CN112111250A - Phase-change heat storage large capsule with ceramic shell coated with metal core material and preparation method thereof - Google Patents
Phase-change heat storage large capsule with ceramic shell coated with metal core material and preparation method thereof Download PDFInfo
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B19/00—Machines or methods for applying the material to surfaces to form a permanent layer thereon
Abstract
The invention discloses a phase-change heat storage large capsule with a metal core material coated by a ceramic shell and a preparation method thereof. The large capsule is a spherical capsule with the diameter of 1-50mm, and structurally comprises a ceramic shell layer and a metal core, wherein the diameter of the metal core is 0.5-30mm, and holes are formed in the metal core layer. The spherical macrocapsule prepared by the invention can effectively solve the problems of volume expansion of metal at high temperature and liquid phase leakage at high temperature, has simple preparation process, is green and environment-friendly, and is suitable for industrial batch production.
Description
Technical Field
The invention belongs to the technical field of phase change energy storage, relates to a phase change heat storage big capsule, and particularly relates to a phase change heat storage big capsule with a ceramic shell coated with a metal core material and a preparation method thereof.
Background
In the places and fields of energy application in China, heat energy is generated not only in the process of direct combustion of fuel, but also indirectly in the application of other energy sources (wind energy, solar energy, geothermal energy and the like), most of the generated heat energy can directly exchange heat with the external environment and is not effectively utilized, and then waste of the heat energy is caused, so that the development of a simple and effective heat storage technology is very important. In recent years, new energy storage gradually occupies an important position in the energy field of China, and heat energy serving as one of main energy sources of China still occupies a main position in the new energy field at present. For example, a solar thermal power plant directly generating electricity by using thermal energy, and residual waste heat generated in factories in traditional manufacturing industries such as steel, chemical industry, cement and the like need to be further utilized, so that development of an efficient medium-high temperature heat storage technology is an effective way for improving utilization efficiency of energy.
The existing heat storage modes mainly comprise chemical reaction heat storage, sensible heat storage and latent heat storage according to the type of energy storage. Although the heat storage density is high by utilizing the chemical reaction heat storage, the large-scale application of the heat storage is limited by the defects of complex reaction process and equipment, high technical difficulty, high cost and the like. Sensible heat storage is to store and release heat by the heat capacity of a sensible heat material, and the heat is stored and released along with the increase and decrease of the temperature. Compared with sensible heat materials, latent heat materials have the advantages of high heat storage density, larger heat storage capacity and stable heat storage and release platforms when phase change occurs, but the problems of leakage, container corrosion and the like are easily caused when the phase change occurs in the latent heat materials. Common medium-high temperature phase change materials include molten salt, metal and the like. However, the molten salt has the disadvantages of low thermal conductivity, poor chemical stability, strong corrosivity and the like, which greatly limit the application of the molten salt, and the metal material has the advantages of high energy storage density, high thermal conductivity, excellent thermal cycle stability and the like, which are very beneficial to the utilization of heat energy in the medium-high temperature field, but also has the problems of liquid phase leakage, container corrosion and the like during high-temperature phase change. Therefore, the development of an effective and reliable packaging technology is very important for promoting the application of the metal phase-change material in the field of heat storage.
At present, a relatively mature packaging technology for phase change materials is a capsule packaging technology, and the encapsulation technology is the most common method for solving the problem of melting and flowing of the phase change materials. However, since the metal material has a large volume change rate during high-temperature phase change, for example, when the metal aluminum ball is packaged at room temperature, the metal aluminum ball will expand in large volume during high-temperature phase change, so that the shell membrane is burst and leaked, and cannot be recycled, which becomes a main problem for packaging the metal material.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a phase-change heat storage big capsule with a metal core material coated by a ceramic shell, which can encapsulate the metal core material in a compact ceramic shell and prevent the metal material from leaking during high-temperature phase change.
The invention also aims to provide the phase-change heat storage large capsule with the metal core material coated by the ceramic shell prepared by the method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a phase-change heat storage big capsule with a metal core material coated by a ceramic shell comprises the following steps:
(1) stirring and mixing metal powder and an organic binder solution according to a certain proportion, molding by using a ball forming mill or a ball forming die after uniform mixing to obtain a spherical metal blank, and drying the spherical metal blank at 40-150 ℃ for 1-72h to obtain a spherical metal core material;
(2) stirring and mixing ceramic powder and an organic binder solution according to a certain proportion, uniformly mixing, uniformly coating a layer of ceramic slurry on the surface of the spherical metal core material prepared in the step (1), then molding by adopting a ball forming mill or a ball forming die to obtain a spherical capsule blank, and drying the spherical capsule blank at 40-150 ℃ for 1-72 hours to obtain a large capsule with the metal core material coated by a ceramic shell;
(3) carrying out two-stage heat treatment on the large capsule with the metal core material coated by the ceramic shell prepared in the step (2), 1) heating to 600 ℃ at 300 ℃ in an oxygen-containing atmosphere, pre-sintering for 1-24h, and removing the organic binder contained in the blank; 2) after pre-sintering, heating to 700-1500 ℃ in an oxygen-containing or non-oxidizing atmosphere, carrying out high-temperature heat treatment for 1-48h, and naturally cooling to room temperature to obtain the phase-change heat storage large capsule with the metal core material coated by the ceramic shell.
Preferably, the metal powder In step (1) is selected from one or more of elemental silicon Si, elemental metals, binary alloys, ternary alloys and quaternary alloys, and the elemental metals are selected from one or more of nickel Ni, cobalt Co, iron Fe, titanium Ti, vanadium V, chromium Cr, manganese Mn, copper Cu, magnesium Mg, calcium Ca, aluminum Al, zinc Zn, tin Sn, bismuth Bi, indium In, antimony Sb, lead Pb, cadmium Cd, gallium Ga, germanium Ge, molybdenum Mo, niobium Nb, zirconium Zr, silver Ag, platinum Pt, molybdenum Mo, tungsten Wu, tantalum Ta, rhenium Re, boron B, hafnium Hf, thallium Tl, scandium, yttrium Y, arsenic As, ruthenium Ru, rhodium Rh, palladium Pd, osmium Os and iridium Ir; the binary alloy is formed by alloying the two elementary metals or the elementary metal and the elementary silicon; the ternary alloy is formed by alloying the three elementary metals or the two elementary metals with the elementary silicon; the quaternary alloy is formed by alloying the four elementary metals or the three elementary metals with the elementary silicon.
Preferably, the organic binder is selected from one or more of polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyacrylic acid (PAA), sodium carboxymethyl cellulose (CMC), starch, vinyl butyral ester (PVB), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), chitosan, silicone resin and synthetic rubber.
Preferably, the ceramic powder is selected from silicon carbide SiC and aluminum oxide Al2O3Magnesium oxide MgO, silicon dioxide SiO2Zirconium oxide ZrO2Hafnium oxide HfO2Kaolin, clay, bentonite, porcelain clay, diatomite, bentonite, aluminum nitride AlN, silicon nitride SiN, boron nitride BN, SiAlON, yttrium oxide Y2O3Molybdenum disilicide MoSi2TaSi, tantalum disilicide2Hafnium diboride HfB2One or more of aluminosilicate, mullite and cordierite.
Preferably, in the step (1) and the step (2), the organic binder solution is prepared by dissolving an organic binder in a corresponding solvent, and the mass fraction of the organic binder is 0.1-50%.
Preferably, in the step (1), the mass ratio of the metal powder to the organic binder is 99.5:0.5-50: 50; in the step (2), the mass ratio of the ceramic powder to the organic binder is 99.5:0.5-50: 50.
Preferably, the particle size of the metal powder is 5nm-500 μm, and the particle size of the ceramic powder is 5nm-500 μm.
The invention also provides a phase-change heat storage large capsule with a metal core material coated by the ceramic shell, which is prepared by the method, the large capsule is a spherical capsule with the diameter of 1-50mm, the structure of the large capsule comprises a ceramic shell layer and a metal core, the diameter of the metal core is 0.5-30mm, and holes are arranged inside the metal core.
The phase-change heat storage big capsule with the ceramic shell coating the metal core material is a metal phase-change material, has the advantages of high heat storage density, good thermal cycle performance, strong oxidation resistance, high heat conductivity coefficient, low steam pressure, long service life and the like, and can be widely applied to the technical fields of phase-change heat storage such as industrial waste heat recycling, solar heat storage systems and the like.
Compared with the prior art, the invention has the following beneficial effects:
1. the phase-change heat storage spherical macro capsule with the metal core material coated by the ceramic shell film and the cavity is prepared by preparing the spherical metal blank, coating the ceramic shell layer and sintering and shaping. The raw material of the metal core material is formed by mixing powder into balls, the metal core material is formed into balls by a ball forming machine or a ball forming die, the powder in the metal core material is not in a 100% strict state, and then the organic binder is removed by combustion, and then the micro-pores with different sizes exist in the balls, so that a buffer space is reserved for the volume expansion of the macrocapsule in the high-temperature phase change process, and the problems of volume expansion of metal at high temperature and liquid phase leakage at high temperature can be effectively solved.
2. The preparation method has the advantages of simple preparation process, low preparation cost, environmental protection and easy realization of large-scale and continuous production, and the compact ceramic shell can not only prevent the leakage of the internal metal material, but also effectively prolong the service life of the heat accumulator.
Drawings
FIG. 1 is a schematic structural diagram of a phase-change heat storage macro-capsule, in which 1 represents a ceramic shell, 2 represents a metal core, and 3 represents holes existing after sintering;
FIG. 2(a) is a schematic diagram of a spherical Al-Si metal core material blank dried and molded in example 1;
FIG. 2(b) is a schematic diagram of a spherical capsule blank of Al-Si alloy core material coated with an alumina shell film formed by drying in example 1;
FIG. 2(c) is a 1300 ℃ sintering-shaped alumina shell film coated Al-Si alloy core material macro-capsule object diagram;
FIG. 2(d) is a cross-sectional view of a 1300 ℃ sintered and shaped alumina shell film coated Al-Si alloy core material macro-capsule.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
The invention provides a phase-change heat storage large capsule with a metal core material coated by a ceramic shell, as shown in figure 1, the large capsule is a spherical capsule with the diameter of 1-50mm, the structure of the large capsule comprises a ceramic shell layer 1 and a metal core 2, the diameter of the metal core 2 is 0.5-30mm, and a hole 3 is formed in the metal core 2.
Example 1: preparing alumina ceramic shell coated spherical Al-Si metal core macrocapsule
(1) Al-Si alloy metal powder with the particle size of 50 mu m is taken as a metal core raw material, a CMC binder is dissolved in deionized water (the mass of the CMC binder is 0.16g, and the mass of the deionized water is 4g), 10g of Al-Si alloy metal powder is added into the binder solution to be stirred and mixed, after uniform mixing, the Al-Si alloy powder is manually pelletized to prepare spherical metal Al-Si blanks with the diameters of 1mm, 2mm, 3mm, 4mm, 6mm and 8mm, and then the spherical metal Al-Si alloy core material is prepared after drying for 72h at 40 ℃, wherein the physical object is shown in figure 2 (a).
(2) With 20nm particle size of Al2O3CMC binder was also dissolved in deionized water as a ceramic powder feedstock(CMC binder mass 0.16g, deionized water mass 4g), then 1.5g Al2O3Adding ceramic powder into the binder solution, stirring and mixing, and uniformly coating a layer of Al on the surface of the prepared spherical Al-Si metal core material2O3Preparing the ceramic slurry into spherical capsule blanks with the diameters of 3mm, 4mm, 6mm, 8mm, 10mm and 15mm, and drying at 150 ℃ for 72h, wherein the material is shown in figure 2 (b).
(3) Two-stage heat treatment process: 1) heating to 600 ℃ at the heating rate of 10 ℃/min in the air atmosphere, pre-sintering for 1h, and removing organic binders contained in the green body through the combustion process; 2) and after pre-sintering, continuously heating to 1300 ℃ at the heating rate of 10 ℃/min in the air atmosphere, and carrying out high-temperature heat treatment for 2h to prepare the phase-change heat storage spherical large capsule with the metal core material coated by the ceramic shell with holes inside.
The spherical macrocapsule material object sintered at the high temperature of 1300 ℃ is shown in fig. 2(c), after being longitudinally cut, an internal metal core and a ceramic shell layer coated outside the metal core layer can be seen as shown in fig. 2(d), holes with different sizes can be clearly seen in the metal core, and the holes reserve a buffer space for volume expansion of the macrocapsule in the high-temperature phase change process, so that the problems of volume expansion of metal at high temperature and liquid phase leakage at high temperature can be effectively solved.
Example 2: preparing the magnesium oxide ceramic shell coated spherical Al metal core macrocapsule
(1) Al metal powder with the particle size of 500 mu m is taken as a metal core raw material, a CMC binder is dissolved in deionized water (the mass of the CMC binder is 0.16g, and the mass of the deionized water is 4g), 10g of Al metal powder is added into the binder solution to be stirred and mixed, after uniform mixing, spherical metal Al blanks with the diameters of 10mm, 15mm, 20mm, 25mm and 30mm are respectively prepared by a spherical mould, and then the spherical Al metal core material is prepared by drying at 150 ℃ for 1 h.
(2) MgO with the particle size of 5 mu m is taken as a ceramic powder raw material, a CMC binder is dissolved in deionized water (the mass of the CMC binder is 0.16g, and the mass of the deionized water is 4g) in the same way, then 1.5g of MgO ceramic powder is taken and added into the above binder solution to be stirred and mixed, after uniform mixing, a layer of MgO ceramic slurry is uniformly coated on the surface of the prepared spherical Al metal core material, spherical capsule blanks with the diameters of 18mm, 25mm, 30mm, 40mm and 50mm are respectively prepared by a spherical mould, and then the blank is dried for 24 hours at the temperature of 100 ℃.
(3) Two-stage heat treatment process: 1) heating to 300 ℃ at the heating rate of 10 ℃/min in the oxygen atmosphere, pre-sintering for 1h, and removing organic binders contained in the green body through the combustion process; 2) and after pre-sintering, continuously heating to 1200 ℃ at the heating rate of 10 ℃/min in the nitrogen atmosphere, and carrying out high-temperature heat treatment for 2h to prepare the phase-change heat storage spherical large capsule with the metal core material coated by the ceramic shell with holes inside.
Example 3: preparing the silicon nitride ceramic shell coated spherical Al-Si-Cu metal core macrocapsule
(1) Al-Si-Cu metal powder with the particle size of 1 mu m is taken as a metal core raw material, a polyvinyl alcohol binder is dissolved in deionized water (the mass fraction of polyvinyl alcohol is 10%), Al-Si-Cu metal powder is added into the binder solution, the mixture is stirred and mixed (the mass ratio of the metal powder to the binder is 80: 20), spherical metal Al-Si-Cu blanks with the diameters of 8mm, 12mm and 16mm are respectively prepared by a ball forming mill after the mixture is uniformly mixed, and then the spherical Al-Si-Cu metal core material is prepared by drying for 24 hours at 70 ℃.
(2) Silicon nitride micro powder with the particle size of 13 mu m is taken as a ceramic powder raw material, a polyvinyl alcohol binder is dissolved in deionized water (the mass fraction of polyvinyl alcohol is 20%), the silicon nitride micro powder is added into the binder solution to be stirred and mixed (the mass ratio of silicon nitride to the binder is 90: 10), after uniform mixing, a layer of silicon nitride ceramic slurry is uniformly coated on the surface of the prepared spherical Al-Si-Cu metal core material, spherical capsule blanks with the diameters of 15mm, 20mm and 30mm are respectively prepared through a spherical mould, and then the drying is carried out for 24 hours at the temperature of 70 ℃.
(3) Two-stage heat treatment process: 1) heating to 400 ℃ at the temperature rise rate of 2 ℃/min in the oxygen atmosphere, pre-sintering for 1h, and removing organic binders contained in the green body through the combustion process; 2) and after pre-sintering, continuously heating to 1000 ℃ at the temperature rise rate of 5 ℃/min in the argon atmosphere, and carrying out high-temperature heat treatment for 2h to prepare the phase-change heat storage spherical large capsule with the metal core material coated by the ceramic shell with holes inside.
Example 4: preparing kaolin ceramic shell coated spherical Sn-Zn-In metal core macrocapsule
(1) Taking Sn-Zn-In metal powder with the particle size of 100 mu m as a metal core raw material, dissolving a CMC binder In deionized water (the mass fraction of CMC is 0.5%), adding the Sn-Zn-In metal powder into the binder solution, stirring and mixing (the mass ratio of the metal powder to the binder is 99: 1), preparing spherical Sn-Zn-In metal blanks with the diameters of 5mm, 7mm, 9mm, 11mm and 13mm respectively through a spherical mould after uniform mixing, and then drying at 70 ℃ for 24h to prepare the spherical Sn-Zn-In metal core material.
(2) Taking kaolin with the particle size of 10 mu m as a ceramic powder raw material, adding the kaolin powder into a prepared CMC binder solution with the mass fraction of 0.5%, stirring and mixing (the mass ratio of the kaolin to the binder is 99.5: 0.5), uniformly mixing, uniformly coating a layer of kaolin ceramic slurry on the surface of a prepared spherical Sn-Zn-In metal core material, respectively preparing spherical capsule blanks with the diameters of 13mm, 16mm, 18mm, 22mm and 30mm by a spherical mould, and drying at 70 ℃ for 24 hours.
(3) Two-stage heat treatment process: 1) heating to 300 ℃ at the heating rate of 1 ℃/min in the oxygen atmosphere, pre-sintering for 2h, and removing organic binders contained in the green body through the combustion process; 2) and after pre-sintering, continuously heating to 700 ℃ at the temperature rise rate of 5 ℃/min in the nitrogen atmosphere, and carrying out high-temperature heat treatment for 2h to prepare the phase-change heat storage spherical large capsule with the metal core material coated by the ceramic shell with holes inside.
Example 5: preparing the diatomite ceramic shell coated spherical Sn metal core macrocapsule
(1) Taking Sn metal powder with the particle size of 45 mu m as a metal core raw material, adding the Sn metal powder into an aqueous solution of a starch binder with the mass fraction of 50%, stirring and mixing (the mass ratio of the metal powder to the starch is 90: 10), uniformly mixing, preparing spherical metal Sn blanks with the diameters of 5mm, 10mm, 15mm, 20mm and 25mm by using a ball forming mill, and drying at 80 ℃ for 24 hours to prepare the spherical Sn metal core material.
(2) Diatomite with the particle size of 20 mu m is used as a ceramic powder raw material, the diatomite powder and a starch aqueous solution with the mass fraction of 10% are stirred and mixed (the mass ratio of the diatomite to the starch is 80: 20), after uniform mixing, a layer of diatomite ceramic slurry is uniformly coated on the surface of the prepared spherical Sn metal core material, spherical capsule blanks with the diameters of 11mm, 18mm, 24mm, 32mm and 50mm are respectively prepared through a spherical mould, and then drying is carried out for 24 hours at the temperature of 90 ℃.
(3) Two-stage heat treatment process: 1) heating to 300 ℃ at the heating rate of 10 ℃/min in the oxygen atmosphere, pre-sintering for 3h, and removing organic binders contained in the green body through the combustion process; 2) and after pre-sintering, continuously heating to 900 ℃ at the heating rate of 10 ℃/min in the oxygen atmosphere, and carrying out high-temperature heat treatment for 1h to prepare the phase-change heat storage spherical large capsule with the metal core material coated by the ceramic shell with holes inside.
Example 6: preparation of ZrO2Large capsule with spherical Cu metal core coated by ceramic shell
(1) Taking Cu metal powder with the particle size of 200 mu m as a metal core raw material, stirring and mixing the Cu metal powder with an aqueous solution of a polyvinyl alcohol binder with the mass fraction of 10% (the mass ratio of metal to binder is 95: 5), respectively preparing spherical metal Cu blanks with the diameters of 6mm, 8mm, 10mm, 12mm and 14mm by a spherical mould after uniform mixing, and then drying for 24 hours at 70 ℃ to prepare the spherical Cu metal core material.
(2) ZrO in a particle size of 100nm2Is prepared from ceramic powder as raw material, mixing with 5% polyvinyl alcohol as adhesive (98: 2 mass ratio), coating a layer of ZrO on the surface of prepared spherical Cu metal core2And (3) respectively preparing the ceramic slurry into spherical capsule blanks with the diameters of 12mm, 14mm, 18mm, 20mm and 22mm by using a spherical mould, and then drying at 70 ℃ for 24 h.
(3) Two-stage heat treatment process: 1) heating to 300 ℃ at the heating rate of 10 ℃/min in the oxygen atmosphere, pre-sintering for 1h, and removing organic binders contained in the green body through the combustion process; 2) and after pre-sintering, continuously heating to 1200 ℃ at the heating rate of 10 ℃/min in the argon atmosphere, and carrying out high-temperature heat treatment for 3h to prepare the phase-change heat storage spherical large capsule with the metal core material coated by the ceramic shell with holes inside.
Example 7: preparing a SiAlON ceramic shell coated spherical Al-Si-Cu-Sn metal core macrocapsule
(1) Taking Al-Si-Cu-Sn metal powder with the particle size of 50 mu m as a metal core raw material, stirring and mixing the metal core raw material with a CMC (CMC) binder aqueous solution with the mass fraction of 2% (the mass ratio of the metal powder to the binder is 50: 50), uniformly mixing, respectively preparing spherical metal Al-Si-Cu-Sn blanks with the diameters of 5mm, 7mm, 9mm, 11mm and 13mm by a spherical mould, and then drying for 24 hours at 70 ℃ to prepare the spherical Al-Si-Cu-Sn metal core material.
(2) SiAlON with the particle size of 20 mu m is used as a ceramic powder raw material, the ceramic powder raw material is mixed with an aqueous solution of a CMC binder with the mass fraction of 2% (the mass ratio of the ceramic to the binder is 50: 50), after uniform mixing, a layer of SiAlON ceramic slurry is uniformly coated on the surface of the prepared spherical Al-Si-Cu-Sn metal core material, spherical capsule blanks with the diameters of 13mm, 15mm, 17mm, 19mm and 21mm are respectively prepared through a spherical mould, and then the spherical capsule blanks are dried for 24 hours at the temperature of 70 ℃.
(3) Two-stage heat treatment process: 1) heating to 300 ℃ at the heating rate of 10 ℃/min in the oxygen atmosphere, pre-sintering for 1h, and removing organic binders contained in the green body through the combustion process; 2) and after pre-sintering, continuously heating to 1300 ℃ at the heating rate of 10 ℃/min in the oxygen atmosphere, and carrying out high-temperature heat treatment for 2h to prepare the phase-change heat storage spherical large capsule with the metal core material coated by the ceramic shell with holes inside.
Example 8: preparing the silicon carbide ceramic shell coated spherical Sn-Zn-In-Al metal core macrocapsule
(1) Taking Sn-Zn-In-Al metal powder with the particle size of 50 mu m as a metal core raw material, uniformly mixing the Sn-Zn-In-Al metal powder with an aqueous solution of a CMC binder with the mass fraction of 2% (the mass ratio of the metal powder to the binder is 85: 15), respectively preparing spherical Sn-Zn-In-Al metal blanks with the diameters of 6mm, 8mm, 10mm, 12mm and 14mm by using a spherical mould, and then drying for 24 hours at 70 ℃ to prepare the spherical Sn-Zn-In-Al metal core material.
(2) Silicon nitride with the particle size of 15 mu m is used as a ceramic powder raw material, the silicon nitride powder raw material and a CMC (CMC) binder with the mass fraction of 1% are uniformly mixed (the mass ratio of the ceramic powder to the binder is 90: 10), a layer of silicon nitride ceramic slurry is uniformly coated on the surface of a prepared spherical Sn-Zn-In-Al metal core material, spherical capsule blanks with the diameters of 12mm, 14mm, 18mm, 20mm and 22mm are respectively prepared through a spherical mould, and then the blank is dried for 24 hours at the temperature of 70 ℃.
(3) Two-stage heat treatment process: 1) heating to 300 ℃ at the heating rate of 10 ℃/min in the oxygen atmosphere, pre-sintering for 1h, and removing organic binders contained in the green body through the combustion process; 2) and after pre-sintering, continuously heating to 800 ℃ at the heating rate of 10 ℃/min in the oxygen atmosphere, and carrying out high-temperature heat treatment for 2h to prepare the phase-change heat storage spherical large capsule with the metal core material coated by the ceramic shell with holes inside.
Claims (8)
1. A preparation method of a phase-change heat storage big capsule with a metal core material coated by a ceramic shell is characterized by comprising the following steps:
(1) stirring and mixing metal powder and an organic binder solution according to a certain proportion, molding by using a ball forming mill or a ball forming die after uniform mixing to obtain a spherical metal blank, and drying the spherical metal blank at 40-150 ℃ for 1-72h to obtain a spherical metal core material;
(2) stirring and mixing ceramic powder and an organic binder solution according to a certain proportion, uniformly mixing, uniformly coating a layer of ceramic slurry on the surface of the spherical metal core material prepared in the step (1), then molding by adopting a ball forming mill or a ball forming die to obtain a spherical capsule blank, and drying the spherical capsule blank at 40-150 ℃ for 1-72 hours to obtain a large capsule with the metal core material coated by a ceramic shell;
(3) carrying out two-stage heat treatment on the large capsule with the metal core material coated by the ceramic shell prepared in the step (2), 1) heating to 600 ℃ at 300 ℃ in an oxygen-containing atmosphere, pre-sintering for 1-24h, and removing the organic binder contained in the blank; 2) after pre-sintering, heating to 700-1500 ℃ in an oxygen-containing or non-oxidizing atmosphere, carrying out high-temperature heat treatment for 1-48h, and naturally cooling to room temperature to obtain the phase-change heat storage large capsule with the metal core material coated by the ceramic shell.
2. The method for preparing a phase-change heat storage macro-capsule with a metal core covered by a ceramic shell according to claim 1, wherein the metal powder in step (1) is selected from one or more of elemental silicon, elemental metal, binary alloy, ternary alloy and quaternary alloy, and the elemental metal is selected from one or more of nickel, cobalt, iron, titanium, vanadium, chromium, manganese, copper, magnesium, calcium, aluminum, zinc, tin, bismuth, indium, antimony, lead, cadmium, gallium, germanium, molybdenum, niobium, zirconium, silver, platinum, molybdenum, tungsten, tantalum, rhenium, boron, hafnium, thallium, scandium, yttrium, arsenic, ruthenium, rhodium, palladium, osmium and iridium; the binary alloy is formed by alloying the two elementary metals or the elementary metal and the elementary silicon; the ternary alloy is formed by alloying the three elementary metals or the two elementary metals with the elementary silicon; the quaternary alloy is formed by alloying the four elementary metals or the three elementary metals with the elementary silicon.
3. The method for preparing the phase-change heat storage macro-capsule with the metal core material coated by the ceramic shell according to claim 1, wherein the organic binder is selected from one or more of polyvinyl alcohol, polyethylene glycol, polyacrylic acid, sodium carboxymethylcellulose, starch, vinyl butyral, polymethyl methacrylate, polyvinylidene fluoride, chitosan, silicone resin and synthetic rubber.
4. The method of claim 1, wherein the ceramic powder is selected from one or more of silicon carbide, aluminum oxide, magnesium oxide, silicon dioxide, zirconium oxide, hafnium oxide, kaolin, clay, attapulgite, china clay, diatomaceous earth, bentonite, aluminum nitride, silicon nitride, boron nitride, sialon, yttrium oxide, molybdenum disilicide, tantalum disilicide, hafnium diboride, aluminosilicate, mullite, and cordierite.
5. The method for preparing the phase-change heat storage macro-capsule with the metal core material coated by the ceramic shell as claimed in claim 1, wherein in the step (1) and the step (2), the organic binder solution is prepared by dissolving an organic binder in a corresponding solvent, and the mass fraction of the organic binder is 0.1-50%.
6. The method for preparing the phase-change heat storage big capsule with the metal core material coated by the ceramic shell as claimed in claim 1, wherein in the step (1), the mass ratio of the metal powder to the organic binder is 99.5:0.5-50: 50; in the step (2), the mass ratio of the ceramic powder to the organic binder is 99.5:0.5-50: 50.
7. The method for preparing the phase-change heat storage macro capsule with the metal core material coated by the ceramic shell as claimed in claim 1, wherein the particle size of the metal powder is 5nm-500 μm, and the particle size of the ceramic powder is 5nm-500 μm.
8. The phase-change heat storage macrocapsule having a metal core material covered with a ceramic shell prepared by the method of any one of claims 1 to 7, wherein the macrocapsule is a spherical capsule having a diameter of 1 to 50mm and has a structure comprising a ceramic shell layer and a metal core having a diameter of 0.5 to 30mm and having a hole inside.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717695A (en) * | 2021-09-10 | 2021-11-30 | 中国矿业大学 | Preparation method and application of fused salt-based composite phase-change heat storage large capsule |
| CN114644780A (en) * | 2022-03-03 | 2022-06-21 | 江苏圣天新材料有限公司 | Preparation method of electronic grade superfine composite silicon micro powder for integrated circuit substrate |
| CN114716268A (en) * | 2022-04-02 | 2022-07-08 | 陕西科技大学 | Preparation of Glass-MoSi on surface of carbon/carbon composite material2@Y2O3Method for preparing-SiC oxidation-resistant coating |
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| CN116005056A (en) * | 2022-12-06 | 2023-04-25 | 宁波大学 | Ceramic-based metal microcapsule/organic phase change composite material and preparation method thereof |
| EP4282930A1 (en) * | 2022-05-24 | 2023-11-29 | Shinko Electric Industries Co., Ltd. | Latent heat storage and method for manufacturing latent heat storage |
| EP4282931A1 (en) * | 2022-05-24 | 2023-11-29 | Shinko Electric Industries Co., Ltd. | Latent heat storage and method for manufacturing latent heat storage |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361534A (en) * | 2013-07-15 | 2013-10-23 | 曹南萍 | Metal ceramic with phase change heat storage function and manufacturing method thereof |
| DE102012111707A1 (en) * | 2012-12-03 | 2014-06-05 | Bernhard Sixt | Latent heat storage and process for its preparation |
| CN107988506A (en) * | 2017-11-29 | 2018-05-04 | 武汉科技大学 | A kind of composite material phase change heat storage balls and preparation method thereof |
-
2020
- 2020-09-15 CN CN202010968208.8A patent/CN112111250A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102012111707A1 (en) * | 2012-12-03 | 2014-06-05 | Bernhard Sixt | Latent heat storage and process for its preparation |
| CN103361534A (en) * | 2013-07-15 | 2013-10-23 | 曹南萍 | Metal ceramic with phase change heat storage function and manufacturing method thereof |
| CN107988506A (en) * | 2017-11-29 | 2018-05-04 | 武汉科技大学 | A kind of composite material phase change heat storage balls and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717695A (en) * | 2021-09-10 | 2021-11-30 | 中国矿业大学 | Preparation method and application of fused salt-based composite phase-change heat storage large capsule |
| CN114644780A (en) * | 2022-03-03 | 2022-06-21 | 江苏圣天新材料有限公司 | Preparation method of electronic grade superfine composite silicon micro powder for integrated circuit substrate |
| CN114644780B (en) * | 2022-03-03 | 2022-12-09 | 江苏圣天新材料有限公司 | Preparation method of electronic-grade superfine composite silicon micropowder for integrated circuit substrate |
| CN114716268A (en) * | 2022-04-02 | 2022-07-08 | 陕西科技大学 | Preparation of Glass-MoSi on surface of carbon/carbon composite material2@Y2O3Method for preparing-SiC oxidation-resistant coating |
| CN114716268B (en) * | 2022-04-02 | 2022-11-29 | 陕西科技大学 | Preparation of Glass-MoSi on surface of carbon/carbon composite material 2 @Y 2 O 3 Method for preparing-SiC oxidation-resistant coating |
| EP4282930A1 (en) * | 2022-05-24 | 2023-11-29 | Shinko Electric Industries Co., Ltd. | Latent heat storage and method for manufacturing latent heat storage |
| EP4282931A1 (en) * | 2022-05-24 | 2023-11-29 | Shinko Electric Industries Co., Ltd. | Latent heat storage and method for manufacturing latent heat storage |
| 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 |
| CN116005056A (en) * | 2022-12-06 | 2023-04-25 | 宁波大学 | Ceramic-based metal microcapsule/organic phase change composite material and preparation method thereof |
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