The phase diagram of the system was determined by using X-ray diffraction and differential thermal analysis. It was found that the system contained 2 intermediate compounds: Li6CoCl8 (with a Mg6MnO8-type structure) and Li2CoCl4 (with a spinel structure). The crystal structure of the former compound was determined by using X-ray powder Rietveld refinement at room temperature. This phase had a Mg6MnO8-type structure, with an ordered cation and vacancy arrangement over octahedral sites and a cubic lattice parameter of 1.02584nm. The Li6CoCl8 compound changed reversibly into the LiCl-type structure at 350C. Electrical measurements revealed that the ionic conductivity was equal to 0.093S/cm at 400C.

R.Kanno, Y.Takeda, A.Takahashi, O.Yamamoto, R.Suyama, M.Koizumi: Journal of Solid State Chemistry, 1987, 71[1], 189-95