A fossa electrode and a preparation method and application thereof

Abstract

The application discloses a kind of fossa electrode and its preparation method and application, belong to water electrolysis hydrogen electrode technical field.The fossa electrode has honeycomb surface structure, honeycomb surface structure includes diffuse distribution's fossa hole and wrinkle, and the surface of fossa electrode is attached with active catalytic material particle.The above-mentioned diffuse distribution's fossa hole and wrinkle can give electrode higher specific surface area, combined with the surface of fossa electrode attached active catalytic material particle, can effectively improve the catalytic activity of electrode.The preparation of the fossa electrode includes: preparation raw material is combined with matrix, and the intermediate electrode is obtained;Fossa processing and pore processing are carried out on the intermediate electrode.The method is easy to mass production, scale production, electrode size, shape is not limited, can be streamlined operation, with the advantages of low cost, high production efficiency, high cost performance.The fossa electrode can be used for water electrolysis hydrogen, and is conducive to obtaining better hydrogen production effect.

Description

Technical Field

[0001] This invention relates to the field of electrode technology for hydrogen production by water electrolysis, and more specifically, to a dimpled electrode, its preparation method, and its application. Background Technology

[0002] Hydrogen energy is a secondary energy technology that uses hydrogen as a carrier. It is considered the cleanest and most efficient future energy technology and a crucial technological support for my country's dual-carbon strategy. Efficient, large-scale, and green hydrogen production is a primary condition for the development of hydrogen energy technology. Water electrolysis, a technology that uses external electrical energy to decompose water into hydrogen and oxygen, is one of the most efficient and mature hydrogen production technologies currently available.

[0003] Hydrogen and oxygen evolution during water electrolysis occur at the catalytically active cathode and anode, respectively. In alkaline systems, nickel-based catalysts are primarily used at both the cathode and anode. A catalytic layer is typically prepared by spraying onto a nickel mesh, followed by chemical etching to remove the pore-forming agent and obtain a porous catalytic layer. However, this method results in catalytic layers with limited catalytic performance.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The purpose of this invention is to provide a honeycomb electrode, its preparation method, and its application, so as to solve or improve the above-mentioned technical problems.

[0006] This application can be implemented as follows:

[0007] In a first aspect, this application provides a honeycomb electrode having a honeycomb surface structure, the honeycomb surface structure including diffusely distributed pores and folds, and the surface of the honeycomb electrode is coated with active catalytic material particles.

[0008] In an optional embodiment, the dimpled electrode also has at least one of the following features:

[0009] Feature 1: The equivalent diameter of the pores in the dented electrode does not exceed 10 μm;

[0010] Feature 2: The thickness of the folds in the dimpled electrode does not exceed 2μm;

[0011] Feature 3: The length of the folds in the dimpled electrode is not less than 5μm;

[0012] Feature 4: In the dimpled electrode, the surface of the folds is diffusely distributed with microporous structures. Preferably, the pore size of the microporous structures does not exceed 1 μm; more preferably, the surface of the microporous structures is coated with active catalytic material particles.

[0013] Feature 5: The active catalytic material particles are transition metal element catalytic material particles. Preferably, the active catalytic material particles include at least one of NiCu alloy and its oxide, NiFe alloy and its oxide, FeCu alloy and its oxide, and NiFeCu alloy and its oxide.

[0014] Secondly, the present invention provides a method for preparing a dimpled electrode as described in the foregoing embodiments, comprising the following steps: combining the raw materials with a substrate to obtain an intermediate electrode; and performing dimpling and pore-forming treatment on the intermediate electrode.

[0015] The raw materials used in the preparation include those containing catalytic materials, pore-forming materials, and pore-forming materials.

[0016] In an optional embodiment, the raw materials comprise, by weight percentage, 50% to 90% of the catalyst material, 5% to 20% of the pore-forming material, and 5% to 40% of the nest-forming material.

[0017] In an optional embodiment, the catalytic material includes at least one of Ni, Ni-based alloys, nickel oxide, nickel phosphide, and nickel nitride.

[0018] In an optional embodiment, the pore-forming material includes at least one of Al and Zn; and / or, the particle size of the pore-forming material does not exceed 5 μm.

[0019] In an optional embodiment, the fogging material includes at least one of Cu, C, Mn, and Co; and / or, the particle size of the fogging material does not exceed 10 μm.

[0020] In optional embodiments, the raw materials may be in the form of solids, gels, pastes, or slurries.

[0021] In an optional embodiment, the solid preparation raw material is a raw material with a particle size of no more than 1 μm.

[0022] In an optional embodiment, the gel-like preparation material is obtained by mixing solid raw materials with water and gelling materials.

[0023] In an optional embodiment, the paste or slurry preparation material is obtained by mixing solid raw materials with solvents and crosslinking agents.

[0024] In an optional embodiment, the gel-like preparation raw material contains 40wt% to 60wt% of solid raw materials and 5wt% to 20wt% of gelling material, with the balance being water;

[0025] Alternatively, the preparation raw materials in paste or slurry form may contain 40wt% to 80wt% of solid raw materials, 10wt% to 50wt% of solvent, and 5wt% to 10wt% of crosslinking agent.

[0026] In an optional embodiment, the gelling material includes at least one of polyacrylic acid and its derivatives, polyvinyl alcohol, polyoxyethylene, polyacrylamide, and ethyl cellulose.

[0027] In an optional embodiment, the solvent includes at least one of terpineol, polyvinyl alcohol, ethanol, and propylene glycol.

[0028] In an optional embodiment, the crosslinking agent includes at least one selected from ethyl cellulose, dipropylene glycol methyl ether acetate, divinylbenzene, diisocyanate, dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, and diethylenetriamine.

[0029] In optional embodiments, the preparation of the raw material and matrix composite can be achieved by spraying, coating or impregnation.

[0030] In optional embodiments, when the raw material is in solid or solid-liquid mixture form, the raw material is coated with a spraying method to combine it with the substrate; when the raw material is in slurry form, the raw material is coated with a spraying method or an impregnation method to combine it with the substrate; when the raw material is in gel or paste form, the raw material is coated with a coating method or a spraying method to combine it with the substrate.

[0031] In optional embodiments, spraying includes thermal spraying, cold spraying, or wet spraying, wherein thermal spraying includes plasma spraying, supersonic flame spraying, detonation spraying, low-pressure plasma spraying, or arc spraying.

[0032] In an optional embodiment, the plasma spraying process conditions include: spraying power of 20kW to 50kW, main spraying gas argon flow rate of 40NL / min to 60NL / min, auxiliary spraying gas hydrogen flow rate of 0NL / min to 5NL / min, spraying current of 450A to 650A, spraying distance of 15cm to 30cm, spraying angle of 75° to 90°, gun speed of 400mm / s to 1000mm / s, and powder feed rate of 50g / min to 150g / min.

[0033] In an optional embodiment, the process conditions for supersonic flame spraying include: a spraying gas flow rate of 10L / min to 50L / min, an oxygen or air flow rate of 50L / min to 200L / min, a spraying distance of 5cm to 20cm, a spraying angle of 85° to 95°, a gun travel speed of 500mm / s to 1500mm / s, and a powder feed rate of 50g / min to 200g / min.

[0034] In an optional embodiment, the process conditions for explosive spraying include: gas flow rate of 5L / min to 30L / min, oxygen flow rate of 5L / min to 30L / min, spraying distance of 10cm to 20cm, spraying angle of 85° to 95°, explosion frequency of 3Hz to 10Hz, gun speed of 600mm / s to 2000mm / s, and powder feed rate of 30g / min to 150g / min.

[0035] In an optional embodiment, the process conditions for low-pressure plasma spraying include: spraying power of 40kW to 150kW, main spraying gas argon flow rate of 40NL / min to 60NL / min, auxiliary spraying gas hydrogen flow rate of 0NL / min to 5NL / min, spraying current of 500A to 1000A, and spraying pressure of 1×10⁻⁶. -5 Pa~1000Pa, spraying distance 20cm~50cm, gun speed 800mm / s~2000mm / s, powder feed rate 30g / min~100g / min.

[0036] In an optional embodiment, the process conditions for arc spraying include: spraying voltage of 20V to 50V, current of 150A to 1000A, physicochemical gas pressure of 0.2MPa to 1MPa, spraying distance of 10cm to 20cm, powder feed rate of 200g / min to 800g / min, and gun speed of 500mm / s to 2000mm / s.

[0037] In an optional embodiment, the process conditions for cold spraying include: spraying power of 25kW to 70kW, nitrogen pressure of spraying gas of 4MPa to 8MPa, gun chamber temperature of 400℃ to 850℃, spraying distance of 20mm to 50mm, spraying angle of 85° to 95°, gun travel speed of 600mm / s to 2000mm / s, and powder feed rate of 100g / min to 500g / min.

[0038] In an optional embodiment, the wet spraying process conditions include: a spraying distance of 300mm to 800mm, a main compressed air pressure of 0.2MPa to 1MPa, a gun speed of 200mm / s to 500mm / s, and a spraying angle of 60° to 90°.

[0039] In an optional embodiment, the nesting process includes: immersing the electrode in a nesting solution to perform chemical nesting.

[0040] In an optional embodiment, the nest-forming solution includes a corrosive agent, a dispersant, a modifier, a complexing agent, and water.

[0041] In an optional embodiment, the nest-forming solution comprises, by mass percentage, 10% to 30% of a corrosive agent, 0.5% to 5% of a dispersant, 1% to 10% of a modifier, and 1% to 10% of a complexing agent, with the balance being water.

[0042] In an optional embodiment, the corrosive agent includes at least one of copper chloride solution, copper sulfate solution, ferric chloride solution, hydrochloric acid solution, and sodium hydroxide solution.

[0043] In an optional embodiment, the dispersant includes at least one of sodium oleate, carboxylates, sulfates, sulfonates, and polyphosphates.

[0044] In an optional embodiment, the modifier includes at least one of sodium hydroxide, potassium hydroxide, ammonia, and hydrochloric acid.

[0045] In optional embodiments, the complexing agent includes at least one of monoethanolamine, diethanolamine, triethanolamine, potassium sodium tartrate, heptahydrate, sodium gluconate, sodium alginate, sodium ethylenediaminetetramethylene phosphate, diethylenetriaminepentamethylene phosphonate, aminetrimethylene phosphate, hydrolyzed polymaleic anhydride, polyacrylic acid, polyhydroxyacrylic acid, maleic acid-acrylic acid copolymer, and polyacrylamide.

[0046] In an optional embodiment, the soaking temperature is 30℃~95℃ and the soaking time is 5h~48h.

[0047] In an optional embodiment, the pore-forming process includes immersing the electrode obtained after the pore-forming process in a pore-forming alkaline solution to form pores.

[0048] In an optional embodiment, the pore-forming alkaline solution comprises 5 wt% to 30 wt% of an aqueous solution of NaOH or 5 wt% to 30 wt% of a KOH solution.

[0049] In an optional embodiment, the pore-forming alkaline solution further includes 0.5 wt% to 10 wt% of additives.

[0050] In an optional embodiment, the additive includes at least one of sodium citrate, potassium sodium tartrate, sodium ethylenediaminetetramethylene phosphate, sodium diethylenetriaminepentamethylenephosphonate, sodium aminetrimethylene phosphate, and sodium alginate.

[0051] In an optional embodiment, the temperature of the pore-forming alkaline solution does not exceed 90°C, and is preferably 20°C to 90°C.

[0052] In an optional implementation, the hole-forming time does not exceed 24 hours, preferably 3 hours to 24 hours.

[0053] Thirdly, this application provides an application of the dimpled electrode as described in the foregoing embodiments in hydrogen production by water electrolysis.

[0054] The beneficial effects of this application include:

[0055] The diffusely distributed pits and folds in the socket electrode provided in this application endow the electrode with a high specific surface area. Combined with the active catalytic material particles attached to the surface of the socket electrode, the catalytic activity of the electrode can be effectively improved. The preparation method of this socket electrode is simple, easy to mass-produce, and the electrode size and shape are not limited. It can be produced in an assembly line and has the advantages of low cost, high production efficiency, and high cost-effectiveness. The above-mentioned socket electrode can be used for hydrogen production by water electrolysis and can achieve good hydrogen production results. Attached Figure Description

[0056] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0057] Figure 1 The main flow chart of the fabrication process of the nested electrode provided in this application;

[0058] Figure 2 This is a microscopic morphology diagram of the dimpled electrode provided in Embodiment 1 of this application;

[0059] Figure 3 This is a morphology diagram of the active material deposited on the surface of the crater electrode in Example 1 of this application;

[0060] Figure 4 This is a microscopic morphology diagram of the dimpled electrode provided in Embodiment 2 of this application;

[0061] Figure 5 for Figure 4 A magnified view of the surface morphology of the centrally located electrode;

[0062] Figure 6 This is a microscopic morphology diagram of the dimpled electrode provided in Embodiment 3 of this application;

[0063] Figure 7 This is a morphology diagram of the active material deposited on the surface of the crater electrode in Example 3 of this application;

[0064] Figure 8 This is a microscopic morphology diagram of the dimpled electrode provided in Embodiment 4 of this application;

[0065] Figure 9 This is a microscopic morphology diagram of the dimpled electrode provided in Embodiment 5 of this application;

[0066] Figure 10 A microscopic image of the surface morphology of the electrode provided in Comparative Example 1 of this application;

[0067] Figure 11 The image shows the surface microstructure of the electrode provided in Comparative Example 3 of this application. Detailed Implementation

[0068] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0069] The following provides a detailed description of the trough electrode, its preparation method, and its application.

[0070] This application proposes a honeycomb electrode with a honeycomb surface structure, which includes diffusely distributed pores and folds, and the surface of the honeycomb electrode is coated with active catalytic material particles.

[0071] The aforementioned diffusely distributed pits and folds can impart a high specific surface area to the electrode. Combined with the active catalytic material particles attached to the surface of the pitted electrode, the catalytic activity of the electrode can be effectively improved.

[0072] For reference, the equivalent diameter of the pores in the aforementioned pore electrode does not exceed 10 μm, and can be 10 μm, 8 μm, 6 μm, 4 μm, 2 μm or 1 μm, or any other value within the range not exceeding 10 μm.

[0073] The shape of the aforementioned dimples can be exemplified, but not limited to, irregular, nearly circular, conical, triangular, elliptical, circular, or polygonal. Different shapes of dimples may be contained simultaneously in the same dimple electrode.

[0074] The thickness of the folds in the aforementioned dimpled electrode does not exceed 2μm, and can be 2μm, 1.8μm, 1.5μm, 1.2μm, 1μm, 0.8μm, 0.5μm or 0.2μm, or any other value within the range not exceeding 2μm.

[0075] The length of the folds in the aforementioned dimpled electrode is not less than 5 μm, such as 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, or other values ​​within the range of not less than 5 μm.

[0076] In the aforementioned dimpled electrode, the surface of the folds is diffusely distributed with microporous structures. For example, the pore size of the microporous structure does not exceed 1 μm, such as 1 μm, 0.8 μm, 0.5 μm, or 0.2 μm.

[0077] The surface of the aforementioned microporous structure is coated with active catalytic material particles. These active catalytic material particles are transition metal element catalytic material particles, containing no precious metals, which can significantly reduce costs. For example, the active catalytic material particles may include at least one of NiCu alloys and their oxides, NiFe alloys and their oxides, FeCu alloys and their oxides, and NiFeCu alloys and their oxides.

[0078] It is important to emphasize that existing technologies primarily employ large Al particles for pore formation, typically with particle sizes ranging from 50 μm to 100 μm. This results in large, often irregularly shaped pores, limiting mass transfer efficiency. Furthermore, the existing electrode pore structures exhibit weak inter-pore support, leading to a brittle and easily detached catalytic layer. The water-dwelling electrode provided in this application significantly enhances surface area through the presence of pits with an equivalent diameter not exceeding 10 μm, micropores with a pore size not exceeding 1 μm, and numerous fine folds (thickness not exceeding 2 μm and length not less than 5 μm), effectively improving the electrode's catalytic activity. Simultaneously, a large number of active particles adhere to the micropore surface, further enhancing the electrode's catalytic activity. Moreover, due to the fine and uniform pore structure, the catalytic layer in this electrode exhibits high stability and is less prone to detachment.

[0079] Accordingly, please refer to Figure 1 This application provides a method for preparing the above-mentioned dimpled electrode, comprising the following steps: combining the raw materials with a substrate to obtain an intermediate electrode; and performing dimpling and pore-forming treatment on the intermediate electrode.

[0080] The substrate can be, by way of example but not by way of limitation, a nickel mesh, but it can also be a non-nickel-based mesh.

[0081] For reference, the matrix is ​​pretreated before being combined with the raw materials.

[0082] In some implementations, the cut nickel mesh can be placed into a sandblasting machine for sandblasting treatment. A certain mesh size of corundum sand, stainless steel beads, or other media are used. Driven by compressed air, the sandblasting media impacts the surface of the nickel mesh at a certain speed to achieve a roughening effect.

[0083] In other embodiments, the cut nickel mesh can be placed in a grinding machine and ground by a grinding head with a certain roughness to achieve the effect of roughening the surface.

[0084] In other embodiments, the cut nickel mesh can be placed in a scraping machine, and the surface can be roughened by repeated scraping by the scraping head.

[0085] In other embodiments, the cut nickel mesh can be placed in an embossing machine and embossed with a press head with tiny spikes to leave uneven indentations on the surface of the nickel mesh, thereby achieving the effect of roughening the surface.

[0086] In other embodiments, the cut nickel mesh can be placed in a chemical acid treatment solution, and the surface of the nickel mesh can be corroded by the principle of acid corrosion to form a surface with micro-roughness, thereby achieving a surface roughening effect.

[0087] In other embodiments, a non-nickel-based screen substrate is used, and an alkaline treatment solution can be employed to impart microscopic roughness to the screen surface using the principle of alkaline corrosion. Alternatively, the screen can be placed in a chemical plating solution composed of nickel salts, and a layer of dispersed nickel particles can be deposited on the screen surface using the principle of chemical displacement reaction to achieve a surface roughening effect.

[0088] In this application, the raw materials used for preparation include raw materials containing catalytic materials, pore-forming materials, and pore-forming materials.

[0089] For reference, by mass percentage, the raw materials include 50%–90% catalytic material, 5%–20% pore-forming material, and 5%–40% pore-forming material. Specifically, the content of catalytic material in the raw materials can be 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90%, etc.; the content of pore-forming material in the raw materials can be 5%, 8%, 10%, 12%, 15%, 18%, or 20%, etc.; and the content of pore-forming material in the raw materials can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, or 40%, etc.

[0090] The catalytic material described above may, but is not limited to, include at least one of Ni, Ni-based alloys, nickel oxide, nickel phosphide, and nickel nitride. The pore-forming material may, but is not limited to, include at least one of Al and Zn. The pore-forming material may, but is not limited to, include at least one of Cu, C, Mn, and Co.

[0091] The particle size of the aforementioned pore-forming material is preferably no more than 5 μm, and the particle size of the pore-forming material is preferably no more than 10 μm.

[0092] In this application, the raw materials may be in the form of solid, gel, paste or slurry.

[0093] Understandably, the above-mentioned solid preparation raw materials are solid raw materials, preferably raw materials with a particle size of no more than 1 μm.

[0094] The gel-like preparation material can be obtained by mixing the above-mentioned solid raw materials with water and gelling materials.

[0095] For reference, the raw materials for preparing gels may contain 40wt% to 60wt% (e.g., 40wt%, 45wt%, 50wt%, 55wt%, or 60wt%) of solid raw materials and 5wt% to 20wt% (e.g., 5wt%, 10wt%, 15wt%, or 20wt%) of gelling materials, with the balance being water.

[0096] The gelling material may, by way of example but not by way of limitation, include at least one of polyacrylic acid and its derivatives, polyvinyl alcohol, polyoxyethylene, polyacrylamide and ethyl cellulose.

[0097] Similarly, paste-like or slurry-like raw materials can be obtained by mixing the above-mentioned solid raw materials with solvents and crosslinking agents.

[0098] For reference, the preparation raw materials in paste or slurry form each independently contain 40wt% to 80wt% (e.g., 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, or 80wt%) of solid raw materials, 10wt% to 50wt% (e.g., 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, or 50wt%) of solvent, and 5wt% to 10wt% (e.g., 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, or 10wt%) of crosslinking agent.

[0099] The solvent may, by way of example but not by way of limitation, include at least one of terpineol, polyvinyl alcohol, ethanol and propylene glycol.

[0100] Crosslinking agents may, by way of example but not by way of limitation, include at least one of ethyl cellulose, dipropylene glycol methyl ether acetate, divinylbenzene, diisocyanate, dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, and diethylenetriamine.

[0101] In this application, the methods for preparing the raw material and matrix composite include spraying, coating or impregnation.

[0102] When the raw material is in solid or solid-liquid mixture form, it can be coated with a spraying method to combine the raw material with the substrate; when the raw material is in slurry form, it can be coated with a spraying method or impregnated with a slurry method to combine the raw material with the substrate; when the raw material is in gel or paste form, it can be coated with a coating or spraying method to combine the raw material with the substrate.

[0103] In terms of spraying, it can be carried out by thermal spraying, cold spraying or wet spraying. Among them, thermal spraying can include plasma spraying, supersonic flame spraying, explosive spraying, low-pressure plasma spraying or arc spraying.

[0104] For reference, when using plasma spraying, the corresponding process conditions may include: spraying power of 20kW to 50kW (e.g., 20kW, 25kW, 30kW, 35kW, 40kW, 45kW, or 50kW, etc.), main spraying gas argon flow rate of 40NL / min to 60NL / min (e.g., 40NL / min, 45NL / min, 50NL / min, 55NL / min, or 60NL / min, etc.), auxiliary spraying gas hydrogen flow rate of 0NL / min to 5NL / min (e.g., 0NL / min, 1NL / min, 2NL / min, 3NL / min, 4NL / min, or 5NL / min, etc.), and spraying... The current is 450A to 650A (e.g., 450A, 500A, 550A, 600A, or 650A), the spraying distance is 15cm to 30cm (e.g., 15cm, 20cm, 25cm, or 30cm), the spraying angle is 75° to 90° (e.g., 75°, 80°, 85°, or 90°), the gun speed is 400mm / s to 1000mm / s (e.g., 400mm / s, 600mm / s, 800mm / s, or 1000mm / s), and the powder feed rate is 50g / min to 150g / min (e.g., 50g / min, 80g / min, 100g / min, 120g / min, or 150g / min).

[0105] When using supersonic flame spraying, the corresponding process conditions may include: a spraying gas flow rate of 10 L / min to 50 L / min (e.g., 10 L / min, 20 L / min, 30 L / min, 40 L / min, or 50 L / min), an oxygen or air flow rate of 50 L / min to 200 L / min (e.g., 50 L / min, 100 L / min, 150 L / min, or 200 L / min), and a spraying distance of 5 cm to 20 cm (e.g., 5 cm). The spraying angle is 85-95° (e.g., 85°, 90°, or 95°), the gun speed is 500mm / s-1500mm / s (e.g., 500mm / s, 800mm / s, 1000mm / s, 1200mm / s, or 1500mm / s), and the powder feed rate is 50g / min-200g / min (e.g., 50g / min, 100g / min, 150g / min, or 200g / min).

[0106] When using explosive spraying, the corresponding process conditions may include: gas flow rate of 5L / min to 30L / min (e.g., 5L / min, 10L / min, 15L / min, 20L / min, 25L / min, or 30L / min), oxygen flow rate of 5L / min to 30L / min (e.g., 5L / min, 10L / min, 15L / min, 20L / min, 25L / min, or 30L / min), and spraying distance of 10cm to 20cm (e.g., 10cm, 15cm, or 20cm). The spraying angle is 85-95° (e.g., 85°, 90°, or 95°), the explosion frequency is 3Hz-10Hz (e.g., 3Hz, 5Hz, 8Hz, or 10Hz), the gun speed is 600mm / s-2000mm / s (e.g., 600mm / s, 1000mm / s, 1500mm / s, or 2000mm / s), and the powder feed rate is 30g / min-150g / min (e.g., 30g / min, 50g / min, 80g / min, 100g / min, 120g / min, or 150g / min).

[0107] When using low-pressure plasma spraying, the corresponding process conditions may include: spraying power of 40kW to 150kW (e.g., 40kW, 60kW, 80kW, 100kW, 120kW, or 150kW), main spraying gas argon flow rate of 40NL / min to 60NL / min (e.g., 40NL / min, 45NL / min, 50NL / min, 55NL / min, or 60NL / min), auxiliary spraying gas hydrogen flow rate of 0NL / min to 5NL / min (e.g., 0NL / min, 1NL / min, 2NL / min, 3NL / min, 4NL / min, or 5NL / min), spraying current of 500A to 1000A (e.g., 500A, 600A, 700A, 800A, 900A, or 1000A), and spraying pressure of 1×10⁻⁶. -5 Pa ~ 1000 Pa (e.g., 1×10) -5 Pa, 1×10 -4 Pa, 1×10 -3 Pa, 1×10 -2 Pa, 1×10 -1The spraying distance is 20cm to 50cm (e.g., 20cm, 30cm, 40cm, or 50cm), the spray gun speed is 800mm / s to 2000mm / s (e.g., 800mm / s, 1000mm / s, 1500mm / s, or 2000mm / s), and the powder feed rate is 30g / min to 100g / min (e.g., 30g / min, 50g / min, 80g / min, or 100g / min).

[0108] When using arc spraying, the corresponding process conditions may include: spraying voltage of 20V to 50V (e.g., 20V, 25V, 30V, 35V, 40V, 45V, or 50V), current of 150A to 1000A (e.g., 150A, 200A, 500A, 800A, or 1000A), and physicochemical gas pressure of 0.2MPa to 1MPa (e.g., 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa, or 1MPa). The spraying pressure is MPa, etc., the spraying distance is 10cm to 20cm (e.g., 10cm, 15cm or 20cm), the powder feed rate is 200g / min to 800g / min (e.g., 200g / min, 400g / min, 600g / min or 800g / min), and the gun speed is 500mm / s to 2000mm / s (e.g., 500mm / s, 1000mm / s, 1500mm / s or 2000mm / s).

[0109] When using cold spraying, the corresponding process conditions may include: spraying power of 25kW to 70kW (e.g., 25kW, 30kW, 35kW, 40kW, 45kW, 50kW, 55kW, 60kW, 65kW, or 70kW, etc.), nitrogen pressure of spraying gas of 4MPa to 8MPa (e.g., 4MPa, 5MPa, 6MPa, 7MPa, or 8MPa, etc.), and gun chamber temperature of 400℃ to 850℃ (e.g., 400℃, 450℃, 500℃, 550℃, 600℃, 650℃, 700℃, 750℃, 800℃, or 850℃, etc.), spraying... The spraying distance is 20mm to 50mm (e.g., 20mm, 25mm, 30mm, 35mm, 40mm, 45mm, or 50mm, etc.), the spraying angle is 85° to 95° (e.g., 85°, 90°, or 95°, etc.), the spray gun speed is 600mm / s to 2000mm / s (e.g., 600mm / s, 1000mm / s, 1500mm / s, or 2000mm / s, etc.), and the powder feed rate is 100g / min to 500g / min (e.g., 100g / min, 200g / min, 300g / min, 400g / min, or 500g / min, etc.).

[0110] When using wet spraying, the corresponding process conditions may include: a spraying distance of 300mm to 800mm (e.g., 300mm, 400mm, 500mm, 600mm, 700mm, or 800mm), a main compressed air pressure of 0.2MPa to 1MPa (e.g., 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa, or 1MPa), a gun speed of 200mm / s to 500mm / s (e.g., 200mm / s, 300mm / s, 400mm / s, or 500mm / s), and a spraying angle of 60° to 90° (e.g., 60°, 70°, 80°, or 90°).

[0111] In terms of impregnation, the substrate (such as a mesh) can be impregnated in the preparation material, then removed, and dried (drying temperature can be 100℃~200℃) and sintered (sintering temperature can be 300℃~1000℃) to obtain the intermediate electrode.

[0112] In terms of coating, the preparation material can be attached to the substrate (such as a stencil) by coating, and then cured (the curing temperature can be 300℃~1000℃) to obtain the intermediate electrode.

[0113] In this application, the nesting process may include: immersing the electrode in a nesting solution to perform chemical nesting.

[0114] The nest-forming solution may include corrosive agents, dispersants, regulators, complexing agents, and water.

[0115] For reference, by mass percentage, the nest-building solution may include 10% to 30% (e.g., 10%, 15%, 20%, 25%, or 30%) of corrosive agent, 0.5% to 5% (e.g., 0.5%, 1%, 2%, 3%, 4%, or 5%) of dispersant, 1% to 10% (e.g., 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%) of regulator, and 1% to 10% (e.g., 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%) of complexing agent, with the balance being water.

[0116] The corrosive agents described above may, by way of example but not by way of limitation, include at least one of copper chloride solution, copper sulfate solution, ferric chloride solution, hydrochloric acid solution and sodium hydroxide solution.

[0117] Dispersants may, by way of example but not by way of limitation, include at least one of sodium oleate, carboxylates, sulfates, sulfonates, and polyphosphates.

[0118] The regulator may include, by way of example but not by way of limitation, at least one of sodium hydroxide, potassium hydroxide, ammonia and hydrochloric acid.

[0119] Complexing agents may, by way of example but not by way of limitation, include at least one of monoethanolamine, diethanolamine, triethanolamine, sodium potassium tartrate, heptahydrate, sodium gluconate, sodium alginate, sodium ethylenediaminetetramethylene phosphate, diethylenetriaminepentamethylene phosphonate, aminetrimethylene phosphate, hydrolyzed polymaleic anhydride, polyacrylic acid, polyhydroxyacrylic acid, maleic acid-acrylic acid copolymer and polyacrylamide.

[0120] For reference, the soaking temperature can be 30℃~95℃ (e.g., 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃ or 95℃, etc.), and the soaking time can be 5h~48h (e.g., 5h, 12h, 24h, 36h or 48h, etc.).

[0121] In this application, the pore-forming process may include: immersing the electrode obtained after the pore-forming process into a pore-forming alkaline solution to form a pore.

[0122] For reference, the pore-forming alkaline solution may include 5 wt% to 30 wt% (e.g., 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, or 30 wt%) of NaOH aqueous solution or 5 wt% to 30 wt% (e.g., 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, or 30 wt%) of KOH solution.

[0123] Furthermore, the above-mentioned pore-forming alkaline solution may also include 0.5wt% to 10wt% (such as 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, or 10wt%) of additives.

[0124] The additives may, by way of example but not by way of limitation, include at least one of sodium citrate, potassium sodium tartrate, sodium ethylenediaminetetramethylene phosphate, sodium diethylenetriaminepentamethylenephosphonate, sodium aminetrimethylene phosphate, and sodium alginate.

[0125] For reference, the temperature of the pore-forming alkaline solution should not exceed 90°C, and may be 90°C, 80°C, 70°C, 60°C, 50°C, 40°C, 30°C, 20°C, or 10°C, etc. In some preferred embodiments, the temperature of the pore-forming alkaline solution is preferably 20°C to 90°C.

[0126] The pore-forming time should not exceed 24 hours, and can be 24 hours, 18 hours, 12 hours, 6 hours, 2 hours, etc. In some preferred embodiments, it is preferably 3 hours to 24 hours.

[0127] As mentioned above, the method for preparing the trough electrode provided in this application is easy to mass-produce and scale up, and the electrode size and shape are not limited. It can be carried out in an assembly line and has the advantages of low cost, high production efficiency and high cost performance.

[0128] In addition, this application also provides an application of the above-mentioned trough electrode in water electrolysis for hydrogen production, which can achieve better hydrogen production results.

[0129] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0130] Example 1

[0131] S1: Place a 40-mesh nickel mesh with a size of 1m×1m into the sandblasting machine and perform sandblasting treatment with 0.5kg pressure and 180-mesh corundum sand.

[0132] S2: Nickel powder with an average particle size of 45 μm, aluminum powder with an average particle size of 2.5 μm, and copper powder with an average particle size of 5 μm are mixed evenly in a mass ratio of 70:20:10 to obtain a solid raw material.

[0133] S3: The prepared raw materials were plasma-sprayed onto a sandblasted nickel mesh to obtain the intermediate electrode. The plasma spraying parameters were: power 30kW, current 600A, argon flow rate 60L / min, hydrogen flow rate 5L / min, spraying distance 25cm, spray gun speed 800mm / s, spraying angle 90°, and powder feed rate 140g / min. After spraying, the nickel mesh weight gain was 280g / m². 2 .

[0134] S4: Prepare a pore-forming solution by mixing copper chloride, potassium polyphosphate, ammonia, potassium sodium tartrate, and water in a mass ratio of 20:1:1:10:68; prepare a pore-forming alkaline solution by mixing potassium hydroxide, sodium citrate, and water in a mass ratio of 20:3:77.

[0135] S5: Heat the pore-forming solution to 80°C, place the intermediate electrode into the heated pore-forming solution, soak for 24 hours, remove it, rinse with clean water, and then place it into a pore-forming alkaline solution at 70°C for 24 hours to perform pore-forming treatment, thus obtaining a pore-shaped electrode.

[0136] The microstructure of the honeycomb electrode obtained in this embodiment is as follows: Figure 2 As shown, the morphology of the active material deposited on the electrode surface is as follows: Figure 3 As shown. The surface porosity of this nested electrode is as high as 42%, and the specific surface area of ​​the electrode coating after deducting the weight of the nickel mesh is as high as 39m². 2 / g. 0.5A / cm 2 At a current density of , its hydrogen evolution overpotential is only 345mV, and its oxygen evolution overpotential is 428mV.

[0137] Example 2

[0138] S1: Place a 46-mesh nickel mesh with a size of 1m×1m into an imprinting machine, and imprint it with an array of imprinting heads with an average diameter of 20μm under a pressure of 10kg to leave indentations with an average depth of 10μm and an average diameter of 20μm on the surface of the nickel mesh to roughen the surface of the nickel mesh.

[0139] S2: Same as Example 1.

[0140] S3: Same as Example 1.

[0141] S4: Prepare a pore-forming solution by mixing copper sulfate solution, sodium oleate, 0.1 mol / L dilute hydrochloric acid, sodium citrate and water in a mass ratio of 15:2.5:1.5:5:76; prepare a pore-forming alkaline solution by mixing potassium hydroxide, sodium citrate and water in a mass ratio of 20:3:77.

[0142] S5: Heat the pore-forming solution to 90°C, place the intermediate electrode into the heated pore-forming solution, soak for 12 hours, remove it, rinse with water, and then place it into a pore-forming alkaline solution at 70°C for 10 hours to perform pore-forming treatment, thus obtaining a pore-shaped electrode.

[0143] The microstructure of the honeycomb electrode obtained in this embodiment is as follows: Figure 4 and Figure 5 As shown. The surface porosity of this nested electrode is 33.4%, and after deducting the weight of the nickel mesh, the specific surface area of ​​the electrode coating is as high as 24 m². 2 / g. 0.5A / cm 2 At a current density of , its hydrogen evolution overpotential is 386mV and its oxygen evolution overpotential is 457mV.

[0144] Example 3

[0145] S1: Place a 46-mesh nickel mesh with a size of 1m×1m into the sandblasting machine and perform sandblasting treatment with 1.5kg pressure and 140-mesh corundum sand.

[0146] S2: Nickel powder with an average particle size of 300 nm, aluminum powder with an average particle size of 300 nm, copper powder with an average particle size of 500 nm, and manganese powder with an average particle size of 500 nm are mixed evenly in a mass ratio of 68:16:10:6 to obtain a solid raw material. The above solid raw material, polyvinyl alcohol, ethyl cellulose, and water are mixed in a mass ratio of 55:12:5.5:27.5 and stirred at 200 rpm for 6 hours to obtain a paste-like preparation material that can be used for electrode preparation.

[0147] S3: The prepared raw materials were wet-sprayed onto a sandblasted nickel mesh to obtain the intermediate electrode. The spraying distance was 450 mm, the main compressed air pressure was 0.6 MPa, the gun speed was 300 mm / s, and the spraying angle was 80°. After spraying, the intermediate electrode was dried in a 200°C oven for 3 hours, and then sintered and cured at 800°C under argon protection. After curing, the nickel mesh gained 300 g / m². 2 .

[0148] S4: Prepare a pore-forming solution by mixing ferric chloride solution, sodium sulfate, sodium hydroxide, sodium citrate and water in a mass ratio of 25:4:1.5:3.5:66; prepare a pore-forming alkaline solution by mixing potassium hydroxide, sodium potassium tartrate and water in a mass ratio of 20:10:70.

[0149] S5: Heat the pore-forming solution to 90°C, then place the solidified nickel mesh into the heated pore-forming solution and soak for 12 hours. After soaking, remove the mesh, rinse it with water, and then place it into a pore-forming alkaline solution at 70°C for 12 hours to perform pore-forming treatment, thus obtaining a pore-forming electrode.

[0150] The microstructure of the honeycomb electrode obtained in this embodiment is as follows: Figure 6 As shown, the morphology of the active material deposited on the electrode surface is as follows: Figure 7 As shown. The surface porosity of this nested electrode is 53.4%, and after deducting the weight of the nickel mesh, the specific surface area of ​​the electrode coating reaches as high as 47 m². 2 / g. 0.5A / cm 2 At a current density of , its hydrogen evolution overpotential is 213mV and its oxygen evolution overpotential is 355mV.

[0151] Example 4

[0152] S1: A 40-mesh nickel mesh with a size of 1.8m×1.8m is soaked in 0.5mol / L dilute hydrochloric acid for 5 hours at room temperature, and then washed with deionized water and dried to obtain a nickel mesh that can be used for spraying.

[0153] S2: Nickel powder with an average particle size of 30 μm, aluminum powder with an average particle size of 5 μm, and cobalt powder with an average particle size of 5 μm are mixed evenly in a mass ratio of 70:20:10 to obtain a solid raw material.

[0154] S3: The prepared raw materials were sprayed onto a sandblasted nickel mesh using supersonic flame spraying to obtain the intermediate electrode. The spraying gas flow rate was 15 L / min, the oxygen flow rate was 50 L / min, the spraying distance was 15 cm, the spraying angle was 90°, the gun speed was 600 mm / s, and the powder feed rate was 150 g / min. After spraying, the nickel mesh gained 300 g / m³. 2 .

[0155] S4: Prepare a pore-forming solution by mixing 0.2 mol / L hydrochloric acid solution, potassium polyphosphate, ammonia, sodium trimethylamine phosphate and water in a mass ratio of 10:2.5:1:10:76.5; prepare a pore-forming alkaline solution by mixing potassium hydroxide, sodium citrate and water in a mass ratio of 20:3:77.

[0156] S5: Heat the pore-forming solution to 95°C, place the intermediate electrode into the heated pore-forming solution, soak for 10 hours, remove it, rinse with water, and then place it into a pore-forming alkaline solution at 70°C for 12 hours to perform pore-forming treatment, thus obtaining a pore-shaped electrode.

[0157] The microstructure of the honeycomb electrode obtained in this embodiment is as follows: Figure 8 As shown. The surface porosity of this nested electrode is 35%, and after deducting the weight of the nickel mesh, the specific surface area of ​​the electrode coating reaches as high as 30 μm². 2 / g. 0.5A / cm 2 At the given current density, its hydrogen evolution overpotential is 359 mV and its oxygen evolution overpotential is 441 mV.

[0158] Example 5

[0159] S1: Same as Example 1.

[0160] S2: Same as Example 1.

[0161] S3: The prepared raw materials were sprayed onto a sandblasted nickel mesh using a cold spray method to obtain the intermediate electrode. The cold spray power was 45kW, the nitrogen gas pressure was 6MPa, the gun chamber temperature was 550℃, the spray distance was 40mm, the spray angle was 90°, the gun travel speed was 700mm / s, and the powder feed rate was 200g / min. After spraying, the nickel mesh weight gain was 298g / m². 2 .

[0162] S4: Same as Example 1.

[0163] S5: Heat the pore-forming solution to 80°C, place the intermediate electrode into the heated pore-forming solution, soak for 12 hours, remove it, rinse with clean water, and then place it into a pore-forming alkaline solution at 50°C for 10 hours to perform pore-forming treatment, thus obtaining a pore-shaped electrode.

[0164] The microstructure of the honeycomb electrode obtained in this embodiment is as follows: Figure 9 As shown. The surface porosity of this nested electrode is 27%, and the specific surface area of ​​the electrode coating after deducting the weight of the nickel mesh is 19 m². 2 / g. 0.5A / cm 2 At a current density of , its hydrogen evolution overpotential is 413mV and its oxygen evolution overpotential is 473mV.

[0165] Example 6

[0166] S1: Same as Example 3.

[0167] S2: Nickel powder with an average particle size of 300 nm, aluminum powder with an average particle size of 300 nm, copper powder with an average particle size of 500 nm, and manganese powder with an average particle size of 500 nm are mixed evenly in a mass ratio of 68:16:10:6 to obtain a solid raw material. The above solid raw material, terpineol, divinylbenzene, and water are mixed in a mass ratio of 45:10:7:38 and stirred at 200 rpm for 6 hours to obtain a slurry-like preparation material that can be used for electrode preparation.

[0168] S4: The prepared raw materials are adhered to a sandblasted nickel mesh using an impregnation coating method to obtain the intermediate electrode. During impregnation, the nickel mesh is vertically immersed in the slurry and left for 30 seconds. Then, the impregnated nickel mesh is lifted out at a speed of 5 cm / s and hung to dry for 2 hours to obtain the intermediate electrode. Subsequently, the intermediate electrode is placed in a drying oven at 200°C for 3 hours, and then sintered and solidified at 800°C under argon protection. After solidification, the nickel mesh weight gain is 245 g / m². 2 .

[0169] S5: Same as Example 3.

[0170] The porosity of the honeycomb electrode surface obtained in this embodiment is 47.9%, and the specific surface area of ​​the electrode coating after deducting the weight of the nickel mesh is as high as 43m². 2 / g. 0.5A / cm 2 At a current density of , its hydrogen evolution overpotential is 235mV and its oxygen evolution overpotential is 369mV.

[0171] Comparative Example 1

[0172] The difference between this comparative example and Example 6 is that only nickel powder is added in S2, and no pore-forming material or hole-forming material is added.

[0173] S1: Same as Example 6.

[0174] S2: Nickel powder with an average particle size of 300 nm, terpineol, divinylbenzene and water are mixed in a mass ratio of 45:10:7:38 and stirred at 200 rpm for 6 hours to obtain a slurry-like raw material that can be used for electrode preparation.

[0175] S3: Same as Example 6.

[0176] S4: Same as Example 6.

[0177] S5: Same as Example 6.

[0178] The microstructure of the electrode obtained in this comparative example is as follows: Figure 10As shown. The surface porosity of this electrode is 15.5%, and after deducting the weight of the nickel mesh, the specific surface area of ​​the electrode coating is only 11 m². 2 / g. 0.5A / cm 2 At the given current density, its hydrogen evolution overpotential is only 492mV and its oxygen evolution overpotential is 530mV, which is significantly worse than that of Example 6.

[0179] Comparative Example 2

[0180] The difference between this comparative example and Example 1 is that only the dimpling process was performed in S5, and no pore-forming process was performed.

[0181] S1: Same as Example 1.

[0182] S2: Same as Example 1.

[0183] S3: Same as Example 1.

[0184] S4: Prepare a pore-forming alkaline solution by mixing potassium hydroxide, sodium citrate, and water in a mass ratio of 20:3:77.

[0185] S5: The intermediate electrode is placed in a pore-forming alkaline solution at a temperature of 70°C and soaked for 24 hours to perform pore-forming treatment, thereby obtaining a porous electrode without a pitted structure.

[0186] The surface porosity of the comparative electrode is 18%, and the specific surface area of ​​the electrode coating after deducting the weight of the nickel mesh is 15m². 2 / g. 0.5A / cm 2 At the given current density, its hydrogen evolution overpotential is only 463mV and its oxygen evolution overpotential is 501mV, which is significantly worse than that of Example 1.

[0187] Comparative Example 3

[0188] The difference between this comparative example and Example 1 is that only hole-making treatment was performed in S5, and no nest-making treatment was performed.

[0189] S1: Same as Example 1.

[0190] S2: Same as Example 1.

[0191] S3: Same as Example 1.

[0192] S4: Prepare a nest-building solution by mixing copper chloride, potassium polyphosphate, ammonia, potassium sodium tartrate, and water in a mass ratio of 20:1:1:10:68.

[0193] S5: Heat the nesting solution to 80°C, place the intermediate electrode into the heated nesting solution, soak for 24 hours, remove it, and wash it with water to obtain an electrode containing a nested structure but without a porous structure.

[0194] The surface morphology of the comparative electrode is as follows: Figure 11As shown, the surface porosity is 22%, and the specific surface area of ​​the electrode coating after deducting the weight of the nickel mesh is 18 m². 2 / g. 0.5A / cm 2 At the given current density, its hydrogen evolution overpotential is 426mV and its oxygen evolution overpotential is 487mV, both of which are worse than those in Example 1.

[0195] Comparative Example 4

[0196] The difference between this comparative example and Example 1 is that the nest-building solution in S4 was prepared by mixing copper chloride, potassium polyphosphate, ammonia, potassium sodium tartrate and water in a ratio of 35:1:1:10:53 (that is, the amount of corrosive agent in the nest-building solution is too large).

[0197] S1: Same as Example 1.

[0198] S2: Same as Example 1.

[0199] S3: Same as Example 1.

[0200] S4: Prepare a pore-forming solution by mixing copper chloride, potassium polyphosphate, ammonia, potassium sodium tartrate, and water in a mass ratio of 35:1:1:10:53; prepare a pore-forming alkaline solution by mixing potassium hydroxide, sodium citrate, and water in a mass ratio of 20:3:77.

[0201] S5: Same as Example 1.

[0202] The porosity of the honeycomb electrode surface obtained in this comparative example is 47%, and the specific surface area of ​​the electrode coating after deducting the weight of the nickel mesh is 38 m². 2 / g. 0.5A / cm 2 At the given current density, its hydrogen evolution overpotential is 351 mV and its oxygen evolution overpotential is 433 mV, which is slightly worse than that of Example 1.

[0203] Comparative Example 5

[0204] The difference between this comparative example and Example 1 is that the burr-forming solution in S4 was prepared by mixing copper chloride, potassium polyphosphate, ammonia, potassium sodium tartrate and water in a ratio of 8:1:1:10:80 (that is, the amount of corrosive agent in the burr-forming solution is too small).

[0205] S1: Same as Example 1.

[0206] S2: Same as Example 1.

[0207] S3: Same as Example 1.

[0208] S4: Prepare a pore-forming solution by mixing copper chloride, potassium polyphosphate, ammonia, potassium sodium tartrate, and water in a mass ratio of 8:1:1:10:80; prepare a pore-forming alkaline solution by mixing potassium hydroxide, sodium citrate, and water in a mass ratio of 20:3:77.

[0209] S5: Same as Example 1.

[0210] The porosity of the honeycomb electrode surface obtained in this comparative example is 23%, and the specific surface area of ​​the electrode coating after deducting the weight of the nickel mesh is 22 m². 2 / g. 0.5A / cm 2 At the given current density, its hydrogen evolution overpotential is 419 mV and its oxygen evolution overpotential is 481 mV, which is worse than that of Example 1.

[0211] Comparative Example 6

[0212] The difference between this comparative example and Example 1 is that the pore-forming alkaline solution in S4 was prepared by potassium hydroxide, sodium citrate and water in a ratio of 40:7:53 (that is, the amount of alkali in the pore-forming alkaline solution is too large).

[0213] S1: Same as example 1.

[0214] S2: Same as example 1.

[0215] S3: Same as Example 1.

[0216] S4: Prepare a pore-forming solution by mixing copper chloride, potassium polyphosphate, ammonia, potassium sodium tartrate, and water in a mass ratio of 20:1:1:10:68; prepare a pore-forming alkaline solution by mixing potassium hydroxide, sodium citrate, and water in a mass ratio of 40:7:53.

[0217] S5: Same as Example 1.

[0218] The porosity of the honeycomb electrode surface obtained in this comparative example is 39%, and the specific surface area of ​​the electrode coating after deducting the weight of the nickel mesh is 38 m². 2 / g. 0.5A / cm 2 At the given current density, its hydrogen evolution overpotential is 349 mV and its oxygen evolution overpotential is 430 mV, which is worse than that of Example 1.

[0219] Comparative Example 7

[0220] The difference between this comparative example and Example 1 is that the pore-forming alkaline solution in S4 is prepared by mixing potassium hydroxide and water in a ratio of 23:77 (that is, there are no additives in the pore-forming alkaline solution).

[0221] S1: Same as Example 1.

[0222] S2: Same as Example 1.

[0223] S3: Same as Example 1.

[0224] S4: Prepare a pore-forming solution by mixing copper chloride, potassium polyphosphate, ammonia, potassium sodium tartrate, and water in a mass ratio of 20:1:1:10:68; prepare a pore-forming alkaline solution by mixing potassium hydroxide and water in a mass ratio of 23:77.

[0225] S5: Same as Example 1.

[0226] The porosity of the honeycomb electrode surface obtained in this comparative example is 38%, and the specific surface area of ​​the electrode coating after deducting the weight of the nickel mesh is 32 m². 2 / g. 0.5A / cm 2 At the given current density, its hydrogen evolution overpotential is 354 mV and its oxygen evolution overpotential is 452 mV, which is worse than that of Example 1.

[0227] Comparative Example 8

[0228] The difference between this comparative example and Example 1 is that the pore-forming temperature in S5 is 95°C (that is, the pore-forming temperature exceeds 90°C).

[0229] S1: Same as Example 1.

[0230] S2: Same as Example 1.

[0231] S3: Same as Example 1.

[0232] S4: Same as Example 1.

[0233] S5: Heat the pore-forming solution to 95°C, place the intermediate electrode into the heated pore-forming solution, soak for 10 hours, remove it, rinse with clean water, and then place it into a pore-forming alkaline solution at 95°C for 12 hours to perform pore-forming treatment, thus obtaining a pore-shaped electrode.

[0234] The porosity of the honeycomb electrode surface obtained in this comparative example is 45%, and the specific surface area of ​​the electrode coating after deducting the weight of the nickel mesh is 34 m². 2 / g. 0.5A / cm 2 At the given current density, its hydrogen evolution overpotential is 363 mV and its oxygen evolution overpotential is 469 mV, which is worse than that of Example 1.

[0235] The statistical data of the above embodiments and comparative examples are shown in Table 1.

[0236] Table 1 Data Results

[0237]

[0238] In summary, the trough electrode provided in this application exhibits high catalytic activity and can be used for hydrogen production via water electrolysis, achieving good hydrogen production results. The preparation method of this trough electrode is easy for mass production, with no restrictions on electrode size or shape, allowing for assembly line operations. It offers advantages such as low cost, high production efficiency, and high cost-effectiveness.

[0239] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A recessed electrode, characterized in that, The dimpled electrode has a honeycomb surface structure, which includes diffusely distributed pores and wrinkles, and the surface of the dimpled electrode is coated with active catalytic material particles. The preparation of the dimpled electrode includes: combining the raw materials with a matrix to obtain an intermediate electrode; performing dimpling and pore-forming treatments on the intermediate electrode; the raw materials include raw materials containing catalytic materials, pore-forming materials, and dimpling materials; by mass percentage, the raw materials include 50%~90% of the catalytic materials, 5%~20% of the pore-forming materials, and 5%~40% of the dimpling materials; The nesting process includes: immersing the intermediate electrode in a nesting solution to perform chemical nesting; the nesting solution comprises, by mass percentage, 10%~30% etchant, 0.5%~5% dispersant, 1%~10% regulator and 1%~10% complexing agent, with the remainder being water; The pore-forming process includes: immersing the electrode obtained after the pore-forming process into a pore-forming alkaline solution for pore-forming; the pore-forming alkaline solution includes 5wt%~30wt% NaOH aqueous solution or 5wt%~30wt% KOH solution; the pore-forming alkaline solution also includes 0.5wt%~10wt% additives; the temperature of the pore-forming alkaline solution does not exceed 90℃, and the pore-forming time does not exceed 24h; The catalytic material includes at least one of Ni, Ni-based alloys, nickel oxide, nickel phosphide, and nickel nitride; the pore-forming material includes at least one of Al and Zn; and / or, the particle size of the pore-forming material does not exceed 5 μm; the pitting material includes at least one of Cu, C, Mn, and Co; and / or, the particle size of the pitting material does not exceed 10 μm; the etchant includes at least one of copper chloride solution, copper sulfate solution, ferric chloride solution, hydrochloric acid solution, and sodium hydroxide solution; the dispersant includes at least one of sodium oleate, carboxylates, sulfates, sulfonates, and polyphosphates; The regulator includes at least one of sodium hydroxide, potassium hydroxide, ammonia, and hydrochloric acid; the complexing agent includes at least one of monoethanolamine, diethanolamine, triethanolamine, potassium sodium tartrate, heptaphosphate, sodium gluconate, sodium alginate, sodium ethylenediaminetetramethylene phosphate, diethylenetriaminepentamethylene phosphonate, aminetrimethylene phosphate, hydrolyzed polymaleic anhydride, polyacrylic acid, polyhydroxyacrylic acid, maleic acid-acrylic acid copolymer, and polyacrylamide; the additive includes at least one of sodium citrate, potassium sodium tartrate, sodium ethylenediaminetetramethylene phosphate, sodium diethylenetriaminepentamethylene phosphonate, aminetrimethylene phosphate, and sodium alginate.

2. The recessed electrode according to claim 1, characterized in that, The dimpled electrode also has at least one of the following characteristics: Feature 1: The equivalent diameter of the pores in the pore-shaped electrode does not exceed 10 μm; Feature 2: The thickness of the folds in the recessed electrode does not exceed 2 μm; Feature 3: The length of the folds in the dimpled electrode is not less than 5 μm; Feature 4: In the dimpled electrode, the surface of the folds has a diffusely distributed microporous structure; Feature 5: The active catalytic material particles are transition metal element catalytic material particles.

3. The recessed electrode according to claim 2, characterized in that, The pore size of the microporous structure does not exceed 1 μm.

4. The recessed electrode according to claim 3, characterized in that, The surface of the microporous structure is coated with the active catalytic material particles.

5. The recessed electrode according to claim 2, characterized in that, The active catalytic material particles include at least one of NiCu alloy and its oxide, NiFe alloy and its oxide, FeCu alloy and its oxide, and NiFeCu alloy and its oxide.

6. A method for preparing a recessed electrode as described in any one of claims 1 to 5, characterized in that, The process includes the following steps: combining the raw materials with a matrix to obtain an intermediate electrode; and performing a pore-forming and perforation-forming process on the intermediate electrode. The raw materials for preparation include raw materials containing catalytic materials, pore-forming materials, and pore-forming materials; by mass percentage, the raw materials include 50% to 90% of the catalytic materials, 5% to 20% of the pore-forming materials, and 5% to 40% of the pore-forming materials; The nesting process includes: immersing the intermediate electrode in a nesting solution to perform chemical nesting; the nesting solution comprises, by mass percentage, 10% to 30% of the etchant, 0.5% to 5% of the dispersant, 1% to 10% of the regulator, and 1% to 10% of the complexing agent, with the balance being water; The pore-forming process includes: immersing the electrode obtained after the pore-forming process into a pore-forming alkaline solution for pore-forming; the pore-forming alkaline solution includes 5wt%~30wt% NaOH aqueous solution or 5wt%~30wt% KOH solution; the pore-forming alkaline solution also includes 0.5wt%~10wt% additives; the temperature of the pore-forming alkaline solution does not exceed 90℃, and the pore-forming time does not exceed 24h; The catalytic material includes at least one of Ni, Ni-based alloys, nickel oxide, nickel phosphide, and nickel nitride; the pore-forming material includes at least one of Al and Zn; and / or, the particle size of the pore-forming material does not exceed 5 μm; the pitting material includes at least one of Cu, C, Mn, and Co; and / or, the particle size of the pitting material does not exceed 10 μm; the etchant includes at least one of copper chloride solution, copper sulfate solution, ferric chloride solution, hydrochloric acid solution, and sodium hydroxide solution; the dispersant includes at least one of sodium oleate, carboxylates, sulfates, sulfonates, and polyphosphates; The regulator includes at least one of sodium hydroxide, potassium hydroxide, ammonia, and hydrochloric acid; the complexing agent includes at least one of monoethanolamine, diethanolamine, triethanolamine, potassium sodium tartrate, heptaphosphate, sodium gluconate, sodium alginate, sodium ethylenediaminetetramethylene phosphate, diethylenetriaminepentamethylene phosphonate, aminetrimethylene phosphate, hydrolyzed polymaleic anhydride, polyacrylic acid, polyhydroxyacrylic acid, maleic acid-acrylic acid copolymer, and polyacrylamide; the additive includes at least one of sodium citrate, potassium sodium tartrate, sodium ethylenediaminetetramethylene phosphate, sodium diethylenetriaminepentamethylene phosphonate, aminetrimethylene phosphate, and sodium alginate.

7. The preparation method according to claim 6, characterized in that, The raw materials used in the preparation can be in the form of solid, gel, paste, or slurry. The solid raw material used in the preparation is a raw material with a particle size not exceeding 1 μm; The gel-like raw material is obtained by mixing solid raw materials with water and gelling materials; The paste or slurry-like raw material is obtained by mixing solid raw materials with solvents and crosslinking agents; The gel-like preparation raw material contains 40wt%~60wt% of the solid raw material and 5wt%~20wt% of the gelling material, with the balance being water; The paste or slurry preparation materials each independently contain 40wt% to 80wt% of the solid raw materials, 10wt% to 50wt% of the solvent, and 5wt% to 10wt% of the crosslinking agent.

8. The preparation method according to claim 7, characterized in that, The gelling material includes at least one of polyacrylic acid and its derivatives, polyvinyl alcohol, polyoxyethylene, polyacrylamide, and ethyl cellulose.

9. The preparation method according to claim 7, characterized in that, The solvent includes at least one of terpineol, polyvinyl alcohol, ethanol, and propylene glycol; The crosslinking agent includes at least one of ethyl cellulose, dipropylene glycol methyl ether acetate, divinylbenzene, diisocyanate, dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, and diethylenetriamine.

10. The preparation method according to claim 6, characterized in that, The method of combining the raw material with the matrix includes spraying, coating, or impregnation. When the raw material is in solid or solid-liquid mixture form, it is coated with a spraying method to bond it to the substrate; when the raw material is in slurry form, it is coated with a spraying method or impregnated with a dipping method to bond it to the substrate; when the raw material is in gel or paste form, it is coated with a coating or spraying method to bond it to the substrate. Spraying includes thermal spraying, cold spraying, or wet spraying. Thermal spraying includes plasma spraying, supersonic flame spraying, detonation spraying, low-pressure plasma spraying, or arc spraying. The process conditions for plasma spraying include: spraying power of 20kW~50kW, main spraying gas argon flow rate of 40NL / min~60NL / min, auxiliary spraying gas hydrogen flow rate of 0NL / min~5NL / min, spraying current of 450A~650A, spraying distance of 15cm~30cm, spraying angle of 75°~90°, gun speed of 400mm / s~1000mm / s, and powder feed rate of 50g / min~150g / min; The process conditions for supersonic flame spraying include: a spraying gas flow rate of 10L / min to 50L / min, an oxygen or air flow rate of 50L / min to 200L / min, a spraying distance of 5cm to 20cm, a spraying angle of 85° to 95°, a gun travel speed of 500mm / s to 1500mm / s, and a powder feed rate of 50g / min to 200g / min. The process conditions for explosive spraying include: gas flow rate of 5L / min~30L / min, oxygen flow rate of 5L / min~30L / min, spraying distance of 10cm~20cm, spraying angle of 85~95°, explosion frequency of 3Hz~10Hz, gun speed of 600mm / s~2000mm / s, and powder feed rate of 30g / min~150g / min. The process conditions for low-pressure plasma spraying include: spraying power of 40kW~150kW, main spraying gas argon flow rate of 40NL / min~60NL / min, auxiliary spraying gas hydrogen flow rate of 0NL / min~5NL / min, spraying current of 500A~1000A, and spraying pressure of 1×10⁻⁶. -5 Pa~1000Pa, spraying distance 20cm~50cm, gun speed 800mm / s~2000mm / s, powder feed rate 30g / min~100g / min; The process conditions for arc spraying include: spraying voltage of 20V~50V, current of 150A~1000A, physicochemical gas pressure of 0.2MPa~1MPa, spraying distance of 10cm~20cm, powder feed rate of 200g / min~800g / min, and gun speed of 500mm / s~2000mm / s. The process conditions for cold spraying include: spraying power of 25kW~70kW, nitrogen pressure of spraying gas of 4MPa~8MPa, gun chamber temperature of 400℃~850℃, spraying distance of 20mm~50mm, spraying angle of 85~95°, gun travel speed of 600mm / s~2000mm / s, and powder feed rate of 100g / min~500g / min; The process conditions for wet spraying include: spraying distance of 300mm~800mm, main compressed air pressure of 0.2MPa~1MPa, gun speed of 200mm / s~500mm / s, and spraying angle of 60°~90°.

11. The preparation method according to claim 6, characterized in that, The soaking temperature is 30℃~95℃, and the soaking time is 5h~48h.

12. The preparation method according to claim 6, characterized in that, The temperature of the pore-forming alkaline solution is 20℃~90℃; the pore-forming time is 3h~24h.

13. The application of a trough electrode as described in any one of claims 1 to 5 in hydrogen production by water electrolysis.

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