CN117403159A - Method for improving electrochemical oxygen evolution catalytic performance of nickel-iron-based amorphous alloy - Google Patents
Method for improving electrochemical oxygen evolution catalytic performance of nickel-iron-based amorphous alloy Download PDFInfo
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- CN117403159A CN117403159A CN202311230376.7A CN202311230376A CN117403159A CN 117403159 A CN117403159 A CN 117403159A CN 202311230376 A CN202311230376 A CN 202311230376A CN 117403159 A CN117403159 A CN 117403159A
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 256
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 78
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000001301 oxygen Substances 0.000 title claims abstract description 64
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 64
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000956 alloy Substances 0.000 claims abstract description 95
- 238000011282 treatment Methods 0.000 claims abstract description 56
- 238000010438 heat treatment Methods 0.000 claims abstract description 52
- 239000002131 composite material Substances 0.000 claims abstract description 50
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 76
- 229910052786 argon Inorganic materials 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 238000005266 casting Methods 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 229910001315 Tool steel Inorganic materials 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 13
- 238000004381 surface treatment Methods 0.000 claims description 13
- 238000011068 loading method Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 239000012670 alkaline solution Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 229910045601 alloy Inorganic materials 0.000 description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- 239000003792 electrolyte Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 10
- 230000005489 elastic deformation Effects 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D18/00—Pressure casting; Vacuum casting
- B22D18/06—Vacuum casting, i.e. making use of vacuum to fill the mould
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/34—Methods of heating
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D10/00—Modifying the physical properties by methods other than heat treatment or deformation
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/001—Heat treatment of ferrous alloys containing Ni
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/0081—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for slabs; for billets
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- 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
- C22C1/11—Making amorphous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/003—Making ferrous alloys making amorphous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/02—Amorphous alloys with iron as the major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
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- 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
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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- 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
- C22F3/00—Changing the physical structure of non-ferrous metals or alloys by special physical methods, e.g. treatment with neutrons
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- 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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- 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
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Abstract
The invention discloses a method for improving electrochemical oxygen evolution catalytic performance of a nickel-iron-based amorphous alloy, and relates to the field of electrolytic water catalysts. Firstly preparing a nickel-iron-based amorphous alloy with micro-doped Y and La composite rare earth elements through rapid cooling, improving the energy state of the surface of the amorphous alloy by utilizing high-frequency vibration, forming a current loop with the amorphous alloy through a high-frequency vibration pressure head, and further improving the energy state of the surface of the amorphous alloy by applying current. The invention adopts high-density mechanical energy input and cooperated current heating energy input to ensure that the surface of the amorphous alloy material in an unbalanced state is in a higher energy state, thereby improving the oxygen evolution reaction activity and the catalytic efficiency of the amorphous alloy in alkaline solution. The treatment process is simple and efficient, energy-saving and environment-friendly, and is suitable for preparing the high-performance nickel-iron-based amorphous alloy electrolytic water oxygen evolution catalyst material.
Description
Technical Field
The invention relates to the technical field of metal catalysts for producing hydrogen by water electrolysis, in particular to a method for improving electrochemical oxygen evolution catalytic performance of a nickel-iron-based amorphous alloy.
Background
As a novel efficient clean energy source, the hydrogen energy has great significance for constructing a low-carbon energy system, and the wide utilization of the hydrogen energy plays a great role in national strategies of carbon reaching peaks and carbon neutralization. As a simple hydrogen production method, electrolytic water hydrogen production is widely used in industrial applications, and thus improvement of the performance of an electrochemical oxygen evolution catalyst is an important subject in the field. Unlike conventional crystalline metallic materials, amorphous alloys are amorphous metallic materials formed by rapid cooling of a high temperature melt. The amorphous alloy has a unique long-range disordered microstructure, so that the amorphous alloy has excellent properties different from crystalline alloy, such as high strength, high hardness, soft magnetic property and the like, and therefore, the amorphous alloy has a wide application prospect in the field of modern materials. In addition, amorphous alloys can also be used as potential functional catalytic materials due to their non-equilibrium energy state.
The iron-based amorphous alloy is used as a non-noble metal oxygen evolution catalytic material, and is widely focused by scientific researchers in the field of electrolytic water catalysis. Patent application publication No. CN115637459A discloses an electrocatalytic oxygen evolution catalyst and a method for preparing the same. The invention adopts a co-sputtering method to prepare a FeNiC amorphous alloy film doped with pore-forming metal elements on the surface of a substrate, carries out vacuum evaporation treatment on the FeNiC amorphous alloy film doped with pore-forming metal elements, removes pore-forming metal to obtain a FeNiC amorphous alloy film with a nano porous structure, carries out vulcanization treatment on the FeNiC amorphous alloy film with the nano porous structure by a chemical vapor deposition method through sulfur powder, and can effectively reduce oxygen evolution overpotential in an alkaline environment. Patent application publication No. CN113549952A discloses a method for preparing Fe-based porous catalytic materials for efficient oxygen evolution reactions based on dealloying. The Fe-based amorphous alloy strip is subjected to electrochemical dealloying treatment, so that the required Fe-based porous catalytic material is obtained. The Fe-based porous material has controllable specific surface area, good conductivity, multiple active sites and high electrocatalytic activity, and is a good oxygen evolution reaction electrocatalyst. The preparation method has relatively complex process, can produce pollution such as waste liquid discharge, is unfavorable for large-scale industrial production, and can not realize the regulation and control of the energy transformation of the amorphous alloy.
In order to further improve the activity of the amorphous alloy electrochemical oxygen evolution electrode material, a green energy-saving treatment method capable of regulating and controlling the intrinsic energy state of the amorphous alloy is required.
Disclosure of Invention
The invention aims to: the invention aims to provide a method for improving electrochemical oxygen evolution catalytic performance of a nickel-iron-based amorphous alloy by regulating and controlling the atomic energy state of the surface of the amorphous alloy.
The technical scheme is as follows: a method for improving electrochemical oxygen evolution catalytic performance of a nickel-iron-based amorphous alloy, the preparation method comprising the following steps:
(1) Preparing a ferronickel-based amorphous alloy containing Y and La composite rare earth elements in a micro-doped manner;
(2) The energy state of the surface of the nickel-iron-based amorphous alloy is changed by using high-frequency vibration of the pressure head, a current loop is formed by the high-frequency vibration pressure head and the amorphous alloy, and the energy state of the surface of the amorphous alloy is further improved by current heating, so that the surface of the amorphous alloy material is in a higher unbalanced energy state.
The method utilizes high-frequency vibration to change the energy state of the surface of the amorphous alloy, and simultaneously forms a current loop with the amorphous alloy through a high-frequency vibration pressure head, and the energy state of the surface of the amorphous alloy is further improved by cooperative current heating, so that the surface of the amorphous alloy in an unbalanced state is in a higher energy state, and the activity and the reaction rate of oxygen evolution reaction in the high-alkaline solution of the amorphous alloy are improved.
Preferably, in the step (1), the molar percentage range of the ferronickel-based amorphous alloy is as follows: fe:30-40%, si:5-8%, B:3-6%, pd:3-5%, (y+la): 3-5%, and the balance of Ni.
Further, the preparation method of the ferronickel-based amorphous alloy comprises the following steps: according to the chemical formula of the alloy material, ni, fe, si, pd, Y, la and FeB high-purity raw materials with corresponding weight are weighed, are uniformly melted in a vacuum arc furnace, and are subjected to suction casting by adopting a liquid nitrogen cooling copper mold to obtain the nickel-iron-based amorphous alloy plate.
Further, in the step (2), a high-frequency vibration load is applied to the surface of the ferronickel-based amorphous alloy by adopting a pressure head, and a current loop is formed by the conductive pressure head and the ferronickel-based amorphous alloy at the same time, so that the appointed position of the ferronickel-based amorphous alloy is treated; and then moving the position of the nickel-iron-based amorphous alloy, and sequentially finishing the treatment of the surface of the nickel-iron-based amorphous alloy.
Furthermore, the pressure head is square in shape, the pressure head material is conductive grinding tool steel, and the side length of the pressure head is 1-5mm.
Further, the pressure exerted by the pressure head is 300-700MPa; the vibration frequency of the high-frequency vibration is 20-50kHz, the vibration amplitude is 50-100 mu m, and the vibration loading time is 0.1-0.5 seconds.
Further, the pressure head and the ferronickel base amorphous alloy form a current loop, and the current density of the loop is 600-6000A/mm 2 。
Further, the moving distance of the pressure head is set to be the value of the side length of the pressure head, and the surface treatment of the nickel-iron-based amorphous alloy is sequentially completed.
Furthermore, flowing high-purity argon is used for protection in high-frequency vibration, and the argon flow rate of the contact area of the pressure head and the ferronickel-based amorphous alloy is 50-200L/min.
The invention provides a method for improving electrochemical oxygen evolution catalysis performance of a nickel-iron-based amorphous alloy, which is characterized in that a nickel-iron-based amorphous alloy containing Y and La and being doped with trace rare earth elements is prepared, the energy state and stress state of the surface of the amorphous alloy are changed by utilizing high-frequency vibration, meanwhile, a current loop is formed by a high-frequency vibration pressure head and the amorphous alloy, the energy state of the surface of the amorphous alloy is further improved by cooperative current heating, and the coupling effect is generated between the current heating energy and mechanical vibration energy input, so that the surface of the amorphous alloy in an unbalanced state is in a higher energy state, and the catalysis activity of oxygen evolution reaction of the amorphous alloy in an alkaline solution is improved. In addition, the invention reduces the surface oxidation degree of the nickel-iron-based amorphous alloy in the treatment process by micro doping of the Y and La composite rare earth elements, changes the semiconductor characteristic of the material surface in the energy input process, and obviously improves the oxygen evolution reaction rate and the cycle stability of the nickel-iron-based amorphous alloy in alkaline solution.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) The process is simple, energy-saving and environment-friendly, and no solid-liquid waste is discharged.
(2) The amorphous alloy matrix is directly treated, and the catalytic active sites are firmly combined with the matrix, so that the stability of the oxygen evolution electrode in the working process is improved.
(3) According to different sizes and functions of the sample, different processes can be selectively carried out on specific positions, and personalized design of material functions is realized.
(4) The crystallization of the amorphous alloy is not caused in the treatment process, and the excellent mechanical property of the amorphous alloy is maintained.
Drawings
FIG. 1 is a schematic diagram of a high frequency vibratory composite current heat treatment of amorphous alloys.
FIG. 2 is an X-ray diffraction pattern of the as-cast and high frequency vibration composite current heat treated nickel-iron based amorphous alloy of example 1.
FIG. 3 is a graph showing the linear voltammetric sweep of an as-cast and high frequency vibratory composite current heat treated nickel-iron based amorphous alloy in a 1M KOH electrolyte as described in example 1.
FIG. 4 is an electrochemical impedance spectrum of the as-cast and high frequency vibration composite current heat treated ferronickel-based amorphous alloy of example 1 in a 1M KOH electrolyte.
FIG. 5 shows that the oxygen evolution current density of the nickel-iron-based amorphous alloy in the 1M KOH electrolyte is constantly 10mA/cm after the heating treatment of the as-cast and high-frequency vibration composite current in example 1 2 And a change curve of the potential with time.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
According to the embodiment of the invention, the surface energy state and stress state of the nickel-iron-based amorphous alloy are changed by high-frequency vibration composite current heating treatment, the oxygen evolution performance of the material is tested in 1M KOH electrolyte by using an electrochemical workstation, and the influence of different process treatments on the electrochemical oxygen evolution catalytic performance of the iron-nickel-based amorphous alloy is evaluated.
Example 1
The embodiment provides a method for improving electrochemical oxygen evolution catalytic performance of a nickel-iron-based amorphous alloy, which comprises the following steps:
preparing a nickel-iron-based amorphous alloy material: according to the chemical formula of the amorphous alloy material, the high-purity Ni, fe, si, pd, Y, la and FeB raw materials with corresponding weight are weighed and melted in a vacuum arc furnace to obtain Ni with the mole percentage of 47 Fe 35 Si 6 B 4 Pd 4 Y 2 La 2 Is a uniform alloy ingot. Under the protection of high-purity argon, the alloy is melted uniformly in a vacuum arc furnace, and a ferronickel-based amorphous alloy plate with the thickness of 1mm and the width of 10mm is obtained by adopting liquid nitrogen cooling copper die suction casting. The prepared material was structurally characterized using an X-ray diffractometer.
High-frequency vibration composite current heating treatment of nickel-iron-based amorphous alloy: and ultrasonically cleaning the amorphous alloy material by using deionized water and absolute ethyl alcohol. As shown in fig. 1, the energy state and stress state of the amorphous alloy surface are changed by using high-frequency loading of a pressure head; the high-frequency vibration pressure head and the amorphous alloy form a current loop, and the energy state of the surface of the amorphous alloy is further improved through current heating, so that the designated position is treated. The sample was then moved along the X, Y axis, which in turn completes the treatment of the amorphous alloy surface. Fixing the amorphous alloy on a high-frequency vibration workbench, applying a load to the surface of the amorphous alloy material by using a square pressure head of high-conductivity grinding tool steel with the side length of 2mm, wherein the load pressure is 500MPa, so that a sample is in an elastic deformation area, the high-frequency vibration load frequency is 25kHz, the amplitude is 70 mu m, the pressure head and the amorphous alloy sample form a current loop, and the conducting current density of the loop is 3000A/mm 2 The processing time per location was 0.3 seconds. And then the sample positions are respectively moved along the direction X, Y according to the step length of 2mm, and the amorphous alloy surface treatment is sequentially completed. And (3) protecting the contact area of the pressure head and the sample by flowing high-purity argon, wherein the flow rate of the argon is 100L/min.
Characterization of electrochemical oxygen evolution catalytic performance of nickel-iron-based amorphous alloy: the electrochemical oxygen evolution catalysis performance of the amorphous alloy under the room temperature condition is tested by adopting an electrochemical workstation, a standard three-electrode system is adopted, wherein a platinum sheet electrode is a counter electrode, a Hg/HgO electrode is a reference electrode, and the electrolyte is 1M KOH aqueous solution. The linear cyclic voltammogram was tested at a scan rate of 20 mV/s. And (3) characterizing the charge transfer resistance value of the surface of the amorphous alloy material by using electrochemical impedance spectroscopy. The stability of the oxygen evolution catalytic performance was evaluated using a constant current test.
Ni in as-cast state and after high-frequency vibration composite current heating treatment 47 Fe 35 Si 6 B 4 Pd 4 Y 2 La 2 The X-ray diffraction pattern of the amorphous alloy material is shown in fig. 2. As can be seen from FIG. 2, there is no sharp diffraction peak in the diffraction pattern, indicating that Ni was produced 47 Fe 35 Si 6 B 4 Pd 4 Y 2 La 2 The material is amorphous. FIG. 3 is a graph showing the linear voltammetric sweep of an as-cast and high frequency vibratory composite current heat treated amorphous alloy material in a 1M KOH electrolyte. At a current density of up to 10mA/cm 2 When the overpotential of the as-cast amorphous alloy is 381mV, the overpotential of the amorphous alloy after high-frequency vibration composite current heating treatment is 276mV, and the overpotential of oxygen evolution reaction is reduced by 105mV, which shows that the high-frequency vibration composite current heating treatment improves Ni 47 Fe 35 Si 6 B 4 Pd 4 Y 2 La 2 Electrochemical oxygen evolution catalytic performance of amorphous alloys. FIG. 4 is an electrochemical impedance spectrum of an as-cast amorphous alloy material after high frequency vibration composite current heating treatment in a 1M KOH electrolyte. Fitting to obtain the charge transfer resistance of 983Ω·cm of the as-cast amorphous alloy 2 The charge transfer resistance of the amorphous alloy after high-frequency vibration composite current heating treatment is 450 Ω & cm 2 . The electric resistance of the surface charge transfer of the material is reduced, which indicates that the surface conductivity and the catalytic activity of the amorphous alloy material are improved after the high-frequency vibration composite current heating treatment. FIG. 5 shows that the oxygen evolution current density of the alloy in a 1M KOH electrolyte is constantly 10mA/cm after the alloy is heated by high-frequency vibration composite current in an as-cast state 2 And a change curve of the potential with time. Through a constant current catalytic test for 80 hours, the overpotential of the amorphous alloy material is increased by 47mV, which proves that the ferronickel-based amorphous alloy after high-frequency vibration composite current heating treatment has good catalytic stability.
From the above results, it can be derived that: the energy state and stress state of the nickel-iron-based amorphous alloy material can be changed through high-frequency vibration composite current heating treatment, and the electrochemical oxygen evolution catalysis performance of the nickel-iron-based amorphous alloy in alkaline solution is improved.
Example 2
The embodiment provides a method for improving electrochemical oxygen evolution catalytic performance of a nickel-iron-based amorphous alloy, which comprises the following steps:
preparing a nickel-iron-based amorphous alloy material: according to the chemical formula of the amorphous alloy material, the high-purity Ni, fe, si, pd, Y, la and FeB raw materials with corresponding weight are weighed and melted in a vacuum arc furnace to obtain Ni with the mole percentage of 53 Fe 30 Si 8 B 3 Pd 3 Y 2 La 1 Is a uniform alloy ingot. Under the protection of high-purity argon, the alloy is melted uniformly in a vacuum arc furnace, and a ferronickel-based amorphous alloy plate with the thickness of 1mm and the width of 10mm is obtained by adopting liquid nitrogen cooling copper die suction casting. The prepared material was structurally characterized using an X-ray diffractometer.
High-frequency vibration composite current heating treatment of nickel-iron-based amorphous alloy: and ultrasonically cleaning the amorphous alloy material by using deionized water and absolute ethyl alcohol. Fixing the amorphous alloy on a high-frequency vibration workbench, applying a load to the surface of the amorphous alloy material by using a square pressure head of high-conductivity grinding tool steel with the side length of 1mm, wherein the load pressure is 700MPa, so that a sample is in an elastic deformation area, the high-frequency vibration load frequency is 40kHz, the amplitude is 100 mu m, the pressure head and the amorphous alloy sample form a current loop, and the on-current density of the loop is 600A/mm 2 The processing time per location was 0.1 seconds. And then the sample positions are respectively moved along the direction X, Y according to the step length of 1mm, and the amorphous alloy surface treatment is sequentially completed. And (3) protecting the contact area of the pressure head and the sample by flowing high-purity argon, wherein the flow rate of the argon is 50L/min.
Linear voltammetric scan curves in 1M KOH electrolyte showed: at a current density of up to 10mA/cm 2 When the overvoltage of the as-cast amorphous alloy is 385mV, the overvoltage of the amorphous alloy after high-frequency vibration composite current heating treatment is 289mV, and the oxygen evolution reaction overvoltage is reduced by 96mV, which shows that the high-frequency vibration composite current heating treatment improves the electrochemical oxygen evolution catalysis performance of the iron-nickel-based amorphous alloy.
Example 3
The embodiment provides a method for improving electrochemical oxygen evolution catalytic performance of a nickel-iron-based amorphous alloy, which comprises the following steps:
preparing a nickel-iron-based amorphous alloy material: according to the chemical formula of the amorphous alloy material, the high-purity Ni, fe, si, pd, Y, la and FeB raw materials with corresponding weight are weighed and melted in a vacuum arc furnace to obtain Ni with the mole percentage of 47 Fe 40 Si 5 B 6 Pd 5 Y 3 La 2 Is a uniform alloy ingot. Under the protection of high-purity argon, the alloy is melted uniformly in a vacuum arc furnace, and a ferronickel-based amorphous alloy plate with the thickness of 1mm and the width of 10mm is obtained by adopting liquid nitrogen cooling copper die suction casting. The prepared material was structurally characterized using an X-ray diffractometer.
High-frequency vibration composite current heating treatment of nickel-iron-based amorphous alloy: and ultrasonically cleaning the amorphous alloy material by using deionized water and absolute ethyl alcohol. Fixing the amorphous alloy on a high-frequency vibration workbench, applying a load to the surface of the amorphous alloy material by using a square pressure head of high-conductivity grinding tool steel with the side length of 5mm, wherein the load pressure is 300MPa, so that a sample is in an elastic deformation area, the high-frequency vibration load frequency is 50kHz, the amplitude is 50 mu m, the pressure head and the amorphous alloy sample form a current loop, and the conducting current density of the loop is 6000A/mm 2 The processing time per location was 0.5 seconds. And then the sample positions are respectively moved along the direction X, Y according to the step length of 5mm, and the amorphous alloy surface treatment is sequentially completed. And (3) protecting the contact area of the pressure head and the sample by flowing high-purity argon, wherein the flow rate of the argon is 200L/min.
Linear voltammetric scan curves in 1M KOH electrolyte showed: at a current density of up to 10mA/cm 2 When the overpotential of the as-cast amorphous alloy is 384mV, the overpotential of the amorphous alloy after high-frequency vibration composite current heating treatment is 287mV, and the overpotential of the oxygen evolution reaction is reduced by 97mV, which indicates that the electrochemical oxygen evolution catalysis performance of the iron-nickel based amorphous alloy is improved by the high-frequency vibration composite current heating treatment.
Example 4
The embodiment provides a method for improving electrochemical oxygen evolution catalytic performance of a nickel-iron-based amorphous alloy, which comprises the following steps:
preparing a nickel-iron-based amorphous alloy material: according to amorphousAlloy material chemical formula, weighing high-purity Ni, fe, si, pd, Y, la and FeB raw materials with corresponding weight, and melting in a vacuum arc furnace to obtain Ni with mole percentage 39 Fe 43 Si 6 B 4 Pd 5 Y 2 La 1 Is a uniform alloy ingot. Under the protection of high-purity argon, the alloy is melted uniformly in a vacuum arc furnace, and a ferronickel-based amorphous alloy plate with the thickness of 1mm and the width of 10mm is obtained by adopting liquid nitrogen cooling copper die suction casting. The prepared material was structurally characterized using an X-ray diffractometer.
High-frequency vibration composite current heating treatment of nickel-iron-based amorphous alloy: and ultrasonically cleaning the amorphous alloy material by using deionized water and absolute ethyl alcohol. Fixing the amorphous alloy on a high-frequency vibration workbench, applying a load to the surface of the amorphous alloy material by using a square pressure head of high-conductivity grinding tool steel with the side length of 4mm, wherein the load pressure is 500MPa, so that a sample is in an elastic deformation area, the high-frequency vibration load frequency is 20kHz, the amplitude is 80 mu m, the pressure head and the amorphous alloy sample form a current loop, and the conducting current density of the loop is 3000A/mm 2 The processing time per location was 0.3 seconds. And then the sample positions are respectively moved along the direction X, Y according to the step length of 4mm, and the amorphous alloy surface treatment is sequentially completed. And (3) protecting the contact area of the pressure head and the sample by flowing high-purity argon, wherein the flow rate of the argon is 100L/min.
Linear voltammetric scan curves in 1M KOH electrolyte showed: at a current density of up to 10mA/cm 2 When the over potential of the as-cast amorphous alloy is 382mV, the over potential of the amorphous alloy after high-frequency vibration composite current heating treatment is 284mV, and the over potential of the oxygen evolution reaction is reduced by 98mV, which shows that the electrochemical oxygen evolution catalysis performance of the ferronickel-based amorphous alloy is improved by the high-frequency vibration composite current heating treatment.
Example 5
The embodiment provides a method for improving electrochemical oxygen evolution catalytic performance of a nickel-iron-based amorphous alloy, which comprises the following steps:
preparing a nickel-iron-based amorphous alloy material: according to the chemical formula of the amorphous alloy material, the high-purity Ni, fe, si, pd, Y, la and FeB raw materials with corresponding weight are weighed and are in true conditionMelting in an empty arc furnace to obtain Ni with mole percent 37 Fe 46 Si 6 B 4 Pd 3 Y 2 La 2 Is a uniform alloy ingot. Under the protection of high-purity argon, the alloy is melted uniformly in a vacuum arc furnace, and a ferronickel-based amorphous alloy plate with the thickness of 1mm and the width of 10mm is obtained by adopting liquid nitrogen cooling copper die suction casting. The prepared material was structurally characterized using an X-ray diffractometer.
High-frequency vibration composite current heating treatment of nickel-iron-based amorphous alloy: and ultrasonically cleaning the amorphous alloy material by using deionized water and absolute ethyl alcohol. Fixing the amorphous alloy on a high-frequency vibration workbench, applying a load to the surface of the amorphous alloy material by using a high-conductivity grinding tool steel square pressure head with the side length of 3mm, wherein the load pressure is 400MPa, so that a sample is in an elastic deformation area, the high-frequency vibration load frequency is 30kHz, the amplitude is 70 mu m, the pressure head and the amorphous alloy sample form a current loop, and the conducting current density of the loop is 5000A/mm 2 The processing time per location was 0.3 seconds. And then the sample positions are respectively moved along the direction X, Y according to the step length of 3mm, and the amorphous alloy surface treatment is sequentially completed. And (3) protecting the contact area of the pressure head and the sample by flowing high-purity argon, wherein the flow rate of the argon is 150L/min.
Linear voltammetric scan curves in 1M KOH electrolyte showed: at a current density of up to 10mA/cm 2 When the overvoltage of the as-cast amorphous alloy is 390mV, the overvoltage of the amorphous alloy after high-frequency vibration composite current heating treatment is 287mV, and the oxygen evolution reaction overvoltage is reduced by 103mV, which shows that the high-frequency vibration composite current heating treatment improves the electrochemical oxygen evolution catalysis performance of the ferronickel-based amorphous alloy.
Comparative example 1
The comparative example differs from example 1 in that the amorphous alloy was treated using only high-frequency vibration, and no current was applied between the high-frequency vibration ram and the amorphous alloy.
Preparing a nickel-iron-based amorphous alloy material: according to the chemical formula of the amorphous alloy material, the high-purity Ni, fe, si, pd, Y, la and FeB raw materials with corresponding weight are weighed and melted in a vacuum arc furnace to obtain Ni with the mole percentage of 47 Fe 35 Si 6 B 4 Pd 4 Y 2 La 2 Is a uniform alloy ingot. Under the protection of high-purity argon, the alloy is melted uniformly in a vacuum arc furnace, and a ferronickel-based amorphous alloy plate with the thickness of 1mm and the width of 10mm is obtained by adopting liquid nitrogen cooling copper die suction casting. The prepared material was structurally characterized using an X-ray diffractometer.
High-frequency vibration treatment of nickel-iron-based amorphous alloy: and ultrasonically cleaning the amorphous alloy material by using deionized water and absolute ethyl alcohol. The amorphous alloy is fixed on a high-frequency vibration workbench, a square pressure head of high-conductivity grinding tool steel with the side length of 2mm is used for applying load to the surface of the amorphous alloy material, the load pressure is 500MPa, the sample is positioned in an elastic deformation area, the high-frequency vibration load frequency is 25kHz, the amplitude is 70 mu m, and the treatment time of each position is 0.3 seconds. And then the sample positions are respectively moved along the direction X, Y according to the step length of 2mm, and the amorphous alloy surface treatment is sequentially completed. And (3) protecting the contact area of the pressure head and the sample by flowing high-purity argon, wherein the flow rate of the argon is 100L/min.
The results of the linear voltammetric scan in 1M KOH electrolyte showed that: at a current density of up to 10mA/cm 2 When the overpotential of the as-cast amorphous alloy is 381mV, the overpotential of the amorphous alloy after high-frequency vibration treatment is 345mV, and the overpotential of the oxygen evolution reaction is reduced by 36mV, which shows that Ni can be improved only by high-frequency vibration treatment 47 Fe 35 Si 6 B 4 Pd 4 Y 2 La 2 The electrochemical oxygen evolution catalysis performance of the amorphous alloy is improved by only 34 percent of that of the amorphous alloy after the high-frequency vibration composite current heating treatment.
Comparative example 2
The present comparative example is different from example 1 in that the amorphous alloy is treated only by applying a current between the indenter and the amorphous alloy, and the amorphous alloy is not subjected to high-frequency vibration treatment using the indenter.
Preparing a nickel-iron-based amorphous alloy material: according to the chemical formula of the amorphous alloy material, the high-purity Ni, fe, si, pd, Y, la and FeB raw materials with corresponding weight are weighed and melted in a vacuum arc furnace to obtain Ni with the mole percentage of 47 Fe 35 Si 6 B 4 Pd 4 Y 2 La 2 Is a uniform alloy ingot. Under the protection of high-purity argon, the alloy is melted uniformly in a vacuum arc furnace, and a ferronickel-based amorphous alloy plate with the thickness of 1mm and the width of 10mm is obtained by adopting liquid nitrogen cooling copper die suction casting. The prepared material was structurally characterized using an X-ray diffractometer.
And (3) carrying out surface current heating treatment on the nickel-iron-based amorphous alloy: and ultrasonically cleaning the amorphous alloy material by using deionized water and absolute ethyl alcohol. Fixing the amorphous alloy on a high-frequency vibration workbench, forming a current loop by using a square pressure head of high-conductivity grinding tool steel with the side length of 2mm and the amorphous alloy, wherein the conducting current density of the loop is 3000A/mm 2 The processing time per location was 0.3 seconds. And then the sample positions are respectively moved along the direction X, Y according to the step length of 2mm, and the amorphous alloy surface treatment is sequentially completed. And (3) protecting the contact area of the pressure head and the sample by flowing high-purity argon, wherein the flow rate of the argon is 100L/min.
The results of the linear voltammetric scan in 1M KOH electrolyte showed that: at a current density of up to 10mA/cm 2 When the overpotential of the as-cast amorphous alloy is 381mV, the overpotential of the oxygen evolution reaction of the amorphous alloy is 389mV after the amorphous alloy is treated by applying current between the pressure head and the amorphous alloy, and the rise of 9mV indicates that the amorphous alloy is treated by forming a current loop between the pressure head and the amorphous alloy, thereby forming a heating annealing effect on the surface of the amorphous alloy and not improving Ni 47 Fe 35 Si 6 B 4 Pd 4 Y 2 La 2 Electrochemical oxygen evolution performance of amorphous alloys in alkaline solutions.
Comparative example 3
This comparative example differs from example 1 in the alloy composition.
Preparing a nickel-iron-based amorphous alloy material: according to the chemical formula of the amorphous alloy material, the high-purity Ni, fe, si, pd, Y, la and FeB raw materials with corresponding weight are weighed and melted in a vacuum arc furnace to obtain Ni with the mole percentage of 72 Fe 10 Si 6 B 4 Pd 4 Y 2 La 2 Are all of (1)And (5) homogenizing alloy cast ingots. And under the protection of high-purity argon, uniformly melting in a vacuum arc furnace, and performing suction casting by adopting a liquid nitrogen cooling copper die to obtain the nickel-iron-based alloy plate with the thickness of 1mm and the width of 10 mm. The X-ray diffraction result shows that the alloy plate has a crystalline structure and the ferronickel base amorphous alloy cannot be prepared.
Comparative example 4
The comparative example differs from example 1 in that the amorphous alloy component does not contain La and Y complex rare earth elements.
Preparing a nickel-iron-based amorphous alloy material: according to the chemical formula of the amorphous alloy material, the high-purity Ni, fe, si, pd and FeB raw materials with corresponding weight are weighed and melted in a vacuum arc furnace to obtain Ni with the mole percentage of 51 Fe 35 Si 6 B 4 Pd 4 Is a uniform alloy ingot. Under the protection of high-purity argon, the alloy is melted uniformly in a vacuum arc furnace, and a ferronickel-based amorphous alloy plate with the thickness of 1mm and the width of 10mm is obtained by adopting liquid nitrogen cooling copper die suction casting. The prepared material was structurally characterized using an X-ray diffractometer.
High-frequency vibration composite current heating treatment of nickel-iron-based amorphous alloy: and ultrasonically cleaning the amorphous alloy material by using deionized water and absolute ethyl alcohol. Fixing the amorphous alloy on a high-frequency vibration workbench, applying a load to the surface of the amorphous alloy material by using a square pressure head of high-conductivity grinding tool steel with the side length of 2mm, wherein the load pressure is 500MPa, so that a sample is in an elastic deformation area, the high-frequency vibration load frequency is 25kHz, the amplitude is 70 mu m, the pressure head and the amorphous alloy sample form a current loop, and the conducting current density of the loop is 3000A/mm 2 The processing time per location was 0.3 seconds. And then the sample positions are respectively moved along the direction X, Y according to the step length of 2mm, and the amorphous alloy surface treatment is sequentially completed. And (3) protecting the contact area of the pressure head and the sample by flowing high-purity argon, wherein the flow rate of the argon is 100L/min.
The results of the linear voltammetric scan in 1M KOH electrolyte showed that: at a current density of up to 10mA/cm 2 When the overpotential of the as-cast amorphous alloy is 381mV, the overpotential of the amorphous alloy after high-frequency vibration composite current heating treatment is 318mV, and oxygen evolution reaction is carried outThe overpotential is reduced by 63mV, which indicates that the high-frequency vibration composite current heating treatment improves Ni 51 Fe 35 Si 6 B 4 Pd 4 Electrochemical oxygen evolution catalytic performance of amorphous alloys. As the amorphous alloy treatment surface is partially oxidized in the high-frequency vibration composite current heating treatment process, the overpotential reduction amplitude is only 60 percent of that of the La and Y composite rare earth micro-doped nickel-iron-based amorphous alloy.
Comparative example 5
The present comparative example is different from example 1 in that the dither ram applied pressure in the dither compound current heating process is different.
Preparing a nickel-iron-based amorphous alloy material: according to the chemical formula of the amorphous alloy material, the high-purity Ni, fe, si, pd, Y, la and FeB raw materials with corresponding weight are weighed and melted in a vacuum arc furnace to obtain Ni with the mole percentage of 47 Fe 35 Si 6 B 4 Pd 4 Y 2 La 2 Is a uniform alloy ingot. Under the protection of high-purity argon, the alloy is melted uniformly in a vacuum arc furnace, and a ferronickel-based amorphous alloy plate with the thickness of 1mm and the width of 10mm is obtained by adopting liquid nitrogen cooling copper die suction casting. The prepared material was structurally characterized using an X-ray diffractometer.
High-frequency vibration composite current heating treatment of nickel-iron-based amorphous alloy: and ultrasonically cleaning the amorphous alloy material by using deionized water and absolute ethyl alcohol. Fixing the amorphous alloy on a high-frequency vibration workbench, applying a load to the surface of the amorphous alloy material by using a square pressure head of high-conductivity grinding tool steel with the side length of 2mm, wherein the load pressure is 100MPa, so that a sample is in an elastic deformation area, the high-frequency vibration load frequency is 25kHz, the amplitude is 70 mu m, the pressure head and the amorphous alloy sample form a current loop, and the conducting current density of the loop is 3000A/mm 2 The processing time per location was 0.3 seconds. And then the sample positions are respectively moved along the direction X, Y according to the step length of 2mm, and the amorphous alloy surface treatment is sequentially completed. And (3) protecting the contact area of the pressure head and the sample by flowing high-purity argon, wherein the flow rate of the argon is 100L/min.
The results of the linear voltammetric scan in 1M KOH electrolyte showed that: at a current density ofTo 10mA/cm 2 When the overpotential of the as-cast amorphous alloy is 381mV, the overpotential of the amorphous alloy after high-frequency vibration composite current heating treatment is 350mV, and the overpotential of oxygen evolution reaction is reduced by 31mV, which shows that the high-frequency vibration composite current heating treatment improves Ni 47 Fe 35 Si 6 B 4 Pd 4 Y 2 La 2 Electrochemical oxygen evolution catalytic performance of amorphous alloys. But the energy state change amplitude of the surface of the amorphous alloy material is smaller due to the too low loading pressure.
Comparative example 6
The present comparative example is different from example 1 in the current value of the current loop in the dither composite current heating process.
Preparing a nickel-iron-based amorphous alloy material: according to the chemical formula of the amorphous alloy material, the high-purity Ni, fe, si, pd, Y, la and FeB raw materials with corresponding weight are weighed and melted in a vacuum arc furnace to obtain Ni with the mole percentage of 47 Fe 35 Si 6 B 4 Pd 4 Y 2 La 2 Is a uniform alloy ingot. Under the protection of high-purity argon, the alloy is melted uniformly in a vacuum arc furnace, and a ferronickel-based amorphous alloy plate with the thickness of 1mm and the width of 10mm is obtained by adopting liquid nitrogen cooling copper die suction casting. The prepared material was structurally characterized using an X-ray diffractometer.
High-frequency vibration composite current heating treatment of nickel-iron-based amorphous alloy: and ultrasonically cleaning the amorphous alloy material by using deionized water and absolute ethyl alcohol. Fixing the amorphous alloy on a high-frequency vibration workbench, applying a load to the surface of the amorphous alloy material by using a square pressure head of high-conductivity grinding tool steel with the side length of 2mm, wherein the load pressure is 500MPa, so that a sample is in an elastic deformation area, the high-frequency vibration load frequency is 25kHz, the amplitude is 70 mu m, the pressure head and the amorphous alloy sample form a current loop, and the on-current density of the loop is 100A/mm 2 The processing time per location was 0.3 seconds. And then the sample positions are respectively moved along the direction X, Y according to the step length of 2mm, and the amorphous alloy surface treatment is sequentially completed. And (3) protecting the contact area of the pressure head and the sample by flowing high-purity argon, wherein the flow rate of the argon is 100L/min.
The results of the linear voltammetric scan in 1M KOH electrolyte showed that: at a current density of up to 10mA/cm 2 When the overpotential of the as-cast amorphous alloy is 381mV, the overpotential of the amorphous alloy after high-frequency vibration composite current heating treatment is 336mV, and the overpotential of oxygen evolution reaction is reduced by 45mV, which shows that the high-frequency vibration composite current heating treatment improves Ni 47 Fe 35 Si 6 B 4 Pd 4 Y 2 La 2 Electrochemical oxygen evolution catalytic performance of amorphous alloys. But the change of the energy state of the surface of the amorphous alloy is smaller due to the smaller current density.
Comparative example 7
The present comparative example is different from example 1 in that the dither composite current heating treatment loading time is different.
Preparing a nickel-iron-based amorphous alloy material: according to the chemical formula of the amorphous alloy material, the high-purity Ni, fe, si, pd, Y, la and FeB raw materials with corresponding weight are weighed and melted in a vacuum arc furnace to obtain Ni with the mole percentage of 47 Fe 35 Si 6 B 4 Pd 4 Y 2 La 2 Is a uniform alloy ingot. Under the protection of high-purity argon, the alloy is melted uniformly in a vacuum arc furnace, and a ferronickel-based amorphous alloy plate with the thickness of 1mm and the width of 10mm is obtained by adopting liquid nitrogen cooling copper die suction casting. The prepared material was structurally characterized using an X-ray diffractometer.
High-frequency vibration composite current heating treatment of nickel-iron-based amorphous alloy: and ultrasonically cleaning the amorphous alloy material by using deionized water and absolute ethyl alcohol. Fixing the amorphous alloy on a high-frequency vibration workbench, applying a load to the surface of the amorphous alloy material by using a square pressure head of high-conductivity grinding tool steel with the side length of 2mm, wherein the load pressure is 500MPa, so that a sample is in an elastic deformation area, the high-frequency vibration load frequency is 25kHz, the amplitude is 70 mu m, the pressure head and the amorphous alloy sample form a current loop, and the conducting current density of the loop is 3000A/mm 2 The processing time per location is 10 seconds. And then the sample positions are respectively moved along the direction X, Y according to the step length of 2mm, and the amorphous alloy surface treatment is sequentially completed. Flowing high-purity argon gas in contact area between pressure head and sampleThe argon flow is 100L/min.
The results of the linear voltammetric scan in 1M KOH electrolyte showed that: at a current density of up to 10mA/cm 2 When the overpotential of the as-cast amorphous alloy is 381mV, the overpotential of the amorphous alloy after high-frequency vibration composite current heating treatment is 355mV, and the overpotential of oxygen evolution reaction is reduced by 26mV, which shows that the high-frequency vibration composite current heating treatment improves Ni 47 Fe 35 Si 6 B 4 Pd 4 Y 2 La 2 Electrochemical oxygen evolution catalytic performance of amorphous alloys. However, the influence degree of the current heating annealing effect is increased due to the overlong current heating time, so that the improvement of the surface energy state of the amorphous alloy is inhibited.
The foregoing examples are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, but various modifications, combinations, partial combinations and substitutions made according to the design concept of the present invention fall within the scope of the present invention.
Claims (9)
1. The method for improving the electrochemical oxygen evolution catalytic performance of the nickel-iron-based amorphous alloy is characterized by comprising the following steps of:
(1) Preparing a ferronickel-based amorphous alloy containing Y and La composite rare earth elements in a micro-doped manner;
(2) The energy state of the surface of the nickel-iron-based amorphous alloy is changed by using high-frequency vibration of the pressure head, a current loop is formed by the high-frequency vibration pressure head and the amorphous alloy, and the energy state of the surface of the amorphous alloy is further improved by current heating, so that the surface of the amorphous alloy material is in a higher unbalanced energy state.
2. The method for improving electrochemical oxygen evolution catalytic performance of a nickel-iron-based amorphous alloy according to claim 1, wherein in the step (1), the molar percentage range of the nickel-iron-based amorphous alloy is as follows: fe:30-40%, si:5-8%, B:3-6%, pd:3-5%, (y+la): 3-5%, and the balance of Ni.
3. The method for improving electrochemical oxygen evolution catalytic performance of a nickel-iron-based amorphous alloy according to claim 1, wherein in the step (1), the preparation method of the nickel-iron-based amorphous alloy is as follows: according to the chemical formula of the alloy material, ni, fe, si, pd, Y, la and FeB high-purity raw materials with corresponding weight are weighed, are uniformly melted in a vacuum arc furnace, and are subjected to suction casting by adopting a liquid nitrogen cooling copper mold to obtain the nickel-iron-based amorphous alloy plate.
4. The method for improving electrochemical oxygen evolution catalytic performance of a nickel-iron-based amorphous alloy according to claim 1, wherein in the step (2), a high-frequency vibration load is applied to the surface of the nickel-iron-based amorphous alloy by a pressure head, and a current loop is formed by a conductive pressure head and the nickel-iron-based amorphous alloy at the same time, so that the designated position of the nickel-iron-based amorphous alloy is treated; and then moving the position of the nickel-iron-based amorphous alloy, and sequentially finishing the treatment of the surface of the nickel-iron-based amorphous alloy.
5. The method for improving electrochemical oxygen evolution catalytic performance of nickel-iron-based amorphous alloy according to claim 4, wherein the pressure head is square in shape, made of high-conductivity grinding tool steel, and has a side length of 1-5mm.
6. The method for improving electrochemical oxygen evolution catalytic performance of a nickel-iron-based amorphous alloy according to claim 4, wherein the pressure applied by the pressure head is 300-700MPa; the vibration frequency of the high-frequency vibration is 20-50kHz, the vibration amplitude is 50-100 mu m, and the vibration loading time is 0.1-0.5 seconds.
7. The method for improving electrochemical oxygen evolution catalytic performance of nickel-iron-based amorphous alloy according to claim 4, wherein the pressure head and the nickel-iron-based amorphous alloy form a current loop, and the current density is 600-6000A/mm 2 。
8. The method for improving electrochemical oxygen evolution catalytic performance of a nickel-iron-based amorphous alloy according to claim 4, wherein the moving distance of the pressing head is set to be the value of the side length of the pressing head, and the surface treatment of the nickel-iron-based amorphous alloy is sequentially completed.
9. The method for improving electrochemical oxygen evolution catalytic performance of the nickel-iron-based amorphous alloy according to claim 4, wherein the high-frequency vibration is protected by flowing high-purity argon, and the argon flow rate of the contact area of the pressure head and the nickel-iron-based amorphous alloy is 50-200L/min.
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