Synergistic Engineering of Nonmagnetic Ions Enables Decoupling of Magnetic Frustration and Structural Dynamics in Cobalt‐Free High‐Nickel Cathodes

Abstract Cobalt‐free high‐nickel layered oxides have emerged as promising cathode candidates for next‐generation lithium‐ion batteries, owing to their exceptional capacity and cost‐effectiveness. However, their large‑scale application remains constrained by intrinsic deficiencies stemming from cobalt absence—namely, magnetic‑ordering imbalance and sluggish structural dynamics. Here, a synergistic doping strategy involving nonmagnetic ions (B–Al–W) is presented to achieve atomic‐scale coordination between bulk lattice stabilization (via Al/W doping) and near‐surface interface passivation (through B enrichment). Precise substitution of non‑magnetic cations effectively mitigates magnetic frustration and superexchange interactions, while strengthened metal–oxygen bonding alleviates anisotropic lattice strain. Simultaneously, the constructed layered–spinel mortise and tenon structure significantly enhances Li + diffusion kinetics. The optimized cathode material delivers a reversible capacity of 162.2 mAh g −1 at 10 C, retains 88.6% capacity after 100 cycles at 5 C, and markedly suppresses voltage fade. This work provides a novel design paradigm for the synergistic magnetic–electrochemical regulation of Co‑free, high‐Ni cathodes in next‑generation, high‑performance LIBs.