A Cobalt-Free Li(Li Ni Fe Mn )O Cathode with More Oxygen-Involving Charge Compensation for Lithium-Ion Batteries.

High-energy-density and low-cost lithium-ion batteries are sought to meet increasing demand for portable electronics. In this study, a cobalt-free Li(Li Ni Fe Mn )O (LNFMO) cathode material is chosen, owing to the reversible anionic redox couple O /O . The aim is to elucidate the Fe-substitution function and oxygen redox mechanism of experimentally synthesized Li(Li Ni Fe Mn )O by DFT. The redox processes of cobalt-containing Li(Li Ni Co Mn )O (LNCMO) are compared with those of LNFMO. Redox couples including Ni /Ni /Ni , Fe /Fe or Co /Co , and O /O are found, confirmed by a X-ray photoelectron spectroscopy, and explained by redox competition between O and transition metals. In LNFMO and LNCMO, O ions with an Li-O-Li configuration readily participate in oxidation, and the most active O ions are coordinated to Mn and Li . Oxidation of O in LNCMO is triggered earlier, along with that of Co. Fe substitution activates O ions, contributes additional oxygen redox charge compensation of 0.44 e per formula unit, avoids concentrated accumulation of oxygen oxidation, and improves structural stability. This work provides new scope for designing cobalt-free, low-cost, and higher-energy-density cathode materials for Li-ion batteries.