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Deciphering charge-storage mechanisms in 3D MnOx@carbon electrode nanoarchitectures for rechargeable zinc-ion cells

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Abstract

We previously demonstrated that electrode architectures comprising nanoscale birnessite-like MnOx affixed to three-dimensional carbon nanofoam (CNF) scaffolds offer performance advantages when used as cathodes in rechargeable zinc-ion cells. To discern chemical and physical changes at the Mn0x@CNF electrode upon deep charge/discharge in aqueous Zn2+-containing electrolytes, we deploy electroanalytical methods and ex situ characterization by microscopy, elemental analysis, x-ray photoelectron spectroscopy, x-ray diffraction, and x-ray pair distribution function analyses. Our findings verify that redox processes at the MnOx are accompanied by reversible precipitation/dissolution of crystalline zinc hydroxide sulfate (Zn4(0H)6(S04)·xH20), mediated by the more uniformly reactive electrode structure inherent to the CNF scaffold.

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Acknowledgments

This work was supported by the U.S. Office of Naval Research. J.S.K. is an NRL-NRC Postdoctoral Associate (2016-2018). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The authors would like to thank Dr. Olaf Borkiewicz of Argonne National Laboratory for data acquisition, integration, and assistance.

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Authors and Affiliations

  1. Naval Research Laboratory-National Research Council Postdoctoral Associate, Washington, DC, 20375, USA

    Jesse S. Ko

  2. Exponent, Inc., 9 Strathmore Road, Natick, Massachusetts, 01760, USA

    Martin D. Donakowski

  3. U.S. Naval Research Laboratory, Surface Chemistry Branch, Code 6170, Washington, DC, 20375, USA

    Megan B. Sassin, Joseph F. Parker, Debra R. Rolison & Jeffrey W. Long

Authors
  1. Jesse S. Ko
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  2. Martin D. Donakowski
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  3. Megan B. Sassin
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  4. Joseph F. Parker
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  5. Debra R. Rolison
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  6. Jeffrey W. Long
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Corresponding author

Correspondence to Jeffrey W. Long.

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The supplementary material for this article can be found at https://doi.org/10.1557/mrc.2019.3.

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Ko, J.S., Donakowski, M.D., Sassin, M.B. et al. Deciphering charge-storage mechanisms in 3D MnOx@carbon electrode nanoarchitectures for rechargeable zinc-ion cells. MRS Communications 9, 99–106 (2019). https://doi.org/10.1557/mrc.2019.3

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  • DOI: https://doi.org/10.1557/mrc.2019.3

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