components in parts by weight: multi-walled carbon nanotubes: 5 parts of a mixture; superconducting carbon black: 40 parts of a mixture; short carbon fiber: 60 parts of multi-wall carbon nano tubes, wherein the multi-wall carbon nano tubes are carbon nano tube black powder, the length-diameter ratio is 500-2000, the tube length is 5-10 mu m, the superconducting carbon black is carbon black produced by a superconducting carbon black superconducting electric furnace method, the resistivity of the superconducting carbon black is 0.5-0.8 omega.m, the average particle size is 15-18 nm, the short carbon fibers are non-adhesive polyacrylonitrile carbonized carbon fibers, the diameter of each monofilament fiber is 6-7 mu m, the resistivity is 1.2-1.6 omega.m, the short length is 1.5-2.5 mm, and the energy storage filler is a microencapsulated phase change material.
Example 5
The difference from example 1 is that: the water-based electrothermal energy storage coating comprises the following components in percentage by weight: aqueous resin emulsion: 15 parts of (1); auxiliary agent: 5 parts of a mixture; conductive filler: 45 parts of (1); energy storage filler: 35 parts of an aqueous resin emulsion, wherein the aqueous resin emulsion is one or more of an aqueous acrylic emulsion, an aqueous polyurethane emulsion and an aqueous epoxy resin emulsion, the solid content of the aqueous resin emulsion is 40%, and the auxiliary agent comprises an antifoaming agent: 5 parts of a mixture; wetting agent: 65 parts of (1); film-forming auxiliary agent: 45 parts of conductive filler, which comprises the following components in part by weight: multi-walled carbon nanotubes: 1 part; superconducting carbon black: 50 parts of a mixture; short carbon fiber: 55 parts, wherein the multi-wall carbon nanotube is carbon nanotube black powder, the length-diameter ratio is 500-2000, the length of the tube is 5-10 microns, the superconducting carbon black is one or more of superconducting acetylene carbon black, superconducting furnace carbon black and superconducting pigment carbon black, the resistivity of the superconducting carbon black is 0.2-1.0 omega.m, the average particle size is 10-25 nm, the short carbon fiber is non-adhesive polyacrylonitrile carbonized carbon fiber, the diameter of the monofilament fiber is 5-10 microns, the resistivity is 1.0-2.5 omega.m, the short length is 1.0-5.0 mm, and the energy storage filler is an adsorption type phase change material.
Tests prove that the performance of the water-based electric heating energy storage coating obtained in the embodiments 4 and 5 meets the requirements, and the time required for naturally cooling to 30 ℃ is more than 2 hours after the water-based electric heating energy storage coating is heated to the same temperature (70 ℃) and is powered off in the environment without strong convection at the room temperature of 20 ℃.
Claims (6)
1. The water-based electric heating energy storage coating is characterized by comprising the following raw materials in parts by weight: aqueous resin emulsion: 10-15 parts; auxiliary agent: 3-5 parts; conductive filler: 35-45 parts of a solvent; energy storage filler: 35-45 parts of conductive filler, wherein the conductive filler comprises the following components in parts by weight: multi-walled carbon nanotubes: 1-5 parts; superconducting carbon black: 40-50 parts; short carbon fiber: 55-60 parts of carbon nanotube black powder, a length-diameter ratio of 500-2000, a tube length of 5-10 microns, superconducting carbon black of one or more of superconducting acetylene carbon black, superconducting furnace carbon black and superconducting pigment carbon black, a resistivity of the superconducting carbon black of 0.2-1.0 omega-m and an average particle size of 10-25 nm, wherein the short-cut carbon fiber is non-adhesive polyacrylonitrile carbonized carbon fiber, a diameter of the monofilament fiber of 5-10 microns, a resistivity of 1.0-2.5 omega-m and a short-cut length of 1.0-5.0 mm, the energy storage filler is one or two of microencapsulated phase change material and adsorption type phase change material, and the phase change material is n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-eicosane, n-heneicosane, n-docosane, n-tricosane, glycerol, ethanol lithium chloride, polyethylene glycol 600, lactic acid, methyl palmitate, cyanamide, palmitic acid, glyceryl stearate, calcium chloride hexahydrate, sodium sulfate decahydrate, sodium carbonate decahydrate, ferric trichloride hexahydrate, ferric nitrate nonahydrate, magnesium sulfate heptahydrate, magnesium chloride tetrahydrate, a neopentyl glycol/pentaerythritol/trimethylolethane mixture and one or more of calcium chloride/sodium chloride/potassium chloride/water mixture, wherein the microencapsulated phase change material is a phase change material which is emulsified and then coated by an in-situ polymerization method or an interface polymerization method, the mass ratio of a shell to a core is 5-30%, the adsorption type phase change material is a phase change material which is melted and then adsorbed by porous materials such as diatomite, zeolite and expanded perlite, the mass ratio of the phase change material is 30-80%, and the preparation method of the aqueous electrothermal energy storage coating, the method comprises the following steps:
(1) mixing the aqueous resin emulsion and the auxiliary agent according to the weight ratio, and dispersing by adopting a stirring paddle, wherein the dispersing speed of the stirring paddle is 500-1000 r/min, and the stirring time is 5-10 min;
(2) adding a conductive filler into the dispersed emulsion in the step (1), stirring the mixture into paste, and adding zirconia balls with the weight being 1.5-5 times that of the dispersed emulsion and the particle size being 1-10 mm into the paste for ball milling dispersion, wherein the dispersion time is 5-8 hours;
(3) and (3) adding the energy storage filler into the slurry dispersed in the step (2), and dispersing by adopting a stirring paddle, wherein the dispersing speed of the stirring paddle is lower than 200-400 r/min, and the stirring time is 1-2 h.
2. The aqueous electrothermal energy storage coating of claim 1, wherein: the water-based resin emulsion is one or more of water-based acrylic emulsion, water-based polyurethane emulsion and water-based epoxy resin emulsion, and the solid content in the water-based resin emulsion is 40-60%.
3. The aqueous electrothermal energy storage coating of claim 1, wherein: the auxiliary agent is one or more of a defoaming agent, a wetting agent and a film-forming auxiliary agent.
4. An aqueous electrothermal energy storage coating according to claim 3, wherein: the auxiliary agent comprises the following components in parts by weight: defoaming agent: 5-8 parts; wetting agent: 50-65 parts; film-forming auxiliary agent: 30-45 parts.
5. Use of an aqueous electrothermal energy storage coating according to any one of claims 1 to 4, comprising the steps of:
(1) selecting an insulating and drying plane or a surface with a certain curvature, and controlling the surface power to be 100-300W/m according to the input voltage of 24-36V2Calculating and obtaining the construction area of the water-based electric heating energy storage coating, and constructing a coating electrode according to the use area in a bonding mode;
(2) performing construction of the water-based electric heating energy storage coating between the electrodes laid in the step (1) by adopting a roll coating and silk screen printing mode;
(3) and after the coating is dried, testing the resistance of the coating between two electrodes, and electrifying and heating to check the electric heating performance until the electric heating performance of the coating meets the design requirement.
6. The application of the water-based electrothermal energy storage coating according to claim 5, wherein: the method also comprises the step of embedding a container filled with the phase change material in an insulating and drying plane or a surface with a certain curvature in advance before the step (1).
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