CN115159986B - Method for preparing p-type bismuth telluride-based thermoelectric material by free forging process - Google Patents
Method for preparing p-type bismuth telluride-based thermoelectric material by free forging process Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000005242 forging Methods 0.000 title claims abstract description 36
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 29
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 27
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 230000007547 defect Effects 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 21
- 238000004857 zone melting Methods 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 238000003723 Smelting Methods 0.000 claims description 10
- 238000004806 packaging method and process Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005388 borosilicate glass Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000009461 vacuum packaging Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 238000005204 segregation Methods 0.000 abstract description 3
- 238000005538 encapsulation Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/547—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on sulfides or selenides or tellurides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
- B21J5/002—Hybrid process, e.g. forging following casting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
- B21J5/02—Die forging; Trimming by making use of special dies ; Punching during forging
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Abstract
The invention belongs to the technical field of bismuth telluride-based thermoelectric materials, and in particular relates to a method for preparing a p-type bismuth telluride-based thermoelectric material by a free forging process. The forging process improves the defects in the material, so that the internal structure of the material is more uniform, the segregation is eliminated, and the thermoelectric performance is more stable.
Description
Technical Field
The invention belongs to the technical field of bismuth telluride-based thermoelectric materials, and in particular relates to a method for preparing a p-type bismuth telluride-based thermoelectric material by a free forging process.
Background
With the continuous innovation and progress of technology in various fields, the use environment and conditions of thermoelectric devices are becoming more severe, so high thermoelectric performance, high reliability and miniaturization are the directions of efforts, which are required to improve the mechanical strength of materials while improving the ZT value of the materials. The traditional large-scale thermoelectric material preparation method mainly comprises zone melting, and the prepared monocrystal has good orientation and high ZT value, but has poor mechanical processing performance, so that the stability is poor, and the application range is limited.
Disclosure of Invention
The invention aims to rapidly prepare the p-type bismuth telluride-based thermoelectric material with fine grains and uniform texture by a free forging process, and the mechanical property and the thermoelectric property of the p-type bismuth telluride-based thermoelectric material are obviously improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is a method for preparing a p-type bismuth telluride-based thermoelectric material by a free forging process, which comprises the following specific steps:
Step 1, bi, sb and Te are used as raw materials, and are mixed according to a stoichiometric ratio Bi xSb2-xTe3, wherein x is more than or equal to 0.3 and less than or equal to 0.5; vacuum packaging and smelting to obtain a crystal bar, carrying out zone smelting on the crystal bar obtained by smelting to obtain a zone-melting crystal bar, crushing the zone-melting crystal bar to prepare powder, and carrying out hot-pressing sintering on the powder to obtain a block, namely an initial block material;
step 2, the initial block material prepared in the step 1 is sealed in a copper pipe, and the shape of the copper pipe is matched with that of the initial block material;
Step 3, heating the copper pipe sealed with the initial block material to raise the temperature, and starting free forging when the temperature is raised to 380-450 ℃, wherein the forging pressure is 100-1000 Mpa, continuously overturning the material while forging, and forging along three directions of X, Y, Z shafts, wherein the forging ratio is 3-10;
And 4, forging the material into a square die cavity on a workbench, cooling, and stripping the copper tube to obtain the p-type bismuth telluride-based thermoelectric material.
In addition, the purity of Bi, te and Se in the step 1 is more than 99.99%.
The encapsulation in step 1 is encapsulation using a borosilicate glass tube or a quartz glass tube.
Moreover, when the high borosilicate glass tube is adopted for packaging, the smelting temperature is 590-650 ℃; when the quartz glass tube is used for packaging, the smelting temperature is 590-850 ℃.
In addition, the zone melting in the step 1 is carried out by a zone melting furnace, and the specific zone melting condition when the high borosilicate glass tube is adopted for packaging is that the zone melting temperature is 650-780 ℃, the crystal pulling rate is 20-35 mm/h, and the diameter of a crystal rod is 30mm; the specific zone-melting condition when the quartz glass tube is adopted for packaging is that the zone-melting temperature is 650-850 ℃, the crystal pulling rate is 20-35 mm/h, and the diameter of the crystal rod is 30mm.
Moreover, the initial bulk material and copper tubing in step 2 are square or cylindrical.
And the heating rate in the step 3 is 20-100 ℃/min.
Compared with the prior art, the invention has the beneficial effects that: 1. free forging of the brittle thermoelectric material is realized, the forging process improves the defects in the material, so that the internal structure of the material is more uniform, segregation is eliminated, and the performance is more stable; 2. refining grains by using a forging process, improving grain orientation, eliminating segregation and eliminating pores, thereby improving performance; 3. the p-type bismuth telluride-based thermoelectric material is a brittle material at normal temperature, and is difficult to forge directly, the method seals a block material into a copper pipe with excellent plasticity, and then heats up, so that free forging of the brittle thermoelectric material is successfully realized, the p-type bismuth telluride-based thermoelectric material obtained through an improved process has the characteristics of fine crystal grains, uniform texture and high compactness, the thermoelectric property and mechanical property of the material are obviously improved, and the p-type bismuth telluride-based thermoelectric material has very high practical value; 4. the copper pipe adopted by the invention can perform diffusion reaction with bismuth telluride material at high temperature, cu element is easy to diffuse into Te-Te basal plane of bismuth telluride crystal lattice, and Te vacancy formation can be increased to inhibit Te vacancy and Bi Te inversion defect formation, thereby reducing donor-like effect and improving the stability of thermoelectric performance of p-type bismuth telluride alloy.
Detailed Description
The present invention will be described in detail with reference to the following examples, but the present invention is not limited to the following examples.
Taking a produced zone-melting crystal bar, crushing the zone-melting crystal bar into powder, adopting SPS sintering equipment to prepare a block material, then sealing the block material into a copper pipe, placing the copper pipe sealed with the material on a workbench of forging equipment, heating, keeping the temperature at a heating rate of 20-100 ℃/min, keeping the temperature at 380-450 ℃, simultaneously forging and pressing at a forging pressure of 100-1000 Mpa, forging along three directions of X, Y and a Z axis, forging the block material with a forging ratio of 3-8, finally forging the material into a square die cavity on the workbench, and cooling to obtain the p-type bismuth telluride-based thermoelectric material of the block.
The performance index of the comparative examples and examples under several different conditions is shown in table 1 below.
TABLE 1 maximum zT values for p-type bismuth telluride-based thermoelectric materials before and after free forging
From the above table, the bending strength and the maximum ZT value of the thermoelectric material prepared by the method are remarkably improved, that is, the thermoelectric performance and the mechanical performance are remarkably improved.
Claims (5)
1. A method for preparing a p-type bismuth telluride-based thermoelectric material by a free forging process is characterized by comprising the following specific steps:
Step 1, bi, sb and Te are used as raw materials, and are mixed according to a stoichiometric ratio Bi xSb2-xTe3, wherein x is more than or equal to 0.3 and less than or equal to 0.5; vacuum packaging and smelting to obtain a crystal bar, wherein the packaging refers to packaging by using a high borosilicate glass tube or a quartz glass tube, carrying out zone smelting on the crystal bar obtained by smelting to obtain a zone-melting crystal bar, crushing the zone-melting crystal bar to prepare powder, and carrying out hot-pressing sintering on the powder to obtain a block, namely an initial block material; the zone melting is carried out by a zone melting furnace, and the specific zone melting condition when the high borosilicate glass tube is used for packaging is that the zone melting temperature is 650-780 ℃, the crystal pulling rate is 20-35 mm/h, and the diameter of a crystal rod is 30mm; the specific zone melting condition when the quartz glass tube is adopted for packaging is that the zone melting temperature is 650-850 ℃, the crystal pulling rate is 20-35 mm/h, and the diameter of a crystal rod is 30mm;
step 2, the initial block material prepared in the step 1 is sealed in a copper pipe, and the shape of the copper pipe is matched with that of the initial block material;
Step 3, heating the copper pipe sealed with the initial block material, and when the temperature is raised to 400-450 ℃, starting free forging, wherein the forging pressure is 500-1000 MPa, continuously turning over the material while forging, and forging along three directions of X, Y, Z axes, wherein the forging ratio is 6-10; the copper pipe and bismuth telluride material are subjected to diffusion reaction at high temperature, cu element is diffused between Te-Te basal planes of bismuth telluride crystal lattice, the formation energy of Te vacancies is increased, the formation of Te vacancies and Bi Te inversion defects is inhibited, donor-like effect is reduced, and the stability of thermoelectric performance of p-type bismuth telluride alloy is improved;
And 4, forging the material into a square die cavity on a workbench, cooling, and stripping the copper tube to obtain the p-type bismuth telluride-based thermoelectric material.
2. The method for preparing the p-type bismuth telluride-based thermoelectric material by the free forging process according to claim 1, wherein: in the step 1, the purity of Bi, sb and Te is more than 99.99 percent.
3. The method for preparing the p-type bismuth telluride-based thermoelectric material by the free forging process according to claim 1, wherein: when the high borosilicate glass tube is used for packaging, the smelting temperature is 590-650 ℃; when the quartz glass tube is used for packaging, the smelting temperature is 590-850 ℃.
4. The method for preparing the p-type bismuth telluride-based thermoelectric material by the free forging process according to claim 1, wherein: in the step 2, the initial block material and the copper pipe are square or cylindrical.
5. The method for preparing the p-type bismuth telluride-based thermoelectric material by the free forging process according to claim 1, wherein: in the step 3, the heating temperature rising rate is 20-100 ℃/min.
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| CN202210836853.3A CN115159986B (en) | 2022-07-15 | 2022-07-15 | Method for preparing p-type bismuth telluride-based thermoelectric material by free forging process |
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| CN115159986B true CN115159986B (en) | 2024-06-04 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502865A (en) * | 2009-02-23 | 2009-08-12 | 浙江大学 | Hot forging processing method for optimizing performance of polycrystal bismuth telluride-based thermoelectric alloy material |
| CN102534278A (en) * | 2010-12-28 | 2012-07-04 | 北京有色金属研究总院 | Sleeve forging and pressing preparation method of bismuth-telluride-base thermoelectric material |
| WO2012138979A2 (en) * | 2011-04-08 | 2012-10-11 | The Trustees Of Boston College | Thermoelectric materials and methods for synthesis thereof |
| CN112670399A (en) * | 2021-01-13 | 2021-04-16 | 武汉理工大学 | Method for eliminating donor-like effect of bismuth telluride-based thermoelectric material |
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- 2022-07-15 CN CN202210836853.3A patent/CN115159986B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502865A (en) * | 2009-02-23 | 2009-08-12 | 浙江大学 | Hot forging processing method for optimizing performance of polycrystal bismuth telluride-based thermoelectric alloy material |
| CN102534278A (en) * | 2010-12-28 | 2012-07-04 | 北京有色金属研究总院 | Sleeve forging and pressing preparation method of bismuth-telluride-base thermoelectric material |
| WO2012138979A2 (en) * | 2011-04-08 | 2012-10-11 | The Trustees Of Boston College | Thermoelectric materials and methods for synthesis thereof |
| CN112670399A (en) * | 2021-01-13 | 2021-04-16 | 武汉理工大学 | Method for eliminating donor-like effect of bismuth telluride-based thermoelectric material |
Non-Patent Citations (1)
| Title |
|---|
| 孙立峰等 主编，哈尔滨工业大学出版社.《金工实习（第2版）》.2017,(第2版),第69-72页. * |
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