CN1786229A - Preparation method of CoSb3 pyroelectric material having nanometer/micron composite crystal structure - Google Patents
Preparation method of CoSb3 pyroelectric material having nanometer/micron composite crystal structure Download PDFInfo
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- CN1786229A CN1786229A CN 200510117532 CN200510117532A CN1786229A CN 1786229 A CN1786229 A CN 1786229A CN 200510117532 CN200510117532 CN 200510117532 CN 200510117532 A CN200510117532 A CN 200510117532A CN 1786229 A CN1786229 A CN 1786229A
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- cosb3
- micron
- nanometer
- thermoelectric material
- cosb
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000013078 crystal Substances 0.000 title abstract description 4
- 229910018985 CoSb3 Inorganic materials 0.000 title abstract 4
- 239000002131 composite material Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910018989 CoSb Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 230000005619 thermoelectricity Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
The invention belongs to thermoelectric material manufacturing technology field. The current micron crystal grain CoSb3 material thermal conductivity is high. Although nanometer is low, its electric conductivity is greatly reduced to make ZT maximum only be 0.057 in 300-800K temperature range. The features of a nanometer/micron compound grain structure CoSb3 thermoelectric material manufacturing are using 80-100nm metallic cobalt and 20-40um antimony simple substance elemental powder as raw material; weighting and mixing by CoSb3 compound chemical formula under the protection of argon gas; grinding powder; doing SPS reaction in situ synthesis; and the pressure is 30-50MPa; heating rate is 120-150 centigrade degree per minute; temperature is 450-550 centigrade degree; holding time is 3-5min; atmosphere is vacuum. The thermoelectric material has nanometer/micron compound grain structure. The ZT value is 0.34 at 700K.
Description
Technical field
The present invention relates to the CoSb of the compound crystalline-granular texture of a kind of Nano/micron
3Thermoelectric material and preparation method thereof belongs to the manufacturing technology field of thermoelectric material.
Background technology
Thermoelectric material is the new function material that utilizes Seebeck (Seebeck) effect and Pei Er Supreme Being (Peltier) effect that heat energy and electric energy are changed mutually, be the critical material of hi-tech new energy field, having broad application prospects aspect thermoelectric power generation and the thermoelectric refrigeration.The performance of thermoelectric material characterizes with zero dimension figure of merit ZT usually: ZT=(α
2The T of σ/κ), in the formula, α is the Seebeck coefficient, and σ is a specific conductivity, and κ is a thermal conductivity, and T is a temperature.Good thermoelectric material should have high ZT value.
In numerous thermoelectric material systems, CoSb
3Have a potential high performance novel thermoelectric material as a kind of, be subjected to extensive concern both domestic and external.But this material exists complicated process of preparation, thermal conductivity height at present, thereby causes its ZT value lower, can not satisfy practical requirement.Therefore how to reduce CoSb
3The thermal conductivity of material improves the emphasis that its thermoelectricity capability has become domestic and international research.In existing technology, in Japanese Patent [open communique 1996 186492A number] and the Yang Jun disclosed patent of friend [CN14229669A], CoSb
3Mechanical alloying (MA), solid reaction process and scorification are adopted in the preparation of material more, these methods not only reaction time long, complex procedures, and grain size is difficult to regulation and control.In our previous work, adopted the SPS technology to successfully synthesize to have the CoSb of single micron and nanocrystal structure
3Thermoelectric material (ZL 02 1 56680.1), performance test show, the CoSb of micron crystal grain
3Material thermal conductivity height, and the CoSb of nanocrystal
3Though material has very low thermal conductivity, descending significantly also appears in specific conductivity simultaneously, makes its ZT maximum value in the 300-800K temperature range have only 0.057.In order to improve CoSb
3The ZT value of material must make it when guaranteeing lower thermal conductivity, has high Seebeck coefficient and specific conductivity, the present invention proposes the CoSb of the compound crystalline-granular texture of a kind of Nano/micron for this reason
3Thermoelectric material and preparation method thereof has not yet to see report.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, the fast preparation method that a kind of preparation time is short, technology is simple, cost is low is provided, to obtain CoSb with the compound crystalline-granular texture of Nano/micron
3The compact block thermoelectric material.
The CoSb of the compound crystalline-granular texture of Nano/micron provided by the invention
3The thermoelectric material preparation method is characterized in that:
With 80-100nm cobalt metal and 20-40 μ m antimony simple substance element powders is raw material, presses CoSb
3The chemical formula weighing and burden of compound, under argon shield, the powder ground and mixed; it is synthetic to carry out discharge plasma sintering (SPS) reaction in then, pressure 30-50MPa, temperature rise rate 120-150 ℃/min; temperature 450-550 ℃, soaking time 3-5min, atmosphere is vacuum.
Prepared thermoelectric material has the compound crystalline-granular texture of Nano/micron, and wherein the nanocrystal yardstick is about 100nm, and the micron crystal particle scale is 1-3 μ m, and the relative density of material is greater than 93.0%.This material is obtained maximum ZT value 0.34 at 700K.
Description of drawings
Fig. 1: CoSb
3The TEM photo of thermoelectric material;
Fig. 2: CoSb
3The relation of the thermal conductivity κ of thermoelectric material and grain-size and temperature T;
Fig. 3: CoSb
3The relation of the conductivity of thermoelectric material and grain-size and temperature T;
Fig. 4: CoSb
3The Seebeck factor alpha of thermoelectric material and the relation of grain-size and temperature T;
Fig. 5: CoSb
3The ZT value of thermoelectric material and the relation of grain-size and temperature T
Embodiment
Example 1: with cobalt metal (80nm) and antimony (20 μ m) simple substance element powders is raw material, presses CoSb
3The chemical formula weighing and burden of compound under argon shield, carries out the SPS reaction in and synthesizes in the graphite jig of packing into after the powder ground and mixed.Sintering condition is: pressure 30MPa, 120 ℃/min of temperature rise rate, 450 ℃ of temperature, soaking time 3min.Acquisition has the CoSb of the compound crystalline-granular texture of Nano/micron
3Compact block material, its weave construction as shown in Figure 1, relative density is 93.0%.This material is obtained maximum ZT value 0.34 at 700K.
Example 2: with cobalt metal (100nm) and antimony (40 μ m) simple substance element powders is raw material, presses CoSb
3The chemical formula weighing and burden of compound under argon shield, carries out the SPS reaction in and synthesizes in the graphite jig of packing into after the powder ground and mixed.Sintering condition is: pressure 40MPa, 130 ℃/min of temperature rise rate, 500 ℃ of temperature, soaking time 4min.Acquisition has the CoSb of the compound crystalline-granular texture of Nano/micron
3Compact block material, relative density are 95.3%.This material is obtained maximum ZT value 0.34 at 700K.
Example 3: with cobalt metal (90nm) and antimony (30 μ m) simple substance element powders is raw material, presses CoSb
3The chemical formula weighing and burden of compound under argon shield, carries out the SPS reaction in and synthesizes in the graphite jig of packing into after the powder ground and mixed.Sintering condition is: pressure 50MPa, 150 ℃/min of temperature rise rate, 550 ℃ of temperature, soaking time 5min.Acquisition has the CoSb of the compound crystalline-granular texture of Nano/micron
3Compact block material, relative density are 97.0%, and the thermoelectricity capability test result is shown in Fig. 2-5.This material is obtained maximum ZT value 0.34 at 700K.
Claims (1)
1, the CoSb of the compound crystalline-granular texture of a kind of Nano/micron
3The thermoelectric material preparation method is characterized in that: with 80-100nm cobalt metal and 20-40 μ m antimony simple substance element powders is raw material, presses CoSb
3The chemical formula weighing and burden of compound, under argon shield, the powder ground and mixed; it is synthetic to carry out discharge plasma sintering (SPS) reaction in then, pressure 30-50MPa, temperature rise rate 120-150 ℃/min; temperature 450-550 ℃, soaking time 3-5min, atmosphere is vacuum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510117532 CN1786229A (en) | 2005-11-04 | 2005-11-04 | Preparation method of CoSb3 pyroelectric material having nanometer/micron composite crystal structure |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510117532 CN1786229A (en) | 2005-11-04 | 2005-11-04 | Preparation method of CoSb3 pyroelectric material having nanometer/micron composite crystal structure |
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| CN1786229A true CN1786229A (en) | 2006-06-14 |
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|---|---|---|---|
| CN 200510117532 Pending CN1786229A (en) | 2005-11-04 | 2005-11-04 | Preparation method of CoSb3 pyroelectric material having nanometer/micron composite crystal structure |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427631C (en) * | 2006-11-24 | 2008-10-22 | 清华大学 | Nano SiC granule composite CoSb3 base thermoelectric material and its preparing process |
| CN101275192B (en) * | 2008-05-09 | 2013-01-30 | 湖南晟通科技集团有限公司 | Composite nanometer ZnSb-based thermoelectric material and preparation thereof |
| CN103331449A (en) * | 2013-06-05 | 2013-10-02 | 华南理工大学 | Ultrahigh-plasticity double-size-distribution superfine crystal/micrometer crystal block iron material and preparation method thereof |
| CN103887421A (en) * | 2012-12-21 | 2014-06-25 | 财团法人工业技术研究院 | Thermoelectric material and method for producing same |
| CN104335327A (en) * | 2011-11-21 | 2015-02-04 | 研究三角协会 | Nanoparticle compact materials for thermoelectric application |
| CN105149576A (en) * | 2015-09-18 | 2015-12-16 | 复旦大学 | 3D printing method for rapidly forming thermoelectric materials |
| CN109604605A (en) * | 2018-12-29 | 2019-04-12 | 六盘水师范学院 | A kind of solid reaction process quickly prepares CoSb3Method |
| CN112063872A (en) * | 2020-09-09 | 2020-12-11 | 武汉理工大学 | Method for rapidly constructing multi-scale nano composite modified material |
-
2005
- 2005-11-04 CN CN 200510117532 patent/CN1786229A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427631C (en) * | 2006-11-24 | 2008-10-22 | 清华大学 | Nano SiC granule composite CoSb3 base thermoelectric material and its preparing process |
| CN101275192B (en) * | 2008-05-09 | 2013-01-30 | 湖南晟通科技集团有限公司 | Composite nanometer ZnSb-based thermoelectric material and preparation thereof |
| CN104335327A (en) * | 2011-11-21 | 2015-02-04 | 研究三角协会 | Nanoparticle compact materials for thermoelectric application |
| CN103887421A (en) * | 2012-12-21 | 2014-06-25 | 财团法人工业技术研究院 | Thermoelectric material and method for producing same |
| CN103331449A (en) * | 2013-06-05 | 2013-10-02 | 华南理工大学 | Ultrahigh-plasticity double-size-distribution superfine crystal/micrometer crystal block iron material and preparation method thereof |
| CN103331449B (en) * | 2013-06-05 | 2015-09-02 | 华南理工大学 | Ultra-fine Grained/micron crystal block body iron material of the two size distribution of a kind of super-high-plasticity and preparation method thereof |
| CN105149576A (en) * | 2015-09-18 | 2015-12-16 | 复旦大学 | 3D printing method for rapidly forming thermoelectric materials |
| CN109604605A (en) * | 2018-12-29 | 2019-04-12 | 六盘水师范学院 | A kind of solid reaction process quickly prepares CoSb3Method |
| CN112063872A (en) * | 2020-09-09 | 2020-12-11 | 武汉理工大学 | Method for rapidly constructing multi-scale nano composite modified material |
| CN112063872B (en) * | 2020-09-09 | 2022-03-01 | 武汉理工大学 | Method for rapidly constructing multi-scale nano composite modified material |
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