CN1236999C - Bi2Te3 based nano composite thermoelectric materials - Google Patents

Bi2Te3 based nano composite thermoelectric materials Download PDF

Info

Publication number
CN1236999C
CN1236999C CN 200310109130 CN200310109130A CN1236999C CN 1236999 C CN1236999 C CN 1236999C CN 200310109130 CN200310109130 CN 200310109130 CN 200310109130 A CN200310109130 A CN 200310109130A CN 1236999 C CN1236999 C CN 1236999C
Authority
CN
China
Prior art keywords
base
thermoelectric
bi2te3
powder
nanostructural
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.)
Expired - Fee Related
Application number
CN 200310109130
Other languages
Chinese (zh)
Other versions
CN1546369A (en
Inventor
赵新兵
卢波辉
倪华良
吉晓华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN 200310109130 priority Critical patent/CN1236999C/en
Publication of CN1546369A publication Critical patent/CN1546369A/en
Application granted granted Critical
Publication of CN1236999C publication Critical patent/CN1236999C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Abstract

The present invention relates to a Bi2Te3-base nanometer composite thermoelectric material with high performance, which is prepared by that Bi2Te3-base nanostructural powder is added to Bi2Te3-base thermoelectric material powder to form mixture, and then the mixture is compressed, sintered and compounded. Compared with the thermoelectric performance of the Bi2Te3-base thermoelectric materials which do not compound the basal bodies of the nanostructural powder, the thermoelectric performance of the Bi2Te3-base nanometer composite thermoelectric material of the present invention is excellent, because the Bi2Te3-base nanostructural powder has unique microstructure and can generate unique physical and chemical properties, the Bi2Te3-base nanostructural powder makes the material have a specific carrier transport property, and can obviously improve thermoelectric potential coefficients or electric conductivity of the thermoelectric material so as to improve thermoelectric power factors.

Description

Bi 2Te 3The nano combined thermoelectric material of base
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), the R3m 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 (1)

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%, said Bi 2Te 3The base alloy is the n type Bi that has added I and Br 2Te 3Base alloy or the excessive binary Bi of Te 2Te 3The base alloy; Said Bi 2Te 3The base nanostructured powders is binary Bi 2Te 3In nanotube, nano wire and the nano particle one or more, or the adulterated binary Bi of Sn 2Te 3The base nano particle, the diameter of nanotube, nano wire is between 5～150 nanometers, and the particle diameter of nano particle is between 5～150 nanometers.
CN 200310109130 2003-12-05 2003-12-05 Bi2Te3 based nano composite thermoelectric materials Expired - Fee Related CN1236999C (en)

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 CN1546369A (en) 2004-11-17
CN1236999C true CN1236999C (en) 2006-01-18

Family

ID=34335044

Family Applications (1)

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

Country Status (1)

Country Link
CN (1) CN1236999C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI593622B (en) * 2014-01-31 2017-08-01 豐田自動車股份有限公司 Method of production of core/shell type nanoparticles, method of production of sintered body using that method, and thermoelectric conversion material produced by that method

Families Citing this family (5)

* Cited by examiner, † Cited by third party
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
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
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
CN111517292A (en) * 2020-04-30 2020-08-11 西华大学 Tin telluride-based thermoelectric material and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI593622B (en) * 2014-01-31 2017-08-01 豐田自動車股份有限公司 Method of production of core/shell type nanoparticles, method of production of sintered body using that method, and thermoelectric conversion material produced by that method

Also Published As

Publication number Publication date
CN1546369A (en) 2004-11-17

Similar Documents

Publication Publication Date Title
Wei et al. Review of current high-ZT thermoelectric materials
Lin et al. Thermoelectric power generation from lanthanum strontium titanium oxide at room temperature through the addition of graphene
Wu et al. Advances in Ag2Se-based thermoelectrics from materials to applications
Mallick et al. High-performance Ag–Se-based n-type printed thermoelectric materials for high power density folded generators
Lu et al. Enhanced-performance PEDOT: PSS/Cu2Se-based composite films for wearable thermoelectric power generators
Yin et al. Nanocrystalline thermoelectric Ca3Co4O9 ceramics by sol− gel based electrospinning and spark plasma sintering
Wei et al. Ag2Q‐based (Q= S, Se, Te) silver chalcogenide thermoelectric materials
Zhou et al. Significant enhancement in the thermoelectric performance of aluminum-doped ZnO tuned by pore structure
Zheng et al. Unraveling the critical role of melt-spinning atmosphere in enhancing the thermoelectric performance of p-type Bi0. 52Sb1. 48Te3 alloys
CN1974079A (en) Process of preparing bismuth telluride-base thermoelectric material
Tao et al. Enhanced thermoelectric performance of Bi0. 46Sb1. 54Te3 nanostructured with CdTe
CN102931335A (en) Graphene compounded with stibine cobalt base skutterudite thermoelectric material and preparation method of material
KR20140116668A (en) Natural superlattice structured thermoelectric materials
CN112038473B (en) Full-temperature-range high-performance n-type Mg-Sb-based thermoelectric material and preparation method thereof
CN1236999C (en) Bi2Te3 based nano composite thermoelectric materials
Wang et al. Design guidelines for chalcogenide-based flexible thermoelectric materials
Tan et al. Optimization of the thermoelectric properties of Bi 2 O 2 Se ceramics by altering the temperature of spark plasma sintering
CN102403445A (en) Bismuth telluride-based thermoelectric material and preparation method thereof
Guo et al. Minimizing thermal conductivity for boosting thermoelectric properties of Cu–Ni-based alloys through all-scale hierarchical architectures
Zhong et al. Entropy engineering enhances the thermoelectric performance and microhardness of (GeTe) 1− x (AgSb0. 5Bi0. 5Te2) x
Liu et al. Improvement of Thermoelectric Properties of Evaporated ZnO: Al Films by CNT and Au Nanocomposites
CN105556688A (en) Thermoelectric material and method for manufacturing same
KR101094458B1 (en) The method for preparation of nanocomposite with enhanced thermoelectric ability and nanocomposite thereof
Sun et al. Effect of HPHT processing on structural and thermoelectric properties of low-cost type-I clathrate Ba8Cu6Si40
Yang et al. Nanostructured n-type polycrystalline SnSe materials for thermoelectric applications

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20060118

Termination date: 20131205