Structural study of two layered phases in the NaxMnyO2 system. Electrochemical behavior of their lithium substituted derivatives

Two manganese oxide phases, α-Na0.51Mn0.93O2 and β-Na0.52MnO2, have been synthesized and their structures determined by Rietveld analysis: α-Na0.51Mn0.93O2 (isostructural to NaCo2O4) space group P63/mmc, a = 2.8661(4) Å, c = 11.165(4) Å and β-Na0.52MnO2 (isostructural to α-K0.51Mn0.93O2), space group Cmcm, a = 2.834(6) Å, b = 5.216(1) Å and c = 11.280(3) Å. Both phases are layered, with alternate sheets comprised of (MnO6) octahedra and (NaO6) trigonal prisms. Ion exchange of Na for Li in a sample having the mean composition Na0.56Mn0.86O2 that represents a 1∶3 mixture of the α- and β-phases, was effected by immersion in an LiCl/LiNO3 eutectic to obtain the lithiated composition Li0.54Na0.02Mn0.86O2. The latter material displayed excellent electrochemical behavior when employed as a cathode in a lithium battery. A high and relatively stable capacity of 160 mA g−1 was obtained in the 2.5–4.3 V voltage window for a C/15 regime. No transition to a spinel structure occurred, on cycling: the discharge/charge curves showed only a monotonous potential variation even after 50 cycles.