CN105932148A - Ag-doped cubic-phase Ca2Si thermoelectric material - Google Patents
Ag-doped cubic-phase Ca2Si thermoelectric material Download PDFInfo
- Publication number
- CN105932148A CN105932148A CN201610452285.1A CN201610452285A CN105932148A CN 105932148 A CN105932148 A CN 105932148A CN 201610452285 A CN201610452285 A CN 201610452285A CN 105932148 A CN105932148 A CN 105932148A
- Authority
- CN
- China
- Prior art keywords
- powder
- thermoelectric material
- cubic
- mix
- ca2si
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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 an Ag-doped cubic-phase Ca2Si thermoelectric material, which is prepared by the following steps: mixing Ca powder, Si powder and Ag powder evenly in an Ar protective atmosphere, putting the obtained mixture powder and grinding steel balls into a vacuum stainless steel ball mill tank for sealing in the Ar protective atmosphere; and carrying out vacuum sintering and tabletting in a plasma sintering manner after ball-milling reaction to obtain the sheet Ag-doped cubic-phase Ca2Si thermoelectric material. An Ag element has the property similar to that of an alkaline-earth metal; a Ca site is easily replaced by the Ag element as donor doping after the Ag element is added; and conductive electrons are provided as current carriers, so that the conductivity and the thermoelectric properties of the material are improved. The Ag-doped cubic-phase Ca2Si thermoelectric material has the advantages of being simple in process, easy to operate, low in cost and the like; and the obtained Ag-doped cubic-phase Ca2Si thermoelectric material is relatively high in purity, is combined closely and has a relatively good industrialization prospect.
Description
Technical field
The invention belongs to thermoelectricity technical field of function materials, be specifically related to a kind of Ag doping Emission in Cubic Ca2Si thermoelectric material.
Background technology
Thermoelectric material is a kind of to be capable of heat energy and environmental type functional material that electric energy is the most mutually changed；Thermoelectric device can realize the mutual conversion between heat energy and electric energy, is the environmental type energy device that the scope of application is the widest.The semiconductor generator manufactured with semi-conductor thermo-electric generation module and refrigerator, as long as can generate electricity with the presence of the temperature difference, can freeze during power supply, noiselessness during its work, pollution-free, service life was more than 10 years, can be widely applied in the base application that waste-heat power generation, refrigeration for refrigerator etc. are important, thus be a kind of widely used green energy resource device.Currently, owing to being limited by pyroelectric material performance, the application of thermo-electric device is also far from reaching to replace the stage of mechanical refrigerator, and this has become the bottleneck of thermo-electric device large-scale application, and therefore high performance thermoelectric material is one of hot subject of current international material research field.The performance of thermoelectric material is mainly characterized by dimensionless figure factor Z T value: ZT=T σ α2/ κ, wherein T is absolute temperature, and σ is the electrical conductivity of material, and α is Seebeck coefficient, and κ is thermal conductivity.
At present unit's its excellent performance of procatarxis such as Ga, As, In, Pb, Te and be widely used in manufacturing semi-conducting material and semiconductor device, but these element major parts are poisonous, and resource faces exhaustion.The elements such as Fe, Si, Ca reserves on earth are big, harmless to organism.Alkaline earth metal silicide Ca2Si material, its direct band gap is about 0.31eV, is that Ca, the Si extremely grown by resource longevity is elementary composition, can recycle, pollution-free to the earth, and due to calcium silicon compound Ca2Si and existing silicon-based technologies have excellent compatibility it is considered to be the most promising novel environmental close friend's semi-conducting material, have potential application prospect in the field such as solaode and thermoelectric conversion.
From the point of view of current research conditions both domestic and external, relevant Emission in Cubic Ca2The research of Si is all the research that Theoretical Calculation is relevant, to Ca2The rare report of theoretical research of Si doping.The crystallography position of each atom in the unit cell volume and structure cell that can effectively change optical material by adulterating, the electronic structure of modulation material, thus change the electrical property of material.Present invention incorporates mechanical alloying method and the electrion plasma vacuum sintering process of low temperature, enable material to carry out reacting and sintering under the vacuum environment of more high pressure low temperature the Ag doping Emission in Cubic Ca of densification at a lower temperature2Si, is expected to one of thermoelectric material as middle warm area, is widely used in every field.Currently, with respect to Ag doping Emission in Cubic Ca2The most nearly no report of Si thermoelectric material.
Summary of the invention
It is an object of the invention to provide that a kind of operating procedure is simple, the manageable Ag of product component adulterates Emission in Cubic Ca2Si thermoelectric material, it is by doping Ag, to improve Ca2The carrier concentration of Si material, thus improve electrical conductivity and the thermoelectricity capability of material.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of Ag doping Emission in Cubic Ca2Si thermoelectric material, its preparation method comprises the following steps:
1) by Ca powder, Si powder and Ag powder mix homogeneously under Ar gas shielded atmosphere, mix powder is obtained；
2) under Ar gas shielded atmosphere, step 1) gained mix powder is put in Stainless Steel Vacuum ball grinder with grinding steel ball, seal；
3) by step 2) ready Stainless Steel Vacuum ball grinder puts in ball mill, with 500 ~ 2000
The rotating speed ball milling 5 ~ 100 of rpm
H, makes mix powder fully react；
4) powder completely reacted for step 3) is taken out, load in the stainless steel mould of required specification, use the mode of plasma agglomeration, 50 ~ 600
It is warming up to 100 ~ 500 under the pressure of MPa
DEG C, keep 10 ~ 120
Min carries out vacuum-sintering tabletting, obtains lamellar Ag doping Emission in Cubic Ca2Si thermoelectric material.
In step 1), Ca powder, Si powder and Ag powder are that 81:20:0.5 ~ 10 mix by the mol ratio of Ca, Si, Ag.
Step 2) in grind the weight ratio of steel ball and mix powder be 2 ~ 16:1；The particle diameter of described grinding steel ball is 0.2 ~ 1.5 cm, uses acetone, ethanol to carry out ultrasonic waves for cleaning before using successively, and ultrasonic waves for cleaning total time is 10 ~ 30
min。
The speed heated up in step 4) is 5 ~ 20 DEG C/min.
The present invention compared with prior art has the advantage that
(1) sintering process of the present invention uses stainless steel mould is supporting processes such that it is able to bearing higher sintering pressure at a lower temperature, efficiently control oxidation and the volatilization of the Ca often occurred in sintering process, make products obtained therefrom composition purer, density is higher.
(2) gained Ag of the present invention doping Ca2The thermoelectricity capability of Si matrix body is better than existing Ca2Si material, its mechanism is that Ag element has the character similar with alkaline-earth metal, after Ag element adds, easily replaces Ca position, as donor doping, it is provided that conduction electrons is as carrier, thus improves electrical conductivity and the thermoelectricity capability of material.
(3) present invention use Cryomilling and plasma discharging vaccum sintering process combine preparation Ag adulterate Emission in Cubic Ca2Si thermoelectric material, its technique is simple, processing ease, and reaction temperature is relatively low, is difficult to oxidation reaction and Ca Ca atom occur2The decomposition of Si phase.Meanwhile, it can be by controlling the atomic ratio of Ca, Si and Ag, sintering temperature, heating rate and heating-up time etc., it is achieved composition is controlled, to meet large-scale production needs, and reduces cost.
Accompanying drawing explanation
Fig. 1 is undoped p Ag(a) and doping Ag(b) Ca2The scanning electron microscope (SEM) photograph of Si thermoelectric material.
Fig. 2 is undoped p Ag(a) and doping Ag(b) Ca2The transmission electron microscope picture of Si thermoelectric material.
Detailed description of the invention
In order to make content of the present invention easily facilitate understanding, below in conjunction with detailed description of the invention, technical solutions according to the invention are described further, but the present invention is not limited only to this.
The particle diameter grinding steel ball used is 0.2 ~ 1.5 cm, uses acetone, ethanol to carry out ultrasonic waves for cleaning before using successively, and ultrasonic waves for cleaning total time is 10 ~ 30
min。
Embodiment
1
A kind of Ag doping Emission in Cubic Ca2The preparation method of Si thermoelectric material comprises the following steps:
1) it is 81:20:0.5 mix homogeneously under Ar gas shielded atmosphere by Ca powder, Si powder and Ag powder by the mol ratio of Ca, Si, Ag, obtains mix powder；
2) step 1) gained mix powder, grinding steel ball, Stainless Steel Vacuum ball grinder and electronic balance are put in the glove box being filled with an atmospheric pressure Ar gas；In glove box, accurately weigh grinding steel ball and mix powder by weight 3:1, and put it in Stainless Steel Vacuum ball grinder, then by Stainless Steel Vacuum ball grinder good seal, to avoid oxygen to enter；From glove box, then take out Stainless Steel Vacuum ball grinder；
3) by step 2) ready Stainless Steel Vacuum ball grinder puts in ball mill, with rotating speed ball milling 5 h of 2000 rpm, makes mix powder fully react；
4) powder completely reacted for step 3) is taken out, load in the stainless steel mould of required specification, use the mode of plasma agglomeration, by the heating rate of 5 DEG C/min under the pressure of 300 MPa, temperature is risen to 300 DEG C, keep 120 min to carry out vacuum-sintering tabletting, obtain lamellar Ag doping Emission in Cubic Ca2Si thermoelectric material.
Embodiment
2
A kind of Ag doping Emission in Cubic Ca2The preparation method of Si thermoelectric material comprises the following steps:
1) it is 81:20:10 mix homogeneously under Ar gas shielded atmosphere by Ca powder, Si powder and Ag powder by the mol ratio of Ca, Si, Ag, obtains mix powder；
2) step 1) gained mix powder, grinding steel ball, Stainless Steel Vacuum ball grinder and electronic balance are put in the glove box being filled with an atmospheric pressure Ar gas；In glove box, accurately weigh grinding steel ball and mix powder by weight 8:1, and put it in Stainless Steel Vacuum ball grinder, then by Stainless Steel Vacuum ball grinder good seal, to avoid oxygen to enter；From glove box, then take out Stainless Steel Vacuum ball grinder；
3) by step 2) ready Stainless Steel Vacuum ball grinder puts in ball mill, with rotating speed ball milling 50 h of 1000 rpm, makes mix powder fully react；
4) powder completely reacted for step 3) is taken out, load in the stainless steel mould of required specification, use the mode of plasma agglomeration, by the heating rate of 10 DEG C/min under the pressure of 600 MPa, temperature is risen to 100 DEG C, keep 60 min to carry out vacuum-sintering tabletting, obtain lamellar Ag doping Emission in Cubic Ca2Si thermoelectric material.
Fig. 1 is undoped p Ag(a) and embodiment 2 preparation doping Ag(b) Ca2The scanning electron microscope (SEM) photograph of Si thermoelectric material.Contrasted it can be seen that doped with the modified Ca of Ag element by Fig. 1 pattern2Si thermoelectric material is finer and close after sintering, and surface is the most smooth, is conducive to improving the electric conductivity of material.
Fig. 2 is undoped p Ag(a) and embodiment 2 preparation doping Ag(b) Ca2The transmission electron microscope picture of Si thermoelectric material.By the contrast of Fig. 2 transmission scan pattern it can be seen that doped with the modified Ca of Ag element2The nanoparticle edge of Si thermoelectric material is the most smooth, its consistency and the carrier mobility speed that are conducive to improving material sintering, thus improves the electric conductivity of material.
Embodiment
3
A kind of Ag doping Emission in Cubic Ca2The preparation method of Si thermoelectric material comprises the following steps:
1) it is 81:20:6 mix homogeneously under Ar gas shielded atmosphere by Ca powder, Si powder and Ag powder by the mol ratio of Ca, Si, Ag, obtains mix powder；
2) step 1) gained mix powder, grinding steel ball, Stainless Steel Vacuum ball grinder and electronic balance are put in the glove box being filled with an atmospheric pressure Ar gas；In glove box, accurately weigh grinding steel ball and mix powder by weight 16:1, and put it in Stainless Steel Vacuum ball grinder, then by Stainless Steel Vacuum ball grinder good seal, to avoid oxygen to enter；From glove box, then take out Stainless Steel Vacuum ball grinder；
3) by step 2) ready Stainless Steel Vacuum ball grinder puts in ball mill, with rotating speed ball milling 100 h of 500 rpm, makes mix powder fully react；
4) powder completely reacted for step 3) is taken out, load in the stainless steel mould of required specification, use the mode of plasma agglomeration, by the heating rate of 20 DEG C/min under the pressure of 50 MPa, temperature is risen to 500 DEG C, keep 20 min to carry out vacuum-sintering tabletting, obtain lamellar Ag doping Emission in Cubic Ca2Si thermoelectric material.
Table 1 is the EDAX results of embodiment 1-3 gained thermoelectric material.
Table 1 EDAX results
Table 2 is embodiment 1-3 gained Ag doping Emission in Cubic Ca2The electrical property measurement result of Si thermoelectric material.
Table 2 Ag adulterates Emission in Cubic Ca2The electrical property measurement result of Si thermoelectric material
By contrast in table 2 it can be seen that material doped Ag is modified, still it is rendered as P-type semiconductor, the mobility in hole can be improved simultaneously on the basis of improving carrier concentration, for improving the electric conductivity of material, thus improve thermoelectricity capability and have important effect.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent and modification, all should belong to the covering scope of the present invention.
Claims (4)
1. an Ag doping Emission in Cubic Ca2Si thermoelectric material, it is characterised in that: its preparation method comprises the following steps:
1) by Ca powder, Si powder and Ag powder mix homogeneously under Ar gas shielded atmosphere, mix powder is obtained；
2) under Ar gas shielded atmosphere, step 1) gained mix powder is put in Stainless Steel Vacuum ball grinder with grinding steel ball, seal；
3) by step 2) ready Stainless Steel Vacuum ball grinder puts in ball mill, with rotating speed ball milling 5 ~ 100 h of 500 ~ 2000 rpm, makes mix powder fully react；
4) powder completely reacted for step 3) is taken out, load in the stainless steel mould of required specification, use the mode of plasma agglomeration, under the pressure of 50 ~ 600 MPa, be warming up to 100 ~ 500 DEG C, keep 10 ~ 120 min to carry out vacuum-sintering tabletting, obtain lamellar Ag doping Emission in Cubic Ca2Si thermoelectric material.
2. Ag doping Emission in Cubic Ca as claimed in claim 12Si thermoelectric material, it is characterised in that: in step 1), Ca powder, Si powder and Ag powder are that 81:20:0.5 ~ 10 mix by the mol ratio of Ca, Si, Ag.
3. Ag doping Emission in Cubic Ca as claimed in claim 12Si thermoelectric material, it is characterised in that: step 2) in grind the weight ratio of steel ball and mix powder be 2 ~ 16:1；
The particle diameter of described grinding steel ball is 0.2 ~ 1.5 cm, uses acetone, ethanol to carry out ultrasonic waves for cleaning before using successively, and ultrasonic waves for cleaning total time is 10 ~ 30 min.
4.
Ag doping Emission in Cubic Ca as claimed in claim 12Si thermoelectric material, it is characterised in that: the speed heated up in step 4) is 5 ~ 20 DEG C/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610452285.1A CN105932148B (en) | 2016-06-22 | 2016-06-22 | A kind of Ag doping Emission in Cubic Ca2Si thermoelectric materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610452285.1A CN105932148B (en) | 2016-06-22 | 2016-06-22 | A kind of Ag doping Emission in Cubic Ca2Si thermoelectric materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105932148A true CN105932148A (en) | 2016-09-07 |
| CN105932148B CN105932148B (en) | 2018-04-13 |
Family
ID=56831863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610452285.1A Expired - Fee Related CN105932148B (en) | 2016-06-22 | 2016-06-22 | A kind of Ag doping Emission in Cubic Ca2Si thermoelectric materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105932148B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319269A (en) * | 2016-11-01 | 2017-01-11 | 福州大学 | Cubic phase Ca3Si alloy and preparation method thereof |
| CN110451512A (en) * | 2019-08-30 | 2019-11-15 | 福州大学 | A kind of two dimension Al doping Ca2Si nano film material and its liquid phase stripping means |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011040506A (en) * | 2009-08-07 | 2011-02-24 | Toyota Industries Corp | P-type thermoelectric material and method for manufacturing the same |
| 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 |
-
2016
- 2016-06-22 CN CN201610452285.1A patent/CN105932148B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011040506A (en) * | 2009-08-07 | 2011-02-24 | Toyota Industries Corp | P-type thermoelectric material and method for manufacturing the same |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| TATSUYA SAKAMOTO等: "Thermoelectric Characteristics of a Commercialized Mg2Si Source Doped with Al, Bi, Ag, and Cu", 《JOURNAL OF ELECTRONIC MATERIALS》 * |
| 姜洪义 等: "用低温固相反应制备p 型Mg2Si 基热电材料", 《硅酸盐学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319269A (en) * | 2016-11-01 | 2017-01-11 | 福州大学 | Cubic phase Ca3Si alloy and preparation method thereof |
| CN106319269B (en) * | 2016-11-01 | 2017-12-08 | 福州大学 | A kind of Emission in Cubic Ca3Si alloys and preparation method thereof |
| CN110451512A (en) * | 2019-08-30 | 2019-11-15 | 福州大学 | A kind of two dimension Al doping Ca2Si nano film material and its liquid phase stripping means |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105932148B (en) | 2018-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102931335B (en) | A kind of Graphene is combined thermoelectric material of cobalt stibide based skutterudite and preparation method thereof | |
| JP2021515411A (en) | n-type Mg-Sb-based room temperature thermoelectric material and its manufacturing method | |
| CN108374198B (en) | A kind of monocrystalline Bi2Te3The preparation method of thermoelectric material | |
| CN107445621B (en) | Cu-Te nanocrystalline/Cu2SnSe3Thermoelectric composite material and preparation method thereof | |
| CN106116587A (en) | A kind of Emission in Cubic Ca2si thermoelectric material and preparation method thereof | |
| CN105895795A (en) | Method for preparing composite tin selenide based thermoelectric material | |
| CN101736172B (en) | Preparation method of SiGe alloy thermoelectric material | |
| CN106098922B (en) | A kind of Cu doping Emission in Cubic Ca2Si thermoelectric materials | |
| CN107123729B (en) | A kind of nanometer silicon carbide/P-type silicon germanium alloy base thermoelectrical composite material and preparation method thereof | |
| CN107887495A (en) | An a kind of step prepares Cu2The method of Se/BiCuSeO composite thermoelectric materials | |
| CN109650435A (en) | A kind of copper sulfide base thermoelectrical composite material and preparation method thereof | |
| CN107195767B (en) | Five yuan of N-type thermoelectric materials of one kind and preparation method thereof | |
| CN103555986B (en) | Method for preparing (Bi0.8Sb0.2)2Te3 nano thermoelectric material | |
| CN110098310A (en) | A kind of SnSe base thermoelectricity material orientation polycrystalline preparation method | |
| CN105932148B (en) | A kind of Ag doping Emission in Cubic Ca2Si thermoelectric materials | |
| Li et al. | Realization of high thermoelectric performance in solution-synthesized porous Zn and Ga codoped SnSe nanosheets | |
| CN106129241A (en) | Solid reaction process prepares the method for stacking faults chalcogenide thermoelectric material | |
| CN103811653B (en) | Multi-cobalt p type skutterudite filled thermoelectric material and preparation method thereof | |
| CN107240637B (en) | A kind of cubic phase Cu3SbS3Base thermoelectricity material and preparation method thereof | |
| CN107326250B (en) | The method of the supper-fast preparation high-performance ZrNiSn block thermoelectric material of one step | |
| CN103409656B (en) | Thermoelectric material Mg2Sn and preparation method thereof | |
| CN105859299A (en) | Na-doped cubic phase Ca2Si thermoelectric material and preparation method thereof | |
| CN110218888A (en) | A kind of novel Zintl phase thermoelectric material and preparation method thereof | |
| CN104946918A (en) | New method for quickly preparing AgInSe2 based thermoelectric material | |
| CN108423641A (en) | A kind of preparation method with ultralow thermal conductivity bismuth indium selenium thermoelectric material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180413 Termination date: 20210622 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |