A variety of mechanisms lead to the failure of lithium-ion batteries. One is overcharge, a condition in which a battery's voltage rises above its designed end-of-charge potential. Electrolyte additives called redox shuttles limit cell potential by preferentially oxidizing, and cycling between the cathode and anode in their radical cation and neutral forms. Currently, testing requires coin cell assembly and repeated cycling, which can be an expensive and time consuming process. It is commonly accepted that degradation of the radical cation form of a redox shuttle leads to overcharge protection failure. We thus studied the stability of the radical cation forms of a series of redox shuttle additives to determine if there is a correlation between radical cation stability and the number of cycles of overcharge protection. While the reversibility of oxidations in cyclic voltammetry did not correlate to trends in overcharge performance, results from both UV-vis and electron paramagnetic resonance spectroscopy showed a correlation between stability and overcharge protection. Our results reveal trends within a few hours for what otherwise takes months of battery cycling to determine, providing a fast and relatively inexpensive method for predicting redox shuttle performance.
