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

Abstract

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. Furthermore 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.

Authors:
 [1];  [2]; ORCiD logo [1];  [1];  [1];  [3];  [2];  [1];  [3];  [1];  [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Illinois at Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Univ. of Illinois at Chicago, Chicago, IL (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1481175
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 8; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Mg2+ intercalation; PDF; multivalent electrochemistry; nanocrystals; spinel-layered transition

Citation Formats

Nolis, Gene M., Adil, Abdullah, Yoo, Hyun Deog, Hu, Linhua, Bayliss, Ryan D., Lapidus, Saul H., Berkland, Lisa, Phillips, Patrick J., Freeland, John W., Kim, Chunjoong, Klie, Robert F., and Cabana, Jordi. Electrochemical Reduction of a Spinel-Type Manganese Oxide Cathode in Aqueous Electrolytes with Ca2+ or Zn2+. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.7b12084.
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Nolis, Gene M., Adil, Abdullah, Yoo, Hyun Deog, Hu, Linhua, Bayliss, Ryan D., Lapidus, Saul H., Berkland, Lisa, Phillips, Patrick J., Freeland, John W., Kim, Chunjoong, Klie, Robert F., & Cabana, Jordi. Electrochemical Reduction of a Spinel-Type Manganese Oxide Cathode in Aqueous Electrolytes with Ca2+ or Zn2+. United States. https://doi.org/10.1021/acs.jpcc.7b12084
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Nolis, Gene M., Adil, Abdullah, Yoo, Hyun Deog, Hu, Linhua, Bayliss, Ryan D., Lapidus, Saul H., Berkland, Lisa, Phillips, Patrick J., Freeland, John W., Kim, Chunjoong, Klie, Robert F., and Cabana, Jordi. Tue . "Electrochemical Reduction of a Spinel-Type Manganese Oxide Cathode in Aqueous Electrolytes with Ca2+ or Zn2+". United States. https://doi.org/10.1021/acs.jpcc.7b12084. https://www.osti.gov/servlets/purl/1481175.
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@article{osti_1481175,
title = {Electrochemical Reduction of a Spinel-Type Manganese Oxide Cathode in Aqueous Electrolytes with Ca2+ or Zn2+},
author = {Nolis, Gene M. and Adil, Abdullah and Yoo, Hyun Deog and Hu, Linhua and Bayliss, Ryan D. and Lapidus, Saul H. and Berkland, Lisa and Phillips, Patrick J. and Freeland, John W. and Kim, Chunjoong and Klie, Robert F. and Cabana, Jordi},
abstractNote = {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. Furthermore 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.},
doi = {10.1021/acs.jpcc.7b12084},
journal = {Journal of Physical Chemistry. C},
number = 8,
volume = 122,
place = {United States},
year = {Tue Feb 06 00:00:00 EST 2018},
month = {Tue Feb 06 00:00:00 EST 2018}
}
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https://doi.org/10.1021/acs.jpcc.7b12084
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    Progress in Rechargeable Aqueous Zinc- and Aluminum-Ion Battery Electrodes: Challenges and Outlook
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