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Title: First-Cycle Simulation for Li-Rich Layered Oxide Cathode Material xLi 2MnO 3 (1- x)Li MO 2 ( x = 0.4)

Here, lithium-rich layered oxides (LRLO) xLi 2MnO 3 (1- x)Li MO 2 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 = Mn 0.5Ni 0.5 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 Li MO 2 component remains substantially intact for the system with M = Mn 0.5Ni 0.5. First-charge oxygen dimerization in the M = Co system occurs in both the Li MO 2 and the Li 2MnO 3 components of the material, and exceeds than for M = Mn 0.5Ni 0.5, where dimerization is essentially confined to the Li 2MnO 3 component. About half of the oxygen dimers created during the voltagemore » plateau dissociate during the first discharge. Analysis of the redox suggests that some Mn 3+ is generated during the first charge for the system M = Co.« less
Authors:
ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
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
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)
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
OSTI Identifier:
1477746

Benedek, Roy. First-Cycle Simulation for Li-Rich Layered Oxide Cathode Material xLi 2MnO3•(1-x)LiMO2 (x = 0.4). United States: N. p., 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. 2018. "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.
@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}
}

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