Role of Surface Chemistry on Nanoparticle Dispersion and Vanadium Ion Crossover in Nafion Nanocomposite Membranes.

While the introduction of nanoparticles into Nafion membranes has proven to be a viable method to tune the ion selectivity in energy storage technologies such as the vanadium redox flow battery, there still remains a limited understanding of the fundamental mechanism by which the nanoparticles selectively restrict ion crossover. Herein, the surface chemistry and loading of SiO2 nanoparticles (SiNPs) were systematically varied to elucidate the relationship between nanoparticle dispersion (or dispersion state) and vanadium ion permeability in Nafion nanocomposite membranes. Specifically, nanoparticle surface functionalization was altered to achieve both attractive (amine-functionalized) and repulsive (unfunctionalized and sulfonic acid-functionalized) electrostatic interactions between the SiNPs and the ionic groups of Nafion. At a nanoparticle loading of 5 wt %, membranes containing unfunctionalized and amine-functionalized SiNPs demonstrated ∼25% reduction in vanadium ion permeability as compared to unmodified Nafion. Drastically different dispersion states were observed in the electron microscopy images of each nanocomposite membrane, where most notably, aggregates on the order of 500 nm were observed for membranes containing amine-functionalized SiNPs (at all nanoparticle loadings). Results from this work indicate that both dispersion state and surface chemistry of the SiNPs play a critical role in governing the vanadium ion transport in these ionomer nanocomposite membranes.