Conductivity-Driven Origin of the Limiting Current in Concentrated Electrolytes

Next-generation electrolyte materials are hindered by their ability to support high currents essential for fast-charge and high-power battery applications. The maximum current supported by an electrolyte, the limiting current, is dictated by the formation of concentration gradients across the electrolyte under an electric field. Most of the literature attributes the onset of the limiting current in concentrated electrolytes to the salt concentration at the positive electrode approaching the solubility limit. Here, we leverage operando X-ray transmission imaging to measure spatiotemporal salt concentration profiles of a polymer electrolyte in a lithium–indium symmetric cell at a current exceeding the limiting current. The measurement of concentration profiles enables mapping the spatiotemporal electric potential, which comprises an ohmic contribution, governed by conductivity, and an overpotential related to maintaining concentration gradients. We find that a precipitous drop in conductivity at the positive electrode drives the divergence of electric potential, rather than a thermodynamic solubility limit.