Three-dimensional ordered pattern array membrane electrode and preparation method and application thereof
The fabrication of three-dimensional ordered patterned array membrane electrodes by laser masking and hot pressing technology solves the problem of high Ir loading in PEMWE, achieving efficient and simple performance improvement in water electrolysis, and is suitable for large-scale production.
Patent Information
- Application Number
- CN202511102238.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-07
- Publication Date
- 2025-11-14
AI Technical Summary
Existing technologies struggle to effectively reduce iridium (Ir) loading in proton exchange membrane electrolysis (PEMWE) while maintaining catalyst activity and stability. Traditional preparation methods are complex and unsuitable for large-scale production.
A three-dimensional ordered patterned array membrane electrode was fabricated by combining laser masking technology with a hot pressing strategy. By precisely controlling the microstructure of the membrane electrode, the three-phase interface and mass transfer channels were optimized, thereby improving electrolysis efficiency and durability.
It achieves high-efficiency water electrolysis performance under low Ir load, simplifies the preparation process, is suitable for large-scale production, and significantly improves the activity and stability of electrolyzed water, with performance improvement exceeding 50% of traditional methods.
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Figure CN120945401A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of water electrolysis membrane electrode preparation technology, and in particular to a three-dimensional ordered patterned array membrane electrode, its preparation method and application. Background Technology
[0002] Achieving carbon neutrality largely depends on the development of renewable energy technologies. However, the large-scale application of renewable energy requires highly reliable energy storage methods, especially in long-cycle and centralized scenarios. Among these, proton exchange membrane electrolysis (PEMWE) is particularly promising due to its high efficiency, high-purity hydrogen product, and wide dynamic operating range. However, traditional catalyst-coated membranes (CCMs) in PEMWE require 2–3 mg cm⁻¹ of storage. -2 High iridium (Ir) loading in PEMWEs, intended to maintain good performance and stability by providing ample active sites and catalyst degradation margin, limits the large-scale industrial production of PEMWEs. Furthermore, low Ir loading results in insufficient active sites in the CCM (Chemical Motion Matrix), leading to excessively high operating voltages, accelerated catalyst dissolution, increased ohmic resistance, and structural degradation, thus reducing performance and stability. Currently, methods to reduce Ir loading in PEMWEs primarily involve designing Ir-based catalysts with optimized electronic structures, establishing strong interactions between the catalyst and the support, and using ordered intermetallic compounds or high-entropy alloys to improve activity and stability, while minimizing Ir dissolution through strain engineering, interstitial doping, or heteroatom bonding. However, due to the completely different operating environments of three-electrode and membrane electrode assembly (MEA) devices, most of these methods cannot meet the requirements of practical PEMWE equipment.
[0003] Recent advances in low-Ir-loaded MEAs for PEMWEs have focused on designing advanced catalyst layers (CLs). Strategies include embedding Ir nanoparticles into high-surface-area conductive supports or forming ordered catalyst layers. All these strategies aim to maximize active site exposure, enhance charge transfer, and reduce Ir dissolution. Optimizing the structure of porous transport layers (PTLs) and their contact with the catalyst core membrane (CCM) also holds great promise for reducing the inert metal content in MEAs. Currently, ordered MEA design is considered a promising approach for optimizing CLs. Most reported ordered strategies utilize nanomaterials to prepare CLs (e.g., ordered support nanotubes, catalyst nanowires). However, these materials suffer from insufficient contact with the PEM / PTL, leading to discontinuous electron conduction paths and increased interfacial resistance. Introducing three-dimensional ordered patterned structures to improve interfacial contact is becoming an effective strategy, but most traditional preparation methods (e.g., nanoimprinting, vapor phase growth) rely on complex templates or involve cumbersome processes. Therefore, developing a simple and universally applicable method for preparing three-dimensional ordered patterned array MEAs suitable for large-scale production is essential. Summary of the Invention
[0004] In view of this, this application provides a three-dimensional ordered patterned array membrane electrode, its preparation method and application. By precisely controlling the microstructure of the membrane electrode and optimizing the three-phase interface and mass transfer channels, the electrolysis efficiency and durability are significantly improved, which can effectively overcome the defects of the prior art.
[0005] The first aspect of this application provides a method for fabricating a three-dimensional ordered patterned array film electrode, comprising the following steps:
[0006] The cleaned titanium foil is patterned by laser masking, acid-washed, and dried to obtain a titanium foil with patterned pores. The titanium foil with patterned pores is then bonded and hot-pressed with a proton exchange membrane. Finally, a cathode catalyst and an anode catalyst are coated by ultrasonic spraying to obtain a three-dimensional ordered patterned array membrane electrode.
[0007] Preferably, the procedure specifically includes the following steps:
[0008] (1) Dissolve the titanium foil in an ethanol solution, ultrasonically clean it, then take it out, add deionized water and ultrasonically clean it again, and dry it to obtain a clean titanium foil.
[0009] (2) Place the cleaned titanium foil on the worktable of the laser mask processing machine and fix it. Set the laser processing parameters and the required pattern shape. Start the pattern laser drilling process on the cleaned titanium foil. After the laser processing is completed, soak and clean it with a mixture of nitric acid and hydrofluoric acid to remove the oxide layer and slag and restore the surface smoothness. After drying, a titanium foil with patterned pores is obtained.
[0010] (3) The titanium foil with patterned pores and the proton exchange membrane are hot-pressed to obtain a proton exchange membrane with a three-dimensional patterned structure. Then, the cathode catalyst and the anode catalyst are coated by ultrasonic spraying to obtain a three-dimensional ordered patterned array membrane electrode.
[0011] Preferably, in step (1), the titanium foil has a size of 2×2cm. 2 .
[0012] Preferably, in step (1), the ultrasonic cleaning time is 10 to 30 minutes and the drying temperature is 40 to 80°C.
[0013] Preferably, in step (2), the laser drilling frequency is 20–45 kHz, the pulse width is 25–50 μs, the processing power is 100–200 W, the defocusing amount is -0.5–0 mm, and the processing area is 2 × 2 cm. 2 .
[0014] Preferably, in step (2), the mass ratio of nitric acid to hydrofluoric acid in the nitric acid and hydrofluoric acid mixture is 3:1.
[0015] Preferably, in step (2), the pattern shape is selected from one of the following: circle, octagonal star, and petal shape.
[0016] Preferably, in step (3), the hot pressing pressure is 2-5 MPa, the hot pressing temperature is 80-130°C, and the hot pressing time is 5-60 min.
[0017] The second aspect of this application also provides a three-dimensional ordered patterned array film electrode, which is a three-dimensional ordered patterned array film electrode prepared by the above method.
[0018] The third aspect of this application also provides the application of the above-mentioned three-dimensional ordered patterned array membrane electrode in water electrolysis.
[0019] Compared with the prior art, this application has the following advantages:
[0020] 1. This application uses laser mask processing technology combined with a simple hot pressing strategy to realize an ordered and tunable patterned array membrane electrode, which is a general method to improve MEA performance by improving charge and mass transport. It is simple to operate, economical and efficient, and also has the characteristics of large-scale production and reusability, and has potential application prospects in the field of water electrolysis.
[0021] 2. This application provides a simple, low-cost, and adjustable patterned array membrane electrode preparation method, which can realize micron-scale patterned arrays on the catalyst layer, improve the contact area of the membrane electrode assembly, and obtain a larger three-phase reaction boundary.
[0022] 3. This application provides a method for preparing ordered patterned array film electrodes with higher structural precision and controllability. Laser mask processing technology can precisely control the aperture (micrometer / nanometer level), aperture spacing and array arrangement (such as circular or octagonal star), and optimize the gas / liquid transport path. Traditional coating or transfer methods are difficult to achieve high-precision patterned film electrode preparation.
[0023] 4. Existing technologies such as nanoimprinting or chemical vapor deposition (CVD) require complex templates or high-temperature conditions, while this application uses laser one-step forming + hot pressing composite, reducing process complexity and making it suitable for large-scale production; the prepared ordered patterned array membrane electrodes also exhibit excellent activity and stability in PEMWE. For example, a circular array MEA with a diameter of 200 μm can achieve 3.73 Acm at 2V. -2 Its performance far surpasses that of traditional MEAs; furthermore, its stability was verified through accelerated stress testing (AST), which revealed a degradation rate of only 26.6 μV h after 100 hours of dynamic cycling. -1This demonstrates that the preparation method described in this application, while ensuring simplicity and efficiency, can also effectively improve electrolysis efficiency. This provides a universal method for reducing catalyst loading and large-scale commercialization of PEMWE technology.
[0024] 5. This application has prepared a series of high-fidelity patterned film electrodes, providing a variety of options in terms of systematicity and the diversity of ordered patterns. Attached Figure Description
[0025] To more clearly illustrate the technical solutions in this application or the prior art, the drawings used in the description of this application or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0026] Figure 1 This is a SEM cross-sectional view of the circular patterned array MEA obtained in Embodiment 1 of this application;
[0027] Figure 2 This is a performance test diagram of the circular patterned array MEA obtained in Embodiment 1 of this application in PEMWE;
[0028] Figure 3 This is a performance graph of the circular patterned array MEA obtained in Embodiment 1 of this application after accelerated stress testing cycles in PEMWE;
[0029] Figure 4 This is a SEM cross-sectional view of the octagonal star pattern array MEA obtained in Embodiment 2 of this application;
[0030] Figure 5 This is a performance test diagram of the octagonal star patterned array MEA obtained in Embodiment 2 of this application in PEMWE;
[0031] Figure 6 This is a SEM cross-sectional view of the petal-shaped patterned array MEA obtained in Embodiment 3 of this application;
[0032] Figure 7 This is a performance test diagram of the petal-shaped patterned array MEA prepared in Embodiment 3 of this application in PEMWE. Detailed Implementation
[0033] To make the objectives, technical solutions, and advantages of this application clearer, the technical solutions of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.
[0034] Unless otherwise specified, the experimental methods used in the embodiments of this application are all conventional methods.
[0035] In the following examples and comparative examples, unless otherwise specified, all raw materials can be obtained by commercial purchase or conventional methods.
[0036] Example 1: A method for fabricating a circular patterned array (MEA), comprising the following steps:
[0037] (1) The size is 2×2cm 2 The titanium foil was ultrasonically cleaned in 20ml of ethanol and 20ml of deionized water for 15 minutes, and then dried in an oven at 60℃.
[0038] (2) Fix the dried titanium foil on the laser processing worktable, and set the laser working starting point and processing area (2×2cm). 2 A circular pattern with a diameter of 200μm and a pattern spacing of 300μm was designed through pattern programming, and the laser parameters (working frequency 35KHz, pulse width 25μs, processing power 150W, defocusing amount (-0.3mm)) were adjusted.
[0039] (3) Place the titanium foil with the circular pattern into a mixture of 1.5g nitric acid, 0.5g hydrofluoric acid and 18ml deionized water, ultrasonically clean for 20min, and then dry.
[0040] (4) The dried patterned titanium foil is bonded to the proton exchange membrane and hot-pressed, and kept at 5 MPa and 120°C for 30 min.
[0041] (5) Anode and cathode catalysts are sprayed onto PEM with a circular pattern by ultrasonic spraying to obtain a circular array MEA.
[0042] Example 2: A method for fabricating an octagonal star-shaped patterned array MEA, comprising the following steps:
[0043] (1) The size is 2×2cm 2 The titanium foil was ultrasonically cleaned in 20ml of ethanol and 20ml of deionized water for 15 minutes, and then dried in an oven at 60℃.
[0044] (2) Fix the dried titanium foil on the laser processing worktable, and set the laser working starting point and processing area (2*2cm). 2 An octagonal star pattern with a length / width of 500μm and a pattern spacing of 250μm was designed through pattern programming, and the laser parameters (working frequency 40KHz, pulse width 25μs, processing power 150W, defocusing amount (-0.3mm)) were adjusted.
[0045] (3) Place the titanium foil with the octagonal star pattern into a mixture of 1.5g nitric acid, 0.5g hydrofluoric acid and 18ml deionized water, ultrasonically clean for 20min, and then dry.
[0046] (4) The dried patterned titanium foil is bonded to the proton exchange membrane and hot-pressed, and kept at 5 MPa and 130°C for 30 min.
[0047] (5) The cathode and anode catalysts are sprayed onto the PEM with an octagonal star pattern by ultrasonic spraying to obtain an octagonal star array MEA.
[0048] Example 3: A method for preparing a petal-shaped patterned array MEA, comprising the following steps:
[0049] (1) The size is 2×2cm 2 The titanium foil was ultrasonically cleaned in 20ml of ethanol and 20ml of deionized water for 15 minutes, and then dried in an oven at 60℃.
[0050] (2) Fix the dried titanium foil on the laser processing worktable, and set the laser working starting point and processing area (2*2cm). 2 A petal-shaped pattern with a length / width of 500μm and a pattern spacing of 250μm was designed through pattern programming, and the laser parameters (working frequency 40KHz, pulse width 25μs, processing power 150W, defocusing amount (-0.3mm)) were adjusted.
[0051] (3) Place the titanium foil with the petal pattern into a mixture of 1.5g nitric acid, 0.5g hydrofluoric acid and 18ml deionized water, ultrasonically clean for 20min, and then dry.
[0052] (4) The dried patterned titanium foil is bonded to the proton exchange membrane and hot-pressed, and kept at 5 MPa and 130°C for 30 min.
[0053] (5) Anode and cathode catalysts are sprayed onto PEM with a petal-shaped pattern by ultrasonic spraying to obtain a petal-shaped MEA array.
[0054] Comparative Example 1
[0055] Traditional planar MEAs are prepared by spraying DuPont Nafion 115 proton exchange membranes with IrO2 anode and Pt / C cathode catalysts from Momentum Conservation Company.
[0056] Test case
[0057] Patterned MEAs also use the same materials as traditional MEAs. The only difference is that the Nafion 115 proton exchange membrane is further prepared using patterning technology, and then patterns are constructed on the proton exchange membrane. Figure 1 The SEM cross-sectional image of the fabricated circular patterned MEA array is shown, revealing that the patterned structure is fully embedded in the proton exchange membrane. Subsequent characterization verified the performance improvement of the patterned MEA on the PEMWE. Figure 2 This indicates that the circular array MEA exhibits 3.73 Acm at 2V. -2 Superior performance compared to traditional MEA (2.41Acm) -2 Performance improved by 53%. Furthermore, the long-term stability of the patterned MEA was verified through high-dynamic accelerated cycling tests. Figure 3 The circular array showed no significant performance degradation after 2000 cycles. This study shows that: (1) the 3D ordered patterned array structure increases the number of three-phase reaction boundaries, provides additional active sites, and significantly improves catalyst utilization; (2) the unique void structure provides an effective transport channel for gas-liquid transport, reducing mass transfer loss; and (3) the 3D interlocking structure ensures effective charge transport and long-term durability of the MEA. Similarly, the designed octagonal ( Figure 4 ), petal-shaped pattern ( Figure 6 All of them exhibited impressive performance. Figure 5 and Figure 7 The readings at 2V are 3.43Acm. -2 3.30Acm -2 Both are superior to traditional planar MEAs.
[0058] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.
Claims
1. A method for fabricating a three-dimensional ordered patterned array film electrode, characterized in that, Includes the following steps: The cleaned titanium foil is patterned by laser masking, acid-washed, and dried to obtain a titanium foil with patterned pores. The titanium foil with patterned pores is then bonded and hot-pressed with a proton exchange membrane. Finally, a cathode catalyst and an anode catalyst are coated by ultrasonic spraying to obtain a three-dimensional ordered patterned array membrane electrode.
2. The method for fabricating a three-dimensional ordered patterned array film electrode according to claim 1, characterized in that, Specifically, the following steps are included: (1) Dissolve the titanium foil in an ethanol solution, ultrasonically clean it, then take it out, add deionized water and ultrasonically clean it again, and dry it to obtain a clean titanium foil. (2) Place the cleaned titanium foil on the worktable of the laser mask processing machine and fix it. Set the laser processing parameters and the required pattern shape. Start the pattern laser drilling process on the cleaned titanium foil. After the laser processing is completed, soak and clean it with a mixture of nitric acid and hydrofluoric acid to remove the oxide layer and slag and restore the surface smoothness. After drying, a titanium foil with patterned pores is obtained. (3) The titanium foil with patterned pores and the proton exchange membrane are hot-pressed to obtain a proton exchange membrane with a three-dimensional patterned structure. Then, the cathode catalyst and the anode catalyst are coated by ultrasonic spraying to obtain a three-dimensional ordered patterned array membrane electrode.
3. The method for preparing a three-dimensional ordered patterned array film electrode according to claim 2, characterized in that, In step (1), the titanium foil has a size of 2×2cm. 2 .
4. The method for preparing a three-dimensional ordered patterned array film electrode according to claim 2, characterized in that, In step (1), the ultrasonic cleaning time is 10 to 30 minutes and the drying temperature is 40 to 80°C.
5. The method for preparing a three-dimensional ordered patterned array film electrode according to claim 2, characterized in that, In step (2), the laser drilling frequency is 20–45 kHz, the pulse width is 25–50 μs, the processing power is 100–200 W, the defocusing amount is -0.5–0 mm, and the processing area is 2 × 2 cm. 2 .
6. The method for fabricating a three-dimensional ordered patterned array film electrode according to claim 2, characterized in that, In step (2), the mass ratio of nitric acid to hydrofluoric acid in the nitric acid and hydrofluoric acid mixture is 3:
1.
7. The method for preparing a three-dimensional ordered patterned array film electrode according to claim 2, characterized in that, In step (2), the pattern shape is selected from one of the following: circle, octagonal star, and petal.
8. The method for preparing a three-dimensional ordered patterned array film electrode according to claim 2, characterized in that, In step (3), the pressure of hot pressing is 2-5 MPa, the temperature of hot pressing is 80-130°C, and the time of hot pressing is 5-60 min.
9. A three-dimensional ordered patterned array film electrode, characterized in that, A three-dimensional ordered patterned array film electrode prepared by the method described in any one of claims 1 to 8.
10. The application of the three-dimensional ordered patterned array membrane electrode of claim 9 in water electrolysis.