CN115198299A - High-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalysis material and preparation thereof - Google Patents
High-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalysis material and preparation thereof Download PDFInfo
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Abstract
The invention belongs to the field of preparation of full-hydrolysis water electro-catalyst materials, and provides a high-activity micro-nano porous high-entropy alloy full-hydrolysis catalytic material and a preparation method thereof. The alloy is Ni a Fe b Co c Cr d Al e The alloy consists of the following components in atomic ratio: 25 to 45 percent of Ni, 12.5 to 35 percent of Fe, 12.5 to 35 percent of Co, 12.5 to 35 percent of Cr and 12.5 to 17.5 percent of Al. The size of the pores on the surface of the electrocatalyst is regulated and controlled by adopting a method combining alloy component regulation and phase corrosion engineering, so that more specific surface area and catalytic activity are exposedAnd (4) carrying out locus reaction, thus preparing the high-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalysis material. The catalytic material has large surface specific surface area and good conductivity, and can regulate and control the electronic structure of the catalyst in a wider range; the corrosion resistance and the stability are good, so that the efficiency of full water hydrolysis is improved; the process flow is simple and mature, and is easy to realize industrial application, the industrial application of full water decomposition under high current density and other electrocatalysis industries related to oxygen evolution and hydrogen evolution.
Description
Technical Field
The invention belongs to the field of preparation of electrolytic water catalytic materials, and particularly provides a high-activity micro-nano porous high-entropy alloy full-electrolysis water catalytic material and a preparation method thereof.
Background
In the last decades, the number of global population has been continuously increased and the industrial level has been continuously increased, and the problem of global warming and environmental pollution has been intensified due to uncontrolled fossil fuel consumption, so that there is an urgent need to find a feasible method for promoting the development of renewable energy resources, technologies and industries to realize the feasibility of zero-emission energy.
As a secondary energy with high energy density and zero emission, hydrogen energy is known as one of the most ideal renewable energy sources. Among them, the hydrogen production technology by electrolysis of water is considered as one of the most promising methods for producing green hydrogen fuel. Electrocatalytic water splitting is a combination of two half-reactions, the anodic half-reaction commonly referred to as the Oxygen Evolution Reaction (OER) and the cathodic half-reaction commonly referred to as the Hydrogen Evolution Reaction (HER). Electrocatalysts play the most critical role by reducing the activation energy required for the OER and HER reactions to achieve cost utility. Heretofore, noble metal-based catalysts such as platinum (Pt) for HER and iridium oxide (IrO) for OER 2 ) And ruthenium oxide (RuO) 2 ) Are considered the most efficient electrocatalysts, but the low inventory high cost leads to lower economic attractiveness of noble metal-based electrocatalysts. Therefore, the method develops the economic, applicable, high-efficiency and stable non-noble metal-based dual-functional electrocatalyst and benefits the related energy technologyThe technology can better meet the requirements of economic and social sustainable development.
The structure of the electrocatalyst reported at present is mainly divided into a self-supporting electrode and a supported electrode. Compared with a self-supporting electrode, the load type electrode has the following characteristics: firstly, in order to ensure good conductivity and mass transfer performance of a catalyst structure loaded on a current collector, the loading capacity of the catalyst is limited; secondly, since the powdered catalyst needs a binder to be coated on the current collector, the process of generating gas by high-current catalysis can cause the catalyst to be separated from the current collector, and the catalytic efficiency and stability of the catalyst are affected. Therefore, the development of the bifunctional electrocatalyst with a self-supporting structure can greatly promote the development of the sustainable green energy industry. When the lower self-supporting MOF structure is hotter, the problems of low stability, poor conductivity, unfavorable mass transfer of a microporous structure, low catalytic active sites and the like exist, and the industrial application prospect is poor. Therefore, the development of a novel self-supporting bifunctional electrocatalyst with good conductivity, stable structure, high catalytic activity and good industrial application prospect has reached the key period of opportunity and challenge coexistence.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a high-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalysis material and a preparation method thereof, and the size of the surface pores of the electro-catalysis material and the electronic structure of the catalytic active sites of the electro-catalysis material can be adjusted in a wider range through different process conditions. The obtained electrocatalytic material has good corrosion resistance and stability, so that the efficiency of full water splitting is improved; and the preparation process flow is simple and mature, the industrial application is easy to realize, and the full water decomposition industrial application under high current density and other electrocatalysis industries related to oxygen evolution and hydrogen evolution are realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalysis material is characterized in that: the high-entropy alloy is Ni a Fe b Co c Cr d Al e The alloy consists of the following components in atomic ratio: 25 to 45 percent of Ni and 12.5 percent of Fe％～35％，Co:12.5％～35％，Cr:12.5％～35％，Al:12.5％～17.5％。
The invention also provides a preparation method of the high-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalysis material, which is characterized by comprising the following steps of:
step 1) according to Ni a Fe b Co c Cr d Al e Respectively weighing Ni, fe, co, cr and Al metal particles according to the atomic proportion in the alloy;
step 2), smelting the metal block particles prepared in the step 1) in a high vacuum arc smelting furnace, and obtaining Ni in a copper mold crucible a Fe b Co c Cr d Al e High-entropy alloy ingot casting;
step 3) of reacting the Ni obtained in step 2) a Fe b Co c Cr d Al e Putting the high-entropy alloy cast ingot into a vacuum turning furnace to prepare Ni a Fe b Co c Cr d Al e A high-entropy alloy plate;
step 4) of reacting Ni in step 3) a Fe b Co c Cr d Al e The high-entropy alloy plate is directly cut or cold-rolled to obtain Ni a Fe b Co c Cr d Al e A high entropy alloy sheet;
step 5) of reacting Ni in step 4) a Fe b Co c Cr d Al e And (3) soaking the high-entropy alloy sheet in corrosive liquid to prepare the high-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalysis material.
As a preferable technical scheme:
in the step 2), the smelting process parameters are as follows:
the required vacuum degree before smelting is 3.5X 10 -3 Pa～5.0×10 -3 Pa；
Filling argon with the mass percent of 99.999 percent of 0.03-0.05 Mpa as protective atmosphere;
the smelting current is 250-500A;
smelting time: 10-30 s;
the smelting times are as follows: 5-8 times.
In step 3), ni a Fe b Co c Cr d Al e The crystal structure of the high-entropy alloy is an FCC + BCC structure.
In the step 4), the rolling directions of the cold rolling are consistent, and the deformation amount is 50-90%.
In the step 5), the corrosive liquid is 3-10g of Cr 2 O 3 Adding 3-5mol of HCl solution (preferably 5g of Cr) 2 O 3 Adding 3mol of HCl solution), and soaking for 1-24 h.
The method can be used for preparing large-size electrocatalytic materials (such as 80 mm-100 mm in length, 20 mm-100 mm in width and 0.5 mm-1 mm in thickness); the surface of the electrocatalytic material is in a micro-nano porous shape, the porosity is 40-70%, and the pore diameter is 0.1-40um.
In the crystal structure of the prepared electro-catalytic material, the FCC accounts for more than or equal to 50 percent by volume percentage. According to the invention, the active area of the catalyst can be increased by carrying out phase corrosion engineering on the prefabricated alloy, and more catalytic active sites are exposed, so that the non-noble metal bifunctional electrolytic water catalyst with high activity is prepared.
The material of the invention can be used as anode and/or cathode material in full-hydrolyzed water.
The surface of the high-activity micro-nano porous high-entropy alloy full-hydrolytic electro-catalytic material prepared by the method is in a micro-nano porous shape, the bifunctional catalyst can be used as an anode material and a cathode material in full-hydrolytic water, and the solution has the pH =14 and the current density of 10 mA-cm -2 Under the condition of (2), the overpotential of the anode is 200-300 mV, the overpotential of the cathode is 150-250 mV, and the anode and the cathode still have lower overpotential under the condition of high current density.
Compared with the prior art, the high-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalysis material and the preparation method have the following advantages:
1. the high-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalysis material prepared by the method has many surface active sites and very excellent conductivity, so that the full-electrolysis efficiency is improved;
2. the surface pore diameter of the high-activity micro-nano porous high-entropy alloy total-hydrolysis water electro-catalysis material prepared by the method can be regulated and controlled through rolling deformation and alloy components of the preform, so that the specific surface area of the electro-catalyst is regulated and controlled, and the total-hydrolysis efficiency is improved.
3. The high-activity micro-nano porous high-entropy alloy full-electrolysis hydro-electro-catalysis material prepared by the invention has good corrosion resistance and stability under severe service environment (corrosion and high electrochemical potential), and further improves the full-electrolysis efficiency;
4. the active micro-nano porous high-entropy alloy full-hydrolysis water electro-catalysis material prepared by the method disclosed by the invention is simple and mature in process, easy to realize industrial application and capable of realizing full-hydrolysis industrial application under high current density.
Drawings
FIG. 1 shows high-activity Ni in example 1 of the present invention 33.4 Fe 16.65 Co 16.65 Cr 16.65 Al 16.65 X-ray diffraction pattern of the electrolyzed water catalytic material.
FIG. 2 shows high-activity Ni in example 1 of the present invention 33.4 Fe 16.65 Co 16.65 Cr 16.65 Al 16.65 Scanning electron microscope pictures of the surface of the electrolyzed water catalytic material.
FIG. 3 shows high-activity Ni in example 2 of the present invention 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 Scanning electron microscope pictures of the surface of the electrolyzed water catalytic material.
FIG. 4 shows high-activity Ni in example 1 of the present invention 33.4 Fe 16.65 Co 16.65 Cr 16.65 Al 16.65 The linear voltammetry scanning curve diagrams of oxygen evolution and hydrogen evolution of the electrolyzed water catalytic material.
FIG. 5 shows high-activity Ni in example 1 of the present invention 33.4 Fe 16.65 Co 16.65 Cr 16.65 Al 16.65 The total water electrolysis current of the water electrolysis catalytic material is plotted with the change of the cell voltage (voltage drop is subtracted according to the resistance of 85 percent solution).
FIG. 6 shows high-activity Ni in example 2 of the present invention 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 The linear voltammetry scanning curve diagram of oxygen evolution and hydrogen evolution of the electrolyzed water catalytic material.
FIG. 7 shows high-activity Ni in example 3 of the present invention 42.8 Fe 14.3 Co 14.3 Cr 14.3 Al 14.3 The linear voltammetry scanning curve diagram of oxygen evolution and hydrogen evolution of the electrolyzed water catalytic material.
FIG. 8 shows highly active Ni in example 4 of the present invention 28.6 Fe 14.27 Co 28.6 Cr 14.27 Al 14.26 The linear voltammetry scanning curve diagram of oxygen evolution and hydrogen evolution of the electrolyzed water catalytic material.
FIG. 9 shows comparative example of the present invention, ni 40 Fe 20 Co 20 Al 20 The linear voltammetry scanning curve diagram of oxygen evolution and hydrogen evolution of the electrolyzed water catalytic material.
Detailed Description
The technical features and characteristics of the present invention are described in detail below with reference to the accompanying drawings by way of specific examples, which are not intended to limit the scope of the present invention.
Unless otherwise specified, the smelting process of the alloy ingot in step 2) of the invention is as follows:
putting the weighed Ni, fe, co, cr and Al elements into a vacuum arc melting furnace for melting to obtain Ni 2 A FeCoCrAl alloy ingot.
Smelting parameters are as follows: the required vacuum degree before smelting is 3.5X 10 -3 Pa～5.0×10 -3 Pa；
Argon gas with the mass percent of 99.999 percent of 0.03-0.05 Mpa is filled as protective atmosphere;
the smelting current is 250-500A;
smelting time: 10-30 s;
the smelting times are as follows: 5-8 times.
In the step 4), the corrosive liquid is prepared by mixing 5g of Cr 2 O 3 Adding 3mol of HCl solution to prepare the catalyst.
Example 1
High-activity Ni 33.4 Fe 16.65 Co 16.65 Cr 16.65 Al 16.65 Full electrolysis water electro-catalysis material
1) According to Ni 2 Weighing Ni, fe, co, cr and Al elements respectively according to the nominal composition of FeCoCrAl, wherein the mass percent purity of each element is not lower than 99.99%;
2) Melting alloy ingot
3) Casting and cutting alloy plate
Mix Ni 2 Placing the FeCoCrAl alloy ingot into a high-entropy alloy ingot, placing the high-entropy alloy ingot in a vacuum turning furnace, and preparing a high-entropy alloy plate, wherein the size of the alloy plate is as follows: the length is 100mm, the width is 23mm, and the thickness is 3.7mm;
cutting the alloy plate into alloy sheets with the thickness of 1mm;
4) Performing phase corrosion engineering on the surface of the alloy sheet
Ni obtained by rolling 33.4 Fe 16.65 Co 16.65 Cr 16.65 Al 16.65 The alloy sheet is put into the corrosive agent to be soaked for 4 hours, taken out and cleaned by deionized water, and naturally dried to obtain the high-activity Ni 33.4 Fe 16.65 Co 16.65 Cr 16.65 Al 16.65 The X-ray diffraction pattern of the fully hydrolyzed electro-catalytic material is shown in figure 1, and the scanning electron microscope picture of the surface of the fully hydrolyzed electro-catalytic material is shown in figure 2. (As shown in FIG. 1, preform Ni 33.4 Fe 16.65 Co 16.65 Cr 16.65 Al 16.65 The crystal structure of the alloy is an FCC + BCC two-phase structure, and the electro-catalytic material after being corroded is shown in figure 2, wherein the porosity is 42 percent, and the pore diameter is 10-15um.
5) Testing of electrochemical Performance
Use of silicone rubber to mix Ni 33.4 Fe 16.65 Co 16.65 Cr 16.65 Al 16.65 The non-electrochemical testing part of the full-electrolysis water electro-catalysis material is sealed, and the free surface with a fixed area is exposed for electrochemical testing. Test method for Ni by adopting linear voltammetry scanning 33.4 Fe 16.65 Co 16.65 Cr 16.65 Al 16.65 The fully electrolyzed water electro-catalytic material was tested. The test uses a three-electrode system with a working electrode of Ni 33.4 Fe 16.65 Co 16.65 Cr 16.65 Al 16.65 The reference electrode is mercury/mercury oxide, the auxiliary electrode is platinum sheet, and the electrolyte is made of water electrolysis catalysis material1mol/L potassium hydroxide solution. The oxygen evolution and hydrogen evolution polarization curves obtained are shown in FIG. 4, where FIG. 4 shows that 10mA cm is reached -2 The overpotential for oxygen evolution is only 235mV and the overpotential for hydrogen evolution is 146mV, while the lower overpotential at high current density indicates Ni in example 1 2 The FeCoCrAl full-hydrolysis electro-catalytic material has excellent oxygen evolution and hydrogen evolution catalytic activity. Simultaneously, a two-electrode system was used to test Ni 33.4 Fe 16.65 Co 16.65 Cr 16.65 Al 16.65 The change curve of the current of the fully electrolyzed water electro-catalytic material in a KOH solution of 1mol/L along with the voltage. As shown in FIG. 5, 10mA cm was reached -2 The voltage of the full water-decomposing tank is only 1.62V. This indicates that Ni 33.4 Fe 16.65 Co 16.65 Cr 16.65 Al 16.65 The catalytic performance of the full-electrolysis water electro-catalysis material is excellent.
Example 2
High-activity Ni 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 Full electrolysis water electro-catalysis material
1) According to Ni 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 Nominal components are respectively weighed, wherein the mass percent purity of each element is not less than 99.99 percent;
2) Melting alloy ingot
3) Casting alloy sheet and rolling
Mix Ni 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 Placing the alloy ingot into a high-entropy alloy ingot, placing the alloy ingot into a vacuum turning furnace, and preparing a high-entropy alloy plate, wherein the alloy plate has the following size: the length is 95mm, the width is 25mm, and the thickness is 4mm;
cold rolling the alloy plate into an alloy sheet with the thickness of 1mm;
cold rolling deformation: 50 percent.
4) Performing phase corrosion engineering on the surface of the alloy sheet
Ni obtained by rolling 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 Soaking the alloy sheet in the corrosive agent for 6h, taking out, cleaning with deionized water, and naturally drying to obtain the alloy sheet with high strengthActive Ni 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 The full-electrolysis water electro-catalysis material is shown in figure 3, and the picture shows that the porosity is about 45 percent and the pore diameter is 0.2-0.8um.
5) Testing of electrochemical Performance
Ni Using Silicone rubber 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 The non-electrochemical test part of the full-electrolysis water electro-catalysis material is sealed, and the free surface with a fixed area is exposed for electrochemical test. Test method for Ni by adopting linear voltammetry scanning 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 The fully electrolyzed water electro-catalytic material was tested. The test uses a three-electrode system with a working electrode of Ni 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 The reference electrode is mercury/mercury oxide, the auxiliary electrode is a platinum sheet, and the electrolyte is 1mol/L potassium hydroxide solution. The polarization curves for oxygen evolution and hydrogen evolution obtained are shown in FIG. 6, and FIG. 6 shows that 10mA cm is reached -2 The overpotential for oxygen evolution is only 229mV, and the overpotential for hydrogen evolution is 179mV. This shows Ni in example 2 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 The full-hydrolytic electrocatalytic material has excellent oxygen evolution and hydrogen evolution catalytic activity.
Example 3
High-activity Ni 42.8 Fe 14.3 Co 14.3 Cr 14.3 Al 14.3 Full electrolysis water electro-catalysis material
1) According to Ni 42.8 Fe 14.3 Co 14.3 Cr 14.3 Al 14.3 Nominal components of Ni, fe, co, cr and Al are respectively weighed, wherein the mass percent purity of each element is not lower than 99.99%;
2) Melting alloy ingot
3) Casting alloy sheet and cutting
Mix Ni 42.8 Fe 14.3 Co 14.3 Cr 14.3 Al 14.3 Placing the alloy ingot into a high-entropy alloy ingot casting, placing the alloy ingot casting into a vacuum turning furnace to prepare a high-entropy alloy plate, wherein the size of the alloy plate: the length is 85mm, the width is 21mm, and the thickness is 3.5mm;
cutting the alloy plate into alloy sheets with the thickness of 1mm;
4) Performing phase corrosion engineering on the surface of the alloy sheet
Ni obtained by rolling 42.8 Fe 14.3 Co 14.3 Cr 14.3 Al 14.3 Soaking the alloy sheet in the corrosive agent for 4h, taking out, cleaning the alloy sheet with deionized water, and naturally airing to obtain high-activity Ni 42.8 Fe 14.3 Co 14.3 Cr 14.3 Al 14.3 A fully-hydrolyzed electro-catalytic material.
5) Testing of electrochemical Performance
Ni Using Silicone rubber 42.8 Fe 14.3 Co 14.3 Cr 14.3 Al 14.3 The non-electrochemical testing part of the full-electrolysis water electro-catalysis material is sealed, and the free surface with a fixed area is exposed for electrochemical testing. Test method for Ni by adopting linear voltammetry scanning 42.8 Fe 14.3 Co 14.3 Cr 14.3 Al 14.3 The fully hydrolyzed electrocatalytic materials were tested. The test uses a three-electrode system with a working electrode of Ni 42.8 Fe 14.3 Co 14.3 Cr 14.3 Al 14.3 The reference electrode is mercury/mercury oxide, the auxiliary electrode is a platinum sheet, and the electrolyte is 1mol/L potassium hydroxide solution. The oxygen evolution and hydrogen evolution polarization curves obtained are shown in FIG. 7, and FIG. 7 shows that 10mA cm is reached -2 The overpotential for oxygen evolution is only 265mV, and the overpotential for hydrogen evolution is 225mV. This shows Ni in example 3 42.8 Fe 14.3 Co 14.3 Cr 14.3 Al 14.3 The full water-splitting electrocatalytic material has excellent oxygen-evolution and hydrogen-evolution catalytic activity.
Example 4
High-activity Ni 28.6 Fe 14.27 Co 28.6 Cr 14.27 Al 14.26 Full electrolysis water electro-catalysis material
1) According to Ni 28.6 Fe 14.27 Co 28.6 Cr 14.27 Al 14.26 Nominal components of Ni, fe, co, cr and Al are respectively weighed, wherein the mass percent purity of each element is not less than 99.99％；
2) Melting alloy ingot
3) Casting alloy sheet and cutting
Mix Ni 28.6 Fe 14.27 Co 28.6 Cr 14.27 Al 14.26 Placing the alloy ingot into a high-entropy alloy ingot, placing the alloy ingot in a vacuum turning furnace, and preparing a high-entropy alloy plate, wherein the size of the alloy plate is as follows: the length is 89mm, the width is 26mm, and the thickness is 5mm;
cutting the alloy plate into alloy sheets with the thickness of 1mm;
4) Performing phase corrosion engineering on the surface of the alloy sheet
Ni obtained by rolling 28.6 Fe 14.27 Co 28.6 Cr 14.27 Al 14.26 Soaking the alloy sheet in a corrosive agent for 4 hours, taking out the alloy sheet, cleaning the alloy sheet with deionized water, and naturally airing the alloy sheet to obtain high-activity Ni 28.6 Fe 14.27 Co 28.6 Cr 14.27 Al 14.26 A fully hydrolyzed electro-catalytic material.
5) Testing of electrochemical Performance
Ni Using Silicone rubber 28.6 Fe 14.27 Co 28.6 Cr 14.27 Al 14.26 The non-electrochemical testing part of the full-electrolysis water electro-catalysis material is sealed, and the free surface with a fixed area is exposed for electrochemical testing. Test method for Ni by adopting linear voltammetry scanning 28.6 Fe 14.27 Co 28.6 Cr 14.27 Al 14.26 The fully hydrolyzed electrocatalytic materials were tested. The test uses a three-electrode system, the working electrode is Ni 28.6 Fe 14.27 Co 28.6 Cr 14.27 Al 14.26 The reference electrode is mercury/mercury oxide, the auxiliary electrode is a platinum sheet, and the electrolyte is 1mol/L potassium hydroxide solution. The polarization curves for oxygen evolution and hydrogen evolution obtained are shown in FIG. 8, and FIG. 8 shows that 10mA cm is reached -2 The overpotential for oxygen evolution is 292mV, and the overpotential for hydrogen evolution is 247mV. This shows Ni in example 4 28.6 Fe 14.27 Co 28.6 Cr 14.27 Al 14.26 The full-electrolysis electrocatalytic material has excellent oxygen evolution and hydrogen evolution catalytic activity.
Comparative example
Ni 40 Fe 20 Co 20 Al 20 Full electrolysis water electro-catalysis material
1) According to Ni 40 Fe 20 Co 20 Al 20 Nominal components of Ni, fe, co and Al are respectively weighed, wherein the mass percent purity of each element is not lower than 99.99%;
2) Melting alloy ingot
3) Casting alloy sheet and cutting
Mixing Ni 40 Fe 20 Co 20 Al 20 Placing the alloy ingot into a high-entropy alloy ingot, placing the alloy ingot into a vacuum turning furnace, and preparing a high-entropy alloy plate, wherein the alloy plate has the following size: 94mm long, 30mm wide and 4mm thick.
Cutting the alloy plate into alloy sheets with the thickness of 1mm;
4) Performing phase corrosion engineering on the surface of the alloy sheet
Ni obtained by rolling 40 Fe 20 Co 20 Al 20 Soaking the alloy sheet in the corrosive agent for 4 hours, taking out the alloy sheet, cleaning the alloy sheet with deionized water, and naturally airing the alloy sheet to obtain Ni 40 Fe 20 Co 20 Al 20 A fully hydrolyzed electro-catalytic material.
5) Testing of electrochemical Performance
Ni Using Silicone rubber 40 Fe 20 Co 20 Al 20 The non-electrochemical testing part of the full-electrolysis water electro-catalysis material is sealed, and the free surface with a fixed area is exposed for electrochemical testing. Test method for Ni by adopting linear voltammetry scanning 40 Fe 20 Co 20 Al 20 The fully hydrolyzed electrocatalytic materials were tested. The test uses a three-electrode system with a working electrode of Ni 40 Fe 20 Co 20 Al 20 The reference electrode is mercury/mercury oxide, the auxiliary electrode is a platinum sheet, and the electrolyte is 1mol/L potassium hydroxide solution. The polarization curves for oxygen evolution and hydrogen evolution obtained are shown in FIG. 9, and FIG. 9 shows that 10mA cm is reached -2 The overpotential for oxygen evolution is 335mV and the overpotential for hydrogen evolution is 270mV. This indicates Ni in the comparative example 40 Fe 20 Co 20 Al 20 The full-electrolysis electrocatalytic material does not have excellent oxygen evolution and hydrogen evolution catalytic activity。
The preparation method in example 1 was adopted to obtain the fully hydrolyzed hydro-electro-catalytic materials described in examples 5 to 8 (except that the parameters such as element content, cold rolling deformation, phase corrosion engineering time and the like were slightly different, and other conditions were the same as those in example 1). The details are shown in table 1:
TABLE 1 part parameters of examples 1 to 8
The invention is not the best known technology.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (10)
1. A high-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalysis material is characterized in that: the high-entropy alloy is Ni a Fe b Co c Cr d Al e The alloy consists of the following components in atomic ratio: 25 to 45 percent of Ni, 12.5 to 35 percent of Fe, 12.5 to 35 percent of Co, 12.5 to 35 percent of Cr and 12.5 to 17.5 percent of Al.
2. A preparation method of the high-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalytic material as claimed in claim 1, is characterized by comprising the following steps:
step 1) according to Ni a Fe b Co c Cr d Al e Weighing Ni, fe, co, cr and Al metal particles according to the atomic proportion in the alloy;
step 2), smelting the metal block particles prepared in the step 1) in a high vacuum arc smelting furnace, and obtaining Ni in a copper mold crucible a Fe b Co c Cr d Al e High-entropy alloy ingot casting;
step 3) of subjecting the Ni obtained in step 2) to a Fe b Co c Cr d Al e Putting the high-entropy alloy cast ingot into a vacuum turning furnace to prepare Ni a Fe b Co c Cr d Al e A high-entropy alloy plate;
step 4) mixing Ni in the step 3) a Fe b Co c Cr d Al e The high-entropy alloy plate is directly cut or cold-rolled to obtain Ni a Fe b Co c Cr d Al e A high entropy alloy sheet;
step 5) mixing Ni in the step 4) a Fe b Co c Cr d Al e And (3) soaking the high-entropy alloy sheet in corrosive liquid to prepare the high-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalytic material.
3. The preparation method of the high-activity micro-nano porous high-entropy alloy total electrolysis water electro-catalytic material according to claim 2, characterized in that in the step 2), the smelting process parameters are as follows:
the required vacuum degree before smelting is 3.5X 10 -3 Pa～5.0×10 -3 Pa；
Argon gas with the mass percent of 99.999 percent of 0.03-0.05 Mpa is filled as protective atmosphere;
the smelting current is 250-500A;
smelting time: 10-30 s;
the smelting times are as follows: 5-8 times.
4. The preparation method of the high-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalysis material according to claim 2 is characterized by comprising the following steps: in step 3), ni a Fe b Co c Cr d Al e The crystal structure of the high-entropy alloy is an FCC + BCC structure.
5. The preparation method of the high-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalysis material according to claim 2 is characterized by comprising the following steps: in the step 4), the rolling directions of the cold rolling are consistent, and the deformation amount is 50-90%.
6. The preparation method of the high-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalysis material according to claim 2 is characterized by comprising the following steps: in the step 5), the corrosive liquid is 3-10g of Cr 2 O 3 Adding into 3-5mol HCl solution to prepare the product, and soaking for 1-24 h.
7. The high-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalysis material prepared by the method of claim 2 is characterized in that the size of the electro-catalysis material is as follows: the length is 80 mm-100 mm, the width is 20 mm-100 mm, and the thickness is 0.5 mm-1 mm; the surface of the electrocatalytic material is in a micro-nano porous shape, the porosity is 40-70%, and the pore diameter is 0.1-40um.
8. The high-activity micro-nano porous high-entropy alloy full-electrolysis water electro-catalytic material of claim 7, which is characterized in that: in the crystal structure of the electrocatalytic material, the FCC accounts for more than or equal to 50 percent by volume percentage.
9. Use of a material according to claim 1, 7 or 8 as an anode and/or cathode material in total electrolysis water.
10. Use according to claim 9, characterized in that: at solution pH =14, the anode current density reached 10mA · cm -2 Under the condition that the overpotential is less than or equal to 300mV and the cathode current density reaches 10mA cm -2 In the case of (2), the overpotential is 250mV or less.
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| CN117210858A (en) * | 2023-11-09 | 2023-12-12 | 西北工业大学太仓长三角研究院 | Micron laser melting high-entropy alloy catalytic polar plate, preparation method and electrolyzed water application |
| CN117210858B (en) * | 2023-11-09 | 2024-01-26 | 西北工业大学太仓长三角研究院 | Micron laser melting high-entropy alloy catalytic polar plate, preparation method and electrolyzed water application |
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