CN112289919A - Preparation method of N-type bismuth telluride polycrystalline block thermoelectric material - Google Patents
Preparation method of N-type bismuth telluride polycrystalline block thermoelectric material Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 51
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 49
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 238000004857 zone melting Methods 0.000 claims abstract description 15
- 238000000465 moulding Methods 0.000 claims abstract description 13
- 238000001192 hot extrusion Methods 0.000 claims abstract description 11
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000011049 filling Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 23
- 238000000498 ball milling Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- 239000011669 selenium Substances 0.000 description 8
- 238000007731 hot pressing Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 229910001315 Tool steel Inorganic materials 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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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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- 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
- H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
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Abstract
The invention provides a preparation method of an N-type bismuth telluride polycrystalline block thermoelectric material, which comprises the following steps: weighing the small blocks according to a certain stoichiometric ratio, mixing the small blocks, putting the mixed small blocks into a glass tube, and vacuumizing to seal the glass tube; putting the sealed glass tube into a rocking furnace for high-temperature melting, and melting the obtained cast ingot in a zone melting furnace; grinding the cast ingot to obtain powder, and sieving the powder by using a sieve; filling the sieved powder into a die, and performing cold press molding to obtain a cold press block; and putting the cold pressing block into an extruding machine, and carrying out hot extrusion on the cold pressing block by the extruding machine to obtain the N-type bismuth telluride polycrystalline block thermoelectric material. The invention has the beneficial effect of effectively solving the problem that the service life and the performance of the thermoelectric refrigerator are reduced due to the poor mechanical property and the thermoelectric property of the material because the crystal grains can not be thoroughly refined due to the special structure of the zone-melting bismuth telluride material.
Description
Technical Field
The invention belongs to the technical field of thermoelectric materials, and particularly relates to a preparation method of an N-type bismuth telluride polycrystalline block thermoelectric material.
Background
The thermoelectric material is a functional material which realizes direct interconversion of heat energy and electric energy by utilizing the interaction between current carriers and lattice vibration in the material. The thermoelectric refrigerator made of thermoelectric material has the features of no noise, no vibration, no need of refrigerant, small size, light weight, etc. and is reliable, simple and easy to operate and easy to regulate cold amount. Due to the series of advantages, the thermoelectric refrigerator is widely applied to various fields such as industry, agriculture, scientific research, national defense and the like.
The existing bismuth telluride bulk preparation mainly comprises the following methods: zone melting method, single crystal pulling method, powder metallurgy method and in-situ synthesis method. The bismuth telluride prepared by the zone melting method has good alert orientation and the best thermoelectric property in the growth direction. However, because the Te (l) atoms and the Te (l) atoms between two adjacent cycles in the bismuth telluride are weaker in bonding energy and are bonded by Van der Waals force, the atoms are easy to be cleaved along the (0001) plane, so that the mechanical property of the bismuth telluride crystal is poor, and the condition is serious in an N-type material, thereby causing the service life and the performance of the thermoelectric refrigerator to be reduced. The polycrystalline sample prepared by powder metallurgy can effectively weaken the anisotropy of bismuth telluride, improve the mechanical property of the bismuth telluride, but weaken the thermoelectric property of the material. In the prior art, the raw materials are directly sintered and extruded into the bismuth telluride thermoelectric material after being smelted, and the crystal grains cannot be thoroughly refined by the method, so that the mechanical property and the thermoelectric property of the material are poor.
Disclosure of Invention
The invention aims to provide a preparation method of an N-type bismuth telluride polycrystal block thermoelectric material, which effectively solves the problems that the mechanical property and the thermoelectric property of the material are poor, the service life of a thermoelectric refrigerator is prolonged, and the performance of the thermoelectric refrigerator is reduced because crystal grains cannot be thoroughly refined due to the special structure of a zone-melting bismuth telluride material.
In order to solve the problems, the technical scheme adopted by the invention is as follows: a preparation method of an N-type bismuth telluride polycrystalline block thermoelectric material comprises the following steps: s1: crushing the raw materials into small blocks with the diameter not more than 30mm, and placing the small blocks on filter paper; s2: weighing the small blocks according to a certain stoichiometric ratio, mixing the small blocks, putting the mixed small blocks into a glass tube, and vacuumizing to seal the glass tube; s3: putting the sealed glass tube into a rocking furnace for high-temperature melting, and melting the obtained cast ingot in a zone melting furnace; s4: grinding the cast ingot to obtain powder, and sieving the powder by using a sieve; s5: filling the sieved powder into a die, and performing cold press molding to obtain a cold press block; s6: and putting the cold pressing block into an extruding machine, and carrying out hot extrusion on the cold pressing block by the extruding machine to obtain the N-type bismuth telluride polycrystalline block thermoelectric material.
Preferably, the raw material is a combination of elementary substances of Bi, Te and Se.
Preferably, in the step S2, the stoichiometric ratio is Bi2Te3-xSex(0.1＜x≤0.2)。
Preferably, in the step S3, the melting temperature of the glass tube in high-temperature melting is 700 ℃ to 900 ℃, and the melting time is 1 to 5 hours; the smelting temperature of the ingot in the zone melting furnace is 600-800 ℃, the heating rate is 20-30 ℃/min, the temperature gradient is 20-40 ℃/cm, and the growth rate is 25-30 mm/h.
Preferably, in the step S4, the grinding manner is ball milling, the smelted ingot is put into a ball mill, and ball milling is performed after protective atmosphere is introduced, wherein the ball milling time is 2-24 h.
Preferably, in step S4, the protective atmosphere is one or more of helium, argon, nitrogen and hydrogen-argon mixture.
Preferably, in the step S4, the mesh size is 80-300 mesh.
Preferably, in the step S5, the pressure for cold press molding the powder is 150-250 MPa.
Preferably, in the step S6, the extruder is a horizontal extruder, the preset temperature in the hot extrusion molding is 400-.
As the ball mill is used for thoroughly refining the crystal grains, the grain size is basically uniform, and the mechanical property and the thermoelectric property of the N-type bismuth telluride polycrystal block thermoelectric material are greatly enhanced; the preparation method of the N-type bismuth telluride polycrystalline block thermoelectric material is adopted, the hot-pressing sintering process is utilized, the hot-pressing sintering process parameters are adjusted to enable the N-type bismuth telluride to achieve the appropriate thermal deformation degree, the thermoelectric material with strong texture and good transportation performance is obtained, and the thermal deformation process is accompanied with the further refinement and the strengthening of the texture of crystal grains and the introduction of the nano structure, so the N-type bismuth telluride polycrystalline block thermoelectric material with high strength and high thermoelectric performance can be prepared.
Drawings
FIG. 1 is a schematic diagram of a back scattering morphology of an extruder for a polycrystalline bulk thermoelectric material of bismuth N-telluride according to an embodiment of the present invention
Detailed Description
The invention is further illustrated by the following examples:
example 1
S1, crushing the raw materials: respectively placing the vacuum-packed tellurium ingot, bismuth ingot and selenium ingot on filter paper, and smashing the materials into small pieces through packing by a wood hammer. Opening the packaging bag, clamping small pieces with diameter not more than 30mm with tweezers, and placing on clean filter paper. The crushing of the raw material into small pieces may allow for better melting of the raw material in the S3 step.
S2, vacuum tube sealing: according to Bi2Te2.8Se0.2The raw materials obtained in the step 1 are weighed according to the stoichiometric ratio, mixed and then put into a clean glass tube, and then the tube is sealed by vacuumizing.
S3, zone melting: and (3) putting the glass tube sealed in the step (2) into a rocking furnace for melting at a high temperature of 800 ℃ for 3 hours. And then smelting the obtained cast ingot in a zone melting furnace, wherein the smelting temperature is 700 ℃, the heating rate is 30 ℃/min, the temperature gradient is 30 ℃/cm, and the growth rate is 25 mm/h.
S4, ball milling and sieving: and (3) putting the zone-melted N-type bismuth telluride alloy in the step (3) into a ball milling tank, introducing nitrogen, carrying out ball milling for 8 hours, and sieving the alloy powder obtained after ball milling by using a 200-mesh sieve. The crystal grains are thoroughly refined by ball milling, so that the grain sizes of the crystal grains are basically uniform, and the mechanical property and the thermoelectric property of the N-type bismuth telluride polycrystal block thermoelectric material are greatly enhanced.
S5, cold press molding: and (4) loading the N-type bismuth telluride alloy powder sieved in the step (4) into an alloy tool steel die, and performing compression molding under the pressure of 200 MPa.
S6, hot extrusion molding: and (4) putting the N-type bismuth telluride ingot obtained in the step (5) into a horizontal extruder, heating to 500 ℃, and then carrying out hot extrusion forming, wherein the extrusion ratio is 9, and the extrusion rate is 10 mm/min. The hot-pressing sintering process is utilized, the hot-pressing sintering process parameters are adjusted to enable the bismuth telluride to reach the appropriate thermal deformation degree, the thermoelectric material with strong texture and good transportation performance is obtained, and the thermal deformation process is accompanied with the further refinement and the strengthening of the texture of crystal grains, and the introduction of the nano structure is also adopted, so that the bismuth telluride polycrystal block thermoelectric material with high strength and high thermoelectric performance can be prepared.
Example 2
S1, crushing the raw materials: respectively placing the vacuum-packed tellurium ingot, bismuth ingot and selenium ingot on filter paper, and smashing the materials into small pieces through packing by a wood hammer. Opening the packaging bag, clamping small pieces with diameter not more than 30mm with tweezers, and placing on clean filter paper.
S2, vacuum tube sealing: according to Bi2Te2.95Se0.05The raw materials obtained in the step 1 are weighed according to the stoichiometric ratio, mixed and then put into a clean glass tube, and then the tube is sealed by vacuumizing.
S3, zone melting: and (3) putting the glass tube sealed in the step (2) into a rocking furnace for melting at a high temperature of 700 ℃ for 5 hours. And then smelting the obtained cast ingot in a zone melting furnace, wherein the smelting temperature is 600 ℃, the heating rate is 20 ℃/min, the temperature gradient is 20 ℃/cm, and the growth rate is 25 mm/h.
S4, ball milling and sieving: and (3) putting the zone-melted N-type bismuth telluride alloy in the step (3) into a ball milling tank, introducing nitrogen, carrying out ball milling for 2 hours, and sieving the alloy powder obtained after ball milling by using a 100-mesh sieve.
S5, cold press molding: and (4) loading the N-type bismuth telluride alloy powder sieved in the step (4) into an alloy tool steel die, and performing compression molding under the pressure of 150 MPa.
S6, hot extrusion molding: and (4) putting the N-type bismuth telluride ingot obtained in the step (5) into a horizontal extruder, heating to 400 ℃, and then carrying out hot extrusion forming, wherein the extrusion ratio is 5, and the extrusion speed is 5 mm/min. The hot-pressing sintering process is utilized, the hot-pressing sintering process parameters are adjusted to enable the bismuth telluride to reach the appropriate thermal deformation degree, the thermoelectric material with strong texture and good transportation performance is obtained, and the thermal deformation process is accompanied with the further refinement and the strengthening of the texture of crystal grains, and the introduction of the nano structure is also adopted, so that the bismuth telluride polycrystal block thermoelectric material with high strength and high thermoelectric performance can be prepared.
Example 3
S1, crushing the raw materials: respectively placing the vacuum-packed tellurium ingot, bismuth ingot and selenium ingot on filter paper, and smashing the materials into small pieces through packing by a wood hammer. Opening the packaging bag, clamping small pieces with diameter not more than 30mm with tweezers, and placing on clean filter paper.
S2, vacuum tube sealing: according to Bi2Te2.93Se0.07The raw materials obtained in the step 1 are weighed according to the stoichiometric ratio, mixed and then put into a clean glass tube, and then the tube is sealed by vacuumizing.
S3, zone melting: and (3) putting the glass tube sealed in the step (2) into a rocking furnace for melting at a high temperature of 900 ℃ for 1 hour. And then smelting the obtained cast ingot in a zone melting furnace, wherein the smelting temperature is 800 ℃, the heating rate is 30 ℃/min, the temperature gradient is 40 ℃/cm, and the growth rate is 30 mm/h.
S4, ball milling and sieving: and (3) putting the zone-melted N-type bismuth telluride alloy in the step (3) into a ball milling tank, introducing nitrogen, carrying out ball milling for 24 hours, and sieving the alloy powder obtained after ball milling by using a 300-mesh sieve.
S5, cold press molding: and (4) loading the N-type bismuth telluride alloy powder sieved in the step (4) into an alloy tool steel die, and performing compression molding under the pressure of 250 MPa.
S6, hot extrusion molding: and (4) putting the N-type bismuth telluride ingot obtained in the step (5) into a horizontal extruder, heating to 500 ℃, and then carrying out hot extrusion forming, wherein the extrusion ratio is 25, and the extrusion rate is 10 mm/min.
Although the embodiments of the present invention have been described in detail, the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (9)
1. A preparation method of an N-type bismuth telluride polycrystalline block thermoelectric material comprises the following steps:
s1: crushing the raw materials into small blocks with the diameter not more than 30mm, and placing the small blocks on filter paper;
s2: weighing the small blocks according to a certain stoichiometric ratio, mixing the small blocks, putting the mixed small blocks into a glass tube, and vacuumizing to seal the glass tube;
s3: putting the sealed glass tube into a rocking furnace for high-temperature melting, and melting the obtained cast ingot in a zone melting furnace;
s4: grinding the cast ingot to obtain powder, and sieving the powder by using a sieve;
s5: filling the sieved powder into a die, and performing cold press molding to obtain a cold press block;
s6: and putting the cold pressing block into an extruding machine, and carrying out hot extrusion on the cold pressing block by the extruding machine to obtain the N-type bismuth telluride polycrystalline block thermoelectric material.
2. The method for preparing an N-type bismuth telluride polycrystalline bulk thermoelectric material as claimed in claim 1, wherein: the raw materials are the combination of elementary substances of Bi, Te and Se.
3. The method for preparing an N-type bismuth telluride polycrystalline bulk thermoelectric material as claimed in claim 1, wherein: in the step S2, the stoichiometric ratio is Bi2Te3-xSex(0.1＜x≤0.2)。
4. The method for preparing an N-type bismuth telluride polycrystalline bulk thermoelectric material as claimed in claim 1, wherein: in the step S3, the melting temperature of the glass tube in high-temperature melting is 700-900 ℃, and the melting time is 1-5 h; the smelting temperature of the ingot in the zone melting furnace is 600-800 ℃, the heating rate is 20-30 ℃/min, the temperature gradient is 20-40 ℃/cm, and the growth rate is 25-30 mm/h.
5. The method for preparing an N-type bismuth telluride polycrystalline bulk thermoelectric material as claimed in claim 1, wherein: in the step S4, the grinding mode is ball milling, the smelted cast ingot is placed into a ball mill, protective atmosphere is introduced, and then ball milling is carried out, wherein the ball milling time is 2-24 hours.
6. The method for preparing an N-type bismuth telluride polycrystalline block thermoelectric material as claimed in claim 5, wherein: in the step S4, the protective atmosphere is one or a combination of helium, argon, nitrogen and a mixture of hydrogen and argon.
7. The method for preparing an N-type bismuth telluride polycrystalline bulk thermoelectric material as claimed in claim 1, wherein: in the step S4, the mesh size is 80-300 meshes.
8. The method for preparing an N-type bismuth telluride polycrystalline bulk thermoelectric material as claimed in claim 1, wherein: in the step S5, the pressure for cold press molding the powder is 150-250 MPa.
9. The method for preparing an N-type bismuth telluride polycrystalline bulk thermoelectric material as claimed in claim 1, wherein: in the step S6, the extruder is a horizontal extruder, the preset temperature in the hot extrusion molding is 400-500 ℃, the extrusion ratio is 5-25, and the extrusion rate is 5-10 mm/min.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114210978A (en) * | 2021-12-22 | 2022-03-22 | 中国电子科技集团公司第十八研究所 | Hot extrusion molding method of bismuth telluride thermoelectric material |
| CN114561706A (en) * | 2021-12-16 | 2022-05-31 | 杭州大和热磁电子有限公司 | Method for recycling bismuth telluride crystal bar processing waste and utilization method thereof |
| CN115305567A (en) * | 2022-08-05 | 2022-11-08 | 中国电子科技集团公司第十八研究所 | Method for improving performance uniformity of hot-extrusion N-type bismuth telluride |
| CN115558997A (en) * | 2022-09-20 | 2023-01-03 | 杭州大和热磁电子有限公司 | Preparation method for improving mechanical properties of bismuth telluride-based thermoelectric material |
| CN116804288A (en) * | 2023-08-21 | 2023-09-26 | 杭州大和热磁电子有限公司 | Preparation method of N-type bismuth telluride zone-melting cast ingot for thermoelectric refrigerator |
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| CN114561706A (en) * | 2021-12-16 | 2022-05-31 | 杭州大和热磁电子有限公司 | Method for recycling bismuth telluride crystal bar processing waste and utilization method thereof |
| CN114210978A (en) * | 2021-12-22 | 2022-03-22 | 中国电子科技集团公司第十八研究所 | Hot extrusion molding method of bismuth telluride thermoelectric material |
| CN115305567A (en) * | 2022-08-05 | 2022-11-08 | 中国电子科技集团公司第十八研究所 | Method for improving performance uniformity of hot-extrusion N-type bismuth telluride |
| CN115305567B (en) * | 2022-08-05 | 2024-02-13 | 中国电子科技集团公司第十八研究所 | Method for improving performance uniformity of hot extrusion N-type bismuth telluride |
| CN115558997A (en) * | 2022-09-20 | 2023-01-03 | 杭州大和热磁电子有限公司 | Preparation method for improving mechanical properties of bismuth telluride-based thermoelectric material |
| CN116804288A (en) * | 2023-08-21 | 2023-09-26 | 杭州大和热磁电子有限公司 | Preparation method of N-type bismuth telluride zone-melting cast ingot for thermoelectric refrigerator |
| CN116804288B (en) * | 2023-08-21 | 2023-12-12 | 杭州大和热磁电子有限公司 | Preparation method of N-type bismuth telluride zone-melting cast ingot for thermoelectric refrigerator |
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