One‐Step Calcination Synthesis of Bulk‐Doped Surface‐Modified Ni‐Rich Cathodes with Superlattice for Long‐Cycling Li‐Ion Batteries

Abstract Nickel‐rich (Ni≥90 %) layered cathodes are critical materials for achieving higher‐energy‐density and lower‐cost next‐generation Li‐ion batteries (LIBs). However, their bulk and interface structural instabilities significantly impair their electrochemical performance, thus hindering their widespread adoption in commercial LIBs. Exploiting Ti and Mo diffusion chemistry, we report one‐step calcination to synthesize bulk‐to‐surface modified LiNi 0.9 Co 0.09 Mo 0.01 O 2 (NCMo90) featuring a 5 nm Li 2 TiO 3 coating on the surface, a Mo‐rich Li + /Ni 2+ superlattice at the sub‐surface, and Ti‐doping in the bulk. Such a multi‐functional structure effectively maintains its structural integrity upon cycling. As a result, such NCMo90 exhibits a high initial capacity of 221 mAh g −1 at 0.1 C, excellent rate performance (184 mAh g −1 at 5 C), and high capacity retention of 94.0 % after 500 cycles. This work opens a new avenue to developing industry‐applicable Ni‐rich cathodes for next‐generation LIBs.