CN1755961A - Ag-Pb-Sb-Te thermoelectric materials and preparation process thereof - Google Patents
Ag-Pb-Sb-Te thermoelectric materials and preparation process thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 16
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- 238000005551 mechanical alloying Methods 0.000 claims abstract description 17
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Abstract
The invention discloses new energy resource material and its preparing technique, relating to a Ag-Pb-Sb-Te thermoelectric material of thermoelectric semi-conductor compound with high thermoelectric effect and the relative preparing method. The invention utilizes the mechanical alloying (MA) combined with discharge plasma sinter (SPS) to prepare the PbTe high-performance thermoelectric material, which can be displayed as Ag1-XPb18+YSbTe20, wherein, the x is the amount of deviated Ag amount and y is amount that the raw material powder over the measurement rate of Pb. Compared to traditional powder metallurgy technology, the inventive MA+SPS process has the advantages of short process, high efficiency, lower energy consumption, and application to the industrial mass production and the attained thermoelectric material has better thermoelectric performance while the non-dimensional merit ZT of thermoelectric material of Ag1-XPb18+YSbTe20 prepared by MA and SPS can reach 1.37 in the temperature of 450 Deg. C.
Description
Technical field
The invention belongs to new energy materials and preparing technical field thereof, particularly have a kind of Ag-Pb-Sb-Te thermoelectric material and preparation method thereof of the thermoelectric semiconductor compound of high temperature difference electrical effect.
Background technology
Thermoelectric material, or be referred to as thermoelectric material, refer to based on two basic thermoelectric effects---Seebeck (Seebeck) effect and Peltier (Peltier) effect, thereby a class energy and material of changing between realization heat energy and the electric energy.The thermoelectric power generation device of making by thermoelectric material, compare with traditional generation technology, have simple in structure, sturdy and durable, movement-less part, be easy to microminiaturization, do not need that maintenance reliability is good, life-span length, noiseless, pollution-free, can utilize characteristics such as low-temperature waste heat; The thermoelectric cooling device of making by thermoelectric material, compare with the conventional compression Refrigeration Technique also have floride-free pollution-free, be easy to advantages such as miniaturization, movement-less part, noiseless.Thereby becoming increasingly conspicuous along with recent energy problem and environmental problem, the application of thermoelectric device is increasingly extensive, all has wide application background aspect the used heat in fields such as Aero-Space, national defense construction, geology and meteorological detection, health care, microelectronics and petrochemical industry, metallurgy, power industry utilizes.
Thermoelectric material with above application background is with its Seebeck coefficient S, the conductivity, and thermal conductivity κ is as main performance parameter, and its power factor P=S
2σ and dimensionless figure of merit ZT=(S
2σ/κ) T estimates the most frequently used performance index of thermoelectric material, and good thermoelectric material requires to have high Seebeck coefficient S, high conductivity σ, lower thermal conductivity κ.
At present, the comparatively active thermoelectric material of research comprises: the Bi that is applied to low-temperature space
2Te
3(Bismuth Telluride) and solid solution alloy thereof; The PbTe (Lead Telluride) of warm area and alloy thereof, skutterudite (Skutterudite) structure in being applied to; Be applied to SiGe alloy, huge legendary turtle compound (Clathrate) structure of high-temperature region; And other is such as half-Heusler alloy, rich boron solid, oxide, and polymer thermoelectric material etc.
Wherein, Bi
2Te
3And the application of solid solution alloy is relatively ripe, and ZT is greater than 1 for its dimensionless figure of merit.But because its serviceability temperature is lower, this material is mainly used in electronic cooling.PbTe is that thermoelectric compound is suitable for thermo-electric generation, but its performance has much room for improvement.The dimensionless figure of merit ZT of traditional block PbTe pyroelectric material is less than 1.Have recently document (K.F Hsu et al., Science, 303 (2004), g18) report a kind of PbTe based compound block materials have the Bi of being better than
2Te
3The thermoelectricity capability of alloy, but its preparation technology is more special, and detailed process is not clear.Although there are some research institutions also carrying out the experiment relevant with this material system at present, all far below the reported values of K.F Hsu etc., wherein ZT is up to 1.07 to resulting dimensionless figure of merit ZT.
On the other hand, behind the main at present employing smelting process synthetic compound, use powder metallurgical techniques such as pulverizing and hot pressing to prepare thermoelectric material.It is various that this preparation technology exists operation, the equipment complexity, the production cycle is long, power consumption is big, and material at high temperature open-assembly time long, component volatilization seriously waits deficiency.
For this reason, this patent has been invented a kind of new thermoelectric material and preparation method thereof.This thermoelectric material belongs to the Ag-Pb-Sb-Te based compound, and ZT is up to 1.37 for its dimensionless figure of merit.This thermoelectric material can adopt mechanical alloying (Mechanical Alloying MA) to synthesize its compound powder, uses discharge plasma sintering (Spark Plasma Sintering SPS) technology at lower temperature sintering synthesizing block material.
Summary of the invention
The purpose of this invention is to provide a kind of Ag-Pb-Sb-Te thermoelectric material of the thermoelectric semiconductor compound with high temperature difference electrical effect and preparation method thereof.It is characterized in that: it is the Ag-Pb-Sb-Te thermoelectric material of matrix that the prepared of employing mechanical alloying and discharge plasma sintering goes out with PbTe.Page or leaf: 2 so-called mechanical alloyings are the energy that produce by the collision in the high-energy ball milling process, make the direct chemical combination of metal dust become the technical process of intermetallic compound or alloy.Compare with traditional smelting technology, has synthesis temperature near room temperature, equipment is simple, with low cost, the characteristics that are fit to large-scale production, and resulting alloy grain is tiny, can reduce the thermal conductivity of material by the crystal boundary scattering that increases phonon when significantly not reducing conductivity, thereby obtain better thermoelectricity capability.
So-called discharge plasma sintering, be under vacuum environment, by upper and lower two graphite pressure heads, in to the sintered body pressurization, produce discharge plasma by pulse direct current, make sintered body internal particle generation Joule heat and make surface active, thereby finish the technical process of sintering in a short period of time, characteristics such as sintering temperature is low, the sintering period is short, production efficiency is high, sintered body crystal grain is difficult for growing up that it has.
Material is formed with Ag
1-XPb
18+YSbTe
20Expression.This compound has the rock salt structure identical with PbTe, keeping under the constant condition of PbTe original structure, the Ag of equivalent, Sb replaces the position of Pb: represent that with x it departs from the amount that equivalent replaces, the Pb content of representing to surpass the metering ratio with y, adjust its electricity and thermoelectricity capability with this, obtain having the material of high thermoelectricity capability.
The specific embodiment of preparation comprises:
1) according to Ag
1-XPb
18+YSbTe
20Chemical formula, with Ag, Pb, Sb and Te simple substance powder are raw material, and according to X, the value of Y batching is put into ball grinder, and adds the ethanol of tank volume 0.1% in jar, and the effect of ethanol is to prevent that powder from adhering to the follow-up ball milling effect of influence on tank skin;
2), after feeding is used for the high-purity argon gas of ball milling protective gas, ball grinder is installed in planetary ball mill carries out dry ball milling through forvacuum.In stainless steel jar mill, the stainless steel abrading-ball with the 10mm diameter adopts 300～600 rev/mins rotating speed, and the ball milling time is 3～8 hours, and concrete ball milling time and rotating speed are got by the concrete condition of balls grinding machine and jar and ball and determined;
3) take out the ball milling powder, in the graphite jig of the Φ 20mm that packs into, after the compacting of graphite pressure head, be installed in the SPS machine, under＜6Pa vacuum condition, carry out sintering.The SPS programming rate is 50 ℃/min, and the highest holding temperature is 300-500 ℃, and SPS pressure is 50Mpa, is incubated after 1～10 minute, and sintering furnace is cooled to room temperature;
4) take out sample after, after with the sand paper mill sample surfaces being polished, carry out the thing identification of phases and microstructure analysis, and carry out the thermoelectricity capability test.
Described X value is 0 ~ 0.6, and the Y value is 1 ~ 5.
The invention has the beneficial effects as follows that the Ag-Pb-Sb-Te thermoelectric material that adopts mechanical alloying and discharge plasma sintering process combined (being called for short MA+SPS technology) to be used to prepare has its outstanding advantage: (1) technological process is short, the efficient height is suitable for large-scale industrialization production; (2) do not need high melt and long-time hot pressing, power consumption is few; (3) reduced the volatilization of harmful element, preparation process is less to the influence of environment; (4) the gained material grains is tiny, and thermoelectricity capability is more excellent.
Description of drawings
The Ag that Fig. 1 mechanical alloy is combined to
1-XPb
18+YSbTe
20(x=0.2, y=4) X ray diffracting spectrum of compound powder and SPS sintering block thereof (sintering temperature=400 ℃).
Fig. 2 (a) is (b) at 400 ℃ of Ag by the SPS sintering
1-XPb
18+YSbTe
20(x=0.2, y=4) ESEM of compound block sample (SEM) and transmission electron microscope (TEM) photo.
The different Ag that form of Fig. 3
1-XPb
18+YSbTe
20The resistivity of compound S PS sintered sample and the relation of temperature.
The different Ag that form of Fig. 4
1-XPb
18+YSbTe
20The Seebeck coefficient of compound S PS sintered sample and the relation of temperature.
The different Ag that form of Fig. 5
1-XPb
18+YSbTe
20The power factor of compound S PS sintered sample and the relation of temperature.
Fig. 6 has the composition (Ag of the peak power factor
0.8Pb
22SbTe
20) the dimensionless figure of merit ZT of pairing SPS agglomerated material and the relation of temperature.
Embodiment
The present invention is a kind of Ag-Pb-Sb-Te thermoelectric material and preparation method thereof.It is the Ag-Pb-Sb-Te thermoelectric material of matrix that this thermoelectric material adopts the prepared of mechanical alloying and discharge plasma sintering to go out with PbTe.This material is formed with Ag
1-XPb
18+YSbTe
20Expression.This compound has the rock salt structure identical with PbTe, keeping under the constant condition of PbTe original structure, the Ag of equivalent, Sb replaces the position of Pb: represent that with x Ag departs from the amount that equivalent replaces, represent to surpass the Pb content that measures ratio with y, adjust its electricity and thermoelectricity capability, obtain having the material of high thermoelectricity capability with this, described X value is 0～0.6, and the Y value is 1 ~ 5.
The specific embodiment of preparation above-mentioned material comprises:
1) according to Ag
1-XPb
18+YSbTe
20Chemical formula, with Ag, Pb, Sb and Te simple substance powder are raw material, and according to X, the value of Y batching is put into ball grinder, and adds the ethanol of tank volume 0.1% in jar, and the effect of ethanol is to prevent that powder from adhering to the follow-up ball milling effect of influence on tank skin.
2), after feeding is used for the high-purity argon gas of ball milling protective gas, ball grinder is installed in planetary ball mill carries out dry ball milling through forvacuum.The QM-2 type planet-shaped ball mill that the present invention adopts Nanjing Univ. Instrument Factory to produce, the stainless steel abrading-ball of the stainless steel jar mill of 250mL and 10mm diameter, when the rotating speed that adopts 300 rev/mins, the required ball milling time is 5 hours.
3) take out the ball milling powder, in the graphite jig of the Φ 20mm that packs into, after the compacting of graphite pressure head, be installed in the SPS machine, under＜6Pa vacuum condition, carry out sintering.The SPS programming rate is 50 ℃/min, and the highest holding temperature is 300-500 ℃, and SPS pressure is 50Mpa, and the insulation insulation is after 1～10 minute, and stove is chilled to room temperature.
4) take out sample after, after with the sand paper mill sample surfaces being polished, carry out the thing identification of phases and microstructure analysis, and carry out the thermoelectricity capability test.
Enumerating embodiment is below illustrated.
Embodiment 1
With silver (Ag) powder, antimony (Sb) powder, plumbous (Pb) powder, tellurium (Te) powder is a raw material, according to Ag
0.8Pb
22SbTe
20Metering than weighing the altogether powder of 20g of total amount, put into stainless steel jar mill (volume 250mL), and to add diameter be the stainless steel abrading-ball (weight ratio of abrading-ball and powder 18: 1) of 10mm.Charge into Ar in the ball grinder as protective gas, at planetary ball mill (QM-2 type, Nanjing Univ. Instrument Factory) planetary ball mill 5h (rotating speed is 300r/min), by mechanical alloying (MA) prepared in reaction Ag
0.8Pb
22SbTe
20Compound powder.Shown in Fig. 1 (a), after above-mentioned MA handled, resulting powder became single-phase, and has cubic structure, and each diffraction maximum can be demarcated mutually by PbTe.The powder that obtains is 50Mpa at pressure, under 400 ℃, is incubated 2 minutes and carries out sintering, and its relative density is all at (referring to SEM photo shown in Figure 2) more than 98%.Shown in Fig. 1 (b), the powder basically identical before its phase structure and the SPS sintering does not change.That shown in Figure 2 is Ag
0.8Pb
22SbTe
2.0The SEM photo and the TEM photo of the SPS sintered body of forming show the Ag by MA and SPS preparation
0.8Pb
22SbTe
20The density height of compound thermoelectric material, crystal grain tiny (the about 1m of average crystal grain) and more even.
Embodiment 2
With silver (Ag) powder, antimony (Sb) powder, plumbous (Pb) powder, tellurium (Te) powder is a raw material, according to Ag
0.8Pb
21SbTe
20, Ag
0.8Pb
22SbTe
20, Ag
0.8Pb
23SbTe
20Metering is than weighing the total amount powder of 20g altogether, three groups of different samples of preparation Pb content respectively.Powder is synthetic and the SPS sintering condition is identical with embodiment 1.Fig. 3 and 4 is three kinds of composition Ag relatively
1-XPb
18+YSbTe
20The relation of the resistivity () of the SPS sintered sample of compound and Seebeck coefficient (S) and temperature.Compare Ag with other two compositions
0.8Pb
22SbTe
20Have minimum resistivity, the order of magnitude of its Seebeck coefficient is between between the two.Fig. 5 is the power factor (S that utilizes the data computation of Fig. 3 and 4 to obtain
2/ with the relation of temperature.As shown in the figure, Ag
0.8Pb
22SbTe
20The power factor of forming is the highest, reaches 1766W/mK at 650K.Fig. 6 is this composition (Ag
0.8Pb
22SbTe
20) dimensionless figure of merit ZT and the relation of temperature. ZT reaches 1.37 at the highest probe temperature (673K).
Embodiment 3
With silver (Ag) powder, antimony (Sb) powder, plumbous (Pb) powder, tellurium (Te) powder is a raw material, according to Ag
0.8Pb
22SbTe
20, Ag
0.8Pb
22SbTe
20And Ag
0.8Pb
22SbTe
20Metering than weighing the total amount powder of 20g altogether, three groups of different samples of preparation Ag content respectively.Powder is synthetic and the SPS sintering condition is identical with embodiment 1.Silver content is that the room temperature resistivity of 0.4,0.6 and 0.8 sample is respectively 0.125m, 0.185m, 0.175 * 10
-3M.It is too high that silver content is respectively the resistivity of two samples of 0.4 and 0.6, and Ag content is about 0.8 sample and has resistivity far below other two compositions.Therefore, its comprehensive thermoelectricity capability height, ZT is up to 1.37 for the dimensionless figure of merit.
Claims (3)
1. Ag-Pb-Sb-Te thermoelectric material is characterized in that: adopting the prepared of mechanical alloying and discharge plasma sintering to go out with PbTe is the Ag-Pb-Sb-Te thermoelectric material of matrix, and this material is formed with Ag
1-XPb
18+YSbTe
20Expression, this compound has the rock salt structure identical with PbTe, keeping under the constant condition of PbTe original structure, the Ag of equivalent, Sb replaces the position of Pb: represent that with x Ag departs from the amount that equivalent replaces, represent to surpass the Pb content that measures ratio with y, adjust its electricity and thermoelectricity capability, obtain having the material of high thermoelectricity capability with this.
2. the preparation method of an Ag-Pb-Sb-Te thermoelectric material, it is characterized in that: the specific embodiment of preparation comprises:
1) according to Ag
1-XPb
18+YSbTe
20Chemical formula, with Ag, Pb, Sb and Te simple substance powder are raw material, and according to X, the value of Y batching is put into ball grinder, and adds the ethanol of tank volume 0.1% in jar, and the effect of ethanol is to prevent that powder from adhering to the follow-up ball milling effect of influence on tank skin;
2), after feeding is used for the high-purity argon gas of ball milling protective gas, ball grinder is installed in planetary ball mill carries out dry ball milling through forvacuum, in stainless steel jar mill, with the stainless steel abrading-ball of 10mm diameter, adopt 300～600 rev/mins rotating speed, the ball milling time is 3～8 hours;
3) take out the ball milling powder, pack in the graphite jig of Φ 20mm, after the compacting of graphite pressure head, be installed in the SPS machine, carry out sintering under the vacuum condition of pressure＜6Pa, the SPS programming rate is 50 ℃/min, the highest holding temperature is 300-500 ℃, SPS pressure is 50Mpa, is incubated after 1～10 minute, and sintering furnace is cooled to room temperature;
4) take out sample after, after with sand paper sample surfaces being polished, carry out the thing identification of phases and microstructure analysis, and carry out the thermoelectricity capability test.
3. according to claim 1 or 2 any one described Ag-Pb-Sb-Te thermoelectric material, it is characterized in that: described X value is 0.2～0.6, and the Y value is 1～5.
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| JP2006282380A JP4291842B2 (en) | 2005-10-21 | 2006-10-17 | Compound thermoelectric material and method for producing the same |
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|---|---|---|---|
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Also Published As
| Publication number | Publication date |
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| CN100391021C (en) | 2008-05-28 |
| JP2007116156A (en) | 2007-05-10 |
| JP4291842B2 (en) | 2009-07-08 |
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