On the Elusive Crystallography of Lithium‐Rich Layered Oxides: Novel Structural Models

Lithium-rich layered oxides (LRLOs) are one of the most attractive families among future positive electrode materials for the so-called fourth generation of lithium-ion batteries (LIBs). Their electrochemical performance is enabled by the unique ambiguous crystal structure that is still not well understood despite decades of research. In the literature, a clear structural model able to describe their crystallographic features is missing thereby hindering a clear rationalization of the interplay between synthesis, structure, and functional properties. Here, the structure of a specific LRLO, Li1.28Mn0.54Ni0.13Co0.02Al0.03O2, using synchrotron X-ray diffraction (XRD), neutron diffraction (ND), and High-Resolution Transmission Electron Microscopy (HR-TEM), is analyzed. A systematic approach is applied to model diffraction patterns of Li1.28Mn0.54Ni0.13Co0.02Al0.03O2 by using the Rietveld refinement method considering the R3 over bar $\bar{3}$m and C2/m unit cells as the prototype structures. Here, the relative ability of a variety of structural models is compared to match the experimental diffraction pattern evaluating the impact of defects and supercells derived from the R3 over bar $\bar{3}$m structure. To summarize, two possible models able to reconcile the description of experimental data are proposed here for the structure of Li1.28Mn0.54Ni0.13Co0.02Al0.03O2: namely a monoclinic C2/m defective lattice (prototype Li2MnO3) and a monoclinic defective supercell derived from the rhombohedral R3 over bar $\bar{3}$m unit cell (prototype LiCoO2).Here, a detailed investigation of the crystal structure of Lithium-Rich layered Oxides is reported, using Synchrotron X-ray diffraction, Neutron diffraction, and Transmission Electron Microscopy. The introduction of defects into a monoclinic unit cell and the supercells approach can describe all main structural features, opening new frontiers in rationalization of the interplay between synthesis, structure, and electrochemical properties.image