PNNL

Abstract

In situ transmission electron microscopy (TEM) studies were carried out to observe directly in real time the lithiation and delithiation of silicon (Si) nanowires with significant amounts of tin (Sn). The incorporation of Sn significantly enhances the lithiation rate compared to typical Si nanowires. For instance, surface diffusion is enhanced by two orders of magnitude and the bulk lithiation rate by one order of magnitude, resulting in a sequential surface-then-core lithiation mechanism. Pore formation was observed in the nanowires during delithiation, most likely as a result of the fast delithiation kinetics of the nanowires. Pore formation was reversible and the pores disappeared during subsequent lithiation. When an amorphous Si shell was applied to the nanowires, pore formation was not observed during the in situ TEM experimences. Ex situ TEM analysis of Sn-containing Si nanowires cycled in coin cell batteries also showed that the application of an a-Si shell significantly retards pore formation in these nanowires.