⁷Li 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 ⁷Li NMR chemical shift imaging and electron microscopy to track Li microstructural growth in the garnet-type solid electrolyte, Li_6.5La₃Zr_1.5Ta_0.5O₁₂. 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, ⁷Li 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.