Variations in structure and electrochemistry of iron- and titanium-doped lithium nickel manganese oxyfluoride spinels

Cycling in a voltage range of 2.0-5.0 V leads to a cooperative Jahn-Teller distortion accompanied by a phase transformation from cubic to tetragonal symmetry. This causes a severe capacity fade. To improve capacity retention, the as-prepared spinel is post-doped with fluorine. Influence of different fluorine amounts in LiNi0.5Mn1.4Fe0.1Ti0.027O4−xFx (x = 0-0.3) on the capacity and stability is analyzed. The initial capacities decrease with increasing fluorine content but the low voltage capacity is stabilized. Best electrochemical results are obtained with a fluorine content of x = 0.15. Furthermore, an additional redox couple is found. The intensity of this depends on the fluorine content. It is assumed that manganese, either in the tetrahedral sites or in octahedral sites, bound to fluorine lead to a higher voltage.