Direct Visualization of Electrochemical Reactions and Heterogeneous Transport Within Porous Electrodes in Operando by Fluorescence Microscopy

Optical fluorescence microscopy is shown to enable both high spatial and temporal resolution of redox-dependent fluorescence in flowing electrolytes. We report the use of fluorescence microscopy coupled with electrochemistry to directly observe the reaction and transport of redox-active quinones within porous carbon electrodes in operando. We observe surprising electrolyte channeling features within several porous electrodes, leading to spatially distinguishable advection-dominated and diffusion-dominated regions. These results challenge the common assumption that transport in porous electrodes can be approximated by a homogeneous Darcy-like permeability, particularly at the length scales relevant to many electrochemical systems such as redox flow batteries. This work presents a new platform to provide highly resolved spatial and temporal insight into electrolyte reactions and transport behavior within porous electrodes.