Structural Modulation of Cu-Mn-Fe Prussian Blue Analogs for Practical Sodium Ion Cylinder Cells.

Gao, Yun; Zhang, Hang; Peng, Jian; Wang, Jinsong; Liu, Xiaohao; Zhang, Lingling; Xiao, Yao; Li, Li et al. · Adv Mater · 2025

basic_science · Level V

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Abstract

High-performance, cost-effective cathodes are essential for grid-scale sodium-ion batteries (SIBs). Prussian blue analogs (PBAs) have shown great potential as SIB cathodes, but achieving both high capacity and long lifespan remains challenging. In this study, a series of low-cost ternary PBAs synthesized through structural regulation is presented to simultaneously achieve high capacity, stable cycling performance, and broad temperature adaptability. Among them, CuHCF-3 demonstrates a specific capacity of 132.4 mAh g<sup>-1</sup> with 73.3% capacity retention over 1000 cycles. In-depth analyses, using in situ techniques and density functional theory calculations, reveal a highly reversible three-phase transition (monoclinic ↔ cubic ↔ tetragonal) in Na<sub>1.96</sub>Cu<sub>0.45</sub>Mn<sub>0.55</sub>[Fe(CN)<sub>6</sub>]<sub>0.91</sub>·□<sub>0.09</sub>·2.14H<sub>2</sub>O (CuHCF-3), which is driven by synergistic interactions between Mn and Cu. Mn enhances conductivity, increases the operating voltage, and introduces additional redox centers, while Cu mitigates the Jahn-Teller distortions associated with Mn and buffers volume changes during cycling. This structural synergy results in excellent temperature stability across a wide temperature range (-20 to 55 °C). 18650-type cylindrical cells based on CuHCF-3 with high loading density achieve 73.54% capacity retention over 850 cycles. This study offers valuable insights for designing durable, high-capacity electrode materials for SIB energy storage applications.