CN113265675B - Preparation method of self-supporting high-entropy alloy electrode for electrolytic hydrogen production - Google Patents

Preparation method of self-supporting high-entropy alloy electrode for electrolytic hydrogen production Download PDF

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CN113265675B
CN113265675B CN202110576599.3A CN202110576599A CN113265675B CN 113265675 B CN113265675 B CN 113265675B CN 202110576599 A CN202110576599 A CN 202110576599A CN 113265675 B CN113265675 B CN 113265675B
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entropy alloy
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CN113265675A (en
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徐吉林
张林伟
唐剑
罗军明
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Nanchang Hangkong University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129—Flame spraying
    • 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
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    • 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

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Abstract

The invention provides a preparation method of a self-supporting high-entropy alloy electrode for electrolytic hydrogen production, which comprises the following steps: (1) Firstly, carrying out sand blasting roughening treatment on a substrate by using white corundum, wherein the sand blasting angle is 60-80 degrees, the air pressure is 0.3-0.5 MPa, the sand blasting distance is 80-150 mm, and the surface roughness of the substrate after the sand blasting roughening treatment is Ra (3-10) mu m; (2) And (3) spraying the high-entropy alloy powder on the surface of the substrate subjected to roughening treatment in the step (1) by adopting a spraying process to obtain a high-entropy alloy coating, and cooling the substrate to obtain the self-supporting high-entropy alloy electrode. The preparation method of the self-supporting high-entropy alloy electrode provided by the invention has the advantages of no need of any adhesive, good conductivity, rich raw materials of the coating electrode, controllable preparation conditions, high bonding strength, high catalytic activity, excellent catalytic stability and extremely strong practical applicability, greatly promotes the energy conversion efficiency of electrolytic water, and provides a novel oxygen evolution catalytic electrode.

Description

Preparation method of self-supporting high-entropy alloy electrode for electrolytic hydrogen production
Technical Field
The invention relates to the technical field of high-entropy alloy electrocatalysis and energy storage, in particular to a preparation method of a self-supporting high-entropy alloy electrode for electrolytic hydrogen production.
Background
The intermittent clean energy sources such as solar energy, wind energy, geothermal energy and the like are converted into hydrogen energy through the water electrolysis technology, so that the current increasingly serious energy crisis and environmental problems are relieved, and an ideal method for carbon neutralization is finally realized. The traditional electrolytic water tank has the voltage of 1.8V which is far greater than the theoretical water decomposition voltage (1.23V), and the electrocatalysts such as Pt, irO2, ruO2 and the like have excellent performance, but cannot be practically applied commercially because of high price and rare reserves.
In recent years, researchers have developed electrocatalysts typified by inexpensive transition metal groups, but the use of binders has resulted in difficulty in obtaining superior stability of the prepared electrocatalyst and a relatively complex process for preparing the electrocatalyst material. Currently, high-entropy alloys with simple structure and unique properties have been demonstrated to have an unparalleled nature in the catalytic field and to exhibit excellent catalytic properties in the electrolysis of water. Therefore, research and development of a preparation method of a self-supporting high-entropy alloy electrode for electrolytic hydrogen production are needed.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a self-supporting high-entropy alloy electrode for electrolytic hydrogen production, which comprises the following steps:
(1) Firstly, carrying out sand blasting roughening treatment on a substrate by using white corundum, wherein the sand blasting angle is 60-80 degrees, the air pressure is 0.3-0.5 MPa, the sand blasting distance is 80-150 mm, and the surface roughness of the substrate after the sand blasting roughening treatment is Ra (3-10) mu m;
(2) And (3) spraying the high-entropy alloy powder on the surface of the substrate subjected to roughening treatment in the step (1) by adopting a spraying process to obtain a high-entropy alloy coating, and cooling the substrate to obtain the self-supporting high-entropy alloy electrode.
Wherein the substrate is a titanium alloy plate or a stainless steel plate.
Wherein the high-entropy alloy component is any one of CoCrFeNiMn, coCrFeNiAl, coCrFeNiNb, coFeNiMoAl, coFeNiCuAl or CoNiFeMnCu.
Wherein the temperature of the spraying is controlled to be 70-95 ℃.
And spraying 1-10 layers of high-entropy alloy on the surface of the substrate, wherein the thickness of a single layer is 5-20 mu m.
Wherein the total thickness of the high-entropy alloy coating is 5-200 mu m.
Wherein the spraying process is plasma spraying, supersonic flame spraying or cold air power spraying.
Wherein, the plasma spraying process is as follows: the spraying main gas is argon, and the flow of the argon is 2-3.5 m 3 And/h, the spraying auxiliary gas is hydrogen, and the flow rate of the hydrogen is 0.3-0.8 m 3 /h; the current is 600-900A, the powder feeding rate is 30-50 g/min, and the spraying distance is 60-120 mm.
Wherein, the process of the supersonic flame spraying is as follows: the fuel gas is aviation kerosene, the flow rate of the kerosene is 5-6.5gal/h, the combustion-supporting gas is high-pressure oxygen, the flow rate of the oxygen is 1600-2200scf/h, the powder feeding gas is nitrogen, and the flow rate of the nitrogen is 20-30SCFH; the powder feeding rate is 20-80g/min, and the spraying distance is 300-400mm.
Wherein, nitrogen is used as working gas and powder carrying gas, the pressure of nitrogen is 5-10Mpa, the temperature is 300-1000 ℃, the powder feeding rate is 50-100g/min, and the spraying distance is 20-30mm.
The invention has the beneficial effects that:
the self-supporting high-entropy alloy electrode is prepared by spraying the high-entropy alloy powder on a titanium alloy plate or a stainless steel plate by adopting a multilayer spraying technology, and the electrode does not need any adhesive and has good conductivity; the coating electrode has the advantages of abundant raw materials, controllable preparation conditions and high bonding strength; at a current density of 10mA/cm 2 And 100 mA/cm 2 When the oxygen evolution overpotential is 312mV and 335mV respectively, the catalyst shows excellent electrocatalytic performance. The coated electrode with high catalytic activity, excellent catalytic stability and extremely strong practical applicability greatly promotes the water electrolysis energy conversion efficiency, and is a novel oxygen evolution catalytic electrode.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the drawings that need to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort to those skilled in the art.
FIG. 1 is an XRD pattern of the high entropy alloy coating prepared in example 1;
FIG. 2 is a surface SEM image of a high entropy alloy coating prepared according to example 1;
FIG. 3 is a cross-sectional SEM image of a high entropy alloy coating prepared according to example 1;
FIG. 4 is an EDS diagram of the high entropy alloy coating prepared in example 1;
FIG. 5 is a graph showing the polarization of oxygen evolution of the high entropy alloy electrode prepared in example 1 in an alkaline electrolyte solution for catalyzing water electrolysis;
FIG. 6 is a graph of oxygen evolution Tafel of the high entropy alloy electrode prepared in example 1 in alkaline electrolyte solution for catalyzing water electrolysis;
FIG. 7 is a graph showing the catalytic stability of oxygen evolution of the high entropy alloy electrode prepared in example 1 in alkaline electrolyte solution for catalyzing water electrolysis.
Detailed Description
The following are preferred embodiments of the present invention, and it should be noted that modifications and variations can be made by those skilled in the art without departing from the principle of the present invention, and these modifications and variations are also considered as the protection scope of the present invention.
Example 1
The invention provides a preparation method of a self-supporting high-entropy alloy electrode for electrolytic hydrogen production, which comprises the following steps:
(1) Firstly, carrying out sand blasting roughening treatment on a titanium alloy substrate with the specification of 300 multiplied by 100 multiplied by 2mm by using white corundum, wherein the sand blasting angle is 60 degrees, the air pressure is 0.5MPa, the sand blasting distance is 100mm, and the surface roughness of the substrate after the sand blasting roughening treatment is Ra5 mu m;
(2) And (2) spraying high-entropy alloy powder on the surface of the titanium alloy substrate subjected to roughening treatment in the step (1) by adopting a supersonic flame spraying process, wherein 7 layers of high-entropy alloy are sprayed, the thickness of a single layer of high-entropy alloy is 15-20 mu m, the total thickness of a high-entropy alloy coating is 125 mu m, and the self-supporting high-entropy alloy electrode is obtained after the titanium alloy substrate is cooled after spraying.
The high entropy alloy powder used in example 1 was FeCoCrNiMn with a particle size of 20-53. Mu.m.
The process parameters for the supersonic flame spraying in example 1 were: the fuel gas is aviation kerosene, the flow rate of the kerosene is 5.5gal/h, the combustion-supporting gas is high-pressure oxygen, the flow rate of the oxygen is 1900scf/h, the powder feeding gas is nitrogen, and the flow rate of the nitrogen is 25SCFH; the powder feeding rate is 30g/min, and the spraying distance is 300mm.
Fig. 1 is an XRD pattern of the high-entropy alloy coating prepared in example 1, from which it can be seen that the prepared high-entropy alloy coating has a simple face-centered cubic structure.
FIG. 2 is a surface SEM image of the high entropy alloy coating prepared in example 1, as can be seen from the figure: the surface of the coating presents a typical spray pattern, the surface is free of unmelted particles, the particle spreading condition is good, and the rough surface provides a very large specific surface area.
FIG. 3 is a cross-sectional SEM image of a high entropy alloy coating prepared according to example 1, from which it can be seen that the coating has a thickness of 125 μm.
Fig. 4 is an EDS diagram of the high-entropy alloy coating prepared in example 1, from which it can be seen that the ratio of the amounts of the substances of the coating components is Co: cr: fe: ni: mn=1:1:1:1.
FIG. 5 is a graph showing the polarization of oxygen evolution of the high-entropy alloy electrode prepared in example 1 in alkaline electrolyte solution by catalytic water electrolysis, as can be seen from the graph, at a current density of 10mA/cm 2 And 100A/cm 2 When the overpotential is 312mV and 335mV respectively, the catalytic oxygen generating performance is excellent. Wherein:iR s deducted, electrolyte: 1 mol/L KOH solution.
FIG. 6 is a graph showing the oxygen evolution Tafel of the high-entropy alloy electrode prepared in example 1 in an alkaline electrolyte solution by catalyzing water electrolysis, wherein the Tafel slope is 30.3mV/dec -1 Indicating rapid oxygen evolution reaction kinetics. Wherein:iR s deducted, electrolyte: 1 mol/L KOH solution.
FIG. 7 is a graph showing the catalytic stability of oxygen evolution of the high-entropy alloy electrode prepared in example 1 in alkaline electrolyte solution for water electrolysis, as can be seen from the graph, at a current density of 10mA/cm 2 When the material works for 10 hours for a long time, the potential is basically unchanged, and the catalytic performance is stable.
Example 2
The invention provides a preparation method of a self-supporting high-entropy alloy electrode for electrolytic hydrogen production, which comprises the following steps:
(1) Firstly, carrying out sand blasting roughening treatment on a stainless steel substrate with the specification of 500 multiplied by 5mm by using white corundum, wherein the sand blasting angle is 60 degrees, the air pressure is 0.5MPa, the sand blasting distance is 100mm, and the surface roughness of the substrate after the sand blasting roughening treatment is Ra5 mu m;
(2) And (2) spraying high-entropy alloy powder on the surface of the stainless steel substrate subjected to roughening treatment in the step (1) by adopting a supersonic flame spraying process, wherein 7 layers of high-entropy alloy are sprayed, the thickness of a single layer of high-entropy alloy is 15-20 mu m, the total thickness of a high-entropy alloy coating is 125 mu m, and a self-supporting high-entropy alloy electrode is obtained after the stainless steel substrate is cooled after spraying is finished.
The high entropy alloy powder used in example 2 was FeCoCrNiMn with a particle size of 20-53. Mu.m.
The process parameters for the supersonic flame spraying in example 2 were: the fuel gas is aviation kerosene, the flow rate of the kerosene is 5.5gal/h, the combustion-supporting gas is high-pressure oxygen, the flow rate of the oxygen is 1900scf/h, the powder feeding gas is nitrogen, and the flow rate of the nitrogen is 25SCFH; the powder feeding rate is 30g/min, and the spraying distance is 300mm.
High-entropy alloy electrode catalytic oxygen evolution performance prepared in example 2: at a current density of 10mA/cm 2 And 100 mA/cm 2 When the overpotential is 316mV and 347mV, the matrix has no influence on the catalytic performance.
Example 3
The invention provides a preparation method of a self-supporting high-entropy alloy electrode for electrolytic hydrogen production, which comprises the following steps:
(1) Firstly, carrying out sand blasting roughening treatment on a titanium alloy substrate with the specification of 300 multiplied by 100 multiplied by 2mm by using white corundum, wherein the sand blasting angle is 60 degrees, the air pressure is 0.5MPa, the sand blasting distance is 100mm, and the surface roughness of the substrate after the sand blasting roughening treatment is Ra5 mu m;
(2) And (2) spraying high-entropy alloy powder on the surface of the titanium alloy substrate subjected to roughening treatment in the step (1) by adopting a supersonic flame spraying process, wherein 7 layers of high-entropy alloy are sprayed, the thickness of a single layer of high-entropy alloy is 15-20 mu m, the total thickness of a high-entropy alloy coating is 125 mu m, and the self-supporting high-entropy alloy electrode is obtained after the titanium alloy substrate is cooled after spraying.
The high entropy alloy powder used in example 3 was CoCrFeNiAl with a particle size of 20-53. Mu.m.
The process parameters for the supersonic flame spraying in example 3 were: the fuel gas is aviation kerosene, the flow rate of the kerosene is 5.5gal/h, the combustion-supporting gas is high-pressure oxygen, the flow rate of the oxygen is 1900scf/h, the powder feeding gas is nitrogen, and the flow rate of the nitrogen is 25SCFH; the powder feeding rate is 30g/min, and the spraying distance is 300mm.
High-entropy alloy electrode catalytic oxygen evolution performance prepared in example 3: at a current density of 10mA/cm 2 And 100 mA/cm 2 When the overpotential was 344mV and 396mV, respectively.
Example 4
The invention provides a preparation method of a self-supporting high-entropy alloy electrode for electrolytic hydrogen production, which comprises the following steps:
(1) Firstly, carrying out sand blasting roughening treatment on a titanium alloy substrate with the specification of 300 multiplied by 100 multiplied by 2mm by using white corundum, wherein the sand blasting angle is 60 degrees, the air pressure is 0.5MPa, the sand blasting distance is 100mm, and the surface roughness of the substrate after the sand blasting roughening treatment is Ra5 mu m;
(2) And (2) spraying high-entropy alloy powder on the surface of the titanium alloy substrate subjected to roughening treatment in the step (1) by adopting a supersonic flame spraying process, wherein 7 layers of high-entropy alloy are sprayed, the thickness of a single layer of high-entropy alloy is 15-20 mu m, the total thickness of a high-entropy alloy coating is 125 mu m, and the self-supporting high-entropy alloy electrode is obtained after the titanium alloy substrate is cooled after spraying.
The high entropy alloy powder used in example 4 was CoCrFeNiNb with a particle size of 20-53. Mu.m.
The process parameters for the supersonic flame spraying in example 4 were: the fuel gas is aviation kerosene, the flow rate of the kerosene is 5.5gal/h, the combustion-supporting gas is high-pressure oxygen, the flow rate of the oxygen is 1900scf/h, the powder feeding gas is nitrogen, and the flow rate of the nitrogen is 25SCFH; the powder feeding rate is 30g/min, and the spraying distance is 300mm.
High-entropy alloy electrode catalytic oxygen evolution performance prepared in example 4: at a current density of 10mA/cm 2 And 100 mA/cm 2 When the overpotential was 327mV and 368mV, respectively.
Example 5
The invention provides a preparation method of a self-supporting high-entropy alloy electrode for electrolytic hydrogen production, which comprises the following steps:
(1) Firstly, carrying out sand blasting roughening treatment on a titanium alloy substrate with the specification of 300 multiplied by 100 multiplied by 2mm by using white corundum, wherein the sand blasting angle is 60 degrees, the air pressure is 0.5MPa, the sand blasting distance is 100mm, and the surface roughness of the substrate after the sand blasting roughening treatment is Ra5 mu m;
(2) And (2) spraying high-entropy alloy powder on the surface of the titanium alloy substrate subjected to roughening treatment in the step (1) by adopting a plasma spraying process, wherein 7 layers of high-entropy alloy are sprayed, the thickness of a single layer of high-entropy alloy is 15-20 mu m, the total thickness of a high-entropy alloy coating is 125 mu m, and the self-supporting high-entropy alloy electrode is obtained after the titanium alloy substrate is cooled after spraying.
The high entropy alloy powder used in example 5 was FeCoCrNiMn with a particle size of 20-53. Mu.m.
Example 5 the process parameters for plasma spraying were: the main spraying gas is argon, and the flow of the argon is 2.5m 3 And/h, the spraying auxiliary gas is hydrogen, and the flow rate of the hydrogen is 0.5m 3 /h; the current is 750A, the powder feeding rate is 340g/min, and the spraying distance is 80mm.
High-entropy alloy electrode catalytic oxygen evolution performance prepared in example 5: at a current density of 10mA/cm 2 And 100 mA/cm 2 When the overpotential was 337mV and 380mV, respectively.
Example 6
The invention provides a preparation method of a self-supporting high-entropy alloy electrode for electrolytic hydrogen production, which comprises the following steps:
(1) Firstly, carrying out sand blasting roughening treatment on a titanium alloy substrate with the specification of 300 multiplied by 100 multiplied by 2mm by using white corundum, wherein the sand blasting angle is 60 degrees, the air pressure is 0.5MPa, the sand blasting distance is 100mm, and the surface roughness of the substrate after the sand blasting roughening treatment is Ra5 mu m;
(2) And (2) spraying the high-entropy alloy powder on the surface of the titanium alloy substrate subjected to roughening treatment in the step (1) by adopting a cold air dynamic spraying process, wherein 7 layers of high-entropy alloy are sprayed, the thickness of a single layer of high-entropy alloy is 15-20 mu m, the total thickness of a high-entropy alloy coating is 125 mu m, and the self-supporting high-entropy alloy electrode is obtained after the titanium alloy substrate is cooled after spraying.
The high entropy alloy powder used in example 6 was FeCoCrNiMn with a particle size of 20-53. Mu.m.
The process parameters for cold aerodynamic spraying in example 6 were: nitrogen is used as working gas and powder carrying gas, the pressure of the nitrogen is 7MPa, the temperature is 800 ℃, the powder feeding rate is 80g/min, and the spraying distance is 30mm.
High-entropy alloy electrode catalytic oxygen evolution performance prepared in example 6: at a current density of 10mA/cm 2 And 100 mA/cm 2 When the overpotential was 325mV and 373mV, respectively.
Example 7
The invention provides a preparation method of a self-supporting high-entropy alloy electrode for electrolytic hydrogen production, which comprises the following steps:
(1) Firstly, carrying out sand blasting roughening treatment on a titanium alloy substrate with the specification of 300 multiplied by 100 multiplied by 2mm by using white corundum, wherein the sand blasting angle is 70 degrees, the air pressure is 0.4MPa, the sand blasting distance is 120mm, and the surface roughness of the substrate after the sand blasting roughening treatment is Ra7 mu m;
(2) And (2) spraying high-entropy alloy powder on the surface of the titanium alloy substrate subjected to roughening treatment in the step (1) by adopting a plasma spraying process, wherein 5 layers of high-entropy alloy are sprayed, the thickness of a single layer of high-entropy alloy is 10-15 mu m, the total thickness of a high-entropy alloy coating is 65 mu m, and the self-supporting high-entropy alloy electrode is obtained after the titanium alloy substrate is cooled after spraying.
The high entropy alloy powder used in example 7 was CoCrFeNiNb with a particle size of 20-53. Mu.m.
Example 7 the process parameters for plasma spraying were: the main spraying gas is argon, and the flow of the argon is 2.5m 3 And/h, the spraying auxiliary gas is hydrogen, and the flow rate of the hydrogen is 0.6m 3 /h; the current is 800A, the powder feeding rate is 35g/min, and the spraying distance is 100mm.
High-entropy alloy electrode catalytic oxygen evolution performance prepared in example 7: at a current density of 10mA/cm 2 And 100 mA/cm 2 When the over potential is 328mV and 384mV respectively.
Example 8
The invention provides a preparation method of a self-supporting high-entropy alloy electrode for electrolytic hydrogen production, which comprises the following steps:
(1) Firstly, carrying out sand blasting roughening treatment on a stainless steel substrate with the specification of 500 multiplied by 5mm by using white corundum, wherein the sand blasting angle is 65 degrees, the air pressure is 0.3MPa, the sand blasting distance is 90mm, and the surface roughness of the substrate after the sand blasting roughening treatment is Ra6 mu m;
(2) And (2) spraying high-entropy alloy powder on the surface of the roughened stainless steel substrate in the step (1) by adopting a supersonic flame spraying process, wherein 3 layers of high-entropy alloy are sprayed, the thickness of a single layer of high-entropy alloy is 15-20 mu m, the total thickness of a high-entropy alloy coating is 50 mu m, and the self-supporting high-entropy alloy electrode is obtained after the stainless steel gold substrate is cooled after spraying.
The high entropy alloy powder used in example 8 was CoFeNiMoAl with a particle size of 20-53. Mu.m.
The process parameters for the supersonic flame spraying in example 8 are: the fuel gas is aviation kerosene, the flow rate of the kerosene is 6.5gal/h, the combustion-supporting gas is high-pressure oxygen, the flow rate of the oxygen is 2000scf/h, the powder feeding gas is nitrogen, and the flow rate of the nitrogen is 20SCFH; the powder feeding rate is 65g/min, and the spraying distance is 350mm.
High-entropy alloy electrode catalytic oxygen evolution performance prepared in example 8: at a current density of 10mA/cm 2 And 100 mA/cm 2 The overpotential was 322mV and 356mV, respectively.
Example 9
The invention provides a preparation method of a self-supporting high-entropy alloy electrode for electrolytic hydrogen production, which comprises the following steps:
(1) Firstly, carrying out sand blasting roughening treatment on a titanium alloy substrate with the specification of 300 multiplied by 100 multiplied by 2mm by using white corundum, wherein the sand blasting angle is 75 degrees, the air pressure is 0.4MPa, the sand blasting distance is 130mm, and the surface roughness of the substrate after the sand blasting roughening treatment is Ra4 mu m;
(2) And (2) spraying high-entropy alloy powder on the surface of the titanium alloy substrate subjected to roughening treatment in the step (1) by adopting a plasma spraying process, wherein 6 layers of high-entropy alloy are sprayed, the thickness of a single layer of high-entropy alloy is 10-15 mu m, the total thickness of a high-entropy alloy coating is 80 mu m, and the self-supporting high-entropy alloy electrode is obtained after the titanium alloy substrate is cooled after spraying is finished.
The high entropy alloy powder used in example 9 was CoFeNiCuAl with a particle size of 20-53. Mu.m.
Example 9 the process parameters for plasma spraying were: the main spraying gas is argon, and the flow of the argon is 3.0m 3 And/h, the spraying auxiliary gas is hydrogen, and the flow rate of the hydrogen is 0.3m 3 /h; the current was set to 700A and,the powder feeding rate is 45g/min, and the spraying distance is 70mm.
High-entropy alloy electrode catalytic oxygen evolution performance prepared in example 9: at a current density of 10mA/cm 2 And 100 mA/cm 2 The overpotential was 319mV and 364mV, respectively.
Example 10
The invention provides a preparation method of a self-supporting high-entropy alloy electrode for electrolytic hydrogen production, which comprises the following steps:
(1) Firstly, carrying out sand blasting roughening treatment on a stainless steel substrate with the specification of 500 multiplied by 5mm by using white corundum, wherein the sand blasting angle is 80 degrees, the air pressure is 0.5MPa, the sand blasting distance is 140mm, and the surface roughness of the substrate after the sand blasting roughening treatment is Ra8 mu m;
(2) And (2) spraying high-entropy alloy powder on the surface of the coarsened stainless steel substrate in the step (1) by adopting a cold air dynamic spraying process, wherein 8 layers of high-entropy alloy are sprayed, the thickness of a single-layer high-entropy alloy is 5-10 mu m, the total thickness of a high-entropy alloy coating is 55 mu m, and the self-supporting high-entropy alloy electrode is obtained after the stainless steel substrate is cooled after the spraying is completed.
The high entropy alloy powder used in example 10 was CoNiFeMnCu with a particle size of 20-53. Mu.m.
The process parameters for cold aerodynamic spraying in example 10 were: nitrogen is used as working gas and powder carrying gas, the pressure of the nitrogen is 8Mpa, the temperature is 850 ℃, the powder feeding rate is 75g/min, and the spraying distance is 25mm.
High-entropy alloy electrode catalytic oxygen evolution performance prepared in example 10: at a current density of 10mA/cm 2 And 100 mA/cm 2 The overpotential was 324mV and 363mV, respectively.
The invention is verified by repeated experiments:
when the thickness of the sprayed high-entropy alloy monolayer is 5-10 mu m, 6-10 layers are sprayed, and the total thickness of the high-entropy alloy coating is 40-100 mu m, the prepared self-supporting high-entropy alloy electrode has excellent electrocatalytic performance;
when the thickness of the sprayed high-entropy alloy monolayer is 10-15 mu m, 4-8 layers are sprayed, and the total thickness of the high-entropy alloy coating is 50-120 mu m, the prepared self-supporting high-entropy alloy electrode has the most excellent electrocatalytic performance;
when the thickness of the sprayed high-entropy alloy monolayer is 15-20 mu m, 3-6 layers are sprayed, and the total thickness of the high-entropy alloy coating is 50-120 mu m, the prepared self-supporting high-entropy alloy electrode has excellent electrocatalytic performance;
in order to obtain the self-supporting high-entropy alloy electrode with the most excellent electrocatalytic performance, the industrialized popularization is facilitated, the cost is effectively controlled, when the thickness of a sprayed high-entropy alloy is preferably 10-15 mu m, 4-8 layers of the high-entropy alloy is sprayed, and the total thickness of the high-entropy alloy coating is 50-120 mu m.
The self-supporting high-entropy alloy electrode is prepared by spraying the high-entropy alloy powder on a titanium alloy plate or a stainless steel plate by adopting a multilayer spraying technology, and the electrode does not need any adhesive and has good conductivity; the coating electrode has the advantages of abundant raw materials, controllable preparation conditions and high bonding strength; at a current density of 10mA/cm 2 And 100 mA/cm 2 When the oxygen evolution overpotential is 312mV and 335mV respectively, the catalyst shows excellent electrocatalytic performance. The coated electrode with high catalytic activity, excellent catalytic stability and extremely strong practical applicability greatly promotes the water electrolysis energy conversion efficiency, and is a novel oxygen evolution catalytic electrode.
The foregoing examples merely illustrate specific embodiments of the invention, which are described in greater detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (8)

1. The preparation method of the self-supporting high-entropy alloy electrode for electrolytic hydrogen production is characterized by comprising the following steps of:
(1) Firstly, carrying out sand blasting roughening treatment on a substrate by using white corundum, wherein the sand blasting angle is 60-80 degrees, the air pressure is 0.3-0.5 MPa, the sand blasting distance is 80-150 mm, and the surface roughness of the substrate after the sand blasting roughening treatment is Ra (3-10) mu m;
(2) Spraying the high-entropy alloy powder on the surface of the substrate subjected to roughening treatment in the step (1) by adopting a spraying process to obtain a high-entropy alloy coating, and cooling the substrate to obtain a self-supporting high-entropy alloy electrode;
and spraying 1-10 layers of high-entropy alloy on the surface of the substrate, wherein the single-layer thickness of the high-entropy alloy coating is 5-20 mu m, and the total thickness is 5-200 mu m.
2. The method for preparing the self-supporting high-entropy alloy electrode for electrolytic hydrogen production according to claim 1, which is characterized in that: the substrate is a titanium alloy plate or a stainless steel plate.
3. The method for preparing the self-supporting high-entropy alloy electrode for electrolytic hydrogen production according to claim 1, which is characterized in that: the high-entropy alloy component is any one of CoCrFeNiMn, coCrFeNiAl, coCrFeNiNb, coFeNiMoAl, coFeNiCuAl or CoNiFeMnCu.
4. A method for preparing a self-supporting high-entropy alloy electrode for electrolytic hydrogen production according to any one of claims 1 to 3, characterized in that: the spraying temperature is controlled to be 70-95 ℃.
5. A method for preparing a self-supporting high-entropy alloy electrode for electrolytic hydrogen production according to any one of claims 1 to 3, characterized in that: the spraying process is plasma spraying, supersonic flame spraying or cold air power spraying.
6. The method for preparing the self-supporting high-entropy alloy electrode for electrolytic hydrogen production according to claim 5, wherein the plasma spraying process is as follows: the spraying main gas is argon, and the flow of the argon is 2-3.5 m 3 And/h, the spraying auxiliary gas is hydrogen, and the flow rate of the hydrogen is 0.3-0.8 m 3 /h; the current is 600-900A, the powder feeding rate is 30-50 g/min, and the spraying distance is 60-120 mm.
7. The method for preparing the self-supporting high-entropy alloy electrode for electrolytic hydrogen production according to claim 5, wherein the process of supersonic flame spraying is as follows: the fuel gas is aviation kerosene, the flow rate of the kerosene is 5-6.5gal/h, the combustion-supporting gas is high-pressure oxygen, the flow rate of the oxygen is 1600-2200scf/h, the powder feeding gas is nitrogen, and the flow rate of the nitrogen is 20-30SCFH; the powder feeding rate is 20-80g/min, and the spraying distance is 300-400mm.
8. The method for preparing the self-supporting high-entropy alloy electrode for electrolytic hydrogen production according to claim 5, wherein the cold air power spraying process is as follows: nitrogen is used as working gas and powder carrying gas, the pressure of the nitrogen is 5-10Mpa, the temperature is 300-1000 ℃, the powder feeding rate is 50-100g/min, and the spraying distance is 20-30mm.
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