CN102251283B - Single crystal zinc antimonide nano comb with high thermoelectric figure of merit and preparation method thereof - Google Patents

Single crystal zinc antimonide nano comb with high thermoelectric figure of merit and preparation method thereof Download PDF

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CN102251283B
CN102251283B CN201110194388.XA CN201110194388A CN102251283B CN 102251283 B CN102251283 B CN 102251283B CN 201110194388 A CN201110194388 A CN 201110194388A CN 102251283 B CN102251283 B CN 102251283B
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merit
comb
gas generator
zinc antimonide
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CN102251283A (en
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周少敏
吴小平
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Henan University
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Abstract

The invention belongs to the technical field of new energy thermoelectric conversion materials, in particular to relates to a single crystal zinc antimonide nano comb with a high thermoelectric figure of merit and a preparation method thereof. The thermoelectric figure of merit of the single crystal zinc antimonide nano comb is higher than or equal to 1.50. Compared with the traditional zinc antimonide, the zinc antimonide nano comb provided by the invention has the advantages of higher thermoelectric figure of merit, greatly-reduced thermal conductivity, simple preparation process, low requirement for equipment and high degree of controllability.

Description

A kind of high thermoelectric figure of merit monocrystalline zinc antimonide nanometer comb and preparation method thereof
Technical field
The invention belongs to new forms of energy thermo-electric converting material technical field, particularly a kind of high thermoelectric figure of merit monocrystalline zinc antimonide nanometer comb and preparation method thereof.
Background technology
The conversion efficiency of thermoelectric of thermoelectric material depends on zero dimension thermoelectric figure of merit (ZT)
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, T is absolute temperature,
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The Seebeck coefficient,
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Specific conductivity,
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Be thermal conductivity, and equal lattice thermal conductivity With the current carrier thermal conductivity Sum (
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,
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Be the Lorenz constant).Reduce
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, increase
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With
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Three kinds of approach that improve the ZT value, but
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,
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With
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Generally be associated.In general,
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Reduce then
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Reduce, increase Shi Ze
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Decrease.Coordinated regulation how
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,
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With
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, realize that it is the target that thermoelectric material scholar and physicist pursue that the ZT value increases considerably always.
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Belong to the hexagonal system compound, exist
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,
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With
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Three kinds many types of, and their equilibrium temperature interval is respectively to be lower than 263K, 263-765K and be higher than 765K.
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Compound is a kind of P-type semiconductor, have low-down thermal conductivity and higher specific conductivity, be considered to have one of warm thermoelectric material of application prospect most, its preparation technology, thermoelectricity capability and crystalline structure etc. have been widely studied, and its ZT value reaches 1.3[T. Caillat when 672K, J-P. Fleurial, and A. Borshchevsky, Journal Physical Chemistry Solids, Vol. 58, pp. 1119 – 1125,1997.].
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At least there is the gap Zn atom of 3 chaotic distribution in the unit cell, causes this compound to have lower thermal conductivity, high conductance.In recent years, the techniques such as vacuum fusion, machine-alloying, hot pressed sintering, discharge plasma sintering are successively for the preparation of high performance
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Block thermoelectric material (Zhao Wenyu, patent CN.101073831A, Xiao are faithful and upright, patent CN. 101275192A), but up to the present, the ZT value is still paced up and down 1.3.
Therefore how to prepare the thermoelectricity capability excellence
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Base thermoelectricity material is still the problem of need exploring, because the introducing of the microstructural defects of nanoscale, coarse Surface and interface can make phonon transmission scattering process strengthen, thereby reduces lattice thermal conductivity, reaches high conversion efficiency of thermoelectric.Therefore, various Thermoelectric Nano-materials are produced out.Although β-Zn 4Sb 3Nanostructure recently by widely research [S. Schlecht, C. Erk, and M. Yosef, Inorganic Chemistry, Vol. 45, pp. 1693 – 1697,2006.; D. M. Triches, S. M. Souza, J. C. de Lima, T. A. Grandi, C. E. M. Campos, A. Polian, J. P. Itie, F. Baudelet, and J. C. Chervin, Journal of Applied Physics, Vol. 106, pp. 013509-1 – 013509-6,2009; C. S. Birkel, E. Mugnaioli, T. Gorelik, U. Kolb, M. Panthofer, and W. Tremel, Journal of the American Chemical Society, Vol. 132, pp. 9881 – 9889,2010.].But the highest ZT value of products obtained therefrom does not reach 1.5 yet.Therefore, investigators need the novel method of exploring and enhance ZT value, nearest a lot of research finds that the nano-array material is material [the S.G. Kim with high thermal efficiency, I.I.Mazin, and D.J. Singh, First-Principles Study of Zn-Sb Thermoelectrics, Physical Review B, vol. 57, pp. 6199 – 6203,1998.; M. Martin-Gonzalez, A.L. Prieto, M.S. Knox, R. Gronsky, T. Sands, and A.M. Stacy, Electrodeposition of Bi1-xSbx Films and 200 nm Wire Arrays from a Nonaqueous Solvent, Chemistry of Materials, vol. 15, pp. 1676 – 1681,2003.].Yet, as far as our knowledge goes, the sacrificial mold plate technique is the good method of preparation nano-array material, its at present success utilize sacrificial mold plate technique grown high-quality CdS nanotube [S. M. Zhou, Y. S. Feng, and L. D. Zhang, European Journal of Inorganic Chemistry, pp. 1794 – 1797,2003.], ZnO nano-wire [S. M. Zhou, He. C. Gong, B. Zhang, Z. L. Du, X. T. Zhang, and S. X. Wu, Nanotechnology, Vol. 19, pp. 175303-1-175303 – 4,2008.].Therefore how to utilize the sacrificial mold plate technique to prepare special nano-array
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Matrix body heat electric material improves
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The conversion efficiency of thermoelectric of matrix body heat electric material becomes the problem of research.
Summary of the invention
The object of the present invention is to provide a kind of high thermoelectric figure of merit monocrystalline zinc antimonide nanometer comb and preparation method thereof.
The technical solution used in the present invention is as follows:
A kind of high thermoelectric figure of merit monocrystalline zinc antimonide nanometer comb, thermoelectric figure of merit is not less than 1.50.
Thermoelectric figure of merit is 1.50-1.51.
Described nanometer comb staple length 0.2 ~ 10 μ m, width is 0.05 ~ 1 μ m, thermal conductivity coefficient is 0.350-0.576 W/mK.
The present invention also provides a kind of preparation method of high thermoelectric figure of merit monocrystalline zinc antimonide nanometer comb, the ZnO nano comb is put into the silica tube of tube furnace, utilizing rare gas element that stibine is loaded onto in the silica tube reacts, tube furnace is incubated 25-60min after being warming up to 500-700 ℃ with 5-30 ℃/min by room temperature, namely gets high thermoelectric figure of merit monocrystalline zinc antimonide nanometer comb after being cooled to room temperature.
The rare gas element flow velocity is 200-400cm 3/ min.Described rare gas element refers to not the gas that reacts with stibine.
Rare gas element is preferably nitrogen.
The purity of ZnO is not less than 98% in the ZnO nano comb.
H 3The method of the preparation of Sb is as follows: 1 ~ 6 mass parts (g) Sb 2O 3, 1 ~ 8 mass parts (g) Zn is put into the middle part of kipp gas generator, 30 ~ 60 parts by volume (ml) mass concentration is the H of 10-50% 2SO 4Add in the spherical hopper of kipp gas generator, open the valve of kipp gas generator, allow under the sulfuric acid stream and Sb 2O 3With the Zn reaction, obtain H 3Sb gas.
Described Sb 2O 3Purity 98%, the purity of Zn〉98%.
Concrete, the ZnO nano comb is put into the silica tube of tube furnace; Sb 2O 3, Zn is placed on kipp gas generator middle part, rare H 2SO 4Be added in the spherical hopper of kipp gas generator, connect kipp gas generator and silica tube, the H of acquisition with conduit 3Sb gas is by entering in the silica tube with conduit that kipp gas generator is connected with silica tube; In tube furnace, heat up, heat.
The present invention also provides the device with the supporting high thermoelectric figure of merit monocrystalline of the preparation zinc antimonide nanometer comb of method, described device comprises kipp gas generator, tube furnace and the conduit that connects kipp gas generator and tube furnace, described conduit one end is connected in the stage casing of kipp gas generator, and the other end links to each other with silica tube in the tube furnace; Be equipped with silicon chip and ceramic boat in the silica tube.
The present invention has following advantage with respect to prior art:
Zinc antimonide nanometer comb of the present invention is compared with existing zinc antimonide, has higher thermoelectric figure of merit (can reach 1.51), and the thermal conductivity decrease; Preparation technology is simple, and is low for equipment requirements, and controllable degree is high.
Description of drawings
Fig. 1 is the reaction unit schematic diagram;
Fig. 2 is SEM and the EDS figure of the zinc antimonide nanometer comb of embodiment 1 acquisition.
Fig. 3 be under the differing temps embodiment of the invention 1 zinc antimonide nanometer comb (note is NC S) and conventional powder (CP S) thermoelectric figure of merit.
Embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited to this:
The used ZnO nano comb purity of the present invention is not less than 98%, staple length 0.2 ~ 10 μ m of nanometer comb, and width is 0.05 ~ 1 μ m, its preparation can with reference to published document, belong to prior art.
The concrete steps that the present invention obtains high thermoelectric figure of merit monocrystalline zinc antimonide nanometer comb thermoelectric material are as follows:
(1) highly purified precursor powder ZnO is put into the silica tube of tube furnace, Sb 2O 3, Zn puts into kipp gas generator middle part, mass concentration is the H of 10-50% 2SO 4Solution (available diluting concentrated sulfuric acid acquisition) adds in the spherical hopper of kipp gas generator; The purity of raw material ZnO〉98%, Sb 2O 3Purity 98%, the purity of Zn〉98%, the purity of the vitriol oil is 99.9%.
(2) at above-mentioned tube furnace, be raised to 500-700 ℃ with the heat-up rate of 10 ~ 30 ℃/min from room temperature, constant temperature 25 ~ 50min passes into nitrogen simultaneously as transportation gas, is cooled to subsequently room temperature, can collect monocrystalline zinc antimonide nanometer comb.
The device that adopts comprises kipp gas generator 1, tube furnace 2 and the conduit 3 that connects kipp gas generator and tube furnace, and described conduit 3 one ends are connected in the stage casing of kipp gas generator 1, and the other end links to each other with silica tube 4 in the tube furnace 2; Be equipped with silicon chip 5 and ceramic boat 6 in the silica tube 4.
Embodiment 1
(1) the highly purified precursor powder ZnO of 9.72 grams is placed in the ceramic boat, places the position, middle of tube furnace silica tube.
(2) with 5.84 gram Sb 2O 3, 7.80 gram Zn put into kipp gas generator middle part, the 60ml mass concentration is 15% H 2SO 4Add in the spherical hopper of kipp gas generator, open the valve of kipp gas generator, reaction obtains H 3Sb gas.
(3) above-mentioned gas is filled with in the silica tube in the tube furnace, is raised to 550 ℃ with the heat-up rate of 20 ℃/min from room temperature, at 550 ℃ of constant temperature 30min, pass into simultaneously nitrogen as transportation gas, flow velocity is 300 cm 3/ min, this system is naturally cooled to room temperature subsequently, can obtain material of the present invention, and when 675K, thermal conductivity is 0.350 W/mK, and the ZT value is 1.51.The staple length of nanometer comb is about 1.4 μ m, width is about 0.5 ~ 0.8 μ m.
Embodiment 2
(1) the highly purified precursor powder ZnO of 4.86 grams is placed in the ceramic boat, places the position, middle of tube furnace silica tube.
(2) with 2.92 gram Sb 2O 3, 3.90 gram Zn put into kipp gas generator middle part, the H of 30ml 15% 2SO 4Add in the spherical hopper of kipp gas generator, open the valve of kipp gas generator, reaction obtains H 3Sb gas.
(3) above-mentioned gas is filled with in the silica tube in the tube furnace by conduit, is raised to 550 ℃ with the heat-up rate of 20 ℃/min from room temperature, at 550 ℃ of constant temperature 30min, pass into simultaneously nitrogen as transportation gas, flow velocity is 300 cm 3/ min, this system is naturally cooled to room temperature subsequently, obtains monocrystalline zinc antimonide nanometer comb.When 675K, thermal conductivity is 0.350 W/mK, and thermoelectric figure of merit is 1.51.The staple length of nanometer comb is about 1.4 μ m, width is about 0.5 ~ 0.8 μ m.
Embodiment 3
(1) the highly purified precursor powder ZnO of 2.43 grams is placed in the ceramic boat, places the position, middle of tube furnace silica tube.
(2) with 2.92 gram Sb 2O 3, 3.90 gram Zn put into kipp gas generator middle part, the H of 30ml 15% 2SO 4Add in the spherical hopper of kipp gas generator, open the valve of kipp gas generator, reaction obtains H 3Sb gas.
(3) above-mentioned gas is filled with in the silica tube in the tube furnace, is raised to 550 ℃ with the heat-up rate of 20 ℃/min from room temperature, at 550 ℃ of constant temperature 30min, pass into simultaneously nitrogen as transportation gas, flow velocity is 300 cm 3/ min, this system is naturally cooled to room temperature subsequently, obtains monocrystalline zinc antimonide nanometer comb.When 675K, thermal conductivity is 0.350 W/mK, and thermoelectric figure of merit is 1.51.The staple length of nanometer comb is about 1.4 μ m, width is about 0.5 ~ 0.8 μ m.
Embodiment 4
(1) the highly purified precursor powder ZnO of 2.43 grams is placed in the ceramic boat, places the position, middle of tube furnace silica tube.
(2) with 4.38 gram Sb 2O 3, 5.85 gram Zn put into kipp gas generator middle part, the H of 45ml 15% 2SO 4Add in the spherical hopper of kipp gas generator, open the valve of kipp gas generator, reaction obtains H 3Sb gas.
(3) above-mentioned gas is filled with in the silica tube in the tube furnace, is raised to 550 ℃ with the heat-up rate of 20 ℃/min from room temperature, at 550 ℃ of constant temperature 30min, pass into simultaneously nitrogen as transportation gas, flow velocity is 300 cm 3/ min, this system is naturally cooled to room temperature subsequently, obtains monocrystalline zinc antimonide nanometer comb.When 675K, thermal conductivity is 0.361 W/mK, and thermoelectric figure of merit is 1.50.The staple length of nanometer comb is about 1.45 μ m, width is about 0.6 ~ 0.85 μ m.
Embodiment 5
(1) the highly purified precursor powder ZnO of 2.43 grams is placed in the ceramic boat, places the position, middle of tube furnace silica tube.
(2) with 2.92 gram Sb 2O 3, 3.90 gram Zn put into kipp gas generator middle part, the H of 30ml 15% 2SO 4Add in the spherical hopper of kipp gas generator, open the valve of kipp gas generator, reaction obtains H 3Sb gas.
(3) above-mentioned gas is filled with in the silica tube in the tube furnace, is raised to 550 ℃ with the heat-up rate of 20 ℃/min from room temperature, at 550 ℃ of constant temperature 30min, pass into simultaneously nitrogen as transportation gas, flow velocity is 200 cm 3/ min, this system is naturally cooled to room temperature subsequently, obtains monocrystalline zinc antimonide nanometer comb.When 675K, thermal conductivity is 0.355 W/mK, and thermoelectric figure of merit is 1.505.The staple length of nanometer comb is about 1.5 μ m, width is about 0.6 ~ 0.8 μ m.
Embodiment 6
(1) the highly purified precursor powder ZnO of 2.43 grams is placed in the ceramic boat, places the position, middle of tube furnace silica tube.
(2) with 2.92 gram Sb 2O 3, 3.90 gram Zn put into kipp gas generator middle part, the H of 30ml 15% 2SO 4Add in the spherical hopper of kipp gas generator, open the valve of kipp gas generator, reaction obtains H 3Sb gas.
(3) above-mentioned gas is filled with in the silica tube in the tube furnace, is raised to 550 ℃ with the heat-up rate of 20 ℃/min from room temperature, at 550 ℃ of constant temperature 30min, pass into simultaneously nitrogen as transportation gas, flow velocity is 400 cm 3/ min, this system is naturally cooled to room temperature subsequently, obtains monocrystalline zinc antimonide nanometer comb.When 675K, thermal conductivity is 0.358 W/mK, and thermoelectric figure of merit is 1.503.The staple length of nanometer comb is about 1.3 μ m, width is about 0.45 ~ 0.7 μ m.
Embodiment 7
(1) the highly purified precursor powder ZnO of 2.43 grams is placed in the ceramic boat, places the position, middle of tube furnace silica tube.
(2) with 2.92 gram Sb 2O 3, 3.90 gram Zn put into kipp gas generator middle part, the H of 30ml 15% 2SO 4Add in the spherical hopper of kipp gas generator, open the valve of kipp gas generator, reaction obtains H 3Sb gas.
(3) above-mentioned gas is filled with in the silica tube in the tube furnace, is raised to 550 ℃ with the heat-up rate of 30 ℃/min from room temperature, at 550 ℃ of constant temperature 30min, pass into simultaneously nitrogen as transportation gas, flow velocity is 300 cm 3/ min, this system is naturally cooled to room temperature subsequently, obtains monocrystalline zinc antimonide nanometer comb.When 675K, thermal conductivity is 0.352 W/mK, and thermoelectric figure of merit is 1.508.The staple length of nanometer comb is about 1.4 μ m, width is about 0.5 ~ 0.8 μ m.
Embodiment 8
(1) the highly purified precursor powder ZnO of 2.43 grams is placed in the ceramic boat, places the position, middle of tube furnace silica tube.
(2) with 2.92 gram Sb 2O 3, 3.90 gram Zn put into kipp gas generator middle part, the H of 30ml 15% 2SO 4Add in the spherical hopper of kipp gas generator, open the valve of kipp gas generator, reaction obtains H 3Sb gas.
(3) above-mentioned gas is filled with in the silica tube in the tube furnace, is raised to 550 ℃ with the heat-up rate of 10 ℃/min from room temperature, at 550 ℃ of constant temperature 30min, pass into simultaneously nitrogen as transportation gas, flow velocity is 300 cm 3/ min, this system is naturally cooled to room temperature subsequently, obtains monocrystalline zinc antimonide nanometer comb.When 675K, thermal conductivity is 0.352 W/mK, and thermoelectric figure of merit is 1.508.The staple length of nanometer comb is about 1.4 μ m, width is about 0.6 ~ 0.8 μ m.
Embodiment 9
(1) the highly purified precursor powder ZnO of 2.43 grams is placed in the ceramic boat, places the position, middle of tube furnace silica tube.
(2) with 2.92 gram Sb 2O 3Put into kipp gas generator middle part, the H of 30ml 15% with 3.90 gram Zn 2SO 4Add in the spherical hopper of kipp gas generator, open the valve of kipp gas generator, reaction obtains H 3Sb gas.
(3) above-mentioned gas is filled with in the silica tube in the tube furnace, is raised to 500 ℃ with the heat-up rate of 20 ℃/min from room temperature, at 500 ℃ of constant temperature 30min, pass into simultaneously nitrogen as transportation gas, flow velocity is 300 cm 3/ min, this system is naturally cooled to room temperature subsequently, obtains monocrystalline zinc antimonide nanometer comb.When 675K, thermal conductivity is 0.358 W/mK, and thermoelectric figure of merit is 1.503.The staple length of nanometer comb is about 1.3 μ m, width is about 0.5 ~ 0.75 μ m.
Embodiment 10
(1) the highly purified precursor powder ZnO of 2.43 grams is placed in the ceramic boat, places the position, middle of tube furnace silica tube.
(2) with 2.92 gram Sb 2O 3Put into kipp gas generator middle part, the H of 30ml 15% with 3.90 gram Zn 2SO 4Add in the spherical hopper of kipp gas generator, open the valve of kipp gas generator, reaction obtains H 3Sb gas.
(3) above-mentioned gas is filled with in the silica tube in the tube furnace, is raised to 600 ℃ with the heat-up rate of 20 ℃/min from room temperature, at 600 ℃ of constant temperature 30min, pass into simultaneously nitrogen as transportation gas, flow velocity is 300 cm 3/ min, this system is naturally cooled to room temperature subsequently, obtains monocrystalline zinc antimonide nanometer comb.The sample that makes is when 675K, and thermal conductivity is 0.355 W/mK, and thermoelectric figure of merit is 1.505.The staple length of nanometer comb is about 1.5 μ m, width is about 0.4 ~ 0.7 μ m.
Embodiment 11
(1) the highly purified precursor powder ZnO of 2.43 grams is placed in the ceramic boat, places the position, middle of tube furnace silica tube.
(2) with 2.92 gram Sb 2O 3Put into kipp gas generator middle part, the H of 30ml 15% with 3.90 gram Zn 2SO 4Add in the spherical hopper of kipp gas generator, open the valve of kipp gas generator, reaction obtains H 3Sb gas.
(3) above-mentioned gas is filled with in the silica tube in the tube furnace, is raised to 550 ℃ with the heat-up rate of 20 ℃/min from room temperature, at 550 ℃ of constant temperature 25min, pass into simultaneously nitrogen as transportation gas, flow velocity is 300 cm 3/ min, this system is naturally cooled to room temperature subsequently, obtains monocrystalline zinc antimonide nanometer comb.The sample that makes is when 675K, and thermal conductivity is 0.352 W/mK, and thermoelectric figure of merit is 1.508.The staple length of nanometer comb is about 1.4 μ m, width is about 0.5 ~ 0.8 μ m.
Embodiment 12
(1) the highly purified precursor powder ZnO of 2.43 grams is placed in the ceramic boat, places the position, middle of tube furnace silica tube.
(2) with 2.92 gram Sb 2O 3Put into kipp gas generator middle part, the H of 30ml 15% with 3.90 gram Zn 2SO 4Add in the spherical hopper of kipp gas generator, open the valve of kipp gas generator, reaction obtains H 3Sb gas.
(3) above-mentioned gas is filled with in the silica tube in the tube furnace, is raised to 550 ℃ with the heat-up rate of 20 ℃/min from room temperature, at 550 ℃ of constant temperature 40min, pass into simultaneously nitrogen as transportation gas, flow velocity is 300 cm 3/ min, this system is naturally cooled to room temperature subsequently, obtains monocrystalline zinc antimonide nanometer comb.The sample that makes is when 675K, and thermal conductivity is 0.352 W/mK, and thermoelectric figure of merit is 1.508.The staple length of nanometer comb is about 1.5 μ m, width is about 0.6 ~ 0.85 μ m.
Comparative Examples
(1) the highly purified precursor powder ZnO of 10.50 grams is placed in the ceramic boat, places the position, middle of tube furnace silica tube.
(2) with 6.28 gram Sb 2O 3Put into kipp gas generator middle part, the H of 20ml 20% with 8.44 gram Zn 2SO 4Add in the spherical hopper of kipp gas generator, open the valve of kipp gas generator, reaction obtains H 3Sb gas.
(3) above-mentioned gas is filled with in the silica tube in the tube furnace, is raised to 450 ℃ with the heat-up rate of 20 ℃/min from room temperature, at 450 ℃ of constant temperature 20min, pass into simultaneously nitrogen as transportation gas, pressure is that 1 MPa(is equivalent to flow velocity 100 cm 3/ min), this system is naturally cooled to room temperature subsequently, obtains monocrystalline zinc antimonide nanometer comb.The sample that makes is when 675K, and thermal conductivity is 0.375 W/mK, and thermoelectric figure of merit is 1.49.Staple length 2.3 μ m, the width 100nm of nanometer comb.
Conventional beta-Zn 4Sb 3The preparation of powder:
The preparation of conventional powder: starting raw material adopts high-purity Zn powder (99.99% Tianjin Da Mao chemical reagent factory) and Sb powder (99.99% Shanghai reagent head factory), carries out proportioning by desirable stoichiometry.Be sealed in the vitreosil pipe (10 after the mixing -1Pa).2h is warmed up to 1023K in tube furnace, keeps temperature 2h, and rear Slow cooling can obtain its block materials to room temperature.Then, sample is pulverized as under the ball mill, the gained sample is collected, just obtained conventional beta-Zn 4Sb 3Powder.Conventional beta-Zn 4Sb 3The curve of nanometer comb thermoelectric figure of merit under differing temps of powder and the embodiment of the invention 1 is seen Fig. 3.

Claims (7)

1. one kind high thermoelectric figure of merit monocrystalline zinc antimonide nanometer comb, it is characterized in that, the thermoelectric figure of merit of described monocrystalline zinc antimonide nanometer comb is 1.50-1.51, described nanometer comb staple length 0.2 ~ 10 μ m, width is 0.05 ~ 1 μ m, and thermal conductivity coefficient is 0.350-0.576 W/mK.
2. the preparation method of the high thermoelectric figure of merit monocrystalline zinc antimonide nanometer comb of claim 1, it is characterized in that, the ZnO nano comb is put into the silica tube of tube furnace, utilizing rare gas element that stibine is loaded onto in the silica tube reacts, tube furnace is incubated 25-60min after being warming up to 500-700 ℃ with 5-30 ℃/min by room temperature, namely gets high thermoelectric figure of merit monocrystalline zinc antimonide nanometer comb after being cooled to room temperature.
3. the preparation method of high thermoelectric figure of merit monocrystalline zinc antimonide nanometer comb as claimed in claim 2 is characterized in that, the rare gas element flow velocity is 200-400cm 3/ min.
4. the preparation method of high thermoelectric figure of merit monocrystalline zinc antimonide nanometer comb as claimed in claim 2 or claim 3 is characterized in that, the purity of ZnO is not less than 98% in the ZnO nano comb.
5. the preparation method of high thermoelectric figure of merit monocrystalline zinc antimonide nanometer comb as claimed in claim 4 is characterized in that H 3The preparation method of Sb is as follows: 1 ~ 6 mass parts Sb 2O 3, 1 ~ 8 mass parts Zn is put into the middle part of kipp gas generator, 30 ~ 60 parts by volume mass concentrations are the H of 10-50% 2SO 4Add in the spherical hopper of kipp gas generator, open the valve of kipp gas generator, allow under the sulfuric acid stream and Sb 2O 3With the Zn reaction, obtain H 3Sb gas.
6. the preparation method of high thermoelectric figure of merit monocrystalline zinc antimonide nanometer comb as claimed in claim 5 is characterized in that the H of acquisition 3Sb gas is by entering in the silica tube with conduit that kipp gas generator is connected with silica tube.
7. the device for preparing high thermoelectric figure of merit monocrystalline zinc antimonide nanometer comb, it is characterized in that, comprise kipp gas generator, tube furnace and the conduit that connects kipp gas generator and tube furnace, described conduit one end is connected in the stage casing of kipp gas generator, and the other end links to each other with silica tube in the tube furnace; Be equipped with silicon chip and ceramic boat in the silica tube.
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