CN102443848B - Method for improving thermoelectric properties of bismuth sulfide polycrystal - Google Patents
Method for improving thermoelectric properties of bismuth sulfide polycrystal Download PDFInfo
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- CN102443848B CN102443848B CN201210020143.XA CN201210020143A CN102443848B CN 102443848 B CN102443848 B CN 102443848B CN 201210020143 A CN201210020143 A CN 201210020143A CN 102443848 B CN102443848 B CN 102443848B
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Abstract
The invention relates to a method for improving thermoelectric properties of bismuth sulfide polycrystal and belongs to the technical field of energy materials. The method is characterized by comprising the following steps of: mixing bismuth sulfide nano powder prepared by a mechanical alloying method with (001)-oriented monocrystal bismuth sulfide nanorod powder synthesized by a hydrothermal method, ultrasonically dispersing in absolute ethanol for 10-200 minutes, drying and then manually grinding in an agate mortar for 10-100 minutes; and placing ground powder in a graphite mold, sintering at 300-500 DEG C by adopting a spark plasma sintering process, and maintaining the temperature for 0-30 minutes to prepare a bismuth sulfide polycrystal block. Because the spark plasma sintering process has high heating rate, thus the growth and fusion of crystals are inhibited, the monocrystal nanorod structure is retained in the polycrystal block to form a fast channel for carrier migration, and the electric transmission performance and thermoelectric property of the bismuth sulfide polycrystal are greatly improved; and the method has the advantages of simplicity in required equipment, easiness in operation, low cost, significant effect and the like.
Description
Technical field
The invention belongs to energy and material technical field, particularly a kind of method that improves thermoelectric properties of bismuth sulfide polycrystal, relates to mechanical alloying, Hydrothermal Synthesis and discharge plasma sintering technique.
Background technology
Along with socioeconomic development, environment and energy problem are more and more paid attention to by the mankind.Thermoelectric material can directly be realized the mutual conversion of heat energy and electric energy, and thermo-electric device is pollution-free, zero release and structure is light, volume is little, the life-span is long, day by day receives people's concern.Electrothermal module taking thermo-electric device as core parts has a wide range of applications at the aspect such as semiconductor refrigerating, thermoelectric cell.With the competition of conventional refrigeration modes and conventional power source in, the key that thermo-electric device is realized widespread use is the raising of thermoelectric refrigeration and thermopower generation efficiency.Thermoelectricity capability characterizes with zero dimension thermoelectric figure of merit ZT,
zT=TS 2 σ/κ, S is Seebeck coefficient, and σ is specific conductivity, and κ is thermal conductivity, and T is absolute temperature; S
2σ is called power factor, is used for characterizing the electrical transmission performance of thermoelectric material.
As everyone knows, single crystal is compared with polycrystal, high, the bad mechanical property of thermal conductance when specific conductivity is high.For polycrystal, grain-size is larger, and specific conductivity and thermal conductivity are just larger, and grain-size is less, and specific conductivity and thermal conductivity are also less.Therefore for good polycrystalline thermoelectric material, require high specific conductivity and low thermal conductivity, in the optimization of grain-size, have contradiction, cannot solve and not only want the contradiction that obtains high conductivity but also want to obtain lower thermal conductivity by adjusting grain-size.
Bismuth sulfide is a kind of important semiconductor material, energy gap 1.4 eV, it is at a, on b direction of principal axis with weak Van der Waals force combination, in c-axis direction with strong ionic linkage or covalent bonds.This structural strong anisotropy, makes the virtual mass of current carrier also have obvious anisotropy, and the current carrier virtual mass of a direction is 3.0 ± 0.5 (Cantarero, A. with the ratio of the current carrier virtual mass of c direction; Martinez-Pastor, J.; Segura, A. Transport Properties of Bismuth Sulfide Single Crystals,
phys. Rev. B,
1987, 35,9586.).Therefore, during with the synthetic bismuth sulfide of solution method, easily obtain along the single crystal of c-axis orientation, and will be far above along a along the mobility of c-axis direction current carrier, the mobility of b axle (Shaban, H.T.; Nassary, M.M.; El-Sadek, M.S. Transport Properties of Bi
2s
3single Crystals,
physica B 2008, 403,1655-1659.).
Discharge plasma sintering technique, is a kind ofly can realize the new technology that powder low temperature Fast Sintering is prepared block materials, can suppress crystal grain and in sintering process, grows up and be out of shape.
Summary of the invention
A kind of method that improves bismuth sulfide thermoelectricity capability provided by the invention, based on electronic selection transmission route, phonon is not selected the ultimate principle of transmission route, adopt discharge plasma sintering method, the monocrystalline bismuth sulfide nano-rod of orientation is solidificated in polycrystalline bismuth sulfide block, form quick carrier mobility passage, make polycrystalline bulk there is the high mobility comparable with single crystal and high conductivity, there is again lower thermal conductivity, solved highlightedly the difficult problem that single crystal and polycrystal electrical property and thermal characteristics are difficult to optimize simultaneously simultaneously.
A method that improves thermoelectric properties of bismuth sulfide polycrystal, is characterized in that:
1, the monocrystalline bismuth sulfide nano-rod that the bismuth sulfide nano powder of preparing with mechanical alloying method (001) synthetic with hydrothermal method is orientated mixes with mass ratio (1:0.01 ~ 1), ultrasonic dispersion 10 ~ 200 minutes in dehydrated alcohol, hand lapping 10 ~ 100 minutes in agate mortar after oven dry.Ground powder is placed in to graphite jig, adopts discharge plasma sintering technique at 300 ~ 500 DEG C of sintering, be incubated and within 0 ~ 30 minute, prepare bismuth-sulfide polycrystalline block.
2, the bismuth sulfide nano powder that prepared by above-mentioned mechanical alloying method is characterized in that: particle size is at the random pattern nano-powder of 5 ~ 500 nm.
3, the feature of the synthetic monocrystalline bismuth sulfide nano-rod of above-mentioned hydrothermal method is: have (001) orientation, nanometer rod is of a size of diameter 50 ~ 200 nm, length 0.2 ~ 5 μ m.
The present invention utilizes discharge plasma sintering technique, and the monocrystalline bismuth sulfide nano-rod with good conductive channel is incorporated in polycrystalline bismuth sulfide block, in keeping the pattern and conductive characteristic of monocrystalline, significantly improves the electrical transmission performance of polycrystalline bismuth sulfide.
brief description of the drawings:
fig. 1 isa kind of principle schematic that improves thermoelectric properties of bismuth sulfide polycrystal.
fig. 2 isbismuth sulfide nano-rod is cured in the scanning electron microscope (SEM) photograph in kind in polycrystalline.
Embodiment
The monocrystalline bismuth sulfide nano-rod (NR powder) that the bismuth sulfide nano powder (MA powder) of preparing with mechanical alloying method (001) synthetic with hydrothermal method is orientated mixes with mass ratio, ultrasonic dispersion minute in dehydrated alcohol, 30 ~ 150 DEG C of oven dry hand lappings in agate mortar after 30 ~ 300 minutes.Ground powder is placed in to graphite jig, adopts discharge plasma sintering process to prepare bismuth-sulfide polycrystalline block.
Test conditions is as follows: the mass ratio of the nanometer rod powder of nano powder prepared by mechanical alloying method and Hydrothermal Synthesis is: 1:0.01 ~ 1.The time of ultrasonic dispersion is: 10 ~ 200 minutes, the hand lapping time was: 10 ~ 100 minutes.Discharge plasma sintering process is 300 ~ 500 DEG C of sintering, is incubated 0 ~ 30 minute, and pressure is 20-60 MPa.
Specific embodiment is in table 1.
Table 1 several preferred embodiments of the present invention:
The advantages such as in sum, by the introducing of nanometer rod, significantly improved the carrier mobility of bismuth-sulfide polycrystalline material, improved thermoelectricity capability, present method has, convenient, simple, easy to operate.
Claims (1)
1. one kind is improved the method for thermoelectric properties of bismuth sulfide polycrystal, it is characterized in that: the grain-size of preparing taking mechanical alloying method is mixed with mass ratio 1:0.01 ~ 1 as the monocrystalline bismuth sulfide nano-rod powder with (001) orientation of the random pattern bismuth sulfide nano of 5 ~ 500 nm powder and Hydrothermal Synthesis, nanometer rod is of a size of diameter 50 ~ 200 nm, length 0.2 ~ 5 μ m, ultrasonic dispersion 10 ~ 200 minutes in dehydrated alcohol, hand lapping 10 ~ 100 minutes in agate mortar after oven dry; Ground powder is placed in to graphite jig, adopts discharge plasma sintering process 300 ~ 500 DEG C of sintering under 20 ~ 60 Mpa pressure, be incubated 0 ~ 30 minute, prepare bismuth-sulfide polycrystalline block.
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| CN109659425A (en) * | 2018-12-29 | 2019-04-19 | 昆明理工大学 | A kind of bismuthino thermoelectric material and preparation method thereof promoting doping effect using barrier layer |
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| US20140116491A1 (en) * | 2012-10-29 | 2014-05-01 | Alphabet Energy, Inc. | Bulk-size nanostructured materials and methods for making the same by sintering nanowires |
| CN104894646B (en) * | 2015-04-01 | 2017-07-11 | 中国科学院上海高等研究院 | A kind of method for improving bismuth-sulfide polycrystalline electrical conductivity |
| CN104894647B (en) * | 2015-04-01 | 2017-11-10 | 中国科学院上海高等研究院 | A kind of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material and preparation method thereof |
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| CN106283173A (en) * | 2016-07-21 | 2017-01-04 | 昆明理工大学 | A kind of method reducing Tellurobismuthite. polycrystalline lattice thermal conductivity |
| CN106278271A (en) * | 2016-08-23 | 2017-01-04 | 昆明理工大学 | A kind of preparation method of bismuth-sulfide polycrystalline thermoelectric material |
| CN111690985B (en) * | 2019-03-13 | 2021-10-01 | 中国科学院上海高等研究院 | Quantum dot doped cuprous sulfide polycrystalline material and preparation method thereof |
| CN112299482B (en) * | 2020-09-22 | 2022-09-27 | 南京理工大学 | Method for reducing thermal conductivity of bismuth sulfide 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 |
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| DE102005008865A1 (en) * | 2005-02-24 | 2006-08-31 | Basf Ag | Modified bismuth sulfide composition, useful in semiconductor material, which is used in e.g. thermoelectric modules and photovoltaic cells is new |
| CN101271955B (en) * | 2008-05-09 | 2011-08-24 | 北京科技大学 | Bi-S binary system pyroelectric material and production method |
| CN102002757B (en) * | 2010-10-14 | 2012-09-05 | 北京科技大学 | Method for controlling bismuth-sulfide polycrystalline thermoelectric material texture |
| CN102161507A (en) * | 2011-04-11 | 2011-08-24 | 北京科技大学 | Method for preparing polycrystalline textured thermoelectric material from single-crystal bismuth sulfide precursor powder |
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| CN109659425A (en) * | 2018-12-29 | 2019-04-19 | 昆明理工大学 | A kind of bismuthino thermoelectric material and preparation method thereof promoting doping effect using barrier layer |
| CN109659425B (en) * | 2018-12-29 | 2020-07-10 | 昆明理工大学 | Bismuth-based thermoelectric material with doping effect improved by using barrier layer and preparation method thereof |
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