Membrane electrode, preparation method thereof and electrolytic bath
By employing a combination design of a porous metal diffusion layer, a conductive polymer layer, and a high-entropy alloy catalyst in the AEM membrane electrode, the problem of insufficient dynamic response performance was solved, enabling efficient and stable hydrogen production through water electrolysis in renewable energy power generation systems.
Patent Information
- Application Number
- CN202511327341.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-16
- Publication Date
- 2026-01-27
AI Technical Summary
AEM membrane electrodes exhibit poor dynamic response performance in water electrolysis hydrogen production systems coupled with renewable energy power generation. In particular, they are difficult to adjust ion transport, charge transfer, and reaction rates rapidly during fast current loading or unloading, resulting in large voltage fluctuations, reduced efficiency, and even material aging and failure.
An anode catalytic diffusion layer composed of a porous metal diffusion layer and an anode catalytic layer, combined with a conductive polymer layer and a cathode catalytic layer, optimizes ion transport and electron conduction through the combination of rigid and flexible structures, enhancing the mechanical-electrochemical coupling performance. The use of transition metal oxide modified foam metal layer and pentagonal high-entropy alloy catalyst improves dynamic response capability and durability.
It improves the membrane electrode's ability to quickly regulate power and its durability under fluctuating power supply conditions, extends its service life, and reduces the voltage fluctuation rate and material aging risk of the electrolyzer.
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Figure CN121407149A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application relates to the technical field of hydrogen production by water electrolysis, and particularly relates to a membrane electrode and a preparation method thereof and an electrolytic cell. BACKGROUND
[0002] Anion exchange membrane water electrolysis (AEMWE) technology combines some advantages of traditional alkaline water electrolysis and PEM water electrolysis technology, and is an important embodiment of continuous development and innovation of water electrolysis hydrogen production technology. Among them, the AEM (anion exchange membrane) membrane electrode, as the core component of the AEM electrolytic cell, is in the center position of the electrolysis process, and plays an important role in providing an electrochemical reaction site, ion conduction, gas separation, electron conduction and circuit connection.
[0003] At present, in the water electrolysis hydrogen production system directly coupled with renewable energy power generation (such as wind power and photovoltaic power), due to the intermittency and instability of energy, the dynamic response capability of the AEM membrane electrode is required to be extremely high. However, in the related technology, the dynamic response performance of the AEM membrane electrode is generally poor, especially when facing rapid current loading or unloading and frequent load changes, the traditional membrane electrode is difficult to quickly adjust the ion transport, charge transfer and reaction rate in the internal thereof, resulting in large voltage fluctuation, sharp reduction of electrolysis efficiency, and even causing accelerated aging and failure of the electrode material, which becomes a bottleneck restricting the efficient and stable operation of the anion exchange membrane water electrolysis system. SUMMARY
[0004] Embodiments of the application provide a membrane electrode and a preparation method thereof and an electrolytic cell, which can improve the dynamic response performance of the membrane electrode, improve the rapid power regulation capability and durability under fluctuating power, and prolong the service life.
[0005] In a first aspect, embodiments of the application provide a membrane electrode, comprising:
[0006] An anode catalytic diffusion layer, the anode catalytic diffusion layer comprising a porous metal diffusion layer and an anode catalytic layer formed on one side of the porous metal diffusion layer;
[0007] An anion exchange membrane, the anion exchange membrane being arranged on the side of the anode catalytic diffusion layer with the anode catalytic layer;
[0008] A conductive polymer layer, the conductive polymer being arranged on the side of the anion exchange membrane away from the anode catalytic diffusion layer;
[0009] A cathode catalytic diffusion layer, the cathode catalytic diffusion layer comprising a cathode gas diffusion layer and a cathode catalytic layer arranged on one side of the cathode gas diffusion layer, the cathode catalytic layer being located between the conductive polymer layer and the cathode gas diffusion layer.
[0010] The membrane electrode provided in this application embodiment employs a composite anodic catalytic diffusion layer consisting of a porous metal diffusion layer and an anodic catalytic layer. This ensures the anodic catalytic effect while improving the rigidity of the anodic catalytic diffusion layer. Furthermore, its close fit with a flexible anion exchange membrane effectively reduces pore blockage in the flexible anodic gas diffusion layer, thus improving the stability of the anodic catalytic layer. The combination of rigid and flexible structures enhances the membrane electrode's rapid power regulation capability and durability under fluctuating power supplies. By placing a conductive polymer layer between the cathode catalytic diffusion layer and the anion exchange membrane, the mass transfer effect between the cathode catalytic layer and the anion exchange membrane, as well as the catalytic activity of the cathode catalytic layer, is improved. This mitigates the mechanical-electrochemical coupling phenomenon under dynamic operating conditions, achieving high dynamic response while maintaining good adaptability to fluctuating power supplies. In other words, the membrane electrode provided in this application embodiment improves the dynamic response performance of the membrane electrode, enhances its rapid power regulation capability and durability under fluctuating power supplies, and extends its service life.
[0011] In some embodiments, the porous metal diffusion layer includes a foamed metal layer;
[0012] One side of the foam metal layer is modified to generate a transition metal compound, forming an anode catalyst layer; wherein the transition metal compound includes at least one of transition metal oxides, transition metal phosphides and transition metal sulfides.
[0013] The foamed metal layer possesses excellent mechanical strength, supporting the overall structure of the anolyte catalytic active layer. Its unique pore structure shortens ion diffusion paths and enhances electron conduction efficiency, enabling a rapid response to current changes. One side of the foamed metal layer is modified to form transition metal oxides, exhibiting good oxygen evolution reaction (OER) catalytic activity, ensuring optimal catalytic performance. Transition metal oxides, transition metal phosphides, and transition metal sulfides possess unique electronic structures, tunable active sites, and good stability, resulting in excellent catalytic effects.
[0014] In some embodiments, the thickness of the anodic catalytic diffusion layer is 0.25 mm to 0.35 mm;
[0015] And / or, the porosity of the anode catalytic diffusion layer is 80%-95%;
[0016] And / or, the flexural strength of the anode catalytic diffusion layer is 50MPa-200MPa;
[0017] And / or, the surface roughness Ra of the anodic catalytic diffusion layer near the anion exchange membrane is ≤0.8μm.
[0018] By ensuring that the thickness, porosity, flexural strength, and roughness of the anode catalytic diffusion layer are within the aforementioned ranges, the mechanical strength and rapid response performance of the anode catalytic active layer can be guaranteed, the contact performance between the anode catalytic layer and the anion exchange membrane can be improved, and the catalytic activity can be guaranteed.
[0019] In some embodiments, the thickness of the anion exchange membrane is 70 μm-80 μm;
[0020] And / or, the ion exchange capacity of the anion exchange membrane is 2.8 mmol / g-3.2 mmol / g;
[0021] And / or, the sheet resistance of the anion exchange membrane is <0.1 Ω·cm 2 ;
[0022] And / or, the elongation at break of the anion exchange membrane is 50%-150%.
[0023] By keeping the thickness, sheet resistance, and elongation at break of the anion exchange membrane within the aforementioned ranges, the ion transport path can be shortened, mechanical strength and flexibility can be balanced, the efficiency of hydrogen production from water electrolysis can be improved, and the stability of the anion exchange membrane can be guaranteed.
[0024] In some embodiments, the thickness of the conductive polymer layer is 4 μm-6 μm;
[0025] And / or, the porosity of the conductive polymer layer is 40%-60%.
[0026] The conductive polymer layer can serve as an electron conduction bridge connecting the anion exchange membrane and the cathode catalyst layer, improving contact performance. By ensuring the thickness and porosity of the conductive polymer are within the aforementioned ranges, electron conduction efficiency can be improved, ion transport resistance reduced, and mechanical stability guaranteed.
[0027] In some embodiments, the conductive polymer layer comprises a poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid composite material.
[0028] Poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid composites possess advantages such as high electrical conductivity and good flexibility. When applied to conductive polymer layers, they can improve electron conduction efficiency. The sulfonic acid groups in these composites enable bifacial bonding with anion exchange membranes and anion catalyst layers, mitigating the difference in expansion coefficients between the rigid cathode catalyst layer and the flexible anion exchange membrane. This effectively improves poor interfacial contact between the anion exchange membrane and the cathode catalyst layer, addresses interfacial delamination caused by mechanical stress, and reduces the performance degradation of the cathode catalyst layer under high current densities.
[0029] In some embodiments, the cathode gas diffusion layer includes at least one of a carbon-based support and a metal-based support.
[0030] Carbon-based and metal-based supports can provide more catalyst attachment sites, have higher specific surface area and porosity, and better mechanical properties, thus providing abundant catalyst attachment sites and ensuring excellent diffusion performance.
[0031] In some embodiments, the cathode catalyst layer includes a cathode catalyst, which includes a pentagonal high-entropy alloy.
[0032] Five-element high-entropy alloys include at least one of nickel-cobalt-iron-molybdenum-chromium alloys and platinum-ruthenium-iridium-palladium alloys.
[0033] Five-element high-entropy alloys (HEAs) can rapidly adsorb and dissociate reactants under dynamic operating conditions, accelerating the electrochemical reaction process and ensuring efficient charge transfer. The multi-element combination can regulate the surface electronic structure to adapt to dynamic pH fluctuations during water electrolysis for hydrogen production.
[0034] Nickel-cobalt-iron-molybdenum-chromium alloys (Ni-Co-Fe-Mo-Cr) are non-precious metal systems with low cost, abundant active sites, and good chemical and structural stability. Platinum-ruthenium-iridium-palladium alloys (Pt-Ru-Ir-Pd-Au) have diverse active sites, synergistic effects among multiple elements, improved reaction efficiency, and excellent stability.
[0035] In some embodiments, the cathode catalyst comprises a nickel-cobalt-iron-molybdenum-chromium alloy;
[0036] In nickel-cobalt-iron-molybdenum-chromium alloys, the atomic ratio of nickel, cobalt, iron, molybdenum and chromium is (20-25):(15-20):(15-20):(30-35):(5-10);
[0037] And / or, the average particle size of the nickel-cobalt-iron-molybdenum-chromium alloy is 5nm-15nm.
[0038] By ensuring the atomic ratios of each element in the nickel-cobalt-iron-molybdenum-chromium alloy are within the aforementioned range, nickel can play a dominant role, ensuring sufficient active sites and lowering the energy barrier for the hydrogen evolution reaction. Cobalt and iron exhibit a synergistic effect, molybdenum enhances activity and provides corrosion resistance, while chromium improves oxidation resistance and stability. Maintaining the average particle size of the nickel-cobalt-iron-molybdenum-chromium alloy within the aforementioned range increases its specific surface area, exposing more active sites and enhancing catalytic activity.
[0039] In some embodiments, molybdenum in the nickel-cobalt-iron-molybdenum-chromium alloy is partially replaced by tungsten, wherein the atomic ratio of molybdenum to tungsten is (3-5):1.
[0040] By replacing part of the molybdenum element with tungsten and keeping the atomic ratio of molybdenum to tungsten within the aforementioned range, the melting point and stability can be improved, compensating for the insufficient performance of molybdenum under extreme conditions, and balancing the catalytic activity and stability of nickel-cobalt-iron-molybdenum-chromium alloys.
[0041] In some embodiments, the thickness of the cathode catalyst layer is 25 μm-35 μm;
[0042] And / or, the porosity of the cathode catalyst layer is 60%-70%.
[0043] And / or, the overpotential for hydrogen evolution reaction in the cathode catalyst layer is ≤35mV@10mA / cm 2 .
[0044] The thickness, porosity, and hydrogen evolution reaction overpotential of the cathode catalyst layer are within the above range, which can balance catalytic activity and transport performance, provide sufficient electrolyte-gas-solid three-phase interface, and maintain good mechanical strength and durability.
[0045] In some embodiments, an adhesive layer is provided between the conductive polymer layer and the anion exchange membrane.
[0046] By setting an adhesive layer between the conductive polymer layer and the anion exchange membrane, the interfacial bonding force between the conductive polymer layer and the anion exchange membrane can be enhanced, improving ion transport performance. In addition, the adhesive layer can also buffer the difference in thermal expansion coefficient and reduce stress concentration.
[0047] Secondly, embodiments of this application provide a method for preparing a membrane electrode, comprising:
[0048] An anode catalytic diffusion layer, an anion exchange membrane, a conductive polymer layer, and a cathode catalytic diffusion layer are provided; wherein, the anode catalytic diffusion layer includes a porous metal diffusion layer and an anode catalytic layer formed on one side of the porous metal diffusion layer, and the cathode catalytic diffusion layer includes a cathode gas diffusion layer and a cathode catalytic layer disposed on one side of the cathode gas diffusion layer;
[0049] An anode catalytic diffusion layer, anion exchange membrane, conductive polymer layer, and cathode catalytic diffusion layer are stacked sequentially and hot-pressed to form a membrane electrode; wherein, the anion exchange membrane is disposed between the anode catalytic diffusion layer and the conductive polymer layer, and the cathode catalytic layer is disposed between the conductive polymer layer and the cathode gas diffusion layer.
[0050] The method for preparing the membrane electrode provided in this application has all the beneficial effects of the membrane electrode as described above, and will not be repeated here.
[0051] In some embodiments, the method for preparing the anodic catalytic diffusion layer includes:
[0052] Provide a foamed metal layer;
[0053] A transition metal compound is grown on one side of the foam metal layer to form an anode catalytic layer, thereby obtaining an anode catalytic diffusion layer; wherein the transition metal compound includes at least one of transition metal oxides, transition metal phosphides, and transition metal sulfides.
[0054] By growing transition metal compounds in situ on a foamed metal layer, the mechanical strength of the anode catalytic diffusion layer can be ensured to support the overall structure, shorten the ion diffusion path, enhance electron conduction efficiency, and rapidly respond to changes in current. Compared to the separate structure of the anode catalytic layer and the anode gas diffusion layer in traditional technologies, this method can improve overall rigidity and reduce the risk of cracking and detachment of the anode catalytic layer.
[0055] In some embodiments, a transition metal compound is grown on one side of the foamed metal layer, including:
[0056] A transition metal compound is grown on one side of the foam metal layer using a hydrothermal-annealing process; wherein the annealing temperature is 400℃-500℃.
[0057] Hydrothermal treatment allows for the in-situ growth of transition metal compounds on one side of the foamed metal layer, enabling a tight bond between the transition metal compounds and the foamed metal layer. This ensures both catalytic activity and good mechanical properties. Annealing at 400℃-500℃ further strengthens the bond between the transition metal oxides and the foamed metal layer, maintaining their excellent catalytic activity.
[0058] In some embodiments, before the anode catalytic diffusion layer, anion exchange membrane, conductive polymer layer, and cathode catalytic diffusion layer are stacked sequentially, the method further includes:
[0059] The anion exchange membrane was heat-treated at 80℃-120℃ to reduce its thermal shrinkage rate to ≤0.5%.
[0060] By subjecting the anion exchange membrane to heat treatment under the above conditions, the internal stress of the anion exchange membrane can be eliminated and its mechanical stability improved, resulting in a lower thermal shrinkage rate of the anion exchange membrane.
[0061] In some embodiments, hot pressing includes:
[0062] Hot pressing for 3-8 minutes at a temperature of 120℃-140℃ and a pressure of 1MPa-2MPa yields a compression rate of 10%-30%.
[0063] By hot-pressing under the above conditions, the anode catalytic diffusion layer, anion exchange membrane, conductive polymer layer and cathode catalytic diffusion layer can be combined into a whole, balancing the bonding strength and structural integrity of the membrane electrode, and ensuring the performance of the membrane electrode.
[0064] Thirdly, embodiments of this application provide an electrolytic cell including the membrane electrode as described above, and / or the membrane electrode prepared by the method described above.
[0065] The electrolytic cell provided in this application embodiment has all the beneficial effects of the membrane electrode as described above, which will not be repeated here. Attached Figure Description
[0066] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0067] Figure 1 This is a schematic diagram of the cross-sectional structure of the membrane electrode provided in the embodiments of this application. Figure 1 ;
[0068] Figure 2 This is a schematic diagram of the cross-sectional structure of the membrane electrode provided in the embodiments of this application. Figure 2 ;
[0069] Figure 3 Electrolyzers having the membrane electrodes of Example 1 and Comparative Example 1 were directly stretched to 1 Acm. -2 Curve of recovery to steady state;
[0070] Figure 4 These are fluctuation test curves of electrolyzers with membrane electrodes as described in Example 1 and Comparative Example 1, respectively, under dynamic operating conditions.
[0071] Figure 5 The electrolytic cell with the membrane electrode in Example 1 is at 1Acm -2 A graph showing the continuous operation for 1000 hours at current density.
[0072] Explanation of reference numerals in the attached figures:
[0073] 10. Anode catalytic diffusion layer; 11. Porous metal diffusion layer; 12. Anode catalytic layer; 20. Anion exchange membrane; 30. Conductive polymer layer; 40. Cathode catalytic diffusion layer; 41. Cathode gas diffusion layer; 42. Cathode catalytic layer; 50. Adhesive layer. Detailed Implementation
[0074] The technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. Furthermore, it should be understood that the specific implementation methods described herein are only for illustration and explanation of this application and are not intended to limit this application.
[0075] In a first aspect, embodiments of this application provide an electrolytic cell, including the membrane electrode described below, and / or the membrane electrode prepared by the method described below.
[0076] Secondly, such as Figure 1 and Figure 2 As shown, an embodiment of this application provides a membrane electrode, including an anode catalytic diffusion layer 10, an anion exchange membrane, a conductive polymer layer 30, and a cathode catalytic diffusion layer 40. The anode catalytic diffusion layer 10 includes a porous metal diffusion layer 11 and an anode catalytic layer 12 formed on one side of the porous metal diffusion layer 11. The anion exchange membrane 20 is disposed on the side of the anode catalytic diffusion layer 10 with the anode catalytic layer 12. The conductive polymer is disposed on the side of the anion exchange membrane 20 opposite to the anode catalytic diffusion layer 10. The cathode catalytic diffusion layer 40 includes a cathode gas diffusion layer 41 and a cathode catalytic layer 42 disposed on one side of the cathode gas diffusion layer 41. The cathode catalytic layer 42 is located between the conductive polymer layer 30 and the cathode gas diffusion layer 41.
[0077] The membrane electrode provided in this application embodiment employs an anode catalytic diffusion layer 10, which is a composite of a porous metal diffusion layer 11 and an anode catalytic layer 12. This ensures the anode catalytic effect while improving the rigidity of the anode catalytic diffusion layer 10. Furthermore, it is bonded to the flexible anion exchange membrane 20, effectively reducing pore blockage in the flexible anode gas diffusion layer and improving the stability of the anode catalytic layer 12. The combination of rigid and flexible structures enhances the membrane electrode's rapid power regulation capability and durability under fluctuating power supplies. By providing a conductive polymer layer 30 between the cathode catalytic diffusion layer 40 and the anion exchange membrane 20, the mass transfer effect between the cathode catalytic layer 42 and the anion exchange membrane 20, as well as the catalytic activity of the cathode catalytic layer 42, is improved. This alleviates the mechanical-electrochemical coupling phenomenon under dynamic operating conditions, achieving high dynamic response while maintaining good adaptability to fluctuating power supplies. In other words, the membrane electrode provided in this application embodiment improves the dynamic response performance of the membrane electrode, enhances its rapid power regulation capability and durability under fluctuating power supplies, and extends its service life.
[0078] In some embodiments, the porous metal diffusion layer 11 includes a foamed metal layer. One side surface of the foamed metal layer is modified to form a transition metal compound, thereby forming the anodic catalyst layer 12. The transition metal compound includes at least one of transition metal oxides, transition metal phosphides, and transition metal sulfides.
[0079] In related technologies, a separate design of the anode gas diffusion layer and the anode catalyst layer is typically used. The anode gas diffusion layer is usually made of metal mesh, while the anode catalyst layer is usually applied to one side of the anode gas diffusion layer by spraying anode catalyst material. Because the catalytic activity of the metal mesh anode gas diffusion layer is inherently weak, and the physical bond between the sprayed anode catalyst layer and the anode gas diffusion layer is weak, they are prone to detachment during operation, leading to pore blockage of the anode gas diffusion layer and consequently, impaired mass transfer.
[0080] The foamed metal layer possesses excellent mechanical strength, supporting the overall structure of the anolyte catalytic active layer. Its unique pore structure shortens ion diffusion paths and enhances electron conduction efficiency, enabling a rapid response to current changes. One side of the foamed metal layer is modified to form transition metal oxides, exhibiting good oxygen evolution reaction (OER) catalytic activity, ensuring optimal catalytic performance. Transition metal oxides, transition metal phosphides, and transition metal sulfides possess unique electronic structures, tunable active sites, and good stability, resulting in excellent catalytic effects.
[0081] The integrated design of the anode catalytic diffusion layer 10 can significantly reduce the complexity of assembling the anode catalytic layer and the anode gas diffusion layer, and achieve high-efficiency oxygen evolution reaction (OER) performance while reducing OER overpotential.
[0082] In some embodiments, the thickness of the anodic catalytic diffusion layer 10 is 0.25 mm to 0.35 mm.
[0083] By setting the thickness of the anode catalytic diffusion layer 10 within the above-mentioned range, the mechanical strength, catalytic activity, and ion transport performance of the anode catalytic diffusion layer 10 can be balanced.
[0084] For example, the thickness of the anodic catalytic diffusion layer 10 can be 0.25 mm, 0.26 mm, 0.27 mm, 0.28 mm, 0.29 mm, 0.3 mm, 0.31 mm, 0.32 mm, 0.33 mm, 0.34 mm or 0.35 mm.
[0085] In some embodiments, the porosity of the anode catalytic diffusion layer 10 is 80%-95%.
[0086] By keeping the porosity of the anode catalytic diffusion layer 10 within the aforementioned range, the mechanical strength, ion transport performance, and water transport performance of the anode catalytic diffusion layer 10 can be balanced, thereby improving electrolysis efficiency and stability.
[0087] For example, the porosity of the anode catalytic diffusion layer 10 can be 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, or 95%.
[0088] In some embodiments, the flexural strength of the anodic catalytic diffusion layer 10 is 50 MPa-200 MPa.
[0089] By ensuring that the bending strength of the anode catalytic diffusion layer 10 is within the aforementioned range, the mechanical strength of the anode catalytic diffusion layer 10 can be guaranteed, providing sufficient rigid support. This, combined with the anion exchange membrane 20, achieves a "combination of rigidity and flexibility," thereby improving the dynamic response performance and stability of the membrane electrode.
[0090] For example, the flexural strength of the anode catalytic diffusion layer 10 can be 50 MPa, 100 MPa, 150 MPa or 200 MPa.
[0091] In some embodiments, the surface roughness Ra of the anodic catalytic diffusion layer 10 near the anion exchange membrane 20 is ≤0.8 μm.
[0092] By ensuring that the surface roughness of the anodic catalytic diffusion layer 10 near the anion exchange membrane 20 is within the aforementioned range, the interfacial bonding performance between the anodic catalytic layer 12 and the anion exchange membrane 20 in the anodic catalytic diffusion layer 10 can be improved, the contact resistance can be reduced, and the mechanical damage to the anion exchange membrane 20 can be reduced.
[0093] For example, the roughness Ra of the surface of the anodic catalytic diffusion layer 10 near the anion exchange membrane 20 can be 0.8 μm, 0.7 μm, 0.6 μm, 0.5 μm, 0.4 μm, 0.3 μm, 0.2 μm or 0.1 μm.
[0094] In some embodiments, the thickness of the anion exchange membrane 20 is 70 μm-80 μm.
[0095] The thickness of the anion exchange membrane 20 is within the above range, which can ensure mechanical properties while reducing the ion transport path, avoiding local concentration polarization, and improving the structural stability of the anion exchange membrane 20.
[0096] For example, the thickness of the anion exchange membrane 20 can be 70 μm, 72 μm, 75 μm, 77 μm or 80 μm.
[0097] In some embodiments, the ion exchange capacity of the anion exchange membrane 20 is 2.8 mmol / g to 3.2 mmol / g.
[0098] By ensuring that the ion exchange capacity of the anion exchange membrane 20 is within the aforementioned range, the ion conduction efficiency of the anion exchange membrane 20 can be improved, thus guaranteeing the performance of the anion exchange membrane 20.
[0099] For example, the ion exchange capacity of the anion exchange membrane 20 may be 2.8 mmol / g, 3 mmol / g, or 3.2 mmol / g.
[0100] In some embodiments, the sheet resistance of the anion exchange membrane 20 is <0.1 Ω·cm. 2 .
[0101] By ensuring that the sheet resistance of the anion exchange membrane 20 is within the aforementioned range, energy efficiency can be improved, operational stability enhanced, and dynamic response performance improved.
[0102] In some embodiments, the elongation at break of the anion exchange membrane 20 is 50%-150%.
[0103] By keeping the elongation at break of the anion exchange membrane 20 within the above-mentioned range, mechanical strength and flexibility can be balanced, thus ensuring the stability of the anion exchange membrane 20.
[0104] In some embodiments, the thickness of the conductive polymer layer 30 is 4 μm-6 μm.
[0105] In some embodiments, the porosity of the conductive polymer layer 30 is 40%-60%.
[0106] The conductive polymer layer 30 serves as an electron conduction bridge connecting the anion exchange membrane 20 and the cathode catalyst layer 42, improving contact performance. By keeping the thickness and porosity of the conductive polymer within the aforementioned range, electron conduction efficiency can be improved, ion transport resistance reduced, and mechanical stability ensured.
[0107] In some embodiments, the conductive polymer layer 30 comprises a poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid composite material.
[0108] Poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS) composite materials possess advantages such as high electrical conductivity and good flexibility. When applied to the conductive polymer layer 30, they can improve electron conduction efficiency. The sulfonic acid groups in the poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid composite material can achieve a double-sided bonding effect with the anion exchange membrane 20 and the anion catalyst layer. This alleviates the difference in expansion coefficients between the rigid cathode catalyst layer 42 and the flexible anion exchange membrane 20, effectively improving poor interfacial contact between the anion exchange membrane 20 and the cathode catalyst layer 42, interfacial delamination caused by mechanical stress, and the performance degradation of the cathode catalyst layer 42 under high current density.
[0109] In some embodiments, the cathode gas diffusion layer 41 includes at least one of a carbon-based support and a metal-based support.
[0110] Carbon-based and metal-based supports can provide more catalyst attachment sites, have higher specific surface area and porosity, and better mechanical properties, thus providing abundant catalyst attachment sites and ensuring excellent diffusion performance.
[0111] Among them, carbon-based carriers include materials such as carbon cloth and carbon paper, while metal-based carriers include materials such as foamed metal and nickel felt.
[0112] In some embodiments, the cathode catalyst layer 42 includes a cathode catalyst, which includes a pentagonal high entropy alloy (HEA), and the pentagonal high entropy alloy includes at least one of nickel-cobalt-iron-molybdenum-chromium alloy and platinum-ruthenium-iridium-palladium alloy.
[0113] Five-element high-entropy alloys (HEAs) can rapidly adsorb and dissociate reactants under dynamic operating conditions, accelerating the electrochemical reaction process and ensuring efficient charge transfer. The multi-element combination can regulate the surface electronic structure to adapt to dynamic pH fluctuations during water electrolysis for hydrogen production.
[0114] Nickel-cobalt-iron-molybdenum-chromium alloys (Ni-Co-Fe-Mo-Cr) are non-precious metal systems with low cost, abundant active sites, and good chemical and structural stability. Platinum-ruthenium-iridium-palladium alloys (Pt-Ru-Ir-Pd-Au) have diverse active sites, synergistic effects among multiple elements, improved reaction efficiency, and excellent stability.
[0115] For example, pentagonal high-entropy alloys can be prepared using a microwave-assisted polyol method: mixing metal salts (e.g., NiCl2, CoCl2, FeCl3, MoO4) in ethylene glycol. 2-Nanoalloy particles were generated by microwave irradiation (180℃, 30 min) using NaBH4 as a reducing agent, with Cr(NO3)3 as the reducing agent. Microwave synthesis ensures uniform elemental distribution and avoids compositional segregation caused by high-temperature annealing in traditional techniques. Then, the nanoalloy particles were coupled with nitrogen-doped carbon supports (such as N-CNTs) through a support conformation and defect process strategy. Surface defects were then introduced through low-temperature plasma treatment (Ar / H2 atmosphere) to simultaneously remove surface oxides.
[0116] In some embodiments, the cathode catalyst comprises a nickel-cobalt-iron-molybdenum-chromium alloy, wherein the atomic ratio of nickel, cobalt, iron, molybdenum and chromium in the nickel-cobalt-iron-molybdenum-chromium alloy is (20-25):(15-20):(15-20):(30-35):(5-10).
[0117] By ensuring the atomic ratios of each element in the nickel-cobalt-iron-molybdenum-chromium alloy are within the aforementioned range, nickel can play a dominant role, ensuring sufficient active sites and lowering the energy barrier for the hydrogen evolution reaction. Cobalt and iron exhibit a synergistic effect, molybdenum enhances activity and provides corrosion resistance, while chromium improves oxidation resistance and stability.
[0118] In some embodiments, the average particle size of the nickel-cobalt-iron-molybdenum-chromium alloy is 5 nm-15 nm.
[0119] By ensuring that the average particle size of the nickel-cobalt-iron-molybdenum-chromium alloy is within the aforementioned range, the specific surface area of the alloy can be increased, exposing more active sites and enhancing catalytic activity.
[0120] In some embodiments, molybdenum in the nickel-cobalt-iron-molybdenum-chromium alloy is partially replaced by tungsten, wherein the atomic ratio of molybdenum to tungsten is (3-5):1.
[0121] By replacing part of the molybdenum element with tungsten and keeping the atomic ratio of molybdenum to tungsten within the aforementioned range, the melting point and stability can be improved, compensating for the insufficient performance of molybdenum under extreme conditions, and balancing the catalytic activity and stability of nickel-cobalt-iron-molybdenum-chromium alloys.
[0122] In some embodiments, the thickness of the cathode catalyst layer 42 is 25 μm-35 μm.
[0123] In some embodiments, the porosity of the cathode catalyst layer 42 is 60%-70%.
[0124] In some embodiments, the hydrogen evolution reaction overpotential of the cathode catalyst layer 42 is ≤35mV@10mA / cm 2 .
[0125] The thickness, porosity, and hydrogen evolution reaction overpotential of the cathode catalyst layer 42 are within the above range, which can balance catalytic activity and transport performance, provide sufficient electrolyte-gas-solid three-phase interface, and maintain good mechanical strength and durability.
[0126] In some embodiments, such as Figure 2 As shown, an adhesive layer 50 is provided between the conductive polymer layer 30 and the anion exchange membrane 20.
[0127] By providing an adhesive layer 50 between the conductive polymer layer 30 and the anion exchange membrane 20, the interfacial bonding force between the conductive polymer layer 30 and the anion exchange membrane 20 can be enhanced, improving ion transport performance. Furthermore, the adhesive layer 50 can buffer the difference in thermal expansion coefficients and reduce stress concentration.
[0128] For example, the adhesive layer 50 can be obtained by coating with a Nafion solution of 0.1%-0.5% by mass. Pre-compression for 30-60 seconds at a pressure of 0.5-1 MPa and a temperature of 100-120°C enables the conductive polymer layer 30 and the anion exchange membrane 20 to be initially bonded together.
[0129] The membrane electrode provided in this application embodiment, when applied to an electrolyzer, enables a faster cold start current density step response time (0→1.0 A / cm). 2 (Until stable operation) < 2 hours, voltage fluctuation rate < 3% under dynamic operating conditions, at 60℃ and 1.0 A / cm 2 Performance degradation is less than 5% after 1000 hours of continuous operation.
[0130] Thirdly, embodiments of this application provide a method for preparing a membrane electrode, comprising:
[0131] An anode catalytic diffusion layer 10, an anion exchange membrane 20, a conductive polymer layer 30, and a cathode catalytic diffusion layer 40 are provided; wherein, the anode catalytic diffusion layer 10 includes a porous metal diffusion layer 11 and an anode catalytic layer 12 formed on one side of the porous metal diffusion layer 11, and the cathode catalytic diffusion layer 40 includes a cathode gas diffusion layer 41 and a cathode catalytic layer 42 disposed on one side of the cathode gas diffusion layer 41.
[0132] An anode catalytic diffusion layer 10, anion exchange membrane 20, conductive polymer layer 30 and cathode catalytic diffusion layer 40 are stacked sequentially and hot-pressed to form a membrane electrode; wherein, the anion exchange membrane 20 is disposed between the anode catalytic diffusion layer 10 and the conductive polymer layer 30, and the cathode catalytic layer 42 is disposed between the conductive polymer layer 30 and the cathode gas diffusion layer 41.
[0133] The method for preparing the membrane electrode provided in this application has all the beneficial effects of the membrane electrode as described above, and will not be repeated here.
[0134] In some embodiments, the method for preparing the anodic catalytic diffusion layer 10 includes:
[0135] Provide a foamed metal layer;
[0136] A transition metal compound is grown on one side of the foam metal layer to form an anode catalytic layer 12, thereby obtaining an anode catalytic diffusion layer 10; wherein the transition metal compound includes at least one of transition metal oxides, transition metal phosphides and transition metal sulfides.
[0137] By growing transition metal compounds in situ on the foamed metal layer, the mechanical strength of the anode catalytic diffusion layer 10 can be ensured to support the overall structure, shorten the ion diffusion path, enhance electron conduction efficiency, and respond quickly to changes in current. Compared with the separate structure of the anode catalytic layer 12 and the anode gas diffusion layer in the traditional technology, the overall rigidity can be improved and the risk of cracking and falling off of the anode catalytic layer 12 can be reduced.
[0138] In some embodiments, a transition metal compound is grown on one side of the foamed metal layer, including:
[0139] A transition metal compound is grown on one side of the foam metal layer using a hydrothermal-annealing process; wherein the annealing temperature is 400℃-500℃.
[0140] Hydrothermal treatment allows for the in-situ growth of transition metal compounds on one side of the foamed metal layer, enabling a tight bond between the transition metal compounds and the foamed metal layer. This ensures both catalytic activity and good mechanical properties. Annealing at 400℃-500℃ further strengthens the bond between the transition metal oxides and the foamed metal layer, maintaining their excellent catalytic activity.
[0141] For example, the annealing conditions are as follows: under an inert atmosphere containing 5%-10% by volume H2, the temperature is increased to 400℃-500℃ at a rate of 1℃ / min-5℃ / min and held for 1h-3h.
[0142] In some embodiments, before the anode catalytic diffusion layer 10, anion exchange membrane 20, conductive polymer layer 30 and cathode catalytic diffusion layer 40 are sequentially stacked, the method further includes:
[0143] The anion exchange membrane 20 is heat-treated at 80℃-120℃ to reduce its thermal shrinkage rate to ≤0.5%.
[0144] By subjecting the anion exchange membrane 20 to heat treatment under the above conditions, the internal stress of the anion exchange membrane 20 can be eliminated and its mechanical stability can be improved, resulting in a lower thermal shrinkage rate of the anion exchange membrane 20.
[0145] In some embodiments, the method for preparing the cathode catalytic diffusion layer 40 includes:
[0146] The pentagonal high-entropy alloy and the anion exchange membrane 20 ionomer were dispersed in ethanol and aqueous solution and coated onto a carbon support to obtain the cathode catalytic diffusion layer 40.
[0147] In some embodiments, hot pressing includes:
[0148] Hot pressing for 3-8 minutes at a temperature of 120℃-140℃ and a pressure of 1MPa-2MPa yields a compression rate of 10%-30%.
[0149] By hot pressing under the above conditions, the anode catalytic diffusion layer 10, the anion exchange membrane 20, the conductive polymer layer 30 and the cathode catalytic diffusion layer 40 can be combined into a whole, balancing the bonding strength and the structural integrity of the membrane electrode, and ensuring the performance of the membrane electrode.
[0150] For example, using a high-precision positioning fixture (tolerance ±50μm), the anode catalytic diffusion layer 10, the anion exchange membrane 20, the conductive polymer layer 30 and the cathode catalytic diffusion layer 40 are stacked sequentially, hot-pressed and then laser-cut to obtain the membrane electrode.
[0151] The embodiments of this application are further illustrated below with reference to specific examples. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of this application. Experimental methods in the following embodiments that do not specify specific conditions are generally performed according to the conditions recommended by the manufacturer.
[0152] Example 1
[0153] In this embodiment, the membrane electrode includes an anode catalytic diffusion layer 10, an anion exchange membrane, a conductive polymer layer 30, and a cathode catalytic diffusion layer 40. The anode catalytic diffusion layer 10 includes a porous metal diffusion layer 11 and an anode catalytic layer 12 formed on one side of the porous metal diffusion layer 11. The anion exchange membrane 20 is disposed on the side of the anode catalytic diffusion layer 10 with the anode catalytic layer 12. The conductive polymer is disposed on the side of the anion exchange membrane 20 opposite to the anode catalytic diffusion layer 10. The cathode catalytic diffusion layer 40 includes a cathode gas diffusion layer 41 and a cathode catalytic layer 42 disposed on one side of the cathode gas diffusion layer 41. The cathode catalytic layer 42 is located between the conductive polymer layer 30 and the cathode gas diffusion layer 41.
[0154] The anolyte catalytic diffusion layer 10 comprises a foamed metal layer and a transition metal compound grown in situ on one side of the foamed metal layer. The anolyte catalytic diffusion layer 10 has a thickness of 0.3 mm, a porosity of 82%, a flexural strength of 200 MPa, and a surface roughness Ra of 0.8 μm on the side closest to the anion exchange membrane 20. The anion exchange membrane 20 has a thickness of 75 μm, an ion exchange capacity of 3 mmol / g, and a sheet resistivity of 0.08 Ω·cm. 2 The elongation at break is 105%. The conductive polymer layer 30 is made of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS) composite material, with a thickness of 5 μm and a porosity of 50%. The cathode catalytic diffusion layer 40 includes carbon cloth and a cathode catalytic layer 42 coated on one side of the carbon cloth. The catalyst in the cathode catalytic layer 42 is a nickel-cobalt-iron-molybdenum-chromium alloy (atomic ratio of nickel, cobalt, iron, molybdenum, and chromium is 22:18:18:32:10). The average particle size of the nickel-cobalt-iron-molybdenum-chromium alloy is 10 nm. The cathode catalytic layer 42 has a thickness of 30 μm, a porosity of 65%, and a hydrogen evolution reaction overpotential of 31 mV@10 mA / cm. 2 .
[0155] The preparation method of the membrane electrode includes: sequentially stacking the anode catalytic diffusion layer 10, the anion exchange membrane, the conductive polymer layer 30 and the cathode catalytic diffusion layer 40, hot-pressing them at a temperature of 130℃ and a pressure of 1.5MPa with a compression rate of 20%, and laser cutting them to obtain the membrane electrode.
[0156] Example 2
[0157] The difference between this embodiment and Embodiment 1 is that the thickness of the anodic catalytic diffusion layer 10 is 0.25 mm and the porosity is 85%, the thickness of the anion exchange membrane 20 is 70 μm, and the thickness of the conductive polymer layer 30 is 4 μm and the porosity is 60%. The other conditions are the same as in Embodiment 1.
[0158] Example 3
[0159] The difference between this embodiment and Embodiment 1 is that the thickness of the anodic catalytic diffusion layer 10 is 0.35 mm and the porosity is 90%, the thickness of the anion exchange membrane 20 is 80 μm, and the thickness of the conductive polymer layer 30 is 6 μm and the porosity is 40%. All other conditions are the same as in Embodiment 1.
[0160] Example 4
[0161] The difference between this embodiment and Embodiment 1 is that the membrane electrode further includes an adhesive layer 50, which is located between the anion exchange membrane 20 and the conductive polymer layer 30. The adhesive layer 50 is obtained by coating with a 0.3% by mass Nafion solution. The conductive polymer layer 30 and the anion exchange membrane 20 are initially bonded together by pre-pressing at a pressure of 0.7 MPa and a temperature of 110°C for 45 seconds, and then assembled. All other conditions remain the same as in Embodiment 1.
[0162] Example 5
[0163] The difference between this embodiment and Embodiment 1 is that the anion exchange membrane 20 is heat-treated at a temperature of 100°C before assembly, while the other conditions remain the same as in Embodiment 1.
[0164] Comparative Example 1
[0165] The difference between this comparative example and Example 1 is that the metal mesh is used as the anode gas diffusion layer, the anode catalyst is sprayed on one side of the surface of the metal mesh to form the anode catalyst layer, no conductive polymer layer is provided in the membrane electrode, and the cathode catalyst in the cathode catalyst layer is a Pt / C catalyst.
[0166] The metal mesh is made of stainless steel, with a thickness of 0.65 mm and a porosity of 60%. The anode catalyst is nickel ferrite with a loading of 0.8 mg / cm³. 2 The loading of the cathode Pt / C catalyst was 0.3 mg / cm³. 2 .
[0167] The membrane electrodes from Example 1 and Comparative Example 1 were assembled into a 1kW electrolyzer and directly loaded to 1Acm in the electrolyzer. -2 The test results are shown in Table 1 and Figure 3 As shown:
[0168] Table 1
[0169] Name Transient tank pressure (V) Steady state tank pressure (V) Response time (h) Example 1 1.80 1.76 2.0 Example 2 1.79 1.74 1.8 Example 3 1.78 1.74 1.9 Example 4 1.81 1.76 2.1 Example 5 1.82 1.77 2.0 Comparative Example 1 1.91 1.79 4.0
[0170] From Table 1 and Figure 3 It can be seen that the electrolytic cell with the membrane electrode in Example 1 performs well under direct tensile loading to 1 Acm. -2 At that time, the cell voltage was 1.80V, and it only took 2 hours to recover to stable operation (1.76V). In contrast, the electrolytic cell with the membrane electrode in Comparative Example 1 was directly loaded to 1Acm. -2 At that time, the tank voltage was 1.91V, and it took 4 hours to recover to a stable operating level (1.79V). The time to recover to a stable state increased significantly, and the dynamic response performance was poor.
[0171] The membrane electrodes from Example 1 and Comparative Example 1 were assembled into a 1kW electrolyzer, and the electrolyzer was set to a current of 1Acm. -2The system alternates between running at current density for 1 hour and resting for 1 hour to simulate the dynamic response after multiple start-stop processes in actual operation.
[0172] like Figure 4 As shown, after 100 hours of start-stop cycles, the cell voltage decay rate of the electrolyzer with the membrane electrode in Example 1 was only 0.18 mV / h, while the decay rate of the electrolyzer with the membrane electrode in Comparative Example 1 was 0.74 mV / h, indicating significant voltage fluctuations.
[0173] The membrane electrode from Example 1 was assembled into a 1kW electrolyzer, and the electrolyzer was maintained at 1Acm. -2 Under current density, the cell voltage is <1.8V, and the system operates continuously for 1000 hours. Figure 5 As shown, the attenuation rate is only 2.9%.
[0174] In summary, the membrane electrode provided in this application embodiment has excellent performance and fast response performance, and can output for a long time under low voltage loss conditions.
[0175] The embodiments of this application have been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The description of the above embodiments is only for the purpose of helping to understand the method and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.
Claims
1. A membrane electrode, characterized in that, include: An anode catalytic diffusion layer, the anode catalytic diffusion layer comprising a porous metal diffusion layer and an anode catalytic layer formed on one side of the porous metal diffusion layer; An anion exchange membrane is disposed on one side of the anode catalytic diffusion layer containing the anode catalytic layer. A conductive polymer layer, wherein the conductive polymer is disposed on the side of the anion exchange membrane opposite to the anode catalytic diffusion layer; A cathode catalytic diffusion layer, comprising a cathode gas diffusion layer and a cathode catalytic layer disposed on one side of the cathode gas diffusion layer, wherein the cathode catalytic layer is located between the conductive polymer layer and the cathode gas diffusion layer.
2. The membrane electrode according to claim 1, characterized in that, The porous metal diffusion layer includes a foamed metal layer; One side of the foamed metal layer is modified to generate a transition metal compound, forming the anode catalyst layer; wherein the transition metal compound includes at least one of transition metal oxides, transition metal phosphides, and transition metal sulfides.
3. The membrane electrode according to claim 1, characterized in that, The thickness of the anodic catalytic diffusion layer is 0.25mm-0.35mm; And / or, the porosity of the anode catalytic diffusion layer is 80%-95%; And / or, the flexural strength of the anode catalytic diffusion layer is 50MPa-200MPa; And / or, the surface roughness Ra of the anodic catalytic diffusion layer near the anion exchange membrane is ≤0.8μm.
4. The membrane electrode according to claim 1, characterized in that, The thickness of the anion exchange membrane is 70μm-80μm; And / or, the ion exchange capacity of the anion exchange membrane is 2.8 mmol / g-3.2 mmol / g; And / or, the sheet resistivity of the anion exchange membrane is <0.1 Ω·cm. 2 ; And / or, the elongation at break of the anion exchange membrane is 50%-150%.
5. The membrane electrode according to claim 1, characterized in that, The thickness of the conductive polymer layer is 4μm-6μm; And / or, the porosity of the conductive polymer layer is 40%-60%.
6. The membrane electrode according to claim 1, characterized in that, The conductive polymer layer comprises a poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid composite material.
7. The membrane electrode according to claim 1, characterized in that, The cathode gas diffusion layer includes at least one of a carbon-based support and a metal-based support.
8. The membrane electrode according to claim 1, characterized in that, The cathode catalyst layer includes a cathode catalyst, which includes a pentagonal high-entropy alloy. The five-element high-entropy alloy includes at least one of nickel-cobalt-iron-molybdenum-chromium alloy and platinum-ruthenium-iridium-palladium alloy.
9. The membrane electrode according to claim 8, characterized in that, The cathode catalyst includes the nickel-cobalt-iron-molybdenum-chromium alloy; In the nickel-cobalt-iron-molybdenum-chromium alloy, the atomic ratio of nickel, cobalt, iron, molybdenum and chromium is (20-25):(15-20):(15-20):(30-35):(5-10); And / or, the average particle size of the nickel-cobalt-iron-molybdenum-chromium alloy is 5nm-15nm.
10. The membrane electrode according to claim 9, characterized in that, In the nickel-cobalt-iron-molybdenum-chromium alloy, the molybdenum element is partially replaced by tungsten element, wherein the atomic ratio of molybdenum element to tungsten element is (3-5):
1.
11. The membrane electrode according to any one of claims 1-10, characterized in that, The thickness of the cathode catalyst layer is 25μm-35μm; And / or, the porosity of the cathode catalyst layer is 60%-70%. And / or, the hydrogen evolution reaction overpotential of the cathode catalyst layer is ≤35mV@10mA / cm 2 .
12. The membrane electrode according to any one of claims 1-10, characterized in that, An adhesive layer is provided between the conductive polymer layer and the anion exchange membrane.
13. A method for preparing a membrane electrode, characterized in that, include: An anode catalytic diffusion layer, an anion exchange membrane, a conductive polymer layer, and a cathode catalytic diffusion layer are provided; wherein, the anode catalytic diffusion layer includes a porous metal diffusion layer and an anode catalytic layer formed on one side of the porous metal diffusion layer, and the cathode catalytic diffusion layer includes a cathode gas diffusion layer and a cathode catalytic layer disposed on one side of the cathode gas diffusion layer; The anode catalytic diffusion layer, the anion exchange membrane, the conductive polymer layer, and the cathode catalytic diffusion layer are stacked sequentially and hot-pressed to form the membrane electrode; wherein the anion exchange membrane is disposed between the anode catalytic diffusion layer and the conductive polymer layer, and the cathode catalytic layer is disposed between the conductive polymer layer and the cathode gas diffusion layer.
14. The method for preparing a membrane electrode according to claim 13, characterized in that, The method for preparing the anodic catalytic diffusion layer includes: Provide a foamed metal layer; A transition metal compound is grown on one side of the foamed metal layer to form the anode catalytic layer, thereby obtaining the anode catalytic diffusion layer; wherein the transition metal compound includes at least one of transition metal oxides, transition metal phosphides, and transition metal sulfides.
15. The method for preparing a membrane electrode according to claim 14, characterized in that, The growth of a transition metal compound on one side of the foamed metal layer includes: The transition metal compound is grown on one side of the surface of the foam metal layer using a hydrothermal-annealing process; wherein the annealing temperature is 400℃-500℃.
16. The method for preparing a membrane electrode according to claim 13, characterized in that, Before the sequential stacking of the anode catalytic diffusion layer, the anion exchange membrane, the conductive polymer layer, and the cathode catalytic diffusion layer, the method further includes: The anion exchange membrane is heat-treated at 80℃-120℃ to reduce its thermal shrinkage rate to ≤0.5%.
17. The method for preparing a membrane electrode according to claim 13, characterized in that, The hot pressing process includes: Hot pressing for 3-8 minutes at a temperature of 120℃-140℃ and a pressure of 1MPa-2MPa yields a compression rate of 10%-30%.
18. An electrolytic cell, characterized in that, The membrane electrode includes the membrane electrode as described in any one of claims 1-12, and / or the membrane electrode prepared by the method described in any one of claims 13-17.