Hybrid Conductive Network Enabling Synergistic Polarization Mitigation and Cathode Electrolyte Interphase (CEI)...

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.