Short-Range Order and Unusual Modes of Nickel Redox in a Fluorine-Substituted Disordered Rocksalt Oxide Lithium-Ion Cathode

Fluorine substitution for oxygen in cation-disordered lithium-excess transition metal oxides (Li<sub>1+<em>x</em></sub>TM<sub>1-<em>x</em></sub>O<sub>2</sub>) used as lithium-ion cathodes was recently demonstrated to improve the reversibility of the processes taking place on charge and discharge by reducing the amount of oxygen loss on charge and preventing major structural rearrangements at high voltage. Yet, little is understood about how fluorine incorporates the oxide structure and impacts its electrochemical properties. Here, we use a combination of experimental (solid-state nuclear magnetic resonance (NMR) spectroscopy) and theoretical techniques (density functional theory (DFT) calculations and Monte Carlo simulations) to investigate the evolution of the local structure around fluorine and lithium and the oxidation state of redox-active nickel during charge and discharge of the Li<sub>1.15</sub>Ni<sub>0.45</sub>Ti<sub>0.3</sub>Mo<sub>0.1</sub>O<sub>1.85</sub>F<sub>0.15</sub> (LNF15) cathode. We show that fluorine doping introduces short-range order in as-synthesized LNF15 by incorporating in lithium-rich sites with five or six lithium nearest neighbors. We observe the emergence of new signals in the ex situ <sup>19</sup>F NMR spectra taken at high states of charge, which we tentatively assign to undercoordinated, diamagnetic fluorine environments seen in our computed models. Our theoretical results also suggest that octahedral nickel ions directly bonded to fluorine follow a different oxidation mechanism than those surrounded by six oxygens, forming Ni<sup>3+</sup> intermediates instead of oxidizing from Ni<sup>2+</sup> directly to Ni<sup>4+</sup>. While the oxidation of Ni<sup>2+</sup> toward Ni<sup>4+</sup> is incomplete in oxides, due to overlap between the oxygen and the nickel valence states, this result suggests that fluorination may be an efficient strategy to utilize the Ni<sup>2+</sup>/Ni<sup>4+</sup> redox reservoir to a greater extent.