CN112626539B - Alloy electrocatalyst for ultra-stable PEM oxygen evolution reaction and preparation method thereof - Google Patents

Alloy electrocatalyst for ultra-stable PEM oxygen evolution reaction and preparation method thereof Download PDF

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CN112626539B
CN112626539B CN202011363360.XA CN202011363360A CN112626539B CN 112626539 B CN112626539 B CN 112626539B CN 202011363360 A CN202011363360 A CN 202011363360A CN 112626539 B CN112626539 B CN 112626539B
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CN112626539A (en
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胡飞
李睿
熊宇杰
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China Hydrogen Energy Technology Guangdong Co ltd
Xinyu Jintong Technology Co ltd
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Xinyu Jintong Technology Co ltd
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C16/00—Alloys based on zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • 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
    • 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
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention discloses an alloy electrocatalyst for an ultra-stable PEM oxygen evolution reaction, which is a (W, mo, nb, ta, zr, hf, re, os) -Ir block alloy material, and the specific components of the alloy are (W, mo, nb, ta, zr, hf, re, os) x-Iry, x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 20 and less than or equal to 40, wherein x and y are atomic percent of elements. The invention also discloses a preparation method of the alloy electrocatalyst for the ultra-stable PEM oxygen evolution reaction. The method is simple, easy to operate and suitable for large-scale industrial production. The material can be directly used as an oxygen evolution reaction electrode, shows excellent electrochemical oxygen evolution activity in an acid medium, and can stably work for more than 1000 hours under the condition of high current density. The material can be used as the anode of an industrial acid water electrolysis hydrogen production device, and is beneficial to the large-scale application of a proton exchange membrane water electrolysis technology.

Description

Alloy electrocatalyst for ultra-stable PEM oxygen evolution reaction and preparation method thereof
Technical Field
The invention relates to an alloy electrocatalyst and a preparation method thereof, belongs to the field of application of electrocatalysis materials, and particularly relates to an alloy electrocatalyst for an ultra-stable PEM oxygen evolution reaction and a preparation method thereof.
Background
Under the trends of energy transformation and green development, the utilization efficiency of renewable energy sources such as hydropower, wind power, photovoltaic and biomass in China is remarkably improved, and the power generation installation and the power generation amount of the renewable energy sources in energy consumption are steadily increased. The proportion of renewable energy resources is steadily improved, and the consumption structure is promoted to clean low-carbon transformation. In the energy storage and use based on renewable energy, electrohydrogen production will become an important component, and hydrogen will also develop into an important energy carrier. The electrolytic water technology is the most practical method for producing hydrogen gas from renewable energy sources.
The water electrolysis hydrogen production technology is mainly divided into alkaline electrolytic cell hydrogen production, solid polymer Proton Exchange Membrane (PEM) electrolysis hydrogen production and high-temperature solid oxide electrolysis hydrogen production, wherein the PEM electrolysis hydrogen production can work under high current density, the hydrogen production purity is high, and the electrolysis efficiency is high. The current density of the existing commercial PEM electrolytic hydrogen production is 0.5-1.5A/cm 2 Alkaline electrolytic hydrogen production is usually 0.3A/cm 2 And therefore, the volume of PEM electrolytic hydrogen production is smaller, and the distributed collection of renewable energy sources is easier. More importantly, PEM hydrogen production can be operated at 0-120% of power consumption, while alkaline electrolysis hydrogen production is operated at 50-100% of power consumption, so PEM hydrogen production is more easily matched with unstable power output generated by renewable energy sources.
Ir material is considered to be the best electrocatalyst for oxygen evolution reaction under acidic conditions, and Chinese patent CN 1874841 discloses a noble metal oxide catalyst for water electrolysis, and the invented composite catalyst material comprises iridium oxide and optionally ruthenium oxide and high surface area inorganic oxide (e.g. TiO) 2 、Al 2 O 3 、ZrO 2 And mixtures thereof). The examples show that the cell voltage is 1.5V, the current density is lower, 0.23mA/mg, and is better than that of the comparative example 1.48mA/mg, however, the method for measuring the catalyst performance in the invention is not universal. Chinese patent CN85107320 discloses a porous high surface area composite conductive catalytic material, which is a mixed catalytic material composed of platinum group metal oxide and at least one valve metal oxide. The examples show that the life of the electrodes is up to 85 hours. Chinese patent CN103055853 discloses a method for preparing water electrolysis oxygen evolution catalyst by taking a silicon oxide molecular sieve as a template, and noble metal oxide nanoparticles of Ru or Ir are obtainedWhen the catalyst is used for a water electrolysis anode catalyst, the catalyst has better oxygen evolution activity and stability. The above catalysts all have high specific surface area, thereby bringing about higher activity. However, due to the strong acidity of the proton exchange membrane, this corresponds to 0.5 MH 2 SO 4 Or 1M HClO 4 Noble metals such as Ir and Ru and other inorganic oxides serving as anode catalysts are extremely easy to corrode in a strong oxidation environment and a strong acid medium, so that the catalysts are changed, and the overall performance of PEM electrolytic hydrogen production equipment is reduced. In order to solve the problem of stability of the anode catalyst, the development of a catalyst with high activity and high stability still has great significance in the field of industrial PEM electrolyzed water.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an alloy electrocatalyst for an ultra-stable PEM oxygen evolution reaction and a preparation method thereof. The invention aims to improve the intrinsic activity of the catalyst instead of the specific surface area of the catalyst. The material has excellent electro-catalytic activity of acid OER and ultrahigh stability, can be used as an anode of an industrial PEM water electrolysis hydrogen production device, is simple in preparation method and easy to operate, and is beneficial to large-scale application of PEM water electrolysis technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an alloy electrocatalyst for an ultra-stable PEM oxygen evolution reaction, which is a (W, mo, nb, ta, zr, hf, re, os) -Ir block alloy material.
Furthermore, the specific components of the alloy are (W, mo, nb, ta, zr, hf, re, os) x-Iry, x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 20 and less than or equal to 40, wherein x and y are atomic percent of elements.
Further, the electrocatalytic activity of the alloy material reaches 10mA/cm in an acidic medium with pH =0 2 The overpotential required for the catalytic current density is in the range of 300 to 650mV.
Still further, the electrocatalytic activity of the alloy material reaches 10mA/cm in an acidic medium with pH =0 2 The overpotential required for the catalytic current density is in the range of 300 to 350mV.
Further, the alloy material can be 100mA/cm 2 The stable running time under the current density condition exceeds 1000 hours, and the overpotential rising rate ranges from 3 to 8 muV/h.
The invention provides a preparation method of an alloy electrocatalyst for an ultra-stable PEM oxygen evolution reaction, wherein the alloy electrocatalyst is a (W, mo, nb, ta, zr, hf, re, os) -Ir bulk alloy material, the specific components of the alloy are (W, mo, nb, ta, zr, hf, re, os) x-Iry, x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 20 and less than or equal to 40, x and y are atomic percent of elements, the alloy electrocatalyst is directly cast and molded by adopting an electric arc melting technology, and the melting temperature is more than 3500 ℃.
Further, the method comprises the following steps:
(1) Preparing a master alloy ingot: according to nominal components (W, mo, nb, ta, zr, hf, re, os) x-Iry of a master alloy, wherein x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 20 and less than or equal to 40, and x and y are atomic percent of elements, alloy raw materials (with the purity of 98.0-99.9 wt%) are mixed, arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is 200-300A, and in order to ensure the uniformity of the alloy components, the master alloy is repeatedly turned and melted in a furnace to obtain a master alloy ingot;
(2) Alloy casting and forming: and (2) remelting the uniform master alloy ingot in the step (1) through electric arc melting, then infiltrating the molten alloy into a water-cooled copper mold through a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain the (W, mo, nb, ta, zr, hf, re, os) -Ir electrocatalyst bar or plate with a certain shape and size.
Further, in the step (1), the master alloy is repeatedly turned and smelted in the furnace for more than four times to obtain a master alloy ingot.
The invention provides an alloy electrocatalyst for an ultra-stable PEM oxygen evolution reaction, which is W 80 Ir 20 A bulk alloy material; where 80 and 20 are atomic percentages of the elements.
Further, the electrocatalytic activity of the alloy material reaches 10mA/cm in an acidic medium with pH =0 2 The overpotential range required by the catalytic current density is 300-350 mV; what is needed isThe alloy material can be 100mA/cm 2 The stable running time under the current density condition exceeds 1000 hours, and the overpotential rising rate ranges from 3 to 8 muV/h.
Further, the preparation method comprises the following steps:
(1) Preparing a master alloy ingot: according to the nominal composition W of the master alloy 80 Ir 20 80 and 20 are atomic percentages of elements, alloy raw materials (with the purity of 98.0-99.9 wt%) are mixed, arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is 200A-300A, and in order to ensure that the alloy components are uniform, the master alloy is repeatedly turned and melted in a furnace to obtain a master alloy ingot;
(2) Alloy casting and forming: remelting the uniform master alloy ingot in the step (1) by arc melting, infiltrating the molten alloy into a water-cooled copper mold by a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain W 80 Ir 20 Electrocatalyst rods or plates.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention is a block material, and compared with a powder material, the intrinsic activity of the catalyst is improved.
(2) The oxygen evolution reaction electrocatalyst prepared by the invention has ultrahigh stability under an acidic condition, and the problem of limitation of insufficient long-term service stability of the existing acidic oxygen evolution reaction electrocatalyst is solved.
(3) The method of electric arc melting is adopted for direct casting and molding, the preparation process is simple, complex chemical synthesis process is not needed, and the method is suitable for large-scale industrial production.
Drawings
FIG. 1 is W prepared in example 1 80 Ir 20 Linear sweep voltammogram of electrocatalyst material.
FIG. 2 is W prepared in example 1 80 Ir 20 The electrocatalyst material was at 100mA/cm 2 Voltage versus time plot under current density conditions.
FIG. 3 is Hf prepared in example 7 80 Ir 20 Electro-catalystLinear sweep voltammogram of a material.
Detailed Description
The alloy electrocatalyst for the ultra-stable PEM oxygen evolution reaction is a (W, mo, nb, ta, zr, hf, re, os) -Ir block alloy material, and the design characteristics of the alloy components are that a noble metal active element Ir and a high-melting-point metal element, the specific components of the alloy are (W, mo, nb, ta, zr, hf, re, os) x-Iry, x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 20 and less than or equal to 40, and x and y are the atomic percent of the elements. The alloy material can be directly used as an anode material for oxygen evolution reaction, has excellent electrocatalytic activity and reaches 10mA/cm in an acid medium with pH =0 2 The overpotential required for catalytic current density is in the range of 300 to 350mV. It is used as acidic oxygen evolution electrocatalyst, shows ultrahigh stability and can be 100mA/cm 2 The stable running time under the current density condition exceeds 1000 hours, and the overpotential rising rate ranges from 3 to 8 muV/h.
The invention will now be further described with reference to the accompanying drawings and specific embodiments.
Example 1
In this example, the nominal composition of the alloy selected is W 80 Ir 20 The electrocatalyst material was prepared as follows:
(1) Preparing a master alloy ingot: according to the nominal composition W of the master alloy 80 Ir 20 Alloy raw materials W and Ir (with the purity of 98.0-99.9 wt%) are mixed, arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is 200A-300A, and in order to ensure the uniformity of alloy components, the master alloy is repeatedly turned and melted for more than four times in a furnace to obtain a master alloy ingot.
(2) Alloy casting and forming: remelting the uniform master alloy ingot in the step (1) by arc melting, infiltrating the molten alloy into a water-cooled copper mold by a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain W with the diameter of 2mm 80 Ir 20 An electrocatalyst rod.
The obtained alloy is subjected to acidic oxygen evolution reaction performance test, a three-electrode device with fixed exposed area is adopted for the testW 80 Ir 20 Alloy pattern (bare area 0.322 cm) 2 ) As a working electrode, a counter electrode is a platinum wire electrode, a reference electrode is a standard Ag/AgCl electrode, an electrolyte is a 0.5mol/L sulfuric acid solution, and the scanning speed is 5mV/s. As shown in FIG. 1, W 80 Ir 20 The alloy electrode material reaches 10mA/cm 2 The overpotential required for catalytic current density is as low as about 347 mV.
When the constant current test was performed on each electrode, the voltage-time curve was as shown in FIG. 2, and it was found that when the current density was 100mA/cm 2 W as prepared in example 1 80 Ir 20 The alloy electrocatalyst electrode can stably operate for more than 1000h in 0.5mol/L sulfuric acid electrolyte, still maintain high electrocatalytic activity, and the overpotential rising rate is lower than 6 muV/h within 1000 h. Demonstration of W prepared according to the invention 80 Ir 20 The alloy electrocatalyst has excellent stability of acidic oxygen evolution reaction.
Example 2
In this example, the nominal composition of the alloy selected is W 60 Ir 40 The preparation method of this electrocatalyst material is the same as in example 1.
The obtained alloy is subjected to acidic oxygen evolution reaction performance test by adopting a three-electrode device, the test scheme is the same as that of the embodiment 1, W 60 Ir 40 The alloy electrode material reaches 10mA/cm 2 The overpotential required for catalytic current density is as low as about 300 mV. Preparation of the resulting W 60 Ir 40 The alloy electrocatalyst electrode can stably run for more than 1000h in 0.5mol/L sulfuric acid electrolyte, and still maintain high electrocatalytic activity, and the overpotential rise rate is lower than 4 muV/h within 1000 h. Certificate W 60 Ir 40 The alloy electrode material has electrocatalytic oxygen evolution activity.
Example 3
In this example, mo is the nominal component of the alloy 80 Ir 20 The preparation method of this electrocatalyst material is the same as in example 1.
The obtained alloy is subjected to acidic oxygen evolution reactionTest using a three-electrode apparatus, the same test protocol as in example 1, mo 80 Ir 20 The alloy electrode material reaches 10mA/cm 2 The overpotential required for catalytic current density is as low as around 643 mV. Prepared Mo 80 Ir 20 The alloy electrocatalyst electrode can stably operate for more than 1000h in 0.5mol/L sulfuric acid electrolyte, still maintain high electrocatalytic activity, and the overpotential rising rate is lower than 7 muV/h within 1000 h. Prove Mo 80 Ir 20 The alloy electrode material has electrocatalytic oxygen evolution activity.
Example 4
In this example, the nominal alloy component selected is Nb 80 Ir 20 The preparation method of this electrocatalyst material is the same as in example 1.
The obtained alloy is subjected to an acid oxygen evolution reaction performance test by adopting a three-electrode device, the test scheme is the same as that of the example 1, and Nb is 80 Ir 20 The alloy electrode material reaches 10mA/cm 2 The overpotential required for catalytic current density is around 436mV lower. Prepared Nb 80 Ir 20 The alloy electrocatalyst electrode can stably operate for more than 1000h in 0.5mol/L sulfuric acid electrolyte, still maintain high electrocatalytic activity, and the overpotential rising rate is lower than 8 muV/h within 1000 h. Prove Nb 80 Ir 20 The alloy electrode material has electrocatalytic oxygen evolution activity.
Example 5
In this example, ta is the nominal component of the alloy selected 80 Ir 20 The preparation method of this electrocatalyst material is the same as in example 1.
The obtained alloy is subjected to an acid oxygen evolution reaction performance test by adopting a three-electrode device, the test scheme is the same as that of the embodiment 1, and Ta 80 Ir 20 The alloy electrode material reaches 10mA/cm 2 The overpotential required for catalytic current density is low around 398 mV. Preparation of the obtained Ta 80 Ir 20 The alloy electrocatalyst electrode can stably operate for more than 1000h in 0.5mol/L sulfuric acid electrolyte and still maintain high electrocatalysisActivity, overpotential rise rate less than 6 μ V/h in 1000 hours. Proving Ta 80 Ir 20 The alloy electrode material has electrocatalytic oxygen evolution activity.
Example 6
In this example, the nominal composition of the alloy selected is Zr 80 Ir 20 The preparation method of this electrocatalyst material is the same as in example 1.
The obtained alloy is subjected to an acid oxygen evolution reaction performance test, a three-electrode device is adopted in the test, the test scheme is the same as that of the embodiment 1, and Zr is adopted 80 Ir 20 The alloy electrode material reaches 10mA/cm 2 The overpotential required for the catalytic current density is as low as 615mV or so. Preparation of the obtained Zr 80 Ir 20 The alloy electrocatalyst electrode can stably run for more than 1000h in 0.5mol/L sulfuric acid electrolyte, and still maintain high electrocatalytic activity, and the overpotential rise rate is lower than 7 muV/h within 1000 h. Zr 80 Ir 20 The alloy electrode material has electrocatalytic oxygen evolution activity.
Example 7
In this example, the nominal composition of the alloy selected is Hf 80 Ir 20 The preparation method of the electrocatalyst material is the same as in example 1.
The obtained alloy is subjected to an acid oxygen evolution reaction performance test, a three-electrode device is adopted in the test, the test scheme is the same as that of the embodiment 1, and Hf (hafnium) is adopted 80 Ir 20 The alloy electrode material reaches 10mA/cm 2 The overpotential required for catalytic current density is as low as about 451 mV. Prepared Hf 80 Ir 20 The alloy electrocatalyst electrode can stably operate for more than 1000h in 0.5mol/L sulfuric acid electrolyte, still maintain high electrocatalytic activity, and the overpotential rising rate is lower than 8 muV/h within 1000 h. As shown in FIG. 3, hf 80 Ir 20 The alloy electrode material has electrocatalytic oxygen evolution activity.
Example 8
In this example, the nominal composition of the alloy selected is Re 80 Ir 20 The electrocatalyst materialThe material was prepared in the same manner as in example 1.
The obtained alloy is subjected to an acid oxygen evolution reaction performance test by adopting a three-electrode device, the test scheme is the same as that of the example 1, and Re 80 Ir 20 The alloy electrode material reaches 10mA/cm 2 The overpotential required for catalytic current density is low at around 340 mV. Preparation of the obtained Re 80 Ir 20 The alloy electrocatalyst electrode can stably run for more than 1000h in 0.5mol/L sulfuric acid electrolyte, and still maintain high electrocatalytic activity, and the overpotential rise rate is lower than 8 muV/h within 1000 h. Re 80 Ir 20 The alloy electrode material has electrocatalytic oxygen evolution activity.
Example 9
In this example, the nominal composition of the alloy we chose is Os 80 Ir 20 The preparation method of this electrocatalyst material is the same as in example 1.
The obtained alloy is subjected to acidic oxygen evolution reaction performance test by adopting a three-electrode device, the test scheme is the same as that of the embodiment 1, and Os is 80 Ir 20 The alloy electrode material reaches 10mA/cm 2 The overpotential required for catalytic current density is as low as about 301 mV. Preparing the obtained Os 80 Ir 20 The alloy electrocatalyst electrode can stably operate for more than 1000h in 0.5mol/L sulfuric acid electrolyte, still maintain high electrocatalytic activity, and the overpotential rising rate is lower than 5 muV/h within 1000 h. Os 80 Ir 20 The alloy electrode material has electrocatalytic oxygen evolution activity.
In the other examples, (W, mo, nb, ta, zr, hf, re, os) -Ir-based electrocatalysts were prepared in the same manner as in this example, except that only the nominal composition of the raw materials was changed to obtain bars or plates with different compositions, and these materials all had good electrocatalytic activity and the stability of acidic oxygen evolution reaction was especially excellent.
The present invention is not limited to the above-described embodiments, and various changes and modifications of the present invention are intended to be included within the scope of the claims and the equivalent technology of the present invention if they do not depart from the spirit and scope of the present invention.

Claims (5)

1. A preparation method of an alloy electrocatalyst for hyperstable PEM oxygen evolution reaction comprises the following specific components of Wx-Iry, x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 20 and less than or equal to 40, wherein x and y are atomic percent of elements, and the preparation method is characterized in that: the method adopts an electric arc melting technology for direct casting molding, the melting temperature is more than 3500 ℃, and the method comprises the following steps:
(1) Preparing a master alloy ingot: according to the nominal composition Wx-Iry of the master alloy, x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 20 and less than or equal to 40, wherein x and y are atomic percent of elements, alloy raw materials with the purity of 98.0 to 99.9wt% are prepared, then arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is 200A to 300A, and in order to ensure that the alloy components are uniform, the master alloy is repeatedly turned and melted in a furnace to obtain a master alloy ingot;
(2) Alloy casting and forming: and (2) remelting the uniform master alloy ingot in the step (1) through arc melting, then infiltrating the molten alloy into a water-cooled copper mold through a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain the Wx-Iry electrocatalyst bar or plate.
2. The method of claim 1, wherein: in the step (1), the master alloy is repeatedly turned and smelted for four to ten times in the furnace to obtain a master alloy ingot.
3. The method of claim 1, wherein the preparation of the alloy electrocatalyst for ultra-stable PEM oxygen evolution reaction comprises: the alloy electrocatalyst is W 80 Ir 20 A bulk alloy material; where 80 and 20 are atomic percentages of the elements.
4. The production method according to claim 3, characterized in that: the electrocatalytic activity of the alloy material reaches 10mA/cm in an acidic medium with pH =0 2 The overpotential range required by the catalytic current density is 300 to 350mV; the alloy material can be 100mA/cm 2 The stable running time under the current density condition is more than 1000 hours, and the overpotential rising rate ranges from 3 to 8 μ V/h.
5. The method of claim 4, comprising the steps of:
(1) Preparing a master alloy ingot: according to the nominal composition W of the master alloy 80 Ir 20 80 and 20 are atomic percent of elements, alloy raw materials with the purity of 98.0 to 99.9wt% are mixed, arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is 200A to 300A, and in order to ensure that the alloy components are uniform, the master alloy is repeatedly turned and melted in a furnace to obtain a master alloy ingot;
(2) Alloy casting and forming: remelting the uniform master alloy ingot obtained in the step (1) by arc melting, infiltrating the molten alloy into a water-cooled copper mold by a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain W 80 Ir 20 Electrocatalyst rods or plates.
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