Permeable characteristics of surface film deposited on LiMn2O4 positive electrode revealed by redox-active indicator

Herein, the ferrocene redox indicator-based surface film characteristics of spinel lithium manganese oxide (LMO) were evaluated. The pre-cycling of spinel LMO generated a film on the LMO surface. The surface film deposited on LMO surface suppresses further electrolyte decomposition, while the penetration of approximately 0.7 nm-sized redox indicator is not prevented. The facile self-discharge of LMO and regeneration current from the ferrocenium molecule was observed from the redox indicator in a specifically designed four-electrode cell. From this electrochemical behavior, a small-sized HF molecule attack on the LMO surface through a carbonate-based electrolyte-derived film is defined; hence, the prevention of small-sized molecules into the deposited surface film is crucial for the enhancement of LiMn2O4-based lithium-ion batteries.

Enhancing Lithium Manganese Oxide Electrochemical Behavior by Doping and Surface Modifications

Lithium manganese oxide is regarded as a capable cathode material for lithium-ion batteries, but it suffers from relative low conductivity, manganese dissolution in electrolyte and structural distortion from cubic to tetragonal during elevated temperature tests. This review covers a comprehensive study about the main directions taken into consideration to supress the drawbacks of lithium manganese oxide: structure doping and surface modification by coating. Regarding the doping of LiMn2O4, several perspectives are studied, which include doping with single or multiple cations, only anions and combined doping with cations and anions. Surface modification approach consists in coating with different materials like carbonaceous compounds, oxides, phosphates and solid electrolyte solutions. The modified lithium manganese oxide performs better than pristine samples, showing improved cyclability, better behaviour at high discharge c-rates and elevated temperate and improves lithium ions diffusion coefficient.