CN112473579A - Metal phase change microcapsule with thermal expansion cavity and preparation method thereof - Google Patents
Metal phase change microcapsule with thermal expansion cavity and preparation method thereof Download PDFInfo
- Publication number
- CN112473579A CN112473579A CN202011461243.7A CN202011461243A CN112473579A CN 112473579 A CN112473579 A CN 112473579A CN 202011461243 A CN202011461243 A CN 202011461243A CN 112473579 A CN112473579 A CN 112473579A
- Authority
- CN
- China
- Prior art keywords
- phase change
- change microcapsule
- layer
- metal phase
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-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
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
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 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 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.
Further, in step S2, a certain amount of volatile organic compounds that are easily decomposed are mixed into the inorganic source, and the organic compounds are 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 metal phase change microcapsules having thermally expanded 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 metal phase change microcapsules with 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 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 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 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 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 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 PMMA/Sn phase change microcapsules obtained in the step S1 at 50 ℃ and an ultrasonic stirring speed of 800rpm, 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 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 sol, and then performing step SWeighing 2g of PMMA/Sn phase change microcapsule obtained by 1, adding the weighed PMMA/Sn phase change microcapsule into the sol, ultrasonically stirring the mixture for 1h at the temperature of 70 ℃, stopping reaction, forming gel on the surface of the sol, cleaning the gel with ethanol for a plurality of times, filtering and drying the gel 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; and (2) putting the phase-change microcapsule with the thermal expansion cavity and 3-aminopropyltrimethoxysilane into an ethanol solution with the temperature of 80 ℃ and the pH value of 4.5 for coating again, and hydrolyzing the 3-aminopropyltrimethoxysilane to form a silicon dioxide coating on the surface of the capsule so as to seal pores on the surface of the capsule, thereby finally forming the metal phase-change microcapsule with the thermal expansion cavity.
The detection result shows that 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 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 (11)
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 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.
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 metal phase change microcapsule with a thermally expandable cavity according to claim 1, wherein the organic material in the organic layer is at least one of polymethyl methacrylate, zein, urea-formaldehyde resin, melamine-formaldehyde resin and chitosan.
5. 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.
6. The method for preparing a metal phase change microcapsule with a thermally expansive cavity according to any one of claims 1 to 5, wherein the method for preparing 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.
7. The method for preparing a metallic phase change microcapsule having a thermally expandable cavity according to claim 6, wherein in step S2, a certain amount of easily decomposable organic substances which decompose and escape at the heat treatment temperature are further mixed into the inorganic source.
8. The method for preparing a metal phase-change microcapsule with a thermally expandable cavity according to claim 6, wherein the metal phase-change microcapsule after heat treatment is further coated with a dense inorganic wall material layer by sol-gel reaction to obtain the metal phase-change microcapsule with a thermally expandable cavity.
9. The method for preparing a metal phase change microcapsule with a thermally expansive cavity according to claim 6, wherein in step S1, the weight-to-volume ratio of the metal particles 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.
10. the method for preparing the metal phase change microcapsule with the thermally expansive cavity according to claim 6, wherein in step S2, the inorganic source accounts for 1-8% of the sol by mass, and the mass ratio of the organic layer coating metal phase change microcapsule to the inorganic source is 1: 0.75 to 2.5.
11. The method for preparing a metal phase change microcapsule with a thermally expandable cavity according to claim 6, wherein in step S3, the heat treatment is protected by a nitrogen atmosphere and the treatment temperature is 350-450 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011461243.7A CN112473579B (en) | 2020-12-12 | 2020-12-12 | Metal phase change microcapsule with thermal expansion cavity and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011461243.7A CN112473579B (en) | 2020-12-12 | 2020-12-12 | Metal phase change microcapsule with thermal expansion cavity and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112473579A true CN112473579A (en) | 2021-03-12 |
| CN112473579B CN112473579B (en) | 2022-07-12 |
Family
ID=74917807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011461243.7A Active CN112473579B (en) | 2020-12-12 | 2020-12-12 | Metal phase change microcapsule with thermal expansion cavity and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112473579B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113193301A (en) * | 2021-03-31 | 2021-07-30 | 华中科技大学 | Fire extinguishing diaphragm for actively inhibiting thermal runaway of lithium battery and preparation method and application thereof |
| CN114656935A (en) * | 2022-03-25 | 2022-06-24 | 大连海事大学 | Liquid metal phase change microcapsule and preparation method thereof |
| CN115318211A (en) * | 2022-09-08 | 2022-11-11 | 宁波大学 | Nanoparticle core material doped metal phase change microcapsule and preparation method thereof |
| CN115382475A (en) * | 2022-09-08 | 2022-11-25 | 宁波大学 | Nano particle wall material doped metal phase change microcapsule and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20170044415A1 (en) * | 2014-04-24 | 2017-02-16 | National University Corporation Hokkaido University | Latent heat storage body, method for producing latent heat storage body and heat exchange material |
| 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 |
-
2020
- 2020-12-12 CN CN202011461243.7A patent/CN112473579B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1459330A (en) * | 2003-04-09 | 2003-12-03 | 天津工业大学 | High temp. resistance capsule, and its prepn. method |
| US20170044415A1 (en) * | 2014-04-24 | 2017-02-16 | National University Corporation Hokkaido University | Latent heat storage body, method for producing latent heat storage body and heat exchange material |
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113193301A (en) * | 2021-03-31 | 2021-07-30 | 华中科技大学 | Fire extinguishing diaphragm for actively inhibiting thermal runaway of lithium battery and preparation method and application thereof |
| CN114656935A (en) * | 2022-03-25 | 2022-06-24 | 大连海事大学 | Liquid metal phase change microcapsule and preparation method thereof |
| CN115318211A (en) * | 2022-09-08 | 2022-11-11 | 宁波大学 | Nanoparticle core material doped metal phase change microcapsule and preparation method thereof |
| CN115382475A (en) * | 2022-09-08 | 2022-11-25 | 宁波大学 | Nano particle wall material doped metal phase change microcapsule and preparation method thereof |
| CN115382475B (en) * | 2022-09-08 | 2023-11-17 | 宁波大学 | Nanoparticle wall material doped metal phase change microcapsule and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112473579B (en) | 2022-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112473579B (en) | Metal phase change microcapsule with thermal expansion cavity and preparation method thereof | |
| Zhou et al. | Recent advances in organic/composite phase change materials for energy storage | |
| CN100422076C (en) | Silicon/charcoal core-shell structure nanometer composite material and its preparation method and uses | |
| CN103979608B (en) | A kind of preparation method of hollow core-shell Vanadium Pentoxide in FLAKES microballoon | |
| CN103509528B (en) | A kind of nuclear shell structure nano high-temperature heat-storage material, Preparation Method And The Use | |
| CN108832077A (en) | A kind of preparation method of Copper-cladding Aluminum Bar core-shell structure Si-C composite material | |
| CN105038720B (en) | It is a kind of efficiently to utilize stable phase change composite material of solar energy and preparation method thereof | |
| CN109679585B (en) | Phase-change microcapsule synthesized by adopting photocuring method and preparation method thereof | |
| CN108865079B (en) | Method for packaging high-temperature molten salt particle phase change material by using inorganic glass powder | |
| CN108251073A (en) | A kind of phase change heat storage material with nucleocapsid and preparation method thereof | |
| CN107768617A (en) | Lithium-sulfur battery composite anode material and preparation method thereof | |
| CN110707392B (en) | Preparation method of composite phase change coating beneficial to heat dissipation of lithium ion battery | |
| CN109585829A (en) | A kind of silicon based anode material and its preparation method and application | |
| CN113881404A (en) | Organic phase change microcapsule with high coating rate, high thermal conductivity and high thermal cycle stability and preparation method thereof | |
| CN107895651B (en) | One kind can in-situ heat temperature adjust electrode material and preparation method thereof | |
| CN102746831B (en) | Method for preparing composite phase-change material with nuclear shell structure by using coupling agent aluminium-containing alloy | |
| Ma et al. | Synthesis of phase change microcapsules with binary fatty acid ester core and their feasibility investigation in energy conservation of cementitious materials | |
| Mohammadi Khoshraj et al. | Microencapsulation of butyl palmitate in polystyrene-co-methyl methacrylate shell for thermal energy storage application | |
| CN106784737B (en) | Capacitive Ni-MH power cell spherical hydrogen-storage alloy and preparation method thereof | |
| CN104592946A (en) | Preparation method of nano-capsule composite phase change material | |
| Han et al. | MnO2 decorated double-shell microencapsulated phase change materials for photothermal conversion and storage | |
| CN109261170B (en) | Pd @ Pd4S-porous carbon nano material and preparation method and application thereof | |
| CN106654228A (en) | Preparation method of porous SiOx core-shell microspheres | |
| CN109913182A (en) | Phase-change thermal storage capsule for the regulation of dynamic lithium battery heat | |
| CN114410281A (en) | High-cycle inorganic hydrated salt phase change nanocapsule and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |