Preparation method of phase change energy storage gypsum board

Abstract

A preparation method of a phase change energy storage gypsum board, comprising: mixing and reacting three-dimensional porous graphene with a phenylalanine aqueous solution to obtain modified porous graphene powder; mixing and impregnating with a phase change material to obtain graphene powder with the phase change material impregnated in the pores; and mixing with an epoxy resin solution, ultrasonic spraying on the surface of a gypsum board substrate to form a film, to obtain the phase change energy storage gypsum board.In the method, porous graphene with high heat conduction function is mixed with a resin solution to form a film by ultrasonic spraying, and the porous graphene is modified with phenylalanine first, a large number of lipophilic groups are generated in the graphene pore channel through the interaction of pi-pi, and when mixed with the phase change material, especially paraffin, the phase change material can be firmly adsorbed in the graphene pore channel and is not easy to seep out, and heat can be rapidly transmitted from the decorative film layer to the phase change gypsum board inside.

Description

Technical Field

[0001] This invention relates to a method for preparing phase change energy storage gypsum board, and more particularly to a gypsum board with a decorative film having energy storage and heat conduction functions sprayed on its surface, using a phase change energy storage gypsum board mixed with phase change microcapsules as a substrate. Background Technology

[0002] Phase change materials (PCMs) are substances that change their state of matter and provide latent heat while maintaining a constant temperature. PCMs can be classified into organic and inorganic PCMs, and further divided into hydrated salt PCMs and waxy PCMs. PCMs possess heat storage capabilities, undergoing a phase change in response to changes in ambient temperature. During this phase change, they absorb or release heat, exhibiting advantages such as high heat storage density, large heat storage capacity, and strong chemical stability. Combining PCMs with building material matrices creates PCM energy storage building materials. These materials are thermally functional composite materials capable of storing energy in the form of latent heat of phase change, enabling energy conversion between different locations in time and space.

[0003] There are three main methods for combining phase change materials (PCMs) with building material matrices: First, the immersion method, which involves soaking PCMs into a porous building material matrix, such as gypsum wallboard or cement concrete test blocks. This method is simple to implement, has low production costs, and can be used to prepare PCM energy storage building materials according to actual needs. Second, the phase change microsphere method, which uses microencapsulation or nanocomposite technology to encapsulate PCMs into microspheres, which are then incorporated into the building material matrix to prepare PCM energy storage building materials. Third, the direct mixing method, which involves directly mixing PCMs with the building material matrix, such as by absorbing PCMs into semi-fluid silica powder and then incorporating it into the building material matrix.

[0004] Phase change energy storage gypsum board is mainly used for interior wall cladding. It can greatly increase the heat storage capacity of the building envelope, reduce the amplitude and delay the heat flow fluctuations between the interior and exterior of the building, thereby improving the building's temperature self-regulation capability and improving the indoor environment, achieving the goals of energy saving and comfort. However, after cladding the interior walls with phase change energy storage gypsum board, wall panels or paint layers still need to be installed for decoration. This inevitably creates an insulation layer between the phase change energy storage gypsum board and the indoor air, reducing the efficiency of heat storage and release of the phase change energy storage gypsum board and failing to achieve the desired effect. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a phase change energy storage gypsum board. The phase change energy storage gypsum board, prepared by mixing phase change microcapsules with gypsum powder, serves as the substrate. A decorative film with thermal conductivity and energy storage functions is added to the surface, which can be directly applied to the cladding of interior walls, improving energy storage efficiency and achieving good results.

[0006] To achieve the above-mentioned technical objectives, the technical solution of the present invention is as follows:

[0007] A method for preparing phase change energy storage gypsum board, comprising:

[0008] (1) The three-dimensional porous graphene was washed, placed in an aqueous solution of phenylalanine for reaction, filtered and dried to obtain modified porous graphene powder.

[0009] (2) The three-dimensional porous graphene powder obtained in step (1) is mixed and impregnated with phase change material. After filtration and washing, graphene powder with phase change material impregnated in the pores is obtained.

[0010] (3) After the three-dimensional porous graphene powder with phase change material impregnated in the pores obtained in step (2) is mixed evenly with epoxy resin solution, a thin film is formed on the surface of the gypsum board substrate by ultrasonic spraying to obtain the phase change energy storage gypsum board.

[0011] Furthermore, the three-dimensional porous graphene described in step (1) has an average pore size range of 50-100 nm and a specific surface area of ​​700-1000 m². 2 / g, with a particle size of 10-20μm and a thermal conductivity of 4500-5000W / (m·K).

[0012] Furthermore, the washing in step (1) is performed using deionized water, 3-5 times, at a temperature of 30-40°C.

[0013] Furthermore, the phenylalanine in the aqueous solution of phenylalanine in step (1) is 10-20% by weight, the reaction temperature in step (1) is 30-60℃, preferably 30-40℃, and the reaction time is 6-10 hours.

[0014] Furthermore, the drying temperature in step (1) is 40-60℃ and the drying time is 6-8 hours.

[0015] Furthermore, the phase change material mentioned in step (2) is phase change paraffin, with a phase change temperature of 23-28℃ and an enthalpy of 150-170J / g.

[0016] Furthermore, the amount of phase change material used in step (2) is such that it can at least completely immerse the three-dimensional porous graphene powder.

[0017] Furthermore, the immersion temperature in step (2) is 50-80℃, and the immersion time is 2-4 hours.

[0018] Furthermore, after the impregnation in step (2) is completed, rinse with anhydrous ethanol at a temperature of 30-40℃ 1-3 times.

[0019] Furthermore, the epoxy resin in step (3) is bisphenol F type epoxy resin, accounting for 50-70% of the weight percentage of the solution.

[0020] Furthermore, the epoxy resin solution in step (3) also includes a curing agent, an organic solvent, and a colorant. The curing agent is a cycloaliphatic amine curing agent, especially type 9035 and type 2215 curing agents, accounting for 10-30% of the mass percentage of the resin mixture. The organic solvent is acetone or dimethylformamide, accounting for 10-18% of the mass percentage of the resin mixture. The colorant is a commonly used colorant for paints or coatings, accounting for 1-2% of the mass percentage of the resin mixture.

[0021] Furthermore, in step (3), the graphene powder and epoxy resin solution are thoroughly mixed for 10-20 minutes, with a weight ratio of 1:3-1:10.

[0022] Furthermore, the temperature of ultrasonic spraying in step (3) is 40-50℃.

[0023] Furthermore, the substrate is preferably a gypsum board doped with phase change microcapsules.

[0024] Furthermore, after the coating is applied to form a thin film, a drying step is also included, with a temperature of 30-40℃ and a drying time of 12-24 hours.

[0025] Furthermore, in step (3), the enthalpy of the mixed solution formed by graphene powder and epoxy resin solution is 10-20 J / g, the thermal conductivity is 30-60 W / (m·K), and the viscosity is 5-20 mPa·s.

[0026] Compared with the prior art, the present invention has the following advantages:

[0027] (1) In the method of the present invention, porous graphene with high thermal conductivity is mixed with resin solution and ultrasonically sprayed to form a film. Phenylalanine is first used to modify the porous graphene. Through the interaction of π-π bonds, a large number of oleophilic groups are generated inside the graphene channels. When mixed with phase change material, the phase change material, especially paraffin, can be firmly adsorbed inside the graphene channels and is not easy to seep out. It can also quickly transfer heat to the interior of the phase change gypsum substrate through the decorative film layer.

[0028] (2) In the method of the present invention, a thin film is ultrasonically sprayed on the gypsum substrate to form a decorative film with heat conduction and energy storage functions on the surface of the substrate. The gypsum substrate is further adopted as a phase change energy storage gypsum board. The gypsum decorative board has high thermal conductivity and high enthalpy value, and can be directly applied to the decoration and maintenance of indoor walls. It has good heat preservation and temperature control effects, improves energy storage and energy saving efficiency, and reduces decoration and maintenance costs.

[0029] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0030] The following non-limiting embodiments are intended to enable those skilled in the art to more fully understand the invention, but do not limit the invention in any way.

[0031] Unless otherwise specified, all percentages (%) in the following examples and comparative examples refer to mass percentages. The core material, paraffin wax, was provided by the Dalian Petrochemical Research Institute, with a phase transition temperature of 25°C and a phase transition enthalpy of 165 KJ / kg.

[0032] Example 1

[0033] Preparation of phase change energy storage gypsum board:

[0034] (1) Weigh out three-dimensional porous graphene (average pore size of 90 nm, specific surface area of ​​930 m²). 2 100g of powder (particle size 14μm, thermal conductivity 4800W / (m·K)) was washed three times with deionized water at 30℃, reacted in a 15% phenylalanine solution for 8 hours at 30℃, and then dried at 50℃ for 6 hours.

[0035] (2) Weigh 200g of phase change paraffin, heat it to 60℃, and soak it with the graphene powder obtained in step (1) for 2 hours. After filtration, rinse it three times with anhydrous ethanol at 30℃ to obtain graphene powder with paraffin phase change material impregnated in the pores.

[0036] (3) Prepare 400g of epoxy resin mixture solution, wherein bisphenol F type epoxy resin accounts for 70%, curing agent 9035 accounts for 18%, acetone accounts for 11%, and colorant accounts for 1%. Mix the material obtained in step (2) with the epoxy resin mixture solution for 20 minutes to obtain resin-graphene mixture solution. Spray the resin-graphene mixture solution onto the phase change energy storage gypsum substrate with an ultrasonic spraying device to form a film. The spraying temperature is 40℃, the drying temperature is 40℃, and the drying time is 12 hours to obtain phase change energy storage gypsum board.

[0037] Example 2

[0038] Preparation of phase change energy storage gypsum board:

[0039] (1) Weigh out three-dimensional porous graphene (average pore size of 90 nm, specific surface area of ​​930 m²). 2 100g of powder (particle size 14μm, thermal conductivity 4800W / (m·K)) was washed three times with deionized water at 30℃, reacted in an 18% phenylalanine solution for 8 hours at 35℃, and then dried at 50℃ for 8 hours.

[0040] (2) Weigh 200g of phase change paraffin, heat it to 65℃, and soak it with the graphene powder obtained in step (1) for 3 hours. After filtration, rinse it three times with anhydrous ethanol at 30℃ to obtain graphene powder with paraffin phase change material impregnated in the pores.

[0041] (3) Prepare 400g of epoxy resin mixture solution, wherein bisphenol F type epoxy resin accounts for 65%, curing agent 9035 accounts for 22%, acetone accounts for 12%, and colorant accounts for 1%. Mix the material obtained in step (2) with the epoxy resin mixture solution for 20 minutes to obtain resin-graphene mixture solution. Spray the resin-graphene mixture solution onto the phase change energy storage gypsum substrate with ultrasonic spraying equipment to form a film. The spraying temperature is 40℃, the drying temperature is 40℃, and the drying time is 12 hours to obtain phase change energy storage gypsum board.

[0042] Example 3

[0043] Preparation of phase change energy storage gypsum decorative board:

[0044] (1) Take three-dimensional porous graphene (average pore size of 90 nm, specific surface area of ​​930 m²) 2 100g of powder (particle size 14μm, thermal conductivity 4800W / (m·K)) was washed three times with deionized water at 30℃, reacted in a 20% phenylalanine solution for 8 hours at 30℃, and then dried at 50℃ for 6 hours.

[0045] (2) Weigh 200g of phase change paraffin, heat it to 60℃, and soak it with the graphene powder obtained in step (1) for 3 hours. After filtration, rinse it three times with anhydrous ethanol at 30℃ to obtain graphene powder with paraffin phase change material impregnated in the pores.

[0046] (3) Prepare 400g of epoxy resin mixture solution, wherein bisphenol F type epoxy resin accounts for 68%, curing agent 9035 accounts for 18%, acetone accounts for 13%, and colorant accounts for 1%. Mix the material obtained in step (2) with the epoxy resin mixture solution for 20 minutes to obtain resin-graphene mixture solution. Spray the resin-graphene mixture solution onto the phase change energy storage gypsum substrate with ultrasonic spraying equipment to form a film. The spraying temperature is 40℃, the drying temperature is 40℃, and the drying time is 12 hours to obtain phase change energy storage gypsum board.

[0047] Example 4

[0048] Preparation of phase change energy storage gypsum board:

[0049] (1) Weigh out three-dimensional porous graphene (average pore size of 90 nm, specific surface area of ​​930 m²). 2100g of powder (particle size 14μm, thermal conductivity 4800W / (m·K)) was washed three times with deionized water at 30℃, reacted in a 20% phenylalanine solution for 8 hours at 40℃, and then dried at 50℃ for 6 hours.

[0050] (2) Weigh 200g of phase change paraffin, heat it to 60℃, and soak it with the graphene powder obtained in step (1) for 4 hours. After filtration, rinse it three times with anhydrous ethanol at 30℃ to obtain graphene powder with paraffin phase change material impregnated in the pores.

[0051] (3) Prepare 400g of epoxy resin mixture solution, wherein bisphenol F type epoxy resin accounts for 65%, curing agent 9035 accounts for 20%, acetone accounts for 14%, and colorant accounts for 1%. Mix the material obtained in step (2) with the epoxy resin mixture solution for 20 minutes to obtain resin-graphene mixture solution. Spray the resin-graphene mixture solution onto the phase change energy storage gypsum substrate with ultrasonic spraying equipment to form a film. The spraying temperature is 40℃, the drying temperature is 40℃, and the drying time is 12 hours to obtain phase change energy storage gypsum board.

[0052] Example 5

[0053] Preparation of phase change energy storage gypsum board:

[0054] (1) Weigh out three-dimensional porous graphene (average pore size of 90 nm, specific surface area of ​​930 m²). 2 100g of powder (particle size 14μm, thermal conductivity 4800W / (m·K)) was washed three times with deionized water at 30℃, reacted in a 17% phenylalanine solution for 8 hours at 30℃, and then dried at 50℃ for 6 hours.

[0055] (2) Weigh 200g of phase change paraffin, heat it to 60℃, and soak it with the graphene powder obtained in step (1) for 2 hours. After filtration, rinse it three times with anhydrous ethanol at 30℃ to obtain graphene powder with paraffin phase change material impregnated in the pores.

[0056] (3) Prepare 400g of epoxy resin mixture solution, wherein bisphenol F type epoxy resin accounts for 70%, curing agent 9035 accounts for 19%, acetone accounts for 10%, and colorant accounts for 1%. Mix the material obtained in step (2) with the epoxy resin mixture solution for 20 minutes to obtain resin-graphene mixture solution. Spray the resin-graphene mixture solution onto the phase change energy storage gypsum substrate to form a film using an ultrasonic spraying device. The spraying temperature is 40℃, the drying temperature is 40℃, and the drying time is 12 hours to obtain phase change energy storage gypsum decorative board.

[0057] Example 6

[0058] Preparation of phase change energy storage gypsum decorative board:

[0059] (1) Weigh out three-dimensional porous graphene (average pore size of 90 nm, specific surface area of ​​930 m²). 2 100g of powder (particle size 14μm, thermal conductivity 4800W / (m·K)) was washed three times with deionized water at 30℃, reacted in a 15% phenylalanine solution for 8 hours at 30℃, and then dried at 50℃ for 8 hours.

[0060] (2) Weigh 200g of phase change paraffin, heat it to 60℃, and soak it with the graphene powder obtained in step (1) for 3 hours. After filtration, rinse it three times with anhydrous ethanol at 30℃ to obtain graphene powder with paraffin phase change material impregnated in the pores.

[0061] (3) Prepare 400g of epoxy resin mixture, in which bisphenol F epoxy resin accounts for 60%, curing agent 9035 accounts for 25%, acetone accounts for 14%, and colorant accounts for 1%; d. Mix the graphene obtained in step b with the epoxy resin mixture for 20 minutes to obtain a resin-graphene mixture. Spray the resin-graphene mixture onto the phase change energy storage gypsum board using an ultrasonic spraying device to form a film. The spraying temperature is 40℃, the drying temperature is 40℃, and the drying time is 12 hours to obtain a phase change energy storage gypsum board.

[0062] Comparative Example 1

[0063] Except for step (1) which is omitted, and step (2) which involves directly mixing and impregnating graphene powder with phase change paraffin, the other processes are the same as in Example 4.

[0064] Comparative Example 2

[0065] Except for replacing graphene powder with silicon dioxide powder, the other processes are the same as in Example 4. The silicon dioxide powder has an average pore size of 25 nm and a specific surface area of ​​730 m². 2 / g, particle size 80μm).

[0066] Comparative Example 3

[0067] In step (1), oleophilic ethyl laurate was used instead of phenylalanine for modification, and the other processes were the same as in Example 4.

[0068] Comparative Example 4

[0069] In step (1), the phenylalanine in the aqueous solution used for modification is 5% by weight, and the other processes are the same as in Example 4.

[0070] The performance of the phase change energy storage gypsum boards prepared in the examples and comparative examples was analyzed. A differential scanning calorimeter (DSC) and a thermal conductivity meter were used to measure the enthalpy and thermal conductivity of the treated graphene powder obtained in step (2) of each example and comparative example, the phase change energy storage gypsum substrate used in each example and comparative example, and the modified phase change energy storage gypsum board. The test data are shown in Table 1.

[0071] Table 1.

[0072]

[0073] The phase change energy storage gypsum board with decorative film prepared in the examples has improved enthalpy and thermal conductivity, thus improving the heat preservation and temperature control performance of the gypsum board. Compared with the gypsum boards prepared in other comparative examples, it has better performance.

Claims

1. A method for preparing phase change energy storage gypsum board, comprising: (1) The three-dimensional porous graphene was washed, placed in an aqueous solution of phenylalanine for reaction, filtered and dried to obtain modified porous graphene powder. (2) The three-dimensional porous graphene powder obtained in step (1) is mixed and impregnated with phase change material, and after filtration and washing, graphene powder with phase change material impregnated in the pores is obtained. (3) After the three-dimensional porous graphene powder with phase change material impregnated in the pores obtained in step (2) is mixed evenly with epoxy resin solution, a thin film is formed on the surface of the gypsum board substrate by ultrasonic spraying to obtain the phase change energy storage gypsum board.

2. The preparation method according to claim 1, characterized in that, The three-dimensional porous graphene described in step (1) has an average pore size range of 50-100 nm and a specific surface area of ​​700-1000 m². 2 / g, with a particle size of 10-20μm.

3. The preparation method according to claim 1, characterized in that, The phenylalanine in the aqueous solution of phenylalanine in step (1) has a weight percentage of 10-20%.

4. The preparation method according to claim 1, characterized in that, The reaction temperature in step (1) is 30-60℃ and the reaction time is 6-10 hours.

5. The preparation method according to claim 1, characterized in that, The drying temperature in step (1) is 40-60℃ and the drying time is 6-8 hours.

6. The preparation method according to claim 1, characterized in that, The phase change material mentioned in step (2) is phase change paraffin, with a phase change temperature of 23-28℃ and an enthalpy of 150-170J / g.

7. The preparation method according to claim 1, characterized in that, The immersion temperature in step (2) is 50-80℃ and the immersion time is 2-4 hours.

8. The preparation method according to claim 1, characterized in that, After the impregnation is completed in step (2), rinse with anhydrous ethanol at a temperature of 30-40℃ 1-3 times.

9. The preparation method according to claim 1, characterized in that, The epoxy resin in step (3) is bisphenol F type epoxy resin, accounting for 50-70% of the weight of the solution.

10. The preparation method according to claim 1, characterized in that, The epoxy resin solution in step (3) also includes a curing agent, an organic solvent, and a colorant.

11. The preparation method according to claim 10, characterized in that, The curing agent is type 9035 or type 2215, accounting for 10-30% of the mass percentage of the resin mixture; the organic solvent is acetone or dimethylformamide, accounting for 10-18% of the mass percentage of the resin mixture; the tinting agent is paint or coating tinting agent, accounting for 1-2% of the mass percentage of the resin mixture.

12. The preparation method according to claim 1, characterized in that, In step (3), the graphene powder and epoxy resin solution are thoroughly mixed for 10-20 minutes, with a weight ratio of 1:3-1:

10.

13. The preparation method according to claim 1, characterized in that, In step (3), the ultrasonic spraying temperature is 40-50℃; after coating into a thin film, a drying step is also included, with a temperature of 30-40℃ and a drying time of 12-24 hours.

14. The preparation method according to claim 1, characterized in that, The enthalpy of the mixed solution formed by graphene powder and epoxy resin solution in step (3) is 10-20 J / g, the thermal conductivity is 30-60 W / (m·K), and the viscosity is 5-20 mPa·s.

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