CN101560377A - Foamed-metal based high-temperature phase change heat storage composite material and preparation method thereof - Google Patents
Foamed-metal based high-temperature phase change heat storage composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a foamed-metal based high-temperature phase change heat storage composite material and a preparation method thereof, which relate to the technical field of heat storage materials. The composite material is characterized by comprising a foamed metal framework material which is attached with a solid-liquid phase change heat storage material when the temperature is more than or equal to 600 DEG C, and a high temperature phase change heat storage material which accounts for 60 to 95 percent of the total weight. The composite material has the advantages of quick heat storage and release, high heat storage density, good heat conductivity and small volume shrinkage; besides, the composite material has wide applications, and is applicable to various fields of solar energy heat power generating systems for a space station, solar electrical energy generation, high temperature waste heat recovery and the like, particularly to a heat absorber of a space solar energy heat power generating system; and the preparation method is simple and convenient, has high recombination rate, and is easy to guarantee the product quality.
Description
Technical field
The present invention relates to the heat-storing material technical field.
Background technology
The application of high temperature phase change material (pcm) mainly concentrates on the fields such as sun power utilization, industrial afterheat recovery and electric power peak load shifting of space station.In the solar thermal power power generation system of space station, can utilize the amplitude transformer intercepting sun power of parabolical, it is gathered in the cylindrical cavity of heat absorption/thermophore, change heat energy into, wherein a part of thermal energy transfer gives cycle fluid driving thermo-mechanical power generation, and another part heat then is encapsulated in the phase-changing energy storage material in a plurality of small vesselss to absorb by fusing and stores.In the track shade phase, phase-changing energy storage material solidifies heat release near transformation temperature, serves as hot machine thermal source and comes heating cycle working medium, makes the space station be in shade and still can non-stop run generate electricity during the phase.The phase change material heat storage container is the major parts of space station solar thermal power power generation system heat absorption-holder.In solar energy thermal-power-generating factory, adopt the trough shaped solar panel, sunlight is gathered in the solar collector, change heat energy into, a part is in order to the heating steam generating, and another part stores, and treats to use when sunlight is not enough, to guarantee uninterruptable power generation.In addition, can produce a large amount of heat in Industrial processes, these heats do not obtain usually utilizing and just are wasted, and at this moment just need a kind of material that these high-temperature residual heats are reclaimed in order to use in the future.
Heat absorber for the space solar thermodynamic power generation system, the restriction of machine circulating temperature (more than 700 ℃) owing to be heated, require to adopt the high temperature latent-heat storage, after a large amount of phase change materials having been carried out research, villiaumite becomes main alternative, and its major advantage is the latent heat of phase change height, and passes through the mixing of the villiaumite of different melting points, can obtain having the heat storage medium of different transformation temperatures, thereby in very broad temperature range, satisfy the requirement of space solar dynamic power system round-robin.The consistency of villiaumite and metal vessel material is also relatively good.The solar thermal power power generation system of U.S. freedom space station has been selected LiF-CaF for use
2The eutectic thing is as heat storage medium.
Villiaumite can satisfy the demand of its thermal performance and consistency, but its distinct disadvantage to be its thermal conductivity lower and volumetric shrinkage very big (LiF is up to 23%) when solidifying.These two shortcomings form the hole in container when causing in the shade phase phase change material solidification shrinkage, cause and occur " heat gets loose " and " hot spot " in sunshine period, these two kinds of phenomenons all can cause the thermal fatigue of container to damage, understand the bigger heat transfer property that influences heat-storing material, thereby can have influence on the thermal characteristics and the reliability of total system.In addition, the salt phase change material at high temperature has stronger corrodibility, and container material must adopt corrosion resistant superalloy, is conceived to superalloys such as cobalt-based, Ni-based, niobium base at present mostly.
Summary of the invention
The purpose of this invention is to provide a kind of foamed-metal based high-temperature phase change heat storage composite material and preparation method thereof, this matrix material has the advantage that the accumulation of heat heat release is fast, thermal storage density is high, heat conductivility is good, volumetric shrinkage is less; Purposes is wide, applicable to multiple fields such as space station solar thermal power power generation system, solar electrical energy generation and high-temperature residual heat recovery, is specially adapted to the heat absorber of space solar thermodynamic power generation system; Its preparation method is easy, recombination rate is high, is easy to guarantee quality product.
One of the present invention's main technical schemes is: a kind of foamed-metal based high-temperature phase change heat storage composite material, it is characterized in that having the foamed metal framework material, be attached with on the foamed metal framework material 〉=solid-liquid phase change heat-storing material 600 ℃ the time, the per-cent that the high-temperature phase change heat accumulation material accounts for gross weight is 60%～95%.
Described foamed metal framework material is that foamed metal Ni or foamed metal Cu framework material are good.
The solid-liquid phase change heat-storing material is preferably villiaumite LiF during described 〉=600 ℃; Or LiF and CaF
2Mixture: LiF and CaF in the mixture
2The quality ratio of components be 2～1.1=1; The solid-liquid phase change heat-storing material accounts for 80～95% of gross weight in the time of 〉=600 ℃.
The present invention's two main technical schemes is: the preparation method of above-mentioned various foamed-metal based high-temperature phase change heat storage composite materials is characterized in that having following steps:
A, be ready to the foamed metal framework material and put in the container molding.
B, quality are on request formed solid-liquid phase change heat-storing material when preparing 〉=600 ℃, mix thoroughly, put into the vacuum furnace bake out and dewater and make it be molten state, the process furnace temperature of fusion is at the high 〉=above 50-100 of transformation temperature ℃ of solid-liquid phase change heat-storing material 600 ℃ the time; The container molding that will hold the foamed metal framework material is simultaneously together put into the stove internal heating.
C, will be molten state 〉=solid-liquid phase change heat-storing material quality is on request formed under the argon shield aerosol 600 ℃ the time; pour in the container molding quickly and accurately; heating is compound in vacuum furnace, the recombination process temperature be controlled at than this 〉=fusing point of solid-liquid phase change heat-storing material is high 80～200 ℃ 600 ℃ the time.
After d, the compound end, turn off container molding slowly cooling in stove that furnace power will hold foamed-metal based high-temperature phase change heat storage composite material, will hold packaged the getting product of top cover of foamed-metal based high-temperature phase change heat storage composite material container then.
The material of described container molding is cobalt-based, Ni-based or niobium based high-temperature alloy: as Inconel617, and Haynes188, Haynes230,316ss etc.
Positively effect of the present invention is: the solid-liquid phase change heat-storing material more evenly is fully distributed in the foamed metal framework material matrix in the time of 〉=600 ℃, metallic framework solid-liquid phase change heat-storing material 〉=600 ℃ the time is divided into numerous small thermal storage unit, these small thermal storage units are when improving heat absorption, heat release, also stop the phase change material outflow of fusing because of the capillary tension effect, its recombination rate height, heat storage capacity is good, the heat conductivility height; Utilize and the formation in control hole with enhancement of heat transfer, bigger volumetric shrinkage in the time of also can limiting solid-liquid phase change; This matrix material has the advantage that the accumulation of heat heat release is fast, thermal storage density is high, heat conductivility is good, volumetric shrinkage is less; Not only heat storage capacity is good, has especially solved the lower and big difficult problem of volumetric shrinkage when solidifying of the medium-term and long-term thermal conductivity that exists of prior art; Its purposes is wide, applicable to multiple fields such as space station solar thermal power power generation system, solar electrical energy generation and high-temperature residual heat recovery, is specially adapted to the heat absorber of space solar thermodynamic power generation system; Its preparation method is easy, recombination rate is high, is easy to guarantee quality product.
Be described further below in conjunction with example, but not as a limitation of the invention.
Embodiment
The embodiment production technique is as follows: solid-liquid phase change heat-storing material lithium fluoride during with 〉=600 ℃, or lithium fluoride and Calcium Fluoride (Fluorspan) are mixed into the molten mixture of certainweight by certain mass percent, the foamed metal framework material that in this melting salt eutectic, adds the weighing certainweight, be put into jointly in vacuum furnace, carry out in the accumulation of heat phase variodenser compound, the control combined temp, behind the compound certain hour, finished product is cooled to take out after the certain temperature in a vacuum, and packaged accumulation of heat phase variodenser gets product.
Step 1: clean porous matter foam metal material, remove the greasy dirt that may exist in its surface or the hole, and put in the container molding by certain mass.
Step 2: press villiaumite LiF absolutely, or LiF and CaF
2Mixture LiF and CaF
2The quality ratio of components be 2～1.1=1, take by weighing villiaumite, mechanical stirring is even as far as possible, puts into the vacuum furnace bake out, dewaters and fusion; The container molding that will hold the foamed metal framework material is simultaneously together put into the stove internal heating.
Step 3: the Al for preparing 100ml
2O
3Pottery beaker or high purity graphite crucible are some, can adorn high temperature solid-liquid phase change heat-storing material in the beaker and be no less than 60g, under the argon shield aerosol, will pour in the container molding quickly and accurately.Heating is carried out compoundly in vacuum furnace, and the recombination process temperature is controlled at the high 80-200 of fusing point ℃ of specific latent heat heat-storing material, 2-3 hour recombination time.
Step 4: turn off container molding slowly cooling in stove that electric furnace will hold foamed-metal based high-temperature phase change heat storage composite material, the container molding end cap seal is good after taking out with the vacuum electron beam welding.
Example 1: continuous poriferous foamed metal framework material adopts foamed metal Ni, and the high-temperature phase change heat accumulation material adopts lithium fluoride and Calcium Fluoride (Fluorspan) quality ratio of components by 1.1: 1, presses, and accumulation of heat metal vessel (being the moulding container) material adopts Haynes188, and processing condition are as follows:
1, the heat fused temperature of latent-heat storage material in process furnace is 820-870 ℃ (being that high temperature solid-liquid phase change heat-storing material is molten into temperature at the above 50-100 of its transformation temperature ℃ in process furnace);
2, the recombination process temperature is 850-970 ℃ (be the recombination process temperature is controlled at higher 80～200 ℃ than the fusing point of this high-temperature phase change heat accumulation material), and be 3 hours recombination time;
3, lithium fluoride and Calcium Fluoride (Fluorspan) heat-storing material account for 95% of foamed-metal based high-temperature phase change heat storage composite material gross weight.
Result of implementation: prepared combined high temperature phase change heat storage material latent heat of phase change 870.6kJ/kg, transformation temperature is 769.8 ℃.
Example 2: continuous poriferous foamed metal framework material adopts foamed metal Ni, and the high-temperature phase change heat accumulation material adopts lithium fluoride and Calcium Fluoride (Fluorspan) quality ratio of components by 2: 1, and accumulation of heat metal vessel (being the moulding container) material adopts Haynes188, and processing condition are as follows:
1, the heat fused temperature of latent-heat storage material in process furnace is 810-870 ℃ (being that the high-temperature phase change heat accumulation material is molten into temperature at the above 50-100 of its transformation temperature ℃ in process furnace);
2, the recombination process temperature is 850-960 ℃ (be the recombination process temperature is controlled at higher 80～200 ℃ than the fusing point of this high-temperature phase change heat accumulation material), and be 2.8 hours recombination time;
3, lithium fluoride and Calcium Fluoride (Fluorspan) heat-storing material account for 80% of foamed-metal based high-temperature phase change heat storage composite material gross weight.
Result of implementation: prepared compound combined high temperature phase change heat storage material latent heat of phase change 851.4kJ/kg, transformation temperature is 762.6 ℃.
Example 3: continuous poriferous foamed metal framework material adopts foamed metal Ni, and the high-temperature phase change heat accumulation material adopts the quality ratio of components of lithium fluoride and Calcium Fluoride (Fluorspan) by 1.5: 1, and accumulation of heat metal vessel (being the moulding container) material adopts Haynes188, and processing condition are as follows:
1, the heat fused temperature of latent-heat storage material in process furnace is 810-860 ℃ (being that the high-temperature phase change heat accumulation material is molten into temperature at the above 50-100 of its transformation temperature ℃ in process furnace);
2, the recombination process temperature is 840-960 ℃ (be the recombination process temperature is controlled at higher 80～200 ℃ than the fusing point of this high-temperature phase change heat accumulation material), and be 2.5 hours recombination time;
3, lithium fluoride and Calcium Fluoride (Fluorspan) heat-storing material account for 88% of foamed-metal based high-temperature phase change heat storage composite material gross weight.
Result of implementation: prepared compound combined high temperature phase change heat storage material latent heat of phase change 832.9kJ/kg, transformation temperature is 758.7 ℃.
Example 4: continuous poriferous foamed metal framework material adopts foamed metal Ni, and the high-temperature phase change heat accumulation material adopts lithium fluoride, and accumulation of heat metal vessel (being the moulding container) material adopts Haynes188, and processing condition are as follows:
1, the heat fused temperature of latent-heat storage material in process furnace is 900-950 ℃;
2, the recombination process temperature is 930-1040 ℃, 2-3 hour recombination time;
3, the lithium fluoride heat-storing material accounts for 60% of foamed-metal based high-temperature phase change heat storage composite material gross weight.
Result of implementation: prepared combined high temperature phase change heat storage material latent heat of phase change 1032.8kJ/kg, transformation temperature is 850.0 ℃.
Example 5: continuous poriferous foamed metal framework material adopts foamed metal Ni, and the high-temperature phase change heat accumulation material adopts lithium fluoride, and accumulation of heat metal vessel (being the moulding container) material adopts Haynes188, and processing condition are as follows:
1, the heat fused temperature of latent-heat storage material in process furnace is 920-980 ℃;
2, the recombination process temperature is 950-1060 ℃, 2-3 hour recombination time;
3, the lithium fluoride heat-storing material accounts for 95% of foamed-metal based high-temperature phase change heat storage composite material gross weight.
Result of implementation: prepared compound combined high temperature phase change heat storage material latent heat of phase change 1095.6kJ/kg, transformation temperature is 870.0 ℃.
Product is made up of foamed metal framework material, high-temperature phase change heat accumulation material and phase-transition heat-storage container, uses the phase-transition heat-storage container encloses.High temperature phase change material (pcm) is the solid-liquid phase change heat-storing material, be uniformly distributed in the inorganic metal porous continuous material, the porous based phase-change material utilizes the little characteristics of porous medium internal void, phase change material is dispersed into very little particle, improve the reliability that phase change material is stored by capillary effect in porous medium, make it when solid-liquid phase change takes place, or not liquid and reveal, utilize the high characteristics of porous medium thermal conductivity to improve heat exchange efficiency simultaneously.Melting salt more evenly is fully distributed in the matrix of porous endoplasmic reticular structural metal, metallic framework is divided into numerous small thermal storage unit to phase change heat storage material, these small thermal storage units are when improving heat absorption, heat release, also stop the phase change material outflow of fusing because of the capillary tension effect, the recombination rate height, heat storage capacity is good.The combined high temperature phase change heat storage material that is provided is used for the heat absorber of space solar thermodynamic power generation system, can utilize and control the formation in hole with enhancement of heat transfer, restriction bigger volumetric shrinkage during solid-liquid phase change improves the thermal conductivity of phase change material, strengthens the heat-transfer capability of thermophore.
Advantage:
1, with the high-temperature phase change heat accumulation Material cladding to the foam metal sill, both well avoided nothing Machine salt can improve again the mechanical strength of high-temperature phase-change energy storage material well with the sintering of matrix.
2, because fuse salt is because of the spontaneous infiltration of capillary tension effect, need not to exert pressure in addition, Simplified preparation technology.
3, the combined high temperature phase change heat storage material is used for the heat absorption of space solar thermodynamic power generation system Device, the formation that can utilize and control the hole be with augmentation of heat transfer, bigger body during the restriction solid-liquid phase change The long-pending contraction, than the high-temperature phase change heat accumulation material volume that does not add foam metal shrink reduce 15% with On, improved the thermal conductivity of phase-change material, strengthen the heat-transfer capability of storage heater. The product phase of making It is big to become latent heat, can be up to 870.6kJ/kg, than the high-temperature phase change heat accumulation material that does not add foam metal The material latent heat of phase change is high by more than 10%, and the energy storage density height has improved the hot property that of material.
Solid-liquid phase change heat-storing material other materials also can comprise following high-temperature phase-change material in the time of above-mentioned 600 ℃ Material etc. see Table 1 (mechanism is same, and embodiment slightly).
Table 1:
| The phase-change material title | Phase transition temperature (℃) |
| MgF 2 | 1263 |
| KF | 857 |
| MgCl 2 | 714 |
| Na 2CO 3 | 854 |
| LiOH+LiF | 700 |
| Na 2SO 4/SiO 2 | 879 |
| Na 2CO 3-BaCO 3/MgO | 686 |
Claims (5)
1, a kind of foamed-metal based high-temperature phase change heat storage composite material, it is characterized in that having the foamed metal framework material, be attached with on the foamed metal framework material 〉=solid-liquid phase change heat-storing material 600 ℃ the time, the per-cent that the high-temperature phase change heat accumulation material accounts for gross weight is 60%～95%.
2, foamed-metal based high-temperature phase change heat storage composite material according to claim 1 is characterized in that described foamed metal framework material is foamed metal Ni or foamed metal Cu framework material.
3, foamed-metal based high-temperature phase change heat storage composite material according to claim 1 and 2, the solid-liquid phase change heat-storing material is villiaumite LiF when it is characterized in that described 〉=600 ℃; Or LiF and CaF
2Mixture: LiF and CaF in the mixture
2The quality ratio of components be 2～1.1=1; The solid-liquid phase change heat-storing material accounts for 80～95% of gross weight in the time of 〉=600 ℃.
4, the preparation method of a kind of claim 1,2 or 3 described foamed-metal based high-temperature phase change heat storage composite materials is characterized in that having following steps:
A, prepare the foamed metal framework material, and put in the container molding by certain mass.
B, quality are on request formed solid-liquid phase change heat-storing material when preparing 〉=600 ℃, mix thoroughly, put into the vacuum furnace bake out and dewater and make it be molten state, the process furnace temperature of fusion is at the high 〉=above 50-100 of transformation temperature ℃ of solid-liquid phase change heat-storing material 600 ℃ the time; The container molding that will hold the foamed metal framework material is simultaneously together put into the stove internal heating.
C, be molten state 〉=solid-liquid phase change heat-storing material quality is on request formed to add and is led in the container molding that is placed with the foamed metal skeleton 600 ℃ the time, the material of container molding is the superalloy of cobalt-based, Ni-based or niobium base.In vacuum furnace that foamed-metal based high-temperature phase change heat storage material heating is compound, the recombination process temperature be controlled at than this 〉=fusing point of solid-liquid phase change heat-storing material is high 80～200 ℃ 600 ℃ the time.
After d, the compound end, will hold container molding slowly cooling in stove of foamed-metal based high-temperature phase change heat storage composite material, the container molding end cap seal is good after taking out with the vacuum electron beam welding.
5, the preparation method of foamed-metal based high-temperature phase change heat storage composite material according to claim 4, the material that it is characterized in that described container molding are cobalt-based, Ni-based or niobium based high-temperature alloy.
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| CN111022385B (en) * | 2019-11-04 | 2021-04-27 | 浙江大学 | Ocean temperature difference energy capture heat engine, manufacturing method thereof and ocean profile motion platform |
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| CN111560235B (en) * | 2020-05-20 | 2021-08-03 | 贵州梅岭电源有限公司 | High-viscosity high-heat-storage type phase-change material for thermal battery and preparation method and application thereof |
| CN113943555A (en) * | 2021-11-18 | 2022-01-18 | 北京华能长江环保科技研究院有限公司 | Power plant fly ash based high-value heat storage material synthesis system and synthesis method |
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