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Multivalent Electrochemistry of Spinel MgxMn3–xO4 Nanocrystals

  • Chunjoong Kim
    Chunjoong Kim
    Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States
    Department of Materials Science and Engineering, Chungnam National University, Daejeon, South Korea
    Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
  • Abdullah A. Adil
    Abdullah A. Adil
    Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States
    Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
  • Ryan D. Bayliss
    Ryan D. Bayliss
    Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States
    Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
  • Tiffany L. Kinnibrugh
    Tiffany L. Kinnibrugh
    X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Lemont, Illinois 60439, United States
  • Saul H. Lapidus
    Saul H. Lapidus
    X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Lemont, Illinois 60439, United States
  • Gene M. Nolis
    Gene M. Nolis
    Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States
    Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
  • John W. Freeland
    John W. Freeland
    X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Lemont, Illinois 60439, United States
  • Patrick J. Phillips
    Patrick J. Phillips
    Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
    Department of Physics, University of Illinois at Chicago, Chicago, Illinois 60607, United States
  • Tanghong Yi
    Tanghong Yi
    Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States
    Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
    More by Tanghong Yi
  • Hyun Deog Yoo
    Hyun Deog Yoo
    Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States
    Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
  • Bob Jin Kwon
    Bob Jin Kwon
    Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States
    Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
    More by Bob Jin Kwon
  • Young-Sang Yu
    Young-Sang Yu
    Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  • Robert Klie
    Robert Klie
    Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
    Department of Physics, University of Illinois at Chicago, Chicago, Illinois 60607, United States
    More by Robert Klie
  • Peter J. Chupas
    Peter J. Chupas
    X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Lemont, Illinois 60439, United States
  • Karena W. Chapman
    Karena W. Chapman
    X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Lemont, Illinois 60439, United States
  • , and 
  • Jordi Cabana*
    Jordi Cabana
    Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States
    Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
    *E-mail: [email protected]
    More by Jordi Cabana
Cite this: Chem. Mater. 2018, 30, 5, 1496–1504
Publication Date (Web):February 20, 2018
https://doi.org/10.1021/acs.chemmater.7b03640
Copyright © 2018 American Chemical Society

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    Abstract

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    Oxides undergoing reversible electrochemical cycling of Mg2+ ions would enable novel battery concepts beyond Li+, capable of storing large amounts of energy. However, materials showing this chemical reactivity are scarce. Suitable candidates require small particles to shorten transport lengths, together with chemically complex structures that promote cation mobility, such as spinel. These goals pose a challenge for materials chemists. Here, nanocrystals of spinel-type Mg0.5Mn2.5O4 were prepared using colloidal synthesis, and their electrochemical activity is presented. Cycling in an aqueous Mg2+ electrolyte led to a reversible transformation between a reduced spinel and an oxidized layered framework. This reaction involves large amounts of capacity because of the full oxidation to Mn4+, through the extraction of both Mg2+ and, in the first cycle, Mn2+ ions. Re-formation of the spinel upon reduction resulted in enrichment with Mg2+, indicating that its insertion is more favorable than that of Mn2+. Incorporation of water into the structure was not indispensable for the transformation, as revealed by experiments in non-aqueous electrolytes and infrared spectroscopy. The findings open the door for the use of similar nanocrystals in Mg batteries provided that electrolytes with suitable anodic stability are discovered, thereby identifying novel routes toward electrode materials for batteries with high energy.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.7b03640.

    • Material characterization and electrochemical properties (XRD, TEM, PDF, LSV, and GCPL) (PDF)

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    This article is cited by 23 publications.

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