Preparation method of FeP / Co2P / NF electro-catalysis seawater hydrogen evolution chlorine-resistant electrode plate

Abstract

The invention discloses a preparation method of a FeP / Co2P / NF electrocatalytic seawater hydrogen evolution chlorine-resistant electrode plate, relates to a preparation method of an electrode, and aims to solve the technical problems of poor chlorine resistance, few active sites and poor catalytic effect of the conventional TMPs electrode. The method comprises the following steps: after removing oil and an oxide layer from a foamed nickel substrate, putting the foamed nickel substrate into a mixed solution of cobalt salt, ammonium chloride and urea for hydrothermal reaction; then putting into a mixed solution of ferric salt, urea, aluminum nitrate nonahydrate and sodium dodecyl sulfate for hydrothermal reaction; and soaking with an alkaline solution and then carrying out high-temperature phosphorization to obtain the electrode plate. The overpotential of the electrode plate is 30-38 mV when water is electrolyzed for hydrogen production under the current density of 10 mA. Cm <-2 >, the overpotential of the electrode plate is 66-77 mV when seawater is electrolyzed for hydrogen production, the current density is reduced by 15%-20% after the electrode plate works for 100 hours, and the electrode plate has good chlorine resistance and can be used in the field of water electrolysis for hydrogen production.

Description

TECHNICAL FIELD

[0001] The application relates to a preparation method and application of an anti-chlorine electrode. BACKGROUND

[0002] As a high-efficiency clean secondary energy, hydrogen energy has the advantages of high energy density (142 MJ / kg) and combustion product only being water, and can be produced by electrolysis of water through renewable energy (such as solar energy and wind energy), and is an ideal substitute for fossil fuels. In the hydrogen energy industry chain, electrolysis of seawater to produce hydrogen is a core link for large-scale production of green hydrogen. As the electrocatalytic hydrogen evolution reaction (HER) of the cathodic half-reaction (2H + + 2e - → H2) of water electrolysis, the efficiency directly affects the energy conversion efficiency and economy of the whole system.

[0003] As a substitute for noble metal-based HER catalysts, transition metal phosphides (TMPs) have attracted extensive attention. However, it is still a long-term challenge to design and prepare TMPs HER electrocatalysts with high efficiency and durability. At present, the electrocatalytic material itself has low hydrogen evolution performance in seawater due to the interference of chloride ions; there are also problems of regular structure (such as crystal completeness and smooth surface) and few defects (such as edge and vacancy as sources of active sites), that is, insufficient active sites, and the stability and preparation cost have not met the requirements of industrial applications. SUMMARY

[0004] The application aims to solve the technical problems of poor anti-chlorine performance, few active sites and poor catalytic effect of the existing TMPs electrode, and provides a preparation method of FeP / Co2P / NF electrocatalytic seawater hydrogen evolution anti-chlorine electrode sheet.

[0005] The preparation method of the FeP / Co2P / NF electrocatalytic seawater hydrogen evolution anti-chlorine electrode sheet of the application is carried out in the following steps:

[0006] First, the nickel foam (NF) is subjected to oil removal and surface oxide layer removal treatment, and then is ultrasonically cleaned with deionized water to obtain a clean nickel foam substrate;

[0007] Second, after cobalt salt, ammonium chloride and urea are mixed and dissolved in water to obtain a mixed solution, the clean nickel foam substrate and the mixed solution are added to a stainless steel autoclave, and then are placed in an oven and heated to 100-120 DEG C and kept for 300-420 min, then the nickel foam is taken out and cleaned with deionized water and ethanol, and then is dried to obtain a primary precursor.

[0008] III. The iron salt, urea and aluminum nitrate nonahydrate are added to a 0.5% mass percentage sodium dodecyl sulfate (SDS) aqueous solution, stirred and dissolved to obtain a mixed solution; the mixed solution and the primary precursor are added to a stainless steel autoclave and placed in an oven to heat to 100-120℃ for 600-900 min, then taken out and washed with deionized water and ethanol, and dried to obtain a secondary precursor;

[0009] IV. The secondary precursor is immersed in a 3-5 mol / L NaOH solution for 20-24 h, taken out and washed with distilled water and ethanol until neutral, and dried to obtain a precursor; −1

[0010] V. The precursor is placed downstream of a quartz tube furnace, and a phosphorus source is placed upstream of the quartz tube furnace, argon is introduced into the quartz tube furnace at a flow rate of 100-120 sccm, and the temperature is raised to 300-400℃ at a rate of 2-5℃ / min and maintained for 2-4 h for phosphorization to obtain a FeP / Co2P / NF seawater electrocatalytic hydrogen evolution and chlorine-resistant electrode sheet. -1

[0011] Further, the oil removal and surface oxide layer removal treatment in step I is one or a combination of solvent cleaning, ultrasonic cleaning and pickling.

[0012] Further, the cobalt salt is one or a combination of CoCl2 and CoSO4.

[0013] The molar ratio of the cobalt salt, ammonium fluoride and urea in step II is (0.25-0.75):0.7:1.

[0014] Further, the drying in step II is performed at 60℃ for 2-4 h.

[0015] Further, the iron salt in step IV is one or more of FeCl3 and Fe2(SO4)3.

[0016] Further, the molar ratio of the iron salt, urea and aluminum nitrate nonahydrate in step IV is 0.185:1:0.2.

[0017] Further, the phosphorus source in step V is sodium hypophosphite.

[0018] ​​The preparation method of the FeP / Co2P / NF electrocatalytic seawater hydrogen evolution chlorine-resistant electrode sheet of the application adds aluminum nitrate nine-water in the preparation process of the secondary precursor, and a hydroxide or hydroxyl oxide intermediate (such as Al(OH)3) is formed in the hydrothermal treatment process. These intermediates are partially dissolved in the subsequent alkali soaking treatment, forming a rich pore structure, significantly increasing the specific surface area and active site exposure of the material. At the same time, the introduction of aluminum changes the crystallization behavior of the precursor, promoting the formation of nanosheets or nanometer arrays. This porous structure is beneficial to electrolyte penetration and gas diffusion.

[0019] The FeP / Co2P / NF electrocatalytic seawater hydrogen evolution chlorine-resistant electrode sheet of the application forms nanoparticles, nanosheets and other low-dimensional structures through the loading process. Its high surface energy and rich edges, steps and other defects improve the active sites and charge transfer rate, and synergistically improve the HER performance. The CoP / Fe2P / NF electrocatalytic seawater hydrogen evolution chlorine-resistant electrode sheet of the application has a current density of 10 mA·cm -2 The overpotential of the electrode sheet when electrolyzing water to produce hydrogen is 30-38 mV, and the overpotential of the electrode sheet when electrolyzing seawater to produce hydrogen is 66-77 mV. The electrode sheet has low chlorine-resistant overpotential when electrolyzing seawater to produce hydrogen, high HER performance, a 15%-20% reduction in current density after 100 hours of electrolyzing seawater, and good chlorine resistance.

[0020] The preparation method of the FeP / Co2P / NF electrocatalytic seawater hydrogen evolution chlorine-resistant electrode sheet of the application has high process controllability, mild reaction conditions, easy operation, low cost, and less equipment investment, and is suitable for commercial promotion and application. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 The XRD spectrum of the electrode sheet FeP / Co2P / NF-1 prepared in Example 1 is shown in the figure;

[0022] Figure 2 The scanning electron microscope picture of the electrode sheet FeP / Co2P / NF-1 prepared in Example 1 is shown in the figure;

[0023] Figure 3 The linear sweep voltammetry curve of the electrode sheet FeP / Co2P / NF-1 prepared in Example 1 is shown in the figure;

[0024] Figure 4 The XRD spectrum of the electrode sheet FeP / Co2P / NF-2 prepared in Example 2 is shown in the figure;

[0025] Figure 5 The scanning electron microscope picture of the electrode sheet FeP / Co2P / NF-2 prepared in Example 2 is shown in the figure;

[0026] Figure 6Linear sweep voltammogram of the electrode sheet FeP / Co2P / NF-2 prepared for Example 2;

[0027] Figure 7 Scanning electron microscope photograph of the Co2P / NF electrocatalytic seawater hydrogen evolution resistant chlorine electrode sheet prepared for Comparative Example 1;

[0028] Figure 8 Linear sweep voltammogram of the Co2P / NF electrocatalytic seawater hydrogen evolution resistant chlorine electrode sheet prepared for Comparative Example 1;

[0029] Figure 9 Scanning electron microscope photograph of the FeP / NF electrocatalytic seawater hydrogen evolution resistant chlorine electrode sheet prepared for Comparative Example 2;

[0030] Figure 10 Linear sweep voltammogram of the FeP / NF electrocatalytic seawater hydrogen evolution resistant chlorine electrode sheet prepared for Comparative Example 2;

[0031] Figure 11 Linear sweep voltammogram of the electrode sheets of Examples 1, 2 and Comparative Examples 1, 2 in seawater;

[0032] Figure 12 Stability test graph of the electrode sheets of Examples 1, 2 and Comparative Examples 1, 2 in seawater;

[0033] Figure 13 Cdl graph of the electrode sheets of Examples 1, 2 and Comparative Examples 1, 2 before the stability test in seawater;

[0034] Figure 14 Cdl graph of the electrode sheets of Examples 1, 2 and Comparative Examples 1, 2 after the stability test in seawater.

[0035] Figure 15 Cdl graph of the electrode sheet of Comparative Example 3;

[0036] Figure 16 Linear sweep voltammogram of the electrode sheet of Comparative Example 3 in aqueous potassium hydroxide solution;

[0037] Figure 17 Linear sweep voltammogram of the electrode sheet of Comparative Example 3 in seawater. DETAILED DESCRIPTION

[0038] The present application will be described in detail below with reference to the accompanying drawings and examples. The various raw materials used in the examples, unless otherwise specified, are commercially available.

[0039] Example 1: The method for preparing the FeP / Co2P / NF electrocatalytic seawater hydrogen evolution resistant chlorine electrode sheet of the present example was carried out in the following steps:

[0040] I. A 3 cm x 4 cm piece of nickel foam was sequentially immersed in acetone and a 3 M hydrochloric acid solution, and was subjected to ultrasonic oil removal and surface oxide layer removal treatment, and was then ultrasonically cleaned with deionized water to obtain a clean nickel foam substrate;

[0041] II. 0.595 g of CoCl2·6H2O, 0.6 g of urea (CO(NH2)2), and 0.37 g of NH4Cl were added to 35 mL of deionized water, and stirring was continued at a stirring speed of 80 r / min for 30 min to obtain a mixed solution A; the clean nickel foam substrate and the mixed solution A were transferred to a 50 mL stainless steel autoclave, and were placed in an oven and heated to 120 °C and maintained for 6 h, and were then cooled to room temperature; the nickel foam was removed and washed with deionized water and ethanol, and was then maintained at 60 °C for 2 h to obtain a primary precursor;

[0042] III. 0.3 g of FeCl3, 0.75 g of Al(NO3)3·9H2O, and 0.6 g of CO(NH2)2 were added to 36 mL of a 0.5% sodium dodecyl sulfonate (SDS) aqueous solution, and magnetic stirring was continued for 20 min to obtain a mixed solution B; the mixed solution B and the primary precursor were transferred to a 50 mL stainless steel autoclave, and were placed in an oven and heated to 120 °C and maintained for 12 h, and were then removed and washed with deionized water and ethanol, and were then dried to obtain a secondary precursor;

[0043] IV. The secondary precursor was immersed in a 5 mol / L NaOH solution for 24 h, was removed and rinsed with distilled water and ethanol until neutral, and was then dried at 60 °C for 12 h to obtain a precursor;

[0044] V. The precursor was placed in a porcelain boat, and the porcelain boat was placed downstream of a quartz tube furnace, and sodium hypophosphite was placed upstream of the quartz tube furnace; argon was introduced into the quartz tube furnace at a flow rate of 100 sccm, and the quartz tube furnace was heated to 350 °C at a heating rate of 5 °C·min -1 and maintained for 2.5 h to perform phosphorization, to obtain a FeP / Co2P / NF seawater electrolysis hydrogen evolution chlorine-resistant electrode sheet, denoted as FeP / Co2P / NF-1.

[0045] The XRD spectrum of the electrode sheet FeP / Co2P / NF-1 prepared in Example 1 is shown in Figure 1 From Figure 1 it can be seen that the electrode sheet in Example 1 contains phosphorus iron and phosphorus cobalt.

[0046] The scanning electron microscope image of the electrode sheet FeP / Co2P / NF-1 prepared in Example 1 is shown in Figure 2 From Figure 2As can be seen, the surface of FeP / Co2P / NF-1 has a porous structure, which increases the specific surface area and provides more accessible active sites for HER.

[0047] A 1.0 M potassium hydroxide solution was prepared as the electrolyte for electrocatalysis. FeP / Co₂P / NF₁₁, Hg / HgO, and graphite electrodes were used as the working electrode, reference electrode, and counter electrode, respectively, and connected to an electrochemical workstation. The electrochemical reaction was carried out at 0.01 V·s⁻¹. -1 The electrode material was subjected to linear voltammetry testing at a scanning rate of [value missing], and the resulting linear scanning voltammetry curve is shown below. Figure 3 As shown, from Figure 3 It can be seen that FeP / Co2P / NF-1 at a current density of 10 mA·cm -2 The overpotential is 38 mV.

[0048] Example 2: This example differs from Example 1 in that “0.595g CoCl2·6H2O” in step two is replaced with “1.785g CoCl2·6H2O”. The other steps and parameters are the same as in Example 1, resulting in a FeP / Co2P / NF electrocatalytic seawater hydrogen evolution antichlorine electrode, denoted as FeP / Co2P / NF-2.

[0049] The XRD pattern of the FeP / Co2P / NF-2 electrode sheet prepared in Example 2 is shown below. Figure 4 As shown, from Figure 4 It can be seen that the electrode sheet in Example 2 contains iron phosphide and cobalt phosphide.

[0050] Scanning electron microscope (SEM) images of the FeP / Co2P / NF-2 electrode sheet prepared in Example 2 are shown below. Figure 5 As shown, from Figure 5 As can be seen, the surface of FeP / Co2P / NF-2 has a porous structure, which increases the specific surface area and provides more accessible active sites for HER.

[0051] A 1.0 M potassium hydroxide solution was prepared as the electrolyte for electrocatalysis. FeP / Co₂P / NF₂, Hg / HgO, and graphite electrodes were used as the working electrode, reference electrode, and counter electrode, respectively, and connected to an electrochemical workstation. The electrochemical reaction was carried out at 0.01 V·s⁻¹. -1 The electrode material was subjected to linear voltammetry testing at a scanning rate of [value missing], and the resulting linear scanning voltammetry curve is shown below. Figure 6 As shown, from Figure 6 It can be seen that FeP / Co2P / NF-2 at a current density of 10 mA·cm -2 The overpotential is 30 mV.

[0052] Comparative Example 1: Comparative Example 1 is to prepare Co2P / NF, and the specific preparation method is completed according to the following steps:

[0053] I. First, the foam nickel with a size of 3 cm x 4 cm is sequentially immersed in an acetone solution and a 3 M molar fraction hydrochloric acid solution, and is subjected to ultrasonic oil removal and surface oxide layer removal treatment, and then is ultrasonically cleaned with deionized water to obtain clean foam nickel;

[0054] II. 0.595 g of CoCl2·6H2O, 0.6 g of CO(NH2)2, and 0.259 g of NH4F are dissolved in 35 mL of deionized water, and stirring is continuously performed at a stirring speed of 80 r / min for 30 min to obtain a mixed solution;

[0055] III. The mixed solution and the clean foam nickel are transferred to a 50 mL stainless steel autoclave, the autoclave is placed in an oven and heated at 120°C for 6 hours, and then cooled to room temperature, the foam nickel is washed clean with distilled water and alcohol, and dried at 60°C for 2 hours to obtain a precursor;

[0056] IV. High-temperature phosphorization: the precursor is placed in a porcelain boat, the porcelain boat is placed downstream of a quartz tube furnace, sodium hypophosphite is placed upstream of the quartz tube furnace, argon gas is introduced into the quartz tube furnace at a flow rate of 100 sccm, the temperature is raised to 350°C at a rate of 5°C / min and maintained for 2.5 h for phosphorization, and a Co2P / NF seawater hydrogen evolution and chlorine-resistant electrode sheet is obtained.

[0057] The scanning electron microscope photo of the Co2P / NF seawater hydrogen evolution and chlorine-resistant electrode sheet prepared in Comparative Example 1 is shown in Figure 7 , and it can be seen from Figure 7 that the surface of Comparative Example 1 has a thorn-like structure.

[0058] A 1.0 M potassium hydroxide solution is prepared as an electrocatalytic electrolyte. The Co2P / NF, Hg / HgO electrode, and graphite electrode are connected to an electrochemical workstation as a working electrode, a reference electrode, and a counter electrode, respectively. The electrode material is subjected to linear voltammetry test at a scan rate of 0.01 V·s -1 , and the linear sweep voltammetry curve is shown in Figure 8 , and it can be seen from Figure 8 that the overpotential of Co2P / NF at a current density of 10 mA·cm -2 is 96 mV.

[0059] Comparative Example 2: This comparative example is to prepare FeP / NF, and the specific preparation method is as follows:

[0060] First, immerse a 3 cm × 4 cm piece of nickel foam in acetone and a 3 M hydrochloric acid solution in sequence for ultrasonic degreasing and removal of the surface oxide layer. Then, ultrasonically clean it with deionized water to obtain clean nickel foam.

[0061] 2. Dissolve 0.3 g CoCl3, 0.6 g CO(NH2)2 and 0.259 g NH4F in 35 mL of deionized water and stir continuously at 80 r / min for 30 min to obtain a mixed solution;

[0062] 3. Transfer the mixed solution and cleaned nickel foam to a 50 mL stainless steel autoclave, then place the autoclave in an oven and heat at 120°C for 6 hours, then cool to room temperature; remove the nickel foam, wash it with distilled water and alcohol, and dry it at 60°C for 2 hours to obtain the precursor;

[0063] IV. High-temperature phosphating: The precursor is placed in a ceramic boat, which is then placed downstream of a quartz tube furnace. Sodium hypophosphite is placed upstream of the quartz tube furnace. Argon gas is introduced into the quartz tube furnace at a flow rate of 100 sccm, while the temperature is increased to 350℃ at a rate of 5℃ / min and maintained for 2.5h for phosphating, thus obtaining the FeP / NF catalytic seawater hydrogen evolution antichloride electrode sheet.

[0064] Scanning electron microscope (SEM) image of the FeP / NF catalytic seawater hydrogen evolution antichloride electrode prepared in Comparative Example 2 is shown below. Figure 9 As shown, from Figure 9 The blocky structure on the surface of the electrode sheet in Comparative Example 2 can be seen.

[0065] A 1.0 M potassium hydroxide solution was prepared as the electrolyte for electrocatalysis. FeP / NF, Hg / HgO, and graphite electrodes were used as the working electrode, reference electrode, and counter electrode, respectively, and connected to an electrochemical workstation. The electrochemical reaction was carried out at 0.01 V·s. -1 The electrode material was subjected to linear voltammetry testing at a certain scan rate, and the linear scan voltammetry curve is shown below. Figure 10 As shown, from Figure 10 It can be seen that FeP / NF at a current density of 10 mA·cm -2 The overpotential is 142 mV.

[0066] Seawater hydrogen evolution test was carried out by taking the electrode sheet FeP / Co2P / NF-1 of Example 1, the electrode sheet FeP / Co2P / NF-2 of Example 2, the Co2P / NF electrode sheet of Comparative Example 1, and the FeP / NF electrode sheet of Comparative Example 2 as the working electrode, respectively. The specific steps are as follows: seawater was used as the electrolyte for electrocatalysis, and a Hg / HgO electrode and a graphite electrode were used as the reference electrode and the counter electrode, respectively. The working electrode, the reference electrode, and the counter electrode were connected to an electrochemical workstation. Linear voltammetry test was carried out on the electrode material at a scan rate of 0.01 V·s -1 . The linear sweep voltammetry curve obtained is shown in Figure 11 , and the stability test graph in seawater is shown in Figure 12 . It can be seen from Figure 11 that the overpotential of FeP / Co2P / NF-1 is 66 mV at a current density of 10 mA·cm -2 . The overpotential of FeP / Co2P / NF-2 is 77 mV at a current density of 10 mA·cm -2 . The overpotential of Co2P / NF is 128 mV at a current density of 10 mA·cm -2 . The overpotential of FeP / NF is 154 mV at a current density of 10 mA·cm -2 . The overpotential data of the electrode sheets prepared in Examples 1 and 2 and Comparative Examples 1 and 2 are listed in Table 1. It can be clearly seen from Table 1 that the performance of the electrode sheets prepared in Examples 1 and 2 is much higher than that of the electrode sheets prepared in Comparative Examples 1 and 2, which is due to the maximization of active sites by the porous structure, high dispersion design, and morphology optimization of the bimetallic material, thereby improving the performance. It can also be seen from Table 1 that the hydrogen evolution performance of the electrode sheets prepared in Examples 1, 2, and Comparative Examples 1 and 2 all decreases in seawater due to the interference of calcium and magnesium ions.

[0067] It can be seen from Figure 12 that after working in seawater for 100 hours, the current density of FeP / Co2P / NF-1 decreases by 15%, the current density of FeP / Co2P / NF-2 decreases by 20.93%, the current density of Co2P / NF decreases by 41.46%, and the current density of FeP / NF decreases by 54.04%. The current density of the electrodes of Examples 1 and 2 decreases less, while the current density of the electrodes of Comparative Examples 1 and 2 decreases more, indicating that the electrodes prepared in Examples 1 and 2 have good resistance to chlorine and can be stably operated in seawater for a long time.

[0068] Table 1 Overpotential data of the catalysts prepared in Examples 1 and 2 and Comparative Examples 1 and 2

[0069]

[0070] Figure 13 Cdl diagrams of the electrode sheets of Examples 1 and 2 and Comparative Examples 1 and 2 before stability testing in seawater; Figure 14 Cdl graphs of the electrode sheets of Examples 1 and 2 and Comparative Examples 1 and 2 after stability testing in seawater. From... Figure 13 It can be seen that the Cdl value of FeP / Co2P / NF-2 is much higher than that of FeP / Co2P / NF-1, indicating that the surface structure of FeP / Co2P / NF-2 is more optimized than that of FeP / Co2P / NF-1, such as the formation morphology, which significantly increases the exposure of active sites. Furthermore, the Cdl values ​​of both FeP / Co2P / NF-2 and FeP / Co2P / NF-1 are higher than those of the single-metal catalysts Co2P / NF and FeP / NF. (Comparison) Figure 13 and Figure 14 It can be seen that the Cdl values ​​of all four electrode sheets decreased after the stability test, indicating that the material underwent particle agglomeration or physical shedding during the stability test, resulting in a reduction of active sites.

[0071] Comparative Example 3: This comparative example differs from Example 1 in that "0.75 g Al(NO3)3·9H2O" in step three is omitted, and step four is also omitted. Other steps and parameters are the same as in Example 1.

[0072] In this comparative example, Al(NO3)3·9H2O was not added during the preparation process. The Cdl diagram of the resulting electrode sheet is shown in Figure 15. Figure 15 It can be seen that the Cdl value is 21.38 mF·cm. -2 This value is less than the Cdl value of comparative examples 1 and 2, indicating that Al(NO3)3·9H2O can increase the specific surface area and active site exposure of the material.

[0073] Using the electrode sheet prepared in Comparative Example 3 as the working electrode, 1.0 M potassium hydroxide solution and seawater were used as the electrolytes for electrocatalysis, respectively. An Hg / HgO electrode and a graphite electrode were used as the reference and counter electrodes, respectively. The working electrode, reference electrode, and counter electrode were connected to an electrochemical workstation. The electrochemical reaction was carried out at 0.01 V·s. -1 The electrode material was subjected to linear voltammetry tests at a scan rate of [value missing], and its performance in potassium hydroxide solution is shown in the figure below. Figure 16 As shown in the diagram, the performance in seawater is as follows: Figure 17 As shown. From Figure 16 It can be seen that the electrode sheet prepared in Comparative Example 3, in potassium hydroxide solution at a current density of 10 mA·cm⁻¹, -2 The overpotential is 142 mV, from Figure 17 It can be seen that the electrode sheet prepared in Comparative Example 3 performs well in seawater at a current density of 10 mA·cm⁻¹. -2 The overpotential is 164 mV.

Claims

1. A method for preparing a FeP / Co2P / NF electrocatalytic seawater hydrogen evolution antichloride electrode, characterized in that, This method is performed in the following steps: First, the nickel foam is degreased and the surface oxide layer is removed, followed by ultrasonic cleaning with deionized water to obtain a clean nickel foam substrate.

2. Cobalt salt, ammonium chloride, and urea are added to water and mixed to dissolve, resulting in a mixed solution. The clean nickel foam matrix and the mixed solution are added to a stainless steel autoclave and placed in an oven to be heated to 100~120 ℃ and maintained for 300~420 min. The nickel foam is then removed, washed with deionized water and ethanol, and dried to obtain the primary precursor.

3. Add iron salt, urea and aluminum nitrate nonahydrate to an aqueous solution of sodium dodecyl sulfonate with a mass percentage concentration of 0.5%, stir and dissolve to obtain a mixed solution; add the mixed solution and the primary precursor to a stainless steel autoclave, place it in an oven and heat to 100~120 ℃ for 600~900 min, then remove it, wash it with deionized water and ethanol, and dry it to obtain the secondary precursor; IV. Immerse the secondary precursor in an atmosphere with a concentration of 3-5 mol / L. −1 Soak in NaOH solution for 20-24 hours, remove and rinse with distilled water and ethanol until neutral, then dry to obtain the precursor; 5. Place the precursor downstream of the quartz tube furnace and the phosphorus source upstream of the quartz tube furnace. Introduce argon gas into the quartz tube furnace at a flow rate of 100-120 sccm, while simultaneously introducing argon gas at a flow rate of 2-5 °C / min. -1 The temperature was increased to 300-400℃ and held for 2-4 hours for phosphating to obtain FeP / Co2P / NF electrocatalytic seawater hydrogen evolution antichlorine electrode sheet.

2. The method for preparing a FeP / Co2P / NF electrocatalytic seawater hydrogen evolution antichloride electrode sheet according to claim 1, characterized in that, The degreasing and surface oxide layer removal treatments described in step one are performed using one or more of the following: solvent cleaning, ultrasonic cleaning, and acid pickling.

3. The preparation method of the FeP / Co2P / NF electrocatalytic seawater hydrogen evolution antichlorine electrode sheet according to claim 1 or 2, characterized in that, The cobalt salt mentioned in step two is one or a combination of two of CoCl2 and CoSO4.

4. A method for preparing a FeP / Co2P / NF electrocatalytic seawater hydrogen evolution antichloride electrode sheet according to claim 1 or 2, characterized in that, The molar ratio of cobalt salt, ammonium fluoride, and urea in step two is (0.25~0.75):0.7:

1.

5. A method for preparing a FeP / Co2P / NF electrocatalytic seawater hydrogen evolution antichloride electrode sheet according to claim 1 or 2, characterized in that, The iron salt mentioned in step four is one or more of FeCl3 and Fe2(SO4)3.

6. A method for preparing a FeP / Co2P / NF electrocatalytic seawater hydrogen evolution antichloride electrode sheet according to claim 1 or 2, characterized in that, The molar ratio of iron salt, urea and aluminum nitrate nonahydrate mentioned in step four is 0.185:1:0.

2.

7. A method for preparing a FeP / Co2P / NF electrocatalytic seawater hydrogen evolution antichloride electrode sheet according to claim 1 or 2, characterized in that, The phosphorus source mentioned in step five is sodium hypophosphite.

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