CN102161507A - Method for preparing polycrystalline textured thermoelectric material from single-crystal bismuth sulfide precursor powder - Google Patents
Method for preparing polycrystalline textured thermoelectric material from single-crystal bismuth sulfide precursor powder Download PDFInfo
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- CN102161507A CN102161507A CN 201110089254 CN201110089254A CN102161507A CN 102161507 A CN102161507 A CN 102161507A CN 201110089254 CN201110089254 CN 201110089254 CN 201110089254 A CN201110089254 A CN 201110089254A CN 102161507 A CN102161507 A CN 102161507A
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Abstract
The invention belongs to the technical field of energy materials, in particular relates to a method for preparing polycrystalline textured thermoelectric materials from single-crystal bismuth sulfide precursor powder. Specifically, the method comprises the following steps of: selecting uniformly-orientated single-crystal bismuth sulfide [Bi2S(3-x), 0<=x<=0.5] powder (including nanoflakes, nanotubes and nanowires) as precursor powder; performing rapid sintering under increased pressure by using a spark plasma sintering technique so that the single-crystal powder trends to be arranged in the direction perpendicular to the pressure and freeze to form highly-textured dense polycrystalline bulk thermoelectric materials; and controlling the texture degree, the crystal grain degree and the density of the bulk materials by adjusting the applied pressure, the sintering temperature and the heat retention time. Owing to the texture, the polycrystalline materials show strong anisotropy, so that the power transmission performance is greatly improved.
Description
Technical field
The invention belongs to the energy and material technical field, particularly simple, quick, a kind of method for preparing the polycrystal thermoelectric material with the monocrystalline precursor powder that helps improving the polycrystalline bulk pyroelectric material performance of preparation technology.
Background technology
In recent years, environment and energy problem more and more are subjected to the attention of human society, as realizing directly that heat energy and electric energy transform mutually, help improving the comprehensive utilization of energy rate, and thermoelectric material pollution-free, zero release also is subjected to people's attention day by day.With the thermoelectric material is the thermounit of nucleus module, has advantages such as structure is light, volume is little, the life-span is long, Working environment gentleness, has a wide range of applications at aspects such as semiconductor refrigerating, thermoelectric cells.With the competition of the refrigeration modes of routine and conventional power source in, the key of thermo-electric device is to improve the efficient of electronic cooling and thermoelectric cell, its main path is to improve the performance of thermoelectric material.Thermoelectricity capability characterizes ZT=TS with zero dimension thermoelectric figure of merit ZT
2σ/κ, S are Seebeck coefficients, and σ is a specific conductivity, and κ is a thermal conductivity, and T is an absolute temperature.Well behaved thermoelectric material need have high Seebeck coefficient, high specific conductivity and low thermal conductivity.
Tellurobismuthite Bi
2Te
3Be the best thermoelectric material of current room temperature performance, obtained practice, its ZT reaches 1.4[B. Poudel, Q. Hao, Y. Ma, Y. C. Lan, A. Minnich, B. Yu, X. Yan, D. Z. Wang, A. Muto, D. Vashaee, X. Y. Chen, J. M. Liu, M. S. Dresselhaus, G. Chen, Z. F. Ren
Science2008,320,634.].As the Bi that is the IV-VA compounds of group equally
2S
3, have high Seebeck coefficient and low thermal conductivity, make it be expected to become alternative Bi
2Te
3Novel thermoelectric material, and the earth abundance of S element is higher than Te far away, toxicity is little, and is cheap and easy to get.But, Bi
2S
3Resistivity is far longer than Bi
2Te
3, can effectively reduce Bi by means such as microstructure regulation and control, doping
2S
3Specific conductivity [L.D. Zhao, B.P. Zhang, W.S. Liu, H.L. Zhang, J.F. Li.:
J. Solid State Chem.181 (2008), 3278.; B. X. Chen, C. Uher, L. Iordanidis, M. G. Kanatzidis:
Chem.Mater .9(1997), 1655 – 1658.].
The existing texture degree that improves material that studies show that can effectively improve its thermoelectricity capability.The forge hot method is one of major technique of the highly-textured pottery of preparation at present, this method close on sintering temperature exert pressure make crystal grain along slip plane slide [T. Takenaka and K. Sakata:
Jpn. J. Appl. Phys., 1980,19,31.].This seminar has obtained the Bi of high orientation by adopting the method for secondary electricity plasma agglomeration thermal distortion
2Te
3Thermoelectric material, its ZT value are compared and are not carried out thermal distortion and handle sample and improved nearly 25%[L.D. Zhao, B.P. Zhang, and J.F. Li, H.L. Zhang, W.S. Liu:
Solid Stat. Sci., 10 (2008) 651-658].Bi after taking the method texturing of same secondary electricity plasma agglomeration thermal distortion to handle
2Te
2.7Se
0.3[Y. Xiao, Bed Poudel, Y. Ma, W.-S. Liu, et al.:
Nano lett., 10 (2010), 3373 – 3378.] the ZT value also obtained significantly improving.This seminar has synthesized the Bi of non-stoichiometric by ball milled
2S
3Nano-powder (patent No.: ZL200810106199.0), sinter this nano powder into block by discharge plasma sintering technique after, prepared Bi with secondary electricity plasma agglomeration forge hot method with texture
2S
2.90(publication number: CN101358313B), its thermoelectricity capability more not sample of forge hot processing is improved block thermoelectric material, but its texture phenomenon is not obvious, texture degree also very limited [L.D. Zhao, B.P. Zhang, W.S. Liu, H.L. Zhang, J.F. Li.
J. Solid State Chem.181 (2008), 3278].
Forge hot method needs at least twice or multiple discharge plasma agglomeration, each sintering all needs die change is become a more preceding bigger mould of size, its texturing process relates to multicrystal fragmentation, slippage and solidifies, cause there is internal stress in the firing sample, and the most highly-textured degree that can reach is limited, long heat treatment time also can cause the texturing The grain size to be grown up, and is unfavorable for reducing the thermal conductivity of material.The present invention directly with the oriented structure quick freezing or the curing of precursor powder, prepares the texture polycrystal by a step discharge plasma sintering directly with the precursor powder with monocrystal nanostructure.Highly-textured degree and fine and close thermoelectric bismuth sulfide polycrystal can obtain by adjusting sintering pressure, temperature and soaking time.Advantages such as that this technology not only has is simple to operate, energy-conserving and environment-protective, and under the prerequisite that does not change the nano-powder precursor structures, promote the texture degree, and then improve the thermoelectricity capability of material.
Summary of the invention
In order to address the above problem, the purpose of this invention is to provide a kind of use monocrystalline bismuth sulfide nano sheet, nanotube, nano wire as precursor powder, prepare the texture polycrystal with discharge plasma sintering, simple, the consuming time weak point of technology, power consumption less, the texture degree easily regulation and control prepare the method for polycrystal thermoelectric material with monocrystalline bismuth sulfide precursor powder.
Technical scheme of the present invention is: a kind ofly prepare the method for polycrystal thermoelectric material with monocrystalline bismuth sulfide precursor powder,
Concrete technical process is as follows:
Step 1: will be orientated consistent monocrystalline Bi
2S
3-xNanometer sheet, nanotube or nano wire powder be placed at ultra-sonic dispersion 10 ~ 60 min in the alcohol, oven dry is placed on and grinds 10 ~ 60 min in the agate mortar, makes the macroscopic particles refinement and removes and reunite; Wherein, the value of X is: 0≤x≤0.5;
Step 2: will be positioned in the graphite jig that diameter is 10 ~ 30 mm through the described precursor powder of getting that above-mentioned steps was handled, described graphite jig is placed in the discharge plasma sintering stove, at pressure is 20 ~ 80 MPa, temperature is that 573 ~ 873 K carry out sintering, be incubated 0 ~ 10 min, promptly obtain the dense multicrystalline block thermoelectric material of highly-textured degree.
Beneficial effect of the present invention is: after adopting technique scheme that the monocrystalline powder is reunited through ultra-sonic dispersion and grinding releasing, as precursor powder, adopt discharge plasma sintering technique pressurization Fast Sintering, by adjusting sintering temperature, pressure and soaking time, texture degree, grain fineness number and the density of control polycrystalline bulk material, and then the thermoelectricity capability of raising material.
?
Description of drawings
Fig. 1 is the texture polycrystalline Bi of precursor powder preparation with the nanometer monocrystalline pipe
2S
3The block sample is composed in XRD figure vertical and that be parallel on the pressure direction.
Fig. 2 is the texture polycrystalline Bi of precursor powder preparation with the nanometer monocrystalline pipe
2S
3The block sample is vertical and be parallel to fracture FESEM photo on the pressure direction.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further.
Example 1
Monocrystalline Bi with (0 0 l) orientation
2S
3The nanometer sheet powder is ultra-sonic dispersion 10 min in alcohol, and 30 min are ground as precursor powder in the oven dry back in agate mortar.Get in the graphite jig that precursor powder is positioned over diameter 10 mm, mould is placed in the discharge plasma sintering stove, 40 MPa that keep-up pressure, sintering temperature is 773 K, is incubated 0 min, obtains the dense multicrystalline block thermoelectric material of highly-textured degree.Through XRD test and quantitative Analysis, the texture degree F=0.79 of (h k 0) face, the thermoelectricity capability test result shows that it has excellent temperature stability, is 200 ~ 220 μ Wm in room temperature to 300 a ℃ test specification internal power factor
-1K
-2
Example 2
Monocrystalline Bi with (0 0 l) orientation
2S
2.75Nanotube dust is ultra-sonic dispersion 30 min in alcohol, and 60 min are ground as precursor powder in the oven dry back in agate mortar.Get in the graphite jig that precursor powder is positioned over diameter 15 mm, mould is placed in the discharge plasma sintering stove, 80 MPa that keep-up pressure, sintering temperature is 673 K, is incubated 3 min, obtains the dense multicrystalline block thermoelectric material of highly-textured degree.Through XRD test and quantitative Analysis, the texture degree F=0.91 of (h k 0) face, the thermoelectricity capability test result shows that it has excellent temperature stability, is 250 ~ 300 μ Wm in room temperature to 300 a ℃ test specification internal power factor
-1K
-2
Example 3
Monocrystalline Bi with (0 0 l) orientation
2S
2.8The nano wire powder is ultra-sonic dispersion 10 min in alcohol, and 10 min are ground as precursor powder in the oven dry back in agate mortar.Get in the graphite jig that precursor powder is positioned over diameter 20 mm, then mould is placed in the discharge plasma sintering stove, 20 MPa that keep-up pressure, sintering temperature is 573 K, sintering 5 min obtain the dense multicrystalline block thermoelectric material of highly-textured degree.Through XRD test and quantitative Analysis, the texture degree F=0.69 of (h k 0) face, the thermoelectricity capability test result shows that it has excellent temperature stability, is 80 ~ 90 μ Wm in room temperature to 300 a ℃ test specification internal power factor
-1K
-2
Example 4
Monocrystalline Bi with (0 0 l) orientation
2S
2.9Nanotube dust is ultra-sonic dispersion 30 min in alcohol, and 40 min are ground as precursor powder in the oven dry back in agate mortar.Get in the graphite jig that precursor powder is positioned over diameter 30 mm, mould is placed in the discharge plasma sintering stove, 50 MPa that keep-up pressure, sintering temperature is 873 K, is incubated 3 min, obtains the dense multicrystalline block thermoelectric material of highly-textured degree.Through XRD test and quantitative Analysis, the texture degree F=0.81 of (h k 0) face, the thermoelectricity capability test result shows that it has excellent temperature stability, is 180 ~ 200 μ Wm in room temperature to 300 a ℃ test specification internal power factor
-1K
-2
Example 5
Monocrystalline Bi with (0 0 l) orientation
2S
2.5The nano wire powder is ultra-sonic dispersion 60 min in alcohol, and 50 min are ground as precursor powder in the oven dry back in agate mortar.Get in the graphite jig that precursor powder is positioned over diameter 25 mm, mould is placed in the discharge plasma sintering stove, 30 MPa that keep-up pressure, sintering temperature is 823 K, is incubated 5 min, obtains the dense multicrystalline block thermoelectric material of highly-textured degree.Through XRD test and quantitative Analysis, the texture degree F=0.59 of (h k 0) face, the thermoelectricity capability test result shows that it has excellent temperature stability, is 80 ~ 90 μ Wm in room temperature to 300 a ℃ test specification internal power factor
-1K
-2
Claims (6)
1. one kind prepares the method for polycrystal thermoelectric material with monocrystalline bismuth sulfide precursor powder, it is characterized in that concrete technical process is as follows:
Step 1: will be orientated consistent monocrystalline Bi
2S
3-xNanometer sheet, nanotube or nano wire powder be placed at ultra-sonic dispersion 10 ~ 60 min in the alcohol, oven dry is placed on and grinds 10 ~ 60 min in the agate mortar, makes the macroscopic particles refinement and removes and reunite; Wherein, the value of X is: 0≤x≤0.5;
Step 2: will be positioned in the graphite jig that diameter is 10 ~ 30 mm through the described precursor powder of getting that above-mentioned steps was handled, described graphite jig is placed in the discharge plasma sintering stove, at pressure is 20 ~ 80 MPa, temperature is that 573 ~ 873 K carry out sintering, be incubated 0 ~ 10 min, promptly obtain the dense multicrystalline block thermoelectric material of highly-textured degree.
2. according to claim 1ly prepare the method for polycrystal thermoelectric material, it is characterized in that with monocrystalline bismuth sulfide precursor powder, will the consistent monocrystalline Bi of orientation
2S
3The nanometer sheet powder is ultra-sonic dispersion 10 min in alcohol, 30 min are ground as precursor powder in the oven dry back in agate mortar, get in the graphite jig that precursor powder is positioned over diameter 10 mm, mould is placed in the discharge plasma sintering stove, 40 MPa keep-up pressure, sintering temperature is 773 K, is incubated 0 min, obtains the dense multicrystalline block thermoelectric material of highly-textured degree.
3. according to claim 1ly prepare the method for polycrystal thermoelectric material, it is characterized in that with monocrystalline bismuth sulfide precursor powder, will the consistent monocrystalline Bi of orientation
2S
2.75Nanotube dust is ultra-sonic dispersion 30 min in alcohol, 60 min are ground as precursor powder in the oven dry back in agate mortar, get in the graphite jig that precursor powder is positioned over diameter 15 mm, mould is placed in the discharge plasma sintering stove, 80 MPa keep-up pressure, sintering temperature is 673 K, is incubated 3 min, obtains the dense multicrystalline block thermoelectric material of highly-textured degree.
4. according to claim 1ly prepare the method for polycrystal thermoelectric material, it is characterized in that, the monocrystalline Bi of will orientation consistent orientation with monocrystalline bismuth sulfide precursor powder
2S
2.8The nano wire powder is ultra-sonic dispersion 10 min in alcohol, 10 min are ground as precursor powder in the oven dry back in agate mortar, get in the graphite jig that precursor powder is positioned over diameter 20 mm, mould is placed in the discharge plasma sintering stove then, 20 MPa keep-up pressure, sintering temperature is 573 K, and sintering 5 min obtain the dense multicrystalline block thermoelectric material of highly-textured degree.
5. according to claim 1ly prepare the method for polycrystal thermoelectric material, it is characterized in that with monocrystalline bismuth sulfide precursor powder, will the consistent monocrystalline Bi of orientation
2S
2.9Nanotube dust is ultra-sonic dispersion 30 min in alcohol, 40 min are ground as precursor powder in the oven dry back in agate mortar, get in the graphite jig that precursor powder is positioned over diameter 30 mm, mould is placed in the discharge plasma sintering stove, 50 MPa keep-up pressure, sintering temperature is 873 K, is incubated 3 min, obtains the dense multicrystalline block thermoelectric material of highly-textured degree.
6. according to claim 1ly prepare the method for polycrystal thermoelectric material, it is characterized in that with monocrystalline bismuth sulfide precursor powder,
The monocrystalline Bi that orientation is consistent
2S
2.5The nano wire powder is ultra-sonic dispersion 60 min in alcohol, 50 min are ground as precursor powder in the oven dry back in agate mortar, get in the graphite jig that precursor powder is positioned over diameter 25 mm, mould is placed in the discharge plasma sintering stove, 30 MPa keep-up pressure, sintering temperature is 823 K, is incubated 5 min, obtains the dense multicrystalline block thermoelectric material of highly-textured degree.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443848A (en) * | 2012-01-29 | 2012-05-09 | 北京科技大学 | Method for improving thermoelectric properties of bismuth sulfide polycrystal |
| CN107522489A (en) * | 2017-08-23 | 2017-12-29 | 重庆大学 | A kind of preparation method of polycrystalline SnS e thermoelectric materials |
| CN108585879A (en) * | 2018-05-07 | 2018-09-28 | 西安交通大学 | A kind of method of quick preparation anisotropy titanium nitride ceramic block materials |
| CN112939078A (en) * | 2021-01-26 | 2021-06-11 | 昆明理工大学 | Method for improving performance of bismuth sulfide-based thermoelectric material |
| CN113511897A (en) * | 2021-04-25 | 2021-10-19 | 郑州大学 | Bi2S3Block thermoelectric material and high-voltage preparation method thereof |
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| CN101269837A (en) * | 2008-05-09 | 2008-09-24 | 北京科技大学 | Process for producing Bi2S3 nano-powder body |
| CN101358313A (en) * | 2008-05-09 | 2009-02-04 | 北京科技大学 | Method for improving Bi-S binary system thermoelectric material performance |
| CN102002757A (en) * | 2010-10-14 | 2011-04-06 | 北京科技大学 | Method for controlling bismuth-sulfide polycrystalline thermoelectric material texture |
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2011
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| CN101269837A (en) * | 2008-05-09 | 2008-09-24 | 北京科技大学 | Process for producing Bi2S3 nano-powder body |
| CN101358313A (en) * | 2008-05-09 | 2009-02-04 | 北京科技大学 | Method for improving Bi-S binary system thermoelectric material performance |
| CN102002757A (en) * | 2010-10-14 | 2011-04-06 | 北京科技大学 | Method for controlling bismuth-sulfide polycrystalline thermoelectric material texture |
Non-Patent Citations (1)
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443848A (en) * | 2012-01-29 | 2012-05-09 | 北京科技大学 | Method for improving thermoelectric properties of bismuth sulfide polycrystal |
| CN107522489A (en) * | 2017-08-23 | 2017-12-29 | 重庆大学 | A kind of preparation method of polycrystalline SnS e thermoelectric materials |
| CN107522489B (en) * | 2017-08-23 | 2020-10-23 | 重庆大学 | Preparation method of polycrystalline SnSe thermoelectric material |
| CN108585879A (en) * | 2018-05-07 | 2018-09-28 | 西安交通大学 | A kind of method of quick preparation anisotropy titanium nitride ceramic block materials |
| CN108585879B (en) * | 2018-05-07 | 2020-08-28 | 西安交通大学 | Method for rapidly preparing anisotropic titanium nitride ceramic block material |
| CN112939078A (en) * | 2021-01-26 | 2021-06-11 | 昆明理工大学 | Method for improving performance of bismuth sulfide-based thermoelectric material |
| CN112939078B (en) * | 2021-01-26 | 2023-02-28 | 昆明理工大学 | Method for improving performance of bismuth sulfide-based thermoelectric material |
| CN113511897A (en) * | 2021-04-25 | 2021-10-19 | 郑州大学 | Bi2S3Block thermoelectric material and high-voltage preparation method thereof |
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Application publication date: 20110824 |