Engineering nanofluid electrodes: controlling rheology and electrochemical activity of γ-Fe2O3 nanoparticles

Abstract

Nanofluid electrodes or nanoelectrofuels have significant potential in the field of flow batteries, as at high loadings of solid battery active nanoparticles, their energy density can be orders of magnitude higher than in traditional redox flow battery electrolytes. Nanofluid electrodes must have a manageable viscosity at high particle concentrations (i.e., easily pumpable) and exhibit good electrochemical activity toward charge and discharge reactions. Engineering of such nanofluid electrodes involves development of new and unique approaches to stabilization of nanoparticle suspensions. In this work, we demonstrate a surface modification approach that allows controlling the viscosity of nanofluids at high solid loading, while simultaneously retaining electrochemical activity of the nanoparticles. A scalable single step procedure for the surface grafting of small organic molecules onto iron (III) oxide nanoparticles (γ-Fe2O3, maghemite, 40–150 nm) is demonstrated. Modified iron oxide nanoparticles reported here have ~5 wt% of the grafting moiety on the surface, which helps forming stable dispersions with up to 40 wt% of solid loading in alkali aqueous electrolytes with a maximum viscosity of 12 cP at room temperature. The maximum particle concentration achievable in the same electrolyte with pristine nanoparticles is 15 wt%. Electrochemical testing of the pristine and modified nanomaterials in the form of solid-casted electrodes showed a maximum reversible discharge capacity of 280 and 155 mAh/g, respectively, indicating that electrochemical activity of modified nanoparticles is partially suppressed due to the surface grafted moiety.