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Updated: Jun 19, 2026

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Tandem Mn─O─Fe Orbital Hybridization in α-MnO2 to Decouple Stability and Kinetics for High-Rate Aqueous Zinc-Ion
Jinghua Yang1, Xiaoke Li1, Lingling Tian1
1State Key Laboratory of Organic-Inorganic Composites, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing, P. R. China.
Abstract:
Aqueous zinc-ion batteries (ZIBs) are promising for safe and sustainable energy storage, yet MnO2 cathodes suffer from rapid capacity decay and sluggish kinetics due to Mn3+-induced Jahn-Teller (J-T) distortions and poor electronic conductivity. Herein, we propose a tandem orbital hybridization strategy in α-MnO2, 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-MnO2 cathode exhibits durable Zn2+ 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.
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