Using cells with lithium reference electrodes, the power-limiting behavior in the lithium–SVO cell was shown to be due to a rapid voltage transition at the anode. A novel test cell was developed to explore the influence of current density, bulk LiAsF6 concentration, separator type and separator proximity to the anode on the time to onset (τ) of the anode polarization. The results were found to follow a relationship, iτ 1/2∝C bulk, consistent with the Sand equation. This relationship also predicts that the critical concentration of LiAsF6, at which onset of the anode polarization occurs, is near the solubility limit of LiAsF6 in our system (around 3.5–4.0M). This general phenomenon was found to be quantitatively similar for two dissimilar separator types, and the anode polarization could also be induced in the absence of separator at high concentration and current density. However, it appears that τ decreases with closer proximity of the separator to the anode surface (i.e. cell stack pressure), suggesting that the effect of separator is to inhibit convective transport to and from the Li surface.