CN103436240A - Foam metal composite phase-change material and preparation method thereof - Google Patents
Foam metal composite phase-change material and preparation method thereof Download PDFInfo
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- CN103436240A CN103436240A CN2013103261418A CN201310326141A CN103436240A CN 103436240 A CN103436240 A CN 103436240A CN 2013103261418 A CN2013103261418 A CN 2013103261418A CN 201310326141 A CN201310326141 A CN 201310326141A CN 103436240 A CN103436240 A CN 103436240A
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Abstract
The invention relates to a foam metal composite phase-change material and a preparation method thereof, and belongs to the technical field of phase-change energy storage materials. A crystallized hydrated salt-foam metal composite phase-change energy storage material is prepared by adopting the adsorption characteristic of a porous foam metal skeleton structure, and a vacuum argon filling state is kept in a preparation process, so that impurities are prevented from entering, and the quality of a product is ensured. The phase-change material is relatively uniformly and sufficiently distributed in a substrate of the foam metal skeleton material, and the shaping characteristic of the composite material is maintained under the combined action of a capillary force and surface tension of foam metal, so that the phase-change material does not leak easily in a phase-change process, and the preparation method of the phase-change material is simple and convenient, high in recombination rate and good in operability. The composite phase-change material has the advantages of high phase-change latent heat in unit volume, high heat storage and release rates, good heat-conducting property, lower supercooling degree, and the like; and the lower heat conductivity and supercooling problems existing after the crystallized hydrated salt phase-change material is applied for a long time are solved effectively.
Description
Technical field
The present invention relates to the phase-changing energy storage material technical field, figuration composite phase-changing material that particularly a kind of crystalline hydrate salt phase transformation material and foamed metal form and preparation method thereof.
Background technology
Along with the aggravation of energy scarcity problem, the storage of renewable energy source, development and utilization more and more become the emphasis of World Focusing.Energy storage not only can effectively reduce the dissipation of total energy and reduce unnecessary waste of fuel, and can improve the Performance And Reliability of whole system.Among numerous energy storage methods, utilize solid-liquid phase change material advantage such as constant transformation temperature and high latent heat density in phase transition process to realize storage and the utilization of energy, be widely used in the aspects such as sun power utilization, industrial afterheat recovery, building energy conservation and the analysis of electronics heat, become an active study hotspot in energy science and material science.
Solid-liquid phase change material is divided into organic and mineral-type usually.What the organic phase change material was commonly used is paraffin, the organic phase change material generally was not prone to the cold-peace phenomenon of phase separation, the thermochemical property of material is stable, corrodibility is little, toxicity is little and cost compare is cheap, but there is the less and easy oxidizing fire under hot conditions of thermal conductivity in the organic phase change material.The mineral-type phase change material is most typical is crystalline hydrate salt, and crystalline hydrate salt is a kind of typical middle low-temperature phase-change energy-storing material, and when temperature raises, crystalline hydrate salt is deviate from crystal water makes the salt dissolving and heat absorbing; Inverse process occurs when temperature reduces, and absorbs the crystal water heat release.Crystalline hydrate salt is compared with the organic phase change material, has a thermal conductivity larger, the thermal storage density advantages of higher of the large and unit volume of density, but crystalline hydrate salt exist condensate depression large, be separated and the shortcoming such as corrodibility.In order to eliminate or to slow down its condensate depression and inhibition is separated, the way usually adopted is to add a certain amount of nucleator and thickening material, and the method is mainly tested searching by a large amount of materials, requires a great deal of time and energy.Therefore, suppress the condensate depression of crystalline hydrate salt and improve its heat conductivility is the focus of paying close attention in phase change energy storage technology research always.
Summary of the invention
The purpose of this invention is to provide a kind of crystalline hydrate salt-foamed metal composite phase-change material and preparation method thereof, this matrix material has the advantages such as thermal characteristics is stable, and thermal storage density is high, and heat transfer property is good, and condensate depression is little.
According to an aspect of the present invention, provide a kind of preparation method of foamed metal composite phase-change material, it is characterized in that comprising:
A) phase change material after grinding is evenly added in vacuum argon filling case in heat storage container, by the vacuum system vacuum pump, the argon filling case is evacuated to predetermined vacuum level;
B) subsequently, in casing, be filled with argon gas, after argon pressure and atmospheric equilibrium, close the argon filling main valve;
C) carry out the water bath with thermostatic control heating, realize the indirect homogeneous heating of phase change material, and will process foamed metal framework material after cleaning and together put into heat storage container and heat, make the phase change material under the enough absorption molten states of foamed metal, thereby realize compound.
According to a further aspect of the present invention, provide a kind of foamed metal composite phase-change material of making by above-mentioned preparation method.
The accompanying drawing explanation
The endothermic curve that Fig. 1 is foamed metal composite phase-change energy storage material and pure phase change energy-storage material in embodiment 1;
The exotherm that Fig. 2 is foamed metal composite phase-change energy storage material and pure phase change energy-storage material in embodiment 1.
The endothermic curve that Fig. 3 is foamed metal composite phase-change energy storage material and pure phase change energy-storage material in embodiment 2;
The exotherm that Fig. 4 is foamed metal composite phase-change energy storage material and pure phase change energy-storage material in embodiment 2.
In Fig. 1-4 ,-be the suction exotherm of foamed metal composite phase-change energy storage material; The suction exotherm that ┄ is the pure phase change energy-storage material.
Embodiment
The present invention utilizes the foamed metal framework material of high porosity as matrix, and enough absorption crystalline hydrate salt phase transformation materials, prepare composite phase-change energy storage material.
Foamed metal framework material according to an embodiment of the invention is foam copper, foamed aluminium or nickel foam stephanoporate framework material.
According to the preparation method of foamed metal composite phase-change material of the present invention, comprise:
-phase change material of purity after grinding>=98% is evenly added in vacuum argon filling case in heat storage container, by the vacuum system vacuum pump, the argon filling case is vacuumized, vacuum tightness is not less than 1 * 10
-2torr;
-subsequently, in casing, be filled with high-purity (purity is more than or equal to 99.99%) argon gas, after argon pressure and atmospheric equilibrium, close the argon filling main valve;
-(because most of crystalline hydrate salt phase transformation material melting point is low) carried out the water bath with thermostatic control heating, realize the indirect homogeneous heating of phase change material, the foamed metal framework material that simultaneously will process after clearing up is together put into the heat storage container heating, make the phase change material under the enough absorption molten states of foamed metal, adsorptive capacity accounts for 85～90% of the theoretical filling of phase change material total amount, thereby realizes compound;
-finish compoundly, then will hold heat storage container Slow cooling in vacuum argon filling case of foamed metal composite phase-change material;
-open the door of vacuum argon filling case, take out composite phase-change material and clear up overall size, obtain finished product.
Described phase change material is crystalline hydrate salt, as a kind of in barium hydroxide, Sodium acetate trihydrate, calcium chloride hexahydrate, five water Sulfothiorine, Sodium carbonate decahydrate or the multiple composition in them.
Utilize capillary force and the capillary acting in conjunction of porous foam metal framework material to make the spontaneous infiltration of crystalline hydrate salt phase transformation material under molten state, simplified the preparation technology of composite phase-change material.
Beneficial effect of the present invention comprises: adopt the vacuum argon filling case of good airproof performance to prepare the foamed metal composite phase-change material, prevent that air, water vapour and other obnoxious flavoures and particle from sneaking into, contribute to improve the quality of product.Crystalline hydrate salt phase transformation material more evenly is fully distributed in foamed metal framework material matrix inside, the setting characteristic that has kept matrix material under the capillary force of foamed metal and capillary acting in conjunction, make phase change material easy to leak not in phase transition process, its making is easy to process, recombination rate is high, has good operability.The advantages such as it is large that this composite phase-change material has a unit volume latent heat of phase change, stores hot speed fast, and heat conductivility is good, and condensate depression is less, solved that thermal conductivity that crystallization hydrous salt phase change material prolonged application exists is low reached cold problem effectively.
Embodiment 1:
The porous foam metal framework material adopts foam copper, and it is long that foam copper is of a size of 120mm() * 120mm(is wide) * 16mm(is high), foam copper density is 0.31g/cm
3, foam copper hole density (pores per inch, PPI) is 25.Crystalline hydrate salt phase transformation material adopts barium hydroxide, and adopting differential scanning calorimeter (DSC) to measure transformation temperature is 78 ℃, and latent heat of phase change is 276.8kJ/kg, and temperature data acquisition module records condensate depression is 8.2 ℃.
A kind of foamed metal composite phase-change material of this test and preparation method thereof carries out according to following steps: (1) takes the barium hydroxide of 500g; (2) barium hydroxide step 1 taken evenly adds in heat storage container, will process the foam copper of the PPI25 after clearing up simultaneously and put into heat storage container; (3) heat storage container of step 2 having been loaded to phase change material and foam copper is placed in the Water Tank with Temp.-controlled in vacuum argon filling case; (4) by the vacuum system vacuum pump, the argon filling case is evacuated to and is not less than 1 * 10
-2torr, and be filled with high purity argon; (5) the Water Tank with Temp.-controlled Heating temperature in step 3 is set to 95 ℃, heats 2 hours; Make foamed metal fully adsorb the phase change material under molten state; (6) will hold heat storage container Slow cooling in vacuum argon filling case of foam composite phase-change material, open the door of vacuum argon filling case, take out composite phase-change material and clear up overall size, the theoretical loading level of barium hydroxide phase change material is 431g, the actual adsorptive capacity of barium hydroxide phase change material is 380g, the charging efficiency of barium hydroxide phase change material is 88%, obtains foamed metal composite phase-change material finished product.
Utilize capillary force and the capillary acting in conjunction of porous foam metal framework material to make the spontaneous infiltration of crystalline hydrate salt phase transformation material under molten state, simplified the preparation technology of composite phase-change material.
In Fig. 1-2, the suction exotherm of continuous curve representation foamed metal composite phase-change energy storage material; Long and short dash line means the suction exotherm of pure phase change energy-storage material.
From Fig. 1,2, the suction exotherm of foamed metal composite phase-change energy storage material and pure phase change energy-storage material can be found out, the foamed metal composite phase-change material becomes material than the pure phase that there is no filled and process copper and compares, the foamed metal composite phase-change material has and stores faster hot speed, fusing and the process of setting of phase change material have been accelerated, reduced the suction heat release cycle, and effectively reduced the condensate depression of crystallization hydrous salt phase change material, made phase change material there is better thermostability.
Embodiment 2:
The porous foam metal framework material adopts foam copper, and it is long that foam copper is of a size of 120mm() * 120mm(is wide) * 16mm(is high), foam copper density is 0.26g/cm
3, foam copper density (pores per inch, PPI) is 10.Crystalline hydrate salt phase transformation material adopts barium hydroxide, and adopting differential scanning calorimeter (DSC) to measure transformation temperature is 78 ℃, and latent heat of phase change is 276.8kJ/kg, and temperature data acquisition module records condensate depression is 8.2 ℃.
A kind of foamed metal composite phase-change material of this test and preparation method thereof carries out according to following steps: (1) takes the barium hydroxide of 500g; (2) barium hydroxide step 1 taken evenly adds in heat storage container, will process the foam copper of the PPI10 after clearing up simultaneously and put into heat storage container; (3) heat storage container of step 2 having been loaded to phase change material and foam copper is placed in the Water Tank with Temp.-controlled in vacuum argon filling case; (4) by the vacuum system vacuum pump, the argon filling case is evacuated to and is not less than 1 * 10
-2torr, and be filled with high purity argon; (5) the Water Tank with Temp.-controlled Heating temperature in step 3 is set to 95 ℃, heats 2 hours; Make foamed metal fully adsorb the phase change material under molten state; (6) will hold heat storage container Slow cooling in vacuum argon filling case of foam composite phase-change material, open the door of vacuum argon filling case, take out composite phase-change material and clear up overall size, the theoretical loading level of barium hydroxide phase change material is 431g, the actual adsorptive capacity of barium hydroxide phase change material is 371g, the charging efficiency of barium hydroxide phase change material is 86%, obtains foamed metal composite phase-change material finished product.
Utilize capillary force and the capillary acting in conjunction of porous foam metal framework material to make the spontaneous infiltration of crystalline hydrate salt phase transformation material under molten state, simplified the preparation technology of composite phase-change material.
In Fig. 3 and 4, the suction exotherm of continuous curve representation foamed metal composite phase-change energy storage material; Long and short dash line means the suction exotherm of pure phase change energy-storage material.
From Fig. 3 and Fig. 4, the suction exotherm of foamed metal composite phase-change energy storage material and pure phase change energy-storage material can be found out, the foamed metal composite phase-change material becomes material than the pure phase that there is no filled and process copper and compares, the foamed metal composite phase-change material has and stores faster hot speed, fusing and the process of setting of phase change material have been accelerated, reduced the suction heat release cycle, and effectively reduced the condensate depression of crystallization hydrous salt phase change material, made phase change material there is better thermostability.
Claims (8)
1. the preparation method of a foamed metal composite phase-change material is characterized in that comprising:
A) phase change material after grinding is evenly added in vacuum argon filling case in heat storage container, by the vacuum system vacuum pump, the argon filling case is evacuated to predetermined vacuum level;
B) subsequently, in casing, be filled with argon gas, after argon pressure and atmospheric equilibrium, close the argon filling main valve;
C) carry out the water bath with thermostatic control heating, realize the indirect homogeneous heating of phase change material, and will process foamed metal framework material after cleaning and together put into heat storage container and heat, make the phase change material under the enough absorption molten states of foamed metal, thereby realize compound.
2. according to the method for claim 1, it is characterized in that further comprising:
D) composition operation of ending step C, then will hold heat storage container Slow cooling in vacuum argon filling case of foamed metal composite phase-change material.
3. according to the method for claim 1, it is characterized in that described foamed metal framework material is a kind of for what select from following material:
Foam copper stephanoporate framework material,
Foamed aluminium stephanoporate framework material,
Nickel foam stephanoporate framework material.
4. according to the method for claim 1, it is characterized in that the purity of the phase change material after described grinding >=98%.
5. according to the method for claim 1, it is characterized in that described steps A) in described predetermined vacuum level be not less than 1 * 10
-2torr, and described step B) in purity of argon be more than or equal to 99.99%.
6. according to the method for claim 1, it is characterized in that described step C) in make the adsorptive capacity of the phase change material under foamed metal absorption molten state account for theoretical 85～90% of the total amount of filling of phase change material.
7. according to the method for claim 1, it is characterized in that further comprising:
E) open the door of vacuum argon filling case, take out composite phase-change material and clear up overall size, obtain finished product.
8. a foamed metal composite phase-change material, is characterized in that described foamed metal composite phase-change material is to use according to the method for one of claim 1-7 to make.
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| CN105131908A (en) * | 2015-07-16 | 2015-12-09 | 江苏七政新能源有限公司 | Inorganic composite phase-change thermal-storage material and preparation method thereof |
| CN105131909A (en) * | 2015-07-16 | 2015-12-09 | 江苏七政新能源有限公司 | Inorganic composite high-heat-conductive phase-change thermal-storage material and preparation method thereof |
| CN105154018A (en) * | 2015-07-16 | 2015-12-16 | 江苏七政新能源有限公司 | Inorganic composite shaped phase-change heat-storage material and preparation method thereof |
| CN105154020A (en) * | 2015-07-16 | 2015-12-16 | 江苏七政新能源有限公司 | Multi-component finalized phase change heat storage material and preparation method therefor |
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| CN105131908A (en) * | 2015-07-16 | 2015-12-09 | 江苏七政新能源有限公司 | Inorganic composite phase-change thermal-storage material and preparation method thereof |
| CN106701026A (en) * | 2015-11-12 | 2017-05-24 | 镇江新梦溪能源科技有限公司 | Novel inorganic composite phase change thermal energy storage material and preparation method thereof |
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Application publication date: 20131211 |