A highly corrosion-resistant nickel-based seawater electrolysis oxygen-decomposing integrated electrode and its preparation method and application

Abstract

The present invention discloses a highly corrosion-resistant nickel-based seawater electrolysis oxygen-decomposition integrated electrode, and its preparation method and application. The preparation method of the seawater electrolysis oxygen-decomposition integrated electrode comprises the following steps: S1, dispersing zirconium phosphate in water, adding an alcohol amine aqueous solution and stirring, further adding an organic amine aqueous solution to continue the reaction, and centrifuging and drying to obtain product A; S2, dispersing product A in water, adding an iron salt aqueous solution and stirring, adding a heteropoly acid aqueous solution to continue the reaction, and centrifuging and drying to obtain product B; S3, dispersing product B in an ethanol aqueous solution, adding a binder solution, coating it on a nickel substrate, and drying to obtain a highly corrosion-resistant nickel-based seawater electrolysis oxygen-decomposition integrated electrode. The highly corrosion-resistant nickel-based seawater electrolysis oxygen-decomposition integrated electrode proposed by the present invention has opened up a new path for the development of low-cost, highly active, and highly stable OER electrodes for dynamically corrosive seawater environments, and provides a sustainable technical solution for promoting the conversion of offshore wind energy into chemical energy.

Description

Technical Field

[0001] The present invention relates to the technical field of seawater electrolysis, and in particular to a highly corrosion-resistant nickel-based seawater electrolysis oxygen-decomposing integrated electrode, a preparation method thereof, and applications thereof. Background Art

[0002] As a crucial component of renewable energy development, the direct utilization of offshore wind energy offers broad prospects for the global energy transition. Against this backdrop, extracting hydrogen directly through seawater electrolysis has become a key path to achieving the clean energy vision. Compared to traditional freshwater electrolysis methods, seawater electrolysis offers numerous advantages, including convenient access to materials and abundant resources. However, the unique characteristics of the marine environment, particularly the presence of high concentrations of chloride ions (Cl⁻ ~0.5 M), present significant technical challenges to the electrolysis process.

[0003] Currently, commercial alkaline electrolyzers mostly use nickel-based anode materials, such as Raney nickel and nickel foam. However, these materials face severe chloride ion corrosion and competitive chlorine evolution reactions in seawater environments, leading to rapid failure and limiting their prospects for industrial application. Even currently advanced NiFe layered double hydroxide catalysts cannot withstand chloride ion corrosion at high current densities, resulting in irreversible structural damage and performance degradation. Recent research has attempted to construct blocking layers on the catalyst surface to mitigate chloride ion corrosion. For example, Amar A. Bhardwaj et al. [https: / / doi.org / 10.1021 / acscatal.0c04343] deposited an ultrathin silicon oxide layer on a platinum catalyst, achieving highly selective oxygen evolution reaction (OER) under seawater electrolysis conditions. This technique provides a new approach to addressing the issues of chloride corrosion and competitive chlorine evolution. However, while the coating effectively inhibits chloride ion diffusion, it also hinders the transport of water and oxygen, resulting in reduced OER performance. This "activity-stability trade-off" has become a bottleneck restricting the development of seawater electrolysis technology.

[0004] Therefore, to promote the efficient utilization of offshore wind energy resources, it is urgent to develop innovative modification strategies to enhance the inherent oxygen evolution reaction activity and stability of nickel-based materials in seawater environments to meet practical application requirements. This is not only necessary to address current technical challenges, but will also promote the large-scale application of seawater electrolysis hydrogen production technology in offshore wind energy utilization, opening up new paths for global sustainable energy development. Summary of the Invention

[0005] The present invention solves the problems existing in the prior art and provides a highly corrosion-resistant nickel-based seawater electrolysis oxygen-splitting integrated electrode, as well as its preparation method and application. The present invention constructs a layered nanomaterial that responds to alkaline electrolyte and electric field stimulation, and coats it on a nickel substrate to construct an integrated adaptive electrode, which is applied to seawater electrolysis, opening up a new path for the development of low-cost and high-performance OER electrodes for dynamic corrosive seawater environments.

[0006] The present invention is achieved through the following technical solutions:

[0007] The first object of the present invention is to provide a method for preparing a highly corrosion-resistant nickel-based seawater electrolysis oxygen-splitting integrated electrode, comprising the following steps:

[0008] S1, dispersing zirconium phosphate in water to obtain a zirconium phosphate aqueous solution, then adding an alcoholamine aqueous solution with stirring, further adding an organic amine aqueous solution to continue the reaction, and finally centrifuging and drying to obtain product A;

[0009] S2, dispersing the product A obtained in S1 in water, subsequently adding an iron salt aqueous solution with stirring, further adding a heteropoly acid aqueous solution to continue the reaction, and finally centrifugally drying to obtain product B, i.e., a zirconium phosphate-based nanomaterial;

[0010] S3. Disperse the product B obtained in S2 in an ethanol aqueous solution, add a binder solution, mix well, then apply it on a nickel substrate, and dry it to obtain the highly corrosion-resistant nickel-based seawater electrolysis oxygen-splitting integrated electrode.

[0011] The present invention constructs a layered nanomaterial that responds to alkaline electrolyte and electric field stimulation, and coats it on a nickel substrate to construct an integrated adaptive electrode. During the electrolysis process, the layered nanomaterial releases active species in situ and reconstructs the nickel foam interface, reconstructing the nickel foam interface into an anti-chlorine armor rich in active sites. The layered nanomaterial proposed in the present invention can achieve adaptive optimization of the catalytic surface to the working conditions, thereby promoting the OER activity and durability of the nickel foam electrode in real seawater. The invention includes three major elements (such as Figure 1 As shown): (1) Construction of “energy storage layer”: Synthesis of zirconium phosphate-based nanomaterials as active species (Fe 3+ 、MoO4 2- PO4 3- and ZrO3 2- ) modular reserve. (2) Strong base triggered release: Under strong base solution conditions, ZDD-Fe-PMo12 nanosheets dissociate to form Fe 3+ 、MoO4 2- PO4 3- and ZrO3 2- (3) Electric field mediated self-optimization interface: Under anodic polarization, the Fe released by the dissociation of zirconium phosphate-based nanomaterials3+ It can significantly promote the OER activity of nickel substrate, while ZrO3 2- PO4 3- and MoO4 2- Anions are concentrated on the anode surface due to electrostatic effects, forming an anion shielding layer to repel Cl - This enables a zero-gap electrolyzer with an integrated anode armored with zirconium phosphate-based nanomaterials to operate at 500 mA cm in an alkaline seawater environment. -2 The industrial current density can be operated for more than 300 h.

[0012] Preferably, in step S1, the alcoholamine in the aqueous alcoholamine solution is selected from one or more of diglycolamine, triethanolamine and diethanolamine, and the mass ratio of alcoholamine to zirconium phosphate is 0.1:1-0.5:1; the organic amine in the aqueous organic amine solution is selected from one or more of diethylenetriamine, tetraethylenepentamine and polyethyleneimine, and the mass ratio of organic amine to zirconium phosphate is 0.2:1-0.8:1.

[0013] More preferably, in step S1, the mass ratio of the alcoholamine to the zirconium phosphate is 0.250:1-0.375:1; and the mass ratio of the organic amine to the zirconium phosphate is 0.25:1-0.50:1.

[0014] Preferably, in step S1, the mass concentration of the zirconium phosphate aqueous solution is 0.02-0.05 g / mL, the mass concentration of the alcoholamine aqueous solution is 0.050-0.075 g / mL, and the mass concentration of the organic amine aqueous solution is 0.02-0.04 g / mL.

[0015] Further preferably, in step S1, the mass concentration of the zirconium phosphate aqueous solution is 0.03 g / mL.

[0016] In step S1, zirconium phosphate is dispersed in water to obtain a zirconium phosphate aqueous solution, followed by adding an alcohol amine aqueous solution and stirring for 0.5-1.5 h, further adding an organic amine aqueous solution and continuing the reaction for 0.5-1.5 h, and finally centrifugally drying to obtain product A.

[0017] Preferably, the specific steps of step S2 are: dispersing the product A obtained in S1 in water, the mass volume ratio of product A to water is 0.01-0.02 g / mL, then adding an iron salt aqueous solution and stirring for 0.1-0.8 h, the mass ratio of iron in the iron salt aqueous solution to product A is 0.03:1-0.10:1, further adding a heteropoly acid aqueous solution and continuing the reaction for 6-18 h, the mass ratio of heteropoly acid in the heteropoly acid aqueous solution to product A is 0.5:1-1.5:1, and finally centrifuging and drying to obtain product B, that is, zirconium phosphate-based nanomaterial.

[0018] Further preferably, the mass volume ratio of product A to water is 0.015 g / mL, the mass ratio of iron in the iron salt aqueous solution to product A is 0.112:3-0.224:3, and the heteropolyacid aqueous solution is further added to continue the reaction, and the mass ratio of heteropolyacid in the heteropolyacid aqueous solution to product A is 2:3-3.65:3.

[0019] Preferably, the iron salt is selected from one of ferric nitrate, ferric chloride, and ferrous sulfate, the molar concentration of the iron salt aqueous solution is 0.3-0.8 mol / L, and the heteropolyacid is selected from one of phosphotungstic acid, phosphomolybdic acid, and silicomolybdic acid. The mass concentration of the heteropolyacid in the heteropolyacid aqueous solution is 0.05-0.09125 g / mL.

[0020] Step S3 comprises the following steps: dispersing the product B obtained in S2 in an ethanol aqueous solution at a mass volume ratio of 0.001-0.002 g / mL to the ethanol aqueous solution; adding a binder solution; continuing ultrasonication for 0.2-0.8 h to mix uniformly; then coating the solution on a nickel substrate; and drying the solution to obtain the highly corrosion-resistant nickel-based seawater electrolytic oxygen evolution integrated electrode. The volume ratio of ethanol to water in the ethanol aqueous solution is 1:1.

[0021] Preferably, in step S3, the binder solution is a Nafion solution, the mass ratio of Nafion to product B in the binder solution is 0.002:1-0.003:1, and the unit area loading of product B on the nickel substrate is 0.1-10 mg / cm 2 The mass concentration of Nafion solution is 5%.

[0022] More preferably, the unit area loading of product B on the nickel substrate is 0.4 mg / cm 2 .

[0023] The nickel substrate proposed by the present invention includes nickel foam, nickel mesh, nickel felt, nickel iron foam and other nickel substrates.

[0024] The second object of the present invention is to provide a highly corrosion-resistant nickel-based seawater electrolysis oxygen-splitting integrated electrode prepared by the preparation method.

[0025] A third object of the present invention is to provide the application of the highly corrosion-resistant nickel-based seawater electrolysis oxygen-stripping integrated electrode in seawater electrolysis. The seawater electrolysis oxygen-stripping integrated electrode proposed in the present invention can be applied to wind-powered hydrogen production. Specifically, the highly corrosion-resistant nickel-based seawater electrolysis oxygen-stripping integrated electrode is used as the anode for seawater electrolysis, and a carbon rod is used as the cathode, and wind power is used to drive seawater electrolysis.

[0026] The present invention also protects a method for controlling the structure of a highly corrosion-resistant nickel-based seawater electrolysis oxygen electrode, wherein a Hg / HgO electrode is used as a reference electrode, a platinum electrode is used as a counter electrode, and the highly corrosion-resistant nickel-based seawater electrolysis oxygen integrated electrode is used as a working electrode.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) The zirconium phosphate-based nanomaterials synthesized in the present invention will undergo dissociation and recombination in alkaline electrolytes, and can trigger a dynamic adaptive process during the electrolysis process, thereby achieving adaptive optimization of the catalytic surface to the working conditions, significantly improving the OER activity and chlorine corrosion resistance of nickel-based materials, and extending the stability of nickel-based electrodes at industrial current density.

[0029] (2) Zirconium phosphate-based nanomaterials are easy to synthesize and can be easily loaded on nickel substrates, which is conducive to large-scale production. This meets the needs of large-scale industrial seawater hydrogen production applications and opens up a new path for the development of low-cost and high-performance OER electrodes for dynamic corrosive seawater environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 : Schematic diagram of the design of the present invention.

[0031] Figure 2 : Actual picture of zirconium phosphate-based nanomaterials obtained by amplifying the production of Example 1.

[0032] Figure 3 : SEM image of the integrated electrode obtained in Example 1.

[0033] Figure 4 : Device stability diagram of electrolyzing alkaline seawater using the electrodes of Example 1 and Comparative Example 7 as anodes of a zero-gap seawater electrolyzer.

[0034] Figure 5 : Schematic diagram of the application of the electrode prepared in Example 1 in wind energy-driven hydrogen production. DETAILED DESCRIPTION

[0035] The present invention will be described in further detail below with reference to the examples. These examples are intended to illustrate the present invention only and are not intended to limit the scope of the present invention. Experimental methods in the following examples, where specific conditions are not specified, generally follow conventional conditions in the art or conditions recommended by the manufacturer; raw materials and reagents used, unless otherwise specified, are considered to be commercially available through conventional markets.

[0036] Example 1

[0037] A method for preparing a highly corrosion-resistant nickel-based seawater electrolytic oxygen separation integrated electrode comprises the following steps:

[0038] S1. Disperse 8 g of zirconium phosphate in 260 mL of deionized water, then add 40 mL of a diglycolamine aqueous solution (containing 3 g of diglycolamine) and stir for 1 h. Further add 100 mL of a diethylenetriamine aqueous solution (containing 2 g of diethylenetriamine) and continue the reaction for 1 h. Finally, centrifuge and air dry to obtain product A.

[0039] S2. Weigh 3 g of product A prepared in S1 and disperse it in 196 mL of deionized water. Then add 4 mL of ferric chloride solution (0.5 mol / L) and stir for 0.5 h. Further add 40 mL of phosphomolybdic acid aqueous solution (containing 3.65 g of phosphomolybdic acid) and continue the reaction for 12 h. Finally, centrifuge and air dry to obtain product B, i.e., zirconium phosphate-based nanomaterial.

[0040] S3, weigh 20 mg of product B prepared in S2 and disperse it in 20 mL of ethanol and water (ethanol and water ratio is 1:1), add 0.8 mL of Nafion binder solution, continue ultrasonication for 0.5 h, and then apply it on a 20 cm 2 The integrated electrode was obtained by drying with air at 60℃ on nickel foam.

[0041] The zirconium phosphate-based nanomaterial obtained by the scaled-up production of Example 1 was digitally photographed ( Figure 2 The integrated electrode obtained in Example 1 was characterized by SEM, which showed that the porous skeleton was loaded with layered nanosheets ( Figure 3 ).

[0042] Example 2

[0043] A method for preparing a highly corrosion-resistant nickel-based seawater electrolytic oxygen separation integrated electrode comprises the following steps:

[0044] S1. Disperse 8 g of zirconium phosphate in 260 mL of deionized water, then add 40 mL of a diglycolamine aqueous solution (containing 3 g of diglycolamine) and stir for 1 h. Further add 100 mL of a diethylenetriamine aqueous solution (containing 2 g of diethylenetriamine) and continue the reaction for 1 h. Finally, centrifuge and air dry to obtain the product.

[0045] S2. Weigh 3 g of the product prepared in S1 and disperse it in 196 mL of deionized water. Then, add 4 mL of ferric nitrate solution (0.5 mol / L) and stir for 0.5 h. Further add 40 mL of phosphotungstic acid aqueous solution (containing 3.65 g of phosphomolybdic acid) and continue the reaction for 12 h. Finally, centrifuge and air dry to obtain the product, i.e., zirconium phosphate-based nanomaterial.

[0046] S3, weigh 40 mg of the product prepared in S2 and disperse it in 20 mL of ethanol and water (the ratio of ethanol to water is 1:1), add 0.8 mL of Nafion binder solution, continue ultrasonication for 0.5 h, and then apply it on a 20 cm 2 The integrated electrode was obtained by drying with air at 60℃ on nickel foam.

[0047] Example 3

[0048] A method for controlling the structure of a highly corrosion-resistant nickel-based seawater electrolytic oxygen-splitting electrode and its application, comprising the following steps:

[0049] S1. Disperse 8 g of zirconium phosphate in 260 mL of deionized water, then add 40 mL of a diethanolamine aqueous solution (containing 2 g of diethanolamine) and stir for 1 h. Further add 100 mL of a polyethyleneimine aqueous solution (containing 4 g of polyethyleneimine) and continue the reaction for 1 h. Finally, centrifuge and air dry to obtain the product.

[0050] S2. Weigh 3 g of the product prepared in S1 and disperse it in 196 mL of deionized water. Then add 8 mL of ferrous sulfate solution (0.5 mol / L) and stir for 0.5 h. Further add 40 mL of silicomolybdic acid aqueous solution (containing 2 g of phosphomolybdic acid) and continue the reaction for 12 h. Finally, centrifuge and air dry to obtain the product, i.e., zirconium phosphate-based nanomaterial.

[0051] S3, weigh 20 mg of the product prepared in S2 and disperse it in 20 mL of ethanol and water (the ratio of ethanol to water is 1:1), add 0.8 mL of Nafion binder solution, continue ultrasonication for 0.5 h, and then apply it on a 20 cm 2 The integrated electrode was obtained by drying with air at 60℃ on nickel felt.

[0052] Example 4

[0053] Same as Example 1, except that:

[0054] In step S1, the mass concentration of the zirconium phosphate aqueous solution is 0.02 g / mL, and an alcoholamine aqueous solution is added and stirred for 0.5 h, the mass concentration of the alcoholamine aqueous solution is 0.050 g / mL, the alcoholamine in the alcoholamine aqueous solution is specifically triethanolamine, and the mass ratio of triethanolamine to zirconium phosphate is 0.2:1; an organic amine aqueous solution is added and the reaction is continued for 0.5 h, the mass concentration of the organic amine aqueous solution is 0.02 g / mL, the organic amine in the organic amine aqueous solution is specifically tetraethylene pentamine, and the mass ratio of tetraethylene pentamine to zirconium phosphate is 0.2:1, and finally centrifugation and drying are performed to obtain product A.

[0055] In step S2, the product A obtained in step S1 is dispersed in water, the mass volume ratio of product A to water is 0.01 g / mL, and then an aqueous ferric nitrate solution is added and stirred for 0.1 h, the mass ratio of iron in the aqueous ferric nitrate solution to product A is 0.03:1, and an aqueous heteropolyacid solution is further added to continue the reaction for 6 h, the mass ratio of heteropolyacid in the aqueous heteropolyacid solution to product A is 0.5:1, and finally centrifuged and dried to obtain product B.

[0056] In step S3, the binder solution was added, ultrasonicated for 0.2 h, mixed evenly, and then coated on the nickel substrate. The unit area loading of product B on the nickel substrate was 0.1 mg / cm 2 , and drying to obtain a highly corrosion-resistant nickel-based seawater electrolysis oxygen integrated electrode.

[0057] Example 5

[0058] Same as Example 1, except that:

[0059] In step S1, the mass concentration of the zirconium phosphate aqueous solution is 0.05 g / mL, and an alcoholamine aqueous solution is added and stirred for 1.5 hours. The mass concentration of the alcoholamine aqueous solution is 0.075 g / mL, the alcoholamine in the alcoholamine aqueous solution is specifically triethanolamine, and the mass ratio of triethanolamine to zirconium phosphate is 0.5:1; an organic amine aqueous solution is added and the reaction is continued for 1.5 hours. The mass concentration of the organic amine aqueous solution is 0.04 g / mL, the organic amine in the organic amine aqueous solution is specifically tetraethylene pentamine, and the mass ratio of tetraethylene pentamine to zirconium phosphate is 0.8:1. Finally, the product A is obtained by centrifugation and drying.

[0060] In step S2, the product A obtained in step S1 is dispersed in water, the mass volume ratio of product A to water is 0.02 g / mL, and then an aqueous ferric nitrate solution is added and stirred for 0.8 h, the mass ratio of iron in the aqueous ferric nitrate solution to product A is 0.10:1, and an aqueous heteropolyacid solution is further added to continue the reaction for 18 h, the mass ratio of heteropolyacid in the aqueous heteropolyacid solution to product A is 1.5:1, and finally centrifuged and dried to obtain product B.

[0061] In step S3, the binder solution was added, ultrasonicated for 0.8 h, mixed evenly, and then coated on the nickel substrate. The unit area loading of product B on the nickel substrate was 10 mg / cm 2 , and drying to obtain a highly corrosion-resistant nickel-based seawater electrolysis oxygen integrated electrode.

[0062] Comparative Example 1

[0063] The difference between Comparative Example 1 and Example 1 is that no diglycolamine is added to S1, and the amount of diethylenetriamine added is 5 g. The rest is the same as Example 1.

[0064] Comparative Example 2

[0065] The difference between Comparative Example 2 and Example 1 is that no diethylenetriamine is added to S1, and the amount of diglycolamine added is 5 g. The rest is the same as Example 1.

[0066] Comparative Example 3

[0067] The difference between Comparative Example 3 and Example 1 is that diglycolamine and diethylenetriamine are not added to S1. The rest is the same as Example 1.

[0068] Comparative Example 4

[0069] Comparative Example 4 differs from Example 1 in that no phosphomolybdic acid is added to S2, and the amount of ferric chloride added is 3.974 g. The rest is the same as Example 1.

[0070] Comparative Example 5

[0071] The difference between Comparative Example 5 and Example 1 is that no ferric chloride is added to S2, and the amount of phosphomolybdic acid added is 3.974 g. The rest is the same as Example 1.

[0072] Comparative Example 6

[0073] The difference between Comparative Example 6 and Example 1 is that diglycolamine and diethylenetriamine are not added to S1, and ferric chloride and phosphomolybdic acid are not added to S2. The rest is the same as Example 1.

[0074] Comparative Example 7

[0075] Nickel foam without any treatment.

[0076] The integrated electrodes prepared in Examples 1-3 and Comparative Examples 1-7 were tested for seawater electrolysis OER. The electrochemical tests were conducted on an electrochemical workstation (CHI660E) using a standard three-electrode system, with the Hg / HgO electrode as the reference electrode, the platinum electrode as the counter electrode, the products prepared in Examples 1-3 and Comparative Examples 1-7 as the working electrode (cut to a geometric area of 1 cm × 1 cm), and the electrolyte being 1 M KOH + seawater. 50 mA cm -2 The overpotential under current density was compared, and the results are shown in Table 1. Scaled preparation of zirconium phosphate-based nanomaterials in Example 1 ( Figure 2 ).

[0077] Table 1 The results of the examples and comparative examples in alkaline seawater electrolyte at 50 mA cm -2 Comparison of overpotential data under current density

[0078]

[0079] As can be seen from Table 1, in the process of three-electrode OER test (electrolyte is 1M KOH + seawater), Example 1 only needs 313 mV overpotential to reach 50 mA / cm 2 Compared with unloaded nickel foam, the zirconium phosphate-based nanomaterial prepared by the technology of the present invention can significantly improve the OER activity of nickel foam, and the nanomaterial can be prepared at the hundred-gram level ( Figure 2 ), and the zirconium phosphate-based nanomaterials were effectively loaded on the surface of the nickel substrate ( Figure 3 ), laying a solid foundation for the development of industrial-grade seawater electrolysis technology. In addition, the comparison of the catalyst activity of Example 1 and Comparative Examples 1-3 shows that there is a synergistic effect between alcoholamine and organic amine. And the comparison of the catalyst activity of Example 1 and Comparative Examples 4-5 shows that there is also a synergistic effect between iron ions and heteropolyacids. In addition, the electrodes of Example 1 and Comparative Example 7 were used as the anode of the zero-gap seawater electrolysis cell to conduct device stability tests for the electrolysis of alkaline seawater. The test results are as follows: Figure 4 As shown. It can be seen that the integrated electrode prepared in Example 1 has a high -2 The chronoamperometric curve under the current density shows that the electrolysis of seawater lasts for up to 300 h with almost no attenuation; while the commercial nickel foam electrode of Comparative Example 7 completely fails in less than 4 h, which shows that the patented technology can significantly improve the operating stability of the seawater electrolyzer.

[0080] In addition, the electrode prepared in Example 1 was used as the anode for electrolyzing seawater, and the carbon rod was used as the cathode. Wind-driven seawater electrolysis was used ( Figure 5 ), it can be seen that the highly corrosion-resistant nickel-based seawater electrolysis oxygen integrated electrode provided by the present invention can be well coupled with renewable energy to produce green hydrogen.

[0081] In summary, the highly corrosion-resistant nickel-based seawater electrolysis oxygen integrated electrode provided by the present invention has opened up a new path for the development of low-cost, highly active, and highly stable OER electrodes to cope with dynamic corrosive seawater environments, and provides a sustainable technical solution for promoting the conversion of offshore wind energy into chemical energy.

[0082] The description of the above embodiments is only used to help understand the technical solution and core ideas of the present invention. It should be pointed out that for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principles of the present invention. These improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a highly corrosion-resistant nickel-based integrated electrode for electrolysis of alkaline seawater and oxygen evolution, characterized in that: The steps include: S1, dispersing zirconium phosphate in water to obtain a zirconium phosphate aqueous solution, then adding an alcoholamine aqueous solution and stirring, wherein the alcoholamine in the alcoholamine aqueous solution is selected from one or more of diglycolamine, triethanolamine and diethanolamine, further adding an organic amine aqueous solution to continue the reaction, wherein the organic amine in the organic amine aqueous solution is selected from one or more of diethylenetriamine, tetraethylenepentamine and polyethyleneimine, and finally centrifuging and drying to obtain product A; S2, dispersing the product A obtained in S1 in water, then adding an aqueous solution of an iron salt with stirring, wherein the iron salt is selected from one of ferric nitrate, ferric chloride and ferrous sulfate, further adding an aqueous solution of a heteropoly acid to continue the reaction, wherein the heteropoly acid is selected from one of phosphomolybdic acid and silicomolybdic acid, and finally centrifuging and drying to obtain a product B, i.e., a zirconium phosphate-based nanomaterial; S3. Disperse the product B obtained in S2 in an ethanol aqueous solution, add a binder solution, mix well, then apply it on a nickel substrate, and dry it to obtain the highly corrosion-resistant nickel-based electrolysis alkaline seawater oxygen evolution integrated electrode.

2. The preparation method according to claim 1, characterized in that In step S1, the mass ratio of the alcohol amine to the zirconium phosphate is 0.1:1-0.5:1; the mass ratio of the organic amine to the zirconium phosphate is 0.2:1-0.8:

1.

3. The preparation method according to claim 2, characterized in that In step S1, the mass ratio of the alcoholamine to the zirconium phosphate is 0.250:1-0.375:1; the mass ratio of the organic amine to the zirconium phosphate is 0.25:1-0.50:

1.

4. The preparation method according to claim 1 or 2, characterized in that In step S1, the mass concentration of the zirconium phosphate aqueous solution is 0.02-0.05 g / mL, the mass concentration of the alcoholamine aqueous solution is 0.050-0.075 g / mL, and the mass concentration of the organic amine aqueous solution is 0.02-0.04 g / mL.

5. The preparation method according to claim 1 or 2, characterized in that The specific steps of step S2 are: dispersing the product A obtained in S1 in water, the mass volume ratio of product A to water is 0.01-0.02 g / mL, then adding an iron salt aqueous solution and stirring for 0.1-0.8 h, the mass ratio of iron in the iron salt aqueous solution to product A is 0.03:1-0.10:1, further adding a heteropoly acid aqueous solution and continuing the reaction for 6-18 h, the mass ratio of heteropoly acid in the heteropoly acid aqueous solution to product A is 0.5:1-1.5:1, and finally centrifuging and drying to obtain product B, that is, zirconium phosphate-based nanomaterial.

6. The preparation method according to claim 1, characterized in that The molar concentration of the iron salt aqueous solution is 0.3-0.8 mol / L.

7. The preparation method according to claim 1 or 2, characterized in that In step S3, the binder solution is a Nafion solution, the mass ratio of Nafion to product B in the binder solution is 0.002:1-0.005:1, and the unit area loading of product B on the nickel substrate is 0.1-10 mg / cm 2 .

8. A highly corrosion-resistant nickel-based integrated electrode for electrolysis of alkaline seawater and oxygen evolution prepared by the preparation method according to any one of claims 1 to 7.

9. Use of the highly corrosion-resistant nickel-based integrated electrode for electrolysis of alkaline seawater and oxygen evolution according to claim 8 in the electrolysis of alkaline seawater.

10. A method for controlling the structure of a highly corrosion-resistant nickel-based electrolytic alkaline seawater oxygen evolution electrode, characterized in that: The Hg / HgO electrode is used as the reference electrode, the platinum electrode is used as the counter electrode, and the highly corrosion-resistant nickel-based electrolysis alkaline seawater oxygen evolution integrated electrode described in claim 8 is used as the working electrode.

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