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Surface-substituted Prussian blue analogue cathode for sustainable potassium-ion batteries

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Abstract

While lithium-ion batteries still dominate energy storage applications, aqueous potassium-ion batteries have emerged as a complementary technology due to their combined advantages in cost and safety. Realizing their full potential, however, is not without challenges. One is that among the limited choices of cathode materials, the more sustainable Prussian blue analogues suffer from fast capacity fading when manganese is present. Here we report a potassium manganese hexacyanoferrate K1.82Mn[Fe(CN)6]0.96·0.47H2O cathode featuring an in situ cation engineered surface where iron is substituted for manganese. With this engineered surface, the cathode design exhibits a discharge capacity of 160 mAh g−1 and 120 mAh g−1 at 300 mA g−1 and 2,500 mA g−1, respectively, and sustains 130,000 cycles (more than 500 days) with negligible capacity loss. Pairing the current cathode with a 3,4,9,10-perylenetetracarboxylic diimide anode yields a full potassium-ion cell that delivers an energy density as high as 92 Wh kg−1 and retains 82.5% of the initial capacity after 6,500 cycles at 1,500 mA g−1. The unprecedented electrochemical performance could be attributed to the suppressed manganese dissolution as a result of the shielding surface layer. This work may open an avenue for the rational design of high-performance cathode materials with redox-active manganese for rechargeable batteries.

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Fig. 1: In situ substitution of Mn with Fe in KMnF.
Fig. 2: The K-storage performance of the KMnF electrode in the modified electrolyte.
Fig. 3: Investigation of the reaction mechanism and in situ Fe substitution.
Fig. 4: Elemental content across the cross-sectional areas of the initial and modified electrodes.
Fig. 5: First-principle calculations and Fe/Mn element content.
Fig. 6: The electrochemical performance of the KMnF//modified electrolyte//PTCDI full battery.

Data availability

The data that support the plots depicted in this manuscript and other findings of this study are available upon request from the corresponding author.

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Acknowledgements

B.L. acknowledges support from the National Natural Science Foundation of China (grant no. U20A2047 and 51922038) and A.M.R. acknowledges funding through the NASA-EPSCoR Award no. NNH17ZHA002C.

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Contributions

B.L. conceived the project. J.G. and B.L. developed the concept. J.G. conducted the experiments and data analysis. J.G., B.L. and A.M.R wrote the manuscript. All authors discussed and commented on the manuscript.

Corresponding author

Correspondence to Bingan Lu.

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Peer review information Nature Sustainability thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary discussion, Figs. 1–34 and Tables 1–10.

Supplementary Video 1

The STEM-EELS surface line of the initial electrode.

Supplementary Video 2

The STEM-EELS surface line of the modified electrode.

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Ge, J., Fan, L., Rao, A.M. et al. Surface-substituted Prussian blue analogue cathode for sustainable potassium-ion batteries. Nat Sustain 5, 225–234 (2022). https://doi.org/10.1038/s41893-021-00810-7

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