CN117923901A - Germanium telluride-based thermoelectric material and preparation method and application thereof - Google Patents
Germanium telluride-based thermoelectric material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 66
- GPMBECJIPQBCKI-UHFFFAOYSA-N germanium telluride Chemical compound [Te]=[Ge]=[Te] GPMBECJIPQBCKI-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 10
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 8
- 238000000137 annealing Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 4
- 239000001670 anatto Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010248 power generation Methods 0.000 abstract description 8
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 239000010453 quartz Substances 0.000 description 25
- 229910002804 graphite Inorganic materials 0.000 description 21
- 239000010439 graphite Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 16
- 238000005245 sintering Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 14
- 238000004321 preservation Methods 0.000 description 12
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- 238000010791 quenching Methods 0.000 description 10
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- 238000007789 sealing Methods 0.000 description 10
- 229910005900 GeTe Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
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- 238000002844 melting Methods 0.000 description 6
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- 238000010438 heat treatment Methods 0.000 description 5
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- 238000005516 engineering process Methods 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- 229910052714 tellurium Inorganic materials 0.000 description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 238000010304 firing Methods 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The application discloses a germanium telluride-based thermoelectric material and application thereof, and the chemical formula is Ge 1‑nMn Te; wherein M is at least one selected from Bi, in and Cd; the mole fraction of M is n, n is more than 0 and less than or equal to 0.11. The method adopts a strategy of co-doping three elements, and the co-doping of three different elements not only optimizes the carrier concentration and the energy band structure of the germanium telluride, but also effectively reduces the lattice thermal conductivity of the germanium telluride under the condition of keeping high carrier mobility. Therefore, the thermoelectric merit of germanium telluride is improved under the comprehensive regulation and control effect of electric and thermal properties. The germanium telluride-based thermoelectric material has the advantages of simple, stable and efficient preparation process and excellent thermoelectric performance, and can well meet the requirements of thermoelectric power generation application in a medium temperature area.
Description
Technical Field
The application relates to a germanium telluride-based thermoelectric material, a preparation method and application thereof, and belongs to the technical field of thermoelectric materials.
Background
Thermoelectric technology is the simplest technology capable of directly converting heat energy and electric energy into each other, and can convert solar energy, geothermal energy, motor vehicles and industrial waste heat into electricity, and conversely can also be used as a heat pump to realize refrigeration. The thermoelectric device has the advantages of full solid state, light weight, compact structure, quick response, no moving parts, harmful working medium and the like. The modularity makes it easy to use with other energy conversion technologies, a very important feature for new energy applications, as no single technology can meet the world's energy needs. The thermoelectric performance of a thermoelectric material is measured primarily by the dimensionless figure of merit zt=s 2σT/κtot, where S is the seebeck coefficient, σ is the electrical conductivity, κ tot is the total thermal conductivity, and T is the absolute temperature. The mutual coupling between these thermoelectric transport parameters interacts, which makes the enhancement of thermoelectric performance challenging.
The thermoelectric material germanium telluride in the medium temperature area has a crystal structure and an electronic energy band structure similar to those of lead telluride, and does not contain toxic element lead, so that the thermoelectric material germanium telluride is expected to be an effective substitute of lead telluride. Aiming at optimizing the thermoelectric performance of a germanium telluride system, the traditional means is to utilize doping and other modes to generate a unique uncoupled variable which is a nano second phase, a micro-size structure and the like in a matrix to reduce the lattice heat conductivity, so that the heat transport performance is improved, and the thermoelectric performance of the material is improved. In recent years, energy band engineering is also widely used to optimize the electrical transport performance of germanium telluride material systems for energy band defects of germanium telluride. The common defect design and energy band regulation can optimize the effective mass and lattice thermal conductivity of the carriers, but can also reduce the mobility of the carriers, so that the average thermoelectric figure of merit of the germanium telluride thermoelectric material is improved only to a limited extent.
Disclosure of Invention
Maintaining high carrier mobility is critical to improving the average thermoelectric figure of merit of a material over a wide temperature range.
According to one aspect of the application, the germanium telluride-based thermoelectric material is provided, and the strategy of co-doping of three elements Bi, in and Cd can effectively balance carrier and phonon scattering, and cooperatively regulate and control the relation among carrier mobility, effective mass and carrier concentration, so that germanium telluride can obtain a great improvement of thermoelectric figure of merit In a wide temperature range.
According to one aspect of the present application, there is provided a germanium telluride-based thermoelectric material having the chemical formula Ge 1-nMn Te.
Wherein M is at least one selected from Bi, in and Cd.
The mole fraction of M is n, n is more than 0 and less than or equal to 0.11.
Further, the chemical formula of the germanium telluride-based thermoelectric material is Ge 1-x-y-zBixInyCdz Te;
Wherein x represents the mole fraction of the doping element Bi, and the value range of x is more than or equal to 0 and less than or equal to 0.06; the value range of x is independently selected from any value in 0, 0.02, 0.04 and 0.06 or a range value between any two.
Y represents the mole fraction of the doping element In, and the value range of y is more than or equal to 0 and less than or equal to 0.01; alternatively, the value range of y is independently selected from any value or range of values between any two of 0, 0.002, 0.004, 0.006, 0.008, 0.01.
Z represents the mole fraction of the doped element Cd, and the value range of the doped element Cd is more than or equal to 0 and less than or equal to 0.04; optionally, the value range of z is independently selected from any value or range of values between any two of 0, 0.01, 0.02, 0.03, 0.04;
according to another aspect of the present application, there is provided a method for preparing the germanium telluride-based thermoelectric material, comprising the steps of:
Mixing the raw materials containing Ge simple substance, M simple substance and Te simple substance, roasting and annealing to obtain the germanium telluride-based thermoelectric material.
The roasting temperature is 900-950 ℃;
optionally, the firing temperature is any value or range of values between any two of 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃.
The roasting time is 1-3 h.
Optionally, the firing time is any value or range of values between any two of 1h, 2h, 3 h.
The roasting is carried out in a vacuum environment;
the vacuum degree of the vacuum environment is 5 Pa-10 Pa.
Optionally, the vacuum environment has a vacuum degree of any value or a range of values between any two of 5Pa, 6Pa, 7Pa, 8Pa, 9Pa, 10 Pa.
The annealing temperature is 600-650 ℃;
Optionally, the temperature of the annealing is any value or range of values between any two of 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃.
The annealing time is 48-72 h.
Optionally, the time of the annealing is any value or range of values between any two of 48h, 56h, 64h, 72 h.
Further, when M includes Bi, in, cd:
the method comprises the following steps:
placing raw materials containing a Ge source, a Bi source, an In source, a Cd source and a Te source under a vacuum condition, and melting, quenching, annealing, cooling and ball milling to obtain powder;
Sintering the powder at high temperature to obtain the germanium telluride-based thermoelectric material;
the addition amounts of the Ge source, the Bi source, the In source, the Cd source and the Te source meet the molar ratio of each element In the formula I.
Optionally, the Ge source in the raw material is selected from Ge simple substance; the Bi source is selected from Bi simple substance; the In source is selected from In simple substance; the Cd source is selected from Cd; the Te source is selected from Te simple substance; the N source is selected from N simple substance.
Optionally, the conditions of melting are: the melting temperature is 900-950 ℃; the melting time is 1-3 h.
Optionally, the quenched medium is: ice water or liquid nitrogen.
Optionally, the annealing conditions are: the annealing temperature is 600-650 ℃; the annealing time is 48-72 h.
Alternatively, the high temperature sintering has an upper temperature limit independently selected from 560 ℃, 500 ℃, 450 ℃, 400 ℃, and a lower temperature limit independently selected from 360 ℃, 500 ℃, 450 ℃, 400 ℃.
Optionally, the conditions of the high-temperature sintering are: sintering temperature is 500-600 ℃, sintering pressure is 50-60 Mpa, and sintering time is 5-15 min.
As a specific embodiment, the germanium telluride-based thermoelectric material employs the following steps:
Step 1: the chemical components in the formula I are weighed and put into a clean quartz glass tube; sealing under <1Pa vacuum.
Step 2: melting and swinging, and melting for 0.5 hour at 950 ℃ and swinging for 0.5 hour.
Step 3: quenching, namely rapidly placing the high-temperature molten material obtained in the step 2 into ice water until the molten material is completely condensed into an ingot.
Step 4: annealing, namely placing the cast ingot obtained in the step 3 into an annealing furnace, wherein the annealing temperature is 600 ℃; the annealing time was 48h.
Step 5: and (3) crushing the cast ingot, namely crushing the cast ingot obtained in the step (4) in a glove box by using an agate mortar, wherein the grinding time is 10-30 minutes, and the inert gas is used for protection.
Step 6: and (3) hot-pressing sintering, namely placing the powder obtained in the step (5) into a metal/graphite die, uniformly heating and boosting to 60MPa, maintaining the temperature at 550 ℃ for 10 minutes, and finally cooling to room temperature and uniformly releasing pressure to obtain a sample.
Specifically, when the germanium telluride-based thermoelectric material prepared in the application is used for the electrothermal transport performance test, the thermoelectric material is cut into samples of 3mm×3mm×13mm and 1.5mm×10 mm.
According to another aspect of the present application, there is provided an application of the germanium telluride-based thermoelectric material or the germanium telluride-based thermoelectric material prepared by the preparation method for a medium temperature zone thermoelectric converter.
The working temperature of the thermoelectric converter in the medium temperature region is 177-500 ℃.
The application has the beneficial effects that:
The method adopts a strategy of co-doping three elements, and the co-doping of three different elements not only optimizes the carrier concentration and the energy band structure of the germanium telluride, but also effectively reduces the lattice thermal conductivity of the germanium telluride under the condition of keeping high carrier mobility. Therefore, the thermoelectric merit of germanium telluride is improved under the comprehensive regulation and control effect of electric and thermal properties. The germanium telluride-based thermoelectric material has the advantages of simple, stable and efficient preparation process and excellent thermoelectric performance, and can well meet the requirements of thermoelectric power generation application in a medium temperature area.
Specifically:
1) The germanium telluride-based thermoelectric material for low-medium temperature region power generation provided by the application has the advantages that the effective mass of state density is obviously improved, and the overall electrical performance of the material is effectively improved.
2) The germanium telluride-based thermoelectric material for low-medium temperature region power generation provided by the application obviously maintains high carrier mobility and effectively maintains the overall electrical property of the material.
3) The germanium telluride-based thermoelectric material for low-medium temperature region power generation provided by the application effectively enhances the selective scattering of phonons, thereby reducing the lattice thermal conductivity of the germanium telluride-based thermoelectric material.
4) The germanium telluride-based thermoelectric material for low-medium temperature region power generation provided by the application can greatly improve the thermoelectric figure of merit ZT of the germanium telluride-based thermoelectric material in a wide temperature region, and improve the thermoelectric conversion efficiency of the germanium telluride-based thermoelectric material in a low-medium temperature environment.
5) The preparation method of the germanium telluride-based thermoelectric material provided by the application has the advantages of short preparation period and simple process.
6) The preparation method of the compact block thermoelectric material provided by the application can avoid sample cracking and rupture.
Drawings
FIG. 1 is a graph showing the relationship between the conductivities of examples 1 to 3 and comparative example 1 and the temperature.
Fig. 2 is a graph showing the relationship between seebeck coefficients of examples 1 to 3 and comparative example 1 with respect to temperature.
Fig. 3 is a graph showing the power factor versus temperature for examples 1 to 3 and comparative example 1.
Fig. 4 is a graph of thermal conductivity versus temperature for examples 1-3 and comparative example 1.
Fig. 5 is a graph of lattice thermal conductivity versus temperature for examples 1-3 and comparative example 1.
FIG. 6 is a graph showing thermoelectric figure of merit versus temperature for examples 1 to 3 and comparative example 1.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Comparative example 1
This comparative example is a comparative example of examples 1,2, 3 below. This comparative example is a germanium telluride-based bulk thermoelectric material that is undoped with Bi, in, and Cd. The method comprises the following steps:
(1) Weighing 15g of raw materials, weighing germanium particles (99.999%) and tellurium particles (99.999%) according to a chemical formula GeTe, loading the raw materials into a clean quartz tube, fixing the quartz tube on a tube sealing device, and sealing the quartz tube under the condition that the vacuum degree negative pressure is not higher than 0.8 Pa; placing the sealed quartz tube in a rocking furnace with the temperature of 950 ℃, and starting a rocking switch after heat preservation for half an hour so as to facilitate better combination between the quartz tube and the rocking furnace; taking out the quartz tube filled with the high-temperature molten material after swinging for half an hour, and immediately inserting the quartz tube into ice water for quenching; placing the ingot obtained after quenching in an annealing furnace, and annealing for two days at 600 ℃; the obtained ingot was manually ground into powder and ground for 10min.
(2) Pouring the prepared powder into a graphite grinding tool, sealing the upper and lower parts by using graphite carbon paper and a graphite carbon rod, and then placing the graphite carbon paper and the graphite carbon rod into a vacuum hot pressing furnace for vacuum sintering. Sintering temperature is 550 ℃, pressure is 60MPa, and heat preservation time is 10min. And after the heat preservation is finished, turning off a heating power supply, removing pressure when the temperature is reduced to 40 ℃, cooling to room temperature, breaking a vacuum state, and taking out a sample to obtain the germanium telluride cylindrical block thermoelectric material.
(3) The sintered cylindrical block thermoelectric material was cut into 2.5mm×2.5mm×12mm strips and 1.5mm×10mm sheets for measuring the electric transport property and the heat transport property, respectively.
Example 1
(1) 15G of raw material is weighed, germanium particles (99.999%), bismuth particles (99.999%) and tellurium particles (99.999%) are weighed according to the chemical formula Ge 0.94Bi0.06 Te, the raw material is put into a clean quartz tube and fixed on a tube sealing device, and the quartz tube is sealed under the condition that the vacuum degree negative pressure is not higher than 0.8 Pa; placing the sealed quartz tube in a rocking furnace with the temperature of 950 ℃, and starting a rocking switch after heat preservation for half an hour so as to facilitate better combination between the quartz tube and the rocking furnace; taking out the quartz tube filled with the high-temperature molten material after swinging for half an hour, and immediately inserting the quartz tube into ice water for quenching; placing the ingot obtained after quenching in an annealing furnace, and annealing for two days at 600 ℃; the obtained ingot was manually ground into powder and ground for 10min.
(2) Pouring the prepared powder into a graphite grinding tool, sealing the upper and lower parts by using graphite carbon paper and a graphite carbon rod, and then placing the graphite carbon paper and the graphite carbon rod into a vacuum hot pressing furnace for vacuum sintering. Sintering temperature is 550 ℃, pressure is 60MPa, and heat preservation time is 10min. And after the heat preservation is finished, turning off a heating power supply, removing pressure when the temperature is reduced to 40 ℃, cooling to room temperature, breaking a vacuum state, and taking out a sample to obtain the germanium telluride cylindrical block thermoelectric material.
(3) The sintered cylindrical block thermoelectric material was cut into 2.5mm×2.5mm×12mm strips and 1.5mm×10mm sheets for measuring the electric transport property and the heat transport property, respectively.
Example 2
(1) 15G of raw materials are weighed, germanium particles (99.999%), bismuth particles (99.999%), indium particles (99.999%) and tellurium particles (99.999%) are weighed according to chemical formula Ge 0.94Bi0.06In0.01 Te, the raw materials are filled into a clean quartz tube and fixed on a tube sealing device, and the quartz tube is sealed under the condition that the vacuum degree negative pressure is not higher than 0.8 Pa; placing the sealed quartz tube in a rocking furnace with the temperature of 950 ℃, and starting a rocking switch after heat preservation for half an hour so as to facilitate better combination between the quartz tube and the rocking furnace; taking out the quartz tube filled with the high-temperature molten material after swinging for half an hour, and immediately inserting the quartz tube into ice water for quenching; placing the ingot obtained after quenching in an annealing furnace, and annealing for two days at 600 ℃; the obtained ingot was manually ground into powder and ground for 10min.
(2) Pouring the prepared powder into a graphite grinding tool, sealing the upper and lower parts by using graphite carbon paper and a graphite carbon rod, and then placing the graphite carbon paper and the graphite carbon rod into a vacuum hot pressing furnace for vacuum sintering. Sintering temperature is 550 ℃, pressure is 60MPa, and heat preservation time is 10min. And after the heat preservation is finished, turning off a heating power supply, removing pressure when the temperature is reduced to 40 ℃, cooling to room temperature, breaking a vacuum state, and taking out a sample to obtain the germanium telluride cylindrical block thermoelectric material.
(3) The sintered cylindrical block thermoelectric material was cut into 2.5mm×2.5mm×12mm strips and 1.5mm×10mm sheets for measuring the electric transport property and the heat transport property, respectively.
Example 3
(1) 15G of raw materials are weighed, germanium particles (99.999%), bismuth particles (99.999%), indium particles (99.999%), cadmium particles (99.999%) and tellurium particles (99.999%) are weighed according to chemical formula Ge 0.94Bi0.06In0.01Cd0.04 Te, the raw materials are filled into a clean quartz tube and fixed on a tube sealing device, and the quartz tube is sealed under the condition that the vacuum degree negative pressure is not higher than 0.8 Pa; placing the sealed quartz tube in a rocking furnace with the temperature of 950 ℃, and starting a rocking switch after heat preservation for half an hour so as to facilitate better combination between the quartz tube and the rocking furnace; taking out the quartz tube filled with the high-temperature molten material after swinging for half an hour, and immediately inserting the quartz tube into ice water for quenching; placing the ingot obtained after quenching in an annealing furnace, and annealing for two days at 600 ℃; the obtained ingot was manually ground into powder and ground for 10min.
(2) Pouring the prepared powder into a graphite grinding tool, sealing the upper and lower parts by using graphite carbon paper and a graphite carbon rod, and then placing the graphite carbon paper and the graphite carbon rod into a vacuum hot pressing furnace for vacuum sintering. Sintering temperature is 550 ℃, pressure is 60MPa, and heat preservation time is 10min. And after the heat preservation is finished, turning off a heating power supply, removing pressure when the temperature is reduced to 40 ℃, cooling to room temperature, breaking a vacuum state, and taking out a sample to obtain the germanium telluride cylindrical block thermoelectric material.
(3) The sintered cylindrical block thermoelectric material was cut into 2.5mm×2.5mm×12mm strips and 1.5mm×10mm sheets for measuring the electric transport property and the heat transport property, respectively.
Test example 1
Thermoelectric performance testing
FIG. 1 is a graph showing the relationship between the electric conductivity and the temperature of thermoelectric materials prepared in examples 1 to 3 of the present invention and thermoelectric materials of the GeTe base of comparative example 1. It can be observed that the GeTe matrix conductivity is at a higher level throughout the temperature range: the conductivity at room temperature was 7302 S.cm 1. With increasing doping concentration, the room temperature conductivity of example 1 was 2298s·cm 1, the room temperature conductivity of example 2 was 1511s·cm 1, and the room temperature conductivity of example 3 was 836s·cm 1. The decrease in conductivity is mainly due to a decrease in carrier concentration.
FIG. 2 is a graph showing the relationship between Seebeck coefficient and temperature of thermoelectric materials prepared in examples 1 to 3 of the present invention and that of thermoelectric material of GeTe base of comparative example 1. Compared to comparative example 1, the seebeck coefficients of examples 1 to 3 were significantly improved over the entire temperature range with increasing doping concentration. The improvement of the seebeck coefficient is mainly due to two aspects: 1) A decrease in carrier concentration; 2) And the In and Cd doping improves the effective quality of the state density brought by the optimization of the energy band structure.
FIG. 3 is a graph showing the power factor versus temperature for thermoelectric materials prepared in examples 1 to 3 of the present invention and for thermoelectric materials of the GeTe matrix of comparative example 1. It can be observed that the power factor of the samples of examples 1 to 3 is significantly increased in the low-medium temperature region, compared to comparative example 1. The phenomenon is beneficial to the improvement of the thermoelectric performance of the low and medium temperature area, thereby better meeting the application requirements of high-efficiency power generation of the low and medium temperature area.
FIGS. 4 and 5 are graphs showing the total heat conductivity and the lattice heat conductivity versus temperature of thermoelectric materials prepared in examples 1 to 3 according to the present invention and thermoelectric materials of the GeTe base of comparative example 1. The total thermal conductivity and lattice thermal conductivity of the samples of examples 1-3 were significantly reduced over the entire temperature range compared to comparative example 1. The reduction In thermal conductivity is mainly due to the doping of Bi, in and Cd elements which effectively enhances the selective scattering of phonons.
FIG. 6 is a graph showing the relationship between thermoelectric figure of merit and temperature of thermoelectric materials prepared in examples 1 to 3 of the present invention and thermoelectric material of the GeTe base of comparative example 1. The thermoelectric figure of merit of examples 1-3 increased significantly due to the increase in power factor and decrease in thermal conductivity; for example 3, the peak thermoelectric figure of merit increased from 0.99 to 2.12 compared to comparative example 1. Meanwhile, the average thermoelectric figure of merit (300-773K) of the material is greatly improved, and the thermoelectric efficiency of the material in a low-medium temperature environment is improved, so that the material can be efficiently used for a low-medium temperature power generation module.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (8)
1. A germanium telluride-based thermoelectric material is characterized in that,
The chemical formula of the germanium telluride-based thermoelectric material is Ge 1-nMn Te;
Wherein M is at least one selected from Bi, in and Cd;
the mole fraction of M is n, n is more than 0 and less than or equal to 0.11.
2. The germanium telluride-based thermoelectric material according to claim 1,
The chemical formula of the germanium telluride-based thermoelectric material is Ge 1-x-y-zBixInyCdz Te;
wherein x represents the mole fraction of the doping element Bi, and the value range of x is more than or equal to 0 and less than or equal to 0.06;
y represents the mole fraction of the doping element In, and the value range of y is more than or equal to 0 and less than or equal to 0.01;
z represents the mole fraction of the doped element Cd, and the value range of the doped element Cd is more than or equal to 0 and less than or equal to 0.04;
x, y, z are not 0 at the same time.
3. A method for producing a germanium telluride-based thermoelectric material according to any one of claim 1 or 2, wherein,
The method comprises the following steps:
Mixing the raw materials containing Ge simple substance, M simple substance and Te simple substance, roasting and annealing to obtain the germanium telluride-based thermoelectric material.
4. A process according to claim 3, wherein,
The roasting temperature is 900-950 ℃;
the roasting time is 1-3 h.
5. A process according to claim 3, wherein,
The roasting is carried out in a vacuum environment;
preferably, the vacuum degree of the vacuum environment is 5 Pa-10 Pa.
6. A process according to claim 3, wherein,
The annealing temperature is 600-650 ℃;
the annealing time is 48-72 h.
7. A germanium telluride-based thermoelectric material according to claim 1 or 2 or the use of germanium telluride-based thermoelectric material prepared by the method of any one of claims 3-6,
The thermoelectric converter is used for a thermoelectric converter in a medium temperature zone.
8. The use according to claim 7, wherein,
The working temperature of the thermoelectric converter in the medium temperature region is 177-500 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211238764.5A CN117923901A (en) | 2022-10-11 | 2022-10-11 | Germanium telluride-based thermoelectric material and preparation method and application thereof |
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| CN202211238764.5A CN117923901A (en) | 2022-10-11 | 2022-10-11 | Germanium telluride-based thermoelectric material and preparation method and application thereof |
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