The loss of electrochemical active surface area (ECSA) at the cathode is one of the main causes of performance degradation in Polymer Electrolyte Membrane Fuel Cells (PEMFCs). In order to investigate the catalyst degradation and the influence of the operating conditions we develop a multiscale degradation model which includes the formation and reduction of platinum oxides, platinum dissolution, particle growth due to Ostwald ripening, platinum ion transport through the ionomer and platinum band formation in the membrane. This degradation model is coupled with a 2D PEMFC performance model and predictions regarding ion concentration, ECSA evolution and particle growth are validated with dedicated experiments and literature data. Degradation under several AST protocols and under steady state operation are compared and discussed. The importance of a spatially resolved catalyst degradation model is conveyed by the occurrence of a depletion zone in the catalyst layer close to the membrane due to the platinum migration into the membrane. By comparing the correlation between platinum mass loss in the catalyst layer and the ECSA loss we conclude that catalyst degradation under AST conditions with nitrogen is not representative for the degradation under normal operation.

This study combines local electrochemical diagnostics with ex situ analysis to investigate degradation mechanism associated to start-up/shut-down (SU/SD) of PEMFC and mitigation strategies adopted in automotive stacks. Local degradation resulting from repeated SU/SD was analyzed with and without mitigation strategies by means of a macro-segmented cell setup provided with Reference Hydrogen Electrodes (RHEs) at both anode and cathode to measure local electrodes potential and current. Accelerated Stress Test (AST) for start-up with and without mitigation strategies are proposed and validated. A ten-fold acceleration of performance loss due to un-mitigated SU/SD has been calculated with respect to AST for catalyst support. Under mitigated SU/SD, instead, a strong degradation was observed as localized at cathode inlet region (i.e. −38% ECSA loss and −22 mV voltage loss after 200 cycles) due to local potentials transient reaching up to 1.5 V vs RHE. These localized stress conditions were additionally reproduced in a zero-gradient and a new AST protocol (named start-up AST) was proposed to mimic the potential profile observed upon SU/SD cycling. Representativeness of the start-up AST for real world degradation was confirmed up to 200 cycles. Platinum dissolution and diffusion/precipitation within the polymer electrolyte was shown to be the dominant mechanism affecting performance loss.

The electrochemical impedance spectroscopy (EIS) characterization technique, although widely adopted in electrochemistry for understanding operational issues and degradation, has a less consolidated physical interpretation in lithium‐ion batteries (LIBs), often relying on circuital methods. Herein, the Doyle–Fuller–Newman model is adapted and experimentally validated for the physical simulation of electrochemical impedance; then, it is applied in a comprehensive one‐factor‐at‐time sensitivity analysis on an impedance spectrum from 4 kHz to 0.005 Hz; 28 physical parameters, which represent the kinetic, resistive, diffusive, and geometric characteristics of the battery, are varied within broad literature‐based ranges of values, for each of the 20 analyzed battery states, characterized by different state‐of‐charge and temperature values. The results show a miscellaneous sensitivity of parameters on impedance spectra, which ranges from highly sensitive to negligible, often resulting in a strong dependence on operating conditions and impedance frequency. Such results consolidate the understanding of LIB electrochemical impedance and demonstrate that 40% of the parameters, 12 out of 28, can be considered poorly sensitive or insensitive parameters; therefore, fitting the experimental EIS data, their value can be assumed from the literature without significantly losing accuracy.