CN115122461A - Method for preparing n-type bismuth telluride-based thermoelectric material by free forging process - Google Patents
Method for preparing n-type bismuth telluride-based thermoelectric material by free forging process Download PDFInfo
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- CN115122461A CN115122461A CN202210836851.4A CN202210836851A CN115122461A CN 115122461 A CN115122461 A CN 115122461A CN 202210836851 A CN202210836851 A CN 202210836851A CN 115122461 A CN115122461 A CN 115122461A
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- Prior art keywords
- bismuth telluride
- preparing
- thermoelectric material
- type bismuth
- based thermoelectric
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- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000005242 forging Methods 0.000 title claims abstract description 35
- 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 25
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 238000004857 zone melting Methods 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 238000004806 packaging method and process Methods 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 7
- 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
- 238000003723 Smelting Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 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
- 238000005204 segregation Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 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
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B3/00—Producing shaped articles from the material by using presses; Presses specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B13/00—Feeding the unshaped material to moulds or apparatus for producing shaped articles; Discharging shaped articles from such moulds or apparatus
- B28B13/02—Feeding the unshaped material to moulds or apparatus for producing shaped articles
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Forging (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 free forging process. The method utilizes the forging process to refine the crystal grains, improve the crystal grain orientation, eliminate the segregation and eliminate the pores so as to improve the thermoelectric property and the mechanical property, realizes the free forging of the brittle thermoelectric material, improves the defects in the material, enables the internal structure of the material to be more uniform and eliminates the segregation, and has more stable thermoelectric property.
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 free forging process.
Background
With continuous innovation and progress of technologies in various fields, the use environment and conditions of thermoelectric devices become more severe, and therefore, high thermoelectric performance, high reliability and miniaturization are directions in which efforts are needed, which needs to improve the mechanical strength of materials while improving the ZT value of the materials. The traditional large-scale thermoelectric material preparation method is mainly zone melting, and although the prepared single crystal has good orientation and high ZT value, the prepared single crystal has poor mechanical processing performance, so that the stability of the prepared single crystal is poor, and the application range of the thermoelectric material is limited.
Disclosure of Invention
The invention aims to rapidly prepare the n-type bismuth telluride-based thermoelectric material with fine crystal grains and uniform texture by a free forging process, and the mechanical property and the thermoelectric property of the n-type bismuth telluride-based thermoelectric material are both 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 free forging 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 Preparing materials, wherein x is more than or equal to 0.15 and less than or equal to 0.6; vacuum packaging and smelting to prepare a crystal bar, carrying out zone melting 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 prepare a block, namely an initial block material;
step 2, sealing the initial block material prepared in the step 1 into a copper pipe, wherein 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, starting free forging and pressing when the temperature is raised to 380-520 ℃, wherein the forging and pressing pressure is 100-1000 Mpa, continuously turning over the material while forging and pressing along three directions of an X, Y, Z shaft, and the forging ratio is 3-10;
and step 4, forging the material into a square die cavity on a workbench, cooling and peeling the copper pipe 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.
Further, the encapsulation in step 1 means encapsulation using a borosilicate glass tube or a quartz glass tube.
Moreover, when a high borosilicate glass tube is adopted for packaging, the melting temperature is 590-650 ℃; when the quartz glass tube is adopted for packaging, the melting temperature is 590-850 ℃.
In addition, zone melting is carried out by adopting a zone melting furnace in the step 1, and the specific zone melting conditions when a high borosilicate glass tube is adopted for packaging are that the zone melting temperature is 650-780 ℃, the crystal pulling rate is 20-35 mm/h, and the diameter of a crystal bar is 30 mm; the specific zone melting conditions when the quartz glass tube is adopted for packaging are that the zone melting temperature is 650-850 ℃, the crystal pulling speed is 20-35 mm/h, and the diameter of a crystal bar is 30 mm.
Furthermore, the initial bulk material and copper tube in step 2 are square or cylindrical.
And in the step 3, the heating rate is 20-100 ℃/min.
Compared with the prior art, the invention has the beneficial effects that: 1. the free forging of the brittle thermoelectric material is realized, the defect in the material is improved by the forging process, the internal structure of the material is more uniform, the segregation is eliminated, and the performance is more stable; 2. the forging process is utilized to refine the crystal grains, improve the crystal grain orientation, eliminate segregation and eliminate pores, thereby improving the performance; 3. the method comprises the steps of sealing a block material into a copper pipe with excellent plasticity, heating and raising the temperature, successfully realizing free forging of the brittle thermoelectric material, wherein the n-type bismuth telluride-based thermoelectric material obtained by an improved process has the characteristics of fine crystal grains, uniform texture and high density, the thermoelectric property and the mechanical property of the material are obviously improved, and the n-type bismuth telluride-based thermoelectric material has very high practical value; 4. the copper tube adopted by the invention can generate diffusion reaction with the bismuth telluride material at high temperature, Cu element is easy to 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 Te vacancy and Bi Te The formation of the inversion defect reduces the donor-like effect, thereby solving the problem of poor thermoelectric property repeatability of the n-type bismuth telluride alloy.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
Taking a produced zone-melting crystal bar, crushing the zone-melting crystal bar into powder, preparing a block material by adopting SPS sintering equipment, sealing the block material in a copper pipe, putting the copper pipe sealed with the material on a workbench of forging equipment, heating to raise the temperature at the rate of 20-100 ℃/min, keeping the temperature when the temperature is raised to 380-520 ℃, simultaneously forging and pressing at the pressure of 100-1000 MPa, forging along X, Y and Z-axis in three directions at the forging ratio of 3-8, finally forging the material into a square die cavity on the workbench, and cooling to obtain the block n-type bismuth telluride-based thermoelectric material.
The performance index of the comparative example and the examples under several different conditions are shown in table 1.
TABLE 1 maximum zT values of n-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 significantly improved, that is, the thermoelectric performance and the mechanical performance are significantly improved.
Claims (7)
1. A method for preparing an n-type bismuth telluride-based thermoelectric material by a free forging 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; vacuum packaging and smelting to prepare a crystal bar, carrying out zone melting 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 prepare a block, namely an initial block material;
step 2, sealing the initial block material prepared in the step 1 into a copper pipe, wherein 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, starting free forging and pressing when the temperature is raised to 380-520 ℃, wherein the forging and pressing pressure is 100-1000 Mpa, continuously turning over the material while forging and pressing along three directions of an X, Y, Z shaft, and the forging ratio is 3-10;
and 4, forging the material into a square die cavity on a workbench, cooling and stripping the copper pipe 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 free forging process of claim 1, wherein the method 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 free forging process of claim 1, wherein the method comprises the following steps: the packaging in the step 1 is to use a high borosilicate glass tube or a quartz glass tube for packaging.
4. The method for preparing the n-type bismuth telluride-based thermoelectric material according to the free forging process of claim 3, wherein the method comprises the following steps: when a high borosilicate glass tube is adopted for packaging, the smelting temperature is 590-650 ℃; when the quartz glass tube is adopted for packaging, the melting temperature is 590-850 ℃.
5. The method for preparing the n-type bismuth telluride-based thermoelectric material according to the free forging process of claim 3, wherein the method comprises the following steps: the zone melting in the step 1 is carried out by adopting a zone melting furnace, and the specific zone melting conditions when a high borosilicate glass tube is adopted for packaging are that the zone melting temperature is 650-780 ℃, the crystal pulling rate is 20-35 mm/h, and the diameter of a crystal bar is 30 mm; the specific zone melting conditions when the quartz glass tube is adopted for packaging are that the zone melting temperature is 650-850 ℃, the crystal pulling speed is 20-35 mm/h, and the diameter of a crystal bar is 30 mm.
6. The method for preparing the n-type bismuth telluride-based thermoelectric material according to the free forging process of claim 1, wherein the method comprises the following steps: in the step 2, the initial block material and the copper pipe are square or cylindrical.
7. The method for preparing the n-type bismuth telluride-based thermoelectric material according to the free forging process of claim 1, wherein the method comprises the following steps: in the step 3, the heating rate is 20-100 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210836851.4A CN115122461A (en) | 2022-07-15 | 2022-07-15 | Method for preparing n-type bismuth telluride-based thermoelectric material by free forging process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210836851.4A CN115122461A (en) | 2022-07-15 | 2022-07-15 | Method for preparing n-type bismuth telluride-based thermoelectric material by free forging process |
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| CN115122461A true CN115122461A (en) | 2022-09-30 |
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| CN202210836851.4A Pending CN115122461A (en) | 2022-07-15 | 2022-07-15 | Method for preparing n-type bismuth telluride-based thermoelectric material by free forging process |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1526637A (en) * | 2003-09-25 | 2004-09-08 | 浙江大学 | Prepn of Bi2Te3-base compound nanotube |
| JP2006063415A (en) * | 2004-08-30 | 2006-03-09 | Hitachi Powdered Metals Co Ltd | Manufacturing method of sinter forged aluminum-based parts with high strength |
| 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 |
| US20180138386A1 (en) * | 2016-11-16 | 2018-05-17 | Korea Institute Of Science And Technology | Method for manufacturing thermoelectric material having high efficiency and method for manufacturing thermoelectric module |
| CN114477102A (en) * | 2022-01-20 | 2022-05-13 | 深圳热电新能源科技有限公司 | N-type bismuth telluride-based thermoelectric material and preparation method and application thereof |
| WO2022126952A1 (en) * | 2020-12-14 | 2022-06-23 | 深圳先进电子材料国际创新研究院 | Bismuth telluride thermoelectric material and preparation method therefor |
-
2022
- 2022-07-15 CN CN202210836851.4A patent/CN115122461A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1526637A (en) * | 2003-09-25 | 2004-09-08 | 浙江大学 | Prepn of Bi2Te3-base compound nanotube |
| JP2006063415A (en) * | 2004-08-30 | 2006-03-09 | Hitachi Powdered Metals Co Ltd | Manufacturing method of sinter forged aluminum-based parts with high strength |
| 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 |
| US20180138386A1 (en) * | 2016-11-16 | 2018-05-17 | Korea Institute Of Science And Technology | Method for manufacturing thermoelectric material having high efficiency and method for manufacturing thermoelectric module |
| WO2022126952A1 (en) * | 2020-12-14 | 2022-06-23 | 深圳先进电子材料国际创新研究院 | Bismuth telluride thermoelectric material and preparation method therefor |
| CN114477102A (en) * | 2022-01-20 | 2022-05-13 | 深圳热电新能源科技有限公司 | N-type bismuth telluride-based thermoelectric material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
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