MSb (M = Ni, Co, Fe, Mn) alloys with a NiAs type structure were synthesized by ceramic route and evaluate as a negative electrode material for rechargeable lithium batteries. Electrochemical tests demonstrated that initial charge and discharge capacities of this materials were ca. 390 and 330 mAhg(-1), respectively. Ex situ XRD of MnSb electrodes showed that LiMnSb and Li3Sb were successively formed during lithium insertion. The Sb-121 Mossbauer spectra show that the insertion mechanism during discharge involves the formation of several lithium-containing compounds such as LiMnSb, Li3Sb with manganese extrusion. During the subsequent charge a more complex mechanism occurs involving MnSb, modified LiMnSb alloy and metallic Sb formation. (c) 2005 Elsevier B.V. All rights reserved.