A nickel-based electrode with high corrosion resistance and strong gas evolution performance and a preparation method thereof

Abstract

The application discloses a nickel-based electrode with high corrosion resistance and strong gas evolution performance and a preparation method thereof. The application has high safety, does not involve high-temperature and high-pressure processes, and does not use organic solvents, thereby reducing environmental and operation risks and ensuring the safety and reliability of a production process. Secondly, the method supports macro-preparation, acid treatment can be performed at room temperature, and plasma treatment can be completed at low temperature, so that the process conditions are mild and suitable for large-scale production and practical application. In addition, the method has a simple and efficient process flow, raw materials are easy to obtain, and equipment requirements are low, thereby significantly reducing production costs. This feature makes the method have good economy and generalization, and can meet the demand of industrialized preparation. The nitrogen-doped aluminum-nickel alloy coating nickel mesh prepared through the process not only has excellent electrochemical performance, but also has good corrosion resistance and gas evolution performance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of material surface treatment, and particularly relates to a nickel-based electrode with high corrosion resistance and strong gas analysis performance and a preparation method thereof. BACKGROUND

[0002] Hydrogen energy is considered as an efficient and clean energy carrier of sustainable energy system due to its high energy density and less pollution. Compared with acidic water electrolysis and neutral water electrolysis, alkaline water electrolysis is widely studied due to its lower corrosion and more cost-effective equipment. Because seawater is the most abundant water resource on earth, it has great potential for large-scale production of H2, and can also avoid the increase of fresh water use, so the current development is mainly on seawater electrolysis to produce hydrogen. However, the main challenge of directly decomposing natural seawater is the chlorine evolution reaction competing with the oxygen evolution reaction (OER), which not only reduces the durability of the catalyst due to corrosion, but also reduces the efficiency of decomposing natural seawater. An effective method to solve the current problems in direct seawater electrolysis is to increase the pH value of seawater to slightly alkaline (i.e. alkaline seawater electrolysis), and another method is to develop effective electrocatalysts. Although noble metal-based electrocatalysts are the benchmark catalysts for hydrogen evolution reaction (HER) and OER in alkaline electrolyte, they cannot be widely used due to high cost, scarcity and unstable performance.

[0003] Therefore, it is crucial to develop efficient, low-cost, non-noble metal alkaline seawater electrolysis electrocatalysts. At present, most of the electrocatalysts used for alkaline seawater electrolysis are integrated self-supporting structure electrodes, in which most of the electroactive materials (such as: Pt / Ni-Mo-N-O, Pt-Co-Mo, Mo-CoPX / NF, CoFe@CoNi, etc.) are grown on three-dimensional substrates (such as: nickel mesh, nickel foam, etc.). Nickel-based alloy is a kind of electrocatalytic hydrogen evolution material with excellent electrochemical performance. In recent years, people have actively developed nickel-based electrodes with high hydrogen evolution activity from the aspects of energy factors and geometric factors, which has greatly developed nickel-based alloys. Among them, compared with other alloy materials, aluminum-nickel alloy is more mature in the industrial application of alkaline water electrolysis, but it still has a high overpotential in alkaline electrolyte, and its application in alkaline seawater electrolysis is less.

[0004] On the other hand, nickel mesh is listed as the first choice among many substrate materials due to its good electrical conductivity, low price and 3D network structure. Nickel mesh not only allows active materials to grow from bottom to top on its support, but also makes electrolyte more easily penetrate. As a whole electrocatalyst, the catalytic activity of nickel mesh can be enhanced by different surface modification strategies. For example, T. Shahrabi et al. published an article entitled Surface modification of Ni foam by the dendrite Ni-Cu electrode for hydrogen evolution reaction in an alkaline solution in the Journal of Electroanalytical Chemistry, which proposed that the original nickel foam was optimized by dendritic coating to synthesize Ni-Cu catalyst, and the HER activity was enhanced. However, few studies have modified alloy-coated nickel mesh into a whole electrode with strong corrosion resistance and strong gas evolution to realize a bifunctional integrated electrocatalyst for HER and OER in alkaline seawater. Therefore, in order to realize efficient alkaline seawater electrolysis, it is crucial to modify alloy catalysts and prepare nickel-based electrodes with high corrosion resistance and strong gas evolution.

[0005] Therefore, the present application is proposed. SUMMARY

[0006] The technical problem solved by the present application is to overcome the shortcomings of the prior art and provide a nickel-based electrode with high corrosion resistance and strong gas evolution performance and a preparation method thereof, which solves the problems proposed in the above background art.

[0007] To solve the above technical problems, the basic idea of the technical solution of the present application is:

[0008] The preparation method of the nickel-based electrode with high corrosion resistance and strong gas evolution performance comprises the following steps:

[0009] Step A: use aluminum-nickel alloy coated nickel mesh as precursor material, immerse it in acid solution at room temperature for 10-120 minutes, and then rinse with deionized water and ethanol to remove acid residues;

[0010] Step B: dry the rinsed nickel mesh in a vacuum environment, and obtain the acid-treated aluminum-nickel alloy coated nickel mesh after drying;

[0011] Step C: place the acid-treated aluminum-nickel alloy coated nickel mesh in a plasma treatment machine and perform plasma treatment in a vacuum environment, and obtain a self-supported nitrogen-doped aluminum-nickel alloy water electrolysis electrode after plasma treatment.

[0012] Optionally, the number of times of rinsing in step A is 3-5 times using deionized water and ethanol.

[0013] Optionally, the acid solution in step A is one of sulfuric acid solution, hydrochloric acid solution or nitric acid solution, and the concentration of the acid solution is 0.01-2.0 mol / L.

[0014] Optionally, nitrogen is needed to be introduced during the plasma treatment in step C, wherein the flow rate of the nitrogen is 50-200 ml / min, and the treatment time is 0.1-2.0 hours.

[0015] Optionally, the nickel mesh in step A is selected from any one of 20 mesh, 40 mesh, 46 mesh, 60 mesh and 80 mesh.

[0016] Optionally, the alloy in the aluminum-nickel alloy coating in step A is Ni 1.1 Al 0.9 .

[0017] The preparation method of the nickel-based electrode with high corrosion resistance and strong gas evolution performance.

[0018] After the above technical solution is adopted, the present application has the following beneficial effects compared with the prior art, of course, any product implementing the present application does not necessarily need to achieve all the advantages described below:

[0019] The present application has high safety, does not involve high-temperature and high-pressure processes, and does not use organic solvents, thereby reducing environmental and operation risks and ensuring the safety and reliability of the production process. Secondly, the method supports macro-preparation, acid treatment can be carried out at room temperature, and plasma treatment can be completed at low temperature, the process conditions are mild, and it is suitable for large-scale production and practical application. In addition, the process flow of the method is simple and efficient, the raw materials used are easy to obtain, and the equipment requirements are low, thereby significantly reducing the production cost. This feature makes it have good economy and generalizability, and can meet the needs of industrialized preparation. The nitrogen-doped aluminum-nickel alloy coated nickel mesh prepared by the process not only has excellent electrochemical performance, but also exhibits good corrosion resistance and gas evolution performance.

[0020] The specific embodiments of the present application will be described in further detail below with reference to the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0021] The drawings in the following description are only some embodiments, and other drawings can be obtained by those skilled in the art without creative labor on the basis of these drawings. In the drawings:

[0022] Figure 1 The characterization results of the nitrogen-doped aluminum-nickel alloy coated nickel mesh electrode prepared in Example 1 of the present application; wherein,Figure 1 (a) is an XRD pattern; Figure 1 (b) is an SEM pattern; Figure 1 (c) is an elemental mapping; Figure 1 (d) is an EDS pattern;

[0023] Figure 2 The HER-LSV (a), OER-LSV (b) and overall water splitting activity-LSV (c) curves of the nitrogen-doped aluminum-nickel alloy coated nickel mesh prepared in Example 1 of the present application and the nitrogen-doped nickel mesh, the pickled aluminum-nickel alloy coated nickel mesh and the non-pickled directly nitrogen-doped aluminum-nickel alloy coated nickel mesh prepared in Comparative Examples 1, 2 and 3;

[0024] Figure 3 The photos of the gas bubbles generated in the process of electrolysis of water of the nitrogen-doped aluminum-nickel alloy coated nickel mesh (a) prepared in Example 1 and the aluminum-nickel alloy coated nickel mesh (b) without nitrogen doping;

[0025] Figure 4 The SEM pattern (a) and the elemental distribution pattern (b) of the aluminum-nickel alloy coated nickel mesh prepared in Example 2;

[0026] Figure 5 The SEM pattern of the nitrogen-doped aluminum-nickel alloy coated nickel mesh prepared in Example 4;

[0027] Figure 6 The SEM pattern, the elemental mapping and the EDS pattern of the nitrogen-doped nickel mesh prepared in Comparative Example 1.

[0028] It should be noted that these drawings and written description are not intended to limit the scope of the inventive concept in any way, but rather to illustrate the inventive concept to those skilled in the art by reference to specific embodiments. DETAILED DESCRIPTION

[0029] The various illustrative embodiments of the present application will now be described in detail below. The detailed description is made in connection with the illustrative figures. The detailed description describes certain aspects, features, and embodiments of the present application. It is to be understood that the detailed description is included solely for the purpose of illustrating the present application, but not intended to limit the present application, which is defined solely by the claims.

[0030] It should be understood that the terms used in the present application are merely used to describe particular embodiments and are not intended to limit the present application. In addition, for the numerical ranges in the present application, it should be understood that each intermediate value between the upper limit and the lower limit of the range is also specifically disclosed. Each smaller range within the range of the intermediate values and any other stated value or intermediate value within the range is also included in the present application. The upper limit and the lower limit of these smaller ranges can be independently included or excluded from the range.

[0031] Unless otherwise indicated, all technical and scientific terms have the same meaning as those one of ordinary skill in the art of the disclosure would understand. Although preferred methods and materials are described, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure. All documents mentioned herein are incorporated by reference to disclose and describe in further detail the methods and / or materials associated with the documents. In the case of conflict between the present specification and any incorporated document, the present specification controls.

[0032] Many modifications and variations of the present disclosure described in the detailed description of the specification can be made without departing from the scope or spirit of the present disclosure, which will be apparent to those skilled in the art. Other implementations of the disclosure will be apparent to those skilled in the art from the specification. The specification and examples of the present disclosure are merely illustrative.

[0033] As used herein, "comprise", "comprising", "have", "having", "include", "including", "contain", "containing", and the like, are open-ended terms that are intended to mean including, but not limited to.

[0034] See Figures 1-6 As shown in the present embodiment, a method for preparing a nickel-based electrode with high corrosion resistance and strong gas evolution performance is provided, comprising the following steps:

[0035] Step A: Use aluminum-nickel alloy coated nickel mesh as precursor material, immerse it in an acid solution at room temperature for 10-120 minutes, then use deionized water and ethanol to rinse to remove acid residues;

[0036] Step B: Dry the rinsed nickel mesh in a vacuum environment, and obtain the acid-treated aluminum-nickel alloy coated nickel mesh after drying;

[0037] Step C: Place the acid-treated aluminum-nickel alloy coated nickel mesh in a plasma treatment machine and perform plasma treatment in a vacuum environment, and obtain a self-supported nitrogen-doped aluminum-nickel alloy water electrolysis electrode after plasma treatment.

[0038] In the present embodiment, the number of times of rinsing with deionized water and ethanol in step A is 3-5 times.

[0039] In the present embodiment, the acid solution in step A is one of sulfuric acid solution, hydrochloric acid solution or nitric acid solution, and the concentration of the acid solution is 0.01-2.0 mol / L.

[0040] In the present embodiment, nitrogen gas needs to be introduced during plasma treatment in step C, wherein the nitrogen gas flow is 50-200 ml / min, and the treatment time is 0.1-2.0 hours.

[0041] In the embodiment, the nickel mesh in step A is selected from any one of 20 mesh, 40 mesh, 46 mesh, 60 mesh and 80 mesh.

[0042] In the embodiment, the alloy in the aluminum-nickel alloy coating in step A is Ni 1.1 Al 0.9 .

[0043] The application will be further described in detail in combination with the embodiments.

[0044] It should be noted that all raw materials in the embodiments of the application are obtained through commercial channels.

[0045] Embodiment 1: A preparation method of a nickel-based electrode with high corrosion resistance and strong gas evolution performance is provided, comprising the following steps:

[0046] Step A: Prepare a hydrochloric acid solution with a concentration of 0.5 mol / L as an acid treatment solution. Soak the commercially available aluminum-nickel alloy coated nickel mesh with a size of 1×4 cm -2 in the hydrochloric acid solution. Stand and soak at room temperature for 30 minutes to remove impurities on the surface of the nickel mesh and improve the surface activity. After soaking, rinse with deionized water and ethanol three times respectively to ensure that the residual acidic substances on the surface are completely removed. After rinsing, dry the nickel mesh in a vacuum environment to obtain an aluminum-nickel alloy coated nickel mesh after acid treatment.

[0047] Step B: Put the nickel mesh after acid treatment into a plasma treatment machine for plasma treatment. During the treatment process, the treatment machine is vacuumized and nitrogen gas is introduced with a flow rate controlled at 150 ml / min. The plasma treatment in the nitrogen environment lasts for 1 hour to ensure that the nitrogen element is uniformly doped into the surface of the aluminum-nickel alloy coated nickel mesh, thereby enhancing the chemical performance and catalytic activity of the electrode.

[0048] Step C: After plasma treatment, a self-supporting nitrogen-doped aluminum-nickel alloy water electrolysis electrode is prepared.

[0049] The microstructure of the nitrogen-doped aluminum-nickel alloy coated nickel mesh prepared in the embodiment is characterized by SEM (scanning electron microscope) and XRD (X-ray diffraction) tests. As shown in Figure 1 the SEM image, the nitrogen element is uniformly doped on the surface of the nickel-based electrode, indicating that the plasma treatment realizes the uniformity of the nitriding of the material surface. The aluminum-nickel alloy particles are uniformly distributed on the nickel mesh matrix to form an ideal three-dimensional structure, which helps to improve the rapid evolution and mass transfer efficiency of the gas in the electrolysis process.

[0050] From Figure 1XRD patterns in (a) can be observed, the appearance of (111), (200) and (220) crystal face peaks of nickel mesh at 44.507°, 51.846° and 76.37° respectively, indicating that the crystal structure of nickel mesh is retained. At the same time, the diffraction peaks at 31.211°, 44.680°, 55.508°, 65.021° and 73.867° correspond to the (100), (110), (111), (200) and (210) crystal faces of Al 1.1 Ni 0.9 alloy, indicating that the aluminum-nickel alloy grows uniformly in the electrode. It can be seen that the electrode maintains good crystal structure and conductivity after nitrogen doping.

[0051] In addition, through elemental mapping analysis Figure 1 (c), it can be clearly seen that Al, Ni and N elements are uniformly distributed on the surface of the electrode. This indicates that the nitrogen element not only successfully doped into the aluminum-nickel alloy, but also achieved uniform diffusion in the entire nickel mesh structure. Further EDS (energy spectrum analysis) test shows that the doping amount of nitrogen is 1.8wt%, indicating that the introduction amount of nitrogen element reaches the ideal level, ensuring the corrosion resistance and catalytic performance of the material.

[0052] HER (hydrogen evolution reaction) and OER (oxygen evolution reaction) performance tests in simulated seawater environment show excellent performance of the electrode. As shown in Figure 2 (a), the hydrogen evolution reaction overpotential of the nitrogen-doped electrode is 182mV at a current density of 100mA / cm², which is significantly better than other comparative samples, such as: nitrogen-doped nickel mesh (514mV), acid-washed aluminum-nickel alloy coated nickel mesh (342mV), and aluminum-nickel alloy coated nickel mesh without acid washing and direct nitrogen doping (283mV). These results show that the synergistic effect of acid washing and nitrogen doping effectively reduces the overpotential and improves the efficiency of the hydrogen evolution reaction.

[0053] Similarly, in the OER test shown in Figure 2 (b), the overpotential of the nitrogen-doped aluminum-nickel alloy coated nickel mesh is 180mV, which is much better than other comparative samples, such as: nitrogen-doped nickel mesh (460mV), acid-washed aluminum-nickel alloy coated nickel mesh (320mV), and nitrogen-doped aluminum-nickel alloy coating without acid washing (230mV). These data prove that the electrode has excellent oxygen evolution reaction activity in alkaline environment.

[0054] In addition, in Figure 2The full electrolysis water activity test in (b) shows that the electrolysis potential of this electrode is only 1.2V at a current density of 100mA / cm², which is significantly better than other samples, such as: nitrogen-doped nickel mesh (2.2V), acid-washed aluminum-nickel alloy coated nickel mesh (1.83V), and non-acid-washed nitrogen-doped aluminum-nickel alloy coating (1.87V). This result demonstrates the superiority of the prepared electrode in the overall electrolysis water reaction.

[0055] From Figure 3 the bubble release photos in (b), it can be further verified that the nitrogen doping has a positive effect. During the electrolysis of water, the nitrogen-doped nickel-based electrode (a) releases bubbles that are much finer and denser than the non-nitrogen-doped nickel mesh (b), indicating that nitrogen doping not only improves the surface activity of the electrode, but also optimizes the kinetic characteristics of gas release. Figure 3 Figure 3 (b) compared to the non-nitrogen-doped nickel mesh (b), the released bubbles are much finer and denser, indicating that nitrogen doping not only improves the surface activity of the electrode, but also optimizes the kinetic characteristics of gas release.

[0056] In summary, the nitrogen-doped aluminum-nickel alloy coated nickel mesh electrode prepared in this embodiment has significant corrosion resistance and excellent electrochemical performance, and exhibits high hydrogen and oxygen evolution reaction activity in alkaline environment, making it an ideal electrolysis water electrode material.

[0057] Example 2: A method for preparing a nickel-based electrode with high corrosion resistance and strong gas evolution performance is provided, comprising the following steps:

[0058] Step A: Prepare a hydrochloric acid solution with a concentration of 0.01mol / L as an acid treatment solution. Soak a commercially available aluminum-nickel alloy coated nickel mesh with a size of 1x4cm -2 in the hydrochloric acid solution. Place it in a room temperature environment for 120 minutes of soaking to remove impurities on the surface of the nickel mesh and improve its surface activity. After soaking, rinse it with deionized water and ethanol three times each to ensure that the residual acidic substances on the surface are completely removed. After rinsing, dry the nickel mesh in a vacuum environment to obtain an acid-treated aluminum-nickel alloy coated nickel mesh.

[0059] Step B: Place the acid-treated nickel mesh in a plasma treatment machine for plasma treatment. During the treatment process, the treatment machine is evacuated and nitrogen gas is introduced at a flow rate of 200ml / min. The plasma treatment in a nitrogen environment lasts for 2 hours to ensure that nitrogen elements are uniformly doped onto the surface of the aluminum-nickel alloy coated nickel mesh, enhancing the chemical properties and catalytic activity of the electrode.

[0060] Step C: After plasma treatment, a self-supported nitrogen-doped aluminum-nickel alloy electrolysis water electrode is obtained.

[0061] The microstructure of the nitrogen-doped aluminum-nickel alloy coated nickel mesh can be observed through SEM images (such as Figure 4 ​(a) and (b) show the elemental mapping of the nickel mesh surface. As can be seen from the figures, the aluminum-nickel alloy particles remain intact and uniformly distributed on the surface of the nickel mesh, indicating that the nitrogen doping process did not cause significant damage to the microstructure of the material. The aluminum-nickel alloy particles on the surface of the nickel mesh maintain an ideal crystalline state, which helps to maintain the electrical conductivity and structural stability of the electrode, ensuring its long-term durability in the process of electrolyzing water. In addition, this particle structure provides good channels for the penetration of electrolyte and the rapid evolution of gas, which is beneficial to improve the overall catalytic performance of the electrode.

[0062] The elemental mapping test results are shown in FIGS. 1 Figure 4 (b), which shows the distribution of nitrogen, aluminum and nickel elements on the surface of the nickel mesh. As can be seen from the elemental mapping, although the nitrogen doping process was carried out, the distribution of nitrogen element in the nickel mesh structure is not obvious, indicating that nitrogen has not been effectively doped on the surface of the material.

[0063] Example 3: A method for preparing a nickel-based electrode with high corrosion resistance and strong gas evolution performance is provided, comprising the following steps:

[0064] Step A: Prepare a hydrochloric acid solution with a concentration of 0.01 mol / L as an acid treatment solution. Soak the commercially available aluminum-nickel alloy coated nickel mesh with a size of 1 x 4 cm -2 in the hydrochloric acid solution. Place it in a room temperature environment for 120 minutes of soaking to remove impurities on the surface of the nickel mesh and improve its surface activity. After soaking, rinse it with deionized water and ethanol three times each to ensure that the residual acidic substances on the surface are completely removed. After rinsing, dry the nickel mesh in a vacuum environment to obtain an acid-treated aluminum-nickel alloy coated nickel mesh.

[0065] Step B: Place the acid-treated nickel mesh into a plasma treatment machine for plasma treatment. During the treatment process, the treatment machine is vacuumed and nitrogen gas is introduced at a flow rate of 200 ml / min. The plasma treatment in the nitrogen environment lasts for 2 hours.

[0066] Step C: After plasma treatment, a self-supported nitrogen-doped aluminum-nickel alloy water electrolysis electrode is obtained.

[0067] Example 4: A method for preparing a nickel-based electrode with high corrosion resistance and strong gas evolution performance is provided, comprising the following steps:

[0068] Step A: Prepare a hydrochloric acid solution with a concentration of 2 mol / L as an acid treatment solution. Soak the commercially available aluminum-nickel alloy coated nickel mesh with a size of 1 x 4 cm -2aluminum-nickel alloy coated nickel mesh is immersed in the hydrochloric acid solution. The immersion is carried out at room temperature for 30 minutes to remove impurities on the surface of the nickel mesh and improve its surface activity. After the immersion is completed, the nickel mesh is rinsed with deionized water and ethanol three times each to ensure that the residual acidic substances on the surface are completely removed. After rinsing, the nickel mesh is dried in a vacuum environment to obtain the acid-treated aluminum-nickel alloy coated nickel mesh.

[0069] Step B: The acid-treated nickel mesh is placed in a plasma treatment machine for plasma treatment. During the treatment process, the treatment machine is vacuumed and nitrogen gas is introduced at a flow rate of 150 ml / min. The plasma treatment in the nitrogen environment lasts for 0.5 hours.

[0070] Step C: After plasma treatment, a morphology-damaged nickel-based electrode is obtained.

[0071] The SEM image of the nitrogen-doped aluminum-nickel alloy coated nickel mesh is shown in Figure 5 , which shows its microstructure after immersion in a high-concentration acid solution. As can be clearly seen from the figure, part of the aluminum-nickel alloy particles are etched during the acid treatment, and the surface of the particles becomes rough and no longer uniform. The connection between the local particles also appears to be broken or collapsed, indicating that the material has undergone significant chemical erosion in the strong acid environment. This morphology damage may reduce the structural integrity of the electrode and affect its long-term stability.

[0072] In a high-concentration acid solution, the aluminum element in the aluminum-nickel alloy is more prone to corrosion and dissolution because the corrosion resistance of aluminum under acidic conditions is relatively poor. This etching effect causes some particles to have holes and depressions on their surfaces, resulting in a decrease in the effective specific surface area of the electrode. Although a certain degree of etching may help to expose more active sites, excessive damage will weaken the mechanical strength of the nickel mesh and even cause structural failure of the electrode in the electrolysis reaction.

[0073] In addition, the damage of acid etching may also affect the electrochemical performance of the electrode. After acid immersion, the pore structure inside the material may be weakened, causing the penetration path of the electrolyte to be blocked, which will reduce the effective evolution rate of the gas. At the same time, the irregular morphology of the surface may cause uneven local current distribution, which will reduce the efficiency of the electrocatalytic reaction of the electrode. Therefore, the concentration of acid and the immersion time need to be carefully controlled in the process to avoid excessive etching and ensure the integrity of the aluminum-nickel alloy particles and the stability of the electrode.

[0074] Example 5: A method for preparing a nickel-based electrode with high corrosion resistance and strong gas evolution performance is provided, comprising the following steps:

[0075] Step A: Prepare a hydrochloric acid solution with a concentration of 0.5 mol / L as an acid treatment solution. A commercially available aluminum-nickel alloy coated nickel mesh with a size of 1×4 cm -2nickel mesh coated with aluminum-nickel alloy is immersed in the hydrochloric acid solution. The immersion is carried out at room temperature for 120 minutes to remove the impurities on the surface of the nickel mesh and to improve its surface activity. After the immersion is completed, the nickel mesh is rinsed with deionized water and ethanol for three times each to ensure that the acidic substances remaining on the surface are completely removed. After the rinsing, the nickel mesh is dried in a vacuum environment to obtain the acid-treated nickel mesh coated with aluminum-nickel alloy.

[0076] Step B: The acid-treated nickel mesh is placed into a plasma treatment machine for plasma treatment. During the treatment, the machine is vacuumed and nitrogen gas is introduced at a flow rate of 150 ml / min. The plasma treatment under the nitrogen gas environment is carried out for 0.5 hour to ensure that the nitrogen element is uniformly doped into the surface of the nickel mesh coated with aluminum-nickel alloy, thereby enhancing the chemical performance and catalytic activity of the electrode.

[0077] Step C: After the plasma treatment, a self-supported nitrogen-doped aluminum-nickel alloy water electrolysis electrode is obtained.

[0078] Example 6: A method for preparing a nickel-based electrode with high corrosion resistance and strong gas evolution performance is provided, which comprises the following steps:

[0079] Step A: A hydrochloric acid solution with a concentration of 0.5 mol / L is prepared as an acid treatment solution. A commercially available nickel mesh coated with aluminum-nickel alloy with a size of 1 x 4 cm -2 is immersed in the hydrochloric acid solution. The immersion is carried out at room temperature for 120 minutes to remove the impurities on the surface of the nickel mesh and to improve its surface activity. After the immersion is completed, the nickel mesh is rinsed with deionized water and ethanol for three times each to ensure that the acidic substances remaining on the surface are completely removed. After the rinsing, the nickel mesh is dried in a vacuum environment to obtain the acid-treated nickel mesh coated with aluminum-nickel alloy.

[0080] Step B: The acid-treated nickel mesh is placed into a plasma treatment machine for plasma treatment. During the treatment, the machine is vacuumed and nitrogen gas is introduced at a flow rate of 200 ml / min. The plasma treatment under the nitrogen gas environment is carried out for 2 hours to ensure that the nitrogen element is uniformly doped into the surface of the nickel mesh coated with aluminum-nickel alloy, thereby enhancing the chemical performance and catalytic activity of the electrode.

[0081] Step C: After the plasma treatment, a self-supported nitrogen-doped aluminum-nickel alloy water electrolysis electrode is obtained.

[0082] Example 7: A method for preparing a nickel-based electrode with high corrosion resistance and strong gas evolution performance is provided, which comprises the following steps:

[0083] Step A: A hydrochloric acid solution with a concentration of 0.5 mol / L is prepared as an acid treatment solution. A commercially available nickel mesh coated with aluminum-nickel alloy with a size of 1 x 4 cm -2The aluminum-nickel alloy coated nickel mesh was immersed in the hydrochloric acid solution. It was left to stand at room temperature for 30 minutes to remove impurities from the surface and enhance its surface activity. After immersion, it was rinsed three times each with deionized water and ethanol to ensure that any residual acidic substances were completely removed. After rinsing, the nickel mesh was dried in a vacuum environment to obtain the acid-treated aluminum-nickel alloy coated nickel mesh.

[0084] Step B: The acid-treated nickel mesh is placed in a plasma treatment machine for plasma treatment. During the treatment, the machine is evacuated and nitrogen gas is introduced at a flow rate of 150 ml / min. The plasma treatment in the nitrogen atmosphere lasts for 1.0 hour to ensure that nitrogen is uniformly doped onto the surface of the aluminum-nickel alloy coated nickel mesh, thereby enhancing the chemical properties and catalytic activity of the electrode.

[0085] Step C: After plasma treatment, a self-supporting nitrogen-doped aluminum-nickel alloy electrolytic water electrode is obtained.

[0086] Example 8: A method for preparing a nickel-based electrode with high corrosion resistance and strong gas evolution performance is provided, comprising the following steps:

[0087] Step A: Prepare a 0.5 mol / L hydrochloric acid solution as the acid treatment solution. Use a commercially available 1×4 cm... -2 The aluminum-nickel alloy coated nickel mesh was immersed in the hydrochloric acid solution. It was left to stand at room temperature for 30 minutes to remove impurities from the surface and enhance its surface activity. After immersion, it was rinsed three times each with deionized water and ethanol to ensure that any residual acidic substances were completely removed. After rinsing, the nickel mesh was dried in a vacuum environment to obtain the acid-treated aluminum-nickel alloy coated nickel mesh.

[0088] Step B: The acid-treated nickel mesh is placed in a plasma treatment machine for plasma treatment. During the treatment, the machine is evacuated and nitrogen gas is introduced at a flow rate of 150 ml / min. The plasma treatment in the nitrogen atmosphere lasts for 1.0 hour to ensure that nitrogen is uniformly doped onto the surface of the aluminum-nickel alloy coated nickel mesh, thereby enhancing the chemical properties and catalytic activity of the electrode.

[0089] Step C: After plasma treatment, a self-supporting nitrogen-doped aluminum-nickel alloy electrolytic water electrode is prepared, thus obtaining the self-supporting nitrogen-doped aluminum-nickel alloy electrolytic water electrode.

[0090] Comparative Example 1: This comparative example provides a method for preparing a nitrogen-doped nickel mesh, comprising the following steps:

[0091] (1) Prepare a 0.5 mol / L hydrochloric acid solution;

[0092] (2) Take the commercially available 1*4cm -246 mesh nickel mesh was soaked in the hydrochloric acid solution prepared in step 1, and after standing for 30 min, it was taken out and vacuum dried to obtain a pretreated nickel-based electrode;

[0093] (3) The pretreated aluminum-nickel alloy coated nickel mesh was placed in a plasma treatment machine, vacuumed, and then 150 ml / min of nitrogen was introduced and plasma treated for 1.0 h to obtain a self-supported nitrogen-doped aluminum-nickel alloy electrolytic water electrode.

[0094] The nitrogen-doped nickel mesh was subjected to SEM, element surface distribution, and EDS tests, as shown in FIGS. 1-3. Figure 6 As can be seen from the figures, on the bare nickel mesh, in addition to the Al element, the N element is also uniformly distributed in the selected area. In addition, the nitrogen-doped aluminum-nickel alloy coated nickel mesh was subjected to EDS, and as can be seen from the figure, the nitrogen content is 1.2 wt%. The above tests prove the successful doping of nitrogen element.

[0095] Comparative Example 2: This comparative example provides a preparation method of an acid-washed aluminum-nickel alloy coated nickel mesh, comprising the following steps:

[0096] (1) A hydrochloric acid solution with a concentration of 0.5 mol / L was prepared;

[0097] (2) A commercially available 1*4 cm -2 The aluminum-nickel alloy coated nickel mesh was soaked in the hydrochloric acid solution prepared in step 1, and after standing for 30 min, it was taken out and vacuum dried to obtain a pretreated acid-washed nickel-based electrode;

[0098] Comparative Example 3: This comparative example provides a preparation method of a nitrogen-doped aluminum-nickel alloy coated nickel mesh, comprising the following steps:

[0099] The commercially available aluminum-nickel alloy coated nickel mesh was directly placed in a plasma treatment machine, vacuumed, and then 150 ml / min of nitrogen was introduced and plasma treated for 1.0 h to obtain a self-supported nitrogen-doped aluminum-nickel alloy electrolytic water electrode.

[0100] The present application is not limited to the above embodiments, and any person should know that structural changes made under the inspiration of the present application, any technical solution with the same or similar to the present application, falls within the scope of the present application. The technical, shape, and structure parts not described in detail in the present application are well-known technologies.

Claims

1. A method for preparing a nickel-based electrode with high corrosion resistance and strong gas evolution performance, characterized in that, Includes the following steps: Step A: Using an aluminum-nickel alloy coated nickel mesh as the precursor material, place it in an acid solution and soak it at room temperature for 10-120 minutes. Then rinse it with deionized water and ethanol to remove acid residues. Step B: Place the rinsed nickel mesh in a vacuum environment to dry. After drying, you will get an acid-treated aluminum-nickel alloy coated nickel mesh. Step C: Place the acid-treated aluminum-nickel alloy coated nickel mesh in a plasma treatment machine and perform plasma treatment in a vacuum environment. After the plasma treatment is completed, a self-supporting nitrogen-doped aluminum-nickel alloy electrolytic water electrode is obtained. The acid solution in step A is one of sulfuric acid solution, hydrochloric acid solution or nitric acid solution, and the concentration of the acid solution is 0.01-0.5 mol / L.

2. The method for preparing a nickel-based electrode with high corrosion resistance and strong gas evolution performance according to claim 1, characterized in that, In step A, the rinsing process is performed 3-5 times using deionized water and ethanol.

3. The method for preparing a nickel-based electrode with high corrosion resistance and strong gas evolution performance according to claim 1, characterized in that, In step C, nitrogen gas needs to be introduced during the plasma treatment. The nitrogen flow rate is 50-200 ml / min, and the treatment time is 0.1-2.0 hours.

4. The method for preparing a nickel-based electrode with high corrosion resistance and strong gas evolution performance according to claim 1, characterized in that, In step A, the nickel mesh is selected from any one of 20 mesh, 40 mesh, 46 mesh, 60 mesh, or 80 mesh.

5. The method for preparing a nickel-based electrode with high corrosion resistance and strong gas evolution performance according to claim 1, characterized in that, The alloy in the aluminum-nickel alloy coating in step A is Ni. 1.1 Al 0.9 .

6. A nickel-based electrode with high corrosion resistance and strong gas evolution performance prepared by the method of preparing a nickel-based electrode with high corrosion resistance and strong gas evolution performance according to any one of claims 1-5.

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