CN113161474A - P-type bismuth telluride-based alloy material and preparation method thereof - Google Patents
P-type bismuth telluride-based alloy material and preparation method thereof Download PDFInfo
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- CN113161474A CN113161474A CN202110490905.1A CN202110490905A CN113161474A CN 113161474 A CN113161474 A CN 113161474A CN 202110490905 A CN202110490905 A CN 202110490905A CN 113161474 A CN113161474 A CN 113161474A
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Abstract
The invention discloses a p-type bismuth telluride-based alloy material and a preparation method thereof, belonging to the technical field of thermoelectric materials. The preparation method of the preferred orientation p-type bismuth telluride-based alloy material comprises the following steps: (1) performing zone melting on the p-type bismuth telluride base alloy precursor to obtain a p-type bismuth telluride base alloy crystal rod; (2) and (2) putting the p-type bismuth telluride base alloy crystal rod obtained in the step (1) into a hammer mill sieving machine for hammering and sieving to obtain the p-type bismuth telluride base alloy material. The preparation method combining zone melting and hammering screening is adopted, the prepared p-type bismuth telluride-based alloy material has high orientation in the (00l) crystal plane direction, high-orientation raw materials can be provided for research and improvement of p-type bismuth telluride-based thermoelectric materials by applying a powder metallurgy process for experimental development, and the thermoelectric property and the mechanical property of the material are easily improved.
Description
Technical Field
The invention belongs to the technical field of thermoelectric materials, and particularly relates to a p-type bismuth telluride-based alloy material and a preparation method thereof.
Background
The thermoelectric material can realize the direct conversion of heat energy and electric energy, is a novel clean renewable energy material, has the excellent characteristics of no pollution, no loss, high reliability and the like, and is expected to greatly improve the energy utilization rate and relieve the environmental pollution.
Among them, the bismuth telluride-based compound is a thermoelectric material which is currently commercially used and has the best performance in the vicinity of room temperature. Due to the intrinsic layered structure characteristics of the bismuth telluride based material, the bismuth telluride based material is very easy to cleave along a c-axis crystal plane, so that the processing strength of the material is very weak, the processing yield is very low, and the processing difficulty is high. In order to improve the thermoelectric conversion efficiency and the mechanical property of the bismuth telluride-based material, the powder metallurgy process for producing the thermoelectric material is developed in China in the last 10 years, and the better progress is achieved.
The performance of the p-type bismuth telluride-based thermoelectric material on the market is relatively good, so that the preparation and production of the p-type bismuth telluride-based thermoelectric material powder with preferred orientation and high orientation in the (00l) crystal plane direction are the preferred way for producing the thermoelectric material by the powder metallurgy process, and the thermoelectric conversion efficiency of the p-type bismuth telluride-based thermoelectric material is improved. Therefore, a production method of p-type bismuth telluride-based alloy powder material highly oriented in the (00l) crystal plane direction is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a p-type bismuth telluride-based alloy material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a p-type bismuth telluride-based alloy material comprises the following steps:
(1) performing zone melting on the p-type bismuth telluride base alloy precursor to obtain a p-type bismuth telluride base alloy crystal rod;
(2) and (2) putting the p-type bismuth telluride base alloy crystal rod obtained in the step (1) into a hammer mill sieving machine for hammering and sieving to obtain the p-type bismuth telluride base alloy material.
The p-type bismuth telluride-based alloy material is a p-type bismuth telluride-based alloy material with a (00l) crystal face orientation. The preparation method combining zone melting and hammering screening is adopted, the prepared p-type bismuth telluride-based alloy material has high orientation in the (00l) crystal plane direction, high-orientation raw materials can be provided for research and improvement of p-type bismuth telluride-based thermoelectric materials by applying a powder metallurgy process for experimental development, and the thermoelectric property and the mechanical property of the material are easily improved.
As a preferred embodiment of the invention, in the step (2), the p-type bismuth telluride-based alloy crystal rod is horizontally placed in a hammer mill sieving machine in the direction of the long axis of the crystal rod; the long axis of the crystal bar is in the zone melting direction; the hammering direction is hammering along a direction perpendicular to the long axis of the crystal bar.
Through a large number of experiments and explorations, the p-type bismuth telluride-based alloy material with high orientation in the (00l) crystal face direction can be obtained only by horizontally placing the p-type bismuth telluride-based alloy crystal rod obtained in the step (1) in a hammer mill sieving machine along the long axis direction of the crystal rod and hammering the p-type bismuth telluride-based alloy crystal rod by using force vertical to the long axis direction of the crystal rod.
In a preferred embodiment of the present invention, in the step (2), the p-type bismuth telluride-based alloy material is obtained by repeatedly hammering and sieving.
In the step (2), a sieve of 100 mesh or 325 mesh is used as a preferable embodiment of the present invention.
The screen is an aviation screen.
As a preferred embodiment of the present invention, the step (2) is performed under a protective gas atmosphere, and the protective gas is at least one of nitrogen, hydrogen, helium, and argon.
As a preferred embodiment of the invention, in the step (1), the bottom tip of the glass tube filled with the p-type bismuth telluride-based alloy precursor is preheated and insulated in a heating zone of a zone melting furnace; the heating area vertically rises at a speed of 25-35 mm/h along with the vertical lifting frame and passes through the glass tube, when all materials in the glass tube pass through the heating area, the heating area stops rising, the heating area keeps warm for 30min, and then the heating area stops heating and is cooled; obtaining a p-type bismuth telluride base alloy crystal bar; the glass tube is a high borosilicate glass tube or a quartz glass tube.
As a preferred embodiment of the invention, the temperature of the heating zone is 690-720 ℃; the preheating and heat preservation time of the heating zone is 30 min; and after the heat preservation of the heating zone is finished, cooling the heating zone to 300 ℃ at the speed of 10 ℃/s, and then stopping heating.
As a preferred embodiment of the present invention, the preparation method of the p-type bismuth telluride-based alloy precursor is as follows:
s1: the single raw materials of Bi, Sb and Te are as BixSb2-xTe3X is more than or equal to 0.4 and less than or equal to 0.7, and the ingredients are weighed according to the stoichiometric ratio;
s2: placing the ingredients weighed in the S1 into a glass tube, vacuumizing, sealing, preheating in a swinging furnace, and heating for smelting to obtain a p-type bismuth telluride-based alloy precursor; the glass tube is a high borosilicate glass tube or a quartz glass tube.
In the preferred embodiment of the invention, in the step S2, the preheating temperature of the rocking furnace is 690-720 ℃, and the preheating time is 3-5 min; after the preheating is finished, carrying out swing smelting for 5-7 min; refining for 2-3 min; obtaining the precursor of the p-type bismuth telluride-based alloy.
In a preferred embodiment of the present invention, after the rocking melting, the high borosilicate glass tube is taken out, shaken well, and then returned to the rocking furnace to continue the refining.
As a preferred embodiment of the invention, after the refining is finished, the high borosilicate glass tube is taken out and vertically leaned against a frame, the molten liquid on the wall of the glass tube slides downwards by tapping the wall of the glass tube, bubbles in the molten liquid rise upwards, the bubbles are exhausted, and the molten liquid is naturally cooled to room temperature to obtain the p-type bismuth telluride-based alloy precursor.
In a preferred embodiment of the present invention, in S2, a ratio of a total mass of the ingredients to a volume of the glass tube is 1.2 to 1.5 kg: 450-500 cm3。
In a preferred embodiment of the present invention, the raw materials Bi and Sb have a purity of 99.99% or more; the purity of the raw material Te is more than 99.999%.
The invention also claims a p-type bismuth telluride-based alloy material prepared by the preparation method of the p-type bismuth telluride-based alloy material.
The invention also claims that the p-type bismuth telluride-based alloy material is a p-type bismuth telluride-based alloy material with (00l) crystal face orientation.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method can be used for efficiently preparing the p-type bismuth telluride-based alloy material, the p-type bismuth telluride-based alloy material has high orientation in the (00l) crystal face direction, high orientation raw materials can be provided for improving the p-type bismuth telluride-based thermoelectric material by applying powder metallurgy process research for experimental development, and the thermoelectric property and the mechanical property of the material are easily improved.
(2) The preparation method of the p-type bismuth telluride-based alloy material overcomes the defects that the p-type bismuth telluride-based material prepared by a zone melting process in the current market is easy to cleave in the c-axis direction, and the p-type bismuth telluride-based material has poor mechanical property, is difficult to cut and process at the rear end and has low material loss due to low orientation of (00l) crystal face direction.
(3) The p-type bismuth telluride-based alloy material prepared by the method has high orientation in the (00l) crystal plane direction, and has great research significance for improving the mechanical properties of the p-type bismuth telluride-based material.
Drawings
FIG. 1 is a schematic illustration of the peening process of the present invention;
FIG. 2 is an XRD pattern of a p-type bismuth telluride-based alloy material prepared in examples 1-6;
FIG. 3 is an XRD pattern of the p-type bismuth telluride-based alloy materials prepared in comparative examples 1 to 3 and example 4;
FIG. 4 is a scanning electron micrograph of a p-type bismuth telluride-based alloy material produced in example 4, wherein (a) is a 50-fold magnification of a picture with a scale of 1mm, (b) is a 100-fold magnification of a picture with a scale of 100 μm, (c) is a 500-fold magnification of a picture with a scale of 100 μm, and (d) is a 1000-fold magnification of a picture with a scale of 10 μm.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
FIG. 1 is a schematic diagram of the hammering process of the present invention, in which F represents hammering force, a cylindrical rod represents a p-type bismuth telluride-based alloy crystal bar, and a rectangular frame represents a hammer mill sieving machine, and it can be seen from the diagram that the p-type bismuth telluride-based alloy crystal bar is horizontally placed in the hammer mill sieving machine along the long axis direction of the crystal bar; the long axis of the crystal bar is in the zone melting direction; and the hammering direction is perpendicular to the long axis direction of the p-type bismuth telluride base alloy crystal rod.
The raw materials Bi and Sb used in examples 1 to 6 and comparative examples 1 to 3 had a purity of 99.99% or more; the purity of the raw material Te is more than 99.999 percent; the volume of the high borosilicate glass tube used in examples 1 to 6 and comparative examples 1 to 3 was 490cm3。
Example 1
The embodiment of the invention relates to a p-type bismuth telluride-based alloy material and a preparation method thereof, which comprises the following steps:
(1) with p-type Bi0.5Sb1.5Te3Weighing 1.2Kg of bulk materials of Bi, Sb and Te according to the stoichiometric ratio, adding the bulk materials into a high borosilicate glass tube according to the charging sequence of Sb, Bi and Te, and carrying out vacuum tube sealing;
(2) preheating a high borosilicate glass tube in a rocking furnace at 700 ℃ for 5min, carrying out rocking smelting for 5min, taking out the high borosilicate glass tube, uniformly rocking, putting the high borosilicate glass tube back in the rocking furnace for refining for 2min, taking out the high borosilicate glass tube, vertically leaning against an iron frame, tapping the glass tube to enable the melt on the wall of the glass tube to slide downwards, enabling bubbles in the melt to rise upwards, exhausting the bubbles, and naturally cooling to room temperature;
(3) fixing the glass tube cooled in the step (2) on a vertical lifting frame of a vertical zone melting furnace, and enabling the tip of the bottom of the glass tube to be in a heating area; the vertical zone melting furnace starts to heat up to 700 ℃, and after reaching the temperature, the bottom tip of the glass tube is preheated and insulated for 30min to be fully melted. After preheating, the heating area vertically rises at the speed of 25mm/h along with the vertical lifting frame to pass through the high borosilicate glass tube, when all materials of the high borosilicate glass tube pass through the heating area, the heating area stops rising, and after the heating area is insulated for 30min, the heating area stops heating after being cooled to 300 ℃ at the speed of 10 ℃/s;
(4) cooling the high borosilicate glass tube to room temperature in a vertical zone melting furnace, taking out, and crushing the high borosilicate glass tube to obtain a p-type bismuth telluride-based alloy crystal rod;
(5) and (3) putting the p-type bismuth telluride base alloy crystal bar into a hammer mill sieving machine in the direction of the long axis of the crystal bar for repeated hammering, wherein the hammering force application direction is as shown in figure 1, and sieving the crystal bar through a 100-mesh aviation sieve by using a vibrating sieve while hammering to obtain the p-type bismuth telluride base alloy material.
Example 2
The embodiment of the invention relates to a p-type bismuth telluride-based alloy material and a preparation method thereof, which comprises the following steps:
(1) with p-type Bi0.5Sb1.5Te3Weighing 1.2Kg of bulk materials of Bi, Sb and Te according to the stoichiometric ratio, adding the bulk materials into a high borosilicate glass tube according to the charging sequence of Sb, Bi and Te, and carrying out vacuum tube sealing;
(2) preheating a high borosilicate glass tube in a rocking furnace at 700 ℃ for 3min, carrying out rocking smelting for 5min, taking out the high borosilicate glass tube, uniformly rocking, returning the high borosilicate glass tube to the rocking furnace for refining for 3min, taking out the high borosilicate glass tube, vertically leaning against an iron frame, tapping the glass tube to enable the melt on the wall of the glass tube to slide downwards, enabling bubbles in the melt to rise upwards, exhausting the bubbles, and naturally cooling to room temperature;
(3) fixing the glass tube cooled in the step (2) on a vertical lifting frame of a vertical zone melting furnace, and enabling the tip of the bottom of the glass tube to be in a heating area; heating the vertical zone melting furnace to 720 ℃, and after reaching the temperature, preheating and preserving the temperature of the top end of the bottom of the glass tube for 30min to fully melt the glass tube; after preheating, the heating area vertically rises at the speed of 25mm/h along with the vertical lifting frame to pass through the high borosilicate glass tube, when all materials of the high borosilicate glass tube pass through the heating area, the heating area stops rising, and after the heating area is insulated for 30min, the heating area stops heating after being cooled to 300 ℃ at the speed of 10 ℃/s;
(4) cooling the high borosilicate glass tube to room temperature in a vertical zone melting furnace, taking out, and crushing the high borosilicate glass tube to obtain a p-type bismuth telluride-based alloy crystal rod;
(5) and (3) putting the p-type bismuth telluride base alloy crystal bar into a hammer mill sieving machine in the direction of the long axis of the crystal bar for repeated hammering, wherein the hammering force application direction is as shown in figure 1, and sieving the crystal bar through a 100-mesh aviation sieve by using a vibrating sieve while hammering to obtain the p-type bismuth telluride base alloy material.
Example 3
The embodiment of the invention relates to a p-type bismuth telluride-based alloy material and a preparation method thereof, which comprises the following steps:
(1) with p-type Bi0.5Sb1.5Te3Weighing 1.5Kg of bulk materials of Bi, Sb and Te according to the stoichiometric ratio, adding the bulk materials into a high borosilicate glass tube according to the charging sequence of Sb, Bi and Te, and carrying out vacuum tube sealing;
(2) preheating a high borosilicate glass tube in a rocking furnace at 700 ℃ for 5min, carrying out rocking smelting for 7min, taking out the high borosilicate glass tube, uniformly rocking, putting the high borosilicate glass tube back in the rocking furnace for refining for 3min, taking out the high borosilicate glass tube, vertically leaning against an iron frame, tapping the glass tube to enable the melt on the wall of the glass tube to slide downwards, enabling bubbles in the melt to rise upwards, exhausting the bubbles, and naturally cooling to room temperature;
(3) fixing the glass tube cooled in the step (2) on a vertical lifting frame of a vertical zone melting furnace, and enabling the tip of the bottom of the glass tube to be in a heating area; heating the vertical zone melting furnace to 720 ℃, and after reaching the temperature, preheating and preserving the temperature of the top end of the bottom of the glass tube for 30min to fully melt the glass tube; after preheating, the heating area vertically rises at the speed of 25mm/h along with the vertical lifting frame to pass through the high borosilicate glass tube, when all materials of the high borosilicate glass tube pass through the heating area, the heating area stops rising, and after the heating area is insulated for 30min, the heating area stops heating after being cooled to 300 ℃ at the speed of 10 ℃/s;
(4) cooling the high borosilicate glass tube to room temperature in a vertical zone melting furnace, taking out, and crushing the high borosilicate glass tube to obtain a p-type bismuth telluride-based alloy crystal rod;
(5) and (2) putting the p-type bismuth telluride-based alloy crystal bar into a hammer mill sieving machine in the direction of the long axis of the crystal bar for repeated hammering, wherein the force application direction of the hammer mill is as shown in figure 1, and sieving the crystal bar through a 100-mesh aviation sieve while hammering to obtain the p-type bismuth telluride-based alloy material.
Example 4
The embodiment of the invention relates to a p-type bismuth telluride-based alloy material and a preparation method thereof, which comprises the following steps:
(1) with p-type Bi0.7Sb1.3Te3Weighing 1.2Kg of bulk materials of Bi, Sb and Te according to the stoichiometric ratio, adding the bulk materials into a high borosilicate glass tube according to the charging sequence of Sb, Bi and Te, and carrying out vacuum tube sealing;
(2) preheating a high borosilicate glass tube in a rocking furnace at 700 ℃ for 5min, carrying out rocking smelting for 5min, taking out the high borosilicate glass tube, uniformly rocking, putting the high borosilicate glass tube back in the rocking furnace for refining for 2min, taking out the high borosilicate glass tube, vertically leaning against an iron frame, tapping the glass tube to enable the melt on the wall of the glass tube to slide downwards, enabling bubbles in the melt to rise upwards, exhausting the bubbles, and naturally cooling to room temperature;
(3) fixing the glass tube cooled in the step (2) on a vertical lifting frame of a vertical zone melting furnace, and enabling the tip of the bottom of the glass tube to be in a heating area; heating the vertical zone melting furnace to 710 ℃, and after the temperature is reached, preheating and preserving the temperature of the top end of the bottom of the glass tube for 30min to fully melt the glass tube; after preheating, the heating area vertically rises at the speed of 25mm/h along with the vertical lifting frame to pass through the high borosilicate glass tube, when all materials of the high borosilicate glass tube pass through the heating area, the heating area stops rising, and after the heating area is insulated for 30min, the heating area stops heating after being cooled to 300 ℃ at the speed of 10 ℃/s;
(4) cooling the high borosilicate glass tube to room temperature in a vertical zone melting furnace, taking out, and crushing the high borosilicate glass tube to obtain a p-type bismuth telluride-based alloy crystal rod;
(5) and (3) putting the p-type bismuth telluride base alloy crystal bar into a hammer mill sieving machine in the direction of the long axis of the crystal bar for repeated hammering, wherein the hammering force application direction is as shown in figure 1, and sieving the crystal bar through a 100-mesh aviation sieve by using a vibrating sieve while hammering to obtain the p-type bismuth telluride base alloy material.
Example 5
The embodiment of the invention relates to a p-type bismuth telluride-based alloy material and a preparation method thereof, which comprises the following steps:
(1) with p-type Bi0.7Sb1.3Te3Weighing 1.2Kg of bulk materials of Bi, Sb and Te according to the stoichiometric ratio, adding the bulk materials into a high borosilicate glass tube according to the charging sequence of Sb, Bi and Te, and carrying out vacuum tube sealing;
(2) preheating a high borosilicate glass tube in a rocking furnace at 700 ℃ for 3min, carrying out rocking smelting for 5min, taking out the high borosilicate glass tube, uniformly rocking, putting the high borosilicate glass tube back in the rocking furnace for refining for 2min, taking out the high borosilicate glass tube, vertically leaning against an iron frame, tapping the glass tube to enable the melt on the wall of the glass tube to slide downwards, enabling bubbles in the melt to rise upwards, exhausting the bubbles, and naturally cooling to room temperature;
(3) fixing the glass tube cooled in the step (2) on a vertical lifting frame of a vertical zone melting furnace, and enabling the tip of the bottom of the glass tube to be in a heating area; heating the vertical zone melting furnace to 710 ℃, and after the temperature is reached, preheating and preserving the temperature of the top end of the bottom of the glass tube for 30min to fully melt the glass tube; after preheating, the heating area vertically rises at the speed of 35mm/h along with the vertical lifting frame to pass through the high borosilicate glass tube, when all materials of the high borosilicate glass tube pass through the heating area, the heating area stops rising, and after the heating area is insulated for 30min, the heating area stops heating after being cooled to 300 ℃ at the speed of 10 ℃/s;
(4) cooling the high borosilicate glass tube to room temperature in a vertical zone melting furnace, taking out, and crushing the high borosilicate glass tube to obtain a p-type bismuth telluride-based alloy crystal rod;
(5) and (3) putting the p-type bismuth telluride base alloy crystal bar into a hammer mill sieving machine in the direction of the long axis of the crystal bar for repeated hammering, wherein the hammering force application direction is as shown in figure 1, and sieving the crystal bar through a 100-mesh aviation sieve by using a vibrating sieve while hammering to obtain the p-type bismuth telluride base alloy material.
Example 6
The embodiment of the invention relates to a p-type bismuth telluride-based alloy material and a preparation method thereof, which comprises the following steps:
(1) with p-type Bi0.7Sb1.3Te3Weighing 1.5Kg of bulk materials of Bi, Sb and Te according to the stoichiometric ratio, adding the bulk materials into a high borosilicate glass tube according to the charging sequence of Sb, Bi and Te, and carrying out vacuum tube sealing;
(2) preheating a high borosilicate glass tube in a rocking furnace at 700 ℃ for 5min, carrying out rocking smelting for 5min, taking out the high borosilicate glass tube, uniformly rocking, putting the high borosilicate glass tube back in the rocking furnace for refining for 2min, taking out the high borosilicate glass tube, vertically leaning against an iron frame, tapping the glass tube to enable the melt on the wall of the glass tube to slide downwards, enabling bubbles in the melt to rise upwards, exhausting the bubbles, and naturally cooling to room temperature;
(3) fixing the glass tube cooled in the step (2) on a vertical lifting frame of a vertical zone melting furnace, and enabling the tip of the bottom of the glass tube to be in a heating area; heating the vertical zone melting furnace to 710 ℃, and after the temperature is reached, preheating and preserving the temperature of the top end of the bottom of the glass tube for 30min to fully melt the glass tube; after preheating, the heating area vertically rises at the speed of 25mm/h along with the vertical lifting frame to pass through the high borosilicate glass tube, when all materials of the high borosilicate glass tube pass through the heating area, the heating area stops rising, and after the heating area is insulated for 30min, the heating area stops heating after being cooled to 300 ℃ at the speed of 10 ℃/s;
(4) cooling the high borosilicate glass tube to room temperature in a vertical zone melting furnace, taking out, and crushing the high borosilicate glass tube to obtain a p-type bismuth telluride-based alloy crystal rod;
(5) and (3) putting the p-type bismuth telluride base alloy crystal bar into a hammer mill sieving machine in the direction of the long axis of the crystal bar for repeated hammering, wherein the hammering force application direction is as shown in figure 1, and sieving the crystal bar through a 100-mesh aviation sieve by using a vibrating sieve while hammering to obtain the p-type bismuth telluride base alloy material.
Comparative example 1
The invention relates to a p-type bismuth telluride-based alloy material and a comparative example of a preparation method thereof, which specifically comprise the following steps:
(1) with p-type Bi0.5Sb1.5Te3Weighing 1.2Kg of bulk materials of Bi, Sb and Te according to the stoichiometric ratio, adding the bulk materials into a high borosilicate glass tube according to the charging sequence of Sb, Bi and Te, and carrying out vacuum tube sealing;
(2) preheating a high borosilicate glass tube in a rocking furnace at 700 ℃ for 5min, carrying out rocking smelting for 5min, taking out the high borosilicate glass tube, uniformly rocking, putting the high borosilicate glass tube back in the rocking furnace for refining for 2min, taking out the high borosilicate glass tube, vertically leaning against an iron frame, tapping the glass tube to enable the melt on the wall of the glass tube to slide downwards, enabling bubbles in the melt to rise upwards, exhausting the bubbles, and naturally cooling to room temperature;
(3) crushing the glass tube cooled in the step (2) to obtain a p-type bismuth telluride base alloy crystal rod;
(4) and ball-milling the p-type bismuth telluride base alloy crystal bar, and sieving the crystal bar by a 100-mesh aviation screen to obtain the p-type bismuth telluride base alloy material.
Comparative example 2
The invention relates to a p-type bismuth telluride-based alloy material and a comparative example of a preparation method thereof, which specifically comprise the following steps:
(1) with p-type Bi0.5Sb1.5Te3Weighing 1.2Kg of bulk materials of Bi, Sb and Te according to the stoichiometric ratio, adding the bulk materials into a high borosilicate glass tube according to the charging sequence of Sb, Bi and Te, and carrying out vacuum tube sealing;
(2) preheating a high borosilicate glass tube in a rocking furnace at 700 ℃ for 5min, carrying out rocking smelting for 5min, taking out the high borosilicate glass tube, uniformly rocking, putting the high borosilicate glass tube back in the rocking furnace for refining for 2min, taking out the high borosilicate glass tube, vertically leaning against an iron frame, tapping the glass tube to enable the melt on the wall of the glass tube to slide downwards, enabling bubbles in the melt to rise upwards, exhausting the bubbles, and naturally cooling to room temperature;
(3) and (3) fixing the glass tube cooled in the step (2) on a vertical lifting frame of a vertical zone melting furnace, and enabling the bottom tip of the glass tube to be in a heating area. Heating the vertical zone melting furnace to 700 ℃, and after the temperature is reached, preheating the top end of the bottom for heat preservation for 30min to fully melt the top end of the bottom; after preheating, the heating area vertically rises at the speed of 25mm/h along with the vertical lifting frame to pass through the high borosilicate glass tube, when all materials of the high borosilicate glass tube pass through the heating area, the heating area stops rising, and after heat preservation is carried out for 30min, the heating area stops heating after being cooled to 300 ℃ at the speed of 10 ℃/s;
(4) cooling the high borosilicate glass tube to room temperature in a vertical zone melting furnace, taking out, and crushing the high borosilicate glass tube to obtain a p-type bismuth telluride-based alloy crystal rod;
(5) and ball-milling the p-type bismuth telluride base alloy crystal bar, and sieving the crystal bar by a 100-mesh aviation screen to obtain the p-type bismuth telluride base alloy material.
Comparative example 3
The invention relates to a p-type bismuth telluride-based alloy material and a comparative example of a preparation method thereof, which specifically comprise the following steps:
(1) with p-type Bi0.5Sb1.5Te3Transformation ofWeighing 1.2Kg of bulk materials of Bi, Sb and Te in a stoichiometric ratio, adding the bulk materials into a high borosilicate glass tube according to the charging sequence of Sb, Bi and Te, and carrying out vacuum tube sealing;
(2) preheating a high borosilicate glass tube in a rocking furnace at 700 ℃ for 5min, carrying out rocking smelting for 5min, taking out the high borosilicate glass tube, uniformly rocking, putting the high borosilicate glass tube back in the rocking furnace for refining for 2min, taking out the high borosilicate glass tube, vertically leaning against an iron frame, tapping the glass tube to enable the melt on the wall of the glass tube to slide downwards, enabling bubbles in the melt to rise upwards, exhausting the bubbles, and naturally cooling to room temperature;
(3) crushing the glass tube cooled in the step (2) to obtain a p-type bismuth telluride base alloy crystal rod;
(4) and (3) putting the p-type bismuth telluride base alloy crystal bar into a hammer mill sieving machine in the direction of the long axis of the crystal bar for repeated hammering, wherein the hammering force application direction is as shown in figure 1, and sieving the crystal bar through a 100-mesh aviation sieve by using a vibrating sieve while hammering to obtain the p-type bismuth telluride base alloy material.
Effect example 1
Test samples: examples 1-6 and comparative examples 1-3.
Fig. 2 shows XRD patterns of samples prepared in example 1, example 2, example 3, example 4, example 5, and example 6 from bottom to top, and it can be seen from fig. 2 that all samples prepared in examples 1 to 6 are p-type bismuth telluride-based alloy materials, and the peak intensities of the (0015) (006) (0018) (009) (0021) crystal planes are high, which indicates that the prepared preferentially oriented p-type bismuth telluride-based alloy material has high orientation in the (00l) crystal plane direction.
FIG. 3 is an XRD pattern of samples prepared in turn from bottom to top in PDF #49-1713, comparative example 1, comparative example 2, comparative example 3 and example 4, the XRD peak of PDF #49-1713 is the peak on a standard card of a p-type bismuth telluride-based alloy material, and it can be seen from FIG. 3 that the p-type bismuth telluride-based alloy material was successfully prepared in both example 4 and comparative examples 1-3 compared with the peak on the standard card, and the XRD peak of the sample of example 4 according to the present invention has a high intensity of the crystal plane peak in the (0015) (006) (0018) (009) direction and a low intensity of the crystal plane peak in the (110) direction compared with the XRD peak of the sample prepared in comparative example, indicating that the prepared material has a high orientation in the (00l) crystal plane direction, while the sample prepared in comparative examples 1-3 has a low orientation in the (00l) crystal plane.
Fig. 4 is a scanning electron microscope image of a sample prepared in example 4, and it can be seen from the image that the p-type bismuth telluride-based alloy material prepared in the present invention has a lamellar structure, which illustrates that the p-type bismuth telluride-based alloy material has an obvious orientation.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a p-type bismuth telluride-based alloy material is characterized by comprising the following steps:
(1) performing zone melting on the p-type bismuth telluride base alloy precursor to obtain a p-type bismuth telluride base alloy crystal rod;
(2) and (2) putting the p-type bismuth telluride base alloy crystal rod obtained in the step (1) into a hammer mill sieving machine for hammering and sieving to obtain the p-type bismuth telluride base alloy material.
2. The method for preparing the p-type bismuth telluride-based alloy material as claimed in claim 1, wherein in the step (2), the p-type bismuth telluride-based alloy crystal rod is horizontally placed in a hammer mill sieving machine in the direction of the long axis of the crystal rod; the long axis of the crystal bar is in the zone melting direction; the hammering direction is hammering along a direction perpendicular to the long axis of the crystal bar.
3. The method for preparing the p-type bismuth telluride-based alloy material as set forth in claim 1, wherein in the step (2), the sieving is performed by using a 100 mesh or 325 mesh sieve.
4. The method for preparing a p-type bismuth telluride-based alloy material as in claim 1, wherein the step (2) is performed in a protective gas atmosphere, and the protective gas is at least one of nitrogen, hydrogen, helium and argon.
5. The method for preparing the p-type bismuth telluride-based alloy material as in claim 1, wherein in the step (1), the bottom tip of the glass tube filled with the p-type bismuth telluride-based alloy precursor is preheated and insulated in a heating zone of a zone melting furnace; the heating area vertically rises at a speed of 25-35 mm/h along with the vertical lifting frame and passes through the glass tube, when all materials in the glass tube pass through the heating area, the heating area stops rising, the heating area keeps warm for 30min, and then the heating area stops heating and is cooled; obtaining a p-type bismuth telluride base alloy crystal bar; the glass tube is a high borosilicate glass tube or a quartz glass tube.
6. The method for preparing the p-type bismuth telluride-based alloy material as in claim 5, wherein the temperature of the heating zone is 690-720 ℃; the preheating and heat preservation time of the heating zone is 30 min; and after the heat preservation of the heating zone is finished, cooling the heating zone to 300 ℃ at the speed of 10 ℃/s, and then stopping heating.
7. The method for preparing the p-type bismuth telluride-based alloy material as claimed in claim 1, wherein the method for preparing the precursor of the p-type bismuth telluride-based alloy is as follows:
s1: the single raw materials of Bi, Sb and Te are as BixSb2-xTe3X is more than or equal to 0.4 and less than or equal to 0.7, and the ingredients are weighed according to the stoichiometric ratio;
s2: placing the ingredients weighed in the S1 into a glass tube, vacuumizing, sealing, preheating in a swinging furnace, and heating for smelting to obtain a p-type bismuth telluride-based alloy precursor; the glass tube is a high borosilicate glass tube or a quartz glass tube.
8. The method for preparing the p-type bismuth telluride-based alloy material as in claim 7, wherein in S2, the preheating temperature of the rocking furnace is 690-720 ℃, and the preheating time is 3-5 min; after the preheating is finished, carrying out swing smelting for 5-7 min; refining for 2-3 min; obtaining the precursor of the p-type bismuth telluride-based alloy.
9. The p-type bismuth telluride-based alloy material prepared by the method for preparing the p-type bismuth telluride-based alloy material as claimed in any one of claims 1 to 9.
10. The p-type bismuth telluride-based alloy material as set forth in claim 9, wherein the p-type bismuth telluride-based alloy material is a p-type bismuth telluride-based alloy material oriented in a (00l) crystal plane.
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