WO2022062340A1 - 一种热循环高效率相变蓄热材料及其制备方法 - Google Patents

一种热循环高效率相变蓄热材料及其制备方法 Download PDF

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WO2022062340A1
WO2022062340A1 PCT/CN2021/082338 CN2021082338W WO2022062340A1 WO 2022062340 A1 WO2022062340 A1 WO 2022062340A1 CN 2021082338 W CN2021082338 W CN 2021082338W WO 2022062340 A1 WO2022062340 A1 WO 2022062340A1
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nano
heat storage
storage material
change heat
thermal cycle
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French (fr)
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黄奥
张美杰
顾华志
韩藏娟
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武汉科技大学
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    • C—CHEMISTRY; METALLURGY
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    • 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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  • the invention belongs to the technical field of phase-change heat storage composite materials. Specifically, it relates to providing a thermal cycle high-efficiency phase-change heat storage material and a preparation method thereof.
  • Thermal storage technology is a kind of energy storage technology that uses thermal storage materials to store temporarily unnecessary heat, and then releases the heat when it is needed. Thermal storage technology solves the contradiction between the time difference between heat supply and demand, and improves the utilization of heat. Therefore, it can be used for peak shaving and valley filling of electric load, solar energy storage and industrial waste heat recovery, etc., so as to achieve the goal of developing new energy and saving old energy. Purpose.
  • phase-change thermal storage materials among which phase-change thermal storage materials have great potential due to their high energy storage and adjustable phase transition temperature.
  • the phase change heat storage materials are prone to problems such as leakage of the phase change medium and volume changes during the phase change, which limit the practical application of the phase change heat storage materials.
  • the preparation of phase change materials into phase change heat storage microcapsules is one of the main methods to solve the above problems.
  • the phase-change heat storage microcapsule is composed of the phase-change material as the core and the coating material as the shell. Phase change thermal storage microcapsules have become a research hotspot in recent years due to their advantages of non-corrosiveness, medium leakage prevention, high thermal storage density and constant temperature during phase transition.
  • Phase change materials are classified according to the phase change temperature, and the phase change material whose phase change temperature is above 500°C is called a high temperature phase change material.
  • Aluminum and aluminum-silicon alloys are one of the high temperature phase change heat storage materials, which have the advantages of good thermal conductivity, good thermal stability, large latent heat of phase change, high thermal conductivity and high heat storage density. If aluminum or aluminum-silicon alloy is used as the core of phase change heat storage microcapsules, the following requirements are required for the coating material: good corrosion resistance, good cycle stability, high temperature stress strength, and good oxidation resistance.
  • phase-change thermal storage materials examples include aluminum and aluminum-silicon alloys as phase-change thermal storage materials, and disclosed some composite phase-change thermal storage materials containing aluminum or aluminum-silicon alloys.
  • a high temperature composite phase change heat storage material and its preparation method 201310175016.1 patented technology, this technology uses white mud, high alumina bauxite and aluminum powder as raw materials, directly mixes, presses and shapes, and roasts at high temperature to obtain a A high-temperature composite phase change heat storage material;
  • a cermet with phase change heat storage function and its preparation method 201310293700.X
  • a cermet with phase change heat storage function is prepared using aluminum-silicon alloy powder and corundum powder as raw materials, and magnesium oxide as sintering Auxiliary, through dry ball milling, molding and calcination, a cermet with phase change heat storage function is prepared.
  • phase change material as a raw material directly in the preparation of the composite phase change heat storage material, and utilize the heat absorption and heat release of the phase change material when the phase change occurs to achieve the purpose of heat storage.
  • the aluminum or aluminum-silicon alloy powder is easily leaked and overflowed after melting during the roasting process, and the aluminum or aluminum-silicon alloy in the liquid phase will also reduce the high-temperature physical properties of the material.
  • a high-temperature phase change heat storage microcapsule and its preparation method (201710502031.0) patented technology, using aluminum-silicon alloy powder as raw material, and directly treating it with aluminum dihydrogen phosphate solution to form a phase change heat storage microcapsule blank, or After the green body is calcined, a high temperature phase change heat storage microcapsule with a dense shell layer is formed.
  • the preparation method of this kind of microcapsules is simple, but the prepared microcapsules have adhesion between them, which is difficult to meet the industrial application with high requirements on dispersibility, and the thermal cycle resistance needs to be strengthened.
  • the present invention provides a preparation method of a thermal cycle high-efficiency phase change thermal storage material with simple process and easy industrial production; the thermal cycle high-efficiency phase change thermal storage material prepared by the method is dispersed Good performance, many thermal cycles and high heat utilization.
  • the present invention provides a method for preparing a thermal cycle high-efficiency phase change thermal storage material, comprising the following steps:
  • the mixed slurry is filtered, dried, and then calcined in an air atmosphere with a humidity of more than 90% and under the conditions of 600-850° C. for 3-6 hours to obtain a thermal cycle high-efficiency phase-change heat storage material.
  • the aluminum-silicon alloy powder, the nano-calcium oxide powder, the nano-silica powder and the solvent are mixed according to the following weight ratios:
  • the aluminum-silicon alloy powder is 40-60%
  • the nano-calcium oxide powder is 5-20%
  • the nano-silicon oxide powder is 0.5-3%
  • the nano-alumina powder is 0.5-2%
  • the solvent is 30-40%.
  • the particle size of the aluminum-silicon alloy powder is ⁇ 88 ⁇ m, and the Si content in the aluminum-silicon alloy powder is ⁇ 21%.
  • the CaO content in the nano-calcium oxide powder is ⁇ 99%, and the particle size is ⁇ 0.1 ⁇ m.
  • the SiO 2 content in the nano-silica powder is ⁇ 99%, and the particle size is ⁇ 0.1 ⁇ m.
  • the Al 2 O 3 content in the nano-alumina powder is ⁇ 99%, and the particle size is ⁇ 0.1 ⁇ m.
  • the aluminum-silicon alloy powder, the nano-calcium oxide powder, the nano-silicon oxide powder and the solvent are stirred at 25-35 ° C for 15- 25 minutes to achieve mixing.
  • the solvent is ethanol, and the concentration of the ethanol is ⁇ 90%.
  • the calcination is performed in an air atmosphere with a humidity of 90-97%.
  • the present invention also provides the thermal cycle high-efficiency phase change heat storage material prepared according to the above preparation method.
  • the phase-change heat storage material prepared by the invention has a core-shell structure, which solves the problem that the aluminum-silicon alloy as a phase-change heat-storage material is easily leaked after being melted during the application process;
  • the loss of aluminum-silicon alloy and the resulting corrosion increase the number of cycles of aluminum-silicon alloy.
  • the preparation process of the invention is simple, easy to control, and easy to realize industrialized production.
  • the present invention provides a method for preparing a thermal cycle high-efficiency phase change thermal storage material, comprising the following steps:
  • the aluminum-silicon alloy powder, nano-calcium oxide powder, nano-silicon oxide powder and solvent are mixed according to the following weight ratio: aluminum-silicon alloy powder 40-60%, nano-calcium oxide powder 5-20% %, nano-silica powder 0.5-3%, nano-alumina powder 0.5-2%, solvent 30-40%.
  • the nano-calcium oxide powder used in the preparation method of the thermal cycle high-efficiency phase-change heat storage material of the present invention will be hydrated and release a large amount of heat during the high-humidity and high-temperature treatment process, while the nano-silica powder and nano-alumina powder are It can control the speed of the reaction of the mixture, so that the aluminum in the aluminum-silicon alloy powder can form aluminum oxide and aluminum oxide-calcium aluminate composite coated on the surface of the aluminum-silicon alloy to form a composite core-shell structure, and the surface is clean and has good dispersibility.
  • the prepared phase change heat storage material with a core-shell structure solves the problem of easy leakage of aluminum-silicon alloy as a phase change heat storage material after melting during the application process; it can effectively provide protection for the molten aluminum-silicon alloy, Avoid the loss of aluminum-silicon alloy and the resulting corrosion, and increase the number of cycles of aluminum-silicon alloy.
  • the particle size of the aluminum-silicon alloy powder is less than or equal to 88 ⁇ m; the Si content in the aluminum-silicon alloy powder is less than or equal to 21%.
  • the CaO content in the nano-calcium oxide powder is ⁇ 99%, and the particle size is ⁇ 0.1 ⁇ m.
  • the SiO 2 content in the nano-silicon oxide powder is ⁇ 99%, and the particle size is ⁇ 0.1 ⁇ m.
  • the Al 2 O 3 content in the nano-alumina powder is ⁇ 99%, and the particle size is ⁇ 0.1 ⁇ m. Since the particle size has a certain influence on the heat treatment temperature, the surface smoothness of the shell layer of the final product and the thermal conductivity of the shell layer (for example, the smaller the particle size, the lower the heat treatment temperature, the smoother and cleaner the shell surface, but the thermal conductivity of the shell at the same time.
  • the coefficient will also be lower, the commutation efficiency will be worse, and the commutation time during service will be longer), so the selection of particle size of each raw material is particularly important.
  • the finally prepared composite core-shell structure phase change heat storage material has the best performance in terms of surface cleanliness and comprehensive performance of thermal conductivity.
  • the specific operation for preparing the mixed slurry is: mixing aluminum-silicon alloy powder, nano-calcium oxide powder, nano-silica powder, nano-oxide powder
  • the aluminum powder and the solvent are stirred at 25-35° C. for 15-25 minutes to achieve mixing. Further preferably, the mixture is stirred at a constant temperature of 30°C for 20 minutes, and the mixture is uniform.
  • the solvent used for preparing the mixed slurry may be a common organic solvent, for example, ethanol, propanol, hexane, ethylene glycol, etc. can be used as the solvent.
  • the present invention uses ethanol as a solvent.
  • the concentration of the ethanol is greater than or equal to 90%.
  • the mixed slurry is filtered, dried to a constant weight, and then loaded into a corundum crucible and placed in a muffle furnace for roasting.
  • the calcination is carried out under the conditions of 90-97% humidity air and 600-850° C. for 3-6 hours.
  • the high humidity and high temperature of the roasting ensures that the nano-calcium oxide powder is hydrated and releases a large amount of heat.
  • the present invention also provides a thermal cycle high-efficiency phase change thermal storage material prepared according to the above preparation method, the thermal cycle high-efficiency phase change thermal storage material has good dispersibility, many thermal cycles and high heat utilization rate.
  • the aluminum-silicon alloy powder, nano-calcium oxide powder, nano-silicon oxide powder and ethanol with a concentration of 93% were stirred for 25 minutes at a constant temperature of 25 ° C and mixed uniformly to obtain a mixed slurry: aluminum-silicon alloy powder: 40% of calcium oxide powder, 20% of nano-calcium oxide powder, 2% of nano-silica powder, 2% of nano-alumina powder, 36% of ethanol.
  • the mixed slurry was filtered, dried to constant weight, then put into a corundum crucible and placed in a muffle furnace, calcined for 6 hours in an air atmosphere with 95% humidity and 600°C, and cooled to room temperature to obtain high thermal cycle efficiency. Phase change heat storage material.
  • the thermal cycle high-efficiency phase change heat storage material prepared in this example was subjected to 5000 thermal cycles at 650° C., and the phase change latent heat retention rate was 92%.
  • the aluminum-silicon alloy powder, nano-calcium oxide powder, nano-silicon oxide powder and ethanol with a concentration of 95% were stirred for 20 minutes at a constant temperature of 30 ° C and evenly mixed to obtain a mixed slurry: aluminum-silicon alloy powder: 45% of solid, 15% of nano-calcium oxide powder, 1.5% of nano-silica powder, 1.5% of nano-alumina powder, 37% of ethanol.
  • the mixed slurry was filtered, dried to a constant weight, then put into a corundum crucible and placed in a muffle furnace, roasted for 5 hours in an air atmosphere of 95% humidity and 650°C, and cooled to room temperature to obtain high thermal cycle efficiency.
  • Phase change heat storage material Phase change heat storage material.
  • the thermal cycle high-efficiency phase change heat storage material prepared in this example was subjected to 5000 thermal cycles at 650° C., and the phase change latent heat retention rate was 93%.
  • the aluminum-silicon alloy powder, nano-calcium oxide powder, nano-silicon oxide powder and ethanol with a concentration of 92% were stirred for 20 minutes at a constant temperature of 35 ° C and mixed uniformly to obtain a mixed slurry: aluminum-silicon alloy powder: 50% of calcium oxide powder, 10% of nano-calcium oxide powder, 1% of nano-silica powder, 0.5% of nano-alumina powder, 38.5% of ethanol.
  • the mixed slurry was filtered, dried to constant weight, then put into a corundum crucible, placed in a muffle furnace, calcined for 4.5 hours in an air atmosphere of 93% humidity and 700°C, and cooled to room temperature to obtain a high thermal cycle. Efficient phase change heat storage material.
  • the thermal cycle high-efficiency phase change heat storage material prepared in this example was subjected to 5000 thermal cycles at 650° C., and the phase change latent heat retention rate was 93%.
  • the aluminum-silicon alloy powder, nano-calcium oxide powder, nano-silicon oxide powder and ethanol with a concentration of 93% were stirred for 20 minutes at a constant temperature of 30 ° C and mixed uniformly to obtain a mixed slurry: aluminum-silicon alloy powder: 55% of calcium oxide powder, 5% of nanometer calcium oxide powder, 0.5% of nanometer silicon oxide powder, 1% of nanometer alumina powder, 38.5% of ethanol.
  • the mixed slurry was filtered, dried to constant weight, then put into a corundum crucible and placed in a muffle furnace, calcined for 4 hours in an air atmosphere with 90% humidity and 750°C, and cooled to room temperature to obtain high thermal cycle efficiency.
  • Phase change heat storage material Phase change heat storage material.
  • the thermal cycle high-efficiency phase change heat storage material prepared in this example was subjected to 5000 thermal cycles at 650° C., and the phase change latent heat retention rate was 94%.
  • the aluminum-silicon alloy powder, nano-calcium oxide powder, nano-silicon oxide powder and ethanol with a concentration of 93% were stirred for 25 minutes at a constant temperature of 25 ° C and mixed uniformly to obtain a mixed slurry: aluminum-silicon alloy powder: 60% of calcium oxide powder, 6% of nanometer calcium oxide powder, 2.5% of nanometer silicon oxide powder, 1.5% of nanometer alumina powder, 30% of ethanol.
  • the mixed slurry was filtered, dried to constant weight, then loaded into a corundum crucible and placed in a muffle furnace, roasted for 3 hours in an air atmosphere with 97% humidity and 850°C, and cooled to room temperature to obtain high thermal cycle efficiency.
  • Phase change heat storage material Phase change heat storage material.
  • the thermal cycle high-efficiency phase change heat storage material prepared in this example was subjected to 5000 thermal cycles at 650° C., and the phase change latent heat retention rate was 95%.
  • the aluminum-silicon alloy powder, nano-calcium oxide powder, nano-silicon oxide powder and ethanol with a concentration of 93% were stirred for 20 minutes at a constant temperature of 30 ° C and mixed uniformly to obtain a mixed slurry: aluminum-silicon alloy powder: 50% of calcium oxide powder, 6% of nanometer calcium oxide powder, 3% of nanometer silicon oxide powder, 1% of nanometer alumina powder, and 40% of ethanol.
  • the mixed slurry was filtered, dried to constant weight, then put into a corundum crucible and placed in a muffle furnace, calcined for 4 hours in a 95% humidity air atmosphere and 800°C, and cooled to room temperature to obtain high thermal cycle efficiency.
  • Phase change heat storage material Phase change heat storage material.
  • the thermal cycle high-efficiency phase change heat storage material prepared in this example was subjected to 5000 thermal cycles at 650°C, and the phase change latent heat retention rate was 93%.
  • Comparative Examples 1-11 the aluminum-silicon alloy powder, nano-calcium oxide powder, nano-silica powder and ethanol were mixed according to the weight ratio in Table 1, and other parameters were the same as those in Example 5.
  • the present invention is precisely due to the addition of nano-calcium oxide powder, nano-silicon oxide powder, and nano-alumina powder, which synergize with the aluminum-silicon alloy powder to generate
  • the phase change heat storage material with high thermal cycle efficiency effectively utilizes the phase change latent heat of the aluminum-silicon alloy powder, and has a high latent heat retention rate, which improves the heat utilization rate.
  • the ratio of each component of aluminum-silicon alloy powder, nano-calcium oxide powder and nano-silicon oxide powder also has an important influence on the final performance of the phase change heat storage material with high thermal cycle efficiency.
  • the weight ratio of 60%, nano-calcium oxide powder 5-20%, nano-silica powder 0.5-3%, nano-alumina powder 0.5-2%, and solvent 30-40% increases the number of thermal cycles and maintains a relatively There are obvious advantages in the high rate of latent heat of phase transition.
  • the particle sizes of the aluminum-silicon alloy powder, nano-calcium oxide powder, nano-silica powder, and nano-alumina powder have great influence on the final thermal cycle efficiency of the phase change thermal storage material.
  • the performance has an important influence.
  • the phase change heat storage material has obvious advantages in increasing the number of thermal cycles and maintaining a high rate of latent heat of phase change.

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Abstract

一种热循环高效率相变蓄热材料的制备方法，包括如下步骤：将铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体、纳米氧化铝粉体与溶剂混合，制成混合浆体；将混合浆体过滤、烘干，然后在90％以上湿度空气气氛和600～850℃条件下焙烧3～6h，冷却至室温，得到热循环高效率相变蓄热材料。

Description

一种热循环高效率相变蓄热材料及其制备方法
相关申请的交叉引用
本申请要求享有于2020年9月22日提交的名称为“一种热循环高效率相变蓄热材料及其制备方法”的中国专利申请CN 202011002795.1的优先权，上述申请的全部内容通过引用并入本文中。
技术领域
本发明属于相变蓄热复合材料技术领域。具体涉及提供一种热循环高效率相变蓄热材料及其制备方法。
背景技术
蓄热技术是利用蓄热材料将暂时不需要的热量储存，等需要热量时，再将热量释放出来的一种储能技术。蓄热技术解决了热量供给与需求的时间差矛盾，提高了热量的利用，因此可用于电力负荷的削峰填谷、太阳能的储备和工业余热的回收等，以达到发展新能源和节约旧能源的目的。
蓄热技术的核心问题是蓄热材料的制备和应用，其中相变蓄热材料因其储能高和相变温度可调而成为具有很好潜力的蓄热材料。但相变蓄热材料因在相变时易产生相变介质泄露、体积变化等问题，从而限制了相变蓄热材料的实际应用。将相变材料制备成相变蓄热微胶囊是解决上述问题的主要方法之一。相变蓄热微胶囊由相变材料为核、包覆材料为壳构成。由于相变蓄热微胶囊具有无腐蚀性、防介质泄漏、蓄热密度较大和相变时恒温等优点而成为近年来研究的热点。
相变材料按相变温度分类，其中相变温度在500℃以上的相变材料称为高温相变材料。铝及铝硅合金属于高温相变蓄热材料中的一种，具有导热性好、热稳定性较好、相变潜热大、导热系数大和蓄热密度高等优点。若将铝或铝硅合金作为相变蓄热微胶囊的核，则对包覆材料有如下要求：耐腐蚀性好，周期稳定性好，温度应力强度高，抗氧化性好。
近年来，一些学者对铝及铝硅合金作为相变蓄热材料开展了一些研究，公开了一些含有铝或铝硅合金的复合相变蓄热材料。如“一种高温复合相变蓄热材料及其制备方法”(201310175016.1)专利技术，该技术采用白泥、高铝矾土和铝粉为原料，直接混合后压制成型，高温焙烧，制得一种高温复合相变蓄热材料；“一种具有相变蓄热功能的金属陶瓷及其制备方法”(201310293700.X)专利技术，以铝硅合金粉、刚玉粉为原料，以氧化镁为烧结助剂，经干法球磨、成型和焙烧，制得一种具有相变蓄热功能的金属陶瓷。上述技术方法皆是将相变材料作为原料直接用于复合相变蓄热材料的制备中，利用相变材料在发生相变时的吸热和放热实现蓄热目的。但是这种直接混合成型的方法在焙烧过程中铝或铝硅合金粉熔化后极易泄露及溢出，而且液相的铝或者铝硅合金也会降低材料的高温物理性能。
也有一些学者对铝或铝硅合金相变蓄热微胶囊的制作进行了研究：“一种Al/Al 2O 3蓄热材料及其制备方法”(201010127955.5)专利技术，以铝粉为原料，用雾化后氧气气氛冷却法制备了Al 2O 3包裹Al粉的核壳式复合相变蓄热材料。此种核壳结构的复合相变蓄热材料对设备要求高、制备工艺复杂和难于控制，制备的壳层较薄，难以满足强度要求。“一种高温相变蓄热微胶囊及其制备方法”(201710502031.0)专利技术，以铝硅合金粉为原料，用磷酸二氢铝溶液进行直接处理后形成相变蓄热微胶囊坯体，或将坯体焙烧后形成具有致密壳层的高温相变蓄热微胶囊。此种微胶囊的制备方法简单，但是制备的微胶囊之间有粘接、难以满足对分散性要求高的工业应用，且抗热循环有待加强。
发明内容
为了解决现有技术存在的不足，本发明提供了一种工艺简单和易于工业化生产的热循环高效率相变蓄热材料的制备方法；用该方法制备的热循环高效率相变蓄热材料分散性好、热循环次数多和热量利用率高。
一方面，本发明提供了一种热循环高效率相变蓄热材料的制备方法，包括如下步骤：
将铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体、纳米氧化铝粉体与溶剂混合，制成混合浆体；
将所述混合浆体过滤、烘干，然后在90％以上湿度空气气氛和600～850℃条件下焙烧3～6h，得到热循环高效率相变蓄热材料。
可选地，根据本发明的热循环高效率相变蓄热材料的制备方法，所述铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体以及溶剂按照以下重量配比进行混合：铝硅合金粉体40～60％、纳米氧化钙粉体5～20％、纳米氧化硅粉体0.5～3％、纳米氧化铝粉体0.5～2％、溶剂30～40％。
可选地，根据本发明的热循环高效率相变蓄热材料的制备方法，所述铝硅合金粉体的粒径≤88μm，所述铝硅合金粉体中Si含量≤21％。
可选地，根据本发明的热循环高效率相变蓄热材料的制备方法，所述纳米氧化钙粉体中CaO含量≥99％，粒径≤0.1μm。
可选地，根据本发明的热循环高效率相变蓄热材料的制备方法，所述纳米氧化硅粉体中SiO 2含量≥99％，粒径≤0.1μm。
可选地，根据本发明的热循环高效率相变蓄热材料的制备方法，所述纳米氧化铝粉体中Al 2O 3含量≥99％，粒径≤0.1μm。
可选地，根据本发明的热循环高效率相变蓄热材料的制备方法，将铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体与溶剂在25-35℃下搅拌15-25分钟，实现混合。
可选地，根据本发明的热循环高效率相变蓄热材料的制备方法，所述溶剂为乙醇，所述乙醇的浓度≥90％。
可选地，根据本发明的热循环高效率相变蓄热材料的制备方法，在90-97％的湿度空气气氛中进行焙烧。
另一方面，本发明还提供了根据上述制备方法制得的热循环高效率相变蓄热材料。
本发明具有如下有益效果：
本发明制备的相变蓄热材料具有核壳结构，解决了铝硅合金作为相变蓄热材料在应用过程中熔化后易泄露的问题；能有效地为熔融状态的铝硅合金提供保护，避免铝硅合金的流失和由此造成的腐蚀，增加铝硅合金的 循环使用次数。而且，本发明制备工艺简单，易控制，容易实现工业化生产。
具体实施方式
下面结合具体的实施方式对本发明作进一步的描述。
一方面，本发明提供了一种热循环高效率相变蓄热材料的制备方法，包括如下步骤：
将铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体、纳米氧化铝粉体与溶剂混合，制成混合浆体；将所述混合浆体过滤、烘干，然后在90％以上湿度空气气氛和600～850℃条件下焙烧3～6h，冷却至室温，得到热循环高效率相变蓄热材料。
优选地，所述铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体以及溶剂按照以下重量配比进行混合：铝硅合金粉体40～60％、纳米氧化钙粉体5～20％、纳米氧化硅粉体0.5～3％、纳米氧化铝粉体0.5～2％、溶剂30～40％。
本发明热循环高效率相变蓄热材料的制备方法所采用的纳米氧化钙粉体在高湿度高温处理过程中会发生水化同时释放大量热量，纳米氧化硅粉体和纳米氧化铝粉体则能控制混合物发生反应的速度，使铝硅合金粉中的铝能生成氧化铝及氧化铝-铝酸钙复合物包覆在铝硅合金表面，形成复合核壳结构，且表面洁净，分散性好；同时，氧化钙的水化和失水以及与氧化铝的反应过程会使该氧化铝-铝酸钙复合物包覆层形成许多封闭微孔，该封闭微孔能够在防止合金熔体渗漏的同时缓冲热应力，抵抗热循环引起的破坏。由此，制备的具有核壳结构的相变蓄热材料解决了铝硅合金作为相变蓄热材料在应用过程中熔化后易泄露的问题；能有效地为熔融状态的铝硅合金提供保护，避免铝硅合金的流失和由此造成的腐蚀，增加铝硅合金的循环使用次数。
优选地，根据本发明的热循环高效率相变蓄热材料的制备方法，所述铝硅合金粉体的粒径≤88μm；所述铝硅合金粉体中Si含量≤21％。
进一步优选地，根据本发明的热循环高效率相变蓄热材料的制备方 法，所述纳米氧化钙粉体中CaO含量≥99％，粒径≤0.1μm。所述纳米氧化硅粉体中SiO 2含量≥99％，粒径≤0.1μm。所述纳米氧化铝粉体中Al 2O 3含量≥99％，粒径≤0.1μm。由于粒径对热处理温度、最终产品的壳层表面光滑度以及壳层导热系数均有一定影响(例如，粒径小一些，热处理温度就低一些，壳层表面更光滑洁净，但同时壳层导热系数也会低一些，换向效率会差一些，表现为服役时的换向时间会较长些)，因此各原料的粒径选择尤为重要。本发明通过选择合适的粒径范围，配合适宜的热处理温度，使得最终制备得到的复合核壳结构相变蓄热材料在表面洁净度以及导热系数的综合性能方面表现最优。
优选地，根据本发明的热循环高效率相变蓄热材料的制备方法，制备混合浆体的具体操作为：将铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体、纳米氧化铝粉体与溶剂在25-35℃下搅拌15-25分钟，实现混合。进一步优选地，在30℃恒温条件下搅拌20分钟，混合均匀。
本发明的热循环高效率相变蓄热材料的制备方法中，制备混合浆体所用的溶剂采用常见的有机溶剂即可，例如可采用乙醇、丙醇、己烷、乙二醇等作为溶剂。优选地，本发明采用乙醇作为溶剂。进一步优选地所述乙醇的浓度≥90％。
本发明的热循环高效率相变蓄热材料的制备方法中，将所述混合浆体过滤，烘干至恒重，然后装入刚玉坩埚置于马弗炉中进行焙烧。优选地，在90-97％的湿度空气气氛和600～850℃条件下焙烧3～6h。该焙烧的高湿度高温保证了纳米氧化钙粉体发生水化同时释放大量热量。
另一方面，本发明还提供了根据上述制备方法制得的热循环高效率相变蓄热材料，该热循环高效率相变蓄热材料分散性好、热循环次数多和热量利用率高。
为了具体的描述本发明，申请人通过以下示例对本申请的热循环高效率相变蓄热材料制备方法进行说明。应当理解的是，下述具体的实施例仅作为本发明的具体实现方式的示例性说明，而不构成对本发明范围的限制。
实施例1
按照以下重量配比将铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体与浓度为93％的乙醇在25℃恒温条件下搅拌25min混合均匀，得到混合浆体：铝硅合金粉体40％、纳米氧化钙粉体20％、纳米氧化硅粉体2％、纳米氧化铝粉体2％、乙醇36％。
将所述混合浆体过滤，烘干至恒重，然后装入刚玉坩埚置于马弗炉中，在95％湿度空气气氛和600℃条件下焙烧6h，冷却至室温，即得到热循环高效率相变蓄热材料。
将本实施例制备的热循环高效率相变蓄热材料在650℃下经5000次热循环，相变潜热保持率为92％。
实施例2
按照以下重量配比将铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体与浓度为95％的乙醇在30℃恒温条件下搅拌20min混合均匀，得到混合浆体：铝硅合金粉体45％、纳米氧化钙粉体15％、纳米氧化硅粉体1.5％、纳米氧化铝粉体1.5％、乙醇37％。
将所述混合浆体过滤，烘干至恒重，然后装入刚玉坩埚置于马弗炉中，在95％湿度空气气氛和650℃条件下焙烧5h，冷却至室温，即得到热循环高效率相变蓄热材料。
将本实施例制备的热循环高效率相变蓄热材料在650℃下经5000次热循环，相变潜热保持率为93％。
实施例3
按照以下重量配比将铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体与浓度为92％的乙醇在35℃恒温条件下搅拌20min混合均匀，得到混合浆体：铝硅合金粉体50％、纳米氧化钙粉体10％、纳米氧化硅粉体1％、纳米氧化铝粉体0.5％、乙醇38.5％。
将所述混合浆体过滤，烘干至恒重，然后装入刚玉坩埚置于马弗炉中，在93％湿度空气气氛和700℃条件下焙烧4.5h，冷却至室温，即得到热循环高效率相变蓄热材料。
将本实施例制备的热循环高效率相变蓄热材料在650℃下经5000次热循环，相变潜热保持率为93％。
实施例4
按照以下重量配比将铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体与浓度为93％的乙醇在30℃恒温条件下搅拌20min混合均匀，得到混合浆体：铝硅合金粉体55％、纳米氧化钙粉体5％、纳米氧化硅粉体0.5％、纳米氧化铝粉体1％、乙醇38.5％。
将所述混合浆体过滤，烘干至恒重，然后装入刚玉坩埚置于马弗炉中，在90％湿度空气气氛和750℃条件下焙烧4h，冷却至室温，即得到热循环高效率相变蓄热材料。
将本实施例制备的热循环高效率相变蓄热材料在650℃下经5000次热循环，相变潜热保持率为94％。
实施例5
按照以下重量配比将铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体与浓度为93％的乙醇在25℃恒温条件下搅拌25min混合均匀，得到混合浆体：铝硅合金粉体60％、纳米氧化钙粉体6％、纳米氧化硅粉体2.5％、纳米氧化铝粉体1.5％、乙醇30％。
将所述混合浆体过滤，烘干至恒重，然后装入刚玉坩埚置于马弗炉中，在97％湿度空气气氛和850℃条件下焙烧3h，冷却至室温，即得到热循环高效率相变蓄热材料。
将本实施例制备的热循环高效率相变蓄热材料在650℃下经5000次热循环，相变潜热保持率为95％。
实施例6
按照以下重量配比将铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体与浓度为93％的乙醇在30℃恒温条件下搅拌20min混合均匀，得到混合浆体：铝硅合金粉体50％、纳米氧化钙粉体6％、纳米氧化硅粉体3％、纳米氧化铝粉体1％、乙醇40％。
将所述混合浆体过滤，烘干至恒重，然后装入刚玉坩埚置于马弗炉中，在95％湿度空气气氛和800℃条件下焙烧4h，冷却至室温，即得到热循环高效率相变蓄热材料。
将本实施例制备的热循环高效率相变蓄热材料在650℃下经5000次 热循环，相变潜热保持率为93％。
对比例1-11
对比例1-11中，铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体与乙醇按照表1的重量配比进行混合，其他参数与实施例5相同。
表1
Figure PCTCN2021082338-appb-000001
对上述对比例1-11制备的相变蓄热材料进行热循环试验，具体结果如下表2所示。
表2
对比例 热循环温度(℃) 热循环次数(次) 相变潜热保持率(％)
1 600 4500 72
2 600 4500 83
3 600 4500 82
4 600 4500 85
5 600 4500 84
6 600 4500 81
7 600 4500 82
8 600 4500 83
9 600 4500 71
10 600 4500 72
11 600 4500 70
由上述表1和表2可以看出，本发明正是由于添加了纳米氧化钙粉体、纳米氧化硅粉体、纳米氧化铝粉体，该三者与铝硅合金粉体发生协同作用，生成具有热循环高效率的相变蓄热材料，有效利用了铝硅合金粉体的相变潜热，并且潜热保持率高，提高了热量利用率。同时，铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体各组分的配比对热循环高效率的相变蓄热材料的最终性能也有重要影响，铝硅合金粉体40～60％、纳米氧化钙粉体5～20％、纳米氧化硅粉体0.5～3％、纳米氧化铝粉体0.5～2％、溶剂30～40％的重量配比在增加热循环次数，保持较高相变潜热率上有明显优势。
对比例12-15
对比例12-15中，铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体的粒径如下表3所示，其他参数与实施例5相同。
表3
Figure PCTCN2021082338-appb-000002
Figure PCTCN2021082338-appb-000003
对上述对比例12-15制备的相变蓄热材料进行热循环试验，具体结果如下表4所示。
表4
对比例 热循环温度(℃) 热循环温度(次) 相变潜热保持率(％)
12 600 4500 86
13 600 4500 83
14 600 4500 82
15 600 4500 82
由上述表3和表4可以看出，铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体、纳米氧化铝粉体的粒径对热循环高效率的相变蓄热材料的最终性能有重要影响，本发明技术方案限定的粒径范围内，相变蓄热材料在增加热循环次数，保持较高相变潜热率上有明显优势。
应该注意的是，上述实施例对本发明进行说明而不是对本发明进行限制，并且本领域技术人员在不脱离所附权利要求的范围的情况下可设计出替换实施例。在权利要求中，不应将位于括号之间的任何参考符号构造成对权利要求的限制。单词“包含”不排除存在未列在权利要求中的元件或步骤。单词第一、第二以及第三等的使用不表示任何顺序，可将这些单词解释为名称。

Claims (10)

  1. 一种热循环高效率相变蓄热材料的制备方法，包括如下步骤：
    将铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体、纳米氧化铝粉体与溶剂混合，制成混合浆体；
    将所述混合浆体过滤、烘干，然后在90％以上湿度空气气氛和600～850℃条件下焙烧3～6h，得到热循环高效率相变蓄热材料。
  2. 根据权利要求1所述的热循环高效率相变蓄热材料的制备方法，其特征在于：所述铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体以及溶剂按照以下重量配比进行混合：铝硅合金粉体40～60％、纳米氧化钙粉体5～20％、纳米氧化硅粉体0.5～3％、纳米氧化铝粉体0.5～2％、溶剂30～40％。
  3. 根据权利要求1或2所述的热循环高效率相变蓄热材料的制备方法，其特征在于：所述铝硅合金粉体的粒径≤88μm，所述铝硅合金粉体中Si含量≤21％。
  4. 根据权利要求1或2所述的热循环高效率相变蓄热材料的制备方法，其特征在于：所述纳米氧化钙粉体中CaO含量≥99％，粒径≤0.1μm。
  5. 根据权利要求1或2所述的热循环高效率相变蓄热材料的制备方法，其特征在于：所述纳米氧化硅粉体中SiO 2含量≥99％，粒径≤0.1μm。
  6. 根据权利要求1或2所述的热循环高效率相变蓄热材料的制备方法，其特征在于：所述纳米氧化铝粉体中Al 2O 3含量≥99％，粒径≤0.1μm。
  7. 根据权利要求1或2所述的热循环高效率相变蓄热材料的制备方法，其特征在于：将铝硅合金粉体、纳米氧化钙粉体、纳米氧化硅粉体与溶剂在25-35℃下搅拌15-25分钟，实现混合。
  8. 根据权利要求1或2所述的热循环高效率相变蓄热材料的制备方法，其特征在于：所述溶剂为乙醇，所述乙醇的浓度≥90％。
  9. 根据权利要求1或2所述的热循环高效率相变蓄热材料的制备方法，其特征在于：在90-97％的湿度空气气氛中进行焙烧。
  10. 一种根据权利要求1-9任一项所述的制备方法制得的热循环高效率相变蓄热材料。
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