CN103924109B - The supper-fast preparation high-performance CoSb of a kind of Self-propagating Sintering Synthetic 3the method of base thermoelectricity material - Google Patents
The supper-fast preparation high-performance CoSb of a kind of Self-propagating Sintering Synthetic 3the method of base thermoelectricity material Download PDFInfo
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Abstract
The present invention relates to the supper-fast preparation high-performance CoSb of a kind of Self-propagating Sintering Synthetic
3the novel method of base thermoelectricity material, comprises the following steps: 1) by chemical formula Co
4-xm
xsb
12-yte
yin the stoichiometric ratio of each element carries out taking Co powder, M powder, Sb powder, Te powder be raw material,? 0≤x≤1.0,0≤y≤1.0, M is Fe or Ni, and raw material powder mixing is pressed into block idiosome; 2) block for step 1) gained idiosome is caused self-propagating high-temperature building-up reactions, reacted rear cooling and obtained single-phase CoSb
3compound; 3) by step 2) product grind into powder, carries out discharge plasma activated sintering, obtains pure single-phase high-performance CoSb
3base thermoelectricity material.The present invention has the advantages such as speed of response is fast, technique is simple, energy-efficient and reproducible, whole preparation process can complete in 20min, and gained block thermoelectric figure of merit <i>ZT</iGreatT.G reaT.GT can reach 0.98 at 875K.
Description
Technical field
The invention belongs to technical field of new energy material preparation, be specifically related to a kind of high-performance CoSb of preparation fast
3the novel method of base thermoelectricity material.
Background technology
Now, the physical environment that the mankind depend on for existence day by day worsen and fossil energy in exhaustion rapidly, so the development and application of the reproducible new forms of energy of environmentally friendly type has become the common issue that the whole world faces.For alleviating the burden of environmental degradation and energy consumption, in world wide, sight focuses on and finds and develop reproducible new forms of energy by a lot of 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, high conversion efficiency needs material high
zTvalue, wherein
zT=
as 2 t/
k, wherein
a,
swith
trepresent the Seebeck coefficient of material respectively, specific conductivity and absolute temperature,
kfor the thermal conductivity of material.Therefore, the advanced subject that the thermoelectric material with high ZT value is thermoelectric material research field is found.
CoSb
3the thermoelectric material of matrix system, has excellent electrical property and lower thermal conductivity, thus has higher
zTvalue.Meanwhile, CoSb
3have many good qualities: material cost is low, block good mechanical property, component is environmental protection more, and synthesis technique is ripe simple, military service stable performance etc.
At present, CoSb is prepared
3the method of base thermoelectricity material mainly adopts long-time diffusion melting annealing method and melt to revolve methods such as getting rid of.But melting annealing method generally needs 7-14 days, and the cycle is oversize, is unfavorable for commercial applications.Although melt revolves the method for getting rid of shorten preparation time greatly, its single gets rid of band limited quality and higher to the requirement of operating equipment.Therefore, a kind of simple and fast, less energy consumption, reproducible synthetic method are for preparation CoSb
3base thermoelectricity material, seems extremely important.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists for above-mentioned prior art and provides a kind of supper-fast preparation high-performance CoSb
3the novel method of base thermoelectricity material, the advantages such as this method has that speed of response is fast, technique is simple, reproducible, the energy-efficient and conducting material thermoelectricity performance of preparation is excellent.
The technical scheme that the problem that the present invention is the above-mentioned proposition of solution adopts is:
A kind of supper-fast preparation high-performance CoSb
3the novel method of base thermoelectricity material, it comprises the following steps:
1) by Co
4-xm
xsb
12-yte
ythe stoichiometric ratio of each element carries out taking Co powder, M powder, Sb powder, Te powder as raw material, wherein 0≤x≤1.0,0≤y≤1.0, and M is Fe or Ni, then that raw material powder ground and mixed is even, and the powder mixed is pressed into block idiosome;
2) block for step 1) gained idiosome is caused self-propagating high-temperature building-up reactions (SHS, Self-propagatingHigh-temperatureSynthesis) and reacted rear naturally cooling, all can obtain single-phase CoSb
3compound;
3) by step 2) products therefrom grind into powder, carries out discharge plasma activated sintering (PAS, PlasmaActivatedSintering), obtains pure single-phase high-performance CoSb
3base thermoelectricity material.
In such scheme, in described step 1), the quality purity of Co powder, Sb powder, Te powder, M powder is equal; Pressing process is: pressurize 5min under 4MPa.
In such scheme, described step 2) in self-propagating reaction adopt the some end of type of heating to block idiosome to heat, detonate initiation self-propagating reaction in local.
In such scheme, described step 2) in use air atmosphere or vacuum in self-propagating reaction.
In such scheme, the process that described step 3) powder carries out plasma activated sintering is: powder being loaded diameter is compacting in the graphite jig of 15mm, then sinter under vacuum is less than 10Pa and sintering pressure is 40MPa condition, 650 DEG C are warmed up to, sintering densification time 8min with the temperature rise rate of 100 DEG C/min.
Above-mentioned preparation method obtains high-performance CoSb
3base compact block thermoelectric material, wherein Co
4sb
11.4te
0.6the thermoelectricity capability figure of merit
zT0.98 is reached at 875K.
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 Co powder, Sb powder, Te powder, Fe powder and Ni 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 CoSb needed for rear formation
3base thermoelectricity material powder.
With existing CoSb
3preparation method compares, and advantage of the present invention is:
The first, the present invention adopts SHS technology to prepare CoSb first
3base thermoelectricity material, has that speed of response is fast, equipment is simple, an advantage such as reproducible, energy-efficient and temperature rate is fast;
The second, the present invention can prepare CoSb in 20min
3base compact block thermoelectric material, its thermoelectricity capability can reach the optimum value of this composition of report at present
zT~ 0.98.
Accompanying drawing explanation
The XRD figure that Fig. 1 (a) is block after powder after SHS in embodiment 1 and PAS is composed; Fig. 1 (b) is embodiment 1 step 2) in the SEM figure (from left to right amplify respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM that Fig. 1 (c) is gained block thermoelectric material in embodiment 1 step 3) schemes (from left to right amplifying 5.00k times and 20.00k times respectively).
The XRD figure that Fig. 2 (a) is block after powder after SHS in embodiment 2 and PAS is composed; Fig. 2 (b) is embodiment 2 step 2) in the SEM figure (from left to right amplify respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM that Fig. 2 (c) is gained block thermoelectric material in embodiment 2 step 3) schemes (from left to right amplifying 5.00k times and 20.00k times respectively).
The XRD figure that Fig. 3 (a) is block after powder after SHS in embodiment 3 and PAS is composed; Fig. 3 (b) is embodiment 3 step 2) in the SEM figure (from left to right amplify respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM that Fig. 3 (c) is gained block thermoelectric material in embodiment 3 step 3) schemes (from left to right amplifying 5.00k times and 20.00k times respectively).
The XRD figure that Fig. 4 (a) is block after powder after SHS in embodiment 4 and PAS is composed; Fig. 4 (b) is embodiment 4 step 2) in the SEM figure (from left to right amplify respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM that Fig. 4 (c) is gained block thermoelectric material in embodiment 4 step 3) schemes (from left to right amplifying 5.00k times and 20.00k times respectively).
The XRD figure that Fig. 5 (a) is block after powder after SHS in embodiment 5 and PAS is composed; Fig. 5 (b) is embodiment 4 step 2) in the SEM figure (from left to right amplify respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM that Fig. 5 (c) is gained block thermoelectric material in embodiment 5 step 3) schemes (from left to right amplifying 5.00k times and 20.00k times respectively).
The XRD figure that Fig. 6 (a) is block after powder after SHS in embodiment 6 and PAS is composed; Fig. 6 (b) is embodiment 5 step 2) in the SEM figure (from left to right amplify respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM that Fig. 6 (c) is gained block thermoelectric material in embodiment 6 step 3) schemes (from left to right amplifying 5.00k times and 20.00k times respectively).
Fig. 7 (a) is Co after PAS sintering in embodiment 1 step 3)
4sb
12block
zTvalue and bibliographical information method used prepare pure tin white cobalt
zTbe worth temperature variant graph of a relation, the method that wherein bibliographical information is used is: mechanical alloying prepares pure tin white cobalt in conjunction with pressure sintering, and preparation time is approximately 45h.
Fig. 7 (b) is Co after PAS sintering in embodiment 2 step 3)
3.5ni
0.5sb
12block
zTvalue and bibliographical information method used prepare the tin white cobalt mixing Ni
zTbe worth temperature variant graph of a relation, the method that wherein bibliographical information is used is: melting annealing method mixes the tin white cobalt of Ni in conjunction with discharge plasma sintering preparation, and preparation time is approximately 240h.
Fig. 7 (c) is Co after PAS sintering in embodiment 6 step 3)
4sb
11.4te
0.6block
zTvalue and bibliographical information method used prepare the tin white cobalt mixing Te
zTbe worth temperature variant graph of a relation, the method that wherein bibliographical information is used is: melting annealing method mixes the tin white cobalt of Te in conjunction with discharge plasma sintering preparation, and preparation time is approximately 168h.
Embodiment
For a better understanding of the present invention, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
In following embodiment, the quality purity of Co powder, Sb powder, Te powder, Fe powder and Ni powder is equal.
embodiment 1
A kind of high-performance CoSb of preparation fast
3the novel method of base thermoelectricity material, it comprises the following steps:
1) by Co
4sb
12the stoichiometric ratio of each atom carries out weighing Co powder, Sb powder as raw material, raw material powder total mass 4g, then that their ground and mixed is even, the powder mixed is pressed into the cylindrical block block (4MPa pressurize 5min) that diameter is 10mm;
2) step 1) gained block is carried out in air atmosphere lit-end initiation SHS process reaction (SHS, Self-propagatingHigh-temperatureSynthesis) and react rear naturally cooling;
3) by step 2) products therefrom grind into powder, carry out plasma activated sintering (PAS, PlasmaActivatedSintering), powder is loaded compacting in the graphite jig of 16mm, then sinter under vacuum is less than 10Pa and sintering pressure is 40MPa condition, be warmed up to 650 DEG C with the temperature rise rate of 100 DEG C/min, the sintering densification time is 8min, obtains Co
4sb
12compact block thermoelectric material.
The XRD figure that Fig. 1 (a) is block after powder after SHS and PAS is composed; Fig. 1 (b) is step 2) in the SEM figure (from left to right amplify respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM that Fig. 1 (c) is middle step 3) gained block thermoelectric material schemes (from left to right amplifying 5.00k times and 20.00k times respectively).As can be seen from Figure 1, after SHS, products therefrom is single-phase CoSb
3compound, only has the Sb dephasign of minute quantity; After PAS, gained block is complete single-phase Co
4sb
12compound, is dispersed with the nano-pore structure of a lot of 20-100nm at crystal boundary, and intercrystalline combines closely, is the block thermoelectric material of densification.
embodiment 2
A kind of high-performance CoSb of preparation fast
3the novel method of base thermoelectricity material, it comprises the following steps:
1) by Co
3.5ni
0.5sb
12the stoichiometric ratio of each element carries out weighing Co powder, Sb powder and Ni powder as raw material, raw material powder total mass 4g, then that their ground and mixed is even, the powder mixed is pressed into the cylindrical block block (4MPa pressurize 5min) that diameter is 10mm;
2) step 1) gained block is carried out in air atmosphere lit-end initiation self-propagating reaction (SHS, Self-propagatingHigh-temperatureSynthesis) and react rear naturally cooling;
3) by step 2) products therefrom grind into powder, carry out discharge plasma activated sintering (PAS, PlasmaActivatedSintering), powder is loaded compacting in the graphite jig of 16mm, then sinter under vacuum is less than 10Pa and sintering pressure is 40MPa condition, be warmed up to 650 DEG C with the temperature rise rate of 100 DEG C/min, the sintering densification time is 8min, obtains Co
3.5ni
0.5sb
12compact block thermoelectric material.
The XRD figure that Fig. 2 (a) is block after powder after SHS and PAS is composed; Fig. 2 (b) is step 2) in the SEM figure (from left to right amplify respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM that Fig. 2 (c) is middle step 3) gained block thermoelectric material schemes (from left to right amplifying 5.00k times and 20.00k times respectively).As can be seen from Figure 2, after SHS, products therefrom is single-phase CoSb
3compound, only has the Sb dephasign of minute quantity; After PAS, gained block is complete single-phase Co
3.5ni
0.5sb
12compound, is dispersed with the nano-pore structure of a lot of 20-100nm at crystal boundary, and intercrystalline combines closely, is the block thermoelectric material of densification.
embodiment 3
A kind of high-performance CoSb of preparation fast
3the novel method of base thermoelectricity material, it comprises the following steps:
1) by Co
3.8fe
0.2sb
12the stoichiometric ratio of each atom carries out weighing Co powder, Sb powder, Fe powder as raw material, raw material powder total mass 4g, then that their ground and mixed is even, the powder mixed is pressed into the cylindrical block block (4MPa pressurize 5min) that diameter is 10mm;
2) step 1) gained block is carried out in air atmosphere lit-end initiation self-propagating reaction (SHS, Self-propagatingHigh-temperatureSynthesis) and react rear naturally cooling;
3) by step 2) products therefrom grind into powder, carry out discharge plasma activated sintering (PAS, PlasmaActivatedSintering), powder is loaded compacting in the graphite jig of 16mm, then sinter under vacuum is less than 10Pa and sintering pressure is 40MPa condition, be warmed up to 650 DEG C with the temperature rise rate of 100 DEG C/min, the sintering densification time is 8min, obtains Co
3.8fe
0.2sb
12compact block thermoelectric material.
The XRD figure that Fig. 3 (a) is block after powder after SHS and PAS is composed; Fig. 3 (b) is step 2) in the SEM figure (from left to right amplify respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM that Fig. 3 (c) is middle step 3) gained block thermoelectric material schemes (from left to right amplifying 5.00k times and 20.00k times respectively).As can be seen from Figure 3, after SHS, products therefrom is single-phase CoSb
3compound, only has the Sb dephasign of minute quantity; After PAS, gained block is complete single-phase Co
3.8fe
0.2sb
12compound, is dispersed with the nano-pore structure of a lot of 20-100nm at crystal boundary, and intercrystalline combines closely, is the block thermoelectric material of densification.
embodiment 4
A kind of high-performance CoSb of preparation fast
3the novel method of base thermoelectricity material, it comprises the following steps:
1) by Co
4sb
11.8te
0.2the stoichiometric ratio of each atom carries out weighing Co powder, Sb powder, Te powder as raw material, raw material powder total mass 4g, then that their ground and mixed is even, the powder mixed is pressed into the cylindrical block block (4MPa pressurize 5min) that diameter is 10mm;
2) step 1) gained block is carried out in air atmosphere lit-end initiation self-propagating reaction (SHS, Self-propagatingHigh-temperatureSynthesis) and react rear naturally cooling;
3) by step 2) products therefrom grind into powder, carry out discharge plasma activated sintering (PAS, PlasmaActivatedSintering), powder is loaded compacting in the graphite jig of 16mm, then sinter under vacuum is less than 10Pa and sintering pressure is 40MPa condition, be warmed up to 650 DEG C with the temperature rise rate of 100 DEG C/min, the sintering densification time is 8min, obtains Co
4sb
11.8te
0.2compact block thermoelectric material.
The XRD figure that Fig. 4 (a) is block after powder after SHS and PAS is composed; Fig. 4 (b) is step 2) in the SEM figure (from left to right amplify respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM that Fig. 4 (c) is middle step 3) gained block thermoelectric material schemes (from left to right amplifying 5.00k times and 20.00k times respectively).As can be seen from Figure 4, after SHS, products therefrom is single-phase CoSb
3compound, only has the Sb dephasign of minute quantity; After PAS, gained block is complete single-phase Co
4sb
11.8te
0.2compound, is dispersed with the nano-pore structure of a lot of 20-100nm at crystal boundary, and intercrystalline combines closely, is the block thermoelectric material of densification.
embodiment 5
A kind of high-performance CoSb of preparation fast
3the novel method of base thermoelectricity material, it comprises the following steps:
1) by Co
4sb
11.6te
0.4the stoichiometric ratio of each atom carries out weighing Co powder, Sb powder, Te powder as raw material, raw material powder total mass 4g, then that their ground and mixed is even, the powder mixed is pressed into the cylindrical block block (4MPa pressurize 5min) that diameter is 10mm;
2) step 1) gained block is carried out in air atmosphere lit-end initiation self-propagating reaction (SHS, Self-propagatingHigh-temperatureSynthesis) and react rear naturally cooling;
3) by step 2) products therefrom grind into powder, carry out discharge plasma activated sintering (PAS, PlasmaActivatedSintering), powder is loaded compacting in the graphite jig of 16mm, then sinter under vacuum is less than 10Pa and sintering pressure is 40MPa condition, be warmed up to 650 DEG C with the temperature rise rate of 100 DEG C/min, the sintering densification time is 8min, obtains Co
4sb
11.6te
0.4compact block thermoelectric material.
The XRD figure that Fig. 5 (a) is block after powder after SHS and PAS is composed; Fig. 5 (b) is step 2) in the SEM figure (from left to right amplify respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM that Fig. 5 (c) is middle step 3) gained block thermoelectric material schemes (from left to right amplifying 5.00k times and 20.00k times respectively).As can be seen from Figure 5, after SHS, products therefrom is single-phase CoSb
3compound, only has the Sb dephasign of minute quantity.After PAS, gained block is complete single-phase Co
4sb
11.6te
0.4compound, is dispersed with the nano-pore structure of a lot of 20-100nm at crystal boundary, and intercrystalline combines closely, is the block thermoelectric material of densification.
embodiment 6
A kind of high-performance CoSb of preparation fast
3the novel method of base thermoelectricity material, it comprises the following steps:
1) by Co
4sb
11.4te
0.6the stoichiometric ratio of each atom carries out weighing Co powder, Sb powder, Te powder as raw material, raw material powder total mass 4g, then that their ground and mixed is even, the powder mixed is pressed into the cylindrical block block (4MPa pressurize 5min) that diameter is 10mm;
2) step 1) gained block is carried out in air atmosphere lit-end initiation self-propagating reaction (SHS, Self-propagatingHigh-temperatureSynthesis) and react rear naturally cooling;
3) by step 2) products therefrom grind into powder, carry out discharge plasma activated sintering (PAS, PlasmaActivatedSintering), powder is loaded compacting in the graphite jig of 16mm, then sinter under vacuum is less than 10Pa and sintering pressure is 40MPa condition, be warmed up to 650 DEG C with the temperature rise rate of 100 DEG C/min, the sintering densification time is 8min, obtains Co
4sb
11.4te
0.6compact block thermoelectric material.
The XRD figure that Fig. 6 (a) is block after powder after SHS and PAS is composed; Fig. 6 (b) is step 2) in the SEM figure (from left to right amplify respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM that Fig. 6 (c) is middle step 3) gained block thermoelectric material schemes (from left to right amplifying 5.00k times and 20.00k times respectively).As can be seen from Figure 6, after SHS, products therefrom is single-phase CoSb
3compound, only has the Sb dephasign of minute quantity.After PAS, gained block is complete single-phase Co
4sb
11.4te
0.6compound, is dispersed with the nano-pore structure of a lot of 20-100nm at crystal boundary, and intercrystalline combines closely, is the block thermoelectric material of densification; Thermoelectric material prepared by this kind of method can reach current best level and be
zT~ 0.98.
Claims (5)
1. the supper-fast preparation high-performance CoSb of Self-propagating Sintering Synthetic
3the method of base thermoelectricity material, is characterized in that it comprises the following steps:
1) by chemical formula Co
4-xm
xsb
12-yte
yin the stoichiometric ratio of each element carry out taking Co powder, M powder, Sb powder, Te powder as raw material, wherein x and y is all more than or equal to 0 to be less than or equal to 1.0, M is Fe or Ni, then that raw material powder ground and mixed is even, and the powder compression mixed is become block idiosome;
2) block for step 1) gained idiosome is caused self-propagating high-temperature building-up reactions, reacted rear naturally cooling, all can obtain single-phase CoSb
3compound;
3) by step 2) products therefrom grind into powder, carries out discharge plasma activated sintering, obtains pure single-phase high-performance CoSb
3base thermoelectricity material;
In described step 3), powder carries out the process of discharge plasma activated sintering and is: by step 2) products therefrom powder sinters under vacuum is less than 10Pa and sintering pressure is 40MPa condition, 650 DEG C are warmed up to, sintering densification time 8min with the temperature rise rate of 100 DEG C/min.
2. one according to claim 1 prepares high-performance CoSb fast
3the method of base thermoelectricity material, is characterized in that the quality purity of Co powder in described step 1), Sb powder, Te powder, M powder is all more than or equal to 99.9%; Pressing process is: pressurize 5min under 4MPa.
3. one according to claim 1 prepares high-performance CoSb fast
3the method of base thermoelectricity material, is characterized in that described step 2) in self-propagating reaction adopt the some end of type of heating to block idiosome to heat, detonate initiation self-propagating reaction in local.
4. method according to claim 1 obtains high-performance CoSb
3base compact block thermoelectric material.
5. high-performance CoSb according to claim 4
3base compact block thermoelectric material, is characterized in that gained CoSb
3base compact block thermoelectric material is Co
4sb
11.4te
0.6time, its thermoelectricity capability figure of merit
zT0.98 is reached at 875K.
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310567912.2A CN103924109B (en) | 2013-11-15 | 2013-11-15 | The supper-fast preparation high-performance CoSb of a kind of Self-propagating Sintering Synthetic 3the method of base thermoelectricity material |
| JP2015540043A JP6219399B2 (en) | 2013-03-19 | 2014-03-17 | Determination method of self-propagating combustion synthesis and preparation method of thermoelectric compounds based on the new criteria |
| EP14767900.5A EP2977129B1 (en) | 2013-03-19 | 2014-03-17 | Thermoelectric compound preparation based on self-propagating combustion synthesis new criterion |
| US14/441,446 US10500642B2 (en) | 2013-03-19 | 2014-03-17 | Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof |
| PCT/CN2014/000287 WO2014146485A1 (en) | 2013-03-19 | 2014-03-17 | Thermoelectric compound preparation based on self-propagating combustion synthesis new criterion |
| US16/667,143 US10913117B2 (en) | 2013-03-19 | 2019-10-29 | Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof |
| US16/667,158 US10913118B2 (en) | 2013-03-19 | 2019-10-29 | Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof |
| US16/667,081 US10913114B2 (en) | 2013-03-19 | 2019-10-29 | Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof |
| US16/667,110 US10913115B2 (en) | 2013-03-19 | 2019-10-29 | Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof |
| US16/667,173 US10913119B2 (en) | 2013-03-19 | 2019-10-29 | Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof |
| US16/667,180 US11433456B2 (en) | 2013-03-19 | 2019-10-29 | Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof |
| US16/667,128 US10913116B2 (en) | 2013-03-19 | 2019-10-29 | Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof |
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| CN106191522B (en) * | 2016-07-12 | 2017-11-10 | 中国科学院上海硅酸盐研究所 | A kind of method that laser efficiently prepares skutterudite thermoelectric material |
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| CN103165809A (en) * | 2013-03-19 | 2013-06-19 | 武汉理工大学 | Self-propagating high-temperature rapid one-step synthesis thermoelectric material powder with nanostructure Cu2Se method |
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| CN1594623A (en) * | 2004-06-29 | 2005-03-16 | 武汉理工大学 | Preparation method for nano skutterudite compound pyro electric material |
| CN101347838A (en) * | 2008-09-11 | 2009-01-21 | 清华大学 | Method for preparing Ag nano granule compound CoSb3-based pyroelectric material |
| CN102650005A (en) * | 2011-02-28 | 2012-08-29 | 燕山大学 | High-pressure synthesis preparation method of high-performance densification filled skutterudite thermoelectric material |
| CN103165809A (en) * | 2013-03-19 | 2013-06-19 | 武汉理工大学 | Self-propagating high-temperature rapid one-step synthesis thermoelectric material powder with nanostructure Cu2Se method |
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