CN109604605B - Rapid preparation of CoSb by solid-phase reaction method3Method (2) - Google Patents

Rapid preparation of CoSb by solid-phase reaction method3Method (2) Download PDF

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CN109604605B
CN109604605B CN201811629220.5A CN201811629220A CN109604605B CN 109604605 B CN109604605 B CN 109604605B CN 201811629220 A CN201811629220 A CN 201811629220A CN 109604605 B CN109604605 B CN 109604605B
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秦丙克
籍永华
朱红玉
白志玲
宿太超
张金柱
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Liupanshui Normal University
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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
    • B22F3/23—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces involving a self-propagating high-temperature synthesis or reaction sintering step
    • 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
    • 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
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    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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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
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

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Abstract

Rapid preparation of CoSb by solid-phase reaction method3According to the formula CoSb3Taking Co powder and Sb powder according to the stoichiometric ratio, carrying out vacuum ball milling and mixing in a ball milling tank, then taking out the powder for compression molding, sintering in a vacuum furnace after assembling by a sintering mold, keeping the temperature for 1-180 min, and cooling to room temperature along with the furnace to obtain the material. Compared with the prior art, the single-phase skutterudite thermoelectric material can be prepared by adopting vacuum ball milling and mixing combined with a high-temperature solid-phase reaction method within the temperature range of 723-923K, the single-phase skutterudite sample obtained by the experiment is uniformly distributed with micron-sized holes, the diameter of each micropore is about 10 mu m, the crystal grain structure in the sample is fine, and the crystal grain diameter is in the micro-nanometer level.

Description

Rapid preparation of CoSb by solid-phase reaction method3Method (2)
Technical Field
The invention belongs to the technical field of thermoelectric materials, and particularly relates to a method for rapidly preparing CoSb by a solid-phase reaction method3The method of (1).
Background
The thermoelectric material is a semiconductor material capable of directly converting heat energy and electric energy into each other, and the thermoelectric material is made into a thermoelectric device, so that various waste heat can be utilized to generate electricity, and refrigeration can also be realized by utilizing electric energy. Thermoelectric materials have a wide application prospect in the energy crisis today, and thus, in recent years, the thermoelectric materials become one of the hot spots of research in the field of materials. The performance of the thermoelectric material is generally characterized by a dimensionless thermoelectric figure of merit ZT value, ZT = S2S, sigma, lambda and T in the sigma T/lambda formula are Seebeck coefficient, electric conductivity, thermal conductivity and absolute temperature, respectively. From the thermoelectric figure of merit expression, it can be seen that a high-performance thermoelectric material needs to have a higher Seebeck coefficient and a higher electrical conductivity, and in addition, needs to have a lower thermal conductivity.
CoSb of skutterudite thermoelectric material with binary structure3The thermoelectric material has better electrical transport property, and Skutterudite (Skutterudite) thermoelectric materials are taken as one of novel thermoelectric materials to attract great attention. The general preparation method of skutterudite comprises the following steps: smelting, quenching, annealing, Spark Plasma Sintering (SPS), high-temperature high-pressure, ball milling, hot pressing, solid phase reaction, SPS, solvothermal synthesis and the like. Except for the high-temperature high-pressure preparation method, other preparation methods have the characteristics of long preparation and annealing period, complex preparation process and the like. The high-temperature high-pressure preparation method has the advantages of accelerating the reaction rate, effectively preventing phase segregation and the like, but needs equipment specially generating high-pressure conditions.
At present, the industry generally considers that the preparation of skutterudite can be synthesized by long-time heating or long-time annealing treatment after smelting, and common CoSb with a nano structure3The alloy is prepared by a hydrothermal method or a long-time mechanical alloying method, has complex process and high energy consumption, is not easy to realize industrialization, and can cause crystal grain growth after long-time heating.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a solid-phase reaction method for rapidly preparing CoSb3The method utilizes simple experimental conditions of a common vacuum atmosphere furnace, a planetary ball mill and the like to prepare single-phase skutterudite through vacuum ball milling and high-temperature solid-phase reaction, and prepares the CoSb with the nano structure through simple assembly of a sintering mold and short-time high-temperature solid-phase reaction3Vacuum ball milling is combined with low-temperature solid phase reaction, single-phase skutterudite with nano-scale crystal grains can be prepared in a short time, and the fine crystal grains effectively reduce the thermal conductivity of the single-phase skutterudite so as to improve the CoSb3The thermoelectric figure of merit ZT value of (1).
In order to achieve the purpose, the invention adopts the technical scheme that:
rapid preparation of CoSb by solid-phase reaction method3According to the formula CoSb3Taking Co powder and Sb powder according to the stoichiometric ratio, carrying out vacuum ball milling and mixing in a ball milling tank, then taking out the powder for compression molding, adopting a sintering mold for assembly, and then carrying out vacuum ball milling and mixing on the Co powder and the Sb powderSintering in a vacuum furnace, and cooling to room temperature along with the furnace to obtain the material.
The sintering mold adopted by the invention consists of a plug, an isolation material and a cylinder body, and CoSb is formed by powder pressing3The sample is disposed therein.
The plug is made of pure copper or high manganese steel; the isolation material is made of boron nitride or zirconium oxide; the cylinder body is made of heat-resistant steel or stainless steel.
The powder is pressed and molded to obtain a cylinder sample with the diameter of about a mm and the height of about h mm; the diameter of the plug and the diameter of the inner hole of the cylinder sample are standard threaded holes with the diameter of (a +5) mm, and the outer diameter of the cylinder is 1-6 times of the diameter a of the sample.
The ball milling tank is a hard alloy ball milling tank, the ball-material ratio is about 30:1, the rotating speed is about 350r/min, and the mixing time is 1-4 h.
The sintering adopts a vacuum atmosphere furnace, the solid-phase reaction sintering is carried out in vacuum or inert atmosphere, the sintering temperature range is 723-923K, and the heat preservation time is 1-180 min.
Compared with the prior art, the single-phase skutterudite thermoelectric material can be prepared by adopting vacuum ball milling and combining a high-temperature solid-phase reaction method within the temperature range of 723-923K, the single-phase skutterudite sample obtained by the experiment is uniformly distributed with micron-sized holes, the diameter of each micropore is about 10 mu m, the crystal grain structure in the sample is fine, and the crystal grain diameter is in a nanometer level. The sample has higher Seebeck coefficient and higher resistivity through room temperature electrical property test. The Seebeck coefficient of the sample was the largest at preparation temperature 923K, with a maximum value of 315.79 μ V/K. When the preparation temperature is 863K and the holding time is 180min, the resistivity of the prepared sample is minimum, the minimum value is 0.62 m omega cm, and the maximum power factor of 461.22 mu W/(m K) is obtained under the condition2）。
Drawings
FIG. 1 is a schematic diagram of a sample sintering assembly according to the present invention.
FIG. 2 shows CoSb of the present invention3X-ray diffraction patterns at different preparation temperatures.
FIG. 3 shows CoSb of the present invention3X-ray diffraction patterns for different incubation times.
FIG. 4 is sample CoSb of the present invention3The section electron micrograph of (1).
FIG. 5 is sample CoSb of the present invention3 The Seebeck coefficient and the synthesis temperature.
FIG. 6 is sample CoSb of the present invention3Resistivity versus synthesis temperature.
FIG. 7 is sample CoSb of the present invention3Is related to the resulting temperature.
FIG. 8 is sample CoSb of the present invention3The Seebeck coefficient and the holding time.
FIG. 9 is sample CoSb of the present invention3The Seebeck coefficient and the holding time.
FIG. 10 is a graph of power factor as a function of incubation time for samples of the invention.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples.
Referring to fig. 1, the sintering mold adopted by the invention is composed of a plug 1, an isolation material 2 and a cylinder body 4, and CoSb is formed by powder pressing3Sample 3 was set therein. The plug 1 is made of pure copper or high manganese steel; the isolation material 2 is made of boron nitride or zirconium oxide; the cylinder body 4 is made of heat-resistant steel or stainless steel material, CoSb3The sample 3 is a cylinder with the diameter of about a mm and the height of about h mm, the diameter of the plug 1 and the diameter of the sample inner hole of the cylinder body 4 are standard threaded holes with the diameter of (a +5) mm, and the outer diameter of the cylinder body 4 is 1-6 times of the diameter a of the sample.
The invention relates to a solid-phase reaction method for rapidly preparing CoSb3The method adopts Co powder and Sb powder with the purity of 99.99 percent and the average grain size of 74 mu m as starting raw materials, and adopts CoSb powder with the chemical formula3Is weighed on an analytical balance. After weighing and proportioning, the raw materials are quickly put into a hard alloy ball milling tank, and the ball-material ratio is 30: 1. And (3) mixing materials on a planetary ball mill after the hard alloy ball milling tank is vacuumized, wherein the rotating speed is 350r/min, and the mixing time is 1 h. The uniformly mixed raw materials are taken out and then are pressed into a cylinder with the diameter of 10mm and the height of 4 mm. The sample is placed in a vacuum furnace through a sintering mold, sintering preparation is carried out at 723-923K, and certain heat preservation time (1-E)180 min) is cooled to room temperature along with the furnace, and then a sample is taken out.
The sintering of the sample adopts a vacuum atmosphere furnace HMZ-1700-20. The phase analysis of the sample adopts X-ray diffraction (XRD) test and adopts a TD-2500 type X-ray diffractometer (Cu-K radiation, diffraction angle is 20-80 degrees). Electron microscopy and EDS elemental analysis FEI Nova NanoSEM 450 ultra high resolution scanning electron microscopy was used. The resistivity of the sample at room temperature is tested by using an RTS-9 double-electric-measurement four-probe tester, and the Seebeck coefficient is tested by using a self-made Seebeck tester with the error corrected to 7%.
The results of the analysis were analyzed under different conditions of temperature, time, etc.
FIG. 2 shows that CoSb is obtained by a high-temperature solid-phase reaction method under different temperature conditions in a vacuum ball milling time of 1h3XRD phase analysis pattern of (1). The spectrum of the sample at different preparation temperatures is shown in FIG. 2, and since the melting point of Sb is 903K, the maximum temperature examined as a solid phase reaction is 923K. As can be seen from the figure, the prepared sample map and CoSb3The comparison of the standard maps shows that no obvious impurity peak appears, and the single-phase skutterudite structure (Im) can be synthesized at the preparation temperature ranging from 723K to 923K3). The prepared sample has a large test peak value and a small half-peak width, which indicates that the sample has good crystallization.
FIG. 3 shows that CoSb is obtained at different holding times when the vacuum ball milling time is 1h and the preparation temperature is 863K3XRD phase analysis pattern of (1). The graph shows that the single-phase CoSb can be prepared from 1min to 3 hours3A thermoelectric material. When the heat preservation time is overlong about 5 hours, the prepared skutterudite is decomposed into most of elemental antimony and CoSb2Only a small amount of skutterudite is not decomposed.
FIG. 4 is sample CoSb prepared by vacuum ball milling and high temperature solid phase reaction3Scanning Electron Microscopy (SEM) micrograph of cross section. The sample preparation conditions are that the vacuum ball milling is carried out for 1h, the synthesis temperature is 863K, the heat preservation time is 30min, in the figure 4, (a) is a picture of the microstructure of the sample at low magnification, and in the figure 4, (b) is a picture of the microstructure of the sample at higher magnification.From (a) in 4, it can be seen that many pores exist inside the prepared skutterudite sample, and the diameter of the pores is about 50 μm. This is caused as a result of the solid phase reaction, which is the reaction starting material in solid state, the interface of different components is at high temperature, the interface reaction continuously occurs and continuously fuses to form a new phase, thus generating pores in the interior of the material during the reaction fusion process. The existence of microscopic holes in the sample helps to reduce the thermal conductivity of the material. FIG. 4 (b) shows that the skutterudite sample synthesized by the high temperature solid phase reaction method has relatively uniform and fine crystal grains and most of the crystal grains are in the nanometer level. The shape of the crystal is mostly columnar or granular, fine grains increase the grain boundary of the material on the whole, the fine grain structure and crystal defects can enhance the scattering of phonons, so that the lattice thermal conductivity of a sample can be reduced, but the existence of a large number of holes and the grain boundary can also increase the resistivity obviously.
FIG. 5 is CoSb3The Seebeck coefficient measured at room temperature is related to different preparation temperatures. As can be seen from the figure, the Seebeck coefficient is measured to be a positive value in the experiment, which indicates that the sample synthesized by the high-temperature solid-phase reaction is a P-type semiconductor. The Seebeck coefficient of the sample gradually increased with increasing preparation temperature. The Seebeck coefficient of the sample was the largest at preparation temperature 923K, with a maximum value of 315.79 μ V/K.
FIG. 6 is a graph of resistivity measured at room temperature for a sample versus preparation temperature. As can be seen from the graph, the resistivity of the sample shows a tendency to decrease first and then increase slowly as the preparation temperature increases. Within the preparation temperature range of 723-883K, the resistivity changes more smoothly, and the average value of the resistivity is 206.8m omega cm. The room temperature resistivity of skutterudite obtained when the preparation temperature was 843K was the smallest, the smallest value being 191 m Ω · cm.
FIG. 7 shows CoSb at different preparation temperatures3The power factor measured at room temperature shows that the power factor of the sample increases and then decreases with the increase of the preparation temperature. Within the preparation temperature range of 843-923K, the power factor of the sample is higher, wherein the maximum power factor of the sample is 43.3 mu W/(m.k) at the preparation temperature of 883K2）。
FIG. 8 shows the vacuum ball milling for 1h, the preparation temperature is 863K, and the sample CoSb3The Seebeck coefficient of the heat-insulating material and the heat-insulating time. As can be seen from FIG. 8, the Seebeck coefficient of the sample decreases with the increase of the heat preservation time, and when the heat preservation time is 1-60 min, the Seebeck coefficient of the sample is high, the average value is 292.07 μ V/k, and the resistivity of the sample is also high. When the heat preservation time is 1h, the maximum Seebeck coefficient of the sample is higher, and the value is 301.93 mu V/K.
FIG. 9 is a graph of resistivity measured at room temperature versus incubation time for the samples. It can be seen from the graph that the resistivity of the sample shows a tendency to decrease with the time of the incubation. The average value of the resistivity is 213.75m omega cm when the preparation temperature is 863K and the heat preservation time is 1-60 min. When the heat preservation time is 180min, the room temperature resistivity of the obtained skutterudite is minimum, the minimum value is 0.62 m omega cm, and the corresponding Seebeck coefficient is relatively small and is 53.475 mu V/K.
FIG. 10 shows CoSb particles after vacuum ball milling for 1h, preparation temperature of 863K and different holding times3The power factor measured at room temperature, from which it can be seen that the power factor of the sample increases with the incubation time. The Seebeck coefficient of the sample is rapidly reduced after the heat preservation time is increased, the resistivity is also rapidly reduced, and finally the power factor of the sample is increased along with the extension of the heat preservation time. When the heat preservation time is 180min, the maximum power factor of the sample is 461.22 mu W/(m.k)2）。
In conclusion, the sample prepared by the invention has a plurality of micropores uniformly, the diameter of the micropores is about 50 μm, and the fine diameter of the crystal grains in the sample is in a nanometer level. The sample obtained the largest Seebeck coefficient at preparation temperature 923K, with the maximum value being 315.79 μ V/K. When the preparation temperature is 863K and the holding time is 180min, the minimum resistivity of the sample is 0.62 m omega cm, and the maximum power factor of 461.22 mu W/(m K) is obtained under the condition2）。

Claims (1)

1. Rapid preparation of CoSb by solid-phase reaction method3Characterized by the fact that CoSb is present in the formula3Taking Co powder and Sb powder according to the stoichiometric ratio, and putting the Co powder and the Sb powder in a ball milling tankMixing materials by an air ball mill, taking out the materials, performing powder compression molding, assembling the materials by adopting a sintering mold, sintering the materials in a vacuum furnace, and cooling the materials to room temperature along with the furnace to obtain the material, wherein the adopted sintering mold consists of a plug, an isolating material and a cylinder body, and powder compression molded CoSb3Arranging the sample in the sample, and performing powder compression molding to obtain a cylindrical sample with the diameter of 10mm and the height of 4 mm; the diameter of the plug and the diameter of an inner hole of the cylinder sample are both 15 mm, the inner hole of the cylinder sample is a standard threaded hole, the outer diameter of the cylinder is 1-6 times of the diameter of the sample, and the plug is made of pure copper or high manganese steel; the isolation material is made of boron nitride or zirconium oxide; the cylinder body is made of heat-resistant steel or stainless steel, the ball milling tank is made of tungsten carbide, the ball-material ratio is 30:1, the rotating speed is 350r/min, the material mixing time is 1-4 h, the sintering adopts a vacuum atmosphere furnace, solid-phase reaction sintering is carried out in vacuum or inert atmosphere, the sintering temperature range is 723-923K, the heat preservation time is 1-180 min, the single-phase skutterudite thermoelectric material is prepared, micron-sized holes are uniformly distributed on a sample, the diameter of each micropore is 10 mu m, and the diameter of crystal grains in the sample is in a nanoscale; when the sintering temperature is 923K, the Seebeck coefficient of the sample is the maximum, and the maximum value is 315.79 mu V/K; when the sintering temperature is 863K and the holding time is 180min, the resistivity of the prepared sample is minimum, the minimum value is 0.62 m omega cm, and the maximum power factor 461.22 mu W/(m K) is obtained under the condition2）。
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