Insights into Degradation of the Membrane–Electrode Assembly Performance in Low-Temperature PEMFC: the Catalyst, the Ionomer, or the Interface?

Here, we report a study on the structural characteristics of membrane electrode assembly (MEA) samples obtained from a low-temperature (LT) polymer electrolyte membrane (PEM) fuel cell (FC) stack subjected to long-term durability testing for ∼18,500 h of nominal operation along with ∼900 on/off cycles accumulated over the operation time, with the total power production being 3.39 kW h/cm2 of MEA and the overall degradation being 87% based on performance loss. The chemical and physical states of the degraded MEAs were investigated through structural characterizations aiming to probe their different components, namely the cathode and anode electrocatalysts, the Nafion ionomer in the catalyst layers (CLs), the gas diffusion layers (GDLs), and the PEM. Surprisingly, X-ray diffraction and electron microscopy studies suggested no significant degradation of the electrocatalysts. Similarly, the cathode and anode GDLs exhibited no significant change in porosity and structure as indicated by BET analysis and helium ion microscopy. Nevertheless, X-ray fluorescence spectroscopy, elemental analysis through a CHNS analyzer, and comprehensive investigations by X-ray photoelectron spectroscopy suggested significant degradation of the Nafion, especially in terms of sulfur content, that is, the abundance of the −SO3– groups responsible for H+ conduction. Hence, the degradation of the Nafion, in both of the CLs and in the PEM, was found to be the principal mechanism for performance degradation, while the Pt/C catalyst degradation in terms of particle size enlargement or mass loss was minimal. The study suggests that under real-life operating conditions, ionomer degradation plays a more significant role than electrocatalyst degradation in LT-PEMFCs, in contrast to many scientific studies under artificial stress conditions. Mitigation of the ionomer degradation must be emphasized as a strategy to improve the PEMFC's durability.