Li-ion rechargeable batteries based on LiMn2O4 suffer from relatively poor storage and cycling performance at elevated temperatures. In order to address this issue, a structural and electrochemical study of LiMn2O4-based systems at room and elevated temperatures were undertaken. Some of the spinel material characteristics such as morphology, defects, surface area, structural instability, single-Versus two-phase lithium-insertion processes, cation and oxygen stoichiometry, and manganese solubility were investigated. We found that the sample surface area, which also influences the manganese dissolution and electrolyte oxidation, is one of the most critical parameters in controlling the rate of irreversible self-discharge, with the lowest irreversible self-discharge being observed for samples with the lowest surface area. These results are discussed in terms of active surface centers and the possibility of surface treatments to rectify this problem. The elevated temperature storage and room temperature cycling performance was found to be the best for those LixMn2O4+delta samples having a low surface area (0.5-1 m(2)/g), Li in excess (x > 1.00), show no evidence of Jahn-Teller distortion down to -50 degrees C, and for which the Li-extraction mechanism occurs;over a single-phase reaction at room temperature.