Yawen Yan

Benefiting from the anionic redox activity, lithium‐rich layered oxide cathodes exhibit high specific capacity, but the migration of transition metal (TM) can exacerbate vacancy clustering, resulting in domino‐like structural degradation. To stabilize the structure, the electrostatic pinning effect is precisely incorporated into the Li layer to mitigate the TM migration via strong electrostatic repulsion. Concurrently, this configuration effectively modulates the electronic distribution around the oxygen ligands, thereby stabilizing the oxygen redox. Furthermore, robust electrostatic interactions endow the material with the capability to adaptively adjust its interlayer spacing, thereby buffering the structural evolution of the layered framework during (de)lithiation processes. The modified cathode achieves an 89.1% capacity retention over 400 cycles in half‐cells and an impressive 96.2% over 1000 cycles in full cells. To further decouple the capacity‐stability trade‐off while concurrently enhancing both bulk and interfacial stability, we engineered a gradient shielding architecture. This design not only attains 219.8 mAh g ⁻¹ at 0.5C and delivers capacity retention of 90.8% after 400 cycles but also promotes the formation of a compact CEI at the near‐surface region, markedly improving interfacial stability under harsh conditions. This progressive structural engineering paradigm offers fresh insights into overcoming the intrinsic structural challenges of lithium‐rich cathode materials.