A hydrogen production electrode with a multi-stage sharp cone structure and a preparation method and application thereof

Abstract

The application discloses a hydrogen production electrode with a multistage sharp cone structure and a preparation method and application thereof, and belongs to the technical field of water electrolysis hydrogen production electrodes; the preparation method of the hydrogen production electrode comprises the following steps: segmentally performing an electrodeposition process on a conductive substrate as a cathode to obtain the hydrogen production electrode with the multistage sharp cone structure; the segmental electrodeposition process comprises three steps: in the first step, the conductive substrate is placed into an electroplating solution for electrodeposition without magnetic field assistance; in the second step, the conductive substrate is taken out of the electroplating solution and is placed in air; and in the third step, the conductive substrate is placed into the electroplating solution for electrodeposition again without magnetic field assistance; the ratio of the current density in the third step to the current density in the first step is greater than or equal to 1:1; and the electroplating solution comprises an electroplating additive. The prepared hydrogen production electrode has the multistage sharp cone structure, has high activity and high stability for water electrolysis hydrogen production, and has the advantages of simple preparation process and low cost.

Description

Technical Field

[0001] This invention belongs to the field of electrolytic water hydrogen production electrode technology, specifically relating to a hydrogen production electrode with a multi-stage pointed cone structure, its preparation method, and its application. Background Technology

[0002] As the core component of the water electrolysis reaction, the performance of the hydrogen production electrode directly determines the energy consumption, efficiency, and lifespan of the electrolyzer. An ideal alkaline water electrolysis hydrogen production electrode should possess the following key characteristics: first, sufficient active sites to reduce the activation energy and overpotential; second, excellent electrochemical stability to adapt to the alkaline electrolyte environment and long-term electrolysis operation. Industrially widely used alkaline water electrolysis hydrogen production electrodes have several inherent defects: on the one hand, traditional Raney nickel electrodes have limited specific surface area and insufficient active sites, resulting in high reaction overpotentials and excessive energy consumption; on the other hand, highly active multi-element alloy electrodes are prone to catalyst shedding during long-term operation due to the influence of reverse current, leading to electrode performance degradation. Therefore, developing a hydrogen production electrode that simultaneously possesses high active site density and electrochemical stability is particularly important. Summary of the Invention

[0003] To overcome the shortcomings of existing technologies, this invention provides a hydrogen production electrode with a multi-level conical structure, its preparation method, and its application. This invention prepares a catalyst with a multi-level conical structure through segmented electrodeposition, which exhibits excellent catalytic activity and can effectively improve hydrogen production efficiency; thus addressing the current situation of low activity and long-term performance degradation of existing hydrogen production electrodes (such as Raney nickel).

[0004] The technical solution adopted by this invention to solve its technical problem is: This invention provides a method for preparing a hydrogen generation electrode with a multi-level conical structure, comprising the following steps: A segmented electrodeposition process is performed using a conductive substrate as the cathode to obtain a hydrogen production electrode with a multi-level conical structure. The segmented electrodeposition process includes three steps: First, the conductive substrate is immersed in an electroplating solution, and the current density is set to 10-100 mA / cm². 2 The electrodeposition time is 900s-1800s, without magnetic field assistance. The second step involves removing the conductive substrate from the electroplating solution and allowing it to stand in the air for 60s-300s. The third step involves re-immersing the conductive substrate in the electroplating solution with a current density set to 20-200mA / cm². 2 The electrodeposition time is 30s-300s, and no magnetic field is used for assistance; the ratio of the current density in the third step to the current density in the first step is greater than or equal to 1:1. The electroplating solution comprises 0.6-2.5 mol / L of nickel salt, 0.5-1 mol / L of boric acid, 0.005 mol / L-0.05 mol / L of electroplating surfactant, and 0.05 mol / L-0.5 mol / L of electroplating additive, with the balance being water; the electroplating additive comprises one or more of ammonium chloride, ethylenediamine hydrochloride, and cresolsulfonic acid.

[0005] Preferably, the ratio of the current density in the third step to the current density in the first step is greater than or equal to 2:1.

[0006] Preferably, the pH of the electroplating solution is 3-5. The pH of the electroplating solution is adjusted by using hydrochloric acid (0.1-0.5 mol / L) or ammonia (1-3 mol / L).

[0007] More preferably, the pH of the electroplating solution is 4±0.1.

[0008] Preferably, the electroplating surfactant includes one or more of sodium dodecylbenzenesulfonate, hexadecyltrimethylammonium bromide, and sodium dodecyl sulfate.

[0009] Preferably, the nickel salt includes one or more of nickel chloride, nickel sulfate, nickel sulfamate, nickel acetate, and nickel nitrate.

[0010] Preferably, the electrodeposition time in the third step is 120s-300s.

[0011] Preferably, the electroplating solution comprises 0.5-2 mol / L nickel chloride, 0.1-0.5 mol / L non-nickel chloride nickel salt, 0.5-1 mol / L boric acid, 0.005 mol / L-0.05 mol / L electroplating surfactant, 0.05 mol / L-0.5 mol / L electroplating additive, and the balance being water.

[0012] More preferably, the non-chlorinated nickel salt includes one or more of nickel sulfate, nickel aminosulfonate, nickel acetate, and nickel nitrate.

[0013] More preferably, the molar ratio of nickel chloride to non-nickel chloride nickel salt is 20~5:1; the molar ratio of nickel chloride to electroplating additive is 5~1:1; and the molar ratio of nickel chloride to electroplating surfactant is 400~100:1.

[0014] Preferably, the temperature of the electroplating solution is 30℃-60℃, and the stirring speed is 300-600r / min.

[0015] Preferably, the electroplating solution also contains an anode.

[0016] More preferably, the anode is a nickel plate.

[0017] More preferably, the distance between the cathode and the anode is 8-15 cm.

[0018] Preferably, the conductive substrate includes a nickel mesh, nickel foam, nickel felt, or an elastic conductive support mesh.

[0019] Preferably, the conductive substrate has undergone pretreatment.

[0020] More preferably, the pretreatment is as follows: surface activation of the conductive substrate with hydrochloric acid for 5-10 minutes, followed by cleaning and drying.

[0021] More preferably, the concentration of the hydrochloric acid is 10-30%.

[0022] Preferably, after the segmented electrodeposition process is completed, the conductive substrate is cleaned and dried.

[0023] This invention provides a hydrogen generation electrode with a multi-level conical structure prepared by the above-described method.

[0024] This invention provides an application of the above-mentioned hydrogen production electrode with a multi-stage conical structure in water electrolysis for hydrogen production.

[0025] The hydrogen production electrode prepared by this invention has a controllable and adjustable multi-level conical structure. This invention employs a segmented electroplating process, incorporating a natural micro-oxidation stage under open-circuit conditions during the first and second electroplating stages to achieve the preparation of the multi-level structure. Furthermore, by optimizing the process parameters and plating solution formulation of the segmented electroplating, the size of the multi-level conical structure can be controlled, thereby establishing a repeatable and controllable method for preparing a multi-level structured electrocatalyst.

[0026] The hydrogen production electrode prepared by this invention exhibits high activity and high stability. Through an electroplating process, this invention achieves excellent bonding between the micro / nano cone structure and the substrate. Furthermore, the plating solution system does not introduce highly active noble metals, allowing the pure nickel-based electrode to effectively avoid the negative impacts of reverse current and dissimilar metal potential differences, significantly improving the long-term operational stability of the electrode. Simultaneously, the secondary nano cone structure grown on the surface of the primary cone not only constructs abundant electrocatalytic active sites, but its unique micro / nano hierarchical structure also exerts a fine-grained strengthening effect, further enhancing the structural stability of the hydrogen production electrode. Therefore, this hydrogen production electrode has the potential to effectively address the technical pain points of high energy consumption in traditional electrolyzers and performance degradation due to wind and solar power fluctuations.

[0027] The hydrogen production electrode prepared by this invention has promising industrial applications. The electroplating solution of this invention uses common and inexpensive industrial reagents, eliminating the need for adding various reagents containing precious metals. Furthermore, it eliminates the need for the activation process required for traditional Raney nickel electrodes. The hydrogen production electrode is prepared solely through optimizing the electroplating solution formulation and process parameters, effectively controlling the electrode preparation cost and providing the possibility for large-scale industrial production.

[0028] The beneficial effects of this invention are: The hydrogen production electrode prepared by this invention has a multi-level conical structure, which exhibits high activity and high stability when used for hydrogen production by water electrolysis; at the same time, the preparation process is simple and low in cost. Attached Figure Description

[0029] Figure 1 This is a low-magnification scanning electron microscope image of the microstructure of the hydrogen production electrode in Example 1; Figure 2 This is a low-magnification scanning electron microscope image of the microstructure of the hydrogen production electrode in Example 2; Figure 3 This is a low-magnification scanning electron microscope image of the microstructure of the hydrogen production electrode in Example 3; Figure 4 This is a high-magnification scanning electron microscope image of the microstructure of the hydrogen production electrode in Example 3; Figure 5 This is a low-magnification scanning electron microscope image of the microstructure of the hydrogen production electrode in Example 4. Figure 6 This is a low-magnification scanning electron microscope image of the microstructure of the hydrogen production electrode in Example 5; Figure 7 This is a low-magnification scanning electron microscope image of the microstructure of the hydrogen production electrode in Example 6; Figure 8 This is a low-magnification scanning electron microscope image of the microstructure of the hydrogen production electrode in Example 7; Figure 9 This is a monomeric chamber stability test of the hydrogen production electrode in Example 3; Figure 10 These are the average cell voltage test results for the hydrogen production electrode, photofoam nickel, and commercial Raney nickel in Examples 1-7. Detailed Implementation

[0030] The present invention will be further described below with reference to embodiments.

[0031] The following will clearly and completely describe the concept, specific solutions, and technical effects of the present invention with reference to embodiments, so as to fully understand the purpose, features, and effects of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention. The various technical features in the present invention can be combined interactively without contradicting each other.

[0032] This invention provides a method for preparing a hydrogen generation electrode with a multi-level conical structure, comprising the following steps: S1: Substrate pretreatment: The conductive substrate material is surface activated with 10-30% hydrochloric acid for 5-10 minutes to remove the surface metal oxide layer and increase the bonding force between the catalyst and the substrate. The surface of the conductive substrate material is then washed with ultrapure water and dried to obtain the pretreated conductive substrate material. The conductive substrate material can include materials such as nickel mesh, nickel foam, nickel felt or elastic conductive support mesh. S2: Electroplating Solution Preparation: The solution consists of 0.5-2 mol / L nickel chloride, 0.1-0.5 mol / L non-chlorinated nickel salts, 0.5-1 mol / L boric acid, 0.005 mol / L-0.05 mol / L electroplating surfactant, and 0.05 mol / L-0.5 mol / L electroplating additives, with the balance being ultrapure water. The pH of the electroplating solution is adjusted to 3-5 using 0.1-0.5 mol / L hydrochloric acid. The non-chlorinated nickel salts include nickel sulfate, Nickel sulfamate, nickel acetate, nickel nitrate, etc., are all acceptable; electroplating surfactants include sodium dodecylbenzenesulfonate, hexadecyltrimethylammonium bromide, sodium dodecyl sulfate, etc., are all acceptable; electroplating additives include ammonium chloride, ethylenediamine hydrochloride, cresol sulfonic acid, etc., are all acceptable; the molar ratio of nickel chloride to non-nickel chloride nickel salt is 20~5:1; the molar ratio of nickel chloride to electroplating additive is 5~1:1; the molar ratio of nickel chloride to electroplating surfactant is 400~100:1; S3: Segmented Electrodeposition Process: First, a nickel plate is used as the anode and a conductive substrate material as the cathode. The distance between the anode and cathode is 8-15 cm. The temperature of the electroplating solution is controlled at 30℃-60℃, and the stirring speed is 300-600 r / min. The anode is placed in the electroplating solution. The segmented electrodeposition process includes three steps. The first step is to place the conductive substrate material in the electroplating solution and adjust the current density to 10-100 mA / cm. 2 (e.g., 10mA / cm) 2 20mA / cm 2 40mA / cm 2 60mA / cm 2 80mA / cm 2 100mA / cm 2 The electrodeposition time is selected as 900s-1800s (e.g., 900s, 1200s, 1400s, 1600s, 1800s), without magnetic field assistance. The second step involves removing the conductive substrate material from the electroplating solution and allowing it to stand in the air for 60s-300s (e.g., 60s, 90s, 150s, 200s, 240s, 280s, 300s). The third step involves re-immersing the conductive substrate material in the electroplating solution and adjusting the current density to 20-200mA / cm². 2 (e.g., 20mA / cm) 2 40mA / cm 280mA / cm 2 120mA / cm 2 160mA / cm 2 200mA / cm 2 The deposition time is selected from 30s to 300s (e.g., 30s, 60s, 90s, 150s, 200s, 240s, 280s, 300s), and no magnetic field assistance is used; during the segmented electrodeposition process, the pH of the electroplating solution is adjusted to (3-5) ± 0.1 by hydrochloric acid (0.1-0.5mol / L) and ammonia (1-3mol / L); wherein, the ratio of the current density in the third step to the current density in the first step is greater than or equal to 1:1 (preferably greater than or equal to 2:1); S4: Post-processing: After the segmented electrodeposition process, the conductive substrate material is repeatedly washed with ultrapure water three times and then dried to finally prepare a multi-level cone-shaped hydrogen production electrode material on the surface of the conductive substrate.

[0033] Example 1 A method for preparing a hydrogen generation electrode with a multi-level pointed cone structure includes the following steps: S1: Substrate pretreatment: Select 480g / m 2 110PPI nickel foam (50cm×50cm) was used as the conductive substrate material. The conductive substrate material was surface activated with 10% hydrochloric acid for 10min to remove the metal oxide layer on the surface and increase the bonding force between the catalyst and the substrate. The surface of the conductive substrate material was then washed with ultrapure water and dried (120℃, 30min) to obtain the pretreated conductive substrate material. S2: Electroplating solution preparation: Prepare 2 mol / L nickel chloride, 0.1 mol / L nickel sulfate, 0.5 mol / L boric acid, 0.005 mol / L hexadecyltrimethylammonium bromide, and 0.5 mol / L ammonium chloride. The solvent is ultrapure water. Adjust the pH of the electroplating solution to 4 with hydrochloric acid (0.1 mol / L). Stir magnetically for 10 minutes to ensure thorough mixing to obtain the electroplating solution. S3: Segmented Electrodeposition Process: Nickel foam is placed in the electroplating solution as the cathode, and a nickel plate is placed in the electroplating solution as the anode, with a cathode-cathode distance of 10 cm. The electroplating solution temperature is set to 50℃, and the stirring speed is set to 400 r / min. The segmented electrodeposition process is performed. In the first step, the current density is 40 mA / cm². 2 The first step is to remove the nickel foam from the electroplating solution and let it stand in the air for 300 seconds. The second step is to put the nickel foam back into the electroplating solution and adjust the current density to 80 mA / cm². 2 The time was 60s; during the segmented electrodeposition process, the pH of the electroplating solution was adjusted to 4±0.1 by using hydrochloric acid (0.1mol / L) and ammonia (2mol / L); S4: Post-processing: After segmented electrodeposition, the nickel foam is removed, rinsed three times with ultrapure water, and then dried (120℃, 30 min) to obtain a nickel foam hydrogen production electrode with a multi-level cone structure on its surface. Its scanning electron microscope image is shown below. Figure 1 As shown, extremely small secondary cones grow on the surface of the first-stage micron cone, and their number is small. Their catalytic activity is mainly contributed by the first-stage cone.

[0034] Example 2 The difference from Example 1 is that the segmented electrodeposition process is different; in the first step, the current density is 40 mA / cm². 2 The first step is to remove the nickel foam from the electroplating solution and let it stand in the air for 300 seconds. The second step is to put the nickel foam back into the electroplating solution and adjust the current density to 80 mA / cm². 2 The time is 120 seconds.

[0035] Everything else is the same as in Example 1.

[0036] Scanning electron microscope image of the prepared hydrogen production electrode is shown below. Figure 2 As shown, there are obvious secondary nano-cones on the surface of the first-level micron-cone. The secondary nano-cones provide more active sites, and the cones have a tip effect, which can further promote electrochemical reactions, thus achieving better catalytic performance.

[0037] Example 3 The difference from Example 1 is that the segmented electrodeposition process is different; in the first step, the current density is 40 mA / cm². 2 The first step is to remove the nickel foam from the electroplating solution and let it stand in the air for 300 seconds. The second step is to put the nickel foam back into the electroplating solution and adjust the current density to 80 mA / cm². 2 The time is 180 seconds.

[0038] Everything else is the same as in Example 1.

[0039] Scanning electron microscope image of the prepared hydrogen production electrode is shown below. Figure 3 and Figure 4 As shown, from Figure 3 The low-magnification image reveals a large number of secondary cones, from Figure 4 The high-magnification image clearly shows that dense secondary nano-cones have grown on the first-level micron-cones, forming a multi-level micro-nano cone structure.

[0040] Example 4 The difference from Example 1 is that the segmented electrodeposition process is different; in the first step, the current density is 40 mA / cm². 2The time is 1800s, without the process of removing it and letting it stand in the air. The second step is to adjust the current density to 80mA / cm. 2 The time is 180 seconds.

[0041] Everything else is the same as in Example 1.

[0042] Scanning electron microscope image of the prepared hydrogen production electrode is shown below. Figure 5 As shown, the surface only has a large and disordered first-level micron-shaped cone structure, without a secondary cone structure, indicating that a multi-level structure cannot be formed directly through simple multiple electroplating processes.

[0043] Example 5 The difference from Example 1 is that the segmented electrodeposition process is different; in the first step, the current density is 40 mA / cm². 2 The first step is to remove the nickel foam from the electroplating solution and let it stand in the air for 300 seconds. The second step is to put the nickel foam back into the electroplating solution and adjust the current density to 20 mA / cm². 2 The time is 180 seconds.

[0044] Everything else is the same as in Example 1.

[0045] Scanning electron microscope image of the prepared hydrogen production electrode is shown below. Figure 6 As shown, a spherical secondary structure is formed on the top of the primary cone surface. Because the current density in the third step is less than that in the first step, a highly active secondary cone structure cannot be formed.

[0046] Example 6 The difference from Example 1 is that the electroplating solution is different. It uses 2 mol / L nickel chloride, 0.1 mol / L nickel sulfate, 0.5 mol / L boric acid, 0.005 mol / L hexadecyltrimethylammonium bromide, and 0.4 mol / L ethylenediamine hydrochloride. The solvent is ultrapure water. The pH of the electroplating solution is adjusted to 4 by hydrochloric acid (0.1 mol / L). The solution is stirred magnetically for 10 minutes to ensure thorough mixing.

[0047] Everything else is the same as in Example 1.

[0048] Scanning electron microscope image of the prepared hydrogen production electrode is shown below. Figure 7 As shown, different additives can still form a secondary cone structure, but the size will vary.

[0049] Example 7 The difference from Example 1 is that the electroplating solution is different. It uses 2 mol / L nickel chloride, 0.1 mol / L nickel sulfate, 0.5 mol / L boric acid, and 0.005 mol / L hexadecyltrimethylammonium bromide. The solvent is ultrapure water. The pH of the electroplating solution is adjusted to 4 by hydrochloric acid (0.1 mol / L). The solution is stirred magnetically for 10 minutes to ensure thorough mixing.

[0050] Everything else is the same as in Example 1.

[0051] Scanning electron microscope image of the prepared hydrogen production electrode is shown below. Figure 8 As shown, when no additives are added, the surface only has accumulated nickel particles, with an irregular multi-level structure.

[0052] Performance testing of hydrogen production electrode (1) Ultrasonic weightlessness performance test The hydrogen production electrodes prepared in Examples 1-7 and commercial Raney nickel (46 mesh, 25mm wire diameter) were subjected to ultrasonic weight loss tests. The ultrasonic weight loss test was performed according to point 5 of the national standard "Performance Testing and Evaluation of Electrodes for Hydrogen Production via Water Electrolysis" (GB / T45092—2024). The test results are shown in Table 1. The ultrasonic weight loss rate of the hydrogen production electrodes prepared in Examples 1-7 was less than 1%, which is far less than the ultrasonic weight loss rate of traditional commercial Raney nickel. The results indicate that the catalyst prepared by the method of this invention has excellent bonding strength with the substrate material and exhibits better stability and longer service life in practical applications.

[0053] Table 1: Results of ultrasonic weight loss tests on hydrogen production electrodes and commercial Raney nickel in Examples 1-7

[0054] (2) Long-term stability test of single cell The hydrogen production electrode prepared in Example 3 was subjected to performance testing in an alkaline electrolyzer. The test method for average cell voltage was described in point 8 of GB / T45092—2024, "Performance Testing and Evaluation of Electrodes for Hydrogen Production via Water Electrolysis." The hydrogen production electrode served as both the cathode and anode of a single cell. A Toray third-generation diaphragm was used, and 30% potassium hydroxide was used as the electrolyte. The test was conducted at 25°C and 5000 A / m². 2 A stability test was conducted for 600 hours at a current density. The test results are as follows. Figure 9 As shown, after 600 hours of testing, the hydrogen production electrode prepared in Example 3 showed that the chamber electrode was stable at 1.88±0.01V, with no performance degradation, demonstrating excellent catalyst stability and long-term stability.

[0055] (3) Individual cell performance test The hydrogen production electrodes prepared in Examples 1-7 and 480 g / m 2The alkaline electrolyzer performance was tested using 110PPI bright foamed nickel and commercial Raney nickel (46 mesh, 25mm wire diameter). The average cell voltage test, point 8 of the "Electrode Performance Testing and Evaluation for Hydrogen Production via Water Electrolysis" (GB / T45092—2024), was performed. The hydrogen production electrode served as both the cathode and anode of the individual cell. The diaphragm used was a Toray third-generation diaphragm, and the electrolyte was 30% potassium hydroxide. The test was conducted at 25°C and a current density of 5000 A / m². 2 The average cell voltage was recorded over a period of 600 to 672 hours. The test results are as follows: Figure 10 Examples 1-7 shown, light-foamed nickel, and commercial Raney nickel at 5000 A / m 2 The average cell voltages were 1.98V, 1.94V, 1.88V, 2.10V, 2.05V, 1.89V, 2.13V, 2.3V, and 2.2V. The results indicate that the hydrogen production electrode of this invention exhibits a significantly lower cell voltage compared to nickel foam, reaching a maximum of 0.42V, demonstrating excellent catalytic activity.

[0056] In summary, this invention has prepared a multi-level conical hydrogen production electrode with high catalytic activity by optimizing a specific electroplating solution formulation and segmented electrodeposition conditions. The multi-level conical structure provides numerous active reaction centers, and the tip effect of the micro / nanostructure significantly reduces the overpotential of the hydrogen evolution and oxygen evolution reactions. Simultaneously, the stable electroplating process ensures the catalyst's binding force, and the micro / nanostructure generated by electroplating has a grain-refining strengthening effect, improving the overall lifespan and structural stability of the hydrogen production electrode, thus enabling its long-term operation under industrial conditions.

[0057] The above is a detailed description of the preferred embodiments of the present invention. However, the present invention is not limited to the embodiments described. Those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of the present invention. All such equivalent modifications or substitutions are included within the scope defined by the claims of the present invention.

Claims

1. A method for preparing a hydrogen production electrode with a multi-level pointed cone structure, characterized in that, Includes the following steps: A segmented electrodeposition process is performed using a conductive substrate as the cathode to obtain a hydrogen production electrode with a multi-level conical structure. The segmented electrodeposition process includes three steps: First, the conductive substrate is immersed in an electroplating solution, and the current density is set to 10-100 mA / cm². 2 The electrodeposition time is 900s-1800s, without magnetic field assistance. The second step involves removing the conductive substrate from the electroplating solution and allowing it to stand in the air for 60s-300s. The third step involves re-immersing the conductive substrate in the electroplating solution with a current density set to 20-200mA / cm². 2 The electrodeposition time is 30s-300s, and no magnetic field is used for assistance; the ratio of the current density in the third step to the current density in the first step is greater than or equal to 1:

1. The electroplating solution comprises 0.6-2.5 mol / L nickel salt, 0.5-1 mol / L boric acid, 0.005 mol / L-0.05 mol / L electroplating surfactant, 0.05 mol / L-0.5 mol / L electroplating additive, with the balance being water; the electroplating additive includes one or more of ammonium chloride and ethylenediamine hydrochloride.

2. The method for preparing a hydrogen production electrode with a multi-stage conical structure according to claim 1, characterized in that, The ratio of the current density in the third step to the current density in the first step is greater than or equal to 2:1; The pH of the electroplating solution is 3-5; The electroplating surfactant includes one or more of sodium dodecylbenzenesulfonate, hexadecyltrimethylammonium bromide, and sodium dodecyl sulfate. The nickel salt includes one or more of nickel chloride, nickel sulfate, nickel sulfamate, nickel acetate, and nickel nitrate.

3. The method for preparing a hydrogen production electrode with a multi-stage conical structure according to claim 1, characterized in that, The electrodeposition time for the third step is 120s-300s; The pH of the electroplating solution is 4±0.

1.

4. The method for preparing a hydrogen production electrode with a multi-level conical structure according to claim 1, characterized in that, The electroplating solution consists of 0.5-2 mol / L nickel chloride, 0.1-0.5 mol / L non-chlorinated nickel salt, 0.5-1 mol / L boric acid, 0.005 mol / L-0.05 mol / L electroplating surfactant, 0.05 mol / L-0.5 mol / L electroplating additive, and the balance being water.

5. The method for preparing a hydrogen production electrode with a multi-level conical structure according to claim 4, characterized in that, The non-chlorinated nickel salts include one or more of nickel sulfate, nickel aminosulfonate, nickel acetate, and nickel nitrate; The molar ratio of nickel chloride and non-nickel chloride nickel salt is 20~5:1; the molar ratio of nickel chloride to electroplating additive is 5~1:1; and the molar ratio of nickel chloride to electroplating surfactant is 400~100:

1.

6. The method for preparing a hydrogen production electrode with a multi-stage conical structure according to claim 1, characterized in that, The temperature of the electroplating solution is 30℃-60℃, and the stirring speed is 300-600r / min; The electroplating solution also contains an anode; The anode is a nickel plate; The distance between the cathode and the anode is 8-15 cm.

7. The method for preparing a hydrogen production electrode with a multi-stage conical structure according to claim 1, characterized in that, The conductive substrate includes nickel mesh, nickel foam, nickel felt, or elastic conductive support mesh; The conductive substrate has been pretreated; The pretreatment is as follows: the conductive substrate is surface activated with hydrochloric acid for 5-10 minutes, then cleaned and dried.

8. The method for preparing a hydrogen production electrode with a multi-stage conical structure according to claim 1, characterized in that, After the segmented electrodeposition process is completed, the conductive substrate is cleaned and dried.

9. The hydrogen generation electrode with a multi-level conical structure prepared by the preparation method according to any one of claims 1-8.

10. The application of the hydrogen production electrode with a multi-stage conical structure as described in claim 9 in hydrogen production by water electrolysis.

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