Evolution Path of Precursor-Induced High-Temperature Lithiation Reaction during the Synthesis of Lithium-Rich Cathode Materials

High-temperature lithiation is one of the crucial steps for the synthesis of Li- and Mn-rich layered metal oxide (LMLO) cathodes. A profound insight of the micromorphology and crystal structure evolution during calcination helps to realize the finely controlled preparation of final cathodes, finally achieving a desired electrochemical performance. In this work, two typical precursors (hydroxide and oxalate) were selected to prepare LMLO. It is found that the influence of the lithium source on reaction pathways is determined by the properties of precursors. In the case of hydroxide as a precursor, whatever lithium sources it is, the flake morphology of LMLO is inherited from hydroxide precursors. This is because the crystal structure of cathode products has a high similarity with its precursor in terms of the oxygen array arrangement, and the topological transformation occurs from hydroxide (P-3ml) to LMLOs (C/2m and R3m). Thus, the morphology and microstructure of LMLO cathodes could be well controlled only by tuning the properties of hydroxide precursors. Conversely, the decomposition of a lithium source has a great influence on the intermediate transformation when oxalate is used as the precursor. This is because a large amount of CO₂ is released from the oxalate precursor after the decomposition reaction, resulting in drastic structural changes. At this time, the diffusion ability of the lithium source leads to the competition between the spinel phase and layered phase. Based on this point, the formation of a spinel intermediate phase can be reduced by accelerating the decomposition of the lithium source, contributing to the generation of a highly pure layered phase, thus exhibiting higher electrochemical performance. These insights provide an exciting cue to the rational selection and design of raw materials and lithium sources for the controlled synthesis of LMLO cathodes.