Anisotropic Lithiation Onset in Silicon Nanoparticle Anode Revealed by in Situ Graphene Liquid Cell Electron Microscopy

Recent real-time analyses have provided invaluable information on the volume expansion of silicon (Si) nanomaterials during their electrochemical reactions with lithium ions and have thus served as useful bases for robust design of high capacity Si anodes in lithium ion batteries (LIBs). In an effort to deepen the understanding on the critical first lithiation of Si, especially in realistic liquid environments, herein, we have engaged in situ graphene liquid cell transmission electron microscopy (GLC-TEM). In this technique, chemical lithiation is stimulated by electron-beam irradiation, while the lithiation process is being monitored by TEM in real time. The real-time analyses informing of the changes in the dimensions and diffraction intensity indicate that the very first lithiation of Si nanoparticle shows anisotropic volume expansion favoring the ⟨110⟩ directions due to the smaller L…