CN106098922B - A kind of Cu doping Emission in Cubic Ca2Si thermoelectric materials - Google Patents

A kind of Cu doping Emission in Cubic Ca2Si thermoelectric materials Download PDF

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Publication number
CN106098922B
CN106098922B CN201610452327.1A CN201610452327A CN106098922B CN 106098922 B CN106098922 B CN 106098922B CN 201610452327 A CN201610452327 A CN 201610452327A CN 106098922 B CN106098922 B CN 106098922B
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powder
cubic
thermoelectric materials
doping
ball
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CN106098922A (en
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温翠莲
熊锐
萨百晟
裘依梅
林逵
洪云
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Fuzhou University
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Fuzhou University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/06—Metal silicides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment

Abstract

The invention discloses a kind of Cu doping Emission in Cubic Ca2Si thermoelectric materials; its be by Ca powder, Si powder and Cu powder under Ar gas shielded atmosphere after mixing; gained mix powder is put into Stainless Steel Vacuum ball grinder with grinding steel ball in Ar gas shielded atmosphere and is sealed; vacuum-sintering tabletting is carried out by the way of plasma agglomeration after ball-milling reaction, up to sheet Cu doping Emission in Cubic Ca2Si thermoelectric materials.Since Cu elements have the property similar with alkaline-earth metal, after Cu elements add, easily substitution Ca, as donor doping, there is provided conduction electrons is as carrier, so as to improve the electrical conductivity and thermoelectricity capability of material.The present invention has the advantages such as technique is simple, operation is easy, cost is low, gained Cu doping Emission in Cubic Ca2Si thermoelectric material purity is higher, is tightly combined, and has preferable industrialization prospect.

Description

A kind of Cu doping Emission in Cubic Ca2Si thermoelectric materials
Technical field
The invention belongs to thermoelectricity technical field of function materials, and in particular to a kind of Cu doping Emission in Cubic Ca2Si thermoelectric materials.
Background technology
It is special with increasingly serious, clean there is an urgent need to actively push forward and the advocate use regenerative resource of energy crisis It is not to pay attention to regenerative resource new technology development to be combined with industrialization investment, to reduce the utilization cost of regenerative resource.Temperature Poor electrical part can realize the mutual conversion between thermal energy and electric energy, be the very wide environmental type energy device of the scope of application.With half The semiconductor generator and refrigerator of conductor temperature-difference power generation module manufacture, can be into as long as can generate electricity with the presence of the temperature difference, during power supply Row refrigeration, when its work, is noiseless, pollution-free, and service life can be widely applied to waste-heat power generation, refrigeration for refrigerator more than 10 years Etc. in important base application, thus it is a kind of widely used green energy resource device.Currently, due to by pyroelectric material performance Limitation, the application of thermo-electric device are also far from reaching the stage for substituting mechanical refrigerator, this has become thermo-electric device and on a large scale should Bottleneck, therefore high performance thermoelectric material is one of hot subject of current international material research field.The property of thermoelectric material Can mainly it be characterized by dimensionless figure factor Z T values：ZT=Tσα2/ κ, wherein T are absolute temperature, and σ is the electrical conductivity of material, and α is Seebeck coefficients, κ are thermal conductivity.
At present first its excellent performance of procatarxis such as Ga, As, In, Pb, Te and be widely used in manufacturing semi-conducting material and partly lead Body device, but these elements are largely poisonous, and resource faces exhaustion.Reserves are big on earth for the elements such as Fe, Si, Ca, It is harmless to organism.Alkaline earth metal silicide Ca2Si materials, its direct band gap are about 0.31eV, are extremely long by resource longevity Ca, Si element form, and can recycle, pollution-free to the earth, and due to calcium silicon compound Ca2Si has with existing silicon-based technologies Excellent compatibility, it is considered to be very promising novel environmental close friend semi-conducting material, in solar cell and thermoelectricity The fields such as conversion have potential application prospect.
From the point of view of current research conditions both domestic and external, related Emission in Cubic Ca2The research of Si, which is all that theoretical calculation is relevant, grinds Study carefully, to Ca2The rare report of theoretical research of Si doping.Can effectively it be changed in the unit cell volume and structure cell of optical material by doping The crystallography position of each atom, modulates the electronic structure of material, so as to change the electrical property of material.Present invention incorporates low temperature Mechanical alloying method and electrion plasma vacuum sintering process, enable material reacted at a lower temperature and More sinter the Cu doping Emission in Cubic Ca of densification under the vacuum environment of high pressure low temperature into2Si, is expected to the thermoelectricity material as middle warm area One of material, is widely used in every field.At present, on Cu doping Emission in Cubic Ca2The still nearly no report of Si thermoelectric materials.
The content of the invention
It is an object of the invention to provide a kind of operating procedure is simple, the manageable Cu doping Emission in Cubic of product component Ca2Si thermoelectric materials, it is by adulterating Cu, to improve Ca2The carrier concentration of Si materials, thus improve material electrical conductivity and Thermoelectricity capability.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of Cu doping Emission in Cubic Ca2Si thermoelectric materials, its preparation method comprise the following steps：
1）Ca powder, Si powder and Cu powder are uniformly mixed under Ar gas shielded atmosphere, obtain mix powder；
2）Under Ar gas shielded atmosphere, by step 1）Gained mix powder is put into Stainless Steel Vacuum ball milling with grinding steel ball In tank, sealing；
3）By step 2）Ready Stainless Steel Vacuum ball grinder is put into ball mill, with the rotating speed ball of 500 ~ 2000 rpm 5 ~ 100 h are ground, mix powder is fully reacted；
4）By step 3）Completely reacted powder takes out, in the stainless steel mould of specification needed for loading, using plasma agglomeration Mode, be warming up to 100 ~ 500 DEG C under the pressure of 50 ~ 600 MPa, keep 10 ~ 120 min to carry out vacuum-sintering tabletting, i.e., Obtain sheet Cu doping Emission in Cubic Ca2Si thermoelectric materials.
Step 1）Middle Ca powder, Si powder and Cu powder are 81 by the molar ratio of Ca, Si, Cu:20:0.5 ~ 10 is mixed.
Step 2）The weight ratio of middle grinding steel ball and mix powder is 2 ~ 16:1；The particle diameter of the grinding steel ball for 0.2 ~ 1.5 cm, carry out ultrasonic cleaning, ultrasonic cleaning total time is 10 ~ 30 min using acetone, alcohol successively using preceding.
Step 4）The speed of middle heating is 5 ~ 20 DEG C/min.
The present invention has the following advantages compared with prior art:
（1）Handled in sintering process of the present invention using stainless steel mould is supporting, so as at a lower temperature Higher sintering pressure is born, the oxidation and volatilization of the Ca often occurred in sintering process is efficiently controlled, makes products obtained therefrom component Purer, density is higher.
（2）Gained Cu doping Ca of the invention2The thermoelectricity capability of Si matrix bodies is better than existing Ca2Si materials, its mechanism are Cu Element has the property similar with alkaline-earth metal, after Cu elements add, easily substitution Ca, as donor doping, there is provided lead Electronics is as carrier, so as to improve the electrical conductivity and thermoelectricity capability of material.
（3）The present invention is combined using Cryomilling and plasma discharging vaccum sintering process prepares Cu doping cube Phase Ca2Si thermoelectric materials, its technique is simple, and operation is easy, and reaction temperature is relatively low, is less prone to the oxidation reaction of Ca atoms And Ca2The decomposition of Si phases.Meanwhile it is when can be by controlling the atomic ratio of Ca, Si and Cu, sintering temperature, heating rate and heating Between etc., realize that component is controllable, to meet to mass produce needs, and reduce cost.
Brief description of the drawings
Fig. 1 is undoped with Cu（a）With doping Cu（b）Ca2The scanning electron microscope (SEM) photograph of Si thermoelectric materials.
Fig. 2 is undoped with Cu（a）With doping Cu（b）Ca2The transmission electron microscope picture of Si thermoelectric materials.
Embodiment
In order to make content of the present invention easily facilitate understanding, with reference to embodiment to of the present invention Technical solution is described further, but the present invention is not limited only to this.
The particle diameter of grinding steel ball used is 0.2 ~ 1.5 cm, and ultrasonic cleaning is carried out using acetone, alcohol successively using preceding, Ultrasonic cleaning total time is 10 ~ 30 min.
Embodiment 1
A kind of Cu doping Emission in Cubic Ca2The preparation method of Si thermoelectric materials comprises the following steps：
1）It is 81 by the molar ratio that Ca powder, Si powder and Cu powder press Ca, Si, Cu:20:0.5 mixes under Ar gas shielded atmosphere Uniformly, mix powder is obtained；
2）By step 1）Gained mix powder, grinding steel ball, Stainless Steel Vacuum ball grinder and electronic balance are put into and fill In the glove box for having an atmospheric pressure Ar gas；By weight 3 in glove box:1 accurate weigh grinds steel ball and mix powder, And put it into Stainless Steel Vacuum ball grinder, then by Stainless Steel Vacuum ball grinder good seal, enter to avoid oxygen；Then Stainless Steel Vacuum ball grinder is taken out from glove box；
3）By step 2）Ready Stainless Steel Vacuum ball grinder is put into ball mill, with the rotating speed ball milling 5 of 2000 rpm H, makes mix powder fully react；
4）By step 3）Completely reacted powder takes out, in the stainless steel mould of specification needed for loading, using plasma agglomeration Mode, the heating rate of 5 DEG C/min is pressed under the pressure of 300 MPa, temperature is risen to 300 DEG C, keeps 120 min to carry out Vacuum-sintering tabletting, up to sheet Cu doping Emission in Cubic Ca2Si thermoelectric materials.
Embodiment 2
A kind of Cu doping Emission in Cubic Ca2The preparation method of Si thermoelectric materials comprises the following steps：
1）It is 81 by the molar ratio that Ca powder, Si powder and Cu powder press Ca, Si, Cu:20:6 mix under Ar gas shielded atmosphere It is even, obtain mix powder；
2）By step 1）Gained mix powder, grinding steel ball, Stainless Steel Vacuum ball grinder and electronic balance are put into and fill In the glove box for having an atmospheric pressure Ar gas；By weight 16 in glove box:1 accurate weigh grinds steel ball and mixture powder End, and put it into Stainless Steel Vacuum ball grinder, then by Stainless Steel Vacuum ball grinder good seal, enter to avoid oxygen； Stainless Steel Vacuum ball grinder is then taken out from glove box；
3）By step 2）Ready Stainless Steel Vacuum ball grinder is put into ball mill, with the rotating speed ball milling 100 of 500 rpm H, makes mix powder fully react；
4）By step 3）Completely reacted powder takes out, in the stainless steel mould of specification needed for loading, using plasma agglomeration Mode, the heating rate of 20 DEG C/min is pressed under the pressure of 50 MPa, temperature is risen to 500 DEG C, keeps 20 min to carry out Vacuum-sintering tabletting, up to sheet Cu doping Emission in Cubic Ca2Si thermoelectric materials.
Fig. 1 is undoped with Cu（a）The doping Cu prepared with embodiment 2（b）Ca2The scanning electron microscope (SEM) photograph of Si thermoelectric materials. Doped with the modification Ca of Cu elements it can be seen from the contrast of Fig. 1 patterns2It is finer and close after Si thermoelectric materials sintering, and surface is more To be smooth, be conducive to improve the electric conductivity of material.
Fig. 2 is undoped with Cu（a）The doping Cu prepared with embodiment 2（b）Ca2The transmission electron microscope picture of Si thermoelectric materials. Doped with the modification Ca of Cu elements it can be seen from the contrast of Fig. 2 transmission scans pattern2The nanoparticle edge of Si thermoelectric materials is more To be smooth, it is conducive to the consistency and carrier mobility speed that improve material sintering, so as to improve the electric conductivity of material.
Embodiment 3
A kind of Cu doping Emission in Cubic Ca2The preparation method of Si thermoelectric materials comprises the following steps：
1）It is 81 by the molar ratio that Ca powder, Si powder and Cu powder press Ca, Si, Cu:20:10 mix under Ar gas shielded atmosphere It is even, obtain mix powder；
2）By step 1）Gained mix powder, grinding steel ball, Stainless Steel Vacuum ball grinder and electronic balance are put into and fill In the glove box for having an atmospheric pressure Ar gas；By weight 8 in glove box:1 accurate weigh grinds steel ball and mix powder, And put it into Stainless Steel Vacuum ball grinder, then by Stainless Steel Vacuum ball grinder good seal, enter to avoid oxygen；Then Stainless Steel Vacuum ball grinder is taken out from glove box；
3）By step 2）Ready Stainless Steel Vacuum ball grinder is put into ball mill, with the rotating speed ball milling 50 of 1000 rpm H, makes mix powder fully react；
4）By step 3）Completely reacted powder takes out, in the stainless steel mould of specification needed for loading, using plasma agglomeration Mode, the heating rate of 10 DEG C/min is pressed under the pressure of 600 MPa, temperature is risen to 100 DEG C, keeps 60 min to carry out Vacuum-sintering tabletting, up to sheet Cu doping Emission in Cubic Ca2Si thermoelectric materials.
The EDAX results of the thermoelectric material obtained by embodiment 1-3 of table 1.
1 EDAX results of table
The Cu obtained by embodiment 1-3 of table 2 adulterates Emission in Cubic Ca2The electrical property measurement result of Si thermoelectric materials.
2 Cu of table doping Emission in Cubic Ca2The electrical property measurement result of Si thermoelectric materials
Material doped Cu is modified it can be seen from being contrasted in table 2, is still rendered as P-type semiconductor, while can carry The mobility in hole is improved on the basis of high carrier concentration, the electric conductivity for improving material, so as to improve thermoelectricity capability Play the role of important.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, should all belong to the covering scope of the present invention.

Claims (4)

  1. A kind of 1. Cu doping Emission in Cubic Ca2Si thermoelectric materials, it is characterised in that：Its preparation method comprises the following steps：
    1）Ca powder, Si powder and Cu powder are uniformly mixed under Ar gas shielded atmosphere, obtain mix powder；
    2）Under Ar gas shielded atmosphere, by step 1）Gained mix powder is put into Stainless Steel Vacuum ball grinder with grinding steel ball In, sealing；
    3）By step 2）Ready Stainless Steel Vacuum ball grinder is put into ball mill, with the rotating speed ball milling 5 of 500 ~ 2000 rpm ~ 100 h, make mix powder fully react；
    4）By step 3）Completely reacted powder takes out, in the stainless steel mould of specification needed for loading, using the side of plasma agglomeration Formula, is warming up to 100 ~ 500 DEG C under the pressure of 50 ~ 600 MPa, keeps 10 ~ 120 min to carry out vacuum-sintering tabletting, up to piece Shape Cu doping Emission in Cubic Ca2Si thermoelectric materials.
  2. 2. Cu doping Emission in Cubic Ca as claimed in claim 12Si thermoelectric materials, it is characterised in that：Step 1）Middle Ca powder, Si powder and Cu powder is 81 by the molar ratio of Ca, Si, Cu:20:(0.5 ~ 10) is mixed.
  3. 3. Cu doping Emission in Cubic Ca as claimed in claim 12Si thermoelectric materials, it is characterised in that：Step 2）Middle grinding steel ball is with mixing The weight ratio of compound powder is (2 ~ 16):1；
    The particle diameter of the grinding steel ball is 0.2 ~ 1.5 cm, and ultrasonic cleaning, ultrasound are carried out using acetone, alcohol successively using preceding Ripple cleaning total time is 10 ~ 30 min.
  4. 4. Cu doping Emission in Cubic Ca as claimed in claim 12Si thermoelectric materials, it is characterised in that：Step 4）The speed of middle heating is 5~20 ℃/min。
CN201610452327.1A 2016-06-22 2016-06-22 A kind of Cu doping Emission in Cubic Ca2Si thermoelectric materials Expired - Fee Related CN106098922B (en)

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CN108502887A (en) * 2018-04-28 2018-09-07 福州大学 A kind of preparation method of the silicide of chemical method synthesis calcium

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CN105220119A (en) * 2015-10-27 2016-01-06 福州大学 A kind of Ag doped with Mg 2si base thermal electric film and preparation method thereof

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CN105220119A (en) * 2015-10-27 2016-01-06 福州大学 A kind of Ag doped with Mg 2si base thermal electric film and preparation method thereof

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Title
Mg2Si 与掺杂系列的电子结构与热电性能研究;闵新民 等;《功能材料》;20051110;第35卷;全文 *

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