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Title: Unconventional irreversible structural changes in a high-voltage Li–Mn-rich oxide for lithium-ion battery cathodes

Abstract

Making all-electric vehicles (EVs) commonplace in transportation applications will require affordable high-power and high-energy-density lithium-ion batteries (LIBs). The quest for suitable cathode materials to meet this end has currently plateaued with the discovery of high-voltage (≥4.7 V vs. Li+), high capacity (~250 mAh/g) lithium–manganese-rich (LMR) layered composite oxides. In spite of the promise of LMR oxides in high-energy-density LIBs, an irreversible structural change has been identified in this work that is governed by the formation of a ‘permanent’ spin-glass type magnetically frustrated phase indicating a dominant AB2O4 (A = Li, B = Mn) type spinel after a short-term lithium deintercalation (charging) and intercalation (discharging) process. Furthermore, reduction of transition metal (Mn) ions from the 4+ state (pristine LMR) to 3+ (cycled LMR), which alters the intercalation redox chemistry and suggests the presence of ‘unfilled’ lithium vacancies and/or oxygen vacancies in the lattice after cycling, has presented a major stumbling block. Finally, these situations result in both loss of capacity and fading of the voltage profile, and these combined effects significantly reduce the high energy density over even short-term cycling.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). National Transportation Research Center (NTRC); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Manufacturing Demonstration Facility (MDF)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1185786
Alternate Identifier(s):
OSTI ID: 1432075
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Power Sources
Additional Journal Information:
Journal Volume: 283; Journal Issue: C; Journal ID: ISSN 0378-7753
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Mohanty, Debasish, Sefat, Athena S., Payzant, E. Andrew, Li, Jianlin, Wood, David L., and Daniel, Claus. Unconventional irreversible structural changes in a high-voltage Li–Mn-rich oxide for lithium-ion battery cathodes. United States: N. p., 2015. Web. doi:10.1016/j.jpowsour.2015.02.087.
Mohanty, Debasish, Sefat, Athena S., Payzant, E. Andrew, Li, Jianlin, Wood, David L., & Daniel, Claus. Unconventional irreversible structural changes in a high-voltage Li–Mn-rich oxide for lithium-ion battery cathodes. United States. https://doi.org/10.1016/j.jpowsour.2015.02.087
Mohanty, Debasish, Sefat, Athena S., Payzant, E. Andrew, Li, Jianlin, Wood, David L., and Daniel, Claus. Thu . "Unconventional irreversible structural changes in a high-voltage Li–Mn-rich oxide for lithium-ion battery cathodes". United States. https://doi.org/10.1016/j.jpowsour.2015.02.087. https://www.osti.gov/servlets/purl/1185786.
@article{osti_1185786,
title = {Unconventional irreversible structural changes in a high-voltage Li–Mn-rich oxide for lithium-ion battery cathodes},
author = {Mohanty, Debasish and Sefat, Athena S. and Payzant, E. Andrew and Li, Jianlin and Wood, David L. and Daniel, Claus},
abstractNote = {Making all-electric vehicles (EVs) commonplace in transportation applications will require affordable high-power and high-energy-density lithium-ion batteries (LIBs). The quest for suitable cathode materials to meet this end has currently plateaued with the discovery of high-voltage (≥4.7 V vs. Li+), high capacity (~250 mAh/g) lithium–manganese-rich (LMR) layered composite oxides. In spite of the promise of LMR oxides in high-energy-density LIBs, an irreversible structural change has been identified in this work that is governed by the formation of a ‘permanent’ spin-glass type magnetically frustrated phase indicating a dominant AB2O4 (A = Li, B = Mn) type spinel after a short-term lithium deintercalation (charging) and intercalation (discharging) process. Furthermore, reduction of transition metal (Mn) ions from the 4+ state (pristine LMR) to 3+ (cycled LMR), which alters the intercalation redox chemistry and suggests the presence of ‘unfilled’ lithium vacancies and/or oxygen vacancies in the lattice after cycling, has presented a major stumbling block. Finally, these situations result in both loss of capacity and fading of the voltage profile, and these combined effects significantly reduce the high energy density over even short-term cycling.},
doi = {10.1016/j.jpowsour.2015.02.087},
journal = {Journal of Power Sources},
number = C,
volume = 283,
place = {United States},
year = {Thu Feb 19 00:00:00 EST 2015},
month = {Thu Feb 19 00:00:00 EST 2015}
}

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Cited by: 16 works
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Works referenced in this record:

Electrical energy storage for transportation—approaching the limits of, and going beyond, lithium-ion batteries
journal, January 2012

  • Thackeray, Michael M.; Wolverton, Christopher; Isaacs, Eric D.
  • Energy & Environmental Science, Vol. 5, Issue 7
  • DOI: 10.1039/c2ee21892e

Lithium Batteries and Cathode Materials
journal, October 2004

  • Whittingham, M. Stanley
  • Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302
  • DOI: 10.1021/cr020731c

Materials Challenges Facing Electrical Energy Storage
journal, April 2008


Building better batteries
journal, February 2008

  • Armand, M.; Tarascon, J.-M.
  • Nature, Vol. 451, Issue 7179, p. 652-657
  • DOI: 10.1038/451652a

Direct Atomic-Resolution Observation of Two Phases in the Li 1.2 Mn 0.567 Ni 0.166 Co 0.067 O 2 Cathode Material for Lithium-Ion Batteries
journal, April 2013

  • Yu, Haijun; Ishikawa, Ryo; So, Yeong-Gi
  • Angewandte Chemie International Edition, Vol. 52, Issue 23
  • DOI: 10.1002/anie.201301236

Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries
journal, March 2005

  • Thackeray, Michael M.; Johnson, Christopher S.; Vaughey, John T.
  • Journal of Materials Chemistry, Vol. 15, Issue 23, p. 2257-2267
  • DOI: 10.1039/b417616m

Li2MnO3-stabilized LiMO2 (M = Mn, Ni, Co) electrodes for lithium-ion batteries
journal, January 2007

  • Thackeray, Michael M.; Kang, Sun-Ho; Johnson, Christopher S.
  • Journal of Materials Chemistry, Vol. 17, Issue 30, p. 3112-3125
  • DOI: 10.1039/b702425h

Detailed Studies of a High-Capacity Electrode Material for Rechargeable Batteries, Li 2 MnO 3 −LiCo 1/3 Ni 1/3 Mn 1/3 O 2
journal, March 2011

  • Yabuuchi, Naoaki; Yoshii, Kazuhiro; Myung, Seung-Taek
  • Journal of the American Chemical Society, Vol. 133, Issue 12
  • DOI: 10.1021/ja108588y

Layered Cathode Materials Li[Ni[sub x]Li[sub (1/3−2x/3)]Mn[sub (2/3−x/3)]]O[sub 2] for Lithium-Ion Batteries
journal, January 2001

  • Lu, Zhonghua; MacNeil, D. D.; Dahn, J. R.
  • Electrochemical and Solid-State Letters, Vol. 4, Issue 11
  • DOI: 10.1149/1.1407994

Origin of voltage decay in high-capacity layered oxide electrodes
journal, December 2014

  • Sathiya, M.; Abakumov, A. M.; Foix, D.
  • Nature Materials, Vol. 14, Issue 2
  • DOI: 10.1038/nmat4137

Understanding Long-Term Cycling Performance of Li 1.2 Ni 0.15 Mn 0.55 Co 0.1 O 2 –Graphite Lithium-Ion Cells
journal, January 2013

  • Li, Y.; Bettge, M.; Polzin, B.
  • Journal of The Electrochemical Society, Vol. 160, Issue 5
  • DOI: 10.1149/2.002305jes

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

Correlating hysteresis and voltage fade in lithium- and manganese-rich layered transition-metal oxide electrodes
journal, August 2013

  • Gallagher, Kevin G.; Croy, Jason R.; Balasubramanian, Mahalingam
  • Electrochemistry Communications, Vol. 33
  • DOI: 10.1016/j.elecom.2013.04.022

Structural transformation of a lithium-rich Li1.2Co0.1Mn0.55Ni0.15O2 cathode during high voltage cycling resolved by in situ X-ray diffraction
journal, May 2013


Structural evolution and the capacity fade mechanism upon long-term cycling in Li-rich cathode material
journal, January 2012

  • Song, Bohang; Liu, Zongwen; Lai, Man On
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 37
  • DOI: 10.1039/c2cp42068f

Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries
journal, December 2012

  • Gu, Meng; Belharouak, Ilias; Zheng, Jianming
  • ACS Nano, Vol. 7, Issue 1
  • DOI: 10.1021/nn305065u

What can we learn about battery materials from their magnetic properties?
journal, January 2011

  • Chernova, Natasha A.; Nolis, Gene M.; Omenya, Fredrick O.
  • Journal of Materials Chemistry, Vol. 21, Issue 27
  • DOI: 10.1039/c1jm00024a

Unraveling the Voltage-Fade Mechanism in High-Energy-Density Lithium-Ion Batteries: Origin of the Tetrahedral Cations for Spinel Conversion
journal, October 2014

  • Mohanty, Debasish; Li, Jianlin; Abraham, Daniel P.
  • Chemistry of Materials, Vol. 26, Issue 21
  • DOI: 10.1021/cm5031415

Direct Cation- -Cation Interactions in Several Oxides
journal, March 1960


Neutron Diffraction and Magnetic Susceptibility Studies on a High-Voltage Li 1.2 Mn 0.55 Ni 0.15 Co 0.10 O 2 Lithium Ion Battery Cathode: Insight into the Crystal Structure
journal, September 2013

  • Mohanty, Debasish; Huq, Ashfia; Payzant, E. Andrew
  • Chemistry of Materials, Vol. 25, Issue 20
  • DOI: 10.1021/cm402278q

Spin-glass behavior in LiMn2O4 spinel
journal, April 1999

  • Jang, Young-Il; Chou, F. C.; Chiang, Yet-Ming
  • Applied Physics Letters, Vol. 74, Issue 17
  • DOI: 10.1063/1.123021

Low-Temperature Structure and Magnetic Properties of the Spinel LiMn 2 O 4 :  A Frustrated Antiferromagnet and Cathode Material
journal, June 1999

  • Wills, A. S.; Raju, N. P.; Greedan, J. E.
  • Chemistry of Materials, Vol. 11, Issue 6
  • DOI: 10.1021/cm981041l

Magnetic characterization of λ-MnO2 and Li2Mn2O4 prepared by electrochemical cycling of LiMn2O4
journal, May 2000

  • Jang, Young-Il; Huang, Biying; Chou, F. C.
  • Journal of Applied Physics, Vol. 87, Issue 10
  • DOI: 10.1063/1.372997

Demonstrating Oxygen Loss and Associated Structural Reorganization in the Lithium Battery Cathode Li[Ni0.2Li0.2Mn0.6]O2
journal, June 2006

  • Armstrong, A. Robert; Holzapfel, Michael; Novák, Petr
  • Journal of the American Chemical Society, Vol. 128, Issue 26
  • DOI: 10.1021/ja062027+

Correlation Between Oxygen Vacancy, Microstrain, and Cation Distribution in Lithium-Excess Layered Oxides During the First Electrochemical Cycle
journal, April 2013

  • Fell, Christopher R.; Qian, Danna; Carroll, Kyler J.
  • Chemistry of Materials, Vol. 25, Issue 9
  • DOI: 10.1021/cm4000119

Direct In situ Observation of Li 2 O Evolution on Li-Rich High-Capacity Cathode Material, Li[Ni x Li (1–2 x )/3 Mn (2– x )/3 ]O 2 (0 ≤ x ≤0.5)
journal, January 2014

  • Hy, Sunny; Felix, Felix; Rick, John
  • Journal of the American Chemical Society, Vol. 136, Issue 3
  • DOI: 10.1021/ja410137s

Works referencing / citing this record:

Toward Low-Cost, High-Energy Density, and High-Power Density Lithium-Ion Batteries
journal, June 2017