Self-Limiting Lithiation in Silicon Nanowires

The rates of charging and discharging in lithium-ion batteries (LIBs) are critically controlled by the kinetics of Li insertion and extraction in solid-state electrodes. Silicon is being intensively studied as a high-capacity anode material for LIBs. However, the kinetics of Li reaction and diffusion in Si remain unclear. Here we report a combined experimental and theoretical study of the lithiation kinetics in individual Si nanowires. By using in situ transmission electron microscopy, we measure the rate of growth of a surface layer of amorphous Li(x)Si in crystalline Si nanowires during the first lithiation. The results show the self-limiting lithiation, which is attributed to the retardation effect of the lithiation-induced stress. Our work provides a direct measurement of the nanoscale growth kinetics in lithiated Si, and has implications on nanostructures for achieving the high capacity and high rate in the development of high performance LIBs.