Structurally Order‐Disorder‐Amorphous Gradient Interface Toward Extended‐Temperature‐Range Li‐Rich Layered Cathodes

ABSTRACT Li‐rich layered oxide cathodes (LLOs) with anionic redox can substantially elevate the energy density of lithium‐ion batteries (LIBs). Nevertheless, their practical development is hindered by inadequate electrochemical performance across a wide temperature range, particularly under extreme operating temperature environments. This challenge is strongly associated with the interfacial structural stability and lithium‐ion transport. Herein, a structurally order‐disorder‐amorphous (SODA) gradient interface with cation vacancies is innovatively designed to solve this problem. The formed layer‐spinel/rocksalt intergrown structure and Zr─O amorphous layer in SODA interface accommodate the lattice expansion/contraction and suppress strain accumulation during cycling, and synergistically modulate and stabilize the interfacial chemistry. Thus, the irreversible oxygen release, chemo‐mechanical degradation, interfacial side reactions, and metal‐ion dissolution are effectively inhibited. Additionally, the cation vacancy defects and spinel phase within SODA enhance the lithium‐ion diffusion. Benefiting from these merits of enhanced structural/chemical stability and quickened reaction kinetics, the SODA‐modified Li‐rich cathode exhibits remarkable cycling performance with capacity and voltage retentions of 89% and 89% after 500 cycles at 1 C and good rate performance over an extended temperature range (−15°C to 55°C). This gradient interface strategy provides valuable insights into designing long‐cyclability and extended‐temperature‐range LLOs for next‐generation LIBs.