CN103320636B - Novel method for quickly preparing high-performance Mg2Si0.3Sn0.7-based thermoelectric material - Google Patents

Novel method for quickly preparing high-performance Mg2Si0.3Sn0.7-based thermoelectric material Download PDF

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CN103320636B
CN103320636B CN201310252012.9A CN201310252012A CN103320636B CN 103320636 B CN103320636 B CN 103320636B CN 201310252012 A CN201310252012 A CN 201310252012A CN 103320636 B CN103320636 B CN 103320636B
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thermoelectric material
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block
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CN103320636A (en
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唐新峰
张强
郑云
柳伟
尹康
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Wuhan University of Technology WUT
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Abstract

The invention relates to a novel method for quickly preparing a high-performance Mg2Si0.3Sn0.7-based thermoelectric material, which comprises the following steps of: 1) weighing according to the stoichiometric ratio of each atom in a thermoelectric material Mg2(1+0.08)(Si0.3Sn0.7)(1-y)Sby (0<=y<=0.025), uniformly mixing the raw material powder in a mortar, and pressing the uniformly mixed powder into a block; 2) putting the obtained block into a graphite crucible, and performing fusion spin-throwing in melt spin-throwing quenching equipment to obtain a Mg2(Si0.3Sn0.7)(1-y)Sby strip product; and 3) grinding the Mg2(Si0.3Sn0.7)(1-y)Sby strip product into powder, and performing discharge plasma activation sintering to obtain the high-performance Mg2Si0.3Sn0.7-based thermoelectric material. The method provided by the invention has the characteristics of energy saving, short preparation time, simple technological parameters and the like; and the thermoelectric merit figure ZT of the obtained block can reach 1.3.

Description

A kind of high-performance Mg of preparation fast 2si 0.3sn 0.7the novel method of base thermoelectricity material
Technical field
The invention belongs to new energy materials field, be specifically related to a kind of Mg 2si 0.3sn 0.7the preparation method of base thermoelectricity material.
Background technology
The energy and environment play vital effect for the target reaching Sustainable development.The energy can make social economy obtain significant progress, but also inevitably can cause the deterioration of environment simultaneously.Due to present stage the energy short supply state and environmental pollution day by day serious, effective development new energy materials becomes the topic paid close attention in the world.Thermoelectric generation technology, can realize the direct conversion between heat energy and electric energy, to reducing the consumption of fossil energy and alleviating the deterioration of social environment, serves the effect that can not be ignored.Thermoelectric material, based on Seebeck effect, can utilize used heat (industrial gaseous waste used heat, waste heat of automotive exhaust gas etc.) to generate electricity, thus can alleviate the consumption of the energy and the deterioration of environment.
Thermal power transfer directly can be become electric energy by thermoelectric material, has the advantages such as, noiselessness little without drive disk assembly, volume, pollution-free, good reliability, recycles in automobile waste heat, has huge application prospect in industrial afterheat power generation.The efficiency of conversion of thermoelectric material is primarily of zero dimension thermoelectric figure of merit zT( zT= a 2 s T/ k, wherein afor Seebeck coefficient, sfor specific conductivity, kfor thermal conductivity, tfor absolute temperature) determine, zTlarger, the conversion efficiency of thermoelectric of material will be higher.
Mg 2si 0.3sn 0.7based solid solution is a cube antifluorite structure, and due to its raw material rich reserves, nontoxic, cheap, density is little, and thermoelectricity capability is excellent, and the n-type material thermoelectric figure of merit of this system zTreach as high as 1.3, thus receive showing great attention to of international thermoelectricity field.
At present, Mg 2si 0.3sn 0.7the synthesis of base thermoelectricity material mainly adopts scorification and solid reaction process.But, the different melting points that component is larger, the fusing point of Sn 232 DEG C, the fusing point of Mg 649 DEG C, the fusing point of Si 1414 DEG C, and the high saturated vapor pressure of Mg and strong reactive behavior (quite serious to Glass tubing corrosion), make scorification can not obtain the accurate control (volatilization of Mg and oxidation etc.) of composition.Low-temperature solid phase reaction, although the volatilization loss improving Mg preferably, the reaction times is longer, and reaction times is more, and reaction required total time is 48h.Therefore, the synthetic method of a kind of simple and fast, less energy consumption is for Mg 2si 0.3sn 0.7base 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 high-performance Mg of preparation fast 2si 0.3sn 0.7the novel method of base thermoelectricity material, the method technique is simple, and preparation time is short, and the compact block distributed components obtained, thermoelectricity capability are excellent.
The technical scheme that the problem that the present invention is the above-mentioned proposition of solution adopts is:
A kind of high-performance Mg of preparation fast 2si 0.3sn 0.7the novel method of base thermoelectricity material, it comprises the steps:
1) 1) with Mg powder, Si powder, Sn powder and Sb powder for raw material, by Mg 2 (1+0.08)(Si 0.3sn 0.7) 1-ysb yin (Mg excessive 8% is the volatilization loss in order to compensate Mg, and Sb is doped element, 0≤y≤0.025) thermoelectric material, the stoichiometric ratio of each atom weighs, and is mixed by material powder, the powder mixed is pressed into block in mortar;
2) after gained block being placed in plumbago crucible, then being placed in melt and revolving and get rid of fast cooling device and carry out melting and revolve and get rid of, obtain Mg 2(Si 0.3sn 0.7) 1-ysb y(0≤y≤0.025) strand of product;
3) by the Mg of previous step gained 2(Si 0.3sn 0.7) 1-ysb y(0≤y≤0.025) strand of product grind into powder, carries out discharge plasma activation (PAS, Plasma Activated Sintering) sintering to it, obtains high-performance Mg 2(Si 0.3sn 0.7) 1-ysb y(0≤y≤0.025) thermoelectric material.
By such scheme, in described step 1), the quality purity of Mg powder, Si powder, Sn powder and Sb powder is all more than or equal to 99.9%.
By such scheme, described step 2) in, melt revolves that to get rid of in fast cooling device cavity be argon gas atmosphere, relative pressure is-0.05MPa, melt revolves the processing parameter got rid of: copper roller rotating speed is 30m/s, it is 0.04MPa that argon gas sprays relative pressure, and induction voltage is 150V, and it is 1-2min that the band time is got rid of in melting.
By such scheme, in described step 3), the process that powder carries out discharge plasma activated sintering is: powder is loaded compacting in the graphite jig of 15mm, then sinter under vacuum is less than 10Pa and sintering pressure is 33MPa condition, 650 DEG C are warmed up to, sintering densification time 7min with the temperature rise rate of 100 DEG C/min.
Above-mentioned preparation method obtains high-performance Mg 2si 0.3sn 0.7base compact block thermoelectric material.
By such scheme, described high-performance Mg 2si 0.3sn 0.7base compact block thermoelectric material uniform composition, the thermoelectricity capability figure of merit zT1.3 are reached at 800K.
In the present invention, high-frequency induction heating is utilized to be rapidly heated to plumbago crucible, then plumbago crucible carries out rapid heating by multiple thermaltransmission mode (thermal conduction, thermal radiation etc.) to block before reaction, because Mg, Sn fusing point is respectively 649 DEG C, 232 DEG C, therefore, within very short time, these two kinds of main elements of Mg, Sn just can melting, form liquid phase, react with its periphery element simultaneously.Now, in plumbago crucible, carry out spray argon gas, air pressure just forces the melt under current state, and be sprayed onto the copper roller surface of high speed rotating (30m/s) fast, cool rapidly, rate of cooling can reach (10 5~ 10 6k/s), like this, gained strand of product just maintains the homogeneity of high-temperature molten-state.Meanwhile, the simplification of preparation technology and the shortening in reaction times, make the oxidation of Mg obtain good suppression, substantially do not have the generation of MgO second-phase, so gained agglomerate body heat electrical property is very excellent.
Compared with prior art, the invention has the beneficial effects as follows:
1. adopt melt to revolve the method for getting rid of.The present invention has energy-efficient, the feature such as preparation time is extremely short and processing parameter is simple.
2. the Mg prepared by the present invention 2si 0.3sn 0.7base compact block thermoelectric material sintered product distributed components, and thermoelectricity capability can reach the optimum value of this system of report at present zT~ 1.3.
3. the present invention mainly adopts raw material Mg powder, Si powder, Sn powder and Sb powder, rich reserves, cheap.
Accompanying drawing explanation
Fig. 1 is step 2 in embodiment) the XRD figure spectrum of the strand of product fine powder that obtains.
Fig. 2 is the XRD figure spectrum of the block thermoelectric material that in embodiment, step 3) obtains.
Fig. 3 is the micro-structure diagram of the block that in embodiment, step 3) obtains.Wherein Fig. 3 (a) be agglomerate body section different amplification (from left to right, from top to bottom, be followed successively by amplification 500 times, 1.00 k doubly, 5.00 k doubly and 10.00 k doubly) micro-structure diagram; Fig. 3 (b) is the elemental map energy spectrogram after the polishing of sintering block.
Fig. 4 is the thermoelectricity capability figure of the block that in embodiment, step 3) obtains, wherein 4(a) be the electrical property (specific conductivity sintering block s, Seebeck coefficient aand power factor pF) temperature variant graph of a relation; 4(b) be the thermal conductivity sintering block kwith zero dimension thermoelectric figure of merit zTtemperature variant graph of a relation.
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 limited only to the following examples.Embodiment is the Mg of thermoelectricity capability optimum in the present invention below 2si 0.3sn 0.7the preparation method of base thermoelectricity material, now y=0.02; When 0≤y≤0.025, all Mg can be prepared 2si 0.3sn 0.7base thermoelectricity material.
embodiment:
A kind of high-performance Mg of preparation fast 2si 0.3sn 0.7the novel method of base thermoelectricity material, it comprises the steps:
1) with Mg powder, Si powder, Sn powder and Sb powder for raw material, by Mg 2 (1+0.08)(Si 0.3sn 0.7) 0.98sb 0.02(Mg excessive 8% is the volatilization loss in order to compensate Mg) stoichiometric ratio is prepared burden, weighing total amount is 5.5g, by even for material powder manual mixing in mortar, obtain the powder mixed, the powder mixed is pressed on tabletting machine cylindrical block (the 5MPa pressurize 5min that diameter is 12.7mm, then, 8MPa pressurize 10min);
2) above-mentioned cylindrical block is placed in plumbago crucible, be put in melt again to revolve to get rid of in quenching apparatus and carry out melt and revolve and get rid of, cavity is argon gas atmosphere, relative pressure is-0.05MPa, carrying out melt revolves when getting rid of, and induction voltage is 150V, and copper roller rotating speed is 30m/s, it is 0.04MPa that argon gas sprays relative pressure, obtains Mg 2 (1+0.08)(Si 0.3sn 0.7) 0.98sb 0.02strand of product;
3) by step 2) gained Mg 2 (1+0.08)(Si 0.3sn 0.7) 0.98sb 0.02strand of product is ground, again gained fine powder is carried out discharge plasma activated sintering (PAS): powder is loaded compacting in the graphite jig of 15mm, then sinter under vacuum is less than 10Pa and sintering pressure is 33MPa condition, 650 DEG C are warmed up to the temperature rise rate of 100 DEG C/min, the sintering densification time is 7min, obtains Mg 2(Si 0.3sn 0.7) 0.98sb 0.02compact block thermoelectric material.
Strand of product is ground to form fine powder XRD figure spectrum see Fig. 1, as seen from Figure 1, melting revolve and get rid of chilling after gained strand of product powder XRD compose peak be positioned at Mg 2si and Mg 2between Sn, meanwhile, spectrum peak comparatively broadening, illustrates that this product is amorphous or nanocrystalline single phase solid solution.
The XRD figure spectrum of gained sintering block thermoelectric material is shown in Fig. 2, and as shown in Figure 2, the powder X-ray RD of the block obtained after PAS composes peak and is positioned at Mg 2si and Mg 2between Sn, meanwhile, spectrum peak is very sharp-pointed, and after sintering is described, block crystal grain is well grown, and is single phase solid solution.
The microtexture of gained sintering block thermoelectric material is shown in Fig. 3.Wherein Fig. 3 (a) be the different amplification of agglomerate body section (from left to right, from top to bottom, be followed successively by amplification 500 times, 1.00 k doubly, 5.00 k doubly and 10.00 k doubly) micro-structure diagram, can find out in figure, this fracture mode is transgranular fracture, illustrate that the thermoelectric material block intercrystalline that the method obtains combines closely, block is very fine and close.Fig. 3 (b) is the elemental map energy spectrogram after the polishing of sintering block, and as can be seen from the figure, Mg, Si, Sn element is uniformly distributed, and illustrates that the thermoelectric material composition profiles that the method obtains is very even.
The thermoelectricity capability of gained sintering block materials is shown in Fig. 4.Wherein Fig. 4 (a) is the electrical property (specific conductivity of sintering block s, Seebeck coefficient aand power factor pF) temperature variant graph of a relation.Fig. 4 (b) is the thermal conductivity of sintering block kwith zero dimension thermoelectric figure of merit zTtemperature variant graph of a relation, described high-performance Mg 2si 0.3sn 0.7the thermal conductivity of base compact block thermoelectric material raises with temperature, reduces gradually; The thermoelectricity capability figure of merit zTraise with temperature, raise gradually, reach 1.3 at 800K.
Each raw material cited by the present invention, and the bound of each raw material of the present invention, interval value, and the bound of processing parameter (as melting voltage etc.), interval value can realize the present invention, do not enumerate embodiment at this.

Claims (4)

1. prepare high-performance Mg fast for one kind 2si 0.3sn 0.7the method of base thermoelectricity material, is characterized in that it comprises the steps:
1) with Mg powder, Si powder, Sn powder and Sb powder for raw material, by Mg 2(Si 0.3sn 0.7) 1-ysb yin thermoelectric material, the stoichiometric ratio of each atom weighs, and is mixed by material powder in mortar, the powder mixed is pressed into block, wherein 0≤y≤0.025;
2), after gained block being placed in plumbago crucible, being placed in melt and revolving and get rid of fast cooling device and carry out melting and revolve and get rid of, obtain Mg 2(Si 0.3sn 0.7) 1-ysb ystrand of product;
3) by the Mg of previous step gained 2(Si 0.3sn 0.7) 1-ysb ystrand of product grind into powder, carries out discharge plasma activated sintering to it, obtains high-performance Mg 2(Si 0.3sn 0.7) 1-ysb ythermoelectric material;
Described step 2) in, melt revolves that to get rid of in fast cooling device cavity be argon gas atmosphere, and relative pressure is-0.05MPa, melt revolves the processing parameter got rid of: copper roller rotating speed is 30m/s, it is 0.04MPa that argon gas sprays relative pressure, and induction voltage is 150V, and it is 1-2min that the band time is got rid of in melting;
Gained high-performance Mg 2si 0.3sn 0.7base thermoelectricity material distributed components, the thermoelectricity capability figure of merit zT1.3 are reached at 800K.
2. one according to claim 1 prepares high-performance Mg fast 2si 0.3sn 0.7the method of base thermoelectricity material, is characterized in that in described step 1), and the quality purity of Mg powder, Si powder, Sn powder and Sb powder is all more than or equal to 99.9%.
3. one according to claim 1 prepares high-performance Mg fast 2si 0.3sn 0.7the method of base thermoelectricity material, it is characterized in that: in described step 3), the process that powder carries out discharge plasma activated sintering is: powder is loaded compacting in the graphite jig of 15mm, then sinter under vacuum is less than 10Pa and sintering pressure is 33MPa condition, 650 DEG C are warmed up to, sintering densification time 7min with the temperature rise rate of 100 DEG C/min.
4. the high-performance Mg that obtains of the method for claim 1 2si 0.3sn 0.7base compact block thermoelectric material.
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CN104109785B (en) * 2014-04-16 2016-07-06 中国科学院上海高等研究院 A kind of Mg-Si-Sn base nano composite thermoelectric materials and preparation method thereof
CN104109770B (en) * 2014-07-18 2016-05-11 太原理工大学 Microwave is assisted MgH2Solid reaction process is prepared Mg2SixSn1-xBiyThe method of base thermoelectricity material
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CN112279652A (en) * 2020-10-29 2021-01-29 南京工程学院 Rapid non-equilibrium preparation method for Mg-Si-Sn-Sb based thermoelectric material

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CN101693962A (en) * 2009-10-19 2010-04-14 武汉理工大学 Method for preparing p-type filling type skutterudite compound thermoelectric material

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