In Situ Chelating Synthesis of Hierarchical LiNi1/3Co1/3Mn1/3O₂ Polyhedron Assemblies with Ultralong Cycle Life for Li‐Ion Batteries

Layered lithium transition‐metal oxides, with large capacity and high discharge platform, are promising cathode materials for Li‐ion batteries. However, their high‐rate cycling stability still remains a large challenge. Herein, hierarchical LiNi 1/3 Co 1/3 Mn 1/3 O 2 polyhedron assemblies are obtained through in situ chelation of transition metal ions (Ni 2+ , Co 2+ , and Mn 2+ ) with amide groups uniformly distributed along the backbone of modified polyacrylonitrile chains to achieve intimate mixing at the atomic level. The assemblies exhibit outstanding electrochemical performances: superior rate capability, high volumetric energy density, and especially ultralong high‐rate cyclability, due to the superiority of unique hierarchical structures. The polyhedrons with exposed active crystal facets provide more channels for Li + diffusion, and meso/macropores serve as access shortcuts for fast migration of electrolytes, Li + and electrons. The strategy proposed in this work can be extended to fabricate other mixed transition metal‐based materials for advanced batteries.