Hybrid Conductive Network Enabling Synergistic Polarization Mitigation and Cathode Electrolyte Interphase (CEI) Regulation in Disordered Rocksalt Cathodes

ABSTRACT Li‐rich cation‐disordered rocksalt (DRX) oxides are promising high‐energy‐density cathodes, yet their practical application is hindered by severe polarization and interfacial instability under high‐voltage operation, resulting in rapid capacity fading and voltage decay. Herein, we propose an electrode‐level optimization strategy based on conductive‐network engineering. By integrating graphene (Gr) with an extended π‐conjugated framework and Ketjen Black (KB) with high surface area, a hybrid conductive network (K1G3) is constructed. This network provides continuous electronic pathways and reduces interfacial charge accumulation, thereby mitigating polarization and suppressing parasitic side reactions. Furthermore, the strong Gr–Transition metal (TM) ions coordination anchors on cathode surfaces, suppressing TM dissolution and synergistically promoting the formation of a thin, uniform, LiF‐rich cathode electrolyte interphase (CEI). This uniform and robust CEI functions to mitigate degradation of bulk Li‐ion diffusion and enhance bulk structural stability. The optimized Mn‐based DRX cathode delivers a high‐rate capacity of 154 mAh g −1 at 1000 mA g −1 and retains 84.0% of its initial capacity after 100 cycles at 50 mA g −1 , substantially outperforming Super C65 based electrodes. Importantly, these performance advantages are consistently demonstrated in pouch cell configurations. This work highlights conductive‐network engineering as an effective strategy for stabilizing DRX cathodes toward practical applications.