CN111893357A - Self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material and preparation method thereof - Google Patents
Self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material and preparation method thereof Download PDFInfo
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Abstract
A preparation method of a self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material comprises the following steps: the method comprises the following steps: (1) preparing alloy powder: the alloy powder comprises the following components in atomic percentage: mn: 60% -70%; 5 to 20 percent of Ni; cu: 5% -10%; transition metal A: 5% -10%; transition metal B: 5% -15%; (2) preparing a membrane casting solution; (3) scraping the film; (4) sintering; (5) dealloying to obtain the self-supporting three-dimensional nanometer graded-hole high-entropy alloy. According to the preparation method of the self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolyzed water material, the obtained self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolyzed water material can realize self-supporting without any substrate or binder; the parameters of film scraping, sintering and dealloying are controlled, and the thickness and the pore size distribution of the self-supporting three-dimensional nano hierarchical pore high-entropy alloy film are easy to regulate and control.
Description
Technical Field
The invention relates to the field of electrolytic water materials and preparation thereof, in particular to a self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material and a preparation method thereof.
Background
With the development and progress of human society, it is a necessary way to realize sustainable development to explore and develop clean renewable energy. Among various renewable energy sources, hydrogen has attracted more extensive attention due to its low price and simple preparation. The field of electrolysis of water, especially of alkaline water, has been intensively studied and has made great progress as an important way of obtaining hydrogen. In the electrolysis of water, the oxygen evolution reaction is a four-electron reaction process, and the slow reaction kinetics of the oxygen evolution reaction become a great obstacle for limiting the high-efficiency electrolysis of water. At present, noble metal catalysts such as RuO2 and IrO2 show extremely high catalytic activity, but the noble metal reserves are rare, the price is high, and the large-scale application is difficult to achieve.
The transition metal has the advantages of rich reserves, low price and the like, also has higher catalytic activity, is expected to replace a noble metal catalyst, and realizes large-scale application. However, most of the transition metal catalysts are in powder state at present, and need to be coated on a conductive substrate by using a binder, which can seriously affect the number of active sites, stability and conductivity of the catalyst. Therefore, it is very important to develop a self-supporting three-dimensional hierarchical pore transition metal alloy catalyst, and the material can effectively improve the reaction active sites of the catalyst, and meanwhile, the stability and the conductivity of the material can be obviously improved because no binder is needed.
Disclosure of Invention
In view of the above, the present invention aims to provide a self-supporting three-dimensional nano graded-pore high-entropy alloy electrolytic water material and a preparation method thereof, so as to overcome the disadvantages of the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material comprises the following steps:
(1) preparing alloy powder: the alloy powder comprises the following components in atomic percentage: mn: 60% -70%; 5 to 20 percent of Ni; cu: 5% -10%; transition metal A: 5% -10%; transition metal B: 5% -15%, putting alcohol as a dispersing agent and alloy powder into a high-energy ball mill together for ball milling to perform mechanical alloying, and performing vacuum drying after the ball milling is completed to obtain uniformly dispersed alloy powder;
(2) preparing a casting solution: adding the alloy powder prepared in the step (1) and a solvent into a three-neck flask together for mechanical stirring; mechanically stirring for 10-30 min, adding a pore-forming agent and a thickening agent, and continuously stirring for 12-24 hours to obtain a casting solution with alloy powder, the pore-forming agent and the thickening agent uniformly dispersed in a solvent;
(3) film scraping: pouring the casting solution obtained in the step (2) onto a clean glass plate, selecting a film scraping rod with the thickness of 50-250 micrometers, pressing the obtained green film with two glass plates, and naturally drying;
(4) and (3) sintering: putting the green blank obtained in the step (3) into a tubular high-temperature furnace, introducing argon as a protective atmosphere, and heating to 100-200 ℃ at a heating rate of 1-3 ℃; continuously heating to 400-500 ℃ at the heating rate of 3-5 ℃, closing argon, and opening hydrogen as a reducing atmosphere; continuously heating to 850-1000 ℃ at the heating rate of 5-10 ℃, and preserving heat for 1-2 h; naturally cooling to 300 ℃ after heat preservation, closing hydrogen and introducing argon, and cooling to room temperature to obtain the self-supporting three-dimensional nano porous high-entropy alloy;
(5) and (3) carrying out dealloying treatment on the self-supporting three-dimensional nano porous high-entropy alloy obtained in the step (4) in an acid solution for 20-240 min to obtain the self-supporting three-dimensional nano hierarchical porous high-entropy alloy with the hierarchical pore structure.
Further, the method for preparing the alloy powder by mechanical alloying in the step (1) is to use a high-energy ball milling method, wherein the transition metal A is Fe or Ti, and the transition metal B is one of Co or V; adding 10-50 g of alloy powder raw materials into a high-energy ball mill, controlling the mass ratio of balls to materials to be 5: 1-50: 1, ball milling time to be 10-24 h, ball milling rotating speed to be 100-250 r/min, and preparing to obtain uniformly dispersed alloy powder by taking 10-25 ml of alcohol as a dispersing agent.
Further, the pore-forming agent in the step (2) is polyacrylonitrile, the solvent is N-methylpyrrolidone, and the thickening agent is polyvinylpyrrolidone; the mass ratio of the alloy powder to the solvent is 4: 3-2: 3; the adding amount of the pore-foaming agent is 10 to 20 percent of the mass of the alloy powder; the addition amount of the thickening agent is 15-20% of the mass of the pore-foaming agent.
Further, the blank obtained in the film scraping in the step (3) is 50-250 μm.
Furthermore, the introducing amount of the protective gas argon in the sintering in the step (4) is 100-300 sccm, and the introducing amount of the reducing gas hydrogen is 150-250 sccm.
Further, the acid solution in the dealloying treatment in the step (5) is a hydrochloric acid solution with the concentration of 0.025-0.1 mol/L, the dealloying treatment temperature is 20-60 ℃, and the dealloying treatment time is 20-240 min.
The self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material prepared by the preparation method.
Compared with the prior art, the self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material and the preparation method thereof have the following advantages:
1) the alloy powder is prepared by a high-energy ball-milling mechanical alloying method, and the prepared alloy powder is uniformly mixed and has fine particles, and meanwhile, the production cost can be effectively reduced; 2) sintering treatment is carried out in a protective atmosphere and a reducing atmosphere, the sintering temperature and the sintering time are controllable, and the pore diameter distribution on the surface and in the high-entropy alloy can be controlled; 3) the hydrochloric acid concentration, the dealloying time and the dealloying temperature are simple and controllable during dealloying treatment, and the pore size distribution of the hierarchical pores can be effectively regulated and controlled; 4) the obtained self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material can realize self-supporting without any substrate or binder; due to the hierarchical pore structure, more reactive sites can be provided for the water electrolysis process, and the reaction efficiency is improved; the alloy raw material selects transition metal, the price is low, and the production cost of the material can be effectively reduced.
Drawings
FIG. 1 is a macroscopic view of a self-supporting three-dimensional nano-graded-pore high-entropy alloy electrolytic water material in example 1;
FIG. 2 is an XRD pattern of the self-supporting three-dimensional nano-graded-hole high-entropy alloy electrolytic water material in example 1;
FIG. 3 is a diagram of an LSV (oxygen evolution reaction) of the self-supporting three-dimensional nano-graded-pore high-entropy alloy electrolytic water material in example 1;
FIG. 4 is a surface SEM image of the self-supporting three-dimensional nano-graded-hole high-entropy alloy electrolyzed water material in example 1.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
In the invention, the alloy, various solvents, pore-forming agent and thickening agent are purchased from common chemical shops. Is any kind of tube high temperature furnace known in the art. Oxygen evolution performance tests were performed using an electrochemical workstation as known in the art.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
A preparation method of a flexible nano porous metal oxide negative electrode for a lithium ion battery comprises the following steps:
(1) preparing alloy powder: the alloy powder comprises the following components in atomic percentage: mn: 60% -70%; 5 to 20 percent of Ni; cu: 5% -10%; transition metal A: 5% -10%; transition metal B: 5% -15%, putting alcohol as a dispersing agent and alloy powder into a high-energy ball mill together for ball milling to perform mechanical alloying, and performing vacuum drying after the ball milling is completed to obtain uniformly dispersed alloy powder;
(2) preparing a casting solution: adding the alloy powder prepared in the step (1) and a solvent into a three-neck flask together for mechanical stirring; mechanically stirring for 10-30 min, adding a pore-forming agent and a thickening agent, and continuously stirring for 12-24 hours to obtain a casting solution with alloy powder, the pore-forming agent and the thickening agent uniformly dispersed in a solvent;
(3) film scraping: pouring the casting solution obtained in the step (2) onto a clean glass plate, selecting a film scraping rod with the thickness of 50-250 micrometers, pressing the obtained green film with two glass plates, and naturally drying;
(4) and (3) sintering: putting the green blank obtained in the step (3) into a tubular high-temperature furnace, introducing argon as a protective atmosphere, and heating to 100-200 ℃ at a heating rate of 1-3 ℃; continuously heating to 400-500 ℃ at the heating rate of 3-5 ℃, closing argon, and opening hydrogen as a reducing atmosphere; continuously heating to 850-1000 ℃ at the heating rate of 5-10 ℃, and preserving heat for 1-2 h; naturally cooling to 300 ℃ after heat preservation, closing hydrogen and introducing argon, and cooling to room temperature to obtain the self-supporting three-dimensional nano porous high-entropy alloy;
(5) and (3) carrying out dealloying treatment on the self-supporting three-dimensional nano porous high-entropy alloy obtained in the step (4) in an acid solution for 20-240 min to obtain the self-supporting three-dimensional nano hierarchical porous high-entropy alloy with the hierarchical pore structure.
Example 1
A self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material and a preparation method thereof comprise the following steps:
(1) preparing alloy powder: mixing the component powder in atomic ratio: mn: 68 percent; 8 percent of Ni; cu: 8 percent; fe: 8 percent; co: mixing 8% of the raw materials into alloy powder, adding 25g of the alloy powder raw materials into a high-energy ball mill, controlling the mass ratio of ball materials to be 5:1, the ball milling time to be 24 hours, the ball milling speed to be 200r/min, and preparing to obtain uniformly dispersed alloy powder by taking 15ml of alcohol as a dispersing agent;
(2) preparing a casting solution, namely adding 20g of the alloy powder prepared in the step (1) and 25g of a solvent into a three-neck flask together for mechanical stirring; mechanically stirring for 10min, adding 3g of pore-forming agent and 0.5g of thickening agent, and continuously stirring for 24 hours to obtain a casting solution with the alloy powder, the pore-forming agent and the thickening agent uniformly dispersed in a solvent, wherein the pore-forming agent is polyacrylonitrile, the solvent is N-methylpyrrolidone, and the thickening agent is polyvinylpyrrolidone;
(3) film scraping: pouring the casting solution obtained in the step (2) on a clean glass plate, selecting a film scraping rod with the thickness of 200 mu m, pressing the obtained green film with two glass plates, and naturally drying to obtain a green blank with the thickness of 200 mu m;
(4) and (3) sintering: putting the green blank obtained in the step (3) into a tubular high-temperature furnace, introducing 300sccm argon as protective atmosphere, and heating to 100 ℃ at a heating rate of 2 ℃; then, continuously heating to 400 ℃ at the heating rate of 3 ℃, closing argon, and opening 200sccm hydrogen as a reducing atmosphere; continuously heating to 950 ℃ at the heating rate of 5 ℃, and preserving heat for 1 h; naturally cooling to 300 ℃ after heat preservation, closing hydrogen and introducing argon, and cooling to room temperature to obtain the self-supporting three-dimensional nano porous high-entropy alloy;
(5) and (3) carrying out dealloying treatment on the self-supporting three-dimensional nano porous high-entropy alloy in the step (4) in 0.05mol/L hydrochloric acid solution for 30min, wherein the dealloying treatment temperature is 25 ℃, and obtaining the self-supporting three-dimensional nano hierarchical porous high-entropy alloy with the hierarchical pore structure.
(6) Testing the oxygen evolution performance: and testing the oxygen evolution performance of the material by adopting a three-electrode system.
FIG. 1 is a macroscopic view of a self-supporting three-dimensional nano-graded-pore high-entropy alloy electrolytic water material in example 1, and it can be seen from the macroscopic view that an alloy film after sintering is regular in shape, smooth in surface and has certain toughness;
FIG. 2 is an XRD pattern of the self-supporting three-dimensional nano-graded-hole high-entropy alloy electrolytic water material in example 1, and from the XRD pattern, it can be seen that a uniform alloy phase is formed in a green body after ball milling and sintering;
FIG. 3 is a LSV (oxygen evolution reaction) diagram of the self-supporting three-dimensional nano-graded-pore high-entropy alloy electrolytic water material in example 1, and it can be seen from the diagram that when the current density reaches 10mA/cm2, the corresponding voltage is 1.77V, and the self-supporting three-dimensional nano-graded-pore high-entropy alloy electrolytic water material has relatively good catalytic performance.
FIG. 4 is a surface SEM image of the self-supporting three-dimensional nano-graded-pore high-entropy alloy water electrolysis material in example 1, and it can be seen from the surface SEM image that the material surface is a porous structure with uniform distribution and pore size of 2-5 μm.
Example 2
A self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material and a preparation method thereof comprise the following steps:
(1) preparing alloy powder: mixing the component powder in atomic ratio: mn: 60 percent; 10 percent of Ni; cu: 10 percent; ti: 10 percent; v: mixing 10% of the raw materials into alloy powder, adding 25g of the raw materials into a high-energy ball mill, controlling the mass ratio of the ball materials to be 10:1, the ball milling time to be 12 hours, the ball milling speed to be 150r/min, and preparing to obtain uniformly dispersed alloy powder by taking 10ml of alcohol as a dispersing agent;
(2) preparing a casting solution: adding 15g of the alloy powder prepared in the step (1) and 20g of solvent into a three-neck flask together for mechanical stirring; mechanically stirring for 10min, adding 2.5g of pore-forming agent and 0.5g of thickening agent, and continuously stirring for 12h to obtain a casting solution with the alloy powder, the pore-forming agent and the thickening agent uniformly dispersed in a solvent, wherein the pore-forming agent is polyacrylonitrile, the solvent is N-methylpyrrolidone, and the thickening agent is polyvinylpyrrolidone;
(3) film scraping: pouring the casting solution obtained in the step (2) on a clean glass plate, selecting a film scraping rod with the thickness of 150 microns, pressing the obtained green film with two glass plates, and naturally drying to obtain a green blank with the thickness of 150 microns;
(4) and (3) sintering: putting the green blank obtained in the step (3) into a tubular high-temperature furnace, introducing 250sccm argon as protective atmosphere, and heating to 100 ℃ at a heating rate of 2 ℃; then, continuously heating to 400 ℃ at the heating rate of 5 ℃, closing argon, and opening 250sccm hydrogen as a reducing atmosphere; continuously heating to 900 ℃ at the heating rate of 10 ℃, and keeping the temperature for 2 h; naturally cooling to 300 ℃ after heat preservation, closing hydrogen and introducing argon, and cooling to room temperature to obtain the self-supporting three-dimensional nano porous high-entropy alloy;
(5) and (3) carrying out dealloying treatment on the self-supporting three-dimensional nano porous high-entropy alloy in the step (4) in 0.025mol/L hydrochloric acid solution for 60min, wherein the dealloying treatment temperature is 60 ℃, and obtaining the self-supporting three-dimensional nano hierarchical porous high-entropy alloy with the hierarchical pore structure.
(6) Testing the oxygen evolution performance: and testing the oxygen evolution performance of the material by adopting a three-electrode system.
Example 3
A self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material and a preparation method thereof comprise the following steps:
(1) preparing alloy powder: mixing the component powder in atomic ratio: mn: 64 percent; 9 percent of Ni; cu: 9 percent; fe: 9 percent; v: mixing 9% of the raw materials into alloy powder, adding 30g of the alloy powder raw materials into a high-energy ball mill, controlling the mass ratio of ball materials to be 15:1, the ball milling time to be 18h, the ball milling rotating speed to be 250r/min, and preparing to obtain uniformly dispersed alloy powder by taking 15ml of alcohol as a dispersing agent;
(2) preparing a casting solution, namely adding 20g of the alloy powder prepared in the step (1) and 20g of a solvent into a three-neck flask together for mechanical stirring; mechanically stirring for 15min, adding 4g of pore-forming agent and 0.8g of thickening agent, and continuously stirring for 18 hours to obtain a casting solution with the alloy powder, the pore-forming agent and the thickening agent uniformly dispersed in a solvent, wherein the pore-forming agent is polyacrylonitrile, the solvent is N-methylpyrrolidone, and the thickening agent is polyvinylpyrrolidone;
(3) film scraping: pouring the casting solution obtained in the step (2) on a clean glass plate, selecting a film scraping rod with the thickness of 100 microns, pressing the obtained green film with two glass plates, and naturally drying to obtain a green blank with the thickness of 100 microns;
(4) and (3) sintering: putting the green blank obtained in the step (3) into a tubular high-temperature furnace, introducing 200sccm argon as protective atmosphere, and heating to 100 ℃ at a heating rate of 1 ℃; then, continuously heating to 400 ℃ at the heating rate of 3 ℃, closing argon, and opening 150sccm hydrogen as a reducing atmosphere; continuously heating to 800 ℃ at the heating rate of 8 ℃, and keeping the temperature for 2 hours; naturally cooling to 300 ℃ after heat preservation, closing hydrogen and introducing argon, and cooling to room temperature to obtain the self-supporting three-dimensional nano porous high-entropy alloy;
(5) and (3) carrying out dealloying treatment on the self-supporting three-dimensional nano porous high-entropy alloy obtained in the step (4) in 0.1mol/L hydrochloric acid solution for 90min, wherein the dealloying treatment temperature is 30 ℃, and thus obtaining the self-supporting three-dimensional nano hierarchical porous high-entropy alloy with the hierarchical pore structure.
(6) Testing the oxygen evolution performance: and testing the oxygen evolution performance of the material by adopting a three-electrode system.
The alloy powder is directly prepared by a high-energy ball milling mechanical alloying method, and the alloy film with uniform thickness is obtained by preparing a casting film liquid and scraping the film; carrying out heat treatment in a protective atmosphere and a reducing atmosphere to obtain a high-entropy alloy film with uniform pore size distribution, and meanwhile, because the heat treatment process is controllable, the pore sizes on the surface and in the high-entropy alloy film can be regulated and controlled; the alloy film is further processed through dealloying treatment, so that the alloy material forms a hierarchical pore structure, the specific surface area of the material is increased, and more active sites are provided for electrolytic water reaction. Compared with the prior art, the method is simpler, the raw materials are mostly transition metals, the material cost can be effectively reduced, and the pore structure is directly sintered and dealloyed on the alloy film, so that the alloy material can realize self-support without any binder and substrate, and has good toughness.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A preparation method of a self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing alloy powder: the alloy powder comprises the following components in atomic percentage: mn: 60% -70%; 5 to 20 percent of Ni; cu: 5% -10%; transition metal A: 5% -10%; transition metal B: 5% -15%, putting alcohol as a dispersing agent and alloy powder into a high-energy ball mill together for ball milling to perform mechanical alloying, and performing vacuum drying after the ball milling is completed to obtain uniformly dispersed alloy powder;
(2) preparing a casting solution: adding the alloy powder prepared in the step (1) and a solvent into a three-neck flask together for mechanical stirring; mechanically stirring for 10-30 min, adding a pore-forming agent and a thickening agent, and continuously stirring for 12-24 hours to obtain a casting solution with alloy powder, the pore-forming agent and the thickening agent uniformly dispersed in a solvent;
(3) film scraping: pouring the casting solution obtained in the step (2) onto a clean glass plate, selecting a film scraping rod with the thickness of 50-250 micrometers, pressing the obtained green film with two glass plates, and naturally drying;
(4) and (3) sintering: putting the green blank obtained in the step (3) into a tubular high-temperature furnace, introducing argon as a protective atmosphere, and heating to 100-200 ℃ at a heating rate of 1-3 ℃; continuously heating to 400-500 ℃ at the heating rate of 3-5 ℃, closing argon, and opening hydrogen as a reducing atmosphere; continuously heating to 850-1000 ℃ at the heating rate of 5-10 ℃, and preserving heat for 1-2 h; naturally cooling to 300 ℃ after heat preservation, closing hydrogen and introducing argon, and cooling to room temperature to obtain the self-supporting three-dimensional nano porous high-entropy alloy;
(5) and (3) carrying out dealloying treatment on the self-supporting three-dimensional nano porous high-entropy alloy obtained in the step (4) in an acid solution for 20-240 min to obtain the self-supporting three-dimensional nano hierarchical porous high-entropy alloy with the hierarchical pore structure.
2. The preparation method of the self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolyzed water material as claimed in claim 1, characterized in that: the method for preparing the alloy powder by mechanical alloying in the step (1) is to use a high-energy ball milling method, wherein a transition metal A is Fe or Ti, and a transition metal B is one of Co or V; adding 10-50 g of alloy powder raw materials into a high-energy ball mill, controlling the mass ratio of balls to materials to be 5: 1-50: 1, ball milling time to be 10-24 h, ball milling rotating speed to be 100-250 r/min, and preparing to obtain uniformly dispersed alloy powder by taking 10-25 ml of alcohol as a dispersing agent.
3. The preparation method of the self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolyzed water material as claimed in claim 1, characterized in that: the pore-forming agent in the step (2) is polyacrylonitrile, the solvent is N-methyl pyrrolidone, and the thickening agent is polyvinylpyrrolidone; the mass ratio of the alloy powder to the solvent is 4: 3-2: 3; the adding amount of the pore-foaming agent is 10 to 20 percent of the mass of the alloy powder; the addition amount of the thickening agent is 15-20% of the mass of the pore-foaming agent.
4. The self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material and the preparation method thereof according to claim 1 are characterized in that: the blank obtained in the step (3) of film scraping is 50-250 microns.
5. The self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material and the preparation method thereof according to claim 1 are characterized in that: and (4) introducing the protective gas argon into the sintering in the step (4) at a flow rate of 100-300 sccm, and introducing the reducing gas hydrogen into the sintering at a flow rate of 150-250 sccm.
6. The self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material and the preparation method thereof according to claim 1 are characterized in that: the acid solution in the dealloying treatment in the step (5) is hydrochloric acid solution with the concentration of 0.025-0.1 mol/L, the dealloying treatment temperature is 20-60 ℃, and the dealloying treatment time is 20-240 min.
7. The self-supporting three-dimensional nano-graded-pore high-entropy alloy electrolytic water material prepared by the preparation method according to any one of claims 1 to 6.
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| CN112553576A (en) * | 2020-11-30 | 2021-03-26 | 江苏理工学院 | Porous high-entropy alloy oxide film and preparation method thereof |
| CN114763587A (en) * | 2022-04-07 | 2022-07-19 | 天津工业大学 | Self-supporting element co-doped nickel-based high-entropy alloy electrolytic water material and preparation method thereof |
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| CN112553576A (en) * | 2020-11-30 | 2021-03-26 | 江苏理工学院 | Porous high-entropy alloy oxide film and preparation method thereof |
| CN112553576B (en) * | 2020-11-30 | 2022-09-30 | 江苏理工学院 | Porous high-entropy alloy oxide film and preparation method thereof |
| CN114763587A (en) * | 2022-04-07 | 2022-07-19 | 天津工业大学 | Self-supporting element co-doped nickel-based high-entropy alloy electrolytic water material and preparation method thereof |
| CN114763587B (en) * | 2022-04-07 | 2024-01-26 | 天津工业大学 | Self-supporting element co-doped nickel-based high-entropy alloy electrolyzed water material and preparation method thereof |
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