CN116768627A - Germanium telluride-based thermoelectric material and preparation method thereof - Google Patents
Germanium telluride-based thermoelectric material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 105
- GPMBECJIPQBCKI-UHFFFAOYSA-N germanium telluride Chemical compound [Te]=[Ge]=[Te] GPMBECJIPQBCKI-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 238000000498 ball milling Methods 0.000 claims abstract description 37
- 239000000126 substance Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 22
- 239000010439 graphite Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011324 bead Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000010791 quenching Methods 0.000 claims abstract description 9
- 230000000171 quenching effect Effects 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 238000003723 Smelting Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000004806 packaging method and process Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000010453 quartz Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 claims description 2
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- 238000010926 purge Methods 0.000 claims 1
- 238000002490 spark plasma sintering Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 9
- GWNAJLSPZNJDQW-UHFFFAOYSA-N [Na].[Ge] Chemical compound [Na].[Ge] GWNAJLSPZNJDQW-UHFFFAOYSA-N 0.000 description 5
- 238000005275 alloying Methods 0.000 description 5
- 238000009776 industrial production Methods 0.000 description 5
- 229910052732 germanium Inorganic materials 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
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- 239000007789 gas Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910005900 GeTe Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 238000009461 vacuum packaging Methods 0.000 description 2
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 229910001415 sodium ion Inorganic materials 0.000 description 1
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Abstract
The invention provides a germanium telluride-based thermoelectric material and a preparation method thereof, wherein the chemical general formula of the germanium telluride-based thermoelectric material is (Ge) 1‑y Sb y Te) 1‑x (AgInTe 2 ) x Wherein, the value ranges of x and y are respectively as follows: x is more than 0 and less than or equal to 0.2, and y is more than 0 and less than or equal to 0.1. The preparation method comprises the following steps: weighing and mixing elementary substances of each element according to a chemical general formula of the germanium telluride-based thermoelectric material to obtain a mixture, and packaging; smelting the packaged mixture at a high temperature to enable the mixture to fully react in a high-temperature melting state, and quenching to obtain a metal cast ingot; placing the metal cast ingot into a ball milling tank, and ball milling the metal cast ingot after ball milling beads with different diameters are placed according to a certain proportion to obtain powder; and placing the powder material into a graphite mold, performing vacuum discharge plasma sintering, and cooling to obtain the germanium telluride-based thermoelectric material. The germanium telluride-based thermoelectric material provided by the inventionThe material is cubic phase at room temperature, and has the advantages of excellent room temperature thermoelectric property and high structural stability.
Description
Technical Field
The invention relates to the technical field of energy conversion, in particular to a germanium telluride-based thermoelectric material and a preparation method thereof.
Background
With the development of energy science, environmental problems are increasingly prominent, and the search for new energy technologies is urgent. Thermoelectric materials based on Seebeck effect and Peltier effect can directly realize the mutual conversion between heat energy and electric energy, and the prepared thermoelectric device can be directly applied to the fields of power generation and refrigeration. Dimensionless thermoelectric figure of merit zT is a measure of thermoelectric material performance (zt=σα 2 T/kappa, where sigma is electrical conductivity, alpha is the Seebeck coefficient, kappa is thermal conductivity, T is temperature, in K). Excellent thermoelectric materials require a high seebeck coefficient, high electrical conductivity, and low thermal conductivity. Excellent thermoelectric devices not only require high zT, but also ensure long-term stability of device use.
Germanium telluride has great development potential as a thermoelectric material for realizing application in a medium temperature region as a thermoelectric compound which is rising in recent years. Because the formation energy of intrinsic germanium vacancies is low, a large number of germanium vacancies exist in the material matrix, resulting in a carrier concentration that is too high, making the electrical properties of the material poor. In addition, the germanium telluride material can generate phase change at about 700K, the crystal structure is changed from a cubic phase to a trigonal phase, the existence of the structural phase change can lead to the abrupt change of the volume and the thermal expansion coefficient of the material, so that the stress concentration can be generated at the material and the interface when the thermoelectric device is recycled, and the thermoelectric device cannot work stably for a long time. In addition, due to the excessively high carrier concentration and the high forbidden bandwidth, the seebeck coefficient of the germanium telluride at room temperature is excessively low, and the defects limit the engineering application of the germanium telluride material in the room temperature area thermoelectric power generation device.
Disclosure of Invention
In view of the above, the present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a germanium telluride-based thermoelectric material, and a preparation method and application thereof. The germanium telluride-based thermoelectric material provided by the invention is cubic at room temperature, and has the advantages of excellent room temperature thermoelectric performance and high structural stability. Meanwhile, the preparation method has simple process flow and is suitable for large-scale industrial production.
To this end, in a first aspect, embodiments of the present invention provide a germanium telluride-based thermoelectric material having a chemical formula (Ge 1-y Sb y Te) 1-x (AgInTe 2 ) x Wherein, the value ranges of x and y are respectively as follows: x is more than 0 and less than or equal to 0.2, and y is more than 0 and less than or equal to 0.1.
Preferably, the germanium telluride-based thermoelectric material has a chemical formula (Ge 0.94 Sb 0.06 Te) 0.9 (AgInTe 2 ) 0.1 。
In a second aspect, an embodiment of the present invention provides a method for preparing the germanium telluride-based thermoelectric material provided in the first aspect, where the method includes: weighing and mixing elementary substances of each element according to a chemical general formula of the germanium telluride-based thermoelectric material to obtain a mixture, and packaging; smelting the packaged mixture at a high temperature to enable the mixture to fully react in a high-temperature melting state, and quenching to obtain a metal cast ingot; placing the metal cast ingot into a ball milling tank, and ball milling the metal cast ingot after ball milling beads with different diameters are placed according to a certain proportion to obtain powder; and placing the powder material into a graphite mold, performing vacuum discharge plasma sintering, and cooling to obtain the germanium telluride-based thermoelectric material.
Preferably, the mixture is placed in a quartz tube, the quartz tube is sealed with oxyhydrogen flame to form a closed high vacuum tube internal environment and argon is used for washing gas to prevent the mixture from oxidizing.
Preferably, in the mixture, the purity of each element simple substance is more than 99.999 percent.
Preferably, the packaged mixture is placed into a muffle furnace, the muffle furnace is heated to 900-1100 ℃ at a rate of 80-150 ℃ per hour, the temperature is kept for 600-900min, and then the temperature is reduced to 700-800 ℃ within 220min, and then liquid nitrogen is used for quenching, so that the metal cast ingot can be obtained.
Preferably, the ball-milling beads with diameters of 15mm, 12mm, 7mm and 5mm are respectively placed in the ball-milling tank according to the ratio of 1:3:10:22 from large to small.
Preferably, the rotating speed of the ball mill is 800-1200r/min, and the ball milling time is 15-30min.
Preferably, the graphite base-graphite gasket-graphite paper-powder material-graphite paper-graphite gasket-compression bar structure is formed in the graphite die from bottom to top.
Preferably, the discharge plasma sintering process is as follows: heating by current at 80-150deg.C per minute to 450-550deg.C, regulating pressure to 50-70MPa, and sintering at constant temperature and pressure for 5-20min.
The germanium telluride-based thermoelectric material and the preparation method thereof provided by the embodiment of the invention pass AgInTe 2 Alloying suppresses the phase transition of germanium telluride and reduces the too high band gap of germanium telluride. In addition, the Sb element doping improves the structural stability and mechanical property of the material, further promotes germanium telluride to realize room temperature cubic phase, simultaneously reduces carrier concentration and lattice heat conductivity, and optimizes thermoelectric property. Finally, the germanium telluride-based thermoelectric material provided by the invention is cubic at room temperature, and has the advantages of excellent room temperature thermoelectric performance and high structural stability. Meanwhile, the preparation method has simple process flow and is suitable for large-scale industrial production.
Drawings
Fig. 1 is a flowchart of a method for preparing a germanium telluride-based thermoelectric material according to an embodiment of the present invention.
Fig. 2 is an XRD pattern of the positive electrode material of sodium ion battery prepared in comparative example 1 and examples 1 to 8 of the present invention.
Fig. 3 is a graph showing the lattice thermal conductivity of the sodium germanium telluride-based thermoelectric material prepared in comparative example 1 and examples 1 to 8 according to the present invention as a function of temperature.
Fig. 4 is a graph showing zT versus temperature for the sodium germanium telluride-based thermoelectric materials prepared in comparative example 1 and examples 1-8 of the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The following disclosure provides many different embodiments, or examples, for implementing different structures of the invention. In order to simplify the present disclosure, components and arrangements of specific examples are described below. They are, of course, merely examples and are not intended to limit the invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art will recognize the applicability of other processes and/or the use of other materials.
The invention aims to provide a germanium telluride-based thermoelectric material and a preparation method thereof, and the germanium telluride-based thermoelectric material provided by the invention is cubic at room temperature and has the advantages of excellent room temperature thermoelectric performance and high structural stability. Meanwhile, the preparation method provided by the invention has the advantages of simple process flow and low production cost, and is suitable for large-scale industrial production.
Embodiments of the first aspect of the present invention provide a germanium telluride-based thermoelectric material having a chemical formula (Ge 1-y Sb y Te) 1-x (AgInTe 2 ) x Wherein the value ranges of x and y are respectively as follows: x is more than 0 and less than or equal to 0.2, and y is more than 0 and less than or equal to 0.1. The germanium telluride-based thermoelectric material provided by the invention passes through AgInTe 2 Alloying suppresses the phase transition of germanium telluride and reduces the too high band gap of germanium telluride. In addition, the Sb element doping improves the structural stability and mechanical property of the material, further promotes germanium telluride to realize room temperature cubic phase, simultaneously reduces carrier concentration and lattice heat conductivity, and optimizes thermoelectric property. Finally, the germanium telluride-based thermoelectric material provided by the invention is cubic at room temperature, and has excellent room temperature thermoelectric performance, high Vickers hardness and high junctionThe structure stability is improved.
Preferably, when x=0.1, y=0.06, the germanium telluride-based thermoelectric material has a chemical formula (Ge 0.94 Sb 0.06 Te) 0.9 (AgInTe 2 ) 0.1 At this time, the germanium telluride-based thermoelectric material has a Seebeck coefficient of 203.6 μVK at room temperature of 300K -1 The thermal conductivity reaches 1.04Wm -1 K -1 。
An embodiment of the second aspect of the present invention provides a method for preparing a germanium telluride-based thermoelectric material, as shown in fig. 1, the method comprising the steps of:
step S1: weighing and mixing elementary substances of each element according to a chemical general formula of the germanium telluride-based thermoelectric material to obtain a mixture, and packaging;
specifically, a quartz tube with an outer diameter of 20mm and an inner diameter of 17mm can be selected, the quartz tube is burned with grooves and cleaned, the mixture is put into the quartz tube, and the quartz tube is sealed by oxyhydrogen flame to form a sealed high vacuum tube internal environment to 1X 10 -3 Pa and using argon gas to wash gas to prevent the mixture from oxidizing. In addition, the purity of each element simple substance is more than 99.999 percent.
Step S2: smelting the packaged mixture at high temperature to enable the mixture to fully react in a high-temperature molten state, and quenching to obtain a metal cast ingot;
specifically, the packaged mixture is put into a muffle furnace, the muffle furnace is heated to 900-1100 ℃ at a rate of 80-150 ℃ per hour, and the temperature is kept for 600-900min; then cooling to 700-800 ℃ within 220min, quenching by using liquid nitrogen, and taking out the metal cast ingot from the quartz tube. Preferably, the muffle furnace is heated to 1050 ℃ at a rate of 100 ℃ per hour, then is kept for 600min, is cooled to 750 ℃ within 220min, is quenched by liquid nitrogen, and is taken out of the quartz tube.
Step S3: putting the metal cast ingot into a ball milling tank, putting ball milling beads with different diameters according to a certain proportion, and performing ball milling on the metal cast ingot to obtain powder;
wherein the ball-milling beads have diameters of 15mm, 12mm, 7mm and 5mm respectively, and ball-milling beads with diameters from large to small are put into a ball-milling tank according to the ratio of 1:3:10:22. The rotation speed of the ball mill can be 800-1200r/min, and the ball milling time can be 15-30min. Preferably, the rotation speed of the ball mill is 1100r/min, and the ball milling time is 20min.
In the embodiment of the invention, in order to prevent the metal cast ingot from oxidizing in the ball milling process, the ball milling tank can be vacuumized. Further, after the powder is taken out after ball milling, the powder is further manually ground into uniform and fine powder by using an agate mortar, and the powder material is obtained.
Step S4: and placing the powder material into a graphite mold, performing vacuum discharge plasma sintering, and cooling to obtain the germanium telluride-based thermoelectric material.
Wherein, the graphite base-graphite gasket-graphite paper-powder material-graphite paper-graphite gasket-compression bar structure is formed in the graphite die from bottom to top. The discharge plasma sintering process comprises the following steps: heating by current at 80-150deg.C per minute to 450-550deg.C, regulating pressure to 50-70MPa, and sintering at constant temperature and pressure for 5-20min. Preferably, the discharge plasma sintering process is as follows: raising the temperature to the sintering temperature of 500 ℃ at the rate of 100 ℃ per minute, and preserving the heat for 5min under the sintering pressure of 50 MPa.
Germanium telluride-based thermoelectric material prepared by the above-mentioned preparation method of germanium telluride-based thermoelectric material is prepared by AgInTe 2 Alloying suppresses the phase transition of germanium telluride and reduces the too high band gap of germanium telluride. In addition, the Sb element doping improves the structural stability and mechanical property of the material, further promotes germanium telluride to realize room temperature cubic phase, simultaneously reduces carrier concentration and lattice heat conductivity, and optimizes thermoelectric property. The prepared germanium telluride-based thermoelectric material is cubic phase at room temperature, and has the advantages of excellent room temperature thermoelectric performance and high structural stability. Meanwhile, the preparation method has simple process flow and is suitable for large-scale industrial production.
The present invention will be described in more detail by way of examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Comparative example 1
The embodiment provides a method for preparing germanium telluride-based thermoelectric material, wherein the chemical formula of the germanium telluride-based thermoelectric material prepared in the embodiment is (GeTe) 0.9 (AgInTe 2 ) 0.1 (where x=0.1, y=0), comprising the steps of:
according to the chemical formula (GeTe) 0.9 (AgInTe 2 ) 0.1 Weighing simple substance materials Ge, ag, in and Te (the purity of each element is equal to or more than 99.999%) according to stoichiometric ratio, loading the prepared materials into a quartz tube, and sealing the quartz tube by oxyhydrogen flame to form a sealed high vacuum tube internal environment to 1×10 -3 Pa, vacuum packaging; and (3) placing the sealed quartz tube in a muffle furnace for heating, heating the sealed quartz tube to 1050 ℃ at the rate of 100 ℃ per hour, preserving heat for 600min, fully reacting the mixture in a high-temperature melting state, cooling to 750 ℃ within 220min, quenching by liquid nitrogen, and taking out the metal cast ingot from the quartz tube. Putting a metal cast ingot into a ball milling tank, putting ball milling beads with diameters of 15mm, 12mm, 7mm and 5mm into the ball milling tank according to the proportion of 1:3:10:22, wherein the rotating speed of the ball milling tank is 1100r/min, the ball milling time is 20min, and fully grinding to obtain powder materials; and then carrying out vacuum discharge plasma sintering, heating to the sintering temperature of 500 ℃ at the rate of 100 ℃ per minute, keeping the sintering pressure at 50MPa, keeping the temperature for 5 minutes, and cooling to obtain the germanium telluride-based thermoelectric material.
Example 1
The present embodiment provides a method for preparing a germanium telluride-based thermoelectric material, where the chemical formula of the germanium telluride-based thermoelectric material prepared in the present embodiment is (Ge 0.97 Sb 0.03 Te) 0.9 (AgInTe 2 ) 0.1 (in this case x=0.1, y=0.03), comprising the steps of:
according to the chemical formula (Ge 0.97 Sb 0.03 Te) 0.9 (AgInTe 2 ) 0.1 Weighing simple substance materials Ge, sb, ag, in and Te (each element purity is equal to or greater than 99.999%) according to stoichiometric ratio, loading the prepared materials into quartz tube, sealing the quartz tube with oxyhydrogen flame to form a sealed high vacuum tube internal environment to 1×10 -3 Pa, vacuum packaging; and (3) placing the sealed quartz tube in a muffle furnace for heating, heating the sealed quartz tube to 1050 ℃ at the rate of 100 ℃ per hour, preserving heat for 600min, fully reacting the mixture in a high-temperature melting state, cooling to 750 ℃ within 220min, quenching by liquid nitrogen, and taking out the metal cast ingot from the quartz tube. Putting a metal cast ingot into a ball milling tank, putting ball milling beads with diameters of 15mm, 12mm, 7mm and 5mm into the ball milling tank according to the proportion of 1:3:10:22, wherein the rotating speed of the ball milling tank is 1100r/min, the ball milling time is 20min, and fully grinding to obtain powder materials; and then carrying out vacuum discharge plasma sintering, heating to the sintering temperature of 500 ℃ at the rate of 100 ℃ per minute, keeping the sintering pressure at 50MPa, keeping the temperature for 5 minutes, and cooling to obtain the germanium telluride-based thermoelectric material.
Example 2
The preparation process of the germanium telluride-based thermoelectric material in this example 2 is described in example 1, with the only difference that: y=0.04, the chemical formula of the germanium telluride-based thermoelectric material is (Ge 0.96 Sb 0.04 Te) 0.9 (AgInTe 2 ) 0.1 。
Example 3
The preparation process of the germanium telluride-based thermoelectric material in this example 3 is described in example 1, with the only difference that: y=0.05, the chemical formula of the germanium telluride-based thermoelectric material is (Ge 0.95 Sb 0.05 Te) 0.9 (AgInTe 2 ) 0.1 。
Example 4
The preparation process of the germanium telluride-based thermoelectric material in this example 4 is described in example 1, with the only difference that: y=0.06, the chemical formula of the germanium telluride-based thermoelectric material is (Ge 0.94 Sb 0.06 Te) 0.9 (AgInTe 2 ) 0.1 。
Example 5
This practice isThe preparation process of the germanium telluride-based thermoelectric material in example 5 is described in example 1, with the only difference that: y=0.07, the chemical formula of the germanium telluride-based thermoelectric material is (Ge 0.93 Sb 0.06 Te) 0.9 (AgInTe 2 ) 0.1 。
Example 6
The preparation process of the germanium telluride-based thermoelectric material in this example 6 is described in example 1, with the only difference that: y=0.08, the chemical formula of the germanium telluride-based thermoelectric material is (Ge 0.92 Sb 0.08 Te) 0.9 (AgInTe 2 ) 0.1 。
Example 7
The preparation process of the germanium telluride-based thermoelectric material in this example 7 is described in example 1, with the only difference that: y=0.09, the chemical formula of the germanium telluride-based thermoelectric material is (Ge 0.91 Sb 0.09 Te) 0.9 (AgInTe 2 ) 0.1 。
Example 8
The preparation process of the germanium telluride-based thermoelectric material in this example 8 is described in example 1, with the only difference that: y=0.10, the chemical formula of the germanium telluride-based thermoelectric material is (Ge 0.90 Sb 0.10 Te) 0.9 (AgInTe 2 ) 0.1 。
The germanium telluride-based thermoelectric materials prepared in examples 1 to 8 above were tested with the germanium telluride-based thermoelectric material prepared in comparative example 1. Wherein, FIG. 2 is an XRD pattern of the sodium germanium telluride-based thermoelectric material prepared in comparative example 1 and examples 1-8; FIG. 3 is a graph of lattice thermal conductivity as a function of temperature for sodium germanium telluride based thermoelectric materials prepared in comparative example 1 and examples 1-8; fig. 4 is a graph showing zT versus temperature for the sodium germanium telluride-based thermoelectric materials prepared in comparative example 1 and examples 1-8.
According to the above examples and the comparative examples and the comparison of the test results obtained by testing the same, the preparation method provided by the embodiment of the invention introduces Sb element in the preparation process, thereby further promoting AgInTe 2 The dissolution of the room temperature cubic phase germanium telluride is reduced, and the realization of the room temperature cubic phase germanium telluride is promoted. In addition, agInTe 2 The alloying reduces the band gap of germanium telluride, greatly improves the carrier concentration,after the Sb element is introduced, agInTe 2 The solubility is increased, so that the band gap of the germanium telluride is further reduced, the carrier concentration is greatly reduced, and the seebeck coefficient is promoted to be increased. Ultimately resulting in a room temperature power factor in (Ge 0.94 Sb 0.06 Te) 0.9 (AgInTe 2 ) 0.1 When it reaches 2.01X10 3 Wm -1 K -2 And zT reaches 0.9 near room temperature.
In summary, the germanium telluride-based thermoelectric material and the preparation method thereof provided by the embodiment of the invention uses AgInTe 2 Alloying suppresses the phase transition of germanium telluride and reduces the too high band gap of germanium telluride. In addition, the Sb element doping improves the structural stability and mechanical property of the material, further promotes germanium telluride to realize room temperature cubic phase, simultaneously reduces carrier concentration and lattice heat conductivity, and optimizes thermoelectric property. Finally, the germanium telluride-based thermoelectric material provided by the invention is cubic at room temperature, and has the advantages of excellent room temperature thermoelectric performance and high structural stability. Meanwhile, the preparation method has simple process flow and is suitable for large-scale industrial production.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
Claims (10)
1. A germanium telluride-based thermoelectric material characterized in that the germanium telluride-based thermoelectric material has a chemical formula (Ge 1- y Sb y Te) 1-x (AgInTe 2 ) x Wherein, the value ranges of x and y are respectively as follows: x is more than 0 and less than or equal to 0.2, and y is more than 0 and less than or equal to 0.1.
2. The germanium telluride-based thermoelectric material of claim 1, wherein the germanium telluride-based thermoelectric material has a chemical formula (Ge 0.94 Sb 0.06 Te) 0.9 (AgInTe 2 ) 0.1 。
3. A method of preparing the germanium telluride-based thermoelectric material of claim 1, comprising:
weighing and mixing elementary substances of each element according to a chemical general formula of the germanium telluride-based thermoelectric material to obtain a mixture, and packaging;
smelting the packaged mixture at a high temperature to enable the mixture to fully react in a high-temperature melting state, and quenching to obtain a metal cast ingot;
placing the metal cast ingot into a ball milling tank, and ball milling the metal cast ingot after ball milling beads with different diameters are placed according to a certain proportion to obtain powder;
and placing the powder material into a graphite mold, performing vacuum discharge plasma sintering, and cooling to obtain the germanium telluride-based thermoelectric material.
4. The method of manufacturing a germanium telluride-based thermoelectric material according to claim 3, wherein the mixture is placed in a quartz tube, the quartz tube is sealed with oxyhydrogen flame to form a sealed high vacuum tube environment and argon is used for purging, and oxidation of the mixture is prevented.
5. The method for preparing germanium telluride-based thermoelectric material according to claim 3, wherein the purity of each element simple substance in the mixture is more than 99.999%.
6. A method for preparing a germanium telluride-based thermoelectric material according to claim 3, wherein the packaged mixture is placed into a muffle furnace, the muffle furnace is heated to 900-1100 ℃ at a rate of 80-150 ℃ per hour, the temperature is kept for 600-900min, and then the temperature is reduced to 700-800 ℃ within 220min, and then liquid nitrogen is used for quenching, so that the metal ingot is obtained.
7. The method for preparing germanium telluride-based thermoelectric material according to claim 3, wherein the ball-milling beads have diameters of 15mm, 12mm, 7mm and 5mm, respectively, and ball-milling beads with diameters from large to small are placed in the ball-milling tank in a ratio of 1:3:10:22.
8. The method for preparing a germanium telluride-based thermoelectric material according to claim 3, wherein the rotation speed of the ball mill is 800-1200r/min, and the ball milling time is 15-30min.
9. The method of preparing a germanium telluride-based thermoelectric material according to claim 3, wherein the graphite mold has a structure of a graphite base, a graphite gasket, a graphite paper, a powder material, a graphite paper, a graphite gasket, and a compression bar from bottom to top.
10. The method for preparing a germanium telluride-based thermoelectric material according to claim 3, wherein the spark plasma sintering process is as follows: heating by current at 80-150deg.C per minute to 450-550deg.C, regulating pressure to 50-70MPa, and sintering at constant temperature and pressure for 5-20min.
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