In situ study of topography, phase and volume changes of titanium dioxide anode in all-solid-state thin film lithium-ion battery by biased scanning probe microscopy

In this study, local cyclic changes of surface topography, phase and volume of TiO2 anode within an all-solid-state thin film Li-ion battery (TiO2/LiPON/LiNi1/3Co1/3Mn1/3O2) at nanoscale are studied. These changes are caused by reversible bias-induced electric field through an in situ scanning probe microscopy (SPM) without external electrochemical attachment. Combining simultaneous measurements of phase and amplitude images, high spatially resolved mapping of “nano-spots” related to Li+ distribution can be obtained, providing new insight into the ionic transport mechanism and diffusion preferred paths in a real all-solid-state thin film lithium ion battery. In addition, the thin film anode shows reversible topographical changes as the volume expansion/contraction is related to the cyclic Li+ insertion/extraction, which are analogues to the charge/discharge behavior observed in electrochemical atomic force microscopy (EC-AFM) studies. The results suggest that the applications of local reversible biases are very useful for modeling the charge/discharge processes of lithium ion batteries.