CN117139638B - Continuous preparation method of high-entropy alloy micro-nanospheres - Google Patents
Continuous preparation method of high-entropy alloy micro-nanospheres Download PDFInfo
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- CN117139638B CN117139638B CN202311133197.1A CN202311133197A CN117139638B CN 117139638 B CN117139638 B CN 117139638B CN 202311133197 A CN202311133197 A CN 202311133197A CN 117139638 B CN117139638 B CN 117139638B
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- electric heating
- entropy alloy
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 91
- 239000000956 alloy Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 86
- 239000002077 nanosphere Substances 0.000 title claims abstract description 78
- 238000005485 electric heating Methods 0.000 claims abstract description 63
- 239000002243 precursor Substances 0.000 claims abstract description 58
- 230000001052 transient effect Effects 0.000 claims abstract description 58
- 239000012159 carrier gas Substances 0.000 claims abstract description 41
- 238000002347 injection Methods 0.000 claims abstract description 39
- 239000007924 injection Substances 0.000 claims abstract description 39
- 239000007789 gas Substances 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000443 aerosol Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
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- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052793 cadmium Inorganic materials 0.000 claims description 2
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052733 gallium Inorganic materials 0.000 claims description 2
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
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- PAUVIFWBUWVTIV-UHFFFAOYSA-N [Co].[Mn].[Ni].[Ti].[V].[Cr].[Fe].[Cu] Chemical compound [Co].[Mn].[Ni].[Ti].[V].[Cr].[Fe].[Cu] PAUVIFWBUWVTIV-UHFFFAOYSA-N 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009690 centrifugal atomisation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
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- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
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Classifications
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/28—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from gaseous metal compounds
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a continuous preparation method of high-entropy alloy micro-nanospheres. The continuous preparation method comprises the following steps: enabling the vapor containing the precursor to flow through and contact with the electric heating film, and simultaneously carrying out transient pulse electric heating on the electric heating film so as to convert the precursor into high-entropy alloy micro-nano spheres, enabling the high-entropy alloy micro-nano spheres to be separated from the surface of the electric heating film, suspending in a gas phase, and carrying the high-entropy alloy micro-nano spheres away from the electric heating film by carrier gas. The preparation method provided by the invention combines a transient ultrahigh temperature heating technology, an atomization injection technology and a continuous growth technology, so that when a precursor is converted into the high-entropy alloy micro-nanospheres, the formed high-entropy alloy micro-nanospheres are separated from the surface of the electric heating film and suspended in the air flow, and are brought out of a growth area along with the movement of the air flow, thereby realizing a continuous preparation process and remarkably improving the preparation efficiency.
Description
Technical Field
The invention relates to the technical field of alloy micro-nano material growth, in particular to a continuous preparation method of high-entropy alloy micro-nano spheres.
Background
The high-entropy alloy micro-nanospheres have excellent electrical, magnetic and electrochemical characteristics and have wide application prospects in the fields of electric/photo-water splitting hydrogen production/oxygen, carbon dioxide reduction, biomedical imaging, magnetocaloric treatment and the like. The existing high-entropy alloy micro-nanospheres preparation technology comprises a transient ultrahigh temperature heating preparation technology, a moving bed pyrolysis technology, an ultrasonic assisted wet chemical method, a laser assisted preparation technology, an electrosynthesis method and the like.
The transient ultrahigh temperature heating preparation technology is to load a precursor on the surface of an allyl carbon material, and take the transient ultrahigh temperature generated when the carbon material bears large current as a heat source to carry out instantaneous thermal decomposition of raw materials, synthesis of products and rapid cooling. The ultrahigh temperature generated by the technology can melt any known metal, and can break through the limit of the immiscibility of different metal elements, so that the high-entropy alloy micro-nano spheres with highly controllable element types and quantity can be prepared. Meanwhile, the preparation technology can regulate and control the size and the shape of the prepared high-entropy alloy micro-nanospheres by regulating a pulse current program (voltage, frequency, duty ratio and duration), so that the preparation with highly controllable product components, sizes and shapes is realized. In addition, the transient ultrahigh temperature heat generated by the olefinic carbon material is highly concentrated, the energy waste is low, the low-power-consumption preparation of the novel nano material can be realized, and the method accords with the green development route of carbon reaching the standard and carbon neutralization.
However, the existing transient ultrahigh temperature heating preparation technology still has some problems, which limit the preparation efficiency of the high-entropy alloy micro-nanospheres, and the problems at least comprise:
(1) In the prior art, a transient ultrahigh temperature heating technology based on an olefinic carbon film heater can only prepare micro-high-entropy alloy micro-nanospheres or particles on the surface of an olefinic carbon film or fiber, the productivity is limited, and continuous batch preparation cannot be realized;
(2) In the prior art, high-entropy alloy micro-nanospheres or particles prepared by a transient ultrahigh temperature heating technology based on an olefinic carbon film heater are loaded on the surface of an olefinic carbon film or fiber, and are difficult to separate to obtain independent high-entropy alloy micro-nanospheres or particle powder.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a continuous preparation method of high-entropy alloy micro-nanospheres, which solves the problems that the high-entropy alloy micro-nanospheres are difficult to continuously prepare by a transient ultrahigh temperature heating technology and the prepared high-entropy alloy micro-nanospheres are difficult to separate from an olefinic carbon film or fiber in the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
in a first aspect, the invention provides a continuous preparation method of high-entropy alloy micro-nanospheres, which comprises the following steps:
enabling the vapor containing the precursor to flow through and contact with the electric heating film, and simultaneously carrying out transient pulse electric heating on the electric heating film so as to convert the precursor into high-entropy alloy micro-nano spheres, enabling the high-entropy alloy micro-nano spheres to be separated from the surface of the electric heating film, suspending in a gas phase, and carrying the high-entropy alloy micro-nano spheres away from the electric heating film by carrier gas.
When the transient ultrahigh temperature heating technology in the prior art is used for preparing the high-entropy alloy micro-nanospheres, the main technical scheme is that a precursor is firstly loaded on the surface of an electric heating film such as an olefinic carbon film by brushing, spraying or other modes, and then is converted into the high-entropy alloy micro-nanospheres by instantaneous ultrahigh temperature heating; however, unlike available technology, the present invention combines transient superhigh temperature heating technology, atomizing injection technology and continuous growth technology to form high entropy alloy microsphere, which is suspended in carrier gas naturally after being separated from the surface of electrically heated film and is not always supported on the surface of electrically heated film.
Further, a selected included angle is formed between the thickness direction of the electric heating film and the flow direction of the mixed gas of the vapor and the carrier gas; the selected included angle is 0-70 degrees. In order to fully avoid the high-entropy alloy micro-nano spheres in the air flow from being contacted with the surface of the electric heating film again, in the preferred scheme of the invention, the electric heating film has the trend of being arranged along the flowing direction of the air flow, and in the mode, the mixed air flow is laminar along the extending direction of the film on the surface of the film, so that on one hand, the diffusion contact capability of the steam fog and the electric heating film is enhanced, and on the other hand, the air flow along the extending direction of the film prevents the high-entropy alloy micro-nano spheres which are separated from the surface of the electric heating film from being attached to the surface of the film again.
Further, the electrically heated film is provided in a plurality in the thickness direction; and a gap is arranged between any two adjacent electric heating films, and the interval of the gap is 1-10mm. In practice, the inventors found that, in general, the distance that the electrically heated film can perform the thermal reaction is short, which is related to the heat transfer distance and the diffusion distance of the liquid droplets, so that, to ensure the preparation efficiency, the distance between the plurality of electrically heated films should not be too large, otherwise, the area with a long intermediate distance cannot obtain enough heat energy to drive the reaction to occur, and the distance between the liquid droplets is long, which is not easy to contact the surface of the electrically heated film; the spacing is not too small, and the too small spacing increases the diffusion resistance of the vapor, which is not beneficial to the high-efficiency preparation of the high-entropy alloy micro-nanospheres, so that the control of the spacing of a plurality of electric heating films is critical.
Further, with specific preparation details, the droplets suspended in the aerosol have a diameter of 0.1-500 μm; the liquid drops account for 0.01-5% of the volume of the aerosol; the concentration of each precursor in the precursor solution is 0.01-5mol/L, and the total concentration is 0.04-50mol/L.
Further, the precursor comprises an inorganic metal salt and/or an organic metal compound; the metal elements contained in the precursor liquid include any combination of 4 or more of lithium, beryllium, sodium, magnesium, aluminum, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, cesium, barium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth.
Further, the solvent or the dispersing agent in the precursor liquid comprises any one or more than two of ethanol, dimethylformamide, dimethyl sulfoxide, ethylene glycol and methanol; the carrier gas is a protective gas, and specifically includes, for example, any one or a combination of two or more of inert atmospheres such as nitrogen, argon, helium, etc., and of course, a gas that does not significantly chemically react with the microspheres and the electrically heated thin film at high temperatures may be used as the carrier gas, without being limited to the above-exemplified ranges.
Further, the electric heating film is selected from an allyl carbon film, and the composition material of the allyl carbon film comprises any one or more than two of carbon nano tubes, graphene and nano carbon fibers. Of course, the material selection of the electric heating film is not limited to this, and the material selection is characterized by having a certain chemical stability and high temperature resistance, being able to provide a reaction place, being thin and having excellent electric heat conversion performance, being able to instantly raise temperature under current driving.
Further, the transient pulse electric heating has a pulse frequency of 0.1-10000Hz and a current power density of 1-1000W/cm 2 The duty ratio is 10-90%; and/or each corresponds to 10cm 2 The supply rate of the precursor liquid is 1-2000 mu L/min; and/or the calculated flow rate of the carrier gas at the electrically heated film is 1-100m/min, wherein the calculated flow rate refers to the ratio of the injection flow rate of the carrier gas to the flow passage sectional area of the carrier gas at the electrically heated film. It should be noted that, because of the complicated processes involving heating, cooling, mixing with vapor, solvent evaporation, chemical reaction, and the like, the absolute true flow rate of the carrier gas at the electrically heated film is not easy to calculate or measure, and therefore, the "calculated flow rate" having practical operational meaning is defined by the injection flow rate of the carrier gas (for example, converted to the flow rate in a standard state, or the flow rate shown by the flowmeter in actual operation) divided by the flow passage sectional area (for example, the cross-sectional area of the tubular housing).
Further, the preparation method further comprises the following steps: and collecting the high-entropy alloy micro-nanospheres carried in the carrier gas through filtration or adsorption.
In a second aspect, the present invention also provides a continuous preparation device for high-entropy alloy micro-nanospheres, which comprises: the device comprises an airflow control module, an injection module and a reaction module; the reaction module comprises an electric heating film and can perform transient pulse electric heating on the electric heating film; the gas flow control module is used for providing flowing carrier gas; the injection module is used for atomizing a precursor liquid to form vapor, the vapor is mixed with the carrier gas and flows through the electric heating film, and a plurality of precursors for forming the high-entropy alloy micro-nano spheres are dissolved in the precursor liquid. Of course, the device is designed mainly based on the flow of the preparation method, and based on the preparation method, a person skilled in the art can design a device with the same functional module based on the prior art knowledge.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that:
the preparation method provided by the invention combines a transient ultrahigh temperature heating technology, an atomization injection technology and a continuous growth technology, so that when a precursor is converted into the high-entropy alloy micro-nanospheres, the formed high-entropy alloy micro-nanospheres are separated from the surface of the electric heating film and suspended in the air flow, and are brought out of a growth area along with the movement of the air flow, thereby realizing a continuous preparation process and remarkably improving the preparation efficiency.
In addition, the preparation method provided by the invention can establish a database by recording the structure-activity relation between the growth parameters and the product characteristics, so that the controllable preparation has data in application.
The above description is only an overview of the technical solutions of the present invention, and in order to enable those skilled in the art to more clearly understand the technical means of the present application, the present invention may be implemented according to the content of the specification, the following description is given of the preferred embodiments of the present invention with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic structural diagram of a continuous preparation apparatus for high-entropy alloy micro-nanospheres according to an exemplary embodiment of the present invention;
fig. 2 is a scanning electron micrograph of high entropy alloy micro-nanospheres provided in an exemplary embodiment of the invention.
Detailed Description
In view of the shortcomings in the prior art, the inventor of the present invention has long studied and practiced in a large number of ways to propose the technical scheme of the present invention. The technical scheme, the implementation process, the principle and the like are further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
The invention combines a transient ultrahigh temperature heating technology, an ultrasonic atomization technology and a micro-injection technology to develop a method for continuously preparing the high-entropy alloy micro-nanospheres based on the transient ultrahigh temperature, so as to realize batch preparation of the high-entropy alloy micro-nanospheres. Meanwhile, the morphology, structure, preparation speed and yield of the product are regulated and controlled by comprehensively controlling parameters of transient ultrahigh-temperature heating and continuous atomization injection.
Based on the above purpose, the embodiment of the invention provides a continuous preparation method of high-entropy alloy micro-nanospheres, which comprises the following overall steps:
and mixing the vapor with a carrier gas, flowing through an electric heating film, and simultaneously carrying out transient pulse electric heating on the electric heating film so as to convert the precursor into high-entropy alloy micro-nano spheres, wherein the high-entropy alloy micro-nano spheres are suspended in the carrier gas and move along with the carrier gas in a direction away from the electric heating film.
In order to realize the preparation method, referring to fig. 1, the embodiment of the invention further provides a continuous preparation device for the high-entropy alloy micro-nanospheres, which comprises: a gas flow control module, an injection module, and a reaction module (corresponding to the olefinic carbon heating module in this example diagram); the reaction module comprises an electric heating film and can perform transient pulse electric heating on the electric heating film; the gas flow control module is used for providing flowing carrier gas; the injection module is used for atomizing a precursor liquid to form vapor, the vapor is mixed with the carrier gas and flows through the electric heating film, and a plurality of precursors for forming the high-entropy alloy micro-nano spheres are dissolved in the precursor liquid.
Some prior art provides a technical proposal for preparing micro-nano alloy by injecting atomized nitrate solution into a tube furnace, but the invention is based on a transient ultrahigh temperature heating mode of an electric heating film and is different from the traditional heating mode based on the tube furnace in reaction mode; the transient ultrahigh temperature heating can overcome the defects of the traditional heating mode, and the preparation of element microspheres which are difficult to fuse is realized, which is an advantage which is not possessed by the traditional heating mode such as a tube furnace, and the like, for example, the heating mode can only realize the preparation of metal salts which are easy to decompose, such as nitrate, as precursors, and can not realize the preparation of metal salts which are relatively more difficult to decompose as raw materials. However, the current transient ultrahigh temperature heating modes indicate that the transient ultrahigh temperature needs to be realized on the surface of the electric heating film, and the disadvantage that the product is difficult to separate from the electric heating film still exists.
Moreover, the technical scheme only synthesizes seeds for the growth of the carbon material, and the high-entropy alloy nano particles generated by the decomposition of the nitrate cannot be independently obtained.
Thus, in the above technical solution, compared with the prior art, the most critical improvement is to improve the reaction process of a single precursor on the surface of the electrically heated film to the complex chemical and physical processes driven by transient ultra-high temperature at and near the surface of the electrically heated film, and to increase and decrease the temperature (10) 3 -10 5 DEG C/s) can promote the formation of high-entropy alloy micro-nanospheres, the control of particle size and the continuous progress of reaction. Specifically, some atomized liquid drops contact the surface of the electric heating film in a gap (in a relatively cold state) heated by pulse energization, the precursor is thermally decomposed and reacts under the drive of ultrahigh temperature during energization heating to form molten high-entropy alloy liquid drops, and then the molten high-entropy alloy liquid drops are frozen under the effect of ultrahigh-speed cooling to keep a state that multiple metals are uniformly mixed to form solid high-entropy alloy microspheres, and the solid high-entropy alloy microspheres are taken away by carrier gas and collected. In the process, the solvent in the atomized liquid drops can be volatilized in an explosive manner by ultrahigh-speed heating, so that the formed high-entropy alloy micro-nanospheres are separated from the electric heating film and taken away by carrier gas, the electric heating film failure caused by gradual accumulated coverage of the product on the surface of the allyl carbon film is avoided, the reaction can be continuously carried out, and the preparation process with high yield and high continuity is realized. Meanwhile, the miniaturization of the nano-microsphere is promoted by the explosive volatilization of atomized liquid drops and precursors under the action of transient ultrahigh temperature and the expansion and contraction effect caused by repeated transient electric heating and cooling, so that the particle size and the morphology of the formed high-entropy alloy micro-nano-microsphere can be effectively regulated by regulating and controlling the temperature, the frequency and the duration of the transient ultrahigh temperature.
Obviously, the process comprises a transient ultrahigh temperature reaction process on the surface of the electric heating film, and is based on a separation process of the synthesized high-entropy alloy micro-nanospheres caused by pulse electric heating and solvent violent volatilization and a particle size regulation process caused by solvent violent volatilization and ultrahigh temperature rise and fall, which are obviously different from the existing microscopic process of floating heating and continuous preparation in the atmosphere of a tube furnace, wherein the main place of the transient ultrahigh temperature reaction is still on the surface of the electric heating film, but not in a floating gas phase.
As some typical application examples of the above technical solutions, as shown in fig. 1, the preparation apparatus includes a quartz tube as a growth chamber, flanges are disposed at two ends of the quartz tube for air inlet and air outlet, an air inlet end is connected with an air flow control module, such as a gas cylinder and a flow controller, and a carrier gas, such as nitrogen, is supplied into the quartz tube at a preset flow rate; in the quartz tube, the precursor liquid is supplied to the ultrasonic atomizer through the injection pump at a preset flow rate, so that the precursor liquid is atomized into vapor, the vapor flows through the olefinic carbon film (one of the electric heating films) along with the carrier, the extending direction of the olefinic carbon film is arranged along the direction of the air flow, and the olefinic carbon film is connected to the power supply through the circuit, the power supply carries out transient pulse electric heating on the olefinic carbon film, so that the vapor near the olefinic carbon film is subjected to the processes of solvent evaporation, precursor decomposition, melting, combination and solidification into high-entropy alloy micro-nano spheres, and finally, the high-entropy alloy micro-nano spheres are carried out of the reaction zone in a state of being suspended in the carrier gas and are collected at the outlet end of the quartz tube.
Of course, the device can be additionally provided with an infrared temperature measuring module, a product collecting module and the like, wherein the infrared temperature measuring module can mainly measure the temperature of the surface of the electric heating film so as to control the process conditions, and the infrared temperature measuring module is not completely required under the condition of some batch preparation; the product collecting module is used for collecting the formed high-entropy alloy micro-nanospheres in a feasible mode such as filtration, electrostatic adsorption or liquid adsorption, but if the product collecting module is not specially arranged, the solid products can still be collected after the carrier gas brings the high-entropy alloy micro-nanospheres away from the electric heating film area and natural sedimentation is carried out.
In combination with the above device structure, in these application examples, specific preparation operation methods are shown in the following specific steps:
(1) Preparing a precursor liquid according to requirements: dissolving metal salt or organic metal compound of the required metal element in a solvent to prepare a multi-metal mixed solution. If the platinum cobalt nickel iron copper high-entropy alloy micro-nano sphere powder is prepared in a continuous batch mode, chloroplatinic acid, cobalt chloride, nickel chloride, ferric chloride and copper chloride are dissolved in ethanol to prepare mixed solution with each salt concentration of 0.1mol/L, and the mixed solution is filled into a syringe pump.
(2) And (3) connecting the olefinic carbon film into a transient ultrahigh temperature heating device, and connecting the two ends of the olefinic carbon film with electrodes. And vacuumizing a growth area of the heating device, introducing nitrogen to the standard atmospheric pressure, and repeating the vacuumizing-introducing argon process for three times to completely remove oxygen and water in the reaction area, wherein the gas replacement operation belongs to common operation steps in the common heating reaction.
(3) And (3) switching on a pulse power supply, applying pulse voltage to the olefinic carbon film, and performing transient ultrahigh-temperature heating, wherein the heating program is controlled by a pulse current program (comprising peak temperature, pulse frequency, duty ratio and duration).
(4) And opening a gas path system, and introducing nitrogen at a constant rate into the growth area to serve as carrier gas.
(5) And (3) opening an injection pump and an ultrasonic atomization injection device, injecting the precursor liquid into a growth area at a constant injection rate, controlling an aerosol area formed by spraying around the surface of the allyl carbon film, and enabling the precursor to be decomposed by transient ultrahigh temperature generated by the allyl carbon film and react at high temperature to form the high-entropy alloy micro-nano spheres.
(6) The injection pump and the ultrasonic atomizer continuously inject the precursor into the growth area for continuous injection growth, and the carrier gas continuously brings the generated high-entropy alloy micro-nano spheres out of the reaction area. The collecting and filtering device positioned at the rear end of the growth area immediately filters and collects the high-entropy alloy micro-nano spheres, thereby realizing continuous batch preparation.
And, in process research or quality control, may further include:
(7) And changing various growth parameters, determining the influence of the peak temperature, frequency, duration, duty ratio, preparation speed and yield of the transient ultrahigh temperature through characterization analysis of the product, and constructing the structure-activity relationship between the growth parameters and the characteristics of the product, so as to guide the subsequent controllable preparation. The step can build a database by constructing the structure-activity relation between the growth parameters and the product characteristics, so that the controllable preparation process has data dependence.
Of course, if a mature preparation process has already been formed, it is sufficient to prepare according to the set parameters, and the specific preparation process may not include the above step (7).
According to the technical scheme, a transient ultrahigh temperature heating technology based on the olefinic carbon film and an ultrasonic spraying injection technology of the precursor liquid are combined to prepare the independently existing high-entropy alloy micro-nanospheres which are not attached to the olefinic carbon film; on the basis, the injection type growth technology is combined, and the continuous batch preparation of the high-entropy alloy micro-nanospheres is realized by continuously introducing the precursor and taking out the product by utilizing the carrier gas.
Of course, if atomization injection of an equivalent dispersion degree can be achieved, it is not necessarily limited to ultrasonic atomization injection, and other equivalent substitution effects can be achieved by, for example, a high-pressure direct atomization method, a centrifugal atomization method, or the like.
Unlike the specific examples described above, the synthetically grown high entropy alloy micro-nanospheres may be: the element compositions of chromium manganese iron cobalt nickel, titanium zirconium hafnium niobium tantalum, iron cobalt nickel vanadium sulfur, platinum cobalt nickel iron copper and the like can be replaced and matched at will, and the number of elements is adjustable without specific limitation; the olefinic carbon film may be: of course, other kinds of conductive films can also realize the electric heating capability under the same thickness; the growth carrier gas may be: inert gases such as nitrogen or argon; the size of the olefinic carbon film can be cut at will, and the pulse voltage can be adjusted according to the size of the olefinic carbon film; the pulse voltage frequency is adjustable within the range of 0.1-10000Hz, and specific equipment structure size and process conditions can be obtained through orthogonal experiments, and are not limited to the range exemplified by the invention.
The embodiment of the invention belongs to the field of high-temperature growth synthesis of new nano materials, in particular to quantitative preparation of nano and micron-scale high-entropy alloy or high-entropy ceramic microspheres and particles, and the application fields of the prepared products include but are not limited to: as electrodes, as catalysts, as electromagnetically functional particles, etc., for example, hydrogen/oxygen production by electrolysis of water, carbon dioxide reduction, lithium battery electrodes, biomedical imaging, magnetocaloric therapy, etc.
The technical scheme of the invention is further described in detail below through a plurality of embodiments and with reference to the accompanying drawings. However, the examples are chosen to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
The continuous quantitative preparation process of the micron-sized manganese iron cobalt nickel copper five-membered high-entropy alloy micro-nanospheres is specifically as follows:
(1) Precursor configuration: dissolving manganese chloride, ferric chloride, cobalt chloride, nickel chloride and copper chloride into ethanol to prepare mixed solution with each salt concentration of 0.1mol/L, and filling the mixed solution into a syringe pump;
(2) The method comprises the steps of loading an allyl carbon film (5 cm multiplied by 2cm multiplied by 10 mu m) into a transient ultrahigh temperature heating device, and connecting electrodes at two ends of the film to serve as a transient ultrahigh temperature heater. And vacuumizing a growth area of the heating device, introducing high-purity nitrogen to standard atmospheric pressure, and repeating the vacuumizing-introducing argon process for three times to completely remove oxygen and water in the reaction area.
(3) And (3) switching on a pulse power supply, applying pulse voltage to the allyl carbon film, and performing transient ultrahigh-temperature heating at 60V, 0.1Hz and 50% duty ratio.
The gas path system was opened and nitrogen was introduced as a carrier gas into the growth zone at a constant rate of 50 sccm.
(4) And (3) starting an injection pump and an ultrasonic atomization injection device, and injecting precursor liquid into a growth area in an atomization way at a constant injection rate of 50 mu L/min, wherein the spraying area is controlled at the position of the allyl carbon film, and the transient ultrahigh temperature generated by the allyl carbon film can promote the decomposition of metal salt and the high-temperature reaction to form the high-entropy alloy micro-nano spheres.
(5) The injection pump and the ultrasonic atomizer continuously inject the precursor into the growth area for continuous injection growth, and the generated high-entropy alloy micro-nano spheres are continuously taken out of the reaction area by the carrier gas. The collecting and filtering device positioned at the rear end of the growth area is used for filtering and collecting the grown high-entropy alloy micro-nanospheres, so that continuous batch preparation of the micro-sized ferromanganese cobalt nickel copper high-entropy alloy micro-nanospheres is realized. The yield was about 1.1mg/min, 75% (mass ratio of the obtained high-entropy alloy micro-nanospheres to the metal element in the injected precursor solution). The obtained high-entropy alloy micro-nanospheres are spherical microspheres with the particle size below 3 microns, the morphology of the microspheres is shown in figure 2, and the microspheres are reloaded on the surface of a carbon film for electron microscope shooting in order to facilitate observation.
Example 2
The same example of the continuous quantitative preparation process of the micron-sized ferromanganese cobalt nickel copper pentary high-entropy alloy micro-nanospheres is the same as the example 1, and the main difference is that based on the example 1:
(6) The other growth parameters are kept unchanged, the voltages are respectively changed into 10V, 20V, 30V, 40V, 50V, 60V, 70V, 80V, 90V and 100V, and the corresponding power densities are respectively 4W/cm 2 、16W/cm 2 、36W/cm 2 、100W/cm 2 、144W/cm 2 、196W/cm 2 、256W/cm 2 、324W/cm 2 、400W/cm 2 Changing the transient ultrahigh temperature heating peak temperature, repeating the steps 1-5, analyzing and characterizing the product, and determining the influence of the heating temperature on the appearance, the size, the structure, the preparation speed and the yield of the product; the results show that as the voltage increases, the particle size of the product gradually decreases, and the uniformity of the size distribution increases, the morphology of the product gradually transitions from a non-spherical shape to a spherical structure, the preparation speed and yield increase with increasing voltage, to about 60V peak, and then the yield begins to decrease with increasing voltage. The optimum voltage range is 40-70V.
(7) Keeping the rest growth parameters unchanged, respectively setting the pulse voltage frequency to 0, 0.1, 1, 10, 100, 1000 and 10000Hz, repeating the steps 1-5, and determining the influence of the transient ultrahigh temperature frequency and duration on the morphology, size, structure, preparation speed and yield of the product; in the range of 0-1Hz, the product size is larger due to the slower cold-hot alternation rate, the phase separation in the product is serious, a high-entropy alloy structure with uniformly mixed metal elements cannot be completely formed, the subsequent frequency is continuously increased, and the product size is reduced; in addition, the low frequency of 0-1Hz limits the explosive volatilization of the solution and the precursor caused by the ultrahigh-speed temperature rise, the metal is easy to deposit on the vinyl carbon film, the yield is lower, the metal deposition does not exist on the surface of the vinyl carbon film within the range of 10-10000Hz, but the movement speed of atomized liquid drops of the precursor is limited, and the excessively high frequency can be that the liquid drops do not move to the surface of the vinyl carbon film to participate in the reaction, so that the yield is reduced. The optimal frequency range is 10-1000Hz.
(8) Keeping the other growth parameters unchanged, setting the pulse voltage duty ratio to 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, repeating the steps 1-5, and determining the influence of the transient superhigh temperature duty ratio and duration on the morphology, size, structure, preparation speed and yield of the product; the result shows that the duty ratio has little influence on the morphology, the size and the structure of the product, but can greatly influence the preparation speed and the yield, the transient ultrahigh temperature heating duration is short under the condition of low duty ratio (10% -30%), the actual high temperature reaction time is limited, and the preparation speed and the yield are low; under the condition of high duty ratio (70% -90%), the low-temperature time is too short, and the time window for the atomized liquid drops to diffuse to the surface of the vinyl carbon film is shorter, so that the preparation speed and the yield are lower; the optimal duty cycle range is 40% -60%.
(9) Keeping the rest growth parameters unchanged, setting the injection speed of the precursor solution to be 1, 100, 250, 500, 1000, 1500 and 2000 mu L/min respectively, repeating the steps 1-5, and determining the influence of the injection speed of the precursor on the shape, size, structure, preparation speed and yield of the product; with the increase of the injection speed of the precursor solution, the particle size of the product is gradually increased, the uniformity of the particle size distribution is reduced, and the preparation speed and the yield are improved and then reduced, because the injection speed is too high, metal deposition exists on the surface of the vinyl carbon film, and the preparation process is influenced. The optimal injection rate range is 100-1000. Mu.L/min.
(10) Keeping the rest growth parameters unchanged, setting the flow rate of the current-carrying gas to 10, 25, 50, 75, 100, 150, 200, 300, 400, 500, 750 and 1000sccm respectively, repeating the steps 1-5, and determining the influence of the flow rate of the current-carrying gas on the shape, size, structure, preparation speed and yield of the product; the results show that the gas flow has little influence on the morphology, size and structure of the product, but can influence the movement speed of atomized liquid drops, thereby influencing the preparation speed and yield; when the gas flow is increased gradually, the preparation speed and the productivity are improved, and the high flow rate can lead the residence time of the precursor atomized liquid drops on the surface of the carbon film to be too short, thereby reducing the contact probability, further reducing the probability of the ultra-high temperature reaction and influencing the productivity.
(11) According to the characterization result, the structure-activity relation between the growth parameters and the product characteristics is clarified, a database is established, and controllable preparation is realized
Example 3
The embodiment illustrates a continuous quantitative preparation process of the titanium-vanadium-manganese-iron-cobalt-nickel-copper eight-element high-entropy alloy micro-nanospheres, which is specifically as follows:
(1) Precursor configuration: dissolving titanium chloride, vanadium chloride, chromium chloride, manganese chloride, ferric chloride, cobalt chloride, nickel chloride and copper chloride into ethanol to prepare a mixed solution with each salt concentration of 0.1mol/L, and filling the mixed solution into a syringe pump;
(2) The method comprises the steps of loading an allyl carbon film (5 cm multiplied by 2cm multiplied by 10 mu m) into a transient ultrahigh temperature heating device, and connecting electrodes at two ends of the film to serve as a transient ultrahigh temperature heater. And vacuumizing a growth area of the heating device, introducing nitrogen to the standard atmospheric pressure, and repeating the vacuumizing-introducing argon process for three times to completely remove oxygen and water in the reaction area.
(3) And (3) switching on a pulse power supply, applying pulse voltage to the allyl carbon film, and performing transient ultrahigh-temperature heating at 70V, 100Hz and 50% duty ratio.
The gas path system was opened and nitrogen was introduced as a carrier gas into the growth zone at a constant rate of 50 sccm.
(4) And (3) starting an injection pump and an ultrasonic atomization injection device, and injecting precursor liquid into a growth area in an atomization way at a constant injection rate of 2 mu L/min, wherein the spraying area is controlled on the surface of the allyl carbon film, and the transient ultrahigh temperature generated by the allyl carbon film can promote the decomposition of the metal salt and the high-temperature reaction to form the high-entropy alloy micro-nano spheres.
(5) The injection pump and the ultrasonic atomizer continuously inject the precursor into the growth area for continuous injection growth, and the generated high-entropy alloy micro-nano spheres are continuously taken out of the reaction area by the carrier gas. The collecting and filtering device positioned at the rear end of the growth area is used for filtering and collecting the grown high-entropy alloy micro-nanospheres, so that continuous batch preparation of the titanium-vanadium-chromium-manganese-iron-cobalt-nickel-copper high-entropy alloy micro-nanospheres with the micrometer size is realized.
Example 4
The same example of this example also illustrates the continuous quantitative preparation process of eight-element high-entropy alloy micro-nanospheres of titanium-vanadium-manganese-iron-cobalt-nickel-copper, which is substantially the same as example 3, with the main differences that, based on example 3:
(6) Maintaining the rest growth parameters unchanged, changing the voltages into 10V, 20V, 30V, 40V, 50V, 60V, 70V, 80V, 90V and 100V respectively, changing the transient ultrahigh temperature heating peak temperature, repeating the steps 1-5, analyzing and characterizing the product, and determining the influence of the heating temperature on the morphology, the size, the structure, the preparation speed and the yield of the product;
(7) Keeping the rest growth parameters unchanged, respectively setting the pulse voltage frequency to 0, 0.1, 1, 10, 100, 1000 and 10000Hz, repeating the steps 1-5, and determining the influence of the transient ultrahigh temperature frequency and duration on the morphology, size, structure, preparation speed and yield of the product;
(8) Keeping the other growth parameters unchanged, setting the pulse voltage duty ratio to 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, repeating the steps 1-5, and determining the influence of the transient superhigh temperature duty ratio and duration on the morphology, size, structure, preparation speed and yield of the product;
(9) Keeping the rest growth parameters unchanged, setting the injection speed of the precursor liquid to be 1, 2.5, 5, 7.5, 10, 15 and 20 mu L/min respectively, repeating the steps 1-5, and determining the influence of the injection speed of the precursor on the appearance, the size, the structure, the preparation speed and the yield of the product;
(10) Keeping the rest growth parameters unchanged, setting the flow rate of the current-carrying gas to 10, 25, 50, 75, 100, 150, 200, 300, 400, 500, 750 and 1000sccm respectively, repeating the steps 1-5, and determining the influence of the flow rate of the current-carrying gas on the shape, size, structure, preparation speed and yield of the product;
(11) And according to the characterization result, the structure-activity relation between the growth parameters and the product characteristics is clarified, a database is established, and the controllable preparation is realized.
In this embodiment, the influence rule of each growth condition parameter is similar to that in embodiment 2, and will not be described here again.
Example 5
In the above embodiment, the width direction of the olefinic carbon film is parallel to the axial direction of the quartz tube in the device, that is, the length direction of the olefinic carbon film forms an angle of 0 ° with the flow direction of the carrier gas, and the optimization of the included angle is illustrated in this embodiment, and on the basis of embodiment 1, the setting angle of the olefinic carbon film is changed to form an included angle of 45 ° with the flow direction of the carrier gas; the final results showed that the morphology and particle size of the product were consistent with those of example 1, but the yield and yield were improved with the increase in contact area of the atomized droplets with the olefinic carbon film at this angle, with yields above 85%.
Long-term experiments have found that the optimum angle range for maintaining higher yields is between 35-55 °.
Comparative example 1
This comparative example is substantially the same as example 1, except that the temperature is maintained at the highest temperature in example 1, the other parameters are unchanged, the pulse current in example 1 is changed to constant current, no pulse rise and fall exist any more, and the elements in the product cannot be uniformly fused, so that a serious phase separation phenomenon occurs, i.e., although the different elements are aggregated, a high-entropy alloy cannot be formed in a strict sense.
Comparative example 2
This comparative example is substantially the same as example 1, with the main difference that: compared with the embodiment 1, the electric heating film is removed, and the corresponding area of the quartz tube is continuously heated by an electric heating furnace instead, wherein the heating temperature is 1100 ℃, and as the result of the comparison 1, the elements in the product cannot be uniformly fused, a serious phase separation phenomenon is generated, namely, different elements are aggregated, but high-entropy alloy in a strict sense cannot be formed.
This means that, by using a non-transient ultra-high temperature method, it is possible to form a form in which different elements are aggregated in a high-temperature gas phase by using some materials which are easily decomposed, but various advantages of the transient ultra-high temperature cannot be exerted, and the reaction history and reaction place of the transient ultra-high temperature are completely different from those of the floating gas phase heated by some tube furnaces.
Based on the above examples and comparative examples, it can be seen that the preparation method provided by the embodiment of the invention combines the transient ultra-high temperature heating technology, the atomization injection technology and the continuous growth technology, when the precursor is converted into the high-entropy alloy micro-nanospheres, the formed high-entropy alloy micro-nanospheres are separated from the surface of the electric heating film and suspended in the air flow, and are carried out of the growth area along with the movement of the air flow, thereby realizing the continuous preparation process and remarkably improving the preparation efficiency.
In addition, the preparation method provided by the embodiment of the invention can establish a database by recording the structure-activity relation between the growth parameters and the product characteristics, so that the controllable preparation has data in application.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (6)
1. The continuous preparation method of the high-entropy alloy micro-nanospheres is characterized by comprising the following steps of:
enabling the vapor containing the precursor to flow through and contact with an electric heating film, and simultaneously carrying out transient pulse electric heating on the electric heating film so as to convert the precursor into high-entropy alloy micro-nano spheres, enabling the high-entropy alloy micro-nano spheres to be separated from the surface of the electric heating film, suspending in a gas phase, and carrying the high-entropy alloy micro-nano spheres away from the electric heating film by carrier gas;
wherein, the extending direction of the electric heating film and the flowing direction of the mixed gas of the vapor and the carrier gas form a selected included angle, and the selected included angle is 0-70 degrees;
the electric heating film is provided with a plurality of electric heating films in a lamination manner along the thickness direction; gaps are formed between any two adjacent electric heating films, and the interval of the gaps is 1-10 mm;
the diameter of the liquid drops suspended in the aerosol is 0.1-500 mu m; the liquid drops account for 0.01% -5% of the volume of the aerosol; the concentration of each precursor in the precursor liquid for forming the vapor is 0.01-5mol/L, and the total concentration is 0.04-50 mol/L;
the precursor comprises inorganic metal salts and/or organic metal compounds; the metal elements contained in the precursor liquid include any combination of 4 or more of lithium, beryllium, sodium, magnesium, aluminum, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, cesium, barium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth.
2. The continuous production method according to claim 1, wherein the solvent or the dispersant in the precursor liquid comprises any one or a combination of two or more of ethanol, dimethylformamide, dimethyl sulfoxide, ethylene glycol, and methanol;
the carrier gas is a protective gas.
3. The continuous production method according to claim 2, wherein each corresponds to 10cm 2 The supply rate of the precursor liquid is 1-2000 mu L/min;
and/or the calculated flow rate of the carrier gas is 1-100m/min, wherein the calculated flow rate refers to the ratio of the injection flow rate of the carrier gas to the flow passage sectional area of the carrier gas at the electrically heated film.
4. The continuous production method according to claim 1, wherein the transient pulse electric heating has a pulse frequency of 0.1 to 10000Hz and a current power density of 1 to 1000W/cm 2 The duty cycle is 10-90%.
5. The continuous production method according to claim 1, wherein the electrically heated film is selected from the group consisting of an olefinic carbon film, and the constituent material of the olefinic carbon film comprises any one or a combination of two or more of carbon nanotubes, graphene, and carbon nanofibers.
6. The continuous production method according to claim 1, further comprising: and collecting the high-entropy alloy micro-nanospheres carried in the carrier gas through filtration or adsorption.
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