In situ neutron diffraction to investigate the solid‐state synthesis of Ni‐rich cathode materials.

Studying chemical reactions in real time can provide unparalleled insight into the evolution of intermediate species and can provide guidance to optimize the reaction conditions. For solid‐state synthesis reactions, powder diffraction has been demonstrated as an effective tool for resolving the structural evolution taking place upon heating. The synthesis of layered Ni‐rich transition‐metal oxides at a large scale (grams to kilograms) is highly relevant as these materials are commonly employed as cathodes for Li‐ion batteries. In this work, in situ neutron diffraction was used to monitor the reaction mechanism during the high‐temperature synthesis of Ni‐rich cathode materials with a varying ratio of Ni:Mn from industrially relevant hydroxide precursors. Rietveld refinement was further used to model the observed phase evolution during synthesis and compare the behaviour of the materials as a function of temperature. The results presented herein confirm the suitability of in situ neutron diffraction to investigate the synthesis of batches of several grams of electrode materials with well‐controlled stoichiometry. Furthermore, monitoring the structural evolution of the mixtures with varying Ni:Mn content in real time reveals a delayed onset of lithiation as the Mn content is increased, necessitating the use of higher annealing temperatures to achieve layering. [ABSTRACT FROM AUTHOR]