CN104944385A - Novel method for quickly preparing high-performance CuInTe2-base thermoelectric material - Google Patents

Novel method for quickly preparing high-performance CuInTe2-base thermoelectric material Download PDF

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Publication number
CN104944385A
CN104944385A CN201510242185.1A CN201510242185A CN104944385A CN 104944385 A CN104944385 A CN 104944385A CN 201510242185 A CN201510242185 A CN 201510242185A CN 104944385 A CN104944385 A CN 104944385A
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powder
cuinte
performance
base
novel method
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唐新峰
梁涛
马世林
谭晓鸣
刘欢
谢鸿耀
苏贤礼
鄢永高
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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Abstract

The invention discloses a novel method for quickly preparing a high-performance CuInTe2-base thermoelectric material, which comprises the following steps: 1) weighing raw materials Cu powder, In powder and Te powder according to the stoichiometric proportion of the elements in the chemical formula Cu[1-x]InTe2 (0<=x<=0.2), grinding and uniformly mixing the powder raw materials, and pressing into a block billet; 2) initiating high-temperature self-propagating synthesis reaction on the block billet obtained in the step 1), and after the reaction finishes, naturally cooling to obtain the nearly-single-phase CuInTe2-base thermoelectric material. The method has the advantages of high reaction speed, simple technique, high efficiency, energy saving, favorable repetitiveness and the like; the whole preparation process can be completed within 15 minutes; and the optimal thermoelectric value of the obtained block can reach 0.58 under 720K.

Description

A kind of high-performance CuInTe of preparation fast 2the novel method of base thermoelectricity material
Technical field
The invention belongs to technical field of new energy material preparation, be specifically related to a kind of high-performance CuInTe of preparation fast 2the novel method of base thermoelectricity material.
Background technology
Current, global physical environment day by day worsens owing to using non-clean energy, the Sustainable development of the serious threat mankind; As everyone knows, the main source of the energy or fossil energy (coal, oil and natural gas) in current world wide, but these energy deposit is on earth extremely limited, along with the progress of human society, these energy are exploited out continually, cause the rapid exhaustion of fossil energy storage capacity; Moreover, some obnoxious flavoures can be got rid of unavoidably in these non-renewable energy use procedures, severe contamination is caused to physical environment.Therefore development of new, eco-friendly renewable and clean energy resource and Energy conversion technology become the public problem of countries in the world scientist.This wherein can realize the focus that thermoelectric generation technology that heat energy and electric energy directly change becomes numerous scientific worker.
Thermoelectric generation technology is the technology utilizing Sai Beike (Seebeck) effect of semi-conductor thermoelectric material and Peltier (Peltier) effect heat energy and electric energy to be carried out directly conversion, comprises thermoelectric power generation and thermoelectric refrigeration two kinds of modes.This technology has that structure is simple, reliability is high, running cost is low, the life-span is long, without drive disk assembly, noiselessness, the advantage such as pollution-free, use temperature scope is wide.Thermoelectric material thermo-electric generation is not only the topmost power supply of current deep-space detection field, and has all obtained at high-technology fields such as vehicle exhaust and other industrial afterheat power generation, sun power and underground heat thermo-electric generations and generally apply.And thermoelectric refrigeration technology in cooling electronic device (infrared, far-infrared photoconductor, high-speed chip etc.), medical device and high-temperature superconductor etc. and many key areas such as conditioning unit such as aerospacecraft, submarine have boundless application prospect.For thermo-electric device, the ZT value that high conversion efficiency needs material high, wherein ZT=α σ 2t/ κ, wherein α, σ and Τ represent the Seebeck coefficient of material respectively, specific conductivity and absolute temperature, and κ is the thermal conductivity of material.Therefore, the advanced subject that the thermoelectric material with high ZT value is thermoelectric material research field is found.
CuInTe 2be direct band-gap semicondictor thermoelectric material, its band gap is about 1.06eV, is typical yellow copper structure.CuInTe 2be middle temperature p-type thermoelectric material, make because its hole concentration is low specific conductivity relatively very low, finally make its thermoelectricity capability not high, current optimization CuInTe 2the thermoelectricity capability of material is mainly set about from its carrier concentration of increase.Wherein increase Cu vacancy concentration by the disappearance of Cu atom and effectively can regulate hole, due to CuInTe 2structure is relatively stable, and Seebeck coefficient is high, and thermal conductivity is lower, because of but a kind of p-type thermoelectric material having very much application prospect.
At present, CuInTe is prepared 2the method of thermoelectric material mainly adopts melting diffusion annealing method.But melting annealing method generally needs 4 ~ 7 days, the complex process related to, preparation cycle is long, is unfavorable for commercial applications.Therefore, need badly and find simple and fast, less energy consumption, reproducible CuInTe further 2thermoelectric material synthetic method.
Summary of the invention
The object of this invention is to provide a kind of high-performance CuInTe of preparation fast 2the novel method of base thermoelectricity material, the method has the features such as speed of response is fast, technique is simple, reproducible, energy-efficient, and obtained material has excellent thermoelectricity capability.
For achieving the above object, the technical solution used in the present invention is, a kind of high-performance CuInTe of preparation fast 2the novel method of base thermoelectricity material, comprises the following steps:
1) with Cu powder, In powder and Te powder for raw material, by chemical formula Cu 1-xinTe 2in the stoichiometric ratio of each element weigh, wherein 0≤x≤0.2, load weighted raw material powder ground and mixed is even, and be pressed into block base substrate;
2) by step 1) block base substrate initiation self-propagating high-temperature building-up reactions (SHS) of gained, react rear naturally cooling, obtain ingot body;
3) by step 2) gained ingot body grind into powder, carries out discharge plasma activated sintering (PAS), obtains single-phase high performance CuInTe 2base thermoelectricity material.
In such scheme, the quality purity of described Cu powder, In powder and Te powder all >=99.9%.
In such scheme, described step 1) in pressing process be: pressurize 3 ~ 8min under 2 ~ 5MPa.
In such scheme, described self-propagating high-temperature building-up reactions adopts the some end of type of heating to block base substrate to heat, and detonate initiation self-propagating reaction in local.
In such scheme, described discharge plasma activated sintering technique is: under vacuum is less than 10Pa and sintering pressure is 40 ~ 50MPa condition, be warmed up to 500 ~ 600 DEG C, sintering densification time 5 ~ 10min with the temperature rise rate of 80 ~ 120 DEG C/min.
The high-performance CuInTe obtained according to such scheme 2base compact block thermoelectric material, wherein Cu 0.95inTe 2thermoelectricity capability figure of merit ZT can reach 0.58 at 720K.
Based on foregoing, under the prerequisite not departing from basic fundamental thought of the present invention, according to ordinary technical knowledge and the means of this area, the amendment of various ways, replacement or change can also be had, as self-propagating reaction atmosphere can be changed to other gas etc. do not reacted with Cu powder, In powder, Te powder to its content.
The present invention needs to provide necessary energy to bring out thermal chemical reaction to raw material, and form combustion wave, reaction after this just proceeds under the support of reacting institute's release of heat before, and self-propagating high-temperature combustion reactions terminates the base thermoelectricity material powder needed for rear formation.
Beneficial effect of the present invention is:
1) the present invention adopts SHS technology to prepare CuInTe first 2base thermoelectricity material, has that speed of response is fast, equipment is simple, an advantage such as reproducible, energy-efficient and temperature rate is fast;
2) the present invention can prepare CuInTe in 15min 2base compact block thermoelectric material, its thermoelectricity capability can reach ZT ~ 0.58, and the additive method higher than bibliographical information prepares the ZT value with component composition.
Accompanying drawing explanation
Fig. 1 (a) in the embodiment of the present invention 1 after SHS the XRD figure spectrum of block after powder and PAS; Fig. 1 (b) is embodiment 1 step 3) in after PAS the temperature variant graph of a relation of block thermoelectric figure of merit ZT.
Fig. 2 (a) in the embodiment of the present invention 2 after SHS the XRD figure spectrum of block after powder and PAS; Fig. 2 (b) is embodiment 2 step 3) in after PAS the temperature variant graph of a relation of block thermoelectric figure of merit ZT.
Fig. 3 (a) in the embodiment of the present invention 3 after SHS the XRD figure spectrum of block after powder and PAS; Fig. 3 (b) is embodiment 3 step 3) in after PAS the temperature variant graph of a relation of block thermoelectric figure of merit ZT.
Fig. 4 is the embodiment of the present invention 2 FESEM figure of block after powder and PAS after SHS; The wherein SHS product morphology figure of Fig. 4 (a) and 4 (b) to be magnification be respectively 10k and 100k, the PAS agglomerate body section shape appearance figure of Fig. 4 (c) and 4 (d) to be magnification be respectively 10k and 100k.
Fig. 5 is the embodiment of the present invention 2 step 3) in CuInTe after PAS 2matrix body ZT value and the temperature variant graph of a relation of bibliographical information ZT value.
Embodiment
For a better understanding of the present invention, illustrate content of the present invention further below in conjunction with drawings and Examples, but content of the present invention is not only confined to the following examples.
In following examples, the quality purity of Cu powder, In powder, Te powder all >=99.9%.
Embodiment 1
A kind of high-performance CuInTe of preparation fast 2the novel method of base thermoelectricity material, comprises the following steps:
1) by chemical formula Cu 1-xinTe 2in the stoichiometric ratio of each element take Cu powder, In powder and Te powder as raw material, wherein x=0, mixes the raw mill taken, and is then pressed into block base substrate (pressure is 2MPa, and the dwell time is 3min);
2) by step 1) the block base substrate of gained causes self-propagating high-temperature building-up reactions (SHS) with local, one end sparking mode and reacted rear naturally cooling, obtains ingot body (close to single-phase CuInTe 2based compound);
3) by step 2) gained ingot body grind into powder, then carries out discharge plasma activated sintering (PAS), obtains single-phase high-performance CuInTe 2base thermoelectricity material.Wherein sintering process parameter is: under vacuum is less than 10Pa and sintering pressure is the condition of 40MPa, be warming up to 500 DEG C of densification sintering 5min with the speed of 80 DEG C/min.
Fig. 1 (a) is the present embodiment XRD figure spectrum of block after powder and PAS after SHS; Show in figure that can to obtain principal phase after SHS be CuInTe 2compound, single-phase CuInTe can be obtained in conjunction with follow-up PAS sintering technology 2compound, the special diffraction peak of its X-ray and CuInTe 2the characteristic peak coupling of JC-PDF standard card (JCPDS#01-081-1937) good, show in conjunction with SHS and PAS, single-phase CuInTe can be obtained in 15min 2thermoelectric material.Fig. 1 (b) is embodiment 1 step 3) in after PAS gained block thermoelectric figure of merit ZT temperature variant graph of a relation in 300 ~ 720K test specification, its ZT value can reach 0.49 at 720K.
Embodiment 2
A kind of high-performance CuInTe of preparation fast 2the novel method of base thermoelectricity material, comprises the following steps:
1) by chemical formula Cu 1-xinTe 2in the stoichiometric ratio of each element take Cu powder, In powder and Te powder as raw material, wherein x=0.05, mixes the raw mill taken, and is then pressed into block base substrate (pressure is 3MPa, and the dwell time is 5min);
2) by step 1) the block base substrate of gained causes self-propagating high-temperature building-up reactions (SHS) with local, one end sparking mode and reacted rear naturally cooling, obtains ingot body (close to single-phase CuInTe 2based compound);
3) by step 2) gained ingot body grind into powder, then carries out discharge plasma activated sintering (PAS), obtains single-phase high-performance CuInTe 2base thermoelectricity material.Wherein sintering process parameter is: under vacuum is less than 10Pa and sintering pressure is the condition of 45MPa, be warming up to 550 DEG C of densification sintering 8min with the speed of 100 DEG C/min.
Fig. 2 (a) is the present embodiment XRD figure spectrum of block after powder and PAS after SHS; Show in figure after SHS reaction that can to obtain principal phase be CuInTe 2compound, obtain single-phase CuInTe in conjunction with follow-up PAS sintering technology 2compound, the special diffraction peak of its X-ray and CuInTe 2the characteristic peak coupling of JC-PDF standard card (JCPDS#01-081-1937) good, show to obtain single-phase CuInTe in 15min in conjunction with SHS and PAS 2base thermoelectricity material.Fig. 2 (b) is embodiment 2 step 3) in after PAS gained block thermoelectric figure of merit ZT temperature variant graph of a relation in 300 ~ 720K test specification, its maximum ZT value reaches 0.58 at 720K.
Embodiment 3
A kind of high-performance CuInTe of preparation fast 2the novel method of base thermoelectricity material, comprises the following steps:
1) by chemical formula Cu 1-xinTe 2in the stoichiometric ratio of each element take Cu powder, In powder and Te powder as raw material, wherein x=0.1, mixes the raw mill taken, and is then pressed into block base substrate (pressure is 5MPa, and the dwell time is 8min);
2) by step 1) the block base substrate of gained causes self-propagating high-temperature building-up reactions (SHS) with local, one end sparking mode and reacted rear naturally cooling, obtains ingot body (close to single-phase CuInTe 2based compound);
3) by step 2) products therefrom grind into powder, then carries out discharge plasma activated sintering (PAS), obtains single-phase high-performance CuInTe 2base thermoelectricity material.Wherein sintering process parameter is under vacuum is less than 10Pa and sintering pressure is the condition of 50MPa, is warming up to 600 DEG C of densification sintering 10min with the speed of 120 DEG C/min.
Fig. 3 (a) is the present embodiment XRD figure spectrum of block after powder and PAS after SHS; Show in figure after SHS reaction that can to obtain principal phase be CuInTe 2compound, obtain single-phase CuInTe in conjunction with follow-up PAS sintering technology 2compound, the special diffraction peak of its X-ray and CuInTe 2the characteristic peak coupling of JC-PDF standard card (JCPDS#01-081-1937) good, show to obtain single-phase CuInTe in 15min in conjunction with SHS and PAS 2block thermoelectric material.Fig. 3 (b) is embodiment 3 step 3) in after PAS the temperature variant graph of a relation of gained block thermoelectric figure of merit ZT, its ZT value, in 300 ~ 720K test specification, reaches 0.53 at 720K.
Fig. 4 is the embodiment of the present invention 2 FESEM figure of block after powder and PAS after SHS; The wherein SHS product morphology figure of Fig. 4 (a) and 4 (b) to be magnification be respectively 10.0k and 100.0k; Its surface after can finding out SHS in figure distributes a lot of nano particle, and its size range is 20 ~ 500nm; The PAS agglomerate body section shape appearance figure of Fig. 4 (c) and 4 (d) to be magnification be respectively 10.0k and 100.0k, block density is very high, and nano particle still exists after sintering, these nano particles may play an important role to reduction thermal conductivity, thus significantly optimize the thermoelectricity capability of material.
Fig. 5 is embodiment 2 step 3) in PAS sintering after CuInTe 2matrix body ZT value and the temperature variant graph of a relation of bibliographical information ZT value.The method that wherein bibliographical information is used is: scorification prepares CuInTe in conjunction with discharge plasma sintering 2base thermoelectricity material, preparation time is approximately 96h.
The foregoing is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, without departing from the concept of the premise of the invention, make some improvement and conversion, these all belong to protection scope of the present invention.

Claims (7)

1. prepare high-performance CuInTe fast for one kind 2the novel method of base thermoelectricity material, is characterized in that, comprises the following steps:
1) with Cu powder, In powder and Te powder for raw material, by chemical formula Cu 1-xinTe 2in the stoichiometric ratio of each element weigh, wherein 0≤x≤0.2, load weighted raw material powder ground and mixed is even, and be pressed into block base substrate;
2) by step 1) gained block base substrate initiation self-propagating high-temperature building-up reactions, react rear naturally cooling, obtain ingot body;
3) by step 2) gained ingot body grind into powder, carries out discharge plasma activated sintering, obtains single-phase high performance CuInTe 2base thermoelectricity material.
2. quick preparation high-performance CuInTe according to claim 1 2the novel method of base thermoelectricity material, is characterized in that, the quality purity of described Cu powder, In powder and Te powder all>=99.9%.
3. quick preparation high-performance CuInTe according to claim 1 2the novel method of base thermoelectricity material, is characterized in that, described step 1) in pressing process be: pressurize 3 ~ 8min under 2 ~ 5MPa.
4. quick preparation high-performance CuInTe according to claim 1 2the novel method of base thermoelectricity material, is characterized in that, described self-propagating high-temperature building-up reactions adopts the some end of type of heating to block base substrate to heat, and detonate initiation self-propagating reaction in local.
5. quick preparation high-performance CuInTe according to claim 1 2the novel method of base thermoelectricity material, it is characterized in that, described discharge plasma activated sintering technique is: under vacuum is less than 10Pa and sintering pressure is 40 ~ 50MPa condition, be warmed up to 500 ~ 600 DEG C, sintering densification time 5 ~ 10min with the temperature rise rate of 80 ~ 120 DEG C/min.
6. described in claim 1, method obtains high-performance CuInTe 2base compact block thermoelectric material.
7. high-performance CuInTe according to claim 6 2base compact block thermoelectric material, is characterized in that, gained CuInTe 2base compact block thermoelectric material is Cu 0.95inTe 2time, its thermoelectricity capability figure of merit ZT reaches 0.58 at 720K.
CN201510242185.1A 2015-05-12 2015-05-12 Novel method for quickly preparing high-performance CuInTe2-base thermoelectric material Pending CN104944385A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108470817A (en) * 2018-01-19 2018-08-31 宁波工程学院 A kind of P-type Cu containing Sb2.856In4Te8Base high temperature thermoelectric material and its preparation process
CN110335936A (en) * 2019-06-28 2019-10-15 清华大学 A kind of indium sulphur base thermoelectricity material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103864026A (en) * 2014-02-19 2014-06-18 宁波工程学院 Cu-In-Zn-Te quaternary p-type thermoelectric semiconductor and preparation process thereof
CN103909262A (en) * 2013-06-07 2014-07-09 武汉理工大学 High-performance Cu2SnSe3 thermoelectric material and rapid preparing method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103909262A (en) * 2013-06-07 2014-07-09 武汉理工大学 High-performance Cu2SnSe3 thermoelectric material and rapid preparing method thereof
CN103864026A (en) * 2014-02-19 2014-06-18 宁波工程学院 Cu-In-Zn-Te quaternary p-type thermoelectric semiconductor and preparation process thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ATSUKO KOSUGA,ET AL.: "Room-Temperature Pressure-Induced Nanostructural CuInTe2 Thermoelectric Material with Low Thermal Conductivity", 《INORGANIC CHEMISTRY》 *
HAVIV GRISARU,ET AL.: "Microwave-Assisted Polyol Synthesis of CuInTe2 and CuInSe2 Nanoparticles", 《INORGANIC CHEMISTRY》 *
RUIHENG LIU,ET AL.: "Ternary compound CuInTe2: a promising thermoelectric material with diamond-like structure", 《CHEMICAL COMMUNICATIONS 》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108470817A (en) * 2018-01-19 2018-08-31 宁波工程学院 A kind of P-type Cu containing Sb2.856In4Te8Base high temperature thermoelectric material and its preparation process
CN108470817B (en) * 2018-01-19 2021-09-28 宁波工程学院 Sb-containing P-type Cu2.856In4Te8Medium-high temperature thermoelectric material and preparation process thereof
CN110335936A (en) * 2019-06-28 2019-10-15 清华大学 A kind of indium sulphur base thermoelectricity material and preparation method thereof

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