Reference Electrode Reveals Insights on Sodium Metal/Solid Electrolyte Interface Cycling and Voiding Behaviors at High Current Densities and Areal Capacities.

Plating and stripping processes at solid metal electrode/solid electrolyte interfaces are of great significance for high-energy, solid-state batteries. Here, we introduce a Na metal reference electrode to a symmetric Na metal/sodium β″ alumina/Na metal cell and study both cycling and unidirectional protocols with a focus on high current density and areal capacity. For example, in a current ramp test at 5 mAh cm we find a shift from stable to unstable interfacial polarization during stripping at ≳3 mA cm, and at 7.5 mA cm we measure 100s of mV of voltage magnitude rise at the stripping electrode and 10s of mV of voltage changes at the plating electrode. In unidirectional testing (i.e., passing current in a single direction until cell failure), at 1.2 mA cm we find only ∼40% of the initial Na foil could be transferred through the solid electrolyte and again observe 100s of mV (and larger) voltage magnitude rise at the stripping electrode and 10s of mV of voltage change at the plating electrode. This test also shows that the 100s of mV of interfacial polarization can be sustained for hours (at 1.2 mA cm) to tens of hours (in a test at 0.3 mA cm). Hence, across several test protocols we find a Na metal reference electrode provides quantitative insights on electrochemical interfacial behavior that are not revealed in two-electrode testing. We also built a two-dimensional model of our three-electrode symmetric cell to quantify the link between the measured interfacial potentials in our testing and changes in electrochemically active interfacial contact and find that 100s of mV of interfacial potential rise indicates loss of electrochemically active contact area of >80%. Our work provides a promising approach to clarify the coupled interfacial electrochemical and contact mechanics processes at solid metal electrode/solid electrolyte interfaces.