Superlattice Engineering Regulation to Address Structural Defect Evolution in Ni‐Rich Layered Cathodes

ABSTRACT Ni‐rich layered oxides are prime cathodes for high‐energy lithium‐ion batteries but suffer from capacity fading, voltage decay, and safety issues due to coupled bulk and interfacial defect evolution, such as cation disorder, oxygen release, crack formation, and surface degradation. Conventional stabilization efforts mainly focus on screening dopant chemistries and contents, which markedly enhance electrode performance of Ni‐rich cathodes. However, the dopant‐induced functional units underpinning the structural benefits remain elusive. Superlattice engineering via deliberate cation/anion ordering and coherent stacking modulation from the unit‐cell to mesoscopic scales provides a fundamental framework to direct the bulk‐surface defect evolution. By stabilizing the intermediate phase, promoting lithium/transition metal ordering, and regulating the formation and distribution of coherent lattice domains, superlattice motifs can alleviate anisotropic lattice strain and homogenize Li ⁺ transport, thereby mitigating oxygen‐related instabilities during phase transitions. In this mini review, we link the defect‐driven failure pathways with recent advances in superlattice‐based designs and outline strategies for building structurally robust Ni‐rich cathodes with high energy density and long cycle life.