A Solid Electrolyte RHE for Electrode Diagnosis of Proton Exchange Membrane Water Electrolyzers.

Reference electrode is the foundation of electrochemical study; thus, most electrode materials are tested in a three-electrode mode to acquire potential-dependent kinetics. However, it is difficult to directly use conventional reference electrodes to detect potential information in solid electrolyte devices due to their compact assembly structure. Therefore, the kinetic study of an electrochemical device faces challenges in precise identification of specific problems originating from the anode or cathode. Here, focusing on proton exchange membrane water electrolysis, we design a solid electrolyte reversible hydrogen electrode (SE-RHE), which can be used for electrode diagnosis under various operating conditions. Compared to the reference electrodes reported in the literature, which are mainly based on liquid electrolyte, the SE-RHE is highly sensitive and compatible, as well as easy to assemble. The potential deviation is less than ±0.5 mV, and the cell voltage derived from the electrode potential well reproduces the value that was directly measured with a deviation less than 0.2%. The reference electrode developed in this work enables the kinetic study of a specific electrode rather than the entire cell. For instance, an interesting observation is that the cathode shows distinct stability under stable and fluctuating operations. Differing from the high stability under stable operation, the cathode degrades significantly under fluctuating operations.

Optimizing Ionomer Distribution in Anode Catalyst Layer for Stable Proton Exchange Membrane Water Electrolysis.

The high cost of proton exchange membrane water electrolysis (PEMWE) originates from the usage of precious materials, insufficient efficiency, and lifetime. In this work, an important degradation mechanism of PEMWE caused by dynamics of ionomers over time in anode catalyst layer (ACL), which is a purely mechanical degradation of microstructure, is identified. Contrary to conventional understanding that the microstructure of ACL is static, the micropores are inclined to be occupied by ionomers due to the localized swelling/creep/migration, especially near the ACL/PTL (porous transport layer) interface, where they form transport channels of reactant/product couples. Consequently, the ACL with increased ionomers at PTL/ACL interface exhibit rapid and continuous degradation. In addition, a close correlation between the microstructure of ACL and the catalyst ink is discovered. Specifically, if more ionomers migrate to the top layer of the ink, more ionomers accumulate at the ACL/PEM interface, leaving fewer ionomers at the ACL/PTL interface. Therefore, the ionomer distribution in ACL is successfully optimized, which exhibits reduced ionomers at the ACL/PTL interface and enriches ionomers at the ACL/PEM interface, reducing the decay rate by a factor of three when operated at 2.0 A cm-2 and 80 °C. The findings provide a general way to achieve low-cost hydrogen production.

Constructing Robust 3D Ionomer Networks in the Catalyst Layer to Achieve Stable Water Electrolysis for Green Hydrogen Production.

The widespread application of proton exchange membrane water electrolyzers (PEMWEs) is hampered by insufficient lifetime caused by degradation of the anode catalyst layer (ACL). Here, an important degradation mechanism has been identified, attributed to poor mechanical stability causing the mass transfer channels to be blocked by ionomers under operating conditions. By using liquid-phase atomic force microscopy, we directly observed that the ionomers were randomly distributed (RD) in the ACL, which occupied the mass transfer channels due to swelling, creeping, and migration properties. Interestingly, we found that alternating treatments of the ACL in different water/temperature environments resulted in forming three-dimensional ionomer networks (3D INs) in the ACL, which increased the mechanical strength of microstructures by 3 times. Benefitting from the efficient and stable mass transfer channels, the lifetime was improved by 19 times. A low degradation rate of approximately 3.0 µV/h at 80 °C and a high current density of 2.0 A/cm2 was achieved on a 50 cm2 electrolyzer. These data demonstrated a forecasted lifetime of 80 000 h, approaching the 2026 DOE lifetime target. This work emphasizes the importance of the mechanical stability of the ACL and offers a general strategy for designing and developing a durable PEMWE.