Invited Plenary) Correlating Structure and Chemistry of PEM Fuel Cell Materials with Durability and Performance Using Advanced Microscopy Methods

Polymer electrolyte membrane (PEM) fuel cell performance and materials degradation, particularly associated with the cathode catalyst layer (CCL), can be directly attributed to the structure and chemistry of individual material components, as well as their uniformity/homogeneity within a CCL. The individual material constituents used to form the CCL within the membrane electrode assemblies (MEAs), which include the electrocatalyst, catalyst support, and ionomer films, and especially the critical interfaces that are formed between these various constituents, are critically importance in controlling fuel cell perfomance. Understanding the specific microstructural characteristics of the individual materials within the CCL, and how the materials interact to "form" the CCL, is important for identifying materials optimization parameters that can significantly enhance performance and durability. Materials in several states/conditions, e.g., prior to incorporation in the CCL (as-synthesized), after MEA preparation (CCL), and after fuel cell testing, are beig evaluated and quantified using a combination of advanced electron microscopy methods, which are used to interrogate the materials constituents and interfacial structures and chemistries from the μm- to the A-level. The as-processed (prior to and following incorporation into a CCL) microstructural evidence is directly correlated with observations of materials-specific degradation mechanisms that contribute to fuel cell performance loss, and are then used to identify potential processing variables (materials-based mitigation strategies) to improve the microstructure and compositional homogeneity within the electrode structure, and enhance MEA durability and stability during fuel cell operation. Research efforts at Oak Ridge National Laboratory are focused on the high-resolution microstructural and microchemical characterization of MEAs fabricated using different electocatalysts (typically Pt-based) and catalyst loadings, carbon-based support materials, and ionomer solutions, as well as the same MEAs subjected to accelerated stress tests (ASTs) designed to degrade specific MEA components. While a significant microscopy effort has been aimed towards understanding catalyst degradation (e.g., coarsening, de-alloying), recently, high-resolution analytical microscopy methods have been used to directly image/map the distribution and chemistry of the ionomer films/layers within CCLs, results of which are being combined with high-resolution imaging and 3-D tomography data of powder materials and MEAs, to provide unprecedented insight into the MEA architecture and interfaces (ionomer/support, ionomer/catalyst, catalyst/support, ionomer/pore). This presentation will focus on understanding materials distributions within CCLs as a function of materials used and ink/MEA processing variables, e.g., initial ionomer and/or ink chemistry, electrocatalyst (type, content, and dispersion), and the type of carbon support used. Additionally, the stability of the ionomer films, electrocatalysts, and support structures in CCLs following ASTs designed specifically for either catalyst degradation or carbon corrosion, will be evaluated. ________________________________________________________________________ Research sponsored by (1) the Fuel Cell Technologies Office, Office of Energy Efficiency and Renewable Energy, U.S. Department of Energy and (2) Oak Ridge National Laboratory's Center for Nanophase Materials Sciences (CNMS), which is a U.S. Department of Energy, Office of Science User Facility.