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

Mohanty, Debasish; Sefat, Athena S.; Payzant, E. Andrew; Li, Jianlin; Wood, David L.; Daniel, Claus

doi:10.1016/j.jpowsour.2015.02.087

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

Journal Article · Thu Feb 19 00:00:00 EST 2015 · Journal of Power Sources

DOI:https://doi.org/10.1016/j.jpowsour.2015.02.087· OSTI ID:1185786

Mohanty, Debasish ^[1]; Sefat, Athena S. ^[1]; Payzant, E. Andrew ^[1]; Li, Jianlin ^[1]; Wood, David L. ^[1]; Daniel, Claus ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

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.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: 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 Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1185786

Alternate ID(s):: OSTI ID: 1432075

Journal Information:: Journal of Power Sources, Vol. 283, Issue C; ISSN 0378-7753

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 16 works

Citation information provided by
Web of Science

References (28)

Electrical energy storage for transportation—approaching the limits of, and going beyond, lithium-ion batteries Thackeray, Michael M.; Wolverton, Christopher; Isaacs, Eric D. Energy & Environmental Science, Vol. 5, Issue 7 https://doi.org/10.1039/c2ee21892e	journal	January 2012
Lithium Batteries and Cathode Materials Whittingham, M. Stanley Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302 https://doi.org/10.1021/cr020731c	journal	October 2004
Materials Challenges Facing Electrical Energy Storage Whittingham, M. Stanley MRS Bulletin, Vol. 33, Issue 4 https://doi.org/10.1557/mrs2008.82	journal	April 2008
Building better batteries Armand, M.; Tarascon, J.-M. Nature, Vol. 451, Issue 7179, p. 652-657 https://doi.org/10.1038/451652a	journal	February 2008
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 Yu, Haijun; Ishikawa, Ryo; So, Yeong-Gi Angewandte Chemie International Edition, Vol. 52, Issue 23 https://doi.org/10.1002/anie.201301236	journal	April 2013
Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries Thackeray, Michael M.; Johnson, Christopher S.; Vaughey, John T. Journal of Materials Chemistry, Vol. 15, Issue 23, p. 2257-2267 https://doi.org/10.1039/b417616m	journal	March 2005
Li₂MnO₃-stabilized LiMO₂ (M = Mn, Ni, Co) electrodes for lithium-ion batteries Thackeray, Michael M.; Kang, Sun-Ho; Johnson, Christopher S. Journal of Materials Chemistry, Vol. 17, Issue 30, p. 3112-3125 https://doi.org/10.1039/b702425h	journal	January 2007
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 Yabuuchi, Naoaki; Yoshii, Kazuhiro; Myung, Seung-Taek Journal of the American Chemical Society, Vol. 133, Issue 12 https://doi.org/10.1021/ja108588y	journal	March 2011
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 Lu, Zhonghua; MacNeil, D. D.; Dahn, J. R. Electrochemical and Solid-State Letters, Vol. 4, Issue 11 https://doi.org/10.1149/1.1407994	journal	January 2001
Origin of voltage decay in high-capacity layered oxide electrodes Sathiya, M.; Abakumov, A. M.; Foix, D. Nature Materials, Vol. 14, Issue 2 https://doi.org/10.1038/nmat4137	journal	December 2014
Understanding Long-Term Cycling Performance of Li _1.2 Ni _0.15 Mn _0.55 Co _0.1 O ₂ –Graphite Lithium-Ion Cells Li, Y.; Bettge, M.; Polzin, B. Journal of The Electrochemical Society, Vol. 160, Issue 5 https://doi.org/10.1149/2.002305jes	journal	January 2013
Correlating cation ordering and voltage fade in a lithium–manganese-rich lithium-ion battery cathode oxide: a joint magnetic susceptibility and TEM study Mohanty, Debasish; Sefat, Athena S.; Li, Jianlin Physical Chemistry Chemical Physics, Vol. 15, Issue 44 https://doi.org/10.1039/c3cp53658k	journal	January 2013
Correlating hysteresis and voltage fade in lithium- and manganese-rich layered transition-metal oxide electrodes Gallagher, Kevin G.; Croy, Jason R.; Balasubramanian, Mahalingam Electrochemistry Communications, Vol. 33 https://doi.org/10.1016/j.elecom.2013.04.022	journal	August 2013
Structural transformation of a lithium-rich Li1.2Co0.1Mn0.55Ni0.15O2 cathode during high voltage cycling resolved by in situ X-ray diffraction Mohanty, Debasish; Kalnaus, Sergiy; Meisner, Roberta A. Journal of Power Sources, Vol. 229 https://doi.org/10.1016/j.jpowsour.2012.11.144	journal	May 2013
Structural evolution and the capacity fade mechanism upon long-term cycling in Li-rich cathode material Song, Bohang; Liu, Zongwen; Lai, Man On Physical Chemistry Chemical Physics, Vol. 14, Issue 37 https://doi.org/10.1039/c2cp42068f	journal	January 2012
Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries Gu, Meng; Belharouak, Ilias; Zheng, Jianming ACS Nano, Vol. 7, Issue 1 https://doi.org/10.1021/nn305065u	journal	December 2012
Structural and Electrochemical Evidence of Layered to Spinel Phase Transformation of Li and Mn Rich Layered Cathode Materials of the Formulae xLi[Li _1/3 Mn _2/3 ]O ₂ .(1-x)LiMn _1/3 Ni _1/3 Co _1/3 O ₂ (x = 0.2, 0.4, 0.6) upon Cycling Nayak, Prasant Kumar; Grinblat, Judith; Levi, Mikhael Journal of The Electrochemical Society, Vol. 161, Issue 10 https://doi.org/10.1149/2.0101410jes	journal	January 2014
What can we learn about battery materials from their magnetic properties? Chernova, Natasha A.; Nolis, Gene M.; Omenya, Fredrick O. Journal of Materials Chemistry, Vol. 21, Issue 27 https://doi.org/10.1039/c1jm00024a	journal	January 2011
Unraveling the Voltage-Fade Mechanism in High-Energy-Density Lithium-Ion Batteries: Origin of the Tetrahedral Cations for Spinel Conversion Mohanty, Debasish; Li, Jianlin; Abraham, Daniel P. Chemistry of Materials, Vol. 26, Issue 21 https://doi.org/10.1021/cm5031415	journal	October 2014
Direct Cation- -Cation Interactions in Several Oxides Goodenough, John B. Physical Review, Vol. 117, Issue 6 https://doi.org/10.1103/PhysRev.117.1442	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 Mohanty, Debasish; Huq, Ashfia; Payzant, E. Andrew Chemistry of Materials, Vol. 25, Issue 20 https://doi.org/10.1021/cm402278q	journal	September 2013
Spin-glass behavior in LiMn2O4 spinel Jang, Young-Il; Chou, F. C.; Chiang, Yet-Ming Applied Physics Letters, Vol. 74, Issue 17 https://doi.org/10.1063/1.123021	journal	April 1999
Low-Temperature Structure and Magnetic Properties of the Spinel LiMn ₂ O ₄ : A Frustrated Antiferromagnet and Cathode Material Wills, A. S.; Raju, N. P.; Greedan, J. E. Chemistry of Materials, Vol. 11, Issue 6 https://doi.org/10.1021/cm981041l	journal	June 1999
Magnetic characterization of λ-MnO2 and Li2Mn2O4 prepared by electrochemical cycling of LiMn2O4 Jang, Young-Il; Huang, Biying; Chou, F. C. Journal of Applied Physics, Vol. 87, Issue 10 https://doi.org/10.1063/1.372997	journal	May 2000
Demonstrating Oxygen Loss and Associated Structural Reorganization in the Lithium Battery Cathode Li[Ni_0.2Li_0.2Mn_0.6]O₂ Armstrong, A. Robert; Holzapfel, Michael; Novák, Petr Journal of the American Chemical Society, Vol. 128, Issue 26 https://doi.org/10.1021/ja062027+	journal	June 2006
Correlation Between Oxygen Vacancy, Microstrain, and Cation Distribution in Lithium-Excess Layered Oxides During the First Electrochemical Cycle Fell, Christopher R.; Qian, Danna; Carroll, Kyler J. Chemistry of Materials, Vol. 25, Issue 9 https://doi.org/10.1021/cm4000119	journal	April 2013
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) Hy, Sunny; Felix, Felix; Rick, John Journal of the American Chemical Society, Vol. 136, Issue 3 https://doi.org/10.1021/ja410137s	journal	January 2014
Understanding the Anomalous Capacity of Li / Li [ Ni_xLi _{( 1 / 3 − 2x / 3 )} Mn_{( 2 / 3 − x / 3 )} ] O₂ Cells Using In Situ X-Ray Diffraction and Electrochemical Studies Lu, Zhonghua; Dahn, J. R. Journal of The Electrochemical Society, Vol. 149, Issue 7, p. A815-A822 https://doi.org/10.1149/1.1480014	journal	January 2002

Cited By (1)

Toward Low-Cost, High-Energy Density, and High-Power Density Lithium-Ion Batteries Li, Jianlin; Du, Zhijia; Ruther, Rose E. JOM, Vol. 69, Issue 9 https://doi.org/10.1007/s11837-017-2404-9	journal	June 2017

Similar Records

Structure and Voltage Recovery Driven by Defects Elimination in Li-Rich Layered Oxide Cathode Materials

Conference · Tue May 15 00:00:00 EDT 2018 · OSTI ID:1185786

Zhang, Minghao; Liu, Haodong; Meng, Ying Shirley

Li₈MnO₆: A Novel Cathode Material with Only Anionic Redox

Journal Article · Thu Jun 23 00:00:00 EDT 2022 · ACS Applied Materials and Interfaces · OSTI ID:1185786

Luo, Ningjing; Feng, Lianggang; Yin, Huimin; +4 more

Enhancing the surface stability of Ni-rich layered transition metal oxide cathode materials

Journal Article · Sun Dec 15 00:00:00 EST 2019 · Chinese Journal of Structural Chemistry · OSTI ID:1185786

Hu, Jiangtao; Zhang, Jiguang

Related Subjects

25 ENERGY STORAGE

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

Citation Formats

References (28)

Cited By (1)

Similar Records

Related Subjects