Quantifying the Capacity Contributions during Activation of Li2MnO3
Abstract
Though Li2MnO3 was originally considered to be electrochemically inert, its observed activation has spawned a new class of Li-rich layered compounds that deliver capacities beyond the traditional transition-metal redox limit. Despite progress in our understanding of oxygen redox in Li-rich compounds, the underlying origin of the initial charge capacity of Li2MnO3 remains hotly contested. To resolve this issue, we review all possible charge compensation mechanisms including bulk oxygen redox, oxidation of Mn4+, and surface degradation for Li2MnO3 cathodes displaying capacities exceeding 350 mAh g–1. Using elemental and orbital selective X-ray spectroscopy techniques, we rule out oxidation of Mn4+ and bulk oxygen redox during activation of Li2MnO3. Quantitative gas-evolution and titration studies reveal that O2 and CO2 release accounted for a large fraction of the observed capacity during activation with minor contributions from reduced Mn species on the surface. Lastly, these studies reveal that, although Li2MnO3 is considered critical for promoting bulk anionic redox in Li-rich layered oxides, Li2MnO3 by itself does not exhibit bulk oxygen redox or manganese oxidation beyond its initial Mn4+ valence.
- Authors:
-
[1];
[2];
[6];
[2];
[1]
- Binghamton Univ., NY (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Binghamton Univ., NY (United States). NorthEast Center for Chemical Energy Storage (NECCES)
- Univ. of Muenster (Germany). MEET Battery Research Center, Institute of Physical Chemistry
- Helmholtz-Institute Muenster (Germany)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Binghamton Univ., NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1596994
- Grant/Contract Number:
- SC0012583; AC02-05CH11231; SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Energy Letters
- Additional Journal Information:
- Journal Volume: 5; Journal Issue: 2; Journal ID: ISSN 2380-8195
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Rana, Jatinkumar, Papp, Joseph K., Lebens-Higgins, Zachary, Zuba, Mateusz, Kaufman, Lori A., Goel, Anshika, Schmuch, Richard, Winter, Martin, Whittingham, M. Stanley, Yang, Wanli, McCloskey, Bryan D., and Piper, Louis F. J. Quantifying the Capacity Contributions during Activation of Li2MnO3. United States: N. p., 2020.
Web. doi:10.1021/acsenergylett.9b02799.
Rana, Jatinkumar, Papp, Joseph K., Lebens-Higgins, Zachary, Zuba, Mateusz, Kaufman, Lori A., Goel, Anshika, Schmuch, Richard, Winter, Martin, Whittingham, M. Stanley, Yang, Wanli, McCloskey, Bryan D., & Piper, Louis F. J. Quantifying the Capacity Contributions during Activation of Li2MnO3. United States. https://doi.org/10.1021/acsenergylett.9b02799
Rana, Jatinkumar, Papp, Joseph K., Lebens-Higgins, Zachary, Zuba, Mateusz, Kaufman, Lori A., Goel, Anshika, Schmuch, Richard, Winter, Martin, Whittingham, M. Stanley, Yang, Wanli, McCloskey, Bryan D., and Piper, Louis F. J. Mon .
"Quantifying the Capacity Contributions during Activation of Li2MnO3". United States. https://doi.org/10.1021/acsenergylett.9b02799. https://www.osti.gov/servlets/purl/1596994.
@article{osti_1596994,
title = {Quantifying the Capacity Contributions during Activation of Li2MnO3},
author = {Rana, Jatinkumar and Papp, Joseph K. and Lebens-Higgins, Zachary and Zuba, Mateusz and Kaufman, Lori A. and Goel, Anshika and Schmuch, Richard and Winter, Martin and Whittingham, M. Stanley and Yang, Wanli and McCloskey, Bryan D. and Piper, Louis F. J.},
abstractNote = {Though Li2MnO3 was originally considered to be electrochemically inert, its observed activation has spawned a new class of Li-rich layered compounds that deliver capacities beyond the traditional transition-metal redox limit. Despite progress in our understanding of oxygen redox in Li-rich compounds, the underlying origin of the initial charge capacity of Li2MnO3 remains hotly contested. To resolve this issue, we review all possible charge compensation mechanisms including bulk oxygen redox, oxidation of Mn4+, and surface degradation for Li2MnO3 cathodes displaying capacities exceeding 350 mAh g–1. Using elemental and orbital selective X-ray spectroscopy techniques, we rule out oxidation of Mn4+ and bulk oxygen redox during activation of Li2MnO3. Quantitative gas-evolution and titration studies reveal that O2 and CO2 release accounted for a large fraction of the observed capacity during activation with minor contributions from reduced Mn species on the surface. Lastly, these studies reveal that, although Li2MnO3 is considered critical for promoting bulk anionic redox in Li-rich layered oxides, Li2MnO3 by itself does not exhibit bulk oxygen redox or manganese oxidation beyond its initial Mn4+ valence.},
doi = {10.1021/acsenergylett.9b02799},
journal = {ACS Energy Letters},
number = 2,
volume = 5,
place = {United States},
year = {2020},
month = {1}
}
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