Full picture discovery for mixed-fluorine anion effects on high-voltage spinel lithium nickel manganese oxide cathodes

Abstract

Small amounts of fluorine substituting for oxygen deficiencies could reduce Mn dissolution, enhancing the cyclability in spinel-type lithium nickel manganese oxides (LiNi0.5Mn1.5O4). Fluorine anion incorporation simultaneously enhances the C-rate capability and specific capacity fading. We used experimental and theoretical approaches to obtain a full picture of the mixed-anion effects for LiNi0.5Mn1.5O4-xFx cathode materials. The fluorine anion reduced the activation barrier for lithium-ion hopping along the most energetically preferable 8a-16c-8a route, enhancing the C-rate capability. Simultaneously, the coordination bond of the linear F--Mn3+-F- (Mn@2F diagonal) arrangement increased the oxidation potential to 5.1 V (vs Li+/Li). This hampered full extraction of Li+ from the spinel lattice, which was triggered by the oxidation of Mn3+ below the cutoff voltage (3.5-4.8 V (vs Li+/Li)), leading to a capacity loss.