Synergy of Artificial SEI and Electrolyte Additive for Improved Performance of Silicon Electrodes in Li-Ion Batteries

Maintaining the electrochemically and mechanically stable solid electrolyte interphase (SEI) is of highest importance for the performance of high-capacity anode materials such as silicon (Si). Applying flexible Li-ion permeable coatings to the electrode surface using molecular layer deposition (MLD) offers a strategy to improve the properties of the SEI and greatly contributes to an increase in the cycle life and capacity retention of Si electrodes. In this study, the long-term cycling of Si electrodes with an MLD alucone coating is investigated in the context of more stable SEI formation. When the joined strategy introducing both MLD coating and anFEC electrolyte additive was realized, high performance of Si anodes was achieved, capable of delivering more than 1500 mAh g–1 even after 400 cycles. The reason for the significantly improved longevity is the ability of the alucone layer to react with HF present in LiPF6-based electrolytes already under OCV-like conditions, fluorinating most of the available −OH groups in the alucone structure. This reaction not only partially scavenges hydrofluoric acid but also does not disturb the confining effect of alucone-like fluorinated artificial SEI. This study shows the significance of searching for synergetic solutions, such as a combination of electrode surface modification and electrolyte composition, for maximizing the capacity retention of Si as an active material or as a capacity-enhancing additive to graphite electrodes, and as well can be applied to other high-energy battery materials with large volume changes during cycling.