CN110655910B - Preparation method of graphene aerogel phase-change energy storage material - Google Patents
Preparation method of graphene aerogel phase-change energy storage material Download PDFInfo
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Abstract
The invention belongs to the field of nano porous materials, and relates to a preparation method of a graphene aerogel phase change energy storage material. The method comprises the steps of mixing graphene oxide powder with a solvent, adding a phase-change material, obtaining wet gel by a hydrothermal reduction method, and finally washing, drying and the like to finally prepare the phase-change energy storage material which takes the graphene aerogel as a structural framework and is uniformly distributed with the phase-change material. The invention has the advantages of simple preparation process, better leakage resistance, high latent heat and high heat conductivity, and the like, and is easy to realize mass production.
Description
Technical Field
The invention relates to a preparation method of a novel graphene aerogel phase-change energy storage material, in particular to a preparation method of a graphene aerogel phase-change energy storage material, and belongs to the technical field of nano porous materials and phase-change energy storage.
Background
With the rapid development of society and economy, people have more and more demands on heat energy in the fields of heating and heat preservation, food drying, domestic hot water and the like, but redundant heat in the processes of life and production is often regarded as waste heat to be discharged to the external environment. Energy conservation and environmental protection are one of the basic national policies of China, have important effects on social development and progress, and are particularly important for improving the utilization rate of heat energy.
Phase change energy storage is the most popular energy storage mode at present, namely, the phase change material still has extremely high phase change latent heat and a wider phase change temperature selection range under the condition of small temperature change. When the temperature rises to be close to the melting point temperature of the phase-change material, the phase-change material can absorb heat to perform solid-liquid phase transformation to achieve the effect of energy storage, and the ambient temperature is reduced. The phase change energy storage material can be used in the fields of spaceflight, buildings, clothes, refrigeration equipment, military, communication, electric power and the like, and can realize energy storage, building energy conservation and temperature regulation. However, the phase change material has three main problems in the using process: the degradation problem of thermophysical properties in the circulation process, the problem of easy leakage of the phase-change material from the matrix and the problem of the effect of the phase-change material on the matrix material. Therefore, it is necessary to find a porous matrix which does not react with the phase change material, can well encapsulate the phase change material and has stable enthalpy of phase change.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a graphene aerogel phase-change energy storage material so as to improve the current situation of low heat energy utilization rate and overcome some technical problems.
The technical scheme adopted by the invention is as follows: a preparation method of a graphene aerogel phase change energy storage material comprises the following specific steps:
(1) mixing graphene oxide powder and a solvent, and stirring to form a uniform graphene oxide solution;
(2) adding a phase change material into the graphene oxide solution formed in the step (1), and stirring for 1-10 min;
(3) pouring the mixed system formed in the step (2) into a polytetrafluoroethylene hydrothermal reaction kettle, and reacting at the temperature of 90-240 ℃ for 5-20 hours to obtain graphene phase change energy storage wet gel;
(4) replacing the wet gel obtained in the step (3) with a solvent;
(5) and (5) drying the wet gel obtained in the step (4) to finally obtain the graphene aerogel phase change energy storage material.
Wherein the mass ratio of the graphene oxide to the solvent in the step (1) is (1-20): 1000, and the mass ratio of the phase-change material to the graphene oxide added in the step (2) is (10-100): 1.
preferably, the solvent in step (1) and step (4) is one or a mixture of deionized water, ethanol, acetone, isopropanol or sec-butanol.
Preferably, the phase change material in step (2) is any one or a combination of two or more of paraffin, polyethylene glycol, fatty acid, aromatic hydrocarbon, polyolefin, polyamide or polymeric polyol.
Preferably, the replacing times in the step (4) are 3-9 times, and the standing time is 8-24 hours each time.
Preferably, the drying treatment in the step (5) is carbon dioxide supercritical drying and freeze drying; carbon dioxide is used as a drying medium for supercritical drying of carbon dioxide, the reaction temperature is 50-70 ℃, the pressure in a high-pressure reaction kettle is 8-12 MPa, the air release rate is 5-20L/min, and the drying time is 8-20 h; freeze drying at-20 to-80 deg.c for 5-48 hr, and vacuum drying for 12-36 hr.
The prepared graphene aerogel phase change energy storage material comprises graphene aerogel and a phase change material, wherein the graphene aerogel is formed by carrying out hydrothermal reduction on a Graphene Oxide (GO) sheet layer to form an rGO sheet layer, then a three-dimensional space network structure is assembled by two-dimensional rGO, and the phase change material is uniformly distributed in the three-dimensional space network structure.
The graphene aerogel phase-change energy storage material can be used in the fields of aerospace, buildings, clothes, refrigeration equipment, military, communication, electric power and the like, and can realize energy storage, building energy conservation and temperature regulation.
Has the advantages that:
the method and the graphene aerogel phase change energy storage material prepared by the method have the following characteristics:
(1) high latent heat and high thermal conductivity. Graphene is used as a stable carbon material, no chemical action exists between the graphene and a phase-change material, and phase-change coating is carried out only by means of capillary force of graphene aerogel, so that the phase-change material can keep the characteristic of high enthalpy change, and meanwhile, the high heat conduction of the graphene well improves the phase-change response rate.
(2) Better leakage-proof performance. The pore diameter of the graphene aerogel in the graphene aerogel phase-change energy storage material is formed by microporous-mesoporous-macroporous hierarchical pores, so that the graphene aerogel phase-change energy storage material has excellent adsorption performance and can effectively prevent the phase-change material from melting and leaking.
Drawings
Fig. 1 is a photograph of a graphene aerogel polyethylene glycol phase change energy storage material prepared in example 1;
fig. 2 is SEM images of graphene aerogel paraffin phase-change energy storage material prepared in example 3 at different times;
fig. 3 is a DSC curve before and after cycling of the graphene aerogel palmitic acid phase change energy storage material prepared in example 4.
Detailed Description
Example 1
Uniformly mixing and stirring graphene oxide and deionized water according to the mass ratio of 1:1000, then adding polyethylene glycol with the mass ratio of 10:1 to the graphene oxide, stirring for 1min, pouring into a polytetrafluoroethylene hydrothermal reaction kettle, preserving heat at 90 ℃ for 20 hours, taking out a sample, replacing the sample with the deionized water for 3 times, standing for 24 hours each time, then freezing for 5 hours at-20 ℃, vacuumizing and drying for 12 hours to obtain the final graphene aerogel polyethylene glycol phase change energy storage material. The sample diagram is shown in fig. 1, it can be seen from the diagram that the surface of the sample is relatively smooth, the overall color is shown as black of the graphene aerogel, and the white polyethylene glycol phase-change material is well filled in the porous skeleton of the graphene aerogel; the density of the sample was 0.16g/cm3The enthalpy of fusion was 127.6J/g.
Example 2
Uniformly mixing and stirring graphene oxide and ethanol according to a mass ratio of 20:1000, then adding stearic acid with a mass ratio of 100:1 to the graphene oxide, stirring for 10min, pouring into a polytetrafluoroethylene hydrothermal reaction kettle, preserving heat for 5 hours at 240 ℃, taking out a sample, replacing the sample with deionized water for 9 times, standing for 8 hours each time, freezing for 48 hours at-80 ℃, vacuumizing and drying for 36 hours to obtain the final graphene aerogel stearic acid phase change energy storage material. The density of the sample was 0.36g/cm3The enthalpy of fusion is 346.7J/g.
Example 3
Uniformly mixing and stirring graphene oxide and acetone according to the mass ratio of 16:1000, then adding paraffin wax with the mass ratio of 50:1 to the graphene oxide, stirring for 10min, pouring into a polytetrafluoroethylene hydrothermal reaction kettle, preserving heat for 9 hours at 240 ℃, taking out a sample, replacing the sample with ethanol for 9 times, and standing for 8 hours each time. Then placing the graphene oxide into a CO2 supercritical reaction kettle, and drying for 8 hours in a high-pressure reaction kettle with the reaction temperature of 70 ℃, the pressure of 8MPa and the gas release rate of 5L/min, thereby obtaining the final graphene gasGel paraffin phase change energy storage material. The density of the sample was 0.26g/cm3The SEM picture is as shown in fig. 2, the left image shows the lamellar network structure of the graphene aerogel, and the right image shows that the paraffin phase change material is better filled into the skeleton of the graphene aerogel; the enthalpy of fusion was 236.7J/g.
Example 4
Uniformly mixing and stirring graphene oxide and isopropanol according to the mass ratio of 7:1000, then adding palmitic acid with the mass ratio of 40:1 to the graphene oxide, stirring for 10min, pouring into a polytetrafluoroethylene hydrothermal reaction kettle, preserving heat for 13 hours at 90 ℃, taking out a sample, replacing the sample with ethanol for 3 times, and standing for 12 hours each time. Then it is placed in CO2And (3) drying the graphene aerogel palmitic acid phase change energy storage material in a supercritical reaction kettle for 20 hours in a high-pressure reaction kettle with the reaction temperature of 50 ℃, the pressure of 12MPa and the air release rate of 20L/min, thereby obtaining the final graphene aerogel palmitic acid phase change energy storage material. The density of the sample was 0.21g/cm3The cycle DSC curve of the melting and solidification process is shown in FIG. 3, from which it can be seen that the melting enthalpy before the cycle test is 139.4J/g, and the solidification enthalpy is 175.7J/g; the enthalpy of fusion remained unchanged after the cycling test, and was still 139.4J/g, while the enthalpy of solidification decreased to 149.0J/g.
Claims (3)
1. A preparation method of a graphene aerogel phase change energy storage material comprises the following specific steps:
(1) mixing graphene oxide powder and a solvent, and stirring to form a uniform graphene oxide solution;
(2) adding a phase change material into the graphene oxide solution formed in the step (1), and stirring for 1-10 min;
(3) pouring the mixed system formed in the step (2) into a polytetrafluoroethylene hydrothermal reaction kettle, and reacting at the temperature of 90-240 ℃ for 5-20 hours to obtain graphene phase change energy storage wet gel;
(4) replacing the wet gel obtained in the step (3) with a solvent;
(5) and (5) drying the wet gel obtained in the step (4) to finally obtain the graphene aerogel phase change energy storage material.
Wherein the mass ratio of the graphene oxide to the solvent in the step (1) is (1-20): 1000, and the mass ratio of the phase-change material to the graphene oxide added in the step (2) is (10-100): 1; the solvent in the step (1) and the step (4) is one or a mixture of deionized water, ethanol, acetone, isopropanol or sec-butanol; the phase-change material in the step (2) is any one or a combination of more than two of paraffin, polyethylene glycol, fatty acid, aromatic hydrocarbon, polyolefin, polyamide or poly-polyhydric alcohol.
2. The preparation method according to claim 1, wherein the number of times of replacement in the step (4) is 3-9, and each standing time is 8-24 hours.
3. The production method according to claim 1, wherein the drying treatment in the step (5) is carbon dioxide supercritical drying and freeze-drying; carbon dioxide is used as a drying medium for supercritical drying of carbon dioxide, the reaction temperature is 50-70 ℃, the pressure in a high-pressure reaction kettle is 8-12 MPa, the air release rate is 5-20L/min, and the drying time is 8-20 h; freeze drying at-20 to-80 deg.c for 5-48 hr, and vacuum drying for 12-36 hr.
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| CN113527825B (en) * | 2020-04-13 | 2022-06-07 | 中国科学院大连化学物理研究所 | Graphene-based flexible composite shaped phase-change material film and preparation and application thereof |
| CN113698915A (en) * | 2020-05-22 | 2021-11-26 | 中国科学院大连化学物理研究所 | Graphene-based multi-response shaped composite phase change material and preparation and application thereof |
| CN112536004B (en) * | 2020-12-03 | 2022-10-14 | 航天特种材料及工艺技术研究所 | High-temperature-resistant elastic graphene aerogel material and preparation method thereof |
| CN112680195B (en) * | 2020-12-24 | 2021-06-29 | 广东工业大学 | Preparation method and device of graphene-based polyethylene glycol phase-change material |
| CN112724936B (en) * | 2021-01-26 | 2022-08-12 | 山西万家暖节能科技有限公司 | Preparation method of new energy storage material |
| CN113265228A (en) * | 2021-04-26 | 2021-08-17 | 西南交通大学 | Multi-energy-driven shape-stabilized phase change material and preparation method thereof |
| CN113583634A (en) * | 2021-07-22 | 2021-11-02 | 南通强生石墨烯科技有限公司 | Intelligent graphene temperature-sensing phase change fiber |
| CN114525112B (en) * | 2022-02-28 | 2024-01-05 | 重庆大学 | Improved graphene aerogel and polyethylene glycol composite phase change material and preparation method thereof |
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| CN108342187A (en) * | 2018-02-07 | 2018-07-31 | 东南大学 | The high heat conduction graphene aerogel composite phase-change material and preparation method of controlled shape |
| CN109929518A (en) * | 2019-03-29 | 2019-06-25 | 同济大学 | A kind of graphite oxide aerogel heat chemistry heat accumulation composite material and preparation method |
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| CN108342187A (en) * | 2018-02-07 | 2018-07-31 | 东南大学 | The high heat conduction graphene aerogel composite phase-change material and preparation method of controlled shape |
| CN109929518A (en) * | 2019-03-29 | 2019-06-25 | 同济大学 | A kind of graphite oxide aerogel heat chemistry heat accumulation composite material and preparation method |
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