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An artificial interphase enables reversible magnesium chemistry in carbonate electrolytes

Nature Chemistry volume 10, pages 532–539 (2018)Cite this article

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Abstract

Magnesium-based batteries possess potential advantages over their lithium counterparts. However, reversible Mg chemistry requires a thermodynamically stable electrolyte at low potential, which is usually achieved with corrosive components and at the expense of stability against oxidation. In lithium-ion batteries the conflict between the cathodic and anodic stabilities of the electrolytes is resolved by forming an anode interphase that shields the electrolyte from being reduced. This strategy cannot be applied to Mg batteries because divalent Mg2+ cannot penetrate such interphases. Here, we engineer an artificial Mg2+-conductive interphase on the Mg anode surface, which successfully decouples the anodic and cathodic requirements for electrolytes and demonstrate highly reversible Mg chemistry in oxidation-resistant electrolytes. The artificial interphase enables the reversible cycling of a Mg/V2O5 full-cell in the water-containing, carbonate-based electrolyte. This approach provides a new avenue not only for Mg but also for other multivalent-cation batteries facing the same problems, taking a step towards their use in energy-storage applications.

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Fig. 1: TEM imaging and EDS mapping of the artificial Mg2+-conducting interphase.
Fig. 2: XPS analysis of Mg2+-conducting film.
Fig. 3: Voltage responses of symmetric Mg cells under repeated polarization with and without artificial interphase in different electrolyte systems at a current density of 0.01 mA cm−2.
Fig. 4: TOF-SIMS and TGA analysis of Mg2+-conducting interphase.
Fig. 5: Conductivity measurement of Mg2+-conducting interphase on Mg surface and XPS depth profiles.
Fig. 6: Electrochemical performance of the Mg/V2O5 full cell.

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Acknowledgements

This work was supported by the Laboratory Directed Research and Development (LDRD) programme at the National Renewable Energy Laboratory (NREL). The authors greatly appreciate the constructive suggestions from H. Guthrey and D. H. Kim at NREL. The Alliance for Sustainable Energy, LLC (Alliance), is the manager and operator of NREL. Employees of the Alliance, under contract no. DE-AC36-08GO28308 with the US Department of Energy, authored this work.

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Authors and Affiliations

  1. National Renewable Energy Laboratory, Golden, CO, USA

    Seoung-Bum Son, Steve P. Harvey, Adam Stokes, Andrew Norman & Chunmei Ban

  2. Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD, USA

    Tao Gao & Chunsheng Wang

  3. Department of Physics, Colorado School of Mines, Golden, CO, USA

    K. Xerxes Steirer

  4. Department of Materials Science, Colorado School of Mines, Golden, CO, USA

    Adam Stokes

  5. Electrochemistry Branch, Sensor and Electron Devices Directorate, US Army Research Laboratory, Adelphi, MD, USA

    Arthur Cresce & Kang Xu

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  1. Seoung-Bum Son
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Contributions

S.-B.S. and C.B. developed the protocol for fabricating the Mg2+-conducting interphase on Mg electrodes and performed electrochemical testing. C.B. supervised the work. K.X. synthesized APC electrolyte. T.G and C.W. contributed to the conductivity measurements. S.H. measured and analysed TOF-SIMS spectra of the Mg electrode. K.S. and A.C. measured and analysed XPS spectra of the Mg electrode. A.N. and A.S. performed FIB and STEM-EDS analysis. S.-B.S., C.B., K.X. and C.W. prepared the manuscript.

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Correspondence to Chunmei Ban.

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Supplementary data and characterization, Supplementary Figs. 1–15

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Son, SB., Gao, T., Harvey, S.P. et al. An artificial interphase enables reversible magnesium chemistry in carbonate electrolytes. Nature Chem 10, 532–539 (2018). https://doi.org/10.1038/s41557-018-0019-6

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