The sluggish commercial application of proton exchange membrane fuel cells (PEMFCs) with low Pt loading is chiefly hindered by concentration polarization loss, particularly at high current density regions. Addressing this, our study concentrates on the ionomer membranes in the cathode catalyst layer (CCL) and explores the potential of incorporating additional hydrophilic or hydrophobic components to modify these ionomers. Therefore, an all-atom model was constructed and for the ionomer and hydrophilic and hydrophobic modifications were implemented via incorporating SiO2 and PTFE, respectively. The investigation was conducted via molecular dynamics (MD) simulations to predict the morphology and structure of the ionomer and analyze the kinetic properties of oxygen molecules and protons. The simulation results elaborate that the hydrophilic and hydrophobic modifications favor the phase separation and the self-diffusion coefficients of oxygen molecules and protons are enhanced. Considering the hydration level of the ionomer films, hydrophilic modification facilitates mass transfer under low-hydration-level conditions, while hydrophobic modification is more effective in optimizing mass transfer as the hydration level increases. The optimal contents of SiO2 and PTFE for each hydration level in this work are 9.6% and 45%, respectively. This work proposes a reliable model and presents a detailed analysis of hydrophilic and hydrophobic modifications, which provides theoretical guidance for quantitative preparations of various composite membranes.
Keywords: PEMFCs; hydration level; hydrophilicity; hydrophobicity; molecular dynamics simulations; structural and transport properties.