Preparation process method of hydrogen evolution electrode loaded with porous nickel

Abstract

The invention provides a preparation process method of a porous nickel-loaded hydrogen evolution electrode. The preparation process method of the porous nickel-loaded hydrogen evolution electrode comprises the step of loading a nickel-zinc alloy on a substrate through an electroplating process, zinc is reacted and leached through an alkaline activating solution, and the porous nickel electrode is obtained. A nickel-zinc alloy is loaded on a substrate through an electroplating process, and zinc is leached by reaction through an alkaline activating solution, so that the porous nickel electrode is obtained, and the technical problem that an efficient hydrogen evolution electrode is lacked in the prior art for hydrogen production by alkaline electrolysis of water is solved.

Description

Technical field:

[0001] The invention relates to the field of hydrogen production by water electrolysis, and in particular to a process for preparing a hydrogen evolution electrode loaded with porous nickel. Background technology:

[0002] Hydrogen production by water electrolysis is a method of producing hydrogen. By passing direct current into an electrolyzer filled with electrolyte, water molecules undergo oxygen evolution reaction (OER) at the oxygen evolution electrode (anode) to generate oxygen, and hydrogen evolution reaction (HER) at the cathode to generate hydrogen. Among them, the hydrogen evolution electrode material is the key core part of the electrolyzer. The choice of hydrogen evolution electrode material largely determines the voltage and energy consumption of the electrolyzer, which directly affects the cost. Therefore, the development of a low-cost, high-activity and high-durability hydrogen evolution electrode has important practical significance and economic benefits for the application of alkaline water electrolysis to produce hydrogen.

[0003] There is an urgent need for a method for preparing a porous nickel-loaded hydrogen evolution electrode, which will help solve the technical problem of the lack of an efficient hydrogen evolution electrode for the application of alkaline water electrolysis to hydrogen production in the prior art. Summary of the invention:

[0004] In one embodiment, the present invention provides a method for preparing a hydrogen evolution electrode loaded with porous nickel, wherein a nickel-zinc alloy is loaded on a substrate through an electroplating process, and zinc is then leached out through an alkaline activation solution to obtain a porous nickel electrode, which helps to solve the technical problem in the prior art of lacking an efficient hydrogen evolution electrode for the application of alkaline water electrolysis to hydrogen production.

[0005] The method for preparing the hydrogen evolution electrode loaded with porous nickel comprises:

[0006] The nickel-zinc alloy is loaded on the substrate by an electroplating process;

[0007] The zinc is leached out by alkaline activation solution to obtain a porous nickel electrode.

[0008] In one embodiment, the plating solution formula of the electroplating process is 10-20 g / L zinc oxide, 10-20 g / L nickel sulfate, 80-160 g / L sodium hydroxide, 10-20 g / L potassium sodium tartrate, 10-20 g / L tetraethylene pentamine, 0.5-1 g / L vanillin, 2-5 g / L sodium saccharin, and 0.05-0.2 mL / L diethylhexyl sulfate sodium salt;

[0009] Prepare solution A by mixing zinc oxide, sodium hydroxide and a small amount of water;

[0010] Nickel sulfate, sodium potassium tartrate, tetraethylenepentamine and water are prepared into solution B;

[0011] Add solution B to solution A, and add vanillin, sodium saccharin, and sodium diethylhexyl sulfate, add water to a quantitative amount, and stir evenly.

[0012] In one embodiment, before the step of loading the nickel-zinc alloy on the substrate by electroplating, the method further comprises:

[0013] The substrate is placed in degreasing liquid A and electrolyzed at a predetermined temperature to remove oil stains on the surface of the substrate. After being taken out, it is fully washed with pure water and then immersed in pickling liquid B.

[0014] In one embodiment, the substrate may be a metal plate, a perforated metal plate, a metal mesh, or a porous metal structure.

[0015] In one embodiment, the degreasing liquid A is one or a mixture of potassium hydroxide, sodium hydroxide, sodium carbonate, trisodium phosphate, and sodium silicate.

[0016] In one embodiment, the electrolytic degreasing liquid is heated to 60°C to 80°C, the conductive metal plate and the electrode substrate are placed in the electrolytic degreasing liquid, the conductive metal plate is used as the anode, the electrode substrate is used as the cathode, the power is turned on, the electrolysis voltage is controlled to 5V to 8V, the electrolysis time is 5min to 20min, and the degreased electrode substrate is obtained.

[0017] In one embodiment, the electrode substrate after degreasing is immersed in a hydrochloric acid aqueous solution with a mass fraction of 20% to 50% at a temperature of 20° C. to 40° C. for a time of 10 min to 20 min to obtain a pretreated electrode substrate.

[0018] In one embodiment, the plating solution temperature is 25°C to 40°C, a conductive metal plate is used as an anode, a pretreated electrode substrate is used as a cathode, and the distance between the electrodes is 15mm to 25mm; constant current electroplating is performed, the electroplating current density is 1A / dm2 to 3A / dm2, and the electroplating time is 30min to 60min to obtain a hydrogen evolution electrode loaded with a nickel-zinc alloy.

[0019] In one embodiment, a nickel-zinc alloy electrode is placed in an alkaline solution, and the zinc therein is leached out by the reaction of the alkaline solution with zinc, thereby obtaining a hydrogen evolution electrode loaded with porous nickel.

[0020] In one embodiment, the alkali solution may be sodium hydroxide, potassium hydroxide or other alkaline solutions, with a concentration range of 5%-30% by mass, a temperature of 20-80° C., and a leaching time of 6-24 hours. Description of the drawings:

[0021] Figure 1 It is a schematic diagram of the surface of the substrate loaded with nickel-zinc alloy after electroplating in one embodiment of the present invention;

[0022] Figure 2FIG. 1 is a schematic diagram of the surface microstructure after activation in another embodiment of the present invention. Specific embodiment:

[0023] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is described in detail below in conjunction with the accompanying drawings and specific implementation methods.

[0024] Various aspects and features of the present application are described herein with reference to the accompanying drawings.

[0025] These and other characteristics of the present application will become apparent from the following description of a preferred form of embodiment given as a non-limiting example with reference to the accompanying drawings.

[0026] It should also be understood that, although the present application has been described with reference to some specific examples, those skilled in the art will be able to realize many other equivalent forms of the present application that have the features described in the claims and are therefore within the scope of protection defined thereby.

[0027] The above and other aspects, features and advantages of the present application will become more apparent in view of the following detailed description when taken in conjunction with the accompanying drawings.

[0028] Specific embodiments of the present application are described hereinafter with reference to the accompanying drawings; however, it should be understood that the embodiments applied for are merely examples of the present application, which may be implemented in a variety of ways. Well-known and / or repeated functions and structures are not described in detail to determine the true intent based on the user's historical operations and to avoid unnecessary or redundant details that make the present application unclear. Therefore, the specific structural and functional details applied for herein are not intended to be limiting, but are merely used as the basis and representative basis for the claims to teach those skilled in the art to use the present application in a variety of ways with substantially any suitable detailed structure.

[0029] This specification may use the phrases "in one embodiment," "in another embodiment," "in yet another embodiment," or "in other embodiments," all of which may refer to one or more of the same or different embodiments according to the present application.

[0030] Figure 1 It is a schematic diagram of the surface of the substrate loaded with nickel-zinc alloy after electroplating in one embodiment of the present invention; Figure 2 FIG. 1 is a schematic diagram of the surface microstructure after activation in another embodiment of the present invention. Figure 1 and Figure 2 As shown, in one embodiment, the present invention provides a method for preparing a hydrogen evolution electrode loaded with porous nickel, and the method for preparing a hydrogen evolution electrode loaded with porous nickel comprises:

[0031] S101, a nickel-zinc alloy is loaded on a substrate through an electroplating process.

[0032] S102, leaching zinc through alkaline activation solution to obtain a porous nickel electrode.

[0033] During the electroplating process, the plating solution temperature is 25°C to 40°C, a conductive metal plate is used as an anode, a pretreated electrode substrate is used as a cathode, and the distance between the electrodes is 15mm to 25mm; constant current electroplating is used, the electroplating current density is 1A / dm2 to 3A / dm2, and the electroplating time is 30min to 60min to obtain a hydrogen evolution electrode loaded with a nickel-zinc alloy.

[0034] During the alkaline washing process, the nickel-zinc alloy electrode is placed in an alkaline solution, and the zinc therein is leached out by the reaction of the alkaline solution with zinc, thereby obtaining a hydrogen evolution electrode loaded with porous nickel.

[0035] The alkali solution can be sodium hydroxide, potassium hydroxide or other alkaline solutions, with a concentration range of 5% to 30% by mass, a temperature of 20-80° C., and a leaching time of 6 to 24 hours.

[0036] In one embodiment, the plating solution formula of the electroplating process is 10-20 g / L zinc oxide, 10-20 g / L nickel sulfate, 80-160 g / L sodium hydroxide, 10-20 g / L potassium sodium tartrate, 10-20 g / L tetraethylene pentamine, 0.5-1 g / L vanillin, 2-5 g / L sodium saccharin, and 0.05-0.2 mL / L diethylhexyl sulfate sodium salt;

[0037] Prepare solution A by mixing zinc oxide, sodium hydroxide and a small amount of water;

[0038] Nickel sulfate, sodium potassium tartrate, tetraethylenepentamine and water are prepared into solution B;

[0039] Add solution B to solution A, and add vanillin, sodium saccharin, and sodium diethylhexyl sulfate, add water to a quantitative amount, and stir evenly.

[0040] By adopting the above technical scheme, zinc oxide, sodium hydroxide and part of water are mixed to obtain a relatively uniform sodium zincate solution, a ligand, nickel sulfate and part of water are evenly mixed to form an effective coordination between the ligand and nickel ions, and then solution B is added to solution A to make the nickel ions evenly dispersed in the solution system, and the remaining chemicals and remaining water are added and mixed evenly, thereby further improving the dispersion degree of each raw material and increasing the system stability of the electroplating solution.

[0041] In one embodiment, before the step of loading the nickel-zinc alloy on the substrate by electroplating, the method further comprises:

[0042] The substrate is placed in degreasing liquid A and electrolyzed at a predetermined temperature to remove oil stains on the surface of the substrate. After being taken out, it is fully washed with pure water and then immersed in pickling liquid B.

[0043] In one embodiment, the substrate may be a metal plate, a perforated metal plate, a metal mesh, or a porous metal structure.

[0044] In one embodiment, the degreasing liquid A is one or a mixture of potassium hydroxide, sodium hydroxide, sodium carbonate, trisodium phosphate, and sodium silicate.

[0045] In one embodiment, the electrolytic degreasing liquid is heated to 60°C to 80°C, the conductive metal plate and the electrode substrate are placed in the electrolytic degreasing liquid, the conductive metal plate is used as the anode, the electrode substrate is used as the cathode, the power is turned on, the electrolysis voltage is controlled to 5V to 8V, the electrolysis time is 5min to 20min, and the degreased electrode substrate is obtained.

[0046] In one embodiment, the electrode substrate after degreasing is immersed in a hydrochloric acid aqueous solution with a mass fraction of 20% to 50% at a temperature of 20° C. to 40° C. for a time of 10 min to 20 min to obtain a pretreated electrode substrate.

[0047] In one embodiment, the plating solution temperature is 25°C to 40°C, a conductive metal plate is used as an anode, a pretreated electrode substrate is used as a cathode, and the distance between the electrodes is 15mm to 25mm; constant current electroplating is performed, the electroplating current density is 1A / dm2 to 3A / dm2, and the electroplating time is 30min to 60min to obtain a hydrogen evolution electrode loaded with a nickel-zinc alloy.

[0048] In one embodiment, a nickel-zinc alloy electrode is placed in an alkaline solution, and the zinc therein is leached out by the reaction of the alkaline solution with zinc, thereby obtaining a hydrogen evolution electrode loaded with porous nickel.

[0049] In one embodiment, the alkali solution may be sodium hydroxide, potassium hydroxide or other alkaline solutions, with a concentration range of 5%-30% by mass, a temperature of 20-80° C., and a leaching time of 6-24 hours.

[0050] Effects of the invention:

[0051] (1) The present invention provides a nickel-zinc hydrogen evolution electrode, which is prepared by a constant current electrodeposition method, has a short preparation process, and requires simple equipment;

[0052] (2) The present invention provides a nickel-zinc hydrogen evolution electrode, wherein the surface of the nickel-zinc hydrogen evolution electrode coating is rough, thereby increasing the surface area of ​​the electrode. The nickel-zinc hydrogen evolution electrode has a high catalytic hydrogen evolution activity, which is beneficial for reducing the voltage of an alkaline water electrolyzer and reducing the energy consumption of electrolysis;

[0053] (3) The present invention provides a nickel-tin hydrogen evolution electrode, which has high chemical stability in a 30% by mass KOH solution and can be used as a hydrogen evolution electrode in the alkaline water electrolysis hydrogen production industry.

[0054] Example:

[0055] Example 1

[0056] (1) Prepare the plating solution

[0057] The plating solution formula is 10g / L zinc oxide, 12g / L nickel sulfate, 100g / L sodium hydroxide, 15g / L potassium sodium tartrate, 12g / L tetraethylenepentamine, 0.5g / L vanillin, 2g / L sodium saccharin, and 0.2mL / L diethylhexyl sulfate sodium salt.

[0058] Dissolve sodium hydroxide in water that accounts for one third of the total amount of the plating solution, add zinc oxide, stir and dissolve, and prepare solution A;

[0059] Solution B is prepared by mixing nickel sulfate, sodium potassium tartrate, tetraethylenepentamine and one third of the total amount of water in the plating solution;

[0060] Slowly add the solution into solution A, keep stirring, add appropriate amount of vanillin, sodium saccharin, diethylhexyl sulfate sodium salt, add water to quantitative amount, and stir evenly.

[0061] By adopting the above technical scheme, zinc oxide, sodium hydroxide and part of water are mixed to obtain a relatively uniform sodium zincate solution, a ligand, nickel sulfate and part of water are evenly mixed to form an effective coordination between the ligand and nickel ions, and then solution B is added to solution A to make the nickel ions evenly dispersed in the solution system, and the remaining chemicals and remaining water are added and mixed evenly, thereby further improving the dispersion degree of each raw material and increasing the system stability of the electroplating solution.

[0062] (2) Pretreatment of electrode substrate

[0063] Select sodium hydroxide solution as degreasing liquid, put the conductive metal plate and electrode matrix into the electrolytic degreasing liquid, use the conductive metal plate as anode, use the electrode matrix as cathode, turn on the power, control the electrolysis voltage to 6V, and the electrolysis time to 15min to obtain the degreasing electrode matrix. After taking it out, wash it thoroughly with pure water, and soak it in a 20% hydrochloric acid aqueous solution with a soaking temperature of 40°C and a soaking time of 10min to obtain the pretreated electrode matrix.

[0064] (3) Electroplating

[0065] The plating solution temperature is 30°C, a conductive metal plate is used as the anode, a pretreated electrode substrate is used as the cathode, and the distance between the electrodes is 20 mm; constant current electroplating is used, the electroplating current density is 1A / dm2, and the electroplating time is 60 min;

[0066] (4) Alkaline washing

[0067] The electroplated electrode is placed in a potassium hydroxide solution with a mass fraction of 10% and immersed at 60° C. for 24 hours to obtain a hydrogen evolution electrode loaded with porous nickel.

[0068] The above embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention. The protection scope of the present invention is defined by the claims. Those skilled in the art may make various modifications or equivalent substitutions to the present invention within the essence and protection scope of the present invention, and such modifications or equivalent substitutions shall also be deemed to fall within the protection scope of the present invention.

Claims

1. A method for preparing a hydrogen evolution electrode loaded with porous nickel, characterized in that: The method for preparing the hydrogen evolution electrode loaded with porous nickel comprises: The nickel-zinc alloy is loaded on the substrate by an electroplating process; The zinc is leached out by alkaline activation solution to obtain a porous nickel electrode.

2. The method for preparing a hydrogen evolution electrode loaded with porous nickel according to claim 1, characterized in that: The plating solution formula of the electroplating process is 10-20 g / L zinc oxide, 10-20 g / L nickel sulfate, 80-160 g / L sodium hydroxide, 10-20 g / L potassium sodium tartrate, 10-20 g / L tetraethylenepentamine, 0.5-1 g / L vanillin, 2-5 g / L sodium saccharin, and 0.05-0.2 mL / L diethylhexyl sulfate sodium salt; Prepare solution A by mixing zinc oxide, sodium hydroxide and a small amount of water; Nickel sulfate, sodium potassium tartrate, tetraethylenepentamine and water are prepared into solution B; Add solution B to solution A, and add vanillin, sodium saccharin, and sodium diethylhexyl sulfate, add water to a quantitative amount, and stir evenly.

3. The method for preparing a hydrogen evolution electrode loaded with porous nickel according to claim 2, characterized in that: Before the step of loading the nickel-zinc alloy on the substrate by electroplating, the method further comprises: The substrate is placed in degreasing liquid A and electrolyzed at a predetermined temperature to remove oil stains on the surface of the substrate. After being taken out, it is fully washed with pure water and then immersed in pickling liquid B.

4. The method for preparing a hydrogen evolution electrode loaded with porous nickel according to claim 3, characterized in that: The substrate can be a metal plate, a perforated metal plate, a metal mesh, or a porous metal structure.

5. The method for preparing a hydrogen evolution electrode loaded with porous nickel according to claim 4, characterized in that: The degreasing liquid A is a mixture of one or more of potassium hydroxide, sodium hydroxide, sodium carbonate, trisodium phosphate and sodium silicate.

6. The method for preparing a hydrogen evolution electrode loaded with porous nickel according to claim 5, characterized in that: Heat the electrolytic degreasing liquid to 60°C to 80°C, place the conductive metal plate and the electrode substrate into the electrolytic degreasing liquid, use the conductive metal plate as the anode and the electrode substrate as the cathode, turn on the power supply, control the electrolysis voltage to 5V to 8V, and the electrolysis time to 5min to 20min to obtain the degreased electrode substrate.

7. The method for preparing a hydrogen evolution electrode loaded with porous nickel according to claim 6, characterized in that: The electrode substrate after degreasing is immersed in a hydrochloric acid aqueous solution with a mass fraction of 20% to 50%, the immersion temperature is 20° C. to 40° C., and the immersion time is 10 min to 20 min to obtain a pretreated electrode substrate.

8. The method for preparing a hydrogen evolution electrode loaded with porous nickel according to claim 7, characterized in that: The plating solution temperature is 25°C to 40°C, a conductive metal plate is used as an anode, a pretreated electrode substrate is used as a cathode, and the distance between the electrodes is 15mm to 25mm; constant current electroplating is performed, the electroplating current density is 1A / dm2 to 3A / dm2, and the electroplating time is 30min to 60min to obtain a hydrogen evolution electrode loaded with a nickel-zinc alloy.

9. The method for preparing a hydrogen evolution electrode loaded with porous nickel according to claim 8, characterized in that: The nickel-zinc alloy electrode is placed in an alkaline solution, and the zinc therein is leached out by the reaction of the alkaline solution with zinc, thereby obtaining a hydrogen evolution electrode loaded with porous nickel.

10. The method for preparing a hydrogen evolution electrode loaded with porous nickel according to claim 9, characterized in that: The alkali solution can be sodium hydroxide, potassium hydroxide or other alkaline solutions, with a concentration range of 5%-30% by mass, a temperature of 20-80° C., and a leaching time of 6-24 hours.

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