CN116180124B - Preparation method and application of high-entropy alloy electrocatalytic electrode with core-shell structure - Google Patents
Preparation method and application of high-entropy alloy electrocatalytic electrode with core-shell structure Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 76
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 76
- 239000011258 core-shell material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003723 Smelting Methods 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 13
- 238000005303 weighing Methods 0.000 claims abstract description 7
- 230000006698 induction Effects 0.000 claims abstract description 6
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 6
- 238000005266 casting Methods 0.000 claims abstract description 5
- 238000005507 spraying Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000007712 rapid solidification Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940101209 mercuric oxide Drugs 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(II) oxide Inorganic materials [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a preparation method and application of a high-entropy alloy electrocatalytic electrode with a core-shell structure, and aims to solve the problem that the current density applicable to the existing electrocatalytic oxygen evolution/total water electrolysis is small and cannot work stably under industrial current density. The preparation method comprises the following steps: 1. weighing all simple substance metal raw materials according to the atomic percentage; 2. smelting the mixed metal raw materials into a metal cast ingot by adopting a high-vacuum arc smelting furnace, and then smelting and suction-casting the metal cast ingot into a rod-shaped master alloy; 3. and vacuumizing melt spin quenching equipment by using a mechanical pump and a molecular pump, introducing oxygen, starting the copper wheel to rotate, starting an induction coil power supply to heat and melt the rod-shaped master alloy, and spraying the metal melt to the copper wheel to rapidly cool to obtain the high-entropy alloy electrocatalytic thin-strip electrode with the core-shell structure. The invention prepares a high-entropy alloy ribbon with a special core-shell structure, the shell structure is an amorphous-nanocrystalline structure, and the density of the ultra-large current is 2000mA/cm 2 And the device can stably work for more than 330 hours.
Description
Technical Field
The invention relates to a preparation method and application of a high-entropy alloy electrocatalytic electrode.
Background
The hydrogen production by water electrolysis is an important ring for reducing the utilization rate of fossil energy and achieving the aim of green hydrogen, and the electrolytic water electrode currently used in industry is Pt/C and IrO 2 The noble metal element or rare earth element is contained in the hydrogen production material, so that the hydrogen production material is expensive, and the development of hydrogen production by water electrolysis is greatly limited.
The high-entropy alloy has a better development prospect in the field of electrolytic water at present, but the reason for the excellent performance of the high-entropy alloy has not been deeply analyzed. Meanwhile, the current density applied by the existing noble metal-based and transition metal-based water electrolysis catalyst is smaller, and the existing noble metal-based and transition metal-based water electrolysis catalyst cannot be suitable for two working conditions appearing in industry: i.e. fluctuating current density scouring and electrolytic water catalysis at ultra high current densities.
Disclosure of Invention
The invention aims to solve the problems that the current density suitable for the current electrocatalytic oxygen evolution/full electrolysis electrode is smaller and the current density can not work stably under the industrial current density, and provides a preparation method and application of a high-entropy alloy electrocatalytic electrode with a core-shell structure.
The preparation method of the high-entropy alloy electrocatalytic electrode with the core-shell structure is realized according to the following steps:
1. according to the atomic percent content Co a Ni b Mo c Al d O e Weighing all the simple substance metal raw materials according to the chemical formula, and uniformly mixing the simple substance metal raw materials to obtain a mixed metal raw material;
2. smelting the mixed metal raw materials into a metal cast ingot by adopting a high-vacuum arc smelting furnace, and then smelting and suction-casting the metal cast ingot into a rod-shaped master alloy;
3. vacuumizing melt spin quenching equipment by using a mechanical pump and a molecular pump, introducing oxygen, starting a copper wheel to rotate, starting an induction coil power supply to heat and melt the rod-shaped master alloy, and spraying metal melt to the copper wheel to rapidly cool to obtain a high-entropy alloy electrocatalytic thin-strip electrode with a core-shell structure;
wherein in the chemical formula in the first step, a is more than or equal to 10 and less than or equal to 50, b is more than or equal to 10 and less than or equal to 50, c is more than or equal to 0 and less than or equal to 30, d is more than or equal to 0 and less than or equal to 30, e is more than or equal to 10 and less than or equal to 50, and a+b+c+d+e=100.
The invention relates to an application of a high-entropy alloy electrocatalytic electrode with a core-shell structure, which takes the high-entropy alloy electrocatalytic electrode with the core-shell structure as an electrolytic water catalytic reaction electrode.
The surface layer of the high-entropy alloy electrocatalytic electrode with the core-shell structure is of an amorphous-nanocrystalline structure, and the core part is a special core-shell structure thin strip with the high-entropy alloy crystal structure.
According to the high-entropy alloy electrocatalytic electrode, firstly, oxygen is filled in the reaction process, so that the amorphous forming capacity of the alloy is improved, meanwhile, a preparation method of rapid solidification is utilized, the cooling speed of a shell layer is extremely high at the moment that a copper wheel contacts molten liquid, and the cooling speed of the shell layer is higher than that of a core part due to uneven distribution of a thermal field, so that a special core-shell structure is formed.
The special core-shell structure high-entropy alloy prepared by the invention has better performance than commercial noble metal-based electrodes under different working conditions of practical industrial electrolytic water application. At present, the performance regulation and control of the high-entropy alloy still stays at the component regulation and control level, the structure regulation and control is an effective strategy for improving the catalytic performance of the high-entropy alloy, the advantages of alloy body materials can be fully exerted, and the in-situ generated compact structure remarkably improves the stability. The high-entropy alloy electrode with the core-shell structure is characterized in that the shell layer is of an amorphous-nanocrystalline structure, nanocrystalline with the diameter of about 5nm is distributed on an amorphous substrate, the amorphous structure has more active sites and better corrosion resistance, so that the catalyst has better activity and stability, the nanocrystalline comprises metal element oxide, which is an active substance in the catalytic reaction process, an amorphous-nanocrystalline interface generated in situ can accelerate the electron transmission speed, so that the catalytic activity is improved, and meanwhile, the shell layer contains a plurality of venation structures formed by pure metal amorphous and gradually extends downwards and is connected with the high-entropy alloy crystal of the core part, so that the structure greatly increases the conductivity of the catalyst, and the catalyst can obtain lower overpotential under the condition of industrial-level high current density. The high-entropy alloy with the special core-shell structure enables the catalyst to adapt to different industrial working conditions and has good stability, and meanwhile, the catalyst also has good mechanical properties and can be used as a self-supporting electrode.
The preparation method and the application of the high-entropy alloy thin-layer electrolytic water electrode have the following beneficial effects:
1. the high-entropy alloy ribbon with a special core-shell structure is successfully prepared by introducing oxygen in the preparation process and utilizing the principle of rapid solidification; the shell layer is of an amorphous-nanocrystalline structure, the core part is of a high-entropy alloy structure, and the in-situ generated composite structure is tightly combined and has better self-supporting capability.
2. The high-entropy alloy special core-shell structure ribbon has better oxygen evolution catalysis performance and full water decomposition performance, and is 10mA/cm in oxygen evolution catalysis 2 The overpotential at the time was 270mV at 2000mA/cm 2 The overpotential at this time was only 500mV. When fully dissolving water, the industrial battery voltage is 1.8-2.40V and reaches 200-400mA/cm 2 The high entropy alloy electrode with the structure can reach 1000mA/cm when being used as a cathode and an anode at the same time when the voltage of a battery is 2.14V 2 Is suitable for industrial use.
3. The special high-entropy alloy electrode with special core-shell structure has better electrochemical stability at 10, 50, 100 and 500mA/cm 2 Under the flushing of different current densities, the working voltage only has small change and returns to 10mA/cm again 2 The performance is still excellent when working under the current density. At the same time, the ultra-large current density is 2000mA/cm 2 And the device can stably work for more than 330 hours.
4. The high-entropy alloy electrode has low preparation cost and can replace noble metal-based catalysts in terms of performance.
5. The structure of the alloy is regulated and controlled by the preparation method through designing the structure of the high-entropy alloy, so that the high-entropy alloy electrode has better catalytic performance suitable for industrial application.
Drawings
FIG. 1 is a photograph of a thin belt of high entropy alloy obtained in example I;
FIG. 2 is a high-entropy alloy thin strip Co obtained in example I 20 Ni 20 Mo 20 Al 20 O 20 A core-shell structure transmission diagram;
FIG. 3 is a series of high entropy alloy thin strips Co in an embodiment a Ni b Mo c Al d O e The oxygen evolution performance graphs of (2) are sequentially shown in the arrow direction; co (Co) 20 Ni 20 Mo 20 Al 20 O 20 、Co 25 Ni 25 Mo 25 O 25 、Co 25 Ni 75 、Co 34 Ni 33 O 33 、Co 50 Ni 50 And Co 25 Ni 25 Al 25 O 25 ；
FIG. 4 is a high-entropy alloy thin strip Co obtained in example two 20 Ni 20 Mo 20 Al 20 O 20 Is a graph of the full hydrolysis performance of (2);
FIG. 5 is a high-entropy alloy thin strip Co obtained in example III 20 Ni 20 Mo 20 Al 20 O 20 Stability plots at different current densities;
FIG. 6 is a high-entropy alloy thin strip Co obtained in example III 20 Ni 20 Mo 20 Al 20 O 20 2000mA/cm at an ultra-high current density 2 Stability profile of (c).
Detailed Description
The first embodiment is as follows: the preparation method of the high-entropy alloy electrocatalytic electrode with the core-shell structure of the embodiment is implemented according to the following steps:
1. according to the atomic percent content Co a Ni b Mo c Al d O e Weighing all the simple substance metal raw materials according to the chemical formula, and uniformly mixing the simple substance metal raw materials to obtain a mixed metal raw material;
2. smelting the mixed metal raw materials into a metal cast ingot by adopting a high-vacuum arc smelting furnace, and then smelting and suction-casting the metal cast ingot into a rod-shaped master alloy;
3. vacuumizing melt spin quenching equipment by using a mechanical pump and a molecular pump, introducing oxygen, starting a copper wheel to rotate, starting an induction coil power supply to heat and melt the rod-shaped master alloy, and spraying metal melt to the copper wheel to rapidly cool to obtain a high-entropy alloy electrocatalytic thin-strip electrode with a core-shell structure;
wherein in the chemical formula in the first step, a is more than or equal to 10 and less than or equal to 50, b is more than or equal to 10 and less than or equal to 50, c is more than or equal to 0 and less than or equal to 30, d is more than or equal to 0 and less than or equal to 30, e is more than or equal to 10 and less than or equal to 50, and a+b+c+d+e=100.
The high-entropy alloy electrocatalytic electrode with the core-shell structure is of a special high-entropy alloy core-shell structure, namely, the shell layer is of an amorphous-nanocrystalline structure with more active sites, so that the catalysis reaction can quickly jump over the reaction potential barrier when the current density is lower, and the smaller overpotential is obtained; at the ultra-high current density, the conductivity of the catalyst becomes a main factor affecting the performance of the catalyst, and the high-entropy alloy crystal of the core part provides better conductivity for the catalyst, so that the catalyst obtains better high-current density catalytic activity. According to the preparation method based on the rapid solidification mode, the structure is generated at one time, the prepared catalyst has a stable core-shell structure and good self-supporting capacity, and meanwhile, good oxygen evolution and full water dissolution catalytic performances are shown, so that a new scheme is provided for industrial application of non-noble metal base.
The second embodiment is as follows: the difference between the embodiment and the specific embodiment is that in the chemical formula in the step one, a is 15-25, b is 15-25, c is 15-25, d is 15-25, and e is 15-25.
And a third specific embodiment: the present embodiment differs from the specific embodiment in that Co is contained in the first step in terms of atomic percent 20 Ni 20 Mo 20 Al 20 O 20 Weighing each simple substance metal raw material according to the chemical formula.
The specific embodiment IV is as follows: the difference between the present embodiment and the first to third embodiments is that the melting temperature of the mixed metal raw material in the second step is 1500 to 1600 ℃.
Fifth embodiment: the difference between the present embodiment and the first to fourth embodiments is that the rod-shaped master alloy in the second step has a diameter of 1 to 2cm and a length of 4 to 8cm.
Specific embodiment six: the present embodiment differs from one of the first to fifth embodiments in that oxygen is introduced in the third step to make the pressure in the apparatus 4000 to 6000Pa.
Seventh embodiment: the difference between the embodiment and the first to sixth embodiments is that the rotation speed of the copper wheel is controlled to 1600-2000 r/min in the third step.
Eighth embodiment: the difference between the embodiment and the embodiment one to seven is that the induction coil power supply is started in the third step to heat and melt the bar-shaped master alloy, and the temperature is kept for 2 to 5 minutes.
Detailed description nine: the difference between the embodiment and one to eighth embodiments is that the width of the high-entropy alloy electrocatalytic thin-strip electrode with the core-shell structure obtained in the step three is 0.2-1.0 cm.
Detailed description ten: the difference between the embodiment and one of the specific embodiments is that the thickness of the core-shell structure high-entropy alloy electrocatalytic thin-strip electrode obtained in the step three is 40-80 microns.
Embodiment one: the preparation method of the high-entropy alloy electrocatalytic electrode with the core-shell structure is realized according to the following steps:
1. according to the atomic percent content Co 20 Ni 20 Mo 20 Al 20 O 20 Weighing all simple substance metal raw materials according to the chemical formula, and uniformly mixing the metal raw materials after ultrasonic cleaning to obtain mixed metal raw materials;
2. adopting a high vacuum arc melting furnace, performing arc striking by using a tungsten electrode, melting the mixed metal raw material for 4-5 times, each time for 2-3 minutes, ensuring that different elements in the alloy are uniformly mixed, and then melting and suction-casting 50g of metal cast ingot into a rod-shaped master alloy with the diameter of 1cm and the length of 4 cm;
3. and vacuumizing melt spin quenching equipment by using a mechanical pump and a molecular pump, introducing oxygen until the pressure in the equipment is 5000Pa, starting a copper wheel to rotate, starting an induction coil power supply to heat and melt the rod-shaped master alloy, preserving heat for 2 minutes after melting, spraying metal melt to the copper wheel to rapidly cool, instantly obtaining a higher cooling speed by a shell layer, and combining the metal melt with the oxygen in the equipment to obtain the high-entropy alloy electrocatalytic thin-strip electrode with the core-shell structure.
In this example, co was prepared by a similar method 25 Ni 75 、Co 50 Ni 50 、Co 34 Ni 33 O 33 、Co 25 Ni 25 Al 25 O 25 、Co 25 Ni 25 Mo 25 O 25 、Co 20 Ni 20 Mo 20 Al 20 O 20 High entropy alloy ribbon of (1), wherein Co 25 Ni 75 And Co 50 Ni 50 Is prepared by not introducing oxygen into melt spin quenching equipment.
The electrochemical workstation of this example is named Shanghai Chen Hua 760E, the current amplification is carried out by using Shanghai Chen Hua Dianliu amplifier, thus the catalytic performance at high current density is explored, in the test process, the electrolyte is KOH of 1.0mol/L, the reference electrode is mercury-mercuric oxide electrode, the counter electrode is platinum sheet electrode, the high entropy alloy ribbon is placed in a platinum sheet electrode clamp, the high entropy alloy ribbon is all placed in the electrolyte, the platinum electrode is not contacted with the electrolyte, the surface area of the ribbon is calculated, the electrochemical workstation software is opened, the oxygen evolution reaction is carried out for 100 CV cycles at 0V-1.2V, then LSV is tested by using linear voltammetry, the catalytic performance of the electrode is quantified, the measured curve is shown in figure 3, the abscissa is reversible hydrogen potential, the ordinate is current density, when the overpotential of the oxygen evolution reaction is processed, the potential barrier of the oxygen evolution reaction is subtracted by 1.23V at the corresponding current density, and after the processing is found at 10mA/cm 2 The overpotential at the time was 270mV at 2000mA/cm 2 The overpotential at this time was only 500mV. At 10mA/cm 2 Co time 25 Ni 75 、Co 50 Ni 50 、Co 34 Ni 33 O 33 、Co 25 Ni 25 Al 25 O 25 、Co 25 Ni 25 Mo 25 O 25 The overpotential of the thin strips was 321mV, 331mV, 320mV, 331mV, 309mV, respectively.
Embodiment two: this example differs from the first example in that Co is used simultaneously in a three electrode system 20 Ni 20 Mo 20 Al 20 O 20 As a catalytic electrode for hydrogen evolution and oxygen evolution, namely, full water-splitting catalysis is performed.
This example Co 20 Ni 20 Mo 20 Al 20 O 20 The full water-splitting performance test of the electrode is shown in FIG. 4, the abscissa represents the battery voltage, the ordinate represents the current density, and the voltage is 1000mA/cm 2 The battery voltage of the battery is only 2.14V, which is far beyond the industrial application standard.
Embodiment III: the first difference between this embodiment and the first embodiment is the stability of current density under different industrial conditions by using the timed current method of the electrochemical workstation and the current amplifier.
The stability test of this example at different current densities is shown in fig. 5, the abscissa is the test time, the ordinate is the reversible hydrogen potential at different current densities, and the operating voltage of the electrode is only slightly changed at the fluctuating current densities. The embodiment has the ultra-large current density of 2000mA/cm 2 As shown in fig. 6, the electrode can be stably operated for more than 330 hours at an ultra-large current density.
Claims (7)
1. The preparation method of the high-entropy alloy electrocatalytic electrode with the core-shell structure is characterized by comprising the following steps of:
1. according to the atomic percent content Co a Ni b Mo c Al d O e Weighing all the simple substance metal raw materials according to the chemical formula, and uniformly mixing the simple substance metal raw materials to obtain a mixed metal raw material;
2. smelting the mixed metal raw materials into a metal cast ingot by adopting a high-vacuum arc smelting furnace, and then smelting and suction-casting the metal cast ingot into a rod-shaped master alloy;
3. vacuumizing melt spin quenching equipment by using a mechanical pump and a molecular pump, introducing oxygen, starting a copper wheel to rotate, starting an induction coil power supply to heat and melt the rod-shaped master alloy, and spraying out the metal melt to the copper wheel to rapidly cool to obtain a high-entropy alloy electrocatalytic thin strip electrode with a core-shell structure, wherein the width of the thin strip electrode is 0.2-1.0 cm, and the thickness of the thin strip electrode is 40-80 microns;
wherein in the chemical formula in the first step, a is 15-25, b is 15-25, c is 15-25, d is 15-25, e is 15-25, and a+b+c+d+e=100.
2. The method for preparing a high-entropy alloy electrocatalytic electrode with a core-shell structure according to claim 1, wherein in the first step, co is contained according to atomic percentage 20 Ni 20 Mo 20 Al 20 O 20 Weighing each simple substance metal raw material according to the chemical formula.
3. The method for preparing a high-entropy alloy electrocatalytic electrode with a core-shell structure according to claim 1, wherein the smelting temperature of the mixed metal raw material in the second step is 1500-1600 ℃.
4. The method for preparing a high-entropy alloy electrocatalytic electrode with a core-shell structure according to claim 1, wherein the diameter of the rod-shaped master alloy in the second step is 1-2 cm, and the length of the rod-shaped master alloy is 4-8 cm.
5. The method for preparing the high-entropy alloy electrocatalytic electrode with a core-shell structure according to claim 1, wherein oxygen is introduced in the third step to enable the pressure in the device to be 4000-6000 Pa.
6. The method for preparing the high-entropy alloy electrocatalytic electrode with a core-shell structure according to claim 1, wherein the rotating speed of the copper wheel is controlled to be 1600-2000 r/min in the third step.
7. The application of the high-entropy alloy electrocatalytic electrode with the core-shell structure, which is prepared by the method according to claim 1, is characterized in that the high-entropy alloy electrocatalytic electrode with the core-shell structure is used as an electrolytic water catalytic reaction electrode.
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