Structure/Interface Coupling Effect for High‐Voltage LiCoO₂ Cathodes

Abstract LiCoO₂ (LCO) is widely applied in today's rechargeable battery markets for consumer electronic devices. However, LCO operations at high voltage are hindered by accelerated structure degradation and electrode/electrolyte interface decomposition. To overcome these challenges, co‐modified LCO (defined as CB‐Mg‐LCO) that couples pillar structures with interface shielding are successfully synthesized for achieving high‐energy‐density and structurally stable cathode material. Benefitting from the “Mg‐pillar” effect, irreversible phase transitions are significantly suppressed and highly reversible Li⁺ shuttling is enabled. Interestingly, bonding effects between the interfacial lattice oxygen of CB‐Mg‐LCO and amorphous Co_xB_y coating layer are found to elevate the formation energy of oxygen vacancies, thereby considerably mitigating lattice oxygen loss and inhibiting irreversible phase transformation. Meanwhile, interface shielding effects are also beneficial for mitigating parasitic electrode/electrolyte reactions, subsequent Co dissolution, and ultimately enable a robust electrode/electrolyte interface. As a result, the as‐designed CB‐Mg‐LCO cathode achieves a high capacity and excellent cycle stability with 94.6% capacity retention at an extremely high cut‐off voltage of 4.6 V. These findings provide new insights for cathode material modification methods, which serves to guide future cathode material design.