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Vanadium pentoxide(V2O5) is an attractive high capacity cathode material for lithium ion batteries but is limited by the poor structural stability.Although nanostructured V2O5 and conductive coatings have been widely investigated,but modifications of the intrinsic structures are often overlooked.In this paper,we report the synthesis and properties of a new lithium-ordered superstructure of Li0.0625V2O5 through controlled prelithiation treatment.