CN102443848A - 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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- CN102443848A CN102443848A CN201210020143XA CN201210020143A CN102443848A CN 102443848 A CN102443848 A CN 102443848A CN 201210020143X A CN201210020143X A CN 201210020143XA CN 201210020143 A CN201210020143 A CN 201210020143A CN 102443848 A CN102443848 A CN 102443848A
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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 the energy and material technical field, particularly a kind of method that improves bismuth sulfide polycrystalline thermoelectricity capability relates to mechanical alloying, the synthetic and discharge plasma sintering technique of hydro-thermal.
Background technology
Along with socioeconomic continuous 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, receives people's attention day by day.The electrothermal module that with the thermo-electric device is core parts 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, thermo-electric device realizes that the key of widespread use is the raising of thermoelectric refrigeration and thermopower generation efficiency.Thermoelectricity capability characterizes with non-dimensional thermoelectric figure of merit ZT,
ZT=TS 2 σ/κ, S is a Seebeck coefficient, and σ is a specific conductivity, and κ is a thermal conductivity, and T is a T; 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.As far as polycrystal, grain-size is big more, and specific conductivity and thermal conductivity are just big more, and grain-size is more little, and specific conductivity and thermal conductivity are also more little.Therefore for good polycrystalline thermoelectric material, there are contradiction in demanding specific conductivity and low thermal conductivity in the optimization of grain-size, can't solve the contradiction that not only seeks out high conductivity but also want to obtain lower thermal conductivity through the adjustment grain-size.
Bismuth sulfide is a kind of important semiconductor material, energy gap 1.4 eV, it is at a, combine with weak Van der Waals force on the b direction of principal axis, on the c direction of principal axis with strong ionic linkage or covalent bonds.This structural strong anisotropy makes the virtual mass of current carrier also have tangible 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, obtain along the single crystal of c axle orientation easily, and will be far above along a along c direction of principal axis mobility of charge carrier rate, 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 that a kind of powder low temperature Fast Sintering that can realize prepares the new technology of block materials, can suppress crystal grain and in sintering process, grow up and be out of shape.
Summary of the invention
A kind of method that improves the bismuth sulfide thermoelectricity capability provided by the invention; Based on the electronic selection transmission route; Phonon is not selected the ultimate principle of transmission route, adopts the discharge plasma sintering method, and the monocrystalline bismuth sulfide nano-rod that is orientated is solidificated in the polycrystalline bismuth sulfide block; Form quick carrier mobility passage; The high mobility and the high conductivity that make polycrystalline bulk have to compare mutually with single crystal have lower thermal conductivity again simultaneously, have solved the difficult problem that single crystal and polycrystal electrical property and thermal property are difficult to optimize simultaneously highlightedly.
A kind of method that improves bismuth sulfide polycrystalline thermoelectricity capability is characterized in that:
1, the bismuth sulfide nano powder with the mechanical alloying method preparation mixes with mass ratio (1:0.01 ~ 1) with the monocrystalline bismuth sulfide nano-rod of hydrothermal method synthetic (001) orientation; Ultra-sonic dispersion is 10 ~ 200 minutes in absolute ethyl alcohol, the hand lapping 10 ~ 100 minutes in agate mortar of oven dry back.Ground powder is placed graphite jig, adopt discharge plasma sintering technique, be incubated 0 ~ 30 minute and prepare the bismuth sulfide polycrystalline bulk at 300 ~ 500 ℃ of sintering.
2, the bismuth sulfide nano powder of above-mentioned mechanical alloying method preparation is characterized in that: particle size is at the random pattern nano-powder of 5 ~ 500 nm.
3, the characteristic of above-mentioned hydrothermal method synthetic monocrystalline bismuth sulfide nano-rod 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 that will have good conductive channel is incorporated in the polycrystalline bismuth sulfide block, in the pattern and conductive characteristic that keep monocrystalline, significantly improves the electrical transmission performance of polycrystalline bismuth sulfide.
Description of drawings:
Fig. 1 doesA kind of principle schematic that improves bismuth sulfide polycrystalline thermoelectricity capability.
Fig. 2 doesBismuth sulfide nano-rod is cured in the sem photograph in kind in the polycrystalline.
Embodiment
Bismuth sulfide nano powder (MA powder) with the mechanical alloying method preparation mixes with mass ratio with the monocrystalline bismuth sulfide nano-rod (NR powder) of hydrothermal method synthetic (001) orientation; Ultra-sonic dispersion minute in absolute ethyl alcohol is 30 ~ 150 ℃ of oven dry hand lappings in agate mortar after 30 ~ 300 minutes.Ground powder is placed graphite jig, adopt discharge plasma sintering process to prepare the bismuth sulfide polycrystalline bulk.
Test conditions is following: the nano powder of mechanical alloying method preparation and the mass ratio of hydro-thermal synthetic nanometer rod powder are: 1:0.01 ~ 1.The time of ultra-sonic dispersion is: 10 ~ 200 minutes, the hand lapping time was: 10 ~ 100 minutes.Discharge plasma sintering process is 300 ~ 500 ℃ of sintering, is incubated 0 ~ 30 minute, and pressure is 20-60 MPa.
Specific embodiment is seen table 1.
Table 1 several preferred embodiments of the present invention:
Advantages such as in sum, through the introducing of nanometer rod, significantly improved the carrier mobility of bismuth sulfide polycrystalline material, improved thermoelectricity capability, present method has, and is convenient, simple, easy to operate.
Claims (3)
1. method that improves bismuth sulfide polycrystalline thermoelectricity capability; It is characterized in that: have the monocrystalline bismuth sulfide nano-rod powder that (001) be orientated with the bismuth sulfide nano powder and the hydrothermal method synthetic of mechanical alloying method preparation and mix with mass ratio (1:0.01 ~ 1); Ultra-sonic dispersion is 10 ~ 200 minutes in absolute ethyl alcohol, the hand lapping 10 ~ 100 minutes in agate mortar of oven dry back; Ground powder is placed graphite jig, adopt discharge plasma sintering process 300 ~ 500 ℃ of sintering under 20 ~ 60 Mpa pressure, be incubated 0 ~ 30 minute and prepare the bismuth sulfide polycrystalline bulk.
2. a kind of method that improves bismuth sulfide polycrystalline thermoelectricity capability as claimed in claim 1 is characterized in that the bismuth sulfide nano powder of mechanical alloying method preparation is the random pattern nano-powder of size at 5 ~ 500 nm.
3. a kind of method that improves bismuth sulfide polycrystalline thermoelectricity capability as claimed in claim 1 is characterized in that: hydrothermal method synthetic monocrystalline bismuth sulfide nano-rod is: (001) orientation is of a size of diameter 50 ~ 200 nm, length 0.2 ~ 5 μ m.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104823291A (en) * | 2012-10-29 | 2015-08-05 | 阿尔法贝特能源公司 | Bulk-size nanostructured materials and methods for making same by sintering nanowires |
| CN104894646A (en) * | 2015-04-01 | 2015-09-09 | 中国科学院上海高等研究院 | Method for improving conductivity of bismuth sulfide polycrystal |
| CN104894647A (en) * | 2015-04-01 | 2015-09-09 | 中国科学院上海高等研究院 | Low-thermal conductivity bismuth sulfide polycrystalline thermoelectric material and preparation method thereof |
| CN104934527A (en) * | 2015-05-29 | 2015-09-23 | 天津理工大学 | Preparation method for Bi-position-doped N-type Bi2S3 thermoelectric material |
| 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 |
| CN111690985A (en) * | 2019-03-13 | 2020-09-22 | 中国科学院上海高等研究院 | Quantum dot doped cuprous sulfide polycrystalline material and preparation method thereof |
| CN112299482A (en) * | 2020-09-22 | 2021-02-02 | 南京理工大学 | Method for reducing thermal conductivity of bismuth sulfide thermoelectric 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 |
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| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006089938A1 (en) * | 2005-02-24 | 2006-08-31 | Basf Aktiengesellschaft | Semiconducting bismuth sulphides having new combinations of properties and use thereof in thermoelectrics and photovoltaics |
| CN101271955A (en) * | 2008-05-09 | 2008-09-24 | 北京科技大学 | Bi-S binary system pyroelectric material and production method |
| CN102002757A (en) * | 2010-10-14 | 2011-04-06 | 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 |
-
2012
- 2012-01-29 CN CN201210020143.XA patent/CN102443848B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006089938A1 (en) * | 2005-02-24 | 2006-08-31 | Basf Aktiengesellschaft | Semiconducting bismuth sulphides having new combinations of properties and use thereof in thermoelectrics and photovoltaics |
| CN101271955A (en) * | 2008-05-09 | 2008-09-24 | 北京科技大学 | Bi-S binary system pyroelectric material and production method |
| CN102002757A (en) * | 2010-10-14 | 2011-04-06 | 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 |
Non-Patent Citations (1)
| Title |
|---|
| ZHEN-HUA GE ET AL.: "Controllable synthesis: Bi2S3 nanostructure powders and highly textured polycrystals", 《CRYSTENGCOMM》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104823291A (en) * | 2012-10-29 | 2015-08-05 | 阿尔法贝特能源公司 | Bulk-size nanostructured materials and methods for making 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 |
| CN104894646A (en) * | 2015-04-01 | 2015-09-09 | 中国科学院上海高等研究院 | Method for improving conductivity of bismuth sulfide polycrystal |
| CN104894647A (en) * | 2015-04-01 | 2015-09-09 | 中国科学院上海高等研究院 | Low-thermal conductivity bismuth sulfide polycrystalline thermoelectric material and preparation method thereof |
| 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 |
| CN104934527A (en) * | 2015-05-29 | 2015-09-23 | 天津理工大学 | Preparation method for Bi-position-doped N-type Bi2S3 thermoelectric material |
| CN104934527B (en) * | 2015-05-29 | 2018-05-11 | 天津理工大学 | A kind of Bi doped N-type Bi2S3The preparation method of thermoelectric material |
| 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 |
| CN111690985A (en) * | 2019-03-13 | 2020-09-22 | 中国科学院上海高等研究院 | Quantum dot doped cuprous sulfide polycrystalline material and preparation method thereof |
| 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 |
| CN112299482A (en) * | 2020-09-22 | 2021-02-02 | 南京理工大学 | Method for reducing thermal conductivity of bismuth sulfide thermoelectric material |
| CN112299482B (en) * | 2020-09-22 | 2022-09-27 | 南京理工大学 | Method for reducing thermal conductivity of bismuth sulfide thermoelectric 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 |
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Effective date of registration: 20170607 Address after: 065400 No. 7, Po Hai Road, modern industrial park, Xianghe County, Hebei, Langfang Patentee after: Xianghe North China chilling unit Co., Ltd Address before: 100083 Haidian District, Xueyuan Road, No. 30, Patentee before: University of Science and Technology Beijing |
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Effective date of registration: 20220120 Address after: 065400 No. b-08-01, north side of Jingbei Road, Xianghe environmental protection industrial park, Langfang City, Hebei Province Patentee after: XIANGHE HUIWEN ENERGY SAVING TECHNOLOGY CO.,LTD. Address before: 065400 No. 7, Baohai Road, modern industrial park, Xianghe County, Langfang City, Hebei Province Patentee before: HUABEI COOLING DEVICE CO.,LTD. |