To investigate the electrochemical properties of LiMn2O4-xFx (0 < x < 1) as a cathode material for 4-V class lithium secondary batteries, spinel phases synthesized at 800 degrees C are examined. Although the initial discharge capacity of LiMn2O4 is improved by substitution of F-for O-2(-) in the single-phase region, the cycle performance is reduced considerably compared with that of parent LiMn2O4. X-ray diffraction (XRD) data show that the single-phase region of x in LiMn2O4-xFx is 0 < x < 0.2. A secondary phase (Mn2O3) is observed in the region 0.4 < x < 1.0. Voltammetric peaks between 3 and 4.5 V region and XRD data suggest that the oxidation state of Mn in the parent LiMn2O4 increases at the expense of creating second phase (Mn2O3). These results also imply that a second phase spinel can improve the cycling performance of LiMn2O4 by suppressing the Jahn-Teller instability. The oxidation state of Mn in the single-phase spinel and the second-phase coexisting spinel is compared by means of XPS measurements. The electronic conductivity and activation energy of LiMn2O4 is also discussed. (c) 2005 Elsevier B.V. All rights reserved.