Reversible aqueous zinc/manganese oxide energy storage from conversion reactions

Abstract

Rechargeable aqueous batteries such as alkaline zinc/manganese oxide batteries are highly desirable for large-scale energy storage owing to their low cost and high safety; however, cycling stability is a major issue for their applications. Here we demonstrate a highly reversible zinc/manganese oxide system in which optimal mild aqueous ZnSO4-based solution is used as the electrolyte, and nanofibres of a manganese oxide phase, α-MnO2, are used as the cathode. We show that a chemical conversion reaction mechanism between α-MnO2 and H+ is mainly responsible for the good performance of the system. This includes an operating voltage of 1.44 V, a capacity of 285 mAh g−1 (MnO2), and capacity retention of 92% over 5,000 cycles. The Zn metal anode also shows high stability. This finding opens new opportunities for the development of low-cost, high-performance rechargeable aqueous batteries.

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Figure 1: Structural and morphological characterization of MnO2.
Figure 2: Electrochemical behaviours of Zn/MnO2 batteries with 2 M ZnSO4 as electrolyte.
Figure 3: Improved electrochemical performance of Zn/MnO2 batteries in optimal aqueous electrolyte.
Figure 4: TEM/HRTEM images of MnO2 electrodes during electrochemical process.
Figure 5: Characterization of Zn anode electrodes.

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Acknowledgements

This work is supported by the US Department of Energy (DOE), Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under Award KC020105-FWP12152. The TEM, NMR and XRD work were performed using EMSL, a National Scientific User Facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at PNNL. PNNL is a Multi-Program National Laboratory operated for DOE by Battelle. The work at UW was supported by Inamori Foundation.

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Y.S. and J.L. proposed the research. H.P., Y.S. and J.L. designed the experiments. H.P. and Y.S. performed the material process, characterization, electrochemical measurements and analysed the data. Y.C. synthesized the material. P.Y., Y.C. and C.W. conducted the TEM and STEM mapping. K.S.H. and K.T.M. performed NMR characterization. H.P., Y.S. and J.L. co-wrote the paper. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Yuyan Shao or Jun Liu.

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The authors declare no competing financial interests.

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Supplementary Figures 1–9, Supplementary Discussion, Supplementary References. (PDF 949 kb)

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Pan, H., Shao, Y., Yan, P. et al. Reversible aqueous zinc/manganese oxide energy storage from conversion reactions. Nat Energy 1, 16039 (2016). https://doi.org/10.1038/nenergy.2016.39

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