Corrosion-resistant and efficient non-iridium nickel-based catalyst and preparation method thereof

Abstract

The invention relates to a corrosion-resistant and efficient non-iridium nickel-based catalyst and a preparation method thereof. The catalyst is prepared by taking sulfur-fluorine double-coordination induced electron rearrangement modified nickel-cobalt layered double hydroxide as a main body, compounding small organic molecule 2, 4-dihydroxy phenylacetamide containing o-p-phenolic hydroxyl and acylamino, introducing a carbon source, a reducing agent and a stabilizing additive, and carrying out solution dispersion, drying and heat treatment. According to the method, through flexible coordination of a sulfur element and strong electronegativity induction of a fluorine element, directional regulation and control of an electronic structure of the catalyst are realized, and a stable electron transmission channel is formed under the action of an organic small molecule interface. The obtained catalyst shows low overpotential, low Tafel slope and small charge transfer resistance in alkaline electrolyte, and has excellent corrosion resistance and long-term electrochemical stability. The catalyst provided by the invention is superior to a traditional single modified system in activity, conductivity and structural stability, and is suitable for the fields of high-efficiency water electrolysis hydrogen production and other alkaline electrocatalytic reactions.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrochemical catalysis and new energy materials, and particularly relates to a corrosion-resistant and efficient non-iridium-nickel-based catalyst and a preparation method thereof. BACKGROUND

[0002] Water electrolysis is an important technical approach to realize efficient conversion and storage of renewable energy, and has important significance in building a clean energy system. In the alkaline water electrolysis system, the oxygen evolution reaction kinetics is slow, and the charge transfer resistance is large, which is the key link to limit the overall electrolysis efficiency. Traditional noble metal oxide catalysts such as IrO2 and RuO2 have high catalytic activity, but they are scarce in resources, high in cost and easy to be deactivated in strong alkaline environment, which is difficult to meet the needs of large-scale industrial application.

[0003] In recent years, nickel-based and nickel-cobalt double metal layered double hydroxides have attracted widespread attention due to their rich metal active sites and high electrical conductivity, and are considered to be one of the most potential non-noble metal oxygen evolution catalysts. However, traditional nickel-based and nickel-cobalt double metal layered double hydroxides still have problems such as poor structural stability, insufficient exposure of active centers and limited electronic transmission capacity during long-term reaction, especially in high alkaline environment, which is easy to cause interlayer peeling and metal ion dissolution, resulting in degradation of catalytic performance. The single distribution of surface electronic state cannot effectively regulate the reaction intermediates, which further affects the catalytic efficiency.

[0004] Existing modification methods mainly include nitrogen, phosphorus or sulfur single doping and carbon coating modification, etc. These strategies improve the electrochemical performance of nickel-based and nickel-cobalt double metal layered double hydroxides to some extent, but the regulation effect on electronic structure is limited, and it is still difficult to maintain long-term stable work in strong alkaline conditions. Especially, there is a lack of bifunctional coordination modification strategy for metal center electronic rearrangement and stable organic-inorganic interface construction method, so that the corrosion resistance and cycle stability of the catalyst are still insufficient.

[0005] Therefore, it is urgent to develop a non-iridium nickel-based catalyst with a new electronic structure regulation mechanism and a stable interface structure, to significantly improve the alkaline resistance and structural stability while enhancing the utilization rate of catalytic active sites through innovative double coordination modification method and organic small molecule complex strategy, so as to realize the synergistic improvement of efficient water electrolysis hydrogen production. SUMMARY

[0006] To overcome the problems of poor corrosion resistance, low electron transport efficiency, and insufficient structural stability of non-precious metal catalysts in alkaline systems mentioned above, the present invention aims to provide a corrosion-resistant and highly efficient non-iridium nickel-based catalyst and its preparation method. The present invention employs a sulfur-fluorine dual-coordination-induced electron rearrangement modification method to structurally regulate nickel-cobalt layered double hydroxides, and introduces 2,4-dihydroxyphenylacetamide, an organic small molecule containing ortho- and para-phenolic hydroxyl groups and amide groups, to construct a stable organic-inorganic composite interface through hydrogen bonding and coordination. Simultaneously, a carbon source, reducing agent, and stabilizing agent are combined to form a synergistic system of conductivity and corrosion resistance, thereby achieving precise control of the catalyst's electronic structure and improved long-term stability. The present invention exhibits high catalytic activity, strong resistance to alkaline corrosion, excellent structural stability, and a simple preparation process.

[0007] The objective of this invention can be achieved through the following technical solutions: A corrosion-resistant and highly efficient non-iridium nickel-based catalyst comprises the following raw materials in parts by weight: 100 parts of nickel-cobalt layered double hydroxide modified by sulfur-fluorine dual coordination induced electron rearrangement; 5-15 parts of 2,4-dihydroxyphenylacetamide; 10-20 parts of carbon source; 3-8 parts of reducing agent; and 2-6 parts of stabilizing agent; wherein the 2,4-dihydroxyphenylacetamide is an organic small molecule containing ortho- and para-phenolic hydroxyl groups and amide groups.

[0008] Optionally, the nickel-cobalt layered double hydroxide modified by sulfur-fluorine dual coordination induced electron rearrangement comprises the following raw materials in parts by weight: 20-40 parts of nickel nitrate hexahydrate; 10-30 parts of cobalt nitrate hexahydrate; 5-15 parts of thioacetamide; 3-10 parts of ammonium fluoride; 5-20 parts of urea; and 100-200 parts of deionized water.

[0009] Optionally, the preparation method of the nickel-cobalt layered double hydroxide modified by sulfur-fluorine dual coordination induced electron rearrangement includes the following steps: (1) Add nickel nitrate hexahydrate, cobalt nitrate hexahydrate, thioacetamide, ammonium fluoride and urea to deionized water and mix evenly to obtain a mixture; (2) Heat the mixture to react and let it stand to form a precipitate; (3) The precipitate was washed and dried to obtain nickel-cobalt layered double hydroxide modified by sulfur-fluorine dual coordination induced electron rearrangement.

[0010] Optionally, the reaction conditions for step (1) are magnetic stirring at room temperature for 30 to 60 minutes.

[0011] Optionally, the reaction conditions for step (2) are to react at 80-90°C for 8-10 hours.

[0012] Optionally, the reaction conditions for step (3) are drying at 60-70°C for 6-8 hours.

[0013] Optionally, the carbon source is a mixture of glucose and citric acid in a mass ratio of 2:1; the reducing agent is a mixture of sodium borohydride and ascorbic acid in a mass ratio of 1:1; and the stabilizing agent is a mixture of polyvinylpyrrolidone and sodium citrate in a mass ratio of 3:1.

[0014] Optionally, a method for preparing a corrosion-resistant and highly efficient non-iridium nickel-based catalyst includes the following steps: S1, a nickel-cobalt layered double hydroxide modified by sulfur-fluorine dual coordination induced electron rearrangement is dispersed in an ethanol-water mixed solution, and 2,4-dihydroxyphenylacetamide is added to obtain a solution; S2, add carbon source, reducing agent and stabilizing agent to solution, mix well and then dry to obtain solid; S3 involves heat-treating the solid to obtain a corrosion-resistant and highly efficient non-iridium nickel-based catalyst.

[0015] Optionally, the reaction conditions for step S1 are stirring at 60-80°C for 4-6 hours; the drying conditions for step S2 are freeze-drying at low temperature for 8-10 hours; and the heat treatment conditions for step S3 are heating at 300-350°C under a nitrogen atmosphere for 2-3 hours.

[0016] The beneficial effects of this invention are: This invention achieves synergistic regulation of the electron density and local electric field of the metal center in NiCo layered double hydroxides through sulfur-fluorine dual-coordination-induced electron rearrangement modification, forming a stable Ni–S–Co–F multi-coordination network structure, which significantly improves the catalyst's electronic conductivity and corrosion resistance. The introduction of the small organic molecule 2,4-dihydroxyphenylacetamide to construct a dense organic-inorganic interfacial film on the inorganic layer surface enhances interfacial bonding and structural stability, enabling the catalyst to maintain high activity and long-term stability even in strongly alkaline electrolysis environments. Attached Figure Description

[0017] The invention will now be further described with reference to the accompanying drawings.

[0018] Figure 1 The infrared contrast spectra of nickel-cobalt layered double hydroxides and nickel-cobalt layered double hydroxides modified by sulfur-fluorine dual coordination induced electron rearrangement are shown. Figure 2 Line graph comparing overpotential test results for samples with different ratios; Figure 3 Line graph comparing Tafel slope test results for samples with different ratios; Figure 4 Line graph comparing charge transfer resistance test results of samples with different ratios; Figure 5 Line graph comparing the potential drift test results of samples with different ratios; Figure 6 Line graph comparing the test results of double-layer capacitance values ​​of samples with different ratios. Detailed Implementation

[0019] The present invention will be further described below with reference to specific embodiments. However, the present invention is not limited to the following embodiments. Equivalent adjustments made without departing from the spirit and essence of the present invention should also be considered to fall within the protection scope of the present invention.

[0020] Example 1 The purpose of this embodiment is to verify the effect of sulfur-fluorine dual coordination modification on the regulation of the electronic structure and the enhancement of the catalyst's resistance to alkali corrosion under high ratio conditions.

[0021] S1, weigh 40 parts of nickel nitrate hexahydrate, 30 parts of cobalt nitrate hexahydrate, 15 parts of thioacetamide, 10 parts of ammonium fluoride, and 20 parts of urea, add them to 200 parts of deionized water and stir evenly. Then place them in a reaction vessel and react at 90°C for 10 hours. After cooling, centrifuge, wash and dry to obtain nickel-cobalt layered double hydroxide modified by sulfur-fluorine dual coordination induced electron rearrangement. S2, 100 parts of the obtained nickel-cobalt layered double hydroxide were dispersed in an ethanol-water mixture, and 15 parts of 2,4-dihydroxyphenylacetamide, 20 parts of carbon source, 8 parts of reducing agent, and 6 parts of stabilizing agent were added. The carbon source was composed of glucose and citric acid in a mass ratio of 2:1, the reducing agent was composed of sodium borohydride and ascorbic acid in a mass ratio of 1:1, and the stabilizing agent was composed of polyvinylpyrrolidone and sodium citrate in a mass ratio of 3:1. The mixture was stirred at 80°C for 6 hours, and after being mixed evenly, it was freeze-dried for 10 hours to obtain a solid precursor. S3. The precursor was placed in a nitrogen atmosphere and heated at 350°C for 2.5 hours to obtain a corrosion-resistant and highly efficient non-iridium nickel-based catalyst.

[0022] Example 2 The purpose of this embodiment is to verify the overall balance between activity and structural stability of the catalyst under moderate ratio conditions.

[0023] S1, weigh 30 parts of nickel nitrate hexahydrate, 20 parts of cobalt nitrate hexahydrate, 10 parts of thioacetamide, 6 parts of ammonium fluoride, and 12 parts of urea, add them to 150 parts of deionized water and stir evenly. React at 85°C for 8 hours, cool, centrifuge, wash and dry at 65°C for 6 hours to obtain nickel-cobalt layered double hydroxide modified by sulfur-fluorine dual coordination induced electron rearrangement; Figure 1 Infrared spectroscopy showed that the nickel-cobalt layered double hydroxide modified by sulfur-fluorine dual coordination induced electron rearrangement exhibited high activity at 3380 cm⁻¹. -1 The O–H absorption peak at 1550 cm⁻¹ shows a slight red shift and enhancement, indicating enhanced hydrogen bonding. -1The appearance of new N–H and S–O–Ni / Co vibrational peaks at 1230 cm⁻¹ indicates that sulfur successfully participated in metal coordination. -1 The C–N / C–O–Ni / Co absorption peaks demonstrate that small organic molecules form stable bonds with the metal layer surface, 970 cm⁻¹. -1 and 830cm -1 The new peaks correspond to Ni–F / Co–F and S–O bonds, respectively, verifying the dual coordination effect of fluorine and sulfur. (500 cm⁻¹) -1 The presence of Ni / Co–S / Ni / Co–F–Ni / Co vibrational peaks nearby indicates the formation of a stable bridging structure. The overall changes suggest that the sulfur-fluorine dual coordination-induced electron rearrangement successfully constructed multiple coordination active sites, enhancing structural stability and electronic conductivity. S2, 100 parts of the obtained nickel-cobalt layered double hydroxide were dispersed in an ethanol-water mixture, and 10 parts of 2,4-dihydroxyphenylacetamide, 15 parts of carbon source, 5 parts of reducing agent, and 4 parts of stabilizing agent were added. The carbon source was composed of glucose and citric acid in a mass ratio of 2:1, the reducing agent was composed of sodium borohydride and ascorbic acid in a mass ratio of 1:1, and the stabilizing agent was composed of polyvinylpyrrolidone and sodium citrate in a mass ratio of 3:1. The mixture was stirred at 70°C for 5 hours, and then freeze-dried for 9 hours to obtain a solid precursor. S3. The precursor was heated at 325°C for 2 hours under a nitrogen atmosphere to obtain a non-iridium nickel-based catalyst with balanced performance.

[0024] Example 3 The purpose of this embodiment is to verify the preservation of catalyst structural integrity and basic catalytic performance under low-ratio conditions.

[0025] S1, weigh 20 parts of nickel nitrate hexahydrate, 10 parts of cobalt nitrate hexahydrate, 5 parts of thioacetamide, 3 parts of ammonium fluoride, and 5 parts of urea, add them to 100 parts of deionized water and stir evenly. React at 80°C for 8 hours, cool, centrifuge and wash, and dry at 60°C for 6 hours to obtain nickel-cobalt layered double hydroxide modified by sulfur-fluorine dual coordination induced electron rearrangement. S2, 100 parts of the obtained nickel-cobalt layered double hydroxide were dispersed in an ethanol-water mixture, and 5 parts of 2,4-dihydroxyphenylacetamide, 10 parts of carbon source, 3 parts of reducing agent, and 2 parts of stabilizing agent were added. The carbon source was composed of glucose and citric acid in a mass ratio of 2:1, the reducing agent was composed of sodium borohydride and ascorbic acid in a mass ratio of 1:1, and the stabilizing agent was composed of polyvinylpyrrolidone and sodium citrate in a mass ratio of 3:1. The mixture was stirred at 60°C for 4 hours and then freeze-dried for 8 hours to obtain a solid precursor. S3. The precursor was heated at 300°C for 2 hours under a nitrogen atmosphere to obtain a non-iridium nickel-based catalyst with a stable structure and basic catalytic activity.

[0026] Comparative Example 1 The purpose of this comparative example is to verify the changes in catalyst performance under sulfur coordination modification alone.

[0027] S1, weigh 30 parts of nickel nitrate hexahydrate, 20 parts of cobalt nitrate hexahydrate, 10 parts of thioacetamide, 0 parts of ammonium fluoride, and 12 parts of urea, add them to 150 parts of deionized water and stir evenly. React at 85°C for 8 hours, cool, centrifuge, wash and dry at 65°C for 6 hours to obtain a sulfur-cobalt layered double hydroxide. S2, 100 parts of the obtained nickel-cobalt layered double hydroxide were dispersed in an ethanol-water mixture, and 10 parts of 2,4-dihydroxyphenylacetamide, 15 parts of carbon source, 5 parts of reducing agent, and 4 parts of stabilizing agent were added. The carbon source was composed of glucose and citric acid in a mass ratio of 2:1, the reducing agent was composed of sodium borohydride and ascorbic acid in a mass ratio of 1:1, and the stabilizing agent was composed of polyvinylpyrrolidone and sodium citrate in a mass ratio of 3:1. The mixture was stirred at 70°C for 5 hours, and then freeze-dried for 9 hours to obtain a solid precursor. S3, the precursor was heated at 325°C for 2 hours under a nitrogen atmosphere to obtain a non-iridium nickel-based catalyst prepared under sulfur coordination modification conditions only.

[0028] Comparative Example 2 The purpose of this comparative example is to verify the changes in catalyst performance under fluorine coordination modification alone.

[0029] S1, weigh 30 parts of nickel nitrate hexahydrate, 20 parts of cobalt nitrate hexahydrate, 0 parts of thioacetamide, 6 parts of ammonium fluoride, and 12 parts of urea, add them to 150 parts of deionized water and stir evenly. React at 85°C for 8 hours, cool, centrifuge, wash and dry at 65°C for 6 hours to obtain fluorine-cobalt layered double hydroxide. S2, 100 parts of the obtained nickel-cobalt layered double hydroxide were dispersed in an ethanol-water mixture, and 10 parts of 2,4-dihydroxyphenylacetamide, 15 parts of carbon source, 5 parts of reducing agent, and 4 parts of stabilizing agent were added. The carbon source was composed of glucose and citric acid in a mass ratio of 2:1, the reducing agent was composed of sodium borohydride and ascorbic acid in a mass ratio of 1:1, and the stabilizing agent was composed of polyvinylpyrrolidone and sodium citrate in a mass ratio of 3:1. The mixture was stirred at 70°C for 5 hours, and then freeze-dried for 9 hours to obtain a solid precursor. S3, the precursor was heated at 325°C for 2 hours under a nitrogen atmosphere to obtain a non-iridium nickel-based catalyst prepared under fluorine coordination modification only.

[0030] Comparative Example 3 The purpose of this comparative example is to verify the changes in catalyst performance when organic small molecule interfacial components are removed.

[0031] S1, weigh 30 parts of nickel nitrate hexahydrate, 20 parts of cobalt nitrate hexahydrate, 10 parts of thioacetamide, 6 parts of ammonium fluoride, and 12 parts of urea, add them to 150 parts of deionized water and stir evenly. React at 85°C for 8 hours, cool, centrifuge, wash and dry at 65°C for 6 hours to obtain a nickel-cobalt layered double hydroxide modified by sulfur-fluorine dual coordination. S2, 100 parts of the obtained nickel-cobalt layered double hydroxide were dispersed in an ethanol-water mixture without the addition of 2,4-dihydroxyphenylacetamide, and 15 parts of carbon source, 5 parts of reducing agent, and 4 parts of stabilizing agent were added. The carbon source was a mixture of glucose and citric acid in a mass ratio of 2:1, the reducing agent was a mixture of sodium borohydride and ascorbic acid in a mass ratio of 1:1, and the stabilizing agent was a mixture of polyvinylpyrrolidone and sodium citrate in a mass ratio of 3:1. After stirring at 70°C for 5 hours, the mixture was freeze-dried for 9 hours to obtain a solid precursor. S3, the precursor was heated at 325°C for 2 hours under a nitrogen atmosphere to obtain a non-iridium nickel-based catalyst without an organic small molecule interface.

[0032] Performance testing 1. Linear sweep voltammetry A three-electrode system was used to evaluate the oxygen evolution reaction (OER) activity of the catalyst. The electrolyte was a 1 mol / L KOH solution. A glassy carbon electrode or nickel foam was used as the working electrode, Hg / HgO as the reference electrode, and a platinum mesh as the counter electrode. The catalyst was dispersed into an ink and then drop-coated onto the surface of the working electrode, with a loading controlled at 5–10 μg / cm². During testing, a linear scan was performed at a scan rate of 5 mV / s within the range of 1.0–1.75 V. The current density versus potential curves were recorded, and the overpotential values ​​at different current densities were read to characterize the catalytic activity of the sample.

[0033] 2. Tafel Slope Test To analyze the reaction kinetics of the catalyst, current density and overpotential data were extracted from the low-polarization region of the linear sweep voltammetry curve. The curves were plotted and linearly fitted to calculate the Tafel slope. A smaller slope indicates a faster charge transfer rate and better reaction kinetics. This test was used to compare the effects of different coordination modification methods and the organic small molecule interface on the reaction rate.

[0034] 3. Electrochemical impedance spectroscopy (EIS) The charge transport performance at the catalyst interface was analyzed using an alternating current impedance method. Tests were conducted under stable current conditions, with a frequency range of 100 kHz to 0.1 Hz and an AC signal amplitude controlled between 5 and 10 mV. Key parameters such as solution resistance and charge transfer resistance were analyzed based on the obtained impedance spectrum curves. A lower charge transfer resistance indicates stronger interfacial electron transport capability; this test was used to verify the enhancing effect of the sulfur-fluorine dual-coordination structure on electron conduction performance.

[0035] 4. Constant current endurance test To evaluate the long-term operational stability of the catalyst, chronovoltaic galvanostatic tests were performed at current densities of 10 mA / cm² and 50 mA / cm² for at least 200 hours, and the potential changes over time were recorded. Simultaneously, accelerated cyclic voltammetry was conducted within the potential range of 1.0 to 1.7 V, with 5000 cycles and a scan rate of 100 mV / s. The potential changes and differences in electrochemical parameters before and after aging were compared to evaluate the catalyst's structural stability and corrosion resistance.

[0036] 5. Electrochemical active surface area test The electrochemical active surface area of ​​the catalyst was estimated using the electric double-layer capacitance method. Cyclic voltammetry was performed within a non-Radial range at scan rates of 10, 20, 40, 60, 80, and 100 mV / s. The current difference at different scan rates was used to obtain the electric double-layer capacitance value by linear fitting to the scan rate. A larger capacitance value indicates more exposed active sites on the catalyst, reflecting the size of the active surface area and used to compare the activity differences between different samples.

[0037] Table 1 Summary of catalyst performance test results As can be seen from the data in Table 1, the catalytic performance of Example 2 is the best among all indicators. Figure 2 The overpotential was 0.228V, which was 6.2% and 14.0% lower than that of Example 1 (0.243V) and Example 3 (0.265V), respectively. Compared with Comparative Examples 1 to 3 (0.289 to 0.317V), the reduction was 20% to 28%, indicating that the dual-coordination induced and organic interface composite structure significantly improved the electron distribution of the reactive center, reduced the oxygen evolution reaction energy barrier, and improved the reaction efficiency.

[0038] Figure 3 Tafel slope test results showed that the slope of Example 2 was 53 mV / dec, lower than 58 mV / dec of Example 1 and 64 mV / dec of Example 3, while the comparative samples were generally between 74 and 82 mV / dec, indicating that the system had a faster charge transfer rate and better reaction kinetics. This result is attributed to the electron rearrangement effect induced by the sulfur-fluorine dual coordination and the charge regulation effect of 2,4-dihydroxyphenylacetamide at the interface, making the reaction pathway more efficient.

[0039] Figure 4Electrochemical impedance spectroscopy results showed that the charge transfer resistance of Example 2 was 10.1 Ω·cm², which was reduced by 18.5% and 33.9% compared with 12.4 Ω·cm² in Example 1 and 15.3 Ω·cm² in Example 3, respectively, and by nearly 50% compared with 19.6 to 26.4 Ω·cm² in Comparative Examples 1 to 3. These results indicate that the interfacial conductivity of the catalyst was significantly improved, with sulfur providing a flexible coordination environment and fluorine inducing the formation of stable charge channels at negatively charged centers, thus significantly increasing the electron migration rate.

[0040] like Figure 5 In the constant current durability test, the potential drift of Example 2 was 15mV, which was better than 18mV of Example 1 and 25mV of Example 3, and much lower than 38 to 51mV of Comparative Examples 1 to 3. This indicates that the catalyst layer structure is stable, not easy to dissolve or undergo phase change, and has good resistance to alkali corrosion.

[0041] exist Figure 6 Electrochemical active surface area results showed that the double-layer capacitance of Example 2 was 7.5 mF / cm², which was 10.3% and 27.1% higher than that of Example 1 (6.8 mF / cm²) and Example 3 (5.9 mF / cm²), respectively. It was also about 65% to 97% higher than that of the comparative samples (3.8 to 4.5 mF / cm²), indicating that the composite interface structure promoted the full exposure of active sites and enhanced the electrolyte contact area.

[0042] The overall results show that the catalyst constructed by the sulfur-fluorine dual coordination-induced electronic rearrangement and the organic small molecule interface has a lower overpotential, a smaller Tafel slope and charge transfer resistance, while also possessing excellent structural stability and active site exposure capability. This achieves a synergistic improvement in both high activity and high stability, and its overall performance is significantly better than the control system with single coordination modification or no organic interface.

Claims

1. A corrosion-resistant and highly efficient non-iridium nickel-based catalyst, characterized in that, The raw materials include the following parts by weight: 100 parts of nickel-cobalt layered double hydroxide modified by sulfur-fluorine dual coordination induced electron rearrangement; 5-15 parts of 2,4-dihydroxyphenylacetamide; 10-20 parts of carbon source; 3-8 parts of reducing agent; and 2-6 parts of stabilizing agent; wherein the 2,4-dihydroxyphenylacetamide is an organic small molecule containing ortho- and para-phenolic hydroxyl groups and amide groups.

2. The corrosion-resistant and highly efficient non-iridium nickel-based catalyst according to claim 1, characterized in that, The nickel-cobalt layered double hydroxide modified by sulfur-fluorine dual coordination induced electron rearrangement comprises the following raw materials in parts by weight: 20-40 parts of nickel nitrate hexahydrate; 10-30 parts of cobalt nitrate hexahydrate; 5-15 parts of thioacetamide; 3-10 parts of ammonium fluoride; 5-20 parts of urea; and 100-200 parts of deionized water.

3. A corrosion-resistant and highly efficient non-iridium nickel-based catalyst according to any one of claims 1 or 2, characterized in that, The preparation method of the nickel-cobalt layered double hydroxide modified by sulfur-fluorine dual coordination induced electron rearrangement includes the following steps: (1) Add nickel nitrate hexahydrate, cobalt nitrate hexahydrate, thioacetamide, ammonium fluoride and urea to deionized water and mix evenly to obtain a mixture; (2) Heat the mixture to react and let it stand to form a precipitate; (3) The precipitate was washed and dried to obtain nickel-cobalt layered double hydroxide modified by sulfur-fluorine dual coordination induced electron rearrangement.

4. The corrosion-resistant and highly efficient non-iridium nickel-based catalyst according to claim 3, characterized in that, The reaction conditions for step (1) are magnetic stirring at room temperature for 30 to 60 minutes.

5. The corrosion-resistant and highly efficient non-iridium nickel-based catalyst according to claim 3, characterized in that, The reaction conditions for step (2) are to react at 80-90°C for 8-10 hours.

6. The corrosion-resistant and highly efficient non-iridium nickel-based catalyst according to claim 3, characterized in that, The reaction conditions for step (3) are drying at 60-70°C for 6-8 hours.

7. The corrosion-resistant and highly efficient non-iridium nickel-based catalyst according to claim 1, characterized in that, The carbon source is a mixture of glucose and citric acid in a mass ratio of 2:1; the reducing agent is a mixture of sodium borohydride and ascorbic acid in a mass ratio of 1:1; and the stabilizing agent is a mixture of polyvinylpyrrolidone and sodium citrate in a mass ratio of 3:

1.

8. A method for preparing a corrosion-resistant and highly efficient non-iridium nickel-based catalyst, wherein the corrosion-resistant and highly efficient non-iridium nickel-based catalyst is as described in any one of claims 1 to 7, characterized in that, Includes the following steps: S1, a nickel-cobalt layered double hydroxide modified by sulfur-fluorine dual coordination induced electron rearrangement is dispersed in an ethanol-water mixed solution, and 2,4-dihydroxyphenylacetamide is added to obtain a solution; S2, add carbon source, reducing agent and stabilizing agent to solution, mix well and then dry to obtain solid; S3 involves heat-treating the solid to obtain a corrosion-resistant and highly efficient non-iridium nickel-based catalyst.

9. The method for preparing a corrosion-resistant and highly efficient non-iridium nickel-based catalyst according to claim 8, characterized in that, The reaction conditions for step S1 are stirring at 60-80°C for 4-6 hours; the drying conditions for step S2 are freeze-drying at low temperature for 8-10 hours; and the heat treatment conditions for step S3 are heating at 300-350°C under a nitrogen atmosphere for 2-3 hours.

Images