CN1546369A - Bi2Te3 based nano composite thermoelectric materials - Google Patents
Bi2Te3 based nano composite thermoelectric materials Download PDFInfo
- Publication number
- CN1546369A CN1546369A CNA2003101091300A CN200310109130A CN1546369A CN 1546369 A CN1546369 A CN 1546369A CN A2003101091300 A CNA2003101091300 A CN A2003101091300A CN 200310109130 A CN200310109130 A CN 200310109130A CN 1546369 A CN1546369 A CN 1546369A
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- thermoelectric material
- nano
- binary
- nanostructured powders
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 229910002899 Bi2Te3 Inorganic materials 0.000 title abstract 6
- 239000002114 nanocomposite Substances 0.000 title abstract 3
- 239000000843 powder Substances 0.000 claims abstract description 39
- 239000000956 alloy Substances 0.000 claims description 22
- 229910045601 alloy Inorganic materials 0.000 claims description 22
- 239000002071 nanotube Substances 0.000 claims description 8
- 239000002070 nanowire Substances 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 230000006798 recombination Effects 0.000 abstract 2
- 238000005215 recombination Methods 0.000 abstract 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 230000006835 compression Effects 0.000 abstract 1
- 238000007906 compression Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- 239000000758 substrate Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 238000007731 hot pressing Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000005619 thermoelectricity Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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Abstract
The invention discloses a high-performance Bi2Te3 based nano composite thermoelectric material which is prepared by adding Bi2Te3 based nanostructured powder into Bi2Te3 based thermoelectric material powder through compression agglomeration recombination. The thermoelectric property of the prepared Bi2Te3 based nano composite thermoelectric material is superior to that of the Bi2Te3 based thermoelectric material with non-recombination nanostructured powder as base.
Description
Technical field
The present invention relates to thermoelectric material.
Background technology
Thermoelectric material is that a kind of motion by current carrier (electronics or hole) realizes the semiconductor material that electric energy and heat energy are directly changed mutually.When there was the temperature difference in the thermoelectric material two ends, thermoelectric material can be converted into heat energy electric energy output; Otherwise or when passing to electric current in thermoelectric material, thermoelectric material can be converted into heat energy with electric energy, an end heat release and the other end heat absorption.Thermoelectric material has wide practical use at aspects such as refrigeration or generatings.Can be used as the power supply of deep layer space device, field work, ocean beacon, nomadic crowd use with the power generation assembly of thermoelectric material manufacturing, or be used for industrial exhaust heat, waste-heat power generation.Refrigeration plant volume with the thermoelectric material manufacturing is little, do not need chemical mediator, can be applicable to the aspect such as part cooling, portable medical Ultralow Temperature Freezer of small-sized refrigerator, computer chip and laser detector etc., potential widely Application Areas will comprise: home freezer, refrigerator, automobile-used or household air conditioning device etc.Have no mechanical moving parts, noiseless, nothing wearing and tearing, simple in structure, outstanding advantage such as the volume shape can design on demand with the device of thermoelectric material manufacturing.
The performance of thermoelectric material characterizes with " thermoelectric figure of merit " Z: Z=(α
2σ/κ).Here α is the thermoelectric force coefficient of material, and σ is a specific conductivity, and κ is a thermal conductivity.Bi
2Te
3Based compound is the best room temperature type thermoelectric material of present performance, but its thermoelectricity capability still awaits further raising.
Summary of the invention
The objective of the invention is for improving Bi
2Te
3The thermoelectricity capability of base thermoelectricity material and a kind of novel Bi is provided
2Te
3The nano combined thermoelectric material of base.
Bi of the present invention
2Te
3The nano combined thermoelectric material of base is by Bi
2Te
3Base alloy and Bi
2Te
3The base nanostructured powders is composited, wherein Bi
2Te
3The mass percent of base alloy is 80～95%, Bi
2Te
3The mass percent of base nanostructured powders is 5～20%.
Above-mentioned Bi
2Te
3The base alloy comprises: the binary Bi of strict stoichiometric ratio
2Te
3, or the binary Bi that departs from strict stoichiometric ratio that the Bi atom is excessive or the Te atom is excessive
2Te
3And partly replace Bi with Sn, Sb, Pb, or partly replace Te with Se, or added one or more formed p types or n type Bi in the doped elements such as I, Br, Al and Se
2Te
3The base alloy, the crystalline structure of alloy belongs to rhombohedral system (Rhombohedral System is also referred to as rhombic system or trigonal system), R 3m spacer, the carrier concentration in the alloy is 10
24～10
28/ m
3In the scope.
Above-mentioned Bi
2Te
3The chemical ingredients of base nanostructured powders can be the binary Bi of strict stoichiometric ratio
2Te
3, or the Bi atom is excessive or the binary Bi that departs from strict stoichiometric ratio that the Te atom is excessive
2Te
3, or added the doping type Bi of one or more formation in the elements such as Sn, Sb, Pb, I, Br, Al and Se
2Te
3The base nanostructured powders.
Said Bi
2Te
3The base nanostructured powders is one or more among nanotube, nano wire and the nano particle three, and wherein the diameter of nanotube, nano wire is between 5～150 nanometers, and length is in 10 micron number magnitudes, and this nanotube is by Bi
2Te
3The hollow tubular structure that forms of the crooked closed back of (001) crystal face, the axially parallel of nano wire is in Bi
2Te
3(001) crystal face; The particle diameter of nano particle is between 5～150 nanometers.
Bi of the present invention
2Te
3The nano combined thermoelectric material of base can adopt colds pressing powder sintered or the preparation of traditional method such as hot pressed powder sintering.
Bi of the present invention
2Te
3The thermoelectricity capability of the nano combined thermoelectric material of base is better than the not matrix Bi of composite nanostructure powder
2Te
3Base thermoelectricity material, its mechanism is Bi
2Te
3The base nanostructured powders has unique microstructures, can produce unique physics, chemical property, thereby make material possess special carrier transport characteristic, therefore can significantly improve the thermoelectric force coefficient or the specific conductivity of thermoelectric material, thereby improve the thermoelectric (al) power factor of material.
Description of drawings
Fig. 1 is thermoelectric force coefficient～temperature relation curve;
Fig. 2 is specific conductivity～temperature relation curve.
Embodiment
Below in conjunction with embodiment the present invention is done further to state in detail.
Embodiment one
1, raw material:
Bi
2Te
3Base alloy substrate material: with the n-type Bi of the molten oriented growth method preparation in district
2Te
3Billet (having added I, Br), the sieve of mistake 100 orders (154 microns of sieve aperture internal diameters) after crushed;
Bi
2Te
3Base nanostructured powders: with the binary Bi of solvent-thermal method preparation
2Te
3Nanotube and nano wire, its mean diameter are 70 nanometers, about 10 microns of mean length;
2, with Bi
2Te
3Base alloy substrate powder and Bi
2Te
3Nanostructured powders is evenly mixed by 85: 15 mass percent;
3, will mix the powder graphite jig of packing into, hot-forming in the vacuum hotpressing machine, 250 ℃ of pressurizes 0.5 hour, pressure is 50MPa, obtains block matrix material.
Embodiment two
1, raw material:
Bi
2Te
3Base alloy substrate material: with the n-type Bi of the molten oriented growth method preparation in district
2Te
3Billet (having added I, Br), the sieve of mistake 100 orders (154 microns of sieve aperture internal diameters) after crushed;
Bi
2Te
3Base nanostructured powders: with the binary Bi of solvent-thermal method preparation
2Te
3Nanotube and nano wire, its mean diameter are 70 nanometers, about 10 microns of mean length;
2, with Bi
2Te
3Base alloy substrate powder and Bi
2Te
3Nanostructured powders is evenly mixed by 95: 5 mass percent;
3, will mix the powder graphite jig of packing into, hot-forming in the vacuum hotpressing machine, 250 ℃ of pressurizes 0.5 hour, pressure is 50MPa, obtains block matrix material.
Embodiment three
1, raw material:
Bi
2Te
3Base alloy substrate material: with the excessive binary Bi that departs from strict stoichiometric ratio of smelting method for preparing Te atom
2Te
3, cross the sieve of 100 orders (154 microns of sieve aperture internal diameters) after crushed;
Bi
2Te
3Base nanostructured powders: with the binary Bi of solvent-thermal method preparation
2Te
3Nanotube and nano wire, its mean diameter are 70 nanometers, about 10 microns of mean length;
2, with Bi
2Te
3Base alloy substrate powder and Bi
2Te
3Nanostructured powders is evenly mixed by 85: 15 mass percent;
3, will mix the powder graphite jig of packing into, hot-forming in the vacuum hotpressing machine, 250 ℃ of pressurizes 0.5 hour, pressure is 50MPa, obtains block matrix material.
Embodiment four
1, raw material:
Bi
2Te
3Base alloy substrate material: with the n-type Bi of the molten oriented growth method preparation in district
2Te
3Billet (having added I, Br), the sieve of mistake 100 orders (154 microns of sieve aperture internal diameters) after crushed;
Bi
2Te
3Base nanostructured powders: with the binary Bi of solvent-thermal method preparation
2Te
3Nano particle, particle diameter is in 30～100 nanometers;
2, with Bi
2Te
3Base alloy substrate powder and Bi
2Te
3Nanostructured powders is evenly mixed by 85: 15 mass percent;
3, will mix the powder graphite jig of packing into, hot-forming in the vacuum hotpressing machine, 250 ℃ of pressurizes 0.5 hour, pressure is 50MPa, obtains block matrix material.
Embodiment five
1, raw material:
Bi
2Te
3Base alloy substrate material: with the n-type Bi of the molten oriented growth method preparation in district
2Te
3Billet (having added I, Br), the sieve of mistake 100 orders (154 microns of sieve aperture internal diameters) after crushed;
Bi
2Te
3The base nanostructured powders: with the interpolation of solvent-thermal method preparation the adulterated binary Bi of Sn
2Te
3The base nano particle, particle diameter is in 30～100 nanometers;
2, with Bi
2Te
3Base alloy substrate powder and Bi
2Te
3Nanostructured powders is evenly mixed by 85: 15 mass percent;
3, will mix the powder graphite jig of packing into, hot-forming in the vacuum hotpressing machine, 250 ℃ of pressurizes 0.5 hour, pressure is 50MPa, obtains block matrix material.
Comparative Examples one
At Bi
2Te
3Base alloy substrate material is (with the n-type Bi of the molten oriented growth method preparation in district
2Te
3Billet (having added I, Br)) do not add Bi in
2Te
3Nanostructured powders, other operating process and embodiment one are identical.
Comparative Examples two
At Bi
2Te
3Base alloy substrate material is (with the excessive binary Bi that departs from strict stoichiometric ratio of smelting method for preparing Te atom
2Te
3) in do not add Bi
2Te
3Nanostructured powders, other operating process and embodiment three are identical.
Performance Detection:
Along vertical hot pressing directional survey the thermoelectric force factor alpha and the conductivity of embodiment and Comparative Examples material.Wherein: thermoelectric force coefficients by using temperature differential method is measured (the test sample two ends temperature difference is in 3～8 ℃ of scopes) in vacuum environment, and specific conductivity adopts four probe method to measure.Take off data adopts Agilent 34970A to gather and directly imports computer and handle.Measure temperature range and be room temperature to 250 ℃.
Thermoelectric force factor alpha and conductivity's test result is seen accompanying drawing 1 and accompanying drawing 2 respectively.Compare with Comparative Examples, the thermoelectric force coefficient absolute value of embodiment significantly improves, the thermoelectric (al) power factor (α
2σ) also obviously improve.
Claims (6)
1.Bi
2Te
3The nano combined thermoelectric material of base is characterized in that this kind material is by Bi
2Te
3Base alloy and Bi
2Te
3The base nanostructured powders is composited, wherein Bi
2Te
3The mass percent of base alloy is 80～95%, Bi
2Te
3The mass percent of base nanostructured powders is 5～20%.
2. Bi according to claim 1
2Te
3The nano combined thermoelectric material of base is characterized in that said Bi
2Te
3The base alloy comprises: the binary Bi of strict stoichiometric ratio
2Te
3, or the binary Bi that departs from strict stoichiometric ratio that the Bi atom is excessive or the Te atom is excessive
2Te
3, and partly replace Bi with Sn, Sb, Pb, or partly replace Te with Se, or added one or more formed p types or n type Bi in I, Br, Al and the Se doped element
2Te
3The base alloy semiconductor.
3. Bi according to claim 1
2Te
3The nano combined thermoelectric material of base is characterized in that said Bi
2Te
3The base nanostructured powders is one or more among nanotube, nano wire and the nano particle three.
4. Bi according to claim 3
2Te
3The nano combined thermoelectric material of base is characterized in that said Bi
2Te
3The diameter of based nanotube, nano wire is between 5～150 nanometers.
5. Bi according to claim 3
2Te
3The nano combined thermoelectric material of base, the particle diameter that it is characterized in that said nano particle is between 5～150 nanometers.
6. Bi according to claim 1
2Te
3The nano combined thermoelectric material of base is characterized in that said Bi
2Te
3The base nanostructured powders is the binary Bi of strict stoichiometric ratio
2Te
3, or the Bi atom is excessive or the binary Bi that departs from strict stoichiometric ratio that the Te atom is excessive
2Te
3, or added the doping type Bi of one or more formation in Sn, Sb, Pb, I, Br, Al and the Se element
2Te
3The base nanostructured powders.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109130 CN1236999C (en) | 2003-12-05 | 2003-12-05 | Bi2Te3 based nano composite thermoelectric materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310109130 CN1236999C (en) | 2003-12-05 | 2003-12-05 | Bi2Te3 based nano composite thermoelectric materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1546369A true CN1546369A (en) | 2004-11-17 |
| CN1236999C CN1236999C (en) | 2006-01-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310109130 Expired - Fee Related CN1236999C (en) | 2003-12-05 | 2003-12-05 | Bi2Te3 based nano composite thermoelectric materials |
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| Country | Link |
|---|---|
| CN (1) | CN1236999C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8748726B2 (en) | 2009-08-17 | 2014-06-10 | Laird Technologies, Inc. | Synthesis of silver, antimony, and tin doped bismuth telluride nanoparticles and bulk bismuth telluride to form bismuth telluride composites |
| CN104409623A (en) * | 2014-10-21 | 2015-03-11 | 浙江大学 | Processing method for improving performance of N-type bismuth telluride base powder sinter block thermoelectric material |
| WO2016106514A1 (en) * | 2014-12-29 | 2016-07-07 | 中国科学院福建物质结构研究所 | Thermoelectric material, and preparation method therefor and application thereof |
| CN111454060A (en) * | 2020-04-08 | 2020-07-28 | 深圳见炬科技有限公司 | N-type bismuth telluride-based thermoelectric material with modulation structure and preparation method thereof |
| CN111517292A (en) * | 2020-04-30 | 2020-08-11 | 西华大学 | Tin telluride-based thermoelectric material and preparation method thereof |
Families Citing this family (1)
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| JP6001578B2 (en) * | 2014-01-31 | 2016-10-05 | トヨタ自動車株式会社 | Method for producing core / shell type nanoparticles and method for producing sintered body using the method |
-
2003
- 2003-12-05 CN CN 200310109130 patent/CN1236999C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8748726B2 (en) | 2009-08-17 | 2014-06-10 | Laird Technologies, Inc. | Synthesis of silver, antimony, and tin doped bismuth telluride nanoparticles and bulk bismuth telluride to form bismuth telluride composites |
| CN104409623A (en) * | 2014-10-21 | 2015-03-11 | 浙江大学 | Processing method for improving performance of N-type bismuth telluride base powder sinter block thermoelectric material |
| CN104409623B (en) * | 2014-10-21 | 2017-02-15 | 浙江大学 | Processing method for improving performance of N-type bismuth telluride base powder sinter block thermoelectric material |
| WO2016106514A1 (en) * | 2014-12-29 | 2016-07-07 | 中国科学院福建物质结构研究所 | Thermoelectric material, and preparation method therefor and application thereof |
| JP2018509775A (en) * | 2014-12-29 | 2018-04-05 | 中国科学院福建物質結構研究所Ｆｕｊｉａｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｒｅｓｅａｒｃｈ Ｏｎ Ｔｈｅ Ｓｔｒｕｃｔｕｒｅ Ｏｆ Ｍａｔｔｅｒ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Thermoelectric material, method for its production and use |
| CN111454060A (en) * | 2020-04-08 | 2020-07-28 | 深圳见炬科技有限公司 | N-type bismuth telluride-based thermoelectric material with modulation structure and preparation method thereof |
| CN111454060B (en) * | 2020-04-08 | 2021-04-02 | 深圳见炬科技有限公司 | N-type bismuth telluride-based thermoelectric material with modulation structure and preparation method thereof |
| WO2021204162A1 (en) * | 2020-04-08 | 2021-10-14 | 深圳见炬科技有限公司 | N-type bismuth telluride-based thermoelectric material having modulation structure, and preparation method therefor |
| CN111517292A (en) * | 2020-04-30 | 2020-08-11 | 西华大学 | Tin telluride-based thermoelectric material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1236999C (en) | 2006-01-18 |
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