Electrochemical impedance spectroscopy is an important tool for fuel-cell analysis and monitoring. This study focuses on the low-AC frequencies (2–0.1 Hz) to show that the thickness of the catalyst layer significantly influences the overall resistance of the cell. By combining known models, a new equivalent circuit model was generated. The new model is able to simulate the impedance signal in the complete frequency spectrum of 10⁵–10⁻² Hz, usually used in experimental work on polymer electrolyte fuel cells (PEMFCs). The model was compared with experimental data and to an older model from the literature for verification. The electrochemical impedance spectra recorded on different MEAs with cathode catalyst layer thicknesses of approx. 5 and 12 µm show the appearance of a third semicircle in the low-frequency region that scales with current density. It has been shown that the ohmic resistance contribution (R_mt) of this third semicircle increases with the catalyst layer’s thickness. Furthermore, the electrolyte resistance is shown to decrease with increasing catalyst-layer thickness. The cause of this phenomenon was identified to be increased water retention by thicker catalyst layers.

Understanding the degradation mechanisms of Pt‐alloy catalysts is crucial for enhancing their durability. This study investigates the impact of relative humidity on Pt and Pt ₃ Co catalysts using potential‐cycling‐based accelerated stress tests. Two conditions are investigated: 100% relative humidity on both sides, and a gradient with 30% at the anode and over 100% at the cathode. Pt ₃ Co demonstrates sensitivity, with 77% performance loss and reductions in electrocatalyst surface area. Results demonstrate a 30% decrease in potential loss for Pt catalysts and a 77% increase for Pt ₃ Co catalysts, indicating significant performance degradation in high humidity conditions, with Pt ₃ Co exhibiting greater sensitivity. Measurements of electrochemically active surface area reinforce these findings. Resistance analysis using electrochemical impedance spectroscopy using equivalent circuit modeling reveals a threefold increase in Pt ₃ Co MEAs' cathode charge transfer resistance and mass transport resistance during accelerated stress tests. Local current distribution analysis highlights differences between Pt catalyst and Pt ₃ Co, with the latter displaying dealloying effects. Small‐angle X‐ray scattering reveals changes in particle and cluster sizes, indicating structural changes. Scanning electron microscopy highlights catalyst and membrane thickness variations, suggesting heterogeneity in Pt ₃ Co. Under humidity gradients, Ostwald ripening plays a significant role in altering the catalyst's Pt ₃ Co structure and subsequently impacting its performance.

In the past, platinum–copper catalysts have proven to be highly active for the oxygen reduction reaction (ORR), but transferring the high activities measured in thin-film rotating disk electrodes (TF-RDEs) to high-performing membrane electrode assemblies (MEAs) has proven difficult due to stability issues during operation. High initial performance can be achieved. However, fast performance decay on a timescale of 24 h is induced by repeated voltage load steps with H₂/air supplied. This performance decay is accelerated if high relative humidity (>60% RH) is set for a prolonged time and low voltages are applied during polarization. The reasons and possible solutions for this issue have been investigated by means of electrochemical impedance spectroscopy and distribution of relaxation time analysis (EIS–DRT). The affected electrochemical sub-processes have been identified by comparing the PtCu electrocatalyst with commercial Pt/C benchmark materials in homemade catalyst-coated membranes (CCMs). The proton transport resistance (R_pt) increased by a factor of ~2 compared to the benchmark materials. These results provide important insight into the challenges encountered with the de-alloyed PtCu/KB electrocatalyst during cell break-in and operation. This provides a basis for improvements in the catalysts’ design and break-in procedures for the highly attractive PtCu/KB catalyst system.

The shelf-life of catalyst ink for fabricating polymer electrolyte fuel cells (PEFCs) is relevant for large-scale manufacturing with unforeseen production stops. In this study, the storage effects on the physicochemical characteristics of catalyst ink (Pt/C, Nafion, 2-propanol, water) and subsequently manufactured catalyst layers are investigated. Sedimentation analysis showed that catalyst particles are not fully stabilized by charge interaction induced by Nafion. Acetone was found to be an oxidation product, even in freshly prepared ink with platinum catalyzing the reaction. Rotating disk electrode analysis revealed that the electrochemically active surface area is, overall, minimally increased by storage, and the selectivity towards water formation (4-electron pathway) is unharmed within the first 48 h of storage. MEAs prepared from stored ink reach almost the same current density level after conditioning via potential cycling. The open-circuit voltage (OCV) increases due to increased catalyst availability. Scanning electron microscopy and mercury intrusion porosimetry showed that with increasing acetone content, the pore structure becomes finer, with a higher specific surface area. Electrochemical impedance spectroscopy revealed that this results in a more hindered mass transfer but lowered charge transfer resistance. The MEA with the highest OCV and power output and the lowest overall cell resistance was fabricated from catalyst ink stored for a duration of four weeks.