Trigonal polymorph of Li 2 MnO 3

Abstract

We report the discovery of a trigonal polymorph of the prospective Li ion battery material Li 2 MnO 3 and its synthesis in bulk, single crystal form. Crystal growth of trigonal Li 2 MnO 3 is strongly dependent upon the quality of a polycrystalline LiMnO 2 precursor consumed in the synthesis process. The crystal structure of the new trigonal phase is composed of ordered honeycomb layers of LiO 6 and MnO 6 octahedra segregated by layers of LiO 6 octahedra and represents an ordered stacking variant of the known monoclinic polymorph. Diffuse reflectance spectroscopy reveals a direct optical gap of 2.47 ± 0.11 eV and a series of charge excitations that are well explained by the expected Mn 4+ 3d 3 valence. Density functional theory calculations are in excellent agreement with the spectroscopic measurements and find a near degeneracy in the formation energies of the two polymorphs. Furthermore, our results suggest that the trigonal structure resolves the compositional and structural disorder often manifested in the monoclinic phase.