CN100427631C - Nano SiC granule composite CoSb3 base thermoelectric material and its preparing process - Google Patents

Nano SiC granule composite CoSb3 base thermoelectric material and its preparing process Download PDF

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CN100427631C
CN100427631C CNB2006101440061A CN200610144006A CN100427631C CN 100427631 C CN100427631 C CN 100427631C CN B2006101440061 A CNB2006101440061 A CN B2006101440061A CN 200610144006 A CN200610144006 A CN 200610144006A CN 100427631 C CN100427631 C CN 100427631C
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cosb
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powder
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CN1995437A (en
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李敬锋
刘玮书
张波萍
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Tsinghua University
University of Science and Technology Beijing USTB
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Abstract

The invention discloses a composite CoSb3 based heat electric material and making method of nanometer SiC particle in the new-typed energy technical domain, which comprises the following steps: allocating Co, Sb and doped element according to chemical formula as Co1-xMxSb3+ySiC; balling; obtaining the microfine powder evenly; sintering to synthesize block CoSb3 based thermoelectric material of nanometer SiC particle under 250-600 deg. c through discharge plasma; utilizing dispersed SiC to inhibit the growth of CoSb3 crystal.

Description

The compound CoSb of nano SiC granule 3Base thermoelectricity material and preparation method thereof
Technical field
The present invention relates to a kind of thermoelectric material and preparation method thereof, the compound CoSb of particularly a kind of nano SiC granule 3Base thermoelectricity material and preparation method thereof belongs to novel energy material technology field.
Background technology
Thermoelectric material is a kind of functional materials that can realize that heat energy and electric energy are directly changed.Thermoelectric power generation device based on the Seebeck effect can utilize waste-heat power generation, such as the utilization again of the used heat of vehicle exhaust.This is for improving existing rate of energy, and alleviating the increasingly serious energy and environmental problem has the important strategic meaning.The beginning of the nineties in 19th century, Slack has at first proposed the novel thermoelectric material notion of " phonon glass electron crystal; PGEC ", and one of effective way that realizes this PGEC is exactly by synthetic a kind of semiconductor material, contain the hole filling atom that atom hole and weak beam are tied up in its structure, this weak beam is tied up atom can produce very big local anharmonic vibration, also can be described as " sound of movement (rattle) ".The thermal conductivity level that this in theory localization vibration can will be hanged down the value of crystalline thermal conductivity glass.The Sales of U.S.'s Oak Ridge National Laboratory in 1996 has reported the tin white cobalt Ce of filled-type at Science 0.9Fe 3CoSb 12And La 0.9Fe 3CoSb 12Feature with " phonon glass electron crystal ", its zero dimension high-quality ZT can reach 1.4 when 1000K, thereby has started a CoSb 3The upsurge of thermoelectric material research (B.C.Sales, at al., Science, 1996,272:1325-1328).Though it is a lot of that the thermal conductivity of filled-type skutterudite compound does not more descend through the skutterudite compound of filling, its thermal conductivity is still greater than traditional Bi 2Te 3With the PbTe base thermoelectricity material.Can reduce the method that material thermal conductivity improves thermoelectric figure of merit thereby this makes people have to begin to seek other, adopting more method at present is that crystal grain thinning strengthens phon scattering, thereby reduces thermal conductivity.Prepare CoSb such as the method for Toprat by chemical alloying 3Nano-powder, hot pressed sintering is the block materials of relative density 60～70% then.(M.S.Toprat，et?al.Adv.Func.Mater.，2004，14(12)：1189-1196.)。Though the density of expendable material can reduce the thermal conductivity of material, can reduce its mechanical property.
Except crystal grain thinning can reduce the thermal conductivity of material, in thermoelectric semiconducter compound matrix, add a small amount of nanometer scale particle, can reduce thermal conductivity effectively, and little to the specific conductivity influence.Based on this material mentality of designing, we consider at CoSb 3The adding small amounts of nanoparticles increases its phon scattering and reduces thermal conductivity in the base thermoelectricity material, improves CoSb thereby reach 3The sill thermoelectricity capability, and utilize the disperse enhancement of nano particle to improve CoSb 3The mechanical property of matrix and processing characteristics.
Summary of the invention
The object of the present invention is to provide the compound CoSb of a kind of nano SiC granule 3Base thermoelectricity material and preparation method thereof is promptly by the compound further reduction CoSb of nano particle 3The thermal conductivity of base thermoelectricity material improves its thermoelectricity capability, also can improve the mechanical property and the processing characteristics of matrix material simultaneously.
Technology side of the present invention is by as follows:
The compound CoSb of a kind of nano SiC granule 3Base thermoelectricity material is characterized in that: this thermoelectric material has following chemical formula: Co 1-xM xSb 3+ ySiC, wherein: the span of x is 0≤x≤0.15,0＜y≤2.0%, y is that SiC accounts for Co 1-xM xSb 3The mass percent of matrix; M is the containing transition metal element; Described nano SiC granule disperse is distributed in CoSb 3In the base thermoelectricity material matrix.
The diameter of nano SiC granule of the present invention is between 20～200nm; Described doped element is Pt, Ni or Fe.
The present invention also provides a kind of above-mentioned nano SiC granule compound CoSb 3The preparation method of base thermoelectricity material is characterized in that this method carries out as follows:
1) be raw material with Sb, Co element simple substance powder or Sb, Co and doped element simple substance powder, according to Co 1-xM xSb 3The stoichiometric ratio proportioning, wherein the span of x is 0≤x≤0.15;
2) according to chemical formula: Co 1-xM xSb 3+ ySiC, adding accounts for Co 1-xM xSb 3Substrate quality per-cent is the SiC particle of y, and wherein the span of y is 0＜y≤2.0%;
3) above-mentioned raw materials is put into ball grinder, after the forvacuum, charge into Ar gas, the ball grinder ball mill of packing into is made fines as shielding gas;
4) powder behind the ball milling is packed into graphite jig, utilize discharge plasma sintering system sintering under vacuum environment, vacuum tightness is 1～50Pa, sintering temperature is 250～600 ℃, soaking time is 1～20 minute, sintering pressure is 10～60MPa, and heat-up rate is 10 ℃～180 ℃/minute, promptly makes the nano SiC granule disperse and is distributed in CoSb 3Composite thermoelectric material in the base thermoelectricity material matrix.
The present invention compared with prior art, its advantage is: 1. do not need in advance synthetic CoSb 3Therefore based compound can omit the step of pyroreaction, or avoid the demand to special high-energy ball milling equipment, helps to raise the efficiency and 2. low temperature solid phase synthesis CoSb of save energy 3Based compound is avoided the volatilization of Sb, helps the control of composition and reduces pollution to environment; 3. utilize the nano SiC disperse to disperse to be suppressed at grain growth in the plasma discharging process.4. the disperse of nano SiC is dispersed with and helps further reduce thermal conductivity.5. the disperse reinforced effects of nano SiC can improve the mechanical property and the processing characteristics of matrix material.
Preparation method provided by the present invention is after utilizing mechanical ball milling that raw material powder is carried out the mechanical alloying processing, again by discharge plasma sintering directly synthetic CoSb under lower temperature 3Compound, the disperse dissemination that makes full use of nano SiC in the discharge plasma sintering process suppresses grain growth, thereby obtains to have the nano SiC dispersion Co of fine grained texture 1-xM xSb 3Block thermoelectric material, wherein M is a doped element.Disperse the acting in conjunction of the caused crystal boundary scattering of large size scattering and fine grained texture that causes owing to the disperse of nano SiC granule, thermal conductivity is further reduced.In addition because the disperse of SiC disperses to make Co 1-xM xSb 3Mechanical property and processing characteristics be improved.
Description of drawings
Fig. 1 is through the XRD figure of the fine powder of different MA after the treatment time.
XRD figure in Fig. 2 example 1 behind the sample process SPS sintering.
TEM figure in Fig. 3 example 1 behind the sample process SPS sintering.
XRD figure in Fig. 4 example 3 behind the sample process SPS sintering.
The SiC/Co of the different SiC content of Fig. 5 0.9Ni 0.1Sb 3The resistivity of composite thermoelectric material is with variation of temperature.
The SiC/Co of the different SiC content of Fig. 6 0.9Ni 0.1Sb 3The Seebeck coefficient of composite thermoelectric material is with variation of temperature.
The SiC/Co of the different SiC content of Fig. 7 0.9Ni 0.1Sb 3The power factor of composite thermoelectric material is with variation of temperature.
The SiC/Co of the different SiC content of Fig. 8 0.9Ni 0.1Sb 3The thermal conductivity of composite thermoelectric material is with variation of temperature.
The SiC/Co of the different SiC content of Fig. 9 0.9Ni 0.1Sb 3The thermoelectric figure of merit ZT of composite thermoelectric material is with variation of temperature.
Concrete embodiment
The compound CoSb of nano SiC granule provided by the invention 3Base thermoelectricity material has following chemical formula: Co 1-xM xSb 3+ ySiC, wherein: the span of x is 0≤x≤0.3,0＜y≤2.0%, y is that SiC accounts for Co 1-xM xSb 3The mass percent of matrix; M is the containing transition metal element; Described nano SiC granule disperse is distributed in CoSb 3In the base thermoelectricity material matrix.The diameter of nano SiC granule is between 20～200nm.Can the containing transition metal element in the matrix, the containing transition metal element is Pt, Ni or Fe etc.
The compound CoSb of nano SiC granule provided by the invention 3Base thermoelectricity material, its concrete processing step is as follows:
1) batching: be raw material at first, according to Co with Sb, Co element simple substance powder or Sb, Co and doped element simple substance powder 1-xM xSb 3The stoichiometric ratio proportioning, wherein the span of x is 0≤x≤0.3; According to chemical formula: Co 1-xM xSb 3+ ySiC, adding accounts for Co 1-xM xSb 3Substrate quality per-cent is the SiC particle of y, and wherein the span of y is 0＜y≤2.0%;
2) powder is synthetic: raw material is put into ball grinder, after the forvacuum, feed protection of inert gas again.With the ball grinder ball mill of packing into, be under 200～450 rev/mins at rotational speed of ball-mill, ball milling obtained fines after 0.25～48 hour;
3) powder behind the ball milling is packed into graphite jig, utilize discharge plasma sintering system sintering under vacuum environment, vacuum tightness is 1～50Pa, sintering temperature is 250～600 ℃, soaking time is 1～20 minute, sintering pressure is 10～60MPa, and heat-up rate is 10 ℃～180 ℃/minute, promptly makes the nano SiC granule disperse and is distributed in CoSb 3Composite thermoelectric material in the base thermoelectricity material matrix.
4) take out sample after, with sand paper to the sample surfaces polishing after, carry out the thing identification of phases and microstructure analysis, and carry out the test of thermoelectricity capability.
Below by several specific embodiments the present invention is described:
Embodiment 1: with cobalt (Co) powder, antimony (Sb) powder is that raw material is according to CoSb 3Metering than taking by weighing the powder that total amount is 20g, then according to CoSb 30.01% of powder gross weight, the mean diameter that takes by weighing 0.002g are that the SiC powder of 100nm is put into stainless cylinder of steel (volume 250ml), and the adding diameter is the Stainless Steel Ball (abrading-ball and powder weight were than 25: 1) of 6～20mm.Charge into Ar gas in the ball grinder as shielding gas,, obtain fines at planetary ball mill (QM-2 type, Nanjing Univ. Instrument Factory) planetary ball mill 6 hours (450 rev/mins of rotating speeds).Shown in Fig. 1 (a), through in the powder after the MA processing a spot of CoSb being arranged 3And CoSb 2Generate mutually.Powder after will handling through MA then carry out the SPS sintering, be 50MPa at pressure, and temperature is 300 ℃ of insulations 5 minutes down, obtain relative density and be 93% CoSb 3Block materials, its XRD as shown in Figure 2.Fig. 3 is its transmission electron microscope photo, as can be seen from the figure, and about this sample grain-size 50nm.Its power factor in the time of 400 ℃ is 143 μ Wm -1K -2
Embodiment 2: with cobalt (Co) powder, antimony (Sb) powder is that raw material is according to CoSb 3Metering than taking by weighing the powder that total amount is 20g, then according to CoSb 30.1% of powder gross weight, taking by weighing the 0.02g mean diameter is the SiC powder of 100nm, puts into stainless cylinder of steel (volume 250ml), and the adding diameter is the Stainless Steel Ball (abrading-ball and powder weight were than 25: 1) of 6～20mm.Charge into Ar gas in the ball grinder as shielding gas, at planetary ball mill (QM-2 type, Nanjing Univ. Instrument Factory) planetary ball mill 6 hours (450 rev/mins of rotating speeds), obtain dispersive activated fine powder, its XRD and Fig. 1 (a) are close.Powder after will handling through MA then carry out the SPS sintering, be 60MPa at pressure, and temperature is 250 ℃ of insulations 20 minutes down, obtain relative density and be 90% sample.Its power factor is 256 μ Wm in the time of 400 ℃ -1K -2
Embodiment 3: with cobalt (Co) powder, and nickel (Ni) powder, antimony (Sb) powder is that raw material is according to Co 0.9Fe 0.05Sb 3Metering than taking by weighing the powder that total amount is 20g, then according to Co 0.9Fe 0.05Sb 30.01% of powder gross weight, the mean diameter that takes by weighing 0.002g are that the SiC powder of 100nm is put into stainless cylinder of steel (volume 250ml), and the adding diameter is the Stainless Steel Ball (abrading-ball and powder weight were than 25: 1) of 6～20mm.Charge into Ar gas in the ball grinder as shielding gas,, obtain the dispersive fines at planetary ball mill (QM-2 type, Nanjing Univ. Instrument Factory) planetary ball mill 15 hours (450 rev/mins of rotating speeds).Powder after will handling through MA then carry out the SPS sintering, be 50MPa at pressure, and temperature is 400 ℃ of insulations 5 minutes down, obtain relative density and be the monophasic Co more than 95% 0.9Fe 0.05Sb 3Thermoelectric material, its XRD figure spectrum as shown in Figure 4.
Embodiment 4: with cobalt (Co) powder, and nickel (Ni) powder, antimony (Sb) powder is that raw material is according to Co 0.9Ni 0.1Sb 3Metering than taking by weighing the powder that total amount is 2g, then according to Co 0.9Ni 0.1Sb 30.1% of powder gross weight, the mean diameter that takes by weighing 0.02g is the SiC powder of 20nm, puts into stainless cylinder of steel (volume 250ml) and carries out the MA processing, its MA handles identical with example 3 with the SPS synthetic technological condition.Powder after will handling through MA directly synthetic SiC/Co under SPS 0.9Ni 0.1Sb 3Composite thermoelectric material, its XRD figure spectrum is consistent with Fig. 4, is single-phase CoSb 3Diffraction peak, do not have the diffraction peak of SiC to occur.Test-results shows: the monophasic CoSb that has directly synthesized in the SPS process 3Phase, and realized low-temperature sintering according to reaction sintering mechanism, thus obtain density height, the tiny and uniform SiC/CoSb of crystal grain 3Composite thermoelectric material.
Embodiment 5: with cobalt (Co) powder, and nickel (Ni) powder, antimony (Sb) powder is that raw material is according to Co 0.9Ni 0.1Sb 3Metering than taking by weighing the powder that total amount is 20g, then according to Co 0.9Ni 0.1Sb 30.5% of powder gross weight, the mean diameter that takes by weighing 0.1g is the SiC powder of 200nm, puts into stainless cylinder of steel (volume 250ml) and carries out the MA processing, its MA handles identical with example 3 with the SPS synthetic technological condition.Powder after will handling through MA directly synthetic SiC/Co under SPS 0.9Ni 0.1Sb 3Composite thermoelectric material, its XRD figure spectrum is consistent with Fig. 4, is single-phase CoSb 3Diffraction peak, do not have the diffraction peak of SiC to occur equally.Its relative density is that 95% the relative density that adds 0.1% SiC in the 90% relative example 1 slightly descends.
Embodiment 6: with cobalt (Co) powder, and nickel (Ni) powder, antimony (Sb) powder is that raw material is according to Co 0.9Ni 0.1Sb 3Metering than taking by weighing the powder that total amount is 20g, then according to Co 0.9Ni 0.1Sb 32.0% of powder gross weight takes by weighing the 100nmSiC powder of 0.4g, puts into stainless cylinder of steel (volume 250ml) and carries out the MA processing, and its MA handles identical with example 3 with the SPS synthetic technological condition.Will be through the directly synthetic SiC/Co under SPS of the powder after the activation treatment 0.9Ni 0.1Sb 3Composite thermoelectric material.Fig. 5-8 has compared the SiC volume respectively and has been respectively 0.0,0.1,0.5 and 2.0% SiC/Co 0.9Ni 0.1Sb 3The resistivity of composite thermoelectric material, Seebeck coefficient, power factor and thermal conductivity are with variation of temperature, and test-results shows: the add-on of SiC 0.1% near can obtain thermoelectricity capability preferably, its power factor is 2280 μ Wm in the time of 450 ℃ -1K -2, be higher than and do not add the power factor 1840 μ Wms of SiC sample the time at 450 ℃ -1K -2, when the SiC add-on is too high, can cause the decline of thermoelectricity capability.With the increase of the content of SiC, SiC/Co 0.9Ni 0.1Sb 3The thermal conductivity of composite thermoelectric material descends and shows that disperse dispersing nanometer SiC's can effectively reduce whole thermal conductivity.Fig. 9 is that the SiC volume is respectively 0.0,0.1,0.5% SiC/Co 0.9Ni 0.1Sb 3The ZT value of composite thermoelectric material is with variation of temperature, as can be seen from the figure wherein add 0.1%SiC the ZT value can reach 0.672 at 450 ℃, the sample that comparatively adds SiC is high a lot.
Other preferred embodiments of the present invention are as shown in table 1.
Figure C20061014400600071
In sum, method of the present invention is promptly by behind the mechanical alloy metallization processes pre-treatment nano-dispersed composite powder, by the compound CoSb of the direct synthesis of nano SiC of discharge plasma sintering 3Base thermoelectricity material.The growing up of crystal grain of utilizing nano-diffusion SiC to suppress the SPS sintering process, thus preparation crystal grain is tiny, the SiC/CoSb of thermoelectricity capability excellence, mechanical property and good processability 3Base composite thermoelectric material.

Claims (5)

1. compound CoSb of nano SiC granule 3Base thermoelectricity material is characterized in that: this thermoelectric material has following chemical formula: Co 1-xM xSb 3+ ySiC, wherein: the span of x is 0≤x≤0.15,0＜y≤2.0%, y is that SiC accounts for Co 1-xM xSb 3The mass percent of matrix; M is the containing transition metal element; Described nano SiC granule disperse is distributed in CoSb 3In the base thermoelectricity material matrix.
2. according to the compound CoSb of the described nano SiC granule of claim 1 3Base thermoelectricity material is characterized in that: the diameter of described nano SiC granule is between 20～200nm.
3. according to claim 1 or the compound CoSb of 2 described nano SiC granules 3Base thermoelectricity material is characterized in that: described containing transition metal element is Pt, Ni or Fe.
4. compound CoSb of nano SiC granule according to claim 1 3The preparation method of base thermoelectricity material is characterized in that this method carries out as follows:
1) be raw material with Sb, Co element simple substance powder or Sb, Co and doped element simple substance powder, according to Co 1-xM xSb 3The stoichiometric ratio proportioning, wherein the span of x is 0≤x≤0.15;
2) according to chemical formula: Co 1-xM xSb 3+ ySiC, adding accounts for Co 1-xM xSb 3Substrate quality per-cent is the SiC particle of y, and wherein the span of y is 0＜y≤2.0%;
3) above-mentioned raw materials is put into ball grinder, after the forvacuum, charge into Ar gas, the ball grinder ball mill of packing into is made fines as shielding gas;
4) powder behind the ball milling is packed into graphite jig, utilize discharge plasma sintering system sintering under vacuum environment, vacuum tightness is 1～50Pa, sintering temperature is 250～600 ℃, soaking time is 1～20 minute, sintering pressure is 10～60MPa, and heat-up rate is 10 ℃～180 ℃/minute, promptly makes the nano SiC granule disperse and is distributed in CoSb 3Composite thermoelectric material in the base thermoelectricity material matrix.
5. according to the compound CoSb of the described nano SiC granule of claim 4 3The preparation method of base thermoelectricity material is characterized in that: the rotational speed of ball-mill in the step 3) is under 200～450 rev/mins, ball milling 0.25～48 hour.
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CN105525122B (en) * 2016-01-27 2017-03-29 北京工业大学 The preparation method of the compound Mg Si Sn base thermoelectricity materials of nano SiC
CN108198934B (en) * 2017-12-28 2021-03-09 龙南鑫龙业新材料有限公司 Composite thermoelectric material and preparation method thereof
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CN113333698B (en) * 2021-05-31 2023-04-18 东北大学秦皇岛分校 Completely amorphous lead telluride-based alloy strip and preparation method thereof

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