Li NMR Chemical Shift Imaging To Detect Microstructural Growth of Lithium in All-Solid-State Batteries.

All-solid-state batteries potentially offer safe, high-energy-density electrochemical energy storage, yet are plagued with issues surrounding Li microstructural growth and subsequent cell death. We use Li NMR chemical shift imaging and electron microscopy to track Li microstructural growth in the garnet-type solid electrolyte, LiLaZrTaO. Here, we follow the early stages of Li microstructural growth during galvanostatic cycling, from the formation of Li on the electrode surface to dendritic Li connecting both electrodes in symmetrical cells, and correlate these changes with alterations observed in the voltage profiles during cycling and impedance measurements. During these experiments, we observe transformations at both the stripping and plating interfaces, indicating heterogeneities in both Li removal and deposition. At low current densities, Li magnetic resonance imaging detects the formation of Li microstructures in cells before short-circuits are observed and allows changes in the electrochemical profiles to be rationalized.