Unraveling 3d Transition Metal (Ni, Co, Mn, Fe, Cr, V) Ions Migration in Layered Oxide Cathodes: A Pathway to Superior Li‐Ion and Na‐Ion Battery Cathodes

Abstract Li‐ion and Na‐ion batteries are promising systems for powering electric vehicles and grid storage. Layered 3d transition metal oxides A x TMO 2 (A = Li, Na; TM = 3d transition metals; 0 < x ≤ 2) have drawn extensive attention as cathode materials due to their exceptional energy densities. However, they suffer from several technical challenges caused by crystal structure degradation associated with TM ions migration, such as poor cycling stability, inferior rate capability, significant voltage hysteresis, and serious voltage decay. Aiming to tackle these challenges, this review provides an in‐depth discussion and comprehensive understanding of the TM ions migration behaviors in A x TMO 2 . First, the key thermodynamics and kinetics that impact TM ions migration are discussed, covering ionic radius, electronic configuration, crystal structure arrangement, and migration energy barrier. In particular, details are provided regarding the universal and specific migration characteristics of Ni, Co, Mn, Fe, Cr, and V ions in layered cathode materials. Subsequently, the impacts of these migrations on electrochemical performance are emphasized in terms of the fundamental science behind technical issues, and strategies to modulate TM ions migration for advanced cathode materials development are summarized. Besides, characterization techniques for probing the TM ions migration are present, like neutron diffraction (ND), scanning transmission electron microscopy (STEM), nuclear magnetic resonance (NMR), and others. Finally, future directions in this regard are comprehensively concluded. This review offers valuable insights into the basic design of advanced layered oxide cathode materials for Li‐ion and Na‐ion batteries.