CN115247049A - Graphite foam-based phase-change energy storage material and preparation method thereof - Google Patents

Graphite foam-based phase-change energy storage material and preparation method thereof Download PDF

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Publication number
CN115247049A
CN115247049A CN202210112352.0A CN202210112352A CN115247049A CN 115247049 A CN115247049 A CN 115247049A CN 202210112352 A CN202210112352 A CN 202210112352A CN 115247049 A CN115247049 A CN 115247049A
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graphite
foam
solution
energy storage
storage material
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姜丽丽
赵乐
于海涛
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Lanzhou University of Technology
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Lanzhou University of Technology
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/06Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14Thermal energy storage

Abstract

The invention discloses a graphite foam-based phase-change energy storage material and a preparation method thereof, belonging to the technical field of phase-change energy storage materials and comprising the following steps: pretreating polyurethane foam, wherein the pretreatment comprises soaking the polyurethane foam in a sodium hydroxide solution; soaking the pretreated polyurethane foam in a phenolic resin-graphite solution, and drying, curing and sintering to prepare graphite foam; and filling an organic phase-change material into the graphite foam to obtain the graphite foam-based phase-change energy storage material. The graphite foam-based phase-change energy storage material obtained by the invention has the advantages of good heat storage performance, good leakage prevention performance and low cost, and is more suitable for low-temperature waste heat recycling application.

Description

Graphite foam-based phase-change energy storage material and preparation method thereof
Technical Field
The invention relates to the technical field of phase change energy storage materials, in particular to a graphite foam-based phase change energy storage material and a preparation method thereof.
Background
Renewable energy sources represented by wind energy and solar energy have the characteristics of intermittency, volatility and randomness, the development of the renewable energy sources is always disturbed, and an ideal energy storage solution is found to be very important. The heat energy storage is used as a clean and efficient energy storage mode, and a good idea is provided for solving the difficulty in renewable energy utilization. The energy storage technology is widely applied to the fields of solar heat utilization, industrial waste heat and waste heat recovery, building air conditioning energy conservation and the like, and is an important technology for improving the energy utilization efficiency and protecting the environment. The phase-change energy storage technology is that heat of a medium is stored in a phase-change material firstly, so that the phase-change material is subjected to phase change, the energy is stored in a latent heat mode, and when the energy is needed, the phase-change material is subjected to phase change again, the latent heat is released, and heat exchange is completed.
Phase Change Materials (PCM), or phase change energy storage materials, are widely researched because they have the characteristics of large energy storage density, low cost, and stable output temperature and energy. However, the traditional phase change material has low heat conduction performance (0.1-1W/(m.K)), and the heat transfer efficiency of the phase change material in the process of storing/releasing heat is influenced. In addition, the traditional organic phase change material has certain fluidity, so that the traditional organic phase change material has a sealing problem and is difficult to be widely applied to various application scenes. Leakage, low thermal conductivity, is still a major problem limiting the application of phase change materials.
Disclosure of Invention
The invention aims to provide a graphite foam-based phase-change energy storage material and a preparation method thereof, which are used for solving the problems in the prior art.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a graphite foam-based phase-change energy storage material, which comprises the following steps:
pretreating polyurethane foam, wherein the pretreatment comprises soaking the polyurethane foam in a sodium hydroxide solution;
soaking the pretreated polyurethane foam in a phenolic resin-graphite solution, and drying, curing and sintering to prepare graphite foam;
filling an organic phase-change material into the graphite foam to obtain the graphite foam-based phase-change energy storage material, wherein the mass ratio of the organic phase-change material to the graphite foam is 7-9.
Further, the polyurethane foam pretreatment comprises:
soaking polyurethane foam in a sodium hydroxide solution for 60-120min, washing with deionized water to neutrality, washing with absolute ethyl alcohol, and vacuum drying to obtain pretreated polyurethane foam;
wherein the mass fraction of the sodium hydroxide solution is 40%, and the soaking temperature of the sodium hydroxide solution is 80 ℃.
The polyurethane foam is etched and closed in the sodium hydroxide solution, and is cleaned and dried to obtain the polyurethane foam with high aperture ratio, and the sodium hydroxide solution is soaked to open more closed pores to obtain higher porosity, so that higher filling rate is obtained, and the composite phase-change material with strong heat storage capacity is obtained.
Further, the preparation method of the phenolic resin-graphite solution comprises the following steps:
dissolving resorcinol in a mixture of water and ethanol, adding a hydrochloric acid solution after uniformly mixing, then dropwise adding a formaldehyde solution under the stirring condition, and violently stirring to obtain a homogeneous solution;
and adding synthetic graphite and nickel nitrate into the homogeneous phase solution to obtain the phenolic resin-graphite solution.
Further, the mass ratio of water to ethanol in the mixture is 1; the mass ratio of the resorcinol to the mixture is 1.2-4.
Further, the mass fraction of the hydrochloric acid solution is 37%; the mass ratio of the hydrochloric acid solution to the formaldehyde solution is 1.
Further, the mass ratio of the synthetic graphite to the nickel nitrate is 1; the mass ratio of the synthetic graphite to the homogeneous solution is 1.
Further, the pretreated polyurethane foam is soaked in the phenolic resin-graphite solution for 5min, the solution is removed after being taken out, then the solution is dried in vacuum at 80 ℃ for 12h, then the solution is cured at 150 ℃ for 24h, and then the solution is heated to 1000 ℃ under argon flow at the heating rate of 2 ℃/min and carbonized for 1h to prepare the graphite foam.
Further, the step of filling the organic phase change material into the interior of the graphite foam is performed by a method combining melt impregnation and vacuum impregnation.
Further, the method of combining melt impregnation and vacuum impregnation comprises:
after the organic phase change material is melted, adding the graphite foam for soaking for 12 hours; and then transferring the soaking system into a filter flask, blocking the mouth of the filter flask, keeping for 30s after 1min of air suction, repeating for 2-3 times to obtain a composite material sample, placing the composite material sample on filter paper, performing vacuum drying, and continuously replacing the filter paper until no liquid leaks on the filter paper, thereby obtaining the graphite foam-based phase-change energy storage material.
Further, the organic phase change material includes paraffin, decanol, tetradecanol, hexadecanol, or octadecylamine. Still further, the organic phase change material is octadecylamine.
The invention also provides a graphite foam-based phase-change energy storage material which is prepared by adopting any one of the preparation methods of the graphite foam-based phase-change energy storage material.
The invention also provides application of the graphite foam-based phase change energy storage material in the field of low-temperature waste heat recovery.
The invention discloses the following technical effects:
according to the invention, the porous material is combined with the organic phase change material, so that the leakage problem of the phase change material can be solved, the heat conductivity of the phase change material can be improved, the porous material has an excellent structure, has higher pore volume, specific surface area and storage capacity, and simultaneously has excellent adsorption performance, so that the phase change material can be easily combined into pores. Due to various forces such as van der waals force, hydrogen bond, surface tension and the like, the phase change material is fixed in the support matrix, so that the phase change material is prevented from leaking from pores, and the porous material is responsible for keeping the integral shape of all structures in the phase change process. In this way, the phase-change material is not only bonded to the support substrate, but also it is possible to improve the thermal conductivity, chemical stability, and packaging and thermal conductivity of the phase-change energy storage material.
According to the invention, the polyurethane foam is subjected to hole etching by the sodium hydroxide, so that more closed holes of the polyurethane foam template can be effectively opened, the filling rate and the heat conductivity of the graphite foam-based phase-change energy storage material are improved, and the leakage performance of the graphite foam-based phase-change energy storage material is improved.
The graphite foam-based phase-change energy storage material obtained by the invention has the advantages of good heat storage performance, good leakage prevention performance and low cost, and is more suitable for low-temperature waste heat recycling application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph of a polyurethane foam before and after pretreatment with a sodium hydroxide solution, the left graph being untreated with the sodium hydroxide solution and the right graph being treated with the sodium hydroxide solution;
FIG. 2 is a scanning electron microscope image of the graphite foam-based phase change energy storage material of example 1;
FIG. 3 is a differential scanning calorimetry trace of the graphite foam-based phase-change energy storage material of example 1;
fig. 4 is a leakage experimental graph of pure octadecylamine and the graphite foam-based phase-change energy storage material of example 1, the left two graphs are pure octadecylamine, and the right two graphs are the graphite foam-based phase-change energy storage material of example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in the present disclosure, it is understood that each intervening value, to the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including but not limited to.
Example 1
(1) Pretreatment of polyurethane foam (PU foam):
the density is 13kg/m 3 The polyurethane foam (PU foam) is cut into blocks with the size of 3 multiplied by 2 multiplied by 1cm, after being soaked in sodium hydroxide solution with the mass fraction of 40 percent at the temperature of 80 ℃ for 60min, the blocks are repeatedly washed to be neutral by deionized water, then washed by absolute ethyl alcohol for 1 to 2 times, and placed in a vacuum drying oven at the temperature of 80 ℃ for drying for 12h, thus obtaining the polyurethane foam with the hydrolysis degree of 15 percent.
FIG. 1 is a diagram of the polyurethane foam before and after pretreatment with NaOH solution, the left diagram is not treated with NaOH solution, and the right diagram is treated with NaOH solution, so that it is obvious that the porosity of the polyurethane foam in the right diagram is higher.
(2) Preparing graphite foam:
the resorcinol is dissolved in a mixture of water and ethanol (mass ratio of water to ethanol is 1:3.2, and stirring (300 r/min) the mixture for 15min; adding a hydrochloric acid solution with the mass fraction of 37% (mass ratio of the mixture to the hydrochloric acid solution is 30). The reaction mixture was stirred vigorously for a further 1h (1200 r/min) and then a homogeneous solution was obtained.
Adding synthetic graphite and nickel nitrate into the homogeneous solution, and stirring for 2h (1000 r/min), wherein the mass ratio of the synthetic graphite to the nickel nitrate is 1:1, the mass ratio of the synthetic graphite to the homogeneous phase solution is 1.
The PU foam was immersed in the above phenolic resin-graphite solution for 5min, the excess solution was removed with a glass rod, followed by drying in a vacuum oven at 80 ℃ for 12h and then curing at 150 ℃ for 24h. The polymer composite foam was carbonized in a tube furnace at a heating rate of 2 ℃/min under argon flow at 1000 ℃ for 1h to obtain highly interconnected three-dimensional (3D) graphite foam.
(3) Preparing a graphite foam-based phase-change energy storage material:
weighing octadecylamine in a beaker, placing the weighed octadecylamine in an oven at 80 ℃ to be completely melted, adding graphite foam to soak for 12h, wherein the mass ratio of octadecylamine to graphite foam is 50.
The filling rate of the finally prepared graphite foam-based phase change energy storage material is 88.64%, wherein the mass ratio of the octadecylamine to the graphite foam is 8.9.
A Scanning Electron Microscope (SEM) image of the graphite foam-based phase-change energy storage material is shown in figure 2, and therefore, the open-cell and macroporous interconnection network structure of the graphite foam can be seen.
A DSC (differential scanning calorimeter) curve of the graphite foam-based phase-change energy storage material is shown in figure 3, the solidification temperature is 41.33 ℃, the solidification latent heat is 227.8J/g, and the solidification latent heat of the pure octadecylamine phase-change material is 217.9J/g.
The thermal conductivity of the graphite foam-based phase-change energy storage material is characterized by a thermal conductivity meter, the measured thermal conductivity is 0.72W/m.k, and in comparison, the thermal conductivity of pure octadecylamine is 0.32W/m.k, so that the thermal conductivity of the graphite foam-based phase-change energy storage material provided by the embodiment 1 of the application is improved by 125%.
As shown in figure 4, when the octadecylamine and the composite material are placed in a vacuum drying oven at 80 ℃ for 30min, the pure octadecylamine phase change material is obviously leaked, but the composite material is not leaked, and the composite material is proved to have good leakage-proof performance.
Comparative example 1
The density is 13kg/m 3 The polyurethane foam is cut into blocks of 3 multiplied by 2 multiplied by 1cm, soaked in sodium hydroxide solution with mass fraction of 40 percent at 80 ℃ for 180min, repeatedly washed to be neutral by deionized water, then washed by absolute ethyl alcohol for 1 to 2 times, and the polyurethane foam structure is broken and loses resilience in the washing process due to overlong soaking time and excessive hydrolysis, and is dried in a vacuum drying oven at 80 ℃ for 12h, and the hydrolysis degree is 30.11 percent.
Comparative example 2
The density is 13kg/m 3 The polyurethane foam is cut into blocks with the size of 3 multiplied by 2 multiplied by 1cm, soaked in sodium hydroxide solution with the mass fraction of 40 percent at 80 ℃ for 30min, repeatedly washed by deionized water to be neutral, then washed by absolute ethyl alcohol for 1 to 2 times, and placed in a vacuum drying oven at 80 ℃ for drying for 12h to obtain the polyurethane foam with the hydrolysis degree of 0.75 percent.
Comparative example 3
The difference from example 1 is that step (1) is not included, i.e., the polyurethane foam is not pretreated, and the following step is carried out directly using the polyurethane foam which is not pretreated.
The filling rate of the finally prepared graphite foam-based phase change energy storage material is 54%, wherein the mass ratio of the octadecylamine to the graphite foam is 5:1.
the solidification temperature of the graphite foam-based phase change energy storage material is 39.56 ℃, the solidification latent heat is 177.2J/g, and the thermal conductivity is 0.36W/m.k.
Example 2
(1) Pretreatment of polyurethane foam (PU foam):
the density is 13kg/m 3 The polyurethane foam (PU foam) is cut into blocks of 3 multiplied by 2 multiplied by 1cm, soaked in sodium hydroxide solution with the mass fraction of 40% at the temperature of 80 ℃ for 120min, repeatedly washed by deionized water to be neutral, then washed by absolute ethyl alcohol for 1 to 2 times, and placed in a vacuum drying oven at the temperature of 80 ℃ for drying for 12h to obtain the polyurethane foam with the hydrolysis degree of 26.8%, and the foam resilience is poor.
(2) Preparing graphite foam:
the resorcinol is dissolved in a mixture of water and ethanol (mass ratio of water to ethanol is 1:4, stirring (300 r/min) the mixture for 15min; adding a hydrochloric acid solution with the mass fraction of 37% (the mass ratio of the mixture to the hydrochloric acid solution is 30). The reaction mixture was stirred vigorously for a further 1h (1000 r/min) and then a homogeneous solution was obtained.
Adding synthetic graphite and nickel nitrate into the homogeneous solution, and stirring for 2h (800 r/min), wherein the mass ratio of the synthetic graphite to the nickel nitrate is 1: and 1, the mass ratio of the synthetic graphite to the homogeneous phase solution is 1.
The PU foam was immersed in the above phenolic resin-graphite solution for 5min, the excess solution was removed with a glass rod, followed by drying in a vacuum oven at 80 ℃ for 12h and then curing at 150 ℃ for 24h. The polymer composite foam was carbonized in a tube furnace at a heating rate of 2 ℃/min under argon flow at 1000 ℃ for 1h to obtain highly interconnected three-dimensional (3D) graphite foam.
(3) Preparing a graphite foam-based phase-change energy storage material:
weighing octadecylamine in a beaker, placing the weighed octadecylamine in an oven at 80 ℃ to be completely melted, adding graphite foam to soak for 12h, wherein the mass ratio of octadecylamine to graphite foam is 50.
The filling rate of the finally prepared graphite foam-based phase change energy storage material is 77.58%, wherein the mass ratio of the octadecylamine to the graphite foam is 7.6.
The solidification temperature of the graphite foam-based phase change energy storage material is 39.22 ℃, the solidification latent heat is 207.5J/g, and the heat conductivity is 0.43W/m.k.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (10)

1. A preparation method of a graphite foam-based phase change energy storage material is characterized by comprising the following steps:
pretreating polyurethane foam, wherein the pretreatment of the polyurethane foam comprises soaking the polyurethane foam in a sodium hydroxide solution;
soaking the pretreated polyurethane foam in a phenolic resin-graphite solution, and drying, curing and sintering to prepare graphite foam;
filling an organic phase-change material into the graphite foam to obtain the graphite foam-based phase-change energy storage material, wherein the mass ratio of the organic phase-change material to the graphite foam is 7-9.
2. The method of claim 1, wherein the polyurethane foam pre-treatment comprises:
soaking polyurethane foam in a sodium hydroxide solution for 60-120min, washing with deionized water to neutrality, washing with absolute ethyl alcohol, and vacuum drying to obtain pretreated polyurethane foam;
wherein the mass fraction of the sodium hydroxide solution is 40%, and the soaking temperature of the sodium hydroxide solution is 80 ℃.
3. The method according to claim 1, wherein the method for preparing the phenolic resin-graphite solution comprises:
dissolving resorcinol in a mixture of water and ethanol, adding a hydrochloric acid solution after uniformly mixing, then dropwise adding a formaldehyde solution under the stirring condition, and violently stirring to obtain a homogeneous solution;
and adding synthetic graphite and nickel nitrate into the homogeneous phase solution to obtain the phenolic resin-graphite solution.
4. The preparation method according to claim 3, wherein the mass ratio of water to ethanol in the mixture is 1; the mass ratio of the resorcinol to the mixture is 1.2-4.
5. The preparation method according to claim 3, wherein the mass fraction of the hydrochloric acid solution is 37%; the mass ratio of the hydrochloric acid solution to the formaldehyde solution is 1.
6. The production method according to claim 3, wherein the mass ratio of the synthetic graphite to the nickel nitrate is 1; the mass ratio of the synthetic graphite to the homogeneous solution is 1.
7. The method of claim 1, wherein the pre-treated polyurethane foam is soaked in the phenolic resin-graphite solution for 5min, taken out, excess solution is removed, and then dried in vacuum at 80 ℃ for 12h, and then cured at 150 ℃ for 24h, and then heated to 1000 ℃ under argon flow at a heating rate of 2 ℃/min, and carbonized for 1h to prepare the graphite foam.
8. The preparation method according to claim 1, wherein the step of filling the interior of the graphite foam with the organic phase change material is performed by a method combining melt impregnation and vacuum impregnation, and comprises the following steps:
after the organic phase change material is melted, adding the graphite foam for soaking for 12 hours; and then transferring the soaking system into a filter flask, blocking the mouth of the filter flask, keeping for 30s after 1min of air suction, repeating for 2-3 times to obtain a composite material sample, placing the composite material sample on filter paper, performing vacuum drying, and continuously replacing the filter paper until no liquid leaks on the filter paper, thereby obtaining the graphite foam-based phase-change energy storage material.
9. A graphite foam-based phase-change energy storage material, which is prepared by the preparation method of the graphite foam-based phase-change energy storage material as claimed in any one of claims 1 to 8.
10. The application of the graphite foam-based phase-change energy storage material as claimed in claim 9 in the field of low-temperature waste heat recovery.
CN202210112352.0A 2022-01-29 2022-01-29 Graphite foam-based phase-change energy storage material and preparation method thereof Pending CN115247049A (en)

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