Unraveling Depth-Specific Ionic Conduction and Stiffness Behavior across Ionomer Thin Films and Bulk Membranes

Interfacial behavior of submicron thick polymer films critically controls the performance of electrochemical devices. We developed a robust, everyday-accessible, fluorescence confocal laser scanning microscopy (CLSM)-based strategy that can probe the distribution of mobility, ion conduction, and other properties across ionomer samples. When fluorescent photoacid probe 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) was incorporated into <1 mu m thick Nafion films on substrates, the depth-profile images showed thickness- and interface-dependent proton conduction behavior. In these films, proton conduction was weak over a region next to substrate interface, then gradually increased until air interface at 88% RH. Conversely, consistently high proton conduction with no interface dependence was observed across 35-50 mu m thick bulk, free-standing Nafion membranes. A hump-like mobility/stiffness distribution was observed across Nafion films containing mobility-sensitive probe (9-(2-carboxy-2-cyanovinyl)julolidine) (CCVJ). The proton conduction and mobility distribution were rationalized as a combinatorial effect of interfacial interaction, ionomer chain orientation, chain density, and ionic domain characteristics.

Automated summary

The interfacial behavior of submicron thick polymer films plays a critical role in determining the performance of electrochemical devices. A new strategy based on fluorescence confocal laser scanning microscopy was developed to investigate the distribution of mobility, ion conduction, and other properties in ionomer samples. Proton conduction behavior in thin Nafion films was found to be thickness- and interface-dependent, while bulk Nafion membranes exhibited consistent high proton conduction with no interface dependence. The mobility distribution across Nafion films containing a mobility-sensitive probe displayed a hump-like pattern.