CN115521146B - Preparation method of bismuth telluride thermoelectric bar - Google Patents
Preparation method of bismuth telluride thermoelectric bar Download PDFInfo
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Abstract
The application provides a preparation method of a bismuth telluride thermoelectric bar, which comprises four parts of batching, material pretreatment, extrusion molding and heat treatment. The application provides a processing and forming process of reducing hot extrusion, which enables crystal lattices to rotate through shearing action in the reducing hot extrusion process, thereby obtaining a certain number of crystal grains with ideal orientation; because larger strain energy is accumulated in the hot extrusion process, recrystallization is induced, grains are refined, and the electrical and thermal properties and mechanical strength of the material are improved; by arranging a plurality of extrusion die cavities in the die, a plurality of bars with the same cross section as the required elements can be extruded at one time, the bars can be directly used for assembling devices after being sliced, the processing of dicing is not needed, the loss of kerfs and leftover materials in the dicing process is avoided, the manufacturing process of the devices is simplified, and the utilization rate of materials is improved.
Description
Technical Field
The application belongs to the technical field of thermoelectric material preparation, relates to a preparation method of bismuth telluride thermoelectric bars, and in particular relates to a method for preparing bismuth telluride thermoelectric bars by adopting an extrusion processing technology.
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.
In addition, the materials prepared by the currently used process methods are bar materials with certain cross section, the process of processing the bar materials into devices is shown in fig. 1, the bar materials are required to be cut into pieces and then cut into rectangular elements, then the bar materials are assembled and welded, and finally, the utilization rate of the materials used on the devices is generally less than 40%, and about half of the materials are lost in the process.
In order to solve the technical problems, the prior art has been explored in many benefits, for example, the chinese application patent with patent number CN114210978A provides a hot extrusion molding method for bismuth telluride thermoelectric material, which combines powder metallurgy and hot extrusion process, realizes precise molding and performance improvement of high brittleness bismuth telluride thermoelectric material, and solves the problems of low reliability and performance attenuation of thermoelectric refrigerator: firstly, obtaining simple substance raw materials of Bi, te, sb and Se; then crushing the simple substance raw materials into a block body with a preset diameter; weighing and mixing the block-shaped bodies, placing the block-shaped bodies in a vacuum high-frequency induction smelting furnace under a first protective gas environment to smelt into cast ingots, and ball-milling to obtain powder; putting the screened powder into an extrusion die, and performing hot extrusion in a second protective gas environment to obtain bismuth telluride bars; and placing the bismuth telluride bar in a tubular atmosphere furnace, and performing heat treatment in a third protective gas environment to obtain the bismuth telluride thermoelectric material.
But the patent also has obvious drawbacks: (1) The pulverizing time is 2-24 hours, the pulverizing efficiency is low, and the preparation efficiency is seriously affected; (2) The patent has the defect of the structure of a hot extrusion die used in a key process and the description of key control parameters of a hot extrusion process, the pressure angle in the structure of the extrusion die is not described, the pressure value of the key control parameters in the hot extrusion process is not described, and if the two key elements are not provided, the reproduction is difficult; (3) The patent has no data support on whether the implementation effect of the application reaches the aim of the application, and whether the preparation process of the patent can be successfully implemented is difficult to judge.
Disclosure of Invention
The application provides a preparation method of bismuth telluride thermoelectric bars for solving the technical problems. The technical principle of the application is as follows: providing a processing and forming process of reducing hot extrusion, and rotating a crystal lattice through shearing action in the reducing hot extrusion process, so as to obtain a certain number of crystal grains with ideal orientation; because larger strain energy is accumulated in the hot extrusion process, recrystallization is induced, grains are refined, and the electrical and thermal properties and mechanical strength of the material are improved; by arranging a plurality of extrusion die cavities in the die, a plurality of bars with the same cross section as the required elements can be extruded at one time, the bars can be directly used for assembling devices after being sliced, the processing of dicing is not needed, the loss of kerfs and leftover materials in the dicing process is avoided, the manufacturing process of the devices is simplified, and the utilization rate of materials is improved.
In a first aspect of the application, a method for preparing bismuth telluride thermoelectric bars is provided, comprising the steps of:
A. proportioning materials
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 (1) is 88-96%, 12-4% of Bi, te and Se materials are calculated and weighed, and SbI is added 3 As a dopant, an N-type material is configured; the P-type raw material and the N-type raw material which are weighed according to the proportion are respectively put into a quartz container, and the quartz container is sealed after being vacuumized to ensure that the air pressure in the quartz container is less than 2 Pa.
Preferably, the addition amount of the 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; dopant SbI 3 The addition amount of (2) is Bi 2 Te 3 And Bi (Bi) 2 Se 3 200ppm to 800ppm of the total weight of the materials.
B. Pretreatment of materials
Placing the quartz container into a tubular furnace at 700-800 ℃, heating for 1h and swinging for the same time, taking out the quartz container, cooling in the air outside the furnace, mechanically crushing the high-temperature synthesized material for 1-3 min, and pressing and forming at room temperature under the pressure of 100-150 MPa; the blank is put into a heating furnace with the temperature of 500-600 ℃ and is subjected to heat treatment for 5-15 hours under the atmosphere with low oxygen partial pressure of below 20 ppm.
C. Extrusion molding
The P-type material and the N-type material which are subjected to heat treatment in the step B are respectively placed into an extrusion die, and are placed into a heater with the temperature of 300-500 ℃ together with the die, a certain vertical pressure is applied to the material, the material passes through a variable-diameter die cavity under the combined action of the temperature and the pressure, and the material is discharged along the extrusion force action direction, so that a bar-shaped material with a certain section is formed; wherein the compression ratio of the variable diameter extrusion die cavity is 5-45, the pressure angle is 90-130 degrees, the temperature of a heater is 300-500 ℃ (preferably, the temperature of a P-type material heater is 340-380 ℃, the temperature of an N-type material heater is 450-490 ℃), the vertical extrusion force applied to the material is 100-220 MPa, and a plurality of variable diameter hot extrusion die cavities are uniformly distributed along the acting force direction.
D. Heat treatment of
The rod-shaped material is subjected to heat treatment again in a low oxygen partial pressure atmosphere below 20ppm, wherein the heat treatment temperature is 350-400 ℃ and the time is 5-15 hours.
In a second aspect of the application, a bismuth telluride thermoelectric bar is provided and is prepared by the preparation method.
The beneficial effects of the application are as follows:
the application adopts a hot extrusion process, a plurality of extrusion die cavities are arranged in the die, so that a plurality of bars with the same cross section as the required elements can be extruded at one time, the bars can be directly used for assembling devices after being sliced, the processing of dicing is not needed, the loss of kerfs and leftover materials in the dicing process is avoided, the manufacturing process of the devices is simplified, and the utilization rate of materials is improved. In addition, the material crushing of the application only needs 1min-3min, the efficiency is greatly improved, and the manufacturing cost in the process of pulverizing powder is greatly reduced.
In the aspect of microstructure, the crystal lattice is rotated by shearing action in the reducing hot extrusion process, so that a certain number of crystal grains with ideal orientation are obtained; as larger strain energy is accumulated in the hot extrusion process, recrystallization is induced, grains are refined, and the electrical and thermal properties and mechanical strength of the material are improved.
Experiments prove that the thermoelectric material prepared by the method has at least equivalent thermoelectric performance to that of the thermoelectric material prepared by the regional melting method and mechanical performance to that of the thermoelectric material prepared by the regional melting method and the thermoelectric bar prepared by the hot pressing method, and has the advantages of both methods, but the utilization rate of the thermoelectric material is obviously better than that of the thermoelectric bar prepared by the regional melting method and the hot pressing method, and the utilization rate of the thermoelectric bar is improved to be about 60% from the current 40%. The method of the application not only can obtain materials with good thermoelectric performance and mechanical strength, but also can assemble the obtained crystal bar after slicing, thereby omitting the element cutting process and greatly improving the utilization rate of the crystal bar materials.
Drawings
Fig. 1 is a schematic diagram of a prior art process for fabricating devices using bismuth telluride thermoelectric bars.
Fig. 2 is a schematic diagram of a preparation flow of the bismuth telluride thermoelectric bar of the present application.
Fig. 3 is a schematic diagram of the diameter-changing process.
Detailed Description
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Example 1
Raw material Te, bi, sb, se with purity more than 99.99% is taken. According to 18 mol% Bi 2 Te 3 :82％mol Sb 2 Te 3 The stoichiometric ratio of each element is calculated, the corresponding element materials are weighed, the total weight is 3000g, te with the weight ratio of 0.5% is added as a doping agent, and the P-type material is prepared; according to 93 mol% Bi 2 Te 3 :7％mol Bi 2 Se 3 Stoichiometric ratio of each element was calculated and the corresponding element material was weighed, the total weight was 3000g, 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.
Mechanically crushing the high-temperature synthesized material for 3min; pressing at room temperature under 150MPa to obtain a primary blank, maintaining at 540 deg.C, maintaining oxygen partial pressure in the furnace below 20ppm, and cooling in the furnace for 15 hr.
According to fig. 2, the billet is placed in a hot extrusion die, the compression ratio 14, the pressure angle 100 ° of the extrusion die used, and the die is placed in a heater with the heater temperature set: p-type 350 ℃ and N-type 450 ℃; a pressure of 200MPa was applied in the extrusion direction, and 10 bars with a diameter of 2mm were 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.
FIG. 3 shows the variation of the diameter of the rod during the reducing extrusion, with a compression ratio (Φ1/Φ2) 2 The pressure angle is θ.
Cutting the bar into thin slices with a certain thickness according to the design requirement of the device under a multi-wire cutting machine, and welding the thin slices into thermoelectric devices according to the design line of the device.
Example 2
Raw material Te, bi, sb, se with purity more than 99.99% is taken. According to 22 mol percent of Bi 2 Te 3 :78％mol Sb 2 Te 3 The stoichiometric ratio of each element is calculated, the corresponding element materials are weighed, the total weight is 3000g, te with the weight ratio of 0.1% is added as a doping agent, and the P-type material is prepared; according to 90 mol% Bi 2 Te 3 :10％mol Bi 2 Se 3 Stoichiometric ratio of each element was calculated and the corresponding element material was weighed, the total weight was 3000g, sbI was added in a weight ratio of 700ppm 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.
Mechanically pulverizing the high-temperature synthesized material for 3min, pressing at room temperature to obtain a primary blank, maintaining the temperature at 540 ℃, keeping the oxygen partial pressure in the furnace to be less than 20ppm, and cooling along with the furnace after 15 hours.
The billet is placed in a hot extrusion die, the compression ratio of the extrusion die used is 14, the pressure angle is 100 degrees, the billet and the die are placed in a heater, and the temperature of the heater is set in a test way: p-type 340 ℃, N-type 470 ℃; a pressure of 200MPa was applied in the extrusion direction, and 10 bars with a diameter of 2mm were 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.
Cutting the bar material into thin slices with a certain thickness according to the design requirement of the device under a multi-wire cutting machine, and welding the thin slices into thermoelectric devices according to the circuit design of the devices.
Effect contrast
The bars prepared in examples 1 and 2 were cut into sheets of the same thickness and shape as those prepared by Zone Melting (ZM) and hot press sintering (HP), and the thermoelectric properties, mechanical strength and material utilization were compared, and the results are shown in table 1:
wherein, HP, hot press sintering method; ZM, zone melting method; EX1, example 1; EX2, example 2.
According to the results, the thermoelectric performance of the bismuth telluride thermoelectric bar prepared by the method is equivalent to that of a zone melting method (ZM), and the mechanical performance of the bismuth telluride thermoelectric bar is equivalent to or even better than that of a hot press sintering method (HP) bar. However, the method is far superior to the two methods in terms of material utilization rate, and the material utilization rate is between 56% and 58% and is far higher than the current 40%.
While the preferred embodiments of the present application have been described in detail, the present application is not limited to the embodiments, and various equivalent modifications and substitutions can be made by those skilled in the art without departing from the spirit of the present application, and these equivalent modifications and substitutions are intended to be included in the scope of the present application as defined in the appended claims.
Claims (4)
1. The preparation method of the bismuth telluride thermoelectric bar is characterized by comprising the following steps of:
A. proportioning materials
According to Bi 2 Te 3 And Sb (Sb) 2 Te 3 Calculated and weighted Bi, te and Sb with the mol ratio of 15-25 percent to 85-75 percent, te is added as doping agent, and the addition amount of 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, and preparing a P-type material; according to Bi 2 Te 3 And Bi (Bi) 2 Se 3 The molar ratio of (1) is 88-96%, 12-4% of Bi, te and Se materials are calculated and weighed, and SbI is added 3 As dopant, sbI 3 The addition amount of (2) is Bi 2 Te 3 And Bi (Bi) 2 Se 3 200ppm to 800ppm of the total weight of the materials, configuring N-type materials,
respectively placing the P-type raw materials and the N-type raw materials weighed according to the proportion into a quartz container, vacuumizing the quartz container to ensure that the air pressure in the quartz container is less than 2Pa, and sealing the quartz container;
B. pretreatment of materials
Placing the quartz container into a tubular furnace at 700-800 ℃, heating for a certain time and swinging for the same time, taking out the furnace, cooling in the air, mechanically crushing the material synthesized at high temperature for 1-3 min at room temperature
Pressing at 100-180 MPa, and then placing into a heating furnace at 500-600 ℃ for 5-15 hours in a low oxygen partial pressure atmosphere, wherein the oxygen partial pressure in the furnace is below 20 ppm;
C. extrusion molding
The P-type and N-type materials which are heat treated in the step B are respectively put into a variable diameter hot extrusion die, and are put into a heater with the temperature of 300-500 ℃ together with the die, wherein a plurality of variable diameter hot extrusion die cavities are uniformly distributed in the acting force direction of the variable diameter hot extrusion die, a plurality of thermoelectric bars are extruded at one time, the compression ratio of the variable diameter hot extrusion die cavity is 5-45, and the pressure angle is 90 o 130 degrees; 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 ℃; applying a vertical extrusion force with the pressure of 100-220 MPa to the material, and allowing the material to pass through a reducing hot extrusion die cavity under the combined action of temperature and pressure, and discharging the material along the extrusion force action direction to form a rod-shaped material with a certain section;
D. heat treatment of
And (3) carrying out heat treatment again on the rod-shaped material in a low-oxygen partial pressure atmosphere, wherein the heat treatment temperature is 350-400 ℃ and the time is 5-15 hours, and the oxygen partial pressure is below 20 ppm.
2. The method for preparing the bismuth telluride thermoelectric bar according to claim 1, wherein:
in the step A, the quartz container is a quartz ampoule bottle or a quartz test tube.
3. The method for preparing the bismuth telluride thermoelectric bar according to claim 1, wherein:
in the step B, the heating and swinging time is 1 hour.
4. A bismuth telluride thermoelectric bar, characterized in that it is prepared by the preparation method of any one of claims 1 to 3.
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| CN112893497A (en) * | 2021-03-01 | 2021-06-04 | 中国科学院物理研究所 | Preparation method and equipment of thermoelectric material and thermoelectric material |
| CN114713655A (en) * | 2022-04-07 | 2022-07-08 | 深圳先进电子材料国际创新研究院 | Preparation method and extrusion die of bismuth telluride-based thermoelectric material |
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