Synthesis–structure relationships in Li- and Mn-rich layered oxides: phase evolution, superstructure ordering and stacking faults

Abstract

Li- and Mn-rich layered oxides are promising positive electrode materials for future Li-ion batteries. The presence of crystallographic features such as cation-mixing and stacking faults in these compounds make them highly susceptible to synthesis-induced structural changes. Consequently, significant variations exist in the reported structure of these compounds that complicate the understanding of how the crystallographic structure influences its properties. This work investigates the synthesis–structure relations for three widely investigated Li- and Mn-rich layered oxides: Li₂MnO₃, Li_1.2Mn_0.6Ni_0.2O₂ and Li_1.2Mn_0.54Ni_0.13Co_0.13O₂. For each compound, the average structure is compared between two synthetic routes of differing degrees of precursor mixing and four annealing protocols. Furthermore, thermodynamic and synthesis-specific kinetic factors governing the equilibrium crystallography of each composition are considered. It was found that the structures of these compounds are thermodynamically metastable under the synthesis conditions employed. In addition to a driving force to reduce stacking faults in the structure, these compositions also exhibited a tendency to undergo structural transformations to more stable phases under more intense annealing conditions. Increasing the compositional complexity introduced a kinetic barrier to structural ordering, making Li_1.2Mn_0.6Ni_0.2O₂ and Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ generally more faulted relative to Li₂MnO₃. Additionally, domains with different degrees of faulting were found to co-exist in the compounds. This study offers insight into the highly synthesis-dependent subtle structural complexities present in these compounds and complements the substantial efforts that have been undertaken to understand and optimise its electrochemical properties.