CN103409656B - A kind of thermoelectric material Mg2Sn and its preparation method - Google Patents
A kind of thermoelectric material Mg2Sn and its preparation method Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910019743 Mg2Sn Inorganic materials 0.000 title description 10
- 229910019021 Mg 2 Sn Inorganic materials 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 6
- 239000000919 ceramic Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 35
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000013590 bulk material Substances 0.000 claims description 5
- 238000003746 solid phase reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002019 doping agent Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000010671 solid-state reaction Methods 0.000 claims description 3
- 239000012258 stirred mixture Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910012375 magnesium hydride Inorganic materials 0.000 abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract description 5
- WODQBLHHDJHFLM-UHFFFAOYSA-N magnesium;oxotin Chemical compound [Mg].[Sn]=O WODQBLHHDJHFLM-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000498 ball milling Methods 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000005684 electric field Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- RSHAOIXHUHAZPM-UHFFFAOYSA-N magnesium hydride Chemical compound [MgH2] RSHAOIXHUHAZPM-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
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- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
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- 239000005977 Ethylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- RRXGIIMOBNNXDK-UHFFFAOYSA-N [Mg].[Sn] Chemical compound [Mg].[Sn] RRXGIIMOBNNXDK-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种热电材料Mg2Sn及其制备方法，属于无机材料技术领域，其特征在于是一种用以在较低温度下制备热电性能较高的热电材料及其制备方法。所述方法包括：将粉末状的氢化镁MgH2、锡Sn和钇Y按照摩尔比为1.9:1:0.1混合后，放入密封的聚四氟乙烯球磨罐中，在高速振动式球磨机中球磨20~40min得到MgH2、Sn和Y搅拌均匀的粉末状混合物；将所述搅拌均匀的粉末状混合物置于陶瓷管中且密封，将密封后的粉末状混合物放入管式炉中在573-673K温度范围内反应，得到粉末状的热电材料锡化镁Mg2Sn。
A thermoelectric material Mg 2 Sn and a preparation method thereof belong to the technical field of inorganic materials, and are characterized in that it is used to prepare a thermoelectric material with high thermoelectric performance at a relatively low temperature and a preparation method thereof. The method comprises: mixing powdered magnesium hydride MgH 2 , tin Sn and yttrium Y according to a molar ratio of 1.9:1:0.1, putting them into a sealed polytetrafluoroethylene ball mill tank, and ball milling in a high-speed vibration ball mill 20 ~ 40min to obtain MgH 2 , Sn and Y powdery mixture that is uniformly stirred; the powdery mixture that is uniformly stirred is placed in a ceramic tube and sealed, and the sealed powdery mixture is put into a tube furnace at 573- React in the temperature range of 673K to obtain powdered thermoelectric material magnesium tin oxide Mg 2 Sn.
Description
技术领域 technical field
本发明一种热电材料Mg2Sn及其制备方法属于无机材料技术领域，尤其涉及一种采用MgH2反应法合成热电材料Mg2Sn粉末，并结合电场激活压力辅助合成FAPAS实现Mg2Sn基块体材料的快速致密化的热电材料Mg2Sn及其制备方法。 The present invention relates to a thermoelectric material Mg2Sn and a preparation method thereof, which belong to the technical field of inorganic materials, and in particular relate to a MgH2 reaction method for synthesizing thermoelectric material Mg2Sn powder, combined with electric field activation and pressure-assisted synthesis of FAPAS to realize Mg2Sn base block Rapid densification thermoelectric material Mg 2 Sn of bulk material and its preparation method.
背景技术 Background technique
热电材料是一种能够实现热能和电能相互转化的材料，其具有无噪音，无污染、易于维护、安全可靠等优点，在温差发电和热电制冷等领域具有重要的应用价值和广泛的应用前景。 Thermoelectric material is a kind of material that can realize mutual conversion of heat energy and electric energy. It has the advantages of no noise, no pollution, easy maintenance, safety and reliability, etc. It has important application value and broad application prospects in the fields of thermoelectric power generation and thermoelectric refrigeration. the
热电材料的热电性能常用公式ZT=(S2σ/κ)·T来衡量，其中S为Seebeck系数，σ为电导率，κ为热导率。好的热电材料要求材料具有大的电导率和Seebeck系数，以及小的热导率。 The thermoelectric properties of thermoelectric materials are often measured by the formula ZT=(S 2 σ/κ)·T, where S is the Seebeck coefficient, σ is the electrical conductivity, and κ is the thermal conductivity. Good thermoelectric materials require materials with large electrical conductivity and Seebeck coefficient, and small thermal conductivity.
锡镁化合物Mg2Sn是近年来人们研究的比较重要的热电材料。现有技术制作Mg2Sn是通过将镁粉和锡粉按照一定比例混合，混合物加热至一定温度下，使二者充分融化反应。由于Mg的熔点为957.9K，Sn的熔点为504.89K，二者的熔点相差较大，制备Mg2Sn的温度条件较苛刻，且产物成分难以控制。此外，Mg单质在高温条件下很容易挥发且很容易被氧化，形成的产物中会混有大量的氧化镁MgO杂质，严重影响Mg2Sn的性能。 The tin-magnesium compound Mg 2 Sn is an important thermoelectric material that people have studied in recent years. In the prior art, Mg 2 Sn is produced by mixing magnesium powder and tin powder according to a certain ratio, and heating the mixture to a certain temperature to fully melt and react the two. Since the melting point of Mg is 957.9K and that of Sn is 504.89K, there is a large difference between the melting points of the two, the temperature conditions for preparing Mg 2 Sn are relatively harsh, and the product composition is difficult to control. In addition, Mg element is easy to volatilize and be oxidized under high temperature conditions, and the formed product will be mixed with a large amount of magnesium oxide MgO impurities, which seriously affects the performance of Mg 2 Sn.
发明内容 Contents of the invention
本发明一种热电材料Mg2Sn及其制备方法，目的在于克服上述现有技术存在的问题，提供一种采用MgH2反应法合成热电材料Mg2Sn粉末，并结合电场激活压力辅助合成FAPAS实现Mg2Sn基块体材料的快速致密化的热电材料Mg2Sn及其制备方法的技术方案。 The present invention is a thermoelectric material Mg 2 Sn and its preparation method, the purpose is to overcome the problems existing in the above-mentioned prior art, and to provide a thermoelectric material Mg 2 Sn powder synthesized by MgH 2 reaction method, combined with electric field activation pressure assisted synthesis of FAPAS to achieve The invention discloses a rapid densification thermoelectric material Mg 2 Sn of Mg 2 Sn-based bulk material and a technical scheme of a preparation method thereof.
本发明一种热电材料Mg2Sn，其特征在于是一种采用MgH2反应法合成热电材料Mg2Sn粉末，并结合电场激活压力辅助合成FAPAS实现Mg2Sn基块体材料的快速致密化的热电材料Mg2Sn，对应的反应式为：MgH2+Sn→Mg2Sn+H2↑。 The present invention is a thermoelectric material Mg2Sn , which is characterized in that it is a thermoelectric material Mg2Sn powder synthesized by MgH2 reaction method, combined with the electric field activation pressure to assist the synthesis of FAPAS to realize the rapid densification of Mg2Sn -based bulk materials The thermoelectric material Mg 2 Sn, the corresponding reaction formula is: MgH 2 +S n →Mg 2 S n +H 2 ↑.
上述一种热电材料Mg2Sn的制备方法，其特征在于是一种采用MgH2反应法合成热电材料Mg2Sn粉末，并结合电场激活压力辅助合成FAPAS实现Mg2Sn基块体材料的快速致密化的热电材料Mg2Sn的制备方法，该方法用以在低温度下制备热电性能高的Mg2Sn，具体包括以下步骤： The above method for preparing thermoelectric material Mg 2 Sn is characterized in that it uses MgH 2 reaction method to synthesize thermoelectric material Mg 2 Sn powder, and combines electric field activation pressure-assisted synthesis of FAPAS to realize rapid densification of Mg 2 Sn-based bulk materials A method for preparing a thermoelectric material Mg2Sn , which is used to prepare Mg2Sn with high thermoelectric performance at a low temperature, specifically comprises the following steps:
步骤一：将粉末状的氢化镁MgH2、锡Sn和钇Y按照摩尔比为1.9:1:0.1混合，在氩气保护的手套箱中，将MgH2粉、Sn粉和Y粉按照摩尔百分比为1.9:1:0.1混合，得到初步的混合物，MgH2和Sn作为反应物质，Y作为掺杂物，掺杂Y可以改善热电材料的电性能； Step 1: Mix powdered magnesium hydride MgH 2 , tin Sn and yttrium Y in a molar ratio of 1.9:1:0.1, and in an argon-protected glove box, mix MgH 2 powder, Sn powder and Y powder in a molar percentage Mixing for 1.9:1:0.1 to obtain a preliminary mixture, MgH 2 and Sn are used as reaction substances, Y is used as a dopant, and doping Y can improve the electrical properties of thermoelectric materials;
步骤二：对步骤一所述的混合物进行搅拌使其各组分混合均匀，具体地，将所述混合物密封在聚四氟乙烯球磨罐中，然后在高速振动式球磨机中球磨约20～40分钟，使得MgH2、Sn和Y粉充分搅拌均匀； Step 2: Stir the mixture described in Step 1 to make the components evenly mixed, specifically, seal the mixture in a polytetrafluoroethylene ball mill jar, and then ball mill it in a high-speed vibrating ball mill for about 20 to 40 minutes , so that the MgH 2 , Sn and Y powders are fully stirred evenly;
步骤三：将步骤二所述搅拌均匀的粉末状混合物置入炉管反应，以得到Mg2Sn，具体地，将球磨机研磨后的混合物装入氧化铝陶瓷管，将该装有混合物的氧化铝陶瓷管密封在石英玻璃管中，其目的是为了密封所述搅拌后的混合物，将内装混合物的石英玻璃管放入管式炉中，设置管式炉以4K/min的加热速率将管式炉内温度升温至200～230℃，保温15分钟，使得Sn粉完全融化，且与MgH2达到完全润湿，以保证反应的进行；然后再以2K/min的速度将炉管内的温度升温至至少300～350℃，保温10～20h小时，使MgH2和Sn能够充分反应，即发生固相反应，此时以得到高性能的热电材料，此时的Mg2Sn为掺杂有Y的粉末状。 Step 3: put the uniformly stirred powdery mixture described in step 2 into a furnace tube for reaction to obtain Mg 2 Sn, specifically, put the mixture ground by a ball mill into an alumina ceramic tube, and the alumina containing the mixture The ceramic tube is sealed in the quartz glass tube. The purpose is to seal the stirred mixture. The quartz glass tube containing the mixture is put into the tube furnace, and the tube furnace is set to heat the tube furnace at a heating rate of 4K/min. The internal temperature is raised to 200-230°C and kept for 15 minutes, so that the Sn powder is completely melted and completely wetted with MgH 2 to ensure the progress of the reaction; then the temperature in the furnace tube is raised to at least 300～350℃, heat preservation for 10～20 hours, so that MgH 2 and Sn can fully react, that is, a solid phase reaction occurs, at this time to obtain a high-performance thermoelectric material, at this time Mg 2 Sn is powdery doped with Y .
本发明一种热电材料Mg2Sn及其制备方法，优点在于将粉末状的氢化镁MgH2、锡Sn和钇Y按照摩尔比为1.9:1:0.1混合后，放入密封的聚四氟乙烯球 磨罐中研磨，得到MgH2、Sn和Y搅拌均匀的粉末状混合物；将所述搅拌均匀的粉末状混合物置于陶瓷管中且密封，将密封后的粉末状混合物放入管式炉中在573-673K（即300-400℃）温度范围内反应，得到粉末状的热电材料锡化镁Mg2Sn。本发明采用MgH2反应法合成热电材料Mg2Sn粉末，并结合电场激活压力辅助合成（FAPAS）实现Mg2Sn基块体材料的快速致密化。相较于Mg粉和Sn粉的固相反应，MgH2反应法不仅可以在较低的温度（约623K即350℃）完成反应，还可有效地避免Mg单质的氧化与挥发。本发明采用MgH2反应法合成热电材料Mg2Sn粉末，并结合电场激活压力辅助合成（FAPAS）实现Mg2Sn基材料的快速致密化。相较于Mg粉和Sn粉的固相反应，MgH2反应法不仅可以在较低的温度约623K（350℃）完成反应，还可有效地避免Mg单质的氧化与挥发。采用MgH2反应法制备的试样掺杂Y后Mg2Sn试样的电性能有所提高，在350K时获得最大的ZT值(0.033)，此最佳温度区间对于热电材料在废热的回收利用上是十分有利的，本发明实施例提供的上述Mg2Sn的制备方法，采用粉末状的MgH2代替传统工艺中粉末状Mg来制备Mg2Sn基热电材料，可以有效避免Mg粉在反应中的挥发和氧化的问题。同时，MgH2分解可以使得与Sn颗粒接触的Mg颗粒具有较大的表面积和活性，使反应在较低温度就能进行，相应地对反应设备的要求也较低，热电材料易于实现。此外，采用MgH2代替传统工艺中Mg粉来制备Mg2Sn，产物Mg2Sn的晶粒尺寸分布均匀。 A kind of thermoelectric material Mg 2 Sn of the present invention and its preparation method, the advantage is that powdery magnesium hydride MgH 2 , tin Sn and yttrium Y are mixed according to the molar ratio of 1.9:1:0.1, put into the sealed polytetrafluoroethylene Grinding in a ball mill jar to obtain a uniformly stirred powdery mixture of MgH 2 , Sn and Y; placing the uniformly stirred powdery mixture in a ceramic tube and sealing it, and putting the sealed powdery mixture into a tube furnace React in the temperature range of 573-673K (that is, 300-400°C) to obtain powdery thermoelectric material magnesium tin oxide Mg 2 Sn. The invention adopts MgH 2 reaction method to synthesize thermoelectric material Mg 2 Sn powder, and combines electric field activated pressure assisted synthesis (FAPAS) to realize rapid densification of Mg 2 Sn based bulk material. Compared with the solid-state reaction of Mg powder and Sn powder, the MgH 2 reaction method can not only complete the reaction at a lower temperature (about 623K or 350°C), but also effectively avoid the oxidation and volatilization of Mg elemental substance. The invention adopts the MgH 2 reaction method to synthesize the thermoelectric material Mg 2 Sn powder, and combines the electric field activated pressure-assisted synthesis (FAPAS) to realize the rapid densification of the Mg 2 Sn-based material. Compared with the solid-state reaction of Mg powder and Sn powder, the MgH 2 reaction method can not only complete the reaction at a lower temperature of about 623K (350°C), but also effectively avoid the oxidation and volatilization of Mg elemental substance. The electrical properties of the Mg 2 Sn sample prepared by the MgH 2 reaction method were improved after doping Y, and the maximum ZT value (0.033) was obtained at 350K. The above is very advantageous. The above-mentioned Mg 2 Sn preparation method provided by the embodiment of the present invention uses powdered MgH 2 to replace the powdered Mg in the traditional process to prepare Mg 2 Sn-based thermoelectric materials, which can effectively avoid the Mg powder in the reaction The problem of volatilization and oxidation. At the same time, the decomposition of MgH 2 can make the Mg particles in contact with the Sn particles have a larger surface area and activity, so that the reaction can be carried out at a lower temperature, and the requirements for the reaction equipment are relatively low, and the thermoelectric material is easy to realize. In addition, Mg 2 Sn is prepared by using MgH 2 instead of Mg powder in the traditional process, and the grain size distribution of the product Mg 2 Sn is uniform.
附图说明 Description of drawings
图1为本发明实施例提供的热电材料Mg2Sn的制备方法总体流程示意图。 Fig. 1 is a schematic flow diagram of the overall process of the preparation method of the thermoelectric material Mg 2 Sn provided by the embodiment of the present invention.
具体实施方式 Detailed ways
实施方式1 Implementation mode 1
本发明采用MgH2反应法合成热电材料Mg2Sn粉末，并结合电场激活压力辅助合成FAPAS实现Mg2Sn基块体材料的快速致密化的热电材料Mg2Sn，对应的反应式为：MgH2+Sn→Mg2Sn+H2↑该材料制备方法具体包括以下步骤： The present invention adopts the MgH 2 reaction method to synthesize the thermoelectric material Mg 2 Sn powder, and combines the electric field activation pressure to assist the synthesis of FAPAS to realize the rapid densification of the Mg 2 Sn-based bulk material. The corresponding reaction formula is : MgH 2 +S n →Mg 2 S n +H 2 ↑The preparation method of this material specifically includes the following steps:
步骤一：将粉末状的氢化镁MgH2、锡Sn和钇Y按照摩尔比为1.9:1:0.1混合。具体地，在氩气（Ar气）保护的手套箱中，将MgH2粉，Sn粉，以及Y粉按照摩尔百分比为1.9:1:0.1混合，得到初步的混合物； Step 1: Mix powdered magnesium hydride MgH 2 , tin Sn and yttrium Y at a molar ratio of 1.9:1:0.1. Specifically, in an argon (Ar gas) protected glove box, MgH 2 powder, Sn powder, and Y powder were mixed according to a molar percentage of 1.9:1:0.1 to obtain a preliminary mixture;
MgH2和Sn作为反应物质，Y作为掺杂物，掺杂Y可以改善热电材料的电性能； MgH 2 and Sn are used as reactive substances, and Y is used as a dopant. Doping Y can improve the electrical properties of thermoelectric materials;
步骤二：对所述混合物进行搅拌使其各组分混合均匀，具体地，将所述混合物密封在聚四氟乙烯球磨罐（磨球为玛瑙）中，然后在高速振动式球磨机（例如型号为：QM-3B）中球磨约20分钟，较佳地，例如研磨30分钟，使得MgH2、Sn和Y粉充分搅拌均匀； Step 2: Stir the mixture so that the components are evenly mixed. Specifically, seal the mixture in a polytetrafluoroethylene ball mill jar (the ball is agate), and then put it in a high-speed vibratory ball mill (such as a model of : QM-3B) ball milling for about 20 minutes, preferably, for example, grinding for 30 minutes, so that the MgH 2 , Sn and Y powders are fully stirred evenly;
步骤三：将所述搅拌均匀的粉末状混合物置入炉管反应，以得到Mg2Sn，具体地，将球磨机研磨后的混合物装入氧化铝陶瓷管，将该装有混合物的氧化铝陶瓷管密封在石英玻璃管中，其目的是为了密封所述搅拌后的混合物；将内装混合物的石英玻璃管放入管式炉中；设置管式炉以4K/min的加热速率将管式炉内温度升温至503K(即230℃)，保温15分钟，使得Sn粉完全融化，且与MgH2达到完全润湿，以保证反应的进行；然后再以2K/min的速度将炉管内的温度升温至至少623K(350℃)，保温20小时左右，使MgH2和Sn能够充分反应，即发生固相反应。此时以得到高性能的热电材料，此时的Mg2Sn为掺杂有Y的粉末状。MgH2与Sn的反应温度为623K(即350℃)，此温度远低于单质Mg粉与单质Sn粉发生反应的温度803K(即530℃)。实现了在低温条件下制备Mg2Sn的目的。在反应过程中需要持续通入氩气Ar作为保护气体，并且控制保护气体的气压和流量，以防止造成大量热量的流失； Step 3: put the uniformly stirred powder mixture into the furnace tube for reaction to obtain Mg 2 Sn, specifically, put the mixture ground by a ball mill into an alumina ceramic tube, and put the alumina ceramic tube containing the mixture Sealed in a quartz glass tube, the purpose is to seal the stirred mixture; the quartz glass tube containing the mixture is put into a tube furnace; the tube furnace is set to reduce the temperature in the tube furnace at a heating rate of 4K/min Raise the temperature to 503K (that is, 230°C) and keep it warm for 15 minutes, so that the Sn powder is completely melted and completely wetted with MgH 2 to ensure the progress of the reaction; then the temperature in the furnace tube is raised to at least 623K (350°C), heat preservation for about 20 hours, so that MgH 2 and Sn can fully react, that is, a solid phase reaction occurs. At this time, in order to obtain a high-performance thermoelectric material, the Mg 2 Sn at this time is in the powder form doped with Y. The reaction temperature of MgH 2 and Sn is 623K (ie 350°C), which is much lower than the reaction temperature of 803K (ie 530°C) between elemental Mg powder and elemental Sn powder. The purpose of preparing Mg 2 Sn under low temperature condition is realized. During the reaction process, it is necessary to continuously feed argon Ar as a protective gas, and control the pressure and flow of the protective gas to prevent the loss of a large amount of heat;
步骤四：对掺杂有Y的粉末状Mg2Sn进行烧结，得到具有设定形状的块体Mg2Sn，具体地，在保证Mg2Sn冷却至室温后，在真空手套箱中将Mg2Sn取出，同时，装入石墨模具，将装有Mg2Sn粉的石墨模具置于FAPAS炉中，保证FAPAS炉中的真空度不大于15Pa，烧结过程中FAPAS炉中的真空度维持在60MPa左右，在800A的电流下快速（时间不大于7min）加热至800K(即 527℃)使得Mg2Sn烧结，保温15min使得Mg2Sn粉末充分烧结。烧结完成后断电随炉冷却。最后得到一个直径和厚度为D*h（其中，D代表硬币的直径，h代表硬币的厚度）的硬币状热电材料试样，例如得到一个直径和厚度为20*3mm的硬币状热电材料试样。烧结过程中施加在试样上的压强维持在60MPa左右可以使得Mg2Sn粉快速致密化，提高Mg2Sn的热电性能，热电材料的热电性能常用公式ZT=(S2σ/κ)·T来衡量，其中S为Seebeck系数，σ为电导率，κ为热导率。好的热电材料要求材料具有大的电导率和Seebeck系数，以及小的热导率，上述制备热电材料Mg2Sn的过程，在真空环境中进行，无氧化镁MgO生成，MgH2和Sn在623K(350℃)的温度下能够完全反应生成Mg2Sn单相，提高了Mg2Sn的热电性能。其中，实验表明掺杂Y与为掺杂Y相比，Mg2Sn的热电性能提高约三倍。 Step 4: Sinter the powdered Mg 2 Sn doped with Y to obtain a bulk Mg 2 Sn with a set shape. Specifically, after the Mg 2 Sn is cooled to room temperature, the Mg 2 Sn is placed in a vacuum glove box. Take out the Sn, and at the same time, put it into the graphite mold, put the graphite mold with Mg 2 Sn powder in the FAPAS furnace, ensure that the vacuum degree in the FAPAS furnace is not greater than 15Pa, and maintain the vacuum degree in the FAPAS furnace at about 60MPa during the sintering process , under a current of 800A, rapidly (within 7min) heating to 800K (ie 527°C) to sinter the Mg 2 Sn, and hold for 15min to fully sinter the Mg 2 Sn powder. After the sintering is completed, power off and cool down with the furnace. Finally, a coin-shaped thermoelectric material sample with a diameter and thickness of D*h (where D represents the diameter of the coin and h represents the thickness of the coin) is obtained, for example, a coin-shaped thermoelectric material sample with a diameter and thickness of 20*3mm is obtained . Maintaining the pressure on the sample at about 60MPa during the sintering process can rapidly densify the Mg 2 Sn powder and improve the thermoelectric properties of Mg 2 Sn. The thermoelectric properties of thermoelectric materials are commonly used as ZT=(S 2 σ/κ)·T To measure, where S is the Seebeck coefficient, σ is the electrical conductivity, and κ is the thermal conductivity. Good thermoelectric materials require materials with large electrical conductivity and Seebeck coefficient, as well as small thermal conductivity. The above-mentioned process of preparing thermoelectric material Mg 2 Sn is carried out in a vacuum environment without the formation of magnesium oxide MgO. MgH 2 and Sn are at 623K (350°C) temperature can completely react to form Mg 2 Sn single phase, which improves the thermoelectric performance of Mg 2 Sn. Among them, experiments show that the thermoelectric performance of Mg 2 Sn is improved by about three times compared with that without Y doping.
本发明制备的Mg2Sn经HSC模拟结果分析也证实了当温度达到约503K时，系统的焓ΔH突然下降，这是由于此温度达到Sn的熔点，Sn开始熔化放出热量，使得整个系统的吸热量变小，当温度达到600K时，系统的焓ΔH又出现突然下降，推测产生此结果是由于MgH2粉末与Sn在600K时开始进行化合反应放出热量，使得整个系统的吸热量再次变小。而600K时系统的自由能ΔG为负，也说明反应能够进行。 The analysis of the HSC simulation results of the Mg 2 Sn prepared by the present invention also confirmed that when the temperature reaches about 503K, the enthalpy ΔH of the system drops suddenly. The heat becomes smaller. When the temperature reaches 600K, the enthalpy ΔH of the system drops suddenly again. It is speculated that this result is due to the fact that the MgH 2 powder and Sn start to undergo a combination reaction at 600K to release heat, which makes the heat absorption of the entire system smaller again. . At 600K, the free energy ΔG of the system is negative, which also shows that the reaction can proceed.
本发明制备的Mg2Sn通过对其物相分析得到产物的结晶度很好XRD衍射图中没有观察到MgO相的存在，说明在反应过程中MgO的生成量很小或没有，这对于试样的热电性能是有利的。XRD衍射图中掺杂Y后试样的衍射峰发生明显偏移，同时晶胞参数也有所增加，这都说明掺杂的Y进入到Mg2Sn晶格中，引起了晶格畸变，使得其晶胞参数增加，衍射峰也向Y特征峰的方向偏移。 The Mg2Sn that the present invention prepares obtains the crystallinity of the product through its phase analysis very good and does not observe the existence of MgO phase in XRD diffractogram, shows that the generation amount of MgO is very little or not in reaction process, and this is for sample The thermoelectric properties are favorable. In the XRD diffraction pattern, the diffraction peaks of the sample shifted significantly after doping Y, and the unit cell parameters also increased, which indicated that the doped Y entered into the Mg 2 Sn lattice, causing lattice distortion, making its As the unit cell parameters increase, the diffraction peaks also shift to the direction of the Y characteristic peak.
本发明制备的Mg2Sn通过对其热电性能分析，得到试样的电导率均随着温度的升高呈上升趋势，本实验中的试样，电导率均高于现有制备方法制备的Mg2Sn的电导率。 The Mg 2 Sn prepared by the present invention is analyzed by its thermoelectric properties, and the electrical conductivity of the samples obtained shows an upward trend with the increase of temperature. The electrical conductivity of the samples in this experiment is higher than that of the Mg prepared by the existing preparation method. 2 Conductivity of Sn.
实施方式2 Implementation mode 2
参见图1，本发明实施例提供的Mg2Sn的制备方法，将粉末状的氢化镁MgH2、锡Sn和钇Y按照摩尔比为1.9:1:0.1混合后，放入密封的聚四氟乙烯球磨罐中，在高速振动式球磨机中球磨30分钟（min），得到MgH2、Sn和Y搅拌均匀的粉末状混合物；将所述搅拌均匀的粉末状混合物置于陶瓷管中且密封，将密封后的粉末状混合物放入管式炉中在673K（400℃）内反应，得到粉末状的热电材料锡化镁Mg2Sn，其它同实施方式1. Referring to Fig. 1, the preparation method of Mg 2 Sn provided by the embodiment of the present invention is to mix powdered magnesium hydride MgH 2 , tin Sn and yttrium Y according to the molar ratio of 1.9:1:0.1, and put them into a sealed polytetrafluoroethylene In an ethylene ball mill tank, mill in a high-speed vibrating ball mill for 30 minutes (min) to obtain a uniformly stirred powder mixture of MgH 2 , Sn and Y; place the uniformly stirred powder mixture in a ceramic tube and seal it, and place The sealed powdery mixture is put into a tube furnace to react at 673K (400°C) to obtain a powdery thermoelectric material magnesium tin oxide Mg 2 Sn, and the others are the same as in Embodiment 1.
实施方式3 Implementation mode 3
Mg2Sn的石墨模具置于电场激活压力辅助合成FAPAS炉中进行烧结，得到具有与所述石墨模具相对应形状的块体Mg2Sn，将该装有粉末状Mg2Sn的石墨模具置于真空度不大于15Pa的真空FAPAS炉中，设置FAPAS炉的电流速度为800～1000A、在加热时间不大于7min的条件下，将粉末状Mg2Sn加热至800K使其烧结，其它同实施方式1. The graphite mold of Mg 2 Sn is placed in an electric field activated pressure-assisted synthesis FAPAS furnace for sintering to obtain a bulk Mg 2 Sn with a shape corresponding to the graphite mold, and the graphite mold with powdered Mg 2 Sn is placed in In a vacuum FAPAS furnace with a vacuum degree not greater than 15 Pa, set the current speed of the FAPAS furnace to 800-1000A, and heat the powdered Mg 2 Sn to 800K for sintering under the condition that the heating time is not greater than 7 minutes, and the other is the same as that of Embodiment 1 .
显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内，则本发明也意图包含这些改动和变型在内。 Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention also intends to include these modifications and variations. the
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