Preparation method of catalytic electrode

Abstract

The invention provides a preparation method of a catalytic electrode, and the preparation method comprises the following steps: mixing metal powder with a certain particle size with first polymer resin, a first solvent and a first auxiliary agent to obtain a first dispersion liquid; mixing other powder with a certain particle size with second polymer resin, a second solvent and a second auxiliary agent, and stirring and dispersing to obtain a second dispersion liquid; gradually adding the second dispersion liquid into the first dispersion liquid, stirring, dispersing and mixing to obtain a third dispersion liquid; loading the third dispersion liquid on any side surface of a conductive substrate, and carrying out carbonization treatment to obtain a catalytic electrode precursor; and carrying out ultrasonic treatment in an alkaline solution, and sequentially carrying out cleaning treatment and high-temperature treatment to obtain the catalytic electrode. According to the invention, through the design of the preparation method of the catalytic electrode, the prepared catalytic electrode is low in energy consumption and high in binding force between a catalytic material and a base material in the water electrolysis hydrogen production process, meanwhile, the catalytic electrode has very good reverse current resistance, and high-stability hydrogen production is realized.

Description

Technical Field

[0001] This invention belongs to the field of water electrolysis for hydrogen production technology, and relates to a method for preparing a catalytic electrode. Background Technology

[0002] In the energy sector, the hydrogen evolution reaction (HER) is crucial for the development of sustainable energy. For example, in the process of hydrogen production through water electrolysis, a highly efficient HER catalytic electrode can significantly improve hydrogen production efficiency and reduce energy consumption. Traditional HER catalytic electrodes suffer from several problems during preparation, such as insufficient bonding strength between the electrode and the substrate, leading to easy detachment during use and affecting the electrode's lifespan and catalytic performance. Furthermore, commonly used preparation methods often fail to fully utilize the performance of the catalytic material, resulting in material waste and difficulty in further improving catalytic activity. Therefore, developing a novel HER catalytic electrode and its preparation method is of significant practical importance. Summary of the Invention

[0003] To address the shortcomings of existing technologies, the present invention aims to provide a method for preparing a catalytic electrode, particularly a method based on the size reduction effect of nanomaterials. In this invention, through the design of the catalytic electrode preparation method, the prepared catalytic electrode exhibits low energy consumption during water electrolysis for hydrogen production, high bonding strength between the catalytic material and the substrate, and excellent resistance to reverse current, achieving highly stable hydrogen production. In terms of industrial production, it boasts high material utilization, generates no metal dust during the preparation process, and features a simple technology suitable for industrial production, providing a crucial solution for the green hydrogen industry.

[0004] To achieve this objective, the present invention adopts the following technical solution:

[0005] This invention provides a method for preparing a catalytic electrode, the method comprising:

[0006] (1) A metal powder of a certain particle size is mixed with a first polymer resin, a first solvent and a first additive to obtain a first dispersion;

[0007] (2) Mix other powders of a certain particle size with the second polymer resin, the second solvent and the second additive, stir and disperse to obtain the second dispersion;

[0008] (3) The second dispersion obtained in step (2) is gradually added to the first dispersion obtained in step (1), and the mixture is stirred and mixed to obtain the third dispersion;

[0009] (4) Load the third dispersion obtained in step (3) onto the surface of any side of the conductive substrate and carbonize it to obtain the catalytic electrode precursor.

[0010] (5) The catalytic electrode precursor obtained in step (4) is ultrasonically treated in an alkaline solution, and then subjected to cleaning and high-temperature treatment in sequence to obtain the catalytic electrode.

[0011] The order of operations in steps (1) and (2) is not important.

[0012] In this invention, the design of the catalytic electrode preparation method enables the prepared catalytic electrode to have low energy consumption during water electrolysis for hydrogen production, high bonding force between the catalytic material and the substrate, and excellent resistance to reverse current, thus achieving highly stable hydrogen production. In terms of industrial preparation, the material utilization rate is high, no metal dust is generated during the preparation process, and the process technology is simple and easy to industrialize, providing an extremely important solution for the green hydrogen industry.

[0013] It should be noted that in this invention, metal powder of a certain nanoscale size is mixed with polymer materials to form a dispersion slurry of a certain viscosity. Then, another type of metal powder of a certain nanoscale size is added to form a final metal / polymer dispersion slurry. This slurry is then adhered to a conductive substrate through processes such as dip coating, scraping coating, and spraying. A preliminary heat treatment is then performed to remove the carbonization of the polymer and achieve compatibility between the metals. A second heat treatment is then performed to further alloy the powders and enhance their adhesion to the substrate. This results in a catalytic electrode with low energy consumption for hydrogen production, high bonding strength between the catalytic material and the substrate, and excellent reverse current resistance, achieving highly stable hydrogen production.

[0014] It should be noted that the gradual addition of the second dispersion to the first dispersion in this invention can be achieved by dividing the second dispersion into several batches, adding each batch to the first dispersion gradually, until the required amount of the second dispersion has been completely added.

[0015] It should be noted that the specific materials used for the metal powder and other powders in this invention can be the same or different, or partially the same, and can be adapted to the actual situation.

[0016] As a preferred technical solution of the present invention, in step (1), the metal powder is any one of nickel powder, titanium powder, copper powder and cobalt powder.

[0017] Preferably, in step (1), the particle size of the metal powder is 100nm to 5000nm, such as 100nm, 500nm, 1000nm, 1500nm, 2000nm, 2500nm, 3000nm, 3500nm, 4000nm, 4500nm, 5000nm, etc., but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0018] In this invention, the metal powder has a certain particle size of 100nm to 5000nm because within this range, the slurry is easy to disperse evenly, and the prepared catalytic electrode is more uniform; if it is not within this range, it may lead to the preparation of an uneven catalytic electrode.

[0019] Preferably, in step (1), the first polymer resin is an aqueous resin.

[0020] Preferably, the waterborne resin includes any one or a combination of two or more of acrylic resin, polyurethane and cellulose resin.

[0021] Preferably, in step (1), the first solvent is deionized water.

[0022] Preferably, in step (1), the first additive includes a leveling agent and a dispersant.

[0023] Preferably, in step (1), based on the total mass of the first dispersion being 100wt%, the amount of the first auxiliary agent is 0.5‰ to 5‰, for example, 0.5‰, 1‰, 1.5‰, 2‰, 2.5‰, 3‰, 3.5‰, 4‰, 4.5‰, 5‰, etc., but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0024] As a preferred technical solution of the present invention, in step (1), the ratio of the amount of metal powder to the first polymer resin is (50~200)g:10g, for example 50g:10g, 100g:10g, 150g:10g, 200g:10g, etc., but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0025] The ratio of metal powder to the first polymer resin in this invention is (50-200)g:10g because within this range, the slurry is easy to disperse and easy to process in subsequent processes to obtain organic matter or its decomposition products with almost no residue. If it is not within this range, the catalytic electrode prepared later will have more residual impurities, resulting in unstable performance of the catalytic electrode.

[0026] Preferably, in step (1), the total mass of the metal powder and the first polymer resin accounts for 30% to 70% of the mass of the first dispersion, for example, 30%, 40%, 50%, 60%, 70%, etc., but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0027] Preferably, in step (1), the viscosity of the first dispersion is 50,000 cP to 100,000 cP, such as 50,000 cP, 60,000 cP, 70,000 cP, 80,000 cP, 90,000 cP, 100,000 cP, etc., but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0028] In this invention, the viscosity of the first dispersion is 50,000 cP to 100,000 cP because it is easy to disperse and form a uniform slurry within this range. If it is not within this range, the first dispersion may easily settle, which is not conducive to subsequent processing.

[0029] As a preferred technical solution of the present invention, in step (2), the other powders include metal powders and metal oxide powders.

[0030] It should be noted that the other powders in this invention can be a mixture of multiple types of metal powders, a mixture of multiple types of metal oxide powders, or a mixture of multiple types of metal powders and metal oxide powders.

[0031] Preferably, the metal powder is any one or a combination of two or more of cobalt powder, copper powder, nickel powder, molybdenum powder, titanium powder, manganese powder and iron powder.

[0032] Preferably, the metal oxide powder is any one or a combination of two or more of cobalt oxide, nickel oxide, copper oxide and titanium oxide.

[0033] Preferably, in step (2), the particle size of the other powder is 50nm to 200nm, such as 50nm, 100nm, 150nm, 200nm, etc., but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0034] In this invention, the particle size of other powders is 50nm to 200nm because within this range, it is easy to achieve conductive bonding between metal powders and other powders; if it is not within this range, the prepared catalytic electrode will have poor conductivity and poor catalytic performance.

[0035] Preferably, in step (2), the second polymer resin is an aqueous resin.

[0036] Preferably, the waterborne resin includes any one or a combination of two or more of acrylic resin, polyurethane and cellulose resin.

[0037] Preferably, in step (2), the second solvent is deionized water.

[0038] Preferably, in step (2), the second additive includes a leveling agent and a dispersant.

[0039] It should be noted that the leveling agent in this invention can be BYK-333, BYK-346, BYK-3455, TEGO-410, TEGO-270, etc., and the dispersant can be TEGO Dispers 760, TEGO Dispers 755, BYK-151, BYK-190, etc.; those skilled in the art can make adaptive adjustments to the specific material selection of the leveling agent and dispersant according to their needs.

[0040] Preferably, in step (2), based on the total mass of the second dispersion being 100wt%, the amount of the second auxiliary agent is 0.5‰ to 5‰, for example, 0.5‰, 1‰, 1.5‰, 2‰, 2.5‰, 3‰, 3.5‰, 4‰, 4.5‰, 5‰, etc., but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0041] As a preferred technical solution of the present invention, in step (2), the ratio of the other powder to the second polymer resin is (100-200)g:10g, for example 100g:10g, 120g:10g, 140g:10g, 160g:10g, 180g:10g, 200g:10g, etc., but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0042] In this invention, the ratio of other powders to the second polymer resin is (100-200) g: 10 g. This is because within this range, the slurry is easy to disperse and easy to process in subsequent processes to obtain organic matter or its decomposition products with almost no residue. If it is not within this range, it may result in more residual impurities in the catalytic electrode prepared later, and the performance of the catalytic electrode may be unstable.

[0043] Preferably, in step (2), the total mass of the other powders and the second polymer resin accounts for 30% to 50% of the mass of the second dispersion, for example, 30%, 35%, 40%, 45%, 50%, etc., but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0044] As a preferred technical solution of the present invention, in step (3), the ratio of the first dispersion to the second dispersion in the third dispersion is 100g:(30~100)g, for example 100g:30g, 100g:50g, 100g:70g, 100g:90g, 100g:100g, etc., but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0045] In this invention, the ratio of the first dispersion to the second dispersion in the third dispersion is 100g:(30-100)g. This is because within this range, the slurry is easy to disperse and easy to process in subsequent processes, resulting in a catalytic electrode with good conductivity. If it is not within this range, the stability of the catalytic electrode prepared later may be poor, and the catalytic effect may be poor.

[0046] As a preferred technical solution of the present invention, in step (4), the loading method of the third dispersion liquid on the conductive substrate includes dip coating, scraping coating and spraying.

[0047] Preferably, in step (4), the carbonization temperature is 200℃~450℃, such as 200℃, 250℃, 300℃, 350℃, 400℃, 450℃, etc., but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0048] The carbonization temperature in this invention is 200℃~450℃ because within this range, organic matter is easily removed, while conductive connections between metal powders are achieved. If it is outside this range, organic matter will be difficult to remove or overheating will result in poor performance of the catalytic electrode. The carbonization process can remove polymers by carbonization and simultaneously achieve preliminary fusion of metals to prepare the catalytic electrode precursor of this invention.

[0049] As a preferred technical solution of the present invention, in step (5), the alkaline solution is any one of potassium hydroxide, sodium hydroxide and ammonia water.

[0050] It should be noted that the alkaline solution used in this invention to treat the catalytic electrode precursor can remove residual organic matter or decomposition products on the catalytic electrode precursor. If acid solution is used for treatment, there is a risk that the electrode may detach.

[0051] Preferably, in step (5), the amount of alkaline solution used is 10% to 30% based on the mass of the catalytic electrode precursor as 100%, such as 10%, 15%, 20%, 25%, 30%, etc., but not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0052] The amount of alkaline solution used in this invention is 10% to 30% because within this range, it is beneficial to the decomposition of organic matter and the removal of residues. If it is outside this range, the decomposition products may not be easy to remove.

[0053] Preferably, in step (5), the ultrasonic power of the ultrasonic treatment is 100W to 600W, such as 100W, 200W, 300W, 400W, 500W, 600W, etc., but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0054] Preferably, in step (5), the ultrasonic treatment time is 10 min to 30 min, such as 10 min, 15 min, 20 min, 25 min, 30 min, etc., but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0055] As a preferred technical solution of the present invention, in step (5), the cleaning process uses deionized water for cleaning.

[0056] Preferably, in step (5), the temperature of the high-temperature treatment is 500℃~900℃, such as 500℃, 600℃, 700℃, 800℃, 900℃, etc., but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0057] The high-temperature treatment temperature in this invention is 500℃~900℃ because within this range, the conductivity and catalytic performance generated by the interaction between metals can be further enhanced. If it is outside this range, the catalytic effect of the resulting catalytic electrode may be poor.

[0058] Preferably, in step (5), the gas atmosphere for the high-temperature treatment is any one or a combination of two or more of nitrogen, argon and hydrogen.

[0059] As a preferred technical solution of the present invention, the preparation method specifically includes:

[0060] (1) A metal powder of a certain particle size is mixed with a first polymer resin, a first solvent and a first additive to obtain a first dispersion;

[0061] (2) Mix other powders of a certain particle size with the second polymer resin, the second solvent and the second additive, stir and disperse to obtain the second dispersion;

[0062] (3) The second dispersion obtained in step (2) is gradually added to the first dispersion obtained in step (1), and the mixture is stirred and mixed to obtain the third dispersion;

[0063] (4) Load the third dispersion obtained in step (3) onto the surface of any side of the conductive substrate and carbonize it to obtain the catalytic electrode precursor.

[0064] (5) The catalytic electrode precursor obtained in step (4) is ultrasonically treated in an alkaline solution, and then subjected to cleaning and high-temperature treatment in sequence to obtain the catalytic electrode.

[0065] The order of operations in steps (1) and (2) is not important;

[0066] In step (1), the metal powder is any one of nickel powder, titanium powder, copper powder and cobalt powder, and the particle size of the metal powder is 100nm to 5000nm. The first polymer resin is an aqueous resin, which includes any one or a combination of two or more of acrylic resin, polyurethane and cellulose resin. The first solvent is deionized water. The first additive includes leveling agent and dispersant. Based on the total mass of the first dispersion of 100wt%, the amount of the first additive is 0.5‰ to 5‰. The ratio of the amount of metal powder to the amount of the first polymer resin is (50 to 200)g:10g. The total mass of the metal powder and the first polymer resin accounts for 30% to 70% of the mass of the first dispersion. The viscosity of the first dispersion is 50000cP to 100000cP.

[0067] In step (2), the other powders include metal powders and metal oxide powders. The metal powders are any one or a combination of two or more of cobalt powder, copper powder, nickel powder, molybdenum powder, titanium powder, manganese powder, and iron powder. The metal oxide powders are any one or a combination of two or more of cobalt oxide, nickel oxide, copper oxide, and titanium oxide. The particle size of the other powders is 50nm to 200nm. The second polymer resin is an aqueous resin. The aqueous resin includes any one or a combination of two or more of acrylic resin, polyurethane, and cellulose resin. The second solvent is deionized water. The second additive includes leveling agent and dispersant. Based on the total mass of the second dispersion of 100wt%, the amount of the second additive is 0.5‰ to 5‰. The ratio of the amount of the other powders to the amount of the second polymer resin is (100 to 200)g:10g. The total mass of the other powders and the second polymer resin accounts for 30% to 50% of the mass of the second dispersion.

[0068] In step (3), the ratio of the first dispersion to the second dispersion in the third dispersion is 100g:(30-100)g;

[0069] In step (4), the loading methods of the third dispersion on the conductive substrate include dip coating, scraping coating and spraying coating, and the carbonization treatment temperature is 200℃~450℃;

[0070] In step (5), the alkaline solution is any one of potassium hydroxide, sodium hydroxide, and ammonia water. Based on the mass of the catalytic electrode precursor as 100%, the amount of the alkaline solution is 10% to 30%. The ultrasonic power of the ultrasonic treatment is 100W to 600W. The ultrasonic treatment time is 10min to 30min. The cleaning treatment uses deionized water. The temperature of the high-temperature treatment is 500℃ to 900℃. The gas atmosphere of the high-temperature treatment is any one or a combination of two or more of nitrogen, argon, and hydrogen.

[0071] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0072] It should be understood that the description in this section is not intended to identify key or essential features of the embodiments of the present invention, nor is it intended to limit the scope of the invention. Other features of the invention will become readily apparent from the following description.

[0073] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0074] In this invention, the design of the catalytic electrode preparation method enables the prepared catalytic electrode to have low energy consumption during water electrolysis for hydrogen production, high bonding force between the catalytic material and the substrate, and excellent resistance to reverse current, thus achieving highly stable hydrogen production. In terms of industrial preparation, the material utilization rate is high, no metal dust is generated during the preparation process, and the process technology is simple and easy to industrialize, providing an extremely important solution for the green hydrogen industry. Detailed Implementation

[0075] The technical solution of the present invention will be further illustrated below through specific embodiments.

[0076] Example 1

[0077] This embodiment provides a method for preparing a catalytic electrode, the specific steps of which include:

[0078] (1) A metal powder of a certain particle size is mixed with a first polymer resin, a first solvent and a first additive to obtain a first dispersion;

[0079] (2) Mix other powders of a certain particle size with the second polymer resin, the second solvent and the second additive, stir and disperse to obtain the second dispersion;

[0080] (3) The second dispersion obtained in step (2) is gradually added to the first dispersion obtained in step (1), and the mixture is stirred and mixed to obtain the third dispersion;

[0081] (4) Load the third dispersion obtained in step (3) onto the surface of any side of the conductive substrate and carbonize it to obtain the catalytic electrode precursor.

[0082] (5) The catalytic electrode precursor obtained in step (4) is ultrasonically treated in an alkaline solution, and then subjected to cleaning and high-temperature treatment in sequence to obtain the catalytic electrode.

[0083] The order of operations in steps (1) and (2) is not important.

[0084] In step (1), the metal powder is nickel powder with a certain particle size of 1000 nm, the first polymer resin is acrylic resin, the first solvent is deionized water, the first additive includes leveling agent and dispersant, the amount of the first additive is 1‰ based on the total mass of the first dispersion of 100wt%, the ratio of the amount of metal powder to the amount of the first polymer resin is 100g:10g, the total mass of the metal powder and the first polymer resin accounts for 40% of the mass of the first dispersion, and the viscosity of the first dispersion is 60000cP.

[0085] In step (2), the other powders include metal powders, which are a combination of cobalt powder, copper powder and nickel powder. The particle size of the other powders is 50 nm. The second polymer resin is acrylic resin. The second solvent is deionized water. The second additives include leveling agents and dispersants. The amount of the second additives is 0.5‰ based on the total mass of the second dispersion being 100 wt%. The ratio of the amount of other powders to the amount of the second polymer resin is 100 g: 10 g. The total mass of the other powders and the second polymer resin accounts for 30% of the mass of the second dispersion.

[0086] In step (3), the ratio of the first dispersion to the second dispersion in the third dispersion is 100g:40g.

[0087] In step (4), the third dispersion is loaded onto the conductive substrate (46 mesh 25 wire nickel mesh) by dip coating, and the carbonization temperature is 300℃.

[0088] In step (5), the alkaline solution is potassium hydroxide, the amount of alkaline solution is 10% based on the mass of the catalytic electrode precursor being 100%, the ultrasonic power of the ultrasonic treatment is 150W, the ultrasonic time of the ultrasonic treatment is 30min, the cleaning treatment uses deionized water, the temperature of the high-temperature treatment is 550℃, and the gas atmosphere of the high-temperature treatment is nitrogen.

[0089] Ultimately, the load was found to be 255 g / m. 2 The catalytic electrode.

[0090] Example 2

[0091] This embodiment provides a method for preparing a catalytic electrode, the specific steps of which include:

[0092] (1) A metal powder of a certain particle size is mixed with a first polymer resin, a first solvent and a first additive to obtain a first dispersion;

[0093] (2) Mix other powders of a certain particle size with the second polymer resin, the second solvent and the second additive, stir and disperse to obtain the second dispersion;

[0094] (3) The second dispersion obtained in step (2) is gradually added to the first dispersion obtained in step (1), and the mixture is stirred and mixed to obtain the third dispersion;

[0095] (4) Load the third dispersion obtained in step (3) onto the surface of any side of the conductive substrate and carbonize it to obtain the catalytic electrode precursor.

[0096] (5) The catalytic electrode precursor obtained in step (4) is ultrasonically treated in an alkaline solution, and then subjected to cleaning and high-temperature treatment in sequence to obtain the catalytic electrode.

[0097] The order of operations in steps (1) and (2) is not important.

[0098] In step (1), the metal powder is titanium powder, the particle size of the metal powder is 3000nm, the first polymer resin is polyurethane, the first solvent is deionized water, the first additive includes leveling agent and dispersant, the amount of the first additive is 2‰ based on the total mass of the first dispersion being 100wt%, the ratio of the amount of metal powder to the amount of the first polymer resin is 150g:10g, the total mass of the metal powder and the first polymer resin accounts for 50% of the mass of the first dispersion, and the viscosity of the first dispersion is 80000cP.

[0099] In step (2), the other powders include metal oxide powders, which are a combination of cobalt oxide, nickel oxide and copper oxide. The particle size of the other powders is 100 nm. The second polymer resin is polyurethane, the second solvent is deionized water, and the second additives include leveling agents and dispersants. The amount of the second additives is 2‰ based on the total mass of the second dispersion being 100 wt%. The ratio of the amount of other powders to the amount of the second polymer resin is 120 g: 10 g, and the total mass of the other powders and the second polymer resin accounts for 35% of the mass of the second dispersion.

[0100] In step (3), the ratio of the first dispersion to the second dispersion in the third dispersion is 100g:50g.

[0101] In step (4), the third dispersion is loaded onto the conductive substrate by scraping, and the carbonization temperature is 350°C.

[0102] In step (5), the alkaline solution is sodium hydroxide, and the amount of alkaline solution is 20% based on the mass of the catalytic electrode precursor being 100%. The ultrasonic power of the ultrasonic treatment is 200W, the ultrasonic time of the ultrasonic treatment is 20min, the cleaning treatment uses deionized water, the high temperature treatment temperature is 700℃, and the gas atmosphere of the high temperature treatment is a combination of nitrogen and argon.

[0103] Ultimately, the load was found to be 245 g / m. 2 The catalytic electrode.

[0104] Example 3

[0105] This embodiment provides a method for preparing a catalytic electrode, the specific steps of which include:

[0106] (1) A metal powder of a certain particle size is mixed with a first polymer resin, a first solvent and a first additive to obtain a first dispersion;

[0107] (2) Mix other powders of a certain particle size with the second polymer resin, the second solvent and the second additive, stir and disperse to obtain the second dispersion;

[0108] (3) The second dispersion obtained in step (2) is gradually added to the first dispersion obtained in step (1), and the mixture is stirred and mixed to obtain the third dispersion;

[0109] (4) Load the third dispersion obtained in step (3) onto the surface of any side of the conductive substrate and carbonize it to obtain the catalytic electrode precursor.

[0110] (5) The catalytic electrode precursor obtained in step (4) is ultrasonically treated in an alkaline solution, and then subjected to cleaning and high-temperature treatment in sequence to obtain the catalytic electrode.

[0111] The order of operations in steps (1) and (2) is not important.

[0112] In step (1), the metal powder is copper powder with a certain particle size of 4000 nm, the first polymer resin is cellulose resin, the first solvent is deionized water, the first additive includes leveling agent and dispersant, the amount of the first additive is 3‰ based on the total mass of the first dispersion being 100wt%, the ratio of the amount of metal powder to the amount of the first polymer resin is 180g:10g, the total mass of the metal powder and the first polymer resin accounts for 60% of the mass of the first dispersion, and the viscosity of the first dispersion is 90000cP.

[0113] In step (2), the other powders include metal powders and metal oxide powders. The metal powders are a combination of cobalt powder and copper powder, and the metal oxide powders are a combination of cobalt oxide and nickel oxide. The particle size of the other powders is 150 nm. The second polymer resin is cellulose resin, the second solvent is deionized water, and the second additives include leveling agents and dispersants. Based on the total mass of the second dispersion being 100 wt%, the amount of the second additives is 2‰. The ratio of the amount of other powders to the amount of the second polymer resin is 180 g: 10 g, and the total mass of the other powders and the second polymer resin accounts for 45% of the mass of the second dispersion.

[0114] In step (3), the ratio of the first dispersion to the second dispersion in the third dispersion is 100g:80g.

[0115] In step (4), the third dispersion is loaded onto the conductive substrate by spraying, and the carbonization temperature is 450°C.

[0116] In step (5), the alkaline solution is ammonia water, the amount of alkaline solution is 30% based on the mass of the catalytic electrode precursor as 100%, the ultrasonic power of the ultrasonic treatment is 500W, the ultrasonic time of the ultrasonic treatment is 15min, the cleaning treatment uses deionized water, the temperature of the high temperature treatment is 800℃, and the gas atmosphere of the high temperature treatment is nitrogen.

[0117] Ultimately, the load was found to be 233 g / m³. 2 The catalytic electrode.

[0118] Example 4

[0119] This embodiment provides a method for preparing a catalytic electrode. The difference from Example 1 is that the metal powder has a certain particle size of 80 nm, while other parameters and experimental conditions are the same as in Example 1.

[0120] Example 5

[0121] This embodiment provides a method for preparing a catalytic electrode. The difference from Example 1 is that the metal powder has a certain particle size of 5500 nm, while other parameters and experimental conditions are the same as in Example 1.

[0122] Example 6

[0123] This embodiment provides a method for preparing a catalytic electrode. The difference from Example 1 is that the ratio of metal powder to the first polymer resin is 40g:10g, while other parameters and experimental conditions are the same as in Example 1.

[0124] Example 7

[0125] This embodiment provides a method for preparing a catalytic electrode. The difference from Example 1 is that the ratio of metal powder to the first polymer resin is 220g:10g, while other parameters and experimental conditions are the same as in Example 1.

[0126] Example 8

[0127] This embodiment provides a method for preparing a catalytic electrode. Unlike Example 1, the particle size of other powders is 40 nm, while other parameters and experimental conditions are the same as in Example 1.

[0128] Example 9

[0129] This embodiment provides a method for preparing a catalytic electrode. Unlike Example 1, the particle size of other powders is 220 nm, while other parameters and experimental conditions are the same as in Example 1.

[0130] Example 10

[0131] This embodiment provides a method for preparing a catalytic electrode. The difference from Example 1 is that the ratio of other powders to the second polymer resin is 80g:10g, while other parameters and experimental conditions are the same as in Example 1.

[0132] Example 11

[0133] This embodiment provides a method for preparing a catalytic electrode. The difference from Example 1 is that the ratio of other powders to the second polymer resin is 220g:10g, while other parameters and experimental conditions are the same as in Example 1.

[0134] Example 12

[0135] This embodiment provides a method for preparing a catalytic electrode. The difference from Example 1 is that the ratio of the first dispersion to the second dispersion in the third dispersion is 100g:20g, while other parameters and experimental conditions are the same as in Example 1.

[0136] Example 13

[0137] This embodiment provides a method for preparing a catalytic electrode. The difference from Example 1 is that the ratio of the first dispersion to the second dispersion in the third dispersion is 200g:30g, while other parameters and experimental conditions are the same as in Example 1.

[0138] Example 14

[0139] This embodiment provides a method for preparing a catalytic electrode. The difference from Example 1 is that the high-temperature treatment temperature is 450°C, while other parameters and experimental conditions are the same as in Example 1.

[0140] Example 15

[0141] This embodiment provides a method for preparing a catalytic electrode. The difference from Example 1 is that the high-temperature treatment temperature is 1000℃, while other parameters and experimental conditions are the same as in Example 1.

[0142] Comparative Example 1

[0143] This comparative example provides a method for preparing a catalytic electrode. Unlike Example 1, step (2) is omitted. The dispersion obtained in step (1) is directly loaded onto a conductive substrate. Other parameters and experimental conditions are the same as in Example 1.

[0144] Comparative Example 2

[0145] This comparative example provides a method for preparing a catalytic electrode. Unlike Example 1, the catalytic electrode precursor is treated in an acid solution, while other parameters and experimental conditions are the same as in Example 1.

[0146] Hydrogen evolution test and mechanical bonding force test were performed on the catalytic electrodes in the above embodiments and comparative examples; hydrogen evolution overpotential and ultrasonic tests were also performed. The method for the hydrogen evolution overpotential test included a test environment of 30% KOH solution at 80°C and a test temperature of 3000 A / m. 2 The hydrogen evolution overpotential was tested, and the ultrasonic test was conducted at 300W 40KHz, 30% KOH, and 60℃ for 2 hours. The weight change of the electrode before and after the test was measured, and the results are shown in Table 1 below.

[0147] Table 1

[0148] <![CDATA[Loading amount (g / m 2 )]]> Hydrogen evolution overpotential (mV) Ultrasound-induced weight loss (%) Example 1 255 163 ＜1.5 Example 2 245 175 ＜1.0 Example 3 233 156 ＜2.0 Example 4 245 221 ＜2.3 Example 5 262 197 ＜3.0 Example 6 270 175 ＜3.0 Example 7 230 186 ＜2.5 Example 8 216 175 ＜3.5 Example 9 210 191 ＜3.5 Example 10 250 215 ＜3.0 Example 11 213 194 ＜2.5 Example 12 275 225 ＜3.0 Example 13 298 197 ＜3.5 Example 14 276 195 ＜2.5 Example 15 235 215 ＜3.0 Comparative Example 1 205 396 6.5～7.5 Comparative Example 2 203 351 8.2～8.4

[0149] In summary, this invention, through the design of the catalytic electrode preparation method, enables the prepared catalytic electrode to achieve low energy consumption, high bonding force between the catalytic material and the substrate during water electrolysis for hydrogen production, and excellent resistance to reverse current, thus achieving highly stable hydrogen production. In terms of industrial preparation, it has high material utilization, no metal dust is generated during the preparation process, and the process technology is simple and easy to industrialize, providing an extremely important solution for the green hydrogen industry.

[0150] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

[0151] The present invention has been illustrated with the above embodiments to explain the detailed method of the present invention. However, the present invention is not limited to the detailed method described above, that is, it does not mean that the present invention must rely on the detailed method described above to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a catalytic electrode, characterized in that, The preparation method includes: (1) A metal powder of a certain particle size is mixed with a first polymer resin, a first solvent and a first additive to obtain a first dispersion; (2) Mix other powders of a certain particle size with the second polymer resin, the second solvent and the second additive, stir and disperse to obtain the second dispersion; (3) The second dispersion obtained in step (2) is gradually added to the first dispersion obtained in step (1), and the mixture is stirred and mixed to obtain the third dispersion; (4) Load the third dispersion obtained in step (3) onto the surface of any side of the conductive substrate and carbonize it to obtain the catalytic electrode precursor. (5) The catalytic electrode precursor obtained in step (4) is ultrasonically treated in an alkaline solution, and then subjected to cleaning and high-temperature treatment in sequence to obtain the catalytic electrode. The order of operations in steps (1) and (2) is not important.

2. The preparation method according to claim 1, characterized in that, In step (1), the metal powder is any one of nickel powder, titanium powder, copper powder and cobalt powder; Preferably, in step (1), the particle size of the metal powder is 100 nm to 5000 nm; Preferably, in step (1), the first polymer resin is an aqueous resin; Preferably, the waterborne resin includes any one or a combination of two or more of acrylic resin, polyurethane and cellulose resin; Preferably, in step (1), the first solvent is deionized water; Preferably, in step (1), the first additive includes a leveling agent and a dispersant; Preferably, in step (1), the amount of the first auxiliary agent is 0.5‰ to 5‰, based on the total mass of the first dispersion being 100wt%.

3. The preparation method according to claim 1 or 2, characterized in that, In step (1), the ratio of the metal powder to the first polymer resin is (50-200)g:10g. Preferably, in step (1), the total mass of the metal powder and the first polymer resin accounts for 30% to 70% of the mass of the first dispersion. Preferably, in step (1), the viscosity of the first dispersion is 50,000 cP to 100,000 cP.

4. The preparation method according to any one of claims 1-3, characterized in that, In step (2), the other powders include metal powders and metal oxide powders; Preferably, the metal powder is any one or a combination of two or more of cobalt powder, copper powder, nickel powder, molybdenum powder, titanium powder, manganese powder and iron powder; Preferably, the metal oxide powder is any one or a combination of two or more of cobalt oxide, nickel oxide, copper oxide and titanium oxide; Preferably, in step (2), the particle size of the other powders is 50 nm to 200 nm; Preferably, in step (2), the second polymer resin is an aqueous resin; Preferably, the waterborne resin includes any one or a combination of two or more of acrylic resin, polyurethane and cellulose resin; Preferably, in step (2), the second solvent is deionized water; Preferably, in step (2), the second additive includes a leveling agent and a dispersant; Preferably, in step (2), the amount of the second auxiliary agent is 0.5‰ to 5‰, based on the total mass of the second dispersion being 100wt%.

5. The preparation method according to any one of claims 1-4, characterized in that, In step (2), the ratio of the other powders to the second polymer resin is (100-200)g:10g; Preferably, in step (2), the total mass of the other powders and the second polymer resin accounts for 30% to 50% of the mass of the second dispersion.

6. The preparation method according to any one of claims 1-5, characterized in that, In step (3), the ratio of the amount of the first dispersion to the amount of the second dispersion in the third dispersion is 100g:(30-100)g.

7. The preparation method according to any one of claims 1-6, characterized in that, In step (4), the loading methods of the third dispersion onto the conductive substrate include dip coating, blade coating, and spray coating; Preferably, in step (4), the carbonization temperature is 200℃~450℃.

8. The preparation method according to any one of claims 1-7, characterized in that, In step (5), the alkaline solution is any one of potassium hydroxide, sodium hydroxide, and ammonia water; Preferably, in step (5), the amount of alkaline solution used is 10% to 30%, based on the mass of the catalytic electrode precursor being 100%. Preferably, in step (5), the ultrasonic power of the ultrasonic treatment is 100W to 600W; Preferably, in step (5), the ultrasonic treatment time is 10 min to 30 min.

9. The preparation method according to any one of claims 1-8, characterized in that, In step (5), the cleaning process uses deionized water for cleaning; Preferably, in step (5), the temperature of the high-temperature treatment is 500℃~900℃; Preferably, in step (5), the gas atmosphere for the high-temperature treatment is any one or a combination of two or more of nitrogen, argon and hydrogen.

10. The preparation method according to claim 1, characterized in that, The preparation method specifically includes: (1) A metal powder of a certain particle size is mixed with a first polymer resin, a first solvent and a first additive to obtain a first dispersion; (2) Mix other powders of a certain particle size with the second polymer resin, the second solvent and the second additive, stir and disperse to obtain the second dispersion; (3) The second dispersion obtained in step (2) is gradually added to the first dispersion obtained in step (1), and the mixture is stirred and mixed to obtain the third dispersion; (4) Load the third dispersion obtained in step (3) onto the surface of any side of the conductive substrate and carbonize it to obtain the catalytic electrode precursor. (5) The catalytic electrode precursor obtained in step (4) is ultrasonically treated in an alkaline solution, and then subjected to cleaning and high-temperature treatment in sequence to obtain the catalytic electrode. The order of operations in steps (1) and (2) is not important; In step (1), the metal powder is any one of nickel powder, titanium powder, copper powder and cobalt powder, and the particle size of the metal powder is 100nm to 5000nm. The first polymer resin is an aqueous resin, which includes any one or a combination of two or more of acrylic resin, polyurethane and cellulose resin. The first solvent is deionized water. The first additive includes leveling agent and dispersant. Based on the total mass of the first dispersion of 100wt%, the amount of the first additive is 0.5‰ to 5‰. The ratio of the amount of metal powder to the amount of the first polymer resin is (50 to 200)g:10g. The total mass of the metal powder and the first polymer resin accounts for 30% to 70% of the mass of the first dispersion. The viscosity of the first dispersion is 50000cP to 100000cP. In step (2), the other powders include metal powders and metal oxide powders. The metal powders are any one or a combination of two or more of cobalt powder, copper powder, nickel powder, molybdenum powder, titanium powder, manganese powder, and iron powder. The metal oxide powders are any one or a combination of two or more of cobalt oxide, nickel oxide, copper oxide, and titanium oxide. The particle size of the other powders is 50nm to 200nm. The second polymer resin is an aqueous resin. The aqueous resin includes any one or a combination of two or more of acrylic resin, polyurethane, and cellulose resin. The second solvent is deionized water. The second additive includes leveling agent and dispersant. Based on the total mass of the second dispersion of 100wt%, the amount of the second additive is 0.5‰ to 5‰. The ratio of the amount of the other powders to the amount of the second polymer resin is (100 to 200)g:10g. The total mass of the other powders and the second polymer resin accounts for 30% to 50% of the mass of the second dispersion. In step (3), the ratio of the first dispersion to the second dispersion in the third dispersion is 100g:(30-100)g; In step (4), the loading methods of the third dispersion on the conductive substrate include dip coating, scraping coating and spraying coating, and the carbonization treatment temperature is 200℃~450℃; In step (5), the alkaline solution is any one of potassium hydroxide, sodium hydroxide, and ammonia water. Based on the mass of the catalytic electrode precursor as 100%, the amount of the alkaline solution is 10% to 30%. The ultrasonic power of the ultrasonic treatment is 100W to 600W. The ultrasonic treatment time is 10min to 30min. The cleaning treatment uses deionized water. The temperature of the high-temperature treatment is 500℃ to 900℃. The gas atmosphere of the high-temperature treatment is any one or a combination of two or more of nitrogen, argon, and hydrogen.