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Active cation-integration high-entropy Prussian blue analogues cathodes for efficient Zn storage

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Abstract

Mn-based Prussian blue analogues (Mn-PBAs), featuring a three-dimensional (3D) metal-organic framework and multiple redox couples, have gained wide interests in Zn-ion batteries (ZIBs). However, owing to the Jahn-Teller distortion and disproportionation reaction of Mn3+, these materials suffer from poor electrochemical performances and inferior structural stability. Herein, we prepare a typical high-entropy Prussian blue analogue (HE-PBA) with increased configuration entropy through integrating five transition metal elements of Mn, Co, Ni, Fe and Cu into the nitrogen-coordinated -M- lattice sites. Consequently, the HE-PBA presents enhanced uptake of Zn2+ with 80 mAh·g−1 compared to those medium-entropy PBAs, low-entropy PBAs and conventional PBAs, which can be assigned to “cocktail” effect of multiple transition metal active redox couples. Furthermore, a phase transition process from monoclinic phase to rhombohedral phase occurs in HE-PBA cathode, resulting in a stable structure of MN6 (M = Mn, Co, Fe, Ni, Cu) and ZnN4 co-linked to FeC6 through the cyanide ligands. Additionally, the advantages of entropy-driven stability are also confirmed by the calculated reduction energy and the density of states between HE-PBA and KMn[Fe(CN)6] (KMnHCF). This work not only presents a high-performance HE-PBA cathode in ZIBs, but also introduces a novel concept of high entropy benefiting for designing advanced materials.

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Acknowledgements

The authors sincerely acknowledge the financial support received from the National Natural Science Foundation of China (Nos. 21908204, 52074244, 2022TQ0285 and 52206282) and the Center of Advanced Analysis & Computational Science, Zhengzhou University for their characterization.

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  1. Jiangyuan Xing and Yongsheng Zhang contributed equally to this work.

Authors and Affiliations

  1. School of Chemical Engineering, Zhengzhou University, Zhengzhou, 450001, China

    Jiangyuan Xing & Yongsheng Zhang

  2. School of Electrical Engineering, Zhengzhou University, Zhengzhou, 450001, China

    Yang Jin & Qianzheng Jin

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  1. Jiangyuan Xing
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  2. Yongsheng Zhang
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Correspondence to Qianzheng Jin.

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Xing, J., Zhang, Y., Jin, Y. et al. Active cation-integration high-entropy Prussian blue analogues cathodes for efficient Zn storage. Nano Res. 16, 2486–2494 (2023). https://doi.org/10.1007/s12274-022-5020-0

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