CN115196602A - Method for preparing n-type bismuth telluride-based thermoelectric material by drawing process - Google Patents
Method for preparing n-type bismuth telluride-based thermoelectric material by drawing process Download PDFInfo
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- CN115196602A CN115196602A CN202210837619.2A CN202210837619A CN115196602A CN 115196602 A CN115196602 A CN 115196602A CN 202210837619 A CN202210837619 A CN 202210837619A CN 115196602 A CN115196602 A CN 115196602A
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- drawing process
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- thermoelectric material
- bismuth telluride
- type bismuth
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 43
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 27
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 23
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 230000006698 induction Effects 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 description 6
- 238000002490 spark plasma sintering Methods 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910002665 PbTe Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 238000004857 zone melting Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention belongs to the technical field of bismuth telluride base thermoelectric materials, and particularly relates to a method for preparing an n-type bismuth telluride base thermoelectric material by a drawing process. According to the invention, the drawing deformation of the brittle material is realized through the drawing process, the thermoelectric material with fine, uniform and highly oriented crystal grains is rapidly prepared, and the mechanical property and the thermoelectric property are both obviously improved; and because the induction heating is rapid, the drawing process can rapidly prepare the thermoelectric material in batch, and has very strong practical value.
Description
Technical Field
The invention belongs to the technical field of bismuth telluride base thermoelectric materials, and particularly relates to a method for preparing an n-type bismuth telluride base thermoelectric material by a drawing process.
Background
Thermoelectric materials can be divided into low temperature (room temperature) thermoelectric materials such as Bi according to the temperature range of use 2 Te 3 Base alloys, medium temperature regions such as PbTe based alloys, high temperature regions such as SiGe based alloys, and Bi 2 Te 3 The base system thermoelectric material is more mature in application due to better thermoelectric performance at the room temperature. The quality of the thermoelectric material is mainly judged by ZT value, although a lot of Bi with high ZT value is prepared in laboratories at present 2 Te 3 Methods for base materials such as ball milling, mechanical alloying, SPS, melt spinning, wet chemical methods, but are rarely true for practical applications due to limitations. At present, the commercial production is mainly to obtain single crystals by a zone melting method, and although the ZT value is higher, the mechanical property is poorer, so that the further development of the single crystals is restricted. The drawing process is a metallurgical process, is mainly used for forming plastic metal materials such as pipes, bars, wires and other special-shaped parts, can be beneficial to refining metal grains and improving the comprehensive performance of products, and is not applied to the preparation of thermoelectric materials at present.
Disclosure of Invention
The invention aims to provide a brand-new method for preparing a high-performance n-type bismuth telluride thermoelectric material in the field, the thermoelectric material with fine and uniform crystal grains and high orientation is quickly prepared by a drawing process, and the mechanical property, the thermoelectric property and the stability of the thermoelectric material are obviously improved.
In order to achieve the purpose, the technical scheme adopted by the invention is a method for preparing an n-type bismuth telluride-based thermoelectric material by a drawing process, which comprises the following specific steps:
step 1, taking Bi, te and Se as raw materials, and Bi according to stoichiometric ratio 2 Te 3-x Se x (x is more than or equal to 0.15 and less than or equal to 0.6), preparing materials, smelting, preparing crystal bars, crushing the crystal bars into powder, and performing hot-pressing sintering or SPS sintering on the powder to prepare blocks;
step 2, filling the block body prepared in the step 1 into a copper pipe and sealing the copper pipe;
step 3, fixing one end of the copper pipe on the traction rod, heating the copper pipe at the inlet of the die, finally controlling the temperature at any temperature point within the range of 350-520 ℃, then drawing at the drawing speed of 1-10 cm/min for 1-3 times, and controlling the final elongation coefficient between 6-25;
and 4, taking out the substance obtained by drawing to obtain the n-type bismuth telluride-based thermoelectric material.
In step 1, the purity of Bi, te and Se is 99.99% or more.
Moreover, the smelting temperature in the step 1 is 590-850 ℃,
and in the step 2, the copper pipe is made of copper or copper alloy.
In step 3, the die is a drawing die with a die hole wall inclination angle of 5-30 degrees.
Moreover, the heating mode in the step 3 is medium frequency induction heating.
In addition, in the drawing process in the step 3, the inner diameters of the die holes used in each drawing are different, and the inner diameter of the die hole used in the next drawing is smaller than that of the die hole used in the previous drawing.
Compared with the prior art, the invention has the beneficial effects that: 1. the bismuth telluride based thermoelectric material is a brittle material at normal temperature, and is difficult to be directly drawn, and the drawing process is successfully applied to the preparation of the thermoelectric material by sealing a block n-type bismuth telluride based thermoelectric material in a copper pipe with excellent ductility, heating and then drawing; 2. the drawing deformation of the brittle material is realized, and the drawing process can be used for quickly preparing the thermoelectric material in batch due to the rapid induction heating, so that the drawing process has very high practical value; 3. the deformation of the material is large in the drawing process, the recrystallization is sufficient, the thermoelectric material with good orientation and fine and uniform crystal grains can be obtained, and the mechanical property and the thermoelectric property of the final material are obviously improved; 4. the copper mask adopted by the invention can generate diffusion reaction with the bismuth telluride material at high temperature, cu element can easily diffuse and enter between Te-Te base planes of bismuth telluride crystal lattices, and the formation energy of Te vacancy can be increased to inhibit the Te vacancy and Bi Te The formation of the inversion defect reduces the donor-like effect, thereby improving the thermoelectric property repeatability of the n-type bismuth telluride alloy; 5. the drawing process is a brand new production process applied to the field of bismuth telluride-based thermoelectric materials, and has reference value for the preparation of thermoelectric materials of other systems and other functional materials.
Drawings
FIG. 1 is the resistivity in the examples;
FIG. 2 is a Seebeck coefficient in the example;
FIG. 3 is thermal conductivity in examples;
FIG. 4 shows the values of zT in the examples.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
Example 1
According to Bi 2 Te 2.7 Se 0.3 The preparation method comprises the steps of proportioning, crushing a crystal bar into powder after smelting, sintering the powder into a cylindrical block material with the diameter of 90mm by adopting SPS (spark plasma sintering), and filling the prepared initial block material into a circular copper pipe with the diameter of 90 mm. Uniformly coating a layer of lubricating oil on the inner wall of a drawing die, fixing one end of a copper pipe with a traction rod, heating the copper pipe at the inlet of the die, and drawing at the speed of 2cm/min when the temperature is raised to 400 ℃. And 2, drawing is carried out, wherein the inner diameter of the die hole of the 1 st pass is 60mm, and the inner diameter of the die hole of the 2 nd pass is 30mm, namely the total elongation coefficient is 9. After drawing, the strength and thermoelectric performance of the material are tested, the bending strength reaches 65Mpa, and the maximum ZT value reaches 1.04.
Example 2
According to Bi 2 Te 2.79 Se 0.21 The preparation method comprises the steps of proportioning, crushing a crystal bar into powder after smelting, sintering the powder into a cylindrical block material with the diameter of 90mm by adopting SPS, and filling the prepared initial block material into a circular copper pipe with the diameter of 90 mm. Uniformly coating a layer of lubricating oil on the inner wall of a drawing die, fixing one end of a copper pipe with a pull rod, heating the copper pipe at the inlet of the die, and drawing at the speed of 2cm/min when the temperature is raised to 430 ℃. And 2-time drawing is carried out, the inner diameter of the die hole of the 1 st time is 60mm, and the inner diameter of the die hole of the 2 nd time is 25mm, namely the total elongation coefficient is 12.96. After the drawing is finished, the strength and the thermoelectric property of the material are tested, the bending strength reaches 72Mpa, and the maximum ZT value reaches 1.08.
Example 3
According to Bi 2 Te 2.7 Se 0.3 The preparation method comprises the steps of proportioning, crushing a crystal bar into powder after smelting, sintering the powder into a cylindrical block material with the diameter of 80mm by adopting SPS, and filling the prepared initial block material into a circular copper pipe with the diameter of 80 mm. Uniformly coating a layer of lubricating oil on the inner wall of a drawing die, fixing one end of a copper pipe with a traction rod, heating the copper pipe at the inlet of the die, and drawing at the speed of 5cm/min when the temperature is raised to 430 ℃. And 2-time drawing is carried out, the inner diameter of the die hole of the 1 st time is 60mm, and the inner diameter of the die hole of the 2 nd time is 30mm, namely the total elongation coefficient is 7.11. After the drawing is finished, the strength and the thermoelectric property of the material are tested, the bending strength reaches 80Mpa, and the maximum ZT value reaches 1.13.
Claims (7)
1. A method for preparing an n-type bismuth telluride-based thermoelectric material by a drawing process is characterized by comprising the following specific steps:
step 1, taking Bi, te and Se as raw materials, and Bi according to stoichiometric ratio 2 Te 3-x Se x Preparing materials, wherein x is more than or equal to 0.15 and less than or equal to 0.6, preparing a crystal bar by smelting, crushing the crystal bar into powder, and performing hot-pressing sintering or SPS sintering on the powder to prepare a block;
step 2, filling the block body prepared in the step 1 into a copper pipe and sealing the copper pipe;
step 3, fixing one end of the copper pipe on the traction rod, heating the copper pipe at the inlet of the die, finally controlling the temperature at any temperature point within the range of 350-520 ℃, then drawing at the drawing speed of 1-10 cm/min for 1-3 times, and controlling the final elongation coefficient between 6-25;
and 4, taking out the substance obtained by drawing to obtain the n-type bismuth telluride-based thermoelectric material.
2. The method for preparing the n-type bismuth telluride-based thermoelectric material according to the drawing process of claim 1, wherein the drawing process comprises the following steps: in the step 1, the purity of Bi, te and Se is more than 99.99 percent.
3. The method for preparing the n-type bismuth telluride-based thermoelectric material according to the drawing process of claim 1, wherein: in the step 1, the smelting temperature is 590-850 ℃.
4. The method for preparing the n-type bismuth telluride-based thermoelectric material according to the drawing process of claim 1, wherein: the copper pipe in the step 2 is made of copper or copper alloy.
5. The method for preparing the n-type bismuth telluride-based thermoelectric material according to the drawing process of claim 1, wherein the drawing process comprises the following steps: the die in the step 3 is a drawing die with a die hole wall inclination angle of 5-30 degrees.
6. The method for preparing the n-type bismuth telluride-based thermoelectric material according to the drawing process of claim 1, wherein the drawing process comprises the following steps: the heating mode in the step 3 is medium frequency induction heating.
7. The method for preparing the n-type bismuth telluride-based thermoelectric material according to the drawing process of claim 1, wherein the drawing process comprises the following steps: in the drawing process in the step 3, the inner diameters of the die holes used in each drawing are different, and the inner diameter of the die hole used in the next drawing is smaller than that of the die hole used in the previous drawing.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210837619.2A CN115196602B (en) | 2022-07-15 | 2022-07-15 | Method for preparing n-type bismuth telluride-based thermoelectric material by drawing process |
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| CN202210837619.2A CN115196602B (en) | 2022-07-15 | 2022-07-15 | Method for preparing n-type bismuth telluride-based thermoelectric material by drawing process |
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| CN115196602A true CN115196602A (en) | 2022-10-18 |
| CN115196602B CN115196602B (en) | 2024-01-09 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB973756A (en) * | 1960-11-21 | 1964-10-28 | Westinghouse Electric Corp | Process for preparing a thermoelectric material |
| CN102132430A (en) * | 2008-08-11 | 2011-07-20 | 三星电子株式会社 | Anisotropically elongated thermoelectric material, process for preparing the same, and device comprising the material |
| WO2012138979A2 (en) * | 2011-04-08 | 2012-10-11 | The Trustees Of Boston College | Thermoelectric materials and methods for synthesis thereof |
| CN107833695A (en) * | 2017-10-30 | 2018-03-23 | 西北有色金属研究院 | A kind of MgB2The preparation method of multi-core superconducting wire rod |
| CN110002412A (en) * | 2019-04-22 | 2019-07-12 | 武汉科技大学 | A kind of preparation method of preferred orientation N-shaped bismuth telluride-base polycrystalline bulk thermoelectric material |
| CN111875381A (en) * | 2020-08-03 | 2020-11-03 | 深圳见炬科技有限公司 | Preparation method of N-type bismuth telluride thermoelectric block material |
| CN114031046A (en) * | 2021-10-29 | 2022-02-11 | 武汉理工大学 | Fine-grain strong-orientation n-type Bi without donor-like effect2Te3Method for preparing base thermoelectric material |
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2022
- 2022-07-15 CN CN202210837619.2A patent/CN115196602B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB973756A (en) * | 1960-11-21 | 1964-10-28 | Westinghouse Electric Corp | Process for preparing a thermoelectric material |
| CN102132430A (en) * | 2008-08-11 | 2011-07-20 | 三星电子株式会社 | Anisotropically elongated thermoelectric material, process for preparing the same, and device comprising the material |
| WO2012138979A2 (en) * | 2011-04-08 | 2012-10-11 | The Trustees Of Boston College | Thermoelectric materials and methods for synthesis thereof |
| CN107833695A (en) * | 2017-10-30 | 2018-03-23 | 西北有色金属研究院 | A kind of MgB2The preparation method of multi-core superconducting wire rod |
| CN110002412A (en) * | 2019-04-22 | 2019-07-12 | 武汉科技大学 | A kind of preparation method of preferred orientation N-shaped bismuth telluride-base polycrystalline bulk thermoelectric material |
| CN111875381A (en) * | 2020-08-03 | 2020-11-03 | 深圳见炬科技有限公司 | Preparation method of N-type bismuth telluride thermoelectric block material |
| CN114031046A (en) * | 2021-10-29 | 2022-02-11 | 武汉理工大学 | Fine-grain strong-orientation n-type Bi without donor-like effect2Te3Method for preparing base thermoelectric material |
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