CN114539981A - Graphene/carbon nanotube composite low-temperature phase change material, preparation method and application - Google Patents
Graphene/carbon nanotube composite low-temperature phase change material, preparation method and application Download PDFInfo
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- CN114539981A CN114539981A CN202011356396.5A CN202011356396A CN114539981A CN 114539981 A CN114539981 A CN 114539981A CN 202011356396 A CN202011356396 A CN 202011356396A CN 114539981 A CN114539981 A CN 114539981A
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Abstract
The invention discloses a graphene/carbon nano tube composite low-temperature phase change material, a preparation method and application. The graphene/carbon nanotube composite low-temperature phase change material comprises a graphene-based phase change material and a carbon nanotube, wherein the graphene-based phase change material comprises few-layer graphene and an inorganic crystalline hydrated salt material and/or a low-melting-point alloy material. The heat conductivity coefficient of the graphene-based phase-change material is greatly improved under the condition of keeping the low-temperature phase-change temperature of the graphene-based phase-change material unchanged, and the practical application of the low-temperature phase-change material is facilitated; meanwhile, the composite low-temperature phase change material disclosed by the invention is composed of a pure inorganic phase change material, and has the advantages of small phase change volume change, large phase change latent heat, large heat conductivity coefficient and the like.
Description
Technical Field
The invention relates to a phase-change material, in particular to a graphene/carbon nanotube composite low-temperature phase-change material, a preparation method and application, and belongs to the technical field of phase-change materials.
Background
The low-temperature phase-change material is a cold storage functional material in a cold storage system, and the cold quantity is stored and released by utilizing the low-temperature phase-change material in the low-temperature phase-change process, so that the purposes of controlling the environment temperature, using cold for peak staggering, shifting peaks and filling valleys are achieved. The phase change process is an isothermal or approximately isothermal process, and is accompanied by a great amount of energy absorption or release, and the energy storage material should have good thermodynamic, kinetic and chemical properties, and simultaneously, the economical efficiency and the operational feasibility of the material are considered. In order to meet the above requirements of low temperature phase change materials, in recent years, researchers at home and abroad have conducted a lot of research on low temperature phase change energy storage materials, but disadvantages and problems such as low latent heat of phase change, poor thermal conductivity of materials, inappropriate phase change temperature, and poor economy and stability still exist. It has proven difficult to fully satisfy the requirements for low temperature phase change materials with a single composition of material. Therefore, the research on the novel low-temperature phase-change material, especially binary or multi-element composite phase-change material, is carried out early and deeply, the key preparation technology and the core process are broken through, and the method is an effective way for popularizing the application.
At present, the research on solid-liquid phase change materials at home and abroad mainly focuses on two major types, namely organic type and inorganic type, the inorganic phase change materials mainly comprise water, molten salt, hydrated salt, metal alloy, other inorganic substances and the like, and the water and the hydrated salt are more applied in the low-temperature field. The inorganic phase-change material generally has the characteristics of low price, small phase-change volume change, large phase-change latent heat, large heat conductivity coefficient and the like. However, inorganic phase change materials also have supercooling and phase separation phenomena, and thickening agents and nucleating agents are often selected as phase separation and supercooling prevention agents. The organic phase-change energy storage material mainly comprises alcohol, acid, salt, alkane and the like, typically paraffin and fatty acid, and has the advantages of difficult phase separation and supercooling, small corrosivity, low toxicity and the like, but also has the defects of high price, small phase-change latent heat, low thermal conductivity, poor heat transfer performance in the phase-change process, easy volatilization, easy combustion, easy aging and the like.
Disclosure of Invention
The invention mainly aims to provide a graphene/carbon nanotube composite low-temperature phase-change material, a preparation method and application, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a graphene/carbon nanotube composite low-temperature phase-change material, which comprises a graphene-based phase-change material and a carbon nanotube, wherein the graphene-based phase-change material comprises few-layer graphene and an inorganic crystalline hydrated salt material and/or a low-melting-point alloy material, and the content of the carbon nanotube in the graphene/carbon nanotube composite low-temperature phase-change material is 0.1-1 wt%.
The embodiment of the invention also provides a preparation method of the graphene/carbon nanotube composite low-temperature phase-change material, which comprises the following steps: and mixing the graphene-based phase-change material and the carbon nano tube, and then performing ball milling and/or stirring to fully mix the graphene-based phase-change material and the carbon nano tube to obtain the graphene/carbon nano tube composite low-temperature phase-change material.
The embodiment of the invention also provides application of the graphene/carbon nano tube composite low-temperature phase change material in preparation of a phase change energy storage device.
The embodiment of the invention also provides a phase change energy storage device which comprises an accommodating mechanism, wherein the accommodating mechanism is internally provided with the graphene/carbon nano tube composite low-temperature phase change material.
Compared with the prior art, the graphene/carbon nanotube composite low-temperature phase change material provided by the embodiment of the invention greatly improves the heat conductivity coefficient of the material under the condition of keeping the low-temperature phase change temperature unchanged, is beneficial to the practical application of the low-temperature phase change material, and simultaneously has the advantages of small phase change volume change, large phase change latent heat, large heat conductivity coefficient and the like because the graphene/carbon nanotube composite low-temperature phase change material is composed of a pure inorganic phase change material.
Drawings
FIG. 1 is a differential scanning calorimetry curve for phase change materials in examples 1-3 of the present invention and comparative example 1;
fig. 2 is a graph of thermal conductivity of the phase change materials in examples 1 to 3 of the present invention and comparative example 1.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
The embodiment of the invention provides a graphene/carbon nanotube composite low-temperature phase change material, which comprises a graphene-based phase change material and a carbon nanotube, wherein the graphene-based phase change material comprises few-layer graphene and an inorganic crystalline hydrated salt material and/or a low-melting-point alloy material, and the content of the carbon nanotube in the graphene/carbon nanotube composite low-temperature phase change material is 0.1-1 wt%.
Further, the graphene-based phase change material comprises 30-50 wt% of few-layer graphene and 49-69 wt% of an inorganic crystalline hydrated salt material and/or 49-69 wt% of a low-melting-point alloy material.
Further, the carbon nanotubes comprise carboxylated multi-walled carbon nanotubes.
Furthermore, the diameter of the carboxylated multi-wall carbon nano tube is 10-60 nm, the length of the carboxylated multi-wall carbon nano tube is 5-50 mu m, the purity of the carboxylated multi-wall carbon nano tube is more than 98%, and the content of carboxyl is more than 0.5 mmol/g.
Further, the inorganic crystalline hydrated salt material includes LiClO3·3H2O and/or ZnCl2·3H2O。
Further, the low-melting-point alloy material comprises Ga-ln-Zn alloy, and the Ga-ln-Zn alloy comprises 50-70 wt% of Ga, 15-25 wt% of ln and 5-35 wt% of Zn.
Further, the content of the carbon nanotubes in the graphene/carbon nanotube composite low-temperature phase change material is 0.5 wt%.
The embodiment of the invention also provides a preparation method of the graphene/carbon nanotube composite low-temperature phase-change material, which comprises the following steps: and mixing the graphene-based phase-change material and the carbon nano tube, and then performing ball milling and/or stirring to fully mix the graphene-based phase-change material and the carbon nano tube to obtain the graphene/carbon nano tube composite low-temperature phase-change material.
Further, the ball milling and/or stirring time is 15-20 hours.
The embodiment of the invention also provides application of the graphene/carbon nano tube composite low-temperature phase change material in preparation of a phase change energy storage device.
The embodiment of the invention also provides a phase change energy storage device which comprises an accommodating mechanism, wherein the accommodating mechanism is internally provided with the graphene/carbon nano tube composite low-temperature phase change material.
According to the embodiment of the invention, the carbon nano-tube, graphene and other nano-carbon materials are compounded with the inorganic crystal hydrated salt material, the low-melting-point alloy material and other traditional phase-change materials, so that the special nano-structure and chemical stability, excellent mechanical, electrical and optical properties and the like of the carbon nano-tube, graphene and other one-dimensional and two-dimensional nano-materials can be fully utilized, and the materials are mutually cooperated, so that the basic properties of the phase-change material, such as phase-change latent heat, thermal conductivity and the like, are effectively improved.
The technical solution, the implementation process and the principle thereof will be further explained with reference to the specific implementation examples as follows. Unless otherwise specifically indicated below, the various materials, processing equipment, and detection methods employed therein may be those known in the art.
Example 1
A graphene/carbon nanotube composite low-temperature phase change material comprises a pure phase change material serving as a matrix material and a carboxylated carbon nanotube serving as an additive material, wherein the addition amount of the carboxylated carbon nanotube is 0.1 wt%; the pure phase change material is a graphene-based phase change material, and the graphene-based phase change material comprises 30-50 wt% of few-layer graphene and 49-69 wt% of LiClO3·3H2The carboxylated multi-wall carbon nano tube has the diameter of 10-60 nm, the length of 5-50 mu m, the purity of over 98 percent and the content of carboxyl of more than 0.5 mmol/g.
The graphene/carbon nanotube composite low-temperature phase-change material can be prepared by mixing the raw materials of the graphene-based phase-change material with the carbon nanotubes and then performing ball milling.
Example 2
The graphene/carbon nanotube composite low-temperature phase-change material is basically the same as the graphene/carbon nanotube composite low-temperature phase-change material in the embodiment 1, except that: wherein the content of the carboxylated multi-wall carbon nano tube is 0.5 weight percent.
Example 3
A graphene/carbon nanotube composite low-temperature phase-change material comprises pure graphene/carbon nanotube as a matrix materialThe phase change material comprises a phase change material and carboxylated carbon nanotubes serving as an additive material, wherein the addition amount of the carboxylated carbon nanotubes is 1 wt%, the pure phase change material is a graphene-based phase change material, and the graphene-based phase change material comprises 30-50 wt% of few-layer graphene and 49-69 wt% of ZnCl2·3H2O and/or 49-69 wt% Ga67ln20.5Zn12.5The carboxylated multi-wall carbon nano tube has the diameter of 10-60 nm, the length of 5-50 mu m and the purity of more than 98 percent.
The preparation method of the graphene/carbon nanotube composite low-temperature phase-change material is basically the same as that of the embodiments 1 and 2.
Comparative example 1
Comparative example 1 provides a phase change material identical to the graphene-based phase change material of example 1.
Comparative example 2
The composite low-temperature phase-change material provided in the comparative example 2 is basically the same as the graphene/carbon nanotube composite low-temperature phase-change material of the example 2, and the difference is that: SCNC-KJ-2 multi-walled carbon nanotubes provided by Suzhou Jiedi nanotechnology Co., Ltd instead of carboxylated multi-walled carbon nanotubes.
The phase change materials of examples 1 to 3 and comparative example 1 were tested, respectively, and differential scanning calorimetry curves and thermal conductivity curves of the phase change materials of examples 1 to 3 and comparative example 1 were obtained, and the results are shown in fig. 1 and 2.
As can be seen from fig. 1 and 2, the graphene/carbon nanotube composite low-temperature phase change material containing 0.5 wt% of carbon nanotubes improves the thermal conductivity (by 18%) while keeping the low-temperature phase change temperature (about-5 ℃ of the phase change solidification temperature) unchanged, and is beneficial to the practical application of the low-temperature phase change material.
Comparing the carbon nanotube graphene/carbon nanotube composite low-temperature phase change material of example 2 with the composite low-temperature phase change material of comparative example 2, it can be found that the thermal conductivity of the product of example 2 is improved by more than 10% compared with the product of comparative example 2.
The graphene/carbon nanotube composite low-temperature phase-change material provided by the embodiment of the invention has the advantages that the heat conductivity coefficient is obviously improved under the condition that the low-temperature phase-change temperature (about-5 ℃ of phase-change solidification temperature) is kept unchanged, and the practical application of the low-temperature phase-change material is facilitated; and the graphene/carbon nano tube composite low-temperature phase-change material is made of a pure inorganic phase-change material, so that the phase-change volume change of the graphene/carbon nano tube composite low-temperature phase-change material is small, the phase-change latent heat is large, and the heat conductivity coefficient is large.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. The graphene/carbon nanotube composite low-temperature phase change material is characterized by comprising a graphene-based phase change material and a carbon nanotube, wherein the graphene-based phase change material comprises few-layer graphene and an inorganic crystalline hydrated salt material and/or a low-melting-point alloy material, and the content of the carbon nanotube in the graphene/carbon nanotube composite low-temperature phase change material is 0.1-1 wt%.
2. The graphene/carbon nanotube composite low-temperature phase change material according to claim 1, wherein the graphene-based phase change material comprises 30-50 wt% of few-layer graphene and 49-69 wt% of inorganic crystalline hydrated salt material and/or 49-69 wt% of low-melting-point alloy material.
3. The graphene/carbon nanotube composite low-temperature phase change material of claim 1, wherein: the carbon nanotubes include carboxylated multi-walled carbon nanotubes.
4. The graphene/carbon nanotube composite low-temperature phase change material of claim 3, wherein: the carboxylated multi-wall carbon nano tube has the diameter of 10-60 nm, the length of 5-50 mu m, the purity of over 98 percent and the carboxyl content of more than 0.5 mmol/g.
5. According toThe graphene/carbon nanotube composite low-temperature phase-change material of claim 1, wherein: the inorganic crystalline hydrous salt material comprises LiClO3·3H2O and/or ZnCl2·3H2O。
6. The graphene/carbon nanotube composite low-temperature phase change material of claim 1, wherein: the low-melting-point alloy material comprises Ga-ln-Zn alloy, wherein the Ga-ln-Zn alloy comprises 50-70 wt% of Ga, 15-25 wt% of ln and 5-35 wt% of Zn.
7. The graphene/carbon nanotube composite low-temperature phase change material of claim 1, wherein: the content of the carbon nano tube in the graphene/carbon nano tube composite low-temperature phase-change material is 0.5 wt%.
8. The preparation method of the graphene/carbon nanotube composite low-temperature phase change material of any one of claims 1 to 8, characterized by comprising the following steps: mixing the graphene-based phase-change material and the carbon nano tube, and then performing ball milling and/or stirring to fully mix the graphene-based phase-change material and the carbon nano tube to obtain a graphene/carbon nano tube composite low-temperature phase-change material; preferably, the ball milling and/or stirring time is 15-20 hours.
9. Use of the graphene/carbon nanotube composite low-temperature phase change material according to any one of claims 1 to 7 in preparation of a phase change energy storage device.
10. The utility model provides a phase change energy storage device, includes holding mechanism, its characterized in that: the accommodating mechanism is provided with the graphene/carbon nanotube composite low-temperature phase-change material as claimed in any one of claims 1 to 7.
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