Isotopic Depth Profiling of Discharge Products Identifies Reactive Interfaces in an Aprotic Li-O₂ Battery with a...

Prior to the practical application of rechargeable aprotic Li-O₂ batteries, the high charging overpotentials of these devices (which inevitably cause irreversible parasitic reactions) must be addressed. The use of redox mediators (RMs) that oxidatively decompose the discharge product, Li₂O₂, is one promising solution to this problem. However, the mitigating effect of RMs is currently insufficient, and so it would be beneficial to clarify the Li₂O₂ reductive growth and oxidative decomposition mechanisms. In the present work, Nanoscale secondary ion mass spectrometry (Nano-SIMS) isotopic three-dimensional imaging and differential electrochemical mass spectrometry (DEMS) analyses of individual Li₂O₂ particles established that both growth and decomposition proceeded at the Li₂O₂/electrolyte interface in a system containing the Br^-/Br₃^- redox couple as the RM. The results of this study also indicated that the degree of oxidative decomposition of Li₂O₂ was highly dependent on the cell voltage. These data show that increasing the RM reaction rate at the Li₂O₂/electrolyte interface is critical to improve the cycle life of Li-O₂ batteries.