Electronegativity-Guided Dual-Anion Doping for Mn–O Bond Engineering To Boost Stability and Kinetics in Zinc-Ion Batteries

Layered manganese oxide is a promising cathode material for rechargeable MnO 2 //Zn batteries. Nonetheless, its commercial application is severely constrained by the structural instability and sluggish reaction kinetics of MnO 2 cathodes. To tackle these obstacles, this study proposes an electronegativity-guided dual-anion doping strategy, successfully synthesizing N/F codoped layered manganese oxide (N/F-MnO 2 ) through a facile hydrothermal approach. Low-electronegativity N doping facilitates the generation of Mn–N bonds, which weakens the strong interaction between Zn 2+ and lattice oxygen, accelerating Zn 2+ diffusion kinetics. In contrast, fluorine doping (high electronegativity) forms Mn–F bonds with high bonding energy, effectively enhancing structural stability. Meanwhile, NH 4 + ions and additional oxygen vacancies are introduced into the interlayer intervals and host structures of MnO 2, synergistically promoting Zn 2+ migration and increasing zinc storage sites. Benefiting from the multimechanism coordination, the optimized N/F-MnO 2 -2 cathode achieves a high discharge capacity of 496 mAh g –1 at 0.1 A g –1, showing a marked increase in comparison with K-MnO 2 (356 mAh g –1 ). More impressively, it exhibits exceptional cycling durability, maintaining a capacity of 91.3 mAh g –1 under 3 A g –1 following 1000 cycles. This work not only provides an electronegativity-guided dual-anion doping approach for the engineering of advanced cathode materials but also offers valuable insights into high-performance AZIBs by multistrategy optimization.