Spatially Resolved Differentiation of Functional Degradation and Perforating Structural Defects in Membrane Electrode Assemblies Using Diffusion-Cell Coupled DC-SECM

In order to increase the lifetime of polymer electrolyte membrane (PEM) fuel cells (PEMFCs) and water electrolyzers (PEMWEs), understanding local degeneration processes in membrane electrode assemblies (MEAs) is crucial. By a combination of scanning electrochemical microscopy (SECM) with a flow-through diffusion cell (DiffC-DC-SECM) and ferrocyanide and protons as redox mediators, a spatially resolved analytical method was developed that can differentiate between different functional and structural degeneration phenomena in the aging process of a membrane. An SECM scan at cathodic potential detects the diffusion of protons through the membrane and thus its through-plane proton conductivity, while a second SECM scan at anodic potential visualizes the diffusion of the iron complex through the membrane, thus perforating structural damage such as cracks and holes. The method was successfully validated for the spatially resolved differentiation of membrane damage in pristine PEMs and catalyst-coated membranes (CCMs) with artificial holes, chemically aged CCMs, and MEAs in fully assembled operational PEMFCs aged by an open-circuit voltage membrane accelerated stress test. DiffC-DC-SECM thus provides a powerful technique with high local resolution for membrane integrity testing under realistic operation conditions to develop long-term durable materials for PEMFCs and PEMWEs.