CN117715497B - Antioxidant skutterudite-based thermoelectric composite material and preparation method thereof - Google Patents
Antioxidant skutterudite-based thermoelectric composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of thermoelectric materials, and provides an antioxidant skutterudite-based thermoelectric composite material and a preparation method thereof, aiming at the problem of poor oxidation resistance of skutterudite-based materials. The composite material consists of skutterudite thermoelectric material matrix and nano second phase material, wherein the second phase material is silicon or graphite, the second phase material accounts for 0.1-20 vol% of the volume of the composite material, and the composite material is not pulverized at the temperature of 650-850K. The thermoelectric figure of merit is 0.8-1.2 times that of the skutterudite thermoelectric material matrix. The preparation method of the composite material adopts discharge plasma sintering or hot-press sintering. According to the invention, the nano second phase material silicon is added into the skutterudite material, so that the oxidation resistance of the skutterudite-based thermoelectric material is greatly improved while the thermoelectric performance of the skutterudite-based thermoelectric material is not deteriorated.
Description
Technical Field
The invention relates to the field of thermoelectric materials, in particular to an antioxidant skutterudite-based thermoelectric composite material and a preparation method thereof.
Background
The filled skutterudite thermoelectric material has excellent thermoelectric performance in a medium temperature region (room temperature to 500 ℃), and is expected to be used in the field of medium temperature region power generation. Many achievements exist in research of filled skutterudite materials, and thermoelectric properties and mechanical properties of the materials can be remarkably regulated and controlled in modes of single filling, double filling, multiple filling, nano-composite and the like.
Oxidation resistance is one of the important indicators for evaluating the stability of thermoelectric devices in long-term applications. The material needs to be in high temperature for a long time in the service process of the thermoelectric material, and the oxidation resistance determines how much protection measures need to be applied to the device, such as selecting a coating of what material, and the like. The oxidation resistance of the material is improved, so that the design cost of the thermoelectric device can be reduced, and the structure of the thermoelectric device is simplified. According to the report in the prior art, the oxidation resistance of skutterudite materials is poor, and in particular, p-type filled skutterudite materials have worse oxidation resistance （ = 1 \* GB3 ① Qiu, P.; Xia, X.; Huang, X.; Gu, M.; Qiu, Y.; Chen, L., "Pesting"-like oxidation phenomenon of p-type filled skutterudite Ce0.9Fe3CoSb12. Journal of Alloys and Compounds, 2014, 612, 365-371. = 2 \* GB3 ② Xia, X.; Qiu, P.; Huang, X.; Wan, S.; Qiu, Y.; Li, X.; Chen, L., Oxidation Behavior of Filled Skutterudite CeFe4Sb12in Air. Journal of Electronic Materials, 2014, 43 (6), 1639-1644.）,, wherein Ce 0.9Fe3CoSb12 material is powdered between 650 and 850 and K, which is a fatal problem for thermoelectric devices in service. Although the defect of reliability of the device caused by the excessively low oxidation resistance of the thermoelectric material can be partially overcome by the improvement of the design and the integration technology of the device, the use of the thermoelectric material with high oxidation resistance will be obviously improved.
Disclosure of Invention
In order to overcome the problem of poor oxidation resistance of skutterudite-based materials, the invention provides an oxidation-resistant skutterudite-based thermoelectric composite material and a preparation method thereof, wherein nano second-phase material silicon is added into skutterudite materials, so that the oxidation resistance of skutterudite-based thermoelectric materials is greatly improved while the thermoelectric properties of skutterudite-based thermoelectric materials are not deteriorated.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
An antioxidative skutterudite-based thermoelectric composite material consists of a skutterudite thermoelectric material matrix and a nano second phase material, wherein the second phase material is silicon or graphite, the second phase material accounts for 0.1-20 vol% of the composite material by volume, and the composite material is not pulverized at the temperature of 650-850K. The thermoelectric figure of merit is 0.8-1.2 times that of the skutterudite thermoelectric material matrix.
Preferably, the skutterudite thermoelectric material is ① binary pure-phase skutterudite material, or ②CoSb3 -based or FeSb 3 -based filled and/or doped skutterudite thermoelectric material.
"Pure phase skutterudite" refers to a filled skutterudite thermoelectric material having a structure of "CoSb 3" or "FeSb 3", and the chemical formula may be represented by R yM4X12, where R is one or a combination of more of alkali metal, alkaline earth metal, rare earth metal, or electronegative element S, se, m=co, rh, ir; fe, ru, os; x=as, sb. For the filling quantity of CoSb 3 base skutterudite between 0 and 50 percent by mass, fe, ni, pd, pt is generally used for doping M position, sn, ge, se, te is used for doping X position, and the mass fraction of the doping quantity is between 0 and 10 percent. For the filling quantity of FeSb 3 base skutterudite between 10 and 100 percent by mass, co, ni, pd, pt, mn and the like are generally used for doping M positions, sn, ge, se, te is used for doping X positions, and the mass fraction of the doping quantity is between 0 and 10 percent. The filled and/or doped skutterudite thermoelectric material can be prepared by a conventional method. Such as described in the following documents ： Liu, R.; Qiu, P.; Chen, X.; Huang, X.; Chen, L., Composition optimization of p-type skutterudites CeyFexCo4-xSb12and YbyFexCo4-xSb12. Journal of Materials Research, 2011, 26 (15),1813-1819.
The skutterudite thermoelectric material may be in the form of powder, granule or tablet. Preferably, the solid skutterudite material is a powder with a particle size of 0.5-70 μm.
Preferably, the form of the nano second phase material is one of nano powder with the particle size of 10-500 nm, nano tube with the diameter of 10-100 nm or nano wire with the diameter of 5-100 nm and the length of 100nm-2 μm. The shape and the size of the nanometer second phase material are in a reasonable range, and the composite material can obtain more excellent oxidation resistance.
Preferably, the nano second phase material occupies 0.5 to 3 vol percent of the volume of the composite material.
Preferably, the component of the composite material is Ce 0.9Fe3CoSb12/1vol.% Sip,Sip which refers to nano silicon powder; or Ce 0.9Fe3CoSb12/1.5 vol.% Siw,Siw refers to a silicon nanowire; or Ce 0.9Fe3CoSb12/2 vol.% Sit,Sit refers to a silicon nanotube.
The above 3 composite materials are respectively the most excellent oxidation resistance and thermoelectric comprehensive performance of silicon under different forms. It can be seen that the optimal amount of nano second phase material in different forms is different. In contrast, the dispersibility of the powder is optimal, so that the optimal effect can be achieved with a minimum amount.
The invention also provides a preparation method of the antioxidant skutterudite-based thermoelectric composite material, which comprises the following steps: mixing skutterudite thermoelectric material and nano second phase material, and sintering by discharge plasma or hot-press sintering to obtain nano second phase material/skutterudite thermoelectric composite material.
Preferably, the mixing method is one of the following three methods:
① Ball milling under gas protection, wherein the ball-material ratio (3-20) is 1, the rotating speed is 200-500 r/min, the ball milling time is 5-360 min, and the gas is Ar or N 2; the ball milling tank adopts a stainless steel ball milling tank and hard alloy WC balls;
② Firstly adding square cobalt mineral powder into a mortar by a mechanical mixing method, then adding a second phase nano material with strong oxidation resistance into the powder, and manually grinding for 30-60 min;
③ Mixing the materials in the solution, performing suction filtration or suspension evaporation, adding a second phase nano material into the ethanol or water solution, adding the cobalt powder after ultrasonic treatment of 15-30 min, continuing ultrasonic treatment of 30-60 min, performing suction filtration or rotary evaporation in an oil bath to obtain composite material powder, drying in a vacuum drying oven, and grinding in a mortar of 15-30 min.
The mixing method directly affects the dispersion uniformity of the second phase nanomaterial in the skutterudite material, and thus strict control of parameters is required. Only under the proper mixing method, the second phase nano material can be uniformly dispersed in the skutterudite material, and the material with excellent oxidation resistance can be obtained after subsequent sintering.
Preferably, in the spark plasma sintering, the sintering time is 10-60 min, the pressure is 10-100 MPa, the sintering temperature of the n-type filled skutterudite composite material is 590-640 ℃, and the sintering temperature of the p-type filled skutterudite composite material is 560-610 ℃.
Preferably, in the hot press sintering, the pressure is 10-100 MPa, the sintering temperature of the n-type filled skutterudite composite material is 620-690 ℃, and the sintering temperature of the p-type filled skutterudite composite material is 580-660 ℃.
N-type and p-type filled skutterudite composite materials have different optimal sintering temperatures due to the different microstructures.
Therefore, the invention has the beneficial effects that: the nano second phase material silicon and graphite are added into the skutterudite material, so that the prepared nano second phase material/skutterudite thermoelectric composite material greatly improves the oxidation resistance of the skutterudite thermoelectric composite material, and meanwhile, the thermoelectric performance of the composite material is improved or basically maintained unchanged relative to the original matrix.
The silicon and the graphite have strong oxidation resistance, and the nano phases of the silicon and the graphite are distributed on the grain boundary of the skutterudite material, so that the diffusion of oxygen on the grain boundary can be effectively relieved, the oxidation resistance of the material can be improved, and the obtained composite material does not generate powdering phenomenon in the range of 650-850K; more importantly, the addition of silicon and graphite can keep the thermoelectric performance of the composite material to be improved or basically maintained unchanged relative to the original matrix.
The inventor has tried many other antioxidant materials in the early stage, either the improvement of the antioxidant performance is not obvious, or the thermoelectric performance of the composite material is greatly reduced, and only the thermoelectric performance of the skutterudite-based thermoelectric material is not deteriorated, but the antioxidant performance of the skutterudite-based thermoelectric material is greatly improved, so that the inventor has obvious progress compared with the prior art. Because the conductivity is reduced due to the addition of the back scattering carrier into the second phase material, the silicon and the graphite selected by the invention have an energy filtering effect, so that the Zebra coefficient is not greatly changed, and even is slightly improved; the scattering of phonons after the addition of silicon and graphite can lead to the reduction of the thermal conductivity of the composite material compared with a matrix, and finally, the dimensionless figure-of-merit zT value of the composite material disclosed by the invention can be maintained to be 0.8-1.2 times of that of the skutterudite thermoelectric material matrix calculated by zT=S 2 σT/κ.
Drawings
FIG. 1 is a cross-sectional SEM morphology of a Ce 0.9Fe3CoSb12/1: 1 vol.% Si nanoparticle composite made in example 1.
FIG. 2 is a graph showing the thermoelectric transport properties of Ce 0.9Fe3CoSb12/1 vol.% Si nanoparticle composites prepared in example 1 as a function of temperature.
Fig. 3 is an optical photograph of a Ce 0.9Fe3CoSb12 matrix (left) and a Ce 0.9Fe3CoSb12/1 vol.% Si nanoparticle composite (right) heated at 500 ℃ for 10 min.
Detailed Description
The technical scheme of the invention is further described through specific embodiments.
In the present invention, unless otherwise specified, the materials and equipment used are commercially available or are commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
An antioxidative skutterudite-based thermoelectric composite material is composed of skutterudite thermoelectric material matrix and nano second phase material. The skutterudite thermoelectric material is ① binary pure-phase skutterudite material or ②CoSb3 -based or FeSb 3 -based filling and/or doping skutterudite thermoelectric material; the powder, granule or tablet is preferably powder with particle diameter of 0.5-70 μm. The second phase material is silicon or graphite; the form is preferably one of nano powder with the particle size of 10-500 nm, nano tube with the diameter of 10-100 nm or nano wire with the diameter of 5-100 nm and the length of 100 nm-2 μm; the second phase material comprises 0.1-20 vol% by volume of the composite material, more preferably 0.5-3 vol%. The component of the composite material is preferably Ce 0.9Fe3CoSb12/1vol.% Sip,Sip nano silicon powder; or Ce 0.9Fe3CoSb12/1.5 vol.% Siw,Siw refers to a silicon nanowire; or Ce 0.9Fe3CoSb12/2 vol.% Sit,Sit refers to a silicon nanotube.
The invention also provides a preparation method of the antioxidant skutterudite-based thermoelectric composite material, which comprises the following steps:
(1) Mixing skutterudite thermoelectric material and nano second phase material, wherein the mixing method is one of the following three methods:
① Ball milling under gas protection, wherein the ball-material ratio (3-20) is 1, the rotating speed is 200-500 r/min, the ball milling time is 5-360 min, and the gas is Ar or N 2; the ball milling tank adopts a stainless steel ball milling tank and hard alloy WC balls;
② Firstly adding square cobalt mineral powder into a mortar by a mechanical mixing method, then adding a second phase nano material with strong oxidation resistance into the powder, and manually grinding for 30-60 min;
③ Mixing the materials in the solution, performing suction filtration or suspension evaporation, adding a second phase nano material into the ethanol or water solution, adding the cobalt powder after ultrasonic treatment of 15-30 min, continuing ultrasonic treatment of 30-60 min, performing suction filtration or rotary evaporation in an oil bath to obtain composite material powder, drying in a vacuum drying oven, and grinding in a mortar of 15-30 min.
(2) The nanometer second phase material/skutterudite thermoelectric composite material is obtained through spark plasma sintering or hot-pressing sintering. In the spark plasma sintering, the sintering temperature of the n-type filled skutterudite composite material is 590-640 ℃; the sintering temperature of the p-type filled skutterudite composite material is 560-610 ℃, the time is 10-60 min, and the pressure is 10-100 MPa. In the hot-press sintering, the sintering temperature of the n-type filled skutterudite composite material is 620-690 ℃ and the pressure is 10-100 MPa; the sintering temperature of the p-type filled skutterudite composite material is 580-660 ℃.
Example 1
An antioxidant skutterudite-based thermoelectric composite material is a p-skutterudite-based composite material Ce 0.9Fe3CoSb12 +1 vol.% silicon nano-powder composite material.
The preparation method of the antioxidant skutterudite-based thermoelectric composite material comprises the following steps:
Mixing the synthesized Ce-filled p-type filled skutterudite Ce 0.9Fe3CoSb12 powder (average particle size of 10 mu m) with silicon nano powder (average particle size of 50 nm) with a volume ratio of 1 vol% in a glove box in Ar atmosphere, putting into a stainless steel ball grinding tank, selecting hard alloy WC balls, ball-milling at room temperature for 6h by using a high-energy ball mill after sealing with a ball-material ratio of 5:1, and adjusting the rotating speed of 500 r/min to obtain the composite material powder.
And (3) filling the powder into a graphite mold with the diameter phi of 20 mm in a glove box in Ar atmosphere, and sintering by using spark plasma to obtain a compact p-type skutterudite-based composite material Ce 0.9Fe3CoSb12 +1 vol-percent silicon nano powder composite material block. The sintering temperature is 570 ℃, the sintering condition is that the heating rate is 50 ℃/min, the pressure is 50 MPa, the sintering time is 20 min, and the heat preservation is 10 min.
The phase analysis, thermoelectric performance, microstructure observation and oxidation resistance analysis of the prepared composite material are shown in figures 1-3. From the SEM morphology of the composite cross section of FIG. 1, it can be seen that the silicon nanoparticles are macroscopically more uniformly distributed in the matrix. From the relationship of thermoelectric transport properties of the composite material with temperature change in fig. 2, it can be seen that the entering of nano silicon powder, although scattering carriers, causes the conductivity of the composite material containing 1 vol% Si to be reduced compared with the matrix (0 vol%), does not change much, even slightly, due to the energy filtering effect of the nano silicon powder on the interface. Due to the introduction of the nano silicon powder, the thermal conductivity of the 1vol percent Si composite material is reduced compared with that of the matrix (0 vol percent), and finally, the nondimensional figure of merit zT of the 1vol percent Si composite material is calculated from zT=S 2 σT/kappa (the meaning of each physical quantity in the formula is that the electrical conductivity sigma, the Zebeck coefficient S, the temperature T, the thermal conductivity kappa and the thermoelectricity nondimensional figure of merit zT value) and is not reduced compared with that of the matrix (0 vol percent). As can be seen from the optical photograph of the composite of fig. 3 heated at 500 ℃ for 10min, the oxidation resistance of the composite with Si nanoparticles added is significantly enhanced. Heating at the same temperature for the same time, pulverizing and crushing the Ce 0.9Fe3CoSb12 matrix on the left into small blocks, and turning the surface into reddish brown; the surface of the Ce 0.9Fe3CoSb12/1 vol.% Si nanoparticle composite material on the right is provided with a black oxide film protective layer, and the whole block shape is still maintained, and pulverization does not occur.
Example 2
The difference from example 1 is that 1 vol% of silicon nanopowder was replaced with 1.5. 1.5 vol% of silicon nanowires.
An antioxidant skutterudite-based thermoelectric composite material is a p-skutterudite-based composite material Ce 0.9Fe3CoSb12 +1.5: 1.5 vol.% silicon nanowire composite material.
The preparation method of the antioxidant skutterudite-based thermoelectric composite material comprises the following steps:
Mixing the synthesized Ce-filled p-type filled skutterudite Ce 0.9Fe3CoSb12 powder (average particle size of 10 mu m) with silicon nanowire (diameter of 50 nm and length of 100 nm) with volume ratio of 1.5 to vol in a glove box in Ar atmosphere, putting into a stainless steel ball grinding tank, selecting hard alloy WC balls with ball-to-ball ratio of 5:1, ball-milling 6 h at room temperature after sealing by using a high-energy ball mill, and adjusting rotating speed of 500 r/min to obtain the composite material powder.
And (3) filling the powder into a graphite mold with the diameter phi of 20mm in a glove box in Ar atmosphere, and sintering by using spark plasma to obtain a compact p-type skutterudite-based composite material Ce 0.9Fe3CoSb12 +1.5 vol-wt.% silicon nanowire composite material block. The sintering temperature is 570 ℃, the sintering condition is that the heating rate is 50 ℃/min, the pressure is 50 MPa, the sintering time is 20 min, and the heat preservation is 10 min.
Example 3
The difference from example 1 is that 1 vol% of silicon nanopowder was replaced with 2 vol% of silicon nanotubes.
An antioxidant skutterudite-based thermoelectric composite material is a p-skutterudite-based composite material Ce 0.9Fe3CoSb12 +2 vol-percent silicon nanotube composite material.
The preparation method of the antioxidant skutterudite-based thermoelectric composite material comprises the following steps:
Mixing the synthesized Ce-filled p-type filled skutterudite Ce 0.9Fe3CoSb12 powder (average particle size of 10 mu m) with silicon nanotubes (diameter of 10 nm) with volume ratio of 2 vol% in a glove box in Ar atmosphere, putting into a stainless steel ball grinding tank, selecting hard alloy WC balls, ball-milling at room temperature for 6 h by using a high-energy ball mill after sealing with ball-material ratio of 5:1, and regulating rotating speed of 500 r/min to obtain the composite material powder.
And (3) filling the powder into a graphite mold with the diameter phi of 20 mm in a glove box in Ar atmosphere, and sintering by using spark plasma to obtain a compact p-type skutterudite-based composite material Ce 0.9Fe3CoSb12 +2 vol-percent silicon nanotube composite material block. The sintering temperature is 570 ℃, the sintering condition is that the heating rate is 50 ℃/min, the pressure is 50 MPa, the sintering time is 20 min, and the heat preservation is 10 min.
Example 4
The difference from example 1 is that 1 vol% of silicon nanopowder was replaced with 3 vol% of graphite nanopowder.
An antioxidant skutterudite-based thermoelectric composite material is a p-skutterudite-based composite material Ce 0.9Fe3CoSb12 +3 vol-percent graphite nano-powder composite material.
The preparation method of the antioxidant skutterudite-based thermoelectric composite material comprises the following steps:
Mixing the synthesized Ce-filled p-type filled skutterudite Ce 0.9Fe3CoSb12 powder (average particle size of 10 mu m) with graphite nano powder (average particle size of 50 nm) with a volume ratio of 3 vol% in a glove box in Ar atmosphere, putting into a stainless steel ball grinding tank, selecting hard alloy WC balls, ball-milling at room temperature for 6h by using a high-energy ball mill after sealing with a ball-material ratio of 5:1, and regulating the rotating speed of 500 r/min to obtain the composite material powder.
And (3) filling the powder into a graphite mold with the diameter phi of 20 mm in a glove box in Ar atmosphere, and sintering by using spark plasma to obtain a compact p-type skutterudite-based composite material Ce 0.9Fe3CoSb12 +3 vol-type graphite nano powder composite material block. The sintering temperature is 570 ℃, the sintering condition is that the heating rate is 50 ℃/min, the pressure is 50 MPa, the sintering time is 20 min, and the heat preservation is 10 min.
Example 5
An antioxidant skutterudite-based thermoelectric composite material is an n-skutterudite-based composite material Yb 0.3Co4Sb12 +0.5. 0.5 vol% silicon nano-powder composite material.
The preparation method of the antioxidant skutterudite-based thermoelectric composite material comprises the following steps:
Mixing 15.0 g of synthesized Yb-filled n-type filled skutterudite Yb 0.3Co4Sb12 powder (average particle size of 0.5 μm) and silicon nano powder (average particle size of 100 nm) with a volume ratio of 0.5 and vol) in a glove box in Ar atmosphere, putting into a stainless steel ball grinding tank, ball-milling at room temperature for 2 h by using a high-energy ball mill after sealing, and regulating the rotating speed to 200 r/min to obtain composite material powder.
And (3) filling the powder into a graphite mold with the diameter phi of 20 mm in a glove box in Ar atmosphere, and sintering by using spark plasma to obtain a compact n-type skutterudite-based composite material Yb 0.3Co4Sb12 +0.5 vol-percent silicon nano powder composite material block, wherein the sintering temperature is 600 ℃, the sintering condition is that the heating rate is 50 ℃/min, the pressure is 50 MPa, the sintering time is 20min, and the heat preservation is 10 min.
Example 6
An antioxidant skutterudite-based thermoelectric composite material is an n-type binary pure-phase skutterudite material CoSb 3 +0.1 vol.% silicon nano-powder composite material.
The preparation method of the antioxidant skutterudite-based thermoelectric composite material comprises the following steps:
in an Ar atmosphere glove box, a flaky binary pure-phase skutterudite material was first added in an agate mortar, followed by adding silicon nanopowder in a volume ratio of 0.1 vol%, and manually grinding for 50: 50 min.
And (3) filling the powder into a graphite mould with the diameter phi of 20 mm in a glove box in Ar atmosphere, and hot-pressing and sintering to obtain a compact binary pure-phase skutterudite material+0.1: 0.1 vol% silicon nano powder composite material block. The sintering temperature is 670 ℃, the pressure is 50 MPa, and the temperature is kept at 3 h.
Example 7
An antioxidant skutterudite-based thermoelectric composite material is a p-type FeSb 3 -based doped skutterudite thermoelectric material Ce 0.9Fe3CoSb12 +20 vol-percent silicon nano-powder composite material.
The preparation method of the antioxidant skutterudite-based thermoelectric composite material comprises the following steps:
in a glove box in Ar atmosphere, adding silicon nano powder (average particle size 500 nm) with volume ratio of 1 vol percent into ethanol solution, adding p-type FeSb 3 -based doped skutterudite thermoelectric material Ce 0.9Fe3CoSb12 particles (average particle size 0.5 μm) of 15.0 g after ultrasonic treatment of 15. 15 min, continuing ultrasonic treatment of 60 min, rotationally evaporating in an oil bath, finally obtaining composite material powder, drying in a vacuum drying oven, and grinding in an agate mortar for 30 min to obtain the composite material powder.
And (3) filling the powder into a graphite mold with the diameter phi of 20 mm in a glove box in Ar atmosphere, and hot-pressing and sintering to obtain a compact p-type FeSb 3 -based skutterudite-doped thermoelectric material Ce 0.9Fe3CoSb12 +20 vol-silicon nano powder composite material block. The sintering temperature is 640 ℃, the pressure is 50 MPa, and the temperature is kept at 3 h.
Comparative example 1
The difference from example 1 is that 1 vol% of silicon nanopowder was replaced with 5 vol% of silicon nanopowder.
The preparation method of the antioxidation skutterudite-based thermoelectric composite material comprises the steps of mixing 15.0 g synthesized Ce-filled p-type filled skutterudite Ce 0.9Fe3CoSb12 powder (average particle size of 10 mu m) and silicon nano powder with a volume ratio of 5 vol% (average particle size of 50 nm) in a glove box in Ar atmosphere, putting the mixture into a stainless steel ball grinding tank, selecting hard alloy WC balls with a ball material ratio of 5:1, ball-milling the mixture at room temperature by using a high-energy ball mill for 6h after sealing, and adjusting the rotating speed of 500 r/min to obtain composite material powder.
And (3) filling the powder into a graphite mold with the diameter phi of 20 mm in a glove box in Ar atmosphere, and sintering by using spark plasma to obtain a compact p-type skutterudite-based composite material Ce 0.9Fe3CoSb12 +5 vol-silicon nano powder composite material block. The sintering temperature is 570 ℃, the sintering condition is that the heating rate is 50 ℃/min, the pressure is 50 MPa, the sintering time is 20 min, and the heat preservation is 10 min.
The comparative example 1 uses an excessive amount of silicon nanopowder compared to example 1, resulting in a decrease in thermoelectric performance of the material due to agglomeration of the nanopowder.
Comparative example 2
The difference from example 1 is that the silicon nanopowder was replaced with diamond particles.
The preparation method of the antioxidant skutterudite-based thermoelectric composite material comprises the steps of mixing 15.0 g of synthesized Ce-filled p-type filled skutterudite Ce 0.9Fe3CoSb12 powder (average particle size of 10 mu m) and diamond particles with volume ratio of 1 vol) (average particle size of 50 nm) in a glove box in Ar atmosphere, putting the mixture into a stainless steel ball grinding tank, selecting hard alloy WC balls with ball material ratio of 5:1, ball-milling the mixture at room temperature by using a high-energy ball mill for 6h after sealing, and adjusting rotating speed of 500 r/min to obtain composite material powder.
And (3) filling the powder into a graphite mold with the diameter phi of 20 mm in a glove box in Ar atmosphere, and sintering by using spark plasma to obtain a compact p-type skutterudite-based composite material Ce 0.9Fe3CoSb12 +1 vol-percent diamond particle composite material block. The sintering temperature is 570 ℃, the sintering condition is that the heating rate is 50 ℃/min, the pressure is 50 MPa, the sintering time is 20 min, and the heat preservation is 10 min.
The diamond particles also have oxidation resistance, but the addition to the skutterudite-based material does not significantly improve the oxidation resistance of the skutterudite-based thermoelectric composite material without deteriorating the thermoelectric performance of the skutterudite-based thermoelectric material.
Comparative example 3
The difference from example 1 is that the sintering temperature is 520 ℃.
The preparation method of the antioxidant skutterudite-based thermoelectric composite material comprises the steps of mixing 15.0 g of synthesized Ce-filled p-type filled skutterudite Ce 0.9Fe3CoSb12 powder (average particle size of 10 mu m) and silicon nano powder (average particle size of 50 nm) with a volume ratio of 1.1 vol in a glove box in Ar atmosphere, putting the mixture into a stainless steel ball grinding tank, selecting hard alloy WC balls with a ball material ratio of 5:1, ball-grinding the mixture at room temperature by using a high-energy ball mill for 6h after sealing, and adjusting the rotating speed of 500 r/min to obtain composite material powder.
And (3) filling the powder into a graphite mold with the diameter phi of 20 mm in a glove box in Ar atmosphere, and sintering by using spark plasma to obtain a compact p-type skutterudite-based composite material Ce 0.9Fe3CoSb12 +1 vol-percent silicon nano powder composite material block. The sintering temperature is 520 ℃, the sintering condition is that the heating rate is 50 ℃/min, the pressure is 50 MPa, the sintering time is 20 min, and the heat preservation is 10 min.
The sintering temperature of comparative example 3 was too low, and the thermoelectric performance was lowered due to the non-densification of the thermoelectric material block sintering.
Performance table
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalent changes and variations in the above-mentioned embodiments can be made by those skilled in the art without departing from the scope of the present invention.
Claims (9)
1. An antioxidation skutterudite-based thermoelectric composite material is characterized by comprising a skutterudite thermoelectric material matrix and a nanometer second phase material, wherein the second phase material is silicon, the second phase material accounts for 0.1-20% of the volume of the composite material, and the composite material is 650-850K and is not pulverized; the second phase material is one of silicon nano powder with the particle size of 10-500nm, silicon nano tube with the diameter of 10-100nm or silicon nano wire with the diameter of 5-100nm and the length of 100nm-2 mu m.
2. The composite of claim 1, wherein the skutterudite thermoelectric material is ① binary pure phase skutterudite material, or ②CoSb3 -based or FeSb 3 -based filled and/or doped skutterudite thermoelectric material.
3. The composite material according to claim 1 or 2, wherein the skutterudite material is a powder having a particle size of 0.5 to 70 μm.
4. The composite of claim 1, wherein the nano second phase material comprises 0.5 to 3 vol% by volume of the composite.
5. The composite material according to claim 1, wherein the component of the composite material is Ce 0.9Fe3CoSb12/1vol.% Sip,Sip is nano silicon powder; or Ce 0.9Fe3CoSb12/1.5 vol.% Siw,Siw refers to a silicon nanowire; or Ce 0.9Fe3CoSb12/2 vol.% Sit,Sit refers to a silicon nanotube.
6. A method for producing a thermoelectric composite material comprising the oxidation-resistant skutterudite-based material as claimed in any one of claims 1 to 5, characterized by comprising the steps of: mixing skutterudite thermoelectric material and nano second phase material, and sintering by discharge plasma or hot-press sintering to obtain nano second phase material/skutterudite thermoelectric composite material.
7. The method of claim 6, wherein the mixing is one of three methods: ① Ball milling under gas protection, wherein the ball-material ratio (3-20) is 1, the rotating speed is 200-500 r/min, the ball milling time is 5-360 min, and the gas is Ar or N 2; the ball milling tank adopts a stainless steel ball milling tank and hard alloy WC balls;
② Firstly adding square cobalt mineral powder into a mortar by a mechanical mixing method, then adding a second phase nano material with strong oxidation resistance into the powder, and manually grinding for 30-60 min;
③ Mixing the materials in the solution, performing suction filtration or suspension evaporation, adding a second phase nano material into the ethanol or water solution, adding the cobalt powder after ultrasonic treatment of 15-30 min, continuing ultrasonic treatment of 30-60 min, performing suction filtration or rotary evaporation in an oil bath to obtain composite material powder, drying in a vacuum drying oven, and grinding in a mortar of 15-30 min.
8. The method according to claim 6 or 7, wherein in the spark plasma sintering, the sintering time is 10-60 min, the pressure is 10-100 mpa, the sintering temperature of the n-type filled skutterudite composite material is 590-640 ℃, and the sintering temperature of the p-type filled skutterudite composite material is 560-610 ℃.
9. The method according to claim 6 or 7, wherein in the hot press sintering, the sintering temperature of the n-type filled skutterudite composite material is 620-690 ℃ and the sintering temperature of the p-type filled skutterudite composite material is 580-660 ℃ at a pressure of 10-100 mpa.
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