CN108550689B - Preparation method of N-type bismuth telluride-based thermoelectric material - Google Patents
Preparation method of N-type bismuth telluride-based thermoelectric material Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 55
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 45
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 37
- 239000010453 quartz Substances 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 23
- 230000008018 melting Effects 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 20
- 238000004857 zone melting Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000003780 insertion Methods 0.000 claims abstract description 8
- 230000037431 insertion Effects 0.000 claims abstract description 8
- 238000005192 partition Methods 0.000 claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- 238000009461 vacuum packaging Methods 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 238000009830 intercalation Methods 0.000 claims description 28
- 230000002687 intercalation Effects 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 238000000859 sublimation Methods 0.000 claims description 3
- 230000008022 sublimation Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 30
- 238000003723 Smelting Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 239000002178 crystalline material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 229910002899 Bi2Te3 Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 102000002274 Matrix Metalloproteinases Human genes 0.000 description 1
- 108010000684 Matrix Metalloproteinases Proteins 0.000 description 1
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000010168 coupling process Methods 0.000 description 1
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- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N15/00—Thermoelectric devices without a junction of dissimilar materials; Thermomagnetic devices, e.g. using the Nernst-Ettingshausen effect
- H10N15/10—Thermoelectric devices using thermal change of the dielectric constant, e.g. working above and below the Curie point
- H10N15/15—Thermoelectric active materials
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Abstract
The invention discloses a preparation method of an N-type bismuth telluride based thermoelectric material, which comprises the following steps of weighing corresponding raw materials according to the stoichiometric ratio of the N-type bismuth telluride based crystal material, placing the raw materials into a quartz tube for vacuum packaging, carrying out swing melting at high temperature, and preparing the N-type bismuth telluride based crystal material by using a zone melting method; taking an N-type bismuth telluride-based crystal material as a reaction matrix and I2The molecules are used as insertion compounds, and the reaction matrix and the insertion compounds are respectively placed at two ends of the quartz tube; heating the area where the reaction matrix and the inserted compound are placed to a certain temperature simultaneously, and preserving the temperature to realize I under high-temperature steam2Molecular adsorption; then, the two areas are respectively cooled to room temperature by adopting a partition cooling mode to obtain I2The molecule embedded N-type bismuth telluride based thermoelectric material. The method not only ensures the orientation and the electrical property of the N-type bismuth telluride, but also reduces the lattice thermal conductivity, thereby realizing the coordinated regulation and control of the electrical and thermal transport properties of the N-type bismuth telluride based thermoelectric material and the improvement of the ZT value.
Description
Technical Field
The invention relates to the technical field of thermoelectric materials, in particular to a preparation method of an N-type bismuth telluride-based thermoelectric material.
Background
The thermoelectric material is a functional material which realizes direct mutual coupling between heat energy and electric energy based on the Seebeck effect and the Peltier effect of the semiconductor, and has wide application prospect in the aspects of thermoelectric power generation and semiconductor refrigeration because the thermoelectric material has the advantages of no pollution, no noise, small size, long service life, accurate control and the like. The main parameter for measuring the performance of thermoelectric material is called thermoelectric figure of merit, ZT ═ alpha2σ T/κ, where α is the Seebeck coefficient, σ is the electrical conductivity, κ is the thermal conductivity (including lattice thermal conductivity κ)LAnd electron thermal conductivity κe) And T is the absolute temperature. The larger the ZT value, the higher the thermoelectric conversion efficiency of the material. Bi2Te3The base alloy is a thermoelectric material with the best performance near room temperature, commercial bismuth telluride is usually prepared by adopting a zone melting method, the ZT value is about 1.0, but the ZT value is higher than that of the prior artThe major factor is P-type bismuth telluride, the ZT value of the N-type bismuth telluride material is relatively low, mainly because the N-type bismuth telluride is more sensitive and dependent on the orientation of the material, and in practical application, the thermoelectric device with high conversion efficiency needs the P-type material and the N-type material to have high ZT value at the same time, so that the N-type Bi is improved2Te3The thermoelectric property of the bismuth telluride-based thermoelectric material is very critical to the application of the bismuth telluride-based thermoelectric material.
Improving N type Bi in the prior art2Te3The main method for thermoelectric performance is to optimize the electrical performance of the material by doping, but the method has limited improvement on the ZT value of the material; and adopts methods of nanocrystallization and the like to improve the N-type Bi2Te3The thermoelectric property of the composite material can destroy the oriented structure of the composite material, and is not beneficial to the cooperative optimization of the electric and thermal properties.
Disclosure of Invention
The invention aims to provide a preparation method of an N-type bismuth telluride based thermoelectric material, which not only ensures the orientation and the electrical property of the N-type bismuth telluride, but also reduces the lattice thermal conductivity, thereby realizing the cooperative regulation and control of the electrical and thermal transport properties of the N-type bismuth telluride based thermoelectric material and the improvement of the ZT value.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an N-type bismuth telluride-based thermoelectric material comprises the following steps:
In the step 1, the N-type bismuth telluride based crystal material is prepared by taking Bi, Sb, Te and Se as raw materials.
In step 1, the parameters used by the float zone method include:
the melting temperature is 700-800 ℃; the temperature rise speed is 25 ℃/min; the width of the melting zone is 30-40 mm; the temperature gradient is 25-50 ℃/cm; the growth speed is 25-30 mm/h.
The heat preservation temperature in the step 3 is 55-113 ℃, and is in the temperature I2Between the sublimation temperature and the melting point.
In step 4, the cooling method in the subareas specifically comprises:
firstly, reducing the temperature of the area where the intercalation compound is placed at a set cooling rate, and after the temperature of the area where the intercalation compound is placed is reduced by 30 ℃, reducing the temperature of the area where the reaction substrate is placed at the same cooling rate until the temperature of the two areas is reduced to room temperature.
The set cooling rate is 3-5 ℃/min, and the temperature difference of positive 30 ℃ exists between the two areas where the reaction matrix and the inserted compound are placed is ensured all the time in the whole cooling process.
According to the technical scheme provided by the invention, on one hand, the method ensures the electrical property of the N-type bismuth telluride by utilizing the crystal orientation, and on the other hand, the method utilizes the inserted heterogeneous I2The molecules scatter phonons and the lattice thermal conductivity is reduced, so that the coordinated regulation and control of the electrical and thermal transport properties of the N-type bismuth telluride-based thermoelectric material and the improvement of the ZT value are realized.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for preparing an N-type bismuth telluride-based thermoelectric material according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a reaction process provided by an embodiment of the present invention;
FIG. 3 shows an embodiment of the present invention2N-type Bi before and after intercalation2Te2.7Se0.3The graph of the lattice thermal conductivity with the temperature is shown schematically;
FIG. 4 shows an embodiment of the present invention2N-type Bi before and after intercalation2Te2.7Se0.3The thermoelectric figure of merit ZT of (1) is shown as a graph varying with temperature.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Embodiments of the present invention will be described in further detail with reference to the accompanying drawings, and fig. 1 is a schematic flow chart of a method for preparing a N-type bismuth telluride-based thermoelectric material, the method including:
in the step, the N-type bismuth telluride based crystal material is prepared by combining Bi, Sb, Te and Se as raw materials.
The parameters adopted by the zone melting method comprise:
the melting temperature is 700-800 ℃; the temperature rise speed is 25 ℃/min; the width of the melting zone is 30-40 mm; the temperature gradient is 25-50 ℃/cm; the growth speed is 25-30 mm/h.
FIG. 2 is a schematic diagram of the reaction process provided by the embodiment of the present invention, wherein I is shown on the left side of FIG. 22The molecule is taken as a region for inserting the compound, and the right side is a region taking the N-type bismuth telluride-based crystal material as a reaction matrix.
the heat preservation temperature is 55-113 ℃ and is in the temperature range I2Between the sublimation temperature and the melting point of (C) to ensure I2Generating higher steam pressure, the force of the steam pressure can be I2Molecules are inserted between the layers of bismuth telluride to form intercalated compounds, which are sublimed at high temperature as shown in FIG. 22The holding time of the molecule can be 6-24 hours.
In this step, the way of cooling in different zones specifically is:
firstly, reducing the temperature of the area where the intercalation compound is placed at a set cooling rate, and after the temperature of the area where the intercalation compound is placed is reduced by 30 ℃, reducing the temperature of the area where the reaction substrate is placed at the same cooling rate until the temperature of the two areas is reduced to room temperature.
The set cooling rate is 3-5 ℃/min, and the temperature difference of positive 30 ℃ is always ensured between the two areas where the reaction matrix and the inserted compound are placed in the whole cooling process, so that the redundant I is prevented2And finally, the molecules are desublimated on the surface of the bismuth telluride sample.
The above preparation method is described in detail below by specific examples:
example 1 with N-type Bi2Te2.7Se0.3The raw materials of Bi, Te and Se powder are weighed according to the stoichiometric ratio, and the original powder is placed in a quartz tube and vacuumized to 10 degrees-5Packaging after Pa, putting the quartz tube into a rocking furnace, smelting at 800 ℃ for 4 hours, and cooling to room temperature along with the furnace;
then putting the quartz tube into a zone melting growth furnace, and setting zone melting conditions as follows: the melting temperature is 720 ℃, the temperature rising speed is 25 ℃/min, the melting zone width is 30mm, the temperature gradient is 25 ℃/cm, the growth speed is 25mm/h, and the N-type Bi is prepared2Te2.7Se0.3A crystalline material.
Adding N-type Bi2Te2.7Se0.3Crystal as reaction matrix, proper amount of I2Placing the powder as intercalation compound at two ends of quartz tube, and vacuumizing the quartz tube (to 10%-5Pa) sealing treatment, horizontally placing in a tube furnace with zoned temperature control, and mixing the bismuth telluride region with I2The powder area is simultaneously heated to 60 ℃ and kept for 10 hours.
Then, firstly, the temperature I is reduced at the cooling rate of 5 ℃/min2Temperature of the powder region, wait2After the temperature of the powder area is reduced by 30 ℃, the Bi is reduced at the same cooling rate of 5 ℃/min2Te2.7Se0.3Until the temperature of the two zones is reduced to room temperature, finally obtaining I2Molecularly embedded N-type Bi2Te2.7Se0.3The thermoelectric material is intercalated.
Further characterization and measurement of the above-mentioned N-type Bi2Te2.7Se0.3To carry out I2The relative thermoelectric properties before and after intercalation are compared to obtain I shown in FIG. 32N-type Bi before and after intercalation2Te2.7Se0.3A graph of the thermal conductivity of the crystal lattice as a function of temperature, and I shown in FIG. 42N-type Bi before and after intercalation2Te2.7Se0.3The thermoelectric figure of merit ZT of (1) is shown as a graph varying with temperature.
As can be seen from fig. 3: due to the inserted I2The molecules have a stronger scattering effect on phonons, I2Intercalated N-type Bi2Te2.7Se0.3Has a lattice thermal conductivity lower than I over the entire test temperature range2Bi before intercalation2Te2.7Se0.3The lattice thermal conductivity of (a); as can be seen from fig. 4: i is2Intercalated N-type Bi2Te2.7Se0.3ZT value of (A) is higher than I over the entire test temperature range2Bi before intercalation2Te2.7Se0.3ZT value of (1).
The above results illustrate that I prepared by the vapor adsorption method in this example2Intercalation N type Bi2Te2.7Se0.3The thermoelectric performance of the thermoelectric element is optimized.
Example 2 preparation of N-type Bi2Te2.7Se0.3The raw materials of Bi, Te and Se powder are weighed according to the stoichiometric ratio, and the original powder is placed in a quartz tube and vacuumized to 10 degrees-5Packaging after Pa, putting the quartz tube into a rocking furnace, smelting at 800 ℃ for 4 hours, and cooling to room temperature along with the furnace; then putting the quartz tube into a zone melting growth furnace, and setting zone melting conditions as follows: the melting temperature is 720 ℃, the temperature rising speed is 25 ℃/min, the melting zone width is 30mm, the temperature gradient is 25 ℃/cm, the growth speed is 25mm/h, and the N-type Bi is prepared2Te2.7Se0.3A crystalline material. Adding N-type Bi2Te2.7Se0.3Crystal as reaction matrix, proper amount of I2Placing the powder as intercalation compound at two ends of quartz tube, and vacuumizing the quartz tube (to 10%-5Pa) sealing treatment, horizontally placing in a tube furnace with zoned temperature control, and mixing the bismuth telluride region with I2The powder area is simultaneously heated to 60 ℃ and kept for 20 hours. Then, firstly, the temperature I is reduced at the cooling rate of 5 ℃/min2Temperature of the powder region, wait2After the temperature of the powder area is reduced by 30 ℃, the Bi is reduced at the same cooling rate of 5 ℃/min2Te2.7Se0.3Until the temperature of the two zones is reduced to room temperature, finally obtaining I2Molecularly embedded N-type Bi2Te2.7Se0.3The thermoelectric material is intercalated.
Characterization measurement of the above-mentioned N-type Bi2Te2.7Se0.3To carry out I2The relative thermoelectric properties before and after intercalation are compared to obtain results similar to those of FIGS. 3 and 4, indicating that I prepared in this example2Intercalation N type Bi2Te2.7Se0.3The thermoelectric performance of the thermoelectric element is optimized.
Example 3 preparation of Bi of N type2Te2.7Se0.3The raw materials of Bi, Te and Se powder are weighed according to the stoichiometric ratio, and the original powder is placed in a quartz tube and vacuumized to 10 degrees-5Packaging after Pa, putting the quartz tube into a rocking furnace, smelting at 800 ℃ for 4 hours, and cooling to room temperature along with the furnace; then putting the quartz tube into a zone melting growth furnace, and setting zone melting conditions as follows: the melting temperature is 720 ℃, the temperature rising speed is 25 ℃/min, the melting zone width is 30mm, the temperature gradient is 25 ℃/cm, the growth speed is 25mm/h, and the N-type Bi is prepared2Te2.7Se0.3A crystalline material. Adding N-type Bi2Te2.7Se0.3Crystal as reaction matrix, proper amount of I2Placing the powder as intercalation compound at two ends of quartz tube, and vacuumizing the quartz tube (to 10%-5Pa) sealing treatment, horizontally placing in a tube furnace with zoned temperature control, and mixing the bismuth telluride region with I2The powder area is simultaneously heated to 80 ℃ and kept for 10 hours. Then, firstly, the temperature I is reduced at the cooling rate of 5 ℃/min2Temperature of the powder region, wait2After the temperature of the powder area is reduced by 30 ℃, the Bi is reduced at the same cooling rate of 5 ℃/min2Te2.7Se0.3Until the temperature of the two zones is reduced to room temperature, finally obtaining I2Molecularly embedded N-type Bi2Te2.7Se0.3The thermoelectric material is intercalated.
Characterization measurement of the above-mentioned N-type Bi2Te2.7Se0.3To carry out I2The relative thermoelectric properties before and after intercalation are compared to obtain results similar to those of FIGS. 3 and 4, indicating that I prepared in this example2Intercalation N type Bi2Te2.7Se0.3The thermoelectric performance of the thermoelectric element is optimized.
Example 4 preparation of Bi of N type2Te2.7Se0.3The raw materials of Bi, Te and Se powder are weighed according to the stoichiometric ratio, and the original powder is placed in a quartz tube and vacuumized to 10 degrees-5Packaging after Pa, putting the quartz tube into a rocking furnace, smelting at 800 ℃ for 4 hours, and cooling to room temperature along with the furnace; then the quartz tube is put into a zone melting growth furnace, and zone melting strips are arrangedA piece: the melting temperature is 720 ℃, the temperature rising speed is 25 ℃/min, the melting zone width is 30mm, the temperature gradient is 25 ℃/cm, the growth speed is 25mm/h, and the N-type Bi is prepared2Te2.7Se0.3A crystalline material. Adding N-type Bi2Te2.7Se0.3Crystal as reaction matrix, proper amount of I2Placing the powder as intercalation compound at two ends of quartz tube, and vacuumizing the quartz tube (to 10%-5Pa) sealing treatment, horizontally placing in a tube furnace with zoned temperature control, and mixing the bismuth telluride region with I2The powder area is simultaneously heated to 100 ℃ and kept for 10 hours. Then, the temperature I is reduced at the cooling rate of 3 ℃/min2Temperature of the powder region, wait2After the temperature of the powder area is reduced by 30 ℃, the Bi is reduced at the same cooling rate of 3 ℃/min2Te2.7Se0.3Until the temperature of the two zones is reduced to room temperature, finally obtaining I2Molecularly embedded N-type Bi2Te2.7Se0.3The thermoelectric material is intercalated.
Characterization measurement of the above-mentioned N-type Bi2Te2.7Se0.3To carry out I2The relative thermoelectric properties before and after intercalation are compared to obtain results similar to those of FIGS. 3 and 4, indicating that I prepared in this example2Intercalation N type Bi2Te2.7Se0.3The thermoelectric performance of the thermoelectric element is optimized.
Example 5 preparation of Bi of N type2Te2.5Se0.5The raw materials of Bi, Te and Se powder are weighed according to the stoichiometric ratio, and the original powder is placed in a quartz tube and vacuumized to 10 degrees-5Packaging after Pa, putting the quartz tube into a rocking furnace, smelting at 800 ℃ for 4 hours, and cooling to room temperature along with the furnace; then putting the quartz tube into a zone melting growth furnace, and setting zone melting conditions as follows: the melting temperature is 720 ℃, the temperature rising speed is 25 ℃/min, the melting zone width is 30mm, the temperature gradient is 25 ℃/cm, the growth speed is 25mm/h, and the N-type Bi is prepared2Te2.5Se0.5A crystalline material. Adding N-type Bi2Te2.5Se0.5Crystal as reaction matrix, proper amount of I2Placing the powder as intercalation compound at two ends of quartz tube, and vacuumizing the quartz tube (to 10%-5Pa) sealing treatment and horizontally placing in a partitionable wayIn a temperature-controlled tube furnace, the bismuth telluride region is connected with I2The powder area is simultaneously heated to 100 ℃ and kept for 10 hours. Then, the temperature I is reduced at the cooling rate of 3 ℃/min2Temperature of the powder region, wait2After the temperature of the powder area is reduced by 30 ℃, the Bi is reduced at the same cooling rate of 3 ℃/min2Te2.5Se0.5Until the temperature of the two zones is reduced to room temperature, finally obtaining I2Molecularly embedded N-type Bi2Te2.5Se0.5The thermoelectric material is intercalated.
Characterization measurement of the above-mentioned N-type Bi2Te2.5Se0.5To carry out I2The relative thermoelectric properties before and after intercalation are compared to obtain results similar to those of FIGS. 3 and 4, indicating that I prepared in this example2Intercalation N type Bi2Te2.5Se0.5The thermoelectric performance of the thermoelectric element is optimized.
It is noted that those skilled in the art will recognize that embodiments of the present invention are not described in detail herein.
In summary, the preparation method provided by the embodiment of the invention not only ensures the orientation and electrical properties of the N-type bismuth telluride, but also utilizes the inserted heterogeneous I2The lattice thermal conductivity is reduced by the molecular scattering phonons, so that the coordinated regulation and control of the electrical and thermal transport properties of the N-type bismuth telluride-based thermoelectric material and the improvement of the ZT value are realized.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (3)
1. A preparation method of an N-type bismuth telluride-based thermoelectric material is characterized by comprising the following steps:
step 1, weighing corresponding raw materials according to the stoichiometric ratio of the N-type bismuth telluride-based crystal material, placing the raw materials in a quartz tube for vacuum packaging, carrying out swing melting at high temperature, and preparing the N-type bismuth telluride-based crystal material by using a zone melting method;
step 2, taking the prepared N-type bismuth telluride-based crystal material as a reaction matrix, and taking I as2The molecules are used as insertion compounds, and the reaction matrix and the insertion compounds are respectively placed at two ends of the quartz tube;
step 3, the quartz tube in the step 2 is horizontally placed in a tube furnace capable of controlling the temperature in a partition mode after being vacuumized and sealed, the area where the reaction substrate and the inserted compound are placed is simultaneously heated to a certain temperature and is kept warm, and the effect that I under high-temperature steam is achieved2Molecular adsorption; wherein the heat preservation temperature is 55-113 ℃ and is in the temperature range of I2Between the sublimation temperature and the melting point of (c);
step 4, respectively cooling the two areas with the reaction matrix and the inserted compound to room temperature by adopting a partition cooling mode to obtain I2A molecularly-embedded N-type bismuth telluride-based thermoelectric material;
the partition cooling mode specifically comprises the following steps:
firstly, reducing the temperature of a region where an intercalation compound is placed at a set cooling rate, and reducing the temperature of the region where the intercalation compound is placed at the same cooling rate after the temperature of the region where the intercalation compound is placed is reduced by 30 ℃;
the set cooling rate is 3-5 ℃/min, and the whole cooling process always ensures that the two areas where the reaction matrix and the inserted compound are placed have positive 30 ℃ temperature difference until the temperatures of the two areas are respectively cooled to room temperature.
2. The method for producing a bismuth-N-telluride-based thermoelectric material as claimed in claim 1, wherein in step 1, the bismuth-N-telluride-based crystal material is prepared by using Bi, Sb, Te and Se as raw materials.
3. The method for preparing the N-type bismuth telluride-based thermoelectric material as set forth in claim 1, wherein in the step 1, the parameters adopted by the zone melting method include:
the melting temperature is 700-800 ℃; the temperature rise speed is 25 ℃/min; the width of the melting zone is 30-40 mm; the temperature gradient is 25-50 ℃/cm; the growth speed is 25-30 mm/h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201031265Y (en) * | 2007-05-09 | 2008-03-05 | 四川大学 | Two regions gas-phase transport synthesizing container |
| CN107059132A (en) * | 2017-03-29 | 2017-08-18 | 磐石创新（北京）电子装备有限公司 | The Novel single crystal furnace and growth technique of a kind of Te-Zn-Cd monocrystal |
| CN107093560A (en) * | 2017-04-19 | 2017-08-25 | 湖南大学 | A kind of bismuth iodide two-dimensional material, preparation and its application |
| TW201802309A (en) * | 2016-07-13 | 2018-01-16 | 鴻海精密工業股份有限公司 | Semimetal compound of Pt and method for making the same |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN101994155B (en) * | 2010-11-18 | 2012-12-26 | 中国科学院宁波材料技术与工程研究所 | Nanophase doped bismuth telluride-based thermoelectric material and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201031265Y (en) * | 2007-05-09 | 2008-03-05 | 四川大学 | Two regions gas-phase transport synthesizing container |
| TW201802309A (en) * | 2016-07-13 | 2018-01-16 | 鴻海精密工業股份有限公司 | Semimetal compound of Pt and method for making the same |
| CN107620123A (en) * | 2016-07-13 | 2018-01-23 | 清华大学 | A kind of preparation method of the semi metallic compound of metal platinum |
| CN107059132A (en) * | 2017-03-29 | 2017-08-18 | 磐石创新（北京）电子装备有限公司 | The Novel single crystal furnace and growth technique of a kind of Te-Zn-Cd monocrystal |
| CN107093560A (en) * | 2017-04-19 | 2017-08-25 | 湖南大学 | A kind of bismuth iodide two-dimensional material, preparation and its application |
Non-Patent Citations (1)
| Title |
|---|
| 改进的两温区气相输运法合成碘化铅(PbI_2)多晶;赵欣等;《无机化学学报》;20110210(第02期);全文 * |
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