WO2024060114A1 - Mg-sb-based thermoelectric device comprising high-entropy thermoelectric interface material, and preparation method - Google Patents

Mg-sb-based thermoelectric device comprising high-entropy thermoelectric interface material, and preparation method Download PDF

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WO2024060114A1
WO2024060114A1 PCT/CN2022/120435 CN2022120435W WO2024060114A1 WO 2024060114 A1 WO2024060114 A1 WO 2024060114A1 CN 2022120435 W CN2022120435 W CN 2022120435W WO 2024060114 A1 WO2024060114 A1 WO 2024060114A1
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thermoelectric
preparation
conversion material
interface
thermoelectric conversion
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PCT/CN2022/120435
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French (fr)
Chinese (zh)
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刘玮书
吴新志
韩志佳
朱康
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南方科技大学
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Priority to CN202280008446.1A priority Critical patent/CN116889123A/en
Priority to PCT/CN2022/120435 priority patent/WO2024060114A1/en
Publication of WO2024060114A1 publication Critical patent/WO2024060114A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/81—Structural details of the junction
    • H10N10/817—Structural details of the junction the junction being non-separable, e.g. being cemented, sintered or soldered
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur

Definitions

  • the invention relates to the field of inorganic bulk thermoelectric technology, and specifically to a Mg-Sb-based thermoelectric device containing a high-entropy thermoelectric interface material and a preparation method.
  • thermoelectric conversion technology is a green technology that can directly convert waste heat into electrical energy. With the rapid development of the Internet of Things, a large number of sensors and wearable devices must operate independently and continuously. Thermoelectric conversion technology provides an effective solution for self-power supply of micro devices.
  • thermoelectric devices are usually assembled by brazing or soldering. Most thermoelectric materials exhibit poor solderability due to their semiconducting properties. Therefore, between the thermoelectric material and the electrode, a metallization layer is required to achieve reliable bonding.
  • a Ni layer of 3 to 10 ⁇ m is usually used to improve solderability. Nonetheless, in relatively high-temperature working environments, poor interface thermal stability will not only increase contact resistivity, but even lead to mechanical failure of the device.
  • thermoelectric interface material TiM
  • thermoelectric conversion material TcM
  • the traditional single-leg thermoelectric device is composed of TEiM and TEcM, that is A sandwich structure with TEcM in the middle and TEiM at both ends.
  • Existing thermoelectric devices have poor performance, mainly including low shear strength and poor high-temperature stability. After serving at high temperatures for a certain period of time, the shear strength decreases significantly and the contact resistivity increases significantly.
  • thermoelectric device containing a high-entropy thermoelectric interface material, including a thermoelectric conversion material and a thermoelectric interface material, and the thermoelectric interface material is compounded to at least part of the surface of the thermoelectric conversion material,
  • thermoelectric device according to any one of the first aspects, including:
  • thermoelectric interface material is compounded to at least part of the surface of the thermoelectric conversion material and sintered to obtain the thermoelectric device.
  • a wearable device including the thermoelectric device of any one of the first aspect, or the thermoelectric interface material of any one of the third aspect.
  • thermoelectric device including the thermoelectric device according to any one of the first aspect, or the thermoelectric interface material according to any one of the third aspects.
  • the Fe a Ti b Cr c Mn d Mg e /TEcM contact interface not only has excellent comprehensive performance after synthesis, but also After serving for 15 days at 400°C, it still has high shear strength (>30MPa) and low contact resistivity ( ⁇ 10 ⁇ *cm 2 ).
  • Figure 1 shows (a) shear strength and (a) contact resistivity of TEiM/TEcM interface.
  • Figure 2 shows the thermal expansion coefficients of different TEiM and TEcM.
  • Figure 3 shows the thermal stability of the TEiM/TEcM contact interface after service at 400°C (1, 3, 7, and 15 days).
  • Figure 4 shows the in-situ transmission electron microscope image and energy spectrum analysis of the TEiM/TEcM interface.
  • Figure 5 is a statistical diagram of the contact resistivity of each elemental TEiM material.
  • Figure 6 shows the scanning electron microscope and micromorphology picture (Ni).
  • Figure 7 shows the scanning electron microscope and micromorphology picture (Al).
  • Figure 8 shows the scanning electron microscope and micromorphology picture (Cu).
  • Figure 9 is a diagram showing the shear strength between different single metal elements and TEcM blocks.
  • Figure 10 shows the scanning electron microscope and micromorphology picture (Fe 7 Mg 3 ).
  • Figure 11 shows the scanning electron microscope and micromorphology picture (Fe 7 Mg 2 Co).
  • thermoelectric device containing a high-entropy thermoelectric interface material, including a thermoelectric conversion material and a thermoelectric interface material.
  • the thermoelectric interface material is compounded to at least part of the surface of the thermoelectric conversion material.
  • thermoelectric conversion material includes n-type thermoelectric conversion material or p-type thermoelectric conversion material.
  • thermoelectric conversion material includes an n-type thermoelectric conversion material.
  • thermoelectric conversion material includes Mg-Sb based thermoelectric conversion material.
  • thermoelectric conversion material includes an n-type Mg-Sb based thermoelectric conversion material.
  • the oxygen group element includes S, Se or Te.
  • the thickness of the thermoelectric conversion material may be 3-4 mm.
  • the thickness of the thermoelectric interface material layer may be 1 to 1.5 mm.
  • thermoelectric device includes a single leg thermoelectric device.
  • the single-leg thermoelectric device includes a thermoelectric conversion material and a thermoelectric interface material compounded to the upper surface and lower surface of the thermoelectric conversion material.
  • thermoelectric interface material is compounded to at least part of the surface of the thermoelectric conversion material through sintering.
  • thermoelectric device according to any one of the first aspects, including:
  • thermoelectric interface material is compounded onto at least a portion of the surface of the thermoelectric conversion material, and sintered to obtain a thermoelectric device.
  • sintering includes spark plasma sintering.
  • sintering is performed at 500-800°C and 30-60MPa axial pressure.
  • the sintering time is 5 to 10 minutes.
  • the heating rate to the sintering temperature is 50 to 100°C*min -1 .
  • the temperature is raised from room temperature to sintering temperature.
  • the preparation method of the thermoelectric conversion material includes: mixing raw materials according to the proportion, ball milling under the protection of inert gas, and then sintering by discharge plasma under 500-800°C, 5-10 min, and 30-60 MPa axial pressure. sintered into blocks.
  • a method for preparing a thermoelectric interface material includes: mixing raw materials according to a proportion, and ball milling under the protection of an inert gas to obtain an alloy powder, which is a thermoelectric interface material.
  • the raw materials used to prepare the thermoelectric conversion material and the thermoelectric interface material are all single raw materials.
  • the particle size of each elemental raw material is 100-300 mesh, and the purity is greater than 98%.
  • inert gases include but are not limited to nitrogen (N 2 ), helium (He), neon (Ne), argon (Ar), and krypton (Kr). ), at least one of xenon (Xe).
  • a wearable device including the thermoelectric device of any one of the first aspect, or the thermoelectric interface material of any one of the third aspect.
  • thermoelectric device including the thermoelectric device according to any one of the first aspect, or the thermoelectric interface material according to any one of the third aspects.
  • a class of high-entropy thermoelectric interface materials for Mg 3 Sb 2 -based thermoelectric devices is provided.
  • the present invention designs a new high-entropy TEiM. Thermoelectric devices using this series of TEiM have low contact resistivity, high bonding strength and excellent thermal stability.
  • Mechanical alloying method refers to the long-term intense impact and collision of metal or alloy powder between powder particles and grinding balls in a high-energy ball mill, causing the powder particles to repeatedly undergo cold welding and fracture, resulting in the diffusion of atoms in the powder particles, thereby obtaining the alloy.
  • a powder preparation method of chemical powder is described below.
  • the preparation method of the TEiM/TEcM interface includes: passing the high-energy ball-milled TEiM powder and the discharge plasma-sintered TEcM block under 500-800°C, 5-10 min, and 30-60 MPa axial pressure.
  • the spark plasma sintering method is used to diffuse and sinter into blocks to form TEiM/TEcM contact interface.
  • the heating rate during the sintering process is 50 ⁇ 100°C*min -1 .
  • the thicknesses of the TEcM block and TEiM layer are designed to be 3 to 4 mm and 1 to 1.5 mm respectively.
  • the obtained sample is a layered composite interface structure (TEiM/TEcM/TEiM).
  • the Fe a Ti b Cr c Mn d Mg e /TEcM contact interface not only has excellent comprehensive properties after synthesis, but also has high shear strength (>30MPa) and low Contact resistivity ( ⁇ 10 ⁇ *cm 2 ).
  • the TEiM designed for n-type Mg 3 Sb 2- based thermoelectric materials in the present invention has the best comprehensive performance in the industry and improves the practicality of Mg 3 Sb 2 -based thermoelectric materials.
  • thermoelectric device with high interface bonding strength and low interface contact resistance is provided, which can be applied to the self-powered system of the Internet of Things.
  • TEcM and TEiM are prepared using elemental raw materials.
  • the particle size of each elemental raw material is 100-300 mesh, and the purity is greater than 98%.
  • Mg chips purity greater than 99.9%, manufacturer: AcrosOrganics
  • Mn powder 200 mesh, purity 99.5%, manufacturer: Alfa;
  • the preparation method of TEcM is as follows: weigh each elemental raw material according to the designed proportion, and then perform high-energy ball milling (stainless steel ball, diameter 10mm) under argon protection for 8 hours.
  • the TEcM powder obtained after ball milling is heated at 675°C for 5 minutes. , sintered into blocks by spark plasma sintering method under 50MPa axial pressure.
  • the preparation method of TEiM is as follows: weigh each elemental raw material according to the designed proportion, use mechanical alloying method, and obtain alloy powder by high-energy ball milling (stainless steel ball, diameter 10mm) under argon protection for 1 to 2 hours.
  • the preparation method of the TEiM/TEcM interface is as follows: first, the sample is loaded. Specifically, TEiM powder is spread in a graphite mold, that is, spread on the upper and lower surfaces of the TEcM block to form a sandwich-like structure, and then discharge plasma sintering is performed.
  • the TEiM powder and TEcM bulk were formed into a TEiM/TEcM contact interface by spark plasma sintering at 600°C, 10 min, and 30 MPa axial pressure.
  • the heating rate during the sintering process is 100°C*min -1 .
  • the thickness of TEcM bulk and TEiM layer are designed to be 4mm and 1.5mm respectively.
  • the chemical formula of TEcM is as follows: Mg 3.2 Mn 0.01 Sb 1.5 Bi 0.45 Te 0.01 and the chemical formula of TEiM is as follows: FeTiCrMnMg.
  • the FeTiCrMnMg/Mg 3.2 Mn 0.01 Sb 1.5 Bi 0.45 Te 0.01 contact interface is prepared according to the above method.
  • TEcM block Mg 3.2 Mn 0.01 Sb 1.5 Bi 0.45 Te 0.01
  • TEiM 304 stainless steel (304SS)
  • 304SS 304 stainless steel
  • TEcM bulk Mg 3.2 Mn 0.01 Sb 1.5 Bi 0.45 Te 0.01
  • TEiM Fe 7 Mg 2 Ti
  • the Fe 7 Mg 2 Ti/Mg 3.2 Mn 0.01 Sb 1.5 Bi 0.45 Te 0.01 contact interface was prepared by referring to the method of Example 1.
  • TEiM was replaced with Fe 7 Mg 2 Cr, Fe 7 Mg 3 , Mg, Fe, Ni, Cu, Al, Ag, Zn, and Ti respectively.
  • the shear strength and contact resistivity between the high-entropy thermoelectric interface material (TEiM) and the thermoelectric conversion material (TEcM) selected in Example 1 are at ideal levels. As shown in Figure 1, the bonding strength between FeTiCrMnMg and TEcM is in the range of 30 to 35MPa. Contact resistivity is below 5 ⁇ * cm2 . It can be seen that the industry standard is ⁇ 10 ⁇ *cm 2 , and the contact resistivity of the FeTiCrMnMg/Mg 3.2 Mn 0.01 Sb 1.5 Bi 0.45 Te 0.01 contact interface prepared in Example 1 is lower than 1 ⁇ *cm 2 , which is far lower than the industry standard requirement. Has extremely low contact resistivity.
  • the thermal expansion coefficient is an important parameter to measure the degree of strain of a material at different temperatures. This parameter is of great significance for the selection of thermoelectric interface materials. As shown in Figure 2, the thermal expansion of FeTiCrMnMg is closest to TEcM, which shows that in the high temperature range, the FeTiCrMnMg/TEcM interface is subject to less thermal stress than the 304SS/TEcM and Fe 7 Mg 2 Ti/TEcM interfaces, which is conducive to the organization of interface cracks. occurrence, improving the bonding strength and high temperature stability of the interface.
  • Vacuum sealed tubes are used to simulate high temperature environments and the materials are heat treated. Place the interface in a quartz tube and evacuate it. After the vacuum reaches 10 -3 Pa, use a flame gun to seal the quartz tube. Then place the quartz tube in a muffle furnace and raise the temperature at a heating rate of 5°C/min. to 400°C and kept for different times to simulate the real service environment of the device. As shown in Figure 3, according to the slope of the interface shear strength and contact resistivity changing with time, it can be seen that at different service times at 400°C, the FeTiCrMnMg/TEcM interface shear strength has the smallest change with time, indicating that this high-entropy thermoelectric interface Materials are most conducive to improving the thermal stability of the interface.
  • the FeTiCrMnMg/TEcM interface shear strength only decreased from 37Mpa to 35Mpa, and the FeTiCrMnMg/TEcM interface contact resistance The rate only increases from 4 ⁇ *cm 2 to 7 ⁇ *cm 2 .
  • the contact interface still meets the industry requirements of bonding strength >30Mpa and contact resistivity ⁇ 10 ⁇ * cm2 . This is the most competitive interface stability performance in the industry. ⁇
  • thermoelectric devices depends largely on the interfacial contact between the thermoelectric material and the electrodes.
  • the shear strength of the contact interface is >30MPa, and the contact resistivity is ⁇ 10 ⁇ *cm 2 .
  • Figure 5 is a statistical diagram of the contact resistivity of each elemental TEiM material. It can be seen that the contact resistivity of each element is much higher than that of FeCrTiMnMg in Example 1 (contact resistivity ⁇ 10 ⁇ *cm 2 ).
  • Figure 6 shows the scanning electron microscope and micromorphology picture (Ni). It can be seen that the Ni bonding strength is low and a brittle phase is generated due to diffusion at the interface.
  • Figure 7 shows the scanning electron microscope and micromorphology image (Al). It can be seen that the Al bonding strength is low, and cracks occur due to the significant diffusion of thermoelectric materials into the interior of TEiM.
  • Figure 8 shows the scanning electron microscope and micromorphology (Cu). It can be seen that although Cu has higher bonding strength, the interface diffusion is more intense and the interface resistance is large.
  • Figure 9 is a diagram of the shear strength between different single metal elements and TEcM blocks. This figure shows the experimental results of bonding of most transition metals. Indicates that it cannot be bonded, and the rest are the bonding strengths of different metals. It can be seen that Ni, Fe, Zn, Ti, Mg, Al, Ag, and Cu successfully bonded to the TEcM block, and the bonding strength was about 5 to 45 MPa. However, metals with higher melting points (Tm), such as V, Nb, Cr, Mo, W, Mn, and Co, could not bond to the TEcM block.
  • Tm melting points
  • Figure 10 shows the scanning electron microscope and micromorphology (Fe 7 Mg 3 ). It can be seen that the bonding strength of Fe 7 Mg 3 is low. After testing, the shear strength of the contact interface is ⁇ 30MPa.
  • Figure 11 shows the scanning electron microscope and micromorphology (Fe 7 Mg 2 Co). It can be seen that the bonding strength of Fe 7 Mg 2 Co is low. After testing, the shear strength of the contact interface is ⁇ 30MPa.

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Abstract

An Mg-Sb-based thermoelectric device comprising a high-entropy thermoelectric interface material, and a preparation method. The thermoelectric device comprises a thermoelectric conversion material and a thermoelectric interface material. The thermoelectric interface material is compounded onto at least part of the surface of the thermoelectric conversion material; and the thermoelectric interface material comprises the following chemical general formula: FeaTibCrcMndMge, where a = 0.5-1.5; b = 0.5-1.5; c = 0.5-1.5; d = 0.5-1.5; and e = 0.5-1.5. The FeaTibCrcMndMge/TEcM contact interface not only has superior comprehensive performance after synthesis, but also still has a high shear strength (> 30 MPa) and a low contact resistance (< 10 μΩ*cm2) after 15 days of service at 400ºC.

Description

含高熵热电界面材料的Mg-Sb基热电器件及制备方法Mg-Sb-based thermoelectric devices containing high-entropy thermoelectric interface materials and preparation methods 技术领域Technical field
本发明涉及无机块体热电技术领域，具体涉及一种含高熵热电界面材料的Mg-Sb基热电器件及制备方法。The invention relates to the field of inorganic bulk thermoelectric technology, and specifically to a Mg-Sb-based thermoelectric device containing a high-entropy thermoelectric interface material and a preparation method.
背景技术Background technique
热电转换技术是一种能将废热与电能直接转换的绿色技术。随着物联网的快速发展，大量传感器与可穿戴设备必须独立持续运行，热电转换技术为微型器件的自供能提供了一种有效地解决方案。然而，热电器件的组装和可靠性仍然存在问题，特别是热电材料与电极之间的接触界面。目前，热电器件的组装通常采用钎焊或者锡焊的方式。大多数热电材料由于其半导体性质呈现出较差的焊接性。因此，在热电材料和电极之间，需要金属化层来实现可靠结合。在现有Bi 2Te 3基热电器件中，通常采用3～10μm的Ni层来提高可焊性。尽管如此，在相对高温的工作环境中，较差的界面热稳定性不仅会增加接触电阻率，甚至导致器件发生机械失效。 Thermoelectric conversion technology is a green technology that can directly convert waste heat into electrical energy. With the rapid development of the Internet of Things, a large number of sensors and wearable devices must operate independently and continuously. Thermoelectric conversion technology provides an effective solution for self-power supply of micro devices. However, there are still issues with the assembly and reliability of thermoelectric devices, especially the contact interface between the thermoelectric material and the electrodes. At present, thermoelectric devices are usually assembled by brazing or soldering. Most thermoelectric materials exhibit poor solderability due to their semiconducting properties. Therefore, between the thermoelectric material and the electrode, a metallization layer is required to achieve reliable bonding. In existing Bi 2 Te 3- based thermoelectric devices, a Ni layer of 3 to 10 μm is usually used to improve solderability. Nonetheless, in relatively high-temperature working environments, poor interface thermal stability will not only increase contact resistivity, but even lead to mechanical failure of the device.
金属化层的设计是获得高效热电器件的关键。为了对热电器件各部件分类，本文将金属化层定义为热电界面材料(TEiM)，而将狭义的热电材料定义为热电转换材料(TEcM)，传统的单腿热电器件由TEiM以及TEcM构成，即中间为TEcM两端为TEiM的三明治结构。现有的热电器件性能欠佳，主要包括抗剪强度低，高温稳定性差，在高温下服役一定时间后，抗剪强度显著下降，接触电阻率显著升高。The design of metallization layers is key to obtaining efficient thermoelectric devices. In order to classify the components of thermoelectric devices, this article defines the metallization layer as thermoelectric interface material (TEiM), and defines the thermoelectric material in a narrow sense as thermoelectric conversion material (TEcM). The traditional single-leg thermoelectric device is composed of TEiM and TEcM, that is A sandwich structure with TEcM in the middle and TEiM at both ends. Existing thermoelectric devices have poor performance, mainly including low shear strength and poor high-temperature stability. After serving at high temperatures for a certain period of time, the shear strength decreases significantly and the contact resistivity increases significantly.
发明内容Summary of the invention
根据第一方面，在一实施例中，提供一种含高熵热电界面材料的热电器件，包括热电转换材料、热电界面材料，所述热电界面材料复合至所述热电转换材料的至少部分表面，所述热电界面材料包含如下化学通式：Fe aTi bCr cMn dMg e，a＝0.5～1.5；b＝0.5～1.5；c＝0.5～1.5；d＝0.5～1.5；e＝0.5～1.5。 According to the first aspect, in one embodiment, a thermoelectric device containing a high-entropy thermoelectric interface material is provided, including a thermoelectric conversion material and a thermoelectric interface material, and the thermoelectric interface material is compounded to at least part of the surface of the thermoelectric conversion material, The thermoelectric interface material includes the following general chemical formula: Fe a Ti b Cr c Mn d Mg e , a=0.5～1.5; b=0.5～1.5; c=0.5～1.5; d=0.5～1.5; e=0.5～ 1.5.
根据第二方面，在一实施例中，提供第一方面任意一项的热电器件的制备方法，包括：According to the second aspect, in one embodiment, a method for manufacturing a thermoelectric device according to any one of the first aspects is provided, including:
将热电界面材料复合至热电转换材料的至少部分表面，烧结，得到所述热电器件。The thermoelectric interface material is compounded to at least part of the surface of the thermoelectric conversion material and sintered to obtain the thermoelectric device.
根据第三方面，在一实施例中，提供一种热电界面材料，所述热电界面材料包含如下化学通式：Fe aTi bCr cMn dMg e，a＝0.5～1.5；b＝0.5～1.5；c＝0.5～1.5；d＝0.5～1.5；e＝0.5～1.5。 According to the third aspect, in one embodiment, a thermoelectric interface material is provided, and the thermoelectric interface material includes the following general chemical formula: Fe a Ti b Cr c Mn d Mg e , a=0.5～1.5; b=0.5～ 1.5; c=0.5～1.5; d=0.5～1.5; e=0.5～1.5.
根据第四方面，在一实施例中，提供一种可穿戴设备，包含第一方面任意一项的热电器件，或第三方面任意一项的热电界面材料。According to the fourth aspect, in an embodiment, a wearable device is provided, including the thermoelectric device of any one of the first aspect, or the thermoelectric interface material of any one of the third aspect.
根据第五方面，在一实施例中，提供一种传感器，包含第一方面任意一项的热电器件，或第三方面任意一项的热电界面材料。According to the fifth aspect, in one embodiment, a sensor is provided, including the thermoelectric device according to any one of the first aspect, or the thermoelectric interface material according to any one of the third aspects.
依据上述实施例的一种含高熵热电界面材料的Mg-Sb基热电器件及制备方法，Fe aTi bCr cMn dMg e/TEcM接触界面不仅在合成之后具备极佳的综合性能，而且在400℃服役15天后依然具有高剪切强度(>30MPa)、低接触电阻率(<10μΩ*cm 2)。 According to the Mg-Sb-based thermoelectric device containing high-entropy thermoelectric interface material and the preparation method of the above embodiment, the Fe a Ti b Cr c Mn d Mg e /TEcM contact interface not only has excellent comprehensive performance after synthesis, but also After serving for 15 days at 400℃, it still has high shear strength (>30MPa) and low contact resistivity (<10μΩ*cm 2 ).
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为TEiM/TEcM界面的(a)抗剪强度和(a)接触电阻率。Figure 1 shows (a) shear strength and (a) contact resistivity of TEiM/TEcM interface.
图2为不同TEiM与TEcM的热膨胀系数。Figure 2 shows the thermal expansion coefficients of different TEiM and TEcM.
图3为400℃服役(1,3,7,15天)后，TEiM/TEcM接触界面的热稳定性。(a)抗剪强度与服役时间(s 1/2)的关系，(b)接触电阻率与服役时间(s 1/2)的关系。 Figure 3 shows the thermal stability of the TEiM/TEcM contact interface after service at 400°C (1, 3, 7, and 15 days). (a) Relationship between shear strength and service time (s 1/2 ), (b) Relationship between contact resistivity and service time (s 1/2 ).
图4为TEiM/TEcM界面的原位透射电镜图像及能谱分析图。Figure 4 shows the in-situ transmission electron microscope image and energy spectrum analysis of the TEiM/TEcM interface.
图5为各单质TEiM材料的接触电阻率统计图。Figure 5 is a statistical diagram of the contact resistivity of each elemental TEiM material.
图6为扫描电镜及微观形貌图(Ni)。Figure 6 shows the scanning electron microscope and micromorphology picture (Ni).
图7为扫描电镜及微观形貌图(Al)。Figure 7 shows the scanning electron microscope and micromorphology picture (Al).
图8为扫描电镜及微观形貌图(Cu)。Figure 8 shows the scanning electron microscope and micromorphology picture (Cu).
图9为不同单质金属元素与TEcM块体之间的抗剪强度图。Figure 9 is a diagram showing the shear strength between different single metal elements and TEcM blocks.
图10为扫描电镜及微观形貌图(Fe 7Mg 3)。 Figure 10 shows the scanning electron microscope and micromorphology picture (Fe 7 Mg 3 ).
图11为扫描电镜及微观形貌图(Fe 7Mg 2Co)。 Figure 11 shows the scanning electron microscope and micromorphology picture (Fe 7 Mg 2 Co).
具体实施方式Detailed ways
下面通过具体实施方式结合附图对本发明作进一步详细说明。在以下的实施方式中，很多细节描述是为了使得本申请能被更好的理解。然而，本领域技术人员可以毫不费力的认识到，其中部分特征在不同情况下是可以省略的，或者可以由其他材料、方法所替代。在某些情况下，本申请相关的一些操作并没有在说明书中显示或者描述，这是为了避免本申请的核心部分被过多的描述所淹没，而对于本领域技术人员而言，详细描述这些相关操作并不是必要的，他们根据说明书中的描述以及本领域的一般技术知识即可完整了解相关操作。The present invention will be further described in detail below through specific embodiments in conjunction with the accompanying drawings. In the following embodiments, many details are described in order to make the present application better understood. However, those skilled in the art can readily recognize that some of the features may be omitted in different situations, or may be replaced by other materials and methods. In some cases, some operations related to the present application are not shown or described in the specification. This is to avoid the core part of the present application being overwhelmed by excessive descriptions. For those skilled in the art, it is difficult to describe these in detail. The relevant operations are not necessary, and they can fully understand the relevant operations based on the descriptions in the instructions and general technical knowledge in the field.
另外，说明书中所描述的特点、操作或者特征可以以任意适当的方式结合形成各种实施方式。同时，方法描述中的各步骤或者动作也可以按照本领域技术人员所能显而易见的方式进行顺序调换或调整。因此，说明书和附图中的各种顺序只是为了清楚描述某一个实施例，并不意味着是必须的顺序，除非另有说明其中某个顺序是必须遵循的。Additionally, the features, operations, or characteristics described in the specification may be combined in any suitable manner to form various embodiments. At the same time, each step or action in the method description can also be sequentially exchanged or adjusted in a manner that is obvious to those skilled in the art. Therefore, the various sequences in the description and drawings are only for clearly describing a certain embodiment, and do not imply a necessary sequence, unless otherwise stated that a certain sequence must be followed.
本文中为部件所编序号本身，例如“第一”、“第二”等，仅用于区分所描述的对象，不具有任何顺序或技术含义。The serial numbers assigned to components in this article, such as "first", "second", etc., are only used to distinguish the described objects and do not have any sequential or technical meaning.
根据第一方面，在一实施例中，提供一种含高熵热电界面材料的热电器件，包括热电转换材料、热电界面材料，热电界面材料复合至热电转换材料的至少部分表面，热电界面材料包含如下化学通式：Fe aTi bCr cMn dMg e，a＝0.5～1.5；b＝0.5～1.5；c＝0.5～1.5；d＝0.5～1.5；e＝0.5～1.5。 According to the first aspect, in one embodiment, a thermoelectric device containing a high-entropy thermoelectric interface material is provided, including a thermoelectric conversion material and a thermoelectric interface material. The thermoelectric interface material is compounded to at least part of the surface of the thermoelectric conversion material. The thermoelectric interface material includes The following chemical formula: Fe a Ti b Cr c Mn d Mg e , a=0.5～1.5; b=0.5～1.5; c=0.5～1.5; d=0.5～1.5; e=0.5～1.5.
在一实施例中，热电转换材料包含n型热电转换材料或p型热电转换材料。In one embodiment, the thermoelectric conversion material includes n-type thermoelectric conversion material or p-type thermoelectric conversion material.
在一实施例中，热电转换材料包含n型热电转换材料。In one embodiment, the thermoelectric conversion material includes an n-type thermoelectric conversion material.
在一实施例中，热电转换材料包含Mg-Sb基热电转换材料。In one embodiment, the thermoelectric conversion material includes Mg-Sb based thermoelectric conversion material.
在一实施例中，热电转换材料包含n型Mg-Sb基热电转换材料。In one embodiment, the thermoelectric conversion material includes an n-type Mg-Sb based thermoelectric conversion material.
在一实施例中，热电转换材料包含如下化学通式：Mg 3+δMn xSb 2-y-zBi yA z，其中A为氧族元素，-0.2≤δ≤0.3；x＝0.001～0.4；y＝0～1.0；z＝0～0.2。 In one embodiment, the thermoelectric conversion material includes the following general chemical formula: Mg 3+δ Mn x Sb 2-yz Bi y A z , where A is an oxygen group element, -0.2≤δ≤0.3; x=0.001～0.4; y=0～1.0; z=0～0.2.
在一实施例中，氧族元素包括S、Se或Te。In one embodiment, the oxygen group element includes S, Se or Te.
在一实施例中，热电转换材料的厚度可以为3～4mm。In one embodiment, the thickness of the thermoelectric conversion material may be 3-4 mm.
在一实施例中，热电界面材料层的厚度可以为1～1.5mm。In one embodiment, the thickness of the thermoelectric interface material layer may be 1 to 1.5 mm.
在一实施例中，热电器件包括单腿热电器件。In one embodiment, the thermoelectric device includes a single leg thermoelectric device.
在一实施例中，单腿热电器件包含热电转换材料以及复合至热电转换材料上表面以及下表面的热电界面材料。In one embodiment, the single-leg thermoelectric device includes a thermoelectric conversion material and a thermoelectric interface material compounded to the upper surface and lower surface of the thermoelectric conversion material.
在一实施例中，热电界面材料通过烧结的方式复合至热电转换材料的至少部分表面。In one embodiment, the thermoelectric interface material is compounded to at least part of the surface of the thermoelectric conversion material through sintering.
根据第二方面，在一实施例中，提供第一方面任意一项的热电器件的制备方法，包括：According to the second aspect, in one embodiment, a method for manufacturing a thermoelectric device according to any one of the first aspects is provided, including:
将热电界面材料复合至热电转换材料的至少部分表面，烧结，得到热电器件。The thermoelectric interface material is compounded onto at least a portion of the surface of the thermoelectric conversion material, and sintered to obtain a thermoelectric device.
在一实施例中，烧结包括放电等离子烧结。In one embodiment, sintering includes spark plasma sintering.
在一实施例中，烧结是在500～800℃、30～60MPa轴向压力下进行。In one embodiment, sintering is performed at 500-800°C and 30-60MPa axial pressure.
在一实施例中，烧结时间为5～10min。In one embodiment, the sintering time is 5 to 10 minutes.
在一实施例中，烧结时，升温至烧结温度的升温速率为50～100℃*min -1。通常是从室温升温至烧结温度。 In one embodiment, during sintering, the heating rate to the sintering temperature is 50 to 100°C*min -1 . Usually the temperature is raised from room temperature to sintering temperature.
在一实施例中，热电转换材料的制备方法包括：按配比将各原料混合，在惰性气体保护下球磨，然后在500～800℃、5～10min、30～60MPa轴向压力下通过放电等离子烧结法烧结成块。In one embodiment, the preparation method of the thermoelectric conversion material includes: mixing raw materials according to the proportion, ball milling under the protection of inert gas, and then sintering by discharge plasma under 500-800°C, 5-10 min, and 30-60 MPa axial pressure. sintered into blocks.
在一实施例中，热电界面材料的制备方法包括：按配比将各原料混合，在惰性气体保护下球磨，获得合金粉末，即为热电界面材料。In one embodiment, a method for preparing a thermoelectric interface material includes: mixing raw materials according to a proportion, and ball milling under the protection of an inert gas to obtain an alloy powder, which is a thermoelectric interface material.
在一实施例中，制备热电转换材料、热电界面材料所用的原料均为单质原料。In one embodiment, the raw materials used to prepare the thermoelectric conversion material and the thermoelectric interface material are all single raw materials.
在一实施例中，各单质原料的粒度为100～300目，纯度大于98％。In one embodiment, the particle size of each elemental raw material is 100-300 mesh, and the purity is greater than 98%.
在一实施例中，制备热电转换材料、热电界面材料时，惰性气体包括但不限于氮气(N 2)、氦气(He)、氖气(Ne)、氩气(Ar)、氪气(Kr)、氙气(Xe)中的至少一种。 In one embodiment, when preparing thermoelectric conversion materials and thermoelectric interface materials, inert gases include but are not limited to nitrogen (N 2 ), helium (He), neon (Ne), argon (Ar), and krypton (Kr). ), at least one of xenon (Xe).
根据第三方面，在一实施例中，提供一种热电界面材料，热电界面材料包含如下化学通式：Fe aTi bCr cMn dMg e，a＝0.5～1.5；b＝0.5～1.5；c＝0.5～1.5；d＝0.5～1.5；e＝0.5～1.5。 According to the third aspect, in one embodiment, a thermoelectric interface material is provided. The thermoelectric interface material includes the following general chemical formula: Fe a Ti b Cr c Mn d Mg e , a=0.5～1.5; b=0.5～1.5; c=0.5～1.5; d=0.5～1.5; e=0.5～1.5.
根据第四方面，在一实施例中，提供一种可穿戴设备，包含第一方面任意一项的热电器件，或第三方面任意一项的热电界面材料。According to the fourth aspect, in an embodiment, a wearable device is provided, including the thermoelectric device of any one of the first aspect, or the thermoelectric interface material of any one of the third aspect.
根据第五方面，在一实施例中，提供一种传感器，包含第一方面任意一项的热电器件，或第三方面任意一项的热电界面材料。According to the fifth aspect, in one embodiment, a sensor is provided, including the thermoelectric device according to any one of the first aspect, or the thermoelectric interface material according to any one of the third aspects.
在一实施例中，提供一类用于Mg 3Sb 2基热电器件的高熵热电界面材料。针对现有技术存在的问题，本发明设计了全新的高熵TEiM，使用该系列TEiM的热电器件具有低接触电阻率、高的结合强度和优异热稳定性。 In one embodiment, a class of high-entropy thermoelectric interface materials for Mg 3 Sb 2 -based thermoelectric devices is provided. In view of the problems existing in the existing technology, the present invention designs a new high-entropy TEiM. Thermoelectric devices using this series of TEiM have low contact resistivity, high bonding strength and excellent thermal stability.
在一实施例中，TEcM的制备方法包括：按设计比例(Mg 3+δMn xSb 2-y-zBi yA z，其中A为氧族元素S、Se或Te，-0.2≤δ≤0.3；x、y、z为原子比率，x＝0.001～0.4；y＝0～1.0；z＝0～0.2)称量原材料，然后在氩气保护下高能球磨5～10小时，球磨后得到的TEcM粉末在500～800℃、5～10min、30～60MPa轴向压力下通过放电等离子烧结法烧结成块。升温至烧结温度的速率为50～100℃*min -1。 In one embodiment, the preparation method of TEcM includes: according to the design ratio (Mg 3+δ Mn x Sb 2-yz Bi y A z , where A is the oxygen group element S, Se or Te, -0.2≤δ≤0.3; x, y, z are atomic ratios, x=0.001~0.4; y=0~1.0; z=0~0.2) Weigh the raw materials, and then high-energy ball milling under argon protection for 5 to 10 hours, and the TEcM powder obtained after ball milling It is sintered into blocks through discharge plasma sintering at 500~800℃, 5~10min, and 30~60MPa axial pressure. The rate of heating to the sintering temperature is 50~100℃*min -1 .
在一实施例中，TEiM的制备方法包括：按设计比例(Fe aTi bCr cMn dMg e，a、b、c、d、e为原子比率，a＝0.5～1.5；b＝0.5～1.5；c＝0.5～1.5；d＝0.5～1.5；e＝0.5～1.5)称量原材料，通过机械合金化法，在氩气保护下高能球磨10～20小时得到合金粉末。 In one embodiment, the preparation method of TEiM includes: weighing raw materials according to a designed ratio (Fe a Ti b Cr c Mn d Mg e , a, b, c, d, e are atomic ratios, a=0.5-1.5; b=0.5-1.5; c=0.5-1.5; d=0.5-1.5; e=0.5-1.5), and obtaining alloy powder by mechanical alloying method and high-energy ball milling for 10-20 hours under argon protection.
机械合金化法是指金属或合金粉末在高能球磨机中通过粉末颗粒与磨球之间长时间激烈地冲击、碰撞，使粉末颗粒反复产生冷焊、断裂，导致粉末颗粒中原子扩散，从而获得合金化粉末的一种粉末制备方法。Mechanical alloying method refers to the long-term intense impact and collision of metal or alloy powder between powder particles and grinding balls in a high-energy ball mill, causing the powder particles to repeatedly undergo cold welding and fracture, resulting in the diffusion of atoms in the powder particles, thereby obtaining the alloy. A powder preparation method of chemical powder.
在一实施例中，TEiM/TEcM界面的制备方法包括：将高能球磨后的TEiM粉末与放电等离子烧结成块的TEcM块体在500～800℃、5～10min、30～60MPa轴向压力下通过放电等离子烧结法扩散烧结成块，形成TEiM/TEcM接触界面。烧结过程中升温速率为50～100℃*min -1。TEcM块体和TEiM层的厚度分别设计为3～4mm和1～1.5mm。获得的样品为层状复合界面结构(TEiM/TEcM/TEiM)。 In one embodiment, the preparation method of the TEiM/TEcM interface includes: passing the high-energy ball-milled TEiM powder and the discharge plasma-sintered TEcM block under 500-800°C, 5-10 min, and 30-60 MPa axial pressure. The spark plasma sintering method is used to diffuse and sinter into blocks to form TEiM/TEcM contact interface. The heating rate during the sintering process is 50~100℃*min -1 . The thicknesses of the TEcM block and TEiM layer are designed to be 3 to 4 mm and 1 to 1.5 mm respectively. The obtained sample is a layered composite interface structure (TEiM/TEcM/TEiM).
在一实施例中，Fe aTi bCr cMn dMg e/TEcM接触界面不仅在合成之后具备极佳的综合性能，而且在400℃服役15天后依然具有高剪切强度(>30MPa)、低接触电阻率(<10μΩ*cm 2)。本发明为n型Mg 3Sb 2基热电材料设计的TEiM在行业类具有最佳的综合性能，提高了Mg 3Sb 2基热电材料的实用性。 In one embodiment, the Fe a Ti b Cr c Mn d Mg e /TEcM contact interface not only has excellent comprehensive properties after synthesis, but also has high shear strength (>30MPa) and low Contact resistivity (<10μΩ*cm 2 ). The TEiM designed for n-type Mg 3 Sb 2- based thermoelectric materials in the present invention has the best comprehensive performance in the industry and improves the practicality of Mg 3 Sb 2 -based thermoelectric materials.
在一实施例中，提供一种兼具高界面结合强度，低界面接触电阻的单腿热电器件，可应用于物联网自供能系统。In one embodiment, a single-leg thermoelectric device with high interface bonding strength and low interface contact resistance is provided, which can be applied to the self-powered system of the Internet of Things.
以下实施例以及对比例中，使用单质原料制备TEcM、TEiM，各单质原料的粒度为100～300目，纯度大于98％。In the following examples and comparative examples, TEcM and TEiM are prepared using elemental raw materials. The particle size of each elemental raw material is 100-300 mesh, and the purity is greater than 98%.
各单质原料具体如下：The details of each elemental raw material are as follows:
Fe粉，200目，纯度99.9％，生产商为Macklin；Fe powder, 200 mesh, purity 99.9%, manufacturer: Macklin;
Mg屑，纯度大于99.9％，生产商为AcrosOrganics；Mg chips, purity greater than 99.9%, manufacturer: AcrosOrganics;
Cr粉，200目，纯度99.9％，生产商为Macklin；Cr powder, 200 mesh, purity 99.9%, manufacturer is Macklin;
Ti粉，200目，纯度99.9％，生产商为Alfa；Ti powder, 200 mesh, purity 99.9%, manufacturer: Alfa;
Mn粉，200目，纯度99.5％，生产商为Alfa；Mn powder, 200 mesh, purity 99.5%, manufacturer: Alfa;
Sb锭，纯度99.999％，生产商为5N plus；Sb ingot, purity 99.999%, produced by 5N plus;
Bi屑，纯度99.999％，生产商为5N plus；Biscuits, purity 99.999%, manufacturer 5N plus;
Te锭，纯度99.999％，生产商为5N plus。Te ingot, purity 99.999%, manufacturer 5N plus.
实施例1Example 1
本实施例中，TEcM的制备方法如下：按设计比例称量各单质原材料，然后在氩气保护下高能球磨(不锈钢球，直径为10mm)8小时，球磨后得到的TEcM粉末在675℃、5min、50MPa轴向压力下通过放电等离子烧结法烧结成块。In this example, the preparation method of TEcM is as follows: weigh each elemental raw material according to the designed proportion, and then perform high-energy ball milling (stainless steel ball, diameter 10mm) under argon protection for 8 hours. The TEcM powder obtained after ball milling is heated at 675°C for 5 minutes. , sintered into blocks by spark plasma sintering method under 50MPa axial pressure.
本实施例中，TEiM的制备方法如下：按设计比例称量各单质原材料，通过机械合金化法，在氩气保护下高能球磨(不锈钢球，直径为10mm)1～2小时得到合金粉末。In this embodiment, the preparation method of TEiM is as follows: weigh each elemental raw material according to the designed proportion, use mechanical alloying method, and obtain alloy powder by high-energy ball milling (stainless steel ball, diameter 10mm) under argon protection for 1 to 2 hours.
本实施例中，TEiM/TEcM界面的制备方法如下：先进行装样，具体是将TEiM粉末铺在石墨模具中，即铺在TEcM块体的上下表面，形成类三明治结构，随后进行放电等离子烧结， TEiM粉末与TEcM块体在600℃、10min、30MPa轴向压力下通过放电等离子烧结法形成TEiM/TEcM接触界面。烧结过程中升温速率为100℃*min -1。TEcM块体和TEiM层的厚度分别设计为4mm和1.5mm。 In this embodiment, the preparation method of the TEiM/TEcM interface is as follows: first, the sample is loaded. Specifically, TEiM powder is spread in a graphite mold, that is, spread on the upper and lower surfaces of the TEcM block to form a sandwich-like structure, and then discharge plasma sintering is performed. The TEiM powder and TEcM bulk were formed into a TEiM/TEcM contact interface by spark plasma sintering at 600°C, 10 min, and 30 MPa axial pressure. The heating rate during the sintering process is 100℃*min -1 . The thickness of TEcM bulk and TEiM layer are designed to be 4mm and 1.5mm respectively.
本实施例中，TEcM的化学式如下：Mg 3.2Mn 0.01Sb 1.5Bi 0.45Te 0.01，TEiM的化学式如下：FeTiCrMnMg，按上述方法制备得到FeTiCrMnMg/Mg 3.2Mn 0.01Sb 1.5Bi 0.45Te 0.01接触界面。 In this embodiment, the chemical formula of TEcM is as follows: Mg 3.2 Mn 0.01 Sb 1.5 Bi 0.45 Te 0.01 and the chemical formula of TEiM is as follows: FeTiCrMnMg. The FeTiCrMnMg/Mg 3.2 Mn 0.01 Sb 1.5 Bi 0.45 Te 0.01 contact interface is prepared according to the above method.
对比例1Comparative example 1
TEcM块体：Mg 3.2Mn 0.01Sb 1.5Bi 0.45Te 0.01，TEiM：304 stainless steel(304SS)，参照实施例1的方法制备得到304stainless steel/Mg 3.2Mn 0.01Sb 1.5Bi 0.45Te 0.01接触界面。 TEcM block: Mg 3.2 Mn 0.01 Sb 1.5 Bi 0.45 Te 0.01 , TEiM: 304 stainless steel (304SS), refer to the method of Example 1 to prepare a 304stainless steel/Mg 3.2 Mn 0.01 Sb 1.5 Bi 0.45 Te 0.01 contact interface.
对比例2Comparative example 2
TEcM块体：Mg 3.2Mn 0.01Sb 1.5Bi 0.45Te 0.01，TEiM：Fe 7Mg 2Ti，参照实施例1的方法制备得到Fe 7Mg 2Ti/Mg 3.2Mn 0.01Sb 1.5Bi 0.45Te 0.01接触界面。 TEcM bulk: Mg 3.2 Mn 0.01 Sb 1.5 Bi 0.45 Te 0.01 , TEiM: Fe 7 Mg 2 Ti, and the Fe 7 Mg 2 Ti/Mg 3.2 Mn 0.01 Sb 1.5 Bi 0.45 Te 0.01 contact interface was prepared by referring to the method of Example 1.
另外，将TEiM分别更换为Fe 7Mg 2Cr、Fe 7Mg 3、Mg、Fe、Ni、Cu、Al、Ag、Zn、Ti。 In addition, TEiM was replaced with Fe 7 Mg 2 Cr, Fe 7 Mg 3 , Mg, Fe, Ni, Cu, Al, Ag, Zn, and Ti respectively.
实施例1所选的高熵热电界面材料(TEiM)与热电转换材料(TEcM)之间的抗剪强度和接触电阻率都处在理想的水平。如图1所示，FeTiCrMnMg与TEcM结合强度在30～35MPa范围内。接触电阻率在5μΩ*cm 2以下。可见，行业标准是＜10μΩ*cm 2，实施例1的制得的FeTiCrMnMg/Mg 3.2Mn 0.01Sb 1.5Bi 0.45Te 0.01接触界面的接触电阻率低于1μΩ*cm 2，远低于行业标准要求，具有极低的接触电阻率。 The shear strength and contact resistivity between the high-entropy thermoelectric interface material (TEiM) and the thermoelectric conversion material (TEcM) selected in Example 1 are at ideal levels. As shown in Figure 1, the bonding strength between FeTiCrMnMg and TEcM is in the range of 30 to 35MPa. Contact resistivity is below 5μΩ* cm2 . It can be seen that the industry standard is <10μΩ*cm 2 , and the contact resistivity of the FeTiCrMnMg/Mg 3.2 Mn 0.01 Sb 1.5 Bi 0.45 Te 0.01 contact interface prepared in Example 1 is lower than 1μΩ*cm 2 , which is far lower than the industry standard requirement. Has extremely low contact resistivity.
热膨胀系数、抗剪强度、接触电阻率的测试参照本行业的通用标准进行，详细测试流程可参考文献(Acta Materialia 226(2022)117616)Section 2.2(文献报道第二页第三段)。The thermal expansion coefficient, shear strength, and contact resistivity were tested in accordance with the general standards of the industry. The detailed test process can be found in the literature (Acta Materialia 226 (2022) 117616) Section 2.2 (the third paragraph of the second page of the literature report).
热膨胀系数是衡量材料在不同温度下应变程度的重要参数，这一参数对选择热电界面材料具有重要意义。如图2所示，FeTiCrMnMg的热膨胀性与TEcM最为接近，这说明在高温区间，FeTiCrMnMg/TEcM界面比304SS/TEcM和Fe 7Mg 2Ti/TEcM界面所受到的热应力小，有利于组织界面裂纹的发生，提高界面的结合强度和高温稳定性。 The thermal expansion coefficient is an important parameter to measure the degree of strain of a material at different temperatures. This parameter is of great significance for the selection of thermoelectric interface materials. As shown in Figure 2, the thermal expansion of FeTiCrMnMg is closest to TEcM, which shows that in the high temperature range, the FeTiCrMnMg/TEcM interface is subject to less thermal stress than the 304SS/TEcM and Fe 7 Mg 2 Ti/TEcM interfaces, which is conducive to the organization of interface cracks. occurrence, improving the bonding strength and high temperature stability of the interface.
采用真空封管模拟高温环境，对材料进行热处理。将界面置于石英管中，抽真空，待真空度达到10 -3Pa后用火焰枪对石英管进行密封，随后将石英管置于马弗炉中，以5℃/min的升温速度，升温到400℃，保温不同时间，模拟器件的真实服役环境。如图3所示，根据界面抗剪强度、接触电阻率随时间变化的斜率可知，在400℃不同服役时间下，FeTiCrMnMg/TEcM界面抗剪强度随时间变化的趋势最小，说明该高熵热电界面材料最有利于提高界面的热稳定性。服役(约1200s 1/2，其中，s 1/2表示时间的均方根，为热力学常用表达方式)15天后，FeTiCrMnMg/TEcM界面抗剪强度仅仅从37Mpa降低到35Mpa，FeTiCrMnMg/TEcM界面接触电阻率仅仅从4μΩ*cm 2增加到7μΩ*cm 2。400℃服役15天后，接触界面仍然满足结合强度>30Mpa，接触电阻率<10μΩ*cm 2的行业要求，这是目前行业内最具竞争力的界面稳定性能。Σ Vacuum sealed tubes are used to simulate high temperature environments and the materials are heat treated. Place the interface in a quartz tube and evacuate it. After the vacuum reaches 10 -3 Pa, use a flame gun to seal the quartz tube. Then place the quartz tube in a muffle furnace and raise the temperature at a heating rate of 5°C/min. to 400°C and kept for different times to simulate the real service environment of the device. As shown in Figure 3, according to the slope of the interface shear strength and contact resistivity changing with time, it can be seen that at different service times at 400°C, the FeTiCrMnMg/TEcM interface shear strength has the smallest change with time, indicating that this high-entropy thermoelectric interface Materials are most conducive to improving the thermal stability of the interface. After 15 days of service (about 1200s 1/2 , where s 1/2 represents the root mean square of time, which is a commonly used expression in thermodynamics), the FeTiCrMnMg/TEcM interface shear strength only decreased from 37Mpa to 35Mpa, and the FeTiCrMnMg/TEcM interface contact resistance The rate only increases from 4μΩ*cm 2 to 7μΩ*cm 2 . After 15 days of service at 400°C, the contact interface still meets the industry requirements of bonding strength >30Mpa and contact resistivity <10μΩ* cm2 . This is the most competitive interface stability performance in the industry. Σ
图3中，三种界面的斜率如下表1所示。In Figure 3, the slopes of the three interfaces are shown in Table 1 below.
表1Table 1
Figure PCTCN2022120435-appb-000001
Figure PCTCN2022120435-appb-000001
Figure PCTCN2022120435-appb-000002
Figure PCTCN2022120435-appb-000002
可见，实施例1制得的界面材料斜率显著低于对比例1、2，证实其具有优异的界面稳定性。It can be seen that the slope of the interface material prepared in Example 1 is significantly lower than that of Comparative Examples 1 and 2, confirming that it has excellent interface stability.
优异的界面稳定性不仅仅来自匹配的热膨胀系数，还和界面的元素扩散有关，如图4所示，通过透射电镜表征发现，实施例1制得的TEiM/TEcM界面的微观结构几乎没有出现剧烈的元素互扩散现象。Excellent interface stability not only comes from the matching thermal expansion coefficient, but also is related to the diffusion of elements at the interface. As shown in Figure 4, through transmission electron microscopy characterization, it is found that the microstructure of the TEiM/TEcM interface prepared in Example 1 has almost no dramatic changes. interdiffusion of elements.
热电器件的可靠性在很大程度上取决于热电材料与电极之间的界面接触。在一实施例中，本发明提供了一种高熵合金(Fe aTi bCr cMn dMg e，a、b、c、d、e为原子比率，a＝0.5～1.5；b＝0.5～1.5；c＝0.5～1.5；d＝0.5～1.5；e＝0.5～1.5)，用该类高熵合金制备所得的Mg 3Sb 2基热电器件界面抗剪强度>35MPa，接触电阻率<5μΩ*cm 2。此外，经400℃服役15天后，接触界面的抗剪强度>30MPa，接触电阻率<10μΩ*cm 2。 The reliability of thermoelectric devices depends largely on the interfacial contact between the thermoelectric material and the electrodes. In one embodiment, the present invention provides a high-entropy alloy (Fe a Ti b Cr c Mn d Mg e , a, b, c, d, e are atomic ratios, a=0.5～1.5; b=0.5～ 1.5; c=0.5~1.5; d=0.5~1.5; e=0.5~1.5), the interface shear strength of Mg 3 Sb 2- based thermoelectric devices prepared using this type of high-entropy alloy is >35MPa, and the contact resistivity is <5μΩ* cm 2 . In addition, after 15 days of service at 400°C, the shear strength of the contact interface is >30MPa, and the contact resistivity is <10μΩ*cm 2 .
图5为各单质TEiM材料的接触电阻率统计图。可见，各单质的接触电阻率远高于实施例1中的FeCrTiMnMg(接触电阻率<10μΩ*cm 2)。 Figure 5 is a statistical diagram of the contact resistivity of each elemental TEiM material. It can be seen that the contact resistivity of each element is much higher than that of FeCrTiMnMg in Example 1 (contact resistivity <10 μΩ*cm 2 ).
图6为扫描电镜及微观形貌图(Ni)，可见，Ni结合强度低，由于界面发生了扩散，生成了脆性相。Figure 6 shows the scanning electron microscope and micromorphology picture (Ni). It can be seen that the Ni bonding strength is low and a brittle phase is generated due to diffusion at the interface.
图7为扫描电镜及微观形貌图(Al)，可见，Al结合强度低，由于热电材料显著扩散到TEiM内部，产生裂纹。Figure 7 shows the scanning electron microscope and micromorphology image (Al). It can be seen that the Al bonding strength is low, and cracks occur due to the significant diffusion of thermoelectric materials into the interior of TEiM.
图8为扫描电镜及微观形貌(Cu)，可见，Cu虽然结合强度较高，但是界面扩散较为剧烈，界面电阻大。Figure 8 shows the scanning electron microscope and micromorphology (Cu). It can be seen that although Cu has higher bonding strength, the interface diffusion is more intense and the interface resistance is large.
图9为不同单质金属元素与TEcM块体之间的抗剪强度图，该图展示了大部分过渡族金属粘接实验结果，
Figure PCTCN2022120435-appb-000003
表示不能粘接，其余为不同金属的结合强度。可见，Ni、Fe、Zn、Ti、Mg、Al、Ag、Cu成功与TEcM块体结合，结合强度约在5～45MPa范围内。而熔点(Tm)较高的金属，如V、Nb、Cr、Mo、W、Mn和Co，则无法与TEcM块体结合。 Figure 9 is a diagram of the shear strength between different single metal elements and TEcM blocks. This figure shows the experimental results of bonding of most transition metals.
Figure PCTCN2022120435-appb-000003
Indicates that it cannot be bonded, and the rest are the bonding strengths of different metals. It can be seen that Ni, Fe, Zn, Ti, Mg, Al, Ag, and Cu successfully bonded to the TEcM block, and the bonding strength was about 5 to 45 MPa. However, metals with higher melting points (Tm), such as V, Nb, Cr, Mo, W, Mn, and Co, could not bond to the TEcM block.
图10为扫描电镜及微观形貌(Fe 7Mg 3)，可见，Fe 7Mg 3结合强度低，经测试，接触界面的抗剪强度＜30MPa。 Figure 10 shows the scanning electron microscope and micromorphology (Fe 7 Mg 3 ). It can be seen that the bonding strength of Fe 7 Mg 3 is low. After testing, the shear strength of the contact interface is <30MPa.
图11为扫描电镜及微观形貌(Fe 7Mg 2Co)，可见，Fe 7Mg 2Co结合强度低，经测试，接触界面的抗剪强度＜30MPa。 Figure 11 shows the scanning electron microscope and micromorphology (Fe 7 Mg 2 Co). It can be seen that the bonding strength of Fe 7 Mg 2 Co is low. After testing, the shear strength of the contact interface is <30MPa.
以上应用了具体个例对本发明进行阐述，只是用于帮助理解本发明，并不用以限制本发明。对于本发明所属技术领域的技术人员，依据本发明的思想，还可以做出若干简单推演、变形或替换。The above specific examples are used to illustrate the present invention, which are only used to help understand the present invention and are not intended to limit the present invention. For those skilled in the technical field to which the present invention belongs, several simple deductions, modifications or substitutions can be made based on the ideas of the present invention.

Claims (27)

  1. 一种含高熵热电界面材料的热电器件，其特征在于，包括热电转换材料、热电界面材料，所述热电界面材料复合至所述热电转换材料的至少部分表面，所述热电界面材料包含如下化学通式：Fe aTi bCr cMn dMg e，a＝0.5～1.5；b＝0.5～1.5；c＝0.5～1.5；d＝0.5～1.5；e＝0.5～1.5。 A thermoelectric device containing a high-entropy thermoelectric interface material, characterized in that it includes a thermoelectric conversion material and a thermoelectric interface material, the thermoelectric interface material is compounded to at least part of the surface of the thermoelectric conversion material, and the thermoelectric interface material contains the following chemistry General formula: Fe a Ti b Cr c Mn d Mg e , a=0.5～1.5; b=0.5～1.5; c=0.5～1.5; d=0.5～1.5; e=0.5～1.5.
  2. 如权利要求1所述的热电器件，其特征在于，所述热电转换材料包含n型热电转换材料或p型热电转换材料。The thermoelectric device according to claim 1, characterized in that the thermoelectric conversion material comprises an n-type thermoelectric conversion material or a p-type thermoelectric conversion material.
  3. 如权利要求1所述的热电器件，其特征在于，所述热电转换材料包含Mg-Sb基热电转换材料。The thermoelectric device according to claim 1, wherein the thermoelectric conversion material includes an Mg-Sb based thermoelectric conversion material.
  4. 如权利要求1所述的热电器件，其特征在于，所述热电转换材料包含n型Mg-Sb基热电转换材料。The thermoelectric device of claim 1, wherein the thermoelectric conversion material includes an n-type Mg-Sb-based thermoelectric conversion material.
  5. 如权利要求1所述的热电器件，其特征在于，所述热电转换材料包含如下化学通式：Mg 3+δMn xSb 2-y-zBi yA z，其中A为氧族元素，-0.2≤δ≤0.3；x＝0.001～0.4；y＝0～1.0；z＝0～0.2。 The thermoelectric device according to claim 1, wherein the thermoelectric conversion material includes the following general chemical formula: Mg 3+δ Mn x Sb 2-yz Bi y A z , where A is an oxygen group element, -0.2≤ δ≤0.3; x=0.001～0.4; y=0～1.0; z=0～0.2.
  6. 如权利要求5所述的热电器件，其特征在于，所述氧族元素包括S、Se或Te。The thermoelectric device of claim 5, wherein the oxygen group element includes S, Se or Te.
  7. 如权利要求1所述的热电器件，其特征在于，所述热电转换材料的厚度为3～4mm。The thermoelectric device according to claim 1, wherein the thickness of the thermoelectric conversion material is 3 to 4 mm.
  8. 如权利要求1所述的热电器件，其特征在于，所述热电界面材料层的厚度为1～1.5mm。The thermoelectric device according to claim 1, wherein the thickness of the thermoelectric interface material layer is 1 to 1.5 mm.
  9. 如权利要求1所述的热电器件，其特征在于，所述热电器件包括单腿热电器件。The thermoelectric device of claim 1, wherein the thermoelectric device includes a single-leg thermoelectric device.
  10. 如权利要求9所述的热电器件，其特征在于，所述单腿热电器件包含热电转换材料以及复合至所述热电转换材料上表面以及下表面的热电界面材料。The thermoelectric device of claim 9, wherein the single-leg thermoelectric device includes a thermoelectric conversion material and a thermoelectric interface material compounded to the upper surface and lower surface of the thermoelectric conversion material.
  11. 如权利要求1所述的热电器件，其特征在于，所述热电界面材料通过烧结的方式复合至所述热电转换材料的至少部分表面。The thermoelectric device according to claim 1, wherein the thermoelectric interface material is compounded to at least part of the surface of the thermoelectric conversion material by sintering.
  12. 一种热电界面材料，其特征在于，所述热电界面材料包含如下化学通式：Fe aTi bCr cMn dMg e，a＝0.5～1.5；b＝0.5～1.5；c＝0.5～1.5；d＝0.5～1.5；e＝0.5～1.5。 A thermoelectric interface material, characterized in that the thermoelectric interface material includes the following general chemical formula: Fe a Ti b Cr c Mn d Mg e , a=0.5～1.5; b=0.5～1.5; c=0.5～1.5; d=0.5～1.5; e=0.5～1.5.
  13. 一种可穿戴设备，其特征在于，包含权利要求1～11任意一项所述的热电器件，或权利要求12所述的热电界面材料。A wearable device, characterized by comprising the thermoelectric device according to any one of claims 1 to 11, or the thermoelectric interface material according to claim 12.
  14. 一种传感器，其特征在于，包含权利要求1～11任意一项所述的热电器件，或权利要求13所述的热电界面材料。A sensor, characterized by comprising the thermoelectric device according to any one of claims 1 to 11, or the thermoelectric interface material according to claim 13.
  15. 如权利要求1～11任意一项所述热电器件的制备方法，其特征在于，包括：The method for preparing a thermoelectric device according to any one of claims 1 to 11, characterized in that it includes:
    将热电界面材料复合至热电转换材料的至少部分表面，烧结，得到所述热电器件。The thermoelectric interface material is compounded to at least part of the surface of the thermoelectric conversion material and sintered to obtain the thermoelectric device.
  16. 如权利要求15所述的制备方法，其特征在于，所述烧结包括放电等离子烧结。The preparation method of claim 15, wherein the sintering includes spark plasma sintering.
  17. 如权利要求16所述的制备方法，其特征在于，所述放电等离子烧结的温度为500～800℃。The preparation method according to claim 16, characterized in that the temperature of the spark plasma sintering is 500-800°C.
  18. 如权利要求16所述的制备方法，其特征在于，所述放电等离子烧结的时间为5～10min。The preparation method according to claim 16, characterized in that the discharge plasma sintering time is 5 to 10 minutes.
  19. 如权利要求16所述的制备方法，其特征在于，所述放电等离子烧结的轴向压力为30 ～60MPa。The preparation method according to claim 16, characterized in that the axial pressure of the spark plasma sintering is 30-60MPa.
  20. 如权利要求17所述的制备方法，其特征在于，升温至烧结温度的速率为50～100℃*min -1。 The preparation method according to claim 17, characterized in that the rate of heating to the sintering temperature is 50 to 100°C*min -1 .
  21. 如权利要求15所述的制备方法，其特征在于，所述热电转换材料的制备方法包括：按配比将各原料混合，在惰性气体保护下球磨，然后烧结成块，制得所述热电转换材料。The preparation method according to claim 15, characterized in that the preparation method of the thermoelectric conversion material includes: mixing the raw materials according to the proportion, ball milling under the protection of inert gas, and then sintering into blocks to prepare the thermoelectric conversion material. .
  22. 如权利要求21所述的制备方法，其特征在于，所述热电转换材料的制备方法中，所述烧结包括放电等离子烧结。The preparation method of claim 21, wherein in the preparation method of the thermoelectric conversion material, the sintering includes discharge plasma sintering.
  23. 如权利要求22所述的制备方法，其特征在于，所述放电等离子烧结的温度为500～800℃。The preparation method according to claim 22, characterized in that the temperature of the spark plasma sintering is 500-800°C.
  24. 如权利要求22所述的制备方法，其特征在于，所述放电等离子烧结的时间为5～10min。The preparation method according to claim 22, characterized in that the discharge plasma sintering time is 5 to 10 minutes.
  25. 如权利要求22所述的制备方法，其特征在于，所述放电等离子烧结的轴向压力为30～60MPa。The preparation method according to claim 22, characterized in that the axial pressure of the spark plasma sintering is 30 to 60 MPa.
  26. 如权利要求23所述的制备方法，其特征在于，升温至烧结温度的速率为50～100℃*min -1。 The preparation method according to claim 23, characterized in that the rate of heating to the sintering temperature is 50 to 100°C*min -1 .
  27. 如权利要求15所述的制备方法，其特征在于，所述热电界面材料的制备方法包括：按配比将各原料混合，在惰性气体保护下球磨，获得合金粉末，即为所述热电界面材料。The preparation method according to claim 15, characterized in that the preparation method of the thermoelectric interface material includes: mixing raw materials according to the proportion, ball milling under the protection of inert gas to obtain alloy powder, which is the thermoelectric interface material.
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