CN115159986A - 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
- Publication number
- CN115159986A CN115159986A CN202210836853.3A CN202210836853A CN115159986A CN 115159986 A CN115159986 A CN 115159986A CN 202210836853 A CN202210836853 A CN 202210836853A CN 115159986 A CN115159986 A CN 115159986A
- Authority
- CN
- China
- Prior art keywords
- bismuth telluride
- preparing
- thermoelectric material
- type bismuth
- based thermoelectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000005242 forging Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 33
- 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 27
- 238000004857 zone melting Methods 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 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 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007789 sealing Methods 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/0072—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (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 a p-type bismuth telluride base thermoelectric material by a free forging process. The method utilizes the forging process to refine the crystal grains, improve the orientation of the crystal grains, eliminate segregation and eliminate 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 a p-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 p-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 p-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 a p-type bismuth telluride-based thermoelectric material by a free forging process, which comprises the following specific steps:
step 1, taking Bi, sb and Te as raw materials, and Bi according to the stoichiometric ratio x Sb 2-x Te 3 Preparing materials, wherein x is more than or equal to 0.3 and less than or equal to 0.5; 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 380-450 ℃, 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 axis, a Y axis and a Z axis, 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 p-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 quartz glass tube is adopted for packaging, the melting temperature is 590-850 ℃.
In addition, 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 the crystal bar is 30mm; 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 the crystal bar is 30mm.
Furthermore, the initial bulk material and copper tube 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. 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 p-type bismuth telluride based thermoelectric material obtained by the 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 p-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 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 stability of the thermoelectric property of the p-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, then 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, preserving the temperature when the temperature is raised to 380-450 ℃, simultaneously forging and pressing at the pressure of 100-1000 MPa, forging along three directions of an X axis, a Y axis and a Z axis 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 p-type bismuth telluride-based thermoelectric material.
The performance indexes of the comparative example and the examples under several different conditions are shown in table 1 below.
TABLE 1 maximum zT values of 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 significantly improved, that is, the thermoelectric performance and the mechanical performance are significantly improved.
Claims (7)
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, taking Bi, sb and Te as raw materials, and Bi according to stoichiometric ratio x Sb 2-x Te 3 Preparing materials, wherein x is more than or equal to 0.3 and less than or equal to 0.5; 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 380-450 ℃, 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 axis, a Y axis and a Z axis, 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 p-type bismuth telluride-based thermoelectric material.
2. The method for preparing the p-type bismuth telluride-based thermoelectric material according to the free forging process of 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 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 p-type bismuth telluride-based thermoelectric material according to the free forging process of claim 3, wherein: when a high borosilicate glass tube is adopted for packaging, the melting temperature is 590-650 ℃; when quartz glass tube is adopted for packaging, the melting temperature is 590-850 ℃.
5. The method for preparing the p-type bismuth telluride-based thermoelectric material according to the free forging process of claim 3, wherein: 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 30mm; 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 the crystal bar is 30mm.
6. The method for preparing the p-type bismuth telluride-based thermoelectric material according to the free forging process of claim 1, wherein: in the step 2, the initial block material and the copper pipe are square or cylindrical.
7. The method for preparing the p-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 |
|---|---|---|---|
| CN202210836853.3A CN115159986B (en) | 2022-07-15 | 2022-07-15 | Method for preparing p-type bismuth telluride-based thermoelectric material by free forging process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210836853.3A CN115159986B (en) | 2022-07-15 | 2022-07-15 | Method for preparing p-type bismuth telluride-based thermoelectric material by free forging process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115159986A true CN115159986A (en) | 2022-10-11 |
| CN115159986B CN115159986B (en) | 2024-06-04 |
Family
ID=83494576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210836853.3A Active CN115159986B (en) | 2022-07-15 | 2022-07-15 | Method for preparing p-type bismuth telluride-based thermoelectric material by free forging process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115159986B (en) |
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 |
-
2022
- 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 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115159986B (en) | 2024-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110098313B (en) | Preparation method of preferred orientation p-type bismuth telluride-based polycrystalline block thermoelectric material | |
| CN110002412B (en) | Preparation method of preferred orientation n-type bismuth telluride based polycrystalline bulk thermoelectric material | |
| CN114031046A (en) | Fine-grain strong-orientation n-type Bi without donor-like effect2Te3Method for preparing base thermoelectric material | |
| CN112430093A (en) | Preparation method of bismuth antimony tellurium alloy target | |
| CN115159986B (en) | Method for preparing p-type bismuth telluride-based thermoelectric material by free forging process | |
| CN115122461A (en) | Method for preparing n-type bismuth telluride-based thermoelectric material by free forging process | |
| CN112002796B (en) | Rapid preparation of high-performance Bi easy to cut2Te3Method for producing thermoelectric material | |
| CN108520915B (en) | High-performance PbTe-SnTe alloy-based thermoelectric material and preparation method thereof | |
| CN114182123B (en) | Fast Nb preparation method 3 Method for producing Al superconductor | |
| CN115287754B (en) | Preparation method of n-type polycrystalline bismuth telluride-based thermoelectric material based on mold-free upsetting | |
| CN115287753B (en) | Preparation method of p-type polycrystalline bismuth telluride-based thermoelectric material based on mold-free upsetting | |
| CN108172680B (en) | Cubic phase Ca2Ge thermoelectric material and preparation method thereof | |
| CN113161473A (en) | Method for improving performance of p-type polycrystalline bismuth telluride material and preparation method | |
| CN117166039B (en) | Preparation method of bismuth telluride-based thermoelectric material capable of synchronously improving mechanical property and thermoelectric property | |
| CN118042909A (en) | Large-size high-performance p-type bismuth telluride-based thermoelectric material and preparation method thereof | |
| CN115215658A (en) | Preparation method of n-type bismuth telluride-based ultrafine-grained thermoelectric material based on copper-assisted extrusion molding | |
| CN115196965B (en) | N-type bismuth telluride thermoelectric material and preparation method thereof | |
| CN114574724B (en) | Directionally distributed SnO 2 /A 2 Sn 2 O 7 Preparation method of complex phase ceramic reinforced silver-based composite material | |
| CN114551706B (en) | P-type bismuth antimony selenide thermoelectric material and preparation method thereof | |
| CN114874011B (en) | Method for improving electrical property of n-type bismuth telluride-based thermoelectric material | |
| CN115295709A (en) | Preparation method of p-type bismuth telluride-based ultrafine-grained thermoelectric material based on copper-assisted extrusion molding | |
| CN115305567B (en) | Method for improving performance uniformity of hot extrusion N-type bismuth telluride | |
| CN117166039A (en) | Preparation method of bismuth telluride-based thermoelectric material capable of synchronously improving mechanical property and thermoelectric property | |
| JP2003089516A (en) | MgB2 SUPERCONDUCTOR AND METHOD FOR PRODUCING THE SAME | |
| CN115815600A (en) | Preparation method for improving thermoelectric performance of extrusion material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |