Using a new electrolyte composition which is stable against oxidation up to 5 V, the full electrochemical deintercalation of lithium from the spinel LiMn[sub 2]O[sub 4], is studied. The origin of two new reversible oxidation-reduction peaks near 4.5 and 4.9 V are examined. The capacity associated with these peaks depends on both the nominal composition x in Li[sub x]Mn[sub 2]O[sub 4] and the synthesis conditions (annealing temperatures and cooling rates), and thereby can be used as an indicator for electrochemically optimized LiMn[sub 2]O[sub 4] powders. The authors present evidence that these peaks are related to local structural defects. Thermogravimetric measurements (TGA) on Li[sub x]Mn[sub 2]O[sub 4] powders show a reversible loss of oxygen that can reach 5% at 1,000 C. The authors find that some of this weight loss is associated with the conversion of cubic LiMn[sub 2]O[sub 4] to a new tetragonal spinel phase and then to the decomposition of this phase into the orthorhombic LiMnO[sub 2] phase plus other products. This new tetragonal LiMn[sub 2]O[sub 4] spinel is prepared as a single phase, and its electrochemical properties are reported.