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Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries

Nature Sustainability volume 5, pages 890–898 (2022)Cite this article

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Abstract

Rechargeable aqueous Zn–MnO2 technology combines one of the oldest battery chemistries with favourable sustainability characteristics, including safety, cost and environmental compatibility. However, the ambiguous charge storage mechanism presents a challenge to fulfil the great potential of this energy technology. Here we leverage on advanced electron microscopy, electrochemical analysis and theoretical calculations to look into the intercalation chemistry within the cathode material, or α-MnO2 more specifically. We show that Zn2+ insertion into the cathode is unlikely in the aqueous system; rather, the charge storage process is dominated by proton intercalation to form α-HxMnO2. We further reveal anisotropic lattice change as a result of entering protons proceeding from the surface into the bulk of α-MnO2, which accounts for the structural failure and capacity decay of the electrode upon cycling. Our work not only advances the fundamental understanding of rechargeable zinc batteries but also suggests the possibility to optimize proton intercalation kinetics for better-performing cell designs.

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Fig. 1: Structure analysis and battery performance of α-MnO2.
Fig. 2: STEM analysis of discharged α-MnO2 nanowires.
Fig. 3: Atomistic modelling of H+ (versus Zn2+) insertion.
Fig. 4: Morphological/structural analysis of the α-MnO2 electrode during long cycling conditions.

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Data availability

All relevant data that support the findings of this study are presented in the article and Supplementary Information. Source data are available from the corresponding authors upon reasonable request.

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Acknowledgements

The experimental work is primarily supported by the funds from the US National Science Foundation (NSF) under CBET-1805938 and Argonne National Laboratory. Additional supports were provided to Y.Y. by the Natural Science Foundation of China (grant no. 52002287). R.S.-Y., Y.Y., M.C., M.T.S. and W.Y. are thankful to NSF CBET-1805938. R.S. and M.S.I. thank the EPSRC (LiBatt programme grant EP/M0009521/1) and the Faraday Institution (CATMAT project FIRG016, FIRG035) for financial support, and the HEC Materials Chemistry Consortium (EP/R029431), the Isambard HPC (EP/P020224/1) and the Balena HPC service (Bath) for supercomputer facilities. R.S. and M.S.I. gratefully acknowledge useful discussions with P. Zarabadi-Poor (Oxford), L. Morgan (Bath), K. McColl (Bath), M. J. Clarke (Bath) and J. Dawson (Newcastle). Work at Argonne National Laboratory was supported by the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357. Use of the Advanced Photon Source (APS) {Beamline 9-BM} at Argonne National Laboratory, Office of Science user facility, was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. This work made use of instruments in the Electron Microscopy Service (Research Resources Center, UIC). We acknowledge Quantitative Bio-element Imaging Center (QBIC) at Northwestern University (US) for assistance of ICP measurement. We acknowledge Thermo Fisher Scientific’s Shanghai Nanoport, particularly S. Liu, for their consultative help in atomic imaging of light atoms using electron microscopy.

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Author notes

  1. These authors contributed equally: Yifei Yuan, Ryan Sharpe.

Authors and Affiliations

  1. College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, China

    Yifei Yuan, Kun He, Chenghang Li, Huile Jin & Shun Wang

  2. Department of Mechanical and Industrial Engineering, University of Illinois at Chicago, Chicago, IL, USA

    Yifei Yuan, Kun He, Mahmoud Tamadoni Saray, Wentao Yao, Meng Cheng & Reza Shahbazian-Yassar

  3. Department of Chemistry, University of Bath, Bath, UK

    Ryan Sharpe & M. Saiful Islam

  4. Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA

    Tongchao Liu, Khalil Amine & Jun Lu

  5. Department of Materials, University of Oxford, Oxford, UK

    M. Saiful Islam

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Contributions

Y.Y. initiated the experimental design and wrote the manuscript with R.S., M.S.I, K.H., R.S.-Y. and J.L. Y.Y. and R.S.-Y. designed the microscopy experiments, which were carried out and analysed by Y.Y., K.H., M.T.S. and M.C. Y.Y., C.L., T.L., W.Y. and K.A. carried out electrochemical experiments and data analyses. H.J. and S.W. contributed to discussions and offered guidance to the electrochemical data analysis. R.S. and M.S.I. designed, carried out and analysed the DFT calculations. Y.Y. and T.L. carried out synchrotron X-ray experiments. All authors contributed to the results discussion and writing of the manuscript.

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Correspondence to Kun He, Reza Shahbazian-Yassar, M. Saiful Islam or Jun Lu.

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Nature Sustainability thanks Dipan Kundu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–17, Tables 1–4 and Discussion.

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Yuan, Y., Sharpe, R., He, K. et al. Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries. Nat Sustain 5, 890–898 (2022). https://doi.org/10.1038/s41893-022-00919-3

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