CN108218425B - Sb-doped cubic phase Ca2Ge-based thermoelectric material and preparation method thereof - Google Patents
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Abstract
The invention discloses Sb-doped cubic phase Ca2The Ge-based thermoelectric material is prepared by respectively weighing Ca powder, Ge powder and Sb powder in proportion, and then placing the Ca powder, the Ge powder and the Sb powder in an organic solvent for ultrasonic oscillation to fully mix the Ca powder, the Ge powder and the Sb powder; then after the organic solvent is completely volatilized, a block is prepared by dry molding; placing the mixture into an alumina crucible, sealing and filling the alumina crucible with Ca powder, placing the alumina crucible into a microwave vacuum high-temperature heating furnace, and carrying out high-temperature reaction in a high-purity argon atmosphere to obtain Sb-doped cubic phase Ca2A Ge-based thermoelectric material. The invention avoids the phenomenon of abnormal growth of crystal grains in the traditional sintering process by microwave heating, finally obtains the material with an ultrafine crystal grain structure, reduces the synthesis temperature of the material and has better application prospect.
Description
Technical Field
The invention belongs to the field of thermoelectric functional materials, and particularly relates to cubic phase Ca doped with Sb2Ge-based thermoelectric material and a preparation method thereof.
Background
Since the nineties of the last century, materials workers have been devoted to the study of energy conversion materials, making thermoelectric materials a focus of research in materials science. The thermoelectric material is also called as a temperature difference material, and is a novel functional material with mutual conversion of thermal effect and electric effect. The thermoelectric material does not need a transmission part in the using process, has no noise and no waste during working, has the advantages of being comparable to secondary energy sources such as solar energy, wind energy, water energy and the like, has no pollution to the environment, has reliable performance and long service life, and is an environment-friendly material with wide application prospect.
In recent years, since intermetallic compounds have excellent thermoelectric and mechanical properties, a lot of attention has been paid to such novel alloys by material researchers, Ca2Ge is one of them. This is not only because of Ca2Ge has good thermoelectric property, and the alloy elements of Ca and Ge have rich raw material resources, large stratum accumulation and low price, so that the Ge becomes a potential novel structural material which can be widely applied, therefore, Ca2The research of Ge is significant.
Sb doping is an important way for reducing the thermal conductivity, optimizing the electrical property, further improving the thermoelectric property of the material and improving the mechanical property. Cubic phase Ca doped with Sb2Ge is composed of three elements Sb, Ca and Ge with extremely long service life, so that cyclic utilization can be realized, and the Ge is paid much attention to a series of characteristics such as no pollution to the environment basically and the like. At present, from the research conditions at home and abroad, only the bulk Ca is needed in both theoretical research and experimental research2Ge research, and doping Sb with cubic phase Ca2The preparation research of the Ge material is not reported.
Disclosure of Invention
The invention aims to provide Sb-doped cubic phase Ca2The Ge-based thermoelectric material is prepared by doping Sb to reduce thermal conductivity, optimize electrical property, improve thermoelectric property and mechanical property of the material, and obtain Sb-doped cubic phase Ca with high purity and definite composition ratio2A Ge-based thermoelectric material.
In order to achieve the purpose, the invention adopts the following technical scheme:
sb-doped cubic phase Ca2The preparation method of the Ge-based thermoelectric material comprises the following steps:
(1) respectively weighing Ca powder, Ge powder and Sb powder according to a molar ratio of 70:33 (0.3-2), then pouring the Ca powder, the Ge powder and the Sb powder into an organic solvent, and carrying out ultrasonic oscillation for 20-60 min to fully mix the Ca powder, the Ge powder and the Sb powder;
(2) after the organic solvent is completely volatilized from the mixed liquid obtained in the step (1) at the temperature of 25-60 ℃, pressing the mixed liquid into a cylindrical blank body with the diameter of 10-60 mm under the pressure of 20-60 MPa by adopting a dry forming process;
(3) placing the obtained blank body in an alumina crucible, sealing and filling the alumina crucible with Ca powder, then placing the alumina crucible in a microwave vacuum high-temperature heating furnace, introducing high-purity argon, and heating to 400-700 ℃ under the conditions of microwave frequency of 2.45 GHz and microwave power of 1.5-3.5 kW;
(4) when the temperature reaches, carrying out heat preservation treatment for 0.5-6 h under the power of 1.5-2.5 kW, and then cooling the material to room temperature along with the furnace to obtain Sb-doped cubic phase Ca2A Ge-based thermoelectric material.
The organic solvent used in the step (1) is ethanol.
And (4) before the aluminum oxide crucible used in the step (3) is used, ultrasonic cleaning is sequentially carried out by adopting deionized water, alcohol and acetone, and the total ultrasonic cleaning time is 15-50 min. The purity of the argon is 99-99.99%.
Compared with the prior art, the invention has the following advantages:
1) according to the invention, by microwave heating, the phenomenon of abnormal growth of crystal grains in the traditional sintering process is avoided, the material with an ultrafine crystal grain structure is finally obtained, and the reduction of the synthesis temperature of the material is realized;
2) the method has low heating temperature, can avoid the problem of high-temperature evaporation and dissipation of Ca, well controls the composition ratio, and has good repeatability;
3) the invention is prepared under vacuum condition, which can effectively prevent the mixing of impurities and oxidation problem, so as to obtain high-purity product.
Drawings
FIG. 1 is a scanning electron micrograph of a thermoelectric material prepared in example 1;
FIG. 2 is a Seebeck coefficient-temperature curve of thermoelectric materials prepared in example 1 and a comparative example;
FIG. 3 is a graph of conductivity versus temperature for thermoelectric materials prepared in examples 1 and comparative examples;
fig. 4 is a power factor versus temperature curve of thermoelectric materials prepared in example 1 and comparative example.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
The purity of the Ca powder is more than 99%, the purity of the Ge powder is more than 99%, and the purity of the Sb powder is more than 99%. The purity of the argon used was greater than 99%.
Before the aluminum oxide crucible is used, deionized water, alcohol and acetone are sequentially adopted for ultrasonic cleaning, and the total ultrasonic cleaning time is 15-50 min.
Example 1
(1) Respectively weighing Ca powder, Ge powder and Sb powder according to a molar ratio of 70:33:0.5, pouring the Ca powder, the Ge powder and the Sb powder into ethanol, and carrying out ultrasonic oscillation for 30 min to fully mix the Ca powder, the Ge powder and the Sb powder;
(2) after the mixed solution obtained in the step (1) completely volatilizes ethanol at the temperature of 30 ℃, pressing the mixed solution into a cylindrical blank body with the diameter of phi 15 mm under the pressure of 25 MPa by adopting a dry forming process;
(3) placing the obtained blank body in an alumina crucible, sealing and filling the alumina crucible with Ca powder, then placing the alumina crucible in a microwave vacuum high-temperature heating furnace, introducing high-purity argon, and heating to 500 ℃ under the conditions of microwave frequency of 2.45 GHz and microwave power of 1.5 kW;
(4) when the temperature reaches, carrying out heat preservation treatment for 1 h under the power of 1.5 kW, and then cooling the material to room temperature along with the furnace to obtain Sb-doped cubic phase Ca2A Ge-based thermoelectric material.
TABLE 1 Sb-doped cubic phase Ca prepared in this example2Compositional analysis of Ge
FIG. 1 is a scanning electron micrograph of the thermoelectric material prepared in this example. As can be seen from FIG. 1, the resulting final product has a fine and uniform grain size.
Example 2
(1) Respectively weighing Ca powder, Ge powder and Sb powder according to a molar ratio of 70:33:1, pouring the Ca powder, the Ge powder and the Sb powder into ethanol, and carrying out ultrasonic oscillation for 50 min to fully mix the Ca powder, the Ge powder and the Sb powder;
(2) after the mixed solution obtained in the step (1) completely volatilizes ethanol at the temperature of 20 ℃, pressing the mixed solution into a cylindrical blank body with the diameter of phi 30 mm under the pressure of 40 MPa by adopting a dry forming process;
(3) placing the obtained blank body in an alumina crucible, sealing and filling the alumina crucible with Ca powder, then placing the alumina crucible in a microwave vacuum high-temperature heating furnace, introducing high-purity argon, and heating to 400 ℃ under the conditions of microwave frequency of 2.45 GHz and microwave power of 3 kW;
(4) when the temperature reaches, carrying out heat preservation treatment for 4 hours under the power of 2 kW, and then cooling the material to room temperature along with the furnace to obtain Sb-doped cubic phase Ca2A Ge-based thermoelectric material.
Example 3
(1) Respectively weighing Ca powder, Ge powder and Sb powder according to a molar ratio of 70:33:1.8, pouring the Ca powder, the Ge powder and the Sb powder into ethanol, and carrying out ultrasonic oscillation for 40 min to fully mix the Ca powder, the Ge powder and the Sb powder;
(2) after the mixed solution obtained in the step (1) completely volatilizes ethanol at the temperature of 60 ℃, pressing the mixed solution into a cylindrical blank body with the diameter of phi 60 mm under the pressure of 50 Mpa by adopting a dry forming process;
(3) placing the obtained blank body in an alumina crucible, sealing and filling the alumina crucible with Ca powder, then placing the alumina crucible in a microwave vacuum high-temperature heating furnace, introducing high-purity argon, and heating to 600 ℃ under the conditions of microwave frequency of 2.45 GHz and microwave power of 3.5 kW;
(4) when the temperature reaches, the heat preservation treatment is carried out for 5 hours under the power of 2.5 kW, and then the material is cooled to the room temperature along with the furnace to obtain Sb-doped cubic phase Ca2A Ge-based thermoelectric material.
Comparative example
(1) Respectively weighing Ca powder and Ge powder according to a molar ratio of 2.2:1, pouring the Ca powder and the Ge powder into ethanol, and carrying out ultrasonic oscillation for 25 min to fully mix the Ca powder and the Ge powder;
(2) after the mixed solution obtained in the step (1) completely volatilizes ethanol at the temperature of 50 ℃, pressing the mixed solution into a cylindrical blank body with the diameter of phi 20 mm under the pressure of 60 Mpa by adopting a dry forming process;
(3) placing the obtained blank body in an alumina crucible, sealing and filling the alumina crucible with Ca powder, then placing the alumina crucible in a microwave vacuum high-temperature heating furnace, introducing high-purity argon, and heating to 600 ℃ under the conditions of microwave frequency of 2.45 GHz and microwave power of 3 kW;
(4) when the temperature reaches, carrying out heat preservation treatment for 1 h under the power of 2 kW, and then cooling the material to room temperature along with the furnace to obtain cubic phase Ca2A Ge-based thermoelectric material.
TABLE 1 comparison of the Room temperature Electrical Properties of the different example samples
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (5)
1. Sb-doped cubic phase Ca2The preparation method of the Ge-based thermoelectric material is characterized by comprising the following steps: the method comprises the following steps:
(1) respectively weighing Ca powder, Ge powder and Sb powder according to a molar ratio of 70:33 (0.3-2), then pouring the Ca powder, the Ge powder and the Sb powder into an organic solvent, and carrying out ultrasonic oscillation for 20-60 min to fully mix the Ca powder, the Ge powder and the Sb powder;
(2) after the organic solvent in the mixed solution obtained in the step (1) is completely volatilized, pressing the mixed solution into a blank body under certain pressure by adopting a dry forming process;
(3) placing the obtained blank body in an alumina crucible, sealing and filling the alumina crucible with Ca powder, then placing the alumina crucible in a microwave vacuum high-temperature heating furnace, introducing high-purity argon, and heating to 400-700 ℃ under the conditions of microwave frequency of 2.45 GHz and microwave power of 1.5-3.5 kW;
(4) when the temperature reaches, carrying out heat preservation treatment for 0.5-6 h under the power of 1.5-2.5 kW, and then cooling the material to room temperature along with the furnace to obtain the Sb-doped cubic phase Ca2A Ge-based thermoelectric material.
2. The Sb doped cube of claim 1Phase Ca2The preparation method of the Ge-based thermoelectric material is characterized by comprising the following steps: the organic solvent used in the step (1) is ethanol.
3. The Sb-doped cubic phase Ca of claim 12The preparation method of the Ge-based thermoelectric material is characterized by comprising the following steps: in the step (2), the mixed solution is volatilized to dry at the temperature of 25-60 ℃, and then the organic solvent is pressed into a cylindrical blank body with the diameter of 10-60 mm under the pressure of 20-60 Mpa.
4. The Sb-doped cubic phase Ca of claim 12The preparation method of the Ge-based thermoelectric material is characterized by comprising the following steps: the purity of the argon in the step (3) is 99-99.99%.
5. Sb-doped cubic phase Ca prepared by the method of claim 12A Ge-based thermoelectric material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591299A (en) * | 2015-01-16 | 2015-05-06 | 郑州大学 | Microwave sintering synthesis method of oxide thermoelectric material Ca3-xKxCo4O9 |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104591299A (en) * | 2015-01-16 | 2015-05-06 | 郑州大学 | Microwave sintering synthesis method of oxide thermoelectric material Ca3-xKxCo4O9 |
| 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 |
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| Title |
|---|
| Effect of the Fabrication Technique on the Thermoelectric Performance of Mg-Based Compounds-A Case Study of n-Type Mg2Ge;Rafael Santos等;《ACS Omega》;20171117;第8069-8074页 * |
| Investigation of structural,elastic,and lattic-dynamical properties of Ca2Si，Ca2Ge,and Ca2Sn based on first-principles density functional theory;Jun-ichi Tani等;《Computational Materials Science》;20141029;全文 * |
| 微波合成Mg2Si1-xSnx热电固溶体;杜长坤等;《粉末冶金材料科学与工程》;20120831;第475-481页 * |
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