CN112018228B - Low-thermal-conductivity half-heusler alloy thermoelectric material and preparation method thereof - Google Patents
Low-thermal-conductivity half-heusler alloy thermoelectric material and preparation method thereof Download PDFInfo
- Publication number
- CN112018228B CN112018228B CN202010883436.5A CN202010883436A CN112018228B CN 112018228 B CN112018228 B CN 112018228B CN 202010883436 A CN202010883436 A CN 202010883436A CN 112018228 B CN112018228 B CN 112018228B
- Authority
- CN
- China
- Prior art keywords
- thermoelectric
- thermal conductivity
- nisn
- heusler
- thermoelectric material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/854—Thermoelectric active materials comprising inorganic compositions comprising only metals
Abstract
The invention belongs to the technical field of material preparation, relates to a low-thermal conductivity double half-Heusler alloy thermoelectric material and a preparation method thereof, and particularly relates to low-thermal conductivity Sc 0.5‑x M x Nb 0.5‑ y N y NiSn (x is more than or equal to 0 and less than or equal to 0.2,0 and less than or equal to 0.5) based double half-Heusler thermoelectric material and a preparation method thereof, the material design concept is compounded by a hypothetical 17 electronic ScNiSn and 19 electronic NbNiSn based half-Heusler compound, wherein M is one or more of doping elements Nb, ti, zr and Hf, and N is one or two of alloying elements V, ta. The invention prepares Sc by a suspension smelting method 0.5‑x M x Nb 0.5‑y N y NiSn-based double half-Heusler thermoelectric material. The novel half-Heusler thermoelectric material has intrinsic low lattice thermal conductivity, and enriches the thermoelectric material system in medium and high temperature regions; meanwhile, zr can be doped in Sc and Nb positions of the material respectively, so that n-type and p-type semiconductor states of the same substrate material can be realized, and the material has important significance for thermoelectric device application.
Description
Technical Field
The invention belongs to the technical field of material preparation, relates to a low-thermal conductivity double half-Heusler alloy thermoelectric material and a preparation method thereof, and particularly relates to low-thermal conductivity Sc 0.5-x M x Nb 0.5-y N y NiSn-based double half-Heusler thermoelectric material and a preparation method thereof.
Background
In recent years, with the emergence of energy crisis and the deterioration of living environment, the development of clean new energy is urgent, and the search for high-efficiency and pollution-free energy conversion is also a hot problem to be solved in the world. The thermoelectric conversion technology taking thermoelectric materials as the core can realize the direct interconversion of heat energy and electric energy so as to carry out thermoelectric generation and thermoelectric refrigeration, and the thermoelectric device has the advantages of no noise, zero emission, no pollution, long service life, no vibration, small size and the like, is widely applied to the fields of aerospace, military, industry, medical treatment and civil use at present, and plays an irreplaceable role in relieving energy crisis and environmental pollution.
Thermoelectric generation technology is an effective way to convert low-quality heat sources into electric energy, and is mainly applied to the fields of aerospace, military, industry and civilian use. In the aerospace field, the electric energy generated by the isotope thermoelectric generator can not only ensure normal and efficient operation, but also greatly reduce the maintenance cost and realize long-life service. As early as 1961, the navigation satellite of the navy of the united states adopted PbTe as a thermoelectric material, and the output power of the thermoelectric conversion power supplies installed in the following travelers nos. I and II reached 158W. In the field of industrial application, from the 21 st century, reports of thermoelectric power generation by using medium-low temperature industrial waste heat are endless. The thermoelectric power generation can effectively utilize 10-20% of heat in the waste heatThereby improving the utilization rate of energy and realizing energy conservation and emission reduction. In addition, the waste heat of the automobile exhaust can also be used for thermoelectric power generation. The united states department of energy and more than 20 european research institutes have successively released related studies on thermoelectric power generation using automobile exhaust as a heat source. In the civil field, the technologies of low-power supply, medicine constant temperature and the like have gradually entered the lives of people, for example, 1cm 3 The semiconductor thermoelectric power generation device of size just can be enough to maintain the normal work of cardiac pacemaker, and the usable human body temperature of the novel wrist-watch of commercialization supplies power for the wrist-watch etc..
The thermoelectric refrigeration technology is more popular in civil use as an environment-friendly pollution-free quick refrigeration mode, and is widely applied to the fields of military, medical biology, electronic technology and the like. In the military field, thermoelectric refrigeration can be used for local refrigeration of infrared laser detectors of missiles, satellites, aircrafts and the like, so that the response time is greatly shortened, and the sensitivity is improved; in the medical field, the thermoelectric refrigerator can be used for low-temperature storage of medicines such as vaccines, serum and the like, and can also create a low-temperature environment for a medical imaging device, so that the signal-to-noise ratio and the image pickup quality of the image pickup device are improved; in the field of electronic materials, thermoelectric refrigeration technology has been applied to the refrigeration of electronic devices such as computer CPUs, mobile phones and the like, and particularly, the appearance of planar thin film thermoelectric refrigerators has been widely applied to microelectronic integrated circuits due to the miniaturization characteristic and good compatibility with IC circuits. In addition, the refrigerator can avoid the environmental pollution caused by using refrigerants such as Freon and the like, has the advantage of low noise, and is widely applied to civil fields such as environment-friendly refrigerators, thermoelectric air conditioners and the like. In recent years, the emergence of a combined system of thermoelectric refrigeration and other refrigeration methods has made up for the deficiencies of other refrigeration methods while taking advantage of thermoelectric refrigeration.
Therefore, the thermoelectric material has good application prospects in the aspects of environmental protection and energy utilization, can optimize the performance of the conventional thermoelectric material, and has great research significance in developing novel thermoelectric materials.
Thermoelectric conversion technology is an important component of the development of new energy industries, and the efficiency of thermoelectric conversion modules depends largely on the performance of thermoelectric materials. The thermoelectric material is a functional material which realizes direct reversible conversion of heat energy and electric energy by utilizing the transport property and mutual coordination of current carriers and phonons in solids, and the performance optimization of the conventional thermoelectric material and the development of a new high-performance material are always hot problems which are closely concerned by researchers and are also the key points for realizing industrial orientation.
The conversion efficiency of the thermoelectric material is closely related to the temperature difference of the cold end and the hot end and the ZT value. ZT value is dimensionless thermoelectric figure of merit, which is an important index for measuring thermoelectric performance of material, ZT = [ S = [ [ S ] 2 σ/(κ e +κ L )]And T. The thermoelectric material with a high ZT value needs to have a larger Seebeck coefficient S, so that the obvious thermoelectric effect is ensured; a higher conductivity σ, minimizing the generation of joule heat; at the same time, the thermal conductivity k should be small to ensure that heat can be kept near the linker (k can be regarded as k) e And kappa L The sum). However, the three physical parameters are restricted by mutual correlation, and it is difficult to achieve significant improvement of ZT values by regulating a certain parameter, so how to improve ZT values of materials becomes core work in the field of thermoelectric material research.
The Half-Heusler alloy is a thermoelectric material suitable for medium and high temperature, and has the advantages of rich component element reserves, low cost, no pollution, good thermal stability and good mechanical property. However, due to the simple structure, the higher intrinsic lattice thermal conductivity becomes a main factor limiting the performance improvement. Phonon scattering can be enhanced by measures such as nanocrystallization, phase separation, alloying and the like at present, and the effect of reducing lattice thermal conductivity is achieved. The recently derived double half-Heusler alloy is a quaternary compound based on aliovalent substitution, and has an atomic disordered structure due to the fact that the unit cell number is larger than 3, and the double half-Heusler alloy has small phonon group velocity and strong phonon scattering, so that the double half-Heusler alloy becomes a material with intrinsic low lattice thermal conductivity. With Ti 2 FeNiSb 2 For example, it has been shown that the lattice thermal conductivity at room temperature is only 1/3 of that of TiCoSb.
The Half-Heusler alloy has rich component elements, and the known Half-Heusler alloy can be substituted by different valence to obtain the new double-Half-Heusler alloy.
The prior art mainly has the following technical problems:
(1) The Half-Heusler alloys tend to have higher lattice thermal conductivity, and it is necessary to develop thermoelectric materials having intrinsically low lattice thermal conductivity and suitable for medium and high temperatures.
(2) The Half-Heusler alloy is difficult to realize high-performance p-type and n-type materials of the same substrate, and different geometric characteristics and thermal expansion coefficients are unfavorable for long-term service of thermoelectric devices.
(3) At present, only a few kinds of double-half-Heusler thermoelectric materials are researched and reported, and a plurality of double-half-Heusler thermoelectric materials with excellent performance are still required to be discovered.
(4) The double half-Heusler material has poor electrical property, and higher thermoelectric property can be obtained by adjusting the concentration of a current carrier.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a low-thermal conductivity double half-Heusler alloy thermoelectric material and a preparation method thereof, and particularly relates to low-thermal conductivity Sc 0.5-x M x Nb 0.5-y N y NiSn-based double half-Heusler thermoelectric material and a preparation method thereof.
The invention is realized by the following technical scheme:
a low-thermal-conductivity double-half-Heusler alloy thermoelectric material has a double-half-Heusler crystal structure, and is designed based on the principle that a hypothetical 17-electron ScNiSn and 19-electron NbNiSn-based half-Heusler compound are compounded to form the thermoelectric material, wherein the chemical formula of the thermoelectric material is Sc 0.5-x M x Nb 0.5-y N y NiSn, wherein M is one or more of doping elements Nb, ti, zr and Hf, and N is one or two of alloying elements V, ta.
The technology provides a brand-new thermoelectric material design concept, the chemical formula and the atomic proportion of the thermoelectric material design concept are completely different from those of the existing half-Heusler alloy, the thermoelectric material is a novel double-half-Heusler thermoelectric material with low intrinsic lattice thermal conductivity, and comparison shows that the material has relatively low lattice thermal conductivity in the full temperature range, so that a thermoelectric material system in a medium-high temperature region is enriched; by doping Zr element at Sc site and Nb site respectively, n-type and p-type semiconductor states can be realized, which is favorable for solving the problem of thermal expansion coefficient mismatch of thermoelectric devices made of n-type legs and p-type legs of non-same substrates, and has important significance for thermoelectric device application; the thermoelectric performance of the material is further regulated and controlled by methods such as doping, alloying and the like, so that the thermoelectric performance is improved, and a reference value is provided for the performance optimization of the double half-Heusler alloy thermoelectric material system.
As a preferable technical scheme of the invention, the material can be regarded as being formed by compounding a hypothetical 17 electron ScNiSn and 19 electron NbNiSn based half-Heusler compound and has a double half-Heusler crystal structure.
As a preferred technical solution of the present invention, the doping element is one of Nb, ti, zr, and Hf, where x =0.1.
As a preferable embodiment of the present invention, when the doping element is Zr, x =0.05,0.08,0.10,0.12,0.15.
As a preferred technical scheme of the invention, when M is Zr element and x =0.1, the material has higher power factor and lower thermal conductivity, so that ZT value reaches 0.4 at 923K.
As a preferred technical solution of the present invention, the alloying element is one of V, ta, where y =0.1.
As a preferred technical solution of the present invention, when the alloying element is V, ta, the doping element is Zr, wherein x =0.1,0.15, y =0.1.
The invention further provides a preparation method of the low-thermal-conductivity double-half-Heusler alloy thermoelectric material, which comprises the following steps:
and (2) loading the mixture into a crucible of a suspension smelting furnace according to the proportion, repeatedly turning over and smelting in an argon atmosphere, ball-milling the obtained cast ingot, then loading powder obtained by ball milling into a graphite die, and then sintering by discharge plasma.
The sample is prepared by adopting a suspension smelting method, so that the pollution of a container can be avoided; strong electromagnetic stirring in the suspension melting process is beneficial to generating uniform products in a short time; annealing is not needed, the smelting can be completed within three minutes, and the process is efficient; repeated turn-over smelting can ensure better component uniformity. The ingot after smelting usually has microcrack or solid solution defect, which affects the accuracy and reproducibility of performance measurement, therefore, the ingot of suspension smelting needs to be ball-milled into powder. The ball milling time is too long, so that the grain size is reduced, the grain boundary is increased, the scattering effect on current carriers is enhanced, and the electrical property is not favorable; too short a ball milling time may affect the compactness and composition uniformity of the material after hot pressing. The spark plasma sintering has the advantages of simple and convenient operation, rapid and high-speed preparation process, uniform heating and the like, and a sample with high density can be obtained under the high-temperature and high-pressure condition in the sintering process. The temperature is too low, the pressure is too low, and the heat preservation time is too short, so that gaps are not favorably eliminated, and the density of the material is reduced; the temperature is too high, the pressure is too high, and the heat preservation time is too long, so that the crystal grains can be coarsened, and the thermoelectric performance is influenced.
As a preferable embodiment of the present invention, it is preferable that the suspension smelting is performed by repeating the turnover smelting 4 times under an argon atmosphere.
As a preferable embodiment of the present invention, the obtained ingot is preferably ball-milled for 4 hours.
As a preferable embodiment of the present invention, it is preferable that the powder obtained by ball milling is then charged into a graphite mold having an inner diameter of 12.7mm, and is sintered by Spark Plasma Sintering (SPS) at 50MPa,900 to 1000 ℃ for 8 to 10 minutes.
The beneficial effects of the invention compared with the prior art comprise:
the invention takes the intrinsic low thermal conductivity as a starting point, and the Sc is prepared by using a suspension smelting method for the first time 0.5-x M x Nb 0.5- y N y The lattice thermal conductivity of the NiSn-based novel double-half-Heusler thermoelectric material is relatively lower than that of the current mainstream half-Heusler alloy, so that a thermoelectric material system in a medium-high temperature region is enriched; by doping at different positions, two semiconductor states of p type and n type can be realized, and the preparation method provides for the preparation of thermoelectric devicesA foundation; and after doping and alloying regulation and control are further carried out, the thermoelectric figure of merit is improved, and the method has important scientific significance.
Drawings
FIG. 1 shows (a) a ScNiSn-ZrNiSn-NbNiSn pseudoternary phase diagram; (b) Sc (Sc) 0.5 Zr 0.1 Nb 0.4 NiSn and Sc 0.4 Zr 0.1 Nb 0.5 XRD pattern of NiSn.
FIG. 2, sc 0.5 Nb 0.5 NiSn，Sc 0.5 Zr 0.1 Nb 0.4 NiSn and Sc 0.4 Zr 0.1 Nb 0.5 A thermoelectric property map of NiSn, wherein (a) is a thermal conductivity map; (b) is a graph of lattice thermal conductivity; (c) is a conductivity map; (d) is a Seebeck coefficient chart; (e) is a power factor graph; and (f) is a graph of ZT value as a function of temperature.
FIG. 3, sc 0.4 M 0.1 Nb 0.5 XRD pattern of NiSn (M = Sc, nb, ti, zr, hf).
FIG. 4 shows a schematic view of Sc 0.4 M 0.1 Nb 0.5 A thermoelectric property diagram of NiSn (M = Sc, nb, ti, zr, hf), wherein (a) is a thermal conductivity diagram; (b) is a graph of lattice thermal conductivity; (c) is a conductivity map; (d) is a Seebeck coefficient map; (e) is a power factor graph; and (f) is a graph of ZT value as a function of temperature.
FIG. 5, sc 0.5-x Zr x Nb 0.5 XRD pattern of NiSn (x =0,0.05,0.08,0.10,0.12,0.15).
FIG. 6 shows a schematic view of Sc 0.5-x Zr x Nb 0.5 Thermoelectric performance plot of NiSn (x =0,0.05,0.08,0.10,0.12,0.15), where (a) is the thermal conductivity plot; (b) is a graph of lattice thermal conductivity; (c) is a conductivity map; (d) is a Seebeck coefficient chart; (e) is a power factor graph; and (f) is a graph of ZT value versus temperature.
FIG. 7, sc 0.5-x Zr x Nb 0.4 M 0.1 XRD pattern of NiSn (x =0,0.10,0.15, m = v, ta).
FIG. 8 shows a schematic view of Sc 0.5-x Zr x Nb 0.4 M 0.1 A thermoelectric property diagram of NiSn (x =0,0.10,0.15, m = v, ta), wherein (a) is a thermal conductivity diagram; (b) is a graph of lattice thermal conductivity; (c) Is electrical conductivityA drawing; (d) is a Seebeck coefficient chart; (e) is a power factor graph; and (f) is a graph of ZT value as a function of temperature.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the invention are not limited thereto.
General examples
A low-thermal-conductivity double-half-Heusler alloy thermoelectric material has a double-half-Heusler crystal structure with the chemical formula of Sc 0.5-x M x Nb 0.5-y N y NiSn, wherein M is one of doping elements Nb, ti, zr and Hf, and N is one of alloying elements V, ta.
The compositions of the specific compounds are shown in the following table:
TABLE 1 composition List of specific compounds
The thermoelectric material is prepared by the following method: the pure elements are weighed according to the chemical proportion in the table, put into a crucible of a suspension smelting furnace, repeatedly turned over and smelted for 4 times under the argon atmosphere, the obtained cast ingot is put into a ball milling tank for ball milling for 4 hours, then the powder obtained by ball milling is put into a graphite die with the inner diameter of 12.7mm, and is sintered by discharge plasma (SPS) for 8-10 minutes at 50MPa and 900-1000 ℃.
Example 1
In this example, the above preparation methods were used to obtain the base material Sc 0.5 Nb 0.5 NiSn, and doping Zr element at Nb site and Sc site respectively to obtain p-type Sc 0.5 Zr 0.1 Nb 0.4 NiSn and n-type Sc 0.4 Zr 0.1 Nb 0.5 NiSn sample, XRD characterization and thermoelectric performance test are carried out on the sample, and single-phase Sc can be prepared by the method as can be seen from figures 1 and 2 0.5 Nb 0.5 NiSn，Sc 0.5 Zr 0.1 Nb 0.4 NiSn and Sc 0.4 Zr 0.1 Nb 0.5 NiSn material, and can realize a baseThe thermoelectric material has certain thermoelectric performance in n-type and p-type semiconductor states on the same substrate.
Example 2
In this embodiment, the above preparation method is adopted to perform n-type doping of different doping elements on the substrate material to obtain Sc 0.4 Nb 0.6 NiSn、Sc 0.4 Ti 0.1 Nb 0.5 NiSn、Sc 0.4 Zr 0.1 Nb 0.5 NiSn、Sc 0.4 Hf 0.1 Nb 0.5 The NiSn sample is subjected to XRD and thermoelectric performance tests, and the results are shown in figures 3 and 4. The result shows that the material prepared by the method is a single phase, the carrier concentration can be optimized by doping different elements, and the electrical performance is improved, wherein the doped elements are Ti, zr and Hf, the influence on the thermal conductivity is small while the electrical conductivity is improved, and a good doping effect can be achieved.
Example 3
In this embodiment, zr is selected as the main doping element, and Sc is obtained according to the above preparation method 0.5-x Zr x Nb 0.5 A series of samples of NiSn (x =0,0.05,0.08,0.10,0.12,0.15) were subjected to XRD and thermoelectric performance testing, with the results shown in figures 5 and 6. The result shows that the concentration of the current carrier can be changed by adjusting the doping concentration, so that the optimal concentration range of the current carrier is found, and the thermoelectric performance is improved. Wherein, when x =0.1, the power factor reaches the optimal value in the whole temperature range, wherein the maximum value is 1.60 mW m at 923K -1 K -2 While having a room temperature lattice thermal conductivity of about 3.77W m -1 K -1 About 2.43W m at 973K -1 K -1 Finally, the ZT value reaches 0.4 at 923K, which shows that the material has great research prospect.
Example 4
In this example, sc was obtained by the above-mentioned preparation method 0.4 Zr 0.1 Nb 0.4 V 0.1 NiSn、Sc 0.35 Zr 0.15 Nb 0.4 V 0.1 NiSn、Sc 0.4 Zr 0.1 Nb 0.4 Ta 0.1 NiSn、Sc 0.35 Zr 0.15 Nb 0.4 Ta 0.1 The NiSn sample was subjected to XRD and thermoelectric property tests, and the results are shown in fig. 7 and 8. The result shows that phonon scattering can be enhanced through alloying of different elements, so that the room-temperature lattice thermal conductivity is reduced, but impurity phases are easy to appear when doping elements are increased, and a bipolar diffusion effect is easy to occur at a high-temperature section, so that the thermoelectric performance of the material is influenced.
In addition, sc of the above examples 0.5 Zr 0.1 Nb 0.4 NiSn、Sc 0.4 Zr 0.1 Nb 0.5 NiSn、Sc 0.4 Nb 0.6 NiSn、Sc 0.4 Ti 0.1 Nb 0.5 NiSn、Sc 0.4 Hf 0.1 Nb 0.5 The room temperature thermal conductivity and room temperature lattice thermal conductivity of NiSn were compared to the existing ternary mainstream n-type half-Heusler compounds, and the results are shown in table 2. As can be seen from the comparison of the results in table 2, the double half-Heusler compound of the present embodiment has an intrinsic low lattice thermal conductivity compared to the conventional ternary half-Heusler-based compound, which is mainly due to the disordered structure in the crystal structure, which enhances phonon scattering, thereby reducing the lattice thermal conductivity. Therefore, the thermoelectric material of the embodiment is a novel intrinsic low-lattice thermal conductivity material, enriches a medium-high temperature thermoelectric material system, further regulates and controls thermoelectric performance, and can obtain a higher thermoelectric figure of merit, so that the compound has a certain research value.
TABLE 2 comparison of the room temperature thermal conductivity and the room temperature lattice thermal conductivity of the examples and comparative examples
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (5)
1. A low thermal conductivity dual half-Heusler alloy thermoelectric material, wherein said material is selected from the group consisting of: sc (Sc) 0.5 Zr 0.1 Nb 0.4 NiSn、Sc 0.4 Hf 0.1 Nb 0.5 NiSn。
2. A method of making the low thermal conductivity double half-Heusler alloy thermoelectric material of claim 1, comprising:
the materials are loaded into a crucible of a suspension smelting furnace according to the mixture ratio, the materials are repeatedly turned and smelted in the argon atmosphere, the obtained cast ingot is subjected to ball milling, powder obtained by ball milling is loaded into a graphite die, and then the graphite die is subjected to discharge plasma sintering.
3. The preparation method according to claim 2, wherein the method comprises repeating the turnover smelting 4 times under an argon atmosphere by using a suspension smelting method.
4. A method as claimed in claim 2, characterized in that it comprises ball milling the ingot obtained for 4 hours.
5. The production method according to claim 2, characterized by comprising charging the powder obtained by ball milling into a graphite mold having an inner diameter of 12.7mm, and sintering by Spark Plasma Sintering (SPS) at 50mpa,900 to 1000 ℃ for 8 to 10 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010883436.5A CN112018228B (en) | 2020-08-26 | 2020-08-26 | Low-thermal-conductivity half-heusler alloy thermoelectric material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010883436.5A CN112018228B (en) | 2020-08-26 | 2020-08-26 | Low-thermal-conductivity half-heusler alloy thermoelectric material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112018228A CN112018228A (en) | 2020-12-01 |
| CN112018228B true CN112018228B (en) | 2022-12-13 |
Family
ID=73502801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010883436.5A Active CN112018228B (en) | 2020-08-26 | 2020-08-26 | Low-thermal-conductivity half-heusler alloy thermoelectric material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112018228B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006203186A (en) * | 2004-12-24 | 2006-08-03 | Showa Denko Kk | Method of producing thermoelectric semiconductor alloy, thermoelectric conversion module, and thermoelectric power generation device |
| CN108091755A (en) * | 2017-11-28 | 2018-05-29 | 深圳大学 | High entropy thermoelectric material of TiCoSb bases and preparation method thereof and thermo-electric device |
| CN108511589A (en) * | 2018-03-27 | 2018-09-07 | 武汉理工大学 | A kind of high configuration entropy thermoelectric compound and its design method and preparation method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013197156A (en) * | 2012-03-16 | 2013-09-30 | Toto Ltd | Thermoelectric conversion material and thermoelectric conversion module |
| DE102013103896B4 (en) * | 2013-04-17 | 2015-05-28 | Vacuumschmelze Gmbh & Co. Kg | A method of manufacturing a thermoelectric article for a thermoelectric conversion device |
-
2020
- 2020-08-26 CN CN202010883436.5A patent/CN112018228B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006203186A (en) * | 2004-12-24 | 2006-08-03 | Showa Denko Kk | Method of producing thermoelectric semiconductor alloy, thermoelectric conversion module, and thermoelectric power generation device |
| CN108091755A (en) * | 2017-11-28 | 2018-05-29 | 深圳大学 | High entropy thermoelectric material of TiCoSb bases and preparation method thereof and thermo-electric device |
| CN108511589A (en) * | 2018-03-27 | 2018-09-07 | 武汉理工大学 | A kind of high configuration entropy thermoelectric compound and its design method and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| Transmission electron microscopy observation of the half-Heusler compound Ti0.5(Zr0.5Hf0.5)0.5NiSn0.998Sb0.002;Takao Morimura等;《Scripta Materialia》;20081031;第59卷(第8期);全文 * |
| 新型热电材料综述;王超 等;《电子科技大学学报》;20170105;第46卷(第1期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112018228A (en) | 2020-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2017041634A1 (en) | Bisbtese-based thermoelectric material | |
| CN103872237B (en) | Copper-sulfur-based high-performance thermoelectric material and preparation method thereof | |
| CN104263986B (en) | A kind of method of supper-fast preparation high-performance SnTe base thermoelectricity material | |
| Fu et al. | Mg 3 (Bi, Sb) 2-based thermoelectric modules for efficient and reliable waste-heat utilization up to 750 K | |
| CN102280570B (en) | Trace Cu-doped Bi2S3-based thermoelectric material | |
| CN105671344B (en) | One step prepares high-performance CoSb3The method of base thermoelectricity material | |
| CN105895795A (en) | Method for preparing composite tin selenide based thermoelectric material | |
| JP2011514666A (en) | Semiconductor materials containing doped tin telluride for thermoelectric applications | |
| CN109650435B (en) | Copper sulfide-based thermoelectric composite material and preparation method thereof | |
| US20200220063A1 (en) | Low-temperature high-performance thermoelectric material and preparation method thereof | |
| CN108374198A (en) | A kind of monocrystalline Bi2Te3The preparation method of thermoelectric material | |
| CN107195767B (en) | Five yuan of N-type thermoelectric materials of one kind and preparation method thereof | |
| CN106898690A (en) | A kind of rear-earth-doped SnTe base thermoelectricity materials | |
| CN107794387B (en) | A kind of supper-fast preparation β-Zn4Sb3The method of base block thermoelectric material | |
| CN106129241B (en) | The method that solid reaction process prepares stacking faults chalcogenide thermoelectric material | |
| CN101358313B (en) | Method for improving Bi-S binary system thermoelectric material performance | |
| Cheng et al. | Fabrication of nanostructured skutterudite-based thermoelectric module and design of a maximum power point tracking system for the thermoelectric pile | |
| CN112018228B (en) | Low-thermal-conductivity half-heusler alloy thermoelectric material and preparation method thereof | |
| CN111244258B (en) | Cu1.8S-based polycrystalline-amorphous metal composite thermoelectric material and preparation method thereof | |
| CN108640683B (en) | A kind of preparation method of nano composite thermoelectric materials | |
| CN104762501B (en) | Method for preparation of silver antimony telluride thermoelectric material by combining low temperature solid phase reaction with hot pressing process | |
| CN109536821B (en) | Europium-zinc-antimony-based Zintl phase thermoelectric material and preparation method thereof | |
| CN108470817B (en) | Sb-containing P-type Cu2.856In4Te8Medium-high temperature thermoelectric material and preparation process thereof | |
| CN109503147B (en) | Ga element doped In2O3(ZnO)3Thermoelectric material and preparation method and application thereof | |
| CN109904305A (en) | A kind of nickel doping Cu-S base thermoelectricity material of high thermoelectricity capability and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |