CN116117138A - Processing and forming method of bismuth telluride thermoelectric material - Google Patents

Processing and forming method of bismuth telluride thermoelectric material Download PDF

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CN116117138A
CN116117138A CN202211579626.3A CN202211579626A CN116117138A CN 116117138 A CN116117138 A CN 116117138A CN 202211579626 A CN202211579626 A CN 202211579626A CN 116117138 A CN116117138 A CN 116117138A
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bismuth telluride
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吴燕青
贺贤汉
丁金勇
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Shanghai Shenhe Investment Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B22F3/03—Press-moulding apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling

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Abstract

The invention provides a processing and forming method of bismuth telluride thermoelectric material, which comprises the steps of configuring P-type and N-type materials according to a preset molar ratio, respectively carrying out material pretreatment, respectively putting the pretreated P-type and N-type materials into a hot extrusion die with a multi-section variable diameter structure, putting the materials together with the die into a heater with the temperature of 300-500 ℃, applying a certain vertical pressure to the materials, discharging the materials along the extrusion force action direction through the inner cavity of the variable diameter hot extrusion die under the combined action of the temperature and the pressure to form a bar-shaped material with a certain section, and then carrying out heat treatment on the bar-shaped material. Experiments prove that the orientation degree of the thermoelectric material prepared by the method is improved by at least 16 percent, the compressive strength is improved by at least 6 percent, the thermoelectric performance is improved by at least 3 percent compared with the material obtained by the existing processing method, and the thermoelectric performance and the mechanical strength of the material are improved.

Description

Processing and forming method of bismuth telluride thermoelectric material
Technical Field
The invention belongs to the technical field of thermoelectric material preparation, and relates to a processing and forming method of bismuth telluride thermoelectric material.
Background
Thermoelectric materials are key materials for thermoelectric refrigeration or power generation devices, and are represented by Bi 2 Te 3 Thermoelectric materials based on these materials are the best commercial materials around room temperature to date, and industrial manufacturing methods thereof include zone melting and hot press sintering. The regional melting method can lead the material to obtain a certain orientation degree, has good thermoelectric performance, is easy to cleave, and has weak mechanical strength; the mechanical strength of the material prepared by the hot-press sintering method is obviously improved compared with that of the material prepared by the zone melting method, but the thermoelectric performance of the material is relatively low. Excellent thermoelectric performance and high mechanical strength are the targets sought after in the thermoelectric industry.
Bismuth telluride thermoelectric material processing has been studied earlier and more often, as Xu De, semiconductor refrigeration and application technology (Shanghai university of transportation Press 1991) describes Bridgman and zone melting growth of Bi 2 Te 3 A method of crystal; patent nos. ZL 03150425.6) and 200810038766.3 describe a method for preparing thermoelectric materials by sintering; the Chinese patent No. CN114210978A provides a hot extrusion molding method of bismuth telluride thermoelectric material, which combines powder metallurgy with one-time reducing hot extrusion process, realizes precise molding and performance improvement of the high-brittleness bismuth telluride thermoelectric material, and solves the problems of low reliability and performance attenuation of a thermoelectric refrigerator.
The variable diameter extrusion is applied more in the bismuth telluride thermoelectric material processing process, but one variable diameter extrusion operation is adopted more than once. In theory, continuous multi-reducing extrusion is beneficial to the fact that crystal lattices rotate repeatedly towards a preset direction, so that more crystal grains with ideal orientation are obtained, the crystal grains can be further refined through the multi-section reducing continuous hot extrusion mode, bars with large compression ratio can be conveniently processed, the thermoelectric performance and mechanical strength of corresponding materials can be correspondingly changed, and the research on continuous multi-reducing extrusion in the prior art is less.
Disclosure of Invention
Aiming at the defects of the prior art, the invention adopts a multi-section variable diameter continuous hot extrusion processing and forming process, continuously passes bismuth telluride to-be-processed blanks through a multi-section variable diameter hot extrusion die cavity with a certain compression ratio under the combined action of heat and mechanical pressure, and rotates crystal lattice for multiple times towards a preset direction under the shearing action of multiple times of variable diameter hot extrusion, thereby obtaining more ideal oriented crystal grains and optimizing the material orientation; after multiple reducing hot extrusion, the crystal grains are further refined, so that the thermoelectric performance and mechanical strength of the material are further improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided a method for forming a bismuth telluride thermoelectric material, comprising the steps of: the P-type material and the N-type material are configured according to a preset molar ratio, the materials are respectively pretreated, the pretreated P-type material and N-type material are respectively put into a variable diameter hot extrusion die, the P-type material and the N-type material are put into a heater with the temperature of 300 ℃ to 500 ℃ together with the die, a certain vertical pressure is applied to the materials, the materials are discharged along the extrusion force action direction through the inner cavity of the variable diameter hot extrusion die under the combined action of the temperature and the pressure to form a rod-shaped material with a certain section, then the rod-shaped material is subjected to heat treatment,
the inner cavity of the hot extrusion die comprises at least two sections of reducing structures, the side with the larger diameter and the side with the smaller diameter are in transition through a first conical surface with a certain angle with the central axis, and the lower part of the first conical surface is connected with a first cylindrical surface to form a first reducing section; a second conical surface with a certain angle with the central shaft is connected under the first cylindrical surface, the first conical surface and the second conical surface are in transition through a smooth circular arc surface, the second conical surface is connected under the second cylindrical surface to form a second reducing section, further a subsequent reducing section is formed according to the same method,
in each reducing section, the included angle between the conical surface and the central shaft is 45-70 degrees, and the area ratio of the upper circle to the lower circle of the conical surface is 2-15; the length and diameter ratio of the cylindrical surface are 0.3-1.0, and the total compression ratio is the product of the compression ratios of the variable diameter sections.
Preferably, in the processing and forming method of bismuth telluride thermoelectric material provided by the invention, the configuration method of the P-type and N-type materialsThe method is as follows: according to Bi 2 Te 3 And Sb (Sb) 2 Te 3 Calculating and weighing Bi, te and Sb according to the mol ratio of 15-25% to 85-75%, and adding Te as a doping agent to prepare a P-type material; according to Bi 2 Te 3 And Bi (Bi) 2 Se 3 Calculating and weighing Bi, te and Se materials with the molar ratio of 88-96 percent to 12-4 percent, adding doping agents to prepare N-type materials, respectively placing the P-type and N-type materials weighed according to the proportion into a quartz container, vacuumizing and sealing;
wherein the adding amount of the P-type material doping agent Te is Bi 2 Te 3 And Sb (Sb) 2 Te 3 0.1 to 0.5 percent of the total weight of the materials; the dopant of the N-type material is selected from one or more of halogen element F, cl, br, I and its compound, preferably SbI 3 The addition amount is Bi 2 Te 3 And Bi (Bi) 2 Se 3 200ppm to 800ppm of the total weight of the materials.
The quartz container is a quartz ampoule bottle or a quartz test tube, and the air pressure in the quartz container is made to be less than 2Pa after vacuumizing.
Preferably, in the processing and forming method of the bismuth telluride thermoelectric material provided by the invention, the pretreatment method of the P-type and N-type materials is as follows: the quartz container is put into a tubular furnace at 700-800 ℃ and heated for 1 hour, after swinging for 1 hour, the quartz container is taken out of the furnace and cooled in the air, the materials after high-temperature smelting are mechanically crushed and pressed at room temperature, and then the materials are put into a heating furnace at 500-600 ℃ and are subjected to heat treatment for 5-15 hours under the atmosphere of low oxygen partial pressure.
Wherein the mechanical crushing time is preferably 1 min-3 min; when the mixture is pressed and molded at room temperature, the pressure is preferably 100MPa to 180MPa; the oxygen partial pressure in the heating furnace is preferably controlled to 20ppm or less.
Further, there is a difference in heating temperature between the P-type material and the N-type material, the temperature of the P-type material heater is set to 300 to 390 ℃, and the temperature of the N-type material heater is set to 430 to 500 ℃.
Preferably, in the method for processing and molding the bismuth telluride thermoelectric material provided by the invention, when the rod-shaped material is subjected to heat treatment, the rod-shaped material is subjected to heat treatment again in an atmosphere with an oxygen partial pressure lower than 20ppm, and the heat treatment temperature is 350-400 ℃ for 5-15 hours.
In a second aspect, the invention provides a bismuth telluride thermoelectric bar which is processed by the method.
Experiments prove that the orientation degree of the thermoelectric material prepared by the method is improved by at least 16% compared with that of the thermoelectric material prepared by the existing processing method, the compressive strength is improved by at least 6%, the thermoelectric performance is improved by about 3%, and the mechanical performance and the thermoelectric performance are effectively improved.
Drawings
FIG. 1 is a schematic cross-sectional view of an inner cavity of a reducing hot extrusion die according to an embodiment of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Examples
Raw material Te, bi, sb, se with purity more than 99.99% is taken. According to 18% molBi 2 Te 3 :82％molSb 2 Te 3 The stoichiometric ratio of each element is calculated, corresponding element materials are weighed, the total weight is 5000g, te with the weight ratio of 0.5% is added as a doping agent, and a P-type material is prepared; according to 93% mol Bi 2 Te 3 :7％molBi 2 Se 3 Stoichiometric ratio of each element was calculated and the corresponding element material was weighed, the total weight was 6000g, sbI was added in a weight ratio of 500ppm 3 As the dopant, an N-type material is disposed.
And respectively placing the P-type material and the N-type material into a clean quartz glass tube, vacuumizing until the pressure in the tube is less than 2Pa, and sealing. Then the quartz glass tube is put into a tube type heating furnace, the temperature is set at 800 ℃, the temperature is raised for one hour, the temperature is kept constant and swaying for one hour, and the quartz glass tube is cooled outside the furnace.
The high-temperature synthesized material is mechanically crushed for 3min, pressed into a primary blank, kept at the temperature of 540 ℃, and cooled along with a furnace after the oxygen partial pressure in the furnace is less than 20PPm for 15 hours.
The blank is placed on a hot extrusion die with a three-section reducing structure, and the schematic structure diagram of the inner cavity of the die is shown in fig. 1. The diameter of the first reducing section is defined by
Figure BDA0003990187820000031
Become->
Figure BDA0003990187820000032
The diameter of the second reducing section is equal to or greater than that of the first reducing section>
Figure BDA0003990187820000033
Become->
Figure BDA0003990187820000034
The diameter of the third reducing section is equal to->
Figure BDA0003990187820000035
Become->
Figure BDA0003990187820000036
The side with the larger diameter and the side with the smaller diameter are transited through a first conical surface with a certain angle with the central axis, and the lower part of the first conical surface is connected with a first cylindrical surface to form a first reducing section; and a second conical surface with a certain angle with the central shaft is connected below the first cylindrical surface, the first conical surface and the second conical surface are in transition through a smooth circular arc surface, the second conical surface is connected below the second cylindrical surface to form a second reducing section, and then a third reducing section is formed according to the same method.
In the embodiment, the included angle theta between the conical surface and the central shaft in the three reducing sections is 50 degrees, and the maximum circular diameter is 100mm; the area ratio epsilon of the upper circle and the lower circle of the conical surface is epsilon respectively from large to small 1 ＝4.7，ε 2 ＝4.7，ε 3 =4.55; the ratio of the length to the diameter of the cylindrical surface is lambda 1 ＝0.6，λ 2 ＝0.6，λ 3 =1.0, the total compression ratio is the compression ratio of each variable diameter sectionThe product is about 100.
The billet was placed in a heater together with a die, the P-type material temperature was set to 360 ℃ and the N-type material temperature was set to 450 ℃, a pressure of 200MPa was applied in the extrusion direction, and a bar having a diameter of 10mm was extruded in the pressure direction.
The bar after extrusion molding is kept at 360 ℃ for 12 hours and then cooled along with a furnace, and the oxygen partial pressure below 20ppm is maintained in the furnace.
Comparative example
The experimental materials and the processing method are the same as the examples, the only difference is that the adopted variable-diameter extrusion grinding tool is a single variable-diameter section, and the diameter is that
Figure BDA0003990187820000042
Become->
Figure BDA0003990187820000043
Effect contrast
The bars prepared in the examples and comparative examples were processed into test pieces of the same specification, and thermoelectric properties, orientation degree, compressive strength and maximum temperature difference of devices of the materials were compared, and the results are shown in table 1:
table 1 comparison of results of performance tests for examples and comparative examples
Figure BDA0003990187820000041
According to the results, the orientation degree of the thermoelectric material prepared by the method is improved by at least 16% compared with that of the thermoelectric material prepared by the existing processing method, the compressive strength is improved by at least 6%, the thermoelectric performance is improved by about 3%, and the mechanical performance and the thermoelectric performance are effectively improved.
While the preferred embodiments of the present invention have been illustrated and described, the present invention is not limited to the embodiments, and various equivalent modifications and substitutions can be made by one skilled in the art without departing from the spirit of the present invention, and these equivalent modifications and substitutions are intended to be included in the scope of the present invention as defined in the appended claims.

Claims (8)

1. A process for preparing the thermoelectric bismuth telluride material includes such steps as preparing P-type and N-type materials, pretreating, putting the pretreated P-type and N-type materials in a variable-diameter hot-extruding die, putting them together with the die in a heater at 300-500 deg.C, applying a certain vertical pressure to the material, discharging the material from the internal cavity of said die along the action direction of extruding force to form a bar-shaped material with a certain cross section, heat treating,
the inner cavity of the hot extrusion die comprises at least two sections of reducing structures, the side with the larger diameter and the side with the smaller diameter are in transition through a first conical surface with a certain angle with the central axis, and the lower part of the first conical surface is connected with a first cylindrical surface to form a first reducing section; a second conical surface with a certain angle with the central shaft is connected under the first cylindrical surface, the first conical surface and the second conical surface are in transition through a smooth circular arc surface, the second conical surface is connected under the second cylindrical surface to form a second reducing section, further a subsequent reducing section is formed according to the same method,
in each reducing section, the included angle between the conical surface and the central shaft is 45-70 degrees, and the area ratio of the upper circle to the lower circle of the conical surface is 2-15; the length and diameter ratio of the cylindrical surface are 0.3-1.0, and the total compression ratio is the product of the compression ratios of the variable diameter sections.
2. The method of forming a bismuth telluride thermoelectric material as set forth in claim 1, wherein the method of disposing the P-type and N-type materials is as follows:
according to Bi 2 Te 3 And Sb (Sb) 2 Te 3 Calculating and weighing Bi, te and Sb according to the mol ratio of 15-25% to 85-75%, and adding Te as a doping agent to prepare a P-type material; according to Bi 2 Te 3 And Bi (Bi) 2 Se 3 The molar ratio of the Bi, te and Se materials is 88 to 96 percent and 12 to 4 percent, and the doping agent is added to prepare N-type material, and then the N-type material is weighed according to the proportionRespectively placing the P-type raw materials and the N-type raw materials into a quartz container, vacuumizing and sealing;
the adding amount of the P-type material dopant Te is Bi 2 Te 3 And Sb (Sb) 2 Te 3 0.1 to 0.5 percent of the total weight of the materials; the doping agent of the N-type material is selected from one or more of halogen element F, cl, br, I and its compound, and the addition amount is Bi 2 Te 3 And Bi (Bi) 2 Se 3 200ppm to 800ppm of the total weight of the materials.
3. The process for the forming of bismuth telluride thermoelectric material as set forth in claim 2, wherein:
wherein the quartz container is a quartz ampoule bottle or a quartz test tube, the air pressure in the quartz container is made to be less than 2Pa after vacuumizing,
the doping agent of the N-type material is SbI 3 。
4. The method of forming a bismuth telluride thermoelectric material as set forth in claim 1, wherein the pretreatment of the P-type and N-type materials is as follows:
the quartz container is put into a tubular furnace at 700-800 ℃ and heated for 1 hour, after swinging for 1 hour, the quartz container is taken out of the furnace and cooled in the air, the materials after high-temperature smelting are mechanically crushed and pressed at room temperature, and then the materials are put into a heating furnace at 500-600 ℃ and are subjected to heat treatment for 5-15 hours under the atmosphere of low oxygen partial pressure.
5. The process for the forming of bismuth telluride thermoelectric material as set forth in claim 4, wherein:
wherein the mechanical crushing time is 1 min-3 min; when the mixture is pressed and molded at room temperature, the pressure is 100MPa to 180MPa; the oxygen partial pressure in the heating furnace is controlled below 20 ppm.
6. The process for the forming of bismuth telluride thermoelectric material as set forth in claim 1, wherein:
wherein the temperature of the P-type material heater is set to 300-390 ℃ and the temperature of the N-type material heater is set to 430-500 ℃.
7. The process for the forming of bismuth telluride thermoelectric material as set forth in claim 1, wherein:
wherein, when the rod-shaped material is subjected to heat treatment, the rod-shaped material is subjected to heat treatment again in an atmosphere with the oxygen partial pressure lower than 20ppm, and the heat treatment temperature is 350-400 ℃ and the time is 5-15 hours.
8. Bismuth telluride thermoelectric bar, characterized in that it is obtained by processing according to the method of any one of claims 1 to 7.
CN202211579626.3A 2022-12-09 2022-12-09 Processing and forming method of bismuth telluride thermoelectric material Pending CN116117138A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117166039A (en) * 2023-08-03 2023-12-05 武汉理工大学 Preparation method of bismuth telluride-based thermoelectric material capable of synchronously improving mechanical property and thermoelectric property

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117166039A (en) * 2023-08-03 2023-12-05 武汉理工大学 Preparation method of bismuth telluride-based thermoelectric material capable of synchronously improving mechanical property and thermoelectric property

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