Electrochemical and spectroelectrochemical studies were conducted to understand the fundamental processes that occur during the overcharge of lithium-ion batteries with electrolyte solutions containing the StabiLife electrolyte salt (Li2B12F12). Cyclic voltammetric experiments on these electrolyte solutions show well defined, quasi-reversible oxidation and reduction peaks with an onset potential of 4.6-4.9 V, depending upon the dielectric constant of the electrolyte. When oxidized in organic electrolytes, commonly used in lithium-ion batteries, Li2B12F12 forms the stable, pale yellow B12F121-* radical anion. This is confirmed in solution by in situ electron paramagnetic resonance measurements. The overcharge chemistry of the StabiLife electrolyte salts was further probed in full cell configurations with mesocarbon microbeads as an anode and LiCoO2 as a cathode. A Li metal reference electrode was incorporated to monitor the voltage changes associated with both the anode and the cathode during overcharge. Overcharge in cells based on LiPF6 electrolytes very rapidly leads to cell potentials > 5.5 V, while similar cells containing Li2B12F12-based electrolytes exhibit stable voltage holding at similar to 4.7 V. X-ray photoelectron spectroscopy analysis confirms that massive lithium plating has occurred in the LiPF6-based cells. Evidence of only trace lithium plating is observed in Li2B12F12-based cells. A plausible mechanism for the reductive completion of the redox shuttle is proposed. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3523330] All rights reserved.