CN117385255A - High-entropy alloy composite material and preparation method and application thereof - Google Patents
High-entropy alloy composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN117385255A CN117385255A CN202311378226.0A CN202311378226A CN117385255A CN 117385255 A CN117385255 A CN 117385255A CN 202311378226 A CN202311378226 A CN 202311378226A CN 117385255 A CN117385255 A CN 117385255A
- Authority
- CN
- China
- Prior art keywords
- composite material
- alloy composite
- entropy alloy
- entropy
- steps
- 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.)
- Pending
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 151
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 149
- 239000002131 composite material Substances 0.000 title claims abstract description 138
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 230000032683 aging Effects 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 238000003486 chemical etching Methods 0.000 claims abstract description 28
- 238000003723 Smelting Methods 0.000 claims abstract description 19
- 230000000694 effects Effects 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 12
- 230000000171 quenching effect Effects 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 230000007547 defect Effects 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000006104 solid solution Substances 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000006911 nucleation Effects 0.000 claims description 6
- 238000010899 nucleation Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229910004349 Ti-Al Inorganic materials 0.000 description 4
- 229910004692 Ti—Al Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001226 reprecipitation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/089—Alloys
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention provides a high-entropy alloy composite material, a preparation method and application thereof, and belongs to the field of high-entropy alloy. The method comprises the following steps: preparing raw materials according to the designed high-entropy alloy composite material components, preparing a block body by adopting a vacuum smelting method, then carrying out solution treatment and aging treatment, and finally carrying out chemical etching to obtain the high-activity high-entropy alloy composite material catalytic electrode. According to the invention, through multiple times of heat treatment regulation and control, the high-entropy alloy composite material with uniform structure, fine grains and micron-sized precipitated phases is obtained, wherein the precipitated phases are high-entropy intermetallic compound phases with controllable size and high catalytic activity, and further the electrocatalytic hydrogen evolution performance of the high-entropy intermetallic compound phases is remarkably improved.
Description
[ field of technology ]
The invention belongs to the field of high-entropy alloy, and relates to a high-entropy alloy composite material, a preparation method and application thereof.
[ background Art ]
The current energy problems are increasingly serious, and fossil energy is excessively extracted. Hydrogen energy has the advantages of cleanliness, high efficiency, safety and sustainability, and is regarded as the most potential clean energy source in the 21 st century. At present, one of the most ideal methods for obtaining hydrogen is to electrolyze water to produce hydrogen. Noble metal-based catalysts such as Pt, ir and the like are currently considered to be the electrocatalyst with the best hydrogen evolution performance, but have high cost and tight resources, and limit the large-scale application of the water electrolysis hydrogen production technology. Therefore, it is of great importance to find non-noble metal catalysis that can effectively reduce hydrogen evolution overpotential.
The high-entropy alloy consists of five or more elements, and shows physical, chemical and mechanical properties superior to those of the traditional alloy, so that the high-entropy alloy has better catalytic potential. Patent 202011404595.9 discloses a high-entropy alloy for hydrogen evolution catalysis, wherein Fe in a metal raw material: w: mo is 1:1:1, co: ni is 1:1, obtaining the high entropy alloy with submicron porous structure through pressureless sintering, wherein the hydrogen evolution overpotential can reach 50-60mV, and the overpotential is still obviously higher than that of a commercial catalyst Pt/C (37 mV) although the cost of the catalyst is obviously reduced. Intermetallic compounds (IMCs) have long-range ordered superlattice structures with metal bonds and covalent bonds coexisting in the crystal structure, and thus find wide application in catalytic research. The long-range ordered superlattice structure of the compound shows important roles in changing the electronic structure and the active site of the intermetallic compound. The novel alloy design concept combining equimolar ratio multiple principal elements is applied to intermetallic compounds, a class of high-entropy intermetallic compounds (HEIs) is explored, and the novel alloy material is a novel alloy material with unique ordered atomic structure of the traditional intermetallic compounds and synergistic effect generated by multi-component metals of the high-entropy alloy composite material, and compared with the traditional intermetallic compounds, the high-entropy intermetallic compounds are more stable and are easy to form various metastable phases. The high-entropy intermetallic compound has excellent physicochemical properties similar to those of the high-entropy alloy composite material, such as corrosion resistance, electrocatalytic properties and the like.
The heat treatment is an important procedure in material processing, and the proper heat treatment process can eliminate various defects caused by the heat treatment process such as cast-forging welding and the like, refine grains and improve the performance of the material by changing the internal structure of the material. The high-entropy alloy is easy to form an amplitude modulation structure of the nano structure due to the hysteresis diffusion effect, and the electrocatalytic hydrogen evolution performance of the high-entropy alloy can be further improved due to the increase of the active specific surface area caused by the amplitude modulation structure. For the catalyst, the more effective active sites, the better the electrocatalytic hydrogen evolution performance, and the heat treatment process is used for separating out micro-nano precipitated phases with different sizes and numbers from the high-entropy alloy, so that the electrocatalytic hydrogen evolution performance is improved.
At present, the research of adopting a high-entropy alloy composite material with a high-entropy intermetallic compound as a precipitation phase as a hydrogen evolution electrode is less, so that the development of the high-entropy alloy composite material with low cost and high activity has great research significance.
[ invention ]
Aiming at the problems, the invention provides the high-entropy alloy composite material, which has a dual-phase structure with a Fe-Co-Cr-Ni phase as a matrix and a high-entropy intermetallic compound as a precipitated phase, has more excellent electrocatalytic hydrogen evolution performance, and simultaneously, research and development personnel continuously optimize the process to determine the preparation method of the high-entropy alloy composite material.
Thus, the method is applicable to a variety of applications. The invention provides a high-entropy alloy composite material, which comprises the following components in percentage by mass: 18-20%, cobalt: 19-21%, chromium: 17-19%, nickel: 19-21%, titanium: 15-17%, and the balance of aluminum;
further, the high-entropy alloy composite material takes Fe-Co-Cr-Ni phases as a matrix, and the precipitated phases are high-entropy intermetallic compounds;
further, the hydrogen evolution performance of the high-entropy alloy composite material is 10mA/cm 2 Hydrogen evolution overpotential at current density was 352mV;
further, the high entropy intermetallic compound is class A 3 B (Fe, co, ni) 3 (Ti, al) phase;
further. The form of the high-entropy intermetallic compound is in a dendritic structure;
further, the content of the high-entropy intermetallic compound is 20-22% by volume;
further, the high entropy intermetallic compound has a size of 10-50 μm.
On the other hand, the invention also provides a preparation method of the high-entropy alloy composite material, which sequentially comprises the following steps: raw material mixing, drying, pressing, smelting, deep cooling treatment, solution treatment, aging treatment and chemical etching:
further, the raw material mixing step of the invention comprises the following steps: weighing metal raw material powder according to mass proportion, and then putting the weighed metal raw material powder into a three-dimensional mixer for low-speed mixing for 8 hours; the metal raw material powder is iron: 18-20%, cobalt: 19-21%, chromium: 17-19%, nickel: 19-21%, titanium: 15-17%; the balance of aluminum;
further, the drying step of the present invention includes: the mixed powder is put into a vacuum drying oven for drying, the temperature is 60-80 ℃, and the vacuum degree is 0.06-0.08 MPa;
further, the pressing step of the present invention comprises: 3-5 g of metal powder is put into a mould, and is pressed into green bodies by a hydraulic press under the pressure of 60MPa;
further, in the preparation method of the high-entropy alloy composite material, the smelting step comprises; preparing the green body into a high-entropy alloy composite material cast ingot by a vacuum smelting method;
further, the preparation method of the high-entropy alloy composite material of the invention comprises the following steps: placing the high-entropy alloy composite material cast ingot in liquid nitrogen, and performing cryogenic treatment at-180 ℃ to promote the generation of defects and nucleation sites in a matrix;
further, in the preparation method of the high-entropy alloy composite material of the invention, the solution treatment step comprises the following steps: carrying out solution treatment on the high-entropy alloy composite material cast ingot subjected to deep cooling treatment under the protection of argon atmosphere, preserving heat for 30-90min at 1150-1250 ℃, and then carrying out oil quenching or water quenching to promote remelting of netlike high-entropy intermetallic compounds in the high-entropy alloy composite material and breaking dendritic structures;
further, the aging treatment step in the preparation method of the high-entropy alloy composite material of the invention comprises the following steps: aging the high-entropy alloy composite material, wherein the aging treatment process is that the temperature is kept at 600-900 ℃ for 60-180min, and then air cooling is carried out to room temperature, so that the high-entropy intermetallic compound is promoted to precipitate again;
further, the chemical etching step in the preparation method of the high-entropy alloy composite material comprises the following steps: carrying out chemical etching on the high-entropy alloy composite material, wherein the chemical etching method is to soak the high-entropy alloy composite material in mixed acid for 5-20 hours to obtain a high-entropy intermetallic compound skeleton for efficient hydrogen evolution, so as to obtain a high-activity high-entropy alloy composite material electrocatalytic electrode;
further, in the preparation method of the high-entropy alloy composite material, the mixed acid system is CH 3 COOH、H 2 O、HNO 3 、H 2 SO 4 The volume percentages are respectively 35-40%,28-35%,18-22% and 6-10%.
The invention also provides application of the high-entropy alloy composite material, and the high-entropy alloy composite material is applied to a cathode material for producing hydrogen by water electrolysis in an alkaline working environment.
The invention has the beneficial effects that: compared with the prior art, the invention has the advantages that:
(1) The invention adopts non-noble metal elements to prepare the high-entropy alloy composite material, which remarkably reduces the cost, is easy to prepare large-size industrial hydrogen evolution electrodes, and has strong stability and corrosion resistance.
(2) According to the invention, the grains of the high-entropy alloy composite material are refined uniformly through solution aging treatment, and the micron-activity high-entropy intermetallic compound phase is separated out, so that the specific surface area of the material is obviously increased, and the hydrogen evolution overpotential of the high-entropy alloy composite material is obviously reduced.
(3) According to the invention, the high-entropy intermetallic compound skeleton is obtained by a chemical etching method, the electrocatalytic hydrogen evolution performance of the high-entropy alloy composite material is greatly improved, and the overpotential of the obtained hydrogen evolution catalyst is obviously reduced.
(4) The method has the advantages of simple process, high efficiency and low cost, and can be applied to the actual production process to improve the production benefit of enterprises.
[ description of the drawings ]
FIG. 1 is a microstructure of a high entropy alloy composite smelted block prepared in example 1;
FIG. 2 is a microstructure of the high entropy alloy composite prepared in example 1 in solid solution;
FIG. 3 is a microstructure of the high entropy alloy composite prepared in example 1 in an aged state at 600 ℃;
FIG. 4 is a microstructure of the high entropy alloy composite prepared in example 3 in an 800 ℃ aged state;
FIG. 5 is a microstructure of the high entropy alloy composite prepared in example 3 after chemical etching;
FIG. 6 is an LSV plot of samples of the high-entropy alloy composites prepared in examples 1-4, (a) an ingot of the high-entropy alloy composite prepared in example 1, (b) a solid solution of the high-entropy alloy composite prepared in example 1, (c) an aging of the high-entropy alloy composite prepared in example 1 at 600℃and (d) an aging of the high-entropy alloy composite prepared in example 3 at 800 ℃.
[ detailed description ] of the invention
Example 1:
the embodiment 1 of the invention is a preparation method of the high-entropy alloy composite material, which sequentially comprises the following steps: raw material mixing, drying, pressing, smelting, deep cooling treatment, solution treatment, aging treatment and chemical etching:
the raw material mixing step comprises the following steps: weighing metal raw material powder according to mass proportion, and then putting the weighed metal raw material powder into a three-dimensional mixer for low-speed mixing for 8 hours; the metal raw material powder comprises the following components in percentage by mass: 18%, cobalt: 19%, chromium: 17%, nickel: 19%, titanium: 15%; the balance of aluminum;
the drying step comprises the following steps: drying the mixed powder in a vacuum drying oven at 80deg.C under vacuum degree of 0.08MPa;
the pressing step comprises the following steps: 5g of metal powder is put into a mould, and is pressed into green bodies by a hydraulic press under the pressure of 60MPa;
the smelting step in the preparation method of the high-entropy alloy composite material comprises the following steps of; preparing the green body into a high-entropy alloy composite material cast ingot by a vacuum smelting method;
the preparation method of the high-entropy alloy composite material comprises the following steps of: placing the high-entropy alloy composite material cast ingot in liquid nitrogen, and performing cryogenic treatment at-180 ℃ to promote the generation of defects and nucleation sites in a matrix;
the solid solution treatment step in the preparation method of the high-entropy alloy composite material comprises the following steps: carrying out solution treatment on the high-entropy alloy composite material cast ingot subjected to deep cooling treatment under the protection of argon atmosphere, preserving heat for 30min at 1150 ℃ in the solution treatment process, and then carrying out oil quenching or water quenching to promote remelting of netlike high-entropy intermetallic compounds in the high-entropy alloy composite material, wherein dendritic structures are broken;
the aging treatment step in the preparation method of the high-entropy alloy composite material comprises the following steps: aging the high-entropy alloy composite material, wherein the aging treatment process is to keep the temperature at 600 ℃ for 120min, and then air-cooling to room temperature to promote the re-precipitation of high-entropy intermetallic compounds;
the chemical etching step in the preparation method of the high-entropy alloy composite material comprises the following steps: carrying out chemical etching on the high-entropy alloy composite material, wherein the chemical etching method is to soak the high-entropy alloy composite material in mixed acid for 15 hours to obtain a high-entropy intermetallic compound skeleton for efficient hydrogen evolution, and obtaining the high-activity high-entropy alloy composite material electrocatalytic electrode;
in the preparation method of the high-entropy alloy composite material, the mixed acid system is CH 3 COOH、H 2 O、HNO 3 、H 2 SO 4 The volume percentages are 40%,32%,20% and 8% respectively.
Testing and analysis: taking the high-entropy alloy composite material cast ingot, the high-entropy alloy composite material after solution treatment and the high-entropy alloy composite material after aging treatment in the steps respectively, and observing by using a Scanning Electron Microscope (SEM): the microstructure diagram of the Fe-Co-Cr-Ni-Ti-Al high-entropy alloy composite material shown in the figures 1-3 is obtained.
After the high-entropy alloy composite material cast ingot, the high-entropy alloy composite material after solution treatment and the high-entropy alloy composite material after aging treatment in the steps are prepared into electrodes, an electrochemical workstation three-electrode system is adopted, the high-entropy alloy composite material is used as a working electrode, hg/HgO is used as a reference electrode, a Pt sheet electrode is used as a counter electrode, a 1.0MKOH solution is used as electrolyte, open-circuit potential and cathode polarization are carried out to test hydrogen evolution performance, and hydrogen evolution overpotential of the Fe-Co-Cr-Ni-Ti-Al high-entropy alloy composite material at the current density of 10mA/cm < 2 > shown in figure 6 is obtained.
Example 2:
embodiment 2 of the present invention is a preparation method of the above high-entropy alloy composite material, which sequentially includes the following steps: raw material mixing, drying, pressing, smelting, deep cooling treatment, solution treatment, aging treatment and chemical etching:
the raw material mixing step comprises the following steps: weighing metal raw material powder according to mass proportion, and then putting the weighed metal raw material powder into a three-dimensional mixer for low-speed mixing for 8 hours; the metal raw material powder is iron: 18%, cobalt: 19%, chromium: 17%, nickel: 19%, titanium: 15%; the balance of aluminum;
the drying step comprises the following steps: drying the mixed powder in a vacuum drying oven at 80deg.C under vacuum degree of 0.08MPa;
the pressing step comprises the following steps: 5g of metal powder is put into a mould, and is pressed into green bodies by a hydraulic press under the pressure of 60MPa;
the smelting step in the preparation method of the high-entropy alloy composite material comprises the following steps of; preparing the green body into a high-entropy alloy composite material cast ingot by a vacuum smelting method;
the preparation method of the high-entropy alloy composite material comprises the following steps of: placing the high-entropy alloy composite material cast ingot in liquid nitrogen, and performing cryogenic treatment at-180 ℃ to promote the generation of defects and nucleation sites in a matrix;
the solid solution treatment step in the preparation method of the high-entropy alloy composite material comprises the following steps: carrying out solution treatment on the high-entropy alloy composite material cast ingot subjected to deep cooling treatment under the protection of argon atmosphere, preserving heat for 30min at 1150 ℃ in the solution treatment process, and then carrying out oil quenching or water quenching to promote remelting of netlike high-entropy intermetallic compounds in the high-entropy alloy composite material, wherein dendritic structures are broken;
the aging treatment step in the preparation method of the high-entropy alloy composite material comprises the following steps: aging the high-entropy alloy composite material, wherein the aging treatment process is to keep the temperature at 700 ℃ for 120min, and then air-cooling to room temperature to promote the re-precipitation of high-entropy intermetallic compounds;
the chemical etching step in the preparation method of the high-entropy alloy composite material comprises the following steps: carrying out chemical etching on the high-entropy alloy composite material, wherein the chemical etching method is to soak the high-entropy alloy composite material in mixed acid for 15 hours to obtain a high-entropy intermetallic compound skeleton for efficient hydrogen evolution, and obtaining the high-activity high-entropy alloy composite material electrocatalytic electrode;
in the preparation method of the high-entropy alloy composite material, the mixed acid system is CH 3 COOH、H 2 O、HNO 3 、H 2 SO 4 The volume percentages are 40%,32%,20% and 8% respectively.
Example 3:
embodiment 3 of the present invention is a method for preparing the high-entropy alloy composite material, which sequentially includes the following steps: raw material mixing, drying, pressing, smelting, deep cooling treatment, solution treatment, aging treatment and chemical etching:
the raw material mixing step comprises the following steps: weighing metal raw material powder according to mass proportion, and then putting the weighed metal raw material powder into a three-dimensional mixer for low-speed mixing for 8 hours; the metal raw material powder is iron: 18%, cobalt: 19%, chromium: 17%, nickel: 19%, titanium: 15%; the balance of aluminum;
the drying step comprises the following steps: drying the mixed powder in a vacuum drying oven at 80deg.C under vacuum degree of 0.08MPa;
the pressing step comprises the following steps: 5g of metal powder is put into a mould, and is pressed into green bodies by a hydraulic press under the pressure of 60MPa;
the smelting step in the preparation method of the high-entropy alloy composite material comprises the following steps of; preparing the green body into a high-entropy alloy composite material cast ingot by a vacuum smelting method;
the preparation method of the high-entropy alloy composite material comprises the following steps of: placing the high-entropy alloy composite material cast ingot in liquid nitrogen, and performing cryogenic treatment at-180 ℃ to promote the generation of defects and nucleation sites in a matrix;
the solid solution treatment step in the preparation method of the high-entropy alloy composite material comprises the following steps: carrying out solution treatment on the high-entropy alloy composite material cast ingot subjected to deep cooling treatment under the protection of argon atmosphere, preserving heat for 30min at 1150 ℃ in the solution treatment process, and then carrying out oil quenching or water quenching to promote remelting of netlike high-entropy intermetallic compounds in the high-entropy alloy composite material, wherein dendritic structures are broken;
the aging treatment step in the preparation method of the high-entropy alloy composite material comprises the following steps: aging the high-entropy alloy composite material, wherein the aging treatment process is to keep the temperature at 800 ℃ for 120min, and then air-cooling to room temperature to promote the re-precipitation of high-entropy intermetallic compounds;
the chemical etching step in the preparation method of the high-entropy alloy composite material comprises the following steps: carrying out chemical etching on the high-entropy alloy composite material, wherein the chemical etching method is to soak the high-entropy alloy composite material in mixed acid for 15 hours to obtain a high-entropy intermetallic compound skeleton for efficient hydrogen evolution, and obtaining the high-activity high-entropy alloy composite material electrocatalytic electrode;
the high-entropy alloy composite materialIn the preparation method, the mixed acid system is CH 3 COOH、H 2 O、HNO 3 、H 2 SO 4 The volume percentages are 40%,32%,20% and 8% respectively.
Testing and analysis: taking the high-entropy alloy composite material subjected to aging treatment in the steps and the high-entropy alloy composite material subjected to chemical etching, and observing by using a Scanning Electron Microscope (SEM): the microstructure diagrams of the Fe-Co-Cr-Ni-Ti-Al high-entropy alloy composite materials shown in figures 4 and 5 are obtained, and the situation that dendrite remelting occurs to the high-entropy alloy composite materials after solution treatment and the network structure is destroyed can be seen from figures 1 to 4. After aging treatment, a large amount of micro/nano phases are separated out in a light gray tissue, so that the specific surface area of the material is greatly improved.
After the high-entropy alloy composite material after aging treatment is prepared into an electrode, an electrochemical workstation three-electrode system is adopted, the high-entropy alloy composite material is used as a working electrode, hg/HgO is used as a reference electrode, a Pt sheet electrode is used as a counter electrode, a 1.0MKOH solution is used as electrolyte, and open-circuit potential and cathodic polarization are carried out to test the hydrogen evolution performance of the high-entropy alloy composite material, so that the hydrogen evolution overpotential of the Fe-Co-Cr-Ni-Ti-Al high-entropy alloy composite material at the current density of 10mA/cm < 2 > shown in figure 6 is obtained.
Example 4:
embodiment 4 of the present invention is a preparation method of the above high-entropy alloy composite material, which sequentially includes the following steps: raw material mixing, drying, pressing, smelting, deep cooling treatment, solution treatment, aging treatment and chemical etching:
the raw material mixing step comprises the following steps: weighing metal raw material powder according to mass proportion, and then putting the weighed metal raw material powder into a three-dimensional mixer for low-speed mixing for 8 hours; the metal raw material powder is iron: 18%, cobalt: 19%, chromium: 17%, nickel: 19%, titanium: 15%; the balance of aluminum;
the drying step comprises the following steps: drying the mixed powder in a vacuum drying oven at 80deg.C under vacuum degree of 0.08MPa;
the pressing step comprises the following steps: 5g of metal powder is put into a mould, and is pressed into green bodies by a hydraulic press under the pressure of 60MPa;
the smelting step in the preparation method of the high-entropy alloy composite material comprises the following steps of; preparing the green body into a high-entropy alloy composite material cast ingot by a vacuum smelting method;
the preparation method of the high-entropy alloy composite material comprises the following steps of: placing the high-entropy alloy composite material cast ingot in liquid nitrogen, and performing cryogenic treatment at-180 ℃ to promote the generation of defects and nucleation sites in a matrix;
the solid solution treatment step in the preparation method of the high-entropy alloy composite material comprises the following steps: carrying out solution treatment on the high-entropy alloy composite material cast ingot subjected to deep cooling treatment under the protection of argon atmosphere, preserving heat for 30min at 1150 ℃ in the solution treatment process, and then carrying out oil quenching or water quenching to promote remelting of netlike high-entropy intermetallic compounds in the high-entropy alloy composite material, wherein dendritic structures are broken;
the aging treatment step in the preparation method of the high-entropy alloy composite material comprises the following steps: aging the high-entropy alloy composite material, wherein the aging treatment process is to keep the temperature at 900 ℃ for 120min, and then air-cooling to room temperature to promote the re-precipitation of high-entropy intermetallic compounds;
the chemical etching step in the preparation method of the high-entropy alloy composite material comprises the following steps: carrying out chemical etching on the high-entropy alloy composite material, wherein the chemical etching method is to soak the high-entropy alloy composite material in mixed acid for 15 hours to obtain a high-entropy intermetallic compound skeleton for efficient hydrogen evolution, and obtaining the high-activity high-entropy alloy composite material electrocatalytic electrode;
in the preparation method of the high-entropy alloy composite material, the mixed acid system is CH 3 COOH、H 2 O、HNO 3 、H 2 SO 4 The volume percentages are 40%,32%,20% and 8% respectively.
Claims (4)
1. The high-entropy alloy composite material and the preparation method and the application thereof are characterized in that the high-entropy alloy composite material comprises the following components in percentage by mass: 18-20%, cobalt: 19-21%, chromium: 17-19%, nickel: 19-21%, titanium: 15-17%, and the balance of aluminum; the high-entropy alloy composite material takes Fe-Co-Cr-Ni phase asA matrix, wherein the precipitated phase is a high-entropy intermetallic compound; the hydrogen evolution performance of the high-entropy alloy composite material is 10mA/cm 2 The hydrogen evolution overpotential under the current density is 340-400 mV.
2. The high entropy alloy composite of claim 1, wherein the high entropy intermetallic compound is class a 3 B (Fe, co, ni) 3 (Ti, al) phase; the form of the high-entropy intermetallic compound is in a dendritic structure; the content of the high-entropy intermetallic compound is 20-22% by volume; the dendrite length of the high-entropy intermetallic compound is 10-50 mu m.
3. The high-entropy alloy composite material according to claim 1 or 2 and a preparation method thereof, wherein the preparation method sequentially comprises the following steps: raw material mixing, drying, pressing, smelting, deep cooling treatment, solution treatment, aging treatment and chemical etching:
the raw material mixing step comprises the following steps: weighing metal raw material powder according to mass proportion, and then putting the weighed metal raw material powder into a three-dimensional mixer for low-speed mixing for 8 hours; the metal raw material powder is iron: 18-20%, cobalt: 19-21%, chromium: 17-19%, nickel: 19-21%, titanium: 15-17%; the balance of aluminum;
the drying step includes: the mixed powder is put into a vacuum drying oven for drying, the temperature is 60-80 ℃, and the vacuum degree is 0.06-0.08 MPa;
the pressing step comprises the following steps: 3-5 g of metal powder is put into a mould, and is pressed into green bodies by a hydraulic press under the pressure of 60MPa;
the smelting step includes; preparing the green body into a high-entropy alloy composite material cast ingot by a vacuum smelting method;
the cryogenic treatment step comprises the following steps: placing the high-entropy alloy composite material cast ingot in liquid nitrogen, and performing cryogenic treatment at-180 ℃ to promote the generation of defects and nucleation sites in a matrix;
the solid solution treatment step includes: carrying out solution treatment on the high-entropy alloy composite material cast ingot subjected to deep cooling treatment under the protection of argon atmosphere, preserving heat for 30-90min at 1150-1250 ℃, and then carrying out oil quenching or water quenching to promote remelting of netlike high-entropy intermetallic compounds in the high-entropy alloy composite material and breaking dendritic structures;
the aging treatment step comprises the following steps: aging the high-entropy alloy composite material, wherein the aging treatment process is that the temperature is kept at 600-900 ℃ for 60-180min, and then air cooling is carried out to room temperature, so that the high-entropy intermetallic compound is promoted to precipitate again;
the chemical etching step comprises the following steps: chemical etching is carried out on the high-entropy alloy composite material, the chemical etching method is that mixed acid is soaked for 5-20h to obtain a high-entropy intermetallic compound framework for high-efficiency hydrogen evolution, and a high-activity electrocatalytic electrode is obtained, wherein the mixed acid system is CH 3 COOH、H 2 O、HNO 3 、H 2 SO 4 The volume percentages are respectively 35-40%,28-35%,18-22% and 6-10%.
4. Use of the high-entropy alloy composite material according to claims 1-3, characterized in that the use of the high-entropy alloy composite material is applied to cathode materials for hydrogen production by electrolysis of water in alkaline working environments.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2022113427156 | 2022-10-26 | ||
| CN202211342715.6A CN115652228A (en) | 2022-10-26 | 2022-10-26 | Method for improving electrocatalytic hydrogen evolution performance of high-entropy alloy through heat treatment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117385255A true CN117385255A (en) | 2024-01-12 |
Family
ID=84993716
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211342715.6A Pending CN115652228A (en) | 2022-10-26 | 2022-10-26 | Method for improving electrocatalytic hydrogen evolution performance of high-entropy alloy through heat treatment |
| CN202311378226.0A Pending CN117385255A (en) | 2022-10-26 | 2023-10-23 | High-entropy alloy composite material and preparation method and application thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211342715.6A Pending CN115652228A (en) | 2022-10-26 | 2022-10-26 | Method for improving electrocatalytic hydrogen evolution performance of high-entropy alloy through heat treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN115652228A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116103592B (en) * | 2023-04-12 | 2023-06-23 | 北京中辰至刚科技有限公司 | Heat treatment method of high-entropy alloy |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11359266B2 (en) * | 2018-11-20 | 2022-06-14 | City University Of Hong Kong | High entropy alloy structure and a method of preparing the same |
| CN111850372B (en) * | 2020-06-23 | 2021-12-07 | 湘潭大学 | A series of FeCoCrNiW (VC)XPreparation of high-entropy alloy and precipitation strengthening process thereof |
| CN112553517B (en) * | 2020-12-04 | 2022-06-21 | 湘潭大学 | Preparation method and process of wear-resistant CrMoNiTaHfW high-entropy alloy |
| CN112725818B (en) * | 2020-12-10 | 2022-03-01 | 西北工业大学 | Porous high-entropy alloy self-supporting electrode and method for electrolyzing water |
| WO2022132883A1 (en) * | 2020-12-15 | 2022-06-23 | University Of Maryland, College Park | Multi-element compound nanoparticles, and systems and methods of making and use thereof |
-
2022
- 2022-10-26 CN CN202211342715.6A patent/CN115652228A/en active Pending
-
2023
- 2023-10-23 CN CN202311378226.0A patent/CN117385255A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN115652228A (en) | 2023-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107142488B (en) | A kind of porous multiple casing nickel phosphide tiny balloon and its preparation method and application | |
| CN108767277B (en) | Fe-Pd-based nano-porous material and preparation method thereof | |
| CN117385255A (en) | High-entropy alloy composite material and preparation method and application thereof | |
| CN110773171A (en) | Layered nickel-iron-copper hydroxide electrocatalyst and preparation method and application thereof | |
| CN108247060A (en) | A kind of preparation method of nickel-base alloy electrolysis cathode for hydrogen evolution porous material | |
| CN108315596B (en) | Ni-Fe-Mo-Cu porous material and preparation method thereof | |
| CN113122875B (en) | High-activity Mn-rich high-entropy alloy electrolytic water catalytic material and preparation method thereof | |
| CN111893357B (en) | Self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material and preparation method thereof | |
| CN117945361A (en) | Hollow calabash-shaped PtSe2/NiSe2Method for synthesizing heterojunction nanowire and application of heterojunction nanowire in hydrogen production by electrolysis of seawater | |
| CN116288462B (en) | Method for improving electrochemical oxygen evolution catalytic performance of Fe-based amorphous alloy | |
| CN112921335B (en) | Preparation method of molybdenum disulfide-doped metal matrix self-supporting electrode | |
| CN116288480A (en) | Preparation method of nano-porous NiBi alloy catalyst for nitrogen reduction | |
| CN114150330B (en) | FeCoNiMo high-entropy alloy powder oxygen evolution catalyst and preparation method thereof | |
| CN109994744B (en) | Nickel-cobalt binary catalyst for promoting direct oxidation of sodium borohydride | |
| CN114892206B (en) | Multi-metal nitride heterojunction nanorod array composite electrocatalyst and preparation method and application thereof | |
| CN116200773A (en) | Transition metal electrocatalyst rich in twin crystal structure, and preparation method and application thereof | |
| CN113604816B (en) | Preparation method and application of high-entropy alloy fiber electrocatalyst | |
| CN115491699A (en) | Nano copper-based catalyst, preparation method thereof and application of nano copper-based catalyst in electrocatalytic reduction of carbon dioxide and carbon monoxide | |
| CN112981442A (en) | FeCoMoPC amorphous alloy for alkaline full-hydrolysis and preparation method thereof | |
| CN114892062B (en) | Porous high-entropy alloy material for efficiently producing hydrogen and preparation method thereof | |
| CN112921336B (en) | Preparation method of heterostructure-loaded self-supporting catalytic electrode | |
| CN114453587B (en) | Preparation method of nano porous copper-nickel alloy | |
| CN114920303B (en) | Porous iron-nickel hydroxide block material for producing hydrogen by water electrolysis and preparation method thereof | |
| CN115029712B (en) | High-efficiency high-stability full-water-dissolving Cu-based electrocatalyst and preparation method and application thereof | |
| CN115976556A (en) | Self-assembled CoSe 2 /NiSe 2 Composite nano heterostructure electrocatalyst material and preparation method and application 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 |