W-doped LiWxNi0.5Mn1.5-xO4 (x=0.00-0.10) are synthesized via a sol-gel method, and their electrochemical properties are investigated. During synthesis, W4+ is converted to W6+, the amount of which significantly affects the charge-discharge behaviors of LiWxNi0.5Mn1.5-xO4. When limited to x <= 0.005, W-doping enhances the electrochemical activity of cathodes, leading to a greater discharge capacity and less capacity fading than LiWxNi0.5Mn1.5-xO4 at high C-rates. This is interesting since lowering the average valence state of Mn ions by incorporating W6+ can introduce structural instability, extending a 4 V plateau (Mn3+/4+). The reasons for such behavior associated with W-cloping are examined by electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and impedance spectroscopy. It is disclosed that the simultaneous increase in Li-O bond length and decrease in transition metal-oxide bond length, while the unit cell volume is maintained almost invariant, provides LiWxNi0.5Mn1.5-xO4 with optimal high rate performance. When W-doping exceeds x = 0.01,3 factors (intrinsically low electronic conductivity of W6+, the presence of tungsten oxide impurities, and an increase in the inter-metallic distance) aggravates electrochemical performance of LiWxNi0.5Mn1.5-xO4. The last factor also induces structural instability during repeated cycling because of the expansion of a unit cell volume.(C) 2012 Elsevier B.V. All rights reserved.