Unraveling Na and F coupling effects in stabilizing Li, Mn-rich layered oxide cathodes via local ordering modification

Abstract Regardless of the prevailing capacity and energy density of lithium, manganese-rich layered oxide (LMR-NMC) cathodes, continuous decay of voltage and overall energy density during cycling hinders this material from commercialization in Li-ion batteries. Although significant work focuses on single doping of Na and F, analysis in portraying the benefit of these ions in diminishing the structural distortion during activation cycle is in doubt. Herein, the effects of co-doping Na and F into the LMR-NMC structure in stabilizing the structure and mitigating oxygen loss during the first cycle are closely examined via in situ x-ray measurements. Na and F co-doping shows a 30% lower degree of Li+/Ni2+ mixing in the Li layer (C2/m structure), 50% reduced Debye-Waller factor of Mn-O bonding, increase reversible TM migration, and faster Li diffusion relative to the pristine material. Due to the utilization of Ni redox chemistry below 4.4 V, less oxygen redox is required for charge compensation at high voltage. This study offers the first instance to quantitatively evaluate the effects of co-doping Na and F in LMR-NMC cathode in order to minimize voltage degradation by altering the local ordering of O3-type structure, which may rationalize strategies to overcome the issues of the material.