Li8MnO6: A Novel Cathode Material with Only Anionic Redox

Luo, Ningjing; Feng, Lianggang; Yin, Huimin; Stein, Andreas; Huang, Shuping; Hou, Zhufeng; Truhlar, Donald G.

doi:10.1021/acsami.2c06173

Title: Li₈MnO₆: A Novel Cathode Material with Only Anionic Redox

Journal Article · Thu Jun 23 00:00:00 EDT 2022 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.2c06173· OSTI ID:2311169

Luo, Ningjing ^[1]; Feng, Lianggang ^[1]; Yin, Huimin ^[1];

^[2];

^[3];

^[4];

^[5]

Fuzhou Univ. (China)
Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United States
Fuzhou Univ. (China); Fujian Provincial Key Laboratory of Electrochemical Energy Storage Materials (China)
Chinese Academy of Sciences (CAS), Fuzhou (China). Fujian Institute of Research on the Structure of Matter
Univ. of Minnesota, Minneapolis, MN (United States)

In Li-excess transition-metal-oxide cathode materials, anionic oxygen redox can offer high capacity and high voltages, although peroxo and superoxo species may cause oxygen loss, poor cycling performance, and capacity fading. Previous work showed that undesirable formation of peroxide and superoxide bonds is controlled to some extent by Mn substitution, and the present work uses density functional calculations to examine the reasons for this by studying the anionic redox mechanism Li₈MnO₆. This material is obtained by substituting Mn for Sn in Li₈SnO₆ or for Zr in Li₈ZrO₆, and we also compare to previous work on those materials. The calculations predict that Li₈MnO₆ is stable at room temperature (with a band gap of 3.19 eV as calculated HSE06 and 1.82 eV as calculated with the less reliable with PBE+U), and they elucidate the chemical and structural effects involved in the inhibition of oxygen release in this cathode. Throughout the whole delithiation process, only O^2- ions are oxidized. The directional Mn-O bonds formed from unfilled 3d orbitals effectively inhibit the formation of O-O bonds, and the layered structure is maintained even after removing 3 Li per Li₈MnO₆ formula unit. The calculated average voltage for removal of 3 Li is 3.69 V by HSE06, and the corresponding capacity is 389 mAh/g. The high voltage of oxygen anionic redox and the high capacity result in a high energy density of 1436 Wh/kg. The Li-ion diffusion barrier for the dominant interlayer diffusion path along the c-axis is 0.57 eV by PBE+U. Finally, these results help us to understand the oxygen redox mechanism in a new lithium-rich Li₈MnO₆ cathode material and contribute to the design of high-energy-density lithium-ion-battery cathode materials with favorable electrochemical properties based on anionic oxygen redox.

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Research Organization:: Univ. of Minnesota, Minneapolis, MN (United States)

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

Grant/Contract Number:: SC0008688; FG02-17ER16362

OSTI ID:: 2311169

Journal Information:: ACS Applied Materials and Interfaces, Vol. 14, Issue 26; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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