CN110098313B - Preparation method of preferred orientation p-type bismuth telluride-based polycrystalline block thermoelectric material - Google Patents
Preparation method of preferred orientation p-type bismuth telluride-based polycrystalline block thermoelectric material Download PDFInfo
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Abstract
The invention provides a preparation method of a preferred orientation p-type bismuth telluride-based polycrystalline block thermoelectric material, which comprises the following steps: bi, sb and Te simple substance powder are taken as raw materials according to Bi x Sb 2‑x Te 3 Weighing ingredients according to a stoichiometric ratio, filling the raw materials into a quartz glass tube or a high borosilicate glass tube, vacuumizing and sealing, putting the sealed quartz glass tube or high borosilicate glass tube into a swinging furnace for full smelting, rotating a hearth of the swinging furnace to a vertical position after smelting is finished, and cooling to obtain the p-type bismuth telluride base alloy crystal bar; cutting the prepared p-type bismuth telluride base alloy crystal bar into blocks, loading the blocks into an equal channel angular extrusion die, and then placing the blocks into a hot-pressing sintering furnace for sintering extrusion, thus obtaining the p-type bismuth telluride base polycrystalline block thermoelectric material with preferred orientation. The p-type bismuth telluride-based polycrystalline block thermoelectric material prepared by the invention has the advantages of lower resistivity, higher Seebeck coefficient and low thermal conductivity, and the maximum ZT value of 1.55 can be obtained at 343K.
Description
Technical Field
The invention belongs to the technical field of bismuth telluride-based thermoelectric materials, and particularly relates to a preferred orientation p-type bismuth telluride-based polycrystalline block thermoelectric material and a preparation method thereof.
Background
Bi produced by zone melting method 2 Te 3 The base alloy has better thermoelectric performance, and the ZT value at room temperature is about 1, so that the base alloy is widely applied to the thermoelectric industry. Bi produced in the zone melting method 2 Te 3 In the base alloy, te (1) -Te (1) atomic layers are combined together only by virtue of Van der Waals force, and the machining performance is poor. To solve the problem of zone-melting Bi 2 Te 3 The problem of poor mechanical processing property of the base alloy is that many scientific research institutions and manufacturers adopt powderPreparation of polycrystalline Bi by adopting end metallurgical technology 2 Te 3 A thermoelectric material. With greater progress in the study of p-type. Ren et al introduce nanoparticles by high-energy ball milling and direct-current hot pressing process to prepare p-type Bi 2-x Sb x Te 3 The nano composite material greatly reduces the lattice heat conductivity, and the obtained ZT value is as high as 1.3 and 1.4. In addition, the scholars introduce heterojunction through a nano-composite or structure regulation method to generate energy filtering effect, and meanwhile, the Seebeck coefficient and the conductivity are improved to improve the ZT value. Li et al combine high-energy ball milling and spark plasma sintering process by mixing 0.4vol.% SiC nano particles in BiSbTe matrix, and simultaneously improve Seebeck coefficient and electrical conductivity, reduce thermal conductivity, and finally obtain maximum ZT value of 1.33 at 373K; zu et al by reacting Bi 0.5 Sb 1.5 Te 3 And a large number of 60-degree twin crystal boundaries are constructed by combining liquid treatment with melt spinning, ball milling and spark plasma sintering to scatter low-energy carriers, so that the Seebeck coefficient and carrier mobility are improved, the lattice thermal conductivity is reduced, and finally, the maximum ZT value is improved from 1.12 to 1.42 at 348K.
However, when the p-type bismuth telluride-based thermoelectric material is prepared by using a powder metallurgy process, the lattice thermal conductivity is reduced, and meanwhile, as a large number of crystal boundaries and randomly oriented nano crystal grains are introduced, the mobility of carriers in the material is also obviously reduced, so that the resistivity of the material is inevitably increased, and the ZT value is limited to be increased. In the conventional pulverizing process, the problems of easy oxidation of materials, easy introduction of oxide impurities and the like are also exposed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and aims to provide a preparation method of a p-type bismuth telluride-based polycrystalline block thermoelectric material with full grain refinement, good preferential orientation, simple process and high production efficiency, wherein the prepared p-type bismuth telluride-based polycrystalline block thermoelectric material has low resistivity, high Seebeck coefficient and low thermal conductivity, and finally can obtain a maximum ZT value of 1.55 at 343K.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a preferred orientation p-type bismuth telluride-based polycrystalline bulk thermoelectric material comprises the following steps:
(1) Bi, sb and Te simple substance powder are taken as raw materials according to Bi x Sb 2-x Te 3 Weighing ingredients according to a stoichiometric ratio, wherein x is more than or equal to 0.3 and less than or equal to 0.5;
(2) Filling the raw materials into a quartz glass tube or a high borosilicate glass tube, vacuumizing and sealing, putting the sealed quartz glass tube or high borosilicate glass tube into a swinging furnace for full smelting, rotating a hearth of the swinging furnace to a vertical position after smelting is finished, and cooling to obtain a p-type bismuth telluride base alloy crystal bar;
(3) Cutting the p-type bismuth telluride base alloy crystal bar prepared in the step (2) into blocks, loading the blocks into an equal channel angular extrusion die, and then placing the blocks into a hot-pressing sintering furnace for sintering extrusion, thus obtaining the p-type bismuth telluride base polycrystalline block thermoelectric material with preferred orientation.
In the step (1), bi, sb and Te simple substance powder with mass percent more than 99.99% are selected as raw materials.
In the step (2), high-temperature smelting is carried out at 590-750 ℃ for 5-120 min.
The equal channel corner extrusion die in step (3) comprises a pressure head, a punch, a movable baffle, a right-angle clamp and a die body, wherein the die body is square with a chamfer, the right-angle clamp is located at the bottom of the die body, the movable baffle is located at the side of the die body, the right-angle clamp and the movable baffle are used for fixing the die body together, the top of the punch is connected with the pressure head, the bottom of the punch is located in a channel of the die body and extrudes a block located in the die body under the action of the pressure head.
The specific steps of sintering and extrusion in the step (3) are as follows:
(3-1) firstly, heating the furnace body to 300-510 ℃ without applying pressure, and preserving heat for 30min;
(3-2) then applying a main pressure of 50-200 MPa and a back pressure of 10-100 MPa, and extruding the block at an extrusion speed of 5-10 mm/min;
after each extrusion pass, rotating the equal channel angular extrusion die by 90 degrees in the clockwise direction, and extruding the equal channel angular extrusion die by the same technological parameters in step (3-3) for 4 times;
(3-4) the whole extrusion process is completed in air or vacuum or inert atmosphere, and the temperature is kept at 300-510 ℃ until the extrusion is finished.
The p-type bismuth telluride base alloy crystal bar is prepared by high-temperature smelting, and then the preferred orientation p-type bismuth telluride base alloy crystal bar is prepared by equal channel angular extrusion, and compared with the prior art, the invention has the following beneficial effects:
1. the invention takes Bi, sb and Te simple substance powder or particles as raw materials, and melts for 5min at 590 ℃ to obtain single-phase Bi x Sb 2-x Te 3 (x is more than or equal to 0.3 and less than or equal to 0.5) crystal bars; then directly extruding and forming the crystal bar obtained by smelting, so that pollution and oxidation in the process of pulverizing are avoided, and the method is more suitable for large-scale production; the total time of four-pass extrusion is only 20min, namely the preferred orientation p-type bismuth telluride-based polycrystalline thermoelectric material can be rapidly prepared in a short time, the relative density is over 99 percent, and the method has the characteristics of simple process, short production period, high production efficiency and high product density. 2. The invention adopts the equal channel angular extrusion process, which is obviously beneficial to the full refinement and preferential orientation of crystal grains. 3. Since the grains are uniformly refined to the same size, the prepared thermoelectric material has stable performance and good repeatability, and the maximum ZT value at 343K can be 1.55.
In conclusion, the method has the characteristics of simple production process, short production period and high production efficiency, and the prepared preferred orientation p-type bismuth telluride-based polycrystalline block thermoelectric material has the advantages of higher product purity, high density, good grain refinement effect, strong grain preferred orientation, high conductivity and high dimensionless thermoelectric figure of merit.
Drawings
FIG. 1 is a graph of preferred orientation factors for a p-type bismuth telluride-based polycrystalline bulk thermoelectric material prepared in accordance with the present invention;
FIG. 2 is an SEM image of a fracture of a p-type bismuth telluride-based polycrystalline bulk thermoelectric material prepared according to the present invention;
FIG. 3 shows p-type Bi prepared according to the present invention 0.5 Sb 1.5 Te 3 Polycrystalline block thermoelectricA graph of resistivity of the material in different test directions as a function of temperature;
FIG. 4 shows p-type Bi prepared according to the present invention 0.5 Sb 1.5 Te 3 Graph of Seebeck coefficient of polycrystalline block thermoelectric material along with temperature change in different test directions;
FIG. 5 shows p-type Bi prepared according to the present invention 0.5 Sb 1.5 Te 3 Graph of thermal conductivity of polycrystalline block thermoelectric material in different test directions with temperature;
FIG. 6 shows p-type Bi prepared according to the present invention 0.5 Sb 1.5 Te 3 Graph of ZT values of polycrystalline block thermoelectric material in different test directions with temperature change;
FIG. 7 is a schematic view of an equal channel angular extrusion die according to the present invention.
Detailed Description
The present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.
The structure of the equal channel angular extrusion die adopted in the following embodiment is shown in fig. 7, the equal channel angular extrusion die comprises a pressure head 1, a punch 2, a movable baffle 3, a right-angle clamp 4 and a die body 6, wherein the die body 6 is square with a chamfer, the right-angle clamp 4 is positioned at the bottom of the die body 6, the movable baffle 3 is positioned at the side of the die body, the right-angle clamp 4 and the movable baffle 3 jointly fix the die body 6, the top of the punch is connected with the pressure head, and the bottom of the punch is positioned in a channel of the die body and extrudes a block 5 positioned in the die body under the action of the pressure head.
Example 1
The preparation method of the preferred orientation p-type bismuth telluride-based polycrystalline bulk thermoelectric material provided in the embodiment comprises the following steps:
the simple substance powder of Bi, sb and Te with the mass percent of more than 99.99 percent is taken as the raw material, and the Bi is taken as the raw material 0.5 Sb 1.5 Te 3 Stoichiometric proportions are prepared;
the raw materials are filled into a quartz glass tube or a high borosilicate glass tube, vacuum sealing is carried out, and then the sealed quartz glass tube or high borosilicate glass tube is put into a swinging furnace for high-temperature smelting, wherein the smelting temperature is 710 ℃ and the smelting time is 5min. After smelting, rotating a furnace hearth of the swinging furnace to a plumb position, and slowly cooling to obtain a high-density p-type bismuth telluride base alloy crystal bar;
cutting the prepared p-type bismuth telluride base alloy crystal bar into blocks, putting the blocks into an equal channel angular extrusion die, and then placing the blocks into a hot-pressing sintering furnace for extrusion, wherein the extrusion process comprises the following steps:
(1) Firstly, heating the furnace body to 350 ℃ without applying pressure, and preserving heat for 30min;
(2) Then applying 50-200 MPa main pressure and 10-100 MPa back pressure, and extruding the block at an extrusion speed of 5 mm/min;
(3) After each extrusion pass, rotating the die by 90 degrees in the clockwise direction, and then extruding the die by the same technological parameters in step (2), and repeating the steps for 4 times;
(4) The whole extrusion process is completed in air or vacuum or inert atmosphere, and the temperature is kept at 350 ℃ until the extrusion is finished.
After extrusion is finished, the optimal orientation p-type Bi is obtained 0.5 Sb 1.5 Te 3 Polycrystalline bulk thermoelectric material. When the material prepared in this embodiment is tested, its preferred orientation factor is shown in fig. 1, and it can be seen from fig. 1 that as the extrusion pass increases, the orientation factor increases gradually. The SEM sectional view of the fracture of the material is shown in figure 2, and it can be seen from figure 2 that after four-pass extrusion, the size of the internal crystal grains of the material is thinned from millimeter level to micrometer level before extrusion, the uniform distribution is obeyed, and the preferred orientation of the crystal grains is very obvious.
The thermoelectric performance of the material is shown in figures 3-6, and it can be seen from the figures that the carrier mobility is greatly improved due to the excellent preferred grain orientation, the resistivity is greatly reduced along the extrusion direction of the material, the Seebeck coefficient can be maintained at a higher level, and the maximum ZT value of the finally prepared p-type bismuth telluride-based polycrystalline block thermoelectric material can reach 1.55, which is improved by 55% compared with the conventional powder metallurgy products and the conventional zone-melting single crystal products on the market.
Example 2
The preparation method of the preferred orientation p-type bismuth telluride-based polycrystalline bulk thermoelectric material provided in the embodiment comprises the following steps:
the simple substance powder of Bi, sb and Te with the mass percent of more than 99.99 percent is taken as the raw material, and the Bi is taken as the raw material 0.45 Sb 1.55 Te 3 Stoichiometric proportions are prepared;
the raw materials are filled into a quartz glass tube or a high borosilicate glass tube, vacuum sealing is carried out, and then the sealed quartz glass tube or high borosilicate glass tube is put into a swinging furnace for high-temperature smelting, wherein the smelting temperature is 680 ℃, and the smelting time is 10min. After smelting, rotating a furnace hearth of the swinging furnace to a plumb position, and slowly cooling to obtain a high-density p-type bismuth telluride base alloy crystal bar;
cutting the prepared p-type bismuth telluride base alloy crystal bar into blocks, putting the blocks into an equal channel angular extrusion die, and then placing the blocks into a hot-pressing sintering furnace for extrusion, wherein the extrusion process comprises the following steps:
(1) Firstly, heating the furnace body to 400 ℃ without applying pressure, and preserving heat for 30min;
(2) Then applying 50-200 MPa main pressure and 10-100 MPa back pressure, and extruding the block at an extrusion speed of 6 mm/min;
(3) After each extrusion pass, rotating the die by 90 degrees in the clockwise direction, and then extruding the die by the same technological parameters in step (2), and repeating the steps for 4 times;
(4) The whole extrusion process is completed in air or vacuum or inert atmosphere, and the temperature is kept at 400 ℃ until the extrusion is finished.
And after extrusion, the preferred orientation p-type bismuth telluride-based polycrystalline block thermoelectric material is obtained.
Example 3
The preparation method of the preferred orientation p-type bismuth telluride-based polycrystalline bulk thermoelectric material provided in the embodiment comprises the following steps:
the simple substance powder of Bi, sb and Te with the mass percent of more than 99.99 percent is taken as the raw material, and the Bi is taken as the raw material 0.4 Sb 1.6 Te 3 Stoichiometric proportions are prepared;
the raw materials are filled into a quartz glass tube or a high borosilicate glass tube, vacuum sealing is carried out, and then the sealed quartz glass tube or high borosilicate glass tube is put into a swinging furnace for high-temperature smelting, wherein the smelting temperature is 650 ℃ and the smelting time is 15min. After smelting, rotating a furnace hearth of the swinging furnace to a plumb position, and slowly cooling to obtain a high-density p-type bismuth telluride base alloy crystal bar;
cutting the prepared p-type bismuth telluride base alloy crystal bar into blocks with the size, putting the blocks into an equal channel corner extrusion die, and then placing the blocks into a hot-pressing sintering furnace for extrusion, wherein the extrusion process comprises the following steps:
(1) Firstly, heating the furnace body to 450 ℃ without applying pressure, and preserving heat for 30min;
(2) Then applying 50-200 MPa of main pressure and 10-100 MPa of back pressure, and extruding the block at an extrusion speed of 10 mm/min;
(3) After each extrusion pass, rotating the die by 90 degrees in the clockwise direction, and then extruding the die by the same technological parameters in step (2), and repeating the steps for 4 times;
(4) The whole extrusion process is completed in air or vacuum or inert atmosphere, and the temperature is kept at 450 ℃ until the extrusion is finished.
And after extrusion, the preferred orientation p-type bismuth telluride-based polycrystalline block thermoelectric material is obtained.
Claims (1)
1. The preparation method of the preferred orientation p-type bismuth telluride-based polycrystalline bulk thermoelectric material is characterized by comprising the following steps of:
(1) Bi, sb and Te simple substance powder are taken as raw materials according to Bi x Sb 2-x Te 3 Weighing ingredients according to a stoichiometric ratio, wherein x is more than or equal to 0.3 and less than or equal to 0.5;
(2) Filling the raw materials into a quartz glass tube or a high borosilicate glass tube, vacuumizing and sealing, putting the sealed quartz glass tube or high borosilicate glass tube into a swinging furnace for full smelting, rotating a hearth of the swinging furnace to a vertical position after smelting is finished, and cooling to obtain a p-type bismuth telluride base alloy crystal bar;
(3) Cutting the p-type bismuth telluride base alloy crystal bar prepared in the step (2) into blocks, loading the blocks into an equal channel angular extrusion die, and then placing the blocks into a hot-pressing sintering furnace for sintering extrusion to obtain the p-type bismuth telluride base polycrystalline block thermoelectric material with preferred orientation;
the equal channel corner extrusion die comprises a pressing head, a punch, a movable baffle, a right-angle clamp and a die body, wherein the die body is in a cube shape with a chamfer, the right-angle clamp is positioned at the bottom of the die body, the movable baffle is positioned at the side of the die body, the right-angle clamp and the movable baffle are used for fixing the die body together, the top of the punch is connected with the pressing head, and the bottom of the punch is positioned in a channel of the die body and extrudes a block positioned in the die body under the action of the pressing head;
the specific steps of sintering extrusion are as follows:
(3-1) firstly, heating the furnace body to 300-510 ℃ without applying pressure, and preserving heat for 30min;
(3-2) then applying a main pressure of 50-200 MPa and a back pressure of 10-100 MPa, and extruding the block at an extrusion speed of 5-10 mm/min;
after each extrusion pass, rotating the equal channel angular extrusion die by 90 degrees in the clockwise direction, and extruding the equal channel angular extrusion die by the same technological parameters in step (3-3) for 4 times;
(3-4) finishing the whole extrusion process in air or vacuum or inert atmosphere, and keeping the temperature at 300-510 ℃ until the extrusion is finished;
in the step (1), bi, sb and Te simple substance powder with mass percent more than 99.99% are selected as raw materials;
in the step (2), high-temperature smelting is carried out at 590-750 ℃ for 5-120 min.
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CN113328031A (en) * | 2020-09-01 | 2021-08-31 | 中国科学院宁波材料技术与工程研究所 | High-strength and high-efficiency bismuth telluride block and preparation method and application thereof |
CN112079638A (en) * | 2020-09-22 | 2020-12-15 | 哈尔滨工业大学 | P-type bismuth telluride-based thermoelectric material with high thermoelectric and mechanical properties and preparation method thereof |
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CN113421959B (en) * | 2021-06-22 | 2022-10-21 | 深圳大学 | N-type bismuth telluride-based room temperature thermoelectric material and preparation method thereof |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101656293A (en) * | 2004-12-07 | 2010-02-24 | 丰田技术中心美国公司 | Method for forming bulk thermoelectric material |
CN107507909A (en) * | 2017-08-08 | 2017-12-22 | 武汉科技大学 | A kind of porous p-type Bi2Te3Base thermoelectricity material and preparation method thereof |
CN108550689A (en) * | 2018-05-25 | 2018-09-18 | 北京石油化工学院 | A kind of preparation method of N-type bismuth telluride-base thermoelectric material |
-
2019
- 2019-04-22 CN CN201910325213.4A patent/CN110098313B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101656293A (en) * | 2004-12-07 | 2010-02-24 | 丰田技术中心美国公司 | Method for forming bulk thermoelectric material |
CN107507909A (en) * | 2017-08-08 | 2017-12-22 | 武汉科技大学 | A kind of porous p-type Bi2Te3Base thermoelectricity material and preparation method thereof |
CN108550689A (en) * | 2018-05-25 | 2018-09-18 | 北京石油化工学院 | A kind of preparation method of N-type bismuth telluride-base thermoelectric material |
Non-Patent Citations (2)
Title |
---|
Shifting up the optimum figure of merit of p-type bismuth telluride-based thermoelectric materials for power generation by suppressing intrinsic conduction;Lipeng Hu;《NPG Asia Materials》;20140221;正文第2页实验部分 * |
Weishu Liu.Materials for Near-Room Temperatures.《Advanced Thermoelectrics》.Materials, Contacts, Devices, and Systems CRC Press,2017, * |
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