On the composition of LiNi${}_{0.5}$Mn${}_{1.5}$O${}_4$ cathode active materials

LiNi${}_{0.5}$Mn${}_{1.5}$O${}_4$ (LNMO) cathode active materials for lithium-ion batteries have been investigated for over 20 years. Despite all this effort, it has not been possible to transfer their favorable properties into applicable, stable battery cells. To make further progress, the research perspective on these spinel type materials needs to be updated and a number of persisting misconceptions on LNMO have to be overcome. Therefore, the current knowledge on LNMO is summarized and controversial points are addressed by detailed considerations on the composition and crystallography of LNMO. The findings are supported by an in-situ high temperature X-ray diffraction study and the investigation of four different types of LNMO materials, including Mn(III) rich ordered LNMO, and disordered LNMO with low Mn(III) content. It is shown that the importance of cation order is limited to a small composition range. Furthermore, new evidence contradicting the idea of oxygen defects in LNMO is presented and an enhanced classification of LNMO based on the Ni content of the spinel phase is proposed. Moreover, a balanced chemical equation for the formation of LNMO is presented, allowing for comprehensive calculations of key properties of LNMO materials. Finally, suitable target compositions and calcination programs are suggested to obtain better LNMO materials. (© 2023 The Authors. Advanced Energy Materials published by Wiley‐VCH GmbH)