Method for manufacturing high-efficiency hydrogen production catalytic electrode for alkaline electrolyzer

Abstract

This application provides a method for manufacturing an efficient hydrogen-producing catalytic electrode for an alkaline electrolyzer, relating to the technical field of materials for hydrogen production by water electrolysis. The method comprises the following steps: spraying a first metal powder onto the surface of a supporting substrate using a spraying process to obtain a first structure; etching the first structure using an alkaline solution having a first concentration for a first time at a first temperature to obtain a second porous structure having a first specific surface area; placing the second structure in a second metal salt solution having a second concentration, and adding an organic additive solution having a third concentration; and electroplating at a second temperature and a second time to obtain the catalytic electrode. This method for manufacturing the catalytic electrode is simple, efficient, low-cost, and amenable to industrial production.

Description

Technical Field

[0001] The present application relates to the technical field of materials for producing hydrogen by electrolyzing water, and in particular to a method for manufacturing a high-efficiency hydrogen-producing catalytic electrode for an alkaline electrolyzer. Background Art

[0002] my country's current carbon emissions mainly come from the process of fossil energy utilization. The country has now proactively proposed the "dual carbon" goal, which will make carbon emission reduction a development trend. This is also an inevitable choice to promote the upgrading of energy and related industrial industries and achieve long-term healthy and sustainable development of the national economy.

[0003] Hydrogen, due to its clean, pollution-free, and high-calorie properties, has become the most promising clean energy source and a key path to achieving "dual carbon." Hydrogen can be categorized by its source as gray hydrogen, blue hydrogen, and green hydrogen. Green hydrogen, however, is considered the purest green energy source because its production process produces zero carbon emissions.

[0004] Hydrogen comes from a variety of sources. Among them, water electrolysis is a leading renewable energy source for its environmental friendliness, flexible production, and high-purity. Among these technologies, alkaline water electrolysis currently dominates industrial applications due to its low cost. However, compared to proton exchange membrane (PEM) water electrolyzers, alkaline electrolyzers have lower hydrogen production efficiency.

[0005] At present, the catalysts commonly used in alkaline electrolyzers are mainly obtained by spraying nickel-aluminum powder onto a substrate through reaction. Although the cost is low, the hydrogen evolution overpotential is high and the hydrogen production efficiency is very low, resulting in high overall energy consumption in the water electrolysis process. Alternatively, there are also methods that use precious metal heat treatment to obtain low hydrogen evolution overpotential electrodes, but the cost is very high, which is not conducive to industrial production.

[0006] Therefore, there is an urgent need to provide a new type of alkaline electrolyzer to achieve low hydrogen evolution overpotential, high hydrogen production efficiency, good stability, and low cost. Summary of the Invention

[0007] The embodiments of the present application provide a method for manufacturing a high-efficiency hydrogen production catalytic electrode for an alkaline electrolyzer. The method for manufacturing the catalytic electrode is simple, efficient, low-cost, and easy to industrialize. It can also produce a catalytic electrode with a multi-metal structure that has a low hydrogen evolution overpotential, good stability, and high-efficiency hydrogen production, thereby enabling the alkaline electrolyzer based on the catalytic electrode to have a good water electrolysis effect.

[0008] To achieve the above objectives, the embodiments of the present application adopt the following technical solutions:

[0009] In one aspect, a method for manufacturing a catalytic electrode is provided, comprising the following steps:

[0010] Using a spraying process, spraying a first metal powder onto the surface of a supporting substrate to obtain a first structure;

[0011] At a first temperature, etching the first structure with an alkaline solution having a first concentration for a first time to obtain a porous second structure having a first specific surface area;

[0012] placing the second structure in a second metal salt solution having a second concentration, and adding an organic additive solution having a third concentration;

[0013] Electroplating is performed at a second temperature and a second time to obtain the catalytic electrode.

[0014] Furthermore, the second temperature has a value range of 0-60°C;

[0015] The second time has a value range of 5-500 minutes.

[0016] Furthermore, the electroplating current has a value range of 0.01-5A.

[0017] Furthermore, the second metal salt solution includes multiple types of copper sulfate, copper molybdate, copper nitrate, copper chloride, aluminum sulfate, aluminum molybdate, aluminum nitrate, aluminum chloride, silver sulfate, silver molybdate, silver nitrate, silver chloride, platinum sulfate, platinum molybdate, platinum nitrate, platinum chloride, nickel sulfate, nickel molybdate, nickel nitrate, nickel chloride, cobalt sulfate, cobalt molybdate, cobalt nitrate, and cobalt chloride.

[0018] Furthermore, the second concentration has a value range of 1-30%.

[0019] Furthermore, the organic additive includes at least one of sodium citrate and potassium tartrate.

[0020] Furthermore, the third concentration has a value range of 5-60%;

[0021] The ratio of the amount of the organic additive solution to the amount of the second metal salt solution is in the range of 10-50%.

[0022] Furthermore, the alkali solution includes at least one of potassium hydroxide solution, sodium hydroxide solution, sodium bicarbonate solution, potassium bicarbonate solution, a mixed solution of potassium hydroxide and potassium sodium tartrate, a mixed solution of sodium hydroxide and potassium sodium tartrate, and potassium sodium tartrate solution.

[0023] Furthermore, the first concentration ranges from 5% to 50%;

[0024] The first temperature range includes 25-90°C;

[0025] The value range of the first time includes 1-24 hours.

[0026] An embodiment of the present application provides a method for manufacturing a catalytic electrode, comprising the following steps: using a spraying process to spray a first metal powder onto the surface of a supporting substrate to obtain a first structure; etching the first structure with an alkaline solution having a first concentration for a first time at a first temperature to obtain a second structure having a first specific surface area and being porous; placing the second structure in a second metal salt solution having a second concentration, and adding an organic additive solution having a third concentration; and electroplating at a second temperature and a second time to obtain a catalytic electrode. Thus, the present application combines spray pore-forming technology with electroplating technology to produce a multi-element alloy catalytic electrode with low hydrogen evolution overpotential, good stability, not easy to fall off, low cost, and high efficiency in hydrogen production. In addition, the method for manufacturing the catalytic electrode is simple, efficient, low-cost, and has low attenuation in the start-stop test, making it easy to industrialize.

[0027] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0029] Figure 1 A characterization diagram of a catalytic electrode for producing hydrogen by alkaline water electrolysis provided in an embodiment of the present application. DETAILED DESCRIPTION

[0030] In order to make the technical problems, technical solutions and beneficial effects to be solved by this application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit this application.

[0031] In this application, the term "and / or" describes the relationship between associated objects, indicating that three possible relationships exist. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0032] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b or c", or "at least one of a, b and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc or abc, where a, b, c can be single or multiple.

[0033] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution. Some or all of the steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0034] The terms used in the embodiments of the present application are for the purpose of describing specific embodiments only and are not intended to limit the present application. The singular forms "a", "an", "the" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise.

[0035] The weights of the relevant components mentioned in the examples of this application may not only refer to the specific content of each component, but also represent the weight ratio between the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the examples of this application, it is within the scope disclosed in the examples of this application. Specifically, the mass described in the examples of this application may be a mass unit known in the chemical industry, such as μg, mg, g, kg, etc.

[0036] The terms "first" and "second" are used solely for descriptive purposes to distinguish objects, such as substances, from one another and should not be understood to indicate or imply relative importance or to implicitly specify the quantity of the technical features being referred to. For example, without departing from the scope of the embodiments of this application, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX. Thus, features defined as "first" or "second" may explicitly or implicitly include one or more of such features.

[0037] In a first aspect, an embodiment of the present application provides a method for manufacturing a catalytic electrode.

[0038] The method for manufacturing the catalytic electrode comprises the following steps:

[0039] S1. Using a spraying process, spray a first metal powder onto the surface of a supporting substrate to obtain a first structure.

[0040] The present application does not specifically limit the type of the above-mentioned first metal powder. For example, the above-mentioned first metal powder can be any one or a combination of nickel (Ni) powder, copper (Cu) powder, molybdenum (Mo) powder, gold (Au) powder, aluminum (Al) powder, iron (Fe) powder, cobalt (Co) powder, platinum (Pt) powder, silver (Ag) powder, etc.; or, the above-mentioned first metal powder can also be a mixed powder / alloy of multiple metal powders such as nickel powder, copper powder, molybdenum powder, gold powder, aluminum powder, iron powder, cobalt powder, platinum powder, and silver powder.

[0041] Of course, the first metal powder may also be other types of metal powder, depending on the actual application.

[0042] The present application does not specifically limit the diameter of the first metal powder. For example, the average diameter of the first metal powder may be in the range of 10-50 μm. Specifically, the average diameter of the first metal powder may be 10 μm, 20 μm, 30 μm, 40 μm, or 50 μm, etc. This facilitates spraying the first metal powder onto the surface of the supporting substrate.

[0043] S2. Etching the first structure with an alkaline solution having a first concentration for a first time at a first temperature to obtain a porous second structure having a first specific surface area.

[0044] The present application does not make any specific limitation on the first specific surface area. For example, the value range of the first specific surface area can be 5-20m 2 / m 2 Specifically, the first specific surface area can be 5m 2 / m 2 、10m 2 / m 2 、15m 2 / m 2 or 20m 2 / m 2 Etc. The specific surface area is high.

[0045] S3. placing the second structure in a second metal salt solution having a second concentration, and adding an organic additive solution having a third concentration.

[0046] The present application can heal the pores / cracks formed by spraying through a second metal salt solution, thereby achieving high stability of the catalytic electrode; and, by electroplating a variety of metal materials on the surface of the substrate, a multi-element alloy coating can be formed on the surface of the substrate.

[0047] S4. Perform electroplating at a second temperature and a second time to obtain a catalytic electrode.

[0048] In the above step S4 of the present application, electroplating is performed at the second temperature and the second time to obtain a catalytic electrode, which includes:

[0049] S41 , performing electroplating at a second temperature and a second time to form a third structure, and then cleaning the third structure to obtain a catalytic electrode.

[0050] The method for manufacturing a catalytic electrode provided in an embodiment of the present application first sprays a first metal powder onto the surface of a supporting substrate; then uses an alkaline solution to treat it under certain conditions so that the first structure has a high specific surface area and multiple pores / cracks; then uses a variety of second metal salt solutions and organic additive solutions to treat it, so that the pores / cracks formed by spraying can be healed, thereby achieving high stability of the catalytic electrode; finally, electroplating is performed to composite the surface of the supporting substrate with multiple metals to form an alloy catalyst on the surface of the supporting substrate.

[0051] Thus, this application combines spray-coating pore-forming technology with electroplating technology to produce a multi-element alloy catalytic electrode with low hydrogen evolution overpotential, excellent stability, and resistance to shedding, resulting in low-cost, high-efficiency hydrogen production. Furthermore, this catalytic electrode exhibits a simple, efficient, and low-cost manufacturing process, exhibits minimal attenuation during start-stop testing, and is amenable to industrial production, demonstrating good market value.

[0052] In practical applications, the current density attenuation of the catalytic electrode mentioned above in the present application can be less than 1%, indicating that the catalytic electrode has high stability.

[0053] Furthermore, the current density attenuation of the catalytic electrode may range from 0 to 2%. Specifically, the current density attenuation of the catalytic electrode may be 0.1%, 0.2%, 0.3%, 0.5%, 0.6%, 0.7% or 0.8%, etc.

[0054] It should be noted that the catalytic electrode tested above is the current density decay of 1000 start-stop tests at -1.8V.

[0055] In practical applications, the hydrogen evolution overpotential of the catalytic electrode mentioned above in the present application can be lower than 50 mV.

[0056] Furthermore, the hydrogen evolution overpotential of the catalytic electrode may range from 38 to 48 mV (η10 mA). Specifically, the hydrogen evolution overpotential of the catalytic electrode may be 38 mV (η10 mA), 39 mV (η10 mA), 40 mV (η10 mA), 43 mV (η10 mA), 46 mV (η10 mA), or 48 mV (η10 mA), etc.

[0057] The energy consumption of hydrogen production by the catalytic electrode of the present application can be less than 3.8kWh / m 3 .

[0058] It should be noted that the catalytic electrode test was conducted at a temperature of 90°C and a current density of 3000 A / m2 Energy consumption of hydrogen production under .

[0059] Furthermore, the second temperature ranges from 0 to 60° C.; the second time ranges from 5 to 500 minutes.

[0060] The present application does not specifically limit the second temperature. For example, the second temperature may be 1°C, 10°C, 20°C, 30°C, 40°C or 60°C, etc.

[0061] Furthermore, the value range of the second temperature may include 10-30°C. For example, the second temperature may be 10°C, 15°C, 20°C, 25°C, 28°C or 30°C, etc.

[0062] This application does not specifically limit the above-mentioned second time. For example, the above-mentioned second time can be 5 minutes, 50 minutes, 100 minutes, 200 minutes, 300 minutes or 500 minutes, etc.

[0063] Furthermore, the value range of the second time may include 10-50 minutes. For example, the second time may be 10 minutes, 20 minutes, 30 minutes, 40 minutes, 45 minutes or 50 minutes, etc.

[0064] The electroplating temperature and electroplating time provided in the embodiments of the present application are both within an appropriate range, thereby facilitating the acquisition of a catalytic electrode with better performance, high stability, and low hydrogen evolution overpotential.

[0065] Furthermore, the electroplating current has a value range of 0.01-5A.

[0066] The present application does not impose any specific limitation on the electroplating current. For example, the electroplating current may be 0.01A, 1A, 2A, 3A, 4A or 5A, etc.

[0067] The electroplating current provided in the embodiments of the present application is within a suitable range, which is conducive to obtaining a catalytic electrode with better performance, high stability and low hydrogen evolution overpotential.

[0068] Furthermore, the second metal salt solution includes multiple ones of copper sulfate, copper molybdate, copper nitrate, copper chloride, aluminum sulfate, aluminum molybdate, aluminum nitrate, aluminum chloride, silver sulfate, silver molybdate, silver nitrate, silver chloride, platinum sulfate, platinum molybdate, platinum nitrate, platinum chloride, nickel sulfate, nickel molybdate, nickel nitrate, nickel chloride, cobalt sulfate, cobalt molybdate, cobalt nitrate, and cobalt chloride.

[0069] It should be understood that the second metal salt solution includes multiple of copper sulfate, copper molybdate, copper nitrate, copper chloride, aluminum sulfate, aluminum molybdate, aluminum nitrate, aluminum chloride, silver sulfate, silver molybdate, silver nitrate, silver chloride, platinum sulfate, platinum molybdate, platinum nitrate, platinum chloride, nickel sulfate, nickel molybdate, nickel nitrate, nickel chloride, cobalt sulfate, cobalt molybdate, cobalt nitrate, and cobalt chloride, which means that the second metal salt solution can include copper sulfate, copper molybdate, copper nitrate, copper chloride, aluminum sulfate, aluminum molybdate, aluminum nitrate, aluminum chloride, silver sulfate, silver molybdate, silver nitrate, silver chloride, sulfuric acid At least two of platinum, platinum molybdate, platinum nitrate, platinum chloride, nickel sulfate, nickel molybdate, nickel nitrate, nickel chloride, cobalt sulfate, cobalt molybdate, cobalt nitrate, and cobalt chloride; or, the second metal salt solution may include copper sulfate, copper molybdate, copper nitrate, copper chloride, aluminum sulfate, aluminum molybdate, aluminum nitrate, aluminum chloride, silver sulfate, silver molybdate, silver nitrate, silver chloride, platinum sulfate, platinum molybdate, platinum nitrate, platinum chloride, nickel sulfate, nickel molybdate, nickel nitrate, nickel chloride, cobalt sulfate, cobalt molybdate, cobalt nitrate, and cobalt chloride. No specific limitation is given here.

[0070] It should be noted that the second metal salt solution may also be other metal salt solutions, which are not specifically limited here. For example, the metal in the second metal salt solution may also be molybdenum, iron, etc.

[0071] The various second metal salt solutions provided in the embodiments of the present application are simple and easy to obtain, and are conducive to the subsequent electroplating process.

[0072] Furthermore, the second concentration has a value range of 1-30%.

[0073] The present application does not make any specific limitation on the second concentration. For example, the second concentration may be 1%, 5%, 10%, 15%, 20% or 30%, etc.

[0074] Furthermore, the second concentration may be in the range of 5-10%. For example, the second concentration may be 5%, 6%, 7%, 8%, 9% or 10%, etc.

[0075] The concentration of the second metal salt solution provided in the embodiment of the present application is within a suitable range, which is conducive to obtaining a catalytic electrode with better performance, high stability and low hydrogen evolution overpotential.

[0076] Furthermore, the organic additive includes at least one of sodium citrate and potassium tartrate.

[0077] It should be understood that the above-mentioned organic additives including at least one of sodium citrate and potassium tartrate means that the above-mentioned organic additives may include only one of sodium citrate or potassium tartrate; or, the above-mentioned organic additives may include sodium citrate and potassium tartrate, which is not specifically limited here.

[0078] The organic additive provided in the embodiment of the present application is added to the second metal salt solution after it becomes a solution, which is more conducive to the formation of the catalytic electrode.

[0079] Furthermore, the third concentration has a value range of 5-60%; and the ratio of the amount of the organic additive solution to the amount of the second metal salt solution has a value range of 10-50%.

[0080] The present application does not make any specific limitation on the third concentration. For example, the third concentration may be 5%, 10%, 20%, 40%, 50% or 60%, etc.

[0081] The ratio of the amount of the organic additive solution added to the amount of the second metal salt solution added refers to the ratio of the mass of the organic additive solution to the mass of the second metal salt solution. This application does not specifically limit the ratio of the amount of the organic additive solution added to the amount of the second metal salt solution added. For example, the ratio of the amount of the organic additive solution added to the amount of the second metal salt solution added can be 10%, 20%, 30%, 40%, 45%, or 50%, etc.

[0082] The concentration and mass of the organic additives provided in the embodiments of the present application are both within an appropriate range, thereby facilitating the acquisition of a catalytic electrode with better performance, high stability, and low hydrogen evolution overpotential.

[0083] Furthermore, the alkali solution includes at least one of potassium hydroxide (KOH) solution, sodium hydroxide (NaOH) solution, sodium bicarbonate (Na2CO3) solution, potassium bicarbonate (K2CO3) solution, a mixed solution of potassium hydroxide (KOH) and potassium sodium tartrate (NaKC4H4O6), a mixed solution of sodium hydroxide (NaOH) and potassium sodium tartrate (NaKC4H4O6), and potassium sodium tartrate (NaKC4H4O6) solution.

[0084] The alkaline solution provided in the embodiment of the present application can make the supporting substrate with a powder mixture on the surface porous / cracked after etching, and increase its specific surface area, which is conducive to the subsequent electroplating of multiple metals.

[0085] Furthermore, the value range of the first concentration includes 5-50%; the value range of the first temperature includes 25-90° C.; and the value range of the first time includes 1-24 hours.

[0086] The present application does not make any specific limitation on the above-mentioned first concentration. For example, the above-mentioned first concentration may be 5%, 10%, 20%, 30%, 40% or 50%, etc.

[0087] The present application does not specifically limit the first temperature. For example, the first temperature may be 25°C, 30°C, 40°C, 60°C, 80°C or 90°C, etc.

[0088] This application does not make any specific limitation on the above-mentioned first time. For example, the first time can be 1 hour, 5 hours, 10 hours, 15 hours, 20 hours or 24 hours, etc.

[0089] The first concentration, first temperature, and first time provided in the embodiments of the present application are within a suitable range, thereby facilitating the acquisition of a catalytic electrode with better performance, high stability, and low hydrogen evolution overpotential.

[0090] Furthermore, the above step S1, using a spraying process to spray the first metal powder onto the surface of the supporting substrate to obtain the first structure includes:

[0091] S11. Using a plasma spraying process, spray a first metal powder onto the surface of a metal support substrate to obtain a first structure.

[0092] The present application does not specifically limit the above-mentioned plasma spraying process. For example, the conditions for plasma spraying can be: argon (Ar) and hydrogen (H2) are used in the spraying, and the ratio of argon to hydrogen can be in the range of (4.5-5.5): (0.5-1); the spraying power can be in the range of 25-30KW; the spraying distance can be 20cm, the spraying speed can be 250m / s, and the powder feeding amount can be 150g / min.

[0093] There is no specific limitation on the ratio of the argon to hydrogen. For example, the ratio of the argon to hydrogen can be 5:0.5, 5:0.6, 5:0.7, 5:0.8, 5:0.9 or 5:1, etc.

[0094] There is no specific limitation on the spraying power. For example, the spraying power may be 25KW, 26KW, 27KW, 28KW, 29KW or 30KW, etc.

[0095] The present application does not specifically limit the type of the above-mentioned plasma spraying. For example, the plasma spraying can be any one of atmospheric plasma spraying, vacuum plasma spraying, supersonic plasma spraying, etc.

[0096] The embodiment of the present application uses a plasma spraying process for spraying, which can make the powder mixture sprayed onto the surface of the supporting substrate more uniformly.

[0097] The present application does not specifically limit the type of the above-mentioned support substrate. For example, the above-mentioned support substrate can be a metal support substrate.

[0098] The present application does not specifically limit the type of the above-mentioned metal support substrate. For example, the above-mentioned metal support substrate may include any one of a nickel sheet, a nickel mesh, an iron sheet, an iron mesh, a copper sheet, a copper mesh, etc.

[0099] This application does not specifically limit the mesh size of the above-mentioned nickel mesh, iron mesh, copper mesh, etc. For example, the mesh size of the above-mentioned nickel mesh, iron mesh, copper mesh, etc. includes but is not limited to 40 mesh, 46 mesh, 60 mesh, 80 mesh, etc.

[0100] In practical applications, the surfaces of the nickel sheet, nickel mesh, iron sheet, iron mesh, copper sheet, copper mesh, etc. can be sandblasted and polished before being subjected to the plasma spraying process.

[0101] The metal support substrate provided in the embodiments of the present application is simple and easy to implement.

[0102] Furthermore, after etching the first structure with an alkaline solution having a first concentration at a first temperature for a first time to obtain a porous second structure having a first specific surface area in step S2, and before placing the second structure in a second metal salt solution having a second concentration and adding an organic additive solution having a third concentration in step S3, the method for manufacturing the catalytic electrode further includes:

[0103] S21, cleaning and drying the second structure.

[0104] Furthermore, the above step S3, placing the second structure in a second metal salt solution having a second concentration, and adding an organic additive solution having a third concentration, comprises:

[0105] S31. After drying, the second structure is placed in a second metal salt solution with a second concentration, and an organic additive solution with a third concentration and the first number is added.

[0106] The present application does not impose any specific limitation on the first portion. For example, the first portion may range from 20% to 30%. Specifically, the first portion may be 20%, 22%, 24%, 26%, 28%, or 30%, etc.

[0107] Furthermore, the above-mentioned step S41, performing electroplating at the second temperature and the second time to form the third structure, and then cleaning the third structure to obtain the catalytic electrode includes:

[0108] S411 , applying power to perform electroplating at a second temperature and a second time to form a third structure, and then ultrasonically cleaning the third structure in pure water to obtain a catalytic electrode.

[0109] The present application does not specifically limit the power of the ultrasonic cleaning. For example, the power range of the ultrasonic cleaning may be 30-100 W. Specifically, the power of the ultrasonic cleaning process may be 30 W, 40 W, 50 W, 60 W, 80 W or 100 W, etc.

[0110] The present application does not specifically limit the time of the ultrasonic cleaning. For example, the ultrasonic cleaning time range may be 5-30 minutes. Specifically, the ultrasonic cleaning time may be 5 minutes, 7 minutes, 10 minutes, 15 minutes, 20 minutes, or 30 minutes.

[0111] The embodiment of the present application uses ultrasonic cleaning of the third structure, which is beneficial for removing impurities on the surface of the third structure, making the catalytic electrode purer.

[0112] In a second aspect, an embodiment of the present application provides a catalytic electrode, which is manufactured by the above-mentioned method for manufacturing a catalytic electrode.

[0113] The embodiments of the present application provide a catalytic electrode with multiple alloys, low cost, and high efficiency for hydrogen production. The catalytic electrode also has the advantages of low hydrogen evolution overpotential, low energy consumption, and good structural stability under dynamic and static current conditions.

[0114] In a third aspect, an embodiment of the present application provides an alkaline electrolytic cell comprising a diaphragm, an anode, and a catalytic electrode obtained by the above-mentioned method for manufacturing a catalytic electrode, wherein the diaphragm is located between the anode and the catalytic electrode.

[0115] It should be noted that the alkaline electrolytic cell may also include an alkaline solution and a battery.

[0116] The present application does not make any specific limitation on the above alkaline solution. For example, the above alkaline solution can be 1M KOH, and of course it can also be other alkaline solutions, which are not specifically limited here.

[0117] The alkaline electrolytic cell provided in the embodiments of the present application has excellent water electrolysis performance, low cost, and is easy to industrialize because the catalytic electrodes used contain multiple metals and have properties such as high stability and low hydrogen evolution overpotential.

[0118] Two specific embodiments are listed below to illustrate the catalytic electrode, its manufacturing method and application in this application.

[0119] Example 1

[0120] Example 1 requires a catalytic electrode with a hydrogen evolution overpotential of 45±3 mV (η10 mA) and a current density decay of 1±1% after 1000 start-stop tests at -1.8 V.

[0121] The manufacturing process of the catalytic electrode is as follows:

[0122] S011. Use atmospheric plasma spraying process.

[0123] The conditions of the atmospheric plasma spraying process are as follows: argon and hydrogen are used in the spraying, with the ratio of argon to hydrogen being 5:0.5; the spraying power is 25 kW; the spraying distance is 20 cm; the spraying speed is 250 m / s; and the powder feeding amount is 150 g / min.

[0124] Nickel powder with a diameter range of 10-50 μm and aluminum powder with a diameter range of 10-50 μm are sprayed onto the surface of a 46-mesh nickel mesh (sandblasted surface) at a spraying rate of 300 g / m 2 .

[0125] S012. Place the sprayed nickel mesh in a 15% sodium hydroxide solution at 40° C., stir and place for 12 hours until no bubbles are generated, then take it out and clean the surface with pure water. After cleaning, blow dry it.

[0126] S013. Place the dried nickel mesh in a solution containing copper sulfate (10% by mass), cobalt nitrate (15% by mass), and aluminum chloride (10% by mass). At the same time, add 30% of sodium citrate (20% by mass). At this time, the solution temperature is 10°C and the current is 0.5A. Then, power on for 30 minutes.

[0127] S014. The treated electrode is cleaned in clean water with 50W ultrasound for 20 minutes to obtain a high-efficiency hydrogen production catalytic electrode for an alkaline electrolyzer.

[0128] The catalytic electrode prepared in Example 1 was tested and the results were as follows: Figure 1 Characterization diagram of the catalytic electrode for hydrogen production by alkaline water electrolysis. Figure 1 As shown, the horizontal axis is voltage (Voltage), the unit is volt (V), and the vertical axis is current (Current), the unit is ampere (A).

[0129] Depend on Figure 1 It can be seen that the catalytic electrode prepared in Example 1 has low hydrogen evolution overpotential and high stability.

[0130] The hydrogen evolution overpotential, current density decay, ultrasonic vibration loss, high current stability, and hydrogen production energy consumption of the catalytic electrode prepared in Example 1 were tested below to obtain the following Table 1.

[0131] Table 1

[0132]

[0133] It can be seen from Table 1 above that the catalytic electrode provided in Example 1 of the present application has a low hydrogen evolution overpotential, small current density attenuation, small ultrasonic vibration loss, stability under large current, and low energy consumption for hydrogen production. The performance of the catalytic electrode is very good.

[0134] Example 2

[0135] Example 2 requires a catalytic electrode with a hydrogen evolution overpotential of 40±2 mV (η10 mA) and a current density decay of <1% after 1000 start-stop tests at -1.8 V.

[0136] The manufacturing process of the catalytic electrode is as follows:

[0137] S021. Use atmospheric plasma spraying technology.

[0138] The conditions of the atmospheric plasma spraying process are as follows: argon and hydrogen are used in the spraying, with the ratio of argon to hydrogen being 5:1; the spraying power is 30 kW; the spraying distance is 20 cm; the spraying speed is 250 m / s; and the powder feeding amount is 150 g / min.

[0139] Nickel, aluminum, and molybdenum alloy powders with a diameter range of 5-90 μm are sprayed onto the surface of a 46-mesh nickel mesh (sandblasted surface) with a spraying amount of 300 g / m 2 .

[0140] S022. Place the sprayed nickel mesh in a 15% sodium hydroxide solution at 40° C., stir and place for 12 hours until no bubbles are generated, then take it out and clean the surface with pure water. After cleaning, blow dry it.

[0141] S023. Place the dried nickel mesh in a solution containing nickel nitrate (10% by mass) and cobalt molybdate (15% by mass). At the same time, add 20% of potassium tartrate (30% by mass). At this time, the solution temperature is 10°C and the current is 1.2A. Then, power on for 10 minutes.

[0142] S024. The treated electrode is cleaned in clean water with 100W ultrasound for 5 minutes to obtain a high-efficiency hydrogen production catalytic electrode for an alkaline electrolyzer.

[0143] The catalytic electrode prepared in Example 2 was tested below to obtain Figure 1 Characterization diagram of the catalytic electrode for hydrogen production by alkaline water electrolysis. Figure 1 It can be seen that the catalytic electrode prepared in Example 2 has low hydrogen evolution overpotential and high stability.

[0144] The hydrogen evolution overpotential, current density decay, ultrasonic vibration loss, high current stability, and hydrogen production energy consumption of the catalytic electrode prepared in Example 2 were tested below to obtain the following Table 2.

[0145] Table 2

[0146]

[0147] It can be seen from Table 2 above that the catalytic electrode provided in Example 2 of the present application has a low hydrogen evolution overpotential, small current density attenuation, small ultrasonic vibration loss, stability under large current, and low energy consumption for hydrogen production. The performance of the catalytic electrode is very good.

[0148] This application only introduces the contents related to the invention. The remaining structures can be obtained by referring to the relevant technologies and will not be described in detail here.

[0149] An “embodiment” as referred to herein means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present application.

[0150] In the description provided herein, a large number of specific details are described. However, it is understood that the embodiments of the present application can be practiced without these specific details. In some instances, well-known methods, structures, and techniques are not shown in detail so as not to obscure the understanding of this description.

[0151] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for manufacturing a catalytic electrode, characterized in that: The steps include: Using a spraying process, spraying a first metal powder onto the surface of a supporting substrate to obtain a first structure; At 25-90°C, the first structure is etched with an alkaline solution having a concentration of 5-50% for 1-24 hours to obtain a second structure having a first specific surface area and being porous; wherein the first specific surface area is 5-20m 2 / m 2 ; placing the second structure in a second metal salt solution having a concentration of 1-30%, and adding an organic additive solution having a concentration of 5-60%, wherein the ratio of the amount of the organic additive solution added to the amount of the second metal salt solution added ranges from 10-50%; The catalytic electrode is obtained by electroplating for 5-500 minutes at 0-60°C and a current range of 0.01-5A; wherein the current density decay of the catalytic electrode is less than 1%, the current density decay of the catalytic electrode in the -1.8V start-stop test 1000 times is in the range of 0-2%, the hydrogen evolution overpotential of the catalytic electrode is less than 50mV, and the catalytic electrode is 1000A / m at a temperature of 90°C and a current density of 3000A / m 2 The energy consumption of hydrogen production is less than 3.8kWh / m 3 .

2. The method for manufacturing a catalytic electrode according to claim 1, wherein: The second metal salt solution includes multiple ones of copper sulfate, copper molybdate, copper nitrate, copper chloride, aluminum sulfate, aluminum molybdate, aluminum nitrate, aluminum chloride, silver sulfate, silver molybdate, silver nitrate, silver chloride, platinum sulfate, platinum molybdate, platinum nitrate, platinum chloride, nickel sulfate, nickel molybdate, nickel nitrate, nickel chloride, cobalt sulfate, cobalt molybdate, cobalt nitrate, and cobalt chloride.

3. The method for manufacturing a catalytic electrode according to claim 1, wherein: The organic additive includes at least one of sodium citrate and potassium tartrate.

4. The method for manufacturing a catalytic electrode according to claim 1, wherein: The alkali solution includes at least one of potassium hydroxide solution, sodium hydroxide solution, sodium bicarbonate solution, potassium bicarbonate solution, a mixed solution of potassium hydroxide and potassium sodium tartrate, a mixed solution of sodium hydroxide and potassium sodium tartrate, and potassium sodium tartrate solution.

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