Aemwe cathode electrode material under high current density and macro preparation method and application thereof

Abstract

The application provides an AEMWE cathode electrode material, comprising: a metal foam substrate and a modified transition metal-based nanosheet array compounded on the surface of the metal foam substrate; the transition metal comprises one or more of Co, Fe, Ni, Ce, Mn and Mo; and the modification comprises one or more of phosphorus modification, sulfur modification and selenium modification. By utilizing the electric field or the electric field and magnetic field multi-field coupling effect, the application can controllably grow secondary nanosheets on the primary nanosheet array, promote the formation of lattice dislocation / twin / twisted grain boundaries, greatly reduce the charge transfer resistance of the hydrogen evolution process, and through the electron-withdrawing effect of halogen elements, form strong metal ion-halogen ion bonds with metal ions, promote the ion exchange of X ‑ and OH ‑ , effectively improve the hydrogen evolution performance and long-period stability of the electrode material under large current density and industrialization conditions, and the preparation method provided is a green method which can realize macro-preparation.

Description

Technical Field

[0001] This invention belongs to the field of AEMWE electrode materials, and relates to an AEMWE cathode electrode material, its preparation method, and its application, especially to an AEMWE cathode electrode material under high current density, its mass production method, and its application. Background Technology

[0002] Under the dual-carbon goal, exploring clean and sustainable energy is imperative. Hydrogen energy, as a renewable and sustainable energy carrier, has a high energy density (approximately 10 MJ / m³). 3 Hydrogen, with its zero pollution and high energy conversion efficiency (2.75 times that of hydrocarbon fuels), is considered a viable alternative to meet future global energy demands. Currently, hydrogen production still largely relies on fossil fuels. Water electrolysis for green hydrogen production is one of the most promising technologies for the future, with the potential to achieve large-scale and efficient decarbonization of renewable energy. However, conventional water electrolysis requires the use of platinum group metals (Ru, Rh, Pd, Ir, Pt), which possess high hydrogen evolution catalytic activity, acid and alkali corrosion resistance, and good reaction stability. Currently, most commercially available catalysts are Pt / C. Due to the limited Earth's reserves and high cost of these precious metals, large-scale industrial applications are not feasible.

[0003] Among various water electrolysis technologies, the emerging anion exchange membrane electrolyzer (AEMWE) combines the advantages of alkaline water electrolyzers (AWEs) and proton exchange membrane electrolyzers (PEMWEs), featuring low cost, simplicity, and high efficiency. Furthermore, this method can utilize non-precious metal catalysts, demonstrating significant commercial application potential. In recent years, substantial research has focused on developing low-cost non-precious metal electrocatalysts, including transition metal phosphides, sulfides, selenides, carbides, and oxides. Transition metal phosphides, formed by phosphorus atoms embedded in intermetallic voids, increase the metal lattice and d-bandwidth, leading to a contraction of the d-bandwidth and density of states near the Fermi level. Transition metal sulfides / selenides, due to their unique layered structure and electronic properties, have wide applications in electrocatalysis. However, challenges remain regarding conductivity, catalytic stability, and active specific surface area. Furthermore, traditional methods for preparing doped P / P compounds, doped S / S compounds, and doped Se / Se compounds involve high-temperature processing using tube furnaces, resulting in toxic and environmentally unfriendly exhaust gases. For example, the traditional method for preparing doped P / P compounds utilizes the high-temperature decomposition of phosphates to generate PH3, which is then used as a phosphorus source for phosphating. However, PH3 is toxic and flammable at high temperatures (above 38°C), making it unsuitable for large-scale industrial production.

[0004] Therefore, finding a more effective strategy to alter the electronic environment on the catalyst surface to increase the electron transfer rate during hydrogen evolution and thus improve the efficiency of AEMWE at high current densities has become a focus of attention for many leading researchers in the industry. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide an AEMWE cathode electrode material, its preparation method, and its application, especially an AEMWE cathode electrode material for high current density. The cathode electrode material for AEMWE (anion exchange membrane water electrolyzer) provided by the present invention has excellent electrocatalytic hydrogen evolution performance, and its preparation method is simple, mild, and environmentally friendly, making it more suitable for industrial production and application.

[0006] This invention provides an AEMWE cathode electrode material, comprising: a metal foam substrate and a modified transition metal-based nanosheet array composited on the surface of the metal foam substrate;

[0007] The transition metal includes one or more of Co, Fe, Ni, Ce, Mn, and Mo;

[0008] The modification includes one or more of phosphorus modification, sulfur modification and selenium modification.

[0009] Preferably, the nanosheet array has a cluster structure formed by interlaced growth of petals;

[0010] The thickness of the nanosheet is 1–50 nm;

[0011] The nanosheets have a diameter of 10 nm to 10 μm;

[0012] The nanosheets in the nanosheet array form a porous structure.

[0013] Preferably, the composite method includes growth;

[0014] The thickness of the nanosheet array is 10 nm to 20 μm;

[0015] The transition metal-based nanosheets also include halogen elements;

[0016] The halogen elements and the transition metals have transition metal ion-halogen ion bonds;

[0017] The mass ratio of the metal foam substrate to the modified transition metal-based nanosheet array is (3-20):1;

[0018] The modified transition metal-based nanosheets are further coated with modified transition metal-based nanoparticles.

[0019] The modified transition metal-based nanoparticles have a particle size of 1–50 nm.

[0020] Preferably, the modified transition metal-based nanosheets specifically comprise transition metal-based nanosheets composited on the surface of a metal foam substrate and a modified transition metal-based superimposed layer superimposed on the transition metal nanosheets.

[0021] The transition metal-based nanosheets include metal and / or multi-metal alloy compounds;

[0022] The superposition method includes electrodeposition or multi-field coupled deposition of electric and magnetic fields;

[0023] The thickness of the modified transition metal matrix superposition layer is 10 nm to 20 μm;

[0024] The modified transition metal-based superimposed layer includes one or more of the following: transition metal sulfides and / or transition metal sulfoxides, transition metal phosphides and / or transition metal phosphoxides, and transition metal selenides and / or transition metal selenides.

[0025] The transition metal-based nanosheets and the modified transition metal-based superimposed layer have one or more topological structures among lattice dislocations, twins, and distorted grain boundary structures.

[0026] The AEMWE cathode electrode material includes a cathode electrode material for AEMWE under high current density conditions.

[0027] This invention provides a method for preparing an AEMWE cathode electrode material, comprising the following steps:

[0028] 1) The transition metal salt and ammonium salt are mixed and melted to obtain a melt;

[0029] 2) The metal foam substrate is placed in the melt for reaction to obtain a metal foam substrate composited with transition metal nanosheets;

[0030] 3) After mixing the soluble transition metal salt, modifier and water, a solution is obtained. The solution is placed in an electroplating tank. The metal foam substrate with transition metal nanosheets obtained in the above steps is used as the working electrode. Deposition is carried out under the action of electric field or multi-field coupling of electric field and magnetic field and nitrogen-rich atmosphere to obtain AEMWE cathode electrode material.

[0031] Preferably, the transition metal in the transition metal salt includes one or more of Co, Fe, Ni, Ce, Mn, and Mo;

[0032] The transition metal salts include one or more of the following: nitrates, sulfates, chlorides, carbonates, acetates, ammonium salts, naphthenates, stearates, and neodecanoates of transition metals.

[0033] The ammonium salt includes ammonium halides;

[0034] The transition metal salt is calculated based on transition metal atoms, and the ammonium salt is calculated based on NH4+. + The molar ratio of the two is calculated to be 5:(0.1~5);

[0035] The melting temperature is 60–200°C;

[0036] The metal foam substrate includes one or more of the following: nickel foam, iron foam, cobalt foam, cobalt-iron foam, nickel-iron foam, and nickel mesh.

[0037] The reaction time is 1 to 30 minutes.

[0038] Preferably, the transition metal in the soluble transition metal salt includes one or more of Co, Fe, Ni, Ce, Mn, and Mo.

[0039] The soluble transition metal salts include one or more of the following: nitrates, sulfates, chlorides, acetates, and ammonium salts of transition metals.

[0040] The modifier includes one or more of sulfur source modifiers, selenium source modifiers, and phosphorus source modifiers;

[0041] In the solution, the molar ratio of soluble transition metal salt to modifier is (0.05–1.5):1.

[0042] Preferably, the sulfur source modifier includes one or more of sulfur powder, thioacetamide, sodium sulfide, and thiourea;

[0043] The selenium source modifier includes selenium powder and / or selenium dioxide;

[0044] The phosphorus source modifier includes one or more of potassium hypophosphite, potassium dihydrogen phosphate, red phosphorus, and sodium hypophosphite.

[0045] Preferably, the deposition method includes one or more of constant potential deposition, constant current deposition, cyclic voltammetry, and linear voltage scanning;

[0046] The deposition time is 1–60 min;

[0047] The deposition temperature is 20–50°C;

[0048] The deposition process specifically involves using Hg / Hg2Cl2, Ag / AgCl, or Hg / HgO as the reference electrode and a platinum sheet / platinum wire / carbon rod as the counter electrode.

[0049] The magnetic field is added by adding a magnet in the direction perpendicular to the electrode, and adjusting the magnetic field strength at the center point of the magnetic field by changing the distance between the two sets of magnets.

[0050] The magnetic field strength is 0.01–3 T;

[0051] The metal foam substrate is specifically a pretreated metal foam substrate.

[0052] This invention also provides the application of an AEMWE cathode electrode material as described in any one of the above technical solutions, or an AEMWE cathode electrode material prepared by any one of the above technical solutions, in the fields of anion exchange membrane electrolysis of water for hydrogen production and / or alkaline electrolysis of water for hydrogen production.

[0053] This invention provides an AEMWE cathode electrode material, comprising: a metal foam substrate and a modified transition metal-based nanosheet array composited on the surface of the metal foam substrate; the transition metal includes one or more of Co, Fe, Ni, Ce, Mn, and Mo; the modification includes one or more of phosphorus modification, sulfur modification, and selenium modification. Compared with the prior art, this invention provides an AEMWE cathode electrode material with a specific morphology and composition, and is a cathode electrode material that can be used in AEMWE at high current densities. This invention also provides a corresponding method for preparing the AEMWE cathode electrode material, through the controllable growth of a lattice-distorted material of secondary nanosheets on a primary nanosheet array via an electric field or multi-field coupling of electric and magnetic fields, and the modified metal nanosheet material obtained by in-situ construction. The preparation method is simple and easy to implement, and suitable for industrialization and commercial promotion.

[0054] The AEMWE cathode electrode material provided by this invention, through the introduction of halogen atoms, exhibits excellent electrocatalytic hydrogen evolution performance under their strong electron-withdrawing effect. Furthermore, through the macroscopic and microscopic magnetohydrodynamic effects generated by the Lorentz force, the liquid phase mass transfer rate is increased. By influencing various steps in the deposition process, such as liquid phase mass transfer and electrode polarization, the performance of the AEMWE cathode electrode material is improved.

[0055] Test results show that the AEMWE cathode electrode material provided by this invention, in the membrane electrode (industrial-scale test) test, using the self-made catalyst (CN115404505A) as the anode and Xiamen University Jiaming membrane as the anion exchange membrane, achieved a battery voltage of 1.93V at a current of 4A and could operate stably for 1000h (test conditions: 1M KOH, 80℃, membrane electrode assembly size 2*2cm). 2 ). Attached Figure Description

[0056] Figure 1 The F-Co obtained in Example 1 of this invention x Fe y SEM topography of / IF;

[0057] Figure 2 The F-Co obtained in Example 1 of this invention x Fe y (PO4) z SEM topography of / IF;

[0058] Figure 3 The F-Co obtained in Example 1 of this invention x Fe y (PO4) z XRD patterns of / IF;

[0059] Figure 4 The F-Co obtained in Example 1 of this invention x Fe y (PO4) z LSV, AC impedance spectrum (EIS), and current density versus time for the / IF material;

[0060] Figure 5 The AEMWE test curve is for the cathode material prepared in Example 1 of this invention. Detailed Implementation

[0061] To further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention and not for limiting the claims of the present invention.

[0062] There are no particular restrictions on the source of any raw materials used in this invention; they can be purchased from the market or prepared using conventional methods known to those skilled in the art.

[0063] The purity of the raw materials used in this invention is not particularly limited; the purity requirements of the raw materials used in the preparation of AEMWE cathode electrode materials, which are well known to those skilled in the art, are sufficient.

[0064] This invention provides an AEMWE cathode electrode material, comprising: a metal foam substrate and a modified transition metal-based nanosheet array composited on the surface of the metal foam substrate;

[0065] The transition metal includes one or more of Co, Fe, Ni, Ce, Mn, and Mo;

[0066] The modification includes one or more of phosphorus modification, sulfur modification and selenium modification.

[0067] In this invention, the transition metal includes one or more of Co, Fe, Ni, Ce, Mn and Mo, and can be Co, Fe, Ni, Ce, Mn or Mo.

[0068] In this invention, the modification includes one or more of phosphorus modification, sulfur modification and selenium modification, and can be phosphorus modification, sulfur modification or selenium modification.

[0069] In this invention, the nanosheet array preferably has a cluster structure formed by interlaced petal-like growth.

[0070] In this invention, the thickness of the nanosheet is preferably 1-50 nm, more preferably 10-40 nm, and even more preferably 20-30 nm.

[0071] In this invention, the nanosheet diameter is preferably 10 nm to 10 μm, more preferably 100 nm to 6 μm, and even more preferably 1 μm to 2 μm.

[0072] In this invention, the nanosheets of the nanosheet array preferably form a porous structure.

[0073] In this invention, the composite method includes growth.

[0074] In this invention, the thickness of the nanosheet array is preferably 10 nm to 20 μm, more preferably 100 nm to 10 μm, and even more preferably 1 μm to 2 μm.

[0075] In this invention, the transition metal-based nanosheets preferably also include halogen elements.

[0076] In this invention, the halogen element and the transition metal preferably have a transition metal ion-halogen ion bond;

[0077] In this invention, the mass ratio of the metal foam substrate to the modified transition metal-based nanosheet array is preferably (3-20):1, more preferably (7-16):1.

[0078] In this invention, the surface of the modified transition metal-based nanosheets is preferably further composited with modified transition metal-based nanoparticles.

[0079] In this invention, the particle size of the modified transition metal-based nanoparticles is preferably 1 to 50 nm.

[0080] In this invention, the modified transition metal-based nanosheets are preferably transition metal-based nanosheets composited on the surface of a metal foam substrate and a modified transition metal-based stacked layer superimposed on the transition metal nanosheets. Specifically, the stacking in this invention can be deposition or coating, preferably a modified transition metal-based deposition layer deposited on the transition metal nanosheets or a modified transition metal-based coating layer coated on the transition metal nanosheets.

[0081] In this invention, the transition metal-based nanosheets preferably include metal and / or multi-metal alloy compounds, more preferably metal or multi-metal alloy compounds.

[0082] In this invention, the superposition method preferably includes electrodeposition or multi-field coupled deposition of electric and magnetic fields.

[0083] In this invention, the thickness of the modified transition metal base superposition layer is preferably 10 nm to 20 μm, more preferably 100 nm to 10 μm, and even more preferably 1 μm to 2 μm.

[0084] In this invention, the modified transition metal-based superimposed layer preferably includes one or more of transition metal sulfides and / or transition metal sulfoxides, transition metal phosphides and / or transition metal phosphorus oxides, and transition metal selenides and / or transition metal selenides, more preferably one of transition metal sulfides and / or transition metal sulfoxides, transition metal phosphides and / or transition metal phosphorus oxides, and transition metal selenides and / or transition metal selenides.

[0085] In this invention, the transition metal-based nanosheets and the modified transition metal-based stacked layer preferably have one or more of the following topological structures: lattice dislocations, twins, and twisted grain boundaries. Specifically, the transition metal-based nanosheets and the modified transition metal-based stacked layer preferably have a topological structure. More specifically, the topological structure can be one or more of the following: lattice dislocations, twins, and twisted grain boundaries.

[0086] In this invention, the cathode electrode material is preferably an integrated cathode electrode material with catalytic properties.

[0087] In this invention, the AEMWE cathode electrode material preferably includes a cathode electrode material for AEMWE under high current density conditions.

[0088] This invention provides a method for preparing an AEMWE cathode electrode material, comprising the following steps:

[0089] 1) The transition metal salt and ammonium salt are mixed and melted to obtain a melt;

[0090] 2) The metal foam substrate is placed in the melt for reaction to obtain a metal foam substrate composited with transition metal nanosheets;

[0091] 3) After mixing the soluble transition metal salt, modifier and water, a solution is obtained. The solution is placed in an electroplating tank. The metal foam substrate with transition metal nanosheets obtained in the above steps is used as the working electrode. Deposition is carried out under the action of electric field or multi-field coupling of electric field and magnetic field and nitrogen-rich atmosphere to obtain AEMWE cathode electrode material.

[0092] The present invention first mixes and melts a transition metal salt and an ammonium salt to obtain a melt.

[0093] In this invention, the transition metal in the transition metal salt preferably includes one or more of Co, Fe, Ni, Ce, Mn and Mo, and more preferably Co, Fe, Ni, Ce, Mn or Mo.

[0094] In this invention, the transition metal salt preferably includes one or more of the following: nitrate, sulfate, chloride, carbonate, acetate, ammonium salt, naphthenate, stearate, and neodecanoate of a transition metal, and more preferably, nitrate, sulfate, chloride, carbonate, acetate, ammonium salt, naphthenate, stearate, or neodecanoate of a transition metal.

[0095] In this invention, the ammonium salt preferably comprises ammonium halide. Specifically, the halogen element in the ammonium halide preferably includes one of F, Cl, Br, and I.

[0096] In this invention, the transition metal salt is calculated based on transition metal atoms, and the ammonium salt is calculated based on NH4+. + The preferred molar ratio of the two is 5:(0.1 to 5), more preferably 5:(1 to 4), and even more preferably 5:(2 to 3).

[0097] In this invention, the melting temperature is preferably 60-200°C, more preferably 70-150°C.

[0098] This invention involves reacting a metal foam substrate in a melt to obtain a metal foam substrate composited with transition metal nanosheets.

[0099] In this invention, the metal foam substrate preferably includes one or more of nickel foam, iron foam, cobalt foam, cobalt-iron foam, nickel-iron foam, and nickel mesh, and more preferably nickel foam, iron foam, cobalt foam, cobalt-iron foam, nickel-iron foam, or nickel mesh.

[0100] In this invention, the reaction time is preferably 1 to 30 minutes, more preferably 5 to 20 minutes.

[0101] Finally, the present invention mixes soluble transition metal salt, modifier and water to obtain a solution, places the solution in an electroplating tank, and uses the metal foam substrate with transition metal nanosheets obtained in the above steps as the working electrode, and performs deposition under the action of electric field or multi-field coupling of electric field and magnetic field and nitrogen-rich atmosphere to obtain AEMWE cathode electrode material.

[0102] In this invention, the transition metal in the soluble transition metal salt preferably includes one or more of Co, Fe, Ni, Ce, Mn and Mo, more preferably Co, Fe, Ni, Ce, Mn or Mo.

[0103] In this invention, the soluble transition metal salt preferably includes one or more of the transition metal nitrates, sulfates, chlorides, acetates and ammonium salts, more preferably the transition metal nitrates, sulfates, chlorides, acetates or ammonium salts.

[0104] In this invention, the modifier preferably includes one or more of sulfur source modifiers, selenium source modifiers and phosphorus source modifiers, and more preferably sulfur source modifiers, selenium source modifiers or phosphorus source modifiers.

[0105] In this invention, the molar ratio of the soluble transition metal salt to the modifier in the solution is preferably (0.05-1.5):1, more preferably (0.1-1.0):1.

[0106] In this invention, the sulfur source modifier preferably includes one or more of sulfur powder, thioacetamide, sodium sulfide and thiourea, and more preferably sulfur powder, thioacetamide, sodium sulfide or thiourea.

[0107] In this invention, the selenium source modifier preferably includes selenium powder and / or selenium dioxide, more preferably selenium powder or selenium dioxide.

[0108] In this invention, the phosphorus source modifier preferably includes one or more of potassium hypophosphite, potassium dihydrogen phosphate, red phosphorus, and sodium hypophosphite, more preferably potassium hypophosphite, potassium dihydrogen phosphate, red phosphorus, or sodium hypophosphite.

[0109] In this invention, the deposition method preferably includes one or more of constant potential deposition, constant current deposition, cyclic voltammetry and linear voltage scanning, and more preferably constant potential deposition, constant current deposition, cyclic voltammetry or linear voltage scanning.

[0110] In this invention, the deposition time is preferably 1 to 60 minutes, more preferably 5 to 30 minutes.

[0111] In this invention, the deposition temperature is preferably 20-50°C, more preferably 25-45°C, and even more preferably 30-40°C.

[0112] In this invention, the deposition is preferably performed using Hg / Hg2Cl2, Ag / AgCl, or Hg / HgO as the reference electrode and a platinum sheet / platinum wire / carbon rod as the counter electrode.

[0113] In this invention, the preferred method for adding the magnetic field is to add a magnet in the direction perpendicular to the electrode, and adjust the magnetic field strength at the center point of the magnetic field by changing the distance between the two sets of magnets.

[0114] In this invention, the magnetic field strength is preferably 0.01 to 3 T, more preferably 0.1 to 2 T.

[0115] In this invention, the metal foam substrate is preferably a pretreated metal foam substrate.

[0116] The present invention provides an anion exchange membrane water electrolysis device (AEMWE), which includes a cathode electrode;

[0117] The cathode electrode material includes any of the AEMWE cathode electrode materials described in any of the above technical solutions or the AEMWE cathode electrode material prepared by any of the preparation methods described in any of the above technical solutions.

[0118] This invention also provides the application of an AEMWE cathode electrode material as described in any one of the above technical solutions, or an AEMWE cathode electrode material prepared by any one of the above technical solutions, in the fields of anion exchange membrane electrolysis of water for hydrogen production and / or alkaline electrolysis of water for hydrogen production.

[0119] The AEMWE cathode electrode material provided by this invention comprises: a metal foam substrate and a modified transition metal nanosheet array formed on the surface of the metal foam substrate. This invention utilizes the multi-field coupling effect of electric field or electric and magnetic field to controllably grow secondary nanosheets on the primary nanosheet array, promoting the formation of lattice dislocations / twins / twisted grain boundaries, significantly reducing the charge transfer resistance of the hydrogen evolution process (superior to commercial Pt / C). Simultaneously, by utilizing the electron-withdrawing effect of halogen elements, strong metal-halogen ion bonds are formed with metal ions, promoting the formation of X- and OH- ions. - The ion exchange effectively improves the hydrogen evolution performance and long-term (>1000h) stability of the electrode material under high current density and industrial conditions. This invention provides a green method for large-scale preparation.

[0120] This invention aims to complete and refine the overall technical solution, better ensure the specific structure and morphology of the AEMWE cathode electrode material, and further improve the performance of the AEMWE cathode electrode material in anion exchange membrane water electrolysis for hydrogen production. The specific preparation method of the AEMWE cathode electrode material and its large-scale preparation at high current densities may include the following:

[0121] A high current density AEMWE cathode electrode material includes: a metal foam substrate and a modified transition metal nanosheet array formed on the surface of the metal foam substrate;

[0122] The transition metal elements include one, two, or more of Co, Fe, Ni, Ce, Mn, and Mo;

[0123] The modified transition metal nanosheet arrays are phosphorus-modified nanosheet arrays, sulfur-modified nanosheet arrays, and selenium-modified nanosheet arrays.

[0124] Specifically, the elements in the transition metal-based nanosheet array include one of the halogen elements F, CI, Br, and I.

[0125] Specifically, the transition metal includes Co.

[0126] This invention provides a method for the mass production of AEMWE cathode electrode material under high current density, comprising the following steps:

[0127] Step 1: Pre-treat the metal foam substrate by washing and drying;

[0128] Step 2: Take a certain molar mass of cobalt salt and ammonium salt, melt them at high temperature and mix them evenly to obtain melt A;

[0129] Step 3: Place the metal foam substrate treated in Step 1 into the melt A from Step 2 for reaction, wash and dry;

[0130] Step 4: Take a certain molar mass of salt and modifier, add deionized water and dissolve them completely to obtain solution B;

[0131] Step 5: Transfer the solution B obtained in Step 4 into the electroplating tank, use the sample obtained in Step 3 as the working electrode, and deposit it in an electric field or a multi-field coupling of electric and magnetic fields and a nitrogen-rich atmosphere. Wash and dry to obtain the target cathode hydrogen evolution electrode material.

[0132] Specifically, the metal foam substrates used include nickel foam, iron foam, cobalt foam, cobalt-iron foam, nickel-iron foam, nickel mesh, etc.

[0133] Specifically, the salts mentioned in step four include cobalt salts, iron salts, nickel salts, cerium salts, manganese salts, and molybdenum salts. Among them, cobalt salts include cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt carbonate, cobalt acetate, cobalt naphthenate, cobalt stearate, cobalt neodecanoate, and cobalt borylate, etc.; iron salts include ferric chloride, ferric sulfate, ferric nitrate, ferric carbonate, ferric acetate, and ferric ammonium sulfate, etc.; nickel salts include nickel chloride, nickel sulfate, nickel nitrate, nickel carbonate, and nickel acetate, etc.; cerium salts include cerium chloride, cerium sulfate, cerium nitrate, cerium carbonate, and cerium acetate, etc.; manganese salts include manganese chloride, manganese sulfate, manganese nitrate, manganese carbonate, and manganese acetate, etc.; and molybdenum salts include molybdenum chloride, molybdenum sulfate, molybdenum nitrate, molybdenum carbonate, molybdenum acetate, and ammonium molybdate, etc.

[0134] Specifically, the modifier used in step four is a sulfur-based modifier, a selenium-based modifier, or a phosphorus-based modifier.

[0135] The sulfur source modifier is preferably sulfur and / or a sulfur-containing compound, specifically one or more of sulfur powder, thioacetamide, sodium sulfide, and thiourea. The selenium source modifier is preferably selenium and / or a selenium-containing compound, specifically selenium powder and / or selenium dioxide. The phosphorus source modifier is preferably phosphorus and / or a phosphorus-containing compound, specifically one or more of potassium hypophosphite, potassium dihydrogen phosphate, red phosphorus, and sodium hypophosphite.

[0136] Specifically, the electrodeposition methods used in step five include constant potential deposition, constant current deposition, cyclic voltammetry, and linear voltage scanning.

[0137] Specifically, in step five, the fabrication needs to be carried out under the combined action of an electric field or a combination of electric and magnetic fields. The magnetic field is added by adding a permanent magnet in the direction perpendicular to the electrode. The magnetic field strength at the center point of the magnetic field is adjusted by changing the distance between the two sets of magnets. The magnetic field strength is 0 to 3 T.

[0138] Furthermore,

[0139] In the method for preparing AEMWE cathode electrode material under high current density provided by this invention,

[0140] Specifically, the metal foam substrate is preferably foamed iron or foamed nickel iron.

[0141] Specifically, in step one, the pretreatment step includes placing the metal foam substrate in dilute hydrochloric acid solution, anhydrous ethanol and deionized water in sequence for ultrasonic treatment, and then vacuum drying at low temperature.

[0142] Specifically, in step one, the concentration of the dilute hydrochloric acid solution used is 1-4 mol / L, preferably 1 mol / L; the ultrasonic treatment in the dilute hydrochloric acid solution is 1-30 min, preferably 15 min; and the ultrasonic treatment in anhydrous ethanol and deionized water is 1-30 min, preferably 15 min.

[0143] Specifically, in step two, the cobalt salt includes cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt carbonate, cobalt acetate, cobalt naphthenate, cobalt stearate, cobalt neodecanoate, and cobalt borate, etc., preferably including cobalt nitrate and cobalt chloride.

[0144] Specifically, in step two, the ammonium salt includes ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, hexadecyltrimethylammonium bromide, ammonium acetate, ammonium fluoride, ammonium nitrogen, ammonium hydroxide, diammonium sulfate, etc., preferably including ammonium fluoride, ammonium chloride, and ammonium bromide.

[0145] Specifically, in step two, the cobalt salt and ammonium salt, the Co source (calculated as Co atoms) and the NH4+ source... +The preferred molar ratio of the ammonium source in the ion meter is 5:(0.1-5), specifically 5:0.1, 5:0.5, 5:1, 5:1.5, 5:2, 5:2.5, 5:3, 5:3.5, 5:4, 5:4.5, 5:5, etc.

[0146] Specifically, in step two, for the melt A, the melting temperature of the salt is controlled at 60-200℃, with the temperature being sufficient to melt the salt.

[0147] Specifically, in step two, the melt A should be sufficiently covered / immersed in the metal foam substrate.

[0148] Specifically, in step three, the reaction time is controlled to be 1-30 min, preferably 5-15 min.

[0149] Specifically, the salts mentioned in step four include cobalt salts, iron salts, nickel salts, cerium salts, manganese salts, and molybdenum salts. Among these, cobalt salts are preferably cobalt nitrate, cobalt sulfate, or cobalt chloride; iron salts are preferably ferric chloride, ferric sulfate, or ferric nitrate; nickel salts are preferably nickel chloride, nickel sulfate, or nickel nitrate; manganese salts are preferably manganese chloride, manganese sulfate, or manganese nitrate; cerium salts are preferably cerium chloride or cerium nitrate; and molybdenum salts are preferably molybdenum nitrate or ammonium molybdate.

[0150] Specifically, in step four, the solution B is controlled to contain one, two, or more of the following: cobalt salt, iron salt, nickel salt, cerium salt, manganese salt, and molybdenum salt. The molar ratio of the metal salt to the modifier in the solution B is controlled to be (0.05-1.5):1, specifically 0.05:1, 0.25:1, 0.5:1, 0.75:1, 1:1, 1.25:1, 1.5:1, etc.

[0151] Specifically, the modifier used in step four is a sulfur-based modifier, a selenium-based modifier, or a phosphorus-based modifier; wherein, the sulfur-based modifier is preferably sulfur and / or sulfur-containing compounds, specifically one or more of sulfur powder, thioacetamide, sodium sulfide, and thiourea; the selenium-based modifier is preferably selenium and / or selenium-containing compounds, specifically selenium powder and / or selenium dioxide; the phosphorus-based modifier is preferably phosphorus and / or phosphorus-containing compounds, specifically one or more of potassium hypophosphite, potassium dihydrogen phosphate, red phosphorus, and sodium hypophosphite.

[0152] Specifically, the deposition time in solution B in step five is preferably 15-60 minutes.

[0153] Specifically, in step five, the deposition temperature is preferably 20-50℃.

[0154] Specifically, in step five, Hg / Hg2Cl2, Ag / AgCl, or Hg / HgO are used as reference electrodes, and platinum sheets / platinum wires / carbon rods are used as counter electrodes to perform electrode deposition in a three-electrode system.

[0155] Specifically, the electrodeposition methods used in step five include potentiostatic deposition, constant current deposition, and cyclic voltammetry. Specifically, the potential range for potentiostatic deposition is 0.1-10V, the current range for constant current deposition is 0.1-2A, and the scanning range for cyclic voltammetry deposition is -10-10V, the scan rate is 5-100mV / s, and the number of scans is 5-1000.

[0156] Specifically, in step five, the preparation needs to be carried out under the combined action of an electric field or a multi-field coupling of an electric field and a magnetic field. The magnetic field is added by adding a permanent magnet in the direction perpendicular to the electrode. The permanent magnet includes rare earth permanent magnets, samarium cobalt permanent magnets, aluminum nickel cobalt permanent magnets, copper nickel iron permanent magnets, iron cobalt molybdenum permanent magnets, iron cobalt vanadium permanent magnets, manganese bismuth permanent magnets, etc. The permanent magnet is preferably a block-shaped permanent magnet. The magnetic field strength at the center point of the magnetic field is adjusted by changing the distance between the two sets of magnets. The distance adjustment range is 1-50cm, and the magnetic field strength is 0-3T.

[0157] Specifically, in steps three and five, when placing the porous carrier / sample in melt A or solution B, it is required that the porous carrier / sample be completely immersed in melt A or solution B.

[0158] Specifically, the drying in steps one, three, and five refers to drying in a vacuum drying oven at 50–80°C for 6–24 hours.

[0159] Specifically, the size of the AEMWE cathode electrode material can be 1*1cm. 2 2*2cm 2 5*5cm 2 10*10cm 2 15*15cm 2 ……50*50cm 2 .

[0160] The AEMWE cathode electrode material provided by this invention is an integral, one-piece electrode. This electrode can be applied to hydrogen production via anion exchange membrane electrolysis and alkaline water electrolysis under high current density and industrial conditions.

[0161] The present invention provides an AEMWE cathode electrode material for high current density applications, its mass production method, and its applications. The AEMWE cathode electrode material with specific morphology and composition provided by the present invention is suitable for use in AEMWE applications at high current densities. The present invention also provides a corresponding method for preparing the AEMWE cathode electrode material. Through the controllable growth of a lattice-twisted material of secondary nanosheets on a primary nanosheet array via an electric field or a multi-field coupling of electric and magnetic fields, the modified metal nanosheet material obtained through in-situ construction is simple and easy to implement, suitable for industrialization and commercial application.

[0162] The AEMWE cathode electrode material provided by this invention, through the introduction of halogen atoms, exhibits excellent electrocatalytic hydrogen evolution performance under their strong electron-withdrawing effect. Furthermore, through the macroscopic and microscopic magnetohydrodynamic effects generated by the Lorentz force, the liquid phase mass transfer rate is increased. By influencing various steps in the deposition process, such as liquid phase mass transfer and electrode polarization, the performance of the AEMWE cathode electrode material is improved.

[0163] Test results show that the AEMWE cathode electrode material provided by this invention, in the membrane electrode (industrial-scale test) test, using the self-made catalyst (CN115404505A) as the anode and Xiamen University Jiaming membrane as the anion exchange membrane, achieved a battery voltage of 1.93V at a current of 4A and could operate stably for 1000h (test conditions: 1M KOH, 80℃, membrane electrode assembly size 2*2cm). 2 ).

[0164] To further illustrate the present invention, the following detailed description of an AEMWE cathode electrode material, its preparation method, and its application, in conjunction with embodiments, is provided. However, it should be understood that these embodiments are implemented under the premise of the technical solution of the present invention, and detailed implementation methods and specific operating procedures are given only to further illustrate the features and advantages of the present invention, and are not intended to limit the scope of the claims of the present invention. The scope of protection of the present invention is not limited to the following embodiments.

[0165] Example 1

[0166] This embodiment provides the AEMWE cathode electrode material F(fluorine)-Co. x Fe y (PO4) z The preparation method of / IF includes the following steps:

[0167] (1) Cut commercial foam iron into 20mm*20mm sizes, and sonicate it in 1mol / L dilute hydrochloric acid for 15min, then sonicate it in anhydrous ethanol and deionized water for 15min each, and then vacuum dry it at 60℃ for 12h for later use.

[0168] (2) Weigh 30 mmol of cobalt nitrate hexahydrate and 10 mmol of ammonium fluoride, melt them at high temperature and mix them evenly to obtain melt A;

[0169] (3) The treated foamed iron was placed into melt A and reacted for 10 min. The foamed iron was then removed, rinsed with deionized water, and vacuum dried at 60 °C for 12 h to obtain F-Co. x Fe y / IF, its SEM topography is as follows Figure 1 As shown;

[0170] (4) Weigh 1 mmol of cobalt nitrate hexahydrate and 1 mmol of sodium hypophosphite, add 50 mL of deionized water and stir until a clear solution is obtained to obtain solution B;

[0171] (5) The sample treated in step (3) is placed in salt solution B from step (4), and electrodeposition is performed in a water bath at 40°C under an external magnetic field and a nitrogen-rich atmosphere. After washing and drying, F-Co is obtained. x Fe y (PO4) z / IF, its SEM topography is as follows Figure 2 As shown.

[0172] See Figure 1 , Figure 1 The F-Co obtained in Example 1 of this invention x Fe y SEM topography of / IF.

[0173] As attached Figure 1 As shown, the nanosheets are randomly attached to the foamed iron and are densely arranged, which can provide more contact area and active sites.

[0174] See Figure 2 , Figure 2 The F-Co obtained in Example 1 of this invention x Fe y (PO4) z SEM topography of / IF. The image above is... Figure 2 (1), The following figure is Figure 2 (2).

[0175] As attached Figure 2 As shown, from Figure 2 (1) It can be clearly seen that vertically grown nanosheets are uniformly distributed on the sample surface. The estimated diameter of the nanosheets is approximately 5-10 micrometers. Figure 2 As can be seen in (2), smaller nanosheets are growing at the edges of the nanosheets.

[0176] See Figure 3 , Figure 3 The F-Co obtained in Example 1 of this invention x Fe y (PO4) z XRD pattern of / IF.

[0177] As attached Figure 3 As shown in the figure, the material contains CoFe and Co3Fe4(PO4)6. CoFe originates from the interaction between cobalt and iron during the melting process under the influence of electron-withdrawing groups, while Co3Fe4(PO4)6 originates from the deposition process, and Fe is the base foam iron.

[0178] See Figure 4 , Figure 4 The F-Co obtained in Example 1 of this invention x Fe y (PO4) z The LSV, AC impedance spectrum (EIS), and current density versus time plots for the / IF material. Figure 4 (1) is the LSV curve of hydrogen evolution by water electrolysis in alkaline solution. Figure 4 (2) is the electrochemical impedance spectroscopy (EIS) of the material in alkaline solution. Figure 4 (3) To test the stability of the material in the electrolysis of water and hydrogen evolution in alkaline solution.

[0179] As attached Figure 4 As shown, where:

[0180] Figure 4 Figure (1) shows the LSV curve of the material during water electrolysis in alkaline solution to produce hydrogen. The figure shows that the hydrogen evolution performance of the material is within 1000 mA / cm². 2 The voltage was 276mV.

[0181] Figure 4 (2) is the electrochemical impedance spectroscopy (EIS) of the material in alkaline solution. It can be seen from the figure that the charge transfer resistance of the material is 0.18Ω.

[0182] Figure 4 Figure (3) shows the stability test of the material during hydrogen evolution by water electrolysis in an alkaline solution. As can be seen from the figure, the material exhibits good stability at 1000 mA / cm². 2 The current density can remain unchanged for 100 hours, therefore, the AEMWE cathode electrode material prepared in this invention has excellent hydrogen evolution stability.

[0183] Example 2

[0184] This embodiment provides the AEMWE cathode electrode material F-Co. x Fe y Sz The preparation method of / IF includes the following steps:

[0185] (1) Cut commercial foam iron into 20mm*20mm sizes, and sonicate it in 1mol / L dilute hydrochloric acid for 15min, then sonicate it in anhydrous ethanol and deionized water for 15min each, and then vacuum dry it at 60℃ for 12h for later use.

[0186] (2) Weigh 30 mmol of cobalt nitrate hexahydrate and 10 mmol of ammonium fluoride, melt them at high temperature and mix them evenly to obtain melt A;

[0187] (3) The treated foamed iron was placed into melt A and reacted for 10 min. The foamed iron was then removed, rinsed with deionized water, and vacuum dried at 60 °C for 12 h to obtain F-Co. x Fe y / IF;

[0188] (4) Weigh 1 mmol of cobalt nitrate hexahydrate and 1 mmol of sodium sulfide, add 50 mL of deionized water and stir until a clear solution is obtained to obtain solution B;

[0189] (5) The sample treated in step (3) is placed in the salt solution B of step (4), and electrodeposited under an external magnetic field and a nitrogen-rich atmosphere in a water bath at 40°C. The sample is then washed and dried to obtain the target catalyst.

[0190] Example 3

[0191] This embodiment provides the AEMWE cathode electrode material F-Co. x Fe y Se z The preparation method of / IF includes the following steps:

[0192] (1) Cut commercial foam iron into 20mm*20mm sizes, and sonicate it in 1mol / L dilute hydrochloric acid for 15min, then sonicate it in anhydrous ethanol and deionized water for 15min each, and then vacuum dry it at 60℃ for 12h for later use.

[0193] (2) Weigh 30 mmol of cobalt nitrate hexahydrate and 10 mmol of ammonium fluoride, melt them at high temperature and mix them evenly to obtain melt A;

[0194] (3) The treated foamed iron was placed into melt A and reacted for 10 min. The foamed iron was then removed, rinsed with deionized water, and vacuum dried at 60 °C for 12 h to obtain F-Co. x Fe y / IF;

[0195] (4) Weigh out 1 mmol of cobalt nitrate hexahydrate and 1 mmol of selenium oxide, add 50 mL of deionized water and stir until a clear solution is obtained to get solution B;

[0196] (5) The sample treated in step (3) is placed in the salt solution B of step (4), and electrodeposited under an external magnetic field and a nitrogen-rich atmosphere in a water bath at 40°C. The sample is then washed and dried to obtain the target catalyst.

[0197] Example 4

[0198] This embodiment provides the AEMWE cathode electrode material F-Co. x Fe y P z The preparation method of / IF includes the following steps:

[0199] (1) Cut commercial foam iron into 20mm*20mm sizes, and sonicate it in 1mol / L dilute hydrochloric acid for 15min, then sonicate it in anhydrous ethanol and deionized water for 15min each, and then vacuum dry it at 60℃ for 12h for later use.

[0200] (2) Weigh 30 mmol of cobalt nitrate hexahydrate and 10 mmol of ammonium fluoride, melt them at high temperature and mix them evenly to obtain melt A;

[0201] (3) The treated foamed iron was placed into melt A and reacted for 10 min. The foamed iron was then removed, rinsed with deionized water, and vacuum dried at 60 °C for 12 h to obtain F-Co. x Fe y / IF;

[0202] (4) Weigh out 1 mmol of cobalt nitrate hexahydrate and 3 mmol of potassium dihydrogen phosphate, add 50 mL of deionized water and stir until a clear solution is obtained to get solution B;

[0203] (5) The sample treated in step (3) is placed in the salt solution B of step (4), and electrodeposited in a nitrogen-rich atmosphere under a water bath at 40°C. The sample is then washed and dried to obtain the target catalyst.

[0204] Example 5

[0205] This embodiment provides the AEMWE cathode electrode material CI-Co. x Fe y P z The preparation method of / IF includes the following steps:

[0206] (1) Cut commercial foam iron into 20mm*20mm sizes, and sonicate it in 1mol / L dilute hydrochloric acid for 15min, then sonicate it in anhydrous ethanol and deionized water for 15min each, and then vacuum dry it at 60℃ for 12h for later use.

[0207] (2) Weigh 30 mmol of cobalt nitrate hexahydrate and 10 mmol of ammonium chloride, melt them at high temperature and mix them evenly to obtain melt A;

[0208] (3) Place the treated foamed iron into melt A and react for 10 min. Remove the foamed iron, rinse with deionized water, and vacuum dry at 60 °C for 12 h to obtain CI-Co. x Fe y / IF;

[0209] (4) Weigh out 1 mmol of cobalt nitrate hexahydrate and 3 mmol of potassium dihydrogen phosphate, add 50 mL of deionized water and stir until a clear solution is obtained to get solution B;

[0210] (5) The sample treated in step (3) is placed in the salt solution B of step (4), and electrodeposited in a nitrogen-rich atmosphere under a water bath at 40°C. The sample is then washed and dried to obtain the target catalyst.

[0211] Example 6

[0212] This embodiment provides the AEMWE cathode electrode material Br-Co. x Fe y P z The preparation method of / IF includes the following steps:

[0213] (1) Cut commercial foam iron into 20mm*20mm sizes, and sonicate it in 1mol / L dilute hydrochloric acid for 15min, then sonicate it in anhydrous ethanol and deionized water for 15min each, and then vacuum dry it at 60℃ for 12h for later use.

[0214] (2) Weigh 30 mmol of cobalt nitrate hexahydrate and 10 mmol of ammonium bromide, melt them at high temperature and mix them evenly to obtain melt A;

[0215] (3) The treated foamed iron was placed into melt A and reacted for 10 min. The foamed iron was then removed, rinsed with deionized water, and vacuum dried at 60 °C for 12 h to obtain Br-Co. x Fe y / IF;

[0216] (4) Weigh out 1 mmol of cobalt nitrate hexahydrate and 3 mmol of potassium dihydrogen phosphate, add 50 mL of deionized water and stir until a clear solution is obtained to get solution B;

[0217] (5) The sample treated in step (3) is placed in the salt solution B of step (4), and electrodeposited in a nitrogen-rich atmosphere under a water bath at 40°C. The sample is then washed and dried to obtain the target catalyst.

[0218] Example 7

[0219] This embodiment provides the AEMWE cathode electrode material F-Co / Ce. x Fe y S z The preparation method of / IF includes the following steps:

[0220] (1) Cut commercial foam iron into 20mm*20mm sizes, and sonicate it in 1mol / L dilute hydrochloric acid for 15min, then sonicate it in anhydrous ethanol and deionized water for 15min each, and then vacuum dry it at 60℃ for 12h for later use.

[0221] (2) Weigh 30 mmol of cobalt nitrate hexahydrate and 10 mmol of ammonium fluoride, melt them at high temperature and mix them evenly to obtain melt A;

[0222] (3) The treated foamed iron was placed into melt A and reacted for 10 min. The foamed iron was then removed, rinsed with deionized water, and vacuum dried at 60 °C for 12 h to obtain F-Co. x Fe y / IF;

[0223] (4) Weigh 1 mmol of cerium nitrate hexahydrate and 1.25 mmol of sodium sulfide, add 50 mL of deionized water and stir until a clear solution is obtained to get solution B;

[0224] (5) The sample treated in step (3) is placed in the salt solution B of step (4), and electrodeposited in a nitrogen-rich atmosphere under a water bath at 40°C. The sample is then washed and dried to obtain the target catalyst.

[0225] Example 8

[0226] This embodiment provides the AEMWE cathode electrode material F-Co / Ni. x Fe y S z The preparation method of / IF includes the following steps:

[0227] (1) Cut commercial foam iron into 20mm*20mm sizes, and sonicate it in 1mol / L dilute hydrochloric acid for 15min, then sonicate it in anhydrous ethanol and deionized water for 15min each, and then vacuum dry it at 60℃ for 12h for later use.

[0228] (2) Weigh 30 mmol of cobalt nitrate hexahydrate and 10 mmol of ammonium fluoride, melt them at high temperature and mix them evenly to obtain melt A;

[0229] (3) The treated foamed iron was placed into melt A and reacted for 10 min. The foamed iron was then removed, rinsed with deionized water, and vacuum dried at 60 °C for 12 h to obtain F-Co. x Fe y / IF;

[0230] (4) Weigh 1 mmol of nickel nitrate hexahydrate and 2 mmol of sodium sulfide, add 50 mL of deionized water and stir until a clear solution is obtained to get solution B;

[0231] (5) The sample treated in step (3) is placed in the salt solution B of step (4), and electrodeposited in a nitrogen-rich atmosphere under a water bath at 40°C. The sample is then washed and dried to obtain the target catalyst.

[0232] Comparative Example 1

[0233] The materials used in this comparative scheme were those without added ammonium salts (denoted as Co). x Fe y S z / IF), the specific preparation process is as follows:

[0234] (1) Cut commercial foam iron into 20mm*20mm sizes, and sonicate it in 1mol / L dilute hydrochloric acid for 15min, then sonicate it in anhydrous ethanol and deionized water for 15min each, and then vacuum dry it at 60℃ for 12h for later use.

[0235] (2) Weigh 30 mmol of cobalt nitrate hexahydrate, melt it at high temperature and mix it evenly to obtain melt A;

[0236] (3) Place the treated foamed iron into melt A, react for 10 min, remove the foamed iron, rinse with deionized water, and vacuum dry at 60℃ for 12 h;

[0237] (4) Weigh 1 mmol of cobalt nitrate hexahydrate and 1 mmol of sodium sulfide, add 50 mL of deionized water and stir until a clear solution is obtained to obtain solution B;

[0238] (5) The sample treated in step (3) is placed in the salt solution B of step (4), and electrodeposited under an external magnetic field and a nitrogen-rich atmosphere in a water bath at 40°C. The sample is then washed and dried to obtain the target catalyst.

[0239] Comparative Example 2

[0240] The material used in this comparative example is the material without any added modifier (denoted as F-Co). x Fey / IF), the specific preparation process is as follows:

[0241] (1) Cut commercial foam iron into 20mm*20mm sizes, and sonicate it in 1mol / L dilute hydrochloric acid for 15min, then sonicate it in anhydrous ethanol and deionized water for 15min each, and then vacuum dry it at 60℃ for 12h for later use.

[0242] (2) Weigh 30 mmol of cobalt nitrate hexahydrate and 10 mmol of ammonium fluoride, melt them at high temperature and mix them evenly to obtain melt A;

[0243] (3) Place the treated foamed iron into melt A, react for 10 min, remove the foamed iron, rinse with deionized water, and vacuum dry at 60℃ for 12 h;

[0244] (4) Take another 1 mmol of cobalt nitrate hexahydrate, add 50 mL of deionized water and stir until a clear solution is obtained to get solution B;

[0245] (5) The sample treated in step (3) is placed in the salt solution B of step (4), and electrodeposited under an external magnetic field and a nitrogen-rich atmosphere in a water bath at 40°C. The sample is then washed and dried to obtain the target catalyst.

[0246] Comparative Example 3

[0247] The material used in this comparative scheme is a material that undergoes only one chemical deposition step (denoted as F-CoFe / IF). The specific preparation process is as follows:

[0248] (1) Cut commercial foam iron into 20mm*20mm sizes, and sonicate it in 1mol / L dilute hydrochloric acid for 15min, then sonicate it in anhydrous ethanol and deionized water for 15min each, and then vacuum dry it at 60℃ for 12h for later use.

[0249] (2) Weigh 30 mmol of cobalt nitrate hexahydrate and 10 mmol of ammonium fluoride, melt them at high temperature and mix them evenly to obtain melt A;

[0250] (3) The treated foamed iron was placed into melt A and reacted for 10 min. The foamed iron was then removed, rinsed with deionized water, and vacuum dried at 60 °C for 12 h to obtain the target catalyst.

[0251] Comparative Example 4

[0252] The material used in this comparative scheme is a material that only undergoes one electrodeposition step (denoted as Co). min Fe y S z / IF), the specific preparation process is as follows:

[0253] (1) Cut commercial foam iron into 20mm*20mm sizes, and sonicate it in 1mol / L dilute hydrochloric acid for 15min, then sonicate it in anhydrous ethanol and deionized water for 15min each, and then vacuum dry it at 60℃ for 12h for later use.

[0254] (2) Weigh 1 mmol of cobalt nitrate hexahydrate and 1 mmol of sodium sulfide, add 50 mL of deionized water and stir until a clear solution is obtained to obtain solution B;

[0255] (3) The foamed iron treated in step (1) is placed in the salt solution B of step (2), and electrodeposited under an external magnetic field and a nitrogen-rich atmosphere in a water bath at 40°C. The solution is then washed and dried to obtain the target catalyst.

[0256] The performance of the AEMWE cathode electrode material in the examples and comparative examples was tested as follows:

[0257] Electrochemical tests were performed on an electrochemical workstation. The cathode electrode material prepared above was used as the cathode, the carbon rod as the counter electrode, and Hg / HgO as the reference electrode. The linear sweep curve, electrochemical impedance, and stability of the cathode electrode material were measured in 1 mol / L KOH solution.

[0258] The test results are as follows:

[0259] See Table 1, which shows the electrocatalytic hydrogen evolution performance data of different embodiments and comparative materials of the present invention.

[0260] Table 1. Electrocatalytic hydrogen evolution performance data of different embodiments and comparative materials.

[0261]

[0262]

[0263] In addition, the present invention also addresses F-Co x Fe y (PO4) z The performance of / IF cathode electrode materials, commercial nickel foam, and commercial PtC / IrO2 was tested using the following methods:

[0264] Anion exchange membrane electrolysis water test was conducted using a 2cm*2cm anion exchange membrane electrolyzer, with F-Co... x Fe y (PO4) z / IF was used as the cathode electrode material, and a self-made catalyst from our laboratory was used as the AEMWE anode electrode material. For the comparative example, two sheets of pure nickel foam were used, with commercially available PtC and IrO2 serving as the cathode and anode, respectively. All membrane electrodes were constructed using Xiamen University Jiaming membrane as the anion exchange membrane. Membrane electrode tests were performed in 1 M KOH solution. The results showed that... Figure 5 The test results show that the battery voltage is 1.93V under a current of 4A, and the stability shows no degradation after 1000h.

[0265] See Figure 5 , Figure 5 The AEMWE test curve is for the cathode material prepared in Example 1 of this invention.

[0266] Figure 5 In the test, Example 1 used a cathode material consisting of a laboratory-made anode material and a membrane from Xiamen University, forming a 2*2cm structure. 2 According to AEMWE's industrial-grade water electrolysis test, the MEA can reach a battery voltage of 1.93V at a current of 4A and operate stably for 1000 hours.

[0267] In summary, the AEMWE cathode electrode material provided by this invention exhibits excellent hydrogen evolution performance in alkaline solutions.

[0268] The foregoing provides a detailed description of an AEMWE cathode electrode material for high current density, its mass production method, and its applications. Specific examples have been used to illustrate the principles and implementation methods of this invention. The descriptions of these embodiments are merely illustrative of the method and core ideas of this invention, including the best mode, and are intended to enable any person skilled in the art to practice this invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that those skilled in the art can make various improvements and modifications to this invention without departing from its principles, and these improvements and modifications also fall within the scope of protection of the claims. The scope of protection of this patent is defined by the claims and may include other embodiments conceived by those skilled in the art. If these other embodiments have structural elements that are not different from the wording of the claims, or if they include equivalent structural elements that are not substantially different from the wording of the claims, then these other embodiments should also be included within the scope of the claims.

Claims

1. A method for preparing an AEMWE cathode electrode material, characterized in that, Includes the following steps: 1) The transition metal salt and ammonium salt are mixed and melted to obtain a melt; The transition metal in the transition metal salt is Co; The ammonium salt is an ammonium halide; 2) The metal foam substrate is placed in the melt for reaction to obtain a metal foam substrate composited with transition metal nanosheets; The metal foam substrate is foamed iron; 3) After mixing the soluble transition metal salt, modifier and water, a solution is obtained. The solution is placed in an electroplating tank. The metal foam substrate with transition metal nanosheets obtained in the above steps is used as the working electrode. Deposition is carried out under the action of electric field or multi-field coupling of electric field and magnetic field and nitrogen-rich atmosphere to obtain AEMWE cathode electrode material. The transition metal in the soluble transition metal salt includes one or more of Co, Fe, Ni, Ce, Mn, and Mo; The modifier is one or more of sulfur-based modifiers, selenium-based modifiers, and phosphorus-based modifiers.

2. The preparation method according to claim 1, characterized in that, The transition metal salts include one or more of the following: nitrates, sulfates, chlorides, carbonates, acetates, naphthenates, stearates, and neodecanoates of transition metals; The transition metal salt is calculated based on transition metal atoms, and the ammonium salt is calculated based on NH4+. + The molar ratio of the two is calculated to be 5:(0.1~5). The melting temperature is 60~200℃; The reaction time is 1 to 30 minutes.

3. The preparation method according to claim 1, characterized in that, The soluble transition metal salts include one or more of the transition metal nitrates, sulfates, chlorides, and acetates; In the solution, the molar ratio of soluble transition metal salt to modifier is (0.05~1.5):

1.

4. The preparation method according to claim 1, characterized in that, The sulfur source modifier includes one or more of sulfur powder, thioacetamide, sodium sulfide, and thiourea. The selenium source modifier includes selenium powder and / or selenium dioxide; The phosphorus source modifier includes one or more of potassium hypophosphite, potassium dihydrogen phosphate, red phosphorus, and sodium hypophosphite.

5. The preparation method according to claim 1, characterized in that, The deposition method includes one or more of the following: constant potential deposition, constant current deposition, cyclic voltammetry, and linear voltage scanning. The deposition time is 1 to 60 minutes; The deposition temperature is 20~50℃; The deposition process specifically involves using Hg / Hg2Cl2, Ag / AgCl, or Hg / HgO as the reference electrode and a platinum sheet / platinum wire / carbon rod as the counter electrode. The magnetic field is added by adding a magnet in the direction perpendicular to the electrode, and adjusting the magnetic field strength at the center point of the magnetic field by changing the distance between the two sets of magnets. The magnetic field strength is 0.01~3T; The metal foam substrate is specifically a pretreated metal foam substrate.

6. The preparation method according to claim 1, characterized in that, The AEMWE cathode electrode material includes: a metal foam substrate and a modified transition metal-based nanosheet array composited on the surface of the metal foam substrate; Specifically, the modified transition metal-based nanosheets are transition metal-based nanosheets composited on the surface of a metal foam substrate and a modified transition metal-based superimposed layer superimposed on the transition metal nanosheets.

7. The preparation method according to claim 6, characterized in that, The nanosheet array has a cluster-like structure formed by interlaced petal-like growth; The thickness of the nanosheet is 1~50 nm; The nanosheets have a diameter of 10 nm to 10 μm; The nanosheets in the nanosheet array form a porous structure.

8. The preparation method according to claim 6, characterized in that, The thickness of the nanosheet array is 10 nm to 20 μm; The transition metal-based nanosheets also include halogen elements; The halogen elements and the transition metals have transition metal ion-halogen ion bonds; The mass ratio of the metal foam substrate to the modified transition metal-based nanosheet array is (3~20):1; The modified transition metal-based nanosheets are further coated with modified transition metal-based nanoparticles. The modified transition metal-based nanoparticles have a particle size of 1~50 nm.

9. The preparation method according to claim 6, characterized in that, The thickness of the modified transition metal matrix superposition layer is 10 nm to 20 μm; The modified transition metal-based superimposed layer includes one or more of the following: transition metal sulfides and / or transition metal sulfoxides, transition metal phosphides and / or transition metal phosphoxides, and transition metal selenides and / or transition metal selenides. The transition metal-based nanosheets and the modified transition metal-based superimposed layer have one or more topological structures among lattice dislocations, twins, and distorted grain boundary structures.

10. The application of the AEMWE cathode electrode material prepared by the preparation method according to any one of claims 1 to 9 in the fields of anion exchange membrane electrolysis of water for hydrogen production and / or alkaline electrolysis of water for hydrogen production.

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