The crystal structures of the lithium-rich and lithium-deficient spinel phases Li2[Mn2]O4 and Li0.2[Mn2]O4 have been determined by neutron-diffraction techniques. Structure refinements confirm earlier reports that the [Mn2]O4 framework of the Li[Mn2]O4 spinel remains intact during both lithium insertion and extraction, but demonstrate unequivocally that in Li2[Mn2]O4 the Li+ ions reside in face-shared tetrahedra and octahedra of the cubic-close-packed oxygen-anion array; in Li0.2[Mn2]O4 the Li+ ions are located randomly on only the tetrahedral sites of the spinel structure. © 1987.
