Electrocatalyst material, water electrolysis hydrogen production electrode plate and preparation method and device of water electrolysis hydrogen production electrode plate

Abstract

The invention relates to the technical field of water electrolysis hydrogen production, in particular to an electrocatalyst material, a water electrolysis hydrogen production electrode plate and a preparation method and device.The preparation method of the electrocatalyst material comprises the following steps that NiFe-LDH nanosheets, nickel powder and a functional additive system are mixed, and first slurry is obtained; the functional additive system comprises polytetrafluoroethylene, an anionic polymer and a solvent; carrying out ultrasonic crushing on the first slurry to prepare second slurry; shearing and emulsifying the second slurry to prepare third slurry; the third slurry is subjected to ball milling, and the electrocatalyst material is prepared. The electrocatalyst material is good in conductivity, good in electrochemical performance and high in stability.

Description

Technical Field

[0001] The present application relates to the technical field of hydrogen production by electrolysis of water, and in particular to an electrocatalyst material, an electrode sheet for hydrogen production by electrolysis of water, and a preparation method and device thereof. Background Art

[0002] Hydrogen production through water electrolysis is the process of splitting water into hydrogen and oxygen using electricity. This process effectively stores excess renewable energy, ensuring stable grid operation. The resulting high-purity hydrogen, a clean energy source, can be directly applied to fuel cells and high-end chemical industries, contributing to the development of a more sustainable and environmentally friendly energy system.

[0003] The working principle of hydrogen production by water electrolysis involves two half-reactions: the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). The OER is a slow kinetic reaction with four electron transfer, with a high reaction energy barrier and a high overpotential, which is a key bottleneck restricting overall efficiency. Developing OER catalysts can effectively reduce the potential and improve reaction efficiency.

[0004] Currently, there are many reports on OER catalysts, including precious metal-based catalysts (such as IrO2, RuO2, etc.), transition metal-based catalysts (such as NiFe-LDH, Co3O4, NiO / Ni(OH)2, etc.), single-atom catalysts (such as Ni-NC, Co-SA / G, etc.), perovskite oxides (such as LaCoO3, LaNiO3, etc.), and non-oxide catalysts (such as Ni2P, CoP, etc.). Among these materials, layered hydroxide (LDH) catalysts have attracted great interest due to their low cost, high activity, and high alkaline stability. In particular, NiFe-LDH has performed particularly well in terms of activity and stability. NiFe-LDH is composed of Ni and Fe metal atoms connected by surface hydroxyl oxygen atoms, with a high active surface area. The two-dimensional layered structure can provide more active sites. Anions can be inserted between the positively charged layered hydroxide sheets, achieving rapid charge transfer. However, the structure of layered hydroxide is a two-dimensional layered structure with interlayer spacing between sheets, resulting in low conductivity and cannot be used directly.

[0005] Several patent documents such as CN119392290A, CN119530868A, CN118086974A, CN115044939A, CN116926610A, CN119615226A, etc. record methods for preparing NiFe-LDH, but these methods do not solve the problem of low conductivity of NiFe-LDH. In addition, these methods mainly prepare NiFe-LDH on a substrate by hydrothermal growth or electrochemical deposition. The preparation conditions are relatively strict, and in the oxidizing environment of high pressure and concentrated alkali, the binding force between NiFe-LDH and the substrate may change, affecting the long-term stability of the electrode.

[0006] Based on this, it is necessary to develop a NiFe-LDH-based electrocatalyst material with good conductivity, good electrochemical performance and high stability. Summary of the Invention

[0007] Based on this, one or more embodiments of the present application provide an electrocatalyst material, an electrode sheet for producing hydrogen by electrolyzing water, and a method and device for preparing the same.

[0008] It specifically includes the following aspects:

[0009] In a first aspect, the present application provides a method for preparing an electrocatalyst material, comprising the following steps:

[0010] Mixing NiFe-LDH nanosheets, nickel powder and a functional additive system to obtain a first slurry; the functional additive system comprises a binder, an anionic polymer and a solvent;

[0011] Ultrasonic crushing the first slurry to obtain a second slurry;

[0012] Shearing and emulsifying the second slurry to obtain a third slurry;

[0013] The third slurry is ball-milled to obtain the electrocatalyst material.

[0014] In the technical solution of the embodiment of the present application, NiFe-LDH nanosheets, nickel powder and a functional additive system are mixed, and then subjected to ultrasonic crushing, shear emulsification and ball milling treatment to uniformly disperse the NiFe-LDH nanosheets and nickel powder in the functional additive system of a specific composition, and jointly construct a conductive network, thereby improving the conductive properties of the electrocatalyst material.

[0015] In some embodiments, the method for preparing the electrocatalyst material satisfies at least one of the following conditions:

[0016] (1) The NiFe-LDH nanosheets are in powder form with a particle size of 100-300 mesh;

[0017] (2) The NiFe-LDH nanosheets have a hierarchical porous structure;

[0018] (3) The average particle size of the nickel powder is 100-300 mesh;

[0019] (4) In the functional additive system, the weight ratio of the adhesive to the anionic polymer is 1:(0.25-7).

[0020] In this embodiment, by limiting the particle size and structure of the NiFe-LDH nanosheets and the particle size of the nickel powder, the dispersion uniformity of the nickel powder and the NiFe-LDH nanosheets in the system is further improved. When the weight ratio of the binder to the anionic polymer in the functionalized additive system is 1:(0.25-7), the electrode substrate has better bonding strength, and the electrocatalyst material has better dispersion and better conductivity.

[0021] In some embodiments, the method for preparing the NiFe-LDH nanosheets comprises the following steps:

[0022] A nickel-iron metal mixed salt solution is added to a supersaturated sodium bicarbonate solution, the mixture is stirred at a first speed for 20 to 40 minutes, and filtered to obtain a filter residue; the nickel-iron metal mixed salt solution has a molar ratio of nickel to iron of (6-1):1; and the concentration of the supersaturated sodium bicarbonate solution is 1.3 to 2.0 mol / L;

[0023] The filter residue is washed and freeze-dried to obtain the NiFe-LDH nanosheets.

[0024] In this embodiment, NiFe-LDH nanosheets are prepared by a suitable method. The NiFe-LDH nanosheets have a better hierarchical porous structure and expose more active sites, thereby better improving the conductivity of the electrocatalyst material.

[0025] In some embodiments, the method for preparing the electrocatalyst material satisfies at least one of the following conditions:

[0026] (1) In the step of adding the nickel-iron metal mixed salt solution to the supersaturated sodium bicarbonate solution, the addition rate of the nickel-iron metal mixed salt solution is 1-10 mL / min;

[0027] (2) in the step of adding the nickel-iron metal mixed salt solution to the supersaturated sodium bicarbonate solution, maintaining the pH of the mixed solution at 7.0-8.5;

[0028] (3) The first rotation speed is 200-800 rpm.

[0029] In this embodiment, the nickel-iron metal mixed salt solution is added to the supersaturated sodium bicarbonate solution at a suitable rate for mixing, which can ensure that the reaction proceeds at a suitable rate and at the same time ensure that the pH value of the reaction can be maintained in a suitable range, preferably a pH of 7.0-8.5, so as to obtain a good three-dimensional structure, which is beneficial to improving the catalytic activity and conductivity.

[0030] In some embodiments, the first slurry comprises, based on a total weight percentage of 100%, 30%-80% of the NiFe-LDH nanosheets, 10%-60% of the nickel powder, and 10%-50% of the functional additive system;

[0031] The functional additive system, based on a total weight percentage of 100%, comprises 5%-35% of the anionic polymer, 5%-20% of the adhesive and at least 45% of a solvent.

[0032] In this embodiment, the first slurry contains NiFe-LDH nanosheets, nickel powder and a functional additive system in a suitable proportion, which can provide sufficient active sites, construct a continuous conductive network, have suitable viscosity and dispersibility, are conducive to improving the bonding strength between the electrocatalyst material and the electrode substrate, and can evenly load and disperse the NiFe-LDH nanosheets and nickel powder during coating.

[0033] In some embodiments, the step of ultrasonically crushing the first slurry to obtain the second slurry has a processing time of 10-120 min;

[0034] The step of shearing and emulsifying the second slurry to obtain the third slurry includes: stirring the second slurry at a second speed for a second time; the second speed is 1000-20000 r / min; and the second time is 4-24 hours.

[0035] In this embodiment, the first slurry is ultrasonically crushed to form agglomerates of NiFe-LDH nanosheets and nickel powder during the mixing process, and the use of ultrasound can avoid damage to the porous hierarchical structure of the NiFe-LDH nanosheets. The second slurry is sheared at a suitable speed to further refine the particles after ultrasonic crushing, fully exposing the hierarchical porous structure of NiFe-LDH, while allowing the nickel powder to be evenly dispersed between the NiFe-LDH particles, and allowing the adhesive and anionic polymer of the functionalized additive system to fully contact and be evenly adsorbed on the surface of the NiFe-LDH particles and nickel powder, stabilizing the dispersion system and preventing secondary agglomeration. A uniform bonding layer is also formed between the particles, ensuring the stability of the slurry during subsequent coating and avoiding local excessive clogging of pores.

[0036] In some embodiments, the step of ball milling the third slurry to obtain the electrocatalyst material comprises:

[0037] The third slurry and zirconia grinding balls are mixed in a ball-to-material ratio of (1-10):1, and stirred at a third speed for a third time to prepare the electrocatalyst material; the third speed is 200-1000 r / min, and the third time is 12-72 h.

[0038] In this embodiment, the third slurry and zirconia grinding balls are mixed according to a suitable ball-to-material ratio and ball milled at a suitable rotation speed, which is beneficial to avoid the destruction of the NiFe-LDH layered structure, and can further refine the particles, maximize the exposure of active sites, and make the nickel powder more evenly fill the gaps in the layered structure. After the above-mentioned ball milling treatment, the nickel powder can be more tightly bonded to the interface of NiFe-LDH, thereby improving the overall conductivity. The anionic polymer and adhesive in the functional additive can be more evenly adsorbed on the particle surface to form a stable dispersion layer and form a more uniform bonding network between the particles. In addition, a small amount of defects can be introduced on the surface of NiFe-LDH and nickel powder through appropriate ball milling treatment. The introduction of oxygen vacancies on the surface of NiFe-LDH can enhance the adsorption capacity of reaction intermediates and reduce the OER / HER reaction barrier. The lattice dislocation of the nickel powder enhances the HER activity, thereby better enhancing the catalytic activity of the electrocatalyst material.

[0039] In a second aspect, the present application provides an electrocatalyst material prepared using the preparation method described above.

[0040] In the technical solution of the embodiment of the present application, the components of the electrocatalyst material prepared by adopting the above preparation method have good compatibility, uniform dispersion, good conductivity and strong catalytic activity.

[0041] In a third aspect, the present application provides a method for preparing an electrode sheet for producing hydrogen by electrolysis of water, comprising the following steps:

[0042] The electrocatalyst material is loaded onto an electrode substrate, and the loaded electrode substrate is heated to a first temperature at a first rate under nitrogen protection, and kept at this temperature for a third time;

[0043] The first rate is 2-15°C / min; the first temperature is 120-200°C; and the third time is 30-120 min.

[0044] In the technical solution of the embodiment of the present application, since the electrocatalyst material has a suitable viscosity, it can evenly penetrate the pores of the substrate when loaded on the electrode sheet substrate, so that the active material is evenly distributed on the substrate to form a continuous active layer and a conductive network. During the drying and curing process, the use of uniform heating can effectively reduce the thermal stress inside the material and prevent structural damage caused by rapid evaporation of the solvent. Curing at a suitable temperature can promote the full curing of the electrocatalyst material, improve the bonding strength with the interface, maintain structural integrity during long-term electrolysis, and reduce performance degradation.

[0045] In a fourth aspect, the present application provides an electrode sheet for producing hydrogen by electrolyzing water, which is prepared using the preparation method described above.

[0046] In the technical solution of the embodiment of the present application, the water electrolysis hydrogen production electrode sheet prepared by adopting the above preparation method has strong interface bonding, good conductivity, good catalytic performance and long service life.

[0047] In a fifth aspect, the present application provides a water electrolysis hydrogen production device, which includes the water electrolysis hydrogen production electrode sheet described above.

[0048] In the technical solution of the embodiment of the present application, the water electrolysis hydrogen production device includes the above-mentioned water electrolysis hydrogen production electrode sheet, and thus has the advantages of good conductivity, good catalytic performance and long service life.

[0049] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] In order to more clearly illustrate the specific implementation methods of the present application or the technical solutions in the prior art, the following is a brief introduction to the drawings required for use in the specific implementation methods or the description of the prior art. Obviously, the drawings described below are some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0051] Figure 1 This is a SEM image of NiFe-LDH nanosheets according to an embodiment of the present application, with a scale of 2.00 μm.

[0052] Figure 2 This is an XRD pattern of NiFe-LDH nanosheets according to an embodiment of the present application, where the abscissa is 2θ (°) and the ordinate is intensity.

[0053] Figure 3The conductivity comparison results of the electrocatalyst material of Example 1 of the present application and the water electrolysis hydrogen production electrode sheets prepared with pure nickel powder and pure NiFe-LDH nanosheets respectively.

[0054] Figure 4 Comparison results of polarization curves of water electrolysis hydrogen production electrode sheets prepared from the electrocatalyst material of Example 1 of the present application and pure nickel powder and pure NiFe-LDH nanosheets, respectively.

[0055] Figure 5 These are the stability test results of the electrocatalyst material of Example 1 of the present application.

[0056] Figure 6 This is the electrocatalyst life test result of Example 1 of the present application. DETAILED DESCRIPTION

[0057] Below in conjunction with embodiment and example, further elaborate the application.It should be understood that these examples are only used to illustrate the application and are not used to limit the scope of the application.In addition, it should be understood that after reading the content taught in this application, those skilled in the art can make various changes or modifications to the application, and these equivalent forms also fall within the protection scope of the claims appended hereto.

[0058] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application pertains. The terms used herein in the specification of this application are for the purpose of describing specific embodiments only and are not intended to limit this application.

[0059] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0060] The term "and / or" as used herein includes any one of two or more related listed items, and also includes any and all combinations of the related listed items, wherein the any and all combinations include any combination of two related listed items, any more related listed items, or all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or", it should be understood that in this application, the technical solution undoubtedly includes technical solutions connected by "logical AND" and technical solutions connected by "logical OR". For example, "A and / or B" includes three parallel solutions: A, B, and A+B.

[0061] In this application, "further" and the like are used for descriptive purposes to indicate differences in content, but should not be understood as limiting the scope of protection of this application.

[0062] In this application, the terms "first," "second," "third," "fourth," "fifth," etc., are used for descriptive purposes only and should not be understood as indicating or implying relative importance or quantity, nor as implicitly indicating the importance or quantity of the indicated technical features. Furthermore, "first," "second," "third," "fourth," etc., serve only for the purpose of non-exhaustive enumeration and description, and should be understood not to constitute a closed-ended limitation on quantity.

[0063] In this application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0064] In this application, when referring to a numerical interval (i.e., a numerical range), unless otherwise specified, the optional numerical distribution within the numerical interval is considered continuous and includes the two numerical endpoints of the numerical range (i.e., the minimum and maximum values), as well as every numerical value between these two numerical endpoints. Unless otherwise specified, when a numerical interval refers only to integers within the numerical interval, it includes the two numerical endpoints of the numerical range, as well as every integer between the two endpoints. In addition, when multiple ranges are provided to describe a feature or characteristic, these ranges can be combined. In other words, unless otherwise specified, ranges disclosed herein should be understood to include any and all subranges subsumed therein.

[0065] Unless otherwise specified, the temperature parameters in this application may be either constant temperature or fluctuating within a certain temperature range. It should be understood that the constant temperature treatment allows for temperature fluctuations within the precision range of the instrument control. Fluctuations within ranges such as ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are permitted.

[0066] In this application, weight can be mass units known in the field of materials, such as μg, mg, g, and kg.

[0067] In a first aspect, the present application provides a method for preparing an electrocatalyst material, comprising the following steps:

[0068] Mixing NiFe-LDH nanosheets, nickel powder and a functional additive system to obtain a first slurry; the functional additive system comprises a binder, an anionic polymer and a solvent;

[0069] Ultrasonic crushing the first slurry to obtain a second slurry;

[0070] Shearing and emulsifying the second slurry to obtain a third slurry;

[0071] The third slurry is ball-milled to obtain the electrocatalyst material.

[0072] In the technical solution of the embodiment of the present application, NiFe-LDH nanosheets, nickel powder and a functional additive system are mixed, and then subjected to ultrasonic crushing, shear emulsification and ball milling treatment to uniformly disperse the NiFe-LDH nanosheets and nickel powder in the functional additive system of a specific composition, and jointly construct a conductive network, thereby improving the conductive properties of the electrocatalyst material.

[0073] In some embodiments, the NiFe-LDH nanosheets have a hierarchical porous structure. Figure 1 The NiFe-LDH nanosheets in one embodiment of the present application have a fluffy and porous structure, which can provide more active sites.

[0074] The overpotential of NiFe-LDH nanosheets prepared by the preparation method of the present application is significantly lower than that of IrO2; in some embodiments, at 10 mA / cm 2 Under these conditions, the overpotential of the NiFe-LDH nanosheets of this application is 250~280 mV, while the overpotential of IrO2 is around 322 mV.

[0075] In some embodiments, the NiFe-LDH nanosheets are in powder form with a particle size of 100-300 mesh; the nickel powder has an average particle size of 100-300 mesh. By defining the particle sizes of the NiFe-LDH nanosheets and the nickel powder, the nickel powder and NiFe-LDH nanosheets are uniformly dispersed in the system, enabling simultaneous refinement during ultrasonication, shear emulsification, and ball milling, thereby constructing a conductive network.

[0076] In some embodiments, the weight ratio of the adhesive to the anionic polymer in the functionalized additive system is 1:(0.25-7). When the functionalized additive system contains an appropriate ratio of adhesive to anionic polymer, it has better bonding strength to the electrode substrate, better dispersibility of the electrocatalyst material, and better conductivity. For example, the weight ratio of the adhesive to the anionic polymer can be 1:0.25, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, etc.

[0077] Optionally, the adhesive can be selected from polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), polyolefins (PP, PE and other copolymers), polyvinylidene fluoride (PVDF), etc., which has the effect of bonding the catalytically active material to the electrode substrate, and the above adhesive does not affect the catalytic activity and conductivity of the electrocatalyst material.

[0078] The anionic polymer plays a good dispersing role by carrying anionic groups. Optionally, the anionic polymer can be selected from FuMA-tech ion exchange membrane solution, Dioxide Materials Sustainion ion exchange membrane solution, PiperION anion exchange membrane solution, Quinomer polyaromatic quinine-based anion resin solution, polynorbornene-based ion exchange resin solution, KMem polyaryl alkylene anion resin solution, AEMemer polyaromatic anion exchange resin solution, polyaryl ether sulfone anion exchange resin solution, polyaryl piperidine anion exchange resin solution, fully saturated carbon-hydrogen bond anion exchange resin solution, Aemion+™ anion exchange resin solution, perfluoropolyaryl ether sulfone skeleton anion exchange resin solution, AEMion anion exchange resin solution, etc.

[0079] In some embodiments, the method for preparing the NiFe-LDH nanosheets comprises the following steps:

[0080] A nickel-iron metal mixed salt solution is added to a supersaturated sodium bicarbonate solution, and the mixture is stirred at a first speed for 20-40 minutes, and filtered to obtain a filter residue; the nickel-iron metal mixed salt solution has a molar ratio of nickel to iron of (6-1):1; and the concentration of the supersaturated sodium bicarbonate solution is 1.3-2.0 mol / L;

[0081] The filter residue is washed and freeze-dried to obtain the NiFe-LDH nanosheets.

[0082] In this embodiment, after the nickel-iron precursor solution is added to the supersaturated sodium bicarbonate solution and mixed, there is solid sodium bicarbonate that is not dissolved, which can ensure that the pH value of the reaction system is maintained at 7~8. The nickel-iron metal mixed salt solution is added to the saturated sodium bicarbonate solution that is stirred at a uniform speed (first speed) by adopting a reverse dropwise addition strategy. Under the condition that the pH value of the mixed solution is stable, the nickel-iron metal ions are directionally co-precipitated with hydroxyl groups and carbonates to form a layered double hydroxide precursor. After the dropwise addition is completed, mechanical stirring is continued for 20~40 minutes, which can promote crystal maturation and obtain NiFe-LDH nanosheets with a hierarchical porous structure, which can expose more active sites, thereby better improving the conductivity of the electrocatalyst material.

[0083] For example, the molar ratio of nickel to iron in the nickel-iron metal mixed salt solution can be 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, etc.; the time for stirring the mixture at the first speed can be 20 min, 25 min, 30 min, 35 min, 40 min, etc.; the concentration of the supersaturated sodium bicarbonate solution can be 1.3 mol / L, 1.4 mol / L, 1.5 mol / L, 1.6 mol / L, 1.7 mol / L, 1.8 mol / L, 1.9 mol / L, 2.0 mol / L, etc.

[0084] In some embodiments, in the step of adding the nickel-iron metal mixed salt solution to the supersaturated sodium bicarbonate solution, the addition rate of the nickel-iron metal mixed salt solution is 1-10 mL / min; a better layered fluffy porous structure can be obtained, providing more active sites.

[0085] For example, the addition rate of the nickel-iron metal mixed salt solution can be 1 mL / min, 2 mL / min, 3 mL / min, 4 mL / min, 5 mL / min, 6 mL / min, 7 mL / min, 8 mL / min, 9 mL / min, 10 mL / min, etc.

[0086] In some embodiments, in the step of adding the nickel-iron metal mixed salt solution to the supersaturated sodium bicarbonate solution for mixing, the pH of the mixed solution is maintained at 7.0-8.5.

[0087] In some embodiments, the first rotational speed is 200-800 rpm, which can better promote crystal ripening and form a fluffy hierarchical porous structure. For example, the first rotational speed can be 200 rpm, 300 rpm, 400 rpm, 500 rpm, 600 rpm, 700 rpm, 800 rpm, etc.

[0088] In some embodiments, after obtaining the filter residue, the filter residue is washed. In the freeze-drying step, the filter residue is washed alternately with deionized water and ethanol 3 to 6 times. Undissolved sodium bicarbonate solids can be dissolved and removed during the washing process. The freeze-drying time can be 12 to 24 hours, for example, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, 24 hours, etc.

[0089] In some embodiments, the first slurry is composed of 30%-80% of the NiFe-LDH nanosheets, 10%-60% of the nickel powder and 10%-50% of the functionalized additive system, based on a total weight percentage of 100%; on the premise that the total is 100%, in the first slurry, the weight percentage of the NiFe-LDH nanosheets can be freely selected from 30%, 35%, 55%, 60%, 75%, 80%, etc., the weight percentage of the nickel powder can be freely selected from 10%, 20%, 30%, 40%, 50%, 60%, etc., and the weight percentage of the functionalized additive system can be freely selected from 10%, 20%, 35%, 45%, 50%, etc. For example, in some embodiments, when the weight percentage of the NiFe-LDH nanosheets is 35% and the weight percentage of the nickel powder is 30%, the weight percentage of the functionalized additive system should be 35%.

[0090] In some embodiments, the functionalized additive system is calculated as 100% by weight, and its composition includes 5%-35% of the anionic polymer, 5%-20% of the adhesive and at least 45% of the solvent; on the premise that the total is 100%, in the functionalized additive system, the weight percentage of the anionic polymer can be freely selected from 5%, 10%, 15%, 20%, 25%, 30%, 35%, etc.; the weight percentage of the adhesive can be freely selected from 5%, 10%, 15%, 20%, etc.; the solvent contains at least 45%, and can also be 50%, 60%, 70%, 80%, 90%, etc. For example, in some embodiments, the weight percentage of the anionic polymer is 5%, the weight percentage of the adhesive is 5%, and the weight percentage of the solvent should be 90%.

[0091] In this embodiment, the first slurry contains NiFe-LDH nanosheets, nickel powder and a functional additive system in a suitable proportion, which can provide sufficient active sites, construct a continuous conductive network, have suitable viscosity and dispersibility, are conducive to improving the bonding strength between the electrocatalyst material and the electrode substrate, and can evenly load and disperse the NiFe-LDH nanosheets and nickel powder during coating.

[0092] In some embodiments, the step of ultrasonically crushing the first slurry to obtain the second slurry has a processing time of 10-120 min;

[0093] The step of shearing and emulsifying the second slurry to obtain the third slurry includes: stirring the second slurry at a second speed for a second time; the second speed is 1000-20000 r / min; and the second time is 4-24 hours.

[0094] In this embodiment, the first slurry is ultrasonically crushed to initially disperse the NiFe-LDH nanosheets and nickel powder into aggregates formed during the mixing process, and the use of ultrasound can avoid damage to the porous hierarchical structure of the NiFe-LDH nanosheets. The second slurry is sheared at a suitable speed to further refine the particles after ultrasonic crushing, fully exposing the hierarchical porous structure of the NiFe-LDH, while allowing the nickel powder to be evenly dispersed between the NiFe-LDH particles, and allowing the adhesive and anionic polymer of the functionalized additive system to fully contact and be evenly adsorbed on the surface of the NiFe-LDH particles and nickel powder, stabilizing the dispersion system and preventing secondary agglomeration. A uniform bonding layer is also formed between the particles, ensuring the stability of the slurry during subsequent coating and avoiding local excessive clogging of pores.

[0095] In some embodiments, the step of ball milling the third slurry to obtain the electrocatalyst material comprises:

[0096] The third slurry and zirconia grinding balls are mixed in a ball-to-material ratio of (1-10):1, and stirred at a third speed for a third time to prepare the electrocatalyst material; the third speed is 200-1000 r / min, and the third time is 12-72 h.

[0097] In this embodiment, the third slurry and zirconia grinding balls are mixed according to a suitable ball-to-material ratio and ball milled at a suitable rotation speed, which can avoid the destruction of the NiFe-LDH layered structure, further refine the particles, maximize the exposure of active sites, and make the nickel powder more evenly fill the gaps in the layered structure. After the above-mentioned ball milling treatment, the nickel powder can be more tightly bonded to the interface of NiFe-LDH, thereby improving the overall conductivity. The anionic polymer and adhesive in the functional additive can be more evenly adsorbed on the particle surface to form a stable dispersion layer and form a more uniform bonding network between the particles. In addition, a small amount of defects can be introduced on the surface of NiFe-LDH and nickel powder through appropriate ball milling treatment. The introduction of oxygen vacancies on the surface of NiFe-LDH can enhance the adsorption capacity of reaction intermediates and reduce the OER / HER reaction barrier. The lattice dislocation of the nickel powder enhances the HER activity, thereby better enhancing the catalytic activity of the electrocatalyst material.

[0098] In a second aspect, the present application provides an electrocatalyst material prepared using the preparation method described above.

[0099] In the technical solution of the embodiment of the present application, the components of the electrocatalyst material prepared by adopting the above preparation method have good compatibility, uniform dispersion, good conductivity and strong catalytic activity.

[0100] In a third aspect, the present application provides a method for preparing an electrode sheet for producing hydrogen by electrolysis of water, comprising the following steps:

[0101] The electrocatalyst material is loaded onto an electrode substrate, and the loaded electrode substrate is heated to a first temperature at a first rate under nitrogen protection, and kept at this temperature for a third time;

[0102] The first rate is 2-15°C / min; the first temperature is 120-200°C; and the third time is 30-120 min.

[0103] Currently, when preparing electrode sheets from NiFe-LDH materials, a self-supporting method is usually adopted, such as preparing NiFe-LDH on a nickel foam substrate through electrodeposition or hydrothermal growth. The disadvantage of this method is that under the oxidizing environment of high pressure and concentrated alkali, the bonding force between NiFe-LDH and the nickel foam substrate will change, resulting in poor long-term stability of the electrode.

[0104] In the technical solution of the embodiment of the present application, since the electrocatalyst material has a suitable viscosity, it can evenly penetrate the pores of the substrate when loaded on the electrode sheet substrate, so that the active material is evenly distributed on the substrate to form a continuous active layer and a conductive network. During the drying and curing process, the use of uniform heating can effectively reduce the thermal stress inside the material and prevent structural damage caused by rapid evaporation of the solvent. Curing at a suitable temperature can promote the full curing of the electrocatalyst material, improve the bonding strength with the interface, maintain structural integrity during long-term electrolysis, and reduce performance degradation.

[0105] Optionally, the loading method may be coating, spraying, etc.

[0106] Optionally, the substrate may be a nickel felt substrate, which is pretreated by washing with acetone, dilute hydrochloric acid, and ethanol in a gradient manner before loading the electrocatalyst material.

[0107] In some embodiments, the heating rate may be 2-15° C. / min, and further may be 2-10° C. / min.

[0108] The preparation method of the present application has a simple preparation process, does not require harsh conditions, and is suitable for large-scale preparation of electrodes to meet commercial application needs.

[0109] In a fourth aspect, the present application provides an electrode sheet for producing hydrogen by electrolyzing water, which is prepared using the preparation method described above.

[0110] In the technical solution of the embodiment of the present application, the water electrolysis hydrogen production electrode sheet prepared by adopting the above preparation method has strong interface bonding, good conductivity, good catalytic performance and long service life.

[0111] In a fifth aspect, the present application provides a water electrolysis hydrogen production device, which includes the water electrolysis hydrogen production electrode sheet described above.

[0112] In the technical solution of the embodiment of the present application, the water electrolysis hydrogen production device includes the above-mentioned water electrolysis hydrogen production electrode sheet, and thus has the advantages of good conductivity, good catalytic performance and long service life.

[0113] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below.

[0114] The following are some specific examples.

[0115] For experimental parameters not specified in the following specific examples, reference is made to the guidance given in this application document, and reference may also be made to experimental manuals in the art or other experimental methods known in the art, or to the experimental conditions recommended by the manufacturer.

[0116] The raw materials and reagents involved in the following specific examples can be obtained commercially, or can be prepared by those skilled in the art according to known methods.

[0117] 1. Preparation of electrocatalyst materials and electrode sheets for water electrolysis to produce hydrogen.

[0118] Example 1

[0119] 1.1 Preparation of NiFe-LDH nanosheets.

[0120] Weigh appropriate amounts of nickel nitrate (Ni(NO3)2·6H2O), ferric nitrate (Fe(NO3)3·9H2O) and water to prepare a nickel-iron metal salt mixed solution, wherein the molar ratio of nickel to iron in the prepared solution is 3:1.

[0121] Weigh an appropriate amount of sodium bicarbonate and water to prepare a supersaturated sodium bicarbonate solution (about 1.5 mol / L). There should be undissolved solid sodium bicarbonate at the bottom of the prepared solution to ensure that the solution remains supersaturated.

[0122] The nickel-iron metal salt solution was added to a supersaturated sodium bicarbonate solution stirred at a constant speed of 500 rpm at a rate of 1 mL / min. The pH value of the reaction system was monitored during the addition process to maintain the pH value of 8. The reaction temperature was maintained at 25°C in this alkaline environment to allow the metal ions in the nickel-iron metal salt solution to undergo directional coprecipitation with hydroxyl groups and carbonate groups to form a layered double hydroxide precursor.

[0123] After the addition was completed, the mixture was stirred at 500 rpm for 20 min, and then vacuum filtered using a Buchner funnel to obtain a residue.

[0124] The filter residue was washed three times with deionized water and ethanol alternately and freeze-dried for 24 h to obtain NiFe-LDH nanosheets. The nanosheets were found to have a hierarchical porous structure (see Figure 1 ); The freeze-dried NiFe-LDH nanosheets were crushed and passed through a 100-300 mesh sieve to obtain powdered NiFe-LDH nanosheets.

[0125] 1.2 Preparation of electrocatalyst materials.

[0126] A first slurry was prepared by mixing, by weight percentage, 35% powdered NiFe-LDH nanosheets, 30% nickel powder (150 mesh particle size), and 35% functional additive system. (The functional additive system consisted of a mixture of a polytetrafluoroethylene emulsion (McLean, P816262) and an anionic polymer solution (FuMA-tech FAA-3-SOLUT-10 ion exchange membrane solution). The functional additive system, based on a total weight percentage of 100%, comprised 5% polytetrafluoroethylene, 5% anionic polymer, and the remainder solution.)

[0127] The first slurry was ultrasonically crushed for 30 min to preliminarily deagglomerate the nanoparticle agglomerates to obtain a second slurry;

[0128] The second slurry was transferred to a high-speed shear emulsifier and processed at 12,000 r / min for 6 hours to obtain a third slurry;

[0129] The third slurry was ground continuously for 24 h using a planetary ball mill, using zirconia grinding balls, a ball-to-material ratio of 5:1, and a rotation speed of 600 r / min to obtain a black third slurry, and its viscosity was detected to be 500~1500 cp.

[0130] 1.3 Preparation of water electrolysis hydrogen production electrode sheet.

[0131] The obtained black third slurry was loaded onto a pretreated nickel felt substrate (gradiently cleaned with acetone, dilute hydrochloric acid, and ethanol) through a doctor blade device, transferred to a high-temperature oven, and heated to 180°C at 5°C / min under nitrogen protection, and then kept warm for 60 minutes to achieve a strong bond between the active material and the current collector.

[0132] Example 2

[0133] The electrocatalyst material was prepared using a method substantially similar to that of Example 1, except that the molar ratio of nickel to iron in the nickel-iron metal salt mixed solution used was 4:1. The remaining preparation steps, preparation parameters, and raw materials and reagents used in each step were the same as those of Example 1.

[0134] Example 3

[0135] The electrocatalyst material was prepared using a method substantially identical to that used in Example 1, except that the first slurry was prepared by mixing 30% powdered NiFe-LDH nanosheets, 40% nickel powder, and 30% of the functional additive system in a proportional manner. The remaining preparation steps, parameters, and raw materials and reagents used in each step were the same as those used in Example 1.

[0136] Example 4

[0137] An electrocatalyst material was prepared using a method substantially identical to that used in Example 1, except that the functionalized additive system in the first slurry comprised 5% polytetrafluoroethylene, 15% anionic polymer, and the remainder was solution. The remaining preparation steps, parameters, and raw materials and reagents used in each step were the same as those used in Example 1.

[0138] Comparative Example 1

[0139] The electrocatalyst material was prepared using a method substantially similar to that of Example 1, except that the molar ratio of nickel to iron in the nickel-iron metal salt mixed solution used was 7:1. The remaining preparation steps, preparation parameters, and raw materials and reagents used in each step were the same as those of Example 1.

[0140] Comparative Example 2

[0141] The electrocatalyst material was prepared using a method substantially identical to that of Example 1, except that the first slurry comprised a mixture of 10% powdered NiFe-LDH nanosheets, 70% nickel powder, and 20% of the functional additive system. The remaining preparation steps, parameters, and raw materials and reagents used in each step were the same as those of Example 1.

[0142] Comparative Example 3

[0143] An electrocatalyst material was prepared using a method substantially identical to that used in Example 1, except that the functionalized additive system in the first slurry comprised 5% polytetrafluoroethylene, 40% anionic polymer, and the remainder was solution. The remaining preparation steps, parameters, and raw materials and reagents used in each step were the same as those used in Example 1.

[0144] Comparative Example 4

[0145] The electrocatalyst material was prepared using a method substantially similar to that of Example 1, except that carbon powder was used instead of nickel powder. The remaining preparation steps, preparation parameters, and raw materials and reagents used in each step were the same as those of Example 1.

[0146] Example 5

[0147] An electrocatalyst material was prepared using a method substantially similar to that of Example 1, except that 20% NiFe-LDH nanosheets and 40% nickel powder were used. The remaining preparation steps, parameters, and raw materials and reagents used in each step were the same as those of Example 1.

[0148] Example 6

[0149] The electrocatalyst material was prepared using a method substantially similar to that of Example 1, except that the molar ratio of nickel and iron used in preparing the NiFe-LDH nanosheets was 1:1. The remaining preparation steps, preparation parameters, and raw materials and reagents used in each step were the same as those of Example 1.

[0150] Example 7

[0151] An electrocatalyst material was prepared using a method substantially identical to that used in Example 1, except that the functionalized additive system in the first slurry comprised 5% polytetrafluoroethylene, 35% anionic polymer, and the remainder was solution. The remaining preparation steps, parameters, and raw materials and reagents used in each step were the same as those used in Example 1.

[0152] Example 8

[0153] An electrocatalyst material was prepared using a method substantially identical to that used in Example 1, except that the functionalized additive system in the first slurry comprised 25% polytetrafluoroethylene, 10% anionic polymer, and the remainder was solution. The remaining preparation steps, parameters, and raw materials and reagents used in each step were the same as those used in Example 1.

[0154] Example 9

[0155] The electrocatalyst material was prepared using a method substantially similar to that of Example 1, except that the nickel-iron metal salt solution was added at a rate of 1 mL / min. The remaining preparation steps, preparation parameters, and raw materials and reagents used in each step were the same as those of Example 1.

[0156] Example 10

[0157] The electrocatalyst material was prepared using a method substantially similar to that of Example 1, except that the nickel-iron metal salt solution was added at a rate of 10 mL / min. The remaining preparation steps, preparation parameters, and raw materials and reagents used in each step were the same as those of Example 1.

[0158] Example 11

[0159] The electrocatalyst material was prepared using a method substantially identical to that of Example 1, except that the pH of the reaction system was maintained at 7 when the nickel-iron metal salt mixed solution was added to the supersaturated sodium bicarbonate solution. The remaining preparation steps, preparation parameters, and raw materials and reagents used in each step were the same as those of Example 1.

[0160] Example 12

[0161] The electrocatalyst material was prepared using a method substantially identical to that used in Example 1, except that the pH of the reaction system was maintained at 8.5 when the nickel-iron metal salt mixture was added to the supersaturated sodium bicarbonate solution. The remaining preparation steps, parameters, and raw materials and reagents used in each step were the same as those used in Example 1.

[0162] Example 13

[0163] The electrocatalyst material was prepared using a method substantially similar to that of Example 1, except that the pellet-to-material ratio was adjusted to 1:1. The remaining preparation steps, preparation parameters, and raw materials and reagents used in each step were the same as those of Example 1.

[0164] Example 14

[0165] The electrocatalyst material was prepared using a method substantially the same as in Example 1, except that the third time was adjusted to 12 h. The remaining preparation steps, preparation parameters, and raw materials and reagents used in each step were the same as in Example 1.

[0166] Example 15

[0167] The electrocatalyst material was prepared using a method substantially the same as in Example 1, except that the third rotation speed was adjusted to 2000 rpm. The remaining preparation steps, preparation parameters, and raw materials and reagents used in each step were the same as in Example 1.

[0168] Example 16

[0169] The electrocatalyst material was prepared using a method substantially similar to that of Example 1, except that the first heating rate was adjusted to 15°C / min. The remaining preparation steps, preparation parameters, and raw materials and reagents used in each step were the same as those of Example 1.

[0170] Example 17

[0171] The electrocatalyst material was prepared using a method substantially similar to that of Example 1, except that the first temperature of the temperature increase was adjusted to 130° C. / min. The remaining preparation steps, preparation parameters, and raw materials and reagents used in each step were the same as those of Example 1.

[0172] 2. Characterization of NiFe-LDH nanosheets.

[0173] The SEM image of the NiFe-LDH nanosheets of Example 1 is as follows: Figure 1 , showing a fluffy and porous two-dimensional layered structure on the surface; the XRD pattern is as follows Figure 2, compared with the standard card PDF#51-0463, the characteristic peaks are completely consistent, indicating that NiFe-LDH nanosheets were successfully synthesized.

[0174] 3. Electrolysis voltage and attenuation rate of water electrolysis hydrogen production electrode cell.

[0175] Table 1 Electrolysis voltage and attenuation rate of each embodiment and comparative example

[0176]

[0177] According to Table 1, it can be found that the attenuation rate of the electrocatalyst material in each embodiment of the present application is low, at 0.5A / cm 2 The electrolysis voltage is low, indicating that the energy input required for the catalyst-driven reaction (such as OER / HER) is small and the catalytic activity is high, while the electrolysis voltage of each comparative example is significantly higher and the decay rate is higher; Comparative Example 1 increases the ratio of nickel and iron elements in the preparation process of NiFe-LDH, weakens the synergistic effect between nickel and iron, resulting in poor catalyst performance; Comparative Example 2 reduces the amount of NiFe-LDH. Since NiFe-LDH is a catalytically active substance, the reduced amount causes performance deterioration; Comparative Example 3 uses less polytetrafluoroethylene and more anionic polymer, resulting in poor stability of the catalyst; Comparative Example 4 uses carbon powder instead of nickel powder. Since carbon powder has poor antioxidant ability and insufficient conductivity, the catalyst performance is poor and the decay rate is fast.

[0178] 4. Performance comparison of NiFe-LDH, nickel powder and the electrocatalyst material of the present application.

[0179] (1) Conductivity test

[0180] The conductivity of NiFe-LDH, nickel powder and the electrocatalyst material of Example 1 was tested, and the comparison results of the conductivity were as follows: Figure 3 .according to Figure 3 It can be seen that the conductivity of NiFe-LDH itself is low, only 9.35×10 -7 S / cm. Nickel powder itself has a high electrical conductivity of 4.35×10 -1 S / cm. When nickel powder is doped into NiFe-LDH, its conductivity is 3.33×10 -5 S / cm, and the conductivity increased by two orders of magnitude. The experimental results show that the addition of nickel powder greatly improves the conductivity of NiFe-LDH.

[0181] (2) Electrochemical testing

[0182] A NiFe-LDH-based water electrolysis hydrogen production electrode sheet was prepared using a method substantially the same as in Example 1, except that in step 1.2 of preparing the electrocatalyst material, 65% of powdered NiFe-LDH nanosheets and 35% of the functional additive system were mixed in proportion, based on weight percentage, to obtain a first slurry.

[0183] The NiFe self-supporting electrode sheet was prepared by a hydrothermal method, with reference to the preparation method in patent CN106381506B.

[0184] The electrode sheet of Example 1 and the NiFe self-supporting electrode sheet for hydrogen production by electrolysis of water based on NiFe-LDH were loaded into an electrochemical workstation respectively, and polarization curves were obtained by linear sweep voltammetry. The comparison results of the polarization curves are shown in FIG. Figure 4 .according to Figure 4 It can be found that the polarization curve of NiFe-LDH itself is poor, with a performance of 2.01V@0.5A / cm 2 Example 1 After adding nickel powder to improve conductivity, the polarization curve is significantly improved, reaching 2.00V@2.0A / cm 2 The performance is lower than that of Example 1, which is 2.21V@2.0A / cm 2 .

[0185] (3) Stability test

[0186] The NiFe-LDH catalyst had a very poor lifespan and could not be tested, so there is no lifespan test data. 2 The constant current test was carried out under the following conditions. The results of the 80-hour constant current test are as follows: Figure 5 .according to Figure 5 It can be found that the electrode sheet of Example 1 has good stability. After 30 hours, the voltage begins to stabilize. The results of the 350-hour constant current test are as follows: Figure 6 .according to Figure 6 It can be found that the voltage of the electrode sheet of Example 1 has only certain fluctuations during a long test time, showing good stability.

[0187] All documents mentioned in this application are cited as references in this application, just as each document is cited as reference separately. Unless they conflict with the application purpose and / or technical solution of this application, the cited documents involved in this application are cited in their entirety and for all purposes. When cited documents are involved in this application, the definitions of relevant technical features, terms, nouns, phrases, etc. in the cited documents are also cited. When cited documents are involved in this application, the examples and preferred embodiments of the cited relevant technical features may also be incorporated into this application as references, but are limited to the ability to implement this application. It should be understood that when the cited content conflicts with the description in this application, the present application shall prevail or be adaptively amended according to the description in this application.

[0188] The various technical features of the above-mentioned implementation modes and examples can be combined in any appropriate manner. In order to make the description concise, not all possible combinations of the various technical features in the above-mentioned implementation modes and examples are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of the description in this specification.

[0189] The embodiments described above only express several implementation methods of the present application, but they should not be understood as limiting the scope of the patent application. It should be pointed out that, for those of ordinary skill in the art, without departing from the concept of the present application, several variations and improvements can be made, which all fall within the scope of protection of the present application. In addition, it should be understood that after reading the above-mentioned teaching content of the present application, those skilled in the art can make various changes or modifications to the present application, and the equivalent forms obtained also fall within the scope of protection of the present application. It should also be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent application of the present application shall be based on the attached claims, and the description can be used to interpret the content of the claims.

Claims

1. A method for preparing an electrocatalyst material, characterized in that: The steps include: Mixing NiFe-LDH nanosheets, nickel powder and a functional additive system to obtain a first slurry; the functional additive system comprises a binder, an anionic polymer and a solvent; Ultrasonic crushing the first slurry to obtain a second slurry; Shearing and emulsifying the second slurry to obtain a third slurry; The third slurry is ball-milled to obtain the electrocatalyst material.

2. The method for preparing an electrocatalyst material according to claim 1, wherein: Meet at least one of the following conditions: (1) The NiFe-LDH nanosheets are in powder form with a particle size of 100-300 mesh; (2) The NiFe-LDH nanosheets have a hierarchical porous structure; (3) The average particle size of the nickel powder is 100-300 mesh; (4) In the functional additive system, the weight ratio of the adhesive to the anionic polymer is 1:(0.25-7).

3. The method for preparing an electrocatalyst material according to claim 1 or 2, characterized in that: The preparation method of the NiFe-LDH nanosheets comprises the following steps: A nickel-iron metal mixed salt solution is added to a supersaturated sodium bicarbonate solution, the mixture is stirred at a first speed for 20 to 40 minutes, and filtered to obtain a filter residue; the nickel-iron metal mixed salt solution has a molar ratio of nickel to iron of (6-1):1; and the concentration of the supersaturated sodium bicarbonate solution is 1.3 to 2.0 mol / L; The filter residue is washed and freeze-dried to obtain the NiFe-LDH nanosheets.

4. The method for preparing an electrocatalyst material according to claim 3, wherein: Meet at least one of the following conditions: (1) In the step of adding the nickel-iron metal mixed salt solution to the supersaturated sodium bicarbonate solution, the addition rate of the nickel-iron metal mixed salt solution is 1-10 mL / min; (2) in the step of adding the nickel-iron metal mixed salt solution to the supersaturated sodium bicarbonate solution, maintaining the pH of the mixed solution at 7.0-8.5; (3) The first rotation speed is 200-800 rpm.

5. The method for preparing an electrocatalyst material according to claim 1 or 2, characterized in that: The first slurry, based on a total weight percentage of 100%, comprises 30%-80% of the NiFe-LDH nanosheets, 10%-60% of the nickel powder, and 10%-50% of the functional additive system; The functional additive system, based on a total weight percentage of 100%, comprises 5%-35% of the anionic polymer, 5%-20% of the adhesive and at least 45% of a solvent.

6. The method for preparing an electrocatalyst material according to claim 1 or 2, characterized in that: The first slurry is subjected to ultrasonic crushing to obtain a second slurry, the processing time being 10-120 min; The step of shearing and emulsifying the second slurry to obtain the third slurry includes: stirring the second slurry at a second speed for a second time; the second speed is 1000-20000 r / min; and the second time is 4-24 hours.

7. The method for preparing an electrocatalyst material according to claim 1 or 2, characterized in that: The step of ball milling the third slurry to obtain the electrocatalyst material comprises: The third slurry and zirconia grinding balls are mixed in a ball-to-material ratio of (1-10):1, and stirred at a third speed for a third time to prepare the electrocatalyst material; the third speed is 200-1000 r / min, and the third time is 12-72 h.

8. An electrocatalyst material prepared by the preparation method according to any one of claims 1 to 7.

9. A method for preparing an electrode sheet for producing hydrogen by electrolysis of water, characterized in that: The steps include: loading the electrocatalyst material according to claim 8 onto an electrode substrate, heating the loaded electrode substrate to a first temperature at a first rate under nitrogen protection, and maintaining the temperature for a third time; The first rate is 2-15°C / min; the first temperature is 120-200°C; and the third time is 30-120 min.

10. An electrode sheet for producing hydrogen by electrolyzing water prepared by the preparation method according to claim 9.

11. A hydrogen production device by electrolysis of water, characterized in that: The water electrolysis hydrogen production device includes the water electrolysis hydrogen production electrode sheet according to claim 10.

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