CN101502865A - Hot forging processing method for optimizing performance of polycrystal bismuth telluride-based thermoelectric alloy material - Google Patents
Hot forging processing method for optimizing performance of polycrystal bismuth telluride-based thermoelectric alloy material Download PDFInfo
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- CN101502865A CN101502865A CNA2009100963465A CN200910096346A CN101502865A CN 101502865 A CN101502865 A CN 101502865A CN A2009100963465 A CNA2009100963465 A CN A2009100963465A CN 200910096346 A CN200910096346 A CN 200910096346A CN 101502865 A CN101502865 A CN 101502865A
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Abstract
The invention discloses a hot forging processing method for optimizing performance of a polycrystalline bismuth telluride-based thermoelectric alloy material. The polycrystalline bismuth telluride-based blocky thermoelectric alloy, which is subjected to one-time hot press molding, is directly put into a graphite die for hot forging deformation and pressure maintaining so as to obtain the final thermoelectric alloy material. The inventive mechanism mainly comprises that: due to the hot forging deformation, the microstructure of the material is changed; stress induces the generation of point defect and nanometer structure inside the material, and meanwhile, triggers the recrystallization of the material for thinning crystal grains, thus prominently ameliorating thermoelectric performances that impact the material self. The invention has the characteristics of simple technology, low cost, short period and great suitability for large-scale production and application, and the manufactured bismuth telluride-based blocky thermoelectric alloy material has lower thermal conductivity and higher room temperature thermoelectric merit figure than the material prior to the hot forging deformation processing.
Description
Technical field
The present invention relates to optimize the method for thermoelectric semiconductor material performance, especially relate to a kind of hot forging processing method of optimizing performance of polycrystal bismuth telluride-based thermoelectric alloy material.
Background technology
Thermoelectric material is that a kind of motion by carrier (electronics or hole) realizes the semi-conducting material that electric energy and heat energy are directly changed mutually.When there was the temperature difference in the thermoelectric material two ends, thermoelectric material can be converted into heat energy electric energy output; Otherwise or when passing to electric current in thermoelectric material, thermoelectric material can be converted into heat energy with electric energy, an end heat release and other end heat absorption.The thermoelectric material background that is widely used at refrigeration or aspect such as generating.The performance of thermoelectric material characterizes with " thermoelectric figure of merit " ZT: zT=(α
2The T of σ/κ).Here α is the Seebeck coefficient of material, and σ is an electrical conductivity, and κ is a thermal conductivity, and T is an absolute temperature.
Bismuth telluride-based thermoelectric alloy material is present best room temperature thermoelectric material, commercial general use bismuth telluride monocrystalline.Because monocrystalline bismuth telluride mechanical performance is relatively poor, legibility from, be difficult to processing or the like shortcoming, the research to this material in recent years mainly concentrates on polycrystal bismuth telluride-based block electrothermal alloy.The optimum room temperature thermoelectric figure of merit ZT of commercialization bismuth telluride-base monocrystalline thermoelectric alloy material is about 1.Studies show that,, can improve the thermoelectricity capability of bismuth telluride-based thermoelectric alloy material effectively by reducing the thermal conductivity of material.The main means that reduce the thermal conductivity of bismuth telluride-based thermoelectric alloy material at present are nanometer and grain refinement, usually adopt low temperature wet to learn method, mechanical alloy and rapid solidification, in conjunction with vacuum hotpressing, spark plasma sintering or the like method prepares the bismuth telluride-base thermoelectric material that has than lower thermal conductivity.Processing step is comparatively complicated, and is difficult to stablize large-scale industrial production.
Summary of the invention
The purpose of this invention is to provide a kind of hot forging processing method of optimizing performance of polycrystal bismuth telluride-based thermoelectric alloy material.Produce by a large amount of defectives of stress-induced material internal and nanostructured, crystallization again takes place in material under the thermal stress effect simultaneously, further crystal grain thinning, thereby the thermoelectricity that influences material on heterogeneous microstructure transports, further reduce the thermal conductivity of bismuth telluride-based thermoelectric alloy material, make material have higher thermoelectric figure of merit.
The technical solution adopted for the present invention to solve the technical problems is as follows:
With once hot-forming polycrystal bismuth telluride-based block electrothermal alloy, put into directly that graphite jig carries out the forge hot distortion again, pressurize obtains final thermoelectric alloy material.Once hot-forming polycrystal bismuth telluride-based block electrothermal alloy be by the bismuth telluride-base bulk alloy body of casting that melting is obtained pulverize grind sieve after, take by weighing that the appropriate amount alloy powder is once hot-forming to be obtained.
Forge hot described in the present invention uses the internal diameter of graphite jig greater than hot-forming bulk alloy size; Described hot forging temperature is 400 ℃～500 ℃; Described forge hot pressure is 50MPa～100Mpa; The described dwell time is 20～60 minutes.
The polycrystal bismuth telluride-based bulk alloy that melting among the present invention obtains comprises bismuth telluride, the polycrystal bismuth telluride-based bulk alloy of binary such as bismuth telluride antimony and bismuth telluride selenium and ternary.Raw material sources both can be the polycrystal bismuth telluride-based bulk alloys of commercial goodsization, also can be for utilizing bismuth with elementary voluntarily, and antimony, tellurium, selenium prepare the polycrystalline bulk alloy.
The beneficial effect that the present invention has is:
The forge hot deformation processing method of described bismuth telluride-based thermoelectric alloy material, it is simple to have technology, cost is low, cycle is short, adapt to characteristics such as large-scale production and application, the block thermoelectric alloy material of the bismuth telluride-base for preparing has the room temperature thermoelectric figure of merit of lower thermal conductivity and Geng Gao before than the forge hot deformation process.
Specific implementation method
Below in conjunction with embodiment the present invention is further elaborated.
Reference example 1:
Utilize bismuth with elementary, antimony, tellurium vacuum melting obtains the bismuth telluride-base body of casting, with the body of casting pulverize to grind sieve after, take by weighing that the appropriate amount alloy powder is once hot-forming to obtain the cylindric polycrystal bismuth telluride-based bulk alloy that diameter is 10mm.
The density of utilizing Archimedes's method to measure sample is 99.2% of solid density, adopts RigakuD/MAX-2550PC type X ray polycrystalline diffractometer (XRD) and FEI Sirion field emission scanning electron microscope (FESEM) test material all not to find tangible texture.
Obtain thermal conductivity κ according to the density calculation of adopting Netzsch LFA-457 type laser pulse thermal analyzer to measure the thermal diffusion coefficient, specific heat and the material that calculate, the thermal conductivity of the sample that this example makes is κ=1.12Wm when 300K
-1K
-1Adopt Agilent 34970A data collecting instrument to measure and calculate the thermoelectrical potential factor alpha that obtains material to fixed difference difference sample two ends electrical potential difference.Adopt four electrode method to measure conductivity of electrolyte materials σ.Press ZT=(α according to above-mentioned measured value
2σ/κ) T calculates, and the ZT value of the sample that this example makes is 1.04 when 300K.
Reference example 2:
Adopt commercial goods bismuth telluride-base alloy, pulverize after grinding sieves, take by weighing that the appropriate amount alloy powder is once hot-forming to obtain the cylindric polycrystal bismuth telluride-based bulk alloy that diameter is 10mm.
Archimedes's method test sample density is 98.9% of solid density, and XRD and ESEM do not find that all there is obvious texture in sample interior.It is 1.18Wm that Performance Detection obtains this polycrystalline bulk alloy thermal conductivity κ when 300K
-1K
-1, the ZT value is 0.89.
Embodiment 1:
1 hot pressing of reference example is obtained bulk alloy put into the graphite jig that internal diameter is 12.6mm, forge hot becomes under vacuum: 400 ℃ of pressurizes 60 minutes, pressure 80MPa.Taking-up obtains final polycrystal bismuth telluride-based bulk alloy.
Archimedes's method test sample density is 98.8% of solid density, and XRD and ESEM do not find that all there is obvious texture in sample interior.It is 0.88Wm that Performance Detection obtains this polycrystalline bulk alloy thermal conductivity κ when 300K
-1K
-1, the ZT value is 1.32.Contrast reference example 1, the ZT value has improved 27%.
Embodiment 2:
1 hot pressing of reference example is obtained bulk alloy put into the graphite jig that internal diameter is 12.6mm, forge hot distortion under vacuum: 450 ℃ of pressurizes 30 minutes, pressure 80MPa.Taking-up obtains final polycrystal bismuth telluride-based bulk alloy.
Archimedes's method test sample density is 99.1% of solid density, and XRD and ESEM do not find that all there is obvious texture in sample interior.It is 0.83Wm that Performance Detection obtains this polycrystalline bulk alloy thermal conductivity κ when 300K
-1K
-1, the ZT value is 1.40.Contrast reference example 1, the ZT value has improved 35%.
Embodiment 3:
1 hot pressing of reference example is obtained bulk alloy put into the graphite jig that internal diameter is 12.6mm, forge hot distortion under vacuum: 450 ℃ of pressurizes 30 minutes, pressure 100MPa.Taking-up obtains final polycrystal bismuth telluride-based bulk alloy.
Archimedes's method test sample density is 99.3% of solid density, and XRD and ESEM do not find that all there is obvious texture in sample interior.It is 0.75Wm that Performance Detection obtains this polycrystalline bulk alloy thermal conductivity κ when 300K
-1K
-1, the ZT value is 1.56.Contrast reference example 1, the ZT value has improved 50%.
Embodiment 4:
2 hot pressing of reference example is obtained bulk alloy put into the graphite jig that internal diameter is 12.6mm, forge hot distortion under vacuum: 450 ℃ of pressurizes 30 minutes, pressure 80MPa.Taking-up obtains final polycrystal bismuth telluride-based bulk alloy.
Archimedes's method test sample density is 99% of solid density, and XRD and ESEM do not find that all there is obvious texture in sample interior.It is 0.93Wm that Performance Detection obtains this polycrystalline bulk alloy thermal conductivity κ when 300K
-1K
-1, the ZT value is 1.15.Contrast reference example 2, the ZT value has improved 29%.
Embodiment 5:
1 hot pressing of reference example is obtained bulk alloy put into the graphite jig that internal diameter is 12.6mm, forge hot distortion under vacuum: 500 ℃ of pressurizes 20 minutes, pressure 80MPa.Taking-up obtains final polycrystal bismuth telluride-based bulk alloy.
Archimedes's method test sample density is 99.3% of solid density, and XRD and ESEM do not find that all there is obvious texture in sample interior.It is 0.79Wm that Performance Detection obtains this polycrystalline bulk alloy thermal conductivity κ when 300K
-1K
-1, the ZT value is 1.46.Contrast reference example 1, the ZT value has improved 40%.
Embodiment 6:
2 hot pressing of reference example is obtained bulk alloy put into the graphite jig that internal diameter is 12.6mm, forge hot distortion under vacuum: 500 ℃ of pressurizes 30 minutes, pressure 50MPa.Taking-up obtains final polycrystal bismuth telluride-based bulk alloy.
Archimedes's method test sample density is 99% of solid density, and XRD and ESEM do not find that all there is obvious texture in sample interior.It is 0.95Wm that Performance Detection obtains this polycrystalline bulk alloy thermal conductivity κ when 300K
-1K
-1, the ZT value is 1.11.Contrast reference example 2, the ZT value has improved 25%.
Claims (5)
1. hot forging processing method of optimizing performance of polycrystal bismuth telluride-based thermoelectric alloy material, it is characterized in that: will be once hot-forming polycrystal bismuth telluride-based block electrothermal alloy, put into directly that graphite jig carries out the forge hot distortion again, pressurize obtains final thermoelectric alloy material.
2. a kind of hot forging processing method of optimizing performance of polycrystal bismuth telluride-based thermoelectric alloy material according to claim 1 is characterized in that: described forge hot uses the internal diameter of graphite jig greater than hot-forming bulk alloy size.
3. a kind of hot forging processing method of optimizing performance of polycrystal bismuth telluride-based thermoelectric alloy material according to claim 1 is characterized in that: described hot forging temperature is 400 ℃～500 ℃.
4. a kind of hot forging processing method of optimizing performance of polycrystal bismuth telluride-based thermoelectric alloy material according to claim 1 is characterized in that: described forge hot pressure is 50MPa～100MPa.
5. a kind of hot forging processing method of optimizing performance of polycrystal bismuth telluride-based thermoelectric alloy material according to claim 1 is characterized in that: the described dwell time is 20～60 minutes.
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| CN104409623A (en) * | 2014-10-21 | 2015-03-11 | 浙江大学 | Processing method for improving performance of N-type bismuth telluride base powder sinter block thermoelectric material |
| CN104818523A (en) * | 2015-05-01 | 2015-08-05 | 河南鸿昌电子有限公司 | Crystal pulling method for crystal bar |
| CN104831344A (en) * | 2015-04-29 | 2015-08-12 | 河南鸿昌电子有限公司 | Crystal pulling method of semiconductor crystal bar |
| CN115141019A (en) * | 2022-07-15 | 2022-10-04 | 湖北赛格瑞新能源科技有限公司 | Method for preparing p-type bismuth telluride-based thermoelectric material by utilizing accumulated hot heading |
| CN115159986A (en) * | 2022-07-15 | 2022-10-11 | 湖北赛格瑞新能源科技有限公司 | Method for preparing p-type bismuth telluride-based thermoelectric material by free forging process |
| CN115159986B (en) * | 2022-07-15 | 2024-06-04 | 湖北赛格瑞新能源科技有限公司 | Method for preparing p-type bismuth telluride-based thermoelectric material by free forging process |
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| KR20020010768A (en) * | 2000-07-31 | 2002-02-06 | 병 선 천 | Method of producing thermoelectric transform materials by using the twin rolling and the hot forming process |
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| CN100491554C (en) * | 2007-09-28 | 2009-05-27 | 清华大学 | Method for preparing fine grain preferred tropism Bi2Te3 thermoelectric materials |
| CN101220513B (en) * | 2007-09-28 | 2010-12-08 | 北京科技大学 | Thermal treatment method for improving type N polycrystal Bi2Te3thermoelectricity capability |
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| CN104409623A (en) * | 2014-10-21 | 2015-03-11 | 浙江大学 | Processing method for improving performance of N-type bismuth telluride base powder sinter block thermoelectric material |
| CN104409623B (en) * | 2014-10-21 | 2017-02-15 | 浙江大学 | Processing method for improving performance of N-type bismuth telluride base powder sinter block thermoelectric material |
| CN104831344A (en) * | 2015-04-29 | 2015-08-12 | 河南鸿昌电子有限公司 | Crystal pulling method of semiconductor crystal bar |
| CN104818523A (en) * | 2015-05-01 | 2015-08-05 | 河南鸿昌电子有限公司 | Crystal pulling method for crystal bar |
| CN115141019A (en) * | 2022-07-15 | 2022-10-04 | 湖北赛格瑞新能源科技有限公司 | Method for preparing p-type bismuth telluride-based thermoelectric material by utilizing accumulated hot heading |
| CN115159986A (en) * | 2022-07-15 | 2022-10-11 | 湖北赛格瑞新能源科技有限公司 | Method for preparing p-type bismuth telluride-based thermoelectric material by free forging process |
| CN115141019B (en) * | 2022-07-15 | 2023-09-08 | 湖北赛格瑞新能源科技有限公司 | Method for preparing p-type bismuth telluride-based thermoelectric material by utilizing accumulated hot heading |
| CN115159986B (en) * | 2022-07-15 | 2024-06-04 | 湖北赛格瑞新能源科技有限公司 | Method for preparing p-type bismuth telluride-based thermoelectric material by free forging process |
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Effective date of registration: 20171211 Address after: 310016 room B, room 1808, Sam Wo business square, No. 238, Jianggan District nautical Road, Hangzhou, Zhejiang Patentee after: Zhejiang electrical union Mining Technology Development Co., Ltd. Address before: 310027 Hangzhou, Zhejiang Province, Xihu District, Zhejiang Road, No. 38, No. Patentee before: Zhejiang University |