Anion-exchange membrane (AEM) water electrolyzers (AEMWEs) have gained significant attention for their ability to utilize precious-metal-free catalysts and environmentally friendly fluorine-free hydrocarbon polymeric membranes. In this study, we identify and quantify the sources of performance losses in operando AEMWEs using an innovative approach based on electrochemical impedance spectroscopy and MATLAB-based impedance spectroscopy genetic programming. Using this approach, we move beyond conventional equivalent circuit models to develop a proper and analytical model of the distribution function of relaxation times (DFRT), enabling a deeper analysis of Faradaic and non-Faradaic processes. We apply this framework to isolate the critical processes─ohmic, ionic transport, charge transfer, and mass transfer─across various conditions, including KOH concentration, dry cathode operation mode with different anode electrolytes (KOH, K2CO3, and pure water), cell temperature, and membrane type. Our results indicate a considerable performance reduction as the KOH concentration in the anode decreases, primarily due to the relatively high ionic transport resistance. Our observations show that the performance of dry cathode operation with KOH in the anode yields a comparable performance to dual-side electrolyte feeding due to sufficient water back-diffusion from the anode, which efficiently maintains cathode hydration. Conversely, using pure water as an electrolyte in the anode with a dry cathode significantly increases cell resistances and compromises ionic transport, underscoring the urgent need for highly conductive ionomeric materials and strategies. These insights indicate that using DFRT to evaluate the AEMWE operation by separating and associating the electrochemical phenomena could simplify system design while enabling more efficient generation of dry, pure hydrogen and advancing the technology toward commercial application.
