CN105329862B - One kind prepares CsBi4Te6The method of thermoelectric material - Google Patents
One kind prepares CsBi4Te6The method of thermoelectric material Download PDFInfo
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- CN105329862B CN105329862B CN201510887234.7A CN201510887234A CN105329862B CN 105329862 B CN105329862 B CN 105329862B CN 201510887234 A CN201510887234 A CN 201510887234A CN 105329862 B CN105329862 B CN 105329862B
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Abstract
CsBi is prepared the invention discloses one kind4Te6The method of thermoelectric material.It mixes rare earth elements RE, CsX, Bi and Te, and CsBi is prepared at high temperature4Te6Material.Wherein X is halogen.Method provided by the present invention has been abandoned uses expensive Cs simple substance or binary Cs in the prior art2Te compounds, Cs sources are provided using raw material CsX, not only performance is stable for CsCl compounds, so that reaction need to only be carried out in vacuum tightness system, special device is not needed, also the problem of raw material is unstable to be preserved is not present, therefore synthetic method operation is very easy, is adapted to large-scale application.In addition, raw material CsX is cheap, cost is considerably reduced.
Description
Technical field
The present invention relates to materials science field, CsBi is prepared more particularly, to one kind4Te6The method of thermoelectric material.
Background technology
Thermoelectric material is that a kind of utilization solid interior carrier moving realizes the green that heat energy and electric energy are directly mutually changed
Environment protection type functional material.Thermoelectric material can be typically divided into according to operation temperature area low temperature (<500K), middle temperature (500~900K)
With high-temperature region (>900K) thermoelectric material.The performance of thermoelectric material can be characterized with thermoelectric figure of merit ZT, and its calculation formula is ZT=
(S2σ) T/ κ, ZT are bigger, and the performance of material is better.S is the Seebeck coefficient of material in formula, and σ is electrical conductivity, and T is absolute temperature,
κ is total thermal conductivity.At present, low-temperature thermoelectric material has in terms of refrigeration for refrigerator, electronic device cooling and infrared acquisition
Very big potential market, wherein p-type semiconductor CsBi4Te6It is one of low-temperature thermoelectric material representative of superior, the material
Key structural feature is the layer structure that two dimension is formed by Bi and Te, and Cs is filled between layers, and its ZT value reaches in 225K
To maximum 0.82.
2004, the Kanatzidis of Northwestern Univ USA, M.G. seminars reported CsBi4Te6Four kinds of conjunctions of compound
Into method (J.Am.Chem.Soc.2004,126,6414-6428).Four kinds of methods without exception involve the need for Cs simple substance
Or binary Cs2Te compounds are as start material, and these experimental implementations are complicated, with high costs, and there is certain danger
Property is, it is necessary to which special reaction unit, such as Cs simple substance can not be contacted with Te, otherwise can exploded.And binary Cs2Te compounds
Synthesis need liquefied ammonia condition and carried out in special device, while the biproduct is unstable in atmosphere, be difficult to preserve,
Therefore preparing raw material difficulty hard to find is caused.For these reasons, in the subsequent more than ten years, on CsBi4Te6Synthesis do not have
There is any new progress.
The content of the invention
In order to solve to prepare CsBi in the prior art4Te6Danger height, the raw material existed during material is difficult to prepare and preserved
And the problem of with high costs, complex operation, CsBi is prepared the invention provides one kind4Te6The method of thermoelectric material, this method can
With one-step synthesis polycrystalline material, easy to operate, yield is high and cost is low.
Technical scheme is as follows：
A kind of CsBi4Te6The preparation method of material, including：Rare earth elements RE, CsX, Bi and Te are mixed, made at high temperature
It is standby to obtain CsBi4Te6Material.
According to the present invention, X is halogen.It is preferred that X is Cl, Br or I.
According to the present invention, CsX is CsCl.
According to the present invention, rare earth elements RE is used as reducing agent.CsCl is as fluxing agent and provides Cs sources.Compound CsCl
Can be stable, and other raw materials are also stable.
According to the present invention, rare earth elements RE employed in raw material for example can be selected from La, Pr, Nd, Sm, Gd, Tb,
One or more in Dy, Ho, Er, Tm and Lu.
According to the present invention, in rare earth elements RE, tetra- kinds of raw mixtures of CsCl, Bi and Te, its mol ratio is preferably RE:
CsCl:Bi:Te=1:(6~18):12:18.For example can be Pr:CsCl:Bi:Te=1:12:12:18, or mol ratio
Can be La:CsCl:Bi:Te=1:6:12:18；Or Nd:CsCl:Bi:Te=1:18:12:18.
According to the present invention, in above-mentioned preparation method, the temperature of the pyroreaction is preferably greater than 700 DEG C, such as 800~
1200 DEG C, more preferably 900~1100 DEG C.Reaction time is preferably greater than 30 hours, such as 30~100 hours, more preferably 40~
60 hours, such as 50 hours.The pyroreaction is carried out preferably under vacuum atmosphere.
900 DEG C are heated to it is further preferred that raw mixture is placed under vacuum, 50 hours are incubated.
According to the present invention, after isothermal holding, in addition to cooling step, mixture is dropped with the speed no more than 5 DEG C/h
Temperature stops heating, naturally cools to room temperature to 300 DEG C.
According to the present invention, after product cooling prepared by above method high temperature, then by washing drying.It is preferred to use water
Washed.
In a preferred embodiment of the invention, the raw mixture is placed under vacuum and is heated to 700
More than DEG C, at least 50 hours are incubated, product obtains CsBi after repeatedly washing is dried4Te6Thermoelectric material.
The CsBi prepared by preparation method of the present invention4Te6Thermoelectric material is the low-temperature thermoelectric material of superior, the material
Key structural feature be the layer structure that two dimension is formed by Bi and Te, Cs is filled between layers, and its ZT value is in 225K
It can reach maximum 0.82.
Beneficial effects of the present invention include：
The present invention is using rare earth element as reducing agent, and cheap CsX (X is selected from halogen) is as fluxing agent and provides Cs
Source, CsBi has easily been synthesized through a step high temperature method4Te6Thermoelectric material.Synthetic method provided by the present invention has abandoned existing skill
Expensive Cs simple substance or binary Cs employed in art2Te compounds, but use CsX as raw material and Cs sources, CsX are provided
Not only performance is stable for compound so that reaction need to only be carried out in vacuum tightness system, it is not necessary to special device, also not
There is the problem of raw material is unstable to be preserved, therefore synthetic method operation is very easy, is adapted to large-scale application.In addition,
Raw material CsX, especially CsCl are cheap, considerably reduce cost.
Brief description of the drawings
Fig. 1 is sample CsBi4Te6The X ray diffracting spectrum of powder：(a) it is CsBi4Te6Calculated powder X-ray diffraction
Collection of illustrative plates, (b) is the x-ray diffractogram of powder spectrum that experiment measures sample powder.
Embodiment
Technical scheme is described in detail below by way of exemplary specific embodiment.But should not be by these
Embodiment is construed to limiting the scope of the invention.All technologies realized based on the above of the present invention are encompassed by this
Invention is intended in the range of protection.
Unless otherwise indicated, raw material and reagent described in embodiment are commercially available prod.
In the following embodiments, raw material Rare Earth Elements of Praseodymium, lanthanum and neodymium are to open up the limited public affairs of general metal material purchased from Huizhou City
Take charge of purity 99.99%；Cesium chloride is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, and purity is 99.9%；Bismuth granule is purchased from traditional Chinese medicines collection
Chemical reagent Co., Ltd of group, purity is 99.999%；Tellurium block is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, and purity is
99.999%.
Embodiment 1
Sample CsBi4Te6It is prepared by polycrystalline：
By tetra- kinds of raw materials of rare earth element Pr, CsCl, Bi, Te Pr in molar ratio:CsCl:Bi:Te=1:12: 12:18 mixing
It is placed in silica crucible.The silica crucible that will be equipped with raw material is placed in crystal reaction tube, and vacuum is evacuated to 10-2Pa simultaneously uses oxyhydrogen flame
Scorification seals crystal reaction tube.Crystal reaction tube is put into the tube furnace with temperature controller, 900 DEG C are heated to, and keep 50
Hour.Then it is cooled to the speed program no more than 5 DEG C/h after 300 DEG C, stops heating.Naturally cool to room temperature, product
After being dried through repeatedly washing and ethanol, CsBi is produced4Te6Polycrystalline material.
X-ray powder diffraction pattern is penetrated using the D/MAX2500 types X of company (Rigaku Corporation) production of science
Line powder diffractometer is analyzed, Cu targets, K α radiation source (λ=0.154184nm).Fig. 1 is sample CsBi4Te6The X-ray diffraction of powder
Collection of illustrative plates, wherein (a) is CsBi4Te6Calculated powder X ray diffracting spectrum, (b) be embodiment 1 prepare polycrystalline material powder
X ray diffracting spectrum.From figure 1 it appears that the Polycrystalline prepared in the present embodiment is pure phase, other are not observed miscellaneous
The presence of phase.
Embodiment 2
Sample CsBi4Te6It is prepared by polycrystalline：
By rare-earth elements La, tetra- kinds of raw materials of CsCl, Bi, Te La in molar ratio:CsCl:Bi:Te=1:6: 12:18 mixing
It is placed in silica crucible.
The silica crucible that will be equipped with raw material is placed in crystal reaction tube, and vacuum is evacuated to 10-2Pa is simultaneously close with oxyhydrogen flame scorification
Seal crystal reaction tube.Crystal reaction tube is put into the tube furnace with temperature controller, 900 DEG C are heated to, and kept for 50 hours.So
It is cooled to afterwards with the speed program no more than 5 DEG C/h after 300 DEG C, stops heating.Room temperature is naturally cooled to, product is through multiple
After washing and ethanol are dried, CsBi is produced4Te6Polycrystalline material.
The x-ray diffractogram of powder spectrum of polycrystalline material prepared by embodiment 2 is essentially identical with Fig. 1 (b), and it is not observed
The presence of his dephasign.It is pure phase to illustrate the Polycrystalline prepared in the present embodiment.
Embodiment 3
Sample CsBi4Te6It is prepared by polycrystalline：
By rare earth element nd, tetra- kinds of raw materials of CsCl, Bi, Te Nd in molar ratio:CsCl:Bi:Te=1:18: 12:18 mixing
It is placed in silica crucible.
The silica crucible that will be equipped with raw material is placed in crystal reaction tube, and vacuum is evacuated to 10-2Pa is simultaneously close with oxyhydrogen flame scorification
Seal crystal reaction tube.Crystal reaction tube is put into the tube furnace with temperature controller, 900 DEG C are heated to, and kept for 50 hours.So
It is cooled to afterwards with the speed program no more than 5 DEG C/h after 300 DEG C, stops heating.Room temperature is naturally cooled to, product is through 3 water
Wash and ethanol dry after, produce CsBi4Te6Polycrystalline material.
The x-ray diffractogram of powder spectrum of polycrystalline material prepared by embodiment 3 is essentially identical with Fig. 1 (b), and it is not observed
The presence of his dephasign.It is pure phase to illustrate the Polycrystalline prepared in the present embodiment.
Claims (15)
1. one kind prepares CsBi4Te6The method of thermoelectric material, including：Rare earth elements RE, CsX, Bi and Te are mixed, at high temperature
Prepare CsBi4Te6Material, wherein, X is halogen；The rare earth elements RE be selected from La, Pr, Nd, Sm, Gd, Tb, Dy, Ho,
One or more in Er, Tm and Lu；The temperature of the pyroreaction is more than 700 DEG C.
2. according to the method described in claim 1, it is characterised in that X is Cl, Br or I.
3. method according to claim 2, it is characterised in that preferred X is Cl.
4. according to the method described in claim 1, it is characterised in that in tetra- kinds of raw mixtures of RE, CsCl, Bi and Te, press
Mol ratio RE:CsCl:Bi:Te=1:(6~18):12:18.
5. method according to claim 4, it is characterised in that the mol ratio of the raw material is Pr:CsCl:Bi:Te=1:
12:12:18；Or mol ratio is La:CsCl:Bi:Te=1:6：12:18；Or mol ratio is Nd:CsCl:Bi:Te=1:
18:12:18。
6. the method according to any one of claim 1-5, it is characterised in that the temperature of the pyroreaction is 800~
1200℃。
7. method according to claim 6, it is characterised in that the temperature of the pyroreaction is 900~1100 DEG C.
8. according to the method described in claim 1, it is characterised in that the reaction time is more than 30 hours.
9. method according to claim 8, it is characterised in that the reaction time is 30~100 hours.
10. method according to claim 9, it is characterised in that the reaction time is 40~60 hours.
11. method according to claim 10, it is characterised in that the reaction time is 50 hours.
12. according to the method described in claim 1, it is characterised in that the pyroreaction is carried out under vacuum atmosphere.
13. according to the method described in claim 1, it is characterised in that after the product cooling for preparing methods described high temperature, then
By washing drying.
14. method according to claim 13, it is characterised in that after the product cooling for preparing methods described high temperature,
Again washing drying is carried out by water.
15. according to the method described in claim 1, it is characterised in that the raw mixture is placed under vacuum and heated
To more than 700 DEG C, at least 50 hours are incubated, product obtains CsBi after washing is dried4Te6Thermoelectric material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100091333A (en) * | 2009-02-10 | 2010-08-19 | 경북대학교 산학협력단 | Porous organic thermoelectric device |
| CN103050618B (en) * | 2011-10-17 | 2015-08-12 | 中国科学院福建物质结构研究所 | A kind of thermoelectric material and preparation method thereof |
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2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100091333A (en) * | 2009-02-10 | 2010-08-19 | 경북대학교 산학협력단 | Porous organic thermoelectric device |
| CN103050618B (en) * | 2011-10-17 | 2015-08-12 | 中国科学院福建物质结构研究所 | A kind of thermoelectric material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Superconductivity in the Narrow-Gap Semiconductor CsBi4Te6;Christos D.Malliakas et al.;《Journal of the American Chemical Society》;20130912;第135卷;第14540-14543页 * |
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