Effect of transition metal cations on the local structure and lithium transport in disordered rock-salt oxides.

Lithium-excess oxides Li1.2Ti0.4Mn0.4O2 and Li1.3Nb0.3Mn0.4O2 with a disordered rock-salt structure and Mn3+/Mn4+ as a redox couple were compared to analyze the effect of different d0 metal ions on the local structure and Li+ ion migration. These cathode materials were obtained by mechanochemically assisted solid-state synthesis. Using XRD, 7Li NMR and EPR spectroscopy and transmission electron microscopy it was shown that the Mn ions are prone to form clusters, while d0 metal ions are evenly distributed in the crystal lattice. The presence of Nb5+ ions contributes to the formation of noticeably larger Mn clusters and larger gaps in the Li+ migration maps as compared to Ti4+. These results were confirmed by the geometrical-topological method, BVSE simulation and DFT calculations, and are in good agreement with the Li diffusion coefficient determined by GITT, which is 1.5 orders of magnitude higher in Li1.2Ti0.4Mn0.4O2 than that in Li1.3Nb0.3Mn0.4O2.

Crystal structure and migration paths of alkaline ions in NaVPO4F.

A sample with a nominal composition 'NaVPO4F' is prepared by mechanochemically assisted solid-state synthesis using quenching. A detailed study of its crystal and local structure is conducted by means of XRD and FTIR and solid-state 31P NMR spectroscopies in comparison with Na3V2(PO4)2F3. It is shown that the as-prepared 'NaVPO4F' has a multiphase composition, including NaVPO4F as the main phase and Na3V2(PO4)2F3 and Na2.57V4P4O17F as the side products. The crystal structure of NaVPO4F is described in the monoclinic C2/c space group. It is characterized by negligible V3+/V4+ oxidation with the corresponding F-/O2- substitution and the presence of structural disordering. Using the Voronoi-Dirichlet partition (VDP) method, the Na+ and Li+ migration pathways in Tavorite-like NaVPO4F and closely related LiVPO4F (with the triclinic structure, P1[combining macron] S.G.) are analyzed. While the Na+ migration is suppressed in both cases, the Na+/Li+ ion exchange in NaVPO4F with the formation of monoclinic LiVPO4F could occur, but is difficult due to the sodium immobility rather than the instability of the lithium derivatives as was concluded from the DFT calculations.