[en] Intermetallic phases Li-Sn were synthesized by ball-milling and characterized for their structures and electrochemical performances. All phases in Li-Sn binary phase diagram were identified by ¹¹⁹Sn Moessbauer spectroscopy, used as reference materials for the study of lithium insertion into tin-based electrode materials. The observed spectra show two distinct environments of tin; the Sn-rich phases and the Li-rich phases. An example of electrochemical properties of these phases is proposed for Li₂₂Sn₅. Irreversibility of the first cycle is related to the structural change (3D^→2D) of this phase.