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Surface Gradient Doping Enables High‐Capacity and Long‐Life Manganese‐Based Prussian Blue Cathodes for Sodium‐Ion Batteries
发布时间:2026-09-04 点击次数:

DOI码:10.1002/ange.6338402

发表刊物:Angewandte Chemie

摘要:Manganese-based Prussian blue analogues (MnPBAs) are attractive cathodes for sodium-ion batteries (SIBs) due to their high operating voltage, low cost, and sustainability. However, their practical deployment is limited by rapid capacity decay caused by Jahn–Teller distortion and phase-transition-induced lattice strain, which trigger Mn dissolution and structural collapse during cycling. Herein, we introduce a surface Cu concentration-gradient-doped MnPBA (Cu@MnPBA) synthesized via a two-step coprecipitation strategy to stabilize the MnPBA framework while preserving high capacity. A ∼200 nm Cu-gradient surface layer effectively suppresses Jahn–Teller distortion, reduces lattice strain, and inhibits Mn dissolution, while an outer ∼10 nm Cu-rich amorphous layer enhances Na+ surface diffusion and suppresses interfacial side reactions. Unlike conventional coating strategies, the gradient-doping architecture eliminates interfacial mismatch, ensuring robust structural integrity during prolonged cycling. As a result, Cu@MnPBA delivers a high specific capacity of 143.9 mAh g−1 and retains 78% of its capacity after 500 cycles at 100 mA g−1. When paired with a hard carbon anode in a pouch cell configuration, the system maintains 75% capacity after 3000 cycles, demonstrating exceptional durability under practical operating conditions. This work establishes gradient surface doping as an effective design principle for realizing high-capacity, long-life Prussian blue cathodes for SIBs.

论文类型:期刊论文

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发表时间:2026-07-13

发布期刊链接:https://onlinelibrary.wiley.com/doi/abs/10.1002/ange.6338402