ABSTRACT
The interfacial electrochemistry of reversible redox molecules is central to state-of-the-art flow batteries, outer-sphere redox species-based fuel cells, and electrochemical biosensors. At electrochemical interfaces, because mass transport and interfacial electron transport are consecutive processes, the reaction velocity in reversible species is predominantly mass-transport-controlled because of their fast electron-transfer events. Spatial structuring of the solution near the electrode surface forces diffusion to dominate the transport phenomena even under convective fluid-flow, which in turn poses unique challenges to utilizing the maximum potential of reversible species by either electrode or fluid characteristics. We show Coulombic force gated molecular flux at the interface to target the transport velocity of reversible species; that in turn triggers a directional electrostatic current over the diffusion current within the reaction zone. In an iron-based redox flow battery, this gated molecular transport almost doubles the volumetric energy density without compromising the power capability.
