Concurrent Operando Neutron Imaging and Diffraction Analysis Revealing Spatial Lithiation Phase Evolution in an Ultra‐Thick Graphite Electrode

Abstract Energy‐efficient, safe, and reliable Li‐ion batteries (LIBs) are required for a wide range of applications. The introduction of ultra‐thick graphite anodes, desired for high energy densities, meets limitations in internal electrode transport properties, leading to detrimental consequences. Yet, there is a lack of experimental tools capable of providing a complete view of local processes. Here, a multi‐modal operando measurement approach is introduced, enabling quantitative spatio‐temporal observations of Li concentrations and intercalation phases in ultra‐thick graphite electrodes. Neutron imaging and diffraction concurrently provide correlated multiscale information from the scale of the cell down to the crystallographic scale. In particular, the evolving formation of the solid electrolyte interphase (SEI), observation of gradients in total lithium content, as well as in the formation of ordered Li_xC₆ phases and trapped lithium are mapped throughout the first charge–discharge cycle of the cell. Different lithiation stages co‐exist during charging and discharging; delayed lithiation and delithiation processes are observed in central regions of the electrode, while the SEI formation, potential plating, and dead lithium are predominantly found closer to the interface with the separator. The study emphasizes the potential to investigate Li‐ion diffusion and the kinetics of lithiation phase formation in thick electrodes.