Electrolytic water oxygen evolution reaction catalyst, preparation method and device thereof

Abstract

The present invention discloses an electrocatalyst for oxygen evolution reaction in electrolyzed water. The catalyst has a micro-nano multi-level structure with micro-nano columns and micro-nano clusters. The diameters of the micro-nano columns and micro-nano clusters are 500 nm - 20 μm, the surface roughness of the catalyst is 3 - 12 μm, and the phase structure of the catalyst is a duplex structure of Ni-Co alloy and CeO2. The present invention also discloses a preparation method for an electrocatalyst for oxygen evolution reaction in electrolyzed water, which includes the following steps: 1) preparing CeO2 / Ni nano hybrid particles; 2) adding the hybrid particles into an electrolyte solution, connecting the anode of an electrochemical workstation to a Ni rod, connecting the cathode to a substrate material, placing them in an electrolytic cell, stirring the electrolyte solution, and adding a magnetic field intersecting with the surface of the substrate material beside the electrolytic cell to perform electrochemical deposition to obtain the catalyst. The present invention further discloses a magnetic field-assisted electrochemical deposition device. The electrocatalytic activity and stability of the catalyst prepared by the present invention can reach the level of the noble metal RuO2 catalyst, and it has the characteristics of simple production process and low preparation cost.

Description

Technical Field

[0001] The present invention belongs to the field of catalysts. More specifically, the present invention relates to an electrolytic water oxygen evolution reaction catalyst, a preparation method thereof and a device. Background Art

[0002] In recent years, the huge consumption of fossil energy not only induces an energy crisis, but also the large amount of by-products emitted during its combustion has exacerbated the increasingly serious climate warming and air pollution. To alleviate the energy crisis and environmental pollution, it is urgent to seek a more environmentally friendly energy alternative. In this context, hydrogen, as a zero-carbon energy carrier, has the advantages of high energy density, greenness and sustainability, and has received extensive attention. However, at present, more than 95% of the hydrogen production in the world comes from fossil fuel reforming, and a large amount of CO 2 is emitted during the production process, which undoubtedly violates the original intention of carbon reduction. On the contrary, about 3%-5% of hydrogen comes from electrolytic water, and there is no CO 2 emission during the production process. More importantly, hydrogen production by electrolytic water can convert intermittent and regional renewable energy such as wind energy and solar energy into zero-carbon chemical energy storage,

[0003] At present, the main reason why large-scale production of hydrogen by electrolytic water is difficult to achieve is the excessive power consumption. Especially for the anodic oxygen evolution reaction (OER) of electrolytic water, which involves a complex electron transfer process, its kinetics is slow and a high voltage input is required, seriously restricting the development of hydrogen production by electrolytic water.

[0004] In recent years, noble metal catalysts RuO 2 and IrO 2etc. are efficient and stable in the oxygen evolution reaction of electrolyzed water and have been commercially applied. However, their expensive cost, scarcity, and complex preparation process make it difficult to achieve large-scale application of hydrogen production by electrolyzed water. Therefore, there is an urgent need to develop an economical, abundant catalyst with high OER performance to replace noble metal catalysts. In recent years, nickel-based electrodes have shown remarkable activity in catalytic performance and are considered alternatives to noble metal catalytic electrodes. In addition, other studies have shown (J. Li, J. Li, X. Zhou, Z. Xia, W. Gao, Y. Ma, Y. Qu, Highly Efficient and Robust Nickel Phosphides as Bifunctional Electrocatalysts for Overall Water-Splitting, ACS Appl. Mater. Interfaces, 2016, 8, 10826-10834.) that nickel-based micro-nano surface structures with high specific surface area and multiple active centers usually have excellent catalytic performance due to their superior electron conduction and ion diffusion efficiency. The nickel-based composite electrode prepared by compounding active nano-solid particles with a nickel metal matrix can further increase the specific surface area and active sites of the electrode. This indicates that the application of nickel-based composite electrodes in OER catalyst materials has a bright future. However, the current preparation methods of electrolyzed water oxygen evolution reaction catalysts often use sol-gel method, ball milling method, etc. These methods have disadvantages such as relatively complex process control, small mass production, and long production cycle, and there is still a certain distance from large-scale industrial preparation. Y. Pei et al. (Y. Pei, Y. Yang, F. Zhang, P. Dong, R. Baines, Y Ge, H. Chu, P. M. Ajayan, J. Shen, M. Ye, Controlled Electrodeposition Synthesis of Co-Ni-P Film as a Flexible and Inexpensive Electrode for Efficient Overall Water Splitting. ACS Appl. Mater. Interfaces, 2017, 9(37), 31887-31896.) prepared a NiCoP high-efficiency bifunctional catalyst coating by constant current electrodeposition method. This catalyst coating has the advantages of simple preparation, low cost, short production cycle, and catalyst self-supporting. However, the overpotential of this catalyst is relatively high, and the overpotential at a current density of 10 mA cm -2 is 340 mV, and the corresponding Tafel slope is 67 mV dec -1 , and the excellent catalytic activity of nickel-based materials is not fully exerted.

[0005] It can be seen that preparing a nickel-based electrocatalytic water oxidation reaction catalyst with better performance is an important way to promote large-scale industrialization of hydrogen production by water electrolysis. A large number of studies have shown that surface micro-nano structures can effectively increase the surface area of the catalyst, thereby increasing the number of active sites and the charge conduction ability of the catalyst. Based on the above two points, obtaining a nickel-based catalyst coating with surface micro-nano structures has become an important direction for the design of high-performance electrocatalytic water oxidation reaction catalysts. Summary of the Invention

[0006] An object of the present invention is to solve at least the above problems and provide at least the advantages described hereinafter.

[0007] An object of the present invention is to provide an electrocatalytic water oxidation reaction catalyst with good electrochemical stability, and both the electrochemical activity and stability reach the level of the noble metal RuO 2 catalyst, and the production process is simple, the preparation cost is low, and it has the potential for large-scale industrial preparation.

[0008] To achieve these objects and other advantages of the present invention, there is provided an electrocatalytic water oxidation reaction catalyst, the catalyst having a micro-nano multi-level structure of micro-nano columns and micro-nano clusters, the diameters of the micro-nano columns and micro-nano clusters being 500 nm - 20 μm, the surface roughness of the catalyst being 3 - 12 μm, and the catalyst phase structure being a dual-phase structure of Ni-Co alloy and CeO 2 2.

[0009] Preferably, the content of Ni element in the catalyst is 30 - 50%, the content of Co element is 20 - 40%, the content of Ce element is 5 - 15%, and the content of O element is 10 - 30%.

[0010] A preparation method of an electrocatalytic water oxidation reaction catalyst, which comprises the following steps:

[0011] 1) Nano-CeO 2 and nano-Ni are ball-milled by a ball mill to obtain CeO 2 / Ni nano hybrid particles;

[0012] 2) The CeO 2 / Ni nano hybrid particles are added to the electrolyte, the anode of the electrochemical workstation is connected to the Ni rod, the cathode is connected to the substrate material, placed in an electrolytic cell, the electrolyte is stirred, and a magnetic field intersecting the surface of the substrate material is added beside the electrolytic cell for electrochemical deposition to obtain the electrocatalytic water oxidation reaction catalyst.

[0013] Preferably, the particle size of the nano-CeO 2 is 15 - 30 nm, the particle size of the nano-Ni is 50 - 150 nm, and the nano-CeO 2The mass ratio with nano-Ni is 1 - 3:2 - 5.

[0014] Preferably, the rotation speed of the ball mill is 280 - 350 revolutions per minute, and the ball milling time is 3 - 6 hours.

[0015] Preferably, CeO 2 The concentration of the / Ni nano hybrid particles in the electrolyte is 4 - 5 g / L.

[0016] Preferably, the electrolyte includes: NiSO 4 ·6H 2 O 280 - 300 g / L, NiCl 2 ·6H 2 O 40 - 50 g / L, CoSO 4 ·7H 2 O 40 - 50 g / L, H 3 BO 4 40 - 50 g / L, C 7 H 5 O 3 NS 5 - 10 g / L, and the pH value is 4.4 - 4.6.

[0017] Preferably, during electrochemical deposition, a constant current of 2 mA and a constant potential of 1.2 mV are used, the deposition temperature is room temperature, and the stirring speed is 30 - 60 revolutions per minute.

[0018] Preferably, the magnetic field intensity on the surface of the substrate material is 20 - 100 mT.

[0019] A magnetic field-assisted electrochemical deposition device, which includes:

[0020] A magnetic stirring device;

[0021] An electrolytic cell, which is arranged above the magnetic stirring device. A magnetic rotor is placed in the electrolytic cell. The electrolytic cell contains an electrolyte. An anode, a cathode, and a reference electrode are arranged in the electrolytic cell. A permanent magnet is arranged outside the electrolytic cell so that the magnetic field of the permanent magnet penetrates through the cathode;

[0022] An electrochemical workstation, which is electrically connected to the anode, the cathode, and the reference electrode.

[0023] The present invention has at least the following beneficial effects:

[0024] First, the catalyst prepared by the present invention, namely Ni-Co / CeO 2The composite coating has a unique surface micro-nano structure and a large specific surface area, excellent OER catalytic activity, and catalytic performance stability. This is attributed to the micro-nano structure and larger specific surface area of the nickel-based coating, which increase the number of active sites on the catalyst surface and the charge conduction performance. The integrity of the catalyst coating and its tight bonding with the substrate material improve the stability of the catalytic performance.

[0025] Second, the present invention uses Ni, Co, CeO 2 as raw materials, without scarce precious metal elements; the catalyst coating is prepared by magnetic field-assisted electrochemical deposition, which can deposit the catalyst coating on substrate materials such as different metal electrodes or metal devices, without strict requirements for the surface of the substrate material, showing excellent environmental adaptability and flexibility in use.

[0026] Third, the present invention uses the magnetic field-assisted electrochemical deposition method to mix CeO 2 and nano-Ni particles with Ni-Co alloy to obtain the Ni-Co / CeO 2 catalyst coating through magnetic-assisted electrodeposition. The regulation of different micro-nano surface structures can be achieved through magnetic field-assisted electrochemical deposition; with the increase of the concentration of nano-mixed particles, micro-nano hierarchical structures can be introduced on the surface of the substrate material, and a higher magnetic field intensity can significantly reduce the surface roughness, which is beneficial to improving the wetting degree.

[0027] Fourth, the present invention has the advantages of simple operation process, low cost, high output, and short production cycle.

[0028] Other advantages, objectives, and features of the present invention will be partially reflected by the following description, and partially will also be understood by those skilled in the art through the research and practice of the present invention. Brief Description of the Drawings

[0029] Figure 1 is a schematic structural diagram of the magnetic field-assisted electrochemical deposition device in an embodiment of the present invention;

[0030] Figure 2 is a scanning electron microscope image of the catalyst prepared by different processes of the present invention;

[0031] Figure 3 is a three-dimensional diagram of the surface roughness of the catalyst prepared by different processes of the present invention;

[0032] Figure 4 is an X-ray diffraction pattern of the catalyst prepared under different processes of the present invention; among them, Figure 4-1 is the full-spectrum diagram, Figure 4-2 is the partial enlarged view;

[0033] Figure 5Comparison chart of OER catalytic performance curves prepared under different processes; among them, 5-1 is the LSV curve, 5-2 is the Tafel curve, 5-3 is the Cdl curve, and 5-4 is the impedance spectrum;

[0034] Figure 6 Graph of the stability test results of the catalyst prepared by the present invention; among them, 6-1 is the chronopotentiometry curve for 25 hours, and 6-2 is the comparison of LSV curves before and after the test. Detailed implementation manners

[0035] The present invention will be further described in detail below with reference to the accompanying drawings, so that those skilled in the art can implement it according to the description in the specification.

[0036] It should be understood that terms such as "having", "comprising", and "including" used herein do not exclude the presence or addition of one or more other elements or their combinations.

[0037] It should be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials can be obtained from commercial sources unless otherwise specified; in the description of the present invention, it should be noted that unless otherwise clearly defined and limited, the terms "installed", "connected", and "set" should be understood in a broad sense. For example, they can be fixedly connected and set, or detachably connected and set, or integrally connected and set. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific situations. The orientation or positional relationship indicated by terms such as "transverse", "longitudinal", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. is based on the orientation or positional relationship shown in the drawings, and is only for the convenience of describing the present invention and simplifying the description, and does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation of the present invention.

[0038] An electrolytic water oxygen evolution reaction catalyst, the catalyst has a micro-nano multi-stage structure of micro-nano columns and micro-nano clusters, the diameters of the micro-nano columns and micro-nano clusters are 500 nm - 20 μm, the surface roughness of the catalyst is 3 - 12 μm, and the catalyst phase structure is a two-phase structure of Ni-Co alloy and CeO 2 of.

[0039] In another technical solution, the content of Ni element in the catalyst is 30 - 50%, the content of Co element is 20 - 40%, the content of Ce element is 5 - 15%, and the content of O element is 10 - 30%.

[0040] A preparation method of an electrolytic water oxygen evolution reaction catalyst, which includes the following steps:

[0041] 1) Nano-CeO 2 and nano-Ni are ball-milled using a ball mill to obtain CeO 2 / Ni nano hybrid particles;

[0042] 2) The CeO 2 / Ni nano hybrid particles are added to the electrolyte. The anode of the electrochemical workstation is connected to a Ni rod, and the cathode is connected to the substrate material. They are placed in an electrolytic cell, the electrolyte is stirred, and a magnetic field intersecting the surface of the substrate material is added beside the electrolytic cell to perform electrochemical deposition to obtain the electrolytic water oxygen evolution reaction catalyst.

[0043] In this embodiment, the substrate material can be 316L stainless steel or other corrosion-resistant, inexpensive, and easy-to-process steels. Before using the substrate material, it is polished with sandpaper, and the surface is cleaned with dilute hydrochloric acid and deionized water, and then air-dried to remove surface impurities and oxide layers. The direction of the magnetic field can be perpendicular to the surface of the substrate material at a right angle or can intersect the substrate material at an acute angle.

[0044] In another technical solution, the particle size of the nano-CeO 2 is 15 - 30 nm, the particle size of the nano-Ni is 50 - 150 nm, and the mass ratio of the nano-CeO 2 to the nano-Ni is 1 - 3:2 - 5.

[0045] In another technical solution, the rotation speed of the ball mill is 280 - 350 revolutions per minute, and the ball milling time is 3 - 6 hours.

[0046] In another technical solution, the concentration of the CeO 2 / Ni nano hybrid particles in the electrolyte is 4 - 5 g / L.

[0047] In another technical solution, the electrolyte includes the following concentration components: NiSO 4 ·6H 2 O 280 - 300 g / L, NiCl 2 ·6H 2 O 40 - 50 g / L, CoSO 4 ·7H 2 O 40 - 50 g / L, H 3 BO 4 40 - 50 g / L, C 7 H 5 O 3 NS 5 - 10 g / L, and the pH value is 4.4 - 4.6.

[0048] In another technical solution, during electrochemical deposition, a constant current of 2 - 5 mA and a constant potential of 1 - 2 mV are used. The deposition temperature is room temperature, the stirring speed is 30 - 60 revolutions per minute, and the electro - deposition time is 20 - 50 minutes.

[0049] In another technical solution, the magnetic field strength on the surface of the substrate material is 20 - 100 mT.

[0050] A magnetic - field - assisted electrochemical deposition device, which includes:

[0051] A magnetic stirring device;

[0052] An electrolytic cell, which is arranged above the magnetic stirring device. A magnetic rotor is placed in the electrolytic cell. The electrolytic cell contains electrolyte. An anode, a cathode, and a reference electrode are arranged in the electrolytic cell. A permanent magnet is arranged outside the electrolytic cell so that the magnetic field of the permanent magnet penetrates through the cathode;

[0053] An electrochemical workstation, which is electrically connected to the anode, the cathode, and the reference electrode.

[0054] <Example 1>

[0055] A preparation method of an electrolytic water oxygen evolution reaction catalyst, which includes the following steps:

[0056] 1) Nano - CeO with a particle size of 20 nm 2 and nano - Ni with a particle size of 100 nm are placed in a ball mill according to a mass ratio of 1:2 for ball milling. The rotation speed of the ball mill is 320 revolutions per minute, and the ball - milling time is 4 hours to obtain CeO 2 / Ni nano - mixed particles;

[0057] 2) Add the CeO 2 / Ni nano - mixed particles to the electrolyte. The concentration of the CeO 2 / Ni nano - mixed particles in the electrolyte is 4 g / L. The electrolyte includes the following concentration components: NiSO 4 ·6H 2 O 280 g / L, NiCl 2 ·6H 2 O 40 g / L, CoSO 4 ·7H 2 O 40 g / L, H 3 BO 4 40 g / L, C 7 H 5 O 3NS 5 g / L, with a pH value of 4.5. Connect the anode of the electrochemical workstation to a Ni rod and the cathode to a 316L stainless steel plate. Place them in an electrolytic cell, stir the electrolyte with a magnetic rotor at a speed of 40 revolutions per minute, and add a magnetic field perpendicular to the surface of the 316L stainless steel plate beside the electrolytic cell. The magnetic field intensity on the surface of the 316L stainless steel plate is 100 mT. Carry out electrochemical deposition using a constant current of 2 mA and a constant potential of 1.2 mV. The deposition temperature is at room temperature, and the electrodeposition time is 30 min to obtain the electrolytic water oxygen evolution reaction catalyst.

[0058] In this example, before using the 316L stainless steel plate, polish it with sandpaper, clean the surface with dilute hydrochloric acid and deionized water, and then air-dry it to remove surface impurities and oxide layers.

[0059] <Example 2>

[0060] A preparation method of an electrolytic water oxygen evolution reaction catalyst, which includes the following steps:

[0061] 1) Nano-CeO with a particle size of 15 nm 2 and nano-Ni with a particle size of 50 nm are placed in a ball mill according to a mass ratio of 1:5 for ball milling. The rotation speed of the ball mill is 280 revolutions per minute, and the ball milling time is 6 hours to obtain CeO 2 / Ni nano hybrid particles;

[0062] 2) Add the CeO 2 / Ni nano hybrid particles to the electrolyte. The concentration of the CeO 2 / Ni nano hybrid particles in the electrolyte is 5 g / L. The electrolyte includes the following concentration components: NiSO 4 ·6H 2 O 300 g / L, NiCl 2 ·6H 2 O 50 g / L, CoSO 4 ·7H 2 O 50 g / L, H 3 BO 4 50 g / L, C 7 H 5 O 3 NS 10 g / L, with a pH value of 4.6. Connect the anode of the electrochemical workstation to a Ni rod and the cathode to a 316L stainless steel plate. Place them in an electrolytic cell, stir the electrolyte with a magnetic rotor at a speed of 30 revolutions per minute, and add a magnetic field perpendicular to the surface of the 316L stainless steel plate beside the electrolytic cell. The magnetic field intensity on the surface of the 316L stainless steel plate is 20 mT. Carry out electrochemical deposition using a constant current of 2 mA and a constant potential of 1.2 mV. The deposition temperature is at room temperature, and the electrodeposition time is 50 min to obtain the electrolytic water oxygen evolution reaction catalyst.

[0063] Example 3

[0064] A magnetic field-assisted electrochemical deposition device for Example 1 or Example 2, as Figure 1 shown, comprising:

[0065] A magnetic stirring device;

[0066] An electrolytic cell, which is arranged above the magnetic stirring device. A magnetic rotor is placed in the electrolytic cell. An electrolytic solution is contained in the electrolytic cell. An anode, a cathode and a reference electrode are arranged in the electrolytic cell. A permanent magnet is arranged outside the electrolytic cell so that the magnetic field of the permanent magnet penetrates through the cathode;

[0067] An electrochemical workstation, which is electrically connected to the anode, the cathode and the reference electrode.

[0068] During use, the cathode is connected to the substrate material.

[0069] Effect test

[0070] Test a: The preparation method of Example 1 is adopted. The difference from Example 1 is that the concentration of CeO 2 / Ni nano hybrid particles in the electrolytic solution is 4 g / L, and the magnetic field intensity is 40 mT.

[0071] Test b: The preparation method of Example 1 is adopted. The difference from Example 1 is that the concentration of CeO 2 / Ni nano hybrid particles in the electrolytic solution is 6 g / L, and the magnetic field intensity is 40 mT.

[0072] Test c: The preparation method of Example 1 is adopted. The concentration of CeO 2 / Ni nano hybrid particles in the electrolytic solution is 4 g / L, and the magnetic field intensity is 100 mT.

[0073] Test d: The preparation method of Example 1 is adopted. The difference from Example 1 is that the concentration of CeO 2 / Ni nano hybrid particles in the electrolytic solution is 6 g / L, and the magnetic field intensity is 100 mT.

[0074] I. Test results of the surface morphology of the catalyst

[0075] The SEM results of the surface morphology of Tests a-d are as Figure 2 shown. It can be seen from Figure 2 that the catalyst surface has a unique micro-nano multi-level structure of micro-nano columns + micro-nano clusters.

[0076] II. Test results of the surface roughness of the catalyst

[0077] The surface roughness test results of Tests a - d are as Figure 3 shown. As can be seen from Figure 3 , the diameters of the micro - nano columns and micro - nano clusters are about 500 nm - 20 μm, with a relatively large specific surface area, and the surface roughness is about 3 - 12 μm. A lower magnetic flux density will lead to an increase in the surface roughness of the composite electrode.

[0078] III. X - ray diffraction test results of the catalyst

[0079] The X - ray diffraction results of Tests a - d are as Figure 4 shown. As can be seen from Figure 4 , the phase structure of the catalyst is a biphasic structure of Ni - Co alloy and CeO₂.

[0080] IV. OER catalytic performance test results of the catalyst

[0081] The OER catalytic performance of the catalysts in Tests a - d in 1 M KOH is as Figure 5 and Table 1 shown.

[0082] Table 1 Main parameter indicators of the OER catalytic performance of the catalyst

[0083]

[0084] The catalyst prepared by the present invention has a unique micro - nano structure and a relatively large specific surface area, and a lower surface roughness, enabling the catalyst coating to have more surface active sites, higher charge transfer rate and wetting performance, obtaining excellent OER catalytic performance. The over - potential of the oxygen evolution reaction at 10 mA·cm -2 is 309 mV, and the Tafel slope can be as low as 39.52 mV / dec.

[0085] The results of Test d and Test c show that the increase in the concentration of CeO 2 / Ni nano - hybrid particles will introduce more micro - nano hierarchical structures on the surface of the electrode (substrate material), but the micro - nano multi - layer surface structure is not always beneficial to the catalytic performance. When the ratio of the height to the radius of the micro - nano columns on the electrode becomes larger and the top surface area increases, it may lead to the Wenzel - Cassie transition, at which time the contact area between the electrolyte and the micro - nano columns of the electrode decreases, thereby reducing the OER catalytic performance of the catalyst. Therefore, the catalytic performance of the catalyst prepared in Test d is worse than that of the catalyst prepared in Test c.

[0086] The results of Test a and Test c show that a lower magnetic flux density leads to an increase in the surface roughness of the catalyst, resulting in an increase in the wetting angle of the catalyst coating and a decrease in hydrophilicity, thereby deteriorating the catalytic performance of the catalyst.

[0087] The results of Test b and Test c show that a lower magnetic flux density leads to an increase in the surface roughness of the catalyst, while an excessive amount of CeO 2 / Ni nano hybrid particles increases the surface area of the nanocolumns and the micro-nano hierarchical structure, resulting in a significant increase in the wetting angle of the catalyst coating and a decrease in the catalytic performance of the oxygen evolution reaction.

[0088] V. Results of the stability test of the catalyst

[0089] The results of the stability test of the catalyst in Test c are as Figure 6 shown. Figure 6-1 The potentiostatic curve for 25 hours, Figure 6-2 and the comparison of the LSV curves before and after the test. Figure 6 The results show that the catalyst prepared by the present invention has excellent stability, which is attributed to the good bonding strength between the catalyst coating and the matrix material.

[0090] Although the embodiments of the present invention have been disclosed as above, it is not limited to the applications listed in the specification and embodiments. It can be fully applied to various fields suitable for the present invention. For those skilled in the art, additional modifications can be easily made. Therefore, without departing from the general concept defined by the claims and the equivalent scope, the present invention is not limited to the specific details and the illustrated examples here.

Claims

1. Electrolytic water oxygen evolution reaction catalyst, Characterized in that, The catalyst has a micro-nano multi-level structure of micro-nano columns and micro-nano clusters. The diameters of the micro-nano columns and micro-nano clusters are 500 nm - 20 μm, and the surface roughness of the catalyst is 3 - 12 μm. The phase structure of the catalyst is a two-phase structure of Ni-Co alloy and CeO 2 ; wherein the content of Ni element in the catalyst is 30-50%, the content of Co element is 20-40%, the content of Ce element is 5-15%, and the content of O element is 10-30%.

2. The preparation method of the electrolytic water oxygen evolution reaction catalyst according to claim 1, Characterized in that, comprising the following steps: 1) Nano CeO 2 and nano Ni are ball-milled using a ball mill to obtain CeO 2 / Ni nano hybrid particles; 2) Add CeO 2 / Ni nanohybrid particles to the electrolyte. Connect the anode of the electrochemical workstation to the Ni rod and the cathode to the substrate material. Place them in an electrolytic cell, stir the electrolyte, and add a magnetic field intersecting the surface of the substrate material beside the electrolytic cell to perform electrochemical deposition to obtain the electrolytic water oxygen evolution reaction catalyst.

3. The preparation method of the electrolytic water oxygen evolution reaction catalyst according to claim 2, Characterized in that, The nano CeO 2 has a particle size of 15 - 30 nm, the nano Ni has a particle size of 50 - 150 nm, and the mass ratio of nano CeO 2 to nano Ni is 1 - 3:2 - 5.

4. The preparation method of the electrolytic water oxygen evolution reaction catalyst according to claim 2, Characterized in that, The rotation speed of the ball mill is 280-350 revolutions per minute, and the ball milling time is 3-6 hours.

5. The preparation method of the electrolytic water oxygen evolution reaction catalyst according to claim 2, Characterized in that, CeO 2 The concentration of CeO 2 / Ni nano hybrid particles in the electrolyte is 4 - 5 g / L.

6. The preparation method of the electrolytic water oxygen evolution reaction catalyst according to claim 2, Characterized in that, The electrolyte includes: NiSO 4 ·6H 2 O 280 - 300 g / L, NiCl 2 ·6H 2 O 40 - 50 g / L, CoSO 4 ·7H 2 O 40 - 50 g / L, H 3 BO 4 40 - 50 g / L, C 7 H 5 O 3 NS 5 - 10 g / L, and the pH value is 4.4 - 4.

6.

7. The preparation method of the electrolytic water oxygen evolution reaction catalyst according to claim 2, Characterized in that, During electrochemical deposition, a constant current of 2 mA and a constant potential of 1.2 mV are used, the deposition temperature is room temperature, and the stirring speed is 30-60 revolutions per minute.

8. The preparation method of the electrolytic water oxygen evolution reaction catalyst according to claim 2, Characterized in that, The magnetic field strength on the surface of the substrate material is 20-100 mT.

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