CN115403016A - High-performance chalcopyrite system thermoelectric material and preparation method thereof - Google Patents
High-performance chalcopyrite system thermoelectric material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 84
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052951 chalcopyrite Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 34
- 238000000498 ball milling Methods 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000006104 solid solution Substances 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 20
- 238000007731 hot pressing Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000011858 nanopowder Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000000630 rising effect Effects 0.000 claims 2
- 239000000956 alloy Substances 0.000 abstract description 9
- 229910045601 alloy Inorganic materials 0.000 abstract description 7
- 239000002918 waste heat Substances 0.000 abstract description 5
- 238000010248 power generation Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000005057 refrigeration Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 239000010453 quartz Substances 0.000 description 12
- 238000003723 Smelting Methods 0.000 description 7
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- 238000009792 diffusion process Methods 0.000 description 6
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- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
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- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 238000000713 high-energy ball milling Methods 0.000 description 1
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Abstract
The invention discloses a high-performance chalcopyrite thermoelectric material and a preparation method thereof, wherein the chalcopyrite thermoelectric material is prepared by two chalcopyrite materials CuGaTe with the same structure 2 And AgGaTe 2 The chemical composition formed after high-proportion solid solution is Cu 1‑x Ag x GaTe 2 Wherein x is more than 0 and less than or equal to 0.5. The thermoelectric material adopts the scheme design of high-proportion solid solution alloy and the high-energy vibration ball milling process, the maximum ZT figure of merit of the thermoelectric material reaches 1.73 when 873K, and the maximum ZT figure of merit is almost the highest value reported by the system at present. Its average ZT value ZT between 300K-873K ave 0.69, which means that the material can effectively improve the efficiency of interconversion of thermal energy and electric energy, namely the application efficiency in waste heat power generation and thermoelectric refrigeration. In addition, the thermoelectric material also has the advantages of simple and convenient process, easy large-scale production, strong practicability and the like.
Description
Technical Field
The invention belongs to the technical field of energy materials, and particularly relates to a high-performance chalcopyrite thermoelectric material and a preparation method thereof.
Background
The thermoelectric material is a special energy conversion material, which can realize the collection of electric energy from waste heat by virtue of the directional transport of current carriers and phonons, can also reversibly convert the electric energy into heat energy, and does not generate any noise or pollution. Based on this, under the background of increasing energy demand and worsening environmental problems, research and development of thermoelectric materials and thermoelectric devices are urgent.
The thermoelectric conversion technology is essentially a technology for realizing direct interconversion of thermal energy and electric energy by utilizing the Seebeck effect (Seebeck) and the Peltier effect (Peltier) of semiconductor thermoelectric materials. Generally, the dimensionless ZT value is used to measure the performance of thermoelectric materials and can be expressed as:
where S is the Seebeck coefficient, T is the absolute temperature, ρ is the resistivity, σ is the electrical conductivity, κ is the thermal conductivity, κ is the electrical conductivity c Is the carrier thermal conductivity, κ L Is the lattice thermal conductivity. In addition, one also defines the electrical transport properties of thermoelectric materials with a power factor PF (= S2/ρ). According to the formula of ZT value, various ways of improving thermoelectric performance (ZT value) of a sample can be found. For example, the conductivity of the sample may be enhanced by optimizing carrier concentration or optimizing carrier mobility; the Seebeck coefficient of the sample can be improved through means such as energy band flattening, energy band degeneracy, energy filtering effect and energy level resonance; the thermoelectric property of the material can also be optimized by means of inhibiting the lattice thermal conductivity of the material by means of multi-scale phonon scattering, searching intrinsic low-thermal-conductivity materials and the like.
Chalcopyrite structural material CuGaTe in a plurality of thermoelectric material systems 2 Attracts people's attention. T.plirdpring et al report polycrystal CuGaTe in 2012 2 The ZT of the material (1.4 at 950K) indicates that it is a thermoelectric material system that is expected to be commercially used. There are many reports related to the present, which propose different means to optimize CuGaTe 2 Thermoelectric of materialsPerformance, but the highest ZT values reported are almost all below 1.4. Therefore, in the field, it is quite difficult to greatly improve the ZT value of the thermoelectric material, and finding a method for effectively improving the ZT value is also an important research target in the thermoelectric technology field.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a high-performance chalcopyrite-based thermoelectric material and a preparation method thereof. The highest thermoelectric figure of merit ZT of the thermoelectric material of the invention is as high as 1.73 at 873K, which is almost the highest value reported by the system at present. Its average ZT value ZT between 300K-873K ave 0.69, therefore, the application efficiency of thermoelectric material waste heat power generation and thermoelectric refrigeration can be greatly improved. In addition, the thermoelectric material also has the advantages of simple and convenient process, easy large-scale production, strong practicability and the like.
The invention optimizes the P-type chalcopyrite-based thermoelectric material by two chalcopyrite materials CuGaTe with the same structure 2 And AgGaTe 2 The chemical composition formed after high-proportion solid solution is Cu 1-x Ag x GaTe 2 The alloy material of (1).
In the chemical formula of Cu 1-x Ag x GaTe 2 In the formula, x is more than 0 and less than or equal to 0.5; for example, x can take the value of 0.05,0.10,0.15,0.20,0.25,0.30,0.35,0.40,0.45,0.50.
The thermoelectric material adopts Ag element with equal molar ratio to replace CuGaTe 2 Cu element in the base thermoelectric material.
The preparation method of the chalcopyrite-based thermoelectric material comprises the following steps:
step 1: according to the chemical formula Cu 1-x Ag x GaTe 2 (x is more than 0 and less than or equal to 0.5), mixing the single Cu, ag, ga and Te according to the stoichiometric ratio, and then carrying out vacuum melting to obtain an ingot;
step 2: carrying out high-energy vibration ball milling on the cast ingot obtained in the step 1 to obtain powder; and then, carrying out vacuum hot-pressing sintering on the powder to form blocks, thus obtaining the chalcopyrite-based thermoelectric material. And finally, cutting the block sample into different shapes to characterize related microstructure, electrical and thermal properties.
Preferably, in step 1, the purities of the simple substances Cu, ag, ga and Te are all more than 99.99%.
Preferably, in step 1, the temperature of vacuum melting is 900-1100 ℃, preferably 1000 ℃, for example 900 ℃, 925 ℃,950 ℃, 975 ℃, 1025 ℃, 1050 ℃, 1075 ℃ or 1100 ℃; the smelting time is 5-24h, preferably 12h, for example, 5h, 10h, 18h, 20h or 24h; the heating rate of the melting is 1-10 deg.C/min, preferably 3 deg.C/min, and may be, for example, 1 deg.C/min, 2 deg.C/min, 4 deg.C/min, 5 deg.C/min, 6 deg.C/min, 7 deg.C/min, 8 deg.C/min, 9 deg.C/min or 10 deg.C/min.
Preferably, in the step 2, the ball milling is dry vibration ball milling, the ball milling tank is an agate tank, and the ball milling time is 0.2-10h, preferably 1h, and for example, 0.2h,0.5h, 2h, 4h, 6h, 8h or 10h; wherein the volume percentage of the nanopowder in the powder is 0-30%, but not 0%, preferably 0-10%.
Preferably, in step 2, the sintering is performed by vacuum hot pressing, and the sintering temperature is 400-600 ℃, preferably 500 ℃, for example, 400 ℃, 425 ℃, 450 ℃, 475 ℃, 525 ℃, 550 ℃, 575 ℃ or 600 ℃. When the sintering temperature is lower than 400 ℃, the obtained product has low density and poor thermoelectric property; when the sintering temperature is higher than 550 ℃, the raw materials can be softened under the conditions of high temperature and high pressure, so that the preparation of the sample is influenced, and even the preparation of the sample fails; the sintering time is 30-120min, preferably 60min, and may be 30min, 75min, 90min, 100min or 120min.
Preferably, in step 2, the sintering pressure is 10 to 1000MPa, preferably 250MPa, and may be, for example, 50MPa, 100MPa, 150MPa, 200MPa, 300MPa, 350MPa, 400MPa, 500MPa, 600MPa, 700MPa, 800MPa, 900MPa or 1000MPa. When the sintering pressure is lower than 150MPa, the obtained product has low density and poor thermoelectric property; and when the sintering pressure is higher than 500MPa, the sample is broken, resulting in failure of sample preparation.
Cu of the invention 1-x Ag x GaTe 2 In thermoelectric materials, there are localized nanoparticle regions that can be greatly optimized for strong phonon scatteringThermal properties of the material.
Cu of the invention 1-x Ag x GaTe 2 The thermoelectric material comprises CuGaTe 2 、AgGaTe 2 (ii) a composition domain region (composition domain means a local region having the same crystal structure but slightly different chemical composition, i.e., a fluctuation region of Cu/Ag element content at a microscopic scale). The boundaries between the two domains and the strained domains strongly scatter phonons, affecting thermal transport (reducing thermal conductivity) while having less impact on electrical transport.
Compared with the prior art, the thermoelectric material adopts the scheme design of high-proportion solid solution alloy and the experimental process of high-energy vibration ball milling to greatly reduce CuGaTe 2 The thermal conductivity of the base material further improves the thermoelectric property of the base material. Specifically, two kinds of chalcopyrite materials (CuGaTe) with the same structure are adopted 2 And AgGaTe 2 ) High proportion solid solution, the chemical composition formed is Cu 1-x Ag x GaTe 2 The alloy material of (4). When x =0-0.5, the maximum ZT value of the material reaches 1.73 at 873K, which is almost the highest value reported by the system at present. And the average ZT value ZTave of the material is between 300K and 873K and 0.69, which means that the material can effectively improve the efficiency of interconversion of heat energy and electric energy.
Meanwhile, the material can be prepared by adopting the conventional vacuum melting and high-energy ball milling methods, and specifically, the vacuum melting method is firstly adopted to prepare Cu 1-x Ag x GaTe 2 (x is more than 0 and less than or equal to 0.5) ingot casting; then carrying out high-energy vibration ball milling on the obtained cast ingot to obtain powder; and then the powder is sintered into blocks by vacuum hot pressing, and the blocks are cut into different shapes to carry out characterization of related microstructure, electrical property and thermal property. The percentage content of each component in the thermoelectric material is adjusted, and parameters in each working procedure are regulated and controlled, so that the Cu is realized 1-x Ag x GaTe 2 (x is more than 0 and less than or equal to 0.5) regulating and controlling the microstructure and the transport property of the thermoelectric material to finally obtain the p-type CuGaTe with excellent performance (ZT value reaches 1.73 when the ZT value is 873K) 2 A base thermoelectric material. The thermoelectric material has low thermal conductivity, high Seebeck coefficient, high power factor and ZT value, and can greatly improve the application efficiency of thermoelectric material in the aspects of waste heat power generation and thermoelectric refrigerationThe whole preparation method has the advantages of simple and convenient process, easy large-scale production, strong practicability and the like.
Drawings
FIG. 1 is an XRD diffraction pattern of thermoelectric materials obtained in examples and comparative examples of the present invention. As can be seen from FIG. 1, the diffraction peaks of the comparative and example samples are both CuGaTe 2 Diffraction peaks of a material standard card (PDF # 065-2746) correspond to one another and do not have any impurity peaks, which indicates that the synthesized sample is a pure-phase material and does not contain impurity phases.
FIG. 2 is a graph showing the variation of cell parameters with solid solution content of Ag for the samples of the examples of the present invention and the comparative examples. As can be seen from FIG. 2, as the solid solution content of Ag increases, the unit cell parameters of the samples gradually increase, which indicates that Ag atoms are successfully solid-solubilized to CuGaTe 2 In the crystal lattice of (1). As the atomic radius of Ag is larger than that of Cu, the Ag causes lattice expansion after solid solution, and the unit cell parameter is increased.
FIG. 3 is a scanning electron microscope photograph of example 3 of the present invention. As can be seen from FIG. 3, many small grains (500 nm) are distributed between the large grains (5 μm) in the sample. The high-energy vibration ball milling in the synthesis process is benefited, the ball milling can refine grains, and the layered structure in the grains can obviously increase grain boundaries, so that the scattering is enhanced, and the thermal performance of the material is optimized.
FIG. 4 is a schematic diagram of theoretical simulated phonon band structures of comparative example (a) and example 5 (b) of the present invention. As can be seen from fig. 4, the proportion of the phonon spectrum of example 5 is much softened. For example, the Longitudinal (LA), transverse (TA) and out-of-plane (ZA) acoustic modes of example 5 are softened by about 20% -50% at the X/P/N symmetry point versus the comparative example. Furthermore, the phonon spectrum in example 5 is flatter than the comparative example, which demonstrates that phonon-phonon interactions can be dramatically increased by Ag solid solution and results in extremely low lattice thermal conductivity.
FIG. 5 shows the lattice thermal conductivities κ of thermoelectric materials obtained in examples of the present invention and comparative examples L Graph comparing with temperature. As can be seen from FIG. 5, the lattice thermal conductivities of the examples obtained by solid solution of Ag were significantly lower than those of the comparative examples, e.g., in practice, over the entire temperature range testedIn example 5, the lattice thermal conductivity at 873K was 0.32W m -1 K -1 Whereas the comparative example had a lattice thermal conductivity of 0.73Wm under the same conditions -1 K -1 . This indicates that solid-soluted Ag is effective in optimizing thermal properties.
FIG. 6 is a graph comparing thermoelectric figure of merit ZT versus temperature of thermoelectric materials obtained in examples of the present invention and comparative examples. As can be seen from FIG. 6, the ZT value of the comparative example of the present invention is improved uniformly and significantly in the whole temperature zone compared with the comparative example, and the maximum ZT figure of merit of example 3 reaches 1.73 at 873K, which is almost the highest value reported by the system at present. The invention proves that the invention uses two chalcopyrite materials CuGaTe with the same structure 2 And AgGaTe 2 The scheme design of high-proportion solid solution adopts a high-energy vibration ball milling process, and effectively improves the thermoelectric property of the chalcopyrite system material, namely the application efficiency of the system material in the aspects of waste heat power generation and thermoelectric refrigeration.
Detailed Description
The technical solution of the present invention will be described in detail by specific examples.
Example 1:
a P-type high-proportion alloyed thermoelectric material with chalcopyrite structure has a chemical composition of Cu 0.9 Ag 0.1 GaTe 2 The preparation process mainly comprises the following steps:
1. elementary substance particles of Cu, ag, ga and Te with purity of more than 99.99 percent are mixed according to the chemical formula Cu 0.9 Ag 0.1 GaTe 2 The obtained powders were mixed and sealed in a vacuum quartz tube with a degree of vacuum of about 5X 10 -3 Pa. Then putting the vacuum quartz tube into a tube furnace for smelting at 1000 ℃ for 12h to obtain the alloy with the composition of Cu 0.9 Ag 0.1 GaTe 2 The ingot casting of (1);
2. placing the ingot obtained in the step 1 in an agate mortar for crushing, then placing the ingot in a 100ml agate grinding tank, and adopting dry vibration ball milling for 1h; then carrying out vacuum hot-pressing sintering on the ball-milled powder, wherein the sintering temperature is 500 ℃; the sintering time is 60min; a sintering pressure of250MPa. Namely obtaining the chemical composition of Cu 0.9 Ag 0.1 GaTe 2 The disk-like material of (1).
The disc-shaped material is cut into proper sizes, and the relation of the change of the electrical and thermal properties with the temperature (comprising the electrical conductivity (four-electrode method), the Seebeck coefficient (static direct current method) and the thermal diffusion coefficient (laser flash method)) is respectively tested, and the data show that the power factor is 12.77 mu Wcm at 873K -1 K 2 The thermal conductivity of the crystal lattice is 0.56Wm -1 K -1 The thermoelectric figure of merit ZT was 1.42.
Example 2:
a P-type high-proportion alloyed thermoelectric material with chalcopyrite structure has a chemical composition of Cu 0.8 Ag 0.2 GaTe 2 The preparation process mainly comprises the following steps:
1. the elementary substance particles of Cu, ag, ga and Te with the purity of more than 99.99 percent are mixed according to the chemical formula Cu 0.8 Ag 0.2 GaTe 2 The obtained powders were mixed and sealed in a vacuum quartz tube with a degree of vacuum of about 5X 10 -3 Pa. Then putting the vacuum quartz tube into a tube furnace for smelting at the temperature of 1000 ℃ for 12 hours to obtain the alloy with the composition of Cu 0.8 Ag 0.2 GaTe 2 The ingot casting of (1);
2. placing the ingot obtained in the step 1 in an agate mortar for crushing, then placing the ingot in a 100ml agate grinding tank, and adopting dry vibration ball milling for 1h; then carrying out vacuum hot-pressing sintering on the powder subjected to ball milling, wherein the sintering temperature is 500 ℃; the sintering time is 60min; the sintering pressure is 250MPa. Namely obtaining the chemical composition of Cu 0.8 Ag 0.2 GaTe 2 The disk-like material of (1).
The disc-shaped material is cut into proper sizes, and the relation of the change of the electrical and thermal properties with the temperature (comprising the electrical conductivity (four-electrode method), the Seebeck coefficient (static direct current method) and the thermal diffusion coefficient (laser flash method)) is respectively tested, and the data show that the power factor is 12.54 mu Wcm at 873K -1 K 2 The thermal conductivity of the crystal lattice is 0.37Wm -1 K -1 The thermoelectric figure of merit ZT was 1.69.
Example 3:
a P-type high-proportion alloyed thermoelectric material with chalcopyrite structure has a chemical composition of Cu 0.7 Ag 0.3 GaTe 2 The preparation process mainly comprises the following steps:
1. the elementary substance particles of Cu, ag, ga and Te with the purity of more than 99.99 percent are mixed according to the chemical formula Cu 0.7 Ag 0.3 GaTe 2 The obtained powders were mixed and sealed in a vacuum quartz tube with a degree of vacuum of about 5X 10 -3 Pa. Then putting the vacuum quartz tube into a tube furnace for smelting at 1000 ℃ for 12h to obtain the alloy with the composition of Cu 0.7 Ag 0.3 GaTe 2 The ingot casting of (1);
2. placing the ingot obtained in the step 1 in an agate mortar for crushing, then placing the ingot in a 100ml agate grinding tank, and adopting dry vibration ball milling for 1h; then carrying out vacuum hot-pressing sintering on the powder subjected to ball milling, wherein the sintering temperature is 500 ℃; the sintering time is 60min; the sintering pressure was 250MPa. Namely obtaining the chemical composition of Cu 0.7 Ag 0.3 GaTe 2 The disk-like material of (1).
The above-mentioned disk-like material is cut into proper size, and the change relationship of electric and thermal properties with temp. respectively (including conductivity (four-electrode method), seebeck coefficient (static D.C. method) and thermal diffusion coefficient (laser flash method) are tested, and the data show that at 873K, power factor is 10.44. Mu. Wcm -1 K 2 The thermal conductivity of the crystal lattice is 0.35Wm -1 K -1 The thermoelectric figure of merit ZT was 1.73.
Example 4:
a P-type high-proportion alloyed thermoelectric material with chalcopyrite structure has a chemical composition of Cu 0.6 Ag 0.4 GaTe 2 The preparation process mainly comprises the following steps:
1. the elementary substance particles of Cu, ag, ga and Te with the purity of more than 99.99 percent are mixed according to the chemical formula Cu 0.6 Ag 0.4 GaTe 2 The obtained powders were mixed and sealed in a vacuum quartz tube with a degree of vacuum of about 5X 10 -3 Pa. Then the solution is mixed withPutting the vacuum quartz tube into a tube furnace for smelting at 1000 ℃ for 12h to obtain the alloy with the Cu component 0.6 Ag 0.4 GaTe 2 The ingot casting of (1);
2. placing the ingot obtained in the step 1 in an agate mortar for crushing, then placing the ingot in a 100ml agate grinding tank, and adopting dry vibration ball milling for 1h; then carrying out vacuum hot-pressing sintering on the powder subjected to ball milling, wherein the sintering temperature is 500 ℃; the sintering time is 60min; the sintering pressure is 250MPa. Namely obtaining the chemical composition of Cu 0.6 Ag 0.4 GaTe 2 The disc-like material of (1).
The disc-shaped material is cut into proper sizes, and the relation of the change of the electrical and thermal properties with the temperature (comprising the electrical conductivity (four-electrode method), the Seebeck coefficient (static direct current method) and the thermal diffusion coefficient (laser flash method)) is respectively tested, the data show that the power factor is 9.00 mu Wcm at 873K -1 K 2 The thermal conductivity of the crystal lattice is 0.37Wm -1 K -1 The thermoelectric figure of merit ZT is 1.58.
Example 5:
a P-type high-proportion alloyed thermoelectric material with chalcopyrite structure has a chemical composition of Cu 0.5 Ag 0.5 GaTe 2 The preparation process mainly comprises the following steps:
1. the elementary substance particles of Cu, ag, ga and Te with the purity of more than 99.99 percent are mixed according to the chemical formula Cu 0.5 Ag 0.5 GaTe 2 The obtained powders were mixed and sealed in a vacuum quartz tube at a degree of vacuum of about 5X 10 -3 Pa. Then putting the vacuum quartz tube into a tube furnace for smelting at 1000 ℃ for 12h to obtain the alloy with the composition of Cu 0.5 Ag 0.5 GaTe 2 The ingot casting of (1);
2. placing the ingot obtained in the step 1 in an agate mortar for crushing, then placing the ingot in a 100ml agate grinding tank, and adopting dry vibration ball milling for 1h; then carrying out vacuum hot-pressing sintering on the powder subjected to ball milling, wherein the sintering temperature is 500 ℃; the sintering time is 60min; the sintering pressure is 250MPa. Namely obtaining the chemical composition of Cu 0.5 Ag 0.5 GaTe 2 The disc-like material of (1).
The disc-shaped material is cut into proper sizes, and the relation of the change of the electrical and thermal properties with the temperature (comprising the electrical conductivity (four-electrode method), the Seebeck coefficient (static direct current method) and the thermal diffusion coefficient (laser flash method)) is respectively tested, and the data show that the power factor is 7.69 mu Wcm at 873K -1 K 2 The thermal conductivity of the crystal lattice is 0.31Wm -1 K -1 The thermoelectric figure of merit ZT was 1.69.
Comparative example 1:
a P-type high-proportion alloyed thermoelectric material with chalcopyrite structure has a chemical composition of CuGaTe 2 The preparation process mainly comprises the following steps:
1. the elementary substance particles of Cu, ga and Te with the purity of more than 99.99 percent are mixed according to the chemical formula CuGaTe 2 The obtained powders were mixed and sealed in a vacuum quartz tube with a degree of vacuum of about 5X 10 -3 Pa. Then putting the vacuum quartz tube into a tube furnace for smelting at 1000 ℃ for 12h to obtain the CuGaTe composition 2 The ingot casting of (1);
2. placing the ingot obtained in the step 1 in an agate mortar for crushing, then placing the ingot in a 100ml agate grinding tank, and adopting dry vibration ball milling for 1h; then carrying out vacuum hot-pressing sintering on the ball-milled powder, wherein the sintering temperature is 500 ℃; the sintering time is 60min; the sintering pressure is 250MPa. The chemical composition of CuGaTe is obtained 2 The disc-like material of (1).
The sheet material is cut into proper sizes, and the relation of the change of the electrical and thermal properties with the temperature (comprising the conductivity (four-electrode method), the Seebeck coefficient (static direct current method) and the thermal diffusion coefficient (laser flash method)) is respectively tested, the data show that the power factor is 12.98 mu Wcm at 873K -1 K 2 The lattice thermal conductivity of the material is 0.70Wm -1 K -1 The thermoelectric figure of merit ZT was 1.20.
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 person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A high-performance chalcopyrite system thermoelectric material is characterized in that:
the chalcopyrite thermoelectric material is prepared by two chalcopyrite materials CuGaTe with the same structure 2 And AgGaTe 2 The chemical composition formed after high-proportion solid solution is Cu 1-x Ag x GaTe 2 Wherein x is more than 0 and less than or equal to 0.5.
2. A method for producing a high performance chalcopyrite thermoelectric material of claim 1, comprising the steps of:
step 1: according to the chemical formula Cu 1-x Ag x GaTe 2 X is more than 0 and less than or equal to 0.5, and the elementary Cu, ag, ga and Te are mixed according to the stoichiometric ratio and then are smelted in vacuum to obtain cast ingots;
step 2: carrying out high-energy vibration ball milling on the cast ingot obtained in the step 1 to obtain powder; and then, carrying out vacuum hot-pressing sintering on the powder to form blocks, thus obtaining the chalcopyrite-based thermoelectric material.
3. The method of claim 1, wherein:
in the step 1, the purities of the simple substances Cu, ag, ga and Te are all more than 99.99%.
4. The production method according to claim 1, characterized in that:
in the step 1, the temperature of vacuum melting is 900-1100 ℃, the melting time is 5-24h, and the temperature rising and reducing speed is 1-10 ℃/min.
5. The method of claim 4, wherein:
the temperature of vacuum melting is 1000 ℃, the melting time is 12h, and the temperature rising and reducing speed is 3 ℃/min.
6. The method of claim 2, wherein:
in the step 2, dry ball milling is adopted for high-energy vibration ball milling, the ball milling tank is an agate ball milling tank, the ball milling time is 0.2-10h, and the volume percentage of the nano powder in the powder is 0-30%.
7. The production method according to claim 2, characterized in that:
in the step 2, the sintering is carried out by adopting a vacuum hot pressing method, the sintering temperature is 400-600 ℃, and the sintering time is 30-120min.
8. The method for producing according to claim 7, characterized in that:
the sintering temperature is 500 ℃, and the sintering time is 60min.
9. The method of claim 2, wherein:
in the step 2, the sintering pressure is 10-1000MPa.
10. The method of claim 9, wherein:
the sintering pressure is 250MPa.
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