CN117715497A - 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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- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 26
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 110
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- 239000010439 graphite Substances 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 21
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- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
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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 0.1-20vol.% 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 prior art reports, skutterudite materials have poor oxidation resistance, and in particular p-type filled skutterudite materials have poorer oxidation resistance (=1\gb 3 (1) Qiu, p.; xia, x.; huang, x.; gu, m.; qiu, y.; chen, l., "nesting" -like oxidation phenomenon of p-type filled skutterudite Ce) 0.9 Fe 3 CoSb 12 . 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 CeFe 4 Sb 12 in air, journal of Electronic Materials, 2014, 43 (6), 1639-1644), wherein Ce 0.9 Fe 3 CoSb 12 The material may be powdered between 650-850 and K, which is a fatal problem for the thermoelectric device 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 antioxidation skutterudite-based thermoelectric composite material consists of a skutterudite thermoelectric material matrix and a nanometer second phase material, wherein the second phase material is silicon or graphite, the second phase material accounts for 0.1-20vol.% 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.
Preferably, the skutterudite thermoelectric material is (1) a binary pure-phase skutterudite material, or (2) CoSb 3 Radicals or FeSb 3 Filling of the matrix and/or doping of the skutterudite thermoelectric material.
"pure phase skutterudite" means skutterudite having a chemical formula of "CoSb 3 "or" FeSb 3 "structured filled skutterudite thermoelectric material, the chemical formula of which can be expressed as R y M 4 X 12 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 "CoSb 3 The filling amount of the basic skutterudite is between 0 and 50 percent by mass, the M position is doped by Fe, ni, pd, pt, the X position is doped by Sn, ge, se, te, and the mass percent of the filling amount is between 0 and 10 percent. For FeSb 3 The filling amount of the basic skutterudite is between 10 and 100 percent by mass, the M position is doped by Co, ni, pd, pt, mn and the like, the X position is doped by Sn, ge, se, te, and the mass fraction of the doping amount 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., qia, P., chen, X, huang, X, chen, L., composition optimization of p-type skutterudites Ce y Fe x Co x4- Sb 12 and Yb y Fe x Co x4- Sb 12 . 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 nano powder with the particle size of 10-500 nm, a nano tube with the diameter of 10-100 nm, or a 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.% of the composite material.
Preferably, the composite material has a composition of Ce 0.9 Fe 3 CoSb 12 /1vol.% Si p ，Si p Refers to nano silicon powder; or, ce 0.9 Fe 3 CoSb 12 /1.5 vol.% Si w ，Si w Refers to silicon nanowires; or, ce 0.9 Fe 3 CoSb 12 /2 vol.% Si t ，Si t Refers to silicon nanotubes.
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 method under gas protection with ball material ratio (3-20) of 1, rotation speed of 200-500 r/min, ball milling time of 5-360 min, wherein the gas is Ar or N 2 The method comprises the steps of carrying out a first treatment on the surface of the 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, performing ultrasonic treatment for 15-30 min, adding cobalt powder, performing ultrasonic treatment for 30-60 min, performing suction filtration or performing rotary evaporation in an oil bath to obtain composite material powder, drying in a vacuum drying oven, and grinding in a mortar for 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; scattering of phonons after addition of silicon and graphite can lead to reduction of thermal conductivity of the composite material compared with a matrix, and finally the composite material is formed byzT=S 2 σT/κCalculating the dimensionless figure of merit of the composite material of the present inventionzTThe value may be maintained at 0.8 to 1.2 times that of the skutterudite thermoelectric material matrix.
Drawings
FIG. 1 is Ce prepared in example 1 0.9 Fe 3 CoSb 12 1vol.% of Si nanoparticle composite cross-section SEM morphology.
FIG. 2 is Ce prepared in example 1 0.9 Fe 3 CoSb 12 1vol.% of the thermoelectric transport properties of the Si nanoparticle composite as a function of temperature.
FIG. 3 is Ce 0.9 Fe 3 CoSb 12 Matrix (left) and Ce 0.9 Fe 3 CoSb 12 1vol.% Si nanoparticle composite (right) was 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 antioxidizing skutterudite-base thermoelectric composite material is prepared fromSkutterudite thermoelectric material matrix and nano second phase material. The skutterudite thermoelectric material is (1) binary pure-phase skutterudite material, or (2) CoSb 3 Radicals or FeSb 3 Filling of the base and/or doping of the 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 100nm-2 μm; the second phase material comprises 0.1 to 20 vol.% of the composite material, more preferably 0.5 to 3 vol.%. The component of the composite material is preferably Ce 0.9 Fe 3 CoSb 12 /1vol.% Si p ，Si p Refers to nano silicon powder; or, ce 0.9 Fe 3 CoSb 12 /1.5 vol.% Si w ，Si w Refers to silicon nanowires; or, ce 0.9 Fe 3 CoSb 12 /2 vol.% Si t ，Si t Refers to silicon nanotubes.
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 method under gas protection with ball material ratio (3-20) of 1, rotation speed of 200-500 r/min, ball milling time of 5-360 min, wherein the gas is Ar or N 2 The method comprises the steps of carrying out a first treatment on the surface of the 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, performing ultrasonic treatment for 15-30 min, adding cobalt powder, performing ultrasonic treatment for 30-60 min, performing suction filtration or performing rotary evaporation in an oil bath to obtain composite material powder, drying in a vacuum drying oven, and grinding in a mortar for 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 p-skutterudite-based composite material Ce 0.9 Fe 3 CoSb 12 +1 vol.% silicon nanopowder composite.
The preparation method of the antioxidant skutterudite-based thermoelectric composite material comprises the following steps:
15.0. 15.0 g of synthesized Ce-filled p-type filled skutterudite Ce is put in a glove box in Ar atmosphere 0.9 Fe 3 CoSb 12 Mixing the powder (average particle size of 10 μm) with silicon nano powder (average particle size of 50 nm) with volume ratio of 1vol.%, putting into a stainless steel ball grinding tank, selecting hard alloy WC balls with ball-to-material ratio of 5:1, ball milling for 6 h at room temperature by using a high-energy ball mill after sealing, and regulating rotating speed to 500 r/min to obtain the composite material powder.
Filling the powder into a graphite mould with the diameter phi of 20 and mm in a glove box in Ar atmosphere, and sintering by using spark plasma to obtain the compact p-type skutterudite-based composite material Ce 0.9 Fe 3 CoSb 12 +1 vol.% silicon nano-powder composite bulk. 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 of fig. 2, it can be seen that the ingress of nano silicon powder, while scattering carriers, results in a decrease in electrical conductivity of the composite material containing 1vol.% Si compared to the matrix (0 vol.%), is due to the interfaceThe energy filtering effect of the upper nanometer silica powder does not change greatly, and even the zebesk coefficient is improved slightly. Due to the introduction of the nano silicon powder, the scattering of phonons causes the thermal conductivity of the 1vol.% Si composite material to be reduced compared with the matrix (0 vol.%), and finally the silicon composite material is formed byzT=S 2 σT/κ(wherein each physical quantity means conductivityσZebeck coefficientSTemperature (temperature)TThermal conductivity ofκThermoelectric dimensionless figure of meritzTValue) of the Si-containing composite material of 1vol.% was calculatedzTThe values were not reduced compared to the matrix (0 vol.%). As can be seen from the optical photograph of the composite material of fig. 3 heated at 500 ℃ for 10 min, the oxidation resistance of the composite material added with Si nanoparticles is significantly enhanced. Heating at the same temperature and time, ce on the left 0.9 Fe 3 CoSb 12 Pulverizing and crushing the matrix into small blocks, and turning the surface into reddish brown; ce on the right 0.9 Fe 3 CoSb 12 And (3) the surface of the Si nanoparticle composite material is provided with a black oxide film protective layer, and the whole block shape is still maintained, so that pulverization does not occur.
Example 2
The difference from example 1 is that 1vol.% of silicon nanopowder is replaced with 1.5 vol.% of silicon nanowires.
An antioxidant skutterudite-based thermoelectric composite material is p-skutterudite-based composite material Ce 0.9 Fe 3 CoSb 12 +1.5 vol.% silicon nanowire composite.
The preparation method of the antioxidant skutterudite-based thermoelectric composite material comprises the following steps:
15.0. 15.0 g of synthesized Ce-filled p-type filled skutterudite Ce is put in a glove box in Ar atmosphere 0.9 Fe 3 CoSb 12 Mixing the powder (average particle size 10 μm) with silicon nanowires (diameter 50nm, length 100 nm) with volume ratio of 1.5 vol.% and placing into a stainless steel ball grinding tank, selecting hard alloy WC balls with ball-to-material ratio of 5:1, ball milling at room temperature for 6 h after sealing by using a high-energy ball mill, and regulating rotation speed to 500 r/min to obtain the composite material powder.
Filling the powder into a graphite mould with the diameter phi of 20 and mm in a glove box with Ar atmosphere, and sintering by spark plasmaObtaining compact p-type skutterudite-based composite material Ce 0.9 Fe 3 CoSb 12 +1.5 vol.% silicon nanowire composite bulk. 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 1vol.% of silicon nanopowder is replaced with 2 vol.% of silicon nanotubes.
An antioxidant skutterudite-based thermoelectric composite material is p-skutterudite-based composite material Ce 0.9 Fe 3 CoSb 12 +2 vol.% silicon nanotube composite.
The preparation method of the antioxidant skutterudite-based thermoelectric composite material comprises the following steps:
15.0. 15.0 g of synthesized Ce-filled p-type filled skutterudite Ce is put in a glove box in Ar atmosphere 0.9 Fe 3 CoSb 12 Mixing the powder (average particle size 10 μm) with silicon nanotubes (diameter 10 nm) with volume ratio of 2 vol.%, putting into a stainless steel ball grinding tank, selecting hard alloy WC balls with ball-to-material ratio of 5:1, ball milling at room temperature for 6 h by using a high-energy ball mill after sealing, and regulating the rotating speed to 500 r/min to obtain the composite material powder.
Filling the powder into a graphite mould with the diameter phi of 20 and mm in a glove box in Ar atmosphere, and sintering by using spark plasma to obtain the compact p-type skutterudite-based composite material Ce 0.9 Fe 3 CoSb 12 +2 vol.% silicon nanotube composite bulk. 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 1vol.% of silicon nanopowder is replaced with 3 vol.% of graphite nanopowder.
An antioxidant skutterudite-based thermoelectric composite material is p-skutterudite-based composite material Ce 0.9 Fe 3 CoSb 12 +3 vol.% graphite nanopowder composite.
The preparation method of the antioxidant skutterudite-based thermoelectric composite material comprises the following steps:
15.0. 15.0 g of synthesized Ce-filled p-type filled skutterudite Ce is put in a glove box in Ar atmosphere 0.9 Fe 3 CoSb 12 Mixing the powder (average particle size of 10 μm) with graphite nano powder (average particle size of 50 nm) with volume ratio of 3 vol.%, putting into a stainless steel ball grinding tank, selecting hard alloy WC balls with ball-to-material ratio of 5:1, ball milling for 6 h at room temperature by using a high-energy ball mill after sealing, and regulating rotating speed to 500 r/min to obtain the composite material powder.
Filling the powder into a graphite mould with the diameter phi of 20 and mm in a glove box in Ar atmosphere, and sintering by using spark plasma to obtain the compact p-type skutterudite-based composite material Ce 0.9 Fe 3 CoSb 12 +3 vol.% graphite nano-powder composite bulk. 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 antioxidizing skutterudite-based thermoelectric composite material is n-type skutterudite-based composite material Yb 0.3 Co 4 Sb 12 +0.5 vol.% silicon nanopowder composite.
The preparation method of the antioxidant skutterudite-based thermoelectric composite material comprises the following steps:
15.0. 15.0 g of the synthesized Yb-filled n-type filled skutterudite Yb was put in a glove box in Ar atmosphere 0.3 Co 4 Sb 12 Mixing the powder (average grain size of 0.5 μm) with silicon nano powder (average grain size of 100 nm) with volume ratio of 0.5 vol.% and putting into a stainless steel ball grinding tank, ball-grinding with ball-to-material ratio of 5:1, ball-grinding with high-energy ball mill at room temperature for 2 h after sealing, and regulating rotation speed of 200 r/min to obtain composite material powder.
Filling the powder into a graphite mould with the diameter phi of 20 and mm in a glove box in Ar atmosphere, and sintering by using spark plasma to obtain the compact n-type skutterudite-based composite material Yb 0.3 Co 4 Sb 12 +0.5 vol.% of silicon nano powder composite block, the sintering temperature is 600 ℃, the sintering condition is that the temperature rising rate is 50 ℃/min, the pressure is 50 MPa, the sintering time is 20 min, and the heat preservation is 10 min.
Example 6
Antioxidant skutterudite-based heatThe electric composite material is n-type binary pure-phase skutterudite material CoSb 3 +0.1 vol.% silicon nanopowder composite.
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 min.
And (3) filling the powder into a graphite mold with the diameter phi of 20 and mm in a glove box in Ar atmosphere, and hot-pressing and sintering to obtain a compact binary pure-phase skutterudite material+0.1 vol.% silicon nano powder composite material block. The sintering temperature is 670 ℃, the pressure is 50 MPa, and the heat preservation is 3 h.
Example 7
An antioxidative skutterudite-based thermoelectric composite material is p-type FeSb 3 Base doped skutterudite thermoelectric material Ce 0.9 Fe 3 CoSb 12 +20 vol.% silicon nanopowder composite.
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 1vol.% into ethanol solution, adding 15.0 g of p-type FeSb after ultrasonic treatment for 15 min 3 Base doped skutterudite thermoelectric material Ce 0.9 Fe 3 CoSb 12 The particles (average particle diameter of 0.5 μm) continue to be ultrasonic for 60 min, and are rotationally evaporated in an oil bath, and finally the obtained composite material powder is put into a vacuum drying oven for drying, and then put into an agate mortar for grinding for 30 min, so as to obtain the composite material powder.
Filling the powder into a graphite mould with the diameter phi of 20 and mm in a glove box in Ar atmosphere, and obtaining compact p-type FeSb after hot-pressing sintering 3 Base doped skutterudite thermoelectric material Ce 0.9 Fe 3 CoSb 12 +20 vol.% silicon nano-powder composite bulk. The sintering temperature is 640 ℃, the pressure is 50 MPa, and the heat preservation is 3 h.
Comparative example 1
The difference from example 1 is that 1vol.% of silicon nanopowder is replaced with 5 vol.% of silicon nanopowder.
A preparation method of an antioxidant skutterudite-based thermoelectric composite material comprises the steps of synthesizing 15.0 g into Ce-filled p-type filled skutterudite Ce in a glove box in Ar atmosphere 0.9 Fe 3 CoSb 12 Mixing the powder (average particle size of 10 μm) with silicon nano powder (average particle size of 50 nm) with volume ratio of 5 vol.%, putting into a stainless steel ball grinding tank, selecting hard alloy WC balls with ball-to-material ratio of 5:1, ball milling for 6 h at room temperature by using a high-energy ball mill after sealing, and regulating rotating speed to 500 r/min to obtain the composite material powder.
Filling the powder into a graphite mould with the diameter phi of 20 and mm in a glove box in Ar atmosphere, and sintering by using spark plasma to obtain the compact p-type skutterudite-based composite material Ce 0.9 Fe 3 CoSb 12 +5 vol.% silicon nano-powder composite bulk. 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.
A preparation method of an antioxidant skutterudite-based thermoelectric composite material comprises the steps of synthesizing 15.0 g into Ce-filled p-type filled skutterudite Ce in a glove box in Ar atmosphere 0.9 Fe 3 CoSb 12 Mixing the powder (average grain size 10 μm) with diamond particles (average grain size 50 nm) with volume ratio of 1vol.%, putting into a stainless steel ball grinding tank, selecting hard alloy WC balls with ball-to-material ratio of 5:1, ball milling at room temperature for 6 h by using a high-energy ball mill after sealing, and regulating the rotating speed to 500 r/min to obtain the composite material powder.
Filling the powder into a graphite mould with the diameter phi of 20 and mm in a glove box in Ar atmosphere, and sintering by using spark plasma to obtain the compact p-type skutterudite-based composite material Ce 0.9 Fe 3 CoSb 12 +1 vol.% diamond particle composite mass. Sintering temperature is 570 ℃, sintering condition is heating rate50. At the temperature of/min, the pressure of 50 MPa, the sintering time of 20 min and the heat preservation of 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 ℃.
A preparation method of an antioxidant skutterudite-based thermoelectric composite material comprises the steps of synthesizing 15.0 g into Ce-filled p-type filled skutterudite Ce in a glove box in Ar atmosphere 0.9 Fe 3 CoSb 12 Mixing the powder (average particle size of 10 μm) with silicon nano powder (average particle size of 50 nm) with volume ratio of 1vol.%, putting into a stainless steel ball grinding tank, selecting hard alloy WC balls with ball-to-material ratio of 5:1, ball milling at room temperature by using a high-energy ball mill for 6 h after sealing, and regulating the rotating speed to 500 r/min to obtain the composite material powder.
Filling the powder into a graphite mould with the diameter phi of 20 and mm in a glove box in Ar atmosphere, and sintering by using spark plasma to obtain the compact p-type skutterudite-based composite material Ce 0.9 Fe 3 CoSb 12 +1 vol.% silicon nano-powder composite bulk. 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 temperature is kept for 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 (10)
1. An antioxidant skutterudite-based thermoelectric composite material is characterized by comprising 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 0.1-20vol.% of the composite material, and the composite material is not pulverized at the temperature of 650-850K.
2. The composite material of claim 1, wherein the skutterudite thermoelectric material is (1) a binary pure phase skutterudite material, or (2) cosb 3 Radicals or FeSb 3 Filling of the matrix and/or doping of the skutterudite thermoelectric material.
3. The composite material according to claim 1 or 2, wherein the solid skutterudite material is a powder having a particle size of 0.5 to 70 μm.
4. The composite material of claim 1, wherein the nano second phase material is in the form of nano powder with a particle size of 10-500 nm, a nano tube with a diameter of 10-100 nm, or a nano wire with a diameter of 5-100 nm and a length of 100nm-2 μm.
5. The composite material of claim 1 or 4, wherein the nano second phase material comprises 0.5 to 3 vol.% of the composite material.
6. The composite material of claim 1, wherein the composite material has a composition Ce 0.9 Fe 3 CoSb 12 /1vol.% Si p ，Si p Refers to nano silicon powder; or, ce 0.9 Fe 3 CoSb 12 /1.5 vol.% Si w ，Si w Refers to silicon nanowires; or, ce 0.9 Fe 3 CoSb 12 /2 vol.% Si t ，Si t Refers to silicon nanotubes.
7. A method of preparing a composite material according to any one of claims 1 to 6, 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.
8. The method of claim 7, 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 N2; 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, performing ultrasonic treatment for 15-30 min, adding cobalt powder, performing ultrasonic treatment for 30-60 min, performing suction filtration or performing rotary evaporation in an oil bath to obtain composite material powder, drying in a vacuum drying oven, and grinding in a mortar for 15-30 min.
9. The method according to claim 7 or 8, wherein in the spark plasma sintering, the sintering time is 10 to 60 min, the pressure is 10 to 100 mpa, the sintering temperature of the n-type filled skutterudite composite material is 590 to 640 ℃, and the sintering temperature of the p-type filled skutterudite composite material is 560 to 610 ℃.
10. The method according to claim 7 or 8, 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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