Comparative Study on Structural and Transport Properties of SSC and LSC PFSA Ionomers in PEMFCs with Coexistence of O2 and N2: Molecular Dynamics Simulation Approach

Efficient O₂ transport through the ionomer film in cathode catalyst layers (CCLs) is a critical factor for the output performance of proton exchange membrane fuel cells (PEMFCs), yet the molecular mechanisms of gas transport in ionomers remain elusive. Herein, molecular dynamics (MDs) simulations are employed to investigate short-side-chain (SSC) and long-side-chain (LSC) perfluorosulfonic acid (PFSA) ionomers on Pt/C surfaces with the coexistence of O₂/N₂. The results reveal that the side-chain structures significantly modulate the ionomer nanostructures and gas transport. SSC ionomers form compact hydrophobic domains and more interconnected hydrophilic-hydrophobic interfaces, thereby facilitating more efficient O₂ transport pathways than LSC ionomers, particularly at low hydration (λ = 3). At high hydration (λ = 11), swelling of water domains attenuates these structural disparities and becomes the dominant factor governing gas transport. In addition, O₂ diffusion consistently exceeds that of N₂, while the diffusion coefficients of O₂, N₂ and H₃O⁺ become larger at high hydration. Collectively, these findings demonstrate the structural advantages of SSC ionomers in facilitating coupled oxygen and proton transport, offering molecular-level insights to inform the rational design of high-performance PEMFCs.