Over-Lithiation Regulation of Silicon-Based Anodes for High-Energy Lithium-Ion Batteries

Mitigating the growth of dendritic lithium (Li) metal on silicon (Si) anodes has become a crucial task for the pursuit of long-term cycling stability of high energy density Si-based lithium-ion batteries (LIBs) under fast charging or other specific conditions. While it is widely known that Li metal plating on Si-based anodes may introduce inferior cycling stability and cause safety concerns, the evolution of the anode/material structure and electrochemical performance with Li metal plating remains largely unexplored. A comprehensive quantitative investigation of the hybrid Li storage mechanism, combining the Li alloying/dealloying mechanism and plating/stripping mechanism, has been conducted to explore the effect of Li plating on Si-based anodes. The findings reveal that Li plating/stripping accounts for the decay of the overall Coulombic efficiency and cycling stability of the hybrid Li storage mechanism. Furthermore, alloying reactions occurring below 0 V encourage the formation of crystalline Li₁₅Si₄, which subsequently exacerbates voltage hysteresis. The performance decay is amplified as the ratio of Li plating/stripping capacity increases, or in other words, as the over-lithiation level rises, thereby posing a threat to the battery's cycling stability. These results provide valuable insights into the design of advanced Si-based electrodes for high energy density LIBs.