Manufacturing method and device of high-entropy single-crystal thermoelectric material, medium and product

Abstract

The invention discloses a manufacturing method and device of a high-entropy single-crystal thermoelectric material, a medium and a product. The manufacturing method of the high-entropy single-crystal thermoelectric material comprises the following steps: putting a high-entropy raw material into a first container, and vacuumizing and sealing the first container; the sealed first container is smelted, quenched and annealed to generate a high-entropy polycrystalline cast ingot; the high-entropy polycrystalline cast ingot is ground, so that high-entropy single-phase powder of a single-phase structure is obtained; putting the high-entropy single-phase powder into a second container, and vacuumizing and sealing the second container; and performing single-crystal growth on the vacuumized and sealed high-entropy single-phase powder in the second container based on a Bridgman method to obtain the high-entropy single-crystal thermoelectric material. The problem that the integrity, uniformity and quality of the crystal are damaged due to the fact that the second phase is easily separated out in the crystal growth process is solved, and single crystal growth of the high-entropy thermoelectric material is achieved.

Description

Technical Field

[0001] The present application relates to the technical field of preparation of new energy and semiconductor thermoelectric materials, and in particular to a method for manufacturing high-entropy single-crystal thermoelectric materials, an apparatus for manufacturing high-entropy single-crystal thermoelectric materials, a computer-readable storage medium, and a computer program product. Background Art

[0002] Thermoelectric materials can directly convert heat and electricity. They have the advantages of no mechanical components, stability, compactness, environmental friendliness, and low noise. The conversion efficiency of thermoelectric modules mainly depends on the thermoelectric figure of merit of the thermoelectric material. Currently, research has found that high-entropy strategies can achieve the coordinated optimization of electrical and thermal transport parameters and have the potential to lead the development of thermoelectric materials. However, the research on high-entropy thermoelectric materials still focuses on polycrystalline materials. The complexity and uncertainty of their elemental composition make their single crystal growth very challenging. In particular, the precipitation of second phases during crystal growth can easily occur, thereby destroying the integrity, uniformity, and quality of the crystal. Summary of the Invention

[0003] The present application aims to solve at least one of the technical problems existing in the prior art. To this end, the present application proposes a method for manufacturing a high-entropy single-crystal thermoelectric material, an apparatus for manufacturing a high-entropy single-crystal thermoelectric material, a computer-readable storage medium, and a computer program product. These methods avoid the problem of secondary phase precipitation during crystal growth, which can damage the integrity, uniformity, and quality of the crystal, thereby achieving single-crystal growth of high-entropy thermoelectric materials.

[0004] In a first aspect, the present application provides a method for manufacturing a high entropy single crystal thermoelectric material, comprising:

[0005] Putting the high entropy raw material into a first container, and performing vacuuming and sealing operations on the first container;

[0006] Melting, quenching and annealing the vacuumed and sealed first container to produce a high-entropy polycrystalline ingot;

[0007] Grinding the high entropy polycrystalline ingot to obtain a high entropy single-phase powder with a single-phase structure;

[0008] placing the high entropy single-phase powder into a second container, and performing vacuum and sealing operations on the second container;

[0009] The high-entropy single-phase powder in the vacuumed and sealed second container is subjected to single crystal growth based on the Bridgman method to obtain the high-entropy single crystal thermoelectric material.

[0010] In a second aspect, the present application provides a device for manufacturing a high-entropy single crystal thermoelectric material, the device comprising:

[0011] A vacuum suction device, used for vacuuming the first container containing the high entropy raw material;

[0012] a sealing device for sealing the first container;

[0013] a smelting device for smelting, quenching and annealing the vacuumed and sealed first container to produce a high-entropy polycrystalline ingot;

[0014] A grinding device for grinding the high-entropy polycrystalline ingot to obtain a high-entropy single-phase powder with a single-phase structure;

[0015] The vacuum suction device is further used to vacuum the second container containing the high entropy single-phase powder, and the sealing device is used to seal the second container;

[0016] A single crystal growth furnace is used to perform single crystal growth on the high-entropy single-phase powder in the vacuumed and sealed second container based on the Bridgman method to obtain the high-entropy single crystal thermoelectric material.

[0017] In a third aspect, the present application provides a non-transitory computer-readable storage medium having a computer program stored thereon, which, when executed by a processor, implements the above-mentioned method for manufacturing high-entropy single crystal thermoelectric materials.

[0018] In a fourth aspect, the present application provides a computer program product, comprising a computer program, which, when executed by a processor, implements the above-mentioned method for manufacturing high-entropy single crystal thermoelectric materials.

[0019] The present application provides a method for manufacturing a high-entropy single-crystal thermoelectric material, an apparatus for manufacturing a high-entropy single-crystal thermoelectric material, a computer-readable storage medium, and a computer program product. A stable single-phase high-entropy polycrystalline material is synthesized by a melt process, and then a large-scale high-entropy single-crystal thermoelectric material is grown using a Bridgman method. This method has the advantages of being simple, easy to implement, and highly repeatable. Furthermore, during the single crystal growth process, uncertainties caused by the complexity of the chemical composition are avoided, including destructive factors such as second-phase transitions that affect the integrity of the crystal.

[0020] Additional aspects and advantages of the embodiments of the present application will be given in part in the description below, and in part will become obvious from the description below, or will be learned through practice of the embodiments of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which:

[0022] Figure 1 This is a first flow chart of the method for manufacturing a high-entropy single crystal thermoelectric material provided in an embodiment of the present application;

[0023] Figure 2 This is a second flow chart of the method for manufacturing a high-entropy single crystal thermoelectric material provided in an embodiment of the present application;

[0024] Figure 3 This is a physical image and diffraction pattern of the high-entropy single crystal thermoelectric material provided in the examples of this application;

[0025] Figure 4 This is a third flow chart of the method for manufacturing a high-entropy single crystal thermoelectric material provided in an embodiment of the present application;

[0026] Figure 5 This is a schematic diagram of the principle of growing a high-entropy single-crystal thermoelectric material according to the method for manufacturing a high-entropy single-crystal thermoelectric material provided in an embodiment of the present application;

[0027] Figure 6 This is a fourth flow chart of the method for manufacturing a high-entropy single crystal thermoelectric material provided in an embodiment of the present application;

[0028] Figure 7 a and Figure 7 b are Laue diffraction spot plane images of the crystal plane (110) and the crystal plane (100) of the high entropy single crystal thermoelectric material of the embodiment of the present application;

[0029] Figure 7 c and Figure 7 d are the standard Laue diffraction spot patterns of the crystal plane (110) and the crystal plane (100);

[0030] Figure 8 a and Figure 8 b are the SEM (scanning electron microscope) images and corresponding mapping (energy spectrum information) of high entropy GeTe single crystals;

[0031] Figure 8 c and Figure 8 d are STEM images (scanning transmission electron microscopy) of high-entropy GeTe single crystals at low and high magnifications, respectively;

[0032] Figure 9 Schematic diagram of the electrical conductivity σ, Seebeck coefficient S, total thermal conductivity κ, and thermoelectric figure of merit ZT of high-entropy GeTe single crystal;

[0033] Figure 10 Schematic diagram of the structure of the device for manufacturing high entropy single crystal thermoelectric materials provided in an embodiment of the present application;

[0034] Figure 11 This is a schematic diagram of the hardware structure of the electronic device provided in an embodiment of the present application. DETAILED DESCRIPTION

[0035] The following describes in detail embodiments of the present application. Examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present application, and should not be understood as limiting the present application.

[0036] For ease of understanding, the following first introduces the technical background and application scenarios of this application:

[0037] The application of thermoelectric materials is based on the Seebeck effect, discovered in 1821, and the Peltier effect, discovered in 1834. The former aims to induce an electric potential difference by establishing a temperature difference across a thermoelectric material, while the latter is its inverse effect. Based on this, thermoelectric modules can achieve direct conversion between thermal and electrical energy. They have the advantages of being mechanically component-free, stable, compact, environmentally friendly, and low-noise. Thermoelectric materials can be divided into room-temperature thermoelectric materials (such as Bi2Te3-based materials, ~300-500K), intermediate-temperature thermoelectric materials (such as Group IV-VI thermoelectric materials, ~500-800K), and high-temperature thermoelectric materials (such as Half-Heusler thermoelectric materials, ~800-1000K) based on their optimal service temperature. Currently, thermoelectric power generation is mainly used in waste heat management and deep space exploration, while thermoelectric cooling is mainly used in portable refrigeration equipment, electronic equipment cooling, precision temperature control, and medical equipment cooling. The conversion efficiency of a thermoelectric module is primarily determined by the thermoelectric figure of merit (ZT) of the thermoelectric material (ZT = σS 2 *T / (κ e +κ L )), therefore, the research on thermoelectric materials is mainly focused on improving the thermoelectric figure of merit ZT of thermoelectric materials. Due to the strong coupling of key parameters affecting electrical and thermal transport, it is difficult to significantly improve the thermoelectric performance of thermoelectric materials, which limits their large-scale application. In recent years, studies have found that high-entropy strategies can achieve the coordinated optimization of electrical and thermal transport parameters and have a trend of leading the development of thermoelectric materials. However, the research on high-entropy thermoelectric materials is still focused on polycrystalline materials. The complexity and uncertainty of their elemental composition make their single crystal growth full of challenges, especially the precipitation of second phases during crystal growth, which destroys the integrity, uniformity and quality of the crystal.

[0038] Based on this technical problem, the present application creatively uses the melting method to generate a stable single-phase high-entropy polycrystalline material, and then combines it with the Bridgman method for single crystal growth, thereby avoiding the uncertainties caused by the complexity of the chemical composition during the single crystal growth process, including the problem of destructive factors such as the second phase transition affecting the integrity of the crystal.

[0039] Based on the above introduction, the present invention provides a method for manufacturing a high-entropy single crystal thermoelectric material. The following is a detailed introduction to the method for manufacturing a high-entropy single crystal thermoelectric material:

[0040] See also Figure 1 The manufacturing method of a high entropy single crystal thermoelectric material provided in an embodiment of the present application is implemented by steps 011 to 014, which are described in detail below.

[0041] Step 011: Place the high entropy raw material into a first container, and perform vacuum and sealing operations on the first container.

[0042] Among them, high entropy raw materials include materials with an element number greater than or equal to 5, and the proportion of each element in the high entropy raw materials is greater than 5%.

[0043] Here, the proportion can be a mass proportion or a substance amount proportion.

[0044] Optionally, the thermoelectric material system of high entropy raw materials includes one or more of GeTe, Bi2Te3, Cu2S, Ag2Se, SnSe, Mg3Sb2, Group VI-IV thermoelectric materials, CoSb3, and half-Heusler-based thermoelectric materials.

[0045] For example, a thermoelectric material system containing high-entropy raw materials includes GeTe, and by introducing other elements, a high-entropy raw material with at least 5 elements can be generated. For example, by introducing 15% solid solution of Pb, Ag, and Sb as elements in the cation position, a high-entropy raw material can be obtained.

[0046] Optionally, the components of the high entropy raw material include Ge x A y B z C u Te v , A, B, C are the elements at the cation position, and x, y, z, u, v are the proportions of the corresponding elements.

[0047] For example, the components of high entropy raw materials include Ge 0.55 Pb 0.15 Ag 0.15 Sb 0.15 Te.

[0048] The first container is a container for containing high entropy raw materials.

[0049] Optionally, the first container includes a quartz tube, which is not prone to reaction with the thermoelectric material, thereby ensuring manufacturing stability.

[0050] Optionally, the inner wall of the first container is coated with a carbon film, which isolates the high-entropy raw material and the inner wall of the quartz tube. The carbon film will not react with the high-entropy raw material (such as the various elements in the high-entropy raw material), thereby further ensuring the stability of manufacturing.

[0051] After the high entropy raw material is prepared and placed in the first container, the first container needs to be vacuumed and sealed.

[0052] The vacuuming can be achieved by a vacuuming device (such as a vacuum pump, a vacuum sealing system, etc.).

[0053] The sealing operation can be achieved through a sealing device.

[0054] Optionally, the first container has an opening. The sealing device may be a flamethrower that emits flame (e.g., propane) to burn the opening of the first container, thereby sealing the opening and achieving sealing of the first container. For example, if the first container includes a quartz tube and a quartz plug, the quartz plug is inserted into the opening of the quartz tube. Propane is burned at the location of the quartz plug, causing the quartz tube to soften and fully adhere to the quartz plug, thereby achieving sealing of the opening of the first container.

[0055] Optionally, the pressure of the first container after vacuuming is less than 10 -4 Pascal (pa). To ensure that the first container is in a high vacuum state.

[0056] In this way, sealing is achieved after vacuuming, ensuring that the first container is in a high vacuum state during the subsequent melting process, thereby ensuring the melting effect.

[0057] Step 012: Melting, quenching and annealing the vacuumed and sealed first container to generate a high-entropy polycrystalline ingot.

[0058] Specifically, after the materials are prepared, smelting can begin, and quenching and annealing can be performed to generate a high-entropy polycrystalline ingot.

[0059] Optionally, see Figure 2 , step 012 includes:

[0060] Step 0121: placing the vacuumed and sealed first container in a muffle furnace for heating, so that the temperature of the first container is raised to a first preset temperature and kept at this temperature;

[0061] Step 0122: After holding the first container at a temperature for a first preset time, quenching the first container;

[0062] Step 0123: annealing the quenched first container at a second preset temperature for a second preset time;

[0063] Step 0124: When the first container is cooled to a third preset temperature, quenching is performed again to generate a high entropy polycrystalline ingot.

[0064] Among them, the muffle furnace is a general-purpose equipment that achieves a high-temperature environment through resistance heating and is widely used in materials science, metallurgy, ceramics, chemical industry and other fields.

[0065] Specifically, the vacuumed and sealed first container can be placed in a muffle furnace for heating. By controlling the heating process, the temperature of the first container is slowly increased to a first preset temperature, thereby ensuring the stability of the smelting.

[0066] Optionally, the first preset temperature is in the range of [1273 Kelvin (K)*0.8, 1273 K*1.2] to ensure the smelting effect. For example, the first preset temperature is 1273 K.

[0067] Then, the temperature is maintained at the first preset temperature and kept warm for a first preset time to fully melt the high entropy raw material.

[0068] Optionally, the first preset duration is greater than 6 hours (h), such as 12 hours.

[0069] After the high-entropy raw material is fully melted, the first container is quenched, such as in ice water. Then, after quenching, the quenched first container is annealed at a second preset temperature for a second preset time.

[0070] Optionally, the second preset temperature is within the range of [953K*0.8, 953K*1.2], such as the second preset temperature being 953K, to avoid excessive quenching that may affect the smelting effect.

[0071] The temperature of the first container is slowly cooled to a third preset temperature through annealing, and then quenched again, thereby finally generating a high entropy polycrystalline ingot.

[0072] Optionally, the second preset time period is greater than 1.5 hours to ensure that the temperature of the first container is cooled to the third preset temperature.

[0073] Optionally, the third preset temperature is in the interval [753K*0.8, 753K*1.2], for example, the third preset temperature is 753K.

[0074] Alternatively, the first container can be melted, quenched, and annealed using a melting device. For example, the melting device includes a muffle furnace, which is used to melt the first container. After melting, the first container is removed and placed in ice water for quenching. Annealing can then be performed to cool the container naturally or rapidly using a cooling element. In this manner, the melting device can achieve automated melting, quenching, and annealing.

[0075] In this way, after annealing, timely quenching is performed to complete the smelting of the high-entropy raw materials, thereby generating a high-entropy polycrystalline ingot with a stable single-phase structure.

[0076] Step 013: Grind the high-entropy polycrystalline ingot to obtain a high-entropy single-phase powder with a single-phase structure.

[0077] Specifically, after obtaining a high-entropy polycrystalline ingot, the high-entropy polycrystalline ingot is ground to obtain a high-entropy single-phase powder with a single-phase structure.

[0078] Optionally, the high entropy polycrystalline ingot can be ground using an agate mortar to improve the grinding effect.

[0079] Optionally, the agate mortar can be clamped by a grinding device, and then the movement of the agate mortar can be controlled to grind the high entropy polycrystalline ingot to achieve automated grinding.

[0080] It is understandable that there may be deviations in the smelting process, resulting in the generated high-entropy single-phase powder not being a stable single-phase structure.

[0081] Optionally, an X-ray diffraction method (such as XDR diffraction spectrum) can be used to obtain a diffraction pattern of the high-entropy single-phase powder at room temperature to determine whether the high-entropy single-phase powder has a stable single-phase structure.

[0082] When the high entropy single-phase powder is confirmed to be a single-phase structure based on the diffraction pattern, the subsequent single crystal growth process (ie, step 014 and step 015) is carried out.

[0083] The high entropy single-phase powder is placed in a second container, and the second container is vacuumed and sealed.

[0084] Among them, XDR diffraction pattern (X-ray Diffraction Pattern) is a core technical means for analyzing crystal structure in materials science. It reveals key information such as the crystal form, grain size, and stress state of the material by recording the diffraction signals generated by the interaction between X-rays and materials.

[0085] See also Figure 3 , Figure 3 (a) is an example picture of a high-entropy GeTe single crystal, which has a metallic luster and is a dense and complete crystal. Figure 3 (b) is the XDR diffraction spectrum of high-entropy GeTe polycrystalline powder and high-entropy GeTe single crystal bulk. The results show that the high-entropy GeTe polycrystalline powder has a cubic single-phase structure, and the high-entropy GeTe single crystal bulk presents a typical single crystal tendency (200) crystal plane.

[0086] Step 014: Place the high entropy single-phase powder into a second container, and perform vacuum and sealing operations on the second container.

[0087] Specifically, after obtaining a high-entropy single-phase powder with a single-phase structure, the high-entropy single-phase powder can be placed in a second container, and then vacuumed and sealed to complete the single crystal growth.

[0088] The vacuuming can be achieved by a vacuuming device (such as a vacuum pump, a vacuum sealing system, etc.).

[0089] The sealing operation can be achieved through a sealing device.

[0090] Optionally, the second container has an opening. The sealing device may be a flamethrower that emits flame (e.g., propane) to burn the opening of the second container, thereby sealing the opening and achieving a seal for the second container. For example, if the second container comprises a quartz tube and a quartz plug, the quartz plug is inserted into the opening of the quartz tube. Propane is burned at the location of the quartz plug, causing the quartz tube to soften and fully adhere to the quartz plug, thereby achieving a sealed opening for the second container.

[0091] Optionally, the pressure of the second container after evacuation is less than 10 -4 Pascal (pa). To ensure that the second container is in a high vacuum state.

[0092] In this way, sealing is achieved after vacuuming, ensuring that the second container is in a high vacuum state during the subsequent melting process, thereby ensuring the melting effect.

[0093] Optionally, the second container is a container for containing high entropy raw materials.

[0094] Optionally, the second container includes a quartz tube, which is not prone to reaction with the thermoelectric material, thereby ensuring manufacturing stability.

[0095] Optionally, the inner wall of the second container is coated with a carbon film, which isolates the high-entropy raw material and the inner wall of the quartz tube. The carbon film will not react with the high-entropy raw material (such as the various elements in the high-entropy raw material), thereby further ensuring the stability of manufacturing.

[0096] Step 015: Based on the Bridgman method, single crystal growth is performed on the high-entropy single-phase powder in the vacuumed and sealed second container to obtain a high-entropy single crystal thermoelectric material.

[0097] The Bridgman method, also known as the crucible descent method, is a commonly used crystal growth method. The material for crystal growth is placed in a cylindrical crucible and heated to a temperature slightly above its melting point using a heating device such as a resistance furnace or high-frequency furnace. The crucible then slowly descends through a heated area with a temperature gradient. The temperature at the bottom of the crucible first drops below its melting point, initiating crystallization. As the crucible continues to descend, the crystals continue to grow.

[0098] Specifically, after the high entropy single-phase powder is prepared, the high entropy single-phase powder in the vacuumed and sealed second container can be subjected to single crystal growth by the Bridgman method, thereby obtaining a high entropy single crystal thermoelectric material.

[0099] Optionally, see Figure 4 , step 015 includes:

[0100] Step 0151: The vacuumed and sealed second container is placed vertically in a single crystal growth furnace with a temperature gradient, the rotation of the single crystal growth furnace is controlled, and the temperature is raised to a fourth preset temperature. After the temperature is kept at a second preset time, the temperature is lowered and grown to obtain a high-entropy single crystal thermoelectric material.

[0101] Specifically, when growing a single crystal, the vacuumed and sealed second container is first placed vertically in a single crystal growth furnace with a temperature gradient, and then the rotation of the single crystal growth furnace is controlled and heated to a fourth preset temperature.

[0102] See also Figure 5 , wherein the temperature gradient of the single crystal growth furnace is in the range [80 Kelvin (K), 120 K], for example, the temperature gradient is 100 K. If the single crystal growth furnace includes a heating zone, a gradient zone, and a cooling zone, the temperature gradient between the heating zone and the cooling zone is 100 K.

[0103] Optionally, the temperature range of the gradient zone is within the interval [5 cm, 15 cm]. For example, if the temperature range is 10 cm, the vertical height of the gradient zone is 10 cm.

[0104] During heating, the single crystal growth furnace is continuously rotated to ensure uniform heating, for example, at a rotation rate of 6 revolutions per minute.

[0105] After the temperature of the single crystal growth furnace rises to the fourth preset temperature, it is kept at this temperature for a second preset time (eg, 10 hours) and then cooled for growth to obtain a high entropy single crystal thermoelectric material.

[0106] During cooling growth, the second container slowly descends, and the bottom temperature entering the cooling zone first drops below the melting point, and crystallization begins. As the second container continues to descend, the crystals continue to grow, and eventually a high-entropy single crystal thermoelectric material is obtained.

[0107] Optionally, the fourth preset temperature is in the range of [1073K*0.8, 1073K*1.2]. For example, the fourth preset temperature is 1073K to ensure the effect of single crystal growth.

[0108] The method for manufacturing high-entropy single-crystal thermoelectric materials provided in this application synthesizes a stable single-phase high-entropy polycrystalline material through a melt process, and then uses the Bridgman method to grow large-scale high-entropy single-crystal thermoelectric materials. This method has the advantages of simplicity and high repeatability. Furthermore, during the single-crystal growth process, uncertainties caused by the complexity of the chemical composition, including destructive factors such as second-phase transitions, which can affect the integrity of the crystal, are avoided.

[0109] In some embodiments, see Figure 6 , the manufacturing method further comprises:

[0110] Step 016: Obtain scanning electron microscope images, scanning transmission electron microscope images, and energy spectrum information of the high entropy single crystal thermoelectric material;

[0111] Step 017: Based on the scanning electron microscope image, the scanning transmission electron microscope image and the energy spectrum information, determine whether the high entropy single crystal thermoelectric material has a single crystal structure.

[0112] Specifically, in order to determine whether the generated high-entropy single crystal thermoelectric material is a single crystal structure, scanning electron microscope images, scanning transmission electron microscope images and energy spectrum information of the high-entropy single crystal thermoelectric material can be obtained; thereby accurately determining it through scanning electron microscope images, scanning transmission electron microscope images and energy spectrum information.

[0113] like Figure 7 As shown, Figure 7 a and Figure 7 b is the Laue diffraction spots of the high entropy single crystal thermoelectric material (110) and (100) planes. Figure 7 c and Figure 7 d is the corresponding standard Laue diffraction pattern. It can be seen that the high-entropy GeTe single crystal has a single crystal structure.

[0114] like Figure 8 a and Figure 8 As shown in b, they are the SEM (scanning electron microscope) images of high entropy GeTe single crystals and the corresponding mapping (energy spectrum information), Figure 8 c and Figure 8 d is the STEM images (scanning transmission electron microscope) at low and high magnification, respectively. It can be seen that the high-entropy GeTe single crystal has high uniformity.

[0115] like Figure 9 Shown are the electrical conductivity σ, Seebeck coefficient S, total thermal conductivity κ and thermoelectric figure of merit ZT of high-entropy GeTe single crystal.

[0116] It can be seen that the electrical conductivity σ, Seebeck coefficient S, total thermal conductivity κ and thermoelectric figure of merit ZT are all relatively good, with good thermoelectric performance, and can achieve coordinated optimization of electrical and thermal transport parameters.

[0117] See also Figure 10 According to the method described in the above embodiment, the present application also provides an apparatus 10 for manufacturing a high-entropy single crystal thermoelectric material. The apparatus 10 includes:

[0118] A vacuum suction device 11 is used to vacuum the first container containing the high entropy raw material;

[0119] a sealing device 12, for sealing the first container;

[0120] a melting device 13 for melting, quenching and annealing the vacuumed and sealed first container to produce a high-entropy polycrystalline ingot;

[0121] A grinding device 14 is used to grind the high entropy polycrystalline ingot to obtain a high entropy single-phase powder with a single-phase structure;

[0122] The vacuum suction device 11 is also used to vacuum the second container containing the high entropy single-phase powder, and the sealing device 12 is used to seal the second container;

[0123] The single crystal growth furnace 15 performs single crystal growth on the high entropy single-phase powder in the vacuumed and sealed second container based on the Bridgman method to obtain a high entropy single crystal thermoelectric material.

[0124] In the embodiments of the present application, the term "module" or "unit" refers to a computer program or a part of a computer program that has a predetermined function and works together with other related parts to achieve a predetermined goal, and can be implemented in whole or in part by using software, hardware (such as processing circuits or memories) or a combination thereof. Similarly, a processor (or multiple processors or memories) can be used to implement one or more modules or units. In addition, each module or unit can be part of an overall module or unit that includes the function of the module or unit.

[0125] In some embodiments, the method for manufacturing high-entropy single-crystal thermoelectric materials of the present application can be implemented by electronic devices.

[0126] The electronic device may be a terminal device and / or a server.

[0127] Among them, the terminal device can be a smart phone (such as an Android phone, an IOS phone, etc.), a tablet computer, a laptop computer, a desktop computer, a smart speaker, a smart watch, a portable personal computer, a mobile Internet device (Mobile Internet Devices, referred to as MID), an intelligent voice interaction device, a smart home appliance, a vehicle terminal, an aircraft, a wearable device, etc., and the embodiments of this application do not limit this.

[0128] See also Figure 11 , Figure 11 Schematic diagram of the hardware structure of an electronic device provided in an embodiment of the present application. The electronic device can be a terminal or a server. Exemplarily, the electronic device 700 includes a central processing unit (CPU) 701, a system memory 704 including a random access memory (RAM) 702 and a read-only memory (ROM) 703, and a system bus 705 connecting the system memory 704 and the central processing unit 701.

[0129] In some embodiments, the electronic device 700 may also include a basic input / output system (BIOS) 706 for facilitating information transmission between various components within the computer, and a large-capacity storage device 707 for storing an operating system 713, a client 714, and other program modules 715.

[0130] In some embodiments, the basic input / output system 706 includes a display 708 for displaying information and an input device 709 such as a touch panel or other input device for user input of information. A touch panel is also called a touch screen. A touch panel may include two parts: a touch device and a touch controller. Other input devices may include, but are not limited to, a physical keyboard, function keys (such as a volume control button, an on / off button, etc.), a trackball, a mouse, and a joystick, which are not described in detail here.

[0131] The display 708 and input device 709 are both connected to the CPU 701 via an input / output controller 710 connected to the system bus 705. The basic input / output system 706 may also include an input / output controller 710 for receiving and processing input from a touch panel, other input devices, etc. Similarly, the input / output system 706 may also include output devices, such as a display screen, a printer, or other types of output devices.

[0132] The mass storage device 707 is connected to the central processing unit 701 via a mass storage controller (not shown) connected to the system bus 705. The mass storage device 707 and its associated computer-readable media provide non-volatile storage for the electronic device 700. In other words, the mass storage device 707 may include a computer-readable medium (not shown) such as a hard disk or a Compact Disc Read-Only Memory (CD-ROM) drive.

[0133] According to various embodiments of the present application, the electronic device 700 can also be connected to a remote computer on a network via a network such as the Internet. That is, the electronic device 700 can be connected to the network 717 via the network interface unit 716 connected to the system bus 705, or the network interface unit 716 can be used to connect to other types of networks or remote computer systems (not shown).

[0134] An embodiment of the present application also provides a non-transitory computer-readable storage medium, which stores a computer program. When the computer program is executed by a processor, it implements the various processes of the embodiment of the above-mentioned method for manufacturing high-entropy single crystal thermoelectric materials and can achieve the same technical effect. To avoid repetition, it will not be repeated here.

[0135] The processor may be the processor in the electronic device in the above embodiment. The computer readable storage medium may be a computer read-only memory (ROM), a random access memory (RAM), a magnetic disk, or an optical disk.

[0136] Computer-readable media may include computer storage media and communication media. Computer storage media include volatile and non-volatile, removable and non-removable media implemented by any method or technology for storing information such as computer-readable instructions, data structures, program modules or other data. Computer storage media include RAM, ROM, Erasable Programmable Read-Only Memory (EPROM), Electrically Erasable Programmable Read-Only Memory (EEPROM), flash memory or other solid-state memory technology, CD-ROM, Digital Versatile Disc (DVD) or other optical storage, tape cassettes, magnetic tape, disk storage or other magnetic storage devices. Of course, those skilled in the art will appreciate that computer storage media are not limited to the above.

[0137] The present application also provides a computer program product, including a computer program, which, when executed by a processor, implements the above-described method for manufacturing a high-entropy single-crystal thermoelectric material. The processor may be a processor in the electronic device described in the above-described embodiment. When executed by the processor, the computer program implements each of the steps of the above-described method for manufacturing a high-entropy single-crystal thermoelectric material, achieving the same technical effects. To avoid repetition, these steps are not described here.

[0138] It is understandable that in the specific implementation of this application, data related to user identity or characteristics is involved. When the above embodiments of this application are applied to specific products or technologies, user permission or consent is required, and the collection, use and processing of relevant data must comply with relevant laws, regulations and standards of relevant countries and regions.

Claims

1. A method for manufacturing a high entropy single crystal thermoelectric material, characterized in that: include: Putting the high entropy raw material into a first container, and performing vacuuming and sealing operations on the first container; Melting, quenching and annealing the vacuumed and sealed first container to produce a high-entropy polycrystalline ingot; Grinding the high entropy polycrystalline ingot to obtain a high entropy single-phase powder with a single-phase structure; placing the high entropy single-phase powder into a second container, and performing vacuum and sealing operations on the second container; The high-entropy single-phase powder in the vacuumed and sealed second container is subjected to single crystal growth based on the Bridgman method to obtain the high-entropy single crystal thermoelectric material.

2. The method for manufacturing a high entropy single crystal thermoelectric material according to claim 1, characterized in that: The high entropy raw material includes at least 5 elements, and the proportion of each element in the high entropy raw material is greater than 5%.

3. The method for manufacturing a high entropy single crystal thermoelectric material according to claim 1 or 2, characterized in that: The thermoelectric material system of the high entropy raw material includes one or more of GeTe, Bi2Te3, Cu2S, Ag2Se, SnSe, Mg3Sb2, VI-IV group thermoelectric materials, CoSb3, and half-Heusler based thermoelectric materials.

4. The method for manufacturing a high entropy single crystal thermoelectric material according to claim 1, wherein: The components of the high entropy raw material include Ge x A y B z C u Te v , A, B, C are the elements at the cation position, and x, y, z, u, v are the proportions of the corresponding elements.

5. The method for manufacturing a high entropy single crystal thermoelectric material according to claim 1, wherein: The first container and the second container include quartz tubes, and the inner walls of the quartz tubes are coated with a carbon film.

6. The method for manufacturing a high entropy single crystal thermoelectric material according to claim 1, wherein: The pressure of the first container and the second container after evacuation is less than 10 -4 Pascal (pa).

7. The method for manufacturing a high entropy single crystal thermoelectric material according to claim 1, characterized in that: The first container and the second container each include an opening, and the sealing operation includes burning the opening with a propane flame to close the opening.

8. The method for manufacturing a high entropy single crystal thermoelectric material according to claim 1, wherein: The step of melting, quenching, and annealing the vacuumed and sealed first container to generate a high-entropy polycrystalline ingot comprises: placing the vacuumed and sealed first container in a muffle furnace and heating it so that the first container is heated to a first preset temperature and then kept warm; After holding the first container at a temperature for a first preset time, quenching the first container; annealing the first container after quenching at a second preset temperature; When the first container is cooled to a third preset temperature, quenching is performed again to generate the high entropy polycrystalline ingot.

9. The method for manufacturing a high entropy single crystal thermoelectric material according to claim 8, characterized in that: The first preset temperature is in the interval [1273 K*0.8, 1273 K*1.2], the second preset temperature is in the interval [953 K*0.8, 953 K*1.2], the third preset temperature is in the interval [753 K*0.8, 753 K*1.2], and the first preset time is greater than 6 hours (h).

10. The method for manufacturing a high entropy single crystal thermoelectric material according to claim 1, wherein: The grinding of the high entropy polycrystalline ingot to obtain a high entropy single-phase powder with a single-phase structure comprises: The high entropy polycrystalline ingot is ground using an agate mortar to obtain a high entropy single-phase powder with a single-phase structure.

11. The method for manufacturing a high entropy single crystal thermoelectric material according to claim 1, wherein: The method further comprises: Obtaining a diffraction pattern of the high entropy single-phase powder at room temperature using an X-ray diffraction method; The step of placing the high entropy single-phase powder into a second container and performing vacuuming and sealing operations on the second container includes: When the high-entropy single-phase powder is confirmed to have a single-phase structure based on the diffraction pattern, the high-entropy single-phase powder is placed in a second container, and the second container is vacuumed and sealed.

12. The method for manufacturing a high entropy single crystal thermoelectric material according to claim 1 or 11, characterized in that: The method of performing single crystal growth on the high-entropy single-phase powder in the vacuumed and sealed second container based on the Bridgman method to obtain the high-entropy single crystal thermoelectric material includes: The second container after evacuation and sealing is kept vertically placed in a single crystal growth furnace with a temperature gradient, the rotation of the single crystal growth furnace is controlled, and after heating to a fourth preset temperature, it is kept warm for a second preset time, and then cooled and grown to obtain the high entropy single crystal thermoelectric material.

13. The method for manufacturing a high entropy single crystal thermoelectric material according to claim 12, wherein: The temperature gradient of the single crystal growth furnace is in the interval [80 Kelvin (K), 120 K], the temperature field range is in the interval [5 cm, 15 cm], and the fourth preset temperature is in the interval [1073 K*0.8, 1073 K*1.2].

14. The method for manufacturing a high entropy single crystal thermoelectric material according to claim 1, wherein: Also includes: Obtaining a scanning electron microscope image, a scanning transmission electron microscope image, and energy spectrum information of the high-entropy single crystal thermoelectric material; Based on the scanning electron microscope image, the scanning transmission electron microscope image and the energy spectrum information, it is determined whether the high entropy single crystal thermoelectric material has a single crystal structure.

15. A device for manufacturing high entropy single crystal thermoelectric materials, characterized in that: include: A vacuum suction device, used for vacuuming the first container containing the high entropy raw material; a sealing device for sealing the first container; a smelting device for smelting, quenching and annealing the vacuumed and sealed first container to produce a high-entropy polycrystalline ingot; A grinding device for grinding the high-entropy polycrystalline ingot to obtain a high-entropy single-phase powder with a single-phase structure; The vacuum suction device is further used to vacuum the second container containing the high entropy single-phase powder, and the sealing device is used to seal the second container; A single crystal growth furnace is used to perform single crystal growth on the high-entropy single-phase powder in the vacuumed and sealed second container based on the Bridgman method to obtain the high-entropy single crystal thermoelectric material.

16. A non-transitory computer-readable storage medium having a computer program stored thereon, characterized in that: When the computer program is executed by a processor, the method for manufacturing the high-entropy single crystal thermoelectric material according to any one of claims 1 to 14 is implemented.

17. A computer program product, characterized in that The invention comprises a computer program, which, when executed by a processor, realizes the method for manufacturing the high-entropy single crystal thermoelectric material according to any one of claims 1 to 14.

Images