CN103050618A - Thermoelectricity material and preparation method thereof - Google Patents
Thermoelectricity material and preparation method thereof Download PDFInfo
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- CN103050618A CN103050618A CN2011103154332A CN201110315433A CN103050618A CN 103050618 A CN103050618 A CN 103050618A CN 2011103154332 A CN2011103154332 A CN 2011103154332A CN 201110315433 A CN201110315433 A CN 201110315433A CN 103050618 A CN103050618 A CN 103050618A
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Abstract
The invention relates to a thermoelectricity material and a preparation method thereof, belonging to the field of inorganic materials. The thermoelectricity material is synthesized by an inorganic high-temperature solid-phase one-step synthesis method. A CsxRE2Cu6-xTe6 compound synthesized by the method belongs to a hexagonal crystal series, a space group is P63/m. According to the primary thermoelectricity performance test of CsxRE2Cu6-xTe6 (RE=La, Ce, Pr), the compound of the series has relative high conductivity, a medium Seebeck coefficient and relative low thermal conductivity, and the ZT value is 0.26 (La, 614K), 0.17 (Ce, 660K) and 0.23 (La, 660K). The compound of the series probably has potential application value of thermoelectricity.
Description
Technical field
The present invention relates to a kind of thermoelectric material and preparation method thereof, belong to field of inorganic materials.
Background technology
Thermoelectric material is a kind of functional material that can realize by the transportation of charge carrier in the solid the direct conversion of heat energy and electric energy, is considered in the future very competitive energy substitution medium.Thermoelectric generation technology is a kind of new forms of energy switch technology of utilizing the Seebeck effect of thermoelectric material and Peltier effect that heat energy and electric energy are transformed mutually.This technology have cleaning, quiet, use convenient management, wide and the high advantage of security reliability conform.The development and utilization of thermoelectric generation technology is solving following energy crisis, is providing the aspects such as clean energy resource and raising efficiency of energy utilization will play more and more important effect.
The performance of thermoelectric material depends on the hot figure of merit ZT of material, and ZT is typically expressed as ZT=S
2σ T/ κ, S is called Seebeck coefficient or thermoelectric force in the formula, and σ is the conductance of material, and κ is thermal conductivity.σ, S and κ parameter depend on the scattering of electronic structure and charge carrier, κ=κ
L+ κ
e, reduce the κ key and be to reduce κ
LThereby, namely strengthen the lattice dot matrix to the scattering reduction thermal conductivity of phonon.In more than ten years, to the research and development of thermoelectric material, mainly concentrate on two aspects in the past, one, be that tradition is had good thermoelectricity capability bulk such as PbTe, Bi
2Te
3Carry out performance optimization (as mix, superlattice or make nano material), improve its power factor (S
2Thereby σ) or reduce its thermal conductance and improve its hot figure of merit ZT; Two, development and development of new have potential good thermoelectricity capability material, more than ten years in the past, find that in succession some have potential good thermoelectricity capability material, and such as skutterudite, Runge-Kutta integration.Yet although in the past during the last ten years, thermoelectric material reaches experiment in theory very large progress, and thermoelectric material ZT value in the range of 0.4-1.3, does not far reach practical always; Reach and realize thermo-electric generation and the practical target of energising refrigeration, the ZT value reaches more than 3.Meanwhile, more than ten years in the past, because the reaction flux method is in the synthetic application of high temperature solid-state, the successful alkali metal (alkaline-earth metal) of more synthetic novel structures/rare earth/copper/tellurium compound is such as layer structure A
1-xRECu
1+xTe
4, Rb
2CeCu
3Te
5, KEuCu
2Te
4And BaRECuTe
3, tunnel structure A
3RE
4Cu
5Te
10, CsRE
2CuTe
4And CsSc
3Cu
2Te
6But the thermoelectricity capability of these compound reports of at present these discoveries is all poor.At the application's patent, Cs
xRE
2Cu
6-xTe
6Compound preliminary experimental result in twin tunnel shows that this series compound has good thermoelectricity capability, is that thermoelectricity capability is best in this compounds of finding at present, and this performance is also compared with more present famous thermoelectric materials simultaneously.
Summary of the invention
In order to explore novel thermoelectric material, the present invention provides a kind of alkali metal (alkaline-earth metal)/rare earth/copper/tellurium compound by reaction flux method high temperature solid state reaction, and they may have potential thermoelectric applications and be worth.
Among the present invention, Cs
xRE
2Cu
6-xTe
6Compound belongs to hexagonal crystal system, and space group is P6
3/ m.Cs
0.75 (2)La
2Cu
5.25 (2)Te
6Cell parameter is
Z=1; Cs
0.77 (2)Ce
2Cu
5.23 (2)Te
6Cell parameter is
Z=1; Cs
0.73 (2)Pr
2Cu
5.27 (2)Te
6Cell parameter is
Z=1; Cs
0.75 (2)Nd
2Cu
5.25 (2)Te
6Cell parameter is
Z=1.The present invention is synthetic Cs successfully
xRE
2Cu
6-xTe
6(RE=La, Ce, Pr, Nd) monocrystalline and pure phase.
Cs
xRE
2Cu
6-xTe
6(RE=La, Ce, Pr) preliminary thermoelectricity capability test shows that this series compound has relatively high conductivity, medium Seebeck coefficient and relative low thermal conductance, its ZT value: 0.26 (La, 614K), (0.17 Ce, 660K) and 0.23 (La, 660K).
The preparation execution mode of a kind of thermoelectric material of the present invention:
Ratio CsCl by amount of substance: RE: Cu: Te=is excessive: feed intake at 2.4: 5: 6, in the vacuum-sintering reaction, namely obtain the Novel hot electric material of the present invention's development in 850 ℃ of-1150 ℃ of scopes.
Preparation method of the present invention, its outstanding advantages is:
1. with low cost, technology of preparing is simple, and product is Cs
xRE
2Cu
6-xTe
6With accessory substance Cs
3RECl
6, Cs
3RECl
6All soluble in water with CsCl, can obtain target product stable in water and air by washing is Cs
xRE
2Cu
6-xTe
6
2. can synthesize in a large number pure phase, can realize amplifying and produce.
Description of drawings
Fig. 1 is Cs
xRE
2Cu
6-xTe
6The structure chart of (RE=La, Ce, Pr, Nd)
Fig. 2 is Cs
xLa
2Cu
6-xTe
6Simulation single crystal diffraction collection of illustrative plates and powder diffraction spectrum
Embodiment
Example 1
In the glove box operation, press the ratio CsCl of amount of substance: RE (La, Ce, Pr, Nd): Cu: Te=3: feed intake at 2.4: 5: 6, about 10 grams of total weight, packing into, (φ 11 * 13mm) quartz ampoules close quartz ampoule sealing by fusing under vacuum again.Then reactant is placed in the temperature programmed control tube furnace, heating schedule is: rise to 600 ℃ from room temperature with 75 ℃ of/hour speed, then rise to 950 ℃ with 12 ℃ of/hour speed, 950 ℃ of insulations 50 hours, then be down to 600 ℃ with 2 ℃ of/hour speed, the stove of closing the door cools off naturally by it.Quartz ampoule is taken out in cooling, knocks outer field quartz glass open, namely gets Cs
xRE
2Cu
6-xTe
6The sintering stick is pulverized stick, washes multipass with distilled water, removes CsCl and Cs thereof
3RECl
6Behind the accessory substance, then with the absolute alcohol washing, dry again, namely get pure target product.
Example 2
In the glove box operation, press the ratio CsCl of amount of substance: RE (La, Ce, Pr): Cu: Te=2: feed intake at 2.4: 5: 6, about 18 grams of total weight, packing into, (φ 11 * 13mm) quartz ampoules close quartz ampoule sealing by fusing under vacuum again.Then reactant vertically is placed in the temperature programmed control tube furnace, heating schedule is: rise to 600 ℃ from room temperature with 75 ℃ of/hour speed, then rise to 1000 ℃ with 12 ℃ of/hour speed, 1000 ℃ of insulations 50 hours, then be down to 600 ℃ with 10 ℃ of/hour speed, the stove of closing the door cools off naturally by it.Quartz ampoule is taken out in cooling, knocks outer field quartz glass open, namely gets Cs
xRE
2Cu
6-xTe
6The sintering stick, 4-5mm place, quartz ampoule bottom is mainly target product Cs
xRE
2Cu
6-xTe
6, 1mm place, quartz ampoule top is mainly CsCl-Cs
3RECl
6Eutectic mixture.Bottom 4-5mm sample is polished into disk (diameter: 10mm, thick 3mm) and square, and (9 * 3 * 2mm) carry out thermoelectricity capability test, its ZT value: 0.26 (La, 614K), 0.17 (Ce, 660K) and 0.23 (Pr, 660K).
Claims (6)
1. thermoelectric material, its molecular formula is: Cs
xRE
2Cu
6-xTe
6, RE is selected from La, Ce, Pr and Nd in the formula; This compound belongs to hexagonal crystal system, and space group is P6
3/ m.
2. thermoelectric material as claimed in claim 1, it is characterized in that: this material molecule formula is Cs
0.75 (2)La
2Cu
5.25 (2)Te
6Cell parameter is
Z=1.
3. focus material as claimed in claim 1, it is characterized in that: this material molecule formula is Cs
0.77 (2)Ce
2Cu
5.23 (2)Te
6Cell parameter is
Z=1.
4. focus material as claimed in claim 1, it is characterized in that: this material molecule formula is Cs
0.73 (2)Pr
2Cu
5.27 (2)Te
6Cell parameter is
Z=1.
5. focus material as claimed in claim 1, it is characterized in that: this material molecule formula is Cs
0.75 (2)Nd
2Cu
5.25 (2)Te
6Cell parameter is
Z=1.
6. the preparation method of claim 1 thermoelectric material, comprise the steps: the ratio RE by amount of substance: Cu: Te=2.4: feed intake at 5: 6, CsCl is excessive, reacts in vacuum-sintering in 850 ℃ of-1150 ℃ of scopes.
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|---|---|---|---|
| CN201110315433.2A CN103050618B (en) | 2011-10-17 | 2011-10-17 | A kind of thermoelectric material and preparation method thereof |
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| CN103050618B CN103050618B (en) | 2015-08-12 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436729A (en) * | 2013-09-02 | 2013-12-11 | 中国科学院宁波材料技术与工程研究所 | Thermoelectric material and preparation method thereof |
| 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329862B (en) * | 2015-12-04 | 2017-10-24 | 中国科学院福建物质结构研究所 | One kind prepares CsBi4Te6The method of thermoelectric material |
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| US6169245B1 (en) * | 1998-05-05 | 2001-01-02 | Marlow Industries, Inc. | Thermoelectric materials ternary penta telluride and selenide compounds |
| US20090178700A1 (en) * | 2008-01-14 | 2009-07-16 | The Ohio State University Research Foundation | Thermoelectric figure of merit enhancement by modification of the electronic density of states |
| US20090235969A1 (en) * | 2008-01-25 | 2009-09-24 | The Ohio State University Research Foundation | Ternary thermoelectric materials and methods of fabrication |
| CN101960627A (en) * | 2008-08-29 | 2011-01-26 | Lg化学株式会社 | New thermoelectric material, method of manufacture thereof and thermoelectric component using the same |
-
2011
- 2011-10-17 CN CN201110315433.2A patent/CN103050618B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6169245B1 (en) * | 1998-05-05 | 2001-01-02 | Marlow Industries, Inc. | Thermoelectric materials ternary penta telluride and selenide compounds |
| US20090178700A1 (en) * | 2008-01-14 | 2009-07-16 | The Ohio State University Research Foundation | Thermoelectric figure of merit enhancement by modification of the electronic density of states |
| US20090235969A1 (en) * | 2008-01-25 | 2009-09-24 | The Ohio State University Research Foundation | Ternary thermoelectric materials and methods of fabrication |
| CN101960627A (en) * | 2008-08-29 | 2011-01-26 | Lg化学株式会社 | New thermoelectric material, method of manufacture thereof and thermoelectric component using the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436729A (en) * | 2013-09-02 | 2013-12-11 | 中国科学院宁波材料技术与工程研究所 | Thermoelectric material and preparation method thereof |
| CN103436729B (en) * | 2013-09-02 | 2016-01-20 | 中国科学院宁波材料技术与工程研究所 | A kind of thermoelectric material and preparation method thereof |
| 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 |
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| CN103050618B (en) | 2015-08-12 |
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