We have characterised and quantified the ultrafast flipping dynamics between metallic and electrolyte states in concentrated solutions of lithium in liquid ammonia. This allows us to provide the key missing characteristics of these systems, namely, the mean time interval between these flips which turns out to be of the order of a few tens of femtoseconds. We show that band gap properties depend very sensitively on minor changes in molecular geometry and electron density, which then drive switching between a liquid metal and an electrolyte. Moreover, we demonstrate that the densities of states of metallic configurations still to a large extent possess features pertinent to electrolyte configurations, with only a weak filling of the band gap.