Nanoscale in-Situ Characterization of Polymer Electrolyte Membrane Fuel Cell Catalyst Layers for Improved Water Management

Abstract

Polymer electrolyte membrane fuel cells (PEMFCs) facilitate a sustainable energy infrastructure by offering emission-free electricity generation using renewably sourced hydrogen gas. The electrochemical reactions in a fuel cell occur at platinum-loaded catalyst layers (CLs), which are susceptible to degradation. Obstructing catalyst sites (triple phase boundaries1) with reaction by-products, such as water2,3, is the primary degradation mechanism in PEMFCs. Although various CL designs have been tested for improved electrochemical performance, in situ nanoscale visualization of platinum degradation and water accumulation in the CL at controlled temperature and relative humidity (RH) values are required to understand fundamental water mechanics through platinum and carbon nanostructures.In this work, we employed scanning transmission X-ray microscopy (STXM) and X-ray absorption fine structure spectroscopy (XANES) to evaluate the effect of temperature on pristine and broken-in fuel cell CLs. We developed a novel CL in-situ sample cell to enable nanostructured characterization of catalyst layers using STXM in a controlled temperature environment. Carbon 1s, Fluorine 1s, and Oxygen 1s spectral edges were probed utilizing near-edge X-ray absorption fine structure spectroscopy (NEXAFS) to reveal chemical degradation mechanisms and differentiate material structure. Through our custom in-situ cell, we demonstrate that the chemical composition and water accumulation throughout the PEMFC CLs at low, intermediate, and high operating temperatures (25°C, 40°C, and 60°C, respectively) can be quantified, along with thermal expansion analyses of the CL and ionomer membrane. Moreover, we reveal realistic structural and chemical characteristics of nanoscale catalysts by distinguishing regions of Nafion® Ionomer, catalyst carbon support, and platinum throughout the PEMFC’s membrane electrode assembly at industrially relevant fuel cell temperatures. The insights from this work will inform strategies to mitigate water flooding from a nanoscale perspective in addition to the novel in-situ spectromicroscopy characterization of current CL features.1. Fouzaï, I., Gentil, S., Bassetto, V. C., Silva, W. O., Maher, R., & Girault, H. H. (2021). 9(18), 11096-11123.2. Li, H., Tang, Y., Wang, Z., Shi, Z., Wu, S., Song, D., ... & Mazza, A. (2008). 178(1), 103-117.3. Kumsa, D. W., Bhadra, N., Hudak, E. M., Kelley, S. C., Untereker, D. F., & Mortimer, J. T. (2016). 13(5), 052001.