CN103924109A - New method for synthesis of super fast prepared high performance CoSb3-based thermoelectric material by self-propagating combustion - Google Patents
New method for synthesis of super fast prepared high performance CoSb3-based thermoelectric material by self-propagating combustion Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 title abstract description 11
- 238000003786 synthesis reaction Methods 0.000 title abstract description 11
- 229910018985 CoSb3 Inorganic materials 0.000 title abstract 4
- 239000000843 powder Substances 0.000 claims abstract description 108
- 238000005245 sintering Methods 0.000 claims abstract description 48
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract 2
- 229910018989 CoSb Inorganic materials 0.000 claims description 36
- 230000005619 thermoelectricity Effects 0.000 claims description 24
- 238000000280 densification Methods 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000009702 powder compression Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000001902 propagating effect Effects 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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Abstract
The invention relates to a new method for synthesis of a super fast prepared high performance CoSb3-based thermoelectric material by self-propagating combustion. The new method comprises the following steps: 1) weighing Co powder, M powder, Sb powder and Te powder as raw materials according to stoichiometric ratio of each element in the chemical formula Co4-xMxSb12-yTey, wherein 0<= x <=1.0, 0<= y <=1.0, M is Fe or Ni, the raw material powder is mixed and pressed into a bulk blank body; 2) triggering high temperature self-propagating synthesis reaction of the bulk blank body obtained by the step 1), and after the reaction cooling to obtain a single phase CoSb3 compound; 3) grinding the product of the step 2) into powder for discharge plasma activated sintering to obtain the pure single phase high performance CoSb3-based thermoelectric material. The method has the advantages of fast reaction speed, simple process, high efficiency, energy conservation, good repeatability, and the like. The whole preparation process can be completed in 20min, and the bulk thermoelectric figure of merit (ZT) is 0.98 at 875K.
Description
Technical field
The invention belongs to new energy materials preparing technical field, be specifically related to a kind of quick preparation high-performance CoSb
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, a lot of scientific workers focus on sight and find and develop reproducible new forms of energy.
Thermoelectric generation technology is to utilize the Sai Beike of semi-conductor thermoelectric material (Seebeck) effect and Peltier (Peltier) effect that heat energy and electric energy are carried out to the directly technology of conversion, comprises two kinds of modes of thermoelectric power generation and thermoelectric refrigeration.That this technology has is simple in structure, 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 in current survey of deep space field, and has all obtained generally application at high-technology fields such as vehicle exhaust and other industrial afterheat power generation, sun power and underground heat thermo-electric generations.And thermoelectric refrigeration technology at aspects such as cooling electronic device (infrared, far-infrared photoconductor, high-speed chip etc.), medical device and high-temperature superconductors and aerospacecraft, submarine etc. with many key areas such as conditioning units, have boundless application prospect.
For thermo-electric device, high conversion efficiency needs material high
zTvalue, wherein
zT=
as 2 t/
k, wherein
a,
swith
tthe Seebeck coefficient that represents respectively material, specific conductivity and absolute temperature,
kthermal conductivity for material.Therefore, finding the thermoelectric material with high ZT value is the advanced subject of thermoelectric material research field.
CoSb
3the thermoelectric material of matrix system, has excellent electrical property and lower thermal conductivity, thereby 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, preparation CoSb
3the method of base thermoelectricity material such as mainly adopts long-time diffusion melting annealing method and melt to revolve to get rid of at the method.Yet melting annealing method generally needs 7-14 days, the cycle is oversize, is unfavorable for commercial applications.Although melt revolves the method for getting rid of, shortened greatly preparation time, its single gets rid of and having relatively high expectations to operating equipment limited with quality.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 to provide a kind of supper-fast preparation high-performance CoSb for the deficiency of above-mentioned prior art existence
3the novel method of base thermoelectricity material, this method has that speed of response is fast, technique is simple, the advantages such as conducting material thermoelectricity performance excellence of reproducible, energy-efficient and preparation.
The present invention is that the technical scheme that the problem of 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) press Co
4-xm
xsb
12-yte
ythe stoichiometric ratio of each element takes Co powder, M powder, Sb powder, Te powder as raw material, 0≤x≤1.0 wherein, and 0≤y≤1.0, M is Fe or Ni, then that raw material powder ground and mixed is even, and the powder mixing is pressed into block idiosome;
2) the block idiosome of step 1) gained is caused to self-propagating high-temperature building-up reactions (SHS, Self-propagating High-temperature Synthesis) and reacted rear naturally cooling, all can obtain single-phase CoSb
3compound;
3) by step 2) products therefrom grind into powder, carry out discharge plasma activated sintering (PAS, Plasma Activated Sintering), obtain pure single-phase high-performance CoSb
3base thermoelectricity material.
In such scheme, the quality purity equal 99.9% of Co powder, Sb powder, Te powder, M powder in described step 1); Pressing process is: pressurize 5min under 4MPa.
In such scheme, described step 2) in, self-propagating reaction adopts a some type of heating to heat the end of block idiosome, and initiation self-propagating reaction detonates in part.
In such scheme, described step 2) in, in self-propagating reaction, use air atmosphere or vacuum.
In such scheme, the process that described step 3) powder carries out plasma activated sintering is: pack powder in the graphite jig that diameter is 15mm compacting, then in vacuum, be less than 10Pa and sintering pressure is under 40MPa condition, to carry out sintering, temperature rise rate with 100 ℃/min is warmed up to 650 ℃, sintering densification time 8min.
Above-mentioned preparation method has obtained high-performance CoSb
3base compact block thermoelectric material, wherein Co
4sb
11.4te
0.6the thermoelectricity capability figure of merit
zTat 875K, reach 0.98.
Take foregoing as basis, do not departing under the prerequisite of basic fundamental thought of the present invention, according to ordinary skill knowledge and the means of this area, self-propagating reaction atmosphere to its content, can also have modification, replacement or the change of various ways, as can be changed to other gas not reacting with Co powder, Sb powder, Te powder, Fe powder and Ni powder etc.
The present invention need to provide necessary energy to bring out thermal chemical reaction to raw material, forms combustion wave, and reaction after this is just proceeded under the support of reacting before institute's release of heat, and self-propagating high-temperature combustion reactions finishes the required CoSb of 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 self propagating high temperature synthetic 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 current report
zT~ 0.98.
Accompanying drawing explanation
Fig. 1 (a) is the XRD figure of block spectrum after powder and PAS after SHS in embodiment 1; Fig. 1 (b) is embodiment 1 step 2) in the SEM figure (from left to right amplify respectively 5.00 k doubly and 20.00 k doubly) of powder after SHS; The SEM figure that Fig. 1 (c) is gained block thermoelectric material in embodiment 1 step 3) (from left to right amplifying respectively 5.00 k doubly and 20.00 k times).
Fig. 2 (a) is the XRD figure of block spectrum after powder and PAS after SHS in embodiment 2; Fig. 2 (b) is embodiment 2 steps 2) in the SEM figure (from left to right amplifying respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM figure that Fig. 2 (c) is gained block thermoelectric material in embodiment 2 step 3) (from left to right amplifying respectively 5.00 k doubly and 20.00 k times).
Fig. 3 (a) is the XRD figure of block spectrum after powder and PAS after SHS in embodiment 3; Fig. 3 (b) is embodiment 3 steps 2) in the SEM figure (from left to right amplify respectively 5.00 k doubly and 20.00 k doubly) of powder after SHS; The SEM figure that Fig. 3 (c) is gained block thermoelectric material in embodiment 3 step 3) (from left to right amplifying respectively 5.00 k doubly and 20.00 k times).
Fig. 4 (a) is the XRD figure of block spectrum after powder and PAS after SHS in embodiment 4; Fig. 4 (b) is embodiment 4 steps 2) in the SEM figure (from left to right amplifying respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM figure that Fig. 4 (c) is gained block thermoelectric material in embodiment 4 step 3) (from left to right amplifying respectively 5.00 k doubly and 20.00 k times).
Fig. 5 (a) is the XRD figure of block spectrum after powder and PAS after SHS in embodiment 5; Fig. 5 (b) is embodiment 4 steps 2) in the SEM figure (from left to right amplifying respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM figure that Fig. 5 (c) is gained block thermoelectric material in embodiment 5 step 3) (from left to right amplifying respectively 5.00 k doubly and 20.00 k times).
Fig. 6 (a) is the XRD figure of block spectrum after powder and PAS after SHS in embodiment 6; Fig. 6 (b) is embodiment 5 steps 2) in the SEM figure (from left to right amplify respectively 5.00 k doubly and 20.00 k doubly) of powder after SHS; The SEM figure that Fig. 6 (c) is gained block thermoelectric material in embodiment 6 step 3) (from left to right amplifying respectively 5.00k doubly and 20.00k times).
Fig. 7 (a) is Co after PAS sintering in embodiment 1 step 3)
4sb
12block
zTvalue and bibliographical information method used is prepared pure tin white cobalt
zTbe worth temperature variant graph of a relation, wherein bibliographical information method used is: mechanical alloying is prepared 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
zTthe tin white cobalt of Ni is mixed in the method preparation used of value and bibliographical information
zTbe worth temperature variant graph of a relation, wherein bibliographical information method used is: melting annealing method is mixed the tin white cobalt of Ni in conjunction with discharge plasma sintering preparation, preparation time is approximately 240h.
Fig. 7 (c) is Co after PAS sintering in embodiment 6 step 3)
4sb
11.4te
0.6block
zTthe tin white cobalt of Te is mixed in the method preparation used of value and bibliographical information
zTbe worth temperature variant graph of a relation, wherein bibliographical information method used is: melting annealing method is mixed the tin white cobalt of Te in conjunction with discharge plasma sintering preparation, preparation time is approximately 168h.
Embodiment
For a better understanding of the present invention, below in conjunction with embodiment, further illustrate content of the present invention, but content of the present invention is not only confined to the following examples.
The quality purity equal 99.9% of Co powder, Sb powder, Te powder, Fe powder and Ni powder in following embodiment.
embodiment 1
A kind of quick preparation high-performance CoSb
3the novel method of base thermoelectricity material, it comprises the following steps:
1) press Co
4sb
12the stoichiometric ratio of each atom weighs Co powder, Sb powder as raw material, and raw material powder total mass 4g is then even by their ground and mixed, and the powder mixing is pressed into the cylindrical block block that diameter is 10mm (4MPa pressurize 5min);
2) step 1) gained block is carried out in air atmosphere to lit-end initiation self propagating high temperature building-up reactions (SHS, Self-propagating High-temperature Synthesis) and reacted rear naturally cooling;
3) by step 2) products therefrom grind into powder, carry out plasma activated sintering (PAS, Plasma Activated Sintering), powder is packed into compacting in the graphite jig of 16mm, then in vacuum, be less than 10Pa and sintering pressure is under 40MPa condition, to carry out sintering, temperature rise rate with 100 ℃/min is warmed up to 650 ℃, and the sintering densification time is 8min, obtains Co
4sb
12compact block thermoelectric material.
Fig. 1 (a) is the XRD figure of block spectrum after powder and PAS after SHS; Fig. 1 (b) is step 2) in the SEM figure (from left to right amplifying respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM figure that Fig. 1 (c) is middle step 3) gained block thermoelectric material (from left to right amplifying respectively 5.00k doubly and 20.00k times).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, at the distributing nano-pore structure of a lot of 20-100nm of crystal boundary, and intercrystalline is in conjunction with closely, is fine and close block thermoelectric material.
embodiment 2
A kind of quick preparation high-performance CoSb
3the novel method of base thermoelectricity material, it comprises the following steps:
1) press Co
3.5ni
0.5sb
12the stoichiometric ratio of each element weighs Co powder, Sb powder and Ni powder as raw material, and raw material powder total mass 4g is then even by their ground and mixed, and the powder mixing is pressed into the cylindrical block block that diameter is 10mm (4MPa pressurize 5min);
2) step 1) gained block is carried out in air atmosphere to lit-end initiation self-propagating reaction (SHS, Self-propagating High-temperature Synthesis) and reacted rear naturally cooling;
3) by step 2) products therefrom grind into powder, carry out discharge plasma activated sintering (PAS, Plasma Activated Sintering), powder is packed into compacting in the graphite jig of 16mm, then in vacuum, be less than 10Pa and sintering pressure is under 40MPa condition, to carry out sintering, temperature rise rate with 100 ℃/min is warmed up to 650 ℃, and the sintering densification time is 8min, obtains Co
3.5ni
0.5sb
12compact block thermoelectric material.
Fig. 2 (a) is the XRD figure of block spectrum after powder and PAS after SHS; Fig. 2 (b) is step 2) in the SEM figure (from left to right amplify respectively 5.00 k doubly and 20.00 k doubly) of powder after SHS; The SEM figure that Fig. 2 (c) is middle step 3) gained block thermoelectric material (from left to right amplifying respectively 5.00 k doubly and 20.00 k times).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, at the distributing nano-pore structure of a lot of 20-100nm of crystal boundary, and intercrystalline is in conjunction with closely, is fine and close block thermoelectric material.
embodiment 3
A kind of quick preparation high-performance CoSb
3the novel method of base thermoelectricity material, it comprises the following steps:
1) press Co
3.8fe
0.2sb
12the stoichiometric ratio of each atom weighs Co powder, Sb powder, Fe powder as raw material, and raw material powder total mass 4g is then even by their ground and mixed, and the powder mixing is pressed into the cylindrical block block that diameter is 10mm (4MPa pressurize 5min);
2) step 1) gained block is carried out in air atmosphere to lit-end initiation self-propagating reaction (SHS, Self-propagating High-temperature Synthesis) and reacted rear naturally cooling;
3) by step 2) products therefrom grind into powder, carry out discharge plasma activated sintering (PAS, Plasma Activated Sintering), powder is packed into compacting in the graphite jig of 16mm, then in vacuum, be less than 10Pa and sintering pressure is under 40MPa condition, to carry out sintering, temperature rise rate with 100 ℃/min is warmed up to 650 ℃, and the sintering densification time is 8min, obtains Co
3.8fe
0.2sb
12compact block thermoelectric material.
Fig. 3 (a) is the XRD figure of block spectrum after powder and PAS after SHS; Fig. 3 (b) is step 2) in the SEM figure (from left to right amplify respectively 5.00 k doubly and 20.00 k doubly) of powder after SHS; The SEM figure that Fig. 3 (c) is middle step 3) gained block thermoelectric material (from left to right amplifying respectively 5.00 k doubly and 20.00 k times).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, at the distributing nano-pore structure of a lot of 20-100nm of crystal boundary, and intercrystalline is in conjunction with closely, is fine and close block thermoelectric material.
embodiment 4
A kind of quick preparation high-performance CoSb
3the novel method of base thermoelectricity material, it comprises the following steps:
1) press Co
4sb
11.8te
0.2the stoichiometric ratio of each atom weighs Co powder, Sb powder, Te powder as raw material, and raw material powder total mass 4g is then even by their ground and mixed, and the powder mixing is pressed into the cylindrical block block that diameter is 10mm (4MPa pressurize 5min);
2) step 1) gained block is carried out in air atmosphere to lit-end initiation self-propagating reaction (SHS, Self-propagating High-temperature Synthesis) and reacted rear naturally cooling;
3) by step 2) products therefrom grind into powder, carry out discharge plasma activated sintering (PAS, Plasma Activated Sintering), powder is packed into compacting in the graphite jig of 16mm, then in vacuum, be less than 10Pa and sintering pressure is under 40MPa condition, to carry out sintering, temperature rise rate with 100 ℃/min is warmed up to 650 ℃, and the sintering densification time is 8min, obtains Co
4sb
11.8te
0.2compact block thermoelectric material.
Fig. 4 (a) is the XRD figure of block spectrum after powder and PAS after SHS; Fig. 4 (b) is step 2) in the SEM figure (from left to right amplifying respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM figure that Fig. 4 (c) is middle step 3) gained block thermoelectric material (from left to right amplifying respectively 5.00k doubly and 20.00k times).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, at the distributing nano-pore structure of a lot of 20-100nm of crystal boundary, and intercrystalline is in conjunction with closely, is fine and close block thermoelectric material.
embodiment 5
A kind of quick preparation high-performance CoSb
3the novel method of base thermoelectricity material, it comprises the following steps:
1) press Co
4sb
11.6te
0.4the stoichiometric ratio of each atom weighs Co powder, Sb powder, Te powder as raw material, and raw material powder total mass 4g is then even by their ground and mixed, and the powder mixing is pressed into the cylindrical block block that diameter is 10mm (4MPa pressurize 5min);
2) step 1) gained block is carried out in air atmosphere to lit-end initiation self-propagating reaction (SHS, Self-propagating High-temperature Synthesis) and reacted rear naturally cooling;
3) by step 2) products therefrom grind into powder, carry out discharge plasma activated sintering (PAS, Plasma Activated Sintering), powder is packed into compacting in the graphite jig of 16mm, then in vacuum, be less than 10Pa and sintering pressure is under 40MPa condition, to carry out sintering, temperature rise rate with 100 ℃/min is warmed up to 650 ℃, and the sintering densification time is 8min, obtains Co
4sb
11.6te
0.4compact block thermoelectric material.
Fig. 5 (a) is the XRD figure of block spectrum after powder and PAS after SHS; Fig. 5 (b) is step 2) in the SEM figure (from left to right amplifying respectively 5.00k doubly and 20.00k times) of powder after SHS; The SEM figure that Fig. 5 (c) is middle step 3) gained block thermoelectric material (from left to right amplifying respectively 5.00k doubly and 20.00k times).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, at the distributing nano-pore structure of a lot of 20-100nm of crystal boundary, and intercrystalline is in conjunction with closely, is fine and close block thermoelectric material.
embodiment 6
A kind of quick preparation high-performance CoSb
3the novel method of base thermoelectricity material, it comprises the following steps:
1) press Co
4sb
11.4te
0.6the stoichiometric ratio of each atom weighs Co powder, Sb powder, Te powder as raw material, and raw material powder total mass 4g is then even by their ground and mixed, and the powder mixing is pressed into the cylindrical block block that diameter is 10mm (4MPa pressurize 5min);
2) step 1) gained block is carried out in air atmosphere to lit-end initiation self-propagating reaction (SHS, Self-propagating High-temperature Synthesis) and reacted rear naturally cooling;
3) by step 2) products therefrom grind into powder, carry out discharge plasma activated sintering (PAS, Plasma Activated Sintering), powder is packed into compacting in the graphite jig of 16mm, then in vacuum, be less than 10Pa and sintering pressure is under 40MPa condition, to carry out sintering, temperature rise rate with 100 ℃/min is warmed up to 650 ℃, and the sintering densification time is 8min, obtains Co
4sb
11.4te
0.6compact block thermoelectric material.
Fig. 6 (a) is the XRD figure of block spectrum after powder and PAS after SHS; Fig. 6 (b) is step 2) in the SEM figure (from left to right amplifying respectively 5.00 k doubly and 20.00k times) of powder after SHS; The SEM figure that Fig. 6 (c) is middle step 3) gained block thermoelectric material (from left to right amplifying respectively 5.00k doubly and 20.00k times).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, at the distributing nano-pore structure of a lot of 20-100nm of crystal boundary, and intercrystalline is in conjunction with closely, is fine and close block thermoelectric material; Thermoelectric material prepared by this kind of method can reach current best level and be
zT~ 0.98.
Claims (6)
1. a self-propagating combustion synthesizes supper-fast preparation high-performance CoSb
3the novel method of base thermoelectricity material, is characterized in that it comprises the following steps:
1) press chemical formula Co
4-xm
xsb
12-yte
yin the stoichiometric ratio of each element take Co powder, M powder, Sb powder, Te powder as raw material, wherein x and y are all more than or equal to 0 to be less than or equal to 1.0, M are Fe or Ni, then that raw material powder ground and mixed is even, and the powder compression mixing is become to block idiosome;
2) the block idiosome of step 1) gained is caused to 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, carry out discharge plasma activated sintering, obtain pure single-phase high-performance CoSb
3base thermoelectricity material.
2. a kind of quick preparation high-performance CoSb according to claim 1
3the novel 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. a kind of quick preparation high-performance CoSb according to claim 1
3the novel method of base thermoelectricity material, is characterized in that described step 2) in self-propagating reaction adopt a some type of heating to heat the end of block idiosome, initiation self-propagating reaction detonates in part.
4. a kind of quick preparation high-performance CoSb according to claim 1
3the novel method of base thermoelectricity material, it is characterized in that the process that powder in described step 3) carries out discharge plasma activated sintering is: by rapid 2) products therefrom powder powder is less than 10Pa and sintering pressure is under 40MPa condition, to carry out sintering in vacuum, temperature rise rate with 100 ℃/min is warmed up to 650 ℃, sintering densification time 8min.
5. method claimed in claim 1 obtains high-performance CoSb
3base compact block thermoelectric material.
6. high-performance CoSb according to claim 5
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
zTat 875K, reach 0.98.
Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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 |
US14/441,446 US10500642B2 (en) | 2013-03-19 | 2014-03-17 | Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof |
EP14767900.5A EP2977129B1 (en) | 2013-03-19 | 2014-03-17 | Thermoelectric compound preparation based on self-propagating combustion synthesis new criterion |
PCT/CN2014/000287 WO2014146485A1 (en) | 2013-03-19 | 2014-03-17 | Thermoelectric compound preparation based on self-propagating combustion synthesis new criterion |
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 |
US16/667,128 US10913116B2 (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 |
US16/667,173 US10913119B2 (en) | 2013-03-19 | 2019-10-29 | Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof |
US16/667,143 US10913117B2 (en) | 2013-03-19 | 2019-10-29 | Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof |
US16/667,110 US10913115B2 (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 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105671344A (en) * | 2014-11-21 | 2016-06-15 | 武汉理工大学 | Method for preparing high-performance CoSb3-based thermoelectric materials by one step |
CN106191522A (en) * | 2016-07-12 | 2016-12-07 | 中国科学院上海硅酸盐研究所 | A kind of laser efficiently prepares the method for skutterudite thermoelectric material |
CN113462943A (en) * | 2021-06-11 | 2021-10-01 | 武汉理工大学 | Ultra-fast preparation of high-performance YbAl3Method for bulk thermoelectric material |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1199020A (en) * | 1997-04-23 | 1998-11-18 | 松下电器产业株式会社 | Co-Sb thermoelectric materials and mfg. method thereof |
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 |
-
2013
- 2013-11-15 CN CN201310567912.2A patent/CN103924109B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1199020A (en) * | 1997-04-23 | 1998-11-18 | 松下电器产业株式会社 | Co-Sb thermoelectric materials and mfg. method thereof |
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 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105671344A (en) * | 2014-11-21 | 2016-06-15 | 武汉理工大学 | Method for preparing high-performance CoSb3-based thermoelectric materials by one step |
CN105671344B (en) * | 2014-11-21 | 2018-09-18 | 武汉理工大学 | One step prepares high-performance CoSb3The method of base thermoelectricity material |
CN106191522A (en) * | 2016-07-12 | 2016-12-07 | 中国科学院上海硅酸盐研究所 | A kind of laser efficiently prepares the method for skutterudite thermoelectric material |
CN113462943A (en) * | 2021-06-11 | 2021-10-01 | 武汉理工大学 | Ultra-fast preparation of high-performance YbAl3Method for bulk thermoelectric material |
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