CN114210978A - Hot extrusion molding method of bismuth telluride thermoelectric material - Google Patents
Hot extrusion molding method of bismuth telluride thermoelectric material Download PDFInfo
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- CN114210978A CN114210978A CN202111582352.9A CN202111582352A CN114210978A CN 114210978 A CN114210978 A CN 114210978A CN 202111582352 A CN202111582352 A CN 202111582352A CN 114210978 A CN114210978 A CN 114210978A
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 71
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 61
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000001192 hot extrusion Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000000465 moulding Methods 0.000 title claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- 238000003723 Smelting Methods 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 238000000498 ball milling Methods 0.000 claims abstract description 23
- 238000001125 extrusion Methods 0.000 claims abstract description 22
- 230000001681 protective effect Effects 0.000 claims abstract description 21
- 230000006698 induction Effects 0.000 claims abstract description 13
- 238000007689 inspection Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 10
- 238000012216 screening Methods 0.000 claims abstract description 8
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 21
- 238000004321 preservation Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims 5
- 230000008018 melting Effects 0.000 claims 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims 3
- 239000001257 hydrogen Substances 0.000 claims 3
- 229910052739 hydrogen Inorganic materials 0.000 claims 3
- 238000004663 powder metallurgy Methods 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000005204 segregation Methods 0.000 description 6
- 239000011669 selenium Substances 0.000 description 6
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 6
- 238000004857 zone melting Methods 0.000 description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 229910002909 Bi-Te Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910002899 Bi2Te3 Inorganic materials 0.000 description 1
- 230000005679 Peltier effect Effects 0.000 description 1
- 229910017629 Sb2Te3 Inorganic materials 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
- B22F2003/208—Warm or hot extruding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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Abstract
A hot extrusion molding method of a bismuth telluride thermoelectric material comprises the following steps: obtaining simple substance raw materials of Bi, Te, Sb and Se; crushing the simple substance raw material into a block with a preset diameter; weighing the massive bodies according to a preset stoichiometric ratio; mixing the block-shaped bodies and putting the mixed block-shaped bodies in a vacuum high-frequency induction smelting furnace under a first protective gas environment to be smelted into ingots; ball-milling the cast ingot to obtain a powder body; screening the powder body by using an ultrasonic inspection sieve; the screened powder body is put into an extrusion die and is subjected to hot extrusion in a second protective gas environment to obtain a bismuth telluride bar; and placing the bismuth telluride bar in a tubular atmosphere furnace and carrying out heat treatment in a third protective gas environment to obtain the bismuth telluride thermoelectric material. The method combines powder metallurgy with a hot extrusion process, realizes the precision forming and performance improvement of the high-brittleness bismuth telluride thermoelectric material, and solves the problems of low reliability and performance attenuation of the thermoelectric refrigerator.
Description
Technical Field
The invention belongs to the technical field of thermoelectric materials, and particularly relates to a hot extrusion molding method of a bismuth telluride thermoelectric material.
Background
As a functional material capable of directly converting heat energy and electric energy into each other, the thermoelectric material is essentially characterized in that thermoelectric power generation and thermoelectric refrigeration are realized by utilizing the transport property of material carriers through the Seebeck effect or the Peltier effect. In recent half a century, intensive studies on thermoelectric materials have been conducted, and bismuth telluride alloys and solid solutions thereof have been found to be the best thermoelectric materials in the room temperature range. Bismuth telluride has a large Seebeck coefficient and low thermal conductivity, and the ZT value at room temperature is close to 1, so that the bismuth telluride is widely applied to thermoelectric cooling devices.
Bismuth telluride is an intermetallic compound formed by two main group elements of V and VI, belongs to an orthorhombic system, and has a space group of R-3 m. Along the c-axis direction, the structure can be regarded as hexahedral quasi-layer, and each layer is circularly arranged in a mode of-Te (1) -Bi-Te (2) -Bi-Te (1) -. wherein-Bi-Te-in the layers are bonded by covalent bonds, and-Te-Te-in the layers are bonded by Van der Waals forces. Bi2Te3 can form a P-type alloy with Sb2Te3, which is marked as Bi2-xSbxTe 3; an n-type alloy with Se2Te3, noted as Bi2Te 3-ySey.
The preparation of the bismuth telluride bulk material mainly comprises the following methods: zone melting method, single crystal pulling method, powder metallurgy method and in-situ synthesis method. The zone melting method commonly adopted in industry can prepare quasi-single crystal materials with good grain orientation, but the layered structure of the zone melting bismuth telluride material is easy to be dissociated in the processing process, or even if the zone melting bismuth telluride material can be prepared into a thermoelectric device, the zone melting bismuth telluride material can also generate thermal stress due to the stretching and compression effects caused by different thermal expansion coefficients of different materials in the using process, so that the device is failed and damaged, and the reliability is reduced. Therefore, the good mechanical properties of the material are very important considerations for the fabrication of thermoelectric devices. In order to improve the defects of weak mechanical property, poor processability and the like of the bismuth telluride material, it is very important to develop a novel preparation process to obtain a bulk bismuth telluride-based thermoelectric material with good thermoelectric property and excellent mechanical strength.
Disclosure of Invention
In order to solve the above problems, the present invention provides a hot extrusion molding method of a bismuth telluride thermoelectric material, comprising the steps of:
obtaining simple substance raw materials of Bi, Te, Sb and Se;
crushing the simple substance raw material into a block with a preset diameter;
weighing the massive bodies according to a preset stoichiometric ratio;
mixing the block-shaped bodies and putting the mixed block-shaped bodies in a vacuum high-frequency induction smelting furnace under a first protective gas environment to be smelted into ingots;
ball-milling the cast ingot to obtain a powder body;
screening the powder body by using an ultrasonic inspection sieve;
the screened powder body is put into an extrusion die and is subjected to hot extrusion in a second protective gas environment to obtain a bismuth telluride bar;
and placing the bismuth telluride bar in a tubular atmosphere furnace and carrying out heat treatment in a third protective gas environment to obtain the bismuth telluride thermoelectric material.
Preferably, the stoichiometric ratio is: bi2-xSbxTe3 (x is more than or equal to 1.4 and less than or equal to 1.8) or Bi2Te3-ySey (y is more than or equal to 0.1 and less than or equal to 0.3).
Preferably, when the smelting is carried out in the vacuum high-frequency induction smelting furnace, the temperature rise rate of the vacuum high-frequency induction smelting furnace is 10-30 ℃/min, the smelting temperature is 700-900 ℃, and the smelting time is 1-5 h.
Preferably, when the ingot is ball-milled, the ball-to-material ratio is 3-10, the ball-milling rotating speed is 300-600 rpm, and the ball-milling time is 2-24 h.
Preferably, when the powder body is screened by an ultrasonic inspection sieve, the vibration frequency of the ultrasonic inspection sieve is 10000 times/minute to 40000 times/minute, and the sieve specification is 80 meshes to 300 meshes.
Preferably, when the screened powder body is loaded into an extrusion die for hot extrusion, the heating rate is 10 ℃/min-30 ℃/min, the hot extrusion temperature is 350-500 ℃, the heat preservation time is 0.5h-2h, the extrusion ratio is 5-25, and the extrusion rate is 0.5mm/min-5 mm/min.
Preferably, when the bismuth telluride bar is placed in a tubular atmosphere furnace for heat treatment, the heating rate is 10-30 ℃/min, the heat treatment temperature is 350-450 ℃, and the heat preservation time is 2-24 h.
Preferably, the first protective gas is one or more of argon, nitrogen and a hydrogen-argon mixture.
Preferably, the second protective gas is one or more of argon, nitrogen and hydrogen-argon mixed gas.
Preferably, the third protective gas is one or more of argon, nitrogen and hydrogen-argon mixed gas.
According to the hot extrusion molding method of the bismuth telluride thermoelectric material, powder metallurgy and a hot extrusion process are combined, the precise molding and performance improvement of the high-brittleness bismuth telluride thermoelectric material are realized, the large-size bismuth telluride bar with high strength and high thermoelectric figure of merit is prepared, and the problems of low reliability and performance attenuation of a thermoelectric refrigerator are solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic diagram of a bismuth telluride bar product obtained by a bismuth telluride thermoelectric material hot extrusion molding method provided by the invention;
fig. 2 is a schematic diagram of a back scattering morphology of a bismuth telluride bar finished product obtained by the bismuth telluride thermoelectric material hot extrusion molding method provided by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
In an embodiment of the present application, as shown in fig. 1 and 2, the present invention provides a method for hot extrusion molding of a bismuth telluride thermoelectric material, the method including the steps of:
obtaining simple substance raw materials of Bi, Te, Sb and Se;
crushing the simple substance raw material into a block with a preset diameter;
weighing the massive bodies according to a preset stoichiometric ratio;
mixing the block-shaped bodies and putting the mixed block-shaped bodies in a vacuum high-frequency induction smelting furnace under a first protective gas environment to be smelted into ingots;
ball-milling the cast ingot to obtain a powder body;
screening the powder body by using an ultrasonic inspection sieve;
the screened powder body is put into an extrusion die and is subjected to hot extrusion in a second protective gas environment to obtain a bismuth telluride bar;
and placing the bismuth telluride bar in a tubular atmosphere furnace and carrying out heat treatment in a third protective gas environment to obtain the bismuth telluride thermoelectric material.
In the examples of the present application, the stoichiometric ratio is: bi2-xSbxTe3 (x is more than or equal to 1.4 and less than or equal to 1.8) or Bi2Te3-ySey (y is more than or equal to 0.1 and less than or equal to 0.3).
In the embodiment of the application, when the vacuum high-frequency induction smelting furnace is used for smelting, the temperature rise rate of the vacuum high-frequency induction smelting furnace is 10-30 ℃/min, the smelting temperature is 700-900 ℃, and the smelting time is 1-5 h.
In the embodiment of the application, when the ingot is ball-milled, the ball-material ratio is 3-10, the ball-milling rotating speed is 300-600 rpm, and the ball-milling time is 2-24 h.
In the embodiment of the application, when the powder body is screened by an ultrasonic inspection sieve, the vibration frequency of the ultrasonic inspection sieve is 10000 times/minute to 40000 times/minute, and the sieve specification is 80 meshes to 300 meshes.
In the embodiment of the application, when the screened powder body is loaded into an extrusion die for hot extrusion, the heating rate is 10-30 ℃/min, the hot extrusion temperature is 350-500 ℃, the heat preservation time is 0.5-2 h, the extrusion ratio is 5-25, and the extrusion rate is 0.5-5 mm/min.
In the embodiment of the application, when the bismuth telluride bar is placed in a tubular atmosphere furnace for heat treatment, the heating rate is 10-30 ℃/min, the heat treatment temperature is 350-450 ℃, and the heat preservation time is 2-24 h.
In the embodiment of the application, the first protective gas is one or more of argon, nitrogen and hydrogen-argon mixed gas.
In the embodiment of the application, the second protective gas is one or more of argon, nitrogen and hydrogen-argon mixed gas.
In the embodiment of the application, the third protective gas is one or more of argon, nitrogen and hydrogen-argon mixed gas.
The present application is described in detail below with specific examples.
Example 1
S1, crushing the raw materials: taking out the tellurium ingots, bismuth ingots and selenium ingots from the vacuum cabinet, putting the tellurium ingots, bismuth ingots and selenium ingots into a powder tank, and smashing the materials into small pieces. The cover of the powder tank is opened, and the small blocks with the diameter not more than 30mm are clamped by tweezers and placed on clean filter paper. The crushing of the raw material into small pieces may allow for better smelting of the raw material in step S2.
S2, high-frequency smelting: the raw materials obtained in the step S1 are weighed according to the stoichiometric ratio of Bi2Te2.8Se0.2, the raw materials are mixed and then put into a graphite crucible to be smelted in a vacuum high-frequency induction smelting furnace, the temperature rise rate is 20oC/min, the smelting temperature is 800oC, and the smelting time is 4 hours. The defect of segregation or dissociation of material components can be overcome to the maximum extent by adopting high-frequency smelting, and the material with uniform components is prepared.
S3, ball milling and sieving: and (5) putting the cast ingot obtained in the step S2 into a ball milling tank, introducing nitrogen into the ball milling tank, carrying out ball milling for 12 hours at the rotating speed of 450rpm, and screening the alloy powder obtained after ball milling by using an ultrasonic inspection sieve, wherein the vibration frequency is 15000 times/minute, and the sieve specification is 100 meshes.
S4, hot extrusion molding: and (4) loading the bismuth telluride alloy powder screened in the step (S3) into a special extrusion die, heating to 450 ℃ at a heating rate of 15 ℃ per minute under the protection of nitrogen atmosphere, preserving heat at the temperature for 1 hour, and then carrying out hot extrusion forming, wherein the extrusion ratio is 6.25, and the extrusion rate is 1mm per minute. The hot extrusion can be used to refine the microstructure and minimize segregation, thereby improving the properties and characteristics of the material.
S5, heat treatment: and (5) putting the bismuth telluride bar obtained in the step (S4) into a tubular atmosphere furnace for heat treatment, introducing hydrogen-argon mixed gas, heating to 400 ℃ at the heating rate of 10 ℃ per minute, and preserving heat for 20 hours at the temperature. The heat treatment can improve the mechanical property of the material and eliminate the residual stress, so that the large-size bismuth telluride bar with high strength and high thermoelectric figure of merit can be prepared.
Example 2
S1, crushing the raw materials: taking out the tellurium ingots, bismuth ingots and antimony ingots from the vacuum cabinet, putting the tellurium ingots, bismuth ingots and antimony ingots into a powder tank, and smashing the materials into small pieces. The cover of the powder tank is opened, and the small blocks with the diameter not more than 30mm are clamped by tweezers and placed on clean filter paper. The crushing of the raw material into small pieces may allow for better smelting of the raw material in step S2.
S2, high-frequency smelting: and (4) weighing the raw materials obtained in the step S1 according to the stoichiometric ratio of Bi0.4Sb1.6Te3, mixing the raw materials, putting the raw materials into a graphite crucible, and smelting in a vacuum high-frequency induction smelting furnace at the heating rate of 25oC/min and the smelting temperature of 850oC for 3 h. The defect of segregation or dissociation of material components can be overcome to the maximum extent by adopting high-frequency smelting, and the material with uniform components is prepared.
S3, ball milling and sieving: and (5) putting the cast ingot obtained in the step (S2) into a ball milling tank, wherein the ball material ratio is 5, introducing nitrogen, carrying out ball milling for 12 hours at the rotating speed of 500rpm, and screening the alloy powder obtained after ball milling by using an ultrasonic inspection sieve, wherein the vibration frequency is 20000 times/minute, and the sieve specification is 120 meshes.
S4, hot extrusion molding: and (4) loading the bismuth telluride alloy powder screened in the step (S3) into a special extrusion die, heating to 400 ℃ at a heating rate of 10 ℃ per minute under the protection of nitrogen atmosphere, preserving heat at the temperature for 0.5h, and then carrying out hot extrusion forming, wherein the extrusion ratio is 6.25, and the extrusion rate is 0.5mm per minute. The hot extrusion can be used to refine the microstructure and minimize segregation, thereby improving the properties and characteristics of the material.
S5, heat treatment: and (5) putting the bismuth telluride bar obtained in the step (S4) into a tubular atmosphere furnace for heat treatment, introducing hydrogen-argon mixed gas, heating to 380 ℃ at the heating rate of 10 ℃ per minute, and preserving heat for 22 hours at the temperature. The heat treatment can improve the mechanical property of the material and eliminate the residual stress, so that the large-size bismuth telluride bar with high strength and high thermoelectric figure of merit can be prepared.
Example 3
S1, crushing the raw materials: taking out the tellurium ingots, bismuth ingots and selenium ingots from the vacuum cabinet, putting the tellurium ingots, bismuth ingots and selenium ingots into a powder tank, and smashing the materials into small pieces. The cover of the powder tank is opened, and the small blocks with the diameter not more than 30mm are clamped by tweezers and placed on clean filter paper. The crushing of the raw material into small pieces may allow for better smelting of the raw material in step S2.
S2, high-frequency smelting: weighing the raw materials obtained in the step S1 according to the stoichiometric ratio of Bi2Te2.7Se0.3, mixing the raw materials, putting the raw materials into a graphite crucible, and smelting in a vacuum high-frequency induction smelting furnace, wherein the heating rate is 20 ℃ per min, the smelting temperature is 800 ℃ and the smelting time is 4 hours. The defect of segregation or dissociation of material components can be overcome to the maximum extent by adopting high-frequency smelting, and the material with uniform components is prepared.
S3, ball milling and sieving: and (5) putting the cast ingot obtained in the step (S2) into a ball milling tank, wherein the ball material ratio is 4, introducing nitrogen, carrying out ball milling for 10 hours at the rotating speed of 500rpm, and screening the alloy powder obtained after ball milling by using an ultrasonic inspection sieve, wherein the vibration frequency is 10000 times/minute, and the sieve specification is 80 meshes.
S4, hot extrusion molding: and (4) loading the bismuth telluride alloy powder screened in the step (S3) into a special extrusion die, heating to 450 ℃ at a heating rate of 15 ℃ per minute under the protection of nitrogen atmosphere, preserving heat at the temperature for 1 hour, and then carrying out hot extrusion forming, wherein the extrusion ratio is 9, and the extrusion rate is 0.6mm per minute. The hot extrusion can be used to refine the microstructure and minimize segregation, thereby improving the properties and characteristics of the material.
S5, heat treatment: and (5) putting the bismuth telluride bar obtained in the step (S4) into a tubular atmosphere furnace for heat treatment, introducing hydrogen-argon mixed gas, heating to 420 ℃ at the heating rate of 10 ℃ per minute, and preserving heat for 20 hours at the temperature. The heat treatment can improve the mechanical property of the material and eliminate the residual stress, so that the large-size bismuth telluride bar with high strength and high thermoelectric figure of merit can be prepared.
According to the hot extrusion molding method of the bismuth telluride thermoelectric material, powder metallurgy and a hot extrusion process are combined, the precise molding and performance improvement of the high-brittleness bismuth telluride thermoelectric material are realized, the large-size bismuth telluride bar with high strength and high thermoelectric figure of merit is prepared, and the problems of low reliability and performance attenuation of a thermoelectric refrigerator are solved.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (10)
1. A hot extrusion molding method of a bismuth telluride thermoelectric material is characterized by comprising the following steps:
obtaining simple substance raw materials of Bi, Te, Sb and Se;
crushing the simple substance raw material into a block with a preset diameter;
weighing the massive bodies according to a preset stoichiometric ratio;
mixing the block-shaped bodies and putting the mixed block-shaped bodies in a vacuum high-frequency induction smelting furnace under a first protective gas environment to be smelted into ingots;
ball-milling the cast ingot to obtain a powder body;
screening the powder body by using an ultrasonic inspection sieve;
the screened powder body is put into an extrusion die and is subjected to hot extrusion in a second protective gas environment to obtain a bismuth telluride bar;
and placing the bismuth telluride bar in a tubular atmosphere furnace and carrying out heat treatment in a third protective gas environment to obtain the bismuth telluride thermoelectric material.
2. The method for hot extrusion molding of the bismuth telluride thermoelectric material as set forth in claim 1, wherein the stoichiometric ratio is: bi2-xSbxTe3 (x is more than or equal to 1.4 and less than or equal to 1.8) or Bi2Te3-ySey (y is more than or equal to 0.1 and less than or equal to 0.3).
3. The hot extrusion molding method of the bismuth telluride thermoelectric material as set forth in claim 1, wherein when melting in the vacuum high-frequency induction melting furnace, the temperature rise rate of the vacuum high-frequency induction melting furnace is 10 ℃/min to 30 ℃/min, the melting temperature is 700 ℃ to 900 ℃, and the melting time is 1h to 5 h.
4. The hot extrusion molding method of the bismuth telluride thermoelectric material as in claim 1, wherein when the ingot is ball-milled, the ball-to-material ratio is 3-10, the ball-milling rotation speed is 300rpm-600rpm, and the ball-milling time is 2h-24 h.
5. The method for hot extrusion molding of the bismuth telluride thermoelectric material as set forth in claim 1, wherein when the powder body is screened with an ultrasonic testing sieve, the ultrasonic testing sieve has a vibration frequency of 10000 times/min to 40000 times/min and a mesh size of 80 mesh to 300 mesh.
6. The method for hot extrusion molding of the bismuth telluride thermoelectric material as in claim 1, wherein when the powder body after screening is loaded into an extrusion die for hot extrusion, the heating rate is 10 ℃/min to 30 ℃/min, the hot extrusion temperature is 350 ℃ to 500 ℃, the heat preservation time is 0.5h to 2h, the extrusion ratio is 5 to 25, and the extrusion rate is 0.5mm/min to 5 mm/min.
7. The method for hot extrusion molding of the bismuth telluride thermoelectric material as in claim 1, wherein when the bismuth telluride bar is placed in a tubular atmosphere furnace for heat treatment, the heating rate is 10 ℃/min to 30 ℃/min, the heat treatment temperature is 350 ℃ to 450 ℃, and the heat preservation time is 2h to 24 h.
8. The method for hot extrusion molding of the bismuth telluride thermoelectric material as set forth in claim 1, wherein the first protective gas is one or more of argon gas, nitrogen gas and a mixed gas of hydrogen and argon.
9. The method for hot extrusion molding of the bismuth telluride thermoelectric material as set forth in claim 1, wherein the second protective gas is one or more of argon gas, nitrogen gas and a mixed gas of hydrogen and argon.
10. The method for hot extrusion molding of the bismuth telluride thermoelectric material as set forth in claim 1, wherein the third protective gas is one or more of argon gas, nitrogen gas and a mixed gas of hydrogen and argon.
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