Structural Elucidation of Na_2/3NiO₂, a Dynamically Stabilized Cathode Phase with Nickel Charge and Sodium Vacancy Ordering

High Resolution Image Download MS PowerPoint Slide NaNiO 2 (NNO) has been investigated as a promising sodium-ion battery cathode material, but it is limited by degradation-induced capacity fade. On desodiation, NNO forms multiple phases with large superstructures due in part to Na + -ion vacancy ordering; however, their structures are unknown. Here, we report a structural solution to the Na 2/3 NiO 2 (P ′ 3) desodiated phase using combined Rietveld refinement of high-resolution synchrotron X-ray (SXRD) and neutron powder diffraction (NPD) data, magnetic susceptibility, and 23 Na solid-state nuclear magnetic resonance (ssNMR) spectroscopy. Our experimental results are compared to ab initio molecular dynamics (AIMD) simulations, which indicate multiple low-energy structures that are dynamically populated. We observe a combination of competing effects that contribute to the resultant dynamic nature of the structure, including honeycomb ordering of mixed-valence Ni, orbital ordering of Jahn–Teller (JT) distorted Ni 3+, and zigzag Na + /vacancy ordering. Our work provides evidence of multiple contributions to the structures of desodiated Na 2/3 NiO 2, along with a framework for investigating the other unsolved desodiated structures. This work may also inform our understanding of the Jahn–Teller evolution in other nickel-rich lithium- and sodium-ion cathodes, such as LiNiO 2 .