Revisiting Mechanism of Silicon Degradation in Li-Ion Batteries: Effect of Delithiation Examined by Microscopy Combined with ReaxFF.

For the past decade, silicon (Si) as a material for negative electrodes of Li-ion batteries has been considered among the most promising candidates for replacing commonly used graphite. However, Si-based electrodes suffer from severe degradation, which depends on the type of Si materials used. Generally, the degradation of Si is mainly viewed in terms of particle fracturing during lithiation accompanied by constant growth of the solid electrolyte interphase (SEI). At the same time, the reversed process, delithiation, has received little attention. The present work demonstrates the morphological changes of the Si components of electrodes occurring during electrochemical cycling through electron microscopy analyses. These changes are rationalized through the migration of Si, resulting in the formation of Si dendrites embedded in SEI. With the assistance of ReaxFF modeling, we demonstrate that the delithiation predominantly drives this process. The present study reveals that fracturing of Si particles is not the only cause for degradation, as the Si surfaces dramatically change after prolonged cycling, resulting in the formation of Si dendrites.