Correlated interfacial water transport and proton conductivity in perfluorosulfonic acid membranes

Water must be effectively transported and is also essential for maximizing proton conductivity within fuel-cell proton-exchange membranes (PEMs). Therefore, identifying relationships between PEM properties, water transport, and proton conductivity is essential for designing optimal PEMs. Here, we use coherent Raman spectroscopy to quantify real-time, in situ diffusivities of water subspecies, bulk-like and nonbulk-like (interfacial) water, in five different perfluorosulfonic acid (PFSA) PEMs. Although the PEMs were chemically diverse, water transport within them followed the same rule: Total water diffusivity could be represented by a linear combination of the bulk-like and interfacial water diffusivities. Moreover, the diffusivity of interfacial water was consistently larger than that of bulk-like water. These measurements of microscopic transport were combined with through-plane proton conductivity measurements to reveal the correlation between interfacial water transport and proton conductivity. Our results demonstrate the importance of maximizing the diffusivity and fractional contribution of interfacial water to maximize the proton conductivity in PFSA PEMs.