CN112473579B - Metal phase change microcapsule with thermal expansion cavity and preparation method thereof - Google Patents
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Abstract
The invention discloses a metal phase change microcapsule with a thermal expansion cavity, which takes metal particles as a core material, wherein a porous inorganic wall material layer is coated outside the core material, and a thermal expansion cavity is arranged between the core material and the porous inorganic wall material layer; the heat expansion cavity and the porous inorganic wall material layer are obtained by carrying out heat treatment on an organic layer and an inorganic layer which are coated outside the core material, and decomposing organic matters in the organic layer into gas which escapes from the inorganic layer. The metal phase change microcapsule provides a thermal expansion space for metal, solves the microcapsule rupture problem caused by metal thermal expansion from the source, greatly improves the thermal cycle stability, breaks through the technical bottleneck of metal microcapsule preparation, has good functions of heat conduction, energy storage, temperature regulation and the like, and can be widely applied to the fields of heat storage, electronic equipment heat dissipation and the like.
Description
Technical Field
The invention relates to the technical field of phase change microcapsule materials, in particular to a metal phase change microcapsule with a thermal expansion cavity and a preparation method thereof.
Background
A large amount of waste heat exists in the waste gas of steel, chemical industry and marine diesel engines, and the part of heat is difficult to directly utilize and directly discharge due to unstable working conditions, so that the part of heat is recovered by adopting a high-efficiency heat storage medium, and the application prospect is good. With the popularization of electric vehicles, notebook computers, and smart phones, the demand for high energy density lithium ion batteries is increasing. However, batteries generate a large amount of heat during charge and discharge, and the performance of the batteries depends to a large extent on temperature, so that the development of advanced thermal management techniques for lithium ion batteries is crucial to ensure safe use of these batteries and to maintain the battery performance. In addition, a short plate also exists in the aspect of solar heat utilization, and the problems can be effectively solved by adopting a high-efficiency heat storage medium. The Phase Change Material (PCM) is used as an energy storage carrier, can store/release a large amount of heat in the melting/solidifying process, and has wide application prospects in the aspects of waste heat utilization, solar heat utilization, heat dissipation of electronic equipment and the like.
Direct utilization of phase change materials can cause leakage in the phase change process, and microencapsulation of phase change materials is an effective method for solving the problem. The phase change microcapsule (MEPCM) is an energy storage medium with a core-shell structure formed by coating a layer of film (wall material) on the surface of a phase change particle (core material), has the advantages of leakage prevention, heat transfer area increase, isolation from the surrounding environment and the like, and has recently received wide attention of domestic and foreign scholars.
At present, most of the research on microcapsules at home and abroad selects organic phase-change materials such as paraffin as core materials, and reports on metal or metal alloy as the core materials of the phase-change microcapsules are few. The metal or metal alloy has abundant varieties and larger selectable phase transition temperature range, for example, the phase transition temperature of liquid metal Ga is 29.8 ℃, the phase transition temperature of alloy SnBi58 is 138 ℃, and the like, and the unit volume potential heat value of the metal or metal alloy is larger, in recent years, a small amount of reports about metal microcapsules are provided, but the properties are not ideal enough, and the method has a considerable gap from industrial application. Besides the problems of the low-temperature organic phase-change microcapsules, the main problems are: the thermal cycle performance is poor, the thermal expansion of the metal is large at medium and high temperature, the volume of the metal is further increased after the solid-liquid phase change, and the microcapsules are cracked due to thermal expansion when the metal is directly coated.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a metal phase change microcapsule with a thermal expansion cavity and a preparation method thereof, so as to solve the problems that the existing metal microcapsule is poor in thermal cycle performance, easy to break and the like. Based on the method, the inventor designs and provides a method for preparing the metal phase change microcapsule with the thermal expansion cavity by a double-layer coating and inner layer sacrificing method after intensive research, so that the problem of microcapsule rupture caused by metal thermal expansion can be solved from the source.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:
a metal phase-change microcapsule with a thermal expansion cavity takes metal particles as a core material, a porous inorganic wall material layer is coated outside the core material, and a thermal expansion cavity is arranged between the core material and the porous inorganic wall material layer; the heat expansion cavity and the porous inorganic wall material layer are obtained by carrying out heat treatment on an organic layer and an inorganic layer which are coated outside the core material, and decomposing organic matters in the organic layer into gas which escapes from the inorganic layer.
Furthermore, a compact inorganic wall material layer is coated outside the porous inorganic wall material layer.
Further, the metal particles are at least one of tin, bismuth and metal alloy materials containing tin and bismuth.
Further, the organic matter in the organic layer is at least one of polymethyl methacrylate, zein, urea-formaldehyde resin, melamine-formaldehyde resin and chitosan.
Further, the inorganic material in the dense inorganic wall material layer and the porous inorganic wall material layer is at least one of silica, titanium dioxide, and calcium carbonate.
In another aspect of the present invention, there is provided a method for preparing a metal phase change microcapsule with a thermally expandable cavity, the method comprising the following steps:
s1: weighing a certain amount of metal particles, and uniformly dispersing the metal particles in a solvent to obtain a dispersion liquid; then adding easily decomposed and volatile organic matters, and coating the organic matters on the surfaces of the metal particles in an ultrasonic impregnation mode to obtain metal phase change microcapsules coated by an organic layer; or a certain amount of organic monomers are dripped into the dispersion liquid, then a certain amount of initiator is added, after the dripping is finished, the interface polymerization reaction is carried out under the assistance of ultrasonic, and the metal phase change microcapsule coated with the organic layer containing the easily decomposed and volatilized organic matters is obtained after the reaction is finished;
s2: weighing a certain amount of inorganic source, and adding the inorganic source into the mixture according to the mass-volume ratio of 4-6 g: stirring 130-150 ml of surfactant and deionized water to prepare sol, or adding the surfactant and the deionized water in a volume ratio of 8-10: stirring 0.5-1.5 of ethanol and ammonia water to prepare sol; adding the organic layer coated metal phase change microcapsule obtained in the step S1 into the sol to form gel on the surface of the sol, so as to obtain the organic layer and inorganic layer double-layer coated metal phase change microcapsule;
s3: and (4) performing heat treatment on the double-layer coated metal phase change microcapsule obtained in the step (S2) in a furnace, decomposing organic matters in an organic layer to form gas, allowing the gas to escape through the inorganic layer under thermal expansion, and synchronously forming a thermal expansion cavity layer and a porous inorganic wall material layer to obtain the metal phase change microcapsule with the thermal expansion cavity.
Further, in step S2, a certain amount of volatile organic matter that is easily decomposed is mixed into the inorganic source, and the organic matter is decomposed and released at the heat treatment temperature.
Further, a compact inorganic wall material layer is coated outside the metal phase change microcapsule after heat treatment through sol-gel reaction, and the metal phase change microcapsule with the thermal expansion cavity is obtained.
Further, in step S1, the weight-to-volume ratio of the metal fine particles to the solvent is 2 to 6 g: 80-100 ml of the dispersion liquid, wherein the organic matter accounts for 0.4-0.8% of the dispersion liquid by mass percent; the mass ratio of the organic monomer to the initiator to the dispersion liquid is 0.5-2.0: 0.01-0.03: 100.
further, in step S2, the inorganic source accounts for 1 to 8% by mass of the sol, and the mass ratio of the organic layer coating metal phase change microcapsule to the inorganic source is 1: 0.75 to 2.5.
Further, in step S3, the heat treatment is protected by a nitrogen atmosphere, and the treatment temperature is 350 to 450 ℃.
The invention has the beneficial effects that:
the metal phase change microcapsule provides a thermal expansion space for metal, solves the problem of microcapsule rupture caused by metal thermal expansion from the source, greatly improves the thermal cycle stability of the metal phase change microcapsule, and breaks through the technical bottleneck of metal microcapsule preparation.
The metal phase change microcapsule improves the technical level of phase change energy storage, has better functions of heat conduction, energy storage, temperature regulation and the like, and can be applied to the fields of heat storage, heat dissipation of electronic equipment and the like.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) photograph of the metallic phase change microcapsules having the thermal expansion cavities according to example 1 of the present invention.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of the metal phase change microcapsules having the thermal expansion cavities according to example 1 of the present invention, which is thermally cycled 500 times.
FIG. 3 is a Differential Scanning Calorimeter (DSC) photograph of the metal phase change microcapsule with the thermal expansion cavity of example 1 of the present invention after thermal cycling.
Fig. 4 is an Energy Dispersive Spectrometer (EDS) photograph of metal phase change microcapsules with thermally expanded cavities of example 2 of the present invention.
FIG. 5 is X-ray photoelectron spectroscopy (XPS) analysis of metal phase change microcapsules having a thermally expanded cavity according to example 3 of the present invention.
Fig. 6 is a Scanning Electron Microscope (SEM) photograph of the cavity of the metal phase change microcapsule having the thermally expanded cavity according to example 4 of the present invention.
FIG. 7 is a Differential Scanning Calorimeter (DSC) photograph of the metallic phase-change microcapsules having thermal expansion cavities of example 5 of the present invention.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
Example 1
The preparation method of the metal phase change microcapsule with the thermal expansion cavity comprises the following steps:
s1: weighing 6g of spherical metal alloy powder (SnBi58), and uniformly dispersing the spherical metal alloy powder in 100ml of deionized water to obtain a dispersion liquid; then adding 0.55g of methacrylic acid (MAA) monomer, adding 0.02g of ammonium persulfate serving as an initiator, carrying out ultrasonic-assisted interfacial polymerization reaction on the surfaces of the alloy particles under 200w of power for 30min to obtain pre-microcapsules, washing the pre-microcapsules by deionized water for three times, carrying out suction filtration, and drying at 80 ℃ for 5h to obtain PMMA/SnBi58 phase-change microcapsules;
s2: preparing 100g/L ammonium fluotitanate aqueous solution and 100g/L boric acid aqueous solution; taking 5g of PMMA/SnBi58 phase-change microcapsule obtained in the step S1, and adding 0.5g of surface activityCTAB and 30ml deionized water are added, 30ml ammonium fluotitanate aqueous solution and 90ml boric acid aqueous solution are added, reaction is carried out for 5h at 50 ℃ under magnetic stirring, deionized water is washed for three times, and drying is carried out for 5h at 80 ℃ after suction filtration, thus obtaining TiO2Phase-change microcapsule of/PMMA/SnBi 58;
s3: and (3) putting the obtained microcapsule into a box-type atmosphere furnace, heating to 400 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, preserving the heat at 400 ℃ for 1h, and decomposing the PMMA layer to obtain the alloy microcapsule with the thermal expansion cavity.
The detection result shows that as shown in fig. 1 and fig. 2, the obtained metal phase change microcapsule with the thermal expansion cavity keeps a better spherical shape, has a smooth surface and a complete core-shell structure, the particle size of the microcapsule is 30-50 μm, and the differential scanning calorimeter test of the metal phase change microcapsule with the thermal expansion cavity shows that the latent heat value is 43.03J/g, the melting peak temperature is 141.4 ℃, the solidification peak temperature is 129.3 ℃, and the supercooling degree is 7.4 ℃. As shown in FIG. 3, the metal phase change microcapsule has a thermal cycle time of 500 times, and still maintains good thermal stability.
Example 2
The preparation method of the metal phase change microcapsule with the thermal expansion cavity of the embodiment comprises the following steps:
s1: weighing 6g of spherical metal alloy powder (SnBi58), and uniformly dispersing the spherical metal alloy powder in 100ml of deionized water to obtain a dispersion liquid; adding 1g of methacrylic acid (MAA) monomer, adding 0.02g of benzoyl peroxide as an initiator, performing ultrasonic-assisted interfacial polymerization reaction on the surface of alloy particles under 200w of power for 30min to obtain pre-microcapsules, washing the pre-microcapsules by deionized water for three times, performing suction filtration, and drying at 80 ℃ for 5h to obtain PMMA/SnBi58 phase-change microcapsules;
s2: preparing 100g/L ammonium fluotitanate aqueous solution and 100g/L boric acid aqueous solution; taking 5g of PMMA/SnBi58 phase-change microcapsules obtained in the step S1, adding 0.5g of CTAB (cetyl trimethyl ammonium bromide) as a surfactant and 30ml of deionized water, then adding 30ml of ammonium fluotitanate aqueous solution and 90ml of boric acid aqueous solution, reacting for 5 hours at 50 ℃ under magnetic stirring, washing for three times with deionized water, filtering, and drying for 5 hours at 80 ℃ to obtain the PMMA/SnBi58 phase-change microcapsulesTo TiO2Phase-change microcapsule of/PMMA/SnBi 58;
s3: and (3) putting the obtained microcapsule into a box-type atmosphere furnace, heating to 400 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, preserving the heat at 400 ℃ for 1h, and decomposing the PMMA layer to obtain the alloy microcapsule with the thermal expansion cavity.
The detection result shows that as shown in fig. 4, the obtained metal phase change microcapsule with the thermal expansion cavity keeps a better spherical shape, has a smooth surface and a complete core-shell structure, and the particle size of the microcapsule is 30-50 μm; the differential scanning calorimeter test of the metal phase-change microcapsule with the thermal expansion cavity shows that the latent heat value is 42.83J/g, the melting peak temperature is 140.8 ℃, the solidification peak temperature is 128.0 ℃, and the supercooling degree is 6.7 ℃. The thermal cycle times reach 500 times, and good thermal stability is still maintained.
Example 3
The preparation method of the metal phase change microcapsule with the thermal expansion cavity comprises the following steps:
s1: weighing 6g of spherical metal alloy powder (SnBi58), and uniformly dispersing the spherical metal alloy powder in 100ml of deionized water to obtain a dispersion liquid; adding 2g of methacrylic acid (MAA) monomer, adding 0.02g of benzoyl peroxide as an initiator, carrying out ultrasonic-assisted interfacial polymerization reaction on the surfaces of alloy particles under 200w of power for 30min to obtain pre-microcapsules, washing the pre-microcapsules by deionized water for three times, carrying out suction filtration, and drying at 80 ℃ for 5h to obtain PMMA/SnBi58 phase-change microcapsules;
s2: preparing 100g/L ammonium fluotitanate aqueous solution and 100g/L boric acid aqueous solution; taking 5g of PMMA/SnBi58 phase-change microcapsules obtained in the step S1, adding 0.5g of CTAB (cetyl trimethyl ammonium bromide) as a surfactant and 30ml of deionized water, then adding 30ml of ammonium fluotitanate aqueous solution and 90ml of boric acid aqueous solution, reacting for 5 hours at 50 ℃ under magnetic stirring, washing for three times with deionized water, filtering, and drying for 5 hours at 80 ℃ to obtain TiO2Phase-change microcapsule of/PMMA/SnBi 58;
s3: and (3) putting the obtained microcapsule into a box-type atmosphere furnace, heating to 400 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, preserving the heat at 400 ℃ for 1h, and decomposing the PMMA layer to obtain the alloy microcapsule with the thermal expansion cavity.
The detection result shows that the prepared metal phase change microcapsule is TiO, as shown in figure 52The metal phase-change microcapsule with the thermal expansion cavity, which is obtained after the heat treatment of the/PMMA/SnBi 58 phase-change microcapsule, keeps a better spherical shape, has a smooth surface and a complete core-shell structure, the particle size of the microcapsule is 30-50 mu m, and the differential scanning calorimeter test of the metal phase-change microcapsule with the thermal expansion cavity shows that the latent heat value is 48.46J/g, the melting peak temperature is 141.1 ℃, the solidification peak temperature is 128.1 ℃, and the supercooling degree is 6.4 ℃. The thermal cycle times reach 500 times, and good thermal stability is still maintained.
Example 4
The preparation method of the metal phase change microcapsule with the thermal expansion cavity of the embodiment comprises the following steps:
s1: uniformly dispersing 2g of tin powder (Sn) in 80ml of deionized water to obtain a dispersion liquid; adding 0.5g of polymethyl methacrylate (PMMA), coating the PMMA on the surface of tin powder particles in an ultrasonic impregnation mode, and filtering and drying to obtain PMMA/Sn phase change microcapsules;
s2: taking 2g of the PMMA/Sn phase change microcapsule obtained in the step S1 at the ultrasonic stirring speed of 800rpm at 50 ℃, adding 0.5g of surfactant SDBS and 125mL of deionized water, and stirring in a triangular flask for 0.5-1 h; 25ml of CaCl were added at a rate of 1 drop/sec using a constant pressure funnel2Solution of CaCl2Reacting for 0.5-1 h with deionized water at a mass ratio of 1: 25; finally, 25ml of Na were added at a rate of 1 drop/2 seconds2CO3Solution, Na2CO3Reacting for 1-2 h with deionized water at a mass ratio of 1: 25; stopping stirring, respectively washing with deionized water and ethanol for 2-3 times, and drying to obtain CaCO3a/PMMA/Sn phase change microcapsule;
s3: CaCO obtained in step S23The PMMA/Sn phase change microcapsule is subjected to heat treatment at the temperature of 400 ℃, and the metal microcapsule with the thermal expansion cavity can be obtained.
The detection result shows that as shown in fig. 6, the obtained metal phase change microcapsule with the thermal expansion cavity keeps a better spherical shape, has a smooth surface and a complete core-shell structure, the particle size of the microcapsule is 30-50 μm, and the differential scanning calorimeter test of the metal phase change microcapsule with the thermal expansion cavity shows that the latent heat value is 56.05J/g, the melting peak temperature is 235.1 ℃, the solidification peak temperature is 144.0 ℃, and the supercooling degree is 76.7 ℃. The thermal cycle times reach 200 times, and good thermal stability is still maintained.
Example 5
The preparation method of the metal phase change microcapsule with the thermal expansion cavity comprises the following steps:
s1: uniformly dispersing 2g of tin powder (Sn) in 80ml of ethyl acetate to obtain a dispersion liquid; adding 0.5g of polymethyl methacrylate (PMMA), coating the PMMA on the surface of tin powder particles in an ultrasonic impregnation mode, and filtering and drying to obtain PMMA/Sn phase change microcapsules;
s2: uniformly stirring 80mL of ethanol and 10mL of ammonia water respectively to form a mixed solution, adding 1.5g of tetraethyl orthosilicate and 0.5g of hexadecyl trimethyl ammonium bromide while stirring, continuously stirring for a certain time at room temperature to form a sol, then weighing 2g of PMMA/Sn phase change microcapsule obtained in the step S1, adding the PMMA/Sn phase change microcapsule into the sol, performing ultrasonic stirring for 1h at 70 ℃, stopping reaction, forming gel on the surface of the sol, cleaning with ethanol for several times, filtering and drying to obtain hexadecyl trimethyl ammonium bromide @ SiO2a/PMMA/Sn phase change microcapsule;
s3: cetyl trimethyl ammonium bromide @ SiO obtained in the step S22the/PMMA/Sn phase change microcapsule is placed in a box type atmosphere furnace, N2Carrying out heat treatment at 400 ℃ for 1h in the atmosphere to decompose cetyl trimethyl ammonium bromide in the inorganic wall material and PMMA in the organic layer into gas which escapes from the phase change microcapsules, and synchronously forming the porous inorganic wall material and the corresponding thermal expansion cavity layer; the phase-change microcapsule with the thermal expansion cavity and the 3-aminopropyltrimethoxysilane are put into an ethanol solution with the temperature of 80 ℃ and the pH value of 4.5 for coating again, the 3-aminopropyltrimethoxysilane is hydrolyzed to form a silicon dioxide coating on the surface of the capsule so as to seal pores on the surface of the capsule, and finally the thermal expansion cavity is formedMetallic phase change microcapsules of the cavity.
The detection result shows that the obtained metal phase change microcapsule with the thermal expansion cavity keeps a better spherical shape, the surface is smooth, the metal phase change microcapsule has a complete core-shell structure, and the particle size of the microcapsule is 30-50 mu m; as shown in FIG. 7, the differential scanning calorimeter test of the metal phase-change microcapsule with the thermal expansion cavity shows that the latent heat value is 58.01J/g, the melting peak temperature is 235.0 ℃, the solidification peak temperature is 141.7 ℃ and the supercooling degree is 74.8 ℃. The thermal cycle times reach 200 times, and good thermal stability is still maintained.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed.
Claims (9)
1. The metal phase change microcapsule with the thermal expansion cavity is characterized in that metal particles are taken as a core material, a porous inorganic wall material layer is coated outside the core material, and a thermal expansion cavity is arranged between the core material and the porous inorganic wall material layer; the thermal expansion cavity and the porous inorganic wall material layer are obtained by carrying out heat treatment on an organic layer and an inorganic layer which are coated outside the core material, and decomposing organic matters in the organic layer into gas which escapes from the inorganic layer; the organic matter in the organic layer is polymethyl methacrylate; the preparation method of the microcapsule comprises the following steps:
s1: weighing a certain amount of metal particles, and uniformly dispersing the metal particles in a solvent to obtain a dispersion liquid; then adding easily decomposed and volatile organic matters, and coating the organic matters on the surfaces of the metal particles in an ultrasonic impregnation mode to obtain metal phase change microcapsules coated by an organic layer; or dropping a certain amount of organic monomers into the dispersion liquid, then adding a certain amount of initiator, carrying out interfacial polymerization reaction under the assistance of ultrasound after dropping is finished, and obtaining the metal phase change microcapsule coated with the organic layer containing the volatile organic compounds which are easy to decompose after the reaction is finished;
s2: weighing a certain amount of inorganic source, and adding the inorganic source into the mixture according to the mass-volume ratio of 4-6 g: stirring 130-150 ml of surfactant and deionized water to prepare sol, or adding the surfactant and the deionized water in a volume ratio of (8-10): stirring 0.5-1.5 of ethanol and ammonia water to prepare sol; adding the organic layer coated metal phase change microcapsule obtained in the step S1 into the sol to form gel on the surface of the sol, so as to obtain the organic layer and inorganic layer double-layer coated metal phase change microcapsule;
s3: and (4) carrying out heat treatment on the double-layer coated metal phase change microcapsule obtained in the step (S2) in a furnace, decomposing organic matters in the organic layer to form gas, allowing the gas to escape through the inorganic layer under thermal expansion, and synchronously forming a thermal expansion cavity layer and a porous inorganic wall material layer to obtain the metal phase change microcapsule with the thermal expansion cavity.
2. The metal phase change microcapsule with a thermally expansive cavity according to claim 1, wherein the porous inorganic wall material layer is further coated with a dense inorganic wall material layer.
3. The metallic phase change microcapsule with a thermally expansive cavity according to claim 1, wherein the metallic microparticles are at least one of tin, bismuth metal and a metallic alloy material comprising tin and bismuth elements.
4. The metallic phase change microcapsule having a thermally expansive cavity according to claim 2, wherein the inorganic material in the dense inorganic wall material layer and the porous inorganic wall material layer is at least one of silica, titanium dioxide, and calcium carbonate.
5. The metallic phase-change microcapsule according to claim 1 having a thermally expandable cavity, wherein a predetermined amount of easily decomposable organic substances is further mixed into the inorganic source in step S2, and the organic substances are decomposed and released at the heat treatment temperature.
6. The metal phase-change microcapsule with a thermal expansion cavity according to claim 1, wherein the metal phase-change microcapsule with a thermal expansion cavity is obtained by coating a dense inorganic wall material layer outside the metal phase-change microcapsule after heat treatment through sol-gel reaction.
7. The metal phase change microcapsule with a thermally expansive cavity according to claim 1, wherein in step S1, the weight to volume ratio of the metal microparticles to the solvent is 2-6 g: 80-100 ml of the dispersion liquid, wherein the organic matter accounts for 0.4-0.8% of the dispersion liquid by mass percent; the mass ratio of the organic monomer to the initiator to the dispersion liquid is 0.5-2.0: 0.01-0.03: 100.
8. the metal phase change microcapsule with the thermally expansive cavity according to claim 1, wherein in step S2, the inorganic source accounts for 1-8% of the sol by mass, and the organic layer covers the metal phase change microcapsule and the inorganic source at a mass ratio of 1: 0.75 to 2.5.
9. The metal phase change microcapsule with the thermally expandable cavity according to claim 1, wherein in step S3, the heat treatment is performed under a nitrogen atmosphere, and the treatment temperature is 350 to 450 ℃.
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| CN105855537A (en) * | 2016-03-24 | 2016-08-17 | 中国科学院上海应用物理研究所 | Inorganic nonmetal cladding high-temperature phase change heat storage microcapsule and preparation method thereof |
| CN106916573A (en) * | 2017-03-06 | 2017-07-04 | 中国科学院化学研究所 | Metal and alloy phase change accumulation energy microcapsule and preparation method thereof |
| CN111394067A (en) * | 2020-05-09 | 2020-07-10 | 中国科学院化学研究所 | Metal fluoride high-temperature phase change energy storage microcapsule and preparation method and application thereof |
| CN111944491A (en) * | 2020-08-21 | 2020-11-17 | 中国矿业大学 | Preparation method and application of metal phase change microcapsule heat storage particles |
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| CN1459330A (en) * | 2003-04-09 | 2003-12-03 | 天津工业大学 | High temp. resistance capsule, and its prepn. method |
| CN105855537A (en) * | 2016-03-24 | 2016-08-17 | 中国科学院上海应用物理研究所 | Inorganic nonmetal cladding high-temperature phase change heat storage microcapsule and preparation method thereof |
| CN106916573A (en) * | 2017-03-06 | 2017-07-04 | 中国科学院化学研究所 | Metal and alloy phase change accumulation energy microcapsule and preparation method thereof |
| CN111394067A (en) * | 2020-05-09 | 2020-07-10 | 中国科学院化学研究所 | Metal fluoride high-temperature phase change energy storage microcapsule and preparation method and application thereof |
| CN111944491A (en) * | 2020-08-21 | 2020-11-17 | 中国矿业大学 | Preparation method and application of metal phase change microcapsule heat storage particles |
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