CN116281881A - Bismuth telluride-based thermoelectric material, preparation method and application thereof - Google Patents
Bismuth telluride-based thermoelectric material, preparation method and application thereof Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 142
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 142
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 142
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Abstract
The invention discloses a bismuth telluride-based thermoelectric material, a preparation method and application thereof, wherein the bismuth telluride-based thermoelectric material has the following general formula: ag (silver) 0.01 Bi 2 Te 2.7 Se 0.3 ‑xMoSe 2 Wherein 0 is<x is less than or equal to 4wt percent, and the bismuth telluride-based thermoelectric material has excellent mechanical property and thermoelectric property. The bismuth telluride-based thermoelectric material is obtained through high-temperature melting, sintering and texturing treatment of an Ag source, a Mo source, a Se source, a Te source and a Bi source, wherein the doping of Ag can effectively improve the concentration of carriers, and further improve the electrical performance of the bismuth telluride-based thermoelectric material; mo and Se in situ growthFormed MoSe 2 The nanometer second phase forms a phonon scattering center, improves the mobility of carriers, and reduces the lattice heat conductivity, so that the coupling relation between the electric transport property and the heat conduction is decoupled, and the thermoelectric property of the bismuth telluride-based thermoelectric material is cooperatively improved.
Description
Technical Field
The invention belongs to the technical field of energy materials, and relates to a bismuth telluride-based thermoelectric material, a preparation method and application thereof.
Background
Currently, from the world conditions of energy use and development, primary energy sources such as petroleum energy and coal are in front of exhaustion risk, and optimization of energy structure and environmental protection are important problems facing human beings. Therefore, importance is placed on the use of renewable energy sources, and optimizing the use efficiency of non-renewable energy sources becomes a main direction of world energy development; the thermoelectric material is a new energy material with high reliability, environmental protection and simple structure, and has wide application in waste heat recovery and refrigeration.
Bismuth telluride-based thermoelectric materials are the only thermoelectric materials currently in commercial use, and are also thermoelectric materials which are relatively mature in industrialization, and the performance of the bismuth telluride-based thermoelectric materials directly determines preheating recovery efficiency and refrigeration efficiency. Therefore, optimizing the performance of bismuth telluride-based thermoelectric materials is imperative.
The most important index for evaluating thermoelectric materials is thermoelectric non-dimensional thermoelectric figure of merit (ZT), which is the only standard for determining the power generation efficiency of thermoelectric power generation devices and the refrigerating capacity of refrigerating devices, and therefore, increasing the ZT value of thermoelectric materials in the range of device use is the only way to increase their conversion efficiency and refrigerating efficiency.
From an evaluation of thermoelectric dimensionless thermoelectric figure of merit (ZT), zt=s 2 Sigma T/kappa, wherein: s is the seebeck coefficient, σ is the electrical conductivity and κ is the thermal conductivity, and T is the temperature, and it is known that the properties of the material are mainly related to the electrical conductivity σ, the seebeck coefficient S and the thermal conductivity κ, and to improve the quality factor of the bismuth telluride-based thermoelectric material, it is necessary to improve the coupling relationship among the seebeck coefficient, the electrical conductivity and the thermal conductivity, that is, to improve the seebeck coefficient and the electrical conductivity, and to reduce the thermal conductivity at the same time. The current industrialized bismuth telluride-based thermoelectric material has a room temperature ZT value of about 1 due to over high heat conductivity, especially the n-type bismuth telluride-based thermoelectric material has the defects of low ZT value, low carrier and carrier mobility and poor mechanical property。
In view of the above, there is a need in the present invention to develop an n-type bismuth telluride-based thermoelectric material having excellent mechanical properties and being commercially strong.
Disclosure of Invention
In order to overcome the above problems, the present inventors have made intensive studies to develop a bismuth telluride-based thermoelectric material having the following general formula: ag (silver) 0.01 Bi 2 Te 2.7 Se 0.3 -xMoSe 2 Wherein 0 is<x is less than or equal to 4wt percent, and the bismuth telluride-based thermoelectric material has excellent mechanical property and thermoelectric property. Is obtained by high-temperature melting, sintering and texturing of Ag source, mo source, se source, te source and Bi source, wherein Mo and Se generate MoSe in the melting process 2 And uniformly distributed and grown in the matrix phase. Due to MoSe 2 The layered structure of the (2) can uniformly grow in the bismuth telluride matrix layered structure, so that a large amount of scattering can be caused in the carrier and phonon migration process, the Seebeck coefficient of the material is enhanced, and the lattice thermal conductivity is reduced. However, the conductivity is reduced due to the reduction of the carrier mobility, so that the heterojunction structure is adopted on the basis of Ag doping, high conductivity, seebeck coefficient and low thermal conductivity can be ensured, the decoupling purpose between the electric transport property and the thermal transport property is achieved, and the thermoelectric property of the bismuth telluride-based thermoelectric material can be improved, so that the invention is completed.
In particular, it is an object of the present invention to provide the following aspects:
in a first aspect, a bismuth telluride-based thermoelectric material is an n-type bismuth telluride-based material having the chemical formula Ag 0.01 Bi 2 Te 2.7 Se 0.3 -xMoSe 2 Wherein 0 is<x≤4wt％。
In a second aspect, a method for preparing a bismuth telluride-based thermoelectric material, the method comprising:
step 1, melting an Ag source, a Mo source, a Se source, a Te source and a Bi source at high temperature to prepare a bismuth telluride-based cast ingot;
step 2, sintering the bismuth telluride-based cast ingot to obtain an n-type bismuth telluride bulk material;
and 3, texturing the n-type bismuth telluride bulk material to obtain the bismuth telluride-based thermoelectric material.
In step 1, according to Ag 0.01 Bi 2 Te 2.7 Se 0.3 -xMoSe 2 ，0<And weighing an Ag source, a Mo source, a Se source, a Te source and a Bi source, wherein x is less than or equal to 4 wt%.
Wherein the Ag source is an Ag simple substance, the Mo source is an Mo simple substance, the Se source is an Se simple substance, the Te source is a Te simple substance, and the Bi source is a Bi simple substance.
In the step 1, the high-temperature melting temperature is 600-1000 ℃, preferably 700-900 ℃; the time is 3 to 10 hours, preferably 5 to 9 hours.
In step 2, the sintering comprises: heating to 300-410 ℃ when the vacuum degree is less than 10Pa, then adjusting the sintering pressure to 20-60 MPa, heating to 420-510 ℃, and preserving heat and pressure for 3-12 min.
In the step 2, before sintering, ball milling is carried out on the bismuth telluride-based cast ingot.
Wherein the rotation speed of the ball milling is 800-1300 rpm/min, preferably 900-1200 rpm/min, and the time is 30-300 min, preferably 50-200 min.
In step 3, the texturing comprises: heating to 300-410 ℃ when the vacuum degree is less than 10Pa, then adjusting the sintering pressure to 18-55 MPa, heating to 520-580 ℃, and preserving heat and pressure for 3-12 min.
In a third aspect, the bismuth telluride-based thermoelectric material according to the first aspect or the bismuth telluride-based thermoelectric material according to the second aspect is used in thermoelectric devices or refrigeration devices.
The invention has the beneficial effects that:
(1) The bismuth telluride-based thermoelectric material provided by the invention is a polycrystalline n-type bismuth telluride-based thermoelectric material, has excellent mechanical properties, and has a ZT value of up to 1.28 at 375K and a Vickers hardness of up to 1.2GPa.
(2) The preparation method of bismuth telluride-based thermoelectric material provided by the invention uses MoSe 2 Nano second phase structure, and Ag 0.01 Bi 2 Te 2.7 Se 2 The thermoelectric performance of the matrix bismuth telluride thermoelectric material is improved by more than 23% compared with the matrix bismuth telluride thermoelectric material.
(3) According to the preparation method of the bismuth telluride-based thermoelectric material, the concentration of carriers can be effectively improved by doping Ag, so that the electrical performance of the bismuth telluride-based thermoelectric material is improved; mo and Se in situ generation and Bi 2 Te 3 Two-dimensional material MoSe with same base material structure 2 The nanometer second phase forms a phonon scattering center, improves the mobility of carriers and reduces the lattice heat conductivity, so that the coupling relation between the electric transport property and the heat conduction is decoupled, and the thermoelectric property of the bismuth telluride-based thermoelectric material is cooperatively improved.
(4) The preparation method of the bismuth telluride-based thermoelectric material adopts secondary hot pressing and MoSe 2 The texturing of the n-type bismuth telluride-based thermoelectric material is enhanced, so that crystal grains obviously grow along the performance dominant direction, the preferred orientation degree of the material is effectively improved, and the carrier mobility is enhanced.
Drawings
Various other advantages and benefits of the present invention will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. It is evident that the figures described below are only some embodiments of the invention, from which other figures can be obtained without inventive effort for a person skilled in the art.
In the drawings:
FIG. 1 shows a graph of the sigma-T curve comparison in experimental example 1;
FIG. 2 shows a comparison of S-T curves in experimental example 1;
FIG. 3 shows a graph of kappa-T curve comparison in experimental example 1;
fig. 4 shows a ZT-T curve comparison diagram in experimental example 1.
Detailed Description
Specific embodiments of the present invention will be described in more detail below with reference to fig. 1 to 4. While specific embodiments of the invention are shown in the drawings, it should be understood that the invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
It should be noted that certain terms are used throughout the description and claims to refer to particular components. Those of skill in the art will understand that a person may refer to the same component by different names. The description and claims do not identify differences in terms of components, but rather differences in terms of the functionality of the components. As used throughout the specification and claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. The description hereinafter sets forth a preferred embodiment for practicing the invention, but is not intended to limit the scope of the invention, as the description proceeds with reference to the general principles of the description. The scope of the invention is defined by the appended claims.
For the purpose of facilitating an understanding of the embodiments of the present invention, reference will now be made to the drawings, by way of example, and specific examples of which are illustrated in the accompanying drawings.
In a first aspect, the present invention is directed to a bismuth telluride-based thermoelectric material, the bismuth telluride-based thermoelectric material being an n-type bismuth telluride-based material having the chemical formula Ag 0.01 Bi 2 Te 2.7 Se 0.3 -xMoSe 2 Wherein 0 is<x.ltoreq.4% by weight, preferably 1.ltoreq.x.ltoreq.3% by weight, more preferably x is 2% by weight.
The present inventors have found that MoSe formed in situ from Se and Mo 2 The mobility of the carrier of the bismuth telluride-based thermoelectric material can be improved, and the lattice thermal conductivity can be reduced. While the addition amount of Se is more sensitive to the Seebeck coefficient, the electric conductivity and the heat conductivity of the bismuth telluride-based thermoelectric material, namely the influence of thermoelectric dimensionless thermoelectric figure of merit (ZT). With the increase of the x value, the ZT value of the bismuth telluride-based thermoelectric material tends to increase and decrease firstly, when 0<When x is less than or equal to 4wt%, the ZT value of the bismuth telluride-based thermoelectric material reaches more than 1 at normal temperature, and when x is 2wt%, the ZT value of the bismuth telluride-based thermoelectric material can reach as high as 1.28; the doping of Ag can be used for constructing a heterojunction, so that the concentration of carriers is effectively improved, the electrical performance of the bismuth telluride-based thermoelectric material is further improved, and the bismuth telluride-based thermoelectric material cooperatively improve the thermoelectric performance.
In a second aspect, the present invention aims to provide a method for preparing the bismuth telluride-based thermoelectric material of the first aspect, the method comprising:
and step 1, melting an Ag source, a Mo source, a Se source, a Te source and a Bi source at high temperature to prepare the bismuth telluride-based cast ingot.
Wherein the Ag source is an Ag simple substance, the Mo source is an Mo simple substance, the Se source is an Se simple substance, the Te source is a Te simple substance, and the Bi source is a Bi simple substance.
Further, according to Ag 0.01 Bi 2 Te 2.7 Se 0.3 -xMoSe 2 Weighing an Ag source, a Mo source, a Se source, a Te source and a Bi source, wherein the weight ratio of the Ag source to the Mo source is 0<x.ltoreq.4% by weight, preferably 1.ltoreq.x.ltoreq.3% by weight, more preferably x is 2% by weight.
According to the invention, the doping of Ag can effectively improve the concentration of carriers, so as to improve the electrical performance of the bismuth telluride-based thermoelectric material; se and Mo are expressed as MoSe in the bismuth telluride-based thermoelectric material 2 The nanometer second phase structure exists, a phonon scattering center is formed, mobility of carriers is improved, lattice heat conductivity is reduced, coupling relation between electric transport performance and heat conduction is decoupled, thermoelectric performance is improved, interaction of the two is improved, and thermoelectric performance of the bismuth telluride-based thermoelectric material is cooperatively improved.
In step 1, preferably, an Ag source, a Mo source, a Se source, a Te source, and a Bi source are filled in the quartz tube in order of melting point from low to high, and the tube is sealed under vacuum, and then melted under a high temperature environment.
Wherein, ag source, mo source, se source, te source and Bi source are filled into the quartz tube in order from low melting point to high melting point, so that the non-uniformity of components caused by volatilization of materials with lower melting point in the tube sealing process can be reduced.
Wherein the vacuum condition can avoid the defects of low yield caused by oxidation of raw materials, and the vacuum degree is lower than that of<10 -2 Pa is preferred.
Further, the high temperature melting temperature is 600 to 1000 ℃, preferably 700 to 900 ℃, more preferably 800 ℃; the time is 3 to 10 hours, preferably 5 to 9 hours, more preferably 8 hours.
According to the present invention, the reactant can be melted at a high temperature in a short time. However, the temperature is too low or too high, so that the resistance value of the prepared bismuth telluride-based thermoelectric material is low, and the thermoelectric performance is deteriorated; extending the high temperature melting time can allow the reacted materials to be fully alloyed and/or uniformly mixed, slightly improving the thermoelectric properties of bismuth telluride-based thermoelectric materials, but excessive time is not necessary. Therefore, the high temperature melting process parameters need to be tightly controlled. The properties of the finally prepared bismuth telluride-based thermoelectric material are excellent in the above-mentioned parameter range of high-temperature melting.
In the present invention, in order to achieve sufficient reaction, the mixing operation is performed once at intervals of 30 to 200 minutes, preferably at intervals of 60 minutes, for example, at intervals of 30 minutes, when melting at high temperature.
And step 2, sintering the bismuth telluride-based cast ingot to obtain an n-type bismuth telluride bulk material.
In the step 2, before sintering, ball milling is carried out on the bismuth telluride-based cast ingot, and an ultrafine ball milling mixed material is obtained. The rotation speed of the ball milling is 800-1300 rpm/min, preferably 900-1200 rpm/min, such as 1200rpm/min; the time is 30 to 300min, preferably 50 to 200min, for example 50min.
Wherein, the ball milling has remarkable refining effect on bismuth telluride-based cast ingots, and the refining can effectively regulate and control the performance of the bismuth telluride-based cast ingots. The ball milling rotation speed is increased, and the ball milling time is prolonged similarly, so that the ball milling energy is increased, and the performance of bismuth telluride-based cast ingots is influenced. When the ball milling rotating speed is too high, the collision and extrusion of ball milling medium to ball milling materials can be greatly weakened, and the size of bismuth telluride-based cast ingots is not beneficial to regulation and control; the size of the bismuth telluride-based cast ingot gradually decreases and becomes more and more uniform along with the extension of the ball milling time. However, the research shows that the excessively long ball milling time can cause the increase of the number of grain boundaries in the bismuth telluride-based cast ingot, enhance the scattering of carriers, and further cause the increase of resistivity and the decrease of conductivity.
Further, after ball milling, the powder obtained by ball milling is subjected to 120-320 meshes, preferably 200-320 meshes, so as to ensure the size uniformity of the finally prepared bismuth telluride-based thermoelectric material, and further improve the performance of the bismuth telluride-based thermoelectric material, for example, an ultrasonic sieving machine is selected for sieving.
In step 2, the sintering comprises: heating to 300-410 ℃ when the vacuum degree is less than 10Pa, then adjusting the sintering pressure to 20-60 MPa, heating to 420-510 ℃, and preserving heat and pressure for 3-12 min.
According to the invention, the sintering is carried out in a gradual heating mode, so that gas can be discharged in the powder densification process, and the density of the n-type bismuth telluride bulk material obtained by sintering is reduced.
Further, in the sintering process, if the temperature is lower than 420 ℃, the material cannot be sufficiently sintered, so that the density is insufficient, crystal grains cannot be sufficiently grown and are uneven in size, and meanwhile, gaps remain in the prepared bismuth telluride-based thermoelectric material, so that the thermoelectric performance of the sintered material is affected.
In a further preferred embodiment, the sintering comprises: heating to 350-400 ℃ when the vacuum degree is less than 10Pa, then adjusting the sintering pressure to 30-50 MPa, heating to 450-500 ℃, and preserving heat and pressure for 5-10 min.
In a still further preferred embodiment, the sintering comprises: heating to 400 ℃ when the vacuum degree is less than 10Pa, then adjusting the sintering pressure to 50MPa, heating to 500 ℃, and maintaining the temperature for 10min.
And 3, texturing the n-type bismuth telluride bulk material to obtain the bismuth telluride-based thermoelectric material.
In step 3, the texturing comprises: heating to 300-410 ℃ when the vacuum degree is less than 10Pa, then adjusting the sintering pressure to 18-55 MPa, heating to 520-580 ℃, and preserving heat and pressure for 3-12 min.
According to the invention, the crystal structure will directly influence the morphology of the grain growth, and also determine whether the prepared bismuth telluride-based thermoelectric material has anisotropy, because the bismuth telluride-based material (such as n-type Ag 0.01 Bi 2 Te 2.7 Se 2 ) The original crystal structure causes great anisotropy in crystal growth, and thus anisotropy in thermoelectric properties along and perpendicular to the crystal plane growth direction. The present inventors found that two-shot hot pressing and MoSe were used 2 The method is used for enhancing the texture, so that crystal grains of the bismuth telluride-based thermoelectric material obviously grow along the performance dominant direction, the preferred orientation degree of the bismuth telluride-based thermoelectric material is improved, the carrier mobility is enhanced, and the performance of the bismuth telluride-based thermoelectric material is obviously improved.
In a further preferred embodiment, the texturing comprises: heating to 350-400 ℃ when the vacuum degree is less than 10Pa, then adjusting the sintering pressure to 30-50 MPa, heating to 530-550 ℃, and preserving heat and pressure for 4-10 min.
In a still further preferred embodiment, the texturing comprises: heating to 400 ℃ when the vacuum degree is less than 10Pa, then adjusting the sintering pressure to 50MPa, heating to 550 ℃, and maintaining the temperature and pressure for 10min.
In the present invention, by MoSe 2 Nano second phase structure relative n type Ag 0.01 Bi 2 Te 2.7 Se 2 The matrix material is modified, wherein Ag doping can effectively regulate the concentration of carriers, and the electrical property of the material is improved; in situ generation of MoSe 2 The nanometer second phase forms a phonon scattering center, improves the mobility of carriers, reduces the lattice heat conductivity of the carriers, and therefore decouples the coupling relation between the electric transport property and the heat conduction, and cooperatively improves the thermoelectric property. As the prepared bismuth telluride-based thermoelectric material is a polycrystalline material, the mechanical properties can be improved. In particular, two-shot hot pressing and MoSe are used 2 The texture is enhanced, and the performance of the bismuth telluride-based thermoelectric material is further improved.
In a third aspect, the present invention aims to provide the bismuth telluride-based thermoelectric material according to the first aspect or the bismuth telluride-based thermoelectric material obtained by the preparation method of the bismuth telluride-based thermoelectric material according to the second aspect, and the application of the bismuth telluride-based thermoelectric material in a thermoelectric power generation device or a refrigeration device.
Examples
The invention is further described below by means of specific examples, which are however only exemplary and do not constitute any limitation on the scope of protection of the invention.
Example 1
According to stoichiometric ratio Ag 0.01 Bi 2 Te 2.7 Se 0.3 -2wt％MoSe 2 Sequentially weighing 0.1g of Ag simple substance, 0.0756g of Mo simple substance, 0.4257g of Se simple substance, 4.3823g of Te simple substance and 5.3164g of Bi simple substance, filling into a clean reaction quartz tube from low melting point to high melting point, and vacuum-filling<10 -2 Sealing a tube under the Pa condition, then placing the reaction quartz tube into a muffle furnace, heating to 800 ℃, preserving heat for 8 hours, shaking and mixing the reaction quartz tube every 30 minutes during the period, and then cooling to room temperature along with the muffle furnace to prepare a bismuth telluride-based cast ingot;
ball milling and crushing the prepared bismuth telluride-based cast ingot, wherein the ball milling speed is 1200rpm/min, the ball milling time is 50min, sieving through a 320-mesh sieve by an ultrasonic extension to obtain powder with the particle size distribution range of less than 52 mu m, putting the powder into a graphite mold with the diameter of 12.7mm, and sintering in a discharge plasma sintering furnace according to the following procedures: heating to 400 ℃ when the vacuum degree is less than 10Pa, then adjusting the pressure to 50MPa, heating to 500 ℃, preserving heat and pressure for 10min, then cooling to room temperature, and taking out the sample to obtain an n-type bismuth telluride bulk material;
the n-type bismuth telluride block material is placed into a graphite mold with the diameter of 15mm for texturing treatment according to the following procedures: at a vacuum degree<Heating to 400 ℃ at 10Pa, then adjusting sintering pressure to 50MPa, heating to 550 ℃, and maintaining the temperature and pressure for 10min to obtain the bismuth telluride-based thermoelectric material, wherein the chemical formula is as follows: ag (silver) 0.01 Bi 2 Te 2.7 Se 0.3 -2wt％MoSe 2 。
Measuring the Ag produced 0.01 Bi 2 Te 2.7 Se 0.3 -2wt％MoSe 2 ZT value at 375K of 1.28, vickers hardness reached1.2GPa。
Example 2
According to stoichiometric ratio Ag 0.01 Bi 2 Te 2.7 Se 0.3 -1wt％MoSe 2 Sequentially weighing 0.1g of Ag simple substance, 0.0037g of Mo simple substance, 0.3075g of Se simple substance, 4.3822g of Te simple substance and 5.3146g of Bi simple substance, filling into a clean reaction quartz tube from low melting point to high melting point, and vacuum-filling<10 -2 Sealing a tube under the Pa condition, then placing the reaction quartz tube into a muffle furnace, heating to 700 ℃, preserving heat for 5 hours, shaking and mixing the reaction quartz tube every 60 minutes during the period, and then cooling to room temperature along with the muffle furnace to prepare a bismuth telluride-based cast ingot;
ball milling and crushing the prepared bismuth telluride-based cast ingot, wherein the ball milling speed is 800rpm/min, the ball milling time is 200min, sieving the bismuth telluride-based cast ingot with a 200-mesh sieve through an ultrasonic extension to obtain powder with the particle size distribution range of less than 40 mu m, putting the powder into a graphite mold with the diameter of 12.7mm, and sintering the powder in a discharge plasma sintering furnace according to the following procedures: heating to 350 ℃ when the vacuum degree is less than 10Pa, then adjusting the pressure to 30MPa, heating to 450 ℃, preserving heat and pressure for 5min, then cooling to room temperature, and taking out the sample to obtain an n-type bismuth telluride bulk material;
the n-type bismuth telluride block material is placed into a graphite mold with the diameter of 15mm for texturing treatment according to the following procedures: at a vacuum degree<Heating to 350 ℃ at 10Pa, then adjusting sintering pressure to 30MPa, heating to 550 ℃, and maintaining the temperature and pressure for 10min to obtain the bismuth telluride-based thermoelectric material, wherein the chemical formula is as follows: ag (silver) 0.01 Bi 2 Te 2.7 Se 0.3 -1wt％MoSe 2 。
Measuring the Ag produced 0.01 Bi 2 Te 2.7 Se 0.3 -1wt％MoSe 2 ZT at 375K was 1.02 with vickers hardness at 1GPa.
Example 3
According to stoichiometric ratio Ag 0.01 Bi 2 Te 2.7 Se 0.3 -3wt％MoSe 2 0.1g of Ag simple substance, 0.0113g of Mo simple substance, 0.3199g of Se simple substance, 4.3822g of Te simple substance and 5.3146g of Bi simple substance are weighed in sequence, and are filled into a clean reaction quartz tube from low to high according to the melting point,at a vacuum degree<10 -2 Sealing a tube under the Pa condition, then placing the reaction quartz tube into a muffle furnace, heating to 900 ℃, preserving heat for 5 hours, shaking and mixing the reaction quartz tube every 60 minutes during the period, and then cooling to room temperature along with the muffle furnace to prepare a bismuth telluride-based cast ingot;
ball milling and crushing the prepared bismuth telluride-based cast ingot, wherein the ball milling speed is 800rpm/min, the ball milling time is 200min, sieving the bismuth telluride-based cast ingot with a 200-mesh sieve through an ultrasonic extension to obtain powder with the particle size distribution range of less than 40 mu m, putting the powder into a graphite mold with the diameter of 12.7mm, and sintering the powder in a discharge plasma sintering furnace according to the following procedures: heating to 350 ℃ when the vacuum degree is less than 10Pa, then adjusting the pressure to 30MPa, heating to 480 ℃, preserving heat and pressure for 5min, then cooling to room temperature, and taking out the sample to obtain an n-type bismuth telluride bulk material;
the n-type bismuth telluride block material is placed into a graphite mold with the diameter of 15mm for texturing treatment according to the following procedures: at a vacuum degree<Heating to 350 ℃ at 10Pa, then adjusting sintering pressure to 40MPa, heating to 530 ℃, and maintaining the temperature and pressure for 5min to obtain the bismuth telluride-based thermoelectric material, wherein the chemical formula is as follows: ag (silver) 0.01 Bi 2 Te 2.7 Se 0.3 -3wt％MoSe 2 。
Measuring the Ag produced 0.01 Bi 2 Te 2.7 Se 0.3 -3wt％MoSe 2 The ZT value at 375K is 1.1 and the Vickers hardness is 1.1GPa.
Example 4
According to stoichiometric ratio Ag 0.01 Bi 2 Te 2.7 Se 0.3 -4wt％MoSe 2 Sequentially weighing 0.1g of Ag simple substance, 0.01511g of Mo simple substance, 0.3261g of Se simple substance, 4.3822g of Te simple substance and 5.3146g of Bi simple substance, filling into a clean reaction quartz tube from low melting point to high melting point, and vacuum-filling<10 -2 Sealing a tube under the Pa condition, then placing the reaction quartz tube into a muffle furnace, heating to 800 ℃, preserving heat for 7 hours, shaking and mixing the reaction quartz tube every 50 minutes during the period, and then cooling to room temperature along with the muffle furnace to prepare a bismuth telluride-based cast ingot;
ball milling and crushing the prepared bismuth telluride-based cast ingot, wherein the ball milling speed is 900rpm/min, the ball milling time is 100min, sieving with a 280-mesh sieve through an ultrasonic extension to obtain powder with the particle size distribution range of less than 60 mu m, putting the powder into a graphite mold with the diameter of 12.7mm, and sintering in a discharge plasma sintering furnace according to the following procedures: heating to 390 ℃ when the vacuum degree is less than 10Pa, then adjusting the pressure to 40MPa, heating to 490 ℃, preserving heat and pressure for 6min, then cooling to room temperature along with a muffle furnace, and taking out a sample to obtain an n-type bismuth telluride bulk material;
the n-type bismuth telluride block material is placed into a graphite mold with the diameter of 15mm for texturing treatment according to the following procedures: at a vacuum degree<Heating to 390 ℃ at 10Pa, then adjusting sintering pressure to 40MPa, heating to 540 ℃, and maintaining the temperature and pressure for 6min to obtain the bismuth telluride-based thermoelectric material, wherein the chemical formula is as follows: ag (silver) 0.01 Bi 2 Te 2.7 Se 0.3 -4wt％MoSe 2 。
Measuring the Ag produced 0.01 Bi 2 Te 2.7 Se 0.3 -4wt％MoSe 2 ZT value at 375K was 1.06 and vickers hardness was 1.3GPa.
Comparative example
Comparative example 1
According to stoichiometric ratio Ag 0.01 Bi 2 Te 2.7 Se 2 Sequentially weighing 0.1g of Ag simple substance, 0.3013g of Se simple substance, 4.3823g of Te simple substance and 5.3164g of Bi simple substance, filling into a clean reaction quartz tube from low melting point to high melting point, and vacuum-filling<10 -2 Sealing a tube under the Pa condition, then placing the reaction quartz tube into a muffle furnace, heating to 800 ℃, preserving heat for 8 hours, shaking and mixing the reaction quartz tube every 30 minutes during the period, and then cooling to room temperature along with the muffle furnace to prepare a bismuth telluride-based cast ingot;
ball milling and crushing the prepared bismuth telluride-based cast ingot, wherein the ball milling speed is 1200rpm/min, the ball milling time is 50min, sieving through a 320-mesh sieve by an ultrasonic extension to obtain powder with the particle size distribution range of less than 52 mu m, putting the powder into a graphite mold with the diameter of 12.7mm, and sintering in a discharge plasma sintering furnace according to the following procedures: heating to 400 ℃ when the pressure is less than 10Pa, then adjusting the pressure to 50MPa, heating to 500 ℃, preserving heat and pressure for 10min, then cooling to room temperature, and taking out the sample to obtain an n-type bismuth telluride bulk material;
the n-type bismuth telluride block material is placed into a graphite mold with the diameter of 15mm for texturing treatment according to the following procedures: at a vacuum degree<Heating to 400 ℃ at 10Pa, then adjusting sintering pressure to 50MPa, heating to 550 ℃, and maintaining the temperature and pressure for 10min to obtain the bismuth telluride-based thermoelectric material, wherein the chemical formula is as follows: ag (silver) 0.01 Bi 2 Te 2.7 Se 2 。
Measuring the Ag produced 0.01 Bi 2 Te 2.7 Se 2 The ZT value at 375K was 1.04 and the Vickers hardness was 0.8GPa.
Comparative example 2
Bismuth telluride-based thermoelectric material Ag was prepared in a similar manner to example 1 0.01 Bi 2 Te 2.7 Se 0.3 -2wt％MoSe 2 The difference is that: no texturing treatment was performed.
Measuring the Ag produced 0.01 Bi 2 Te 2.7 Se 0.3-2wt％ The ZT value at 375K was 1.15 and the Vickers hardness was 1.1GPa.
Experimental example
Experimental example 1
The bismuth telluride-based thermoelectric materials prepared in example 1, comparative example 1 and comparative example 2 were processed into block samples of 3X3X12mm, respectively, and subjected to electrical property detection after polishing and grinding; the bismuth telluride-based thermoelectric materials prepared in example 1, comparative example 1 and comparative example 2 were processed into 6X2mm block samples, respectively, and after polishing and grinding, electrical properties were measured, and the results are shown in fig. 1 to 4, wherein fig. 1 shows a sigma-T curve comparison graph of the bismuth telluride-based thermoelectric materials prepared in example 1 and comparative example 1-2, and fig. 2 shows an S-T curve comparison graph of the bismuth telluride-based thermoelectric materials prepared in example 1 and comparative example 1-2; FIG. 3 shows a graph comparing the kappa-T curves of bismuth telluride-based thermoelectric materials prepared in example 1 and comparative examples 1-2; fig. 4 shows a graph comparing ZT-T curves of bismuth telluride-based thermoelectric materials prepared in example 1 and comparative examples 1-2.
As can be seen from the figures: example 1 by texturing MoSe compared to comparative example 1 2 Is modified by compounding and improves the scattering of carriers and phononsProbability, carrier mobility is also enhanced, so that conductivity is enhanced; and due to MoSe 2 The uniform distribution in the bismuth telluride matrix phase causes extremely strong scattering on phonons, is favorable for reducing the lattice heat conductivity, and strengthens the relationship of thermoelectric parameters of the decoupling material through synergistic effect, so that the ZT value of the decoupling material is improved by 23% compared with that of comparative example 1, the mechanical property of the decoupling material is improved by 50%, and the properties and the mechanical property of the bismuth telluride-based thermoelectric material are greatly improved.
Compared with comparative example 2, in the bismuth telluride-based thermoelectric material of example 1, anisotropy exists in the growth process, the bismuth telluride-based thermoelectric material will grow along crystal planes with large preferred orientation, the preferred orientation is enhanced by adopting texturing treatment, the probability of enhancing the in-plane orientation of the n-type bismuth telluride bulk material is facilitated, the orientation of the crystal grains is enhanced, the electrical property of the bismuth telluride-based thermoelectric material is improved, the seebeck coefficient is enhanced at the same time, and the lattice thermal conductivity of the material is reduced. The technical scheme of the embodiment 1 can effectively improve the performance of the n-type polycrystalline bismuth telluride-based thermoelectric material, so that the ZT value of the n-type polycrystalline bismuth telluride-based thermoelectric material reaches 1.28 at 375K. Thus enhancing the anisotropy of the n-type bismuth telluride matrix material is a critical step in obtaining a material with high mobility, high thermoelectric properties.
The invention has been described in detail with reference to preferred embodiments and illustrative examples. It should be noted, however, that these embodiments are merely illustrative of the present invention and do not limit the scope of the present invention in any way. Various improvements, equivalent substitutions or modifications can be made to the technical content of the present invention and its embodiments without departing from the spirit and scope of the present invention, which all fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The bismuth telluride-based thermoelectric material is characterized in that the bismuth telluride-based thermoelectric material is an n-type bismuth telluride-based material, and the chemical formula of the bismuth telluride-based thermoelectric material is Ag 0.01 Bi 2 Te 2.7 Se 0.3 -xMoSe 2 Wherein 0 is<x≤4wt％。
2. A method for preparing a bismuth telluride-based thermoelectric material, characterized in that preferably the method comprises:
step 1, melting an Ag source, a Mo source, a Se source, a Te source and a Bi source at high temperature to prepare a bismuth telluride-based cast ingot;
step 2, sintering the bismuth telluride-based cast ingot to obtain an n-type bismuth telluride bulk material;
and 3, texturing the n-type bismuth telluride bulk material to obtain the bismuth telluride-based thermoelectric material.
3. The method according to claim 2, wherein in step 1, according to Ag 0.01 Bi 2 Te 2.7 Se 0.3 -xMoSe 2 ，0<And weighing an Ag source, a Mo source, a Se source, a Te source and a Bi source, wherein x is less than or equal to 4 wt%.
4. A method according to claim 2 or 3, characterized in that the Ag source is an elemental Ag, the Mo source is an elemental Mo, the Se source is an elemental Se, the Te source is an elemental Te, and the Bi source is an elemental Bi.
5. A method according to claim 2, characterized in that in step 1 the high temperature melting temperature is 600-1000 ℃, preferably 700-900 ℃; the time is 3 to 10 hours, preferably 5 to 9 hours.
6. The method according to claim 2, wherein in step 2, the sintering comprises: heating to 300-410 ℃ when the vacuum degree is less than 10Pa, then adjusting the sintering pressure to 20-60 MPa, heating to 420-510 ℃, and preserving heat and pressure for 3-12 min.
7. The method according to claim 2, characterized in that in step 2, the bismuth telluride-based ingot is ball milled before sintering.
8. The method according to claim 7, wherein the ball milling is carried out at a rotational speed of 800-1300 rpm/min, preferably 900-1200 rpm/min, for a period of 30-300 min, preferably 50-200 min.
9. The method of claim 2, wherein in step 3, the texturing comprises: heating to 300-410 ℃ when the vacuum degree is less than 10Pa, then adjusting the sintering pressure to 18-55 MPa, heating to 520-580 ℃, and preserving heat and pressure for 3-12 min.
10. Use of the bismuth telluride-based thermoelectric material of claim 1 or the bismuth telluride-based thermoelectric material obtained by the method for producing the bismuth telluride-based thermoelectric material of any one of claims 2 to 9 in thermoelectric power generation devices or refrigeration devices.
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