Correlative 3D Mapping of Structure, Composition, and Valence State Dynamics in Battery Cathodes via Simultaneous ADF-EDS-EELS Tomography

Understanding degradation in battery cathodes and other functional materials requires simultaneous knowledge of structural, chemical, and electronic changes in three dimensions (3D). Here, we present a simultaneous ADF-EDS-EELS tomography method that enables 3D mapping of atomic structure, composition, valence states, and transition metal inhomogeneity within a single, low-dose STEM tilt series acquisition. Applied to LiNi1/3Co1/3Mn1/3O2 (NCM111) particles at different electrochemical cycling stages, this method reveals nanoscale degradation processes with full spatial correlation. We observe that while chemical composition evolves uniformly throughout the entire primary particle, valence state changes and transition metal segregation are strongly depth-dependent and concentrated near the surface. This coexistence of bulk and surface-driven degradation dynamics reveals distinct mechanisms acting at different spatial scales. The evolution of inhomogeneity and valence states deviates from simple phase transition models, highlighting the roles of ion migration and dissolution-driven segregation. Our findings establish valence state gradients and nanoscale inhomogeneity as active contributors to cathode failure. More broadly, this correlative 3D platform opens new opportunities for studying redox-driven transformations in fields such as neuromorphic computing and heterogeneous catalysis, where composition-structure-function coupling is inherently three-dimensional.