CN101101954A - A cadmium-stibium-based p type thermal electrical material and its making method - Google Patents
A cadmium-stibium-based p type thermal electrical material and its making method Download PDFInfo
- Publication number
- CN101101954A CN101101954A CNA2007100438425A CN200710043842A CN101101954A CN 101101954 A CN101101954 A CN 101101954A CN A2007100438425 A CNA2007100438425 A CN A2007100438425A CN 200710043842 A CN200710043842 A CN 200710043842A CN 101101954 A CN101101954 A CN 101101954A
- Authority
- CN
- China
- Prior art keywords
- cadmium
- stibium
- thermoelectric
- preparation
- type thermal
- 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.)
- Pending
Links
Images
Abstract
The present invention relates to a cadmium-stibium base p type thermoelectric material and its preparation method, belonging to the field of thermoelectric converting material. The present invention thermoelectric material composition formula is: RCd2-xZnxSb2-ySy, wherein R is one or two solid solution with arbitrary proportion of Yb, Eu, Ca, Sr and Ba; x is Zn solid solution component, range is more than or equal to 0 and less than 2; S is one of Ge, Sn, Se and Te; y is S doped real component, range is more than or equal to 0 and less than or equal to 0.2. Method for using vacuum or inert gas solid-phase to synthesis, speed plasma sintering (SPS) or thermal pressing sintering to prepare compact ceramic sample. The sample YbCd2Sb2 ZT value reaches to 0.8 at 430 DEG C, corresponding with the current used for middle temperature section (200 DEG C to 500 DEG C) mature thermoelectric material PbTe alloy (ZT 430 DEG C equals to 0.8), the present invention also increases its thermoelectric converting efficient through solid-phase and doped, the model thermoelectric material preparation method is simple and stable in air, can be used for thermoelectric converting apparatus.
Description
Technical field
The present invention relates to a kind of cadmium antimony based p type metal and ask compound thermo-electric converting material and preparation method thereof, belong to the thermo-electric converting material field.
Background technology
Thermoelectric generation technology is to utilize the Sai Beike of semi-conducting material (Seebeck) effect and Pa Er card (Peltier) effect to carry out heat energy and the directly mutual switch technology of electric energy, comprises thermoelectric power generation and thermoelectric cooling
[1-2]Advantages such as thermoelectric conversion system has that volume is little, reliability is high, pollution-free, noiselessness, Applicable temperature scope are wide have obtained to use widely in high-tech sectors such as space technology, military equipment, IT technology as particular power source and high precision temperature control device.In recent years, thermoelectric generation technology is subjected to extensive concern as a kind of novel clean energy technology in the world, especially be applied to industrial surplus used heat and sunlight-Re compound power-generating field, be expected to for improving rate of energy, alleviating the approach that problem of environmental pollution provides a kind of comprehensive coordination.Although thermoelectric generation technology has so many advantage,, its energy conversion efficiency is lower, and the energy conversion efficiency of the thermoelectric conversion system of the application of succeeing in the world at present only is 7-8%, has seriously limited the extensive use of pyroelectric technology.The conversion efficiency of thermoelectric of system depends primarily on the performance of thermoelectric material, i.e. dimensionless performance index the ZT (=α of material
2σ/κ, α are the Seebeck coefficients of material, and σ is a conductivity of electrolyte materials, and κ is the thermal conductivity of material, and T is an absolute temperature).The ZT value is high more, and the thermoelectric conversion performance of material is good more.According to the difference that transports the charge carrier kind of material, thermoelectric material is divided into n type (electron conduction) and p type (hole conduction).For general thermoelectric material, we can be optimized carrier concentration by the mode of mixing, thereby optimize ZT.Therefore, improve the ZT value of traditional material and seek the main target that novel high ZT value material becomes this area.
In recent decades, the system of comparative maturity has Bi
2Te
3, Zn
4Sb
3Alloy, PbTe alloy, CoSb
3And the heavy doping system, SiGe alloy etc., they in corresponding temperature range separately the ZT value 0.5～1.3.Recently, Zintl type intermetallic compound more and more attracts much attention.So-called Zintl compound is meant the compound that is made of strong metal of electropositivity and the more intense part of electronegativity, defers to the Zintl rule: electronics is transferred to the part-structure that electronegative element forms from electropositive element and is satisfied the requirement of the full layer of eight electronics.This compounds forms narrow gap semiconductor easily, and has abundant complicated structure, causes the lattice thermal conductance lower, and these all are that good thermoelectric material is needed.RT
2S
2The compound of (R is rare earth or alkaline-earth metal, and T is a transition metal, and S is a semimetal) type is a kind of typical Zintl type intermetallic compound, mainly has two kinds of structures, and a kind of Pnma that is cube, another kind are tripartite P-3ml.For compound, recently, there is the reasonable p type of a kind of performance thermoelectric material to be found Ca with a kind of structure in back
xYb
1-xZn
2Sb
2(ZT
750K～0.5), [Frank Gascoin et.al.Adv.Funct.Mater.2005,15,1860].This is a kind of by one deck R
2+And two dimension [T
2S
2]
2-Replace the layer structure of arranging, interlayer phon scattering meeting causes the lattice thermal conductance lower, and low dimensional structures is very favourable to electric property.Compound YbCd among the present invention
2Sb
2Belong to this type, with YbZn
2Sb
2Compare, it contains heavier Elements C d and causes lower lattice thermal conductance, and causes the raising of the more favourable electric property of variation of electronic structure.At present, the thermoelectricity capability of this compound does not appear in the newspapers, we find it have can and the thermoelectricity capability that compares favourably of present commercial thermoelectric material.Because this structure is more stable, compound with this structure is abundanter, the space that can regulate and control is also very big, thereby the mode of taking solid solution or doping further strengthens phon scattering and reduces the lattice thermal conductance, optimize carrier concentration and improve electric property, thereby further improve its conversion efficiency of thermoelectric.
Summary of the invention
The purpose of this invention is to provide a kind of novel lamellar p type thermoelectric material and preparation method thereof.
This materials chemistry general formula that can be used for thermoelectric conversion that the present invention proposes is RCd
2-xZn
xSb
2-yS
y, wherein R is Yb, Eu, Ca, Sr, one or both arbitrary proportion solid solutions among the Ba; X is the solid solution component of Zn, and scope is in 0≤x＜2; S is Ge, Sn, and Se, a kind of among the Te, y are the real composition that S mixes, scope is in 0≤x≤0.2.
The material preparation steps in sequence is as follows among the present invention:
Adopt metal Yb, Eu, Ca, Sr, among the Ba one or both, or metal Yb, Eu, Ca, Sr, any binary compound of Ba is a raw material;
Adopt metal Cd; Cd and Zn; Or Cd and Zn and Ba, Ca, Sr, Yb, any binary of Eu or ternary compound are raw material;
Adopt metal Sb or Sb and Ge, Sn, any binary of Te or ternary compound are raw material;
1) at first with raw material by suitable stoichiometric proportion weighing, put into not in the middle of the container with raw material and product reaction, vacuum or following 700 ℃～1200 ℃ following calcinations of inert atmosphere (as nitrogen or argon gas) at least 12 hours, took out the cooling back then.Sample is pulverized and is promptly got pulverous BaZn
2Sb
2The thermoelectric material of base.
2) powder body material that further previous step is obtained carries out rapid plasma body sintering (SPS) or hot pressed sintering (300 ℃～600 ℃ of SPS sintering temperatures, pressure 30～50MPa; 300 ℃～700 ℃ of hot pressed sintering temperature, pressure 20～60MPa) obtains the ceramics sample of density more than 90%.
This sample synthesis technique is easy to control, can be in room temperature to 450 ℃ stable application, and have good thermoelectricity capability.Such as YbCd
2Sb
2, the room temperature thermal conductivity is 2Wm
-1K
-1, room-temperature conductivity and Seebeck coefficient are respectively 4 * 10
4Sm
-1With 125 μ VK
-1, the ZT value reaches 0.8 in the time of 430 ℃.With the ripe thermoelectric material PbTe alloy (ZT that is used for middle-temperature section (200 ℃～500 ℃) at present
430 ℃=0.8) suitable.Thermoelectric material among the present invention is the p section bar material of hole conduction, can be used for utilizing in the application of thermoelectric transfer principle generating or refrigeration.
Description of drawings
Fig. 1,2,3,4 have provided YbCd in the temperature range of 300K to 700K respectively
2Sb
2Thermal conductivity, conductivity, Seebeck coefficient and thermoelectric figure of merit (ZT value).
Embodiment
In glove box, take by weighing Cd grain (99.999%) 0.674g, Yb metal (99.9%) 0.525g, antimony grain (99.999%) 0.731g, successively raw material is put into the graphite crucible of 25mm * Φ 10mm size that inside is lined with carbon paper from bottom to up, this crucible is put into the quartz ampoule of internal diameter Φ 11mm, rubber stopper takes out from glove box beyond the Great Wall again.With vacuum pump it is vacuumized apace then, treat that vacuum degree reaches 1 * 10
-6With oxyhydrogen flame it is sealed during torr.Put into then in the heating furnace, be warmed up to 900 ℃, be incubated 72 hours, take out with the stove cooling with the heating rate of 1 ℃/min.Product is confirmed as YbCd through powder X-ray RD
2Sb
2Pure phase.The powder of the sample that obtains through grinding to form utilizes rapid plasma body sintering (SPS) at 450 ℃ again, 50MPa, and sintering is about 15 minutes in the vacuum atmosphere.Gained ceramics sample density is about 98%.Then to the thermal conductivity of sample in the 300K-700K scope, conductivity, Seebeck coefficient and thermoelectric figure of merit (ZT value).Fig. 1,2,3,4 have provided the result respectively.
Claims (5)
1, a kind of cadmium-stibium-based p type thermal electrical material and preparation method thereof is characterized in that the chemical composition of described thermoelectric material is: RCd
2-xZn
xSb
2-yS
y, wherein R is Yb, Eu, Ca, Sr, one or both among the Ba, in the time of two kinds with the arbitrary proportion solid solution; X is the solid solution component of Zn, 0≤x＜2; S is Ge, Sn, and Se, a kind of among the Te, y are the real composition that S mixes, 0≤y≤0.2.
2, by the preparation method of the described a kind of cadmium-stibium-based p type thermal electrical material of claim 1, it is characterized in that:
Adopt metal Yb, Eu, Ca, Sr, among the Ba one or both, or metal Yb, Eu, Ca, Sr, any binary compound of Ba is a raw material;
Adopt metal Cd; Cd and Zn; Or Cd and Zn and Ba, Ca, Sr, Yb, any binary of Eu or ternary compound are raw material;
Adopt metal Sb or Sb and Ge, Sn, any binary of Te or ternary compound are raw material;
To put into not in the middle of the container with raw material and product reaction 700 ℃～1200 ℃ following calcinations at least 12 hours under vacuum or inert atmosphere then by the raw material of stoichiometric proportion weighing;
Take out product cooling back after the calcination.
3, by the preparation method of the described a kind of cadmium-stibium-based p type thermal electrical material of claim 2, it is characterized in that the product after the calcination is carried out rapid plasma body sintering or hot pressed sintering.
4, by the preparation method of the described a kind of cadmium-stibium-based p type thermal electrical material of claim 3, the condition that it is characterized in that rapid plasma body sintering is 300 ℃～600 ℃ of sintering temperatures, pressure 30～50Mpa.
5, by the preparation method of the described a kind of cadmium-stibium-based p type thermal electrical material of claim 3, it is characterized in that 300 ℃～700 ℃ of hot pressed sintering temperature, pressure 20～60MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100438425A CN101101954A (en) | 2007-07-16 | 2007-07-16 | A cadmium-stibium-based p type thermal electrical material and its making method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100438425A CN101101954A (en) | 2007-07-16 | 2007-07-16 | A cadmium-stibium-based p type thermal electrical material and its making method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101101954A true CN101101954A (en) | 2008-01-09 |
Family
ID=39036129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100438425A Pending CN101101954A (en) | 2007-07-16 | 2007-07-16 | A cadmium-stibium-based p type thermal electrical material and its making method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101101954A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857929A (en) * | 2010-04-06 | 2010-10-13 | 武汉理工大学 | Zinc antimony based porous p-type thermoelectric material and preparation method thereof |
| CN101728477B (en) * | 2009-12-04 | 2011-08-17 | 北京工业大学 | Method for preparing CeyFe4Sb12/Ca3Co4O9(y=0.8-1.2) based block gradient thermoelectric material |
| CN101345284B (en) * | 2008-08-29 | 2012-04-11 | 中国科学院上海硅酸盐研究所 | P type europium cadmium stibium based pyroelectric material and preparation method thereof |
| CN101359713B (en) * | 2008-09-19 | 2012-06-13 | 中国科学院上海硅酸盐研究所 | P type europium zincium and stibium based thermoelectric material, preparation thereof |
| CN105612625A (en) * | 2013-10-17 | 2016-05-25 | 株式会社Lg化学 | Thermoelectric material and method for manufacturing same |
| CN109641750A (en) * | 2016-08-31 | 2019-04-16 | 达姆施塔特技术大学 | Thermoelectric material |
| CN110265540A (en) * | 2019-05-31 | 2019-09-20 | 上海大学 | Barium copper tellurium based p type thermoelectric material and preparation method thereof |
| CN110299444A (en) * | 2019-05-30 | 2019-10-01 | 同济大学 | A kind of EuCd2Sb2 base thermoelectricity material and preparation method thereof |
| US11627691B2 (en) * | 2016-02-18 | 2023-04-11 | University Of Houston System | Zintl compounds with high thermoelectric performance and methods of manufacture thereof |
-
2007
- 2007-07-16 CN CNA2007100438425A patent/CN101101954A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101345284B (en) * | 2008-08-29 | 2012-04-11 | 中国科学院上海硅酸盐研究所 | P type europium cadmium stibium based pyroelectric material and preparation method thereof |
| CN101359713B (en) * | 2008-09-19 | 2012-06-13 | 中国科学院上海硅酸盐研究所 | P type europium zincium and stibium based thermoelectric material, preparation thereof |
| CN101728477B (en) * | 2009-12-04 | 2011-08-17 | 北京工业大学 | Method for preparing CeyFe4Sb12/Ca3Co4O9(y=0.8-1.2) based block gradient thermoelectric material |
| CN101857929A (en) * | 2010-04-06 | 2010-10-13 | 武汉理工大学 | Zinc antimony based porous p-type thermoelectric material and preparation method thereof |
| CN105612625A (en) * | 2013-10-17 | 2016-05-25 | 株式会社Lg化学 | Thermoelectric material and method for manufacturing same |
| CN105612625B (en) * | 2013-10-17 | 2018-09-25 | 株式会社Lg化学 | Thermoelectric material and its manufacturing method |
| US11627691B2 (en) * | 2016-02-18 | 2023-04-11 | University Of Houston System | Zintl compounds with high thermoelectric performance and methods of manufacture thereof |
| CN109641750A (en) * | 2016-08-31 | 2019-04-16 | 达姆施塔特技术大学 | Thermoelectric material |
| CN109641750B (en) * | 2016-08-31 | 2022-05-27 | 达姆施塔特技术大学 | Thermoelectric material |
| CN110299444A (en) * | 2019-05-30 | 2019-10-01 | 同济大学 | A kind of EuCd2Sb2 base thermoelectricity material and preparation method thereof |
| CN110265540A (en) * | 2019-05-31 | 2019-09-20 | 上海大学 | Barium copper tellurium based p type thermoelectric material and preparation method thereof |
| CN110265540B (en) * | 2019-05-31 | 2022-07-08 | 上海大学 | Barium-copper-tellurium-based p-type thermoelectric material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6069312A (en) | Thermoelectric materials with filled skutterudite structure for thermoelectric devices | |
| JP5042245B2 (en) | Doped lead telluride for thermoelectric applications | |
| CN101101954A (en) | A cadmium-stibium-based p type thermal electrical material and its making method | |
| JP6976012B2 (en) | n-type Mg-Sb group Room temperature thermoelectric material and its manufacturing method | |
| JP2021515411A5 (en) | ||
| JP5468554B2 (en) | Semiconductor materials containing doped tin telluride for thermoelectric applications | |
| CN105671344B (en) | One step prepares high-performance CoSb3The method of base thermoelectricity material | |
| CN109534303B (en) | High-performance low-temperature thermoelectric material and preparation method thereof | |
| CN102643085A (en) | Bi Cu 1-x SeO-based oxide thermoelectric ceramic material and preparation method thereof | |
| JP2001044519A (en) | Clathrate compound and high-efficiency thermoelectric material, manufacture thereof, and thermoelectric module using the high-efficiency thermoelectric material | |
| CN102709461A (en) | Preparation method of category-I topologic thermoelectric material containing rare earth | |
| CN101118946B (en) | Barium zinc antimony based p type thermoelectric material and method for making same | |
| US10937939B2 (en) | Thermoelectric conversion material and thermoelectric conversion element | |
| CN101345284B (en) | P type europium cadmium stibium based pyroelectric material and preparation method thereof | |
| CN103924109B (en) | The supper-fast preparation high-performance CoSb of a kind of Self-propagating Sintering Synthetic 3the method of base thermoelectricity material | |
| CN110218888A (en) | A kind of novel Zintl phase thermoelectric material and preparation method thereof | |
| US20230329115A1 (en) | Thermoelectric Material, Method for Producing Same, and Thermoelectric Power Generation Element | |
| CN101857929A (en) | Zinc antimony based porous p-type thermoelectric material and preparation method thereof | |
| CN103050618B (en) | A kind of thermoelectric material and preparation method thereof | |
| CN101359713A (en) | P type europium zincium and stibium based thermoelectric material, preparation thereof | |
| CN114408874A (en) | Bismuth telluride thermoelectric material based on entropy engineering and preparation method thereof | |
| CN106981564A (en) | P types Ag3In7Te12Base high temperature thermoelectric material and its preparation technology | |
| TW201326048A (en) | Thermoelectric material, method for fabricating the same, and thermoelectric module employing the same | |
| JP3476343B2 (en) | Thermoelectric conversion material | |
| CN110265540B (en) | Barium-copper-tellurium-based p-type thermoelectric material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20080109 |