CN111454060A - N-type bismuth telluride-based thermoelectric material with modulation structure and preparation method thereof - Google Patents
N-type bismuth telluride-based thermoelectric material with modulation structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an n-type bismuth telluride-based thermoelectric material with a modulation structure and a preparation method thereof2Te3And Bi2Te3‑xSexMixing the powders in an equal molar ratio, wherein x is more than or equal to 0.1 and less than or equal to 0.9, the internal structure of the n-type bismuth telluride-based thermoelectric material crystal atom of the modulation structure is a modulation structure, and Bi is2Te3The purity of the powder is more than or equal to 99.99 wt%, and Bi2Te3The grain diameter of the powder is less than or equal to 500 mu m; bi2Te3‑ xSexThe purity of the powder is more than or equal to 99.99 wt%, and Bi2Te3‑xSexThe grain size of the powder is less than or equal to 500 mu m, wherein x is more than or equal to 0.1 and less than or equal to 0.9; the method has the characteristics of simple process, short production period and high production efficiency, and the prepared n-type bismuth telluride-based thermoelectric material with the modulation structure has high purity, low thermal conductivity and high electrical conductivity, has the modulation structure and can synergistically improve the carrier concentration and the mobility.
Description
Technical Field
The invention relates to the technical field of electrothermal materials, in particular to an n-type bismuth telluride-based thermoelectric material with a modulation structure and a preparation method thereof.
Background
Thermoelectric material as new energyThe source material can directly realize the direct interconversion of heat energy and electric energy, the corresponding thermoelectric application device has simple structure, no transmission part, no noise and no emission, is widely applied to the fields of computer/communication base station chip refrigeration, air conditioners, refrigerators, aerospace/polar detection equipment power supplies and the like, and is a hotspot in the current material research field. The most important criterion for evaluating thermoelectric materials is the dimensionless thermoelectric figure of merit (ZT), ZT ═ S2σ/κ) T; wherein: s is the seebeck coefficient, σ is the electrical conductivity and κ is the thermal conductivity, and T is the temperature. The higher the dimensionless thermoelectric figure of merit, the higher the corresponding thermoelectric conversion efficiency. Materials with high thermoelectric properties should have high electromotive force, high electrical conductivity and low thermal conductivity. The conductivity is determined by the carrier concentration and mobility, σ ═ en μ, where e is the electron charge, n is the carrier concentration, and μ is the carrier mobility;
at present, about 200 thermoelectric material systems exist, the most widely applied thermoelectric material is a bismuth telluride-based thermoelectric material, but at present, the domestic bismuth telluride thermoelectric material, especially an n-type bismuth telluride-based thermoelectric material, has a single structure and the problems that the carrier concentration and the mobility can not be synergistically improved and the improvement of thermoelectric performance is limited, so the invention provides the n-type bismuth telluride-based thermoelectric material with a modulated structure and the preparation method thereof so as to solve the problems in the prior art.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide an n-type bismuth telluride-based thermoelectric material with a modulated structure and a preparation method thereof, and the n-type bismuth telluride-based thermoelectric material with the modulated structure and the preparation method thereof have a modulated structure, and can realize the synergistic enhancement of carrier concentration and mobility.
In order to realize the purpose of the invention, the invention is realized by the following technical scheme: an n-type bismuth telluride-based thermoelectric material with a modulation structure comprises n-type Bi2Te3And Bi2Te3-xSexThe powder is mixed according to the equal molar ratio, wherein x is more than or equal to 0.1 and less than or equal to 0.9, and the internal structure of the n-type bismuth telluride based thermoelectric material crystal atom of the modulation structure is the modulation structure.
Further, the method can be used for preparing a novel materialThe improvement lies in that: the Bi2Te3The purity of the powder is more than or equal to 99.99 wt%, and Bi2Te3The grain diameter of the powder is less than or equal to 500 mu m; the Bi2Te3-xSexThe purity of the powder is more than or equal to 99.99 wt%, and Bi2Te3-xSexThe particle size of the powder is less than or equal to 500 mu m, wherein x is more than or equal to 0.1 and less than or equal to 0.9.
A preparation method of an n-type bismuth telluride-based thermoelectric material with a modulation structure comprises the following steps:
step one, according to n type Bi2Te3And Bi2Te3-xSexThe mass ratio of the materials is 1: 1, wherein x is more than or equal to 0.1 and less than or equal to 0.9, and then the materials are uniformly mixed to obtain mixed powder;
step two, putting the mixed powder into a ball milling tank, and carrying out ball milling for 1-12 h under the inert atmosphere condition to prepare n-type Bi2Te3And Bi2Te3-xSexMixing the powder in an equal molar ratio, wherein x is more than or equal to 0.1 and less than or equal to 0.9;
step three, mixing the n-type Bi2Te3And Bi2Te3-xSexPutting the mixed powder with equal molar ratio into a mould, wherein x is more than or equal to 0.1 and less than or equal to 0.9, putting the mixed powder into a plasma activation sintering furnace, then simultaneously starting uniform-speed rising and uniform-speed rising, simultaneously rising to the temperature of 400-550 ℃ and the pressure of 30-100 MPa, keeping the temperature and the pressure for 3-20 min, simultaneously starting uniform-speed cooling and uniform-speed lowering, and simultaneously lowering to the normal temperature and the normal pressure;
and step four, taking out the sintered mold, and demolding to obtain the n-type bismuth telluride-based thermoelectric material with the modulated structure.
The further improvement lies in that: and in the second step, the ball milling tank equipment is a high-energy planetary ball mill, the mass ratio of balls to materials is (10-30) to 1, and the rotating speed of the high-energy planetary ball mill is 100-600 r/min.
The further improvement lies in that: in the third step, the rate of constant temperature rise is 10-100 ℃/min, and the rate of constant temperature drop is 10-50 ℃/min.
The further improvement lies in that: the first step is to prepare the n-type Bi2Te3And Bi2Te3-xSexThe powder is weighed and mixed according to an equal molar ratio, wherein x is more than or equal to 0.1 and less than or equal to 0.9.
The invention has the beneficial effects that:
1. the invention uses n-type Bi2Te3And Bi2Te3-xSexThe powder is used as a raw material, wherein x is more than or equal to 0.1 and less than or equal to 0.9, mechanical alloying and plasma activation sintering processes are adopted, and ball milling is carried out for 1-12 hours to obtain n-type Bi2Te3And Bi2Te3-xSexPreparing mixed powder in an equal molar ratio; the shortest plasma activation sintering time only needs 18min, namely the n-type bismuth telluride-based thermoelectric material with the modulation structure can be quickly prepared in a shorter time, and the relative density of the n-type bismuth telluride-based thermoelectric material with the modulation structure exceeds 97 percent, so that the preparation method has the characteristics of simple process, short production period, high production efficiency, high product purity and high density;
2. the n-type bismuth telluride-based thermoelectric material with the modulated structure, which is prepared by combining mechanical alloying with a plasma activated sintering technology, has fine and flaky crystal grains, can form dispersed nano-phases and can effectively reduce the thermal conductivity of the thermoelectric material;
3. the n-type bismuth telluride-based thermoelectric material prepared by the invention has a modulation structure, namely a modulation mixed structure of a high carrier concentration and ground mobility sample and a low carrier concentration and high mobility sample, and the structure enables the sample to have relatively high carrier concentration, and simultaneously integrates high mobility due to the fact that carriers tend to migrate to a high mobility region, and can maintain relatively high mobility while maintaining relatively high carrier concentration.
In conclusion, the method has the characteristics of simple process, short production period and high production efficiency, and the prepared n-type bismuth telluride-based thermoelectric material with the modulation structure has high purity, low thermal conductivity and high electrical conductivity, has the modulation structure and can synergistically improve the carrier concentration and the mobility.
Drawings
FIG. 1 is a schematic diagram of a modulation scheme according to the present invention.
Detailed Description
In order to further understand the present invention, the following detailed description will be made with reference to the following examples, which are only used for explaining the present invention and are not to be construed as limiting the scope of the present invention.
According to fig. 1, the present embodiment provides an n-type bismuth telluride-based thermoelectric material of a modulation structure, wherein the materials involved are collectively described as follows:
the Bi2Te3The purity of the powder is more than or equal to 99.99 wt%, and Bi2Te3The grain diameter of the powder is less than or equal to 500 mu m, and the Bi2Te3-xSexThe purity of the powder is more than or equal to 99.99 wt%, and Bi2Te3-xSexThe particle size of the powder is less than or equal to 500 mu m, wherein x is more than or equal to 0.1 and less than or equal to 0.9.
Example 1
Comprises the component of n-type Bi2Te3And Bi2Te3-xSexThe powder is mixed according to the equal molar ratio, wherein x is more than or equal to 0.1 and less than or equal to 0.9, and the internal structure of the n-type bismuth telluride based thermoelectric material crystal atom of the modulation structure is the modulation structure.
The preparation method comprises the following steps: step one, according to n type Bi2Te3And Bi2Te3-xSexThe mass ratio of the materials is 1: 1, wherein x is more than or equal to 0.1 and less than or equal to 0.9, and then the materials are uniformly mixed to obtain mixed powder;
step two, putting the mixed powder into a ball milling tank, and carrying out ball milling for 1-12 h under the inert atmosphere condition to prepare n-type Bi2Te3And Bi2Te3-xSexMixing the powder in an equal molar ratio, wherein x is more than or equal to 0.1 and less than or equal to 0.9;
step three, mixing the n-type Bi2Te3And Bi2Te3-xSexPutting the mixed powder with equal molar ratio into a mould, wherein x is more than or equal to 0.1 and less than or equal to 0.9, putting the mixed powder into a plasma activation sintering furnace, then simultaneously starting uniform-speed rising and uniform-speed rising, simultaneously rising to the temperature of 400-550 ℃ and the pressure of 30-100 MPa, keeping the temperature and the pressure for 3-20 min, simultaneously starting uniform-speed cooling and uniform-speed lowering, and simultaneously lowering to the normal temperature and the normal pressure;
and step four, taking out the sintered mold, and demolding to obtain the n-type bismuth telluride-based thermoelectric material with the modulated structure.
The ball milling equipment is a high-energy planetary ball mill, the mass ratio of balls to materials is (10-30) to 1, and the rotating speed of the high-energy planetary ball mill is 100-600 r/min.
The speed of constant temperature rise is 10-100 ℃/min; the speed of uniform cooling is 10-50 ℃/min;
the first step is to prepare the n-type Bi2Te3And Bi2Te3-xSexThe powder is weighed and mixed according to an equal molar ratio, wherein x is more than or equal to 0.1 and less than or equal to 0.9.
The n-type bismuth telluride-based thermoelectric material prepared by the embodiment has high purity, low thermal conductivity and high electrical conductivity, has a modulation structure, and can synergistically improve the carrier concentration and the mobility.
Example 2
Comprises the component of n-type Bi2Te3And Bi2Te3-xSexThe powder is mixed according to the equal molar ratio, wherein x is more than or equal to 0.1 and less than or equal to 0.4, and the internal structure of the n-type bismuth telluride based thermoelectric material crystal atom of the modulation structure is the modulation structure.
The preparation method comprises the following steps: step one, according to n type Bi2Te3And Bi2Te3-xSexThe mass ratio of the materials is 1: 1, wherein x is more than or equal to 0.1 and less than or equal to 0.4, and then the materials are uniformly mixed to obtain mixed powder;
step two, putting the mixed powder into a ball milling tank, and carrying out ball milling for 1-6 h under the inert atmosphere condition to prepare n-type Bi2Te3And Bi2Te3-xSexMixing the powder in an equal molar ratio, wherein x is more than or equal to 0.1 and less than or equal to 0.4;
step three, mixing the n-type Bi2Te3And Bi2Te3-xSexPutting the mixed powder with equal molar ratio into a mould, wherein x is more than or equal to 0.1 and less than or equal to 0.4, putting the mixed powder into a plasma activation sintering furnace, then simultaneously starting uniform-speed rising and uniform-speed rising of pressure, simultaneously rising to the temperature of 400-500 ℃ and the pressure of 30-50 MPa, keeping the temperature and the pressure for 3-6 min, simultaneously starting uniform-speed lowering of pressure and uniform-speed lowering of pressure, and simultaneously lowering the pressureTo normal temperature and normal pressure;
and step four, taking out the sintered mold, and demolding to obtain the n-type bismuth telluride-based thermoelectric material with the modulated structure.
The ball milling equipment is a high-energy planetary ball mill, the mass ratio of balls to materials is (10-20) to 1, and the rotating speed of the high-energy planetary ball mill is 100-200 r/min.
The speed of constant temperature rise is 10-50 ℃/min; the speed of uniform cooling is 10-20 ℃/min;
the first step is to prepare the n-type Bi2Te3And Bi2Te3-xSexThe powder is weighed and mixed according to an equal molar ratio, wherein x is more than or equal to 0.1 and less than or equal to 0.4.
The n-type bismuth telluride-based thermoelectric material prepared by the embodiment has high purity, low thermal conductivity and high electrical conductivity, has a modulation structure, and can synergistically improve the carrier concentration and the mobility.
Example 3
Comprises the component of n-type Bi2Te3And Bi2Te3-xSexThe powder is mixed according to the equal molar ratio, wherein x is more than or equal to 0.2 and less than or equal to 0.5, and the internal structure of the n-type bismuth telluride based thermoelectric material crystal atom of the modulation structure is the modulation structure.
The preparation method comprises the following steps: step one, according to n type Bi2Te3And Bi2Te3-xSexThe mass ratio of the materials is 1: 1, wherein x is more than or equal to 0.2 and less than or equal to 0.5, and then the materials are uniformly mixed to obtain mixed powder;
step two, putting the mixed powder into a ball milling tank, and carrying out ball milling for 2-7 h under the inert atmosphere condition to prepare n-type Bi2Te3And Bi2Te3-xSexMixing the powder in an equal molar ratio, wherein x is more than or equal to 0.2 and less than or equal to 0.5;
step three, mixing the n-type Bi2Te3And Bi2Te3-xSexPutting the mixed powder with equal molar ratio into a mould, wherein x is more than or equal to 0.2 and less than or equal to 0.5, putting the mixed powder into a plasma activated sintering furnace, then simultaneously starting to raise the temperature and the pressure at constant speed, simultaneously raising the temperature to 410-510 ℃ and the pressure to 40-60 MPa, and keeping the temperature and the pressure for a whileThe temperature and the pressure are reduced at the same time to normal temperature and normal pressure within 5-9 min;
and step four, taking out the sintered mold, and demolding to obtain the n-type bismuth telluride-based thermoelectric material with the modulated structure.
The ball milling equipment is a high-energy planetary ball mill, the mass ratio of balls to materials is (20-30) to 1, and the rotating speed of the high-energy planetary ball mill is 200-300 r/min.
The speed of constant temperature rise is 20-60 ℃/min; the speed of uniform cooling is 15-30 ℃/min; the first step is to prepare the n-type Bi2Te3And Bi2Te3-xSexThe powder is weighed and mixed according to an equal molar ratio, wherein x is more than or equal to 0.2 and less than or equal to 0.5.
The n-type bismuth telluride-based thermoelectric material prepared by the embodiment has high purity, low thermal conductivity and high electrical conductivity, has a modulation structure, and can synergistically improve the carrier concentration and the mobility.
Example 4
Comprises the component of n-type Bi2Te3And Bi2Te3-xSexThe powder is mixed according to the equal molar ratio, wherein x is more than or equal to 0.3 and less than or equal to 0.6, and the internal structure of the n-type bismuth telluride based thermoelectric material crystal atom of the modulation structure is the modulation structure.
The preparation method comprises the following steps: step one, according to n type Bi2Te3And Bi2Te3-xSexThe mass ratio of the materials is 1: 1, wherein x is more than or equal to 0.3 and less than or equal to 0.6, and then the materials are uniformly mixed to obtain mixed powder;
step two, putting the mixed powder into a ball milling tank, and carrying out ball milling for 3-8 h under the inert atmosphere condition to prepare n-type Bi2Te3And Bi2Te3-xSexMixing the powder in an equal molar ratio, wherein x is more than or equal to 0.3 and less than or equal to 0.6;
step three, mixing the n-type Bi2Te3And Bi2Te3-xSexPutting the mixed powder with equal molar ratio into a mould, wherein x is more than or equal to 0.3 and less than or equal to 0.6, putting the mixed powder into a plasma activated sintering furnace, then simultaneously starting to heat at a constant speed and raise the pressure at a constant speed, and simultaneously raising the temperature to 420-520 ℃ and raising the pressure to 50-70 MPa, keeping the temperature and the pressure for 7-12 min, and then simultaneously starting uniform cooling and uniform cooling to normal temperature and normal pressure;
and step four, taking out the sintered mold, and demolding to obtain the n-type bismuth telluride-based thermoelectric material with the modulated structure.
The ball milling equipment is a high-energy planetary ball mill, the mass ratio of balls to materials is (10-20) to 1, and the rotating speed of the high-energy planetary ball mill is 300-400 r/min.
The rate of constant temperature rise is 30-70 ℃/min; the speed of uniform cooling is 20-40 ℃/min; the first step is to prepare the n-type Bi2Te3And Bi2Te3-xSexThe powder is weighed and mixed according to an equal molar ratio, wherein x is more than or equal to 0.3 and less than or equal to 0.6.
The n-type bismuth telluride-based thermoelectric material prepared by the embodiment has high purity, low thermal conductivity and high electrical conductivity, has a modulation structure, and can synergistically improve the carrier concentration and the mobility.
Example 5
Comprises the component of n-type Bi2Te3And Bi2Te3-xSexThe powder is mixed according to the equal molar ratio, wherein x is more than or equal to 0.4 and less than or equal to 0.7, and the internal structure of the n-type bismuth telluride based thermoelectric material crystal atom of the modulation structure is the modulation structure.
The preparation method comprises the following steps: step one, according to n type Bi2Te3And Bi2Te3-xSexThe mass ratio of the materials is 1: 1, wherein x is more than or equal to 0.4 and less than or equal to 0.7, and then the materials are uniformly mixed to obtain mixed powder;
step two, putting the mixed powder into a ball milling tank, and carrying out ball milling for 1-12 h under the inert atmosphere condition to prepare n-type Bi2Te3And Bi2Te3-xSexMixing the powder in an equal molar ratio, wherein x is more than or equal to 0.4 and less than or equal to 0.7;
step three, mixing the n-type Bi2Te3And Bi2Te3-xSexThe mixed powder with equal molar ratio is filled into a die, wherein x is more than or equal to 0.4 and less than or equal to 0.7, the mixed powder is placed in a plasma activated sintering furnace, then the uniform temperature rise and the uniform pressure rise are started simultaneously, and the mixed powder is heated to the temperature simultaneouslyThe temperature is 430-530 ℃, the pressure is increased to 60-80 MPa, the time for heat preservation and pressure maintaining is 9-15 min, and then the temperature and the pressure are reduced at the same time and reduced to normal temperature and normal pressure;
and step four, taking out the sintered mold, and demolding to obtain the n-type bismuth telluride-based thermoelectric material with the modulated structure.
The ball milling equipment is a high-energy planetary ball mill, the mass ratio of balls to materials is (20-30) to 1, and the rotating speed of the high-energy planetary ball mill is 400-500 r/min.
The speed of constant temperature rise is 40-80 ℃/min; the speed of uniform cooling is 25-50 ℃/min; the first step is to prepare the n-type Bi2Te3And Bi2Te3-xSexThe powder is weighed and mixed according to an equal molar ratio, wherein x is more than or equal to 0.4 and less than or equal to 0.7.
The n-type bismuth telluride-based thermoelectric material prepared by the embodiment has high purity, low thermal conductivity and high electrical conductivity, has a modulation structure, and can synergistically improve the carrier concentration and the mobility.
Example 6
Comprises the component of n-type Bi2Te3And Bi2Te3-xSexThe powder is mixed according to the equal molar ratio, wherein x is more than or equal to 0.5 and less than or equal to 0.8, and the internal structure of the n-type bismuth telluride based thermoelectric material crystal atom of the modulation structure is the modulation structure.
The preparation method comprises the following steps: step one, according to n type Bi2Te3And Bi2Te3-xSexThe mass ratio of the materials is 1: 1, wherein x is more than or equal to 0.5 and less than or equal to 0.8, and then the materials are uniformly mixed to obtain mixed powder;
step two, putting the mixed powder into a ball milling tank, and carrying out ball milling for 1-12 h under the inert atmosphere condition to prepare n-type Bi2Te3And Bi2Te3-xSexMixing the powder in an equal molar ratio, wherein x is more than or equal to 0.5 and less than or equal to 0.8;
step three, mixing the n-type Bi2Te3And Bi2Te3-xSexThe mixed powder with equal molar ratio is put into a mould, wherein x is more than or equal to 0.5 and less than or equal to 0.8, the mixed powder is placed in a plasma activated sintering furnace, and then the mixed powder starts to rise at a constant speed simultaneouslyIncreasing the pressure at a constant speed, increasing the temperature to 440-540 ℃ and the pressure to 70-90 MPa at the same time, keeping the temperature and the pressure for 11-18 min, and then simultaneously starting uniform cooling and uniform cooling, and reducing the temperature to normal temperature and normal pressure;
and step four, taking out the sintered mold, and demolding to obtain the n-type bismuth telluride-based thermoelectric material with the modulated structure.
The ball milling equipment is a high-energy planetary ball mill, the mass ratio of balls to materials is (10-20) to 1, and the rotating speed of the high-energy planetary ball mill is 500-600 r/min.
The speed of constant temperature rise is 50-90 ℃/min; the speed of uniform cooling is 25-50 ℃/min; the first step is to prepare the n-type Bi2Te3And Bi2Te3-xSexThe powder is weighed and mixed according to an equal molar ratio, wherein x is more than or equal to 0.5 and less than or equal to 0.8.
The n-type bismuth telluride-based thermoelectric material prepared by the embodiment has high purity, low thermal conductivity and high electrical conductivity, has a modulation structure, and can synergistically improve the carrier concentration and the mobility.
Example 7
Comprises the component of n-type Bi2Te3And Bi2Te3-xSexThe powder is mixed according to the equal molar ratio, wherein x is more than or equal to 0.6 and less than or equal to 0.9, and the internal structure of the n-type bismuth telluride based thermoelectric material crystal atom of the modulation structure is the modulation structure.
The preparation method comprises the following steps: step one, according to n type Bi2Te3And Bi2Te3-xSexThe mass ratio of the materials is 1: 1, wherein x is more than or equal to 0.6 and less than or equal to 0.9, and then the materials are uniformly mixed to obtain mixed powder;
step two, putting the mixed powder into a ball milling tank, and carrying out ball milling for 1-12 h under the inert atmosphere condition to prepare n-type Bi2Te3And Bi2Te3-xSexMixing the powder in an equal molar ratio, wherein x is more than or equal to 0.6 and less than or equal to 0.9;
step three, mixing the n-type Bi2Te3And Bi2Te3-xSexThe mixed powder with equal molar ratio is put into a mould, wherein x is more than or equal to 0.6 and less than or equal to 0.9, and the mould is placed in plasma for activation and sinteringAfter the furnace is finished, simultaneously starting constant-speed rising and constant-speed rising, simultaneously rising to the temperature of 450-550 ℃ and rising to the pressure of 80-100 MPa, keeping the temperature and the pressure for 13-20 min, simultaneously starting constant-speed cooling and constant-speed lowering, and simultaneously lowering to normal temperature and normal pressure;
and step four, taking out the sintered mold, and demolding to obtain the n-type bismuth telluride-based thermoelectric material with the modulated structure.
The ball milling equipment is a high-energy planetary ball mill, the mass ratio of balls to materials is (20-30) to 1, and the rotating speed of the high-energy planetary ball mill is 200-300 r/min.
The speed of constant temperature rise is 60-100 ℃/min; the speed of uniform cooling is 25-50 ℃/min; the first step is to prepare the n-type Bi2Te3And Bi2Te3-xSexThe powder is weighed and mixed according to an equal molar ratio, wherein x is more than or equal to 0.6 and less than or equal to 0.9.
The n-type bismuth telluride-based thermoelectric material prepared by the embodiment has high purity, low thermal conductivity and high electrical conductivity, has a modulation structure, and can synergistically improve the carrier concentration and the mobility.
Compared with the prior art, the invention has the following positive effects according to the embodiments 1-7:
1. the invention uses n-type Bi2Te3And Bi2Te3-xSexThe powder is used as a raw material, wherein x is more than or equal to 0.1 and less than or equal to 0.9, mechanical alloying and plasma activation sintering processes are adopted, and ball milling is carried out for 1-12 hours to obtain n-type Bi2Te3And Bi2Te3-xSexPreparing mixed powder in an equal molar ratio; the shortest plasma activation sintering time only needs 18min, namely the n-type bismuth telluride-based thermoelectric material with the modulation structure can be quickly prepared in a shorter time, and the relative density of the n-type bismuth telluride-based thermoelectric material with the modulation structure exceeds 97 percent, so that the preparation method has the characteristics of simple process, short production period, high production efficiency, high product purity and high density;
2. the n-type bismuth telluride-based thermoelectric material with the modulated structure, which is prepared by combining mechanical alloying with a plasma activated sintering technology, has fine and flaky crystal grains, can form dispersed nano-phases and can effectively reduce the thermal conductivity of the thermoelectric material;
3. the n-type bismuth telluride-based thermoelectric material prepared by the invention has a modulation structure, namely a modulation mixed structure of a high carrier concentration and ground mobility sample and a low carrier concentration and high mobility sample, and the structure enables the sample to have relatively high carrier concentration, and simultaneously integrates high mobility due to the fact that carriers tend to migrate to a high mobility region, and can maintain relatively high mobility while maintaining relatively high carrier concentration.
In conclusion, the method has the characteristics of simple process, short production period and high production efficiency, and the prepared n-type bismuth telluride-based thermoelectric material with the modulation structure has high purity, low thermal conductivity and high electrical conductivity, has the modulation structure and can synergistically improve the carrier concentration and the mobility.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. An n-type bismuth telluride-based thermoelectric material of a modulation structure is characterized in that: comprises the component of n-type Bi2Te3And Bi2Te3-xSexThe powder is mixed according to the equal molar ratio, wherein x is more than or equal to 0.1 and less than or equal to 0.9, and the internal structure of the n-type bismuth telluride based thermoelectric material crystal atom of the modulation structure is the modulation structure.
2. The n-type bismuth telluride-based thermoelectric material of a modulation structure as set forth in claim 1, wherein: the Bi2Te3The purity of the powder is more than or equal to 99.99 wt%, and Bi2Te3The grain diameter of the powder is less than or equal to 500 mu m; the Bi2Te3-xSexThe purity of the powder is more than or equal to 99.99 wt%, and Bi2Te3-xSexThe particle size of the powder is less than or equal to 500 mu m, wherein x is more than or equal to 0.1 and less than or equal to 0.9.
3. The method for preparing an n-type bismuth telluride-based thermoelectric material with a modulation structure as claimed in claim 1, comprising the steps of:
the method comprises the following steps: according to n-type Bi2Te3And Bi2Te3-xSexThe mass ratio of the materials is 1: 1, wherein x is more than or equal to 0.1 and less than or equal to 0.9, and then the materials are uniformly mixed to obtain mixed powder;
step two: putting the mixed powder into a ball milling tank, and carrying out ball milling for 1-12 h under the inert atmosphere condition to prepare n-type Bi2Te3And Bi2Te3-xSexMixing the powder in an equal molar ratio, wherein x is more than or equal to 0.1 and less than or equal to 0.9;
step three: the n-type Bi2Te3And Bi2Te3-xSexPutting the mixed powder with equal molar ratio into a mould, wherein x is more than or equal to 0.1 and less than or equal to 0.9, putting the mixed powder into a plasma activation sintering furnace, then simultaneously starting uniform-speed rising and uniform-speed rising, simultaneously rising to the temperature of 400-550 ℃ and the pressure of 30-100 MPa, keeping the temperature and the pressure for 3-20 min, simultaneously starting uniform-speed cooling and uniform-speed lowering, and simultaneously lowering to the normal temperature and the normal pressure;
step four: and taking out the sintered mold, and demolding to obtain the n-type bismuth telluride-based thermoelectric material with the modulated structure.
4. The method for preparing an n-type bismuth telluride-based thermoelectric material having a modulation structure as claimed in claim 3, wherein: and in the second step, the ball milling tank equipment is a high-energy planetary ball mill, the mass ratio of balls to materials is (10-30) to 1, and the rotating speed of the high-energy planetary ball mill is 100-600 r/min.
5. The method for preparing an n-type bismuth telluride-based thermoelectric material having a modulation structure as claimed in claim 3, wherein: in the third step, the rate of constant temperature rise is 10-100 ℃/min, and the rate of constant temperature drop is 10-50 ℃/min.
6. The method for preparing an n-type bismuth telluride-based thermoelectric material having a modulation structure as claimed in claim 3, wherein: the first step is to prepare the n-type Bi2Te3And Bi2Te3-xSexThe powder is weighed and mixed according to an equal molar ratio, wherein x is more than or equal to 0.1 and less than or equal to 0.9.
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| CN113314660A (en) * | 2021-07-30 | 2021-08-27 | 深圳见炬科技有限公司 | Method for synthesizing porous thermoelectric material based on melting centrifugation and porous thermoelectric material |
| WO2021204162A1 (en) * | 2020-04-08 | 2021-10-14 | 深圳见炬科技有限公司 | N-type bismuth telluride-based thermoelectric material having modulation structure, and preparation method therefor |
| CN115216846A (en) * | 2022-05-26 | 2022-10-21 | 杭州大和热磁电子有限公司 | P-type bismuth telluride alloy material, preparation method and application thereof |
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| CN114561706A (en) * | 2021-12-16 | 2022-05-31 | 杭州大和热磁电子有限公司 | Method for recycling bismuth telluride crystal bar processing waste and utilization method thereof |
| CN114890792B (en) * | 2022-05-31 | 2023-07-28 | 先导薄膜材料（广东）有限公司 | High-thermoelectric-performance p-type bismuth telluride-based thermoelectric material, and preparation method and application thereof |
| CN115305567B (en) * | 2022-08-05 | 2024-02-13 | 中国电子科技集团公司第十八研究所 | Method for improving performance uniformity of hot extrusion N-type bismuth telluride |
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