Choreographing Orbital Hybridization Cascades to Unleash Selective Proton Storage in Aqueous Zinc‐Ion Batteries

Abstract Protons (H + ) have emerged as crucial charge carriers alongside Zn 2+ ions in aqueous zinc‐ion batteries (AZIBs). Compared to Zn 2+ , H + storage typically exhibits more favorable thermodynamics and faster reaction kinetics. However, the co‐involvement of H + and Zn 2+ in the electrochemical processes leads to intertwined storage behaviors, posing a significant challenge to achieving selective ion regulation. Here, a cascaded orbital‐oriented hybridization strategy is introduced that selectively enhances H + storage in MnO 2 while preserving Zn 2+ intercalation. By incorporating 1,3‐Propanediamine (DP), an organic–inorganic hybrid framework is constructed wherein the p x and p z orbitals of N in DP engage in antibonding σ‐hybridization with Mn d x 2 ‐y 2 orbitals near the Fermi level. This interaction upshifts the energy of the Mn d x 2 ‐y 2 states, enabling subsequent hybridization with the O p y orbital near the Fermi level within the MnO 2 lattice. Combined experimental analyses and density functional theory (DFT) calculations reveal that this orbital reconstruction selectively accelerates H + storage kinetics with minimal perturbation to Zn 2+ insertion pathways. The resulting DP–MnO 2 composite delivers a high reversible capacity of 357 mAh g −1 at 0.1 A g −1 and maintains 142 mAh g −1 at 5 A g −1 . These findings enable orbital‐level engineering of electrodes, providing an approach for ion‐selective storage in aqueous multivalent batteries.