Nanoscale Mapping of Lithium-Ion Diffusion in a Cathode within an All-Solid-State Lithium-Ion Battery by Advanced Scanning Probe Microscopy Techniques

High-resolution real-space mapping of Li-ion diffusion in the LiNi(1/3)Co(1/3)Mn(1/3)O₂ cathode within an all-solid-state thin film Li-ion battery has been conducted using advanced scanning probe microscopy techniques, namely, band excitation electrochemical strain microscopy (BE-ESM) and conductive atomic force microscopy. In addition, local variations of the electrochemical response in the LiNi(1/3)Co(1/3)Mn(1/3)O₂ thin film cathode at different cycling stages have been investigated. This work demonstrates the unique feature and applications of the BE-ESM technique on battery research. The results allow us to establish a direct relationship of the changes in ionic mobility as well as the electrochemical activity at the nanoscale with the numbers of charge/discharge cycles. Furthermore, various factors influencing the BE-ESM measurements, including sample mechanical properties (e.g., elastic and dissipative properties) as well as surface electrical properties, have also been studied to investigate the coupling effects on the electrochemical strain. The study on the relationships between the Li-ion redistribution and microstructure of the electrode materials within thin film Li-ion battery will provide further understanding of the electrochemical degradation mechanisms of Li-ion rechargeable batteries at the nanoscale.