CN114082968B - Method for preparing filled skutterudite material in large scale by spray spin quenching - Google Patents
Method for preparing filled skutterudite material in large scale by spray spin quenching Download PDFInfo
- Publication number
- CN114082968B CN114082968B CN202111252165.4A CN202111252165A CN114082968B CN 114082968 B CN114082968 B CN 114082968B CN 202111252165 A CN202111252165 A CN 202111252165A CN 114082968 B CN114082968 B CN 114082968B
- Authority
- CN
- China
- Prior art keywords
- filled skutterudite
- skutterudite material
- quenching
- preparing
- spray spin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000010791 quenching Methods 0.000 title claims abstract description 29
- 230000000171 quenching effect Effects 0.000 title claims abstract description 29
- 239000007921 spray Substances 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 claims abstract 3
- 230000006698 induction Effects 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 238000003723 Smelting Methods 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- 238000002490 spark plasma sintering Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 241001062472 Stokellia anisodon Species 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000011049 filling Methods 0.000 abstract description 3
- 238000009987 spinning Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 33
- 150000001875 compounds Chemical class 0.000 description 26
- 239000013590 bulk material Substances 0.000 description 12
- 239000000523 sample Substances 0.000 description 8
- 239000000155 melt Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000005551 mechanical alloying Methods 0.000 description 3
- 238000002074 melt spinning Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RHQQHZQUAMFINJ-GKWSUJDHSA-N 1-[(3s,5s,8s,9s,10s,11s,13s,14s,17s)-3,11-dihydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]-2-hydroxyethanone Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CC[C@H]21 RHQQHZQUAMFINJ-GKWSUJDHSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention discloses a method for preparing filled skutterudite material in large scale by spray spin 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 of a nozzle in the form of atomized metal beams; collecting the atomized metal beam by a metal cover rotating at a high speed, spinning the atomized metal beam on the surface of the metal cover at different linear speeds, and quenching the atomized metal beam to obtain a powdery product with an amorphous/nanocrystalline composite structure; and (5) sintering the powdery product after molding to obtain the blocky filling skutterudite material. The method for preparing the filled skutterudite material in a large scale by utilizing spray spin quenching can realize large-scale production, and the prepared filled skutterudite material has excellent thermoelectric performance.
Description
Technical Field
The invention relates to a preparation method of skutterudite material, in particular to a method for preparing filled skutterudite material in large scale by spray spin 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 critical to address future power crisis. In this regard, energy conversion technologies such as solar cells and fuel cells have a high degree of relevance, but their global commercialization is limited by factors such as low efficiency, high cost, and poor long-term stability. The thermoelectric device can directly convert heat energy into electric energy by utilizing a thermoelectric generation mode, and the thermoelectric generation mode is a full-static direct generation mode for converting heat energy into electric energy by utilizing thermoelectric conversion materials. Theoretically, these thermoelectric devices can 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, aerospace, medicine, microelectronics and the like.
Filled skutterudite compounds have a large carrier mobility, a high electrical conductivity and a large, seebeck coefficient and a low lattice thermal conductivity. Thus RM (R) 4 X 12 As a popular high performance thermoelectric material.
Conventional filled skutterudite polycrystal compound RM 4 X 12 The 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 process: the preparation period is long, the preparation period generally needs 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 liquid phase to solid phase can be avoided, the obtained nano powder is easy to agglomerate and the size distribution is uneven; because the sample is easy to adhere to the grinding ball, the sample collection is difficult, and impurities are easy to be introduced due to the long-time action between the grinding ball and the sample.
3. Melt spinning method: the melt spinning method is characterized in that the melt is sprayed onto a copper roller rotating at a high speed in a fluid mode 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 band-shaped product can be obtained after spinning, and the microstructure of the band-shaped product is nano-scale; however, the quantity of the prepared sample is small (about tens of grams) each time when the melt is spun, and the round hole size is only about 0.30mm, so that too much sample quantity can cause the blocking of the round hole at the bottom of the glass tube, and therefore, the preparation quantity is small each time, and the large-scale preparation cannot be realized.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a method for preparing filled skutterudite material in a large scale by utilizing spray spin quenching, which can be used for mass production, and the prepared filled skutterudite material has excellent thermoelectric performance.
The aim of the invention is achieved by the following technical scheme:
a method for preparing filled skutterudite material in large scale by spray spin 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 raw materials, inputting gas with the pressure of 0.02-0.04 MPa from an air inlet after the raw materials are in a molten state, and spraying the raw materials from a nozzle in the form of atomized metal bundles;
(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 rpm-3000 rpm, the atomized metal beams are collected by the metal cover and are whirled on the surface of the metal cover at different linear speeds, and the atomized metal beams are quenched to obtain a powdery product with an amorphous/nanocrystalline composite structure;
(4) And (3) molding and sintering the powdery product obtained in the step (3) to obtain the blocky filled skutterudite material.
Preferably, the skutterudite material of step (1) has a chemical formula of RM 4 X 12 Wherein R is barium or rare earth element; m is a transition metal element; x is a phosphorus group element.
Preferably, the raw material in the step (1) is elemental substance R, M, X.
Preferably, argon is filled for protection in the smelting process of the raw materials in the step (2).
Preferably, the size of the powdery product with the amorphous/nanocrystalline composite structure in the step (3) is 10-80 μm.
Preferably, the shaping in step (4) specifically comprises 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 melting furnace comprises a tubular furnace body and an induction coil, and the induction coil is wound on the outer surface of the tubular furnace body.
Preferably, the metal cover is a copper cover.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The method for preparing the filled skutterudite material in large scale by utilizing spray spin quenching of the invention utilizes a spray spin quenching method to prepare powdery products, thereby greatly increasing the target productsPreparation amount, RM 4 X 12 Mass production of the material becomes possible.
(2) The method for preparing the filled skutterudite material in large scale by utilizing spray spin quenching utilizes a spray spin quenching method to prepare a powdery product, and then adopts spark plasma sintering, so that the preparation period is short and the operation is simple.
(3) According to the method for preparing the filled skutterudite material in large scale by utilizing spray spin quenching, in the process of preparing the powdery product by utilizing a spray spin quenching method, atomized metal beams are sprayed onto the surface of a high-heat-conductivity metal cover rotating at a high speed through a nozzle, the linear speed of the high-heat-conductivity metal cover from the center to the edge increases progressively, the material spun by the high-heat-conductivity metal cover obtains multi-size nanocrystalline even amorphous powdery product because of different cooling speeds, and the bulk material is obtained by spark plasma sintering, and due to the fact that the spark plasma sintering time is very short, some amorphous structures in the powdery product are reserved in the sintered bulk material, the obtained multi-scale nano composite structure is favorable for scattering phonons in a longer and wider band range, so that the lattice heat conductivity of the material is greatly reduced, and the thermoelectric performance of the material is greatly improved. In addition, the thermoelectric compound components are further uniformly distributed and the thermoelectric performance is more excellent by controlling and optimizing the spray spin quenching process and the spark plasma sintering parameters.
Drawings
FIG. 1 is an XRD pattern of the powdery product prepared in example 1 of the present invention.
FIG. 2 is a field emission scanning electron microscope (FSEM) of the powdery product prepared in example 1 of the present invention.
Fig. 3 is a partial enlarged view of the position a in fig. 2.
Fig. 4 is a partial enlarged view of the position B in fig. 2.
Fig. 5 is a FESEM photograph of a bulk product prepared in example 1 of the present invention.
Fig. 6 is a photograph of FSEM at high magnification of the bulk product prepared in example 1 of the present invention.
FIG. 7 is a Transmission Electron Micrograph (TEM) of a bulk product prepared according to example 1 of the present invention
FIG. 8 is a high-magnification transmission electron microscope (HTEM) of a bulk product prepared in example 1 of the present invention
Fig. 9 is a schematic structural view of an apparatus for realizing the method for mass production of filled skutterudite material by spray spin quenching according to this embodiment.
FIG. 10 shows Yb produced in example 2 of the present invention 0.2 Co 4 Sb 12.6 Thermal conductivity versus temperature dependence of the bulk material of the compound.
FIG. 11 shows Yb produced in example 2 of the present invention 0.2 Co 4 Sb 12.6 Yb of preparation of compound bulk material 0.2 Co 4 Sb 12.6 And a graph of Power Factor (PF) versus temperature dependence of the bulk material of the compound.
FIG. 12 shows In prepared In example 3 of the present invention 0.15 Ce 0.15 Co 4 Sb 12 XRD spectrum of the pyroelectric compound block material.
FIG. 13 shows In prepared In example 3 of the present invention 0.15 Ce 0.15 Co 4 Sb 12 Field emission scanning electron micrographs (FSEM) of free fracture surfaces of bulk thermoelectric compounds.
FIG. 14 shows In prepared In example 3 of the present invention 0.15 Ce 0.15 Co 4 Sb 12 FSEM plot at high magnification of free fracture surface of thermoelectric compound bulk material.
FIG. 15 shows In prepared In this example 0.15 Ce 0.15 Co 4 Sb 12 Thermoelectric figure of merit (ZT) versus temperature dependence plot for thermoelectric compound bulk materials.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1
(1) Raw material preparation: high purity starting material of granular Yb (99.99%), granular Co (99.99%) and granular Sb (99.9999%)According to chemical Yb 0.2 Co 4 Sb 12.6 And (5) weighing. (100-200 g can be prepared in each experiment; the calculation mode is m=ρ) (RM4X12) .V Quartz tube )。
(2) Preparing a powdery product by spray spin quenching: mixing the high-purity raw materials, smelting in induction furnace, and vacuumizing to 5×10 -3 Pa, and then filling high-purity argon for protection to obtain a melt; spraying the melt into a copper cover in the form of metal bundles under the air spraying pressure of 0.04MPa, rotating the copper cover at a high speed with the rotating speed of 3000rpm, throwing the atomized metal bundles out towards the tangential direction of the contact point of the surface of a copper plate, and collecting the atomized metal bundles 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: grinding the obtained powder product fully, sintering under vacuum by spark plasma sintering at 550 deg.C under 40MPa for 5min to obtain Yb with single phase, relative density of more than 99% and excellent thermoelectric performance index 0.2 Co 4 Sb 12.6 Thermoelectric compound bulk material.
As shown in (b) of FIG. 1, the XRD pattern of the powdery product prepared in this example showed a more complex phase composition and a broader diffraction peak as compared with the reference standard skutterudite (a).
The field emission scanning electron micrographs of the powdery product prepared in this example are shown in fig. 2 to 4, wherein fig. 3 and 4 are enlarged views of the A, B position in fig. 2, respectively. As can be seen from FIG. 3, the grain size of the product at the A site is about 20-40 nm, and the product is a fine nano structure; as shown in FIG. 4, the component at the B position has uniform morphology, uniform component distribution and no difference in microscopic details, and is similar to an amorphous structure.
Yb obtained in this example 0.2 Co 4 Sb 12.6 The XRD pattern of the thermoelectric compound bulk material is shown in fig. 1 (c), and it is understood that the powder product is sintered by spark plasma to obtain a single-phase skutterudite compound.
Yb obtained in this example 0.2 Co 4 Sb 12.6 Field emission scanning electron micrographs of bulk thermoelectric compounds such asAs shown in fig. 5 to 6, it is known that the powder product is sintered by spark plasma, and the grains are closely arranged and uniformly distributed.
Yb obtained in this example 0.2 Co 4 Sb 12.6 The transmission electron micrographs of the thermoelectric compound bulk materials are shown in fig. 7-8, wherein fig. 8 is a high magnification graph of fig. 7, and it can be seen that the powder product has different sizes of nano-grains and is distributed in a multi-scale manner after being sintered by spark plasma, and the grain size ranges are about: 20-200 nm. In which amorphous structures of dark areas such as the a-position in the figure remain.
The apparatus for realizing the method for preparing filled skutterudite material in large scale by spray spin quenching of the present embodiment is shown in fig. 9, and comprises an induction melting furnace and a copper hood 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 melting furnace comprises a tubular furnace body 5 and an induction coil 6, wherein the induction coil is wound on the outer surface of the tubular furnace body 5.
Example 2
The procedure of this example was the same as in example 1, except for the following process parameters:
sample 1: in the process of preparing the powdery product by spray spin quenching, the jet pressure is 0.04MPa, and the rotating speed of the copper cover is 1000rpm.
Sample 2: in the process of preparing the powdery product by spray spin quenching, the jet pressure is 0.04MPa, and the rotating speed of the copper cover is 3000rpm.
Sample 3:
in the process of preparing the powdery product by spray spin quenching, the jet pressure is 0.02MPa, and the rotating speed of the copper cover is 3000rpm.
The preparation process of the reference sample comprises the following steps: melt-anneal-SPS process
High-purity granular Yb (99.9%), granular Co (99.99%) and granular Sb (99.9999%) are used as reaction raw materials according to the chemical formula Yb 0.2 Co 4 Sb 12.6 Weighing, placing into quartz tube with inner wall pre-deposited carbonized film, vacuum degree of 10 -3 Sealing under Pa, and then placing into a melting furnace at a speed of 3 ℃/miAnd (3) slowly heating to 1100 ℃, melting for 24 hours, quenching the melt in a water bath, taking out the cooled block material, crushing, compacting, sealing in a quartz tube under vacuum again, and placing in a reaction furnace for diffusion reaction at 700 ℃ for 72 hours. The reaction product was ultrasonically cleaned with acetone to remove small amounts of impurities. Finally, single-phase compound Yb is adopted 0.2 Co 4 Sb 12.6 The powder is used as a raw material, and sintered under vacuum by a Spark Plasma Sintering (SPS) method to obtain a sintered body with the relative density of about 98%, wherein the sintering temperature, the sintering pressure and the sintering time are respectively 550 ℃,40MPa and 5min.
FIG. 10 shows Yb prepared in this example 0.2 Co 4 Sb 12.6 Thermal conductivity and temperature dependence of compound block material, compared with a reference sample, yb prepared by adopting a spray spin quenching and spark plasma sintering method 0.2 Co 4 Sb 12.6 The thermal conductivity of the compound is greatly reduced in the whole test temperature range. At the same time, the high rotation speed of the copper cover can also lead to reduced heat conductivity, thereby improving the thermoelectric performance of the material.
FIG. 11 shows Yb prepared in this example 0.2 Co 4 Sb 12.6 The Power Factor (PF) and temperature dependence of the compound bulk material are higher, and increasing the jet pressure of the jet nozzle can improve the power factor, thereby further improving the thermoelectric performance of the material.
Example 3
(1) The starting material used was high purity granular In (99.999%), granular Ce (99.98%), granular Co (99.99%) and granular Sb (99.9999%). The reaction raw materials are processed according to the chemical formula In 0.15 Ce 0.15 Co 4 Sb 12 Weighing machine
(2) preparation of powdery product, mixing the high-purity raw materials of each component, placing into a quartz glass tube with a circular nozzle at the bottom, placing into a smelting furnace in an induction coil for smelting, and vacuumizing the tube to 5X 10 -3 Pa, and then filling high-purity argon for protection to obtain a melt; spraying the melt onto the surface of concave copper plate in the form of metal beam under the jet pressure of 0.04MPa, rotating the copper plate at 3000rpm, and atomizing the metal beam to the tangential direction of contact point of copper plate surfaceAnd (3) throwing out and gathering in a metal collecting cover to obtain a powdery product with amorphous/nanocrystalline scale.
(3) And (3) block sintering: grinding the obtained powder product, sintering under vacuum by spark plasma sintering at 550deg.C under 40MPa for 5min to obtain In with single phase, relative density of more than 99% and excellent thermoelectric performance 0.15 Ce 0.15 Co 4 Sb 12 Thermoelectric compound bulk material.
In prepared In this example 0.15 Ce 0.15 Co 4 Sb 12 XRD spectra of thermoelectric compound block materials and their reference samples are shown In FIG. 12, and compared with reference standard skutterudite spectra, sintered In 0.15 Ce 0.15 Co 4 Sb 12 The XRD patterns of the thermoelectric compound block materials are not obviously different, which shows that skutterudite with single crystal phase is generated.
In prepared In this example 0.15 Ce 0.15 Co 4 Sb 12 The field emission scanning electron micrographs of the free fracture surface of the thermoelectric compound bulk material are shown in fig. 13-14, wherein fig. 14 is a high magnification view of fig. 13. As can be seen from fig. 13 to 14, in 0.15 Ce 0.15 Co 4 Sb 12 The precipitation of the nano structure is found at the grain boundary of the compound, and the size is about 5-50 nm; these large numbers of uniformly distributed nanophase can effectively reduce the lattice thermal conductivity of the material and increase the Seebeck coefficient of the material.
In prepared In this example 0.15 Ce 0.15 Co 4 Sb 12 The thermoelectric figure of merit (ZT) and the temperature dependence of the thermoelectric compound bulk material are shown In FIG. 15, and the results indicate that In prepared In this example 0.15 Ce 0.15 Co 4 Sb 12 The compound has a higher ZT value in the full test temperature range. At 800K, ZT value reaches 1.45, and In prepared by melting-annealing-sintering process 0.15 Ce 0.15 Co 4 Sb 12 The thermoelectric properties are greatly improved compared to the reference.
The embodiments described above are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments described above, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the present invention should be made in the equivalent manner, and are included in the scope of the present invention.
Claims (6)
1. The method for preparing the filled skutterudite material in large scale by utilizing spray spin quenching is characterized by comprising the following steps:
(1) Will be used for preparing filled skutterudite material In 0.15 Ce 0.15 Co 4 Sb 12 Is placed in an induction smelting furnace after being fully mixed; 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 raw materials, inputting gas with the pressure of 0.02-0.04 MPa from an air inlet after the raw materials are in a molten state, and spraying the raw materials from a nozzle in the form of atomized metal bundles;
(3) Spraying the atomized metal beam obtained in the step (2) onto a metal cover for collecting the atomized metal beam; the metal cover rotates at 1000 rpm-3000 rpm, atomized metal beams are collected by the metal cover and are whirled on the surface of the metal cover at different linear speeds, and the atomized metal beams are quenched to obtain a powdery product with an amorphous and nanocrystalline composite structure;
(4) Performing spark plasma sintering on the powdery product obtained in the step (3) after molding to obtain a blocky filled skutterudite material;
the sintering temperature of the spark plasma is 500-600 ℃, the pressure is 30-40 MPa, and the time is 5-10 min.
2. The method for large-scale preparation of filled skutterudite material by spray spin quenching as claimed in claim 1, wherein argon is filled for protection in the smelting process of raw material in step (2).
3. The method for preparing filled skutterudite material in large scale by spray spin quenching as claimed in claim 1, wherein the size of the powdery product with amorphous and nanocrystalline composite structure in step (3) is 10-80 μm.
4. The method for large-scale production of filled skutterudite material by spray spin quenching as claimed in claim 1, wherein the shaping in step (4) comprises grinding and tabletting.
5. The method for large-scale production of filled skutterudite material by spray spin quenching as claimed in claim 1, characterized in that the induction smelting furnace comprises a tubular furnace body and an induction coil wound on the outer surface of the tubular furnace body.
6. The method for mass production of filled skutterudite material by spray spin quenching as claimed in claim 1 or 5, wherein the metal cover is a copper cover.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111252165.4A CN114082968B (en) | 2021-10-26 | 2021-10-26 | Method for preparing filled skutterudite material in large scale by spray spin quenching |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111252165.4A CN114082968B (en) | 2021-10-26 | 2021-10-26 | Method for preparing filled skutterudite material in large scale by spray spin quenching |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114082968A CN114082968A (en) | 2022-02-25 |
| CN114082968B true CN114082968B (en) | 2023-08-29 |
Family
ID=80297756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111252165.4A Active CN114082968B (en) | 2021-10-26 | 2021-10-26 | Method for preparing filled skutterudite material in large scale by spray spin quenching |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114082968B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5177564A (en) * | 1974-11-26 | 1976-07-05 | Skf Nova Ab | |
| CN2030117U (en) * | 1988-02-06 | 1989-01-04 | 中南工业大学 | Fast condensing equipment for making fine powder |
| CN1899729A (en) * | 2006-07-11 | 2007-01-24 | 武汉理工大学 | Method for preparing high performance bismuth telluride thermoelectric material |
| CN101435029A (en) * | 2008-12-26 | 2009-05-20 | 武汉理工大学 | Rapid preparation of high performance nanostructured filling type skutterudite thermoelectric material |
| CN101693962A (en) * | 2009-10-19 | 2010-04-14 | 武汉理工大学 | Method for preparing p-type filling type skutterudite compound thermoelectric material |
| CN101694010A (en) * | 2009-09-29 | 2010-04-14 | 武汉理工大学 | Preparation method of layered nanostructured InSb pyroelectric material |
| CN107604208A (en) * | 2017-09-25 | 2018-01-19 | 重庆大学 | Device is got rid of in a kind of method for preparing p-type filled skutterudite compound and melt rotation |
| CN107683255A (en) * | 2015-06-12 | 2018-02-09 | 株式会社丰田自动织机 | Silicon materials and its manufacture method |
-
2021
- 2021-10-26 CN CN202111252165.4A patent/CN114082968B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5177564A (en) * | 1974-11-26 | 1976-07-05 | Skf Nova Ab | |
| DE2553131A1 (en) * | 1974-11-26 | 1976-08-12 | Skf Kugellagerfabriken Gmbh | SHOULDING GOODS FROM SECTIONS OF METAL FOR THE PRODUCTION OF METAL POWDER FOR POWDER METALLURGICAL PURPOSES AND METHODS FOR MANUFACTURING THE SHOEING GOODS |
| CN2030117U (en) * | 1988-02-06 | 1989-01-04 | 中南工业大学 | Fast condensing equipment for making fine powder |
| CN1899729A (en) * | 2006-07-11 | 2007-01-24 | 武汉理工大学 | Method for preparing high performance bismuth telluride thermoelectric material |
| CN101435029A (en) * | 2008-12-26 | 2009-05-20 | 武汉理工大学 | Rapid preparation of high performance nanostructured filling type skutterudite thermoelectric material |
| CN101694010A (en) * | 2009-09-29 | 2010-04-14 | 武汉理工大学 | Preparation method of layered nanostructured InSb pyroelectric material |
| CN101693962A (en) * | 2009-10-19 | 2010-04-14 | 武汉理工大学 | Method for preparing p-type filling type skutterudite compound thermoelectric material |
| CN107683255A (en) * | 2015-06-12 | 2018-02-09 | 株式会社丰田自动织机 | Silicon materials and its manufacture method |
| CN107604208A (en) * | 2017-09-25 | 2018-01-19 | 重庆大学 | Device is got rid of in a kind of method for preparing p-type filled skutterudite compound and melt rotation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114082968A (en) | 2022-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101736173B (en) | Method for preparing AgSbTe2 thermoelectric material by combining melt rotatable swinging and spark plasma sintering | |
| CN102689903B (en) | Method for preparing silicon carbide nanometer particle and composite material thereof by evaporating solid raw materials | |
| CN107935596A (en) | One kind prepares MAX phase ceramics Ti using molten-salt growth method low-temperature sintering3AlC2The method of powder | |
| CN103700759B (en) | A kind of nano composite structure Mg 2si base thermoelectricity material and preparation method thereof | |
| CN101125653B (en) | Method for synthesizing homogeneous nano silicon carbide powder by burning | |
| CN107681043B (en) | Bismuth telluride-based composite thermoelectric material of flexible thermoelectric device and preparation method thereof | |
| CN101656292B (en) | Preparation method for bismuth-tellurium nano-porous thermoelectric material | |
| CN107445621B (en) | Cu-Te nanocrystalline/Cu2SnSe3Thermoelectric composite material and preparation method thereof | |
| CN101694010B (en) | Preparation method of layered nanostructured InSb pyroelectric material | |
| CN107400917A (en) | A kind of SnSe2Crystalline compounds and its preparation method and application | |
| WO2015037014A1 (en) | Nanostructured copper-selenide with high thermoelectric figure-of-merit and process for the preparation thereof | |
| KR101143859B1 (en) | Synthesis of conductive zinc oxide by ultrasonic-spray pyrolysis process | |
| CN103910341A (en) | Manufacturing method of nanometer hexagonal sheet-shaped bismuth telluride thermoelectric material | |
| CN101338386B (en) | Method for preparing TiNi Sn based thermoelectric compounds | |
| CN114082968B (en) | Method for preparing filled skutterudite material in large scale by spray spin quenching | |
| CN100453216C (en) | Method for preparing high performance bismuth telluride thermoelectric material | |
| CN101570321A (en) | Method for preparing BixSbyTe(3-z) thermoelectric material with high performance and nano structure | |
| CN101307392B (en) | Process for preparing CoSb3-based thermoelectric material by combining liquid quenching and spark plasma sintering | |
| CN103626495B (en) | Preparation method for CIGS target material through pressureless sintering | |
| JP5660528B2 (en) | Bulk manganese silicide single crystal or polycrystal doped with Ga or Sn and method for producing the same | |
| CN105132725B (en) | Method for rapid microwave synthesis-sintering for preparing TiNiSn block thermoelectric material | |
| CN108172680B (en) | Cubic phase Ca2Ge thermoelectric material and preparation method thereof | |
| CN1327046C (en) | Monocrystalline Si3N4 nanometer belt and micro belt preparation method | |
| CN101692479B (en) | Method for preparing P-type high manganese-silicon thermoelectric material | |
| CN108265188B (en) | A kind of Bi element doping cubic phase germanium calcium thermoelectric material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |