CN113161473B - Method for improving performance of p-type polycrystalline bismuth telluride material and preparation method - Google Patents
Method for improving performance of p-type polycrystalline bismuth telluride material and preparation method Download PDFInfo
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- CN113161473B CN113161473B CN202110416436.9A CN202110416436A CN113161473B CN 113161473 B CN113161473 B CN 113161473B CN 202110416436 A CN202110416436 A CN 202110416436A CN 113161473 B CN113161473 B CN 113161473B
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Abstract
The invention disclosesA method for improving the performance of p-type polycrystalline bismuth telluride material comprises the step of adding p-type polycrystalline Bi 2 Te 3 Placing the compound powder in a non-oxygen atmosphere for a period of time to drive away oxygen adsorbed on the surface of the powder, and then performing spark plasma sintering to obtain the high-performance p-type polycrystalline Bi 2 Te 3 A thermoelectric material. According to the invention, by recovering the defects generated in the crushing process of the material, the reaction of oxygen elements and the material is avoided to reduce the carrier concentration, and the p-type polycrystalline bismuth telluride material with higher conductivity and thermoelectric figure of merit is obtained.
Description
Technical Field
The invention belongs to the technical field of energy materials, and provides a preparation method for improving the performance of a p-type polycrystalline bismuth telluride material.
Background
The thermoelectric material is a clean energy material which can realize the conversion of heat energy and electric energy by utilizing Seebeck and Peltier effects. The thermoelectric device prepared from the thermoelectric material is mainly applied to thermoelectric power generation and thermoelectric refrigeration, has the advantages of light weight, small size, simple structure, no pollution, no noise, no transmission part and high reliability, is widely applied to the fields of micro-area precise temperature control, micro-area refrigeration and the like, and has huge development prospect. The conversion efficiency of the thermoelectric device mainly depends on the thermoelectric performance of the material, and is measured by a dimensionless thermoelectric figure of merit ZT, ZT = S 2 σ T/κ, where S is the Seebeck coefficient, σ is the electrical conductivity, κ is the total thermal conductivity, and T is the absolute temperature. Therefore, in order to obtain a higher ZT value, an excellent thermoelectric material needs to have a higher Seebeck coefficient, a higher electrical conductivity and a lower thermal conductivity.
Bi 2 Te 3 The base alloy is the thermoelectric material with the best performance at room temperature at present, is one of the most mature thermoelectric materials researched at the earliest, has the excellent performance of a dimensionless optimal value ZT about 1 near the room temperature, and is a thermoelectric material produced commercially at present. The common commercial use at present is the zone-melting bismuth telluride material, because the bismuth telluride-based compound is a trigonal crystal system, belongs to the space group R-3m, along the crystalLearning c-axis direction as-Te (1) —Bi—Te (2) —Bi—Te (1) Alternating repeating arrangements of five atomic layers, te (1) -Te (1) The layers are bonded by van der Waals force, and the weaker bonding causes Bi 2 Te 3 Crystal of the compound in Te (1) -Te (1) Easy slippage or cleavage between atomic planes along basal planes, resulting in Bi 2 Te 3 The mechanical properties of compound single crystals are poor. In order to improve the mechanical properties of the material, the polycrystalline material is generally prepared by adopting a powder metallurgy and sintering method, and finally, compared with a single crystal, the electrical conductivity of the material is obviously deteriorated, so that the internal resistance of the prepared thermoelectric device is higher, and the electrothermal conversion efficiency is obviously reduced.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method for improving the performance of the p-type polycrystalline bismuth telluride material aiming at the defects in the prior art, and the p-type polycrystalline bismuth telluride material with higher conductivity and thermoelectric figure of merit is obtained by recovering the defects generated in the crushing process of the material and avoiding the reaction of oxygen elements and the material to reduce the carrier concentration.
The technical scheme adopted by the invention for solving the problems is as follows:
a method for improving the performance of p-type polycrystalline bismuth telluride material is to mix p-type polycrystalline Bi 2 Te 3 Placing the compound powder in a non-oxygen atmosphere at 20-50 ℃ for 1-5 days to drive off oxygen adsorbed on the surface of the powder, and then performing discharge plasma sintering to obtain the high-performance p-type polycrystalline Bi 2 Te 3 A thermoelectric material. Wherein the non-oxygen atmosphere comprises nitrogen, argon, helium, etc.
A preparation method for improving the performance of a p-type polycrystalline bismuth telluride material comprises the following steps:
(1) According to p-type polycrystal Bi 2 Te 3 Weighing high-purity simple substance Bi powder, sb powder and Te powder as raw materials according to the stoichiometric ratio of each element in the chemical composition of the thermoelectric material;
(2) Uniformly mixing the powder of the raw material in the step (1), and then cold-pressing the mixture into a block;
(3) Sealing the block obtained in the step (2) in a glass tube in vacuum, and placing the glass tube in a muffle furnace for thermal explosion reaction;
(4) Grinding and sieving the block obtained by the thermal explosion reaction in the step (3), and then placing the block in an argon atmosphere furnace for 1 to 5 days at the temperature of between 20 and 50 ℃ under the argon atmosphere;
(5) Performing spark plasma activated sintering on the powder obtained in the step (4) to obtain high-performance p-type polycrystalline Bi 2 Te 3 A thermoelectric material.
According to the scheme, the p-type polycrystal Bi 2 Te 3 Chemical composition Bi of thermoelectric material x Sb 2-x Te 3 (x＝0.45～0.55)。
According to the scheme, the raw material powder in the step (1) is generally subjected to ball milling and sieving, and the sieving particle size is preferably 50-400 meshes.
According to the scheme, the pressure of cold pressing in the step (2) is 5-30 MPa, and the pressure maintaining time is 5-30 min.
According to the scheme, in the step (3), the temperature in the thermal explosion process is 673K-873K, and the heat preservation time is 15 s-5 min.
According to the scheme, in the step (4), placing the mixture in an argon atmosphere furnace for 1-5 days at room temperature.
According to the scheme, the temperature of the spark plasma activation sintering is 673K-773K, and the heat preservation time is 5-20 min.
Compared with the prior art, the invention has the beneficial effects that:
the p-type polycrystalline bismuth telluride material with high conductivity and thermoelectric merit value is finally obtained.
Drawings
FIG. 1 is an XRD pattern of a sample prepared in comparative example, examples 1 to 3.
FIG. 2 is a graph showing the relationship between the electric conductivity and the temperature of the samples prepared in comparative example and examples 1 to 3.
FIG. 3 is a graph showing the Seebeck coefficient with respect to temperature for the samples prepared in comparative example and examples 1 to 3.
FIG. 4 is a graph showing the power factor as a function of temperature for the samples prepared in comparative example and examples 1 to 3.
FIG. 5 is a graph showing the thermal conductivity as a function of temperature for the samples prepared in comparative example and examples 1 to 3.
FIG. 6 is a graph showing ZT values of the samples prepared in comparative example and examples 1 to 3 as a function of temperature.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the present invention is not limited to the following examples.
Comparative example
A preparation method of a p-type polycrystalline bismuth telluride material comprises the following steps:
(1) According to Bi 0.5 Sb 1.5 Te 3 Weighing high-purity simple substances Bi, sb and Te (namely, the molar ratio of Bi, sb and Te is 0.5;
(2) Uniformly mixing the powder obtained in the step (1) and cold-pressing the powder into a block body, wherein the pressure is 20MPa, and keeping the pressure for 10min;
(3) Sealing the block obtained in the step (2) in a glass tube in vacuum, and placing the glass tube in a muffle furnace for thermal explosion reaction, wherein the thermal explosion temperature is 823K, and the thermal explosion time is 1min;
(4) Grinding the blocks obtained by thermal explosion and sieving the blocks with a 200-mesh sieve;
(5) And (4) performing discharge plasma activated sintering on the powder obtained in the step (4), wherein the sintering temperature is 723K, and the heat preservation time is 6min, so as to obtain the high-performance p-type polycrystalline bismuth telluride thermoelectric material.
P-type polycrystal Bi prepared by contrast ratio 2 Te 3 The thermoelectric material is subjected to performance tests, and the electric conductivity, the Seebeck coefficient, the power factor, the thermal conductivity and the ZT value within the range of 300-400K are shown in Table 1.
TABLE 1
| 300K | 325K | 350K | 375K | 400K | |
| Electrical conductivity (10) 4 S/m) | 6.98 | 6.07 | 5.27 | 4.66 | 4.17 |
| Seebeck coefficient (μ V/K) | 231 | 243 | 245 | 244 | 240 |
| Power factor (mV/mK) 2 ) | 3.74 | 3.59 | 3.17 | 2.78 | 2.43 |
| Thermal conductivity (W/mK) | 1.08 | 1.04 | 1.05 | 1.1 | 1.2 |
| ZT | 1.04 | 1.1 | 1.0 | 0.94 | 0.82 |
Example 1
The present example differs from the comparative example in that: and (4) grinding the block obtained by thermal explosion, sieving the ground block with a 200-mesh sieve, and placing the ground block in an argon atmosphere furnace for 1 day at room temperature.
For p-type polycrystalline Bi prepared in example 1 2 Te 3 The thermoelectric material is subjected to performance tests, and the electric conductivity, the Seebeck coefficient, the power factor, the thermal conductivity and the ZT value within the range of 300-400K are shown in Table 2.
TABLE 2
| 300K | 325K | 350K | 375K | 400K | |
| Electrical conductivity (10) 4 S/m) | 9.76 | 8.5 | 7.35 | 6.51 | 5.74 |
| Seebeck coefficient (μ V/K) | 196 | 214 | 223 | 231 | 232 |
| Power factor (mV/mK) 2 ) | 3.76 | 3.9 | 3.67 | 3.5 | 3.09 |
| Thermal conductivity (W/mK) | 1.19 | 1.13 | 1.09 | 1.08 | 1.1 |
| ZT | 0.95 | 1.11 | 1.17 | 1.2 | 1.12 |
In this example, p-type polycrystalline Bi was prepared as compared with the comparative example 2 Te 3 In the process of the thermoelectric material, because oxygen is driven away in the argon atmosphere, the electric conductivity of the sintered sample is obviously increased, so that the power factor is obviously optimized, and the thermoelectric material is suitable for preparing thermoelectric devices.
Example 2
The present embodiment is different from embodiment 1 in that: the thermal explosion time of the step (3) is 3min.
For the p-type polycrystalline Bi prepared in example 2 2 Te 3 The thermoelectric material was subjected to performance testing, and the electric conductivity, seebeck coefficient, power factor, thermal conductivity and ZT value in the range of 300 to 400K are shown in table 3.
TABLE 3
| 300K | 325K | 350K | 375K | 400K | |
| Electrical conductivity (10) 4 S/m) | 9.76 | 8.5 | 7.35 | 6.51 | 5.74 |
| Seebeck coefficient (μ V/K) | 196 | 214 | 223 | 231 | 232 |
| Power factor (mV/mK) 2 ) | 3.76 | 3.9 | 3.67 | 3.5 | 3.09 |
| Thermal conductivity (W/mK) | 1.19 | 1.13 | 1.09 | 1.08 | 1.1 |
| ZT | 0.95 | 1.11 | 1.17 | 1.2 | 1.12 |
Example 3
The present embodiment is different from embodiment 2 in that: and (4) placing the furnace in an argon atmosphere for 5 days.
For the p-type polycrystalline Bi prepared in example 3 2 Te 3 Thermoelectric material processThe electrical conductivity, seebeck coefficient, power factor, thermal conductivity and ZT value in the range of 300-400K are shown in Table 4.
TABLE 4
| 300K | 325K | 350K | 375K | 400K | |
| Electrical conductivity (10) 4 S/m) | 10.21 | 8.94 | 7.72 | 6.81 | 5.99 |
| Seebeck coefficient (μ V/K) | 192 | 206 | 220 | 230 | 234 |
| Power factor (mV/mK) 2 ) | 3.77 | 3.79 | 3.72 | 3.61 | 3.28 |
| Thermal conductivity (w/mK) | 1.21 | 1.14 | 1.1 | 1.1 | 1.12 |
| ZT | 0.94 | 1.07 | 1.18 | 1.22 | 1.15 |
In conclusion, in combination with the comparison of data of the embodiment and the comparative example, the p-type polycrystalline bismuth telluride material with high conductivity and thermoelectric figure of merit is finally obtained by using the thermal explosion method to prepare the p-type polycrystalline bismuth telluride, adding the step of processing in an argon atmosphere furnace after crushing and sieving, avoiding the reaction of oxygen elements and the material to reduce the carrier concentration, and combining with the spark plasma activation sintering.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (8)
1. A method for improving the performance of p-type polycrystalline bismuth telluride material is characterized by adding p-type polycrystalline Bi 2 Te 3 Placing the compound powder in a non-oxygen atmosphere at room temperature for 1 to 5 days, and driving off the surface of the powderOxygen absorbed by the surface is then subjected to spark plasma sintering, so that high-performance p-type polycrystalline Bi is obtained 2 Te 3 A thermoelectric material.
2. The method for improving the performance of the p-type polycrystalline bismuth telluride material as claimed in claim 1, wherein the non-oxygen atmosphere is selected from nitrogen, argon, and helium.
3. A preparation method for improving the performance of a p-type polycrystalline bismuth telluride material is characterized by comprising the following steps:
(1) According to p-type polycrystal Bi 2 Te 3 Weighing elementary substance Bi powder, sb powder and Te powder as raw materials according to the stoichiometric ratio of each element in the chemical composition of the thermoelectric material;
(2) Uniformly mixing the powder of the raw material in the step (1), and then cold-pressing the mixture into a block;
(3) Carrying out thermal explosion reaction on the block obtained in the step (2) after vacuum;
(4) Grinding and sieving the block obtained by the thermal explosion reaction in the step (3), and then placing in an atmosphere of inert gas or nitrogen at room temperature for 1 to 5 days;
(5) Performing spark plasma activated sintering on the powder obtained in the step (4) to obtain high-performance p-type polycrystalline Bi 2 Te 3 A thermoelectric material.
4. The preparation method for improving the performance of the p-type polycrystalline bismuth telluride material according to claim 3, wherein the p-type polycrystalline Bi 2 Te 3 Chemical composition Bi of thermoelectric material x Sb 2-x Te 3 ，x=0.45~0.55。
5. The preparation method for improving the performance of the p-type polycrystalline bismuth telluride material according to claim 3, wherein the raw material powder in the step (1) is subjected to ball milling and sieving, and the sieved particle size is 50-400 meshes.
6. The preparation method for improving the performance of the p-type polycrystalline bismuth telluride material according to claim 3, wherein the pressure of the cold pressing in the step (2) is 5-30 MPa, and the pressure maintaining time is 5-30 min.
7. The preparation method for improving the performance of the p-type polycrystalline bismuth telluride material according to claim 3, wherein in the step (3), the temperature in the thermal explosion process is 673K to 873K, and the heat preservation time is 15s to 5min.
8. The preparation method for improving the performance of the p-type polycrystalline bismuth telluride material according to claim 3, wherein the temperature of spark plasma activated sintering is 673K to 773K, and the heat preservation time is 5 to 20min.
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| CN1768986A (en) * | 2005-09-23 | 2006-05-10 | 北京科技大学 | High pressure method for preparing Bi-Te alloy series thermoelectric material |
| CN107706296A (en) * | 2017-09-19 | 2018-02-16 | 中国科学院上海硅酸盐研究所 | Integrative packaging structure thermo-electric device and preparation method thereof |
| CN111244258A (en) * | 2020-01-20 | 2020-06-05 | 昆明理工大学 | Cu1.8S-based polycrystalline-amorphous metal composite thermoelectric material and preparation method thereof |
| CN112201743A (en) * | 2020-11-06 | 2021-01-08 | 武汉理工大学 | Preparation method of n-type bismuth telluride-based thermoelectric material |
| CN112670399A (en) * | 2021-01-13 | 2021-04-16 | 武汉理工大学 | Method for eliminating donor-like effect of bismuth telluride-based thermoelectric material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1768986A (en) * | 2005-09-23 | 2006-05-10 | 北京科技大学 | High pressure method for preparing Bi-Te alloy series thermoelectric material |
| CN107706296A (en) * | 2017-09-19 | 2018-02-16 | 中国科学院上海硅酸盐研究所 | Integrative packaging structure thermo-electric device and preparation method thereof |
| CN111244258A (en) * | 2020-01-20 | 2020-06-05 | 昆明理工大学 | Cu1.8S-based polycrystalline-amorphous metal composite thermoelectric material and preparation method thereof |
| CN112201743A (en) * | 2020-11-06 | 2021-01-08 | 武汉理工大学 | Preparation method of n-type bismuth telluride-based thermoelectric material |
| CN112670399A (en) * | 2021-01-13 | 2021-04-16 | 武汉理工大学 | Method for eliminating donor-like effect of bismuth telluride-based thermoelectric material |
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