Local Cation-Ordered Superlattice Stabilizing Ni-Rich Single-Crystalline Cathodes.

Ni-rich single-crystalline cathodes are pivotal for advancing lithium-ion battery technology due to their high energy density and mechanical stability. However, Ni-rich single-crystalline particles face intrinsic structural heterogeneity due to excessively high sintering temperature required to shape micron-sized morphologies─typically over 150 °C above the polycrystalline optimum, leading to rapid electrochemical decay and unsatisfied rate performance that hinder their practical application. Here, we propose a lithium-deficient presintering strategy to synthesize cation-ordered single-crystalline LiNi0.83Co0.12Mn0.05O2 (S-NCM83), effectively minimizing lattice chemical heterogeneity and defect formation. The resulting cation-ordered percolation network enhances the structural stability of the bulk, reduces the energy barrier for Li+ migration, and stabilizes Li+ diffusion pathways. Consequently, S-NCM83 demonstrates significantly improved cycling stability across various operating temperatures and achieves exceptional rate performance, delivering 206 mAh g-1 at 0.1 C and 170 mAh g-1 at 5 C, without requiring surface coatings or doping. This work introduces a universal strategy to address the long-standing structural instability issues in single-crystalline cathodes, paving the way for simplified and scalable approaches to long-life and high-energy lithium-ion batteries.