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The Li–Al–Si ternary system has been investigated and four ternary phases characterized using both powder and single crystal X-ray diffraction data. LiAlSi and Li 7 Al 3 Si 4  crystallize in the  F 4̅3 m , cubic system, Li 18 Al 2 Si 6  in tetragonal  I 4 1 / amd  and Li 15 Al 3 Si 6  in hexagonal  P 6 3 / m  space group. The structure of LiAlSi ( a  = 5.94 Å), previously reported from powder data, has been confirmed. The new compound Li 7 Al 3 Si 4  has been identified and, due to a higher lithium content, its cell parameter is slightly larger ( a  = 6.115 Å). The tetragonal cell ( a  = 6.179(1) Å,  c  = 12.199(4) Å) of Li 18 Al 2 Si 6  may be considered as a (1 × 1 × 2) supercell of the cubic one. Structural variations are strongly correlated to compositional fluctuations and atomic substitutions, in every case the SI–Al network displays some covalent character. In the Li 15 Al 3 Si 6  hexagonal cell, bonding is more covalent leading to a heterographite-like SI–Al network.

Compositional and structural variations in the ternary system Li – Al – Si