CN215785752U - Equipment for preparing thermoelectric material - Google Patents
Equipment for preparing thermoelectric material Download PDFInfo
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- CN215785752U CN215785752U CN202120439472.2U CN202120439472U CN215785752U CN 215785752 U CN215785752 U CN 215785752U CN 202120439472 U CN202120439472 U CN 202120439472U CN 215785752 U CN215785752 U CN 215785752U
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Abstract
The present invention provides an apparatus for manufacturing a thermoelectric material, comprising: vacuum cavity, extrusion external member, heating device and hold the material chamber, wherein, the extrusion external member is including extrusion post, sleeve, extrusion die and brace table, extrusion die's inner chamber includes reducing part and vertical part, wherein, the reducing part comprises two at least conic sections that half cone angle reduces in proper order, perhaps the lateral wall of reducing part is the arc. The thermoelectric material prepared by the equipment has the advantages of good crystal orientation, uniform components, excellent thermoelectric property and strong mechanical property, and is a key technology for preparing high-end thermoelectric device materials.
Description
Technical Field
The utility model relates to a method for producing thermoelectric materials.
Background
The thermoelectric material is a functional material capable of realizing direct interconversion of heat energy and electric energy, and a thermoelectric component prepared from the thermoelectric material has the advantages of light weight, small volume, simple structure, no noise, zero emission, long service life and the like. This is of great significance to solve the serious problems of energy crisis and environmental pollution, and has therefore received high attention from all countries in the world.
With the design concept of new materials and the development of new processes and new technologies for preparing materials, the performance of thermoelectric materials is gradually optimized and improved. Among them, the hot extrusion deformation method is considered as one of the most important synthetic preparation methods, and the grain orientation and mechanical properties of the material can be effectively controlled. Most of the existing methods for preparing bismuth telluride-based alloy materials by a hot extrusion method are masterbatches of target components obtained by a zone melting method, a mechanized alloy method, a melting method and the like, and then the masterbatches, or crushed masterbatches, or the masterbatches which are crushed and then pressed and formed again are put into a die for hot extrusion to obtain a block material with better thermoelectric property and mechanical property. The method can greatly improve the mechanical property of the material under the condition of keeping the advantage of the anisotropy of the crystal, and is particularly suitable for high-end thermoelectric devices. However, most of the current laboratory researches are mainly laboratory preparation of small-size materials, the performance is relatively poor, and the industrial production cannot be met.
CN201592203U provides a hot extrusion die for bismuth telluride thermoelectric material, which comprises an upper extrusion cylinder, a female die and a lower extrusion cylinder, wherein the female die is arranged in the lower extrusion cylinder, the structure of the female die comprises a conical part and a vertical part, the extrusion angle of the conical part is 30-60 degrees, and the ratio of the total cross-sectional area of the material before extrusion to the total cross-sectional area of the material after extrusion, namely the extrusion ratio, is 2.5-4.5. The raw material rod prepared by the zone melting method is extruded by using the die, the crystal orientation in the material is obviously improved after 823K sintering, and the cleavage plane basically tends to be parallel to the growth direction.
CN101985776A discloses a preparation method of a bismuth telluride-based thermoelectric material with preferred orientation of crystal grains, which comprises the step of directly hot extruding a raw material ingot obtained by a zone melting method by using an extrusion die, wherein the extrusion die comprises an upper die, a lower die and an inner die, a tapered hole and a straight hole are arranged in the inner die, and the included angle of the section of the tapered hole is 30-60 degrees. The results show that Bi prepared by the method2Te3The thermoelectric figure of merit Z of the base thermoelectric material can reach 3.87 multiplied by 10-3and/K, SEM results show that the sizes of the grains in the material are all smaller than 20 microns, the sizes of the grains are uniform, and mechanical property tests show that the flexural strength of the material can reach more than 50 MPa.
US6596226B1 discloses a method for manufacturing a thermoelectric material and a thermoelectric material thereof, which method prepares a BiTe-based material powder by a mechanical alloying method, and obtains an alloy by extrusion with an extruder equipped with a multistage die.
However, the thermoelectric material prepared by the above method still cannot meet the requirements of high-end thermoelectric refrigeration devices. The inventor of the present invention found that, in chinese patents CN201592203U and CN101985776A, since only one time of diameter change is performed in the extrusion process (i.e. only one fixed extrusion angle is used for a single extrusion), the extruded rod has many cracks and the performance is not ideal. In the US patent US6596226B1, since the multi-stage die is used for the reducing extrusion process, the material passes through a die segment with a vertical inner wall in each stage, so that the generation of cracks cannot be avoided to influence the actual production, and the oxidation protection of the material is insufficient, so that the performance of some materials is poor.
Therefore, the extrusion deformation technology has the defects that the technical problem of the neck for the production of high-end thermoelectric devices is restricted at present, and particularly, the high-power density refrigeration device can be processed into a required size only by using the extrusion deformation bismuth telluride material. At present, China does not have the production capacity of competitive high-end thermoelectric refrigeration devices, and the key reason is lack of a method and equipment for preparing thermoelectric materials.
SUMMERY OF THE UTILITY MODEL
Accordingly, an object of the present invention is to provide an apparatus for manufacturing a thermoelectric material to improve crystal orientation inside the material, eliminate cracks during extrusion, and thus obtain a bulk thermoelectric material having both excellent thermoelectric properties and mechanical properties.
Single crystal or directionally solidified thermoelectric materials can take full advantage of the crystal anisotropy, and industry selection of a particular direction of use of such materials can yield the best performance, including thermoelectric figure of merit and conversion power. The high-power thermoelectric refrigerating device needs to cut the thermoelectric material as small as possible (generally, the length, width and height are less than 0.5mm) without considering the interface effect. However, single crystal and directionally solidified samples have insufficient mechanical properties and are not easy to process, and the feasibility is completely unavailable. Although the mechanical properties of the block obtained by hot pressing of fine grains are greatly improved due to the effect of the grain boundaries to block crack propagation, the advantages of anisotropy are lost due to the completely random distribution in crystallographic orientation.
Although the diameter-variable technology is adopted in the conventional method for preparing the thermoelectric material, researchers only pay attention to the change of the diameter of a die or the selection of an extrusion angle, but the conditions are not essential factors for improving the generation of cracks and guaranteeing the thermoelectric performance, so that the thermoelectric material with high quality cannot be prepared by simply optimizing the conditions. The inventors of the present invention have made extensive and intensive studies and have unexpectedly found that: the fundamental factors for reducing cracks to the maximum extent and ensuring the thermoelectric performance of the material are that the shearing force generated by the corner part of the extrusion die to the raw material in the diameter changing process is reduced as much as possible. Based on the discovery, the inventor of the utility model carries out hot extrusion deformation on a fine grain sample by adopting a hot extrusion die with an improved reducing mode to obtain a highly oriented fine grain block material.
The present invention provides an apparatus for producing a thermoelectric material, the apparatus comprising: a vacuum cavity, an extrusion external member, a heating device and a material bearing cavity,
wherein the extrusion suite is positioned in the vacuum cavity, the heating device is used for heating the extrusion suite, the material bearing cavity is connected with the discharge end of the extrusion suite and is used for receiving materials extruded from the extrusion suite,
the extrusion external member comprises an extrusion column, a sleeve, an extrusion die and a supporting table, wherein an inner cavity of the extrusion die comprises a variable diameter part and a vertical part, wherein the variable diameter part is formed by at least two cone sections with half cone angles which are reduced in sequence, or the side wall of the variable diameter part is arc-shaped.
According to the equipment, the diameter-variable part is formed by a plurality of conical sections or the side wall is arc-shaped, so that the shearing force of the corner part of the extrusion die on the raw material in the diameter-variable process is reduced, and the anisotropic thermoelectric property of the material is obtained to a greater extent.
Fig. 3 is a schematic view of an apparatus for preparing a thermoelectric material according to the present invention, which includes: the device comprises a pressure head 1, a vacuum cavity 2, an extrusion external member, a heating device 3 and a material bearing cavity 4.
Fig. 4 is a schematic view of an extrusion kit in an apparatus for preparing a thermoelectric material provided in the present invention, which includes: extrusion column 21, sleeve 22, extrusion die 23 and support table 24. Schematic diagrams of two embodiments of the extrusion die are shown in fig. 1 and 2.
In the present invention, the term "the variable diameter portion is formed by at least two cone segments whose half cone angles are successively reduced" means that: the diameter of the small end of the upstream conical section is equal to the diameter of the large end of the downstream conical section adjacent to the upstream conical section according to the advancing direction of the master batch. The diameter of the small end of the conical section located furthest downstream is equal to the diameter of the vertical section.
Wherein, the half cone angle refers to a half of the vertex angle of the cone section, and represents the included angle between the extrusion direction and the inner wall of the extrusion die. In some embodiments of the utility model, the half cone angle may be from greater than 0 ° to 80 °. In a preferred embodiment of the utility model, the difference between the half cone angles between two adjacent cone segments may be in the range of 5 ° to 20 °.
Fig. 1 is a schematic view of an extrusion die in which a variable diameter portion is composed of two taper segments, where 231A is the variable diameter portion, 232A is a vertical portion, and θ 1 and θ 2 represent half taper angles of a first taper segment and a second taper segment, respectively. In the embodiment of the two-cone variable diameter as shown in fig. 1, the difference (θ 1- θ 2) between the half cone angles of the first cone section and the second cone section may be 5 ° to 20 °.
When the variable diameter portion is composed of more than two conical sections, the difference between the half cone angles of every two adjacent conical sections may be the same or different, as long as the half cone angle of the upstream conical section is larger than that of the downstream conical section.
According to the equipment provided by the utility model, the ratio of the small end diameter to the large end diameter of each conical section can be 1: 1.3-1: 3. The heights of different conical sections can be the same or different.
Preferably, the ratio of the diameter of the vertical part (i.e. the minimum diameter of the variable diameter part) to the diameter of the maximum diameter of the variable diameter part is 1:2 to 1:6, more preferably 1:2.5 to 1: 4.
Preferably, the ratio of the height of the vertical part to the height of the variable diameter part is 1: 4-2: 1.
In the first embodiment of the present invention, the diameter of the small end of the nth taper section (the most downstream taper section, the smallest diameter taper section) of the variable diameter portion is equal to the diameter of the vertical portion. In another embodiment of the utility model, when the number of the conical sections included in the reducing portion tends to be infinite, the side wall of the reducing portion becomes arc-shaped (radian reducing), and the angle of the reducing portion of the radian reducing die is finally almost tangent to the vertical portion. Fig. 2 is a schematic view of an extrusion die with an arc-shaped sidewall of the variable diameter portion, wherein 231B is the variable diameter portion and 232B is the vertical portion.
The method for preparing the thermoelectric material by adopting the equipment provided by the utility model comprises the following steps:
(1) loading the block or powder thermoelectric material master batch into an extrusion die;
(2) placing an extrusion die in a vacuum atmosphere, applying pressure under heating, extruding a thermoelectric material master batch through the extrusion die to obtain the thermoelectric material,
the inner cavity of the extrusion die comprises a variable diameter part and a vertical part, wherein the variable diameter part is formed by at least two cone sections with half cone angles which are reduced in sequence, or the side wall of the variable diameter part is arc-shaped.
The thermoelectric material may be a material commonly used in the art to realize direct interconversion between thermal energy and electric energy, and may be, for example, one of a thermoelectric refrigeration device, a thermoelectric refrigeration micro-device, and a thermoelectric power generation device. Preferably, the thermoelectric material has a chemical formula of (Bi)1-xSbx)2(Te1-ySey)3+zWherein x is 0-1, y is greater than 0 and less than 0.3, z is greater than-0.5 and less than 0.5, optionally including Cu, Pb, I, Br, SbI3And S.
In this context, the terms "thermoelectric material masterbatch" and "thermoelectric material" are materials of the same chemical composition, and they are distinguished only in that "thermoelectric material masterbatch" refers to a material whose density, electronic structure, or grain orientation, etc. do not meet the requirements, and "thermoelectric material" refers to a bulk material whose thermoelectric properties and mechanical properties are significantly improved after hot extrusion.
In a preferred embodiment, the preparation method of the thermoelectric material master batch comprises the following steps: and (2) making the ingot casting prepared by the zone melting method into powder by ball milling, sieving the powder, and then hot-pressing the powder into blocks to be used as the block thermoelectric material master batch in the step (1) of the preparation method.
In the above production method, the degree of vacuum of the vacuum atmosphere in the step (2) is 1Pa or less. The heating temperature may be 320 ℃ to 490 ℃. The time for extrusion may be 0.5 to 8 hours, preferably 1 to 4 hours. The extrusion pressure may be 50 to 500MPa, preferably 70 to 150 MPa. The extrusion speed can be 0.1-5 mm/min.
In a preferred embodiment, the process for preparing a thermoelectric material using the apparatus of the present invention is as follows: putting the block or powder thermoelectric material master batch into a sleeve 22, assembling an extrusion suite 2, controlling a vacuum atmosphere, heating to a specific temperature (320-490 ℃) at a specific speed (5-50K/min), then preserving heat for 1min to 2 hours, increasing the pressure to start extrusion, wherein the extrusion pressure is 50-500 MPa, and the moving speed of a pressure head is 0.1-3 mm/min. The thermoelectric material moves in a reducing way through an extrusion die at a specific temperature and pressureThe product is stored in the material bearing cavity, the shape of the product can be a cylinder, a rectangle or other shapes, and the sectional area can be 25-1500 mm2。
The thermoelectric material prepared by the method or obtained by hot extrusion of the equipment has the compressive strength along the pressure direction of>195MPa, and power factor of 30-50 μ W cm along pressure direction-1K-2The thermoelectric figure of merit at room temperature is 0.80 to 1.1.
The device and the method provided by the utility model give full play to the performance advantage of the anisotropy of the thermoelectric material, and simultaneously utilize the microcrystalline structure to provide good mechanical properties for the material. Taking bismuth telluride thermoelectric material as an example, the utility model greatly improves the thermoelectric property of the material, including the improvement of the power factors of n-type and p-type materials, particularly the thermoelectric figure of merit of the n-type material is greatly improved relative to a hot-pressed sample, and simultaneously the mechanical property of the material is greatly improved relative to single crystal and zone melting samples. Therefore, the thermoelectric material prepared by extrusion deformation is particularly suitable for preparing high-end thermoelectric devices, in particular thermoelectric refrigeration micro-devices used for high-heat-flow-density refrigeration. The synthesis method of the extrusion shrinkage deformation can produce high-quality thermoelectric materials in batches, can replace the existing preparation method in the market, improve the mechanical property of a sample, utilize the advantage of the anisotropic thermoelectric property of the material to the maximum extent, greatly improve the performance of a thermoelectric device, has huge potential on economic benefit and has wide development prospect.
Drawings
Embodiments of the utility model are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a schematic view of an extrusion die with a variable diameter portion formed by two conical sections;
FIG. 2 is a schematic view of an extrusion die with an arc-shaped side wall of the diameter-variable portion;
FIG. 3 is a schematic view of an apparatus for preparing a thermoelectric material according to the present invention;
fig. 4 is a schematic view of an extrusion kit in an apparatus for manufacturing a thermoelectric material according to the present invention.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the utility model.
A schematic diagram of an apparatus used in an embodiment of the present invention is shown in fig. 3 and 4. As shown in fig. 3, the present invention provides an apparatus for manufacturing a thermoelectric material, comprising: the device comprises a pressure head 1, a vacuum cavity 2, an extrusion external member, a heating device 3 and a material bearing cavity 4. As shown in fig. 4, the present invention provides an extrusion kit for use in an apparatus for manufacturing a thermoelectric material, comprising: extrusion column 21, sleeve 22, extrusion die 23 and support table 24.
Schematic diagrams of two embodiments of the extrusion die 23 are shown in fig. 1 and 2. Fig. 1 is a schematic view of an extrusion die in which a variable diameter portion is composed of two taper segments, where 231A is the variable diameter portion, 232A is a vertical portion, and θ 1 and θ 2 represent half taper angles of a first taper segment and a second taper segment, respectively. In the embodiment of the two-cone variable diameter as shown in fig. 1, the difference (θ 1- θ 2) between the half cone angles of the first cone section and the second cone section may be 5 ° to 20 °. Fig. 2 is a schematic view of an extrusion die with an arc-shaped sidewall of the variable diameter portion, wherein 231B is the variable diameter portion and 232B is the vertical portion.
Example 1
The schematic diagram of the apparatus employed in this embodiment is shown in fig. 3 and 4. The specific parameters of the extrusion die are as follows: the ratio of the diameter of the vertical portion to the diameter of the maximum diameter is 1:3. Three-stage reducing is adopted, and the included angles of the sections of the tapered holes are respectively 50 degrees, 30 degrees and 15 degrees.
(1) According to the composition Sb1.6Bi0.4Te3Preparing raw materials, weighing about 200g of corresponding elements, adding a proper amount of Pb as doping, filling into a quartz tube, vacuumizing to below 1Pa, and melting and sealing under a high-temperature flame gun. Melting and combining the materials in the sealed quartz tube in a rocking furnace, heating to 1000 ℃, rocking for 2 hours, quenching, annealing at 500 ℃ for one day, and ball-milling for 4 hours to form powder. Sieving the powder to remove crystal grains larger than 60 μm, and hot pressing in SPS at 450 deg.C to obtain block.
(2) And (2) putting the block material prepared in the step (1) into a sleeve of the device, applying 50MPa of initial pressure, slowly heating to 400 ℃, preserving heat for 20min, pressurizing to 100MPa, and starting extrusion at the extrusion speed of 1mm/min until the extrusion is finished.
The surface of the extruded sample is smooth, and the power factor is 46 mu W cm in the pressure direction through the test of an LSR-3 Seebeck coefficient/resistance tester-1K-2And combining the thermal conductivity data of the LFA1000 test, the thermoelectric figure of merit at room temperature is 1.1.
Example 2
The schematic diagram of the apparatus employed in this embodiment is shown in fig. 3 and 4. The specific parameters of the extrusion die are as follows: the ratio of the diameter of the vertical portion to the diameter of the maximum diameter is 1: 3.5. Four-stage reducing is adopted, and the included angles of the sections of the tapered holes are respectively 60 degrees, 45 degrees, 30 degrees and 15 degrees.
(1) According to the composition Bi2Te2.7Se0.3Preparing raw materials, weighing about 200g of corresponding elements, and adding a proper amount of SbI3As doping, the mixture was put into a quartz tube, evacuated to a pressure of 1Pa or less, and melt-sealed with a high-temperature flame gun. Melting and combining the materials in the sealed quartz tube in a rocking furnace, heating to 1000 ℃, rocking for 2 hours, quenching, annealing at 500 ℃ for one day, and ball-milling for 4 hours to form powder. Sieving the powder to remove crystal grains larger than 60 μm, and hot pressing in SPS at 450 deg.C to obtain block.
(2) And (2) putting the block material prepared in the step (1) into a sleeve of the device, applying 50MPa of initial pressure, slowly heating to 450 ℃, preserving heat for 20min, pressurizing to 150MPa, and starting extrusion at the extrusion speed of 1mm/min until the extrusion is finished.
The surface of the sample after extrusion is smooth, the compressive strength along the pressure direction is 195.86MPa, and the power factor along the pressure direction is 42 mu W cm-1K-2And a thermoelectric figure of merit of 0.85 at room temperature.
Example 3
The schematic diagram of the apparatus employed in this embodiment is shown in fig. 3 and 4. The specific parameters of the extrusion die are as follows: the ratio of the diameter of the vertical portion to the diameter of the maximum diameter is 1:3. Arc-shaped reducing is adopted.
(1) According to the composition Bi2Te2.7Se0.3Preparing raw materials, weighing about 200g of corresponding elements, and adding a proper amount of SbI3And (3) performing high-energy ball milling for 4 hours to form powder for doping. Sieving the powder to remove the crystal grains larger than 60 mu m.
(2) And (2) putting the powder prepared in the step (1) into a sleeve of the equipment, applying 50MPa of initial pressure, slowly heating to 450 ℃, preserving heat for 20min, pressurizing to 150MPa, and starting extrusion at the extrusion speed of 1mm/min until the extrusion is finished.
The surface of the sample after extrusion is smooth, and the power factor is 40 mu W cm along the pressure direction-1K-2And a room temperature thermoelectric figure of merit of 0.81.
Comparative example 1
The extrusion die of the comparative example adopts a reducing grinding tool similar to CN101985776A, and the specific parameters are as follows: the ratio of the diameter of the vertical portion to the diameter of the maximum diameter is 1:3. The section included angle of the tapered hole is 30 degrees.
(1) Same as in step (1) in example 1.
(2) Applying 50MPa of initial pressure, slowly heating to 400 ℃, preserving heat for 20min, pressurizing to 70MPa, and starting extrusion at the extrusion speed of 3mm/min until the extrusion is finished.
The surface cracks of the samples after the extrusion are obvious.
Comparative example 2
The extrusion die of the comparative example adopts a multi-stage reducing grinding tool similar to US6596226B1, and the specific parameters are as follows: the ratio of the diameter of the vertical portion to the diameter of the maximum diameter is 1:3. The included angle of the section of the conical hole is 30 degrees, and the ratio of the variable diameters of the upper stage to the lower stage is 1:2 and 1:1.5 respectively.
(1) Same as in step (1) in example 3.
(2) Applying 50MPa of initial pressure, slowly heating to 490 ℃, preserving heat for 20min, pressurizing to 150MPa, and starting extrusion at the extrusion speed of 1mm/min until the extrusion is finished.
The surface of the sample after the extrusion was finished had a few cracks.
Claims (7)
1. An apparatus for producing a thermoelectric material, the apparatus comprising: a vacuum cavity, an extrusion external member, a heating device and a material bearing cavity,
wherein the extrusion suite is positioned in the vacuum cavity, the heating device is used for heating the extrusion suite, the material bearing cavity is connected with the discharge end of the extrusion suite and is used for receiving materials extruded from the extrusion suite,
the extrusion external member comprises an extrusion column, a sleeve, an extrusion die and a supporting table, wherein an inner cavity of the extrusion die comprises a variable diameter part and a vertical part, wherein the variable diameter part is formed by at least two cone sections with half cone angles which are reduced in sequence, or the side wall of the variable diameter part is arc-shaped.
2. The apparatus of claim 1, wherein the half cone angle is greater than 0 ° to 80 °.
3. The apparatus of claim 1, wherein the difference in half cone angles between two adjacent cone segments is between 5 ° and 20 °.
4. The apparatus of claim 1, wherein the ratio of the small end diameter to the large end radius of each cone segment is 1:1.3 to 1:3.
5. The apparatus of claim 1, wherein a ratio of a diameter of the vertical portion to a diameter of a maximum diameter of the variable diameter portion is 1:2 to 1: 6.
6. The apparatus of claim 1, wherein a ratio of a diameter of the vertical portion to a diameter of a maximum diameter of the variable diameter portion is 1:2.5 to 1: 4.
7. The apparatus of claim 5, wherein a ratio of a height of the vertical portion to a height of the variable diameter portion is 1:4 to 2: 1.
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