CN113399665A - Method for preparing NbFeSb block thermoelectric material - Google Patents
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- 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
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- 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
- B22F2003/1054—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by microwave
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The invention discloses a method for preparing NbFeSb block thermoelectric material, which comprises the steps of synthesizing alloy by a microwave synthesis method, crushing the alloy by a mortar, ball-milling the crushed alloy in a planetary ball mill, and sintering the ball-milled alloy by discharge plasma to obtain the NbFeSb-based thermoelectric material. The method is simple in process, easy to operate, high in efficiency, free of harm to the environment and free of secondary pollution, and a new method is explored for preparing the NbFeSb thermoelectric material.
Description
The technical field is as follows:
the invention relates to the technical field of high-temperature semiconductor thermoelectric power generation, in particular to a method for preparing an NbFeSb block thermoelectric material.
Background art:
the thermoelectric material is a functional emerging green environment-friendly material capable of rapidly converting electric energy and heat energy into each other. The thermoelectric conversion technology is a novel energy technology which can convert electric energy and heat energy into each other by utilizing Seebeck effect and Peltier effect which are peculiar to materials cleanly and efficiently. Secondly, the thermoelectric material also has the obvious advantages of simple structure, small volume, extremely light weight and the like, and the thermoelectric device has no noise and is convenient to maintain in the operation process. In the production process, no large amount of harmful substances polluting the environment are generated, so that the thermoelectric material has high environmental protection property and is a green, environment-friendly and pollution-free instrument. The thermoelectric material has very accurate temperature control, very fast response speed and very long service life. The excellent advantages enable the thermoelectric technology to have extremely wide application prospects in the fields of waste heat recovery and reuse in the aspect of industrial production, power utilization in remote areas, power sources for deep space exploration and the like.
The performance of thermoelectric materials is mainly represented by dimensionless thermoelectric figure of merit ZT, which is S2σ T/κ, where S denotes seebeck number, σ is conductivity, (power factor PF ═ S2σ) T is the temperature in Kelvin and K is the thermal conductivity. As can be seen from the formula, to obtain a high ZT value, the material needs to have a high seebeck coefficient S and electrical conductivity σ, while at the same time needs to have a low thermal conductivity κ. However, there is a coupling relationship between these three parameters, and the seebeck coefficient and the conductivity both depend on the carrier concentration of the material but show opposite change trends, and generally when the carrier concentration is changed by doping to increase or decrease the conductivity, the coefficient is caused to decrease (or increase) at the same time. The thermal and electrical conductivities show the same trend of change, with increasing electrical conductivity increasing thermal conductivity. Therefore, the above three parameters can only be adjusted within a certain range (carrier concentration) to obtain an optimal combination without changing the microstructure of the material. How to maximally adjust the parameters between them to obtain the optimal heatThe electric figure of merit has been a major issue in the study of thermoelectric materials. The thermoelectric materials can be divided into three types according to the application temperature region, namely low-temperature thermoelectric materials with the application temperature lower than 373K, intermediate-temperature thermoelectric materials with the application temperature between 373K and 1000K, and high-temperature thermoelectric materials with the application temperature higher than 1000K. Bi is widely studied in the current low-temperature thermoelectric material2Te3MgAgSb, and the like. Widely-researched filled diamond CoSb for medium-temperature thermoelectric material3And PbTe, and the like. The thermoelectric materials in the high temperature region are widely applied and researched by GeSi alloy and half-heusler alloy. In recent years, NbFeSb-based half-heusler compounds have attracted much attention for their excellent thermoelectric properties, stability and mechanical properties, and have great potential applications in the field of medium-high temperature power generation. Related documents report that double-element co-doping is an effective means for simultaneously regulating carrier concentration and inhibiting lattice thermal conductivity. The room temperature lattice thermal conductivity of the NbFeSb matrix is reduced by about 30 percent compared with the P type NbFeSb singly doped with Ti by using Hf and Ti as two P type dopants. Calculations show that double doping introduces strong mass and stress field fluctuations, enhancing the scattering of phonons and achieving a reduction in lattice thermal conductivity. In addition, the carrier concentration in the system is optimized by double doping, so that the thermoelectric figure of merit of the P-type NbFeSb reaches a maximum value of 1.32 at 1200K. While the thermoelectric performance is kept, the cost of thermoelectric raw materials is greatly saved due to the reduction of the content of Hf doped agent. At present, NbFeSb thermoelectric materials are mostly prepared by a suspension smelting method, the method is long in material consumption, and the obtained sample is poor in mechanical property and easy to crack, so that the research on the novel method for preparing the NbFeSb block material becomes a research hotspot.
The invention content is as follows:
the invention aims to provide a method for preparing a NbFeSb block thermoelectric material, which is used for preparing the NbFeSb-based thermoelectric material by a microwave synthesis method and has the advantages of simple process, easy operation and high efficiency.
The invention is realized by the following technical scheme:
a method of making a NbFeSb bulk thermoelectric material, comprising the steps of:
(1) sequentially putting Nb powder, Fe powder and Sb powder which are weighed according to the stoichiometric ratio into an agate mortar, uniformly mixing in a glove box filled with high-purity argon with the molar content of 99.999 percent, and then filling into a quartz tube for vacuum packaging; placing the sealed quartz tube in an alumina crucible, uniformly paving a wave-absorbing material SiC in the crucible and around the quartz tube, and then integrally placing the quartz tube in a microwave oven to perform microwave heating for 3-15 min under the power of 200-;
(2) the alloy obtained in the step (1) cannot be tested for thermoelectric performance because of the existence of a plurality of holes in the alloy, and is required to be firstly crushed by a mortar and then put into a planetary ball mill for ball milling, argon is filled in a ball milling tank, the ball-material ratio is 20:1, and the rotating speed is 500 r/min. Ball-milling for 10h to obtain powder with the particle size of 100-500 nm, and sintering the powder by discharge plasma at the temperature of 973K-1173K to obtain the NbFeSb-based thermoelectric material.
In particular, the general formula is Nb after doping modification by doping In, La and Sn at Nb position1-xAxA thermoelectric material of FeSb. Wherein A is selected from any one of In, La and Sn, and x is 0.001-0.1. Step (1) Nb powder, Fe powder and Sb powder are Nb powder according to a general formula1- xAxFeSb is weighed out in stoichiometric proportion.
Compared with the prior art, the invention has the following advantages:
1) the invention creatively adopts a microwave synthesis method to synthesize the NbFeSb alloy, the metal absorbs microwaves, so that electrons in the metal move back and forth at high speed to generate huge current, the inside continuously generates heat to melt the metal, and the NbFeSb-based thermoelectric material is successfully obtained. Compared with a suspension smelting method, the method is simpler and more convenient to operate.
2) The invention has simple synthesis process, high efficiency, easy control and no secondary pollution. When microwave is used for heating, after microwave generated by a magnetron in the microwave oven enters the oven cavity, the microwave is emitted because the inner wall of the oven cavity is basically metal, and the microwave is finally absorbed by the used medium material to generate heat through dielectric loss, so the microwave heating efficiency is very high. And the microwave oven can control the generation and the end of the microwave through the control switch, which is very convenient, the microwave heating can control the time, the time and the power are set without being watched by the side for a long time, and the microwave oven can automatically stop heating. In the process of microwave heating, no harm is caused to the environment, no secondary pollution is caused, and a new method is explored for the preparation of the NbFeSb thermoelectric material.
Description of the drawings:
FIG. 1 is an XRD diagram comparing the alloy NbFeSb thermoelectric material obtained by the microwave synthesis method of example 1 with NbFeSb standard PDF card.
FIG. 2 is the SEM photograph and spectrum analysis of the NbFeSb alloy prepared by the microwave synthesis method of example 1.
FIG. 3 shows the element distribution of the energy spectrum of the alloy NbFeSb thermoelectric material obtained by the microwave synthesis method in example 1.
FIG. 4 is a chart of thermoelectric properties of the alloy NbFeSb obtained by the microwave synthesis method of example 1.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1:
sequentially putting metal powder Nb, Fe and Sb into an agate mortar according to the stoichiometric ratio of NbFeSb, and grinding for 20min in a glove box filled with high-purity argon with the molar content of 99.999% to uniformly mix the metal powder Nb, Fe and Sb. Then the mixed powder is filled into a quartz tube for vacuum packaging, and the vacuum degree in the quartz tube is less than 0.1 Pa; and (3) placing the sealed quartz tube in a crucible, uniformly paving a wave-absorbing material SiC in the crucible and around the quartz tube, and then placing the whole crucible in a microwave oven to perform microwave heating for 3min under the power of 200W to obtain the alloy. The obtained alloy cannot be tested for thermoelectric performance due to the existence of a plurality of holes inside, and further experimental treatment is needed. And (3) crushing the alloy synthesized by microwave heating by using a mortar, then placing the crushed alloy into a planetary ball mill for ball milling, filling argon into a ball milling tank, and carrying out ball milling for 10 hours to obtain powder with the particle size of 100-500 nm. The obtained powder is sintered by discharge plasma under the conditions of the diameter of 15mm, the temperature of 973K, the pressure of 20Mpa and the heat preservation of 5min, so as to obtain the NbFeSb block thermoelectric material. Power factor at 823K for the sample prepared in this examplesub-PF 106 μ W m-1K-2,ZT=0.0276。
Example 2:
referring to example 1, except that the microwave heating was performed at a power of 300W for 5min to obtain an alloy. The power factor at 823K of the sample obtained in this example, PF, is 108 μ W m-1K-2,ZT=0.0288。
Example 3:
referring to example 1, except that the microwave heating was performed at a power of 700W for 10min to obtain an alloy. The power factor at 823K of the sample obtained in this example, PF, 102 μ W m-1K-2,ZT=0.0283。
Example 4:
referring to example 1, except that the alloy was obtained after microwave heating at a power of 700W for 10min, and the sintering temperature of discharge plasma was 1073K. The power factor PF of 823K of the sample prepared in this example was 114. mu. Wm-1K-2,ZT=0.0316。
Example 5:
referring to example 1, except that the alloy was obtained after microwave heating at a power of 700W for 10min, and the sintering temperature of discharge plasma was 1073K and the pressure was 30 MPa. The power factor at 823K of the sample obtained in this example, PF, 117 μ W m-1K-2,ZT=0.0329。
Example 6:
referring to example 1, except that the alloy was obtained after microwave heating at a power of 700W for 10min, and the sintering temperature of discharge plasma was 1073K and the pressure was 50 MPa. The power factor at 823K of the sample obtained in this example, PF, 124 μ W m-1K-2,ZT=0.0344。
Example 7:
referring to example 1, except that the alloy was obtained after microwave heating at a power of 700W for 10min, the sintering temperature of the spark plasma was 1173K and the pressure was 50 MPa. The power factor at 823K of the sample obtained in this example, PF, 130 μ W m-1K-2,ZT=0.034。
Example 8:
referring to example 1, the difference is that the alloy is obtained after microwave heating is carried out for 10min under the power of 700W during microwave heating, the sintering temperature of the discharge plasma is 1173K, the pressure is 50Mpa, and the heat preservation time is 10 min. The power factor at 823K of the sample obtained in this example, PF, is 131. mu. W m-1K-2,ZT=0.0374。
Example 9:
referring to example 1, the difference is that the alloy is obtained after microwave heating is carried out for 10min under the power of 700W during microwave heating, the sintering temperature of the discharge plasma is 1173K, the pressure is 50Mpa, and the heat preservation time is 10 min. The power factor at 823K of the sample obtained in this example, PF, 134 μ W m-1K-2,ZT=0.0389。
Example 10:
metal powders Nb, Fe, Sb are mixed to Nb1-xAxFeSb (A is In, x is 0.001) is put into an agate mortar In sequence according to the stoichiometric ratio, and is ground for 20min In a glove box filled with high-purity argon with the molar content of 99.999 percent to be uniformly mixed. Then the mixed powder is filled into a quartz tube for vacuum packaging, and the vacuum degree in the quartz tube is less than 0.1 Pa; and (3) placing the sealed quartz tube in a crucible, uniformly paving a wave-absorbing material SiC in the crucible and around the quartz tube, and then placing the whole crucible in a microwave oven to perform microwave heating for 10min under the power of 700W to obtain the alloy. The obtained alloy cannot be tested for thermoelectric performance due to the existence of a plurality of holes inside, and further experimental treatment is needed. Crushing the alloy synthesized by microwave heating by using a mortar, then putting the crushed alloy into a planetary ball mill for ball milling, and filling argon into a ball milling tank; ball milling for 10h to obtain powder with the particle size of 100-500 nm. The obtained powder is sintered by discharge plasma under the conditions of the diameter of 15mm, the temperature of 1173K, the pressure of 50Mpa and the heat preservation of 15min, so as to obtain the NbFeSb block thermoelectric material. The power factor PF of 823K of the sample prepared in this example was 425 μ W m-1K-2,ZT=0.054。
Example 11:
reference example 10 is repeated except that x is 0.005. The power factor PF of 823K of the sample prepared in this example was 612. mu. Wm-1K-2,ZT=0.072。
Example 12:
reference example 10 is followed except that x is 0.01. The power factor at 823K of the sample obtained in this example, PF, is 829. mu. Wm-1K-2,ZT=0.089。
Example 13:
reference example 10 was repeated except that x was 0.05. The power factor PF of 823K for the sample prepared in this example is 997 μ Wm-1K-2,ZT=0.093。
Example 14:
reference example 10 is followed with the difference that x is 0.1. The power factor at 823K for the sample obtained in this example, PF 1124 μ Wm-1K-2,ZT=0.102。
Example 15:
metal powders Nb, Fe, Sb are mixed to Nb1-xAxFeSb (A is La, x is 0.001) is put into an agate mortar in sequence according to the stoichiometric ratio, and is ground for 20min in a glove box filled with high-purity argon with the molar content of 99.999 percent to be uniformly mixed. Then the mixed powder is filled into a quartz tube for vacuum packaging, and the vacuum degree in the quartz tube is less than 0.1 Pa; and (3) placing the sealed quartz tube in a crucible, uniformly paving a wave-absorbing material SiC in the crucible and around the quartz tube, and then placing the whole crucible in a microwave oven to perform microwave heating for 10min under the power of 700W to obtain the alloy. The obtained alloy cannot be tested for thermoelectric performance due to the existence of a plurality of holes inside, and further experimental treatment is needed. Crushing the alloy synthesized by microwave heating by using a mortar, then putting the crushed alloy into a planetary ball mill for ball milling, and filling argon into a ball milling tank; ball milling for 10h to obtain powder with the particle size of 100-500 nm. The obtained powder is sintered by discharge plasma under the conditions of the diameter of 15mm, the temperature of 1173K, the pressure of 50Mpa and the heat preservation of 15min, so as to obtain the NbFeSb block thermoelectric material. The power factor at 823K of the sample obtained in this example, PF, 921 μ W m-1K-2,ZT=0.083。
Example 16:
reference example 15 was repeated except that x was 0.005. The power factor at 823K of the sample obtained in this example, PF, 1134 μ W m-1K-2,ZT=0.114。
Example 17:
reference example 15 was repeated except that x was 0.01. The power factor at 823K of the sample obtained in this example, PF 1721 μ W m-1K-2,ZT=0.128。
Example 18:
reference example 15 was repeated except that x was 0.05. The sample prepared in this example had a rate factor PF of 2115. mu. Wm at 823K-1K-2,ZT=0.175。
Example 19:
reference example 15 was repeated except that x was 0.1. The power factor PF of 823K for the sample prepared in this example is 2734 μ Wm-1K-2,ZT=0.215。
Example 20:
metal powders Nb, Fe, Sb are mixed to Nb1-xAxFeSb (A is Sn, x is 0.001) is put into an agate mortar in sequence according to the stoichiometric ratio, and is ground for 20min in a glove box filled with high-purity argon with the molar content of 99.999 percent to be uniformly mixed. Then the mixed powder is filled into a quartz tube for vacuum packaging, and the vacuum degree in the quartz tube is less than 0.1 Pa; and (3) placing the sealed quartz tube in a crucible, uniformly paving a wave-absorbing material SiC in the crucible and around the quartz tube, and then placing the whole crucible in a microwave oven to perform microwave heating for 10min under the power of 700W to obtain the alloy. The obtained alloy cannot be tested for thermoelectric performance due to the existence of a plurality of holes inside, and further experimental treatment is needed. Crushing the alloy synthesized by microwave heating by using a mortar, then putting the crushed alloy into a planetary ball mill for ball milling, and filling argon into a ball milling tank; ball milling for 10h to obtain powder with the particle size of 100-500 nm. The obtained powder is sintered by discharge plasma under the conditions of the diameter of 15mm, the temperature of 1173K, the pressure of 50Mpa and the heat preservation of 15min, so as to obtain the NbFeSb block thermoelectric material. Book (I)The power factor at 823K for the sample prepared in the example, PF, is 728 μ W m-1K-2,ZT=0.079。
Example 21:
reference example 20 was repeated except that x was 0.05. The power factor PF of 823K for the sample prepared in this example is 934. mu. Wm-1K-2,ZT=0.097。
Example 22:
reference example 20 was repeated except that x was 0.01. The power factor at 823K for the sample obtained in this example, PF, 1434. mu.Wm-1K-2,ZT=0.119。
Example 23:
reference example 20 was repeated except that x was 0.05. The power factor PF of 823K of the sample prepared in this example was 1734 μ Wm-1K-2,ZT=0.133。
Example 24:
reference example 20 was repeated except that x was 0.1. The power factor PF of 823K for the sample prepared in this example is 2135. mu.Wm-1K-2,ZT=0.179。
Claims (3)
1. A method of making a NbFeSb bulk thermoelectric material, comprising the steps of:
(1) sequentially putting Nb powder, Fe powder and Sb powder which are weighed according to the stoichiometric ratio into an agate mortar, uniformly mixing in a glove box filled with high-purity argon with the molar content of 99.999 percent, and then filling into a quartz tube for vacuum packaging; placing the sealed quartz tube in an alumina crucible, uniformly paving a wave-absorbing material SiC in the crucible and around the quartz tube, and then integrally placing the quartz tube in a microwave oven to perform microwave heating for 3-15 min under the power of 200-;
(2) and (2) crushing the alloy obtained in the step (1) by using a mortar, then placing the crushed alloy into a planetary ball mill for ball milling, filling argon into a ball milling tank, wherein the ball-material ratio is 20:1, the rotating speed is 500r/min, ball milling is carried out for 10 hours to obtain powder with the particle size of 100-500 nm, and the powder is subjected to discharge plasma sintering at the temperature of 973K-1173K to obtain the NbFeSb-based thermoelectric material.
2. The method for preparing NbFeSb bulk thermoelectric material according to claim 1, wherein the general formula of Nb is Nb after doping modification by doping In, La and Sn at Nb position1-xAxThe thermoelectric material of FeSb, wherein A is selected from any one of In, La and Sn, and x is 0.001-0.1.
3. The method of claim 1, wherein the step (1) comprises Nb powder, Fe powder, and Sb powder are represented by the general formula Nb1-xAxFeSb is weighed out in stoichiometric proportion.
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