Tandem Mn─O─Fe Orbital Hybridization in α‐MnO ₂ to Decouple Stability and Kinetics for High‐Rate Aqueous Zinc‐Ion Batteries

ABSTRACT Aqueous zinc‐ion batteries (ZIBs) are promising for safe and sustainable energy storage, yet MnO ₂ cathodes suffer from rapid capacity decay and sluggish kinetics due to Mn ³⁺ ‐induced Jahn–Teller (J–T) distortions and poor electronic conductivity. Herein, we propose a tandem orbital hybridization strategy in α‐MnO ₂ , where Fe doping forms Mn─O─Fe linkages coupling Mn 3d, O 2p, and Fe 3d orbitals. This orbital‐level engineering redistributes charge, lifts 3d orbital degeneracy, and strengthens Mn─O bonding, effectively suppressing J–T distortions while accelerating charge‐carrier transport. The resulting Fe‐MnO ₂ cathode exhibits durable Zn ²⁺ storage over 5500 cycles at 5 A g ⁻¹ with markedly enhanced kinetics. Multiscale characterization and first‐principles calculations reveal that orbital engineering optimizes orbital energies, mitigates lattice distortions, and lowers kinetic barriers for both electrons and ions. This work establishes a generalizable strategy to decouple structural stability from electrochemical kinetics, offering a blueprint for designing high‐performance Mn‐based cathodes and related transition‐metal oxides in aqueous ZIBs.