ABSTRACT
X-ray photoelectron spectroscopy (XPS) is one of the most common techniques used to analyze the surface composition of catalysts and support materials used in polymer electrolyte membrane (PEM) fuel cells and electrolyzers, providing important insights for further improvement of their properties. Characterization of catalyst layers (CLs) is more challenging, which can be at least partially attributed to the instability of ionomer materials such as Nafion during measurements. This work explores the stability of Nafion during XPS measurements, illuminating and addressing Nafion degradation concerns. The extent of Nafion damage as a function of XPS instrumentation, measurement conditions, and sample properties was evaluated across multiple instruments. Results revealed that significant Nafion damage to the ion-conducting sulfonic acid species (>50% loss in sulfur signal) may occur in a relatively short time frame (tens of minutes) depending on the exact nature of the sample and XPS instrument. This motivated the development and validation of a multipoint XPS data acquisition protocol that minimizes Nafion damage, resulting in reliable data acquisition by avoiding significant artifacts from Nafion instability. The developed protocol was then used to analyze both thin film ionomer samples and Pt/C-based CLs. Comparison of PEM fuel cell CLs to Nafion thin films revealed several changes in Nafion spectral features attributed to charge transfer due to interaction with conductive catalyst and support species. This study provides a method to reliably characterize ionomer-containing samples, facilitating fundamental studies of the catalyst-ionomer interface and more applied investigations of structure-processing-performance correlations in PEM fuel cell and electrolyzer CLs.
ABSTRACT
Studies on the hydration properties, proton conductivity, and water content of perfluorinated ionomer thin films at temperatures relevant to fuel cell operation temperatures (around 80 °C) and the effect of ionomer chemistry are scarce. In this work, we report the water content and proton conductivity properties of thin-film ionomers (30 nm) at 80 °C over a wide range of relative humidity (0-90%) for seven different ionomers differing in the side-chain structure, including the number of protogenic groups, with the equivalent weight ranging from 620 to 1100 g/mol of sulfonic acid. The results show that the acid content or equivalent weight of the ionomer is the strongest determinant of both the swelling and the proton conductivity of ionomer films at a given relative humidity. The molar water content (λ) of ionomer films normalized to the molar protogenic group is observed to be equivalent-weight-dependent, implying that the affinity for water is acid-content-dependent. At high relative humidity conditions (>70%) pertinent to fuel cell operations, the proton conductivity of low-equivalent-weight ionomers was higher than that of higher-equivalent-weight ionomers. However, upon correlating the proton conductivity with molar water content (λ), the differences reduce dramatically, highlighting that water content is the controlling factor for proton conduction. Significantly higher values of both water content and proton conductivity are observed at 80 °C compared to those at 30 °C, implying that room temperature data are not reliable for estimating ionomer properties in the fuel cell catalyst layer.
