Visualization of Electrochemical Cycling-Induced Dimension Change in LiMn₂O₄ Nanoparticles by High-Speed Atomic Force...

Exploring dynamic dimension change and lithium-ion diffusion kinetics of active nanoparticles is important to further improve the qualities of lithium-ion batteries (LIBs), such as the cycle life and charge rate. For advancing such research, an imaging technique that is capable of operating in an electrochemical environment with high spatial and temporal resolutions is really needed. In this work, we successfully developed electrochemical high-speed atomic force microscopy (EC-HS-AFM), which enabled nanoscale imaging at the rate of ∼1 frame/s during electrochemical cycling. The dimensional evolutions of LiMn₂O₄ single nanoparticles accompanying an insertion/extraction reaction of lithium ions were visualized. The surface area-potential hysteresis loops of the single nanoparticles at different sweep rates were quantitatively extracted from the successive HS-AFM images or video. The first-order derivative of the hysteresis loop was interestingly similar to the cyclic voltammetry (CV). Moreover, the EC-HS-AFM experiments confirmed that the utilization of the nanoparticles in the cathode can indeed improve the rate performance of the LIBs. These results demonstrated that EC-HS-AFM would be a promising tool to study dimensional evolutions and lithium-ion diffusion kinetics at a nanoscale.