CN102496676B - Niobium-doped bismuth-antimony-system low-temperature thermoelectric material and preparation method thereof - Google Patents
Niobium-doped bismuth-antimony-system low-temperature thermoelectric material and preparation method thereof Download PDFInfo
- Publication number
- CN102496676B CN102496676B CN201110366667.XA CN201110366667A CN102496676B CN 102496676 B CN102496676 B CN 102496676B CN 201110366667 A CN201110366667 A CN 201110366667A CN 102496676 B CN102496676 B CN 102496676B
- Authority
- CN
- China
- Prior art keywords
- thermoelectric material
- antimony
- powder
- niobium
- temperature
- 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
Links
Abstract
The invention discloses a niobium-doped bismuth-antimony-system low-temperature thermoelectric material and a preparation method thereof. The formula is Bi85Sb15-xNbx. In the formula, x is any number between 0 and 15. The preparation method comprises the following steps of: mixing Bi powder, Sb powder and Nb powder according to the chemical proportion, and adopting mechanical alloying and ultrahigh pressure processes to prepare the niobium-doped bismuth-antimony-system low-temperature thermoelectric material; and the niobium-doped bismuth-antimony-system low-temperature thermoelectric material has excellent thermoelectric performance near 200K. In the niobium-doped bismuth-antimony-system low-temperature thermoelectric material, the mechanical strength is high, the thermoelectrical potential and the electrical conductivity are good, the quality is higher under low temperature, the performance is stable, the manufacturing process is simpler and more convenient, the cost is low and the promotion and the application are easy.
Description
Technical field
The present invention relates to a kind of Nb doping Bi-Sb is low-temperature thermoelectric material and preparation method thereof, belongs to the field of thermoelectric refrigerating unit semi-conductor thermoelectric material.
Background technology
Economic growth fast makes the energy and environmental problem become the tightest pretty challenge of new century facing mankind, and the friendly type clean energy technology of development environment is to keep national economy and social production can hold the important foundation of speed development.The major domain of semi-conductor thermoelectric material comprises: temperature difference electricity generation device, Peltier refrigerating plant and temperature sensor.Conventionally mix several Z and describe the efficiency of thermoelectric cooling by the figure of merit, Z=α 2 σ/λ, α is Seebeck coefficient, the conductivity that σ is material, the thermal conductivity that λ is material.Be combined with temperature, become dimensionless factor ZT, ZT value is larger, and refrigerating capacity is stronger.The principal element that affects ZT value is the conductivity of material, Seebeck coefficient and thermal conductivity.
Since finding that ZT value approaches 1 Bi-Te and is p-type semi-conductor thermoelectric material the fifties, the efficiency that improves thermoelectric cooling does not have major progress, although the refrigeration device of preparing with these materials is applied at some special occasions, compared with mechanical refrigeration, only has the efficiency of mechanical refrigeration 30%.Want to be more widely used, this just need to bring up to the ZT value of thermoelectric material more than 3, could realize large-scale application.1996, U.S. Oak Ridge National Laboratory B.C. Sales etc. found RM4X12 (R:La, Ce, Nd etc.; M:Fe, Ru etc.; X:As, Sb etc.) the ZT value of type compound can reach 1.4, and this major progress, for the development of semiconductor thermoelectric refrigeration and new material injects vigour into.In recent years, the country such as the U.S., Japan, Australia was very active in the research of thermoelectric cooling Material Field, and high performance material continues to bring out.United States Naval Research Laboratory at present, several main National Laboratories and some companies actively get involved this direction.Research paper is published in Science again and again, Nature, the influential magazines such as Phys. Rev. Lett..These are broken through is mainly that to reduce material thermal conductivity be that ZT value is improved in breach.
Bi-Sb monocrystalline thermoelectric material is one of best thermoelectric material of current thermoelectricity capability at low temperatures.
Can reach 6.5 × 10 in its figure of merit of 80 K
-3k
-1.Bi be all semi-metallic with Sb, both have identical rhombohedron crystal structure and close lattice is mixed number, and the physical property of Bi-Sb alloy is relevant to the content of Sb. at 0<X<0.07Bi
1-xsb
xalloy shows as semimetal behavior, be N-shaped semiconductor at 0.07<X<0.22, show as again semimetal behavior at X>0.22. still, the manufacturing cycle of monocrystalline is long, machining property is poor, cost is high, is unfavorable for large-scale industrial production.Visible, in prior art, lack one and both there is high mechanical properties, there is again the thermoelectric material of better performance at low temperature warm area.Therefore, explore the material under lower temperature (below 200 K) with high conversion efficiency of thermoelectric is the focus that people study always. this invention people adopts mechanical alloy to add the method for superhigh pressure, has prepared Bi
85sb
15-xnb
xsample bulk.
Summary of the invention
The object of the present invention is to provide a kind of Bi of doping
85sb
15-xnb
xthermoelectric material and preparation method thereof, is exactly to utilize mechanical alloying to add the physical method of superhigh pressure specifically, obtains the Bi with thermoelectricity capability
85sb
15-xnb
xor be expressed as: Bi
85sb
15-0nb
0-15the preparation method of thermoelectric material.
Task of the present invention is to provide a kind of Bi of doping
85sb
15-xnb
xthe preparation method of (wherein x is any number between 0-15) thermoelectric material.The object of the invention is to realize by following steps:
A) 99.999%Bi powder is mixed according to the mass ratio in the described molecular formula of each leisure with the Nb powder of Sb powder and 99.5%, Bi:Sb:Nb=85:15-0:0-15 mixes, and mixture is carried out to ball milling;
B) powder after ball milling is pressed into the bulk material of 5mm diameter;
C) with tantalum paper tinsel parcel, put into again carbon pipe after putting into boron nitride tube, taking boron nitride as transmission medium, then put into pyrophyllite in lumps, on cubic hinge press, to suppress, press temperature is 523K, and pressure is 5GPa, and the press time is 30 minutes, obtains bulk thermoelectric material.
In said method, prepare described Bi
85sb
15-xnb
xthe method of (wherein x is any number between 0-15) powder is: Bi, Sb, Nb powder are put into agate tank, after vacuumizing, pass into high-purity argon gas, carry out ball-milling reaction, Ball-milling Time 100 hours.
The present invention passes through at Bi
85sb
15in mix Nb element, obtaining molecular formula is Bi
85sb
15-xnb
xor be expressed as: Bi
85sb
15-0nb
0-15thermoelectric material, compared with other thermoelectric material under low temperature, Bi provided by the present invention
85sb
15-xnb
xthere is following advantage in thermoelectric material:
1) this thermoelectric material is that low temperature warm area below 150K has larger Seebeck coefficient in temperature, and its Seebeck coefficient can reach about 161
.
2) this thermoelectric material is that low temperature warm area below 200K has larger Seebeck coefficient absolute value in temperature.
3) thermoelectric potential of this thermoelectric material can realize by the content that regulates the Nb element in material.
4) this thermoelectric material mechanical strength is high, and conductivity and thermoelectric potential are better.
5) this thermoelectric material manufacturing process is easier, is easy to apply.
Adopt the beneficial effect of the technical program to be, obtain a kind of novel thermoelectric material in the following temperature of 200k with higher merit figue.A kind of economy, the Bi that simple, near practical low temperature warm area 200K has good thermoelectricity capability are provided
85sb
15-xnb
xthermoelectric material.
Brief description of the drawings
Fig. 1 is that Nb doping Bi-Sb is the XRD diffracting spectrum of low-temperature thermoelectric material sample.
Fig. 2 is Bi
85sb
15-12nb
0-3the graph of relation of sample conductance and temperature.
Fig. 3 is Bi
85sb
15-12nb
0-3the Seebeck of sample is ripe and graph of relation temperature.
Embodiment
The specific embodiment of the present invention realizes by lower technical scheme:
Adopt Bi of the present invention
85sb
15-xnb
x, any number that x is 0-15, thermoelectric material, adopts mechanical alloying to add superhigh pressure method and makes.Its chemical first raw material is simple substance element and the high-purity argon gas such as pure bismuth, antimony, niobium.
Embodiment:
Mass ratio in chemical formula is: 1, Bi:Sb=85:15; 2, Bi:Sb:Nb=85:14.5:0.5; 3, Bi:Sb:Nb=85:14:1; 4, Bi:Sb:Nb=85:13:2; 5, Bi:Sb:Nb=85:12:3.
Its preparation method comprises the steps:
1) bismuth metal, antimony, niobium powder being put into by putting into mechanical ball grinding jar after the mass ratio weighing of chemical formula, is 2 × 10 in vacuum degree
-3when Pa, be filled with pure argon, ball milling 100 hours.
2) powder after mechanical ball milling is pressed into the bulk material of 5mm.
3) with tantalum paper tinsel parcel, put into carbon pipe, taking boron nitride as transmission medium, then putting into pyrophyllite in lumps, then suppressing on cubic hinge press, press temperature is 523K, and pressure is 5GPa, and the press time is 30 minutes, completes the preparation of material.
Claims (2)
1. niobium doping bismuth-antimony is a low-temperature thermoelectric material preparation method, it is characterized in that: the chemical composition of this low-temperature thermoelectric material in mass ratio example is Bi
85sb
15-xnb
x, wherein x is any number between 0-15, at Bi85, in the chemical composition of Sb15, mixes Nb element, part substitutes Bi85, and the Sb element in Sb15, the physical method adding high pressure with mechanical alloying obtains this thermoelectric material; Adopt mechanical alloy to add superhigh pressure method and make, its preparation method comprises the steps:
1) 99.999% metal bismuth meal, antimony powder and 99.5% niobium powder are put into mechanical ball grinding jar and carry out mechanical ball milling, by the Bi obtaining
85sb
15-xnb
x, wherein x is any number between 0-15, powder is pressed into bulk material;
2) powder after ball milling is pressed into the bulk material of 5mm diameter;
3) with tantalum paper tinsel parcel, put into again carbon pipe after putting into boron nitride tube, taking boron nitride as transmission medium, then put into pyrophyllite in lumps, on cubic hinge press, to suppress, press temperature is 523K, and pressure is 5GPa, and the press time is 30 minutes, obtains bulk thermoelectric material.
2. be low-temperature thermoelectric material preparation method according to the niobium doping bismuth-antimony of claim 2, it is characterized in that: Bi
85sb
15-xnb
x, wherein x is any number between 0-15, and above three kinds of powder are put into agate tank by above-mentioned mass ratio and are vacuumized, and vacuum degree is 2 × 10
-3when Pa, be filled with pure argon, ball milling 100 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110366667.XA CN102496676B (en) | 2011-11-18 | 2011-11-18 | Niobium-doped bismuth-antimony-system low-temperature thermoelectric material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110366667.XA CN102496676B (en) | 2011-11-18 | 2011-11-18 | Niobium-doped bismuth-antimony-system low-temperature thermoelectric material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102496676A CN102496676A (en) | 2012-06-13 |
| CN102496676B true CN102496676B (en) | 2014-09-10 |
Family
ID=46188478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110366667.XA Expired - Fee Related CN102496676B (en) | 2011-11-18 | 2011-11-18 | Niobium-doped bismuth-antimony-system low-temperature thermoelectric material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102496676B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103579486B (en) * | 2013-11-20 | 2016-08-10 | 遵义师范学院 | Potassium mixes bismuth-antimony system i.e. Bi85Sb15-xKx low-temperature thermoelectric material and preparation method thereof |
| KR20170115545A (en) * | 2015-02-05 | 2017-10-17 | 보드 오브 리전츠 더 유니버시티 오브 텍사스 시스템 | Bismuth-antimony anode for lithium or sodium ion batteries |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1632959A (en) * | 2003-12-22 | 2005-06-29 | 中国电子科技集团公司第十八研究所 | Segment thermoelement |
| CN101316082A (en) * | 2008-07-23 | 2008-12-03 | 黄加玉 | High-efficiency low-cost solar cogeneration system |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070125416A1 (en) * | 2005-12-07 | 2007-06-07 | Kabushiki Kaisha Toshiba | Thermoelectric material and thermoelectric conversion device using same |
| EP2250126A2 (en) * | 2008-02-07 | 2010-11-17 | Basf Se | Doped tin tellurides for thermoelectric applications |
| CN101969096B (en) * | 2010-08-26 | 2012-07-04 | 中山大学 | Nanostructured thermoelectric material and device and production method thereof |
-
2011
- 2011-11-18 CN CN201110366667.XA patent/CN102496676B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1632959A (en) * | 2003-12-22 | 2005-06-29 | 中国电子科技集团公司第十八研究所 | Segment thermoelement |
| CN101316082A (en) * | 2008-07-23 | 2008-12-03 | 黄加玉 | High-efficiency low-cost solar cogeneration system |
Non-Patent Citations (2)
| Title |
|---|
| 宋春梅.高压合成纳米晶Bi0.85Sb0.15的低温热电性能.《材料研究学报》.2007,第21卷(第2期),第126-130页. |
| 高压合成纳米晶Bi0.85Sb0.15的低温热电性能;宋春梅;《材料研究学报》;20070430;第21卷(第2期);第126-130页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102496676A (en) | 2012-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6976012B2 (en) | n-type Mg-Sb group Room temperature thermoelectric material and its manufacturing method | |
| Skoug et al. | Thermoelectric properties of the Cu2SnSe3–Cu2GeSe3 solid solution | |
| Wang et al. | Effects of mesoporous silica addition on thermoelectric properties of Nb-doped SrTiO3 | |
| Carr et al. | Influence of doping and solid solution formation on the thermoelectric properties of chalcopyrite semiconductors | |
| Du et al. | Enhanced thermoelectric properties of Mg2Si0. 58Sn0. 42 compounds by Bi doping | |
| Zhan et al. | High temperature thermoelectric properties of Dy-doped CaMnO3 ceramics | |
| JP2021515411A5 (en) | ||
| JP5468554B2 (en) | Semiconductor materials containing doped tin telluride for thermoelectric applications | |
| Zou et al. | Enhanced thermoelectric performance via carrier energy filtering effect in β-Zn4Sb3 alloy bulk embedded with (Bi2Te3) 0.2 (Sb2Te3) 0.8 | |
| CN104046876B (en) | A kind of Graphene/Cu2AX3Type thermoelectric composite material and preparation method | |
| CN102931335A (en) | Graphene compounded with stibine cobalt base skutterudite thermoelectric material and preparation method of material | |
| Uchida et al. | Heavily doped silicon and nickel silicide nanocrystal composite films with enhanced thermoelectric efficiency | |
| CN105671344B (en) | One step prepares high-performance CoSb3The method of base thermoelectricity material | |
| Weller et al. | Rapid synthesis of zinc and nickel co-doped tetrahedrite thermoelectrics by reactive spark plasma sintering and mechanical alloying | |
| Li et al. | Developments in semiconductor thermoelectric materials | |
| Yang et al. | Realizing high thermoelectric performance in BaCu2–x Ag x Te2 through enhanced carrier effective mass and point-defect scattering | |
| CN109534303A (en) | A kind of high performance low temperature thermoelectric material and preparation method thereof | |
| CN103818948B (en) | Preparation method of thermoelectric compound | |
| CN102496676B (en) | Niobium-doped bismuth-antimony-system low-temperature thermoelectric material and preparation method thereof | |
| CN107195767A (en) | A kind of five yuan of N-type thermoelectric materials and preparation method thereof | |
| US10937939B2 (en) | Thermoelectric conversion material and thermoelectric conversion element | |
| CN101857928A (en) | P-type Zn4Sb3 based thermoelectric material and preparation method thereof | |
| Goto et al. | Electrical/thermal transport and electronic structure of the binary cobalt pnictides CoPn2 (Pn= As and Sb) | |
| CN102174677B (en) | Solid-phase reaction preparation method for silicious manganese thermoelectric material | |
| Amani et al. | High-temperature thermoelectric properties of compounds in the system Zn x In y O x+ 1.5 y |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140910 Termination date: 20161118 |