Anomalous Stagewise Lithiation of Gold-Coated Silicon Nanowires: A Combined In Situ Characterization and First-Principles Study

Through a combined density functional theory and in situ scanning electron microscopy study, the effects of presence of gold (Au) spreading on the lithiation process of silicon nanowire (SiNW) were systematically examined. Different from a pristine SiNW, an Au-coated SiNW (Au-SiNW) is lithiated in three distinct stages; Li atoms are found to be incorporated preferentially in the Au shell, whereas the thin AuSi interface layer may serve as a facile diffusion path along the nanowire axial direction, followed by the prompt lithiation of the Si core in the radial direction. The underlying mechanism of the intriguing stagewise lithiation behavior is explained through our theoretical analysis, which appears well-aligned with the experimental evidence.