CN114082968A - Method for large-scale preparation of filled skutterudite material by spray rotary quenching - Google Patents
Method for large-scale preparation of filled skutterudite material by spray rotary quenching Download PDFInfo
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- 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
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/10—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying using centrifugal force
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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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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- 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
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Abstract
The invention discloses a method for preparing a filled skutterudite material in a large scale by utilizing spray rotary quenching, which comprises the following steps: fully mixing and melting raw materials for preparing the filled skutterudite material, and inputting gas with the pressure of 0.02-0.04 MPa to enable the raw materials to be sprayed out from a nozzle in the form of atomized metal beams; the atomized metal beam is collected by a metal cover rotating at a high speed and is spun on the surface of the metal cover at different linear speeds, and the atomized metal beam is quenched to obtain a powdery product with an amorphous/nanocrystalline composite structure; and (4) sintering the powder product after forming to obtain the blocky filled skutterudite material. The method for preparing the filled skutterudite material in a large scale by utilizing spray rotary quenching can realize large-scale production, and the prepared filled skutterudite material has excellent thermoelectric property.
Description
Technical Field
The invention relates to a preparation method of a skutterudite material, in particular to a method for preparing a filled skutterudite material in a large scale by utilizing spray rotary quenching.
Background
Thermoelectric materials play a key role in the development of sustainable energy-saving technology, and the current energy demand problem is increasingly serious. With the reduction of fossil fuels, renewable energy sources are crucial to address future electrical crisis. In this regard, energy conversion technologies such as solar cells and fuel cells are highly relevant, but their global commercialization is limited by factors such as low efficiency, high cost, and poor long-term stability. Thermoelectric equipment can directly convert heat energy into electric energy by utilizing a thermoelectric power generation mode, and the thermoelectric power generation is a full-static direct power generation mode for converting heat energy into electric energy by utilizing a thermoelectric conversion material. In theory, these thermoelectric devices may use any heat source, including solar energy and waste heat. In addition, the thermoelectric devices have the advantages of reliable performance, no noise, no abrasion, no leakage, flexible movement and the like, and are applied to the fields of military affairs, aerospace, medicine, microelectronics and the like.
The filled skutterudite compound has large carrier mobility, high electrical conductivity and large Seebeck coefficient and low lattice thermal conductivity. Thus RM4X12The high-performance thermoelectric material is used as a hot door.
Traditional filled skutterudite polycrystalline compound RM4X12The preparation method mainly comprises a solid state reaction method (SSR), a mechanical alloying Method (MA), a melt spinning Method (MS) and the like.
1. Solid state reaction method: the preparation period is long, usually about one week, the time cost is high, and the thermoelectric performance index is general.
2. Mechanical alloying method: has the advantages of high efficiency, low cost, large yield and the like. Although the phenomenon of component segregation in the process from a liquid phase to a solid phase can be avoided, the obtained nano powder is easy to agglomerate and has uneven size distribution; the sample is difficult to collect due to easy adhesion with the grinding ball, and impurities are easy to introduce due to long-time action between the grinding ball and the sample.
3. Melt spinning method: the working mode of the melt spinning method is that the melt is sprayed onto a copper roller rotating at a high speed in a fluid form and is spun out along the tangential direction of the copper roller, so that a strip-shaped product is formed; the preparation period is short (within half an hour), the microstructure is controllable, and a banded product can be obtained after rotary throwing, wherein the microstructure of the banded product is in a nano scale; however, the melt spinning has a small sample amount (about tens of grams) prepared each time, and because the size of the round hole is only about 0.30mm, the round hole at the bottom of the glass tube is blocked due to too much sample amount, so that the prepared amount each time is small, and the large-scale preparation cannot be realized.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for preparing a filled type skutterudite material in a large scale by utilizing spray rotary quenching, which can be used for large-scale production, and the prepared filled type skutterudite material has excellent thermoelectric performance.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a filled skutterudite material in a large scale by spray rotary quenching comprises the following steps:
(1) fully mixing raw materials for preparing the filled skutterudite material and then placing the mixture in an induction smelting furnace; the top of the induction smelting furnace is provided with an air inlet, and the bottom of the induction smelting furnace is provided with an atomizing nozzle;
(2) starting an induction smelting furnace to smelt the raw materials, inputting gas with the pressure of 0.02-0.04 MPa from a gas inlet after the raw materials are in a molten state, and spraying the raw materials out of a nozzle in the form of atomized metal beams;
(3) spraying the atomized metal beam obtained in the step (2) onto a metal cover for collecting the atomized metal beam; the copper cover rotates at the speed of 1000-3000 rpm, the atomized metal beam is collected by the metal cover and is spun on the surface of the metal cover at different linear speeds, and the atomized metal beam is quenched to obtain a powdery product with an amorphous/nanocrystalline composite structure;
(4) and (4) sintering the powdery product obtained in the step (3) after molding to obtain the blocky filled skutterudite material.
Preferably, the skutterudite material in the step (1) has a chemical formula of RM4X12Wherein R is barium or a rare earth element; m is a transition metal element; x is a phosphorus element.
Preferably, the raw material in the step (1) is elemental substance R, M, X.
Preferably, during the smelting of the raw materials in the step (2), argon is filled for protection.
Preferably, the size of the powdery product with the amorphous/nanocrystalline composite structure in the step (3) is 10-80 μm.
Preferably, the molding in the step (4) specifically includes grinding and tabletting.
Preferably, the sintering in step (4) is spark plasma sintering.
Preferably, the sintering temperature is 500-600 ℃, the pressure is 30-40 MPa, and the time is 5-10 min.
Preferably, the induction smelting furnace comprises a tubular furnace body and an induction coil wound around an outer surface of the tubular furnace body.
Preferably, the metal cap is a copper cap.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method for preparing the filled skutterudite material in a large scale by using spray rotary quenching provided by the invention has the advantages that the powdery product is prepared by using the spray rotary quenching method, the preparation amount of a target product is greatly increased, and the RM is enabled to be4X12The mass production of the material becomes possible.
(2) The method for preparing the filled skutterudite material in a large scale by using spray rotary quenching provided by the invention prepares a powdery product by using a spray rotary quenching method, and then adopts discharge plasma sintering, so that the preparation period is short and the operation is simple.
(3) The invention relates to a method for preparing a filled skutterudite material in a large scale by spray rotary quenching, wherein in the process of preparing a powdery product by a spray rotary quenching method, atomized metal beams are sprayed onto the surface of a high-heat-conducting metal cover rotating at high speed through a nozzle, because the linear speed of the high heat-conducting metal cover increases from the center to the edge, the material spun out by the high heat-conducting metal cover obtains multi-size nanocrystalline or even amorphous powdery products because of different cooling rates, the block material is obtained by spark plasma sintering, because the spark plasma sintering time is very short, some amorphous structures in the powdery product are remained in the sintered block material, therefore, the obtained bulk material is a natural nano multi-scale composite structure, and the multi-scale nano composite structure is beneficial to scattering phonons in a longer and wider wave band range, so that the lattice thermal conductivity of the material is greatly reduced, and the thermoelectric performance of the material is greatly improved. In addition, by controlling and optimizing the spray rotary quenching process and the discharge plasma sintering parameters, the thermoelectric compound has the advantages of further uniform distribution of all components and more excellent thermoelectric performance.
Drawings
FIG. 1 is an XRD pattern of a powdery product obtained in example 1 of the present invention.
FIG. 2 is a scanning electron microscope (FSEM) image of the powder prepared in example 1 of the present invention.
Fig. 3 is a partially enlarged view of a position a in fig. 2.
Fig. 4 is a partially enlarged view of a portion B in fig. 2.
FIG. 5 is an FESEM photograph of a bulk product prepared in example 1 of the present invention.
FIG. 6 is a high magnification FSEM photograph of a block product prepared in example 1 of the present invention.
FIG. 7 is a Transmission Electron Micrograph (TEM) of a cake product obtained in example 1 of the present invention
FIG. 8 is a high magnification transmission electron micrograph (HTEM) of a cake product prepared in example 1 of the present invention
Fig. 9 is a schematic structural view of an apparatus for implementing the method for mass-producing a filled skutterudite material using spray spin quenching of the present embodiment.
FIG. 10 shows Yb prepared in example 2 of the present invention0.2Co4Sb12.6Thermal conductivity versus temperature dependence of a compound bulk material is plotted.
FIG. 11 shows Yb produced in example 2 of the present invention0.2Co4Sb12.6Yb production of compound bulk materials0.2Co4Sb12.6Power Factor (PF) versus temperature dependence of the compound bulk material.
FIG. 12 shows In prepared In example 3 of the present invention0.15Ce0.15Co4Sb12XRD spectrum of bulk thermoelectric compound material.
FIG. 13 shows In prepared In example 3 of the present invention0.15Ce0.15Co4Sb12Initiation of free fracture surface of thermoelectric compound bulk materialScanning Electron Micrographs (FSEM).
FIG. 14 shows In prepared In example 3 of the present invention0.15Ce0.15Co4Sb12FSEM plot at high magnification of free fracture surface of bulk thermoelectric compound material.
FIG. 15 shows In prepared In this example0.15Ce0.15Co4Sb12A temperature difference thermoelectric figure of merit (ZT) and temperature dependence curve of thermoelectric compound bulk material.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Preparing raw materials: high-purity starting materials of granular Yb (99.99%), granular Co (99.99%) and granular Sb (99.9999%) are mixed according to the chemical formula Yb0.2Co4Sb12.6And (5) weighing. (100-200 g can be prepared in each experiment; calculation mode: m ═ rho;)(RM4X12).VQuartz tube)。
(2) Preparing a powdery product by spray spinning quenching: mixing the high-purity raw materials, smelting in induction furnace, vacuumizing to 5X 10-3Pa, filling high-purity argon for protection to obtain a melt; and spraying the melt into a copper cover in a metal beam form under the air spraying pressure of 0.04MPa, rotating the copper cover at a high speed of 3000rpm, throwing the atomized metal beam out towards the tangential direction of a contact point on the surface of the copper disc, and collecting the atomized metal beam in a metal collecting cover to obtain a powdery product (10-80 mu m) with an amorphous/nanocrystalline composite structure.
(3) And (3) block sintering: fully grinding the obtained powdery product, sintering the powdery product in vacuum by discharge plasma sintering at 550 ℃ under 40MPa for 5min to obtain single-phase Yb with relative density of more than 99% and excellent thermoelectric property index0.2Co4Sb12.6A bulk material of thermoelectric compound.
The XRD pattern of the powdery product prepared in this example is shown in fig. 1 (b), and it can be seen that the phase composition of the powdery product is more complicated and the diffraction peak is broadened, compared with the reference sample, standard skutterudite (a).
The field emission scanning electron micrographs of the powdery product prepared in this example are shown in fig. 2 to 4, where fig. 3 and 4 are enlarged views of the position A, B in fig. 2, respectively. As shown in FIG. 3, the grain size of the product at the A position is about 20-40 nm, which is a plurality of fine nano-structures; as shown in FIG. 4, the component at the B position has uniform appearance, uniform component distribution, no difference in microscopic details and a similar amorphous structure.
Yb prepared in this example0.2Co4Sb12.6The XRD pattern of the bulk thermoelectric compound material is shown in (c) of FIG. 1, and it can be seen that the powder product is sintered by spark plasma to obtain a single-phase skutterudite compound.
Yb prepared in this example0.2Co4Sb12.6As shown in FIGS. 5-6, it can be seen that the grains of the bulk thermoelectric compound material are closely arranged and uniformly distributed after the powder product is sintered by spark plasma.
Yb prepared in this example0.2Co4Sb12.6The transmission electron microscope photographs of the thermoelectric compound block material are shown in fig. 7-8, wherein fig. 8 is a high magnification diagram of fig. 7, and it can be seen that after the powder product is sintered by the discharge plasma, the nano-crystalline grains are different in size and distributed in a multi-scale manner, and the size range of the crystalline grains is about: 20 to 200 nm. In which some amorphous structure of dark areas, such as the a-position in the figure, remains.
The device for realizing the method for preparing the filled skutterudite material in a large scale by using spray rotary quenching of the embodiment is shown in fig. 9 and comprises an induction melting furnace and a copper cover 1; the top of the induction smelting furnace is provided with an air inlet 2 and a lantern ring 3 for fixing, and the bottom of the induction smelting furnace is provided with an atomizing nozzle 4; the induction smelting furnace comprises a tubular furnace body 5 and an induction coil 6 wound around the outer surface of the tubular furnace body 5.
Example 2
The preparation process of this example is the same as that of example 1 except for the following process parameters:
sample 1: in the process of preparing the powdery product by spray spinning quenching, the air injection pressure is 0.04MPa, and the rotating speed of the copper shield is 1000 rpm.
Sample 2: in the process of preparing the powdery product by spray spinning quenching, the air injection pressure is 0.04MPa, and the rotating speed of the copper shield is 3000 rpm.
Sample 3:
in the process of preparing the powdery product by spray spinning quenching, the air injection pressure is 0.02MPa, and the rotating speed of the copper shield is 3000 rpm.
Wherein, the preparation process of the reference sample comprises the following steps: fusion-annealing-SPS process
High-purity granular Yb (99.9%), granular Co (99.99%) and granular Sb (99.9999%) are used as reaction raw materials, and the chemical formula of Yb is shown in the specification0.2Co4Sb12.6Weighing, placing in a quartz tube with carbide film pre-deposited on inner wall, and vacuum-pumping at 10 deg.C-3Sealing under Pa, placing into a melting furnace, slowly heating to 1100 deg.C at a speed of 3 deg.C/min, melting for 24 hr, quenching the melt in water bath, cooling to obtain block material, pulverizing, compacting, sealing in quartz tube under vacuum condition, and placing in a reaction furnace for diffusion reaction at 700 deg.C for 72 hr. The reaction product was ultrasonically cleaned with acetone to remove a small amount of impurities. Finally using a single-phase compound Yb0.2Co4Sb12.6The powder is used as raw material, and sintered under vacuum by Spark Plasma Sintering (SPS) method to obtain sintered body with relative density of about 98%, sintering temperature, pressure and time are 550 deg.C, 40MPa and 5min respectively.
FIG. 10 shows Yb prepared in this example0.2Co4Sb12.6The thermal conductivity of the compound block material is dependent on the temperature, and compared with a reference sample, Yb prepared by adopting a spray spinning quenching and discharge plasma sintering method0.2Co4Sb12.6The thermal conductivity of the compound is greatly reduced in the range of the full testing temperature range. At the same time, the high rotation speed of the copper cover also leads to a reduction in thermal conductivity, thereby improving the thermoelectric performance of the material.
FIG. 11 shows Yb produced in this example0.2Co4Sb12.6The Power Factor (PF) of the compound block material is dependent on the temperature, the power factor value is higher, and the spraying of the nozzle is increasedThe gas pressure will increase its power factor and thus further improve the thermoelectric performance of the material.
Example 3
(1) Starting materials used high purity particulate In (99.999%), particulate Ce (99.98%), particulate Co (99.99%) and particulate Sb (99.9999%). Reacting raw materials according to a chemical formula In0.15Ce0.15Co4Sb12Weighing
(2 preparation of powdery product: mixing the high-purity raw materials of each component, putting the mixture into a quartz glass tube with a round nozzle at the bottom, putting the quartz glass tube into a smelting furnace in an induction coil for smelting, and vacuumizing the tube to 5 x 10-3Pa, filling high-purity argon for protection to obtain a melt; and spraying the melt to the surface of a concave copper disc in a metal beam mode under the air spraying pressure of 0.04MPa, rotating the copper disc at a high speed of 3000rpm, throwing the atomized metal beam out towards the tangential direction of a contact point on the surface of the copper disc, and gathering the atomized metal beam in a metal collecting cover to obtain a powdery product with an amorphous/nanocrystalline scale.
(3) And (3) block sintering: fully grinding the obtained powdery product, sintering In vacuum by spark plasma sintering at 550 ℃ under 40MPa for 5min to obtain single-phase In with relative density of more than 99% and excellent thermoelectric property0.15Ce0.15Co4Sb12A bulk material of thermoelectric compound.
In prepared In this example0.15Ce0.15Co4Sb12The XRD spectral lines of the thermoelectric compound block material and the reference sample are shown In figure 12, and the In after sintering is compared with the standard skutterudite spectrum of the reference sample0.15Ce0.15Co4Sb12The XRD patterns of the thermoelectric compound bulk materials have no obvious difference, which indicates that the skutterudite of a single crystal phase is generated.
In prepared In this example0.15Ce0.15Co4Sb12The field emission scanning electron microscope photographs of the free fracture surface of the thermoelectric compound bulk material are shown in FIGS. 13-14, wherein FIG. 14 is a high magnification view of FIG. 13. As can be seen from FIGS. 13 to 14, In0.15Ce0.15Co4Sb12Grain boundary of compoundPrecipitates of the nano structure are found, and the size is about 5-50 nm; the large amount of uniformly distributed nano-phases can effectively reduce the lattice thermal conductivity of the material and improve the Seebeck coefficient of the material.
In prepared In this example0.15Ce0.15Co4Sb12The thermoelectric figure of merit (ZT) of the bulk thermoelectric compound material is dependent on temperature as shown In FIG. 15, and the results show that In prepared In this example0.15Ce0.15Co4Sb12The compounds have higher ZT values throughout the temperature range tested. ZT value reaches 1.45 at 800K, and In prepared by melting-annealing-sintering process0.15Ce0.15Co4Sb12Compared with a reference sample, the thermoelectric performance is greatly improved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for preparing a filled skutterudite material in a large scale by utilizing spray rotary quenching is characterized by comprising the following steps:
(1) fully mixing raw materials for preparing the filled skutterudite material and then placing the mixture in an induction smelting furnace; the top of the induction smelting furnace is provided with an air inlet, and the bottom of the induction smelting furnace is provided with an atomizing nozzle;
(2) starting an induction smelting furnace to smelt the raw materials, inputting gas with the pressure of 0.02-0.04 MPa from a gas inlet after the raw materials are in a molten state, and spraying the raw materials out of a nozzle in the form of atomized metal beams;
(3) spraying the atomized metal beam obtained in the step (2) onto a metal cover for collecting the atomized metal beam; the copper cover rotates at the speed of 1000-3000 rpm, the atomized metal beam is collected by the metal cover and is spun on the surface of the metal cover at different linear speeds, and the atomized metal beam is quenched to obtain a powdery product with an amorphous/nanocrystalline composite structure;
(4) and (4) sintering the powdery product obtained in the step (3) after molding to obtain the blocky filled skutterudite material.
2. The method for mass-producing filled skutterudite material by spray spinning quenching as claimed in claim 1, wherein the chemical formula of the skutterudite material in the step (1) is RM4X12Wherein R is barium or a rare earth element; m is a transition metal element; x is a phosphorus element.
3. The method for preparing the filled skutterudite material on a large scale by using spray rotary quenching as claimed in claim 2, wherein the raw material in the step (1) is elemental substance R, M, X.
4. The method for mass production of filled skutterudite material by spray-spin quenching as claimed in claim 1, wherein the raw material is charged with argon gas for protection during the melting of the raw material in the step (2).
5. The method for preparing the filled skutterudite material in a large scale by using spray spinning quenching as claimed in claim 1, wherein the size of the powdery product having the amorphous/nanocrystalline composite structure in the step (3) is 10-80 μm.
6. The method for large-scale preparation of filled skutterudite material by spray rotary quenching as claimed in claim 1, wherein the forming in step (4) comprises grinding and tabletting.
7. The method for large-scale preparation of filled skutterudite material by spray rotary quenching according to claim 1, wherein the sintering in the step (4) is spark plasma sintering.
8. The method for preparing the filled skutterudite material in a large scale by utilizing spray rotary quenching as claimed in claim 1 or 7, wherein the sintering temperature is 500-600 ℃, the pressure is 30-40 MPa, and the time is 5-10 min.
9. The method for mass-producing filled skutterudite material by spray rotary quenching according to claim 1, wherein the induction melting furnace comprises a tubular furnace body and an induction coil wound around an outer surface of the tubular furnace body.
10. The method for mass-producing filled skutterudite material using spray spin quenching according to claim 1 or 9, wherein the metal cap is a copper cap.
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