Nickel-cobalt hydrogen evolution electrode, electroplating solution preparation method, electro-deposition method and application

Abstract

The invention discloses a nickel-cobalt hydrogen evolution electrode, an electroplate liquid preparation method, an electrodeposition method and application, the nickel-cobalt hydrogen evolution electrode comprises a conductive substrate and a Ni-Co coating electroplated on the surface of the conductive substrate, the conductive substrate is any one of a foamed nickel substrate, a nickel net substrate or an iron net substrate, in the Ni-Co coating, the nickel-cobalt coating is a nickel-cobalt coating, and in the nickel-cobalt coating, the nickel-cobalt coating is a nickel-cobalt coating. The mass percentage content of each element is as follows: 30-40% of Ni and 60-70% of Co. The Ni-Co electrode prepared by the method has a relatively large active surface area and high catalytic hydrogen evolution activity. Co has high hydrogen adsorptivity, the hydrogen absorption capacity of the alloy can be effectively improved, so that the binding energy with hydrogen ions is reduced, meanwhile, Ni has low hydrogen overpotential, and the hydrogen evolution performance of the Ni-Co alloy electrode is further improved through the synergistic effect of Co and Ni. Meanwhile, a nanosheet layer structure is formed on the surface of the electrode, so that more active sites are provided.

Description

Technical Field

[0001] The invention relates to the field of preparation of hydrogen evolution catalytic electrodes, and in particular to a nickel-cobalt hydrogen evolution electrode, an electrocatalytic solution preparation method, an electrodeposition method and applications. Background Art

[0002] With the increasing depletion of traditional fossil energy and the increasingly serious environmental pollution, the development of clean and efficient new energy has become an urgent need worldwide. Hydrogen energy is regarded as the most ideal energy carrier in the future due to its high efficiency, pollution-free and easy production. Among the many hydrogen production technologies, alkaline water electrolysis hydrogen production technology is considered to be one of the ideal hydrogen production methods because it can obtain high-purity hydrogen with simple process and no environmental pollution. However, this technology also faces the problems of high electrolysis energy consumption and low hydrogen evolution efficiency. The key to solving this problem lies in the development of efficient hydrogen production catalyst electrodes.

[0003] At present, high-performance catalysts mainly rely on expensive precious metal materials, which limits the possibility of their large-scale application. Therefore, the development of non-precious metal hydrogen evolution catalysts with low cost and excellent performance has become a research hotspot. Among non-precious metal catalysts, transition metal nickel-cobalt-based catalyst electrodes have attracted much attention due to their low cost and huge application potential in the field of electrocatalytic hydrogen evolution.

[0004] Therefore, it is particularly important to develop a nickel-cobalt catalytic electrode with multiple catalytic active sites, simple process operation, and easy implementation.

[0005] In addition, the testing of hydrogen evolution electrodes under traditional laboratory conditions has serious scale effect problems, and the test results are quite different from the test data under industrial environment. Therefore, it is necessary to prepare a hydrogen evolution electrode that can be used under commercial conditions. Summary of the invention

[0006] The purpose of the present invention is to disclose a nickel-cobalt hydrogen evolution electrode, an electrolyte preparation method, an electrodeposition method and applications, so as to solve the problems existing in the background technology.

[0007] To achieve the above object, the present invention provides the following technical solutions: The first technical purpose of the present invention is to provide a porous nickel-cobalt hydrogen evolution catalytic electrode, comprising a conductive substrate and a Ni-Co coating electroplated on the surface of the conductive substrate, wherein the conductive substrate is any one of a foamed nickel substrate, a nickel mesh substrate or an iron mesh substrate, and the mass percentage of each element in the Ni-Co coating is: 30-40% Ni, 60-70% Co.

[0008] The second technical purpose of the present invention is to provide a method for preparing an electroplating solution for depositing a porous nickel-cobalt hydrogen evolution catalytic electrode, which mainly comprises the following steps: respectively weighing nickel chloride hexahydrate, cobalt dichloride hexahydrate, a conductive agent, and a complexing agent, and sequentially adding nickel chloride hexahydrate, cobalt dichloride hexahydrate, a conductive agent, and a complexing agent into deionized water, and fully stirring to obtain a mixed solution, and by adjusting the amount of deionized water added, ensuring that the mass concentration of each substance in the mixed solution is: nickel chloride hexahydrate: 20-40 g / L, cobalt dichloride hexahydrate: 20-50 g / L, conductive agent 1-10 g / L, complexing agent: 20-60 g / L, and then adjusting the pH value of the mixed solution to 2-3 by adding hydrochloric acid to obtain the desired electroplating solution.

[0009] As a further improvement of the present invention, the conductive agent is lithium chloride or sodium chloride or a combination of the two, and the complexing agent includes sodium citrate or ammonium chloride or a mixture of the two.

[0010] It should be noted that the nickel chloride hexahydrate and the cobalt dichloride hexahydrate in the electroplating solution provide metal elements for the alloy, and the nickel and cobalt elements have hydrogen evolution catalytic properties. Therefore, a porous structure can be formed on the surface of the alloy layer through the hydrogen evolution process during the electrodeposition process to obtain a porous nickel-cobalt hydrogen evolution catalytic electrode. The complexing agent plays a role in complexing metal ions, and the adjustment of the content of sodium citrate will change the pH value of the electrolyte. As the pH value of the alkaline electrolyte increases, the hydrogen evolution effect of the electroplating solution will increase, so that the pore structure of the prepared Ni-Co coating increases. The appropriate addition of ammonium chloride can improve the stability of the electrolyte, and it will also affect the pH value of the electrolyte. The addition of sodium chloride or lithium chloride enhances the conductivity of the electrolyte and can improve the current efficiency.

[0011] The third technical object of the present invention is to provide a method for electrodeposition of a porous nickel-cobalt hydrogen evolution catalytic electrode, comprising the following steps: (1) Pre-treating the conductive substrate; the pre-treatment comprises: rinsing the conductive substrate with deionized water, placing the conductive substrate as a cathode and an anode in an electrolyte for degreasing, and then rinsing the degreased conductive substrate with deionized water until the pH value is neutral; then performing an acid wash treatment, and finally rinsing with deionized water until the pH value of the conductive substrate is neutral, and then setting it aside for use; (2) preparing the electroplating solution according to the preparation method of claim 3; (3) The pretreated conductive substrate is used as a cathode and the graphite sheet is used as an anode, and they are immersed in the electroplating solution in step (2), and electrochemical deposition is performed by mechanical stirring. After the electroplating is completed, the plated part is immersed in deionized water to recover the electrolyte on the surface of the plated part, and then rinsed with ethanol and dried to obtain the porous nickel-cobalt hydrogen evolution catalytic electrode.

[0012] As a further improvement of the present invention, in step (3), the drying temperature is 30-50° C., the drying time is 1-5 min, and the mechanical stirring rate is 200 rpm.

[0013] As a further improvement of the present invention, in step (3), the temperature of the electroplating solution is 25°C and the current density is 30 mA / cm 2 , the electrochemical deposition time is 20-60min.

[0014] As a further improvement of the present invention, the conductive body in step (1) is any one of a nickel foam substrate, a nickel mesh substrate or an iron mesh substrate.

[0015] As a further improvement of the present invention, in step (3), the prepared porous nickel-cobalt hydrogen evolution catalytic electrode is further subjected to heat treatment, the heat treatment temperature is 600-900°C, the heat treatment gas atmosphere is N2, and the heat treatment time is 60 min.

[0016] As a further improvement of the present invention, in step (1), nickel foam is selected as the substrate with a size of 270 mm×270 mm.

[0017] An application of a porous nickel-cobalt hydrogen evolution catalytic electrode prepared according to the above method in distributed hydrogen production equipment and fuel cells.

[0018] Distributed hydrogen production equipment: For some small distributed hydrogen production scenarios, such as small hydrogen refueling stations, energy supply stations in remote areas, etc., the 254mm diameter hydrogen evolution Ni-Co electrode can be used in the corresponding small water electrolysis equipment. Its efficient hydrogen evolution performance can meet the demand for hydrogen in these scenarios, and the relatively small equipment size is also easy to install and use.

[0019] Fuel cells: In addition to precious metals Ru, Pd and Ir, non-precious metal nickel (Ni) can also be used as a hydrogen oxidation reaction (HOR) catalyst, but pure Ni has a strong H adsorption energy, which is not conducive to the desorption of intermediate products. Co and Ni form an alloy to improve the electronic structure of Ni, thereby improving the hydrogen binding energy and increasing the HOR catalytic activity, which can greatly reduce the cost of fuel cells.

[0020] Compared with the prior art, the present invention has the following beneficial effects: 1. The Ni-Co electrode prepared by the present invention has a large active surface area and high catalytic hydrogen evolution activity. Co has high hydrogen adsorption, which can effectively increase the hydrogen absorption capacity of the alloy, thereby reducing the binding energy with hydrogen ions. At the same time, Ni has a low hydrogen overpotential. The synergistic effect of the two further improves the hydrogen evolution performance of the Ni-Co alloy electrode. At the same time, a nanosheet structure is formed on the electrode surface, providing more active sites.

[0021] 2. The coating prepared by the electrodeposition method of the present invention has the characteristics of uniform composition, fine grains, uniform thickness, and presents an amorphous structure, so that the metal atoms in the alloy show high reactivity. At the same time, the electrodeposition method ensures the close bonding of the Ni-Co coating and the base material, effectively reducing the shedding phenomenon of the electrode material during the hydrogen evolution reaction, thereby significantly improving the stability of the electrode.

[0022] 3. The present invention conducts electrolysis performance tests on commercial-sized hydrogen evolution electrodes, fills the gap of commercial-sized electrode performance tests in hydrogen evolution electrode research and development, eliminates the scale effect, reduces the difference between industrial electrolysis conditions and laboratory electrolysis conditions, and provides reliable data support and technical reference for the research and development of efficient and low-cost water electrolysis hydrogen evolution electrodes.

[0023] 4. The electroplating solution preparation process of the present invention is simple, and a porous nickel drilling catalytic electrode with a porous distribution can be directly obtained by a simple electrodeposition method. The electroplating process is simple and easy to operate, and it is easy to achieve mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is the SEM image of the prepared Ni-Co-T6 alloy at 3000 times magnification; Figure 2 Linear voltammetry (LSV) diagram of hydrogen evolution electrode of Ni-Co alloy electrode prepared with Ni substrate and different electrodeposition time; Figure 3 Linear voltammetry (LSV) diagrams of hydrogen evolution electrodes of Ni substrate, Ni-Co alloy electrode without heat treatment and Ni-Co alloy electrode with heat treatment temperature of 600, 800 and 900 degrees Celsius; Figure 4 The linear voltammetry (LSV) diagram of the hydrogen evolution electrode of the Ni-Co alloy electrode after electrodeposition with Ni substrate thickness of 0.5, 1.0, 1.5 and 2.0 mm; Figure 5 Polarization curve of a commercial size Ni-Co alloy electrode with a diameter of 254 mm prepared for electrodeposition; DETAILED DESCRIPTION

[0025] The present invention is described in detail below in conjunction with the various embodiments shown in the accompanying drawings, but it should be noted that these embodiments are not limitations of the present invention, and any equivalent transformations or substitutions in functions, methods, or structures made by ordinary technicians in the field based on these embodiments are all within the scope of protection of the present invention.

[0026] The invention discloses a nickel-cobalt hydrogen evolution electrode, a method for preparing an electrolytic solution, an electrodeposition method and applications. The porous nickel-cobalt hydrogen evolution catalytic electrode comprises a conductive substrate and a Ni-Co coating electroplated on the surface of the conductive substrate. The conductive substrate is any one of a foamed nickel substrate, a nickel mesh substrate or an iron mesh substrate. In the Ni-Co coating, the mass percentage of each element is: 30-40% Ni, 60-70% Co.

[0027] A method for preparing an electroplating solution for depositing the porous nickel-cobalt hydrogen evolution catalytic electrode mainly comprises the following steps: weighing nickel chloride hexahydrate, cobalt dichloride hexahydrate, a conductive agent, and a complexing agent respectively, adding nickel chloride hexahydrate, cobalt dichloride hexahydrate, a conductive agent, and a complexing agent to deionized water in sequence, stirring fully to obtain a mixed solution, and adjusting the amount of deionized water added to ensure that the mass concentration of each substance in the mixed solution is: nickel chloride hexahydrate: 20-40g / L, cobalt dichloride hexahydrate: 20-50g / L, conductive agent 1-10g / L, complexing agent: 20-60g / L, and then adjusting the pH value of the mixed solution to 3 by adding hydrochloric acid to obtain the desired electroplating solution. The conductive agent is lithium chloride or sodium chloride or a combination of the two, and the complexing agent includes sodium citrate or ammonium chloride or a mixture of the two.

[0028] It should be noted that the nickel chloride hexahydrate and the cobalt dichloride hexahydrate in the electroplating solution provide metal elements for the alloy, and the nickel and cobalt elements have hydrogen evolution catalytic properties. Therefore, a porous structure can be formed on the surface of the alloy layer through the hydrogen evolution process during the electrodeposition process to obtain a porous nickel-cobalt hydrogen evolution catalytic electrode. The complexing agent plays a role in complexing metal ions, and the adjustment of the content of sodium citrate will change the pH value of the electrolyte. As the pH value of the alkaline electrolyte increases, the hydrogen evolution effect of the electroplating solution will increase, so that the pore structure of the prepared Ni-Co coating increases. The appropriate addition of ammonium chloride can improve the stability of the electrolyte, and it will also affect the pH value of the electrolyte. The addition of sodium chloride or lithium chloride enhances the conductivity of the electrolyte and can improve the current efficiency.

[0029] An electrodeposition method for preparing the porous nickel-cobalt hydrogen evolution catalytic electrode comprises the following steps: (1) Pre-treating the conductive substrate; the pre-treatment comprises: rinsing the conductive substrate with deionized water, placing the conductive substrate as a cathode and an anode in an electrolyte for degreasing, and then rinsing the degreased conductive substrate with deionized water until the pH value is neutral; then performing an acid wash treatment, and finally rinsing with deionized water until the pH value of the conductive substrate is neutral, and then setting it aside for use; (2) preparing the electroplating solution according to the preparation method of claim 3; (3) The pretreated conductive substrate is used as a cathode and the graphite sheet is used as an anode, and they are immersed in the electroplating solution in step (2), and electrochemical deposition is performed by mechanical stirring. After the electroplating is completed, the plated part is immersed in deionized water to recover the electrolyte on the surface of the plated part, and then rinsed with ethanol and dried to obtain the porous nickel-cobalt hydrogen evolution catalytic electrode.

[0030] As a further improvement of the present invention, in step (3), the drying temperature is 30-50°C, the drying time is 1-5 min, and the mechanical stirring rate is 200 rpm.

[0031] As a further improvement of the present invention, in step (3), the temperature of the electroplating solution is 25°C and the current density is 30 mA / cm 2 , the electrochemical deposition time is 20-60min.

[0032] As a further improvement of the present invention, the conductive body in step (1) is any one of a nickel foam substrate, a nickel mesh substrate or an iron mesh substrate.

[0033] As a further improvement of the present invention, in step (3), the prepared porous nickel-cobalt hydrogen evolution catalytic electrode is further subjected to heat treatment, the heat treatment temperature is 600-900°C, the heat treatment gas atmosphere is N2, and the heat treatment time is 60 min.

[0034] As a further improvement of the present invention, in step (1), nickel foam is selected as the substrate with a size of 270 mm×270 mm.

[0035] An application of a porous nickel-cobalt hydrogen evolution catalytic electrode prepared according to the above method in distributed hydrogen production equipment and fuel cells.

[0036] Example 1: (1) Pretreatment of the conductive substrate: The substrate is nickel foam, which is cut into 5 cm × 5 cm in size and 1 mm thick, and then rinsed with deionized water for later use. First, the cut nickel foam is electrolytically degreased; the nickel foam is used as the cathode and anode, respectively, and placed in the electrolyte for electrolysis for 20 min, with a current density of 40 mA / cm 2 After the electrode has been degreased, it is repeatedly rinsed with deionized water until the pH value is neutral. After that, the nickel foam after electrolytic degreasing is pickled: soaked in sulfuric acid for 40 minutes, then rinsed with deionized water until the pH value is neutral, and then set aside.

[0037] (2) Preparation of electroplating solution: NiCl2·6H2O, CoCl2·6H2O, NH4Cl and LiCl were added to deionized water to obtain an electroplating solution. The mass concentration of each substance in the electroplating aqueous solution was 20 g / L NiCl·6H2O, 50 g / L CoCl2·6H2O, 20 g / L NH4Cl and 10 g / L LiCl. The pH value of the electroplating solution was 3.

[0038] (3) Preparation of Ni-Co electrode by electrodeposition: The conductive substrate pretreated in step (1) is used as the cathode and the graphite sheet is used as the anode. Electrodeposition is performed in the electroplating solution of step (2) by an electroplating method. During the electroplating deposition process, the temperature of the electroplating solution is 25°C and the current density is 30 mA / cm 2 The electrochemical times were 20 min, 40 min and 60 min, and the electrode numbers were Ni-Co-T2, Ni-Co-T4 and Ni-Co-T6 respectively.

[0039] (4) The prepared Ni-Co alloy electrode was taken out, washed with water, dried, and stored in a vacuum drying oven for subsequent characterization tests and electrochemical performance tests.

[0040] (5) Hydrogen evolution performance test of Ni-Co alloy electrode Figure 1 The SEM image of the prepared Ni-Co-T6 alloy is Figure 1 It can be seen that the surface of Ni-Co-T6 presents a nanosheet structure, which can significantly increase the specific surface area of ​​the electrode, thereby providing more catalytic active sites.

[0041] The performance of the Ni substrate electrode and the porous electrode prepared in step (3) was tested by linear sweep voltammetry (LSV). A three-electrode system was used, and the prepared electrode was the working electrode. The electrochemical test platform performed electrochemical tests on the foam electrode under an alkaline three-electrode system. The reference electrode was a Hg / HgO electrode filled with 1 mol / L KOH solution, the auxiliary electrode was a 3 mm thick graphite sheet electrode, and the electrolyte was a 1 mol / L KOH solution. The linear sweep curve is shown in FIG. Figure 2 As shown by Figure 2 It can be seen that the addition of Co element improves the hydrogen evolution performance of Ni electrode, and with the increase of electrodeposition time, the hydrogen evolution performance of Ni-Co alloy also increases. 2 The overpotential order at current density is Ni > Ni-Co-T6 > Ni-Co-T4 > Ni-Co-T2, and the overpotential of Ni-Co-T6 alloy is only 6.6% smaller than that of Ni electrode. Example 2: (1) It can be seen from the Ni-Co alloy electrode prepared in Example 1 that compared with the electrodeposition time of 20 min and 40 min, the electrodeposition time of 60 min has better hydrogen evolution performance. In addition, it is found that the ductility of the alloy electrode after electrodeposition deteriorates. Poor electrode ductility will cause the electrode to break during installation and transportation. The present invention increases the ductility of the Ni-Co alloy electrode by heat treatment.

[0042] (2) The preparation method of the Ni-Co alloy electrode in Example 2 is basically the same as that in Example 1, except that when preparing the electroplating solution in step (2), the pH value of the electroplating solution is 2 and the electroplating time is 60 min. A proper reduction in pH is beneficial to reducing the brittleness of the coating. It can be seen from Example 1 that when the electroplating time is 60 min, the prepared Ni-Co alloy electrode has better hydrogen evolution performance, so 60 min is selected here.

[0043] (3) The selected heat treatment temperatures are 600, 800 and 900 degrees Celsius (the commonly used heat treatment temperature for Ni-Co alloy electrodes is 500℃-800℃. In order to more comprehensively understand the effect of heat treatment temperature on the performance of Ni-Co hydrogen evolution electrode, it is usually necessary to set a temperature gradient. The three temperature points of 600℃, 800℃ and 900℃ selected in this experiment cover both the lower temperature range and the points close to and slightly higher than the conventional heat treatment temperature, which helps to comprehensively evaluate the effect of temperature on performance.), the heat treatment gas atmosphere is N2, the heat treatment time is 60 min, and the electrodes after heat treatment are named Ni-Co-600℃, Ni-Co-800℃ and Ni-Co-900℃, respectively. The electrode without heat treatment is named Ni-Co.

[0044] (4) The hydrogen evolution performance of the nickel foam substrate, the electrode without heat treatment and the electrode after heat treatment was tested by linear sweep voltammetry. The test results are as follows: Figure 3 ,Depend on Figure 3 It can be seen that with the increase of heat treatment temperature, the ductility of Ni-Co alloy becomes better, but the hydrogen evolution performance of Ni-Co alloy decreases after heat treatment. Among all heat-treated Ni-Co alloy electrodes, the Ni-Co alloy electrode with a heat treatment temperature of 600°C has relatively good ductility and hydrogen evolution performance.

[0045] Example 3: (1) The preparation method of the Ni-Co alloy electrode in Example 3 is basically the same as that in Example 1, the only difference is that the thickness of the nickel foam in step Example 1 is 0.5 mm, while Example 3 uses four nickel foam substrates with different thicknesses.

[0046] (2) The thicknesses of the nickel foam in Example 3 are 0.5, 1.0, 1.5 and 2.0 mm respectively.

[0047] (3) The hydrogen evolution performance of the electrode after electrodeposition was tested by linear sweep voltammetry. The test results are as follows: Figure 4 ,Depend on Figure 4 It can be seen that the alloy electrode with a thickness of 0.5 mm has the worst hydrogen evolution performance, and the alloy electrode with a thickness of 2 mm has the best hydrogen evolution performance. The current density is 100 mA / cm 2 The overpotential of the 1mm Ni-Co alloy electrode is 7.1% higher than that of the 2mm Ni-Co alloy electrode.

[0048] Example 4: The preparation method of the Ni-Co alloy electrode in Example 4 is basically the same as that in Example 1, the only difference being that Example 4 uses a commercial-sized nickel foam substrate.

[0049] The nickel foam substrate of this embodiment has a length and width of 270 mm × 270 mm, a thickness of 2 mm, and the electroplating time is 20, 40, and 60 min, respectively. The Ni-Co alloy electrode obtained by electrodeposition is cut into a circle with a diameter of 254 mm, respectively named Ni-Co-T20, Ni-Co-T40, and Ni-Co-T60, for commercial size electrode testing. The heat treatment temperature is 600°C.

[0050] The commercial size electrode test of this embodiment was carried out on an 8kW small hydrogen production device. The test conditions were a temperature of 29°C, a system pressure of 0.1MPa, and an alkali solution flow rate of 1.4L / min. The polarization curve test of the Ni-Co alloy electrode of Example 4 was carried out. The test results are shown in FIG. Figure 5 As shown, Ni-Co-T60 has the best hydrogen evolution performance, Ni-Co-T40 has slightly better hydrogen evolution performance than Ni-Co-T20, and the electrolysis test results are consistent with the electrochemical test results. Testing the hydrogen evolution performance of the self-made commercial-sized nickel-based hydrogen evolution electrode provides reliable data support and technical reference for the research and development of efficient and low-cost water electrolysis hydrogen evolution electrodes.

[0051] The commercial application of the produced hydrogen evolution electrode includes the application in distributed hydrogen production equipment and fuel cells: For some small distributed hydrogen production scenarios, such as small hydrogen refueling stations, energy supply stations in remote areas, etc., the 254mm diameter hydrogen evolution Ni-Co electrode can also be used in the corresponding small water electrolysis equipment. Its efficient hydrogen evolution performance can meet the demand for hydrogen in these scenarios, and the relatively small equipment size is also convenient for installation and use.

[0052] Fuel cells: In addition to precious metals Ru, Pd and Ir, non-precious metal nickel (Ni) can also be used as a hydrogen oxidation reaction (HOR) catalyst, but pure Ni has a strong H adsorption energy, which is not conducive to the desorption of intermediate products. Co and Ni form an alloy to improve the electronic structure of Ni, thereby improving the hydrogen binding energy and increasing the HOR catalytic activity, which can greatly reduce the cost of fuel cells.

[0053] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A porous nickel-cobalt hydrogen evolution catalytic electrode, characterized in that: It comprises a conductive substrate and a Ni-Co coating electroplated on the surface of the conductive substrate. The conductive substrate is any one of a foam nickel substrate, a nickel mesh substrate or an iron mesh substrate. In the Ni-Co coating, the mass percentage of each element is: 30-40% Ni, 60-70% Co.

2. A method for preparing an electroplating solution for depositing a porous nickel-cobalt hydrogen evolution catalytic electrode, characterized in that: Weigh nickel chloride hexahydrate, cobalt dichloride hexahydrate, a conductive agent, and a complexing agent respectively, add nickel chloride hexahydrate, cobalt dichloride hexahydrate, a conductive agent, and a complexing agent into deionized water in sequence, stir thoroughly to obtain a mixed solution, adjust the amount of deionized water added to ensure that the mass concentration of each substance in the mixed solution is: nickel chloride hexahydrate: 20-40 g / L, cobalt dichloride hexahydrate: 20-50 g / L, conductive agent 1-10 g / L, complexing agent: 20-60 g / L, and then adjust the pH value of the mixed solution to 2-3 by adding hydrochloric acid to obtain the desired electroplating solution.

3. The method for preparing an electroplating solution for depositing a porous nickel-cobalt hydrogen evolution catalytic electrode according to claim 2, characterized in that: The conductive agent is lithium chloride, and the complexing agent includes sodium citrate or ammonium chloride or a mixture of the two.

4. A method for electrodeposition of a porous nickel-cobalt hydrogen evolution catalytic electrode, characterized in that: The following steps are involved: (1) Pre-treating the conductive substrate; the pre-treatment comprises: rinsing the conductive substrate with deionized water, placing the conductive substrate as a cathode and an anode in an electrolyte for degreasing, and then rinsing the degreased conductive substrate with deionized water until the pH value is neutral; then performing an acid wash treatment, and finally rinsing with deionized water until the pH value of the conductive substrate is neutral, and then setting it aside for use; (2) preparing the electroplating solution according to the preparation method of claim 3; (3) The pretreated conductive substrate is used as a cathode and the graphite sheet is used as an anode, and they are immersed in the electroplating solution in step (2), and electrochemical deposition is performed by mechanical stirring. After the electroplating is completed, the plated part is immersed in deionized water to recover the electrolyte on the surface of the plated part, and then rinsed with ethanol and dried to obtain the porous nickel-cobalt hydrogen evolution catalytic electrode.

5. The method for electrodeposition of a porous nickel-cobalt hydrogen evolution catalytic electrode according to claim 4, characterized in that: In step (3), the drying temperature is 30-50°C, the drying time is 1-5 min, and the mechanical stirring rate is 200 rpm.

6. The method for electrodeposition of a porous nickel-cobalt hydrogen evolution catalytic electrode according to claim 4, characterized in that: In step (3), the temperature of the plating solution is 25°C and the current density is 30 mA / cm 2 , the electrochemical deposition time is 20-60min.

7. The method for electrodeposition of a porous nickel-cobalt hydrogen evolution catalytic electrode according to claim 4, characterized in that: The conductive body in step (1) is any one of a foam nickel substrate, a nickel mesh substrate or an iron mesh substrate.

8. The method for electrodeposition of a porous nickel-cobalt hydrogen evolution catalytic electrode according to claim 4, characterized in that: In step (3), the prepared porous nickel-cobalt hydrogen evolution catalytic electrode is further subjected to heat treatment, the heat treatment temperature is 600-900° C., the heat treatment gas atmosphere is N 2 , and the heat treatment time is 60 min.

9. The method for electrodeposition of a porous nickel-cobalt hydrogen evolution catalytic electrode according to claim 4, characterized in that: In step (1), nickel foam is selected as the substrate, with a size of 270 mm×270 mm.

10. Use of the porous nickel-cobalt hydrogen evolution catalytic electrode prepared by the method according to claim 9 in distributed hydrogen production equipment and fuel cells.

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