Lithium-rich LiF/Fe nanocomposite is prepared by a simple route of mechanical ball-milling of lithium fluoride and iron using rigid TiN nanoparticles as the grinding powders, and studied as a lithium-rich cathode material for satisfying the present Li-ion battery technology. The structural characterizations reveal that the nanocomposite is composed of well-dispersed and intimately contacted LiF and Fe particles created by high-energy ball-milling, forming appropriate electrode-active nanodomains for the reversible conversion reaction of LiF and Fe. Electrochemical measurements demonstrate that the LiF/Fe nanocomposite containing 50 wt% active materials of LiF and Fe can deliver a high reversible capacity of 568 mAh g(-1) at 20 mA g(-1) (calculated using the weight of LiF and Fe only), approaching the theoretical capacity of the composite (600 mAh g(-1)), and also show a strong power capability with a reversible capacity of similar to 300 rnAh g(-1) even at a very high rate of 500 mA g(-1) at room temperature. CV and XRD analyses confirm that the LiF/Fe nanocomposite can nearly realize a three-electron transfer through electrochemical conversion of LiF/Fe to FeF3 and vice versa. These results suggest the possibility to utilize the inexpensive lithium-rich composites of lithium fluoride and metals as high-capacity cathode materials for future-generation Li-ion batteries through the electrochemical conversion. (C) 2012 Elsevier B.V. All rights reserved.