Anchored Oxygen‐Release‐Suppression Phase Stabilizing High‐Voltage Ni‐Rich Cathode Materials

Abstract

ABSTRACT The Ni‐rich LiNi x Co y Mn 1−x−y O 2 (x ≥ 0.9) cathode materials (NCMs) have been considered promising for next‐generation Li‐ion batteries owing to their high‐energy density. However, their practical application is hindered by gas evolution and rapid capacity degradation, primarily caused by irreversible oxygen release and structural instability. Herein, a facile one‐step anchoring strategy is proposed to overcome this challenge by engineering a precisely tailored dual‐architecture LiNi 0.9 Co 0.05 Mn 0.05 O 2 (DA‐NCM). This strategy constructs a dual‐phase surface architecture on Ni‐rich cathodes, where perovskite‐phase La 4 LiNiO 8 mitigates surface oxygen instability and interfacial degradation, and inert La 2 Mo 2 O 9 anchors the lattice to avoid the detachment of La 4 LiNiO 8 during cycling via enhanced La─O bond pinning effect. This dual‐architecture design provides a robust strategy for stabilizing the interface, surface, and bulk phase of Ni‐rich cathodes, enabling durable oxygen regulation, suppressed structural degradation, and stable high‐voltage operation under demanding cycling conditions. Thus, our DA‐NCM cathodes demonstrate excellent capacity retention of 95.7% at 4.3 V and 93.6% at 4.5 V after 200 cycles and remarkable stability even at an elevated temperature (50°C) and high voltage (4.5 V), confirming their markedly enhanced electrochemical stability. This precision design of dual architecture provides a new pathway for developing high‐energy‐density cathode materials with long cycle life.