CN117144185A - Magnesium antimonide-metal particle composite thermoelectric material and preparation method and application thereof - Google Patents
Magnesium antimonide-metal particle composite thermoelectric material and preparation method and application thereof Download PDFInfo
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- CN117144185A CN117144185A CN202311133315.9A CN202311133315A CN117144185A CN 117144185 A CN117144185 A CN 117144185A CN 202311133315 A CN202311133315 A CN 202311133315A CN 117144185 A CN117144185 A CN 117144185A
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- 239000000463 material Substances 0.000 title claims abstract description 106
- 239000011777 magnesium Substances 0.000 title claims abstract description 94
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 62
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000002923 metal particle Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 30
- 229910052715 tantalum Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 16
- 239000011812 mixed powder Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002490 spark plasma sintering Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 27
- 239000002245 particle Substances 0.000 description 18
- 229910052758 niobium Inorganic materials 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002082 metal nanoparticle Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 244000137852 Petrea volubilis Species 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000005036 potential barrier Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910002665 PbTe Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
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- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- PDYNJNLVKADULO-UHFFFAOYSA-N tellanylidenebismuth Chemical compound [Bi]=[Te] PDYNJNLVKADULO-UHFFFAOYSA-N 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C12/00—Alloys based on antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
-
- 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
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
Abstract
The application discloses a magnesium antimonide-metal particle composite thermoelectric material, a preparation method and application thereof. The magnesium antimonide-metal particle composite thermoelectric material comprises the following raw materials in percentage by weight 3.1 Sb 1.5 Bi 0.49 Te 0.01 X y Wherein X is Nb,0.1<y<0.2; x is Ta,0<y<0.2. The magnesium antimonide-metal particle composite thermoelectric material has good crystallinity, compact structure, strong repeatability, excellent electrical property, power factor kept at a higher level, low lattice heat conductivity and higher dimensionless thermoelectric figure of merit ZT value.
Description
Technical Field
The application belongs to the technical field of energy materials, and particularly relates to a magnesium antimonide-metal particle composite thermoelectric material, and a preparation method and application thereof.
Background
Thermoelectric technology can realize direct conversion of heat and electricity, and is an important energy technology for relieving shortage of fossil fuel and promoting sustainable development. However, the conversion efficiency of thermoelectric technology is currently limited by the lower performance of thermoelectric materials, and large-scale application is not realized yet. Therefore, how to further improve the performance of thermoelectric materials is a key to current research. The performance of thermoelectric materials in energy conversion is defined by dimensionless thermoelectric figure of merit zt=σs 2 T/(κ L +κ e ) A decision is made where S is the Seebeck coefficient, σ is the conductivity, T is the absolute temperature, (κ) L +κ e ) Is the heat conductivity, and is formed by lattice heat conductivity kappa L And electron thermal conductivity κ e Two parts. Wherein S, sigma and kappa e The carrier concentrations are closely related and have strong coupling relationship with each other. A general strategy for improving thermoelectric performance is therefore how to synergistically regulate these transmission characteristics or achieve decoupling between parameters.
Current commercial thermoelectric materials are made with bismuth telluride (Bi 2 Te 3 ) Mainly, but its application is mainly focused on near room temperature refrigeration. Although materials such as PbTe and SnSe exhibit excellent properties at high temperatures (above 773K), their near room temperature properties are not satisfactory. At present, materials capable of simultaneously having high thermoelectric properties in near room temperature and high temperature ranges have yet to be explored. In addition, due to the high cost and low reserves of tellurium (Te), there is an urgent need to find and develop Bi 2 Te 3 To further scale up the manufacturing scale of thermoelectric devices.
Disclosure of Invention
The present application aims to solve at least one of the technical problems in the related art to some extent. Therefore, an object of the present application is to provide a magnesium antimonide-metal particle composite thermoelectric material, and a preparation method and application thereof. The magnesium antimonide-metal particle composite thermoelectric material has good crystallinity, compact structure, strong repeatability, excellent electrical property, power factor kept at a higher level, low lattice heat conductivity and higher dimensionless thermoelectric figure of merit ZT value.
In one aspect of the present application, a magnesium antimonide-metal particle composite thermoelectric material is provided. According to an embodiment of the application, the raw material composition of the magnesium antimonide-metal particle composite thermoelectric material is Mg 3.1 Sb 1.5 Bi 0.49 Te 0.01 X y Wherein X is Nb,0.1<y<0.2; x is Ta,0<y<0.2。
According to the magnesium antimonide-metal particle composite thermoelectric material of the embodiment of the application, the raw material composition is Mg 3.1 Sb 1.5 Bi 0.49 Te 0.01 X y Which is provided withWherein X is Nb or Ta. By adding Mg to 3.1 Sb 1.5 Bi 0.49 Te 0.01 Adding Nb or Ta metal simple substance on the matrix component, wherein the Nb or Ta simple substance exists as a second phase in the form of metal nano particles at the grain boundary, and introduces rich heterogeneous interfaces. On the other hand, diffusion of Sb atoms from the matrix into the Nb metal second phase occurs at the hetero-interface, creating a new interfacial second phase Nb 3 Sb, the ratio of Sb in the lattice decreases, increasing the carrier concentration. On the other hand, the addition of Nb or Ta metal phase is beneficial to reducing interface potential barrier, thereby forming carrier fast channel, reducing adverse effect of grain boundary scattering on mobility, and optimizing the material electric transport property by simultaneously improving carrier concentration and mobility of near room temperature region of the material, so that not only conductivity is optimized, but also the material still maintains higher Seebeck coefficient for the above reasons. Meanwhile, since the uniformly dispersed Nb or Ta metal nano-particles and the heterogeneous interfaces thereof can be used as scattering centers, phonon scattering is facilitated, the material has lower heat conductivity, and the thermoelectric performance of the material is improved in the whole test temperature range. And particularly, as the interface potential barrier at the grain boundary is reduced, the conductivity of the near-room temperature region is greatly optimized, and the thermoelectric performance of the material near-room temperature region is remarkably improved. Meanwhile, the inventors found that when the addition amount of Nb or Ta is too large, the high thermal conductivity of the metal particles themselves causes an increase in the overall thermal conductivity of the material, degrading the thermoelectric properties, thus adding Mg 3.1 Sb 1.5 Bi 0.49 Te 0.01 As a matrix, nb or Ta is added in a molar ratio of 0.1, wherein X is Nb<y<0.2; x is Ta,0<y<0.2, introducing metal nanometer second phase at the grain boundary, not only can improve the carrier concentration of the material, but also can remarkably improve the carrier mobility near room temperature, and greatly optimize the electric transport performance. Therefore, the magnesium antimonide-metal particle composite thermoelectric material has good crystallinity, compact structure, strong repeatability, excellent electrical performance, power factor kept at a higher level, low lattice heat conductivity and higher dimensionless thermoelectric figure-of-merit ZT value. Specifically, at 798K, the dimensionless thermoelectric figure of merit ZT of the magnesium antimonide-metal particle composite thermoelectric material is 1.8-2.1.
In some embodiments of the present application, the magnesium antimonide-metal particle composite thermoelectric material has excellent thermoelectric properties when X is Ta and y=0.1.
In a second aspect of the present application, a method of preparing the magnesium antimonide-metal particle composite thermoelectric material is provided. According to an embodiment of the application, it comprises:
(1) According to chemical composition Mg 3.1 Sb 1.5 Bi 0.49 Te 0.01 Nb y Or Mg (Mg) 3.1 Sb 1.5 Bi 0.49 Te 0.01 Ta y Weighing Mg simple substance, sb simple substance, bi simple substance, te simple substance, nb simple substance or Ta simple substance according to the stoichiometric ratio, mixing and then performing ball milling to obtain mixed powder;
(2) And (3) carrying out high-temperature discharge plasma sintering on the mixed powder so as to obtain the magnesium antimonide-metal particle composite thermoelectric material.
Therefore, the magnesium antimonide-metal particle composite thermoelectric material with good crystallinity, compact structure, strong repeatability, excellent electrical performance, high power factor, low lattice heat conductivity and high dimensionless thermoelectric figure of merit ZT value can be prepared by adopting the method.
In addition, the method of preparing a magnesium antimonide-metal particle composite thermoelectric material according to the above embodiment of the present application may further have the following technical characteristics:
in some embodiments of the application, in the step (1), the mass ratio of the grinding balls to the mixed powder in the ball milling process is (1-2) 1, the rotational speed of the ball milling is 1400-1500 r/min, and the time of the ball milling is 5-8 h.
In some embodiments of the application, in step (2), the high temperature discharge plasma sintering has a vacuum degree of 0.1Pa to 10Pa.
In some embodiments of the present application, the pressure applied by the upper and lower pressure heads in the furnace chamber of the high-temperature discharge plasma sintering is 30MPa to 50MPa.
In some embodiments of the application, in step (2), the high temperature discharge plasma sintering temperature is 700 ℃ to 900 ℃. Thus, the thermoelectric performance of the magnesium antimonide-metal particle composite thermoelectric material can be improved.
In some embodiments of the application, the high temperature spark plasma sintering comprises a first stage and a second stage, wherein the first stage is performed according to the following steps: heating the mixed powder from room temperature to a first preset temperature within 5-10 min, and then preserving heat at the first preset temperature for 5-10 min; the second stage is carried out according to the following steps: heating from the first preset temperature to 700-900 ℃ within 4-7 min; then preserving the temperature for 10-20 min. Thus, the thermoelectric performance of the magnesium antimonide-metal particle composite thermoelectric material can be improved.
In some embodiments of the application, the first predetermined temperature is 400 ℃ to 600 ℃. Thus, the thermoelectric performance of the magnesium antimonide-metal particle composite thermoelectric material can be improved.
In a third aspect of the present application, a thermoelectric device is provided. According to an embodiment of the present application, the thermoelectric device includes the above magnesium antimonide-metal particle composite thermoelectric material or the magnesium antimonide-metal particle composite thermoelectric material obtained by the above method. Thus, the thermoelectric device has excellent thermoelectric conversion efficiency.
Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application.
Drawings
The foregoing and/or additional aspects and advantages of the application will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is an X-ray diffraction pattern of thermoelectric materials of examples 1-2 and comparative examples 1-2 of the present application;
FIG. 2 is a sectional scanning electron micrograph and an elemental analysis chart of a magnesium antimonide-metal particle composite thermoelectric material according to example 1 of the present application;
FIG. 3 is a sectional scanning electron micrograph and a spectrum elemental analysis of a magnesium antimonide-based thermoelectric material according to comparative example 1 of the present application;
FIG. 4 is a graph showing the electrical conductivity of bulk samples of thermoelectric materials of examples 1-2 and comparative examples 1-3 according to the present application as a function of temperature;
FIG. 5 is a graph of Seebeck coefficient versus temperature for bulk samples of thermoelectric materials of examples 1-2 and comparative examples 1-3 of the present application;
FIG. 6 is a graph showing the power factor of the thermoelectric material bulk samples of examples 1-2 and comparative examples 1-3 according to the present application as a function of temperature;
FIG. 7 is a graph showing the total heat conductivity of bulk samples of thermoelectric materials of examples 1-2 and comparative examples 1-3 according to the present application as a function of temperature;
FIG. 8 is a graph of lattice thermal conductivity as a function of temperature for bulk samples of thermoelectric materials of examples 1-2 and comparative examples 1-3 of the present application;
fig. 9 is a graph showing the change in the non-dimensional thermoelectric figure of merit ZT values with temperature for bulk samples of thermoelectric materials of example 1 and comparative examples 1-3 of the present application.
Detailed Description
The following detailed description of the embodiments of the application is intended to be illustrative of the application and is not to be taken as limiting the application.
In one aspect of the present application, a magnesium antimonide-metal particle composite thermoelectric material is provided. According to an embodiment of the application, the raw material composition of the magnesium antimonide-metal particle composite thermoelectric material is Mg 3.1 Sb 1.5 Bi 0.49 Te 0.01 X y Wherein X is Nb,0.1<y<0.2; x is Ta,0<y<0.2。
According to the magnesium antimonide-metal particle composite thermoelectric material of the embodiment of the application, the raw material composition is Mg 3.1 Sb 1.5 Bi 0.49 Te 0.01 X y Wherein X is Nb or Ta. By adding Mg to 3.1 Sb 1.5 Bi 0.49 Te 0.01 Adding Nb or Ta metal simple substance on the matrix component, wherein the Nb or Ta simple substance exists as a second phase in the form of metal nano particles at the grain boundary, and introduces rich heterogeneous interfaces. On the other hand, diffusion of Sb atoms from the matrix into the Nb metal second phase occurs at the hetero-interface, creating a new interfacial second phase Nb 3 Sb, the ratio of Sb in the lattice decreases, increasing the carrier concentration.On the other hand, the addition of Nb or Ta metal phase is beneficial to reducing interface potential barrier, thereby forming carrier fast channel, reducing adverse effect of grain boundary scattering on mobility, and optimizing the material electric transport property by simultaneously improving carrier concentration and mobility of near room temperature region of the material, so that not only conductivity is optimized, but also the material still maintains higher Seebeck coefficient for the above reasons. Meanwhile, since the uniformly dispersed Nb or Ta metal nano-particles and the heterogeneous interfaces thereof can be used as scattering centers, phonon scattering is facilitated, the material has lower heat conductivity, and the thermoelectric performance of the material is improved in the whole test temperature range. And particularly, as the interface potential barrier at the grain boundary is reduced, the conductivity of the near-room temperature region is greatly optimized, and the thermoelectric performance of the material near-room temperature region is remarkably improved. Meanwhile, the inventors found that when the addition amount of Nb or Ta is too large, the high thermal conductivity of the metal particles themselves causes an increase in the overall thermal conductivity of the material, degrading the thermoelectric properties, thus adding Mg 3.1 Sb 1.5 Bi 0.49 Te 0.01 As a matrix, nb or Ta is added in a molar ratio of 0.1, wherein X is Nb<y<0.2; x is Ta,0<y<0.2, introducing metal nanometer second phase at the grain boundary, not only can improve the carrier concentration of the material, but also can remarkably improve the carrier mobility near room temperature, and greatly optimize the electric transport performance. Therefore, the magnesium antimonide-metal particle composite thermoelectric material has good crystallinity, compact structure, strong repeatability, excellent electrical performance, power factor kept at a higher level, low lattice heat conductivity and higher dimensionless thermoelectric figure-of-merit ZT value. Specifically, at 798K, the dimensionless thermoelectric figure of merit ZT of the magnesium antimonide-metal particle composite thermoelectric material is 1.8-2.1.
Preferably, in the above magnesium antimonide-metal particle composite thermoelectric material raw material composition, X is Ta, and y=0.1. Specifically, when x=ta, y=0.1, the thermoelectric material obtained finally has a dimensionless thermoelectric figure of merit ZT value up to 2.06 at 798K.
In a second aspect of the present application, a method of preparing the magnesium antimonide-metal particle composite thermoelectric material is provided. According to an embodiment of the application, the method comprises:
s100: preparation of mixed powder
In this step, according to the chemical composition Mg 3.1 Sb 1.5 Bi 0.49 Te 0.01 X y The stoichiometric ratio is to weigh and weigh Mg simple substance, sb simple substance, bi simple substance, te simple substance, nb simple substance or Ta simple substance, and ball milling is carried out under the atmosphere of protective gas, so as to obtain mixed powder, wherein the purity of the Sb simple substance particles and the Bi simple substance particles is 99.999% by mass, the purity of the Mg simple substance particles and the Ta simple substance powder is 99.9%, and the purity of the Nb simple substance powder is 99.95%. Further, in the ball milling process, the mass ratio of the grinding balls to the mixed powder is (1-2): 1, the rotation speed of the adopted ball mill is 1400-1500 r/min, and the ball milling time is 5-8 h. In the method, the raw materials are subjected to ball milling method treatment to obtain mixed powder, so that the method is simple and convenient to operate, short in period, free of high-temperature danger and low in energy consumption, and ensures full reaction among the materials in the subsequent sintering process.
S200: high-temperature discharge plasma sintering of the mixed powder
In the step, the mixed powder prepared by S100 is put into a graphite mould, and high-temperature discharge plasma sintering treatment is carried out by applying pressure in vacuum, specifically, the vacuum degree is 0.1 Pa-10 Pa, the pressure applied by an upper pressure head and a lower pressure head in a furnace chamber is 30-50 MPa, and the pressure applied by the upper pressure head and the lower pressure head in the furnace chamber for high-temperature discharge plasma sintering is 30-50 MPa. In the sintered compact, the Nb or Ta element exists as metal nanoparticles at the grain boundaries and introduces a rich heterogeneous interface. On the one hand, diffusion of Sb atoms from the matrix into the metallic second phase occurs at the above-mentioned hetero-interface, creating a new interfacial second phase, and introducing Sb vacancies into the lattice, increasing the carrier concentration. On the other hand, the addition of Nb or Ta metal phase helps to reduce interface barrier, thereby forming carrier fast channel, reducing adverse effect of grain boundary scattering on mobility, and optimizing material electric transport performance by simultaneously realizing the improvement of carrier concentration and mobility of the material, so that not only conductivity is optimized, but also the material still maintains higher Seebeck coefficient for the above reasons. Meanwhile, since the uniformly dispersed Nb or Ta metal nano-particles and the heterogeneous interfaces thereof can be used as scattering centers, phonon scattering is facilitated, the material has lower heat conductivity, and the thermoelectric performance of the material is improved in the whole test temperature range.
According to an embodiment of the application, the high temperature discharge plasma sintering temperature is 700-900 ℃. The inventor finds that the high temperature discharge plasma sintering temperature has very important influence on the thermoelectric performance of the final magnesium antimonide-metal particle composite thermoelectric material, and if the high temperature discharge plasma sintering temperature is too high, the softening and serious extrusion of a sample can be caused; if the high temperature spark plasma sintering temperature is too low, the resulting grain size is small, i.e. contains a large number of grain boundaries, which have a low resistance, and thus the properties of the final sample are low. Therefore, the application adopts high-temperature discharge plasma sintering condition with the temperature of 700-900 ℃ to prepare the magnesium antimonide-metal particle composite thermoelectric material with excellent thermoelectric performance. Further, the high temperature discharge plasma sintering comprises a first stage and a second stage, wherein the first stage is performed according to the following steps: heating the mixed powder from room temperature to a first preset temperature (400-600 ℃) within 5-10 min, and then preserving heat for 5-10 min at the first preset temperature; the second stage is carried out according to the following steps: heating from a first preset temperature to 700-900 ℃ within 4-7 min; then preserving the temperature for 10-20 min. By setting the first preset temperature, the sample formation and crystallization can be promoted.
Therefore, the magnesium antimonide-metal particle composite thermoelectric material with good crystallinity, compact structure, strong repeatability, excellent electrical performance, high power factor, low lattice heat conductivity and high dimensionless thermoelectric figure of merit ZT value can be prepared by adopting the method. It should be noted that the features and advantages described above for the magnesium antimonide-metal particle composite thermoelectric material are equally applicable to the method, and are not repeated here.
In a third aspect of the present application, a thermoelectric device is provided. According to an embodiment of the present application, the thermoelectric device includes the above magnesium antimonide-metal particle composite thermoelectric material or the magnesium antimonide-metal particle composite thermoelectric material obtained by the above method. Thus, the thermoelectric device has excellent thermoelectric conversion efficiency. It should be noted that the features and advantages described above for the magnesium antimonide-metal particle composite thermoelectric material and the preparation method thereof are equally applicable to the thermoelectric device, and are not repeated here.
The application will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
Example 1
(1) According to the chemical formula of Mg 3.1 Sb 1.5 Bi 0.49 Te 0.01 Ta 0.1 The stoichiometric ratio of (x=ta, y=0.1) 15g of the raw material mixture, specifically 2.9756 g of Mg elemental particles, 7.2144 g of Sb elemental particles, 4.0449 g of Bi elemental particles, 0.0504 g of Te elemental powder, 0.7148 g of Ta elemental powder, was weighed. Cooling to obtain the thermoelectric material. The weighed mixture is put into a stainless steel ball milling tank, wherein the mass ratio of stainless steel grinding balls to raw materials is 1:1, inert gas is filled into the ball milling tank as protective gas, and the ball milling is carried out for 8 hours at the rotating speed of 1450r/min in a high-energy ball mill (SPEX 8000D).
(2) Placing the powder obtained after ball milling into a graphite mold, compacting, placing into a spark plasma sintering furnace (SPS), heating to 500 ℃ in a temperature rising stage for 5min under the vacuum degree of 5Pa and the longitudinal pressure of 50MPa, preserving heat for 5min at 500 ℃, heating to 800 ℃ in 7min (1073K), preserving heat for 20min at 800 ℃, and cooling to obtain the magnesium antimonide-metal particle composite thermoelectric material.
After the surface of the magnesium antimonide-metal particle composite thermoelectric material block prepared in example 1 was polished by sand paper, phase identification and microstructure characterization were performed, and specific reference is made to fig. 1 and 2. FIG. 1 is an X-ray diffraction pattern of the magnesium antimonide-metal particle composite thermoelectric material of the present example, showing that the prepared material is pure phase magnesium antimonide and a small amount of Ta simple substance phase. Fig. 2 is a sectional scanning electron micrograph and a spectrum elemental analysis of a magnesium antimonide-metal particle composite thermoelectric material, and it is clear from fig. 2 that the grain size of a sample with Ta added with y=0.1 is about 5 μm, which is significantly reduced compared with a sample without added Ta; and the enrichment of Ta element exists, and the second phase size is in the micrometer and nanometer scale.
Example 2
The differences between example 2 and example 1 are: in the step (1), the chemical formula is Mg 3.1 Sb 1.5 Bi 0.49 Te 0.01 Nb 0.15 The stoichiometric ratio of (x=nb, y=0.15) weighed 15g of the raw material mixture, specifically 3.0085 g of Mg elemental particles, 7.2943 g of Sb elemental particles, 4.0897 g of Bi elemental particles, 0.0510 g of Te elemental powder, and 0.5565 g of Nb elemental powder. Cooling to obtain the thermoelectric material.
The surface of the magnesium antimonide-metal particle composite thermoelectric material block prepared in example 2 was polished by sand paper, and then subjected to phase identification, see in particular fig. 1. FIG. 1 is an X-ray diffraction pattern of the magnesium antimonide-metal particle composite thermoelectric material of the present example, showing that the prepared material is pure phase magnesium antimonide and a small amount of Nb elementary phase.
Comparative example 1
The difference between comparative example 1 and example 1 is: (1) According to the chemical formula of Mg 3.2 Sb 1.5 Bi 0.49 Te 0.01 15g of raw material mixture is weighed according to the stoichiometric ratio of the powder, namely 3.2037 g of Mg simple substance particles, 7.5248 g of Sb simple substance particles, 4.2189 g of Bi simple substance particles and 0.0526 g of Te simple substance powder.
After polishing the surface of the magnesium antimonide-based thermoelectric material block prepared in comparative example 1 with sand paper, phase identification was performed, see fig. 1 and 3 in particular. FIG. 1 shows that the material prepared is pure phase magnesium antimonide. FIG. 3 is a sectional scanning electron micrograph and an elemental analysis of the magnesium antimonide-based thermoelectric material of comparative example 1, and it is apparent from FIG. 3 that the grain size is large (approximately 10 μm) and no second phase is apparent.
Comparative example 2
In the step (1), the chemical formula is Mg 3.1 Sb 1.5 Bi 0.49 Te 0.01 Nb 0.55 (x=nb, y=0.2) 15g of the raw material mixture, specifically 2.9718 g of Mg elemental particles, 7.2052 g of Sb elemental particles, 4.0397 g of Bi elemental particles, and 0.050 g of Te elemental powder, are weighed in stoichiometric ratio3 g, 0.7330 g of Nb elementary powder. Cooling to obtain the thermoelectric material.
The surface of the magnesium antimonide-metal particle composite thermoelectric material block prepared in comparative example 2 was polished by sand paper, and then subjected to phase identification, see in particular fig. 1. FIG. 1 is an X-ray diffraction pattern of the magnesium antimonide-metal particle composite thermoelectric material of the present example, showing that the prepared material is pure phase magnesium antimonide and a small amount of Nb elementary phase.
Comparative example 3
The difference between comparative example 3 and comparative example 1 is: (1) According to the chemical formula of Mg 3.1 Sb 1.5 Bi 0.49 Te 0.01 15g of raw material mixture is weighed according to the stoichiometric ratio of the powder, namely 3.1245 g of Mg simple substance particles, 7.5754 g of Sb simple substance particles, 4.2473 g of Bi simple substance particles and 0.0529 g of Te simple substance powder.
The thermoelectric properties of the thermoelectric materials of examples 1-2 and comparative examples 1-3 were measured, see in particular FIGS. 4-9. As can be seen from fig. 4-9:
the conductivity of the Ta-added samples of example 1 was slightly increased relative to the non-added samples, with the seebeck coefficient being increased at high temperature, probably due to the interface barrier modulated after the introduction of the metal particles, allowing more energetic carriers to pass through the interface and contributing to the electrical transport. The increase in power factor of the Ta-added sample in the high temperature zone was more pronounced than that of Nb, and at 798K the power factor of the sample was 19.5W cm -1 ·K -2 The method comprises the steps of carrying out a first treatment on the surface of the Because of the larger size of the Ta metal phase and the inferior dispersion effect as compared with Nb, the effect of the intrinsic high thermal conductivity of the Ta metal phase leads to the increase of the total thermal conductivity and the lattice thermal conductivity of the composite material compared with the non-added sample, and the total thermal conductivity is 0.76 W.m -1 ·K -1 The method comprises the steps of carrying out a first treatment on the surface of the But the thermoelectric performance is still optimized thanks to the improvement of the power factor, and the nondimensional thermoelectric figure of merit ZT value is optimized at 798K, which is 2.06.
The conductivity of the sample of example 2 was further improved relative to the non-added sample of comparative example 3, the seebeck coefficient was essentially unchanged, so that the power factor was still significantly improved, and at 798K the power factor of the sample was 18.9w·cm -1 ·K -2 The method comprises the steps of carrying out a first treatment on the surface of the Thermal conductivity and lattice thermal conductivity compared to comparative example 3 without additionThe sample was elevated and the total heat conductivity was 0.79 W.m -1 ·K -1 The method comprises the steps of carrying out a first treatment on the surface of the However, the non-dimensional thermoelectric figure of merit ZT value still achieved a boost of 1.91 at 798K compared to comparative example 3 without the addition of sample.
The pure phase sample of comparative example 1 was slightly over-loaded with Mg in the nominal composition in order to compensate for the degradation of electrical properties by intrinsic Mg vacancies. The conductivity of the sample decreased with increasing temperature, 5.9X10 at room temperature 2 S·cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The seebeck coefficient increases with increasing temperature; the power factor increases and decreases with increasing temperature. At 798K, the power factor of the sample was 16.7W.cm -1 ·K -2 The total heat conductivity was 0.74 W.m -1 ·K -1 The non-dimensional thermoelectric figure of merit ZT value was 1.79.
The sample of comparative example 2 added more Nb than example 2, with y=0.2, and with conductivity higher than that of example 2, the seebeck coefficient was substantially unchanged, the power factor was significant at a high Wen Disheng, and at 798K, the power factor of the sample was 19.6w·cm -1 ·K -2 The method comprises the steps of carrying out a first treatment on the surface of the Similar to example 2, the intrinsic high thermal conductivity of Nb counteracts the reduction of the thermal conductivity by nanoparticle-enhanced phonon scattering, the thermal conductivity and the lattice thermal conductivity increase significantly, since the amount of Nb added is greater than that of example 2, and thus the thermal conductivity is also higher than that of example 2, the total thermal conductivity is 0.86 W.m -1 ·K -1 The method comprises the steps of carrying out a first treatment on the surface of the Although the power factor is obviously increased, the thermal conductivity is also improved, the value of the nondimensional thermoelectric figure of merit ZT is not obviously optimized, and the value is 1.83 at 798K.
The pure phase sample of comparative example 3, which is less excessive in Mg than that of comparative example 1, may contain Mg vacancies, and thus has a conductivity slightly lower than that of comparative example 1, 5.2X10 at room temperature 2 S·cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The seebeck coefficient increases with increasing temperature; the power factor increases and decreases with increasing temperature, and is lower than that of comparative example 1 in the near room temperature region. At 798K, the power factor of the sample was 17.0W cm -1 ·K -2 . The total heat conductivity was 0.74 W.m -1 ·K -1 The non-dimensional thermoelectric figure of merit ZT value was 1.84.
The embodiment 1-2 regulates the composition of the material, so that the magnesium antimonide-metal particle composite thermoelectric material has excellent thermoelectric performance, the electric transport performance is improved, meanwhile, the lower lattice heat conductivity is maintained, and finally, the dimensionless thermoelectric figure-of-merit ZT value is improved.
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 application. 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 application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the application.
Claims (10)
1. A magnesium antimonide-metal particle composite thermoelectric material is characterized in that the raw material composition of the magnesium antimonide-metal particle composite thermoelectric material is Mg 3.1 Sb 1.5 Bi 0.49 Te 0.01 X y Wherein X is Nb,0.1<y<0.2; x is Ta,0<y<0.2。
2. The thermoelectric material according to claim 1, wherein X is Ta and y=0.1.
3. The thermoelectric material according to claim 1, wherein the non-dimensional thermoelectric figure of merit ZT of the magnesium antimonide-metal particle composite thermoelectric material is 1.8 to 2.1 at 798K.
4. A method of making the magnesium antimonide-metal particle composite thermoelectric material of any one of claims 1 to 3, comprising:
(1) According to chemical composition Mg 3.1 Sb 1.5 Bi 0.49 Te 0.01 Nb y Or Mg (Mg) 3.1 Sb 1.5 Bi 0.49 Te 0.01 Ta y Weighing Mg simple substance, sb simple substance, bi simple substance, te simple substance, nb simple substance or Ta simple substance according to the stoichiometric ratio, mixing and then performing ball milling to obtain mixed powder;
(2) And (3) carrying out high-temperature discharge plasma sintering on the mixed powder so as to obtain the magnesium antimonide-metal particle composite thermoelectric material.
5. The method according to claim 4, wherein in the step (1), the mass ratio of the grinding balls to the mixed powder in the ball milling process is (1-2) 1, the rotational speed of the ball milling is 1400-1500 r/min, and the time of the ball milling is 5-8 h.
6. The method according to claim 4, wherein in the step (2), the vacuum degree of the high-temperature discharge plasma sintering is 0.1Pa to 10Pa;
optionally, the pressure applied by the upper pressure head and the lower pressure head in the furnace chamber of the high-temperature discharge plasma sintering is 30MPa to 50MPa.
7. The method of claim 4, wherein in step (2), the high temperature spark plasma sintering temperature is 700 ℃ to 900 ℃.
8. The method of claim 7, wherein the high temperature spark plasma sintering comprises a first stage and a second stage,
wherein the first stage is performed according to the following steps:
heating the mixed powder from room temperature to a first preset temperature within 5-10 min, and then preserving heat at the first preset temperature for 5-10 min;
the second stage is carried out according to the following steps:
heating from the first preset temperature to 700-900 ℃ within 4-7 min; then preserving the temperature for 10-20 min.
9. The method of claim 8, wherein the first predetermined temperature is 400 ℃ to 600 ℃.
10. A thermoelectric device comprising the magnesium antimonide-metal particle composite thermoelectric material according to any one of claims 1 to 3 or obtained by the method according to any one of claims 4 to 9.
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