CN115382475A - Nano particle wall material doped metal phase change microcapsule and preparation method thereof - Google Patents
Nano particle wall material doped metal phase change microcapsule and preparation method thereof Download PDFInfo
- Publication number
- CN115382475A CN115382475A CN202211099537.9A CN202211099537A CN115382475A CN 115382475 A CN115382475 A CN 115382475A CN 202211099537 A CN202211099537 A CN 202211099537A CN 115382475 A CN115382475 A CN 115382475A
- Authority
- CN
- China
- Prior art keywords
- wall material
- phase change
- material layer
- metal phase
- nanoparticle
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 106
- 239000002184 metal Substances 0.000 title claims abstract description 106
- 239000000463 material Substances 0.000 title claims abstract description 103
- 239000003094 microcapsule Substances 0.000 title claims abstract description 101
- 230000008859 change Effects 0.000 title claims abstract description 80
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000011162 core material Substances 0.000 claims abstract description 14
- 239000002923 metal particle Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 16
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002082 metal nanoparticle Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052755 nonmetal Inorganic materials 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 239000010419 fine particle Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000807 Ga alloy Inorganic materials 0.000 claims description 2
- 229910000846 In alloy Inorganic materials 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000954 Polyglycolide Polymers 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 239000004633 polyglycolic acid Substances 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 claims 2
- 229920002307 Dextran Polymers 0.000 claims 1
- 239000011368 organic material Substances 0.000 claims 1
- 238000005338 heat storage Methods 0.000 abstract description 19
- 238000004781 supercooling Methods 0.000 abstract description 16
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000002918 waste heat Substances 0.000 abstract description 3
- 230000017525 heat dissipation Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000012782 phase change material Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
-
- 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 nanoparticle wall material doped metal phase change microcapsule, which takes metal particles as core materials, wherein the core materials are coated with nanoparticle-doped hybrid inorganic wall material layers, and a thermal expansion cavity is formed between the core materials and the nanoparticle-doped hybrid inorganic wall material layers; the thermal expansion cavity is obtained by coating a layer of organic wall material layer by a core material, coating a layer of nano particle-doped hybrid inorganic wall material layer, and then performing heat treatment to decompose organic matters in the organic wall material layer into gas and escape through the nano particle-doped hybrid inorganic wall material layer. The metal phase change microcapsule can improve the heat conductivity while greatly reducing the supercooling degree, and realize the cooperative regulation and control of supercooling and heat conduction of the metal phase change microcapsule; the heat cycle performance is good, the heat storage and temperature control performances are good, and the heat storage and temperature control device has good application prospects in the fields of new energy utilization, electronic heat dissipation, waste heat recovery and the like.
Description
Technical Field
The invention relates to the technical field of metal phase change microcapsule materials, in particular to a nano particle wall material doped metal phase change microcapsule and a preparation method thereof.
Background
New energy development and industrial waste heat recovery are becoming more and more important to solve the increasingly serious energy crisis and environmental pollution problems. However, conventional new energy sources such as solar, wind and waste heat are often unstable, periodic and intermittent. The latent heat storage technology based on the phase change material can ensure high-stability and high-efficiency operation of new energy and industrial waste heat by storing or recovering heat energy in the phase change process through the phase change material.
In order to solve the problem that the phase-change material leaks in the using process, a thin film is usually coated on the surface of phase-change material particles to form an energy storage medium with a core-shell structure, so that the heat transfer can be improved, and the energy storage medium is isolated from the surrounding environment. The traditional organic metal phase change microcapsule has lower heat conductivity and unit volume heat storage density due to the properties of the microcapsule, and the metal phase change microcapsule taking metal as a core material has higher heat conductivity and heat storage density, thereby being widely concerned by domestic and foreign scholars.
At present, the research on the metal phase change microcapsules is still in the initial stage, most researches are carried out around the microencapsulation of metal, and the research on the preparation of the metal phase change microcapsules by different coating modes is carried out. The microcapsule prepared by directly coating a layer of wall material on the surface of the metal particle has poor thermal cycle performance, and the metal phase change microcapsule is easy to break due to thermal expansion after thermal cycle.
The Chinese patent document CN202011461243.7 previously applied by the applicant, namely a metal phase change microcapsule with a thermal expansion cavity and a preparation method thereof, well solves the problem of thermal expansion rupture of the microcapsule. However, the large supercooling degree of the metal microcapsule and the decrease in thermal conductivity after microencapsulation remain as problems that limit the practical use of the metal microcapsule. At present, domestic and foreign researches do not relate to related researches on supercooling and heat conduction of the metal microcapsules. Because the metal core material of the microcapsule is coated with a layer of wall material, the heat conductivity of the microcapsule is reduced to a certain extent, and the heat storage rate of the microcapsule is reduced in practical application. Supercooling of a phase change material is defined as a phenomenon in which a liquid phase of the phase change material does not crystallize at a theoretical solidification temperature under a specific pressure condition and must be lower than the theoretical solidification point to be crystallized. Supercooling causes a delay in the release of stored latent heat due to a decrease in solidification temperature and a delay in solidification time, a mismatch between storage and release temperatures, and a decrease in the utilization rate of thermal energy.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a nanoparticle wall material doped metal phase change microcapsule and a preparation method thereof, so as to solve the problems of heat storage and release mismatching caused by high coldness of the existing metal microcapsule, insufficient heat conductivity of the metal microcapsule for practical application, poor heat cycle performance of the microcapsule caused by heat expansion of metal, easiness in damage and the like. Based on the above, the inventor conceives and provides a method of doping nano particles in an outer wall material by a double-layer coating and inner layer sacrificing method after deep research, and the inner organic wall material is sacrificed after heat treatment to construct a thermal expansion cavity, so as to prepare the nano particle wall material doped metal phase change heat storage microcapsule with the thermal expansion cavity, so that the synergistic regulation and control of supercooling and heat conduction of the metal microcapsule are realized while the thermal expansion cavity is provided for metal, and the problems of heat storage and heat storage mismatch, insufficient thermal conductivity of the metal microcapsule for practical application, poor thermal cycle performance of the microcapsule caused by thermal expansion of the metal, easiness in damage and the like caused by large supercooling degree of the metal can be solved from the source.
In order to achieve the purpose, the invention adopts the technical scheme that:
a metal phase change microcapsule doped with a nanoparticle wall material takes metal particles as a core material, a nanoparticle-doped hybrid inorganic wall material layer is coated outside the core material, and a thermal expansion cavity is formed between the core material and the nanoparticle-doped hybrid inorganic wall material layer; the thermal expansion cavity is obtained by coating a layer of organic wall material layer by a core material, coating a layer of nano particle-doped hybrid inorganic wall material layer, and then performing heat treatment to decompose organic matters in the organic wall material layer into gas and escape through the nano particle-doped hybrid inorganic wall material layer.
Furthermore, a compact inorganic wall material layer is also coated outside the hybrid inorganic wall material layer doped with the nano particles.
Further, the nano particles are non-metal nano particles, preferably, the non-metal nano particles are at least one of carbon nano tubes, graphene and nano boron nitride; or the nanoparticles are nanoparticles of metal and oxides thereof, preferably, the nanoparticles of metal and oxides thereof are at least one of nano silver, nano aluminum oxide, nano iron, nano cesium, nano copper, nano bismuth, nano cobalt, nano nickel and nano platinum.
Further, the metal particles are at least one of gallium, indium, tin, bismuth, aluminum and metal alloy materials including gallium, indium, tin, bismuth and aluminum.
Further, the organic matter of the organic wall material layer is at least one of glucan, chitosan, polyglycolic acid, polylactic acid, polyvinyl chloride, melamine formaldehyde and polymethyl methacrylate.
Further, the nanoparticle-doped hybrid inorganic wall material layer and the outer-wrapped dense inorganic wall material layer are independently at least one of calcium carbonate, silica, titanium dioxide, and magnesium oxide.
The invention also provides a preparation method of the nanoparticle wall material doped metal phase change microcapsule, which comprises the following steps:
s1: weighing a certain amount of solvent, directly adding organic matters and metal particles in the organic wall material layer, and directly coating by magnetic stirring, mechanical stirring or ultrasonic to obtain the metal phase change microcapsule coated by the organic wall material layer; or weighing a certain amount of solvent, adding a certain amount of organic matter monomer and metal particles of the organic wall material layer, then adding a certain amount of initiator to promote the polymerization of the monomer, reacting for a certain time under the assistance of magnetic stirring, mechanical stirring or ultrasound at a certain temperature, and cleaning, filtering and drying after the reaction is finished to obtain the metal phase change microcapsule coated by the organic wall material layer;
s2: weighing a certain amount of solvent, adding the nanoparticles, and uniformly dispersing and suspending the nanoparticles in the solvent in an ultrasonic mode to obtain a nanoparticle suspension; adding a certain amount of inorganic source, and carrying out auxiliary reaction by means of magnetic stirring, mechanical stirring or ultrasound; adding the metal phase change microcapsule coated by the organic wall material layer obtained in the step S1; adding a certain catalyst or initiator, reacting for a period of time, cleaning, filtering and drying to obtain the metal phase change microcapsule with the outer layer being the hybrid inorganic wall material layer doped with the nano particles and the inner layer being the organic wall material layer;
s3: and (3) placing the metal phase change microcapsule obtained in the step (S2) in an atmosphere furnace, introducing nitrogen, setting the temperature to be 300-500 ℃ for heat treatment, heating the organic matters in the organic wall material layer to decompose into gas, escaping through the nanoparticle-doped hybrid inorganic wall material layer, successfully constructing a thermal expansion cavity, and obtaining the nanoparticle wall material-doped metal phase change microcapsule with the thermal expansion cavity.
Further, the preparation method further comprises a step S4: and (4) coating a compact inorganic wall material layer outside the metal phase change microcapsule subjected to the heat treatment in the step (S3) to obtain the nanoparticle wall material doped metal phase change microcapsule.
Further, in step S1, the mass ratio of the organic substance, the metal fine particles, and the solvent is 1 to 5:2 to 8:100; or, in the step S1, the mass ratio of the organic monomer, the initiator, the metal fine particles and the solvent is 1 to 5:0.01 to 0.05:2 to 8:100.
further, in step S2, the mass ratio of the nanoparticles to the solvent is 0.1 to 0.8:30 to 130; the mass ratio of the inorganic source to the solvent is 1:1-4, the mass ratio of the metal phase change microcapsule coated by the organic wall material layer to the inorganic source to the catalyst or the initiator is 1: 6-10: 0.5 to 1.5.
The invention has the beneficial effects that:
the nanoparticle wall material doped metal phase change microcapsule provided by the invention provides a thermal expansion cavity for metal, and simultaneously realizes the cooperative regulation and control of supercooling and heat conduction of the metal microcapsule, so that the problems of heat storage and release mismatching caused by large supercooling degree of the metal, insufficient practical application of heat conductivity of the metal microcapsule, poor thermal cycle performance of the microcapsule caused by thermal expansion of the metal, easiness in damage and the like can be solved from the source.
The nano particle wall material doped metal phase change microcapsule improves the technical level of phase change energy storage, has lower supercooling degree and better functions of heat conduction, heat storage and the like, and can be applied to the fields of new energy utilization, waste heat recovery, energy conservation, emission reduction and the like.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the nanoparticle wall material doped metal phase change microcapsule of example 1 of the present invention.
Fig. 2 is an energy spectrometer (EDS) picture of the nanoparticle wall material doped metal phase change microcapsule of example 1 of the present invention.
Fig. 3 is a Differential Scanning Calorimeter (DSC) picture of the metal phase change heat storage microcapsule of comparative example 1 of the present invention.
Fig. 4 is a Differential Scanning Calorimeter (DSC) picture of the nanoparticle wall material doped metal phase change microcapsule of example 1 of the present invention.
Fig. 5 is a Differential Scanning Calorimeter (DSC) picture of the nanoparticle wall material doped metal phase change microcapsule of example 2 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 nanoparticle wall material doped metal phase change microcapsule comprises the following steps:
s1: weighing 100g of deionized water, adding 0.55g of ethyl methacrylate (MMA) monomer and 5gSn, then adding 1g of surfactant cetyl ammonium bromide, then adding 0.02g of ammonium persulfate, magnetically stirring for 1.5h at the temperature of 50 ℃ at 600r/min, promoting the polymerization of the monomers under the action of ammonium persulfate, finishing the reaction, washing for three times by using the deionized water, then carrying out suction filtration, and drying for 3h at the temperature of 60 ℃ to obtain the metal phase change microcapsule coated by the organic wall material layer, which is abbreviated as PMMA/Sn metal phase change microcapsule;
s2: weighing 100g of formamide, adding 0.5g of nano-iron, and uniformly dispersing and suspending the nano-iron in the formamide in an ultrasonic mode to obtain a nano-iron suspension; subsequently, 40g of tetraethyl silicate are added dropwise, and magnetic stirring is carried out at 600r/minAnd (2) in a stirring mode, reacting for 3 hours at 50 ℃, then adding 6g of PMMA/Sn metal phase change microcapsules obtained in the step S1, adding 5g of ammonia water at the rate of 1 drop/second by using a constant pressure funnel, reacting for 2.5 hours, stopping stirring, respectively washing for 3 times by using deionized water and ethanol to obtain metal phase change microcapsules of which the outer layers are doped nano particles, the hybrid inorganic wall material layers and the inner layers are organic wall material layers, namely SiO 2 -a nanoFe/PMMA/Sn metallic phase change microcapsule;
s3: siO obtained in step S2 2 -placing the metal phase change microcapsule of nano Fe/PMMA/Sn in an atmosphere furnace, introducing nitrogen, setting the temperature at 500 ℃ for heat treatment, and successfully constructing a thermal expansion cavity by heating organic matters in the organic wall material layer to decompose into gas and escaping through the hybrid inorganic wall material layer doped with nano particles;
s4: measuring 80ml of absolute ethyl alcohol, adjusting the pH value to 4, then adding 4g of the metal phase change microcapsule subjected to heat treatment in the step S3 and 2g of 3-aminopropyltrimethoxysilane, reacting for 1.5h at the temperature of 50 ℃ in a magnetic stirring mode at 600r/min, coating a compact inorganic wall material layer on the surface of the metal phase change microcapsule subjected to heat treatment in the step S3, cleaning, filtering and drying to finally form the nanoparticle wall material doped metal phase change microcapsule (or called as a metal phase change heat storage microcapsule) with a heat expansion cavity.
The detection result shows that the obtained nanoparticle wall material doped metal phase change heat storage microcapsule with the thermal expansion cavity keeps a good spherical shape and has a complete core-shell structure as shown in fig. 1, and the energy spectrum EDX analysis of the nanoparticle wall material doped metal phase change microcapsule with the thermal expansion cavity shows that the microcapsule contains Sn, fe, si, O and other elements as shown in fig. 2, which shows that the wall material is successfully doped with nano-iron, and the heat conductivity of the microcapsule is enhanced to a certain degree; as shown in FIG. 4, the nanoparticle wall material doped metal phase change heat storage microcapsule with the thermal expansion cavity has a latent heat value of 56.51J/g, a melting peak temperature of 234.4 ℃, a solidification peak temperature of 175.8 ℃, a supercooling degree of 58.6 ℃ and a supercooling degree reduced by 36.0%.
Comparative example 1
The preparation method of the metal phase change microcapsule of the present comparative example is substantially the same as that of example 1, except that nanoparticles are not doped in the inorganic wall material layer of the outer layer in step S2 of the present comparative example.
As shown in FIG. 3, the differential scanning calorimeter test of the metal phase-change microcapsule of the comparative example shows that the latent heat value is 58.05J/g, the melting peak temperature is 234.6 ℃, the solidification peak temperature is 143.7 ℃ and the supercooling degree is 90.9 ℃.
Example 2
S1: weighing 100g of deionized water, adding 0.55g of ethyl methacrylate (MMA) monomer and 5gSn, then adding 1g of surfactant cetyl ammonium bromide, then adding 0.02g of ammonium persulfate, magnetically stirring at 600r/min for 1.5h at the temperature of 50 ℃, promoting the monomer to polymerize under the action of ammonium persulfate, finishing the reaction, washing for three times by using deionized water, then carrying out suction filtration, and drying at 60 ℃ for 3h to obtain the PMMA/Sn metal phase change microcapsule;
s2: weighing 100g of formamide, adding 0.5g of nano cobalt, and uniformly dispersing and suspending the nano cobalt in the formamide in an ultrasonic mode to obtain a nano cobalt suspension; then 50g of tetraethyl silicate is dripped, the mixture reacts for 3 hours at 50 ℃ in a magnetic stirring mode of 600r/min, 6g of PMMA/Sn metal phase change microcapsule obtained in the step S1 is added, 5g of ammonia water is added by using a constant pressure funnel at the speed of 1 drop/second, the mixture reacts for 1.5 hours, the ultrasonic treatment is stopped, deionized water and ethanol are respectively used for washing for 3 times, and the metal phase change microcapsule with the outer layer being a nano particle doped hybrid inorganic wall material layer and the inner layer being an organic wall material layer is obtained, which is abbreviated as SiO 2 -nanoCo/PMMA/Sn metal phase change microcapsules;
s3: siO obtained in step S2 2 -placing the metal phase change microcapsule of nanoCo/PMMA/Sn in an atmosphere furnace, introducing nitrogen, setting the temperature at 450 ℃ for heat treatment, and successfully constructing a thermal expansion cavity by heating the organic matter in the organic wall material layer to decompose into gas and escaping through the hybrid inorganic wall material layer doped with the nano particles;
s4: measuring 80ml of absolute ethyl alcohol, adjusting the pH value to 5, then adding 3g of the metal phase change microcapsule subjected to heat treatment in the step S3 and 2g of 3-aminopropyltrimethoxysilane, reacting for 1.5 hours at the temperature of 50 ℃ in a magnetic stirring mode at 600r/min, coating a compact inorganic wall material layer on the surface of the metal phase change microcapsule subjected to heat treatment in the step S3, cleaning, filtering and drying to finally form the nanoparticle wall material doped metal phase change microcapsule (or called as metal phase change heat storage microcapsule) with the heat expansion cavity.
Detection results show that the obtained nanoparticle wall material doped metal phase change heat storage microcapsule with the thermal expansion cavity keeps good spherical shape, has a complete core-shell structure, and enhances the heat conductivity of the microcapsule to a certain extent by successfully doping the nano cobalt into the microcapsule wall material. As shown in FIG. 5, the nanoparticle wall material doped metal phase change heat storage microcapsule with the thermal expansion cavity has a latent heat value of 49.88J/g, a melting peak temperature of 233.9 ℃, a solidification peak temperature of 216.5 ℃, a supercooling degree of 17.4 ℃ and a supercooling degree reduced by 80.9%.
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 (10)
1. The nano particle wall material doped metal phase change microcapsule is characterized in that metal particles are used as a core material, a nano particle doped hybrid inorganic wall material layer is coated outside the core material, and a thermal expansion cavity is formed between the core material and the nano particle doped hybrid inorganic wall material layer; the thermal expansion cavity is obtained by coating a layer of organic wall material layer by a core material, coating a layer of nano particle-doped hybrid inorganic wall material layer, and then performing heat treatment to decompose organic matters in the organic wall material layer into gas and escape through the nano particle-doped hybrid inorganic wall material layer.
2. The nanoparticle wall material doped metal phase change microcapsule according to claim 1, wherein a dense inorganic wall material layer is further coated outside the hybrid inorganic wall material layer doped with the nanoparticles.
3. The nanoparticle wall material doped metal phase change microcapsule according to claim 1, wherein the nanoparticle is a non-metal nanoparticle, preferably the non-metal nanoparticle is at least one of carbon nanotube, graphene and nano boron nitride; or the nanoparticles are nanoparticles of metal and oxides thereof, preferably, the nanoparticles of metal and oxides thereof are at least one of nano silver, nano aluminum oxide, nano iron, nano cesium, nano copper, nano bismuth, nano cobalt, nano nickel and nano platinum.
4. The nanoparticle wall material doped metal phase change microcapsule according to claim 1, wherein the metal microparticle is at least one of gallium, indium, tin, bismuth, aluminum and metal alloy materials including gallium, indium, tin, bismuth and aluminum.
5. The nanoparticle wall material doped metal phase change microcapsule according to claim 1, wherein the organic material of the organic wall material layer is at least one of dextran, chitosan, polyglycolic acid, polylactic acid, polyvinyl chloride, melamine formaldehyde, and polymethyl methacrylate.
6. The nanoparticle wall material doped metal phase change microcapsule according to claim 2, wherein the nanoparticle-doped hybrid inorganic wall material layer and the outer-coated dense inorganic wall material layer are independently at least one of calcium carbonate, silica, titanium dioxide, magnesium oxide.
7. The preparation method of the nanoparticle wall material doped metal phase change microcapsule according to any one of claims 1-6, wherein the preparation method comprises the following steps:
s1: weighing a certain amount of solvent, directly adding organic matters and metal particles in the organic wall material layer, and directly coating by magnetic stirring, mechanical stirring or ultrasonic to obtain the metal phase change microcapsule coated by the organic wall material layer; or weighing a certain amount of solvent, adding a certain amount of organic matter monomer and metal particles of the organic wall material layer, then adding a certain amount of initiator to promote the polymerization of the monomer, reacting for a certain time under the assistance of magnetic stirring, mechanical stirring or ultrasound at a certain temperature, and cleaning, filtering and drying after the reaction is finished to obtain the metal phase change microcapsule coated by the organic wall material layer;
s2: weighing a certain amount of solvent, adding the nanoparticles, and uniformly dispersing and suspending the nanoparticles in the solvent in an ultrasonic mode to obtain a nanoparticle suspension; adding a certain amount of inorganic source, and carrying out auxiliary reaction by means of magnetic stirring, mechanical stirring or ultrasound; adding the metal phase change microcapsule coated by the organic wall material layer obtained in the step S1; adding a certain catalyst or initiator, reacting for a period of time, cleaning, filtering and drying to obtain the metal phase change microcapsule with the outer layer being the hybrid inorganic wall material layer doped with the nano particles and the inner layer being the organic wall material layer;
s3: and (3) placing the metal phase change microcapsule obtained in the step (S2) in an atmosphere furnace, introducing nitrogen, setting the temperature to be 300-500 ℃ for heat treatment, heating the organic matters in the organic wall material layer to decompose into gas, escaping through the nanoparticle-doped hybrid inorganic wall material layer, successfully constructing a thermal expansion cavity, and obtaining the nanoparticle wall material-doped metal phase change microcapsule with the thermal expansion cavity.
8. The method for preparing the nanoparticle wall material doped metal phase change microcapsule according to claim 7, wherein the preparation method further comprises the step S4: and (4) coating a compact inorganic wall material layer outside the metal phase change microcapsule subjected to the heat treatment in the step (S3) to obtain the nanoparticle wall material doped metal phase change microcapsule.
9. The method for preparing the nanoparticle wall material doped metal phase change microcapsule according to claim 7, wherein in step S1, the mass ratio of the organic substance, the metal microparticles and the solvent is 1-5: 2 to 8:100, respectively; or, in the step S1, the mass ratio of the organic monomer, the initiator, the metal fine particles and the solvent is 1 to 5:0.01 to 0.05:2 to 8:100.
10. the method for preparing the nanoparticle wall material doped metal phase change microcapsule according to claim 7, wherein in step S2, the mass ratio of the nanoparticle to the solvent is 0.1-0.8: 30 to 130; the mass ratio of the inorganic source to the solvent is 1:1-4, the mass ratio of the metal phase change microcapsule coated by the organic wall material layer to the inorganic source to the catalyst or the initiator is 1: 6-10: 0.5 to 1.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211099537.9A CN115382475B (en) | 2022-09-08 | 2022-09-08 | Nanoparticle wall material doped metal phase change microcapsule and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211099537.9A CN115382475B (en) | 2022-09-08 | 2022-09-08 | Nanoparticle wall material doped metal phase change microcapsule and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115382475A true CN115382475A (en) | 2022-11-25 |
| CN115382475B CN115382475B (en) | 2023-11-17 |
Family
ID=84126782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211099537.9A Active CN115382475B (en) | 2022-09-08 | 2022-09-08 | Nanoparticle wall material doped metal phase change microcapsule and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115382475B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104962240A (en) * | 2015-05-18 | 2015-10-07 | 西安工程大学 | Preparation method of nano particle-doped phase change microcapsule |
| CN105238361A (en) * | 2015-09-23 | 2016-01-13 | 北京化工大学 | Silver/silicon dioxide double layer wall material-based multifunctional microcapsule phase-change material, and preparation method thereof |
| CN106634857A (en) * | 2016-12-09 | 2017-05-10 | 上海电力学院 | Improved microcapsule phase-change material 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 |
| CN112111250A (en) * | 2020-09-15 | 2020-12-22 | 中国矿业大学 | Phase-change heat storage large capsule with ceramic shell coated with metal core material and preparation method thereof |
| WO2021039899A1 (en) * | 2019-08-27 | 2021-03-04 | 国立大学法人北海道大学 | Latent heat storage microcapsule and method for manufacturing same |
| CN112473579A (en) * | 2020-12-12 | 2021-03-12 | 宁波大学 | Metal phase change microcapsule with thermal expansion cavity and preparation method thereof |
| KR20220055765A (en) * | 2020-10-27 | 2022-05-04 | 영남대학교 산학협력단 | Manufacturing method of organic-inorganic hybrid capusle type phase change materials with excellent thermal conductivity and shape stability |
| CN114656935A (en) * | 2022-03-25 | 2022-06-24 | 大连海事大学 | Liquid metal phase change microcapsule and preparation method thereof |
-
2022
- 2022-09-08 CN CN202211099537.9A patent/CN115382475B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104962240A (en) * | 2015-05-18 | 2015-10-07 | 西安工程大学 | Preparation method of nano particle-doped phase change microcapsule |
| CN105238361A (en) * | 2015-09-23 | 2016-01-13 | 北京化工大学 | Silver/silicon dioxide double layer wall material-based multifunctional microcapsule phase-change material, and preparation method thereof |
| CN106634857A (en) * | 2016-12-09 | 2017-05-10 | 上海电力学院 | Improved microcapsule phase-change material 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 |
| WO2021039899A1 (en) * | 2019-08-27 | 2021-03-04 | 国立大学法人北海道大学 | Latent heat storage microcapsule and method for manufacturing same |
| CN114341309A (en) * | 2019-08-27 | 2022-04-12 | 国立大学法人北海道大学 | Microcapsule of latent heat storage and process for producing the same |
| CN112111250A (en) * | 2020-09-15 | 2020-12-22 | 中国矿业大学 | Phase-change heat storage large capsule with ceramic shell coated with metal core material and preparation method thereof |
| KR20220055765A (en) * | 2020-10-27 | 2022-05-04 | 영남대학교 산학협력단 | Manufacturing method of organic-inorganic hybrid capusle type phase change materials with excellent thermal conductivity and shape stability |
| CN112473579A (en) * | 2020-12-12 | 2021-03-12 | 宁波大学 | Metal phase change microcapsule with thermal expansion cavity and preparation method thereof |
| CN114656935A (en) * | 2022-03-25 | 2022-06-24 | 大连海事大学 | Liquid metal phase change microcapsule and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JIAMING BAO, ET AL.,: "A medium-temperature, metal-based, microencapsulated phase change material with a void for thermal expansion", CHEMICAL ENGINEERING JOURNAL, vol. 415, pages 128965, XP093081727, DOI: 10.1016/j.cej.2021.128965 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115382475B (en) | 2023-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107195896B (en) | A kind of preparation method synthesizing silicium cathode material using conductive metal nano particle as carrier low temperature | |
| CN105226257B (en) | A kind of graphene coated honeycombed grain material and preparation method thereof | |
| CN109536137B (en) | Phase-change microcapsule with magnetic and photo-thermal conversion characteristics and preparation method thereof | |
| CN112473579B (en) | Metal phase change microcapsule with thermal expansion cavity and preparation method thereof | |
| CN109244427B (en) | Preparation method of carbon-coated zinc sulfide loaded graphene as potassium ion battery cathode | |
| CN103289653A (en) | High-thermal-conductivity heat-storing nanometer-particle-mixed molten salt and preparation method thereof | |
| CN105038720B (en) | It is a kind of efficiently to utilize stable phase change composite material of solar energy and preparation method thereof | |
| CN107768617B (en) | Lithium-sulfur battery composite cathode material and preparation method thereof | |
| CN110048096A (en) | For lithium/sodium-ion battery cathode tin oxide/carbon fibre composite and preparation method | |
| CN104857945A (en) | Preparation method of zinc oxide/carbon micro-sphere composite material | |
| CN108172416A (en) | The preparation method and applications of three-dimensional carbon aerogels with porous tube wall nanotube | |
| CN109755515A (en) | A kind of lithium ion battery silicon/anode composite and preparation method thereof | |
| CN107195904A (en) | A kind of silicon electrode material preparation method of core shell structure | |
| 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 | |
| CN114525111A (en) | SiO (silicon dioxide)2@ nitrate microcapsule phase-change heat storage composite material and preparation method thereof | |
| CN115382475B (en) | Nanoparticle wall material doped metal phase change microcapsule and preparation method thereof | |
| CN107482193B (en) | The silicon nanowires composite material and preparation method that a kind of nano nickel particles and tantnickel nano-substance are modified jointly | |
| CN109485093B (en) | Anatase type titanium dioxide hollow spherical shell with good spherical shape and preparation method thereof | |
| CN110518216B (en) | Negative electrode composite material of sodium ion battery and preparation method thereof | |
| CN104167532A (en) | Graphite flake /trimanganese tetroxide composite nano-material with sandwich structure, its preparation method, and lithium ion battery using it | |
| CN108091838B (en) | Method for preparing core-shell structure nano α -Fe2O3@ C composite material in one step | |
| Jiang et al. | Effects of carbonization temperature on the thermal characteristics of shape-stable composite phase change materials based on silica aerogel | |
| CN112310386B (en) | Silicon oxide/carbon lithium ion battery cathode material with hollow structure and preparation method and application thereof | |
| CN112375545A (en) | Manganese dioxide-melamine formaldehyde resin double-shell composite phase change material and preparation method 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 |