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Optimizing Fe in Mn-based Prussian blue analogs with dual redox-active sites to enhance operating voltage and durability in Zn-ion batteries
Citation
Fu, H., Wang, X., Ye, L., Wu, Z., Yang, J., Shi, M., & Ang, E. H. (2025). Optimizing Fe in Mn-based Prussian blue analogs with dual redox-active sites to enhance operating voltage and durability in Zn-ion batteries. Chemical Engineering Journal, 506, Article 160308. https://doi.org/10.1016/j.cej.2025.160308
Abstract
Manganese-based Prussian Blue analogues (Mn PBAs) are emerging as highly promising cathode materials for aqueous zinc-ion storage systems due to their impressive specific capacity. However, the structural instability caused by multi-electron reactions results in a reduced lifespan of charge–discharge cycles. In this study, iron hexacyanoferrate (FeHCF) is incorporated into Mn-PBA using a simple in situ solvent method, with precise control over the FeHCF ratio. The optimized FeHCF concentration not only effectively stabilizes the Mn-PBA framework, addressing issues such as Zn2+ deintercalation stress and Mn dissolution, but also increases the operating voltage range due to the increased of Fe content. The Mn@Fe1-PBA delivers a reversible specific capacity of 119.2 mAh/g over 100 cycles at a current density of 1 A/g when used as a cathode material in aqueous zinc-ion batteries. Additionally, it maintains stable performance for over 3,000 cycles at 5 A/g within a voltage window of 0–2.25 V. The diffusion and redox storage mechanisms of Zn2+ in the Mn@Fe1-PBA cathode are explored through comprehensive kinetic analysis, extensive in situ and ex situ characterizations, and supported by theoretical calculations. These studies reveal that Mn@Fe1-PBA has a low diffusion energy barrier for Zn2+, reaching a peak of 0.58 eV, and operates through a dual redox center mechanism. When integrated with a commercial Zn metal anode, it forms a full cell with stable charge–discharge performance, offering a model for enhancing Mn-PBA in aqueous Zn-ion batteries.
Publisher
Elsevier
Journal
Chemical Engineering Journal
Project
RI 1/21 EAH
RI 3/23 EAH
Grant ID
2023M741471
2022M711686
SJCX24_2512
Funding Agency
China Postdoctoral Science Foundation
Postgraduate Research & Practice Innovation Program of Jiangsu Province
National Institute of Education, Singapore