WO2021036544A1 - Magnesium-antimony-based thermoelectric element, preparation method therefor and use thereof - Google Patents
Magnesium-antimony-based thermoelectric element, preparation method therefor and use thereof Download PDFInfo
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- WO2021036544A1 WO2021036544A1 PCT/CN2020/101556 CN2020101556W WO2021036544A1 WO 2021036544 A1 WO2021036544 A1 WO 2021036544A1 CN 2020101556 W CN2020101556 W CN 2020101556W WO 2021036544 A1 WO2021036544 A1 WO 2021036544A1
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- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
Definitions
- the invention relates to a magnesium-antimony-based thermoelectric element, a preparation method thereof, and a thermoelectric refrigeration device containing the magnesium-antimony-based thermoelectric element.
- Thermoelectric material is a kind of functional material that can realize the direct mutual conversion of heat energy and electric energy.
- Thermoelectric components made of thermoelectric materials have the advantages of light weight, small size, simple structure, no noise, zero emission, and long service life. This is of great significance to solving serious problems such as the energy crisis and environmental pollution, and therefore it has been highly valued by countries all over the world.
- thermoelectric materials have been gradually optimized and improved.
- thermoelectric devices have also been commercialized to a certain extent, especially in near-room temperature thermoelectric refrigeration devices, bismuth telluride materials have been widely promoted and applied.
- bismuth telluride materials have been widely promoted and applied.
- the development of new near-room temperature thermoelectric materials and devices is a strategic demand for the development of the entire thermoelectric field, and it is also a bottleneck problem in the development of the thermoelectric refrigeration industry.
- Magnesium-antimony-based alloy is a new type of thermoelectric material, which has become a research hotspot in the thermoelectric field since 2016. After a lot of research, scientific researchers have made the thermoelectric figure of merit of the n-type magnesium antimony-based thermoelectric material have been greatly improved through various means, and the thermoelectric figure of merit ZT at room temperature has been able to approach or reach 0.8.
- thermoelectric refrigeration devices that are now widely used in automotive air-conditioning seats, environmentally friendly refrigerators, etc.
- traditional bismuth telluride-based thermoelectric materials are still used.
- the cost of bismuth telluride-based thermoelectric materials is too high, and the prices of raw materials such as tellurium and bismuth are much higher than those of raw materials such as magnesium and antimony.
- the application of bismuth telluride-based thermoelectric materials in thermoelectric refrigeration devices was irreplaceable.
- magnesium-antimony-based thermoelectric materials are also constantly improving, which can be comparable to bismuth telluride-based thermoelectric materials in the room temperature range, which provides the application of magnesium-antimony-based thermoelectric materials in refrigeration devices. Basics and possibilities.
- thermoelectric materials To realize the application of magnesium-antimony-based thermoelectric materials in thermoelectric devices, only good thermoelectric performance is far from enough. It is also necessary to prepare such thermoelectric materials into thermoelectric components before they can be further assembled into thermoelectric refrigeration systems.
- the key to preparing thermoelectric elements is to develop an electrode layer that can be matched with magnesium-antimony-based thermoelectric materials. So far, there has been no report on a large-scale electrode layer material matched with magnesium-antimony-based thermoelectric materials. Some traditional electrode materials (such as aluminum, silver, copper, nickel, etc.) cannot be closely combined with magnesium-antimony-based thermoelectric materials, some have excessive contact resistance, and some will react with the material matrix. The difficulty of preparing electrode materials affects the further application of magnesium-antimony-based thermoelectric materials in devices.
- thermoelectric cooling performance in the room temperature range.
- the purpose of the present invention is to develop an electrode layer suitable for magnesium-antimony-based thermoelectric materials in view of the limitations and shortcomings of the prior art, and provide a magnesium-antimony-based thermoelectric element and device that can replace N-type bismuth telluride and The preparation method and application thereof realize the application of magnesium-antimony-based thermoelectric materials in devices, save material costs, and improve economic benefits.
- the present invention provides a magnesium-antimony-based thermoelectric element.
- the magnesium-antimony-based thermoelectric element includes: a magnesium-antimony-based thermoelectric material matrix layer located in the center of the thermoelectric element, and a transition layer attached to two surfaces of the matrix layer. And two electrode layers respectively attached to the surfaces of the two transition layers, wherein the transition layer is made of an alloy of copper and titanium and/or magnesium, and the electrode layer is made of copper and/or nickel.
- the alloy of copper and titanium and/or magnesium includes copper-titanium alloy, copper-magnesium alloy and copper-titanium-magnesium alloy.
- the material of the transition layer is a titanium-copper alloy or a magnesium-copper alloy.
- the composition of the titanium-copper alloy is TiCu n , 0 ⁇ n ⁇ 0.5, and the composition of the magnesium-copper alloy is Mg m Cu, 0.5 ⁇ m ⁇ 3.
- the composition of the magnesium-antimony-based thermoelectric material is Mg 3.3-x Z x Bi 0.5 Sb 1.5-y Te y , where 0 ⁇ x ⁇ 0.1, 0.01 ⁇ y ⁇ 0.05, Z is one or more elements selected from Mn, Ni, Cr and Nb.
- the thickness of the substrate layer can be adjusted according to actual applications, and usually can be 0.5-2 mm.
- the thickness of the transition layer may be 5-50 nm, preferably 5-20 nm; the thickness of the electrode layer may be 0.5-10 ⁇ m, preferably 0.5-5 ⁇ m.
- a transition layer and an electrode layer are respectively provided on the upper and lower surfaces of the substrate layer, and the thickness of the transition layer on the upper surface and the thickness of the transition layer on the lower surface can be Same or different; the thickness of the electrode layer on the upper surface and the thickness of the electrode layer on the lower surface can be the same or different.
- the present invention also provides a method for preparing the magnesium-antimony-based thermoelectric element.
- the preparation method includes: forming a substrate layer of the magnesium-antimony-based thermoelectric material by ion beam sputtering and/or magnetron sputtering.
- the transition layer and the electrode layer are formed on the two surfaces respectively, and the magnesium antimony-based thermoelectric element is manufactured.
- the ion beam sputtering method may include: fixing the magnesium antimony-based thermoelectric material matrix layer in an ion beam sputtering apparatus having a transition layer alloy target and an electrode layer metal target , First deposit a transition layer alloy on one surface of the matrix layer to form a transition layer, and then deposit electrode layer metal to form an electrode layer; then deposit a transition layer alloy on the other surface of the matrix layer to form a transition layer, and then deposit electrode layer metal An electrode layer is formed to prepare the magnesium-antimony-based thermoelectric element.
- the ion beam sputtering method includes: first putting the magnesium antimony-based thermoelectric material matrix layer into a beaker containing alcohol, and cleaning with an ultrasonic cleaner 5-10 minutes, then use a hair dryer or drying device for drying treatment, after the treatment is completed, it is fixed in an ion beam sputtering instrument with a transition layer alloy target and an electrode layer metal target.
- the working condition is: the main source energy is 800-1000eV , The beam current is 60-100mA; the auxiliary source energy is 90-120eV, the beam current is 5-20mA, and the vacuum degree is less than 2.4 ⁇ 10 -2 Pa.
- the transition layer is formed by ion beam sputtering, the deposition time is 2-10 minutes, and the electrode layer metal is deposited for 60-210 minutes to form the electrode layer; then close the instrument, open the chamber and take out the sample, turn the sample over, fix the sample again, and continue
- the transition layer and the electrode layer are deposited on the other surface of the magnesium-antimony-based thermoelectric material matrix layer using the same process.
- the magnetron sputtering method may include: fixing the magnesium antimony-based thermoelectric material matrix layer in a magnetron sputtering apparatus having a transition layer alloy target and an electrode layer metal target, and first depositing on one surface of the matrix layer The transition layer alloy forms the transition layer, and then the electrode layer metal is deposited to form the electrode layer; then the transition layer alloy is deposited on the other surface of the matrix layer to form the transition layer, and the electrode layer metal is then deposited to form the electrode layer to obtain the magnesium antimony-based Thermoelectric element.
- the magnetron sputtering method includes: firstly putting the magnesium antimony-based thermoelectric material matrix layer into a beaker containing alcohol, and cleaning with an ultrasonic cleaner 5-10 minutes, then use a hair dryer or a drying device for drying treatment. After the treatment is completed, it is fixed in a magnetron sputtering apparatus with a transition layer alloy target and an electrode layer metal target.
- the working conditions include: evacuating until the vacuum is less than 0.00066Pa, adjust the power of the titanium-copper alloy target to 90-110W or adjust the power of the magnesium-copper alloy target to 70-80W, form the transition layer by magnetron sputtering, the deposition time is 2-20 minutes, and then use the 90-110W Power deposition of the electrode layer metal for 20-60 minutes to form the electrode layer; then turn off the instrument, open the chamber, take out the sample, turn the sample over, fix the sample again, and continue to deposit on the other surface of the magnesium-antimony-based thermoelectric material matrix layer with the same process Transition layer and electrode layer.
- the transition layer alloy is an alloy of copper, titanium and/or magnesium, including copper-titanium alloy, copper-magnesium alloy and copper-titanium-magnesium alloy.
- the electrode layer metal is copper and/or nickel.
- the preparation method further includes the step of preparing a transition layer alloy target: the metal powder is weighed according to the chemical formula and then ball milled for 4-10 hours, and the powder is placed in a graphite mold for spark plasma sintering.
- Sintering in the equipment, sintering conditions include: sintering at a rate of 20-80°C/min to 500-600°C, sintering pressure of 30-50MPa, holding time of 15-30 minutes, and then cooling in the furnace to prepare the desired Transition layer alloy target.
- the preparation method of the Mg 2 Cu alloy target includes: weighing Mg chips and Cu powder according to the chemical formula Mg 2 Cu, ball milling for 4 to 10 hours, and placing the powder in a graphite mold.
- the sintering process is as follows: sintering is carried out at a rate of 20-80°C/min to 500-600°C, the sintering pressure is 30-50MPa, and the holding time is 15-30 minutes and then cooled with the furnace to prepare the required ⁇ Mg 2 Cu target.
- the present invention also provides a thermoelectric refrigeration device comprising an n-type thermoelectric element and a p-type bismuth telluride-based thermoelectric element assembled together, wherein the n-type thermoelectric element is of the present invention Supplied with magnesium-antimony-based thermoelectric elements.
- thermoelectric components made up of N-type magnesium-antimony-based thermoelectric materials and P-type bismuth telluride prepared by this method can achieve the performance of existing bismuth telluride-based thermoelectric refrigeration components, and at the same time achieve a substantial reduction in cost. At present, there are few reports of such thermoelectric components and preparation methods in the world.
- the transition layer and electrode layer that can be applied to magnesium-antimony-based thermoelectric materials developed by the present invention have important application significance and prospects.
- the electrode layer enables magnesium-antimony-based thermoelectric materials to enter the market and realize industrialization.
- the thermoelectric device prepared by the invention has a lower cost, and can also save the rare element tellurium, which is also beneficial in terms of energy saving and environmental protection.
- the magnesium-antimony-based thermoelectric material components provided by the present invention can replace bismuth telluride-based thermoelectric refrigeration devices on the existing market, can realize a new breakthrough in the cost of existing commercial thermoelectric refrigeration devices, and have great potential for improving economic benefits .
- Fig. 1 is a schematic diagram of a magnesium-antimony-based thermoelectric element provided by the present invention.
- the schematic diagram of the magnesium-antimony-based thermoelectric element provided by the present invention is shown in FIG. 1.
- the magnesium-antimony-based thermoelectric element includes: a magnesium-antimony-based thermoelectric material matrix layer located in the center of the thermoelectric element 1, two transition layers 21 and 22 attached to two surfaces of the matrix layer, and two transition layers attached respectively Two electrode layers 31 and 32 on the surface.
- Mg chips, Mn powder, Bi particles, Sb particles, and Te powder are weighed according to the chemical formula Mg 3.275 Mn 0.025 Bi 0.5 Sb 1.49 Te 0.01, then ball milled for 12 hours to obtain the mixture powder, which is sintered by spark plasma to a thickness of 1.2 mm and a diameter 12.7mm cylindrical block material.
- the sintering process is as follows: the heating rate is 50°C per minute, the temperature is kept at 600°C for 2 minutes, then the temperature is raised to 800°C for 2 minutes, and then cooled with the furnace.
- the pressure during the sintering process is 50Mpa.
- step (2) Put the magnesium-antimony-based thermoelectric material matrix layer prepared in step (1) into a beaker containing alcohol, clean it with an ultrasonic cleaner for 5-10 minutes, and then dry it with a hair dryer or a drying device. After completion, it is fixed to an ion beam sputtering instrument containing a copper target and a TiCu 0.3 target.
- the working conditions are: the main source energy is 900eV, the beam current is 80mA; the auxiliary source energy is 100eV, the beam current is 10mA, and the vacuum degree is less than 2.4 ⁇ 10 -2 Pa ,
- the transition layer of TiCu 0.3 is formed by ion beam sputtering.
- the TiCu 0.3 target After 5 minutes of co-deposition, turn off the TiCu 0.3 target, continue to deposit the copper layer for 120 minutes to form the electrode layer; then turn off the instrument, open the chamber, take out the sample, turn the sample over, and re Fix the sample, and continue to use the same process to deposit a transition layer and an electrode layer on the other surface of the magnesium-antimony-based thermoelectric material matrix layer.
- the thickness of the transition layer is about 10 nm
- the thickness of the electrode layer is about 2 ⁇ m. Then the obtained sample is cut into small particles with a size of 1.45mm ⁇ 1.45mm ⁇ 1.20mm, which is the magnesium-antimony-based thermoelectric element of the present invention.
- thermoelectric element (3) The magnesium-antimony-based thermoelectric element prepared in step (2) and the p-type bismuth telluride-based thermoelectric element with a size of 1.0mm ⁇ 1.0mm ⁇ 1.20mm are assembled through a soldering process to produce 127 pairs of thermoelectric arm refrigeration devices. After 12 volts DC voltage, the cold and hot ends can produce a temperature difference of more than 50 °C, which can meet the commercial application standard.
- Mg chips, Mn powder, Bi particles, Sb particles, and Te powder are weighed according to the chemical formula Mg 3.275 Mn 0.025 Bi 0.5 Sb 1.49 Te 0.01, and then ball milled for 12 hours to obtain a mixture powder, which is sintered by spark plasma to a thickness of 1.2 mm and a diameter. 12.7mm cylindrical block material.
- the sintering process is as follows: the heating rate is 50°C per minute, the temperature is kept at 600°C for 2 minutes, then the temperature is raised to 800°C for 2 minutes, and then cooled with the furnace.
- the pressure during the sintering process is 50Mpa.
- step (2) Put the magnesium-antimony-based thermoelectric material matrix layer prepared in step (1) into a beaker containing alcohol, clean it with an ultrasonic cleaner for 5-10 minutes, and then dry it with a hair dryer or a drying device. After completion, it is fixed to an ion beam sputtering instrument containing Ni target and TiCu 0.2 target.
- the working conditions are: main source energy 900eV, beam current 80mA; auxiliary source energy 100eV, beam current 10mA, vacuum degree less than 2.4 ⁇ 10 -2 Pa ,
- the transition layer of TiCu 0.2 is formed by ion beam sputtering.
- the TiCu 0.2 target After 5 minutes of co-deposition, turn off the TiCu 0.2 target and continue to deposit the Ni layer for 180 minutes to form the electrode layer; then turn off the instrument, open the chamber, take out the sample, turn the sample over, and re Fix the sample, and continue to use the same process to deposit a transition layer and an electrode layer on the other surface of the magnesium-antimony-based thermoelectric material matrix layer.
- the thickness of the transition layer is about 10 nm
- the thickness of the electrode layer is about 3 ⁇ m. Then the obtained sample is cut into small particles with a size of 1.45mm ⁇ 1.45mm ⁇ 1.20mm, which is the magnesium-antimony-based thermoelectric element of the present invention.
- thermoelectric element (3) The magnesium-antimony-based thermoelectric element prepared in step (2) and the p-type bismuth telluride-based thermoelectric element with a size of 1.0mm ⁇ 1.0mm ⁇ 1.20mm are assembled through a soldering process to produce 127 pairs of thermoelectric arm refrigeration devices. After 12 volts DC voltage, the cold and hot ends can produce a temperature difference of more than 50 °C, which can meet the commercial application standard.
- Mg chips, Mn powder, Bi particles, Sb particles, and Te powder are weighed according to the chemical formula Mg 3.275 Mn 0.025 Bi 0.5 Sb 1.49 Te 0.01, and then ball milled for 12 hours to obtain a mixture powder, which is sintered by spark plasma to a thickness of 1.2 mm and a diameter. 12.7mm cylindrical bulk magnesium-antimony-based thermoelectric material matrix layer.
- the sintering process is as follows: the heating rate is 50°C per minute, the temperature is kept at 600°C for 2 minutes, then the temperature is raised to 800°C for 2 minutes, and then cooled with the furnace.
- the pressure during the sintering process is 50Mpa.
- the Mg chips and Cu powder are weighed according to the chemical formula Mg 2 Cu and ball milled for 6 hours.
- the powder is placed in a graphite mold in the spark plasma sintering equipment.
- the sintering process is: 50 degrees per minute to 550 degrees Sintering was carried out, the sintering pressure was 40 MPa, the holding time was 20 minutes, and then the furnace was cooled to prepare the Mg 2 Cu target.
- step (3) Put the magnesium-antimony-based thermoelectric material matrix layer prepared in step (1) into a beaker full of alcohol, clean it with an ultrasonic cleaner for 20 minutes, then dry it with a hair dryer or a drying device, and then fix it to In a magnetron sputtering apparatus with a copper target and the Mg 2 Cu target prepared in step (2). Evacuate until the vacuum degree is less than 0.00066Pa, first co-deposit magnesium-copper alloy for about 5 minutes, adjust the power to about 100W to form a magnesium-copper alloy transition layer, then turn off the magnesium target, continue to deposit the copper layer, as the electrode material, adjust the power to About 75W, the time is about 50 minutes.
- the copper layer deposition After the copper layer deposition is completed, turn off the instrument, open the chamber and take out the sample. After re-fixing the sample, continue to use the same process to deposit the transition layer and the electrode layer on the other surface of the magnesium-antimony-based thermoelectric material matrix layer.
- the thickness of the transition layer is 15 nm, and the thickness of the electrode layer is 3 to 4 ⁇ m. Then the obtained sample is cut into small particles with a size of 1.45mm ⁇ 1.45mm ⁇ 1.20mm, which is the magnesium-antimony-based thermoelectric element of the present invention.
- thermoelectric element prepared in step (3) and the p-type bismuth telluride-based thermoelectric element with a size of 1.0mm ⁇ 1.0mm ⁇ 1.20mm are assembled through a soldering process to produce 127 pairs of thermoelectric arm refrigeration devices. After 12 volts DC voltage, the cold and hot ends can produce a temperature difference of more than 50 °C, which can meet the commercial application standard.
Abstract
Provided are a magnesium-antimony-based thermoelectric element, a preparation method therefor and the use thereof. The thermoelectric element comprises: a magnesium-antimony-based thermoelectric material substrate layer located at the center of the thermoelectric element, transition layers adhered to two surfaces of the substrate layer, and two electrode layers adhered to the surface of the two transition layers, respectively, wherein the material of the transition layer is an alloy of copper and titanium and/or magnesium, and the material of the electrode layer is copper and/or nickel. The present invention uses ion beam sputtering and magnetron sputtering to prepare a transition layer and an electrode layer suitable for a magnesium-antimony-based thermoelectric material, such that the magnesium-antimony-based thermoelectric material has the opportunity to enter the market, making it possible to realize industrialization. Compared with the existing bismuth telluride thermoelectric devices on the market, the thermoelectric device prepared by the present invention has a lower cost, and can also save on the rare element tellurium, which is also beneficial in terms of saving energy and protecting the environment.
Description
本发明涉及一种镁锑基热电元件及其制备方法和包含该镁锑基热电元件的热电制冷器件。The invention relates to a magnesium-antimony-based thermoelectric element, a preparation method thereof, and a thermoelectric refrigeration device containing the magnesium-antimony-based thermoelectric element.
热电材料是能够实现热能和电能直接相互转化的一种功能材料。由热电材料制成的热电元器件具有质量轻、体积小、结构简单、无噪声、零排放、使用寿命长等优点。这对于解决能源危机和环境污染等严峻问题具有重大意义，也因此受到了世界各国的高度重视。Thermoelectric material is a kind of functional material that can realize the direct mutual conversion of heat energy and electric energy. Thermoelectric components made of thermoelectric materials have the advantages of light weight, small size, simple structure, no noise, zero emission, and long service life. This is of great significance to solving serious problems such as the energy crisis and environmental pollution, and therefore it has been highly valued by countries all over the world.
随着新材料设计理念以及器件制备新工艺与新技术的发展，热电材料的性能逐步得到优化与提升。与此同时，热电器件也一定程度上实现了商业化，尤其是在近室温热电制冷器件方面，碲化铋材料得到了较为广泛推广和应用。然而，由于碲化铋材料成本高昂，并且有一定的毒性，限制了这类材料在热电制冷方面进一步的大规模使用。因此，发展新型近室温热电材料与器件是整个热电领域发展的战略需求，也是热电制冷产业发展的瓶颈性问题。With the development of new material design concepts and new device preparation processes and new technologies, the performance of thermoelectric materials has been gradually optimized and improved. At the same time, thermoelectric devices have also been commercialized to a certain extent, especially in near-room temperature thermoelectric refrigeration devices, bismuth telluride materials have been widely promoted and applied. However, due to the high cost of bismuth telluride materials and a certain degree of toxicity, the further large-scale use of such materials in thermoelectric refrigeration is restricted. Therefore, the development of new near-room temperature thermoelectric materials and devices is a strategic demand for the development of the entire thermoelectric field, and it is also a bottleneck problem in the development of the thermoelectric refrigeration industry.
镁锑基合金是一种新型热电材料，从2016年开始成为了热电领域的一个研究热点。科研人员经过大量的研究，通过各种手段使得n型镁锑基热电材料的热电优值得到了很大的提高，室温热电优值ZT已经能够接近或达到0.8。Magnesium-antimony-based alloy is a new type of thermoelectric material, which has become a research hotspot in the thermoelectric field since 2016. After a lot of research, scientific researchers have made the thermoelectric figure of merit of the n-type magnesium antimony-based thermoelectric material have been greatly improved through various means, and the thermoelectric figure of merit ZT at room temperature has been able to approach or reach 0.8.
然而，相比于材料而言，有关镁锑基热电元器件的报道非常少。对于现在广泛应用在汽车空调座椅、环保型冰箱等方面的热电制冷器件，仍然使用的是传统的碲化铋基热电材料。碲化铋基热电材料与镁锑基热电材料相比成本过高，碲、铋等原料的价格远远高于镁锑等原料的价格。在高性能镁锑基热电材料被发现之前，碲化铋基热电材料在热电制冷器件方面的应用是无可替代的。但随着不断研究，镁锑基热电材料的性能也在不断的提高，在室温温区内已经可以和碲化铋基热电材料相当，这为镁锑基热电材料在制冷器件上的应用提供了基础和可能性。However, compared with materials, there are very few reports on magnesium-antimony-based thermoelectric components. For thermoelectric refrigeration devices that are now widely used in automotive air-conditioning seats, environmentally friendly refrigerators, etc., traditional bismuth telluride-based thermoelectric materials are still used. Compared with magnesium-antimony-based thermoelectric materials, the cost of bismuth telluride-based thermoelectric materials is too high, and the prices of raw materials such as tellurium and bismuth are much higher than those of raw materials such as magnesium and antimony. Before the discovery of high-performance magnesium-antimony-based thermoelectric materials, the application of bismuth telluride-based thermoelectric materials in thermoelectric refrigeration devices was irreplaceable. However, with continuous research, the performance of magnesium-antimony-based thermoelectric materials is also constantly improving, which can be comparable to bismuth telluride-based thermoelectric materials in the room temperature range, which provides the application of magnesium-antimony-based thermoelectric materials in refrigeration devices. Basics and possibilities.
实现镁锑基热电材料在热电器件中的应用，只有好的热电性能是远远不够的，还需要将这种热电材料制备成热电元器件，才能够将其进一步组装成 热电制冷***。制备热电元件的关键是开发出能与镁锑基热电材料相匹配的电极层。到目前为止，还没有关于与镁锑基热电材料相匹配的规模化电极层材料的报道。传统的电极材料(例如铝、银、铜、镍等)有的无法和镁锑基热电材料紧密结合，有的接触电阻过大，有的还会与材料基体发生反应。电极材料的制备困难影响了镁锑基热电材料在器件方面的进一步应用。To realize the application of magnesium-antimony-based thermoelectric materials in thermoelectric devices, only good thermoelectric performance is far from enough. It is also necessary to prepare such thermoelectric materials into thermoelectric components before they can be further assembled into thermoelectric refrigeration systems. The key to preparing thermoelectric elements is to develop an electrode layer that can be matched with magnesium-antimony-based thermoelectric materials. So far, there has been no report on a large-scale electrode layer material matched with magnesium-antimony-based thermoelectric materials. Some traditional electrode materials (such as aluminum, silver, copper, nickel, etc.) cannot be closely combined with magnesium-antimony-based thermoelectric materials, some have excessive contact resistance, and some will react with the material matrix. The difficulty of preparing electrode materials affects the further application of magnesium-antimony-based thermoelectric materials in devices.
因此，亟需开发一种与镁锑基热电材料相匹配的电极层和相应的制备方法，以实现镁锑基热电材料在热电器件中的应用，从而在保证室温温区内热电制冷性能的同时，降低热电制冷材料的成本，推动热电制冷产业的发展。Therefore, there is an urgent need to develop an electrode layer that matches the magnesium-antimony-based thermoelectric material and a corresponding preparation method to realize the application of magnesium-antimony-based thermoelectric materials in thermoelectric devices, so as to ensure the thermoelectric cooling performance in the room temperature range. , To reduce the cost of thermoelectric refrigeration materials, and promote the development of the thermoelectric refrigeration industry.
发明内容Summary of the invention
本发明的目的是针对现有技术存在的局限性和缺点，开发出适用于镁锑基热电材料的电极层，提供一种可以替代N型碲化铋的、基于镁锑基的热电元器件及其制备方法和应用，从而实现镁锑基热电材料在器件方面的应用、节约材料成本、提高经济效益。The purpose of the present invention is to develop an electrode layer suitable for magnesium-antimony-based thermoelectric materials in view of the limitations and shortcomings of the prior art, and provide a magnesium-antimony-based thermoelectric element and device that can replace N-type bismuth telluride and The preparation method and application thereof realize the application of magnesium-antimony-based thermoelectric materials in devices, save material costs, and improve economic benefits.
一方面，本发明提供了一种镁锑基热电元件，所述镁锑基热电元件包括：位于该热电元件中心的镁锑基热电材料基质层、附着在所述基质层的两个表面的过渡层以及分别附着在两个过渡层表面的两个电极层，其中，所述过渡层的材料为铜与钛和/或镁的合金，所述电极层的材料为铜和/或镍。In one aspect, the present invention provides a magnesium-antimony-based thermoelectric element. The magnesium-antimony-based thermoelectric element includes: a magnesium-antimony-based thermoelectric material matrix layer located in the center of the thermoelectric element, and a transition layer attached to two surfaces of the matrix layer. And two electrode layers respectively attached to the surfaces of the two transition layers, wherein the transition layer is made of an alloy of copper and titanium and/or magnesium, and the electrode layer is made of copper and/or nickel.
根据本发明提供的镁锑基热电元件，其中，其中，铜与钛和/或镁的合金包括铜-钛合金、铜-镁合金和铜-钛-镁合金。优选地，所述过渡层的材料为钛铜合金或镁铜合金。进一步优选地，所述钛铜合金的组成为TiCu
n，0≤n≤0.5，所述镁铜合金的组成为Mg
mCu，0.5≤m≤3。
According to the magnesium-antimony-based thermoelectric element provided by the present invention, wherein the alloy of copper and titanium and/or magnesium includes copper-titanium alloy, copper-magnesium alloy and copper-titanium-magnesium alloy. Preferably, the material of the transition layer is a titanium-copper alloy or a magnesium-copper alloy. Further preferably, the composition of the titanium-copper alloy is TiCu n , 0≦n≦0.5, and the composition of the magnesium-copper alloy is Mg m Cu, 0.5≦m≦3.
根据本发明提供的镁锑基热电元件，其中，所述镁锑基热电材料的组成为Mg
3.3-xZ
xBi
0.5Sb
1.5-yTe
y，其中，0≤x≤0.1，0.01≤y≤0.05，Z为选自Mn、Ni、Cr和Nb中的一种或多种元素。
According to the magnesium-antimony-based thermoelectric element provided by the present invention, the composition of the magnesium-antimony-based thermoelectric material is Mg 3.3-x Z x Bi 0.5 Sb 1.5-y Te y , where 0≤x≤0.1, 0.01≤y≤ 0.05, Z is one or more elements selected from Mn, Ni, Cr and Nb.
根据本发明提供的镁锑基热电元件，其中，所述基质层的厚度可以根据实际应用而进行调整，通常可以为0.5～2mm。所述过渡层的厚度可以为5～50nm，优选为5～20nm；所述电极层的厚度可以为0.5～10μm，优选为0.5～5μm。According to the magnesium-antimony-based thermoelectric element provided by the present invention, the thickness of the substrate layer can be adjusted according to actual applications, and usually can be 0.5-2 mm. The thickness of the transition layer may be 5-50 nm, preferably 5-20 nm; the thickness of the electrode layer may be 0.5-10 μm, preferably 0.5-5 μm.
根据本发明提供的镁锑基热电元件，其中，在所述基质层的上下两个表面上分别具有过渡层和电极层，位于上表面的过渡层的厚度与位于下表面的过渡层的厚度可以相同或不同；位于上表面的电极层的厚度与位于下 表面的电极层的厚度可以相同或不同。According to the magnesium-antimony-based thermoelectric element provided by the present invention, a transition layer and an electrode layer are respectively provided on the upper and lower surfaces of the substrate layer, and the thickness of the transition layer on the upper surface and the thickness of the transition layer on the lower surface can be Same or different; the thickness of the electrode layer on the upper surface and the thickness of the electrode layer on the lower surface can be the same or different.
另一方面，本发明还提供了所述镁锑基热电元件的制备方法，所述制备方法包括：通过离子束溅射和/或磁控溅射方法在所述镁锑基热电材料基质层的两个表面分别形成所述过渡层和电极层，制得所述镁锑基热电元件。On the other hand, the present invention also provides a method for preparing the magnesium-antimony-based thermoelectric element. The preparation method includes: forming a substrate layer of the magnesium-antimony-based thermoelectric material by ion beam sputtering and/or magnetron sputtering. The transition layer and the electrode layer are formed on the two surfaces respectively, and the magnesium antimony-based thermoelectric element is manufactured.
根据本发明提供的制备方法，其中，所述离子束溅射的方法可以包括：将所述镁锑基热电材料基质层固定在具有过渡层合金靶和电极层金属靶的离子束溅射仪中，先在所述基质层的一个表面沉积过渡层合金形成过渡层，再沉积电极层金属形成电极层；然后在所述基质层的另一个表面沉积过渡层合金形成过渡层，再沉积电极层金属形成电极层，制得所述镁锑基热电元件。According to the preparation method provided by the present invention, the ion beam sputtering method may include: fixing the magnesium antimony-based thermoelectric material matrix layer in an ion beam sputtering apparatus having a transition layer alloy target and an electrode layer metal target , First deposit a transition layer alloy on one surface of the matrix layer to form a transition layer, and then deposit electrode layer metal to form an electrode layer; then deposit a transition layer alloy on the other surface of the matrix layer to form a transition layer, and then deposit electrode layer metal An electrode layer is formed to prepare the magnesium-antimony-based thermoelectric element.
根据本发明提供的制备方法，在一种最优选的制备方案中，所述离子束溅射方法包括：首先把镁锑基热电材料基质层放入盛有酒精的烧杯中，用超声波清洗仪清洗5～10分钟，然后用电吹风或烘干装置进行干燥处理，处理完成后固定到具有过渡层合金靶和电极层金属靶的离子束溅射仪中，工作条件为：主源能量800～1000eV，束流60～100mA；辅源能量90～120eV，束流5～20mA，真空度小于2.4×10
-2Pa。通过离子束溅射形成过渡层，沉积时间为2～10分钟，继续沉积电极层金属60～210分钟，形成电极层；然后关闭仪器，开舱取出样品，把样品翻过来，重新固定样品，继续用同样的工艺在镁锑基热电材料基质层的另一个表面沉积过渡层和电极层。
According to the preparation method provided by the present invention, in a most preferred preparation scheme, the ion beam sputtering method includes: first putting the magnesium antimony-based thermoelectric material matrix layer into a beaker containing alcohol, and cleaning with an ultrasonic cleaner 5-10 minutes, then use a hair dryer or drying device for drying treatment, after the treatment is completed, it is fixed in an ion beam sputtering instrument with a transition layer alloy target and an electrode layer metal target. The working condition is: the main source energy is 800-1000eV , The beam current is 60-100mA; the auxiliary source energy is 90-120eV, the beam current is 5-20mA, and the vacuum degree is less than 2.4×10 -2 Pa. The transition layer is formed by ion beam sputtering, the deposition time is 2-10 minutes, and the electrode layer metal is deposited for 60-210 minutes to form the electrode layer; then close the instrument, open the chamber and take out the sample, turn the sample over, fix the sample again, and continue The transition layer and the electrode layer are deposited on the other surface of the magnesium-antimony-based thermoelectric material matrix layer using the same process.
所述磁控溅射方法可以包括：将所述镁锑基热电材料基质层固定在具有过渡层合金靶和电极层金属靶的磁控溅射仪中，先在所述基质层的一个表面沉积过渡层合金形成过渡层，再沉积电极层金属形成电极层；然后在所述基质层的另一个表面沉积过渡层合金形成过渡层，再沉积电极层金属形成电极层，制得所述镁锑基热电元件。The magnetron sputtering method may include: fixing the magnesium antimony-based thermoelectric material matrix layer in a magnetron sputtering apparatus having a transition layer alloy target and an electrode layer metal target, and first depositing on one surface of the matrix layer The transition layer alloy forms the transition layer, and then the electrode layer metal is deposited to form the electrode layer; then the transition layer alloy is deposited on the other surface of the matrix layer to form the transition layer, and the electrode layer metal is then deposited to form the electrode layer to obtain the magnesium antimony-based Thermoelectric element.
根据本发明提供的制备方法，在一种最优选的制备方案中，所述磁控溅射方法包括：首先把镁锑基热电材料基质层放入盛有酒精的烧杯中，用超声波清洗仪清洗5～10分钟，然后用电吹风或烘干装置进行干燥处理，处理完成后固定到具有过渡层合金靶和电极层金属靶的磁控溅射仪中，工作条件包括：抽真空至真空度小于0.00066Pa，将钛铜合金靶功率调至90～110W或者将镁铜合金靶功率调至70～80W，通过磁控溅射形成过渡层，沉积时间为2～20分钟，然后以90～110W的功率沉积20～60分钟电极层金属，形成电极层；然后关闭仪器，开舱取出样品，把样品翻过来，重新固 定样品，继续用同样的工艺在镁锑基热电材料基质层的另一个表面沉积过渡层和电极层。According to the preparation method provided by the present invention, in a most preferred preparation scheme, the magnetron sputtering method includes: firstly putting the magnesium antimony-based thermoelectric material matrix layer into a beaker containing alcohol, and cleaning with an ultrasonic cleaner 5-10 minutes, then use a hair dryer or a drying device for drying treatment. After the treatment is completed, it is fixed in a magnetron sputtering apparatus with a transition layer alloy target and an electrode layer metal target. The working conditions include: evacuating until the vacuum is less than 0.00066Pa, adjust the power of the titanium-copper alloy target to 90-110W or adjust the power of the magnesium-copper alloy target to 70-80W, form the transition layer by magnetron sputtering, the deposition time is 2-20 minutes, and then use the 90-110W Power deposition of the electrode layer metal for 20-60 minutes to form the electrode layer; then turn off the instrument, open the chamber, take out the sample, turn the sample over, fix the sample again, and continue to deposit on the other surface of the magnesium-antimony-based thermoelectric material matrix layer with the same process Transition layer and electrode layer.
其中，所述过渡层合金为铜与钛和/或镁的合金，包括铜-钛合金、铜-镁合金和铜-钛-镁合金。所述电极层金属为铜和/或镍。Wherein, the transition layer alloy is an alloy of copper, titanium and/or magnesium, including copper-titanium alloy, copper-magnesium alloy and copper-titanium-magnesium alloy. The electrode layer metal is copper and/or nickel.
在本发明一种优选的实施方案中，所述制备方法还包括制备过渡层合金靶的步骤：将金属粉按照化学式称量后球磨4～10小时，将粉末置于石墨模具中在放电等离子烧结设备中烧结，烧结的条件包括：以20～80℃/min的速度升至500～600℃进行烧结，烧结压力为30～50MPa，保温时间15～30分钟后随炉冷却，制得所需的过渡层合金靶。In a preferred embodiment of the present invention, the preparation method further includes the step of preparing a transition layer alloy target: the metal powder is weighed according to the chemical formula and then ball milled for 4-10 hours, and the powder is placed in a graphite mold for spark plasma sintering. Sintering in the equipment, sintering conditions include: sintering at a rate of 20-80°C/min to 500-600°C, sintering pressure of 30-50MPa, holding time of 15-30 minutes, and then cooling in the furnace to prepare the desired Transition layer alloy target.
例如，在一种具体的实施方案中，Mg
2Cu合金靶材的制备方法包括：将Mg屑和Cu粉按照化学式Mg
2Cu称量后球磨4～10小时，将粉末置于石墨模具中在放电等离子烧结设备中，烧结工艺为：以20～80℃/min的速度升至500～600℃进行烧结，烧结压力为30～50MPa，保温时间15～30分钟后随炉冷却，制得所需的Mg
2Cu靶材。
For example, in a specific embodiment, the preparation method of the Mg 2 Cu alloy target includes: weighing Mg chips and Cu powder according to the chemical formula Mg 2 Cu, ball milling for 4 to 10 hours, and placing the powder in a graphite mold. In the spark plasma sintering equipment, the sintering process is as follows: sintering is carried out at a rate of 20-80°C/min to 500-600°C, the sintering pressure is 30-50MPa, and the holding time is 15-30 minutes and then cooled with the furnace to prepare the required的Mg 2 Cu target.
再一方面，本发明还提供了一种热电制冷器件，所述热电制冷器件包括组装在一起的n型热电元件和p型碲化铋基热电元件，其中，所述n型热电元件为本发明提供的镁锑基热电元件。In yet another aspect, the present invention also provides a thermoelectric refrigeration device comprising an n-type thermoelectric element and a p-type bismuth telluride-based thermoelectric element assembled together, wherein the n-type thermoelectric element is of the present invention Supplied with magnesium-antimony-based thermoelectric elements.
其中，可以通过常规锡焊工艺将所述n型热电元件与p型碲化铋基热电元件组装在一起。利用此方法制备的由N型镁锑基热电材料和P型碲化铋搭配组成的热电元器件能够达到现有碲化铋基热电制冷元器件的性能，同时实现成本上的大幅降低。目前国际上鲜有这种热电元器件及制备方法的报道。Wherein, the n-type thermoelectric element and the p-type bismuth telluride-based thermoelectric element can be assembled together by a conventional soldering process. The thermoelectric components made up of N-type magnesium-antimony-based thermoelectric materials and P-type bismuth telluride prepared by this method can achieve the performance of existing bismuth telluride-based thermoelectric refrigeration components, and at the same time achieve a substantial reduction in cost. At present, there are few reports of such thermoelectric components and preparation methods in the world.
本发明开发出的能够适用于镁锑基热电材料的过渡层和电极层具有重要的应用意义和前景，此电极层使得镁锑基热电材料有机会进入市场，实现产业化成为可能。本发明制得的热电器件与市场上现有的碲化铋热电器件相比具有更低的成本，同时还能够节约稀有元素碲，对于节约能源，保护环境方面也是有益的。本发明提供的镁锑基热电材料元器件可以替代现有市场上的碲化铋基热电制冷器件，能够实现对现有商业化热电制冷器件成本上的一个新突破，在提升经济效益方面潜力巨大。The transition layer and electrode layer that can be applied to magnesium-antimony-based thermoelectric materials developed by the present invention have important application significance and prospects. The electrode layer enables magnesium-antimony-based thermoelectric materials to enter the market and realize industrialization. Compared with the existing bismuth telluride thermoelectric devices on the market, the thermoelectric device prepared by the invention has a lower cost, and can also save the rare element tellurium, which is also beneficial in terms of energy saving and environmental protection. The magnesium-antimony-based thermoelectric material components provided by the present invention can replace bismuth telluride-based thermoelectric refrigeration devices on the existing market, can realize a new breakthrough in the cost of existing commercial thermoelectric refrigeration devices, and have great potential for improving economic benefits .
附图的简要说明Brief description of the drawings
以下，结合附图来详细说明本发明的实施方案，其中：Hereinafter, the embodiments of the present invention will be described in detail with reference to the drawings, in which:
图1为本发明提供的镁锑基热电元件的示意图。Fig. 1 is a schematic diagram of a magnesium-antimony-based thermoelectric element provided by the present invention.
实施发明的最佳方式The best way to implement the invention
下面结合具体实施方式对本发明进行进一步的详细描述，给出的实施例仅为了阐明本发明，而不是为了限制本发明的范围。The present invention will be further described in detail below in conjunction with specific embodiments. The examples given are only to illustrate the present invention, not to limit the scope of the present invention.
本发明提供的镁锑基热电元件的示意图如图1所示。所述镁锑基热电元件包括：位于该热电元件中心的镁锑基热电材料基质层1、附着在所述基质层的两个表面的两个过渡层21和22以及分别附着在两个过渡层表面的两个电极层31和32。The schematic diagram of the magnesium-antimony-based thermoelectric element provided by the present invention is shown in FIG. 1. The magnesium-antimony-based thermoelectric element includes: a magnesium-antimony-based thermoelectric material matrix layer located in the center of the thermoelectric element 1, two transition layers 21 and 22 attached to two surfaces of the matrix layer, and two transition layers attached respectively Two electrode layers 31 and 32 on the surface.
实施例1Example 1
(1)将Mg屑、Mn粉、Bi颗粒、Sb颗粒、Te粉按照化学式Mg
3.275Mn
0.025Bi
0.5Sb
1.49Te
0.01称量后球磨12小时得到混合物粉末，通过放电等离子烧结成厚度1.2mm，直径12.7mm的圆柱状块体材料。烧结工艺为：升温速率50℃每分钟，600℃保温2分钟后再升温至800℃保温两分钟后随炉冷却，烧结过程中压力为50Mpa。
(1) Mg chips, Mn powder, Bi particles, Sb particles, and Te powder are weighed according to the chemical formula Mg 3.275 Mn 0.025 Bi 0.5 Sb 1.49 Te 0.01, then ball milled for 12 hours to obtain the mixture powder, which is sintered by spark plasma to a thickness of 1.2 mm and a diameter 12.7mm cylindrical block material. The sintering process is as follows: the heating rate is 50°C per minute, the temperature is kept at 600°C for 2 minutes, then the temperature is raised to 800°C for 2 minutes, and then cooled with the furnace. The pressure during the sintering process is 50Mpa.
(2)将步骤(1)制得的镁锑基热电材料基质层放入盛有酒精的烧杯中，用超声波清洗仪清洗5～10分钟，然后用电吹风或烘干装置进行干燥处理，处理完成后固定到含有铜靶、TiCu
0.3靶的离子束溅射仪中，工作条件为：主源能量900eV，束流80mA；辅源能量100eV，束流10mA，真空度小于2.4×10
-2Pa，通过离子束溅射形成TiCu
0.3的过渡层，共沉积5分钟后关掉TiCu
0.3靶，继续沉积铜层120分钟，形成电极层；然后关闭仪器，开舱取出样品，把样品翻过来，重新固定样品，继续用同样的工艺在镁锑基热电材料基质层的另一个表面沉积过渡层和电极层。过渡层厚度约为10nm，电极层厚度约为2μm。再将得到的样品切割成尺寸为1.45mm×1.45mm×1.20mm的小颗粒，即为本发明的镁锑基热电元件。
(2) Put the magnesium-antimony-based thermoelectric material matrix layer prepared in step (1) into a beaker containing alcohol, clean it with an ultrasonic cleaner for 5-10 minutes, and then dry it with a hair dryer or a drying device. After completion, it is fixed to an ion beam sputtering instrument containing a copper target and a TiCu 0.3 target. The working conditions are: the main source energy is 900eV, the beam current is 80mA; the auxiliary source energy is 100eV, the beam current is 10mA, and the vacuum degree is less than 2.4×10 -2 Pa , The transition layer of TiCu 0.3 is formed by ion beam sputtering. After 5 minutes of co-deposition, turn off the TiCu 0.3 target, continue to deposit the copper layer for 120 minutes to form the electrode layer; then turn off the instrument, open the chamber, take out the sample, turn the sample over, and re Fix the sample, and continue to use the same process to deposit a transition layer and an electrode layer on the other surface of the magnesium-antimony-based thermoelectric material matrix layer. The thickness of the transition layer is about 10 nm, and the thickness of the electrode layer is about 2 μm. Then the obtained sample is cut into small particles with a size of 1.45mm×1.45mm×1.20mm, which is the magnesium-antimony-based thermoelectric element of the present invention.
(3)将步骤(2)制得的镁锑基热电元件与尺寸为1.0mm×1.0mm×1.20mm的p型碲化铋基热电元件经过焊锡工艺组装制得127对热电臂制冷器件，通过12伏特直流电压后，冷热端能够产生50℃以上的温差，可以达到商业应用标准。(3) The magnesium-antimony-based thermoelectric element prepared in step (2) and the p-type bismuth telluride-based thermoelectric element with a size of 1.0mm×1.0mm×1.20mm are assembled through a soldering process to produce 127 pairs of thermoelectric arm refrigeration devices. After 12 volts DC voltage, the cold and hot ends can produce a temperature difference of more than 50 ℃, which can meet the commercial application standard.
实施例2Example 2
(1)将Mg屑、Mn粉、Bi颗粒、Sb颗粒、Te粉按照化学式Mg
3.275Mn
0.025Bi
0.5Sb
1.49Te
0.01称量后球磨12小时得到混合物粉末，通过放电等离子烧结成厚度1.2mm，直径12.7mm的圆柱状块体材料。烧结工艺为：升温速率50℃每分钟，600℃保温2分钟后再升温至800℃保温两分钟后随炉冷却，烧结过程中压力为50Mpa。
(1) Mg chips, Mn powder, Bi particles, Sb particles, and Te powder are weighed according to the chemical formula Mg 3.275 Mn 0.025 Bi 0.5 Sb 1.49 Te 0.01, and then ball milled for 12 hours to obtain a mixture powder, which is sintered by spark plasma to a thickness of 1.2 mm and a diameter. 12.7mm cylindrical block material. The sintering process is as follows: the heating rate is 50°C per minute, the temperature is kept at 600°C for 2 minutes, then the temperature is raised to 800°C for 2 minutes, and then cooled with the furnace. The pressure during the sintering process is 50Mpa.
(2)将步骤(1)制得的镁锑基热电材料基质层放入盛有酒精的烧杯中，用超声波清洗仪清洗5～10分钟，然后用电吹风或烘干装置进行干燥处理，处理完成后固定到含有Ni靶、TiCu
0.2靶的离子束溅射仪中，工作条件为：主源能量900eV，束流80mA；辅源能量100eV，束流10mA，真空度小于2.4×10
-2Pa，通过离子束溅射形成TiCu
0.2的过渡层，共沉积5分钟后关掉TiCu
0.2靶，继续沉积Ni层180分钟，形成电极层；然后关闭仪器，开舱取出样品，把样品翻过来，重新固定样品，继续用同样的工艺在镁锑基热电材料基质层的另一个表面沉积过渡层和电极层。过渡层厚度约为10nm，电极层厚度约为3μm。再将得到的样品切割成尺寸为1.45mm×1.45mm×1.20mm的小颗粒，即为本发明的镁锑基热电元件。
(2) Put the magnesium-antimony-based thermoelectric material matrix layer prepared in step (1) into a beaker containing alcohol, clean it with an ultrasonic cleaner for 5-10 minutes, and then dry it with a hair dryer or a drying device. After completion, it is fixed to an ion beam sputtering instrument containing Ni target and TiCu 0.2 target. The working conditions are: main source energy 900eV, beam current 80mA; auxiliary source energy 100eV, beam current 10mA, vacuum degree less than 2.4×10 -2 Pa , The transition layer of TiCu 0.2 is formed by ion beam sputtering. After 5 minutes of co-deposition, turn off the TiCu 0.2 target and continue to deposit the Ni layer for 180 minutes to form the electrode layer; then turn off the instrument, open the chamber, take out the sample, turn the sample over, and re Fix the sample, and continue to use the same process to deposit a transition layer and an electrode layer on the other surface of the magnesium-antimony-based thermoelectric material matrix layer. The thickness of the transition layer is about 10 nm, and the thickness of the electrode layer is about 3 μm. Then the obtained sample is cut into small particles with a size of 1.45mm×1.45mm×1.20mm, which is the magnesium-antimony-based thermoelectric element of the present invention.
(3)将步骤(2)制得的镁锑基热电元件与尺寸为1.0mm×1.0mm×1.20mm的p型碲化铋基热电元件经过焊锡工艺组装制得127对热电臂制冷器件，通过12伏特直流电压后，冷热端能够产生50℃以上的温差，可以达到商业应用标准。(3) The magnesium-antimony-based thermoelectric element prepared in step (2) and the p-type bismuth telluride-based thermoelectric element with a size of 1.0mm×1.0mm×1.20mm are assembled through a soldering process to produce 127 pairs of thermoelectric arm refrigeration devices. After 12 volts DC voltage, the cold and hot ends can produce a temperature difference of more than 50 ℃, which can meet the commercial application standard.
实施例3Example 3
(1)将Mg屑、Mn粉、Bi颗粒、Sb颗粒、Te粉按照化学式Mg
3.275Mn
0.025Bi
0.5Sb
1.49Te
0.01称量后球磨12小时得到混合物粉末，通过放电等离子烧结成厚度1.2mm，直径12.7mm的圆柱状块体镁锑基热电材料基质层。烧结工艺为：升温速率50℃每分钟，600℃保温2分钟后再升温至800℃保温两分钟后随炉冷却，烧结过程中压力为50Mpa。
(1) Mg chips, Mn powder, Bi particles, Sb particles, and Te powder are weighed according to the chemical formula Mg 3.275 Mn 0.025 Bi 0.5 Sb 1.49 Te 0.01, and then ball milled for 12 hours to obtain a mixture powder, which is sintered by spark plasma to a thickness of 1.2 mm and a diameter. 12.7mm cylindrical bulk magnesium-antimony-based thermoelectric material matrix layer. The sintering process is as follows: the heating rate is 50°C per minute, the temperature is kept at 600°C for 2 minutes, then the temperature is raised to 800°C for 2 minutes, and then cooled with the furnace. The pressure during the sintering process is 50Mpa.
(2)将Mg屑和Cu粉按照化学式Mg
2Cu称量后球磨6小时，将粉末置于石墨模具中在放电等离子烧结设备中，烧结工艺为：以每分钟50度的速度升至550度进行烧结，烧结压力为40MPa，保温时间20分钟后随炉冷却，制备出Mg
2Cu靶材。
(2) The Mg chips and Cu powder are weighed according to the chemical formula Mg 2 Cu and ball milled for 6 hours. The powder is placed in a graphite mold in the spark plasma sintering equipment. The sintering process is: 50 degrees per minute to 550 degrees Sintering was carried out, the sintering pressure was 40 MPa, the holding time was 20 minutes, and then the furnace was cooled to prepare the Mg 2 Cu target.
(3)将步骤(1)制得的镁锑基热电材料基质层放入盛满酒精的烧杯中， 用超声波清洗仪清洗20分钟，然后用电吹风或烘干装置进行干燥处理，然后固定到具有铜靶和步骤(2)制备的Mg
2Cu靶的磁控溅射仪中。抽真空至真空度小于0.00066Pa，先共沉积镁铜合金5分钟左右，功率调至100W左右，形成镁铜合金过渡层，之后关掉镁靶，继续沉积铜层，作为电极材料，功率调至75W左右，时间50分钟左右。铜层沉积完成后，关掉仪器，开舱取出样品，重新固定样品后，继续用同样的工艺在镁锑基热电材料基质层的另一个表面沉积过渡层和电极层。过渡层厚度为15nm，电极层厚度为3～4μm。再将得到的样品切割成尺寸为1.45mm×1.45mm×1.20mm的小颗粒，即为本发明的镁锑基热电元件。
(3) Put the magnesium-antimony-based thermoelectric material matrix layer prepared in step (1) into a beaker full of alcohol, clean it with an ultrasonic cleaner for 20 minutes, then dry it with a hair dryer or a drying device, and then fix it to In a magnetron sputtering apparatus with a copper target and the Mg 2 Cu target prepared in step (2). Evacuate until the vacuum degree is less than 0.00066Pa, first co-deposit magnesium-copper alloy for about 5 minutes, adjust the power to about 100W to form a magnesium-copper alloy transition layer, then turn off the magnesium target, continue to deposit the copper layer, as the electrode material, adjust the power to About 75W, the time is about 50 minutes. After the copper layer deposition is completed, turn off the instrument, open the chamber and take out the sample. After re-fixing the sample, continue to use the same process to deposit the transition layer and the electrode layer on the other surface of the magnesium-antimony-based thermoelectric material matrix layer. The thickness of the transition layer is 15 nm, and the thickness of the electrode layer is 3 to 4 μm. Then the obtained sample is cut into small particles with a size of 1.45mm×1.45mm×1.20mm, which is the magnesium-antimony-based thermoelectric element of the present invention.
(4)将步骤(3)制得的镁锑基热电元件与尺寸为1.0mm×1.0mm×1.20mm的p型碲化铋基热电元件经过焊锡工艺组装制得127对热电臂制冷器件，通过12伏特直流电压后，冷热端能够产生50℃以上的温差，可以达到商业应用标准。(4) The magnesium-antimony-based thermoelectric element prepared in step (3) and the p-type bismuth telluride-based thermoelectric element with a size of 1.0mm×1.0mm×1.20mm are assembled through a soldering process to produce 127 pairs of thermoelectric arm refrigeration devices. After 12 volts DC voltage, the cold and hot ends can produce a temperature difference of more than 50 ℃, which can meet the commercial application standard.
虽然已经说明并描述了本发明的具体实施方案，但是对本领域技术人员显而易见的是，在不背离本发明的精神和范围的前提下，可作出各种其它变化和修改。因此，在所附权利要求中，意图涵盖在本发明的范围内的所有这样的变化和修改。Although the specific embodiments of the present invention have been illustrated and described, it is obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the present invention. Therefore, in the appended claims, it is intended to cover all such changes and modifications within the scope of the present invention.
Claims (11)
- 一种镁锑基热电元件，所述镁锑基热电元件包括：位于该热电元件中心的镁锑基热电材料基质层、附着在所述基质层的两个表面的过渡层以及分别附着在两个过渡层表面的两个电极层，其中，所述过渡层的材料为铜与钛和/或镁的合金，所述电极层的材料为铜和/或镍。A magnesium-antimony-based thermoelectric element, the magnesium-antimony-based thermoelectric element comprising: a magnesium-antimony-based thermoelectric material matrix layer located in the center of the thermoelectric element, a transition layer attached to two surfaces of the matrix layer, and two Two electrode layers on the surface of the transition layer, wherein the material of the transition layer is an alloy of copper and titanium and/or magnesium, and the material of the electrode layer is copper and/or nickel.
- 根据权利要求1所述的镁锑基热电元件，其中，所述过渡层的材料为钛铜合金或镁铜合金，优选地，所述钛铜合金的组成为TiCu n，0≤n≤0.5，所述镁铜合金的组成为Mg mCu，0.5≤m≤3。 The magnesium-antimony-based thermoelectric element according to claim 1, wherein the material of the transition layer is a titanium-copper alloy or a magnesium-copper alloy, preferably, the composition of the titanium-copper alloy is TiCu n , 0≤n≤0.5, The composition of the magnesium-copper alloy is Mg m Cu, 0.5≤m≤3.
- 根据权利要求1或2所述的镁锑基热电元件，其中，所述镁锑基热电材料的组成为Mg 3.3-xZ xBi 0.5Sb 1.5-yTe y，其中，0≤x≤0.1，0.01≤y≤0.05，Z为选自Mn、Ni、Cr和Nb中的一种或多种元素。 The magnesium-antimony-based thermoelectric element according to claim 1 or 2, wherein the composition of the magnesium-antimony-based thermoelectric material is Mg 3.3-x Z x Bi 0.5 Sb 1.5-y Te y , wherein 0≤x≤0.1, 0.01≤y≤0.05, Z is one or more elements selected from Mn, Ni, Cr and Nb.
- 根据权利要求1至3中任一项所述的镁锑基热电元件，其中，所述基质层的厚度为0.5～2mm。The magnesium-antimony-based thermoelectric element according to any one of claims 1 to 3, wherein the thickness of the substrate layer is 0.5-2 mm.
- [根据细则91更正 27.08.2020]
根据权利要求1至4中任一项所述的镁锑基热电元件，其中，所述过渡层的厚度为5～50nm，优选为5～20nm；所述电极层的厚度为0.5～10μm，优选为0.5～5μm。 [Corrected according to Rule 91 27.08.2020]
The magnesium-antimony-based thermoelectric element according to any one of claims 1 to 4, wherein the thickness of the transition layer is 5-50nm, preferably 5-20nm; the thickness of the electrode layer is 0.5-10μm, preferably It is 0.5～5μm. - [根据细则91更正 27.08.2020]
权利要求1至5中任一项所述的镁锑基热电元件的制备方法，所述制备方法包括：通过离子束溅射和/或磁控溅射方法在所述镁锑基热电材料基质层的两个表面分别形成所述过渡层和电极层，制得所述镁锑基热电元件。 [Corrected according to Rule 91 27.08.2020]
The preparation method of magnesium antimony-based thermoelectric element according to any one of claims 1 to 5, said preparation method comprising: applying ion beam sputtering and/or magnetron sputtering method on said magnesium antimony-based thermoelectric material matrix layer The transition layer and the electrode layer are formed on the two surfaces of, respectively, to prepare the magnesium-antimony-based thermoelectric element. - [根据细则91更正 27.08.2020]
根据权利要求6所述的制备方法，其中，所述离子束溅射的方法包括：将所述镁锑基热电材料基质层固定在具有过渡层合金靶和电极层金属靶的离子束溅射仪中，先在所述基质层的一个表面沉积过渡层合金形成过渡层，再沉积电极层金属形成电极层；然后在所述基质层的另一个表面沉积过渡层合金形成过渡层，再沉积电极层金属形成电极层，制得所述镁锑基热电元件。 [Corrected according to Rule 91 27.08.2020]
The preparation method according to claim 6, wherein the ion beam sputtering method comprises: fixing the magnesium antimony-based thermoelectric material matrix layer on an ion beam sputtering apparatus having a transition layer alloy target and an electrode layer metal target In the process, a transition layer alloy is deposited on one surface of the matrix layer to form a transition layer, and then an electrode layer metal is deposited to form an electrode layer; then a transition layer alloy is deposited on the other surface of the matrix layer to form a transition layer, and then an electrode layer is deposited The metal forms the electrode layer to prepare the magnesium-antimony-based thermoelectric element. - [根据细则91更正 27.08.2020]
根据权利要求6所述的制备方法，其中，所述磁控溅射方法包括：将所述镁锑基热电材料基质层固定在具有过渡层合金靶和电极层金属靶的磁控溅射仪中，先在所述基质层的一个表面沉积过渡层合金形成过渡层，再沉积电极层金属形成电极层；然后在所述基质层的另一个表面沉积过渡层合金形成过渡层，再沉积电极层金属形成电极层，制得所述镁锑基热电元件. [Corrected according to Rule 91 27.08.2020]
The preparation method according to claim 6, wherein the magnetron sputtering method comprises: fixing the magnesium antimony-based thermoelectric material matrix layer in a magnetron sputtering apparatus having a transition layer alloy target and an electrode layer metal target , First deposit a transition layer alloy on one surface of the matrix layer to form a transition layer, and then deposit electrode layer metal to form an electrode layer; then deposit a transition layer alloy on the other surface of the matrix layer to form a transition layer, and then deposit electrode layer metal An electrode layer is formed to obtain the magnesium-antimony-based thermoelectric element. - [根据细则91更正 27.08.2020]
根据权利要求7或8所述的制备方法，其中，所述离子束溅射仪的工作条件包括：主源能量800～1000eV，束流60～100mA；辅源能量90～120eV，束流5～20mA，真空度小于2.4×10 -2Pa；优选地，过渡层的沉积时间为2～10分钟，电极层的沉积时间为60～210分钟；优选地，所述磁控溅射仪的工作条件包括：真空度小于0.00066Pa，钛铜合金靶功率为90～110W或者镁铜合金靶功率为70～80W；优选地，过渡层的沉积时间为2～20分钟，电极层的沉积功率为90～110W，时间为20～60分钟。[Corrected according to Rule 91 27.08.2020]
The preparation method according to claim 7 or 8, wherein the working conditions of the ion beam sputtering instrument include: main source energy 800~1000eV, beam current 60-100mA; auxiliary source energy 90~120eV, beam current 5~ 20mA, the degree of vacuum is less than 2.4×10 -2 Pa; preferably, the deposition time of the transition layer is 2-10 minutes, and the deposition time of the electrode layer is 60-210 minutes;Preferably, the working conditions of the magnetron sputtering apparatus include: a vacuum degree of less than 0.00066 Pa, a titanium-copper alloy target power of 90-110W, or a magnesium-copper alloy target power of 70-80W; preferably, the deposition time of the transition layer is 2-20 minutes, the deposition power of the electrode layer is 90-110W, and the time is 20-60 minutes. - [根据细则91更正 27.08.2020]
根据权利要求9所述的制备方法，其中，所述制备方法还包括制备过渡层合金靶的步骤：将金属粉按照化学式称量后球磨4～10小时，将粉末置于石墨模具中在放电等离子烧结设备中烧结，烧结的条件包括：以20～80℃/min的速度升至500～600℃进行烧结，烧结压力为30～50MPa，保温时间15～30分钟后随炉冷却，制得所需的过渡层合金靶。 [Corrected according to Rule 91 27.08.2020]
The preparation method according to claim 9, wherein the preparation method further comprises the step of preparing a transition layer alloy target: weighing the metal powder according to the chemical formula and ball milling for 4-10 hours, placing the powder in a graphite mold in the discharge plasma Sintering in the sintering equipment, the sintering conditions include: sintering at a rate of 20-80°C/min to 500-600°C, sintering pressure of 30-50MPa, holding time 15-30 minutes, and then cooling with the furnace to prepare the desired The transition layer alloy target. - [根据细则91更正 27.08.2020]
一种热电制冷器件，所述热电制冷器件包括组装在一起的n型热电元件和p型碲化铋基热电元件，其中，所述n型热电元件为权利要求1至5中任一项所述的镁锑基热电元件或者按照权利要求6至10中任一项所述方法制得的镁锑基热电元件。 [Corrected according to Rule 91 27.08.2020]
A thermoelectric refrigeration device comprising an n-type thermoelectric element and a p-type bismuth telluride-based thermoelectric element assembled together, wherein the n-type thermoelectric element is any one of claims 1 to 5 A magnesium-antimony-based thermoelectric element or a magnesium-antimony-based thermoelectric element made according to any one of claims 6 to 10.
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