Fluoro-Ethylene-Carbonate Plays a Double-Edged Role on the Stability of Si Anode-based Rechargeable Batteries during Cycling and Calendar Aging.

The energy storage density of Li-ion batteries could be improved by replacing graphite anodes with high-capacity Si-based materials, though instabilities have limited their implementation. Performance degradation mechanisms that occur in Si-anodes can be divided into cycling stability (capacity retention after repeated battery cycles) and calendar aging (shelf life). While the cycling stability and improvement strategies have been researched intensively, there is little known about the underlying mechanisms that cause calendar aging. In this work multiple electron microscope techniques were used to explore the mechanism that governs the calendar aging from sub-nanometer-to-electrode scale. Plasma focused ion beam tomography were used to create 3D reconstructions of calendar aged electrodes and revealed the growth of a LiF-rich layer at the interface between the copper current collector and silicon material, which can lead to delamination and increased interfacial impendence. The LiF layer appeared to derive from the fluoro-ethylene-carbonate electrolyte additive, which is commonly used to improve cycling stability in Si-based systems. The results reveal that additives necessary to improve cycling stability can cause performance degradation over the long-term during calendar aging. The results show that high performing, stable system require careful design to simultaneously mitigate both cycling and calendar aging instabilities. This article is protected by copyright. All rights reserved.