Fe content effects on electrochemical properties of Fe-substituted Li2MnO3 positive electrode material

Fe-substituted Li2MnO3 including a monoclinic layered rock-salt structure (C2/m), (Li1+x(FeyMn1−y)1−xO2, 0 < x < 1/3, 0.1 ≤ y ≤ 0.5) was prepared by coprecipitation–hydrothermal–calcination method. The sample was assigned as two-phase composite structure consisting of the cubic rock-salt (Fm3¯m) and monoclinic ones at high Fe content above 30% (y ≥ 0.3), while the sample was assigned as a monoclinic phase (C2/m) at low Fe content less than 20%. In the monoclinic Li2MnO3-type structure, the Fe ion tends to substitute a Li (2b) site, which corresponds to a center position of Mn4+ hexagonal network in Mn–Li layer. The electrochemical properties including discharge characteristics under high current density (<3600 mA g−1 at 30 °C) and low temperature (<−20 °C at 40 mA g−1) were severely affected by chemical composition (Fe content and Li/(Fe + Mn) ratio), crystal structure (monoclinic phase content) and powder property (specific surface area). Under the optimized Fe content (0.2 < y < 0.4), the Li/sample cells showed high initial discharge capacity (240–300 mAh g−1) and energy density (700–950 mWh g−1) between 1.5 and 4.8 V under moderate current density, 40 mA g−1 at 30 °C. Results suggest that Fe-substituted Li2MnO3 would be a non-excludable 3 V positive electrode material.