CN102931336A - Germanium telluride (GeTe) based composite thermoelectric material and preparation method thereof - Google Patents

Germanium telluride (GeTe) based composite thermoelectric material and preparation method thereof Download PDF

Info

Publication number
CN102931336A
CN102931336A CN2012104009576A CN201210400957A CN102931336A CN 102931336 A CN102931336 A CN 102931336A CN 2012104009576 A CN2012104009576 A CN 2012104009576A CN 201210400957 A CN201210400957 A CN 201210400957A CN 102931336 A CN102931336 A CN 102931336A
Authority
CN
China
Prior art keywords
gete
thermoelectric material
composite thermoelectric
preparation
powder
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.)
Granted
Application number
CN2012104009576A
Other languages
Chinese (zh)
Other versions
CN102931336B (en
Inventor
李均钦
黎龙飞
宋申华
王雷
刘福生
敖伟琴
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.)
Shenzhen University
Original Assignee
Shenzhen University
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 Shenzhen University filed Critical Shenzhen University
Priority to CN201210400957.6A priority Critical patent/CN102931336B/en
Publication of CN102931336A publication Critical patent/CN102931336A/en
Application granted granted Critical
Publication of CN102931336B publication Critical patent/CN102931336B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention provides a composite thermoelectric material. A chemical formula of the composite thermoelectric material is (GeTe)1-x(Ag8GeTe6)x, wherein x is between 0.02 and 0.20. The invention also provides a preparation method of the composite thermoelectric material. The composite thermoelectric material provided by the invention is leadless, low in thermal conductivity, high in dimensionless merit figure ZT and high in thermoelectric performance.

Description

A kind of GeTe base composite thermoelectric material and preparation method thereof
Technical field
The present invention relates to novel energy material technology field, especially relate to a kind of unleaded middle temperature composite thermoelectric material and preparation method thereof.
Background technology
Thermoelectric material is a kind of specific function material, utilize its have electric current by the time produce temperature gradient and two ends produce the thermoelectric effect of electromotive force or electric current when having the temperature difference and can realize temperature control, thermo-electric generation and energising refrigeration.It is little, lightweight that these refrigeration and electricity generation system have a volume, without any mechanical rotation part, noiselessness in the work, do not cause environmental pollution, long service life, be easy to the advantages such as control, be considered in the future very competitive energy substitution material, having broad application prospects aspect following environmental protection energy project and the Refrigeration Engineering.
The conversion efficiency of thermoelectric device is to be determined by the performance of thermoelectric material, and the performance of thermoelectric material then is by dimensionless figure of merit ZT=S 2σ T/k weighs, and wherein S is Seebeck (Seebeck) coefficient, and σ and k are respectively conductivity and the thermal conductivities of material, and T is absolute temperature.A kind of thermoelectric material of excellent performance must have high Seebeck coefficient, high conductivity and lower thermal conductivity.
IV-VI family semi-conductor thermoelectric material comprises that PbTe, GeTe and PbSe are middle temperature semi-conductor thermoelectric material, can be used for the temperature difference electricity generation device of warm area (400-800K) work, especially is applied in the fields such as the recovery of industrial waste heat and automobile engine residual heat utilization.Compare with the PbTe base thermoelectricity material, the GeTe thermoelectric material does not contain Pb, although the conductivity of GeTe is higher, its thermal conductivity is also higher, causes its thermoelectric figure of merit ZT less.
Therefore, be necessary to provide a kind of composite thermoelectric material and preparation method thereof, not leaded, have lower thermal conductivity, thereby can have high dimensionless figure of merit.
Summary of the invention
The invention provides a kind of composite thermoelectric material and preparation method thereof.
A kind of composite thermoelectric material, the chemical formula of described composite thermoelectric material are (GeTe) 1-x(Ag 8GeTe 6) x, wherein the span of x is 0.02＜=x＜=0.20.
Wherein, Ag 8GeTe 6Be distributed among the GeTe, x is determining to be distributed in the Ag among the GeTe 8GeTe 6The thermoelectricity capability of phase content and material.
A kind of preparation method of described composite thermoelectric material comprises step: according to (GeTe) 1-x(Ag 8GeTe 6) xThe numerical value of middle x take metal Ge, Te and Ag simple substance as raw material, takes by weighing raw material according to proportioning; The raw material that takes by weighing is made formation GeTe base alloy; Described GeTe base alloying pellet is clayed into power, and the powder that described GeTe base alloying pellet is worn into carries out discharge plasma sintering, obtain described composite thermoelectric material.
Composite thermoelectric material provided by the invention utilizes GeTe-Ag 8GeTe 6The Ag that disperse distributes is introduced in the eutectic transformation of phasor in the GeTe matrix 8GeTe 6Second-phase forms the composite thermoelectric material with eutectic structure, greatly reduces the thermal conductivity of material, thereby has improved its thermoelectricity capability.
Description of drawings
Fig. 1 is (GeTe) 1-x(Ag 8GeTe 6) xThe X-ray diffractogram of (x=0.02,0.05 and 0.11) composite thermoelectric material.
Fig. 2 is (GeTe) 1-x(Ag 8GeTe 6) x(x=0.11) microstructure picture of composite thermoelectric material.
Fig. 3 is (GeTe) 1-x(Ag 8GeTe 6) x(x=0,0.02,0.05, the 0.08 and 0.11) resistivity of composite thermoelectric material and the variation relation schematic diagram of temperature.
Fig. 4 (GeTe) 1-x(Ag 8GeTe 6) x(x=0,0.02,0.05, the 0.08 and 0.11) Seebeck coefficient of composite thermoelectric material and the variation relation schematic diagram of temperature.
Fig. 5 (GeTe) 1-x(Ag 8GeTe 6) x(x=0,0.02,0.05, the 0.08 and 0.11) thermal conductivity of composite thermoelectric material and the variation relation schematic diagram of temperature.
Fig. 6 (GeTe) 1-x(Ag 8GeTe 6) xThe dimensionless figure of merit (ZT) of (x=0,0.02,0.05,0.08 and 0.11) composite thermoelectric material and the variation relation schematic diagram of temperature.
Specific implementation method
A kind of composite thermoelectric material that the technical program is provided below in conjunction with accompanying drawing and preparation method thereof is elaborated.
A kind of composite thermoelectric material, the chemical formula of described composite thermoelectric material are (GeTe) 1-x(Ag 8GeTe 6) x, wherein the span of x is 0.02＜=x＜=0.20, is preferably 0.02＜=x＜=0.15.
Wherein, Ag 8The GeTe6 second-phase is distributed in the GeTe matrix, and x is determining to be distributed in the Ag among the GeTe 8GeTe 6The thermoelectricity capability of phase content and material.
A kind of preparation method of described composite thermoelectric material comprises step:
The first step is according to (GeTe) 1-x(Ag 8GeTe 6) xThe numerical value of middle x take metal Ge, Te and Ag simple substance as raw material, takes by weighing raw material according to proportioning;
Second step is made formation GeTe base alloy with the raw material that takes by weighing;
The 3rd step; Described GeTe base alloying pellet is clayed into power;
In the 4th step, the powder that described GeTe base alloying pellet is worn into carries out discharge plasma sintering, obtains described composite thermoelectric material.
Wherein, in the first step, can obtain according to the difference of x numerical value the proportioning of different metal Ge, Te and Ag.The span of X is 0.02＜=x＜=0.20.
In second step, described raw material was reacted 20 hours under 900 degrees celsius in quartz ampoule, thereby obtain GeTe base alloy.
In the 3rd step, can adopt planetary ball mill that GeTe base alloy is carried out ball milling.
In the 4th step, under vacuum environment, carry out plasma discharging (SPS) sintering, vacuum degree is 1 * 10 -2During Pa, pressure 30 ~ 50MPa, 600 ~ 650 ° of C of sintering temperature, temperature retention time 5 ~ 10 minutes can obtain described composite thermoelectric material.
The composite thermoelectric material that makes (GeTe) 1-x(Ag 8GeTe 6) xAdopt X-ray diffractogram as shown in Figure 1 to characterize.Fig. 1 has showed that x is 0.02,0.05 and the X-ray diffractogram of 0.11 o'clock composite thermoelectric material, and Fig. 2 is the microstructure picture of described composite thermoelectric material (x=0.11), and Fig. 1 and Fig. 2 show that the thermoelectric material that the present invention makes has comprised GeTe matrix phase and Ag 8GeTe 6Second-phase.
See also Fig. 3, composite thermoelectric material (GeTe) 1-x(Ag 8GeTe 6) xResistivity increase along with the rising of temperature.Under uniform temp, composite thermoelectric material (GeTe) 1-x(Ag 8GeTe 6) xResistivity high temperature under less than the conductance of GeTe.See also Fig. 4, composite thermoelectric material (GeTe) 1-x(Ag 8GeTe 6) xSeebeck coefficient increase along with the rising of temperature, under uniform temp, composite thermoelectric material (GeTe) 1-x(Ag 8GeTe 6) xSeebeck coefficient be slightly less than the Seebeck coefficient of GeTe.See also Fig. 5, composite thermoelectric material (GeTe) 1-x(Ag 8GeTe 6) xThermal conductivity reduce along with the rising of temperature.And, under uniform temp, composite thermoelectric material (GeTe) 1-x(Ag 8GeTe 6) xThermal conductivity all significantly be lower than the thermal conductivity of GeTe.And, under the uniform temp, along with the increase of x numerical value, composite thermoelectric material (GeTe) 1-x(Ag 8GeTe 6) xThermal conductivity numerical value reduce.Can be drawn composite thermoelectric material (GeTe) by Fig. 5 1-x(Ag 8GeTe 6) xThan GeTe, can reduce the thermal conductivity of thermoelectric material.See also Fig. 6, composite thermoelectric material (GeTe) 1-x(Ag 8GeTe 6) xThe dimensionless figure of merit increase along with the rising of temperature.And, under uniform temp, composite thermoelectric material (GeTe) 1-x(Ag 8GeTe 6) xThe dimensionless figure of merit all greater than the dimensionless figure of merit of GeTe.And, under the uniform temp, along with the increase of x numerical value, composite thermoelectric material (GeTe) 1-x(Ag 8GeTe 6) xDimensionless figure of merit numerical value increase.Can be drawn composite thermoelectric material (GeTe) by Fig. 6 1-x(Ag 8GeTe 6) xThan GeTe, can increase the dimensionless figure of merit of thermoelectric material, thereby increase the thermoelectricity capability of material.
Below, specifically illustrate that with embodiment 1 to 3 present technique puts composite thermoelectric material that case provides and preparation method thereof.
Embodiment 1
Take Ge, Te and Ag as raw material, according to chemical molecular formula (GeTe) 0.89(Ag 8GeTe 6) 0.11Carry out in weighing proportioning and the quartz ampoule of packing into, vacuumize the good quartz ampoule of rear soldering and sealing and place Muffle furnace to react, reaction temperature is 900 ° of C, and the reaction time is 20 hours, obtains GeTe base alloy; Reaction is obtained GeTe base alloy grind into powder, put into ball grinder with abrading-ball, be filled with Ar gas after the forvacuum, adopt planetary ball mill under the protection of Ar gas, to make attritive powder, 200 rev/mins of drum'ss speed of rotation, ratio of grinding media to material 20:1, Ball-milling Time 8 hours; Powder behind the ball milling is carried out plasma discharging (SPS) sintering under vacuum environment, vacuum degree is 1 * 10 -2Pa, pressure 50MPa, 620 ° of C of sintering temperature, temperature retention time 5 minutes namely obtains Ag 8GeTe 6Be distributed in the unleaded composite thermoelectric material (GeTe) in the matrix GeTe matrix 0.89(Ag 8GeTe 6) 0.11
The composite thermoelectric material that the present embodiment makes (GeTe) 0.89(Ag 8GeTe 6) 0.11Phase, microstructure and thermoelectricity capability shown in Fig. 1-6, its thermal conductivity is 1.23W/m.K at 673K, is 38% of the synthermal lower 3.23W/m.K of pure GeTe; And its maximum figure of merit (ZT) is 1.15, exceeds 125% than 0.51 of pure GeTe.
Embodiment 2
Take Ge, Te and Ag as raw material, according to chemical molecular formula (GeTe) 0.95(Ag 8GeTe 6) 0.05Carry out in weighing proportioning and the quartz ampoule of packing into, vacuumize the good quartz ampoule of rear soldering and sealing and place Muffle furnace to react, reaction temperature is 900 ° of C, and the reaction time is 20 hours, obtains GeTe base alloy; Reaction is obtained GeTe base alloy grind into powder, put into ball grinder with abrading-ball, be filled with Ar gas after the forvacuum, adopt planetary ball mill under the protection of Ar gas, to make attritive powder, 200 rev/mins of drum'ss speed of rotation, ratio of grinding media to material 20:1, Ball-milling Time 8 hours; Powder behind the ball milling is carried out plasma discharging (SPS) sintering under vacuum environment, vacuum degree is 1 * 10 -2Pa, pressure 50MPa, 620 ° of C of sintering temperature, temperature retention time 5 minutes namely obtains Ag 8GeTe 6Be distributed in the unleaded composite thermoelectric material (GeTe) in the matrix GeTe matrix 0.95(Ag 8GeTe 6) 0.05
The composite thermoelectric material that the present embodiment makes (GeTe) 0.95(Ag 8GeTe 6) 0.05Phase and thermoelectricity capability shown in Fig. 1,3-6, its thermal conductivity is 1.98W/m.K at 673K, is 61% of the synthermal lower 3.23W/m.K of pure GeTe; And its maximum figure of merit (ZT) is 1.03, exceeds 102% than 0.51 of pure GeTe.
Embodiment 3
Take Ge, Te and Ag as raw material, according to chemical molecular formula (GeTe) 0.92(Ag 8GeTe 6) 0.08Carry out in weighing proportioning and the quartz ampoule of packing into, vacuumize the good quartz ampoule of rear soldering and sealing and place Muffle furnace to react, reaction temperature is 900 ° of C, and the reaction time is 20 hours, obtains GeTe base alloy; Reaction is obtained GeTe base alloy grind into powder, put into ball grinder with abrading-ball, be filled with Ar gas after the forvacuum, adopt planetary ball mill under the protection of Ar gas, to make attritive powder, 200 rev/mins of drum'ss speed of rotation, ratio of grinding media to material 20:1, Ball-milling Time 8 hours; Powder behind the ball milling is carried out plasma discharging (SPS) sintering under vacuum environment, vacuum degree is 1 * 10 -2Pa, pressure 50MPa, 620 ° of C of sintering temperature, temperature retention time 5 minutes namely obtains Ag 8GeTe 6Be distributed in the unleaded composite thermoelectric material (GeTe) in the matrix GeTe matrix 0.92(Ag 8GeTe 6) 0.08
The composite thermoelectric material that this example makes (GeTe) 0.92(Ag 8GeTe 6) 0.08Phase and thermoelectricity capability shown in Fig. 1,3-6, its thermal conductivity is 1.62W/m.K at 673K, is 50% of the synthermal lower 3.23W/m.K of pure GeTe; And its maximum figure of merit (ZT) is 0.87, exceeds 71% than 0.51 of pure GeTe.
Composite thermoelectric material provided by the invention utilizes (GeTe) 1-x(Ag 8GeTe 6) xEutectic transformation, in the GeTe matrix, introduce the Ag that disperse distributes 8GeTe 6Second-phase forms the composite thermoelectric material with eutectic structure, greatly reduces the thermal conductivity of material, thereby has improved its thermoelectricity capability.

Claims (6)

1. composite thermoelectric material, the chemical formula of described composite thermoelectric material is (GeTe) 1-x(Ag 8GeTe 6) x, wherein the span of x is 0.02＜=x＜=0.20.
2. composite thermoelectric material as claimed in claim 1, the span of x is 0.02＜=x＜=0.15 in the described chemical formula.
3. the preparation method of a right 1 or 2 described composite thermoelectric materials comprises step:
According to (GeTe) 1-x(Ag 8GeTe 6) xThe numerical value of middle x take metal Ge, Te and Ag simple substance as raw material, takes by weighing raw material according to proportioning;
The raw material that takes by weighing is made formation GeTe base alloy;
Described GeTe base alloying pellet is clayed into power; And
The powder that described GeTe base alloying pellet is worn into carries out discharge plasma sintering, obtains described composite thermoelectric material (GeTe) 1-x(Ag 8GeTe 6) x
4. the preparation method of composite thermoelectric material as claimed in claim 3, it is characterized in that, the raw material that takes by weighing is made the method that forms GeTe base alloy is: take by weighing to such an extent that raw material is packed in the quartz ampoule with described, vacuumize the good quartz ampoule of rear soldering and sealing and place Muffle furnace to react, reaction temperature is 900 ° of C, reaction time is 20 hours, obtains GeTe base alloy.
5. the preparation method of composite thermoelectric material as claimed in claim 4; it is characterized in that; the method that described GeTe base alloying pellet is clayed into power is: reaction is obtained GeTe base alloy grind into powder; put into ball grinder with abrading-ball; be filled with Ar gas after the forvacuum, adopt planetary ball mill under the protection of Ar gas, to make attritive powder, 200 ~ 400 rev/mins of drum'ss speed of rotation; ratio of grinding media to material 20:1, Ball-milling Time 0.5 ~ 14 hour.
6. the preparation method of composite thermoelectric material as claimed in claim 5 is characterized in that, the powder that described GeTe base alloying pellet is worn into carries out discharge plasma sintering, obtains described composite thermoelectric material (GeTe) 1-x(Ag 8GeTe 6) xMethod be: powder behind the ball milling is carried out plasma discharging (SPS) sintering under vacuum environment, vacuum degree is 1 * 10 -2Pa, pressure 30 ~ 50MPa, 600 ~ 650 ° of C of sintering temperature, temperature retention time 5 ~ 10 minutes namely obtains Ag 8GeTe 6Be distributed in the unleaded composite thermoelectric material in the matrix GeTe matrix.
CN201210400957.6A 2012-10-19 2012-10-19 A kind of GeTe base composite thermoelectric material and preparation method thereof Active CN102931336B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210400957.6A CN102931336B (en) 2012-10-19 2012-10-19 A kind of GeTe base composite thermoelectric material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210400957.6A CN102931336B (en) 2012-10-19 2012-10-19 A kind of GeTe base composite thermoelectric material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN102931336A true CN102931336A (en) 2013-02-13
CN102931336B CN102931336B (en) 2016-08-03

Family

ID=47646091

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210400957.6A Active CN102931336B (en) 2012-10-19 2012-10-19 A kind of GeTe base composite thermoelectric material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN102931336B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103552998A (en) * 2013-10-17 2014-02-05 厦门大学 Preparation method of GeTe microcrystal
CN104733610A (en) * 2013-12-23 2015-06-24 杭州华为数字技术有限公司 Metal-doped germanium tellurium base resistance change storage material, preparation method and resistance change unit device
CN106098923A (en) * 2016-07-21 2016-11-09 同济大学 A kind of argyrodite thermoelectric material and preparation method thereof
CN107799646A (en) * 2017-09-14 2018-03-13 同济大学 A kind of alloy thermoelectric semiconductor material and preparation method thereof
CN108735888A (en) * 2018-04-27 2018-11-02 同济大学 Novel Ge antimony tellurium compound thermoelectric material with high concentration vacancy and preparation method thereof
CN109950389A (en) * 2019-03-18 2019-06-28 清华大学 Middle warm area high performance thermoelectric material preparation method and middle warm area high performance thermoelectric material
CN110491988A (en) * 2019-07-31 2019-11-22 深圳大学 A kind of GeSe base thermoelectricity material and its preparation method and application of Ag doping

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1943052A (en) * 2004-04-14 2007-04-04 纳幕尔杜邦公司 High performance thermoelectric materials and their method of preparation
CN101246980A (en) * 2008-03-26 2008-08-20 中国矿业大学(北京) Solid-oxide fuel battery and pyroelectric material associated power generation system
CN101579885A (en) * 2009-05-27 2009-11-18 浙江大学 Method for preparing (AgSbTe2)<x>(GeTe)<100-x>-based thermoelectric material by melt-spinning
CN101613814A (en) * 2009-07-17 2009-12-30 武汉理工大学 A kind of quick preparation n type Bi 2(Se xTe 1-x) 3The method of thermoelectric material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1943052A (en) * 2004-04-14 2007-04-04 纳幕尔杜邦公司 High performance thermoelectric materials and their method of preparation
CN101246980A (en) * 2008-03-26 2008-08-20 中国矿业大学(北京) Solid-oxide fuel battery and pyroelectric material associated power generation system
CN101579885A (en) * 2009-05-27 2009-11-18 浙江大学 Method for preparing (AgSbTe2)<x>(GeTe)<100-x>-based thermoelectric material by melt-spinning
CN101613814A (en) * 2009-07-17 2009-12-30 武汉理工大学 A kind of quick preparation n type Bi 2(Se xTe 1-x) 3The method of thermoelectric material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李燕: "GeTe系非晶相变薄膜的制备及性能研究", 《电子科技大学学报》, vol. 25, no. 6, 31 December 1996 (1996-12-31), pages 621 - 624 *
陈玮等: "As2Se3 - GeTe - AgI 和As2Se3 - GeTe - CuI 系统", 《硅酸盐学报》, vol. 26, no. 5, 31 October 1998 (1998-10-31), pages 610 - 617 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103552998A (en) * 2013-10-17 2014-02-05 厦门大学 Preparation method of GeTe microcrystal
CN103552998B (en) * 2013-10-17 2015-02-04 厦门大学 Preparation method of GeTe microcrystal
CN104733610A (en) * 2013-12-23 2015-06-24 杭州华为数字技术有限公司 Metal-doped germanium tellurium base resistance change storage material, preparation method and resistance change unit device
CN104733610B (en) * 2013-12-23 2017-12-15 杭州华为数字技术有限公司 Metal-doped germanium telluro resistance-change memory material and preparation method and resistive element device
CN106098923A (en) * 2016-07-21 2016-11-09 同济大学 A kind of argyrodite thermoelectric material and preparation method thereof
CN107799646A (en) * 2017-09-14 2018-03-13 同济大学 A kind of alloy thermoelectric semiconductor material and preparation method thereof
CN107799646B (en) * 2017-09-14 2020-04-28 同济大学 Alloy thermoelectric semiconductor material and preparation method thereof
CN108735888A (en) * 2018-04-27 2018-11-02 同济大学 Novel Ge antimony tellurium compound thermoelectric material with high concentration vacancy and preparation method thereof
CN109950389A (en) * 2019-03-18 2019-06-28 清华大学 Middle warm area high performance thermoelectric material preparation method and middle warm area high performance thermoelectric material
CN110491988A (en) * 2019-07-31 2019-11-22 深圳大学 A kind of GeSe base thermoelectricity material and its preparation method and application of Ag doping

Also Published As

Publication number Publication date
CN102931336B (en) 2016-08-03

Similar Documents

Publication Publication Date Title
CN102931336A (en) Germanium telluride (GeTe) based composite thermoelectric material and preparation method thereof
Elsheikh et al. A review on thermoelectric renewable energy: Principle parameters that affect their performance
CN104263986B (en) A kind of method of supper-fast preparation high-performance SnTe base thermoelectricity material
CN103910339B (en) Ultrafast preparation method of high-performance BiCuSeO-based blocky thermoelectric material having nanometer layered structure
JP5468554B2 (en) Semiconductor materials containing doped tin telluride for thermoelectric applications
CN105671344B (en) One step prepares high-performance CoSb3The method of base thermoelectricity material
CN103928604A (en) Method for fast manufacturing n-type bismuth telluride based high-performance thermoelectric materials
CN102931335A (en) Graphene compounded with stibine cobalt base skutterudite thermoelectric material and preparation method of material
Weller et al. Rapid synthesis of zinc and nickel co-doped tetrahedrite thermoelectrics by reactive spark plasma sintering and mechanical alloying
CN103436723A (en) Method for quickly preparing high-performance Mg2Si-based thermoelectric material
CN101101954A (en) A cadmium-stibium-based p type thermal electrical material and its making method
CN104402063B (en) A kind of quickly preparation high-performance CuFeS2the method of thermoelectric material
CN104004935B (en) A kind of method of supper-fast preparation high-performance high manganese-silicon thermoelectric material
CN107176589B (en) It is a kind of to prepare nanosizing Mg3Sb2The method of thermoelectric material
JP6250172B2 (en) High performance index P-type FeNbTiSb thermoelectric material and preparation method thereof
CN105219995B (en) A kind of preparation method of n type thermoelectric material NbCoSb
CN103436724B (en) Method for quickly preparing high-performance PbS(1-x)Sex based thermoelectric material
CN101338386B (en) Method for preparing TiNi Sn based thermoelectric compounds
CN101275192B (en) Composite nanometer ZnSb-based thermoelectric material and preparation thereof
CN103247752B (en) Ge-Pb-Te-Se composite thermoelectric material and preparation method thereof
CN104404284B (en) Method for rapid preparation of high performance AgBiSe2 block thermoelectric material
CN106129241A (en) Solid reaction process prepares the method for stacking faults chalcogenide thermoelectric material
CN103924109B (en) The supper-fast preparation high-performance CoSb of a kind of Self-propagating Sintering Synthetic 3the method of base thermoelectricity material
CN103811653B (en) Multi-cobalt p type skutterudite filled thermoelectric material and preparation method thereof
CN101857928A (en) P-type Zn4Sb3 based 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
C14 Grant of patent or utility model
GR01 Patent grant