CN109385254B - Graphene elastic polymer phase-change composite material and preparation method thereof - Google Patents

Graphene elastic polymer phase-change composite material and preparation method thereof Download PDF

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CN109385254B
CN109385254B CN201811419642.XA CN201811419642A CN109385254B CN 109385254 B CN109385254 B CN 109385254B CN 201811419642 A CN201811419642 A CN 201811419642A CN 109385254 B CN109385254 B CN 109385254B
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张东
曹流
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Tongji University
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Abstract

The invention relates to a graphene elastic polymer phase-change composite material and a preparation method thereof. Compared with the prior art, the graphene aerogel is used as the framework to provide heat conduction modification for the composite material, and the complex pore structure provides a packaging environment for the phase-change material, so that the technical bottlenecks of easy leakage and poor heat conduction of the phase-change composite material can be effectively solved; the graphene framework is reinforced by compounding the elastic polymer, and the phase-change material is further encapsulated, so that excellent mechanical properties can be provided for the composite material, and therefore, energy storage application under special conditions can be realized.

Description

Graphene elastic polymer phase-change composite material and preparation method thereof
Technical Field
The invention relates to the technical field of graphene nanocomposite materials, in particular to a graphene elastic polymer phase-change composite material and a preparation method thereof.
Background
Nowadays, with the high development of industrial civilization, the problems of shortage of traditional fossil energy, environmental pollution and the like come along, the development and utilization of renewable energy become the key of social sustainable development, and because the inherent characteristics of uneven energy distribution and uncertainty of renewable energy, an energy storage link is often needed in an energy conversion system, so that the problem of mismatching of energy utilization in time and space is solved, and the utilization rate of energy is improved. Phase change materials, which can store and release energy by using a phase transition process, are ideal energy storage media, and therefore have attracted attention of researchers.
Organic phase change materials that store or release thermal energy in the form of latent heat during phase change are one of the effective advanced energy storage materials for solar energy conversion and storage due to their high storage capacity, adjustable phase change temperature. The organic phase change material has the advantages of excellent thermal stability and chemical stability, no corrosiveness, low supercooling degree and the like, and has great application potential in the aspects of solar energy, buildings, waste heat recovery, electronic/battery thermal management, intelligent textiles and the like. But the wide application of the organic phase change material is limited due to the performance defects of low thermal conductivity and easy leakage. On the other hand, in special fields such as military affairs and electronic devices, certain requirements are often required for the mechanical properties of the phase-change composite material, for example, for a thermal interface material, certain flexibility is often required to better fill interface gaps.
Due to the special two-dimensional honeycomb lattice structure of the graphene, the graphene shows excellent mechanical and electrical properties and has extremely high thermal conductivity, and the laboratory theoretical data is as high as 5300W/(m.K). The preparation methods of graphene include a mechanical stripping method, a chemical vapor deposition method, an epitaxial growth method, a redox method and the like, wherein the redox method has the advantages of simple preparation process and low cost, and is a widely used method for preparing graphene at present. The method specifically comprises three processes of graphite oxidation, graphite oxide stripping and graphene oxide reduction. The graphene oxide is used as an important functional product and a precursor of the graphene, has amphipathy, and is convenient for subsequent treatment and application. At present, in the field of phase change energy storage, aiming at the performance defects of low thermal conductivity and easy leakage of organic phase change materials, graphene and graphene oxide are mainly used as heat conduction fillers or phase change microcapsule wall materials. When the graphene is used as a heat-conducting filler, the graphene is dispersed in the phase-change material mainly in a mechanical blending mode, and the characteristic of high heat conductivity of the graphene is utilized to play a role in improving the heat-conducting property. The phase-change microcapsule wall material is prepared by utilizing the amphipathy of graphene oxide, and the phase-change composite material wrapped by the graphene oxide is packaged to improve the leakage resistance of the phase-change material.
Although graphene has high intrinsic thermal conductivity and better thermal conductivity modification effect than common thermal conductive fillers when used as a thermal conductive filler, the composite material obtained by mechanical blending is extremely unstable in the process of repeated use, the phenomenon of sedimentation and delamination can gradually occur, the modification effect can be slowly reduced, and the repeated use characteristic of the material is influenced. In addition, the graphene oxide is used as a phase change microcapsule wall material, the energy storage performance of the phase change material can be greatly influenced when the doping amount is high, and the leakage of the phase change material can not be avoided under the condition of low doping amount.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a graphene elastic polymer phase-change composite material with excellent heat conductivity and good temperature stability and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme: the utility model provides a graphite alkene elastic polymer phase transition combined material, this combined material includes graphite alkene aerogel skeleton, packs in the elastic polymer in the network that is formed by graphite alkene aerogel skeleton and wraps up the phase transition microcapsule outside graphite alkene aerogel skeleton, elastic polymer selects one of poly 2-chloroprene, phenylpropyl emulsion, butylbenzene emulsion or epoxy, graphite alkene aerogel skeleton's quality accounts for 1% ~ 10% of combined material total mass, the elastic polymer is 1 with the mass ratio of phase transition microcapsule: (1-5).
According to the composite material, the graphene aerogel is used as a framework, the high intrinsic thermal conductivity of the graphene is utilized to provide heat conduction modification for the composite material, a packaging environment is provided for the phase-change material through a complex pore structure, and an effective solution is provided for the technical bottlenecks of easy leakage and poor heat conduction of the phase-change composite material. The graphene framework is reinforced by the compounding of the elastic polymer, so that the phase-change material can be further encapsulated, and the elastic polymer has high elasticity and ductility and can provide excellent mechanical properties for the composite material. And the microstructure of the staggered overlapping of the graphene frameworks can effectively prevent the elastic polymer molecular chains from moving in a staggered manner, improve the deformation resistance of the composite material and simultaneously can not obviously reduce the overall viscoelasticity.
Preferably, the phase-change microcapsule has the following structure: the method comprises the following steps of taking graphene oxide as a shell and a phase-change material as a core body, wherein the phase-change material is selected from paraffin or hexadecanol, and the mass ratio of the graphene oxide to the phase-change material is (1-3): 100.
a preparation method of the graphene elastic polymer phase-change composite material comprises the following steps:
(1) placing graphene oxide in water, stirring and carrying out ultrasonic treatment to obtain a uniform graphene oxide solution, carrying out hydrothermal reaction to obtain graphene hydrogel, and carrying out vacuum freeze drying to obtain a graphene aerogel framework; through hydrothermal reduction, graphene oxide sheets are staggered and overlapped to form a graphene porous network while being reduced to graphene, and water molecules in the graphene porous network are removed through freeze drying, so that the graphene aerogel is obtained.
(2) Mixing graphene oxide and a phase-change material at a temperature higher than the melting point of the phase-change material, stirring to obtain a microcapsule emulsion, and cooling, washing and drying to obtain a phase-change microcapsule; due to the amphipathy of the graphene oxide, the graphene oxide can be used as a Pickering emulsifier to obtain a stable oil-in-water Pickering emulsion in high-speed stirring, and the graphene oxide is used as a shell layer to wrap a phase-change material to form microspheres.
(3) Mixing the phase-change microcapsules obtained in the step (2) with the emulsion of the elastic polymer, compounding the phase-change microcapsules with the graphene aerogel framework prepared in the step (1) through vacuum impregnation, and then performing vacuum freeze drying to obtain a crude product of the composite material;
(4) and (3) mixing the phase-change microcapsules obtained in the step (2) with an elastic polymer, compounding with a crude composite material product through vacuum impregnation, freeze-drying, and repeating the step (4) for multiple times to obtain the phase-change material. And (4) vacuum impregnation is carried out, the aerogel gaps are filled with the mixed solution of the microcapsules and the elastic polymers, vacuum freeze-drying is carried out to remove moisture, and the steps are repeated for multiple times to realize compounding.
Preferably, the stirring speed in the step (1) is 1000-2000 r/min, the stirring time is 15-60 min, the ultrasonic frequency is 20-60 kHz, the ultrasonic time is 1-3 h, the hydrothermal reaction temperature is 150-190 ℃, the hydrothermal reaction time is 8-30 h, the vacuum degree of vacuum freeze drying in the step (1) is less than 2Pa, the temperature is-60-20 ℃, and the time is 20-30 h.
Preferably, the phase-change material is selected from paraffin or cetyl alcohol, the stirring speed in the step (2) is 5000-12000 r/min, the stirring time is 10-50 min, the washing adopts ionized water, the drying temperature is 35-45 ℃, and the drying time is 24-48 h.
Preferably, the emulsion of the elastic polymer has a solid content of 50% to 70%.
Preferably, in the step (3) and the step (4), the vacuum degree of the vacuum impregnation is less than 2Pa, and the vacuum impregnation time is 1-5 h. Through vacuum impregnation, the aerogel gaps are filled with the microcapsule and elastic polymer mixed liquid, and vacuum freeze-drying is carried out to remove water and repeat for many times to realize compounding.
Preferably, in the step (3) and the step (4), the vacuum degree of the vacuum freeze drying is less than 2Pa, the temperature is-60 to-20 ℃, and the time is 20-30 h.
Preferably, the repetition frequency of the step (4) is 1-4 times.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:
(1) according to the invention, the graphene aerogel is used as a heat conducting framework and uniformly dispersed in the composite material, so that the dispersion problem and durability problem of the composite material are solved, and the heat conductivity is obviously improved;
(2) the invention endows the phase-change composite material with high elasticity and ductility by the elastic polymer, and has application advantages in special fields such as military, electronic devices and the like;
(3) the invention can effectively solve the problem that the phase change material is easy to leak on the premise of higher proportion of the phase change material by multiple encapsulation of the phase change material by the microcapsule, the porous framework and the elastic polymer.
(3) The process method is simple, the preparation cost is low, and the industrial expanded production is easy to realize.
Drawings
Fig. 1 is a scanning electron micrograph of the graphene aerogel prepared in example 1;
FIG. 2 is a scanning electron micrograph of the graphene elastic polymer phase change composite prepared in example 1;
fig. 3 is an infrared spectrum of the graphene aerogel and graphene oxide prepared in example 2;
FIG. 4 is a scanning electron micrograph of a phase change microcapsule prepared in example 2;
FIG. 5 is a particle size distribution of the phase-change microcapsules prepared in example 2;
fig. 6 is an AFM image of graphene oxide prepared in example 3;
FIG. 7 is a DSC curve of the graphene elastic polymer phase change composite prepared in example 4;
fig. 8 is a thermal conductivity of the graphene elastic polymer phase-change composite materials prepared in examples 3, 4 and 5.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
(1) Dissolving graphite oxide in water, stirring for 15min, performing ultrasonic treatment for 1h, and preparing graphene oxide solutions with different concentrations: the concentration is 5mg/ml and 3 mg/ml;
(2) and (3) taking 60ml of 5mg/ml graphene oxide solution, placing the solution in a 100ml reaction kettle for hydrothermal reaction for 15 hours at the hydrothermal temperature of 180 ℃ to obtain graphene hydrogel, and freeze-drying the graphene hydrogel in a vacuum drier for 24 hours at the vacuum degree of less than 2Pa and the freezing temperature of-60 ℃ to obtain the graphene aerogel.
(3) And mixing 100ml of 3mg/ml graphene oxide solution with 20g of molten paraffin, stirring at 80 ℃ for 45min at a stirring speed of 10000r/min, cooling, washing with deionized water, and drying on filter paper at room temperature to obtain the phase-change microcapsule.
(3) Styrene-acrylic emulsion with a solids content of 50% was used. And mixing and stirring the phase-change microcapsules and the elastic polymer uniformly according to the mass ratio of 1:1, and compounding the mixed solution and the graphene aerogel through vacuum impregnation. Freeze-drying in vacuum drier for 24 hr with vacuum degree less than 2Pa and freezing temperature of-60 deg.C, and repeating the soaking and freeze-drying process for 3 times. And obtaining the graphene elastic polymer phase-change composite material.
The scanning electron microscope image of the graphene aerogel prepared by the embodiment is shown in fig. 1, and it can be seen that the graphene aerogel skeleton prepared by the method is of a layered porous network structure, and the interlayer spacing is large. The scanning electron microscope image of the graphene elastic polymer phase-change composite material is shown in fig. 2, and it can be seen that the composite material prepared by the method takes graphene aerogel as a framework, the phase-change microcapsules are uniformly distributed on graphene sheets, and the elastic polymer is fully filled in pores.
Example 2
(1) Dissolving graphite oxide in water, stirring for 15min, performing ultrasonic treatment for 1h, and preparing graphene oxide solutions with different concentrations: the concentration is 7mg/ml and 2 mg/ml;
(2) and (3) taking 60ml of 7mg/ml graphene oxide solution, placing the solution in a 100ml reaction kettle for hydrothermal reaction for 15 hours at the hydrothermal temperature of 180 ℃ to obtain graphene hydrogel, and freeze-drying the graphene hydrogel in a vacuum drier for 24 hours at the vacuum degree of less than 2Pa and the freezing temperature of-60 ℃ to obtain the graphene aerogel.
(3) And mixing 100ml of 2mg/ml graphene oxide solution with 20g of molten paraffin, stirring at 80 ℃ for 45min at a stirring speed of 10000r/min, cooling, washing with deionized water, and drying on filter paper at room temperature to obtain the phase-change microcapsule.
(4) Styrene-acrylic emulsion with a solids content of 50% was used. And mixing and stirring the phase-change microcapsules and the elastic polymer uniformly according to the mass ratio of 1:1, and compounding the mixed solution and the graphene aerogel through vacuum impregnation. Freeze-drying in vacuum drier for 24 hr with vacuum degree less than 2Pa and freezing temperature of-60 deg.C, and repeating the soaking and freeze-drying process for 3 times. And obtaining the graphene elastic polymer phase-change composite material.
The infrared spectra of the graphene aerogel and the graphene oxide prepared in example 2 are shown in fig. 3, and for the graphene oxide, different vibration modes of various types of oxygen-containing functional groups can be seen, such as epoxy (C-O-C, 1220-. Through hydrothermal, each oxygen-containing group of graphene is reduced, which indicates that graphene oxide is reduced. The scanning electron microscope image and the particle size distribution of the phase-change microcapsule are shown in fig. 4 and 5, the phase-change material is wrapped by the graphene oxide to be used as a microcapsule shell, and the microcapsule is in a regular spherical shape and has the size of 7-17 mu m.
Example 3
(1) Dissolving graphite oxide in water, stirring for 15min, performing ultrasonic treatment for 1h, and preparing graphene oxide solutions with different concentrations: the concentration is 4mg/ml and 2 mg/ml;
(2) and (3) taking 60ml of 4mg/ml graphene oxide solution, placing the graphene oxide solution in a 100ml reaction kettle for hydrothermal reaction for 15 hours at the hydrothermal temperature of 180 ℃ to obtain graphene hydrogel, and freeze-drying the graphene hydrogel in a vacuum drier for 24 hours at the vacuum degree of less than 2Pa and the freezing temperature of-60 ℃ to obtain the graphene aerogel.
(3) And mixing 100ml of 2mg/ml graphene oxide solution with 20g of molten paraffin, stirring at 80 ℃ for 45min at a stirring speed of 10000r/min, cooling, washing with deionized water, and drying on filter paper at room temperature to obtain the phase-change microcapsule.
(4) Styrene-acrylic emulsion with a solids content of 50% was used. And mixing and stirring the phase-change microcapsules and the elastic polymer uniformly according to the mass ratio of 1:1, and compounding the mixed solution and the graphene aerogel through vacuum impregnation. Freeze-drying in vacuum drier for 24 hr with vacuum degree less than 2Pa and freezing temperature of-60 deg.C, and repeating the soaking and freeze-drying process for 3 times. And obtaining the graphene elastic polymer phase-change composite material.
The AFM image of the graphene oxide prepared in example 3 is shown in fig. 6, and after the ultrasonic treatment, the thickness of the graphene oxide is about 1nm, which indicates that the graphene oxide sheet is a single layer and has a good exfoliation effect.
Example 4
(1) Dissolving graphite oxide in water, stirring for 15min, performing ultrasonic treatment for 1h, and preparing graphene oxide solutions with different concentrations: the concentration is 6mg/ml and 2 mg/ml;
(2) and (3) taking 60ml of 6mg/ml graphene oxide solution, placing the solution in a 100ml reaction kettle for hydrothermal reaction for 15 hours at the hydrothermal temperature of 180 ℃ to obtain graphene hydrogel, and freeze-drying the graphene hydrogel in a vacuum drier for 24 hours at the vacuum degree of less than 2Pa and the freezing temperature of-60 ℃ to obtain the graphene aerogel.
(3) And mixing 100ml of 2mg/ml graphene oxide solution with 20g of molten paraffin, stirring at 80 ℃ for 45min at a stirring speed of 10000r/min, cooling, washing with deionized water, and drying on filter paper at room temperature to obtain the phase-change microcapsule.
(4) Styrene-acrylic emulsion with a solids content of 50% was used. And mixing and stirring the phase-change microcapsules and the elastic polymer uniformly according to the mass ratio of 1:1, and compounding the mixed solution and the graphene aerogel through vacuum impregnation. Freeze-drying in vacuum drier for 24 hr with vacuum degree less than 2Pa and freezing temperature of-60 deg.C, and repeating the soaking and freeze-drying process for 3 times. And obtaining the graphene elastic polymer phase-change composite material.
The DSC curve of the graphene elastic polymer phase-change composite material prepared in example 4 is shown in fig. 7, from which we can find that there are two endothermic peaks in the melting process, the lower temperature peak is attributed to the solid-solid phase change of paraffin, the higher temperature represents the solid-liquid phase change, and the size of the phase change is determined by the content of the phase-change material.
Example 5
(1) Dissolving graphite oxide in water, stirring for 15min, performing ultrasonic treatment for 1h, and preparing graphene oxide solutions with different concentrations: the concentration is 8mg/ml and 2 mg/ml;
(2) and (3) taking 60ml of 8mg/ml graphene oxide solution, placing the graphene oxide solution in a 100ml reaction kettle for hydrothermal reaction for 15 hours at the hydrothermal temperature of 180 ℃ to obtain graphene hydrogel, and freeze-drying the graphene hydrogel in a vacuum drier for 24 hours at the vacuum degree of less than 2Pa and the freezing temperature of-60 ℃ to obtain the graphene aerogel.
(3) And mixing 100ml of 2mg/ml graphene oxide solution with 20g of molten paraffin, stirring at 80 ℃ for 45min at a stirring speed of 10000r/min, cooling, washing with deionized water, and drying on filter paper at room temperature to obtain the phase-change microcapsule.
(4) Styrene-acrylic emulsion with a solids content of 50% was used. And mixing and stirring the phase-change microcapsules and the elastic polymer uniformly according to the mass ratio of 1:1, and compounding the mixed solution and the graphene aerogel through vacuum impregnation. Freeze-drying in vacuum drier for 24 hr with vacuum degree less than 2Pa and freezing temperature of-60 deg.C, and repeating the soaking and freeze-drying process for 3 times. And obtaining the graphene elastic polymer phase-change composite material.
The thermal conductivity of the graphene elastic polymer phase-change composite materials prepared in embodiments 3, 4 and 5 is as shown in fig. 8, and compared with a pure phase-change material, the thermal conductivity of the composite material is improved significantly, and the thermal conductivity increases with the increase of the concentration of graphene oxide in the hydrothermal reaction, because the concentration of graphene oxide increases, the quality of the graphene aerogel obtained by hydrothermal reduction is higher, the connectivity of the graphene thermal conductivity skeleton in the composite material is better, and the thermal conductivity is better.
Example 6
A similar preparation process as in example 1 was used, except that:
(1) dissolving graphite oxide in water, stirring for 60min, performing ultrasonic treatment for 3h, and preparing graphene oxide solutions with different concentrations: the concentration is 8mg/ml and 4 mg/ml;
(2) and (3) taking 60ml of 8mg/ml graphene oxide solution, placing the graphene oxide solution in a 100ml reaction kettle for hydrothermal reaction for 30 hours at the hydrothermal temperature of 150 ℃ to obtain graphene hydrogel, and freeze-drying the graphene hydrogel in a vacuum drier for 20 hours at the vacuum degree of less than 2Pa and the freezing temperature of-20 ℃ to obtain the graphene aerogel framework.
(3) And mixing 100ml of 6mg/ml graphene oxide solution with 20g of molten paraffin, stirring at 80 ℃ for 50min at a stirring speed of 5000r/min, cooling, washing with deionized water, and drying on filter paper at room temperature to obtain the phase-change microcapsule.
(4) A poly 2-chloroprene emulsion having a solids content of 50% was used. And mixing and stirring the phase-change microcapsules and the elastic polymer uniformly according to the mass ratio of 1:1, and compounding the mixed solution and the graphene aerogel through vacuum impregnation. Freeze-drying in vacuum drier for 20 hr with vacuum degree less than 2Pa and freezing temperature of-20 deg.C, and repeating the soaking and freeze-drying process for 4 times. And obtaining the graphene elastic polymer phase-change composite material.
Through detection, the composite material prepared by the embodiment has excellent heat-conducting property and good temperature stability.
Example 7
A similar preparation process as in example 1 was used, except that:
(1) dissolving graphite oxide in water, stirring for 30min, performing ultrasonic treatment for 2h, and preparing graphene oxide solutions with different concentrations: the concentration is 8mg/ml and 4 mg/ml;
(2) and (3) taking 60ml of 8mg/ml graphene oxide solution, placing the graphene oxide solution in a 100ml reaction kettle for hydrothermal reaction for 8 hours at the hydrothermal temperature of 190 ℃ to obtain graphene hydrogel, and freeze-drying the graphene hydrogel in a vacuum drier for 30 hours at the vacuum degree of less than 2Pa and the freezing temperature of-60 ℃ to obtain the graphene aerogel framework.
(3) And mixing 100ml of 6mg/ml graphene oxide solution with 20g of molten paraffin, stirring at the temperature of 80 ℃ for 10min at the stirring speed of 12000r/min, cooling, washing with deionized water, and drying on filter paper at the temperature of 45 ℃ to obtain the phase-change microcapsule.
(4) A poly 2-chloroprene emulsion having a solids content of 50% was used. And mixing and stirring the phase-change microcapsules and the elastic polymer uniformly according to the mass ratio of 1:1, and compounding the mixed solution and the graphene aerogel through vacuum impregnation. Freeze-drying in vacuum drier for 30 hr with vacuum degree less than 2Pa and freezing temperature of-60 deg.C, and repeating the soaking and freeze-drying process for 2 times. And obtaining the graphene elastic polymer phase-change composite material.
Through detection, the composite material prepared by the embodiment has excellent heat-conducting property and good temperature stability.

Claims (8)

1. A preparation method of a graphene elastic polymer phase-change composite material is characterized by comprising the following steps:
(1) placing graphene oxide in water, stirring and carrying out ultrasonic treatment to obtain a uniform graphene oxide solution, carrying out hydrothermal reaction to obtain graphene hydrogel, and carrying out vacuum freeze drying to obtain a graphene aerogel framework;
(2) mixing graphene oxide and a phase-change material at a temperature higher than the melting point of the phase-change material, stirring to obtain a microcapsule emulsion, and cooling, washing and drying to obtain a phase-change microcapsule;
(3) mixing the phase-change microcapsules obtained in the step (2) with the emulsion of the elastic polymer, compounding the phase-change microcapsules with the graphene aerogel framework prepared in the step (1) through vacuum impregnation, and then performing vacuum freeze drying to obtain a crude product of the composite material;
(4) mixing the phase-change microcapsules obtained in the step (2) with the elastic polymer, compounding the mixture with a crude composite material product through vacuum impregnation, freeze-drying the composite material product, and repeating the step (4) for multiple times to obtain the graphene elastic polymer phase-change composite material;
the composite material comprises a graphene aerogel framework, an elastic polymer filled in a network formed by the graphene aerogel framework and a phase-change microcapsule wrapped outside the graphene aerogel framework, wherein the elastic polymer is selected from one of poly-2-chloroprene, styrene-acrylic emulsion, styrene-butadiene emulsion or epoxy resin, the mass of the graphene aerogel framework accounts for 1% -10% of the total mass of the composite material, and the mass ratio of the elastic polymer to the phase-change microcapsule is 1: (1-5).
2. The preparation method of the graphene elastic polymer phase-change composite material according to claim 1, wherein the phase-change microcapsule has the following structure: the method comprises the following steps of taking graphene oxide as a shell and a phase-change material as a core body, wherein the phase-change material is selected from paraffin or hexadecanol, and the mass ratio of the graphene oxide to the phase-change material is (1-3): 100.
3. the preparation method of the graphene elastic polymer phase-change composite material according to claim 1, wherein the stirring speed in the step (1) is 1000-2000 r/min, the stirring time is 15-60 min, the ultrasonic frequency is 20-60 kHz, the ultrasonic time is 1-3 h, the hydrothermal reaction temperature is 150-190 ℃, the hydrothermal reaction time is 8-30 h, the vacuum degree of vacuum freeze drying in the step (1) is less than 2Pa, the temperature is-60-20 ℃, and the time is 20-30 h.
4. The preparation method of the graphene elastic polymer phase-change composite material according to claim 1, wherein the phase-change material is one selected from paraffin or hexadecanol, the stirring speed in the step (2) is 5000-12000 r/min, the stirring time is 10-50 min, deionized water is adopted for washing, the drying temperature is 35-45 ℃, and the drying time is 24-48 h.
5. The method for preparing the graphene elastic polymer phase-change composite material according to claim 1, wherein the emulsion of the elastic polymer has a solid content of 50-70%.
6. The preparation method of the graphene elastic polymer phase-change composite material according to claim 1, wherein in the step (3) and the step (4), the vacuum degree of vacuum impregnation is less than 2Pa, and the vacuum impregnation time is 1-5 h.
7. The preparation method of the graphene elastic polymer phase-change composite material according to claim 1, wherein in the step (3) and the step (4), the vacuum degree of vacuum freeze drying is less than 2Pa, the temperature is-60 to-20 ℃, and the time is 20 to 30 hours.
8. The preparation method of the graphene elastic polymer phase-change composite material according to claim 1, wherein the repetition frequency of the step (4) is 1-4 times.
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