Combining X-ray Nano-CT and XANES Techniques for 3D Operando Monitoring of Lithiation Spatial Composition evolution in NMC Electrode

In this study, we present a well-defined methodology for conducting Operando X-ray absorption near-edge structure spectroscopy (XANES) in conjunction with transmission X-ray nano computed tomography (TXM-nanoCT) experiments on the LiNi$_{0.5}$Mn$_{0.3}$Co$_{0.2}$O$_2$ (NMC) cathode electrode. To minimize radiation-induced damage to the sample during charge and discharge cycles and to gain a comprehensive 3D perspective of the (de)lithiation process of the active material, we propose a novel approach that relies on employing only three energy levels, strategically positioned at pre-edge, edge, and post-edge. By adopting this technique, we successfully track the various (de)lithiation states within the three-dimensional space during partial cycling. Furthermore, we are able to extract the nanoscale lithium distribution within individual secondary particles. Our observations reveal the formation of a core-shell structure during lithiation and we also identify that not all surface areas of the particles exhibit activity during the process. Notably, lithium intercalation exhibits a distinct preference, leading to non-uniform lithiation degrees across different electrode locations. The proposed methodology is not limited to the NMC cathode electrode but can be extended to study realistic dedicated electrodes with high active material (AM) density, facilitating exploration and quantification of heterogeneities and inhomogeneous lithiation within such electrodes. This multi-scale insight into the (de)lithiation process and lithiation heterogeneities within the electrodes is expected to provide valuable knowledge for optimizing electrode design and ultimately enhancing electrode performance in the context of material science and battery materials research.