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

Title: First-Cycle Simulation for Li-Rich Layered Oxide Cathode Material xLi 2MnO3(1-x)LiMO2 (x = 0.4)

Abstract

Here, lithium-rich layered oxides (LRLO) xLi 2MnO3(1-x)LiMO2 continue to attract attention owing to their promise of high capacity and energy density as lithium-ion battery cathodes, despite the degradation of atomic structure and energy density (voltage fade) with cycling. First-principles DFT calculations for the model systems M = Co and M = Mn0.5Ni0.5 provide insights into the atomic-scale transformations in the bulk during the first charge and discharge of LRLO. The simulations were performed with the VASP code at the GGA+U level. Molecular dynamics simulations were conducted at T = 1000 K (charge) and 2000 K (discharge) to accelerate the dynamics. Considerable Co migration to the Li layer occurs during the first charge for the system with M = Co, but the LiMO2 component remains substantially intact for the system with M = Mn0.5Ni0.5. First-charge oxygen dimerization in the M = Co system occurs in both the LiMO2 and the Li2MnO3 components of the material, and exceeds than for M = Mn0.5Ni0.5, where dimerization is essentially confined to the Li2MnO3 component. About half of the oxygen dimers created during the voltage plateau dissociate during the first discharge. Analysis of the redox suggests that some Mn3+ is generated during the first chargemore » for the system M = Co.« less

Authors:
ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1477746
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 165; Journal Issue: 11; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cathode; first principles; Li-ion; migration; point defect; molecular dynamics; battery; energy density

Citation Formats

Benedek, Roy. First-Cycle Simulation for Li-Rich Layered Oxide Cathode Material xLi 2MnO3•(1-x)LiMO2 (x = 0.4). United States: N. p., 2018. Web. doi:10.1149/2.0671811jes.
Benedek, Roy. First-Cycle Simulation for Li-Rich Layered Oxide Cathode Material xLi 2MnO3•(1-x)LiMO2 (x = 0.4). United States. doi:10.1149/2.0671811jes.
Benedek, Roy. Thu . "First-Cycle Simulation for Li-Rich Layered Oxide Cathode Material xLi 2MnO3•(1-x)LiMO2 (x = 0.4)". United States. doi:10.1149/2.0671811jes. https://www.osti.gov/servlets/purl/1477746.
@article{osti_1477746,
title = {First-Cycle Simulation for Li-Rich Layered Oxide Cathode Material xLi 2MnO3•(1-x)LiMO2 (x = 0.4)},
author = {Benedek, Roy},
abstractNote = {Here, lithium-rich layered oxides (LRLO) xLi 2MnO3•(1-x)LiMO2 continue to attract attention owing to their promise of high capacity and energy density as lithium-ion battery cathodes, despite the degradation of atomic structure and energy density (voltage fade) with cycling. First-principles DFT calculations for the model systems M = Co and M = Mn0.5Ni0.5 provide insights into the atomic-scale transformations in the bulk during the first charge and discharge of LRLO. The simulations were performed with the VASP code at the GGA+U level. Molecular dynamics simulations were conducted at T = 1000 K (charge) and 2000 K (discharge) to accelerate the dynamics. Considerable Co migration to the Li layer occurs during the first charge for the system with M = Co, but the LiMO2 component remains substantially intact for the system with M = Mn0.5Ni0.5. First-charge oxygen dimerization in the M = Co system occurs in both the LiMO2 and the Li2MnO3 components of the material, and exceeds than for M = Mn0.5Ni0.5, where dimerization is essentially confined to the Li2MnO3 component. About half of the oxygen dimers created during the voltage plateau dissociate during the first discharge. Analysis of the redox suggests that some Mn3+ is generated during the first charge for the system M = Co.},
doi = {10.1149/2.0671811jes},
journal = {Journal of the Electrochemical Society},
number = 11,
volume = 165,
place = {United States},
year = {2018},
month = {8}
}

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

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Advances in Stabilizing ‘Layered-Layered’ xLi2MnO3·(1-x)LiMO2(M=Mn, Ni, Co) Electrodes with a Spinel Component
journal, January 2014

  • Long, Brandon R.; Croy, Jason R.; Park, Joong Sun
  • Journal of The Electrochemical Society, Vol. 161, Issue 14, p. A2160-A2167
  • DOI: 10.1149/2.0681414jes

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Investigation of the Charge Compensation Mechanism on the Electrochemically Li-Ion Deintercalated Li 1 - x Co 1/3 Ni 1/3 Mn 1/3 O 2 Electrode System by Combination of Soft and Hard X-ray Absorption Spectroscopy
journal, December 2005

  • Yoon, Won-Sub; Balasubramanian, Mahalingam; Chung, Kyung Yoon
  • Journal of the American Chemical Society, Vol. 127, Issue 49
  • DOI: 10.1021/ja0530568

Anionic Redox in Rechargeable Lithium Batteries
journal, June 2017


The Role of Oxygen Release from Li- and Mn-Rich Layered Oxides during the First Cycles Investigated by On-Line Electrochemical Mass Spectrometry
journal, December 2016

  • Strehle, Benjamin; Kleiner, Karin; Jung, Roland
  • Journal of The Electrochemical Society, Vol. 164, Issue 2
  • DOI: 10.1149/2.1001702jes

Electrochemical activation, voltage decay and hysteresis of Li-rich layered cathode probed by various cobalt content
journal, March 2018


The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials
journal, May 2016

  • Seo, Dong-Hwa; Lee, Jinhyuk; Urban, Alexander
  • Nature Chemistry, Vol. 8, Issue 7
  • DOI: 10.1038/nchem.2524

Finite-temperature property-maps of Li–Mn–Ni–O cathode materials from ab initio calculations
journal, January 2018

  • Albina, Jan-Michael; Marusczyk, Anika; Hammerschmidt, Thomas
  • Journal of Materials Chemistry A, Vol. 6, Issue 14
  • DOI: 10.1039/C7TA07221J

Understanding structural changes in NMC Li-ion cells by in situ neutron diffraction
journal, June 2014


Quantifying Hysteresis and Voltage Fade in xLi 2 MnO 3 (1-x)LiMn 0.5 Ni 0.5 O 2 Electrodes as a Function of Li 2 MnO 3 Content
journal, December 2013

  • Croy, Jason R.; Gallagher, Kevin G.; Balasubramanian, Mahalingam
  • Journal of The Electrochemical Society, Vol. 161, Issue 3
  • DOI: 10.1149/2.049403jes

Transition-metal redox evolution in LiNi0.5Mn0.3Co0.2O2 electrodes at high potentials
journal, August 2017


Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries
journal, January 2017

  • Xie, Y.; Saubanère, M.; Doublet, M. -L.
  • Energy & Environmental Science, Vol. 10, Issue 1
  • DOI: 10.1039/C6EE02328B

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


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Lithium- and Manganese-Rich Oxide Cathode Materials for High-Energy Lithium Ion Batteries
journal, August 2016


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

Lithium Extraction Mechanism in Li-Rich Li 2 MnO 3 Involving Oxygen Hole Formation and Dimerization
journal, September 2016


Electron Spectroscopy Study of Li[Ni,Co,Mn]O 2 /Electrolyte Interface: Electronic Structure, Interface Composition, and Device Implications
journal, April 2015

  • Cherkashinin, Gennady; Motzko, Markus; Schulz, Natalia
  • Chemistry of Materials, Vol. 27, Issue 8
  • DOI: 10.1021/cm5047534

First-Cycle Evolution of Local Structure in Electrochemically Activated Li 2 MnO 3
journal, December 2014

  • Croy, Jason R.; Park, Joong Sun; Dogan, Fulya
  • Chemistry of Materials, Vol. 26, Issue 24
  • DOI: 10.1021/cm5039792

Stability of Li- and Mn-Rich Layered-Oxide Cathodes within the First-Charge Voltage Plateau
journal, January 2016

  • Iddir, Hakim; Bareño, Javier; Benedek, Roy
  • Journal of The Electrochemical Society, Vol. 163, Issue 8
  • DOI: 10.1149/2.0011609jes

Exploring Electrochemistry and Interface Characteristics of Lithium-Ion Cells with Li 1.2 Ni 0.15 Mn 0.55 Co 0.1 O 2 Positive and Li 4 Ti 5 O 12 Negative Electrodes
journal, January 2015

  • Li, Yan; Bettge, Martin; Bareño, Javier
  • Journal of The Electrochemical Society, Vol. 162, Issue 13
  • DOI: 10.1149/2.0071513jes

Role of Electronic Structure in the Susceptibility of Metastable Transition-Metal Oxide Structures to Transformation
journal, October 2004

  • Reed, John; Ceder, Gerbrand
  • Chemical Reviews, Vol. 104, Issue 10
  • DOI: 10.1021/cr020733x

Role of Superexchange Interaction on Tuning of Ni/Li Disordering in Layered Li(Ni x Mn y Co z )O 2
journal, November 2017


Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides
journal, December 2017


Improved grid-based algorithm for Bader charge allocation
journal, January 2007

  • Sanville, Edward; Kenny, Steven D.; Smith, Roger
  • Journal of Computational Chemistry, Vol. 28, Issue 5
  • DOI: 10.1002/jcc.20575

Vacancy-induced MnO 6 distortion and its impacts on structural transition of Li 2 MnO 3
journal, January 2017

  • Gao, Yurui; Ma, Jun; Wang, Zhaoxiang
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 10
  • DOI: 10.1039/C6CP08441A

Examining the Electrochemical Impedance at Low States of Charge in Lithium- and Manganese-Rich Layered Transition-Metal Oxide Electrodes
journal, January 2015

  • Gowda, Sanketh R.; Dees, Dennis W.; Jansen, Andrew N.
  • Journal of The Electrochemical Society, Vol. 162, Issue 7
  • DOI: 10.1149/2.0931507jes

Exploring Lithium-Cobalt-Nickel Oxide Spinel Electrodes for ≥3.5 V Li-Ion Cells
journal, October 2016

  • Lee, Eungje; Blauwkamp, Joel; Castro, Fernando C.
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 41
  • DOI: 10.1021/acsami.6b09073

Correlating cation ordering and voltage fade in a lithium–manganese-rich lithium-ion battery cathode oxide: a joint magnetic susceptibility and TEM study
journal, January 2013

  • Mohanty, Debasish; Sefat, Athena S.; Li, Jianlin
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 44
  • DOI: 10.1039/c3cp53658k

Oxygen activity and peroxide formation as charge compensation mechanisms in Li 2 MnO 3
journal, January 2017

  • Marusczyk, Anika; Albina, Jan-Michael; Hammerschmidt, Thomas
  • Journal of Materials Chemistry A, Vol. 5, Issue 29
  • DOI: 10.1039/C7TA04164K

First-charge instabilities of layered-layered lithium-ion-battery materials
journal, January 2015

  • Croy, Jason R.; Iddir, Hakim; Gallagher, Kevin
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 37
  • DOI: 10.1039/C5CP02943K

Pristine-state structure of lithium-ion-battery cathode material Li 1.2 Mn 0.4 Co 0.4 O 2 derived from NMR bond pathway analysis
journal, January 2015

  • Iddir, Hakim; Key, Baris; Dogan, Fulya
  • Journal of Materials Chemistry A, Vol. 3, Issue 21
  • DOI: 10.1039/C5TA01510C