Preparation method and application of water electrolysis hydrogen production electrode
By loading microsphere-structured catalysts onto the substrate surface through electroplating and etching processes, the problem of easy catalyst detachment was solved, catalytic activity and stability were improved, and the energy consumption of the electrolyzer was reduced.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-11
- Publication Date
- 2026-03-13
AI Technical Summary
Existing hydrogen production electrode catalysts have low catalytic activity and are prone to detachment, leading to increased energy consumption in electrolyzers and failing to meet current demands.
The catalyst with microsphere structure was stably loaded onto the substrate surface using an electroplating process, and the specific surface area of the micro-nano structure was increased by anodic electrochemical etching and chemical etching methods, thereby improving the catalytic activity.
It improves the bonding force between the catalyst and the substrate, enhances catalytic activity, reduces the energy consumption of the electrolyzer, and has universality, not limited by the type and structure of the substrate.
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Figure CN121653702A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of electrolytic water hydrogen production electrode technology, specifically relating to a method for preparing and applying an electrolytic water hydrogen production electrode. Background Technology
[0002] Driven by the rapid development of the global hydrogen energy industry and the continuous advancement of electrolyzer technology, the hydrogen production catalytic electrode industry is facing unprecedented development opportunities. As a key component of electrolyzers, the hydrogen production catalytic electrode plays a crucial role in the hydrogen energy industry chain. The most critical challenge facing hydrogen production electrodes is the development of stable and highly active electrocatalysts. Currently, the electrochemical performance of traditional Raney nickel electrodes on the market can no longer meet current demands, while rapidly developing multi-element alloy electrode catalysts are not only expensive but also prone to catalyst detachment, leading to insufficient catalytic activity and stability. Summary of the Invention
[0003] To overcome the shortcomings of existing technologies, this invention provides a method for preparing and applying an electrolytic hydrogen production electrode, addressing the problems of low catalytic activity, easy catalyst detachment leading to decreased electrode performance, and increased energy consumption in the electrolyzer in existing hydrogen production electrodes. This invention first stably loads a catalyst with a microsphere structure onto a substrate surface using an electroplating process. Then, through anodic electrochemical etching followed by chemical etching, the microspheres are etched to form a smaller micro / nano structure, increasing their specific surface area and improving catalytic activity.
[0004] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: This invention provides a method for preparing an electrode for hydrogen production by water electrolysis, comprising the following steps: The substrate material is used as the cathode in a nickel-containing electroplating solution for electroplating, and then as the anode in an acidic solution for electrochemical / chemical etching. The hydrogen ion concentration in the acidic solution is 0.1-1 mol / L; the current density for electrochemical / chemical etching is 0.1-5 mA / cm². 2 The duration is 30~120s.
[0005] Preferably, the base material is nickel mesh, nickel foam, nickel felt, or elastic support mesh.
[0006] Preferably, the substrate material undergoes a surface treatment process before electroplating.
[0007] A further preferred surface treatment process includes acid activation and water cleaning.
[0008] More preferably, the surface treatment process specifically includes: surface activation of the substrate material with 0.5 mol / L-5 mol / L hydrochloric acid for 5-10 minutes, followed by cleaning the surface with ultrapure water.
[0009] Preferably, the concentration of nickel ions in the nickel plating solution is 0.6-2.5 mol / L.
[0010] Preferably, the nickel plating solution comprises 0.5-2 mol / L of non-chlorinated nickel salt, 0.1-0.5 mol / L of nickel chloride, 0.5-1 mol / L of boric acid, and 0.01 mol / L-0.05 mol / L of additives, with water as the solvent.
[0011] Further preferred, non-chlorinated nickel salts include one or more of nickel sulfate, nickel aminosulfonate, nickel acetate, and nickel nitrate.
[0012] More preferably, the additives include one or more of 1,4-butynediol, sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate.
[0013] Preferably, the temperature of the nickel plating solution is 30-60℃ and the pH is 3-5.
[0014] Preferably, the current density for electroplating is 10-100 mA / cm². 2 The time is 20-60 minutes.
[0015] Preferably, the acid in the acidic solution includes one or more of sulfuric acid, hydrochloric acid, and nitric acid.
[0016] More preferably, the concentration of acid in the acidic solution is 0.1-1 mol / L.
[0017] Preferably, the temperature of the acidic solution is room temperature (20-25°C).
[0018] Preferably, the acidic solution also includes additives.
[0019] More preferably, the additives include one or more of salts and crystal facet modifiers.
[0020] More preferably, the concentration of salts in the acidic solution is 0.1-1 mol / L, and the concentration of crystal facet modifier in the acidic solution is 0.1-1 mg / L.
[0021] More preferably, the salts include one or more of sulfates (sodium sulfate) and chlorides (sodium chloride).
[0022] More preferably, the crystal plane modifier includes one or more of N,N-diethylpropynylamine and butynediol ethoxy ether.
[0023] Preferably, the cathode for electrochemical / chemical etching is a nickel mesh.
[0024] This invention provides an electrolytic hydrogen production electrode prepared by the above-described method.
[0025] This invention provides an application of the above-mentioned water electrolysis hydrogen production electrode in water electrolysis hydrogen production.
[0026] The beneficial effects of this invention are: This invention employs an electroplating and etching process to synthesize a hydrogen production electrode with a microspherical nickel catalyst. Electroplating not only ensures a high bonding force between the catalyst and the substrate, preventing catalyst detachment, but also utilizes an anodic electrochemical etching process combined with chemical etching to increase the surface area of the microspheres, thereby enhancing their electrocatalytic activity and effectively reducing the energy consumption of the electrolyzer. Furthermore, this method is not limited by substrate type, specific surface area, or complex structure, making it universally applicable. Attached Figure Description
[0027] Figure 1 This is a scanning electron microscope image of the microstructure of the hydrogen production electrode prepared in Example 1.
[0028] Figure 2 This is a scanning electron microscope image of the microstructure of the hydrogen production electrode prepared in Example 2.
[0029] Figure 3 This is a scanning electron microscope image of the microstructure of the hydrogen production electrode prepared in Example 3.
[0030] Figure 4 This is a scanning electron microscope image of the microstructure of the hydrogen production electrode prepared in Example 4.
[0031] Figure 5 This is a scanning electron microscope image of the microstructure of the hydrogen production electrode prepared in Example 5.
[0032] Figure 6 This is a scanning electron microscope image of the microstructure of the hydrogen production electrode prepared in Example 6.
[0033] Figure 7 This is a scanning electron microscope image of the microstructure of the hydrogen production electrode prepared in Example 7.
[0034] Figure 8 These are comparative graphs showing the ultrasonic weightlessness performance tests of the hydrogen production electrodes prepared in Examples 1-7.
[0035] Figure 9 These are comparative graphs showing the chamber voltage performance tests of the hydrogen production electrodes prepared in Examples 1-7. Detailed Implementation
[0036] The present invention will be further described below with reference to embodiments.
[0037] 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.
[0038] This invention provides a method for preparing an electrode for hydrogen production by water electrolysis, comprising the following steps: S1: Surface treatment process, the substrate material is activated with 0.5mol / L-5mol / L hydrochloric acid for 5-10 minutes to remove the metal oxide layer on the surface, and then the surface is cleaned with ultrapure water. The substrate material can include nickel mesh, nickel foam, nickel felt, or elastic support mesh.
[0039] S2: Electroplating process. The substrate material treated in S1 is electroplated in an electroplating solution containing 0.5-2 mol / L of non-chlorinated nickel salt, 0.1-0.5 mol / L of nickel chloride, 0.5-1 mol / L of boric acid, and 0.01-0.05 mol / L of additives. The non-chlorinated nickel salt may include one or more of nickel sulfate, nickel sulfamate, nickel acetate, and nickel nitrate. The additives may include one or more of 1,4-butynediol, sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate. The electroplating current density is 10-100 mA / cm². 2 The reaction time is 20-60 minutes; the temperature of the electroplating solution is 30-60℃, and the pH is 3-5. After the reaction, the electrode is washed with ultrapure water to obtain a hydrogen production electrode with a microsphere structure.
[0040] S3: Anodic electrochemical etching + chemical etching process. The substrate material after S2 electroplating is immersed in a solution of 0.1-1 mol / L acid and additives. The acid can be any one or more of sulfuric acid, hydrochloric acid, and nitric acid. The additives include salts such as sulfates and chlorides; crystal surface modifiers such as N,N-diethylpropynylamine and butynediol ethoxy ether. Under two electrodes, the nickel mesh is used as the cathode and the substrate material is used as the anode, and an A / cm² of 0.1~5 mA is applied. 2 The current density was set at a constant value, and the reaction time was 30-120 seconds. After the reaction was completed, the electrode was washed with ultrapure water to obtain a hydrogen production electrode with a micro-nano structure.
[0041] Example 1: A method for preparing an electrode for hydrogen production by water electrolysis includes the following steps: S1: Surface treatment process: Select nickel mesh (40 mesh, 19 wire diameter) as the base material, activate the base material with 1 mol / L hydrochloric acid for 8 minutes to remove the metal oxide layer on the surface, and then clean the surface with ultrapure water.
[0042] S2: Electroplating process. A solution is prepared using 0.5 mol / L nickel sulfate, 0.1 mol / L nickel chloride, 0.5 mol / L boric acid, and 0.01 mol / L sodium dodecyl sulfate. The pH is adjusted to 4 with hydrochloric acid, and the temperature is controlled at 40℃. The solution is thoroughly stirred to obtain the electroplating solution. The surface-treated substrate material is placed in the electroplating solution as the cathode, and a nickel plate is used as the anode. The distance between the cathode and anode is 10 cm. Electroplating is performed at a current density of 40 mA / cm². 2 The time is 30 minutes. After completion, it is rinsed with ultrapure water to obtain the nickel mesh hydrogen generation electrode, as shown below. Figure 1 As shown, the surface has a microsphere structure.
[0043] Example 2: A method for preparing an electrode for hydrogen production by water electrolysis includes the following steps: S1 and S2 are the same as in Example 1.
[0044] S3: Anodic electrochemical etching + chemical etching process. The electroplated substrate material is immersed in a mixed solution of 0.1 mol / L sulfuric acid and 0.1 mol / L sodium sulfate. Under two electrodes, a nickel mesh is used as the cathode and the substrate material as the anode, and an application of 1 mA / cm is applied. 2 The current density was set at 120 s, and the reaction time was 120 s. After the reaction was completed, the electrode was washed with ultrapure water to obtain the nickel mesh hydrogen production electrode. Figure 2 As shown, the surface microspheres have obvious etched morphology and a rougher surface.
[0045] Example 3: A method for preparing an electrode for hydrogen production by water electrolysis includes the following steps: S1: Surface treatment process, selected is nickel foam (110PPI, 480g / m²). 2 Using 1 mol / L hydrochloric acid as the base material, the surface of the base material was activated for 8 minutes to remove the metal oxide layer on the surface, and then the surface was cleaned with ultrapure water.
[0046] S2: Electroplating process. A solution is prepared using 1 mol / L nickel sulfamate, 0.2 mol / L nickel chloride, 0.5 mol / L boric acid, and 0.02 mol / L 1,4-butynediol. The pH is adjusted to 4 with hydrochloric acid, and the temperature is controlled at 60℃. The solution is thoroughly stirred to obtain the electroplating solution. The surface-treated substrate material is placed in the electroplating solution as the cathode, and a nickel plate is used as the anode. The distance between the cathode and anode is 10 cm. Electroplating is performed at a current density of 50 mA / cm².2 The time is 30 minutes, and after completion, it is rinsed with ultrapure water to obtain the nickel foam hydrogen production electrode, such as... Figure 3 As shown, the surface has a microsphere structure.
[0047] Example 4: A method for preparing an electrode for hydrogen production by water electrolysis includes the following steps: S1: Surface treatment process, selected is nickel foam (110PPI, 480g / m²). 2 Using 1 mol / L hydrochloric acid as the base material, the surface of the base material was activated for 8 minutes to remove the metal oxide layer on the surface, and then the surface was cleaned with ultrapure water.
[0048] S2: Electroplating process. A solution is prepared using 1 mol / L nickel sulfamate, 0.2 mol / L nickel chloride, 0.5 mol / L boric acid, and 0.02 mol / L 1,4-butynediol. The pH is adjusted to 4 with hydrochloric acid, and the temperature is controlled at 60℃. The solution is thoroughly stirred to obtain the electroplating solution. The surface-treated substrate material is placed in the electroplating solution as the cathode, and a nickel plate is used as the anode. The distance between the cathode and anode is 10 cm. Electroplating is performed at a current density of 50 mA / cm². 2 The treatment time is 30 minutes, and the product is rinsed with ultrapure water afterward.
[0049] S3: Anodic electrochemical etching + chemical etching process. The electroplated substrate material is immersed in a mixed solution of 0.1 mol / L hydrochloric acid and 1 mg / L butynediol ethoxy ether. Under two electrodes, a nickel mesh is used as the cathode and the substrate material as the anode, and an application of 2 mA / cm is applied. 2 The current density was set at 120 s, and after the reaction was complete, the electrode was washed with ultrapure water to obtain the nickel foam hydrogen production electrode. Figure 4 As shown, the surface microspheres have fine etched morphology, making their surface rougher.
[0050] Example 5: A method for preparing an electrode for hydrogen production by water electrolysis includes the following steps: S1 and S2 are the same as in Example 1.
[0051] S3: Immerse the electroplated substrate material in 4 mol / L sulfuric acid. Under two electrodes, with the nickel mesh as the anode and the substrate material as the cathode, apply an A / cm² pressure. 2 The current density was set at 120 s, and the reaction time was 120 s. After the reaction was completed, the electrode was washed with ultrapure water to obtain the nickel mesh hydrogen production electrode. Figure 5 As shown, the surface microspheres have completely disappeared, the rough morphology has changed, and some micropores exist.
[0052] Example 6: A method for preparing an electrode for hydrogen production by water electrolysis includes the following steps: S1 and S2 are the same as in Example 1.
[0053] S3: Anodic electrochemical etching + chemical etching process, immersing the electroplated substrate material in 4 mol / L sulfuric acid, with a nickel mesh as the cathode and the substrate material as the anode under two electrodes, and applying 1 mA / cm. 2 The current density was set at 120 s, and after the reaction was completed, the electrode was washed with ultrapure water to obtain the nickel mesh hydrogen production electrode. Figure 6 As shown, the surface microspheres have completely disappeared, and the surface is relatively flat.
[0054] Example 7: A method for preparing an electrode for hydrogen production by water electrolysis includes the following steps: S1 and S2 are the same as in Example 3.
[0055] S3: The electroplated substrate material is immersed in a mixed solution of 0.1 mol / L hydrochloric acid and 1 mg / L butynediol ethoxy ether. Under two electrodes, a nickel mesh is used as the anode and the substrate material as the cathode, and an application of 2 mA / cm is applied. 2 The current density was set at 120 s, and after the reaction was complete, the electrode was washed with ultrapure water to obtain the nickel foam hydrogen production electrode. Figure 7 As shown, the surface microspheres exhibit an etched morphology that is relatively smooth and has large etched cracks.
[0056] Performance testing (1) Ultrasonic weightlessness performance test The hydrogen production electrodes prepared in Examples 1-7 and commercial Raney nickel were subjected to ultrasonic weight loss tests. The tests were conducted according to point 5 of the national standard "Performance Testing and Evaluation of Electrodes for Hydrogen Production via Water Electrolysis" (GB / T45092—2024), and the results are shown below. Figure 8 The ultrasonic weight loss rate of the prepared Examples 1-7 is less than 2%, while the ultrasonic weight loss rate of conventional commercial Raney nickel is about 5%. The results show that the catalyst prepared by the method of the present invention has excellent bonding force with the substrate material, and has better stability and service life.
[0057] (2) Individual cell performance test The hydrogen production electrodes and nickel photocells prepared in Examples 1-7 were subjected to single-cell testing, with the hydrogen production electrode serving as both the cathode and anode of the single-cell chamber. The diaphragm used was a Toray third-generation diaphragm. The tests were conducted using linear scanning voltammetry on an electrochemical workstation, with a scan range of 0-2V and a scan rate of 5 mV / s. The test results are shown in [Figure number missing]. Figure 9 At 2V, the current densities of Examples 1-7 and the nickel plating are 3674A / m. 2 4970A / m 23869A / m 2 5522A / m 2 3189A / m 2 2860A / m 2 3534A / m 2 2363A / m 2 The hydrogen production electrodes prepared in Examples 2 and 4 show a 3000 A / m improvement compared to nickel photocells. 2 Furthermore, the performance is significantly improved compared to Examples 1, 3, and 5-7, indicating that the hydrogen production electrode prepared by the present invention under low acid concentration and anodic oxidation has excellent electrochemical performance.
[0058] 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 an electrode for hydrogen production by water electrolysis, characterized in that, Includes the following steps: The substrate material is used as the cathode in a nickel-containing electroplating solution for electroplating, and then as the anode in an acidic solution for electrochemical / chemical etching. The hydrogen ion concentration in the acidic solution is 0.1-1 mol / L; the current density for electrochemical / chemical etching is 0.1-5 mA / cm². 2 The duration is 30~120s.
2. The method for preparing the electrolytic hydrogen production electrode according to claim 1, characterized in that, The base material is nickel mesh, nickel foam, nickel felt, or elastic support mesh; Surface treatment process is performed on the substrate material before electroplating; Surface treatment processes include acid activation and water rinsing; The surface treatment process specifically includes: surface activation of the substrate material with 0.5mol / L-5mol / L hydrochloric acid for 5-10 minutes, followed by cleaning the surface with ultrapure water.
3. The method for preparing the water electrolysis hydrogen production electrode according to claim 1, characterized in that, The concentration of nickel ions in the nickel plating solution is 0.6-2.5 mol / L; The temperature of the nickel plating solution is 30-60℃, and the pH is 3-5. The current density for electroplating is 10-100 mA / cm². 2 The time is 20-60 minutes.
4. The method for preparing the water electrolysis hydrogen production electrode according to claim 1, characterized in that, The nickel plating solution includes 0.5-2 mol / L non-chlorinated nickel salt, 0.1-0.5 mol / L nickel chloride, 0.5-1 mol / L boric acid, and 0.01 mol / L-0.05 mol / L additives, with water as the solvent.
5. The method for preparing the water electrolysis hydrogen production electrode according to claim 4, characterized in that, Non-chlorinated nickel salts include one or more of nickel sulfate, nickel aminosulfonate, nickel acetate, and nickel nitrate; The additives include one or more of 1,4-butynediol, sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate.
6. The method for preparing the water electrolysis hydrogen production electrode according to claim 1, characterized in that, The acids in acidic solutions include one or more of sulfuric acid, hydrochloric acid, and nitric acid; The concentration of acid in the acidic solution is 0.1-1 mol / L.
7. The method for preparing the water electrolysis hydrogen production electrode according to claim 1, characterized in that, Acidic solutions also contain additives; Additives include one or more of salts and crystal facet modifiers.
8. The method for preparing the water electrolysis hydrogen production electrode according to claim 7, characterized in that, The concentration of salts in the acidic solution is 0.1-1 mol / L, and the concentration of crystal facet modifier in the acidic solution is 0.1-1 mg / L; Salts include one or more of sulfates and chlorides; Crystal plane modifiers include one or more of N,N-diethylpropynylamine and butynediol ethoxy ether.
9. The water electrolysis hydrogen production electrode prepared by the preparation method according to any one of claims 1-8.
10. The application of the water electrolysis hydrogen production electrode according to claim 9 in water electrolysis hydrogen production.