CN104477991A - Preparation method of low-thermal-conductivity CuSbS<2+x> thermoelectric material - Google Patents
Preparation method of low-thermal-conductivity CuSbS<2+x> thermoelectric material Download PDFInfo
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- CN104477991A CN104477991A CN201410689801.3A CN201410689801A CN104477991A CN 104477991 A CN104477991 A CN 104477991A CN 201410689801 A CN201410689801 A CN 201410689801A CN 104477991 A CN104477991 A CN 104477991A
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- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 238000009837 dry grinding Methods 0.000 claims abstract description 4
- 238000001238 wet grinding Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- 239000002243 precursor Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000005275 alloying Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000005619 thermoelectricity Effects 0.000 description 5
- 239000010949 copper Substances 0.000 description 3
- 239000002305 electric material Substances 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- 229910018989 CoSb Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a low-thermal-conductivity CuSbS<2+x> thermoelectric material and a preparation method thereof, belonging to the technical field of energy materials. Cu, Sb and S are prepared according to the stoichiometric proportion of CuSbS<2+x>, wherein 0<=x<=1. The method comprises the following steps: by using Cu powder (the mass percent is greater than or equal to 99.5%), Cr powder (the mass percent is greater than or equal to 99.5%) and S powder (the mass percent is greater than or equal to 99.5%) as raw materials, mixing, putting into a planetary ball mill, carrying out dry milling at a certain rotation speed to synthesize compound powder, adding a certain amount of anhydrous ethanol to carry out wet milling, drying to obtain CuSbS<2+x> powder, and carrying out discharge plasma sintering into a block. Compared with other moderate-temperature-region thermoelectric materials, the CuSbS<2+x> has lower thermal conductivity, and the minimum thermal conductivity is -0.05Wm<-1>K<-1>. The preparation method is simple in process and easy to operate, has the advantages of low requirements for equipment and preparation environment and short period, and is suitable for large-scale production.
Description
Technical field
The invention belongs to technical field of energy material, relate to a kind of low thermal conductance CuSbS
2+xthermoelectric material and preparation method thereof.
Background technology
Thermoelectric material is a kind of material heat energy and electric energy being carried out directly transform, and the thermo-electric device be made up of it has that volume is little, noiseless, movement-less part, high reliability, has broad application prospects in thermo-electric generation and thermoelectric refrigeration etc." Voyager1 " that within noticeable 1977, launch flies out this year the solar system, and its power supply is
radio isotopethe thermogenerator of heat supply.The thermoelectricity capability of material can weigh ZT=α with zero dimension thermoelectric figure of merit ZT
2σ T/ κ, wherein α is Seebeck coefficient, and σ is specific conductivity, and κ is thermal conductivity, α
2σ is defined as the power factor of material.Prepare the study hotspot that low thermal conductance also keeps being still compared with the thermoelectric material of high electrical performance this field.
Nanometer, as the Main Means reducing thermal conductivity, is widely used in Bi
2te
3, CoSb
3and Ag
npb
msb
nte
m+2netc. in system, but still there is limitation to the reduction of thermal conductivity in it, and under high temperature, nanometer reduces trend for thermal conductivity and weakens gradually, and therefore above-mentioned system thermal conductivity only maintains ~ 1Wm
-1k
-1.For promoting conducting material thermoelectricity performance further and improving its transformation efficiency, in the urgent need to development of new low-heat heat conduction electric material.The identical people of Tsing-Hua University king utilizes mechanical alloying to prepare AgTeSb in conjunction with discharge plasma sintering technique
2low-heat heat conduction electric material, obtains low thermal conductance ~ 0.3 Wm during 673K
-1k
-1with maximum ZT value 1.59 [H. Wang, J.F. Li, M. Zou, T. Sui, Appl. Phys. Lett. 2008,93,202106].
CuSbS
2there is yellow copper structure, as the semiconductor material of narrow band gap, for the field such as absorption layer of infrared-near infrared from detecting and solar-energy photo-voltaic cell.The people such as India Vijay Kumar Gudelli utilize first-principles calculations CuGaTe
2and CuSbS
2energy band structure, density of states(DOS) and thermoelectricity capability parameter, result shows CuGaTe
2and CuSbS
2all there is the potential quality becoming excellent performance thermoelectric material.During 950K, CuGaTe
2minimum thermal conductivity ~ 1 Wm is obtained through Theoretical Calculation
-1k
-1with maximum ZT value 1.69, but do not provide CuSbS
2the calculated value [Vijay K.G. et al., J. Appl. Phys. 2013,114,223707] of thermal conductivity and ZT value.
Summary of the invention
The present invention seeks to the CuSbS preparing a kind of low thermal conductance
2+xblock thermoelectric material, further its thermoelectricity capability of research.
CuSbS provided by the invention
2+xthe preparation method of thermoelectric material, is characterized in that: Cu, Sb and S are compared CuSbS according to chemical quantity
2+xconfiguration, wherein x span is 0≤x≤1; CuSbS is synthesized by machine-alloying
2+xcompound precursor powder, powder grain size is 10 ~ 100nm.Precursor powder is become block through discharge plasma sintering, and grain-size is 0.2 ~ 2 μm.During 300 ~ 500 DEG C of tests, it is 0.05 ~ 0.3Wm that sample obtains lower thermal conductivity
-1k
-1.
The invention provides above-mentioned CuSbS
2+xthermoelectric material its preparation method comprises the steps:
(1) CuSbS
2+xthe preparation of precursor powder:
Stoichiometrically take Cu, Sb, S simple substance powder of matter percentage ratio >99.5%, at 5%H
2under+95%Ar protection, with ratio of grinding media to material 20:1, dry grinding revolution for 425rpm ball milling 10h, wet-milling rotating speed is 300 rpm, and the time is 1 h, prepares CuSbS
2+xpowder;
(2) CuSbS
2+xthe preparation of block materials:
Step (1) is adopted to prepare CuSbS
2+xpowder, by plasma discharging Fast Sintering technology, at pressure 50 ~ 100MPa, heat preservation sintering 1 ~ 20min at temperature 400 ~ 500 DEG C, prepares CuSbS
2+xblock thermoelectric material.
the present invention is prepared by mechanical alloyingcuSbS
2+xpowder, prepares low thermal conductance CuSbS with discharge plasma sintering technique
2+xblock thermoelectric material, reported first CuSbS
2+xthe thermoelectricity capability of material.At present, thermal conductivity is low to moderate ~ 0.05Wm
-1k
-1cuSbS
2+xthermoelectric material has no report.
Accompanying drawing explanation
Fig. 1: 450 DEG C of sintering CuSbS
2xRD diffractogram (a) of block varies with temperature figure with thermal conductivity (b) and ZT value (c).
Embodiment
Stoichiometrically take Cu, Sb, S simple substance powder of mass percent >99.5%, at 5%H
2under+95%Ar protection, with ratio of grinding media to material 20:1, dry grinding revolution for 425rpm ball milling 10h, wet-milling rotating speed is 300 rpm, and the time is 1h, prepares CuSbS
2powder.Gained powder, after discharge plasma sintering, prepares CuSbS
2block thermoelectric material.
Test conditions is as follows: 0≤x≤1, and discharge plasma sintering temperature is 400 ~ 500 DEG C, and pressure is 50 ~ 100MPa.
Table 1 the present invention is the CuSbS of 450 DEG C of discharge plasma sinterings
2several preferred embodiments of block thermoelectric material:
Claims (2)
1. a low thermal conductance CuSbS
2+xthe preparation method of thermoelectric material, is characterized in that: Cu, Sb and S are compared CuSbS according to chemical quantity
2+xconfiguration, wherein x span is 0≤x≤1; By machine-alloying synthesis CuSbS2+x compound precursor powder, powder grain size is 10 ~ 100nm; Precursor powder is become block through discharge plasma sintering, and grain-size is 0.2 ~ 2 μm; During 300 ~ 500 DEG C of tests, it is 0.05 ~ 0.3Wm that sample obtains lower thermal conductivity
-1k
-1.
2. according to thermal conductance CuSbS low described in claim 1
2+xthe preparation method of thermoelectric material, is characterized in that: Cu, Sb, S simple substance powder stoichiometrically taking mass percent>=99.5%, at 5%H
2under+95%Ar protection, with ratio of grinding media to material 20:1, dry grinding revolution for 425rpm ball milling 10h, wet-milling rotating speed is 300 rpm, and the time is 1 h, prepares the CuSbS that grain-size is 10 ~ 100nm
2+xpowder; CuSbS
2+xpowder, by plasma discharging Fast Sintering technology, at pressure 50 ~ 100MPa, is incubated 1 ~ 20min at temperature 400 ~ 500 DEG C, prepares the CuSbS that grain-size is 0.2 ~ 2 μm
2+xblock.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410689801.3A CN104477991B (en) | 2014-11-25 | 2014-11-25 | A kind of low thermal conductance CuSbS2+XThe preparation method of thermoelectric material |
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|---|---|---|---|
| CN201410689801.3A CN104477991B (en) | 2014-11-25 | 2014-11-25 | A kind of low thermal conductance CuSbS2+XThe preparation method of thermoelectric material |
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| Publication Number | Publication Date |
|---|---|
| CN104477991A true CN104477991A (en) | 2015-04-01 |
| CN104477991B CN104477991B (en) | 2016-06-08 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104894635A (en) * | 2015-04-27 | 2015-09-09 | 武汉理工大学 | Size-controlled copper antimony sulfur nano crystal material and preparation method thereof |
| CN105502476A (en) * | 2016-01-27 | 2016-04-20 | 南方科技大学 | Preparation of alkali-doped Cu9S5Method of producing a material |
| CN105858723A (en) * | 2016-05-09 | 2016-08-17 | 武汉理工大学 | Preparation method of nano CuSbS2 material |
| CN105923653A (en) * | 2016-06-21 | 2016-09-07 | 武汉理工大学 | Preparation method for nano Cu3SbS4 ternary semiconductor material |
| CN107089681A (en) * | 2017-04-14 | 2017-08-25 | 武汉理工大学 | Semiconductor antimony trisulfide is nanocrystalline and preparation method thereof and Photocatalyzed Hydrogen Production performance test methods |
| CN107240637A (en) * | 2017-05-04 | 2017-10-10 | 河南理工大学 | Cubic phase Cu3SbS3Base thermoelectric material and preparation method thereof |
| CN109650435A (en) * | 2018-12-29 | 2019-04-19 | 昆明理工大学 | A kind of copper sulfide base thermoelectrical composite material and preparation method thereof |
| CN111392700A (en) * | 2020-03-30 | 2020-07-10 | 中国科学院电工研究所 | Method for preparing alkali metal binary compound or alkaline earth metal binary compound |
| CN112354546A (en) * | 2020-11-09 | 2021-02-12 | 绍兴文理学院 | CuSbS2/SnS2Preparation method and application of nanosheet composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704672A (en) * | 2009-11-13 | 2010-05-12 | 北京科技大学 | Cu-Cr-S ternary thermoelectric material and preparation method thereof |
| CN102674842A (en) * | 2012-05-14 | 2012-09-19 | 北京科技大学 | Cu-S-Se ternary thermoelectric material and preparation method thereof |
-
2014
- 2014-11-25 CN CN201410689801.3A patent/CN104477991B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704672A (en) * | 2009-11-13 | 2010-05-12 | 北京科技大学 | Cu-Cr-S ternary thermoelectric material and preparation method thereof |
| CN102674842A (en) * | 2012-05-14 | 2012-09-19 | 北京科技大学 | Cu-S-Se ternary thermoelectric material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HUILAN SU ET AL.: "A novel one-step solvothermal route to nanocrystalline CuSbS2 and Ag3SbS3", 《SOLID STATE IONICS》 * |
| JOEL VAN EMBDEN ET AL.: "Synthesis and characterisation of famatinite copper antimony sulfide nanocrystals", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104894635A (en) * | 2015-04-27 | 2015-09-09 | 武汉理工大学 | Size-controlled copper antimony sulfur nano crystal material and preparation method thereof |
| CN104894635B (en) * | 2015-04-27 | 2018-03-16 | 武汉理工大学 | Controllable copper antimony sulphur nanocrystalline material of size and preparation method thereof |
| CN105502476A (en) * | 2016-01-27 | 2016-04-20 | 南方科技大学 | Preparation of alkali-doped Cu9S5Method of producing a material |
| CN105858723A (en) * | 2016-05-09 | 2016-08-17 | 武汉理工大学 | Preparation method of nano CuSbS2 material |
| CN105923653A (en) * | 2016-06-21 | 2016-09-07 | 武汉理工大学 | Preparation method for nano Cu3SbS4 ternary semiconductor material |
| CN107089681A (en) * | 2017-04-14 | 2017-08-25 | 武汉理工大学 | Semiconductor antimony trisulfide is nanocrystalline and preparation method thereof and Photocatalyzed Hydrogen Production performance test methods |
| CN107240637A (en) * | 2017-05-04 | 2017-10-10 | 河南理工大学 | Cubic phase Cu3SbS3Base thermoelectric material and preparation method thereof |
| CN107240637B (en) * | 2017-05-04 | 2019-07-09 | 河南理工大学 | Cubic phase Cu3SbS3Base thermoelectric material and preparation method thereof |
| CN109650435A (en) * | 2018-12-29 | 2019-04-19 | 昆明理工大学 | A kind of copper sulfide base thermoelectrical composite material and preparation method thereof |
| CN111392700A (en) * | 2020-03-30 | 2020-07-10 | 中国科学院电工研究所 | Method for preparing alkali metal binary compound or alkaline earth metal binary compound |
| CN112354546A (en) * | 2020-11-09 | 2021-02-12 | 绍兴文理学院 | CuSbS2/SnS2Preparation method and application of nanosheet composite material |
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| Publication number | Publication date |
|---|---|
| CN104477991B (en) | 2016-06-08 |
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Granted publication date: 20160608 |