The Cubic NiP2 crystal was prepared by a mechanical milling technique. All-solid-state cells with the Ni(P)2 electrode and the Li2S-P2S5 glass-ceramic electrolyte exhibited high reversible capacity of over 600 mAh g(-1) for 10 cycles at room temperature. The NiP2 electrode in solid-state cells underwent the conversion process as reported in the cells using a liquid electrolyte. Lithiated nickel phosphides were also prepared by milling. The composites of Li-Ni-P ternary crystal (Li3.4Ni10.6P7 or Li2Ni12P7) and Li3P were obtained and they were used as an electrode with lithium source in an all-solid-state cell. The cell with the electrode was initially charged and then discharged and retained cell capacity of about 600 mAh g(-1). Nickel phosphides are potential negative electrodes with high capacity in all-solid-state lithium rechargeable batteries with sulfide electrolyte. (C) 2008 Elsevier B.V. All rights reserved.