CN109054757B - Preparation method of Al @ C composite phase change heat storage material with core-shell structure - Google Patents
Preparation method of Al @ C composite phase change heat storage material with core-shell structure Download PDFInfo
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Abstract
The invention relates to a preparation method of an Al @ C composite phase-change heat storage material with a core-shell structure, and belongs to the technical field of heat storage materials. Adding aluminum powder into a nickel chloride solution, dropwise adding an ammonia fluoride solution for reaction, and then roasting at high temperature to obtain a precursor Al @ Al2O3(ii) a The precursor Al @ Al2O3And (2) placing the material in a fixed bed, introducing methane gas, and catalytically cracking methane at high temperature to generate carbon and hydrogen, wherein carbon particles uniformly cover the surface of the precursor to obtain the Al @ C composite phase change heat storage material with the core-shell structure. The aluminum in the Al @ C composite phase-change heat storage material has excellent performances of large melting heat, high heat conductivity coefficient, low evaporation pressure and the like; carbon has strong thermal conductivity, and the heat storage material wrapped by carbon has better sealing property. The heat storage material prepared by the invention can bear the chemical corrosion of liquid metal in a molten state and the pressure caused by volume expansion, and can provide better mechanical strength and enhance the heat transfer performance.
Description
Technical Field
The invention relates to a preparation method of an Al @ C composite phase-change heat storage material with a core-shell structure, and belongs to the technical field of heat storage materials.
Background
The scientific development and utilization of renewable energy sources such as solar energy, wind energy, water energy, biomass energy, nuclear energy and the like are one of the most effective ways to solve the problems of energy crisis and environmental pollution at present. Among them, solar energy is receiving attention due to its abundant resources and freely available characteristics. Concentrated Solar Power (CSP) can convert solar energy into heat energy and generate electricity through a steam turbine or a heat engine, thereby achieving carbon emission reduction. However, the power generation capacity of the CSP system is greatly affected by the instability and intermittency of solar energy and regional climate, so that the CSP system is not easy to develop.
The thermal energy storage system (TES) can store energy for later use, and can just make up the defects of the CSP system. The latent heat storage system stores and releases heat at the phase change temperature by using phase change heat storage materials (PCMs), so that a large amount of heat energy can be stored in a small volume, and the latent heat storage system is high in heat storage density, simple and convenient to use, low in cost and high in heat conversion rate.
However, the heat efficiency of the latent heat storage system is improved along with the increase of the operating temperature, the existing phase change heat storage material has low heat conductivity and long reaction preparation period, and shell layer materials cannot bear the change of phase change volume and cause leakage.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of an Al @ C composite phase change heat storage material with a core-shell structure, wherein the phase change temperature of an inner core Al in the Al @ C is 660 ℃, the inner core Al has higher melting heat (about 396.09J/g), high heat conductivity coefficient, low evaporation pressure and low heat storage cost, and the alpha-Al2O3The phase change material Al can be encapsulated to form a core-shell structure Al @ Al2O3(ii) a The existence of nickel can increase the thickness of alumina on the surface of the material to form Al2O3A NiO shell layer which can catalyze the methane catalytic cracking reaction, and carbon generated by methane cracking covers the precursor Al @ Al with the core-shell structure2O3The surface enhances the sealing property and the heat conductivity, the thickness of a shell layer on the surface of the heat storage material is enhanced, the heat transfer area is increased, and the mechanical strength of the material is enhanced; using Al @ Al2O3The Al @ C prepared from the core-shell structure precursor and the carbon covered shell has two shells of aluminum oxide and carbon, so that the mechanical strength of the surface of the material is greatly enhanced, the deformation pressure can be better borne, and the heat transfer area is increased; moreover, a large amount of hydrogen is generated by methane cracking, and the hydrogen can be collected to be used as energy source gas.
Adding aluminum powder into a nickel chloride solution, dropwise adding an ammonia fluoride solution for reaction, and then roasting at high temperature to obtain a precursor Al @ Al2O3(ii) a The precursor Al @ Al2O3And (2) placing the material in a fixed bed, introducing methane gas, and catalytically cracking methane at high temperature to generate carbon and hydrogen, wherein carbon particles uniformly cover the surface of the precursor to obtain the Al @ C composite phase change heat storage material with the core-shell structure.
A preparation method of an Al @ C composite phase change heat storage material with a core-shell structure comprises the following specific steps:
(1) respectively mixing aluminium powder and NiCl2、NH4F is added into deionized water or ultrapure water to prepare aluminum powder turbid liquid and NiCl2Solution and NH4F solution;
(2) placing the aluminum powder turbid liquid obtained in the step (1) in ultrasonic waves for ultrasonic treatment for 5-30 min to obtain an aluminum powder turbid liquid;
(3) adding gelatin to the NiCl of step (1)2Uniformly stirring the solution at the temperature of 35-55 ℃, then adding the aluminum powder suspension obtained in the step (2), and reacting for 5-20 min at the temperature of 35-55 ℃ under stirring to obtain a solution A;
(4) dropwise adding NH in the step (1) into the solution A in the step (3) at the temperature of 35-55 ℃ under the stirring condition4Continuously reacting the solution F for 0.5-3 h; washing for 3-5 times alternately according to the sequence of water, absolute ethyl alcohol and water, carrying out solid-liquid separation, and drying the solid (at 50-100 ℃);
(5) uniformly heating the solid dried in the step (4) to 600-800 ℃ and roasting at high temperature for 2-16 h to obtain a precursor Al @ Al2O3；
(6) Leading the precursor Al @ Al in the step (5)2O3Placing the material in a fixed bed, introducing a methane-inert gas mixed gas, and carrying out methane catalytic cracking reaction for 0.2-5 h at the temperature of 500-750 ℃ to obtain the Al @ C composite phase change heat storage material with the core-shell structure;
aluminum powder and NiCl in the step (1)2、NH4The molar ratio of F is (5-20): (0.5-2): 1-3), the concentration of aluminum powder in the aluminum powder turbid liquid is 0.5-2 mol/L, and NiCl2NiCl in solution2The concentration of (A) is 0.05-0.2 mol/L, NH4NH in solution F4The concentration of F is 0.1-0.3 mol/L;
further, the power of the ultrasonic wave in the step (2) is 40-80W.
Further, in the step (3), gelatin and NiCl are used2The solid-liquid ratio g of the solution is (3-15) to 1;
further, the dropwise adding speed in the step (4) is 1-5 drops/s;
further, the rate of constant temperature rise in the step (5) is 1-10 ℃/min;
furthermore, the volume fraction of methane in the methane-inert gas mixed gas is 1-100%, and the inert gas is nitrogen or argon.
The invention also aims to provide the Al @ C composite phase-change heat storage material prepared by the preparation method of the Al @ C composite phase-change heat storage material with the core-shell structure.
The Al @ C composite phase change heat storage material with the core-shell structure takes alumina and carbon as base materials, takes spherical metal aluminum as a core, and is wrapped by inner-layer alumina and outer-layer carbon; the preparation flow diagram is shown in figure 1; during the heat storage process, the spherical metal aluminum of the inner core absorbs heat to change from a solid state to a liquid state, so that the overall temperature is increased; when the temperature is low, the aluminum is solidified and emits heat; in the period, because the outer layer has higher strength, larger deformation can not occur at higher temperature, and the solid or liquid metal aluminum can be tightly wrapped without leakage.
The invention has the beneficial effects that:
(1) in the prior art, the service temperature of the medium-low temperature heat storage material is not higher than 300 ℃, but the Al @ C composite phase change heat storage material with the core-shell structure has high service temperature, can be used in an environment of 600-1400 ℃, and can more easily meet the industrial requirements of a solar power plant;
(2) the Al @ C composite phase change heat storage material with the core-shell structure is prepared from Al2O3Is wrapped by two layers of C shells, is high temperature resistant and enhances the mechanical strength, and meanwhile, Al @ Al2O3And the C two layers of shells wrap the spherical metal aluminum of the inner core, so that the heat exchange area and the wrapping tightness can be increased;
(3) the nickel of the invention can increase the thickness of the alumina on the surface of the material to form compact Al2O3The NiO shell layer can catalyze the methane catalytic cracking reaction to generate carbon deposition;
(4) the carbon fiber has strong ductility and is covered on a precursor Al @ Al of a core-shell structure2O3The surface improves the sealing property, increases the thickness of a shell layer on the surface of the heat storage material, increases the heat transfer area, increases the mechanical strength of the material, and can better bear the pressure caused by aluminum deformation;
(5) in the method, a large amount of hydrogen is also generated by methane cracking, and the hydrogen can be collected to be used as energy gas;
(6) the method has the advantages of cheap and easily-obtained raw materials, simple process flow and capability of realizing large-scale production.
Drawings
FIG. 1 is a structural flow chart of an Al @ C composite phase change heat storage material with a core-shell structure;
FIG. 2 is a diagram showing the methane catalytic cracking conversion of the Al @ C composite phase-change heat storage material prepared in example 1;
FIG. 3 is a Raman representation of the Al @ C composite phase-change thermal storage material prepared in example 1;
FIG. 4 is a DSC heat absorption and release characteristic diagram of the Al @ C composite phase-change heat storage material prepared in example 1;
fig. 5 is an SEM image of the Al @ C composite phase change heat storage material prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: as shown in fig. 1, a preparation method of an Al @ C composite phase change heat storage material with a core-shell structure comprises the following specific steps:
(1) respectively mixing aluminium powder and NiCl2、NH4F is added into deionized water to prepare aluminum powder turbid liquid and NiCl2Solution and NH4F solution; wherein the aluminum powder and the NiCl2、NH4The molar ratio of F is 15:1.6:2, the concentration of the aluminum powder in the aluminum powder turbid liquid is 1.5mol/L, and NiCl2NiCl in solution2Is 0.16mol/L, NH4NH in solution F4The concentration of F is 0.2 mol/L;
(2) putting the turbid liquid of the aluminum powder in the step (1) into ultrasonic waves with the power of 70W for ultrasonic treatment for 10min to obtain a turbid liquid of the aluminum powder;
(3) adding gelatin to the NiCl of step (1)2In solution, gelatin and NiCl2The solid-liquid ratio g of the solution to L is 10:1, the solution is stirred evenly at the temperature of 40 ℃, then the aluminum powder suspension liquid in the step (2) is added and stirred at the temperature of 40 DEG CReacting for 10min under the condition to obtain a solution A;
(4) dropwise adding NH (1) into the solution A in the step (3) at the temperature of 40 ℃ under stirring4Continuously reacting the solution F for 0.5h, wherein the dropping speed is 1 drop/s; washing for 3 times alternately according to the sequence of water-absolute ethyl alcohol-water, separating solid from liquid, and drying the solid at 100 ℃;
(5) uniformly heating the solid dried in the step (4) to 800 ℃ and roasting at high temperature for 2h to obtain a precursor Al @ Al2O3Wherein the rate of constant temperature rise is 10 ℃/min;
(6) leading the precursor Al @ Al in the step (5)2O3Placing the material in a fixed bed, introducing a methane-nitrogen mixed gas, and carrying out methane catalytic cracking reaction for 2 hours at the temperature of 650 ℃ to obtain the Al @ C composite phase-change heat storage material with the core-shell structure; wherein the volume fraction of methane in the methane-nitrogen mixed gas is 10 percent;
the methane catalytic cracking conversion diagram of the Al @ C composite phase-change heat storage material prepared in the embodiment is shown in FIG. 2, and as can be seen from FIG. 2, methane undergoes a cracking reaction at 650 ℃ and generates hydrogen, and the reaction time is short, so that the industrial production period is favorably shortened;
the Raman characteristic diagram of the Al @ C composite phase-change heat storage material prepared in the embodiment is shown in FIG. 3, and can be seen from FIG. 3, the Raman characteristic diagram is 1500cm-1Two characteristic peaks for characterizing carbon are nearby, which indicates that the carbon is successfully covered on a precursor Al @ Al2O3A surface;
the DSC heat absorption and release characteristic diagram of the Al @ C composite phase-change heat storage material prepared in this example is shown in fig. 4, and as can be seen from fig. 4, the phase-change temperatures of the Al @ C composite phase-change heat storage material obtained in this example are: heat absorption is 660 ℃, and heat release is 629 ℃; wherein the heat absorption and release value is about 300J/g, compared with Al @ NiO-Al2O3The 317J/g of the material is low, which indicates that more carbon is attached to the surface of the material, so that the proportion of aluminum is reduced, the heat absorption and release values are reduced, but the heat absorption and release difference value of Al @ C is not large, namely the energy loss of the process of Al @ C is small;
an SEM image of the Al @ C composite phase-change heat storage material prepared in this example is shown in fig. 5, and it can be seen from fig. 5 that the Al @ C composite phase-change heat storage material obtained in this example has relatively uniform carbon coverage on the surface and good surface wrapping property.
Example 2: as shown in fig. 1, a preparation method of an Al @ C composite phase change heat storage material with a core-shell structure comprises the following specific steps:
(1) respectively mixing aluminium powder and NiCl2、NH4F is added into ultrapure water to prepare aluminum powder turbid liquid and NiCl2Solution and NH4F solution; wherein the aluminum powder and the NiCl2、NH4The molar ratio of F is 5:0.5:1, the concentration of the aluminum powder in the aluminum powder turbid liquid is 0.5mol/L, and NiCl2NiCl in solution2Is 0.05mol/L, NH4NH in solution F4The concentration of F is 0.1 mol/L;
(2) putting the turbid liquid of the aluminum powder in the step (1) into ultrasonic waves with the power of 40W for ultrasonic treatment for 5min to obtain a turbid liquid of the aluminum powder;
(3) adding gelatin to the NiCl of step (1)2In solution, gelatin and NiCl2The solid-liquid ratio g of the solution is 3:1, the solution is uniformly stirred at the temperature of 35 ℃, then the aluminum powder suspension liquid in the step (2) is added, and the solution A is obtained after the reaction for 5min at the temperature of 35 ℃ under the stirring condition;
(4) dropwise adding NH (1) into the solution A in the step (3) at the temperature of 35 ℃ under stirring4Continuously reacting the solution F for 0.5h, wherein the dropping speed is 1 drop/s; washing for 3 times alternately according to the sequence of water-absolute ethyl alcohol-water, separating solid from liquid, and drying the solid at 50 ℃;
(5) uniformly heating the solid dried in the step (4) to 600 ℃ and roasting at high temperature for 2h to obtain a precursor Al @ Al2O3Wherein the rate of constant temperature rise is 1 ℃/min;
(6) leading the precursor Al @ Al in the step (5)2O3Placing the material in a fixed bed, introducing a methane-nitrogen mixed gas, and carrying out methane catalytic cracking reaction for 0.2h at the temperature of 500 ℃ to obtain the Al @ C composite phase change heat storage material with the core-shell structure; wherein the mixing of methane-nitrogenThe volume fraction of methane in the gas is 1%;
from the methane catalytic cracking conversion chart of the Al @ C composite phase-change heat storage material prepared in the embodiment, methane undergoes a cracking reaction at 500 ℃, and generates part of hydrogen, and meanwhile, the reaction time is long;
the Raman characteristic diagram of the Al @ C composite phase-change heat storage material prepared in the embodiment shows that the Raman characteristic diagram is 1500cm-1Two characteristic peaks for characterizing carbon are nearby, which indicates that the carbon is successfully covered on a precursor Al @ Al2O3A surface;
as can be seen from the DSC heat absorption and release characteristic diagram of the Al @ C composite phase-change heat storage material prepared in this example, the phase-change temperature of the Al @ C composite phase-change heat storage material obtained in this example is: heat absorption is 660 ℃, and heat release is 629 ℃; wherein the heat absorption and release value is about 300J/g, compared with Al @ NiO-Al2O3The 317J/g of the material is low, which indicates that more carbon is attached to the surface of the material, so that the proportion of aluminum is reduced, the heat absorption and release values are reduced, but the heat absorption and release difference value of Al @ C is not large, namely the energy loss of the process of Al @ C is small;
as can be seen from the SEM image of the Al @ C composite phase-change heat storage material prepared in this example, the Al @ C composite phase-change heat storage material obtained in this example has relatively uniform carbon coverage on the surface and good surface wrapping property.
Example 3: as shown in fig. 1, a preparation method of an Al @ C composite phase change heat storage material with a core-shell structure comprises the following specific steps:
(1) respectively mixing aluminium powder and NiCl2、NH4F is added into deionized water to prepare aluminum powder turbid liquid and NiCl2Solution and NH4F solution; wherein the aluminum powder and the NiCl2、NH4The molar ratio of F is 20:2:3, the concentration of the aluminum powder in the aluminum powder turbid liquid is 2mol/L, and NiCl2NiCl in solution2Is 0.2mol/L, NH4NH in solution F4The concentration of F is 0.3 mol/L;
(2) putting the turbid liquid of the aluminum powder in the step (1) into ultrasonic waves with the power of 80W for ultrasonic treatment for 30min to obtain a turbid liquid of the aluminum powder;
(3) adding gelatin to the NiCl of step (1)2In solution, gelatin and NiCl2The solid-liquid ratio g of the solution is 15:1, the solution is uniformly stirred at the temperature of 55 ℃, then the aluminum powder suspension liquid in the step (2) is added, and the solution A is obtained after the reaction for 20min at the temperature of 55 ℃ under the stirring condition;
(4) dropwise adding NH (1) into the solution A in the step (3) at the temperature of 55 ℃ under stirring4Continuously reacting the solution F for 3 hours, wherein the dropping speed is 5 drops/s; washing for 5 times alternately according to the sequence of water, absolute ethyl alcohol and water, carrying out solid-liquid separation, and drying the solid at the temperature of 100 ℃;
(5) uniformly heating the solid dried in the step (4) to 800 ℃ and roasting at high temperature for 16h to obtain a precursor Al @ Al2O3Wherein the rate of constant temperature rise is 10 ℃/min;
(6) leading the precursor Al @ Al in the step (5)2O3Placing the material in a fixed bed, introducing a methane-argon mixed gas, and carrying out methane catalytic cracking reaction for 5 hours at the temperature of 750 ℃ to obtain the Al @ C composite phase change heat storage material with the core-shell structure; wherein the volume fraction of methane in the methane-nitrogen mixed gas is 100 percent;
from the methane catalytic cracking conversion chart of the Al @ C composite phase-change heat storage material prepared in the embodiment, methane is subjected to cracking reaction at 750 ℃, a large amount of hydrogen is generated, and the reaction time is short;
the Raman characteristic diagram of the Al @ C composite phase-change heat storage material prepared in the embodiment shows that the Raman characteristic diagram is 1500cm-1Two characteristic peaks for characterizing carbon are nearby, which indicates that the carbon is successfully covered on a precursor Al @ Al2O3A surface;
as can be seen from the DSC heat absorption and release characteristic diagram of the Al @ C composite phase-change heat storage material prepared in this example, the phase-change temperature of the Al @ C composite phase-change heat storage material obtained in this example is: heat absorption is 660 ℃, and heat release is 629 ℃; wherein the heat absorption and release value is about 300J/g, compared with Al @ NiO-Al2O3The 317J/g of the material is low, which indicates that more carbon is attached to the surface of the material, so that the proportion of aluminum is reduced, the heat absorption and release values are reduced, but the heat absorption and release difference value of Al @ C is not large, namely the energy loss of the process of Al @ C is small;
as can be seen from the SEM image of the Al @ C composite phase-change heat storage material prepared in this example, the Al @ C composite phase-change heat storage material obtained in this example has relatively uniform carbon coverage on the surface and good surface wrapping property.
Example 4: as shown in fig. 1, a preparation method of an Al @ C composite phase change heat storage material with a core-shell structure comprises the following specific steps:
(1) respectively mixing aluminium powder and NiCl2、NH4F is added into ultrapure water to prepare aluminum powder turbid liquid and NiCl2Solution and NH4F solution; wherein the aluminum powder and the NiCl2、NH4The molar ratio of F is 10:0.8:1.2, the concentration of the aluminum powder in the aluminum powder turbid liquid is 1mol/L, and NiCl2NiCl in solution2Is 0.08mol/L, NH4NH in solution F4The concentration of F is 0.12 mol/L;
(2) putting the turbid liquid of the aluminum powder in the step (1) into ultrasonic waves with the power of 70W for ultrasonic treatment for 15min to obtain a turbid liquid of the aluminum powder;
(3) adding gelatin to the NiCl of step (1)2In solution, gelatin and NiCl2The solid-liquid ratio g of the solution is 8:1, the solution is uniformly stirred at the temperature of 45 ℃, then the aluminum powder suspension liquid in the step (2) is added, and the solution A is obtained after the reaction for 20min at the temperature of 45 ℃ under the stirring condition;
(4) dropwise adding NH (1) into the solution A in the step (3) at the temperature of 45 ℃ under stirring4Continuously reacting the solution F for 1.8h, wherein the dropping speed is 4 drops/s; washing for 4 times alternately according to the sequence of water, absolute ethyl alcohol and water, carrying out solid-liquid separation, and drying the solid at the temperature of 95 ℃;
(5) uniformly heating the solid dried in the step (4) to 700 ℃ and roasting at high temperature for 4h to obtain a precursor Al @ Al2O3Wherein the rate of constant temperature rise is 6 ℃/min;
(6) leading the precursor Al @ Al in the step (5)2O3Placing in a fixed bed, introducing mixed gas of methane and argon, and performing catalytic cracking reaction of methane at 650 deg.C for 1.8 hr to obtain core-shell structure Al @ C compositeA phase change heat storage material; wherein the volume fraction of methane in the methane-argon mixed gas is 25%;
from the methane catalytic cracking conversion chart of the Al @ C composite phase-change heat storage material prepared in the embodiment, the methane is subjected to cracking reaction at 650 ℃, hydrogen is generated, and the reaction time is short;
the Raman characteristic diagram of the Al @ C composite phase-change heat storage material prepared in the embodiment shows that the Raman characteristic diagram is 1500cm-1Two characteristic peaks for characterizing carbon are nearby, which indicates that the carbon is successfully covered on a precursor Al @ Al2O3A surface;
as can be seen from the DSC heat absorption and release characteristic diagram of the Al @ C composite phase-change heat storage material prepared in this example, the phase-change temperature of the Al @ C composite phase-change heat storage material obtained in this example is: heat absorption is 660 ℃, and heat release is 629 ℃; wherein the heat absorption and release value is about 300J/g, compared with Al @ NiO-Al2O3The 317J/g of the material is low, which indicates that more carbon is attached to the surface of the material, so that the proportion of aluminum is reduced, the heat absorption and release values are reduced, but the heat absorption and release difference value of Al @ C is not large, namely the energy loss of the process of Al @ C is small;
as can be seen from the SEM image of the Al @ C composite phase-change heat storage material prepared in this example, the Al @ C composite phase-change heat storage material obtained in this example has relatively uniform carbon coverage on the surface and good surface wrapping property.
Claims (8)
1. A preparation method of an Al @ C composite phase change heat storage material with a core-shell structure is characterized by comprising the following specific steps:
(1) respectively mixing aluminium powder and NiCl2、NH4F is added into deionized water or ultrapure water to prepare aluminum powder turbid liquid and NiCl2Solution and NH4F solution; wherein the aluminum powder and the NiCl2、NH4The molar ratio of F is (5-20): (0.5-2): 1-3);
(2) placing the aluminum powder turbid liquid obtained in the step (1) in ultrasonic waves for ultrasonic treatment for 5-30 min to obtain an aluminum powder turbid liquid;
(3) adding gelatin to the NiCl of step (1)2Uniformly stirring the solution at the temperature of 35-55 ℃, then adding the aluminum powder suspension liquid obtained in the step (2) and stirring the mixture at the temperature of 35-55 DEG CReacting for 5-20 min at 35-55 ℃ under stirring to obtain a solution A;
(4) dropwise adding NH in the step (1) into the solution A in the step (3) at the temperature of 35-55 ℃ under the stirring condition4Continuously reacting the solution F for 0.5-3 h; washing for 3-5 times alternately according to the sequence of water, absolute ethyl alcohol and water, carrying out solid-liquid separation, and drying the solid at the temperature of 50-100 ℃;
(5) uniformly heating the solid dried in the step (4) to 600-800 ℃ and roasting at high temperature for 2-16 h to obtain a precursor Al @ Al2O3；
(6) Leading the precursor Al @ Al in the step (5)2O3And (3) placing the material in a fixed bed, introducing a methane-inert gas mixed gas, and performing methane catalytic cracking reaction for 0.2-5 h at the temperature of 500-750 ℃ to obtain the Al @ C composite phase change heat storage material with the core-shell structure.
2. The preparation method of the Al @ C composite phase-change heat storage material with the core-shell structure according to claim 1 is characterized in that: in the step (1), the concentration of the aluminum powder in the aluminum powder turbid liquid is 0.5-2 mol/L, and NiCl2NiCl in solution2The concentration of (A) is 0.05-0.2 mol/L, NH4NH in solution F4The concentration of F is 0.1-0.3 mol/L.
3. The preparation method of the Al @ C composite phase-change heat storage material with the core-shell structure according to claim 1 is characterized in that: in the step (2), the power of the ultrasonic wave is 40-80W.
4. The preparation method of the Al @ C composite phase-change heat storage material with the core-shell structure according to claim 1 is characterized in that: gelatin and NiCl in step (3)2The solid-liquid ratio g of the solution to L is (3-15) to 1.
5. The preparation method of the Al @ C composite phase-change heat storage material with the core-shell structure according to claim 1 is characterized in that: the dropwise adding speed in the step (4) is 1-5 drops/s.
6. The preparation method of the Al @ C composite phase-change heat storage material with the core-shell structure according to claim 1 is characterized in that: the rate of constant temperature rise in the step (5) is 1-10 ℃/min.
7. The preparation method of the Al @ C composite phase-change heat storage material with the core-shell structure according to claim 1 is characterized in that: the volume fraction of methane in the methane-inert gas mixed gas is 1-100%, and the inert gas is nitrogen or argon.
8. The Al @ C composite phase-change heat storage material prepared by the preparation method of the Al @ C composite phase-change heat storage material with the core-shell structure as claimed in any one of claims 1 to 7.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549289A (en) * | 2009-05-12 | 2009-10-07 | 武汉大学 | Nucleocapsid energizing agent for propelling agent and method for preparing same |
| CN101775270A (en) * | 2010-03-12 | 2010-07-14 | 重庆大学 | Liquid metal fluid containing phase-change microcapsules |
| CN101798498A (en) * | 2010-03-19 | 2010-08-11 | 昆明理工大学 | Al/Al2O3 heat storage material and preparation method thereof |
| CN102172501A (en) * | 2011-03-14 | 2011-09-07 | 广东工业大学 | Preparation method of carbon-coated silicon carbide nano powder with nuclear shell structure |
| CN102533390A (en) * | 2012-02-16 | 2012-07-04 | 华北电力大学 | Iron-based oxygen carrier with interlayer shell structure and capable of catalyzing direct combustion of coal, and preparation method for iron-based oxygen carrier |
| CN103406156A (en) * | 2013-08-12 | 2013-11-27 | 昆明理工大学 | Preparation method of high-temperature phase-change thermal storage type composite catalyst carrier |
| WO2014062871A1 (en) * | 2012-10-19 | 2014-04-24 | Osram Sylvania Inc. | Index matched composite materials and light sources incorporating the same |
| CN104893674A (en) * | 2015-06-03 | 2015-09-09 | 中国科学院空间应用工程与技术中心 | Foamy carbon/paraffin type phase-change composite material and encapsulation method thereof |
| CN104942553A (en) * | 2015-06-16 | 2015-09-30 | 西安航空制动科技有限公司 | Manufacturing method of phase-change energy storage brake discs |
| CN105505327A (en) * | 2015-11-26 | 2016-04-20 | 浙江工业大学 | Preparation method of carbon nanotube packaged paraffin phase-change material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US7442439B2 (en) * | 2005-12-28 | 2008-10-28 | Kimberly-Clark Worldwide, Inc. | Microencapsulated heat delivery vehicles |
-
2018
- 2018-06-21 CN CN201810640956.6A patent/CN109054757B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549289A (en) * | 2009-05-12 | 2009-10-07 | 武汉大学 | Nucleocapsid energizing agent for propelling agent and method for preparing same |
| CN101775270A (en) * | 2010-03-12 | 2010-07-14 | 重庆大学 | Liquid metal fluid containing phase-change microcapsules |
| CN101798498A (en) * | 2010-03-19 | 2010-08-11 | 昆明理工大学 | Al/Al2O3 heat storage material and preparation method thereof |
| CN102172501A (en) * | 2011-03-14 | 2011-09-07 | 广东工业大学 | Preparation method of carbon-coated silicon carbide nano powder with nuclear shell structure |
| CN102533390A (en) * | 2012-02-16 | 2012-07-04 | 华北电力大学 | Iron-based oxygen carrier with interlayer shell structure and capable of catalyzing direct combustion of coal, and preparation method for iron-based oxygen carrier |
| WO2014062871A1 (en) * | 2012-10-19 | 2014-04-24 | Osram Sylvania Inc. | Index matched composite materials and light sources incorporating the same |
| CN103406156A (en) * | 2013-08-12 | 2013-11-27 | 昆明理工大学 | Preparation method of high-temperature phase-change thermal storage type composite catalyst carrier |
| CN104893674A (en) * | 2015-06-03 | 2015-09-09 | 中国科学院空间应用工程与技术中心 | Foamy carbon/paraffin type phase-change composite material and encapsulation method thereof |
| CN104942553A (en) * | 2015-06-16 | 2015-09-30 | 西安航空制动科技有限公司 | Manufacturing method of phase-change energy storage brake discs |
| CN105505327A (en) * | 2015-11-26 | 2016-04-20 | 浙江工业大学 | Preparation method of carbon nanotube packaged paraffin phase-change material |
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