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Title: Multivalent Electrochemistry of Spinel MgxMn3–xO4 Nanocrystals

Abstract

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. Lastly, 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 withmore » high energy.« less

Authors:
 [1];  [2];  [2];  [3];  [3];  [2];  [3];  [4];  [2]; ORCiD logo [2];  [2];  [5];  [4];  [3]; ORCiD logo [3]; ORCiD logo [2]
+ Show Author Affiliations
  1. Univ. of Illinois at Chicago, Chicago, IL (United States); Chungnam National Univ., Daejeon (South Korea); Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Univ. of Illinois at Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States)
  4. Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Illinois at Chicago, Chicago, IL (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (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:
1461417
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 5; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Mg2+ intercalation; PDF; multivalent electrochemistry; nanocrystals; spinel-layered transition

Citation Formats

Kim, Chunjoong, Adil, Abdullah A., Bayliss, Ryan D., Kinnibrugh, Tiffany L., Lapidus, Saul H., Nolis, Gene M., Freeland, John W., Phillips, Patrick J., Yi, Tanghong, Yoo, Hyun Deog, Kwon, Bob Jin, Yu, Young -Sang, Klie, Robert, Chupas, Peter J., Chapman, Karena W., and Cabana, Jordi. Multivalent Electrochemistry of Spinel MgxMn3–xO4 Nanocrystals. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.7b03640.
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Kim, Chunjoong, Adil, Abdullah A., Bayliss, Ryan D., Kinnibrugh, Tiffany L., Lapidus, Saul H., Nolis, Gene M., Freeland, John W., Phillips, Patrick J., Yi, Tanghong, Yoo, Hyun Deog, Kwon, Bob Jin, Yu, Young -Sang, Klie, Robert, Chupas, Peter J., Chapman, Karena W., & Cabana, Jordi. Multivalent Electrochemistry of Spinel MgxMn3–xO4 Nanocrystals. United States. https://doi.org/10.1021/acs.chemmater.7b03640
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Kim, Chunjoong, Adil, Abdullah A., Bayliss, Ryan D., Kinnibrugh, Tiffany L., Lapidus, Saul H., Nolis, Gene M., Freeland, John W., Phillips, Patrick J., Yi, Tanghong, Yoo, Hyun Deog, Kwon, Bob Jin, Yu, Young -Sang, Klie, Robert, Chupas, Peter J., Chapman, Karena W., and Cabana, Jordi. Tue . "Multivalent Electrochemistry of Spinel MgxMn3–xO4 Nanocrystals". United States. https://doi.org/10.1021/acs.chemmater.7b03640. https://www.osti.gov/servlets/purl/1461417.
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@article{osti_1461417,
title = {Multivalent Electrochemistry of Spinel MgxMn3–xO4 Nanocrystals},
author = {Kim, Chunjoong and Adil, Abdullah A. and Bayliss, Ryan D. and Kinnibrugh, Tiffany L. and Lapidus, Saul H. and Nolis, Gene M. and Freeland, John W. and Phillips, Patrick J. and Yi, Tanghong and Yoo, Hyun Deog and Kwon, Bob Jin and Yu, Young -Sang and Klie, Robert and Chupas, Peter J. and Chapman, Karena W. and Cabana, Jordi},
abstractNote = {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. Lastly, 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.},
doi = {10.1021/acs.chemmater.7b03640},
journal = {Chemistry of Materials},
number = 5,
volume = 30,
place = {United States},
year = {Tue Feb 20 00:00:00 EST 2018},
month = {Tue Feb 20 00:00:00 EST 2018}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.chemmater.7b03640
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Cited by: 20 works
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Figures / Tables:

Figure 1 Figure 1: Figure 1. (a) Schematic of reaction process, representative TEM images, and (b) Rietveld refinement fit of synchrotron powder X-ray diffraction pattern of the Mg0.5Mn2.5O4 nanocrystals as synthesized. (c) Rietveld refinement fit of synchrotron powder X-ray diffraction pattern of a saple after one oxidation-reduction cycle. Diffraction was originally collectedmore » by high-energy X-rays (λ = 0.459 Å) and then converted to the energy of averaged Cu Kα (λ = 1.5418 Å), in order to enable comparison with other figures.« less
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    Works referencing / citing this record:

    Tailoring the electrochemical activity of magnesium chromium oxide towards Mg batteries through control of size and crystal structure
    journal, January 2019

    • Hu, Linhua; Johnson, Ian D.; Kim, Soojeong
    • Nanoscale, Vol. 11, Issue 2
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    Hierarchical porosity via layer-tunnel conversion of macroporous δ-MnO 2 nanosheet assemblies
    journal, January 2020

    • Metz, Peter C.; Ladonis, Alec C.; Gao, Peng
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