CN102897768A - Preparation method for Mg2Si thermoelectricity material - Google Patents

Preparation method for Mg2Si thermoelectricity material Download PDF

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CN102897768A
CN102897768A CN2012103258938A CN201210325893A CN102897768A CN 102897768 A CN102897768 A CN 102897768A CN 2012103258938 A CN2012103258938 A CN 2012103258938A CN 201210325893 A CN201210325893 A CN 201210325893A CN 102897768 A CN102897768 A CN 102897768A
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powder
thermoelectric material
mg2si
mixed powder
atmosphere
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周园
曹萌萌
任秀峰
李翔
年洪恩
张斌斌
孙庆国
曾金波
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Qinghai Institute of Salt Lakes Research of CAS
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Abstract

The present invention relates to a preparation method for an Mg2Si thermoelectricity material. The method comprises the following steps: (1) uniformly mixing Mg powder and Si powder under an Ar protection atmosphere to obtain a mixture; (2) placing the mixture in a glove box filled with Ar, and placing the glove box in a stainless steel vacuum ball milling tank to carry out intermittent ball milling to obtain uniformly-mixed powder; (3) carrying out tableting on the mixed powder to obtain a Mg-Si mixed powder tablet; (4) loading the Mg-Si mixed powder tablet into a graphite mold, and placing graphite mold in a tube furnace under an Ar atmosphere to carry out primary sintering and thermal insulation to obtain Mg2Si thermoelectricity material alloy powder; (5) carrying out tableting on the Mg2Si thermoelectricity material powder to obtain a Mg2Si alloy tablet; and (6) loading the Mg2Si alloy tablet into the graphite mold and placing the graphite mold in the tube furnace under an Ar atmosphere to carry out secondary sintering and thermal insulation to obtain the Mg2Si block thermoelectricity material. The preparation method has characteristics of simple process, easy operation and low cost. The obtained Mg2Si thermoelectricity material has characteristics of high product purity, small particle size and uniform distribution.

Description

A kind of Mg 2The preparation method of Si thermoelectric material
Technical field
The present invention relates to a kind of preparation method of thermoelectric material, relate in particular to a kind of Mg 2The preparation method of Si thermoelectric material.
Background technology
Thermoelectric material is a kind of motion realization heat energy of solid interior current carrier and functional materials that electric energy is changed mutually of utilizing.Along with the quickening of global process of industrialization, lack of energy and environmental pollution have become the problem that countries in the world can not be ignored, and since the last century the nineties, thermoelectric material becomes a study hotspot of Materials science with its unique performance.Its conversion efficiency of thermoelectric thermoelectric figure of merit Z commonly used or zero dimension figure of merit ZT characterize Z=S 2/ ρ κ, wherein S is Seebeck coefficient, and ρ is resistivity, and κ is thermal conductivity.According to existing research, the Mg centered by Mg 2X(X=Si, Ge, Sn) compound is a kind of promising thermoelectric semiconductor material between series metal.Especially with Mg 2Si is the sosoloid of base, is the middle warm area thermoelectric material that is applicable to 450K ~ 800K, has larger virtual mass and less lattice thermal conductivity, according to thermoelectric semiconducter performance index β=m * 3/2μ/k Ph(wherein: m *, μ, k PhRespectively current carrier virtual mass, carrier mobility, lattice thermal conductivity), its β value is 14 far above Mg 2Ge, Mg 2Sn and FeSi 2And Mn 2The value of the thermoelectric system of Si extremely receives publicity in recent years.Mg 2The Si base thermoelectricity material is simple in structure except having taken into account other thermoelectric material, volume is little, outside the high reliability, also has himself distinctive characteristic, raw material resources such as Mg, Si are very abundant, less expensive, nontoxic pollution-free, anti-oxidant, the advantage such as corrosion-resistant is a kind of very potential thermoelectric material, can be widely used in every field.
At present, because the volatile oxidation of Mg and Mg 2The Si compound has serious cleavage brittleness tendency, makes Mg 2Preparation and the application of Si are greatly limited, the preparation method of its block materials mainly is scorification and mechanical alloying method, but scorification can't solve the carburizing reagent in and Mg vaporization at high temperature, Si and molten bath that density difference bring poor by fusing point larger between Mg, the Si and the two is difficult for hybrid reaction, and mechanical alloying method also can be sneaked into a small amount of impurity and partial oxidation.For addressing these problems, some new synthetic methods have appearred recently, synthetic etc. such as discharge plasma sintering, microwave Low Temperature Solid-Phase, these new synthetic methods are slowly paid attention to by people because of its product density advantages of higher, but because its preparation cost is higher, disconnect with practical application, as for reaching the high-compactness requirement, need cost of equipment expensive, cause preparation cost higher, also be not suitable for practical application.
Summary of the invention
Technical problem to be solved by this invention provides that a kind of operating procedure is simple, equipment cost is cheap, the manageable Mg of product component 2The preparation method of Si thermoelectric material.
For addressing the above problem a kind of Mg of the present invention 2The preparation method of Si thermoelectric material may further comprise the steps:
⑴ mix Mg powder and the Si powder mol ratio by 2.01 ~ 2.13:1 under the Ar protective atmosphere, obtain mixture;
⑵ put into described mixture the glove box that is filled with a normal atmosphere Ar, and this glove box packed in the stainless-steel vacuum ball grinder, rotating speed with 200 ~ 300rpm carries out intermittent type ball milling 5 ~ 20h, with activating powder surface and obtain uniform mixed powder, ball material mass ratio (㎏/㎏ wherein) be 10 ~ 20:1;
⑶ carry out compressing tablet with described mixed powder pressurize 3 ~ 10min under the pressure of 10 ~ 20MPa, obtains Mg-Si mixed powder compressing tablet;
⑷ pack described Mg-Si mixed powder compressing tablet in the graphite jig that specification is complementary with it, and place the tube furnace under the Ar atmosphere to carry out once sintered, insulation this graphite jig, namely gets Mg 2The alloy powder of Si thermoelectric material;
⑸ with described Mg 2The powder of Si thermoelectric material pressurize 10 ~ 20 min under the pressure of 20 ~ 30MPa carry out compressing tablet, obtain Mg 2The Si alloy slice;
⑹ with described Mg 2The Si alloy slice is packed in the graphite jig that specification is complementary with it, and places the tube furnace under the Ar atmosphere to carry out double sintering, insulation this graphite jig, namely gets Mg 2The Si block thermoelectric material.
Among the described step ⑵ in the stainless-steel vacuum ball grinder steel ball particle diameter be 0.5 ~ 1.5cm.
Condition once sintered among the described step ⑷, insulation refers to rise to 500 ~ 600 ℃ with the temperature rise rate of 5 ~ 10 ℃/min, and soaking time is 7 ~ 9h.
Described step
Figure 2012103258938100002DEST_PATH_IMAGE001
The condition of middle double sintering, insulation refers to rise to 800 ~ 850 ℃ with the heat-up rate of 5 ~ 10 ℃/min, and soaking time is 0.5 ~ 2h.
The present invention compared with prior art has the following advantages:
1, the present invention combines mechanical alloying and Ar protection pressureless sintering, and technique is simple, processing ease, and preparation cost is cheap.
2, matching used graphite jig in the sintering process of the present invention can effectively control oxidation and the volatilization of Mg in the general sintering process, so product composition is purer, and final phase structure is Mg 2Si.
3, the Mg that adopts the inventive method to obtain 2The Si base thermoelectricity material, particle size is little and be evenly distributed.Through the XRD diffraction analysis (X ' Pert PRO type X-ray diffractometer, Cu target, 2 θ are 5 °~ 80 °, electric current 30mA, voltage 40kV) and product composition is purer.
4, the powder of mechanical alloying of the present invention is carried out the XRD diffraction analysis and show, this phase is single-phase Mg and single-phase Si; The powdered sample that powder after the mechanical alloying prepares after Ar protects sintered heat insulating next time carries out the XRD diffraction analysis and shows the single-phase Mg that all is converted in the sintered heat insulating process 2Si and have a small amount of Mg to exist; Bulk sample behind the double sintering shows through the XRD diffraction analysis, and alloy phase all is Mg 2Si(is referring to Fig. 1, Fig. 2).Draw the final product internal particle by the analysis to the SEM photo and distribute comparatively evenly, density is (referring to Fig. 3) better, from EDS can spectrogram draw final Mg, Si compare be about 2:1(referring to Fig. 4).
 
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
Fig. 1 is the present invention Embodiment 1Corresponding XRD spectra.
Fig. 2 is the present invention Embodiment 2Corresponding XRD spectra.
Fig. 3 is the present invention Embodiment 3The SEM photo of corresponding block thermoelectric material.
Fig. 4 is the present invention Embodiment 3The energy spectrogram of corresponding block thermoelectric material.
Embodiment
Embodiment 1A kind of Mg 2The preparation method of Si thermoelectric material may further comprise the steps:
⑴ mix Mg powder and the Si powder mol ratio by 2.01:1 under the Ar protective atmosphere, obtain mixture.
⑵ put into mixture the glove box that is filled with a normal atmosphere Ar, and this glove box packed in the stainless-steel vacuum ball grinder, rotating speed with 220rpm carries out the every mill of intermittent type ball milling 10h(20min rest 10min, to prevent remnant oxygen generation oxidizing reaction in overheating powder and the tank), with activating powder surface and obtain uniform mixed powder, ball material mass ratio (㎏/㎏ wherein) be 15:1.
⑶ carry out compressing tablet with mixed powder pressurize 5min under the pressure of 15MPa, obtains Mg-Si mixed powder compressing tablet.
⑷ pack Mg-Si mixed powder compressing tablet in the graphite jig that specification is complementary with it, and this graphite jig is placed tube furnace under the Ar atmosphere, rises to 550 ℃ with the temperature rise rate of 5 ℃/min, carries out once sinteredly, then is incubated 8h, namely gets Mg 2The alloy powder of Si thermoelectric material.
⑸ with Mg 2The powder of Si thermoelectric material pressurize 10 min under the pressure of 20MPa carry out compressing tablet, obtain Mg 2The Si alloy slice.
⑹ with Mg 2The Si alloy slice is packed in the graphite jig that specification is complementary with it, and this graphite jig is placed tube furnace under the Ar atmosphere, rises to 800 ℃ with the heat-up rate of 5 ℃/min, carries out double sintering, then is incubated 1h, namely gets Mg 2The Si block thermoelectric material.
Embodiment 2A kind of Mg 2The preparation method of Si thermoelectric material may further comprise the steps:
⑴ mix Mg powder and the Si powder mol ratio by 2.13:1 under the Ar protective atmosphere, obtain mixture.
⑵ put into mixture the glove box that is filled with a normal atmosphere Ar, and this glove box packed in the stainless-steel vacuum ball grinder, rotating speed with 220rpm carries out the every mill of intermittent type ball milling 10h(20min rest 10min, to prevent remnant oxygen generation oxidizing reaction in overheating powder and the tank), with activating powder surface and obtain uniform mixed powder, ball material mass ratio (㎏/㎏ wherein) be 15:1.
⑶ carry out compressing tablet with mixed powder pressurize 5min under the pressure of 15MPa, obtains Mg-Si mixed powder compressing tablet.
⑷ pack Mg-Si mixed powder compressing tablet in the graphite jig that specification is complementary with it, and this graphite jig is placed tube furnace under the Ar atmosphere, rises to 550 ℃ with the temperature rise rate of 5 ℃/min, carries out once sinteredly, then is incubated 8h, namely gets Mg 2The alloy powder of Si thermoelectric material.
⑸ with Mg 2The powder of Si thermoelectric material pressurize 10min under the pressure of 20MPa carries out compressing tablet, obtains Mg 2The Si alloy slice.
⑹ with Mg 2The Si alloy slice is packed in the graphite jig that specification is complementary with it, and this graphite jig is placed tube furnace under the Ar atmosphere, rises to 800 ℃ with the heat-up rate of 5 ℃/min, carries out double sintering, then is incubated 1h, namely gets Mg 2The Si block thermoelectric material.
Embodiment 3A kind of Mg 2The preparation method of Si thermoelectric material may further comprise the steps:
⑴ mix Mg powder and the Si powder mol ratio by 2.03:1 under the Ar protective atmosphere, obtain mixture.
⑵ put into mixture the glove box that is filled with a normal atmosphere Ar, and this glove box packed in the stainless-steel vacuum ball grinder, rotating speed with 220rpm carries out the every mill of intermittent type ball milling 10h(20min rest 10min, to prevent remnant oxygen generation oxidizing reaction in overheating powder and the tank), with activating powder surface and obtain uniform mixed powder, ball material mass ratio (㎏/㎏ wherein) be 15:1.
⑶ carry out compressing tablet with mixed powder pressurize 5min under the pressure of 15MPa, obtains Mg-Si mixed powder compressing tablet.
⑷ pack Mg-Si mixed powder compressing tablet in the graphite jig that specification is complementary with it, and this graphite jig is placed tube furnace under the Ar atmosphere, rises to 550 ℃ with the temperature rise rate of 5 ℃/min, carries out once sinteredly, then is incubated 8h, namely gets Mg 2The alloy powder of Si thermoelectric material.
⑸ with Mg 2The powder of Si thermoelectric material pressurize 10min under the pressure of 20MPa carries out compressing tablet, obtains Mg 2The Si alloy slice.
⑹ with Mg 2The Si alloy slice is packed in the graphite jig that specification is complementary with it, and this graphite jig is placed tube furnace under the Ar atmosphere, rises to 800 ℃ with the heat-up rate of 5 ℃/min, carries out double sintering, then is incubated 0.5h, namely gets Mg 2The Si block thermoelectric material.
Embodiment 4A kind of Mg 2The preparation method of Si thermoelectric material may further comprise the steps:
⑴ mix Mg powder and the Si powder mol ratio by 2.05:1 under the Ar protective atmosphere, obtain mixture.
⑵ put into mixture the glove box that is filled with a normal atmosphere Ar, and this glove box packed in the stainless-steel vacuum ball grinder, rotating speed with 200rpm carries out the every mill of intermittent type ball milling 20h(20min rest 10min, to prevent remnant oxygen generation oxidizing reaction in overheating powder and the tank), with activating powder surface and obtain uniform mixed powder, ball material mass ratio (㎏/㎏ wherein) be 10:1.
⑶ carry out compressing tablet with mixed powder pressurize 10min under the pressure of 10MPa, obtains Mg-Si mixed powder compressing tablet.
⑷ pack Mg-Si mixed powder compressing tablet in the graphite jig that specification is complementary with it, and this graphite jig is placed tube furnace under the Ar atmosphere, rises to 500 ℃ with the temperature rise rate of 10 ℃/min, carries out once sinteredly, then is incubated 7h, namely gets Mg 2The alloy powder of Si thermoelectric material.
⑸ with Mg 2The powder of Si thermoelectric material pressurize 20min under the pressure of 30MPa carries out compressing tablet, obtains Mg 2The Si alloy slice.
⑹ with Mg 2The Si alloy slice is packed in the graphite jig that specification is complementary with it, and this graphite jig is placed tube furnace under the Ar atmosphere, rises to 850 ℃ with the heat-up rate of 10 ℃/min, carries out double sintering, then is incubated 2h, namely gets Mg 2The Si block thermoelectric material.
Embodiment 5A kind of Mg 2The preparation method of Si thermoelectric material may further comprise the steps:
⑴ mix Mg powder and the Si powder mol ratio by 2.10:1 under the Ar protective atmosphere, obtain mixture.
⑵ put into mixture the glove box that is filled with a normal atmosphere Ar, and this glove box packed in the stainless-steel vacuum ball grinder, rotating speed with 300rpm carries out the every mill of intermittent type ball milling 5h(20min rest 10min, to prevent remnant oxygen generation oxidizing reaction in overheating powder and the tank), with activating powder surface and obtain uniform mixed powder, ball material mass ratio (㎏/㎏ wherein) be 20:1.
⑶ carry out compressing tablet with mixed powder pressurize 3min under the pressure of 20MPa, obtains Mg-Si mixed powder compressing tablet.
⑷ pack Mg-Si mixed powder compressing tablet in the graphite jig that specification is complementary with it, and this graphite jig is placed tube furnace under the Ar atmosphere, rises to 600 ℃ with the temperature rise rate of 8 ℃/min, carries out once sinteredly, then is incubated 9h, namely gets Mg 2The alloy powder of Si thermoelectric material.
⑸ with Mg 2The powder of Si thermoelectric material pressurize 15min under the pressure of 25MPa carries out compressing tablet, obtains Mg 2The Si alloy slice.
⑹ with Mg 2The Si alloy slice is packed in the graphite jig that specification is complementary with it, and this graphite jig is placed tube furnace under the Ar atmosphere, rises to 830 ℃ with the heat-up rate of 8 ℃/min, carries out double sintering, then is incubated 1.5h, namely gets Mg 2The Si block thermoelectric material.
Above-mentioned Embodiment 1 ~ 5The steel ball particle diameter is 0.5 ~ 1.5cm in the stainless-steel vacuum ball grinder.
Should be appreciated that, embodiment discussed here and embodiment can propose various modifications and variations just in order to illustrate to the people who is familiar with this field, and these improvement and variation will be included in the application's spirit and scope and the appended claim scope.

Claims (4)

1. Mg 2The preparation method of Si thermoelectric material may further comprise the steps:
⑴ mix Mg powder and the Si powder mol ratio by 2.01 ~ 2.13:1 under the Ar protective atmosphere, obtain mixture;
⑵ put into described mixture the glove box that is filled with a normal atmosphere Ar, and this glove box packed in the stainless-steel vacuum ball grinder, rotating speed with 200 ~ 300rpm carries out intermittent type ball milling 5 ~ 20h, and with activating powder surface and obtain uniform mixed powder, wherein ball material mass ratio is 10 ~ 20:1;
⑶ carry out compressing tablet with described mixed powder pressurize 3 ~ 10min under the pressure of 10 ~ 20MPa, obtains Mg-Si mixed powder compressing tablet;
⑷ pack described Mg-Si mixed powder compressing tablet in the graphite jig that specification is complementary with it, and place the tube furnace under the Ar atmosphere to carry out once sintered, insulation this graphite jig, namely gets Mg 2The alloy powder of Si thermoelectric material;
⑸ with described Mg 2The powder of Si thermoelectric material pressurize 10 ~ 20 min under the pressure of 20 ~ 30MPa carry out compressing tablet, obtain Mg 2The Si alloy slice;
⑹ with described Mg 2The Si alloy slice is packed in the graphite jig that specification is complementary with it, and places the tube furnace under the Ar atmosphere to carry out double sintering, insulation this graphite jig, namely gets Mg 2The Si block thermoelectric material.
2. a kind of Mg as claimed in claim 1 2The preparation method of Si thermoelectric material is characterized in that: among the described step ⑵ in the stainless-steel vacuum ball grinder steel ball particle diameter be 0.5 ~ 1.5cm.
3. a kind of Mg as claimed in claim 1 2The preparation method of Si thermoelectric material is characterized in that: condition once sintered among the described step ⑷, insulation refers to rise to 500 ~ 600 ℃ with the temperature rise rate of 5 ~ 10 ℃/min, and soaking time is 7 ~ 9h.
4. a kind of Mg as claimed in claim 1 2The preparation method of Si thermoelectric material is characterized in that: described step
Figure 2012103258938100001DEST_PATH_IMAGE001
The condition of middle double sintering, insulation refers to rise to 800 ~ 850 ℃ with the heat-up rate of 5 ~ 10 ℃/min, and soaking time is 0.5 ~ 2h.
CN2012103258938A 2012-09-06 2012-09-06 Preparation method for Mg2Si thermoelectricity material Pending CN102897768A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553053A (en) * 2013-11-01 2014-02-05 内蒙古科技大学 Method of preparing rare earth-doped Mg2Si powder by microwave thermal treatment
CN104986768A (en) * 2015-05-18 2015-10-21 中国科学技术大学 Method for synthesizing silicon nanopowder through nitridation, and application thereof
CN105859299A (en) * 2016-06-22 2016-08-17 福州大学 Na-doped cubic phase Ca2Si thermoelectric material and preparation method thereof
CN106116587A (en) * 2016-06-22 2016-11-16 福州大学 A kind of Emission in Cubic Ca2si thermoelectric material and preparation method thereof
CN106159077A (en) * 2015-03-30 2016-11-23 武汉理工大学 A kind of bismuth telluride-based thermoelectric generating element and preparation method thereof
CN106744980A (en) * 2016-11-01 2017-05-31 福州大学 A kind of Ca3Si alloy materials and its high temperature and high pressure preparation process
CN107739034A (en) * 2017-10-11 2018-02-27 西华大学 A kind of method for preparing the tiny magnesium silicide base block thermoelectric material of particle
CN108695429A (en) * 2017-03-31 2018-10-23 丰田自动车株式会社 Thermo-electric converting material and its manufacturing method

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CN101197419A (en) * 2007-12-13 2008-06-11 浙江大学 Rare earth doping Mg2Si0.6Sn0.4 based thermoelectric material
CN101197420A (en) * 2007-12-13 2008-06-11 浙江大学 Rare earth doping Mg2Si based thermoelectric material
CN101264890A (en) * 2008-03-27 2008-09-17 上海交通大学 Method for preparing Mg2Si powder by semi-solid-state reaction

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101197419A (en) * 2007-12-13 2008-06-11 浙江大学 Rare earth doping Mg2Si0.6Sn0.4 based thermoelectric material
CN101197420A (en) * 2007-12-13 2008-06-11 浙江大学 Rare earth doping Mg2Si based thermoelectric material
CN101264890A (en) * 2008-03-27 2008-09-17 上海交通大学 Method for preparing Mg2Si powder by semi-solid-state reaction

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553053A (en) * 2013-11-01 2014-02-05 内蒙古科技大学 Method of preparing rare earth-doped Mg2Si powder by microwave thermal treatment
CN103553053B (en) * 2013-11-01 2015-07-01 内蒙古科技大学 Method of preparing rare earth-doped Mg2Si powder by microwave thermal treatment
CN106159077A (en) * 2015-03-30 2016-11-23 武汉理工大学 A kind of bismuth telluride-based thermoelectric generating element and preparation method thereof
CN104986768A (en) * 2015-05-18 2015-10-21 中国科学技术大学 Method for synthesizing silicon nanopowder through nitridation, and application thereof
CN105859299A (en) * 2016-06-22 2016-08-17 福州大学 Na-doped cubic phase Ca2Si thermoelectric material and preparation method thereof
CN106116587A (en) * 2016-06-22 2016-11-16 福州大学 A kind of Emission in Cubic Ca2si thermoelectric material and preparation method thereof
CN106744980A (en) * 2016-11-01 2017-05-31 福州大学 A kind of Ca3Si alloy materials and its high temperature and high pressure preparation process
CN106744980B (en) * 2016-11-01 2018-12-25 福州大学 A kind of Ca3Si alloy material and its high temperature and high pressure preparation process
CN108695429A (en) * 2017-03-31 2018-10-23 丰田自动车株式会社 Thermo-electric converting material and its manufacturing method
CN108695429B (en) * 2017-03-31 2022-06-03 丰田自动车株式会社 Thermoelectric conversion material and method for producing same
CN107739034A (en) * 2017-10-11 2018-02-27 西华大学 A kind of method for preparing the tiny magnesium silicide base block thermoelectric material of particle
CN107739034B (en) * 2017-10-11 2020-10-30 西华大学 Method for preparing magnesium silicide based bulk thermoelectric material with fine particles

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Application publication date: 20130130