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Electrochemical Reduction of a Spinel-Type Manganese Oxide Cathode in Aqueous Electrolytes with Ca2+ or Zn2+

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Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States
Joint Center for Energy Storage Research, Argonne National Laboratory, Argonne, Illinois 60439, United States
§ X-ray Science Division Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United States
Cite this: J. Phys. Chem. C 2018, 122, 8, 4182–4188
Publication Date (Web):February 6, 2018
Copyright © 2018 American Chemical Society

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    In this report, the feasibility of reversible Ca2+ or Zn2+ intercalation into a crystalline cubic spinel Mn2O4 cathode has been investigated using electrochemical methods in an aqueous electrolyte. A combination of synchrotron XRD and XANES studies identified the partial structural transformation from a cubic to a tetragonally distorted spinel Mn3O4, accompanied by the reduction of Mn4+ to Mn3+ and Mn2+ during discharge. TEM/EDX measurements confirmed that practically no Ca2+ was inserted upon discharge. However, non-negligible amounts of Zn were detected after Mn2O4 was reduced in the Zn2+ electrolyte, but through the formation of secondary phases that, in some cases, appeared adjacent to the surface of a cathode particle. This report aims to identify bottlenecks in the application of manganese oxide cathodes paired with Ca or Zn metal anodes and to justify future efforts in designing prototype multivalent batteries.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.7b12084.

    • Supplemental results of electrochemical, powder X-ray diffraction, and electron microscopy images that support this work. (PDF)

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