High-performance occlusion type ordered membrane electrode as well as preparation method and application thereof

Abstract

The invention provides a high-performance occlusion type ordered membrane electrode as well as a preparation method and application thereof. The electrode comprises an ordered array membrane, a catalytic layer (CL) and a perforated diffusion layer, the ordered array film comprises a film substrate and array cones which are arranged in order; the punching diffusion layer is provided with a plurality of hole structures, and the array cones enter the hole structures; and the catalyst layer is continuously filled between the array cone and the wall surface of the hole structure and between the selected surface and the punching diffusion layer to form mechanical occlusion. According to the invention, an occlusion type structure is constructed, and the hole structure is carved in the surface of the diffusion layer (PTL), so that the prepared membrane electrode can well maintain the array structure, and the advantages of the array structure in the aspects of proton, electron and substance transmission and the like can be well exerted; in addition, due to the occlusion type structure, the catalyst layer and the diffusion layer which are in poor contact originally can be in good contact, the contact resistance of an 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, the demand for clean renewable energy is increasing. Hydrogen, as a clean energy, has the advantages of high energy density and wide sources. It is a promising renewable clean energy. Therefore, a fast, efficient and clean way to prepare hydrogen is needed.

[0003] Hydrogen production by water electrolysis has the advantages of clean and pollution-free preparation process, high purity of prepared hydrogen and less impurity gas. It is an ideal way to produce hydrogen. According to the different electrolyte types 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). Proton exchange membrane water electrolysis and anion exchange membrane water electrolysis have the advantages of high purity of 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, the catalyst layer and the diffusion layer. It is the key three-phase interface for the electrochemical reaction of water, gas, catalyst and other substances, 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 ), but due to the discontinuity of the ionomer in the catalyst layer, the catalyst far from the membrane cannot form a good proton transport, making it difficult to fully exert the catalytic effect, resulting in a low catalyst utilization rate. At the same time, the thicker catalyst layer further hinders the transmission of water and bubbles. Therefore, improving the structure of the membrane electrode and thus improving the transmission of protons, electrons and substances therein can better improve the performance and stability of MEA.

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

[0006] CN114628750A discloses a method for preparing a membrane electrode assembly, which forms a conical, cylindrical or other array structure on the surface of an ion exchange membrane by direct growth, transfer printing, nanoimprinting or other methods, and then uses magnetron sputtering or spraying to load the catalyst on the surface of the membrane, and then the membrane loaded with the catalyst is composited with a gas diffusion layer to obtain a membrane electrode assembly. The method greatly increases the three-phase interface (gas, water, catalyst) where the electrochemical reaction occurs by constructing an array structure, forming a channel for rapid transfer of reactants, protons, and electrons, which is conducive to reducing the catalyst loading, improving the catalyst utilization rate, and improving performance and stability. However, in actual testing, the array structure will be partially destroyed due to the extrusion of the PTL, and the advantages of the array structure cannot be fully utilized; at the same time, the interface contact effect between the catalyst layer and the diffusion layer will also have a significant impact on 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 object of the present invention is to provide a high-performance interlocking ordered membrane electrode, a preparation method and application thereof.

[0009] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes: 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; The ordered array membrane includes a membrane substrate and array cones, wherein 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.

[0010] In a second aspect, the present invention further provides a method for preparing the above-mentioned high-performance interlocking ordered membrane electrode, which comprises: Providing an ordered array membrane and a perforated diffusion layer; 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; 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.

[0011] In a third aspect, the present invention further provides a method for electrolyzing water, comprising: The high-performance interlocking ordered membrane electrode is used as an anode-side electrode and / or a cathode-side electrode to form an electrolysis system with an aqueous solution; An electric current is applied to the electrolysis system to electrolyze water.

[0012] Based on the above technical solution, compared with the prior art, the beneficial effects of the present invention at least include: 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 transportation 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, the charge transfer resistance is reduced, and the performance is further improved.

[0013] In addition, the method for preparing the interlocking ordered membrane electrode provided by the present invention is simple and can be mass-produced, with simple process and low energy consumption.

[0014] 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 the present application and implement them according to the contents of the specification, the following is a description of the preferred embodiments of the present invention in conjunction with detailed drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 It is a schematic flow chart of a method for preparing a high-performance interlocking ordered membrane electrode provided by a typical implementation case of the present invention; Figure 2 This is a structural electron microscope photograph of different parts of a high-performance interlocking ordered membrane electrode provided by a typical implementation case of the present invention; Figure 3 This is a comparative test diagram of IV performance of different pore diameters of a high-performance occlusal ordered membrane electrode provided by a typical implementation case of the present invention; Figure 4 This is a comparative test diagram of impedance performance of high-performance interlocking ordered membrane electrodes with different pore diameters provided by a typical implementation case of the present invention; Figure 5 This is a comparative electron microscope photo of the surface morphologies of different high-performance interlocking ordered membrane electrodes provided in a typical implementation case of the present invention; Figure 6 It is a PEMWE performance comparison diagram of different membrane electrodes provided by a typical implementation case of the present invention; Figure 7 This is a comparison diagram of impedances of different membrane electrodes provided by a typical implementation case of the present invention; 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

[0016] As mentioned above, current commercial membrane electrodes generally have a 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 transmission 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 inability of the array structure 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.

[0017] In view of the deficiencies in the prior art, the inventor of this case has proposed the technical solution of the present invention after long-term research and extensive practice. The technical solution, its implementation process and principle will be further explained as follows.

[0018] In view of the above limitations, the technical idea of ​​the present invention breaks through the original construction method of the interface structure of the membrane electrode. While constructing an orderly array structure on the membrane surface, corresponding holes are also constructed on the surface of the porous transport layer (PTL). After being compounded with the ordered array membrane, a nested interlocking structure can be constructed. The array structure can be better preserved, and the interlocking structure improves the interface contact between the catalyst layer and the PTL, reducing the contact resistance.

[0019] 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 protection scope of the present invention is not limited to the specific embodiments disclosed below.

[0020] An embodiment of the present invention provides a high-performance interlocking ordered membrane electrode, which includes an ordered array membrane, a catalyst 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 catalyst layer is continuously filled between the array cones and the wall of the hole structure and between the selected surface and the perforated diffusion layer, and the array cone-catalyst layer-hole structure forms a mechanical interlock.

[0021] 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 the catalyst is loaded on the surface of the membrane by magnetron sputtering or spraying, and the membrane loaded with the catalyst is composited 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 combination is not firm but not tight, and therefore easily causes 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 formed by targeted opening of holes using a corresponding punching process. After pressing, a tight and firm pure mechanical bite can be formed. This bite is stable, and due to the stress effect, the combination is tighter, which significantly reduces the interface resistance and can significantly improve the electrode performance.

[0022] 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, Piperion, which are very typical ion exchange membrane materials, but are of course not limited to these. Other materials with equivalent functions are feasible for preparing electrodes with equal or similar technical effects.

[0023] In addition, in some embodiments, the material of the catalyst layer includes any one or a combination of two or more of metal, metal oxide, metal-carrier composite material (such as metal-carbon composite material); specifically, Ir, IrO2, IrO2-ionomer carrier composite material, Pt-carbon carrier composite material. The material of the catalyst layer should be selected according to the application of the electrode, such as applied to the anode side or the cathode side, and can be appropriately adjusted or modified according to the composition of the electrolyte; of course, in the preferred embodiment, the cathode and anode can be formed on the surfaces of both sides respectively to realize integrated anode and cathode electrolysis.

[0024] And, in some embodiments, the material of the perforated diffusion layer includes porous metal, metal felt, and metal mesh.

[0025] 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.

[0026] Or in some embodiments, the hole structure is a through hole, and the top of the array cone is exposed from the hole structure.

[0027] 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.

[0028] 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 catalyst 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 catalyst layer. This can be determined through conditional tests in specific implementation.

[0029] In some embodiments, the spacing distance 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.

[0030] Furthermore, in some embodiments, the height of the array cones is 10-30 μm.

[0031] 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: Providing an ordered array membrane and a perforated diffusion layer; 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; 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.

[0032] In some embodiments, the preparation process of the ordered array membrane specifically includes the following steps: Providing a hard template having a shaping surface complementary to the array cones; A polymer emulsion is coated on the shaping surface to form a liquid layer, and heated and cured to form a shaping body; The plastic is peeled off to obtain the ordered array membrane.

[0033] In some embodiments, the formation process of the catalytic layer specifically includes the following steps: 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.

[0034] As some typical applications of the above technical solutions, the third aspect of the embodiments of the present invention further provides a method for electrolyzing water, which comprises the following steps: Using the high-performance interlocking ordered membrane electrode provided by any of the above embodiments as an anode side electrode and / or a cathode side electrode to form an electrolysis system with an aqueous solution; An electric current is applied to the electrolysis system to electrolyze water.

[0035] 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 carry out ion exchange. Therefore, when the two sides are cathode and anode respectively (the corresponding catalyst and diffusion layer are also adapted to the electrolysis reaction of cathode and anode), electrolysis can be realized in an integrated manner. If a single-sided method is adopted, such as a single-sided anode electrode, it is also necessary to set a corresponding cathode in the electrolyte on the side facing away from the anode catalyst, and vice versa.

[0036] 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; When the ordered array membrane is an anion exchange membrane, the hole structure of the diffusion layer is a through hole.

[0037] 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 do not limit the scope of the present invention.

[0038] Example 1 This embodiment illustrates a preparation process of a high-performance interlocking ordered membrane electrode for proton exchange membrane water electrolysis, as shown below: 1. Preparation of ordered array membranes A small amount of the prepared Nafion emulsion was dripped onto the surface of the template with a suitable hole size, and then evenly spread and vacuumed to allow the emulsion to completely fill the hole. Next, the vacuum-treated template was heated at 80 °C while a certain amount of Nafion emulsion (100-150 μL cm -2 ). After the emulsion is completely dry, the temperature is raised to 140 °C and heated for 30 minutes. Then the template is immersed in deionized water for 5-10 minutes, and the membrane is slowly lifted along the edge of the template to obtain a Nafion ordered array membrane for PEMWE.

[0039] 2. Cleaning of ordered array membrane 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 placed in a H2SO4 solution and continued to be cleaned at 80°C for 1 hour. Finally, the membrane was placed in deionized water and continued to be cleaned at 80°C for 1 hour. Finally, the cleaned membrane was stored in deionized water. The AEM ordered array membrane was not specially treated before use and could be stored in deionized water.

[0040] 3. Preparation of Catalytic Layer (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 prepared to a concentration of 0.1-2 mg mL -1 The catalyst slurry is also prepared with 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 disperse uniformly.

[0041] (2) After the 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, and the loading was also 0.5 mg cm -2 .

[0042] 4. Preparation of the perforated anode side diffusion layer For PEMWE, first place the commercially available anode diffusion layer (PTL) titanium foam inside the laser marking machine, and use the laser to carve holes on its surface. The same method is also applicable to engraving materials such as nickel foam and aluminum to meet different needs. Through laser engraving, holes of different arrangements and sizes are engraved on the surface of the PTL to form different bite effects such as full bite, partial bite, random bite, etc. In this embodiment, it is preferred that the arrangement and size of the holes correspond to the array, and the bite effect is best; the cathode side uses the corresponding diffusion layer in the same way.

[0043] Suitable holes can be obtained by changing the spacing, intensity and other parameters of laser engraving. The PTL was then ultrasonically cleaned with ethanol and deionized water to remove the powder produced by laser engraving. It was then pickled with 37 wt.% hydrochloric acid to remove surface oxides. Finally, the PTL was ultrasonically cleaned with deionized water to remove residual acid and a layer of Pt was sputtered on its surface to further enhance its conductivity and prevent it from oxidation.

[0044] 5. Electrode assembly 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 diffusion layer are ensured to be in a fixed position during each test by limiting and other methods, 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 with 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.

[0045] Example 2 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 embodiment 1, except that: The emulsion was replaced with AEM emulsion, dropped on the template, and then heated and cured at 80 °C for 4 hours. The AEM ordered array membrane was then peeled off. The NiFe LDH catalyst was used on the anode side with a loading of 1 mg cm -2 As for the perforated diffusion layer, the nickel foil needs to be laser punched first. 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 the perforated nickel foil is cleaned in the same way, the nickel foil is attached to the perforated surface of the nickel foam to form the anode side diffusion layer.

[0046] 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.

[0047] Specifically, whether it is a non-through hole or a through hole, after being compounded with the array, a bite-type nested structure can be prepared to meet different needs. For non-through holes, since the top of the array can still form a good contact with the PTL, the array structure is more tightly combined with the PTL, and the contact resistance between the two is lower, which is more conducive to the transfer of charges, thereby improving performance. For through holes, the top of the array does not form a good contact with the PTL, but this is more conducive to water / gas transmission during the test process.

[0048] 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. After determining the required hole size, it can be put into use for a long time. The diffusion layer used for through holes is usually a composite PTL composed of nickel foil with through holes and commercial PTL. The steps of assembling the composite PTL are relatively complicated. But at the same time, when responding to different needs, only the nickel foil needs to be replaced, and the commercial PTL can be reused to reduce costs. Therefore, in actual testing, different PTL forms can be selected according to different needs.

[0049] However, since 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.

[0050] Example 3 This embodiment illustrates the application and testing of the above-mentioned high-performance interlocking metal film electrode, as shown below: 1. Test conditions PEMWE performance: PEMWE performance is usually measured by comparing the current density at the same voltage. The higher the current density, the higher the hydrogen production rate and the better the performance. During the test, the perforated PTL on the anode side is compounded with the ordered array membrane loaded with IrO2 and then with the cathode diffusion layer loaded with Pt / C to form an interlocking ordered membrane electrode, which is then loaded into the test fixture for testing.

[0051] Polarization curves of different MEAs were determined using linear sweep voltammetry (LSV). Except for the different structures of the MEAs, other conditions (such as catalyst loading and membrane thickness) were the same. The tests were performed at 80 °C and 1 atm. During the experiment, the anode side was charged at 10 mL min -1 Supply water at a constant flow rate.

[0052] AEMWE performance: The test method of AEMWE performance is similar to that of PEMWE, which is to combine the previously prepared diffusion layer with the ordered array membrane loaded with catalyst to form an ordered MEA to test the polarization curve. The difference is that KOH solution is introduced during the test.

[0053] 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.

[0054] 2. Test results If you want the ordered array film to form good contact with the perforated PTL, thereby reducing resistance and improving conductivity, the size of the array cone needs to match the size of the hole. The array height of the tested ordered array film surface is 10-30μm, the bottom diameter is 15-30μm, and the spacing is 2-30μm.

[0055] Figure 2 a in the figure is the surface morphology of the preferred ordered array film, the height of the array is 22 μm, the bottom diameter is 20 μm, and the spacing is 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 2 Figure d in the figure is the morphology of the interface between the membrane and PTL of the membrane electrode 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.

[0056] 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 under different pore diameters, the optimal pore diameter parameter is determined.

[0057] 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 hole with a diameter of 22 μm is the largest, which is 5.9 A·cm -2 , which is much larger than the current density under other parameters. Further, by comparing the resistance size, it can be seen that when the hole diameter is 22 μm, both the ohmic resistance and the charge transfer resistance are the smallest, especially the charge transfer resistance, which is much smaller than the membrane electrode under other parameters. This shows that when the hole diameter is 22 μm, the perforated PTL forms the best contact with the ordered array membrane, greatly improving the performance and reducing the resistance.

[0058] Furthermore, the system controlled other geometric parameters of the pores, such as pore depth (10-40 μm) and pore spacing (2-30 μm). The final optimal parameters were pore spacing of 18 μm (±3 μm), pore depth of 26 μm (±5 μm), and pore diameter of 22 μm (±2 μm), at which the bite-type ordered membrane electrode had the best performance. Figure 5 Comparison of the surface morphologies of three membrane electrodes. Figure 5 a in the figure 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 a 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.

[0059] On this basis, this embodiment compares the interlocking ordered membrane electrode with the common 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 interlocking 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 the traditional flat membrane electrode. And as the voltage increases, the performance of the interlocking ordered membrane electrode is better than other membrane electrodes. This is because the interlocking ordered membrane electrode can better retain the array structure, so that the advantages of the array structure in proton, electron and material transport at high potential and high current density can be better utilized.

[0060] Furthermore, this embodiment compares the impedance of three membrane electrodes, such as Figure 7 As shown (corresponding to Example 1). Similarly, it can be found that the ohmic resistance and charge transfer resistance of the bite-type ordered membrane electrode are both the smallest, which are reduced by 17% and 37.5% respectively compared with the traditional flat membrane electrode. The significant reduction in charge transfer resistance is mainly due to the fact that the bite-type structure improves the contact between the catalyst layer and the PTL, which is also one of the main advantages of the bite-type structure.

[0061] The AEMWE was tested with an interlocking ordered membrane electrode, such as Figure 8 As shown in the figure, a common ordered membrane electrode was also selected for comparison (corresponding to Example 2). By comparing the polarization curves, it was found that at a voltage of 2 V, the AEMWE performance of the interlocking ordered membrane electrode was significantly improved compared with the common ordered membrane electrode. This shows that the interlocking ordered structure has great advantages in both PEMWE and AEMWE, and has a wide range of applications.

[0062] In addition, the present invention uses a laser to carve a hole structure corresponding to the array structure on the surface of the PTL, 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.

[0063] It should be understood that the above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope 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 film comprises a film substrate and array cones, wherein the array cones are orderly arranged on a selected surface of the film 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 cone 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.

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

4. The high-performance interlocking ordered membrane electrode according to claim 3, 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.

5. The high-performance interlocking ordered membrane electrode according to claim 1, characterized in that: The root diameter of the array cone is 15-30 μm; and / or, the spacing distance between the roots of adjacent array cones is 2-30 μm; And / or, the height of the array cones is 10-30 μm.

6. The method for preparing a high-performance interlocking ordered membrane electrode according to any one of claims 1 to 5, characterized in that: include: Providing an ordered array membrane and a perforated diffusion layer; 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; 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.

7. The preparation method according to claim 6, characterized in that: The preparation process of the ordered array film specifically includes: Providing a hard template having a shaping surface complementary to the array cones; A polymer emulsion is coated on the shaping surface to form a liquid layer, and heated and cured to form a shaping body; The plastic is peeled off to obtain the ordered array membrane.

8. The preparation method according to claim 6, 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.

9. A method for electrolyzing water, characterized in that: include: Using the high-performance interlocking ordered membrane electrode described in any one of claims 1 to 5 as an anode side electrode and / or a cathode side electrode to form an electrolysis system with an aqueous solution; An electric current is applied to the electrolysis system to electrolyze water.

10. The method according to claim 9, 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 hole structure of the diffusion layer is a through hole.

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