Quantifying the Capacity Contributions during Activation of Li2MnO3

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.

doi:10.1021/acsenergylett.9b02799

Title: Quantifying the Capacity Contributions during Activation of Li₂MnO₃

Journal Article · Mon Jan 27 00:00:00 EST 2020 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.9b02799· OSTI ID:1596994

^[1];

^[2]; Lebens-Higgins, Zachary ^[1]; Zuba, Mateusz ^[1]; Kaufman, Lori A. ^[2]; Goel, Anshika ^[3]; Schmuch, Richard ^[4]; Winter, Martin ^[5]; Whittingham, M. Stanley ^[3];

^[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)

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.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Binghamton Univ., NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012583; AC02-05CH11231; SC0012704

OSTI ID:: 1596994

Journal Information:: ACS Energy Letters, Vol. 5, Issue 2; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 87 works

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Title: Quantifying the Capacity Contributions during Activation of Li₂MnO₃