High-performance Occlusal Ordered Membrane Electrode, Preparation Method Thereof and Application

Abstract

The present invention provides a high-performance interlocking ordered membrane electrode, its preparation method and application. The electrode comprises an ordered array membrane, a catalyst layer (CL) and a perforated diffusion layer; the ordered array membrane comprises a membrane substrate and an array of ordered cones; the perforated diffusion layer has a plurality of hole structures, and the array cones enter the hole structures; the catalyst layer is continuously filled between the array cones and the wall surface of the hole structure, and between the selected surface and the perforated diffusion layer to form a mechanical interlock. The present invention constructs an interlocking structure, and by carving a hole structure on the surface of the diffusion layer (PTL), the prepared membrane electrode can better retain the array structure, so that the advantages of the array structure in terms of proton, electron and material transport can be better utilized; because the interlocking structure can make the catalyst layer and the diffusion layer, which originally had poor contact, form good contact, the contact resistance of the interface is reduced, the charge transfer resistance is reduced, and the performance is further improved.

Description

Technical Field

[0001] The present invention relates to the field of energy and clean technology, and in particular to a high-performance interlocking ordered membrane electrode, a preparation method thereof, and applications thereof. Background Art

[0002] With the gradual depletion of fossil energy and environmental pollution, humanity's demand for clean, renewable energy is increasing. Hydrogen, as a clean energy source, offers advantages such as high energy density and widespread availability, making it a promising renewable clean energy source. Therefore, rapid, efficient, and clean methods are needed to produce hydrogen.

[0003] Hydrogen production by water electrolysis offers the advantages of a clean, pollution-free production process, high-purity hydrogen, and low levels of impurity gases. It is an ideal method for hydrogen production. Depending on the electrolyte type and operating conditions, it can be divided into four types: proton exchange membrane water electrolysis (PEMWE), alkaline water electrolysis (AWE), anion exchange membrane water electrolysis (AEMWE), and high-temperature solid oxide water electrolysis (SOEC). PEMWE and anion exchange membrane water electrolysis offer advantages such as high-purity hydrogen production and more efficient hydrogen production.

[0004] In proton exchange membrane water electrolysis and anion exchange membrane water electrolysis, the membrane electrode (MEA) is the most important component, including the proton exchange membrane, catalyst layer and diffusion layer. It is the key three-phase interface where the electrochemical reaction of water, gas, catalyst and other substances occurs, and has a significant impact on the performance and stability of electrolyzed water. In order to obtain good performance and stability, traditional membrane electrodes often require a high catalyst loading (2-4 mg cm -2 However, due to the discontinuous nature of the ionomer in the catalytic layer, the catalyst farther from the membrane cannot achieve effective proton transport, hindering its full catalytic effect and resulting in low catalyst utilization. Furthermore, the thicker catalytic layer further hinders the transport of water and bubbles. Therefore, improving the structure of the membrane electrode and thereby enhancing the transport of protons, electrons, and other substances within it can significantly enhance the performance and stability of the MEA.

[0005] CN112144076B discloses a method for preparing an integrated membrane electrode, which uses inorganic powder and polysulfone to mix to prepare a composite membrane material, and then uses a catalyst, polysulfone and ion exchange resin to mix to prepare a catalyst slurry. After the composite membrane material is compounded with a support body to prepare a composite membrane blank, the catalyst slurry is coated on its surface, and after curing, an integrated membrane electrode can be obtained. Although the method solves the shortcomings of the current membrane electrode, such as high cost, poor stability and low current density, the overall current density is still not high, and the problem of poor proton and water vapor conduction caused by the thick catalyst layer has not been solved.

[0006] CN114628750A discloses a method for preparing a membrane electrode assembly (MEA). This method uses methods such as direct growth, transfer printing, and nanoimprinting to form a conical or cylindrical array structure on the surface of an ion exchange membrane. A catalyst is then loaded onto the membrane surface using magnetron sputtering or spraying. The catalyst-loaded membrane is then composited with a gas diffusion layer to form the MEA. This method significantly enlarges the three-phase interface (gas, water, and catalyst) where the electrochemical reaction occurs, creating a channel for rapid transport of reactants, protons, and electrons. This helps reduce catalyst loading, increase catalyst utilization, and enhance performance and stability. However, in actual testing, the array structure was partially destroyed due to compression from the PTL, preventing it from fully realizing its advantages. Furthermore, the interfacial contact between the catalyst layer and the diffusion layer significantly affects the resistance of the MEA.

[0007] In order to further improve the performance and stability of PEMWE and AEMWE, and to reduce the resistance of MEA while giving full play to the advantages of the array structure in proton, charge and material transport, it is necessary to prepare a new type of membrane electrode that can further improve the interface contact effect between the catalytic layer and the diffusion layer to reduce the contact resistance while retaining the advantages of the ordered array structure. Summary of the Invention

[0008] In view of the deficiencies in the prior art, the present invention aims to provide a high-performance interlocking ordered membrane electrode, a preparation method and application thereof.

[0009] To achieve the aforementioned object of the invention, the technical solutions adopted by the present invention include:

[0010] In a first aspect, the present invention provides a high-performance interlocking ordered membrane electrode, which comprises an ordered array membrane, a catalyst layer and a perforated diffusion layer;

[0011] The ordered array membrane includes a membrane substrate and array cones, and the array cones are arranged in an orderly manner on a selected surface of the membrane substrate; the perforated diffusion layer has a plurality of hole structures, and the array cones enter the hole structures; the catalytic layer is continuously filled between the array cones and the wall surface of the hole structure and between the selected surface and the perforated diffusion layer, and the array cone-catalytic layer-hole structure forms a mechanical bite.

[0012] In a second aspect, the present invention further provides a method for preparing the above-mentioned high-performance interlocking ordered membrane electrode, which comprises:

[0013] Providing an ordered array membrane and a perforated diffusion layer;

[0014] Covering the selected surface of the ordered array membrane with a catalytic layer, and / or covering the contact surface of the perforated diffusion layer and the surface in the hole structure with a catalytic layer;

[0015] The perforated diffusion layer and the selected surface are aligned and pressed together so that the ordered array membrane and the perforated diffusion layer are engaged with each other, and the catalytic layer is located between the ordered array membrane and the perforated diffusion layer.

[0016] In a third aspect, the present invention further provides a method for electrolyzing water, comprising:

[0017] The high-performance interlocking ordered membrane electrode is used as an anode electrode and / or a cathode electrode to form an electrolysis system with an aqueous solution;

[0018] Electric current is applied to the electrolysis system to electrolyze water.

[0019] Based on the above technical solution, compared with the prior art, the beneficial effects of the present invention include at least:

[0020] The technical solution provided by the present invention constructs an interlocking structure. By carving a hole structure corresponding to the array structure on the surface of the PTL, the prepared membrane electrode can better retain the array structure, so that the advantages of the array structure in proton, electron and material transport can be better utilized; because the interlocking structure can make the catalytic layer and the diffusion layer, which originally had poor contact, form good contact, the contact resistance of the interface is reduced, and the charge transfer resistance is reduced, further improving the performance.

[0021] In addition, the preparation method of the interlocking ordered membrane electrode provided by the present invention is simple and can be produced in large quantities, with simple process and low energy consumption.

[0022] The above description is only an overview of the technical solution of the present invention. In order to enable those skilled in the art to more clearly understand the technical means of this application and implement them according to the contents of the specification, the following is an explanation of the preferred embodiments of the present invention with detailed drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a schematic flow chart of a method for preparing a high-performance interlocking ordered membrane electrode provided by a typical embodiment of the present invention;

[0024] Figure 2 This is a structural electron microscope photograph of different parts of a high-performance interlocking ordered membrane electrode provided by a typical embodiment of the present invention;

[0025] Figure 3 This is a comparative test chart of IV performance of high-performance interlocking ordered membrane electrodes with different pore diameters provided by a typical embodiment of the present invention;

[0026] Figure 4This is a comparative test chart of the impedance performance of high-performance interlocking ordered membrane electrodes with different pore diameters provided by a typical embodiment of the present invention;

[0027] Figure 5 This is an electron microscope photo comparing the surface morphologies of different high-performance interlocking ordered membrane electrodes provided in a typical embodiment of the present invention;

[0028] Figure 6 This is a PEMWE performance comparison chart of different membrane electrodes provided by a typical embodiment of the present invention;

[0029] Figure 7 This is a comparison diagram of impedances of different membrane electrodes provided by a typical embodiment of the present invention;

[0030] Figure 8 This is a comparison chart of the AEMWE performance of different membrane electrodes provided in a typical implementation case of the present invention. DETAILED DESCRIPTION

[0031] As mentioned above, current commercial membrane electrodes generally have high catalyst loading or relatively low performance, because the catalysts are mostly precious metals, which leads to high costs. By constructing an ordered array structure on the surface of the membrane, the catalyst loading can be reduced and the catalyst utilization rate can be improved. At the same time, the ordered array structure can improve the transport of protons, electrons and substances at the three-phase interface, thereby improving performance and stability. However, in actual water electrolysis tests, due to the extrusion of the diffusion layer, the array structure on the membrane surface will be partially destroyed, resulting in the array structure being unable to fully function. At the same time, due to the contact problem between the catalyst and the diffusion layer, the overall resistance is relatively large.

[0032] In view of the shortcomings of the prior art, the inventors of this case, after long-term research and extensive practice, have proposed the technical solution of the present invention. The following will further explain this technical solution, its implementation process and principles.

[0033] In light of these limitations, the present invention's technical approach breaks through existing methods for constructing membrane electrode interface structures. While constructing an ordered array structure on the membrane surface, corresponding pores are also created on the surface of the porous transport layer (PTL). Combined with the ordered array membrane, this creates a nested, interlocking structure. This effectively preserves the array structure, while also improving the interface between the catalyst layer and the PTL, reducing contact resistance.

[0034] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Therefore, the scope of protection of the present invention is not limited to the specific embodiments disclosed below.

[0035] An embodiment of the present invention provides a high-performance interlocking ordered membrane electrode, which includes an ordered array membrane, a catalytic layer and a perforated diffusion layer; the ordered array membrane includes a membrane substrate and an array cone, and the array cones are arranged in an orderly manner on a selected surface of the membrane substrate; the perforated diffusion layer has a plurality of hole structures, and the array cones enter the hole structures; the catalytic layer is continuously filled between the array cones and the wall surface of the hole structure and between the selected surface and the perforated diffusion layer, and the array cone-catalytic layer-hole structure forms a mechanical interlock.

[0036] From the perspective of the overall structure, the present invention has a certain connection with the aforementioned prior art, in which conical, cylindrical and other array structures are formed on the surface of the ion exchange membrane by direct growth, transfer, nanoimprinting and other methods, and then the catalyst is loaded on the surface of the membrane by magnetron sputtering or spraying, and then the catalyst-loaded membrane is compounded with the gas diffusion layer to obtain a membrane electrode assembly, but the specific structural features are different. In the above-mentioned prior art, the combination of the catalytic layer and the diffusion layer is not a mechanical bite, but a loose "fit" during the preparation process. This bonding method is not firm but not tight, so it is easy to cause problems of excessive resistance and poor stability. In the present invention, the pore structure of the diffusion layer is not formed by covering, but is targeted by opening holes using a corresponding punching process. After pressing, a tight and firm pure mechanical bite can be formed. This bite method is stable, and due to the stress effect, the bond is tighter, which significantly reduces the interface resistance and can significantly improve the electrode performance.

[0037] Regarding the specific materials of each component in the high-performance interlocking ordered membrane electrode, in some embodiments, the material of the ordered array membrane includes any one or a combination of two or more of perfluorosulfonic acid polymers, partially fluorinated polymers, polyarylether polymers, polyarylpiperidine polymers and fluorine-free polymers; specific examples include Nafion, Aquivion, Alkymer, and Piperion, which are very typical ion exchange membrane materials. Of course, they are not limited to these. Other materials with equivalent functions have the feasibility of preparing electrodes with equal or similar technical effects.

[0038] Furthermore, in some embodiments, the material of the catalytic layer includes any one or a combination of two or more of a metal, a metal oxide, or a metal-support composite material (e.g., a metal-carbon composite material); specific examples include Ir, IrO2, IrO2-ionomer support composite materials, and Pt-carbon support composite materials. The material of the catalytic layer should be selected based on the electrode application, such as whether it will be used on the anode or cathode side, and can be appropriately adjusted or modified based on the composition of the electrolyte. In preferred embodiments, a cathode and anode can be formed on the surfaces of both sides, respectively, to achieve integrated anode-cathode electrolysis.

[0039] Furthermore, in some embodiments, the material of the perforated diffusion layer includes porous metal, metal felt, and metal mesh.

[0040] Regarding specific details of the hole structure, in some embodiments, the hole structure is a blind hole, and the perforated diffusion layer completely covers the selected surface.

[0041] Or in some embodiments, the hole structure is a through hole, and the top of the array cone is exposed from the hole structure.

[0042] For the through-hole structure, in some embodiments, when the hole structure is a through-hole, the perforated diffusion layer is a composite layer of metal foil and porous metal, and the metal foil is located between the selected surface and the porous metal. The metal foil is usually pressed flat and then placed therein for combination.

[0043] Regarding specific size characteristics, in some embodiments, the root diameter of the array cone is 15-30 μm; of course, the root diameter of the array cone plus the thickness of the catalytic layer around it should be roughly equal to the diameter of the hole structure to produce a fit. Otherwise, too large a difference may lead to problems such as too low an engagement ratio or damage to the catalytic layer. This can be determined through conditional tests in specific implementation.

[0044] In some embodiments, the spacing between the roots of adjacent array cones is 2-30 μm; similarly, the spacing and diameter determine the center distance of the array cones, and optimally, the hole structure should completely correspond to the array cone to form the best fit.

[0045] Furthermore, in some embodiments, the height of the arrayed cones is 10-30 μm.

[0046] like Figure 1 As shown, the second aspect of the embodiment of the present invention further provides a method for preparing a high-performance interlocking ordered membrane electrode provided in any of the above embodiments, which comprises the following steps:

[0047] Providing an ordered array membrane and a perforated diffusion layer;

[0048] Covering the selected surface of the ordered array membrane with a catalytic layer, and / or covering the contact surface of the perforated diffusion layer and the surface in the hole structure with a catalytic layer;

[0049] The perforated diffusion layer and the selected surface are aligned and pressed together so that the ordered array membrane and the perforated diffusion layer are engaged with each other, and the catalytic layer is located between the ordered array membrane and the perforated diffusion layer.

[0050] In some embodiments, the preparation process of the ordered array membrane specifically includes the following steps:

[0051] Providing a hard template having a shaping surface complementary to the array cones;

[0052] Applying a polymer emulsion on the shaping surface to form a liquid layer, and heating and curing it to form a shaping body;

[0053] The plastic is peeled off to obtain the ordered array membrane.

[0054] In some embodiments, the process of forming the catalytic layer specifically includes the following steps:

[0055] preparing a catalyst slurry, wherein the catalyst slurry comprises a dispersant, a catalyst and a polymer;

[0056] The catalyst slurry is sprayed on the surface of the ordered array membrane and / or the perforated diffusion layer to form the catalyst layer.

[0057] As some typical applications of the above technical solutions, a third aspect of the embodiments of the present invention further provides a method for electrolyzing water, which includes the following steps:

[0058] Using the high-performance interlocking ordered membrane electrode provided by any of the above embodiments as an anode electrode and / or a cathode electrode to form an electrolysis system with an aqueous solution;

[0059] Electric current is applied to the electrolysis system to electrolyze water.

[0060] Among them, the high-performance interlocking ordered membrane electrode can be a double-sided electrode with integrated anode and cathode, or it can be a single-sided electrode. The material of the ordered array membrane can undergo ion exchange. Therefore, when the two sides are cathode and anode respectively (the corresponding catalyst and diffusion layer are also adapted to the electrolysis reactions of cathode and anode), electrolysis can be achieved in an integrated manner. If a single-sided method is adopted, such as a single-sided anode electrode, a corresponding cathode needs to be set in the electrolyte on the side facing away from the anode catalyst, and vice versa.

[0061] In some embodiments, when the ordered array membrane in the high-performance interlocking ordered membrane electrode is a proton exchange membrane, the hole structure of the diffusion layer is a blind hole;

[0062] When the ordered array membrane is an anion exchange membrane, the pore structure of the diffusion layer is a through hole.

[0063] The technical solution of the present invention is further described in detail below through several embodiments and in conjunction with the accompanying drawings. However, the selected embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0064] Example 1

[0065] This embodiment illustrates a preparation process of a high-performance interlocking ordered membrane electrode for proton exchange membrane water electrolysis, as shown below:

[0066] 1. Preparation of ordered array membranes

[0067] A small amount of the prepared Nafion emulsion was added dropwise to the surface of the template with a suitable pore size, and the pores were evenly coated and vacuumed to completely fill the pores with the emulsion. Next, the vacuumed template was heated at 80 °C while a certain amount of Nafion emulsion (100-150 μL cm) was added dropwise. -2 After the emulsion is completely dry, the temperature is raised to 140°C and cured for 30 minutes. The template is then immersed in deionized water for 5-10 minutes, and the membrane is slowly lifted off along the edge of the template to obtain the Nafion ordered array membrane for PEMWE.

[0068] 2. Cleaning of ordered array membranes

[0069] First, the Nafion ordered array membrane was placed in a 3 wt.% H2O2 solution and cleaned at 80 °C for 1 hour; then the membrane was placed in a 0.5 mol·L -1 The membrane was then rinsed in H2SO4 solution at 80°C for 1 hour. Finally, the membrane was placed in deionized water and cleaned for another hour at 80°C. The cleaned membrane was then stored in deionized water. The AEM ordered array membrane did not require special treatment prior to use and could be stored in deionized water.

[0070] 3. Preparation of catalytic layer

[0071] (1) For PEMWE, the anode and cathode catalysts were IrO2 and 70% Pt / 30% C composite materials by mass, respectively. IrO2 was mixed with water, isopropanol, and ionomer in a certain proportion and then prepared to a concentration of 0.1-2 mg mL -1 The catalyst slurry is also prepared by mixing Pt / C in a certain ratio of 0.1-2 mg·mL -1 The prepared catalyst slurry was placed in an ice-water bath and ultrasonicated for 2 hours to uniformly disperse it.

[0072] (2) After the previously prepared ordered array membrane is dried, it is placed on the adsorption platform with the array side facing up. The anode side catalyst slurry IrO2 is evenly sprayed on the surface of the ordered array membrane using a sprayer with a loading of 0.5 mg cm -2 In order to protect the array structure from being damaged, the cathode side catalyst slurry Pt / C was sprayed on the surface of the cathode side diffusion layer instead of the surface of the ordered array membrane, with the same loading of 0.5 mg cm -2 .

[0073] 4. Preparation of the perforated anode side diffusion layer

[0074] For PEMWE, a commercially available anode diffusion layer (PTL) titanium foam is first placed inside a laser marking machine and laser-engraved with holes. The same method can also be used to engrave nickel foam, aluminum foam, and other materials to meet specific needs. Laser engraving creates holes of varying arrangements and sizes on the PTL surface, creating various interlocking effects, including full, partial, and random interlocking. In this embodiment, the optimal interlocking effect is achieved when the hole arrangement and size correspond to the array. A similar approach is used for the cathode side, using a corresponding diffusion layer.

[0075] The desired holes can be obtained by varying parameters such as laser engraving spacing and intensity. The PTL is then ultrasonically cleaned with ethanol and deionized water to remove the powder produced by the laser engraving. It is then pickled with 37 wt.% hydrochloric acid to remove surface oxides. Finally, the PTL is ultrasonically cleaned with deionized water to remove residual acid, and a layer of Pt is sputtered onto its surface to further enhance its conductivity and prevent oxidation.

[0076] 5. Electrode assembly

[0077] During the assembly process, the perforated PTL is first fixed in the specified position by a sealing gasket, and then the membrane and the cathode side diffusion layer are ensured to be in a fixed position during each test through methods such as limiting, and the arrangement of the holes is ensured to be the same as that of the array. Since the arrangement is the same and the size of the array and the holes are relatively matched, a good bite effect can be formed. Finally, the entire membrane electrode is clamped using a fixture. Under the action of pressure, the array cone will further fill the hole. At the same time, the ordered array membrane, as a flexible material, will form a relatively flat interface structure under the extrusion of the anode and cathode PTL.

[0078] Example 2

[0079] This embodiment illustrates a preparation process of a high-performance interlocking ordered membrane electrode for anion exchange membrane water electrolysis, which is substantially the same as that of Example 1, with the main differences being:

[0080] The emulsion was replaced with an AEM emulsion, which was then dropped onto the template and cured at 80 °C for 4 hours before peeling off the film to obtain an AEM ordered array membrane. The NiFe LDH catalyst was used on the anode side with a loading of 1 mg cm -2As for the perforated diffusion layer, the nickel foil first needs to be laser punched. The laser is used to carve through holes on the surface of the nickel foil so that water vapor can be transmitted. The thickness of the nickel foil is about 10 μm. After cleaning the perforated nickel foil in the same way, the nickel foil is attached to the punched surface of the foam nickel to form the anode side diffusion layer.

[0081] In Example 2, since the electrolysis characteristics of the anion exchange membrane water electrolysis are different from those in Example 1, it is more suitable to adopt a through-hole method to expose part of the top of the cone to facilitate gas exchange. If this structure uses pure foam nickel or pure nickel foil as a diffusion layer, it is easy to cause structural stability problems. Therefore, it is necessary to add a layer of metal nickel foil or metal nickel foam to form a composite layer to improve structural stability.

[0082] Specifically, both non-through holes and through holes, when combined with the array, can create interlocking nested structures to meet different needs. For non-through holes, since the top of the array can still form good contact with the PTL, the array structure is more tightly integrated with the PTL, reducing the contact resistance between the two, which is more conducive to charge transfer and thus improving performance. For through holes, the top of the array does not form good contact with the PTL, but this is more conducive to water / air transmission during testing.

[0083] At the same time, the diffusion layer used for non-through holes is usually directly engraved on the surface of commercial PTL. The steps are relatively simple. Once the required hole size is determined, it can be put into long-term use. The diffusion layer used for through holes is usually a composite PTL composed of nickel foil with through holes and commercial PTL. The assembly steps of the composite PTL are relatively complicated. However, when responding to different needs, only the nickel foil needs to be replaced, and the commercial PTL can be reused, reducing costs. Therefore, in actual testing, different PTL forms can be selected according to different needs.

[0084] However, because PTL must have a certain thickness to ensure strength, the thin nickel foil with through holes cannot be used as PTL alone. Therefore, it is chosen to be combined with commercial PTL to form a composite PTL.

[0085] Example 3

[0086] This embodiment illustrates the application and testing of the high-performance interlocking metal film electrode, as shown below:

[0087] 1. Test conditions

[0088] PEMWE Performance: PEMWE performance is typically measured by comparing current density at the same voltage. A higher current density indicates a higher hydrogen production rate and better performance. During testing, the anode-side perforated PTL is composited with an ordered array membrane loaded with IrO2, which is then composited with a cathode-side diffusion layer loaded with Pt / C. The resulting interlocking ordered membrane electrode is then installed in a test fixture for testing.

[0089] Polarization curves of different MEAs were measured using linear sweep voltammetry (LSV). Aside from the different MEA structures, other conditions (such as catalyst loading and membrane thickness) were identical. The tests were performed at 80°C and 1 atm. During the experiment, the anode was charged at a rate of 10 mL / min. -1 Supply water at a constant flow rate.

[0090] AEMWE Performance: The AEMWE performance test method is similar to that of PEMWE. Similarly, the prepared diffusion layer is combined with a catalyst-loaded ordered array membrane to form an ordered MEA, and the polarization curve is tested. The difference is that a KOH solution is introduced during the test.

[0091] Conductive performance: As an important component of PEMWE, the conductivity of the membrane electrode will have a significant impact on the overall performance. The conductivity of the membrane electrode was evaluated by electrochemical impedance spectroscopy (EIS). The EIS test was performed on an electrochemical workstation with a selected voltage amplitude of 1.5 V and a frequency of 10 -1 Hz to 10 5 Hz, the anode was used as the working electrode through 80 ℃ high-purity water, and the cathode was used as the counter electrode and reference electrode.

[0092] 2. Test results

[0093] To achieve good contact between the ordered array film and the perforated PTL, thereby reducing resistance and improving conductivity, the size of the array cones must closely match the size of the holes. The array height on the surface of the tested ordered array film ranged from 10-30 μm, with a bottom diameter of 15-30 μm and a pitch of 2-30 μm.

[0094] Figure 2 a in the figure is the surface morphology of the preferred ordered array membrane, with an array height of 22 μm, a bottom diameter of 20 μm, and a spacing of 18 μm. Figure 2 Figure b shows the surface morphology of the ordered array membrane loaded with catalyst. It can be observed that the catalyst is well filled into the gaps of the array. Figure 2 Figure c is the surface morphology of the punched PTL, where the orderly arranged hole structure can be seen, corresponding to the array structure. Figure 2Figure d is the morphology of the interface between the membrane electrode and the PTL after testing. It can be observed that the array and the perforated PTL have a good matching effect, and the array structure is well preserved.

[0095] In order to achieve a better matching effect, the present embodiment changes the size of the hole diameter: 18-30 μm Figure 2 By comparing the performance and resistance of PEMWE with different pore diameters, the optimal pore diameter parameter is determined.

[0096] Figure 3 The polarization curves of different pore diameters and traditional flat membrane electrodes are shown. Figure 4 This is an impedance comparison test diagram. It can be seen that at a voltage of 2 V, the current density of the pore with a diameter of 22 μm is the largest, which is 5.9 A·cm -2 , far greater than the current density under other parameters. Furthermore, a comparison of resistance values reveals that when the pore diameter is 22 μm, both the ohmic resistance and the charge transfer resistance are minimized. In particular, the charge transfer resistance is much smaller than that of the membrane electrode under other parameters. This indicates that when the pore diameter is 22 μm, the perforated PTL forms optimal contact with the ordered array membrane, significantly improving performance and reducing resistance.

[0097] Furthermore, the team systematically controlled other pore geometric parameters, such as pore depth (10-40 μm) and pore spacing (2-30 μm). The optimal parameters were ultimately 18 μm (±3 μm) pore spacing, 26 μm (±5 μm) pore depth, and 22 μm (±2 μm) pore diameter, which achieved the best performance for the interlocking ordered membrane electrode. Figure 5 Comparison of the surface morphologies of three membrane electrodes. Figure 5 Figure a is an interlocking ordered membrane electrode, where the well-preserved array structure can be clearly observed, and the catalyst on the surface of the array structure is relatively compact, indicating that it has formed good contact with the PTL. Figure 5 b is an ordered membrane electrode in the prior art. It can be observed that there is still a part of the array structure on its surface, but due to the extrusion of PTL, part of the array structure is destroyed. Figure 5 The c in the figure is a traditional flat membrane electrode with no array structure on its surface.

[0098] On this basis, this embodiment compares the interlocking ordered membrane electrode with the ordinary ordered membrane electrode and the traditional flat membrane electrode (corresponding to Example 1). Figure 6 As shown. At a voltage of 2 V, the current density of the interdigitated ordered membrane electrode is much higher than that of other membrane electrodes, reaching 7.51 A·cm -2, which is 1.5 times that of traditional flat membrane electrodes. Furthermore, as the voltage increases, the performance of the interdigitated ordered membrane electrode becomes better than other membrane electrodes. This is because the interdigitated ordered membrane electrode can better preserve the array structure, allowing the array structure to better utilize its advantages in proton, electron, and material transport at high potentials and high current densities.

[0099] Furthermore, this embodiment compares the impedance of three membrane electrodes, such as Figure 7 As shown in Figure 1 (corresponding to Example 1), the interdigitated ordered membrane electrode also exhibits minimal ohmic resistance and charge transfer resistance, decreasing by 17% and 37.5%, respectively, compared to conventional flat membrane electrodes. This significant reduction in charge transfer resistance is primarily due to the improved contact between the catalyst layer and the PTL achieved by the interdigitated structure, which is one of its key advantages.

[0100] The AEMWE was tested with an interlocking ordered membrane electrode, such as Figure 8 As shown, a conventional ordered membrane electrode was also used for comparison (corresponding to Example 2). Comparing the polarization curves reveals that at a voltage of 2 V, the AEMWE performance of the interdigitated ordered membrane electrode is significantly improved compared to the conventional ordered membrane electrode. This demonstrates that the interdigitated ordered structure offers significant advantages in both PEMWE and AEMWE, and has a wide range of applications.

[0101] In addition, the present invention uses a laser to carve a hole structure corresponding to the array structure on the PTL surface, but other hole-opening methods are also feasible; the same method is also applicable to foam nickel, aluminum, and carbon materials to meet different testing requirements, and the corresponding catalytic layer can also adjust the material and thickness accordingly.

[0102] It should be understood that the above embodiments are merely illustrative of the technical concepts and features of the present invention. Their purpose is to enable those skilled in the art to understand the contents of the present invention and implement them accordingly. They are not intended to limit the scope of protection of the present invention. Any equivalent variations or modifications made in accordance with the spirit and substance of the present invention are intended to be encompassed within the scope of protection of the present invention.

Claims

1. A high-performance interlocking ordered membrane electrode, characterized in that: It includes an ordered array membrane, a catalytic layer and a perforated diffusion layer; The ordered array membrane comprises a membrane substrate and array cones, wherein the array cones are orderly arranged on a selected surface of the membrane substrate; the perforated diffusion layer has a plurality of hole structures, and the array cones enter the hole structures; The catalytic layer is continuously filled between the array cones and the wall surface of the hole structure and between the selected surface and the perforated diffusion layer, and the array cone-catalytic layer-hole structure forms a mechanical bite; the root diameter of the array cone is 15-30 μm, the spacing between the roots of adjacent array cones is 2-30 μm, and the height of the array cone is 10-30 μm; The preparation method of the high-performance interlocking ordered membrane electrode comprises: Providing an ordered array membrane and a perforated diffusion layer, wherein the hole structure in the perforated diffusion layer corresponds to the arrangement and size of the array cones on the ordered array membrane; Covering a catalytic layer on a selected surface of the ordered array membrane, and / or covering a catalytic layer on a contact surface of the perforated diffusion layer and a surface in the pore structure; The perforated diffusion layer and the selected surface are aligned and pressed together so that the array cones of the ordered array membrane and the hole structure of the perforated diffusion layer are fully engaged with each other, and the catalytic layer is located between the ordered array membrane and the perforated diffusion layer.

2. The high-performance interlocking ordered membrane electrode according to claim 1, characterized in that: The material of the ordered array film includes any one or a combination of two or more of a fluorinated polymer, a polyarylether polymer, a polyarylpiperidine polymer and a fluorine-free polymer; The material of the catalytic layer includes any one or a combination of two or more of metal, metal oxide, and metal-support composite material; The material of the perforated diffusion layer includes porous metal, metal felt, and metal mesh.

3. The high-performance interlocking ordered membrane electrode according to claim 2, characterized in that: The fluorinated polymer is selected from perfluorosulfonic acid-based polymers.

4. The high-performance interlocking ordered membrane electrode according to claim 1, characterized in that: The hole structure is a blind hole, and the perforated diffusion layer completely covers the selected surface; Alternatively, the hole structure is a through hole, and the top of the array cone is exposed from the hole structure.

5. The high-performance interlocking ordered membrane electrode according to claim 4, characterized in that: When the hole structure is a through hole, the perforated diffusion layer is a composite layer of metal foil and porous metal, and the metal foil is located between the selected surface and the porous metal.

6. The high-performance interlocking ordered membrane electrode according to claim 1, characterized in that: The preparation process of the ordered array membrane specifically includes: Providing a hard template having a shaping surface complementary to the array cones; Applying a polymer emulsion on the shaping surface to form a liquid layer, and heating and curing it to form a shaping body; The plastic is peeled off to obtain the ordered array membrane.

7. The high-performance interlocking ordered membrane electrode according to claim 1, characterized in that: The formation process of the catalytic layer specifically includes: preparing a catalyst slurry, wherein the catalyst slurry comprises a dispersant, a catalyst and a polymer; The catalyst slurry is sprayed on the surface of the ordered array membrane and / or the perforated diffusion layer to form the catalyst layer.

8. A method for electrolyzing water, characterized in that: include: Using the high-performance interlocking ordered membrane electrode according to any one of claims 1 to 7 as an anode-side electrode and / or a cathode-side electrode to form an electrolysis system with an aqueous solution; Electric current is applied to the electrolysis system to electrolyze water.

9. The method according to claim 8, characterized in that When the ordered array membrane in the high-performance interlocking ordered membrane electrode is a proton exchange membrane, the hole structure of the diffusion layer is a blind hole; When the ordered array membrane is an anion exchange membrane, the pore structure of the diffusion layer is a through hole.

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