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

Abstract

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,more »« less

Authors:

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)

Publication Date:: Thu Jun 23 00:00:00 EDT 2022

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

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

OSTI Identifier:: 2311169

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

Resource Type:: Accepted Manuscript

Journal Name:: ACS Applied Materials and Interfaces

Additional Journal Information:: Journal Volume: 14; Journal Issue: 26; Journal ID: ISSN 1944-8244

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; anionic oxygen redox; battery; cathode; energy storage; lithium-ion battery; Li8MnO6

Citation Formats


                    Luo, Ningjing, Feng, Lianggang, Yin, Huimin, Stein, Andreas, Huang, Shuping, Hou, Zhufeng, and Truhlar, Donald G. Li8MnO6: A Novel Cathode Material with Only Anionic Redox.  United States: N. p., 2022. 
Web.  doi:10.1021/acsami.2c06173.

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                    Luo, Ningjing, Feng, Lianggang, Yin, Huimin, Stein, Andreas, Huang, Shuping, Hou, Zhufeng, & Truhlar, Donald G. Li8MnO6: A Novel Cathode Material with Only Anionic Redox.  United States.  https://doi.org/10.1021/acsami.2c06173

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                    Luo, Ningjing, Feng, Lianggang, Yin, Huimin, Stein, Andreas, Huang, Shuping, Hou, Zhufeng, and Truhlar, Donald G. Thu .  
"Li8MnO6: A Novel Cathode Material with Only Anionic Redox".  United States.  https://doi.org/10.1021/acsami.2c06173.  https://www.osti.gov/servlets/purl/2311169.

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@article{osti_2311169,

  title        = {Li8MnO6: A Novel Cathode Material with Only Anionic Redox},

  author       = {Luo, Ningjing and Feng, Lianggang and Yin, Huimin and Stein, Andreas and Huang, Shuping and Hou, Zhufeng and Truhlar, Donald G.},

  abstractNote = {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 O2- 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.},

  doi          = {10.1021/acsami.2c06173},

  journal      = {ACS Applied Materials and Interfaces},

  number       = 26,

  volume       = 14,

  place        = {United States},

  year         = {Thu Jun 23 00:00:00 EDT 2022},

  month        = {Thu Jun 23 00:00:00 EDT 2022}

}

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Highly reversible oxygen redox in layered compounds enabled by surface polyanions

Journal Article Chen, Qing ; Pei, Yi ; Chen, Houwen ; ... - Nature Communications

Oxygen-anion redox in lithium-rich layered oxides can boost the capacity of lithium-ion battery cathodes. However, the over-oxidation of oxygen at highly charged states aggravates irreversible structure changes and deteriorates cycle performance. Here, we investigate the mechanism of surface degradation caused by oxygen oxidation and the kinetics of surface reconstruction. Considering Li₂MnO₃, we show through density functional theory calculations that a high energy orbital (lO_2p’) at under-coordinated surface oxygen prefers over-oxidation over bulk oxygen, and that surface oxygen release is then kinetically favored during charging. We use a simple strategy of turning under-coordinated surface oxygen into polyanionic (SO₄)^2-, and show thatmore »« less
https://doi.org/10.1038/s41467-020-17126-3

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A review of rechargeable batteries for portable electronic devices
journal, March 2019

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journal, January 2017

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journal, August 2018

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journal, August 1994

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journal, April 1997

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journal, January 1991

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journal, April 2018

A review on progress of lithium-rich manganese-based cathodes for lithium ion batteries
journal, March 2021

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journal, March 2013

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journal, November 2008

Factors affecting Li mobility in spinel LiMn2O4—A first-principles study by GGA and GGA+U methods
journal, August 2010

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journal, September 2016

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journal, November 2015

New O2/P2-type Li-Excess Layered Manganese Oxides as Promising Multi-Functional Electrode Materials for Rechargeable Li/Na Batteries
journal, May 2014

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journal, July 2001

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journal, January 2013

Understanding the Roles of Anionic Redox and Oxygen Release during Electrochemical Cycling of Lithium-Rich Layered Li ₄ FeSbO ₆
journal, April 2015

High-capacity electrode materials for rechargeable lithium batteries: Li ₃ NbO ₄ -based system with cation-disordered rocksalt structure
journal, June 2015

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journal, August 2015

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journal, January 2021

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journal, April 2019

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journal, July 2019

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journal, January 2016

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journal, September 2019

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journal, November 2020

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journal, May 2016

Interplay of cation and anion redox in Li ₄ Mn ₂ O ₅ cathode material and prediction of improved Li ₄ (Mn,M) ₂ O ₅ electrodes for Li-ion batteries
journal, May 2018

Synthesis and electrochemistry of Li3MnO4: Mn in the +5 oxidation state
journal, October 2007

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journal, March 2016

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

Generalized Gradient Approximation Made Simple
journal, October 1996

Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006

Hybrid density functional calculations of redox potentials and formation energies of transition metal compounds
journal, August 2010

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

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journal, August 1995

Rotationally invariant ab initio evaluation of Coulomb and exchange parameters for DFT+U calculations
journal, July 2008

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journal, May 2016

Efficacy of the DFT + $U$ formalism for modeling hole polarons in perovskite oxides
journal, July 2014

DFT+ $U$ study of self-trapping, trapping, and mobility of oxygen-type hole polarons in barium stannate
journal, October 2017

Vacancies and small polarons in ${SrTiO}_{3}$
journal, August 2014

Polaronic contributions to oxidation and hole conductivity in acceptor-doped ${BaZrO}_{3}$
journal, August 2016

Polaronic trapping of electrons and holes by native defects in anatase ${TiO}_{2}$
journal, December 2009

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journal, March 2021

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journal, February 2012

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journal, November 2009

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journal, January 1999

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journal, June 1976

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journal, October 1999

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journal, December 2000

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journal, October 2011

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journal, February 2013

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journal, December 2015

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journal, July 2013

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journal, April 2018

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journal, November 2014

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journal, February 2012

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journal, January 2013

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journal, March 2020