Surface Atomic Rearrangement with High Cation Ordering for Ultra‐Stable Single‐Crystal Ni‐Rich Co‐Less Cathode Materials

Abstract It is crucial to minimize cobalt content in Ni‐rich layered single‐crystal cathodes due to their high price and limited availability, yet it will inevitably lead to cation disordering, capacity degradation, and thermal issues. Herein, to overcome the intrinsic trade‐off between performance and composition of Ni‐rich Co‐less single‐crystal cathodes, a precursor engineering strategy with an epitaxially grown cobalt enrichment on the surface is innovatively proposed. In contrast to traditional coating modifications with random orientation and rigid surface‐bulk boundary, the epitaxially enriched surface cobalt layer on the precursor undergoes rapid interdiffusion with the internal Ni 3+ during the optimized sintering process. This interdiffusion eliminates the surface‐bulk boundary, promoting the uniform distribution of cobalt and synergistically addressing the Li/Ni intermixing. Moreover, an enhanced surface Li + diffusion is obtained, thereby suppressing the Li + concentration gradient and intragranular cracks generation. Consequently, the modified LiNi 0.7 Co 0.07 Mn 0.23 O 2 exhibits impressive cycling stability with increased capacity retention in both coin‐type half‐cells and pouch‐type full‐cells (91% after 1000 cycles), even under the harsh condition of high‐temperature, surpassing the majority of previously reported Ni‐rich cathodes. This work opens new avenues toward the low cost, high energy density, thermal stability, and long cyclic life for Ni‐rich Co‐less cathodes and sheds light on large‐scale commercial production.