Correlated X-Ray 3D Ptychography and Diffraction Microscopy Visualize Links between Morphology and Crystal Structure of Lithium-Rich Cathode Materials

The search for higher performance, improved safety, and lifetime of lithium-ion batteries relies on the understanding of degradation mechanisms. Complementary to methods and studies on primary particles or crystalline structure on bulk materials, here we use spatially correlated ptychographic X-ray computed nanotomography with a 35 nm resolution and scanning X-ray diffraction microscopy with 1 μm resolution to visualize in 3D the hidden morphological and structural degradation processes in individual secondary particles of lithium-rich nickel, cobalt, and manganese oxides. From comparative examination of pristine and cycled particles, we suggest that morphological degradation could have radial dependency and secondary particle size dependency. The same particles were examined to correlate the degradation to crystallinity, which shows surprising core-shell structures. This study reveals the inner 3D structure of the secondary particles while opening up questions on the unexpected crystalline structural distributions, which could offer clues for future studies on this promising cathode material for lithium-ion batteries. [Display omitted] •Correlative ptychographic tomography with 35 nm resolution and diffraction tomography•3D micro-cracks in secondary Li-rich NMC particles correlated with crystal lattice•Radial and secondary-particle-size-dependent material degradation•Intriguing core-shell structure observed in 3D crystalline maps Materials Characterization Techniques; Energy Materials; Crystallography