Weakened Interfacial Hybridization Unlocks High‐Capacity Operation of Commercial Spinel Cathodes

ABSTRACT Despite significant progress in cathode and electrolyte design, interfacial degradation continues to limit the practical capacity of high‐energy secondary batteries. Here, we introduce a thermodynamics‐guided strategy to modulate the interfacial hybridization by aligning the electronic band structures of the cathode and electrolyte. As a proof of concept, we construct a weakly hybridized inner Helmholtz plane (IHP) layer on commercial LiNi 0.5 Mn 1.5 O 4 (LNMO), and unlock an unprecedented practical specific capacity of 333.0 mA h g −1 and a specific energy of 1097.0 Wh kg −1 , far exceeding the conventional operational thresholds (<150 mA h g −1 ). Theoretical calculations and in/ex situ spectroscopic investigations reveal that attenuated hybridization between the cathode and electrolyte anions/solvents suppresses transition metal dissolution and mitigates structural degradation during extended deep cycling. Implemented in commercial Al‐coated electrodes, our approach enables stable long‐term cycling at 300 mA g −1 with 212.5 mA h g −1 specific capacity retained after 300 cycles. These findings establish interfacial hybridization modulation as a universal and scalable design principle for overcoming intrinsic capacity limitations, offering a viable pathway toward practical high‐energy‐density, long‐life lithium‐ion batteries.