skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

Significant research effort has focused on improving the specific energy of lithium-ion batteries for emerging applications, such as electric vehicles. Recently, a rock salt–type Li 4Mn 2O 5 cathode material with a large discharge capacity (~350 mA·hour g –1) was discovered. However, a full structural model of Li 4Mn 2O 5 and its corresponding phase transformations, as well as the atomistic origins of the high capacity, warrants further investigation. We use first-principles density functional theory (DFT) calculations to investigate both the disordered rock salt–type Li 4Mn 2O 5 structure and the ordered ground-state structure. The ionic ordering in the ground-state structure is determined via a DFT-based enumeration method. We use both the ordered and disordered structures to interrogate the delithiation process and find that it occurs via a three-step reaction pathway involving the complex interplay of cation and anion redox reactions: (i) an initial metal oxidation, Mn 3+→Mn 4+ (Li xMn 2O 5, 4 > x > 2); (ii) followed by anion oxidation, O 2– → O 1– (2 > x > 1); and (iii) finally, further metal oxidation, Mn 4+ → Mn 5+ (1 > x > 0). This final step is concomitant with the Mn migration from themore » original octahedral site to the adjacent tetrahedral site, introducing a kinetic barrier to reversible charge/discharge cycles. Armed with this knowledge of the charging process, we use high-throughput DFT calculations to study metal mixing in this compound, screening potential new materials for stability and kinetic reversibility. We predict that mixing with M = V and Cr in Li 4(Mn,M) 2O 5 will produce new stable compounds with substantially improved electrochemical properties.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [1];  [1]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Northwestern Univ., Evanston, IL (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1543999
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 4; Journal Issue: 5; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Science & Technology; Other Topics

Citation Formats

Yao, Zhenpeng, Kim, Soo, He, Jiangang, Hegde, Vinay I., and Wolverton, Chris. Interplay of cation and anion redox in Li4Mn2O5 cathode material and prediction of improved Li4(Mn,M)2O5 electrodes for Li-ion batteries. United States: N. p., 2018. Web. doi:10.1126/sciadv.aao6754.
Yao, Zhenpeng, Kim, Soo, He, Jiangang, Hegde, Vinay I., & Wolverton, Chris. Interplay of cation and anion redox in Li4Mn2O5 cathode material and prediction of improved Li4(Mn,M)2O5 electrodes for Li-ion batteries. United States. doi:10.1126/sciadv.aao6754.
Yao, Zhenpeng, Kim, Soo, He, Jiangang, Hegde, Vinay I., and Wolverton, Chris. Fri . "Interplay of cation and anion redox in Li4Mn2O5 cathode material and prediction of improved Li4(Mn,M)2O5 electrodes for Li-ion batteries". United States. doi:10.1126/sciadv.aao6754. https://www.osti.gov/servlets/purl/1543999.
@article{osti_1543999,
title = {Interplay of cation and anion redox in Li4Mn2O5 cathode material and prediction of improved Li4(Mn,M)2O5 electrodes for Li-ion batteries},
author = {Yao, Zhenpeng and Kim, Soo and He, Jiangang and Hegde, Vinay I. and Wolverton, Chris},
abstractNote = {Significant research effort has focused on improving the specific energy of lithium-ion batteries for emerging applications, such as electric vehicles. Recently, a rock salt–type Li4Mn2O5 cathode material with a large discharge capacity (~350 mA·hour g–1) was discovered. However, a full structural model of Li4Mn2O5 and its corresponding phase transformations, as well as the atomistic origins of the high capacity, warrants further investigation. We use first-principles density functional theory (DFT) calculations to investigate both the disordered rock salt–type Li4Mn2O5 structure and the ordered ground-state structure. The ionic ordering in the ground-state structure is determined via a DFT-based enumeration method. We use both the ordered and disordered structures to interrogate the delithiation process and find that it occurs via a three-step reaction pathway involving the complex interplay of cation and anion redox reactions: (i) an initial metal oxidation, Mn3+→Mn4+ (LixMn2O5, 4 > x > 2); (ii) followed by anion oxidation, O2– → O1– (2 > x > 1); and (iii) finally, further metal oxidation, Mn4+ → Mn5+ (1 > x > 0). This final step is concomitant with the Mn migration from the original octahedral site to the adjacent tetrahedral site, introducing a kinetic barrier to reversible charge/discharge cycles. Armed with this knowledge of the charging process, we use high-throughput DFT calculations to study metal mixing in this compound, screening potential new materials for stability and kinetic reversibility. We predict that mixing with M = V and Cr in Li4(Mn,M)2O5 will produce new stable compounds with substantially improved electrochemical properties.},
doi = {10.1126/sciadv.aao6754},
journal = {Science Advances},
issn = {2375-2548},
number = 5,
volume = 4,
place = {United States},
year = {2018},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells
journal, April 1994


Projector augmented-wave method
journal, December 1994


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

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries
journal, April 1997

  • Padhi, A. K.
  • Journal of The Electrochemical Society, Vol. 144, Issue 4, p. 1188-1194
  • DOI: 10.1149/1.1837571

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


Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries
journal, February 2006

  • Kang, Kisuk; Shirley Meng, Ying; Breger, Julien
  • Science, Vol. 311, Issue 5763, p. 977-980
  • DOI: 10.1126/science.1122152

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


Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Rationale for mixing exact exchange with density functional approximations
journal, December 1996

  • Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
  • The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
  • DOI: 10.1063/1.472933