Cathode material with nickel substrate loaded with nickel-molybdenum-cobalt alloy and preparation method and application of cathode material

Abstract

The invention belongs to the technical field of hydrogen production through water electrolysis, and provides a cathode material of a nickel substrate loaded nickel-molybdenum-cobalt alloy and a preparation method and application of the cathode material. The preparation method comprises the following steps: mixing a nickel source, a molybdenum source, a cobalt source, conductive salt, a complexing agent, a surfactant and water to obtain an electroplating solution; taking a nickel substrate as a cathode and a titanium sheet as an anode, and carrying out electro-deposition reaction in an electroplating solution to obtain a nickel-molybdenum-cobalt self-supporting cathode material; and sequentially carrying out annealing and current excitation on the nickel-molybdenum-cobalt self-supporting cathode material. The transition metal is adopted to prepare the cathode material, so that the use of precious metals such as platinum is avoided, and the production cost is reduced; a porous structure is formed through electro-deposition, so that more active sites are provided for the cathode material; in the cathode material of the nickel substrate loaded with the nickel-molybdenum-cobalt alloy, a synergistic electronic effect exists among Ni, Co and Mo, and the cathode material also shows high catalytic activity on hydrogen production by water electrolysis under an acidic condition, and has high stability and Faraday efficiency at the same time.

Description

Technical Field

[0001] The invention relates to the technical field of hydrogen production by electrolysis of water, and in particular to a cathode material of a nickel substrate loaded with a nickel-molybdenum-cobalt alloy, and a preparation method and application thereof. Background Art

[0002] People's increasing concern about energy crisis and environmental issues has prompted the rapid development of renewable energy to replace traditional fossil fuels. Hydrogen energy has the characteristics of high energy density, low carbon, and a wide range of application scenarios. It is considered to be the cleanest and most sustainable energy. Therefore, efficient hydrogen production methods are an important part of realizing hydrogen energy applications. Compared with traditional hydrogen production technology, water electrolysis hydrogen production is an efficient, environmentally friendly and sustainable hydrogen production technology, but there are still many challenges.

[0003] In order to make the electrolysis of water to produce hydrogen more energy-efficient and efficient, and to improve the efficiency of converting electrical energy into chemical energy, it is necessary to vigorously develop and design catalysts with superior performance. The use of catalysts can accelerate the reaction kinetics, improve the conversion efficiency, and reduce the overpotential by reducing the activation energy, thereby improving the efficiency of electrolysis of water to produce hydrogen. The precious metal platinum is currently recognized as the most effective and stable electrolysis catalyst, but its cost makes it impossible to carry out large-scale commercial applications. At present, people have invested a lot of energy to explore low-cost and efficient electrolysis catalysts, such as various nickel-based compounds (sulfides, nitrides, carbides, oxides and phosphides), transition metal materials (Ni, Co, Mo, Fe), bimetallic materials (Ni-Mo, Ni-Co, Co-Mo), etc., among which transition metals and their complexes have good performance, and the preparation of electrolysis catalysts by transition metals has shown great potential to replace precious metal platinum-based catalysts.

[0004] Among transition metals, Ni-based catalysts have good catalytic activity for hydrogen production from water electrolysis, with the additional advantages of high specific surface area nanostructure and low cost, and the simple composite of two metals to form a bimetallic catalyst is a direct method to promote hydrogen production from water electrolysis. Nickel alloys follow different catalytic activity trends in the hydrogen production reaction from water electrolysis: Ni-Mo>Ni-Co>Ni-Fe>Ni-Cr.

[0005] Therefore, how to make improvements based on Ni-Mo-based catalysts and further improve the catalytic activity for hydrogen production by water electrolysis has broad application prospects. Summary of the invention

[0006] The purpose of the present invention is to provide a cathode material of a nickel substrate loaded with a nickel-molybdenum-cobalt alloy and a preparation method and application thereof in view of the deficiencies in the prior art.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] The present invention provides a method for preparing a cathode material of a nickel substrate loaded with a nickel-molybdenum-cobalt alloy, comprising the following steps:

[0009] 1) mixing a nickel source, a molybdenum source, a cobalt source, a conductive salt, a complexing agent, a surfactant and water to obtain an electroplating solution;

[0010] 2) using the nickel substrate as the cathode and the titanium sheet as the anode, an electrodeposition reaction is carried out in an electroplating solution to obtain a nickel-molybdenum-cobalt self-supporting cathode material;

[0011] 3) The nickel-molybdenum-cobalt self-supporting cathode material is annealed and current excited in sequence to obtain a cathode material of nickel substrate loaded with nickel-molybdenum-cobalt alloy.

[0012] Preferably, the nickel source in step 1) is one or more of nickel acetate, nickel chloride, nickel fluoride, nickel bromide, nickel nitrate and nickel sulfate;

[0013] The molybdenum source is one or more of sodium molybdate, potassium molybdate, lithium molybdate and ammonium molybdate;

[0014] The cobalt source is one or more of cobalt acetate, cobalt chloride, cobalt fluoride, cobalt bromide, cobalt sulfate and cobalt nitrate;

[0015] The conductive salt is one or more of nickel chloride, nickel fluoride and nickel bromide;

[0016] The complexing agent is boric acid, phosphoric acid, citric acid or lactic acid;

[0017] The surfactant is sodium dodecyl sulfate, sodium lauryl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, dioctyl sodium sulfosuccinate or sodium dodecylbenzene sulfonate.

[0018] Preferably, in step 1), the molar ratio of the nickel source, the molybdenum source and the cobalt source is 11-13:1:0.2-1.

[0019] Preferably, in step 1), the molar ratio of the molybdenum source, the conductive salt, the complexing agent and the surfactant is 1:2-6:30-40:0.01-0.1, and the molar volume ratio of the molybdenum source and water is 1.9 mmol:50-70 mL.

[0020] Preferably, the current of the electrodeposition reaction in step 2) is 1 to 100 mA, and the time of the electrodeposition reaction is 0.5 to 5 h.

[0021] Preferably, the annealing temperature in step 3) is 100-1000° C., the annealing time is 1-10 h, and the heating rate to the annealing temperature is 1-10° C. / min.

[0022] Preferably, the annealing in step 3) is carried out in a mixed atmosphere of argon and hydrogen, and the volume fraction of argon in the mixed atmosphere is 5-10%.

[0023] Preferably, the current excitation in step 3) is constant current excitation, the current of the constant current excitation is 1 to 5A, and the time of the constant current excitation is 1 to 100 minutes.

[0024] The invention also provides a cathode material of nickel substrate loaded with nickel-molybdenum-cobalt alloy prepared by the preparation method.

[0025] The present invention also provides the use of the cathode material of the nickel substrate loaded with nickel-molybdenum-cobalt alloy in the electrolysis of water to produce hydrogen under acidic conditions.

[0026] Beneficial effects of the present invention:

[0027] The present invention adopts transition metals to prepare cathode materials for electrolysis of water to produce hydrogen, thus avoiding the use of precious metals such as platinum and reducing production costs; a porous structure is formed by electrodeposition to provide more active sites for the cathode material of the nickel substrate loaded with nickel-molybdenum-cobalt alloy; in the cathode material of the nickel substrate loaded with nickel-molybdenum-cobalt alloy of the present invention, a synergistic electronic effect exists between Ni, Co and Mo, and the cathode material also exhibits high catalytic activity for electrolysis of water to produce hydrogen under acidic conditions, and at the same time has high stability and Faraday efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 is a flow chart of the preparation method of the present invention;

[0029] Figure 2 is a scanning electron microscope image of the nickel substrate of Example 1;

[0030] Figure 3 This is a scanning electron microscope image of the nickel-molybdenum-cobalt self-supporting cathode material of Example 1;

[0031] Figure 4 This is a scanning electron microscope image of the cathode material of the nickel substrate loaded with nickel-molybdenum-cobalt alloy prepared in Example 1;

[0032] Figure 5 This is a scanning electron microscope image of the cathode material prepared in Comparative Example 1;

[0033] Figure 6 The hydrogen evolution activity of different cathode materials in water electrolysis;

[0034] Figure 7 The stability of the cathode material of nickel substrate loaded with nickel-molybdenum-cobalt alloy prepared in Example 1 in hydrogen production by electrolysis of water;

[0035] Figure 8 The cyclic voltammetry curve of the cathode material of nickel substrate loaded with nickel-molybdenum-cobalt alloy prepared in Example 1;

[0036] Fig. 9 The linear sweep voltammetric curves of the cathode material of nickel substrate loaded with nickel-molybdenum-cobalt alloy and Pt / C prepared in Examples 1 to 3. DETAILED DESCRIPTION

[0037] The present invention provides a method for preparing a cathode material of a nickel substrate loaded with a nickel-molybdenum-cobalt alloy, comprising the following steps:

[0038] 1) mixing a nickel source, a molybdenum source, a cobalt source, a conductive salt, a complexing agent, a surfactant and water to obtain an electroplating solution;

[0039] 2) using the nickel substrate as the cathode and the titanium sheet as the anode, an electrodeposition reaction is carried out in an electroplating solution to obtain a nickel-molybdenum-cobalt self-supporting cathode material;

[0040] 3) The nickel-molybdenum-cobalt self-supporting cathode material is annealed and current excited in sequence to obtain a cathode material of nickel substrate loaded with nickel-molybdenum-cobalt alloy.

[0041] In the present invention, the nickel source in step 1) is preferably one or more of nickel acetate, nickel chloride, nickel fluoride, nickel bromide, nickel nitrate and nickel sulfate;

[0042] The molybdenum source is preferably one or more of sodium molybdate, potassium molybdate, lithium molybdate and ammonium molybdate;

[0043] The cobalt source is preferably one or more of cobalt acetate, cobalt chloride, cobalt fluoride, cobalt bromide, cobalt sulfate and cobalt nitrate;

[0044] The conductive salt is preferably one or more of nickel chloride, nickel fluoride and nickel bromide;

[0045] The complexing agent is preferably boric acid, phosphoric acid, citric acid or lactic acid;

[0046] The surfactant is preferably sodium dodecyl sulfate, sodium lauryl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, dioctyl sodium sulfosuccinate or sodium dodecylbenzene sulfonate.

[0047] In the present invention, the molar ratio of the nickel source, molybdenum source and cobalt source in step 1) is preferably 11-13:1:0.2-1, more preferably 11.5-12.5:1:0.3-0.8, and more preferably 12:1:0.5.

[0048] In the present invention, the molar ratio of the molybdenum source, conductive salt, complexing agent and surfactant in step 1) is preferably 1:2-6:30-40:0.01-0.1, more preferably 1:3-5:33-38:0.03-0.08, and more preferably 1:4:35:0.053; the molar volume ratio of the molybdenum source and water is preferably 1.9 mmol:50-70 mL, more preferably 1.9 mmol:55-65 mL, and more preferably 1.9 mmol:60 mL.

[0049] In the present invention, stirring is preferably performed during the mixing process of step 1), and the stirring speed is preferably 450-550 r / min, more preferably 500 r / min; the mixing temperature is preferably 55-65°C, more preferably 60°C.

[0050] In the present invention, the nickel substrate in step 2) is preferably a pretreated nickel substrate, and the nickel substrate is preferably a nickel mesh, a nickel sheet, a nickel foam or a nickel alloy sheet, and the pretreatment preferably includes ultrasonic cleaning and drying; the reagents used for ultrasonic cleaning are preferably hydrochloric acid, anhydrous ethanol and water in sequence, and the concentration of hydrochloric acid is preferably 0.5-2 mol / L, and more preferably 0.8 mol / L; the frequency of the ultrasonic cleaning is independently preferably 20-50 kHz, and more preferably 40 kHz, and the time of the ultrasonic cleaning is independently preferably 30-60 min, and more preferably 45 min; the drying temperature is preferably 55-65°C, and more preferably 60°C, and the drying time is preferably 30-100 min, and more preferably 70 min.

[0051] In the present invention, the anode in step 2) is preferably two titanium sheets, which are connected by wires and are respectively placed on both sides of the cathode.

[0052] In the present invention, the current of the electrodeposition reaction in step 2) is preferably 1-100 mA, more preferably 10-80 mA, and more preferably 30-60 mA; the time of the electrodeposition reaction is preferably 0.5-5 h, more preferably 1-4 h, and more preferably 2-3 h.

[0053] In the present invention, in step 3), the nickel-molybdenum-cobalt self-supporting cathode material is preferably rinsed and dried first, and then annealed and current excited in sequence; the reagent used for the rinsing is preferably water, the drying is preferably vacuum drying, the vacuum drying temperature is preferably 55-65°C, and more preferably 60°C; the vacuum degree of vacuum drying is preferably 0-0.2kPa, and more preferably 0.1kPa; the vacuum drying time is preferably 2-8h, and more preferably 6h.

[0054] In the present invention, the annealing temperature in step 3) is preferably 100-1000°C, more preferably 200-800°C, and more preferably 400-600°C; the annealing time is preferably 1-10h, more preferably 3-8h, and more preferably 5h; the heating rate to the annealing temperature is preferably 1-10°C / min, more preferably 3-8°C / min, and more preferably 5°C / min.

[0055] In the present invention, the annealing in step 3) is preferably carried out in a mixed atmosphere of argon and hydrogen, and the volume fraction of argon in the mixed atmosphere is preferably 5-10%, more preferably 6-9%, and more preferably 7-8%.

[0056] In the present invention, the current excitation in step 3) is preferably constant current excitation, and the current of constant current excitation is preferably 1-5A, more preferably 2-4A, and more preferably 3A; the time of constant current excitation is preferably 1-100min, more preferably 20-80min, and more preferably 40-60min.

[0057] The invention also provides a cathode material of nickel substrate loaded with nickel-molybdenum-cobalt alloy prepared by the preparation method.

[0058] The present invention also provides the use of the cathode material of the nickel substrate loaded with nickel-molybdenum-cobalt alloy in the electrolysis of water to produce hydrogen under acidic conditions.

[0059] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0060] Example 1

[0061] Mix 22.8 mmol nickel sulfate hexahydrate, 1.9 mmol ammonium molybdate tetrahydrate, 1.9 mmol cobalt sulfate hexahydrate, 7.6 mmol nickel chloride hexahydrate, 66.5 mmol boric acid, 0.1007 mmol sodium dodecyl sulfate and 60 mL deionized water, stir at 60° C. and 500 r / min until completely dissolved to obtain an electroplating solution.

[0062] A 1cm×1cm nickel mesh was placed in 0.8mol / L hydrochloric acid, and ultrasonically cleaned at a frequency of 40kHz for 45min. Then, it was placed in anhydrous ethanol, and ultrasonically cleaned at a frequency of 40kHz for 45min. Finally, it was placed in water, and ultrasonically cleaned at a frequency of 40kHz for 45min. After cleaning, the nickel mesh was dried at 60°C for 70min to obtain a nickel substrate.

[0063] The nickel substrate and two titanium sheets are immersed in the electroplating solution, the nickel substrate serves as the cathode, and the two titanium sheets serve as the anode. The two titanium sheets are connected by wires and placed on both sides of the nickel substrate to form a two-electrode system. The constant current method is used to electroplate at 10 mA for 0.5 h, and a nickel-molybdenum-cobalt ternary material is formed on the cathode surface by in-situ growth, which is a nickel-molybdenum-cobalt self-supporting cathode material.

[0064] After the electrodeposition is completed, the cathode is rinsed with water and dried at 60°C and 0.1 kPa for 6 hours, and then placed in a tube furnace, and in a mixed atmosphere of argon and hydrogen (the volume fraction of argon in the mixed atmosphere is 5%), the tube furnace is heated to 100°C at a rate of 5°C / min, and kept at 100°C for 5 hours for annealing. The cathode material after annealing is placed under a 3A current for constant current excitation for 60 minutes to obtain a cathode material of a nickel substrate loaded with a nickel-molybdenum-cobalt alloy.

[0065] The cathode material of the nickel substrate loaded with nickel-molybdenum-cobalt alloy prepared in this embodiment is marked as Ni 12 MoCo@NS.

[0066] Figure 2 This is a scanning electron microscope image of the nickel substrate of Example 1.

[0067] Figure 3 This is a scanning electron microscope image of the nickel-molybdenum-cobalt self-supporting cathode material of Example 1.

[0068] Figure 4 This is a scanning electron microscope image of the cathode material of the nickel substrate loaded with nickel-molybdenum-cobalt alloy prepared in Example 1.

[0069] Example 2

[0070] The cobalt sulfate hexahydrate in Example 1 was modified to 0.38 mmol, and the rest was the same as in Example 1.

[0071] The cathode material of the nickel substrate loaded with nickel-molybdenum-cobalt alloy prepared in this embodiment is marked as Ni 12 MoCo 0.2 @NS.

[0072] Example 3

[0073] The cobalt sulfate hexahydrate in Example 1 was modified to 0.95 mmol, and the rest was the same as in Example 1.

[0074] The cathode material of the nickel substrate loaded with nickel-molybdenum-cobalt alloy prepared in this embodiment is marked as Ni 12 MoCo 0.5 @NS.

[0075] Example 4

[0076] Mix 20.9 mmol nickel chloride, 1.9 mmol potassium molybdate, 0.57 mmol cobalt acetate, 3.8 mmol nickel bromide, 76 mmol phosphoric acid, 0.019 mmol sodium dioctyl succinate sulfonate and 50 mL deionized water, stir at 55° C. and 550 r / min until completely dissolved to obtain an electroplating solution.

[0077] A 1cm×1cm nickel mesh was placed in 0.8mol / L hydrochloric acid, and ultrasonically cleaned at a frequency of 40kHz for 45min. Then, it was placed in anhydrous ethanol, and ultrasonically cleaned at a frequency of 40kHz for 45min. Finally, it was placed in water, and ultrasonically cleaned at a frequency of 40kHz for 45min. After cleaning, the nickel mesh was dried at 55°C for 70min to obtain a nickel substrate.

[0078] The nickel substrate and two titanium sheets are immersed in the electroplating solution, the nickel substrate serves as the cathode, and the two titanium sheets serve as the anode. The two titanium sheets are connected by wires and placed on both sides of the nickel substrate to form a two-electrode system. The constant current method is used to perform electrodeposition at 80 mA for 2 hours, and a nickel-molybdenum-cobalt ternary material is formed by in-situ growth on the cathode surface, which is a nickel-molybdenum-cobalt self-supporting cathode material.

[0079] After the electrodeposition is completed, the cathode is rinsed with water and dried at 55°C and 0.1 kPa for 6 hours, and then placed in a tube furnace, and in a mixed atmosphere of argon and hydrogen (the volume fraction of argon in the mixed atmosphere is 10%), the tube furnace is heated to 800°C at a rate of 1°C / min, and kept at 800°C for 1 hour for annealing. The cathode material after annealing is placed under a current of 1A for constant current excitation for 80 minutes to obtain a cathode material of nickel-molybdenum-cobalt alloy loaded on a nickel substrate.

[0080] Example 5

[0081] 24.7 mmol nickel nitrate, 1.9 mmol sodium molybdate, 1.52 mmol cobalt bromide, 11.4 mmol nickel fluoride, 57 mmol citric acid, 0.19 mmol sodium dodecylbenzene sulfonate and 70 mL deionized water were mixed, and stirred at 65° C. and 450 r / min until completely dissolved to obtain an electroplating solution.

[0082] A 1cm×1cm nickel mesh was placed in 0.8mol / L hydrochloric acid, and ultrasonically cleaned at a frequency of 40kHz for 45min. Then, it was placed in anhydrous ethanol, and ultrasonically cleaned at a frequency of 40kHz for 45min. Finally, it was placed in water, and ultrasonically cleaned at a frequency of 40kHz for 45min. After cleaning, the nickel mesh was dried at 65°C for 70min to obtain a nickel substrate.

[0083] The nickel substrate and two titanium sheets are immersed in the electroplating solution, the nickel substrate serves as the cathode, and the two titanium sheets serve as the anode. The two titanium sheets are connected by wires and placed on both sides of the nickel substrate to form a two-electrode system. The constant current method is used to perform electrodeposition at 60 mA for 5 hours, and a nickel-molybdenum-cobalt ternary material is formed on the cathode surface by in-situ growth, which is a nickel-molybdenum-cobalt self-supporting cathode material.

[0084] After the electrodeposition is completed, the cathode is rinsed with water and dried at 65°C and 0.1 kPa for 6 hours, and then placed in a tube furnace, and the tube furnace is heated to 400°C at a rate of 10°C / min in a mixed atmosphere of argon and hydrogen (the volume fraction of argon in the mixed atmosphere is 8%), and annealed at 400°C for 10 hours. The annealed cathode material is placed under a 5A current for constant current excitation for 20 minutes to obtain a cathode material of a nickel substrate loaded with a nickel-molybdenum-cobalt alloy.

[0085] Comparative Example 1

[0086] The cobalt sulfate hexahydrate in Example 1 is omitted, and the rest is the same as Example 1.

[0087] The cathode material prepared in this comparative example is marked as Ni 12 Mo@NS.

[0088] Figure 5 This is a scanning electron microscope image of the cathode material prepared in Comparative Example 1.

[0089] Comparative Example 2

[0090] Mix 22.8 mmol nickel sulfate hexahydrate, 1.9 mmol ammonium molybdate tetrahydrate, 1.9 mmol cobalt sulfate hexahydrate, 7.6 mmol nickel chloride hexahydrate, 66.5 mmol boric acid, 0.1007 mmol sodium dodecyl sulfate and 60 mL deionized water, stir at 60° C. and 500 r / min until completely dissolved to obtain an electroplating solution.

[0091] A 1cm×1cm nickel mesh was placed in 0.8mol / L hydrochloric acid, and ultrasonically cleaned at a frequency of 40kHz for 45min. Then, it was placed in anhydrous ethanol, and ultrasonically cleaned at a frequency of 40kHz for 45min. Finally, it was placed in water, and ultrasonically cleaned at a frequency of 40kHz for 45min. After cleaning, the nickel mesh was dried at 60°C for 70min to obtain a nickel substrate.

[0092] The nickel substrate and two titanium sheets are immersed in the electroplating solution, the nickel substrate serves as the cathode, and the two titanium sheets serve as the anode. The two titanium sheets are connected by wires and placed on both sides of the nickel substrate to form a two-electrode system. The constant current method is used to electroplate at 10 mA for 0.5 h, and a nickel-molybdenum-cobalt ternary material is formed on the cathode surface by in-situ growth, which is a nickel-molybdenum-cobalt self-supporting cathode material.

[0093] The cathode materials of Examples 1 to 3, Comparative Examples 1 to 2 and the platinum-based material Pt / C were tested for hydrogen evolution activity in water electrolysis. The test method is as follows: a 0.5 mol / L H2SO4 aqueous solution is placed in an electrolytic cell, and Examples 1 to 3, Comparative Examples 1 to 2 or Pt / C are used as working electrodes, platinum sheets are used as counter electrodes, and mercury / mercurous sulfate is used as reference electrodes. The potential range is controlled to be -0.656 to -1.556 V (with the reversible hydrogen electrode RHE as the standard zero potential). The linear sweep voltammetry method is used to test the hydrogen evolution activity of each cathode material at 10 mA / cm 2 , 50mA / cm 2 , 100mA / cm 2 under the overpotential for hydrogen evolution.

[0094] Figure 6 is the hydrogen evolution activity of different cathode materials in water electrolysis. Figure 6 It can be seen that the cathode materials prepared in Examples 1 to 3 have a 2 The hydrogen evolution overpotentials under the conditions are 104mV, 84mV, and 70mV, respectively, which have the same hydrogen evolution activity as Pt / C (Pt / C at 10mA / cm 2 The hydrogen evolution overpotential under the condition of 60mV); Comparative Examples 1 to 2 at 10mA / cm 2 The hydrogen evolution overpotentials under the conditions are 136 mV and 124 mV respectively, and the hydrogen evolution activity needs to be improved.

[0095] Figure 7 The stability of the cathode material of nickel-molybdenum-cobalt alloy loaded on the nickel substrate prepared in Example 1 in the electrolysis of water to produce hydrogen. Figure 7 It can be seen that the cathode material of the nickel substrate loaded with nickel-molybdenum-cobalt alloy in Example 1 is 2 After being used for 100 hours, the original hydrogen evolution potential is still maintained. This indicates that the cathode material of the nickel substrate loaded with nickel-molybdenum-cobalt alloy of the present invention has excellent stability in hydrogen production by electrolysis of water.

[0096] Figure 8 The cyclic voltammetry curve of the cathode material of nickel substrate loaded with nickel-molybdenum-cobalt alloy prepared in Example 1.

[0097] Fig. 9 The linear sweep voltammetric curves of the cathode material of nickel substrate loaded with nickel-molybdenum-cobalt alloy and Pt / C prepared in Examples 1 to 3.

[0098] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a cathode material of a nickel substrate loaded with a nickel-molybdenum-cobalt alloy, characterized in that: The following steps are included: 1) mixing a nickel source, a molybdenum source, a cobalt source, a conductive salt, a complexing agent, a surfactant and water to obtain an electroplating solution; 2) using the nickel substrate as the cathode and the titanium sheet as the anode, an electrodeposition reaction is carried out in an electroplating solution to obtain a nickel-molybdenum-cobalt self-supporting cathode material; 3) The nickel-molybdenum-cobalt self-supporting cathode material is annealed and current excited in sequence to obtain a cathode material of nickel substrate loaded with nickel-molybdenum-cobalt alloy.

2. The preparation method according to claim 1, characterized in that: Step 1) The nickel source is one or more of nickel acetate, nickel chloride, nickel fluoride, nickel bromide, nickel nitrate and nickel sulfate; The molybdenum source is one or more of sodium molybdate, potassium molybdate, lithium molybdate and ammonium molybdate; The cobalt source is one or more of cobalt acetate, cobalt chloride, cobalt fluoride, cobalt bromide, cobalt sulfate and cobalt nitrate; The conductive salt is one or more of nickel chloride, nickel fluoride and nickel bromide; The complexing agent is boric acid, phosphoric acid, citric acid or lactic acid; The surfactant is sodium dodecyl sulfate, sodium lauryl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, dioctyl sodium sulfosuccinate or sodium dodecylbenzene sulfonate.

3. The preparation method according to claim 1 or 2, characterized in that: In step 1), the molar ratio of the nickel source, the molybdenum source and the cobalt source is 11-13:1:0.2-1.

4. The preparation method according to claim 3, characterized in that: Step 1) The molar ratio of the molybdenum source, the conductive salt, the complexing agent and the surfactant is 1:2-6:30-40:0.01-0.1, and the molar volume ratio of the molybdenum source and water is 1.9 mmol:50-70 mL.

5. The preparation method according to claim 4, characterized in that: Step 2) The current of the electrodeposition reaction is 1 to 100 mA, and the time of the electrodeposition reaction is 0.5 to 5 hours.

6. The preparation method according to claim 4 or 5, characterized in that: Step 3) The annealing temperature is 100-1000° C., the annealing time is 1-10 hours, and the heating rate to the annealing temperature is 1-10° C. / min.

7. The preparation method according to claim 6, characterized in that: Step 3) The annealing is carried out in a mixed atmosphere of argon and hydrogen, and the volume fraction of argon in the mixed atmosphere is 5-10%.

8. The preparation method according to claim 7, characterized in that: Step 3) The current excitation is constant current excitation, the current of the constant current excitation is 1 to 5A, and the time of the constant current excitation is 1 to 100 minutes.

9. A cathode material of nickel substrate loaded with nickel-molybdenum-cobalt alloy obtained by the preparation method according to any one of claims 1 to 8.

10. Use of the cathode material of nickel substrate loaded with nickel-molybdenum-cobalt alloy as claimed in claim 9 in producing hydrogen by electrolysis of water under acidic conditions.

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