articleAdvanced Functional MaterialsFeb 16, 2025Closed access

Efficient Modulation d/p‐Band Center Proximity in Birnessite‐Type MnO 2 by Cation/Anion Co‐Doping for Enhanced Dual‐Ion Storage

Xi’an University · Xi'an University of Technology

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Abstract

Abstract The wide band gap of δ‐MnO 2 and the restricted regulation of the p‐band center ( p ) of active oxygen atoms hinder electron conduction and ion diffusion during zinc storage. Heteroatom doping has proven effective in improving zinc storage. However, the regulation of p solely through cation doping is comparatively constrained. Herein, a cation/anion co‐doping strategy is proposed to simultaneously adjust the p of oxygen and the d‐band center ( d ) of Mn by establishing Mn–O–Ca and Mn─N bonds in Ca/N co‐doped δ‐MnO 2 (Ca/N‐MnO 2 ). This co‐doping effect induces a shift in the predominant stretching vibration mode of Mn─O bonds in [MnO 6 ] octahedra, resulting in a decreased d/p‐band center proximity (Δ…

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