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

Title: Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction

Abstract

Neutron diffraction under operando battery cycling is used to study the lithium and oxygen dynamics of high Li-rich Li(Li x/3Ni (3/8-3x/8)Co (1/4-x/4)Mn (3/8+7x/24)O 2 (x = 0.6, HLR) and low Li-rich Li(Li x/3Ni (1/3-x/3)Co (1/3-x/3)Mn(1/3+x/3)O 2 (x = 0.24, LLR) compounds that exhibit different degrees of oxygen activation at high voltage. The measured lattice parameter changes and oxygen position show largely contrasting changes for the two cathodes where the LLR exhibits larger movement of oxygen and lattice contractions in comparison to the HLR that maintains relatively constant lattice parameters and oxygen position during the high voltage plateau until the end of charge. Density functional theory calculations show the presence of oxygen vacancy during the high voltage plateau; changes in the lattice parameters and oxygen position are consistent with experimental observations. Lithium migration kinetics for the Li-rich material is observed under operando conditions for the first time to reveal the rate of lithium extraction from the lithium layer, and transition metal layer is related to the different charge and discharge characteristics. At the beginning of charging, the lithium extraction predominately occurs within the lithium layer. The lithium extraction from the lithium layer slows down and extraction from the transition metal layermore » evolves at a faster rate once the high voltage plateau is reached.« less

Authors:
 [1];  [2];  [3];  [1];  [1];  [1]
  1. Univ. of California, San Diego, CA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Envia Systems, Newark, CA (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1261356
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 6; Journal Issue: 7; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Liu, Haodong, An, Ke, Venkatachalam, Subramanian, Qian, Danna, Zhang, Minghao, and Meng, Ying Shirley. Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction. United States: N. p., 2016. Web. doi:10.1002/aenm.201502143.
Liu, Haodong, An, Ke, Venkatachalam, Subramanian, Qian, Danna, Zhang, Minghao, & Meng, Ying Shirley. Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction. United States. doi:10.1002/aenm.201502143.
Liu, Haodong, An, Ke, Venkatachalam, Subramanian, Qian, Danna, Zhang, Minghao, and Meng, Ying Shirley. Wed . "Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction". United States. doi:10.1002/aenm.201502143. https://www.osti.gov/servlets/purl/1261356.
@article{osti_1261356,
title = {Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction},
author = {Liu, Haodong and An, Ke and Venkatachalam, Subramanian and Qian, Danna and Zhang, Minghao and Meng, Ying Shirley},
abstractNote = {Neutron diffraction under operando battery cycling is used to study the lithium and oxygen dynamics of high Li-rich Li(Lix/3Ni(3/8-3x/8)Co(1/4-x/4)Mn(3/8+7x/24)O2 (x = 0.6, HLR) and low Li-rich Li(Lix/3Ni(1/3-x/3)Co(1/3-x/3)Mn(1/3+x/3)O2 (x = 0.24, LLR) compounds that exhibit different degrees of oxygen activation at high voltage. The measured lattice parameter changes and oxygen position show largely contrasting changes for the two cathodes where the LLR exhibits larger movement of oxygen and lattice contractions in comparison to the HLR that maintains relatively constant lattice parameters and oxygen position during the high voltage plateau until the end of charge. Density functional theory calculations show the presence of oxygen vacancy during the high voltage plateau; changes in the lattice parameters and oxygen position are consistent with experimental observations. Lithium migration kinetics for the Li-rich material is observed under operando conditions for the first time to reveal the rate of lithium extraction from the lithium layer, and transition metal layer is related to the different charge and discharge characteristics. At the beginning of charging, the lithium extraction predominately occurs within the lithium layer. The lithium extraction from the lithium layer slows down and extraction from the transition metal layer evolves at a faster rate once the high voltage plateau is reached.},
doi = {10.1002/aenm.201502143},
journal = {Advanced Energy Materials},
number = 7,
volume = 6,
place = {United States},
year = {2016},
month = {4}
}

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

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

The Li-Ion Rechargeable Battery: A Perspective
journal, January 2013

  • Goodenough, John B.; Park, Kyu-Sung
  • Journal of the American Chemical Society, Vol. 135, Issue 4
  • DOI: 10.1021/ja3091438

Future generations of cathode materials: an automotive industry perspective
journal, January 2015

  • Andre, Dave; Kim, Sung-Jin; Lamp, Peter
  • Journal of Materials Chemistry A, Vol. 3, Issue 13
  • DOI: 10.1039/C5TA00361J

Lithium Batteries and Cathode Materials
journal, October 2004

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

Reversible Oxygen Participation to the Redox Processes Revealed for Li 1.20 Mn 0.54 Co 0.13 Ni 0.13 O 2
journal, January 2013

  • Koga, Hideyuki; Croguennec, Laurence; Ménétrier, Michel
  • Journal of The Electrochemical Society, Vol. 160, Issue 6
  • DOI: 10.1149/2.038306jes

Different oxygen redox participation for bulk and surface: A possible global explanation for the cycling mechanism of Li1.20Mn0.54Co0.13Ni0.13O2
journal, August 2013


Reversible anionic redox chemistry in high-capacity layered-oxide electrodes
journal, July 2013

  • Sathiya, M.; Rousse, G.; Ramesha, K.
  • Nature Materials, Vol. 12, Issue 9
  • DOI: 10.1038/nmat3699

Effect of Morphology and Manganese Valence on the Voltage Fade and Capacity Retention of Li[Li 2/12 Ni 3/12 Mn 7/12 ]O 2
journal, October 2014

  • Verde, Michael G.; Liu, Haodong; Carroll, Kyler J.
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 21
  • DOI: 10.1021/am504701s

Re-entrant Lithium Local Environments and Defect Driven Electrochemistry of Li- and Mn-Rich Li-Ion Battery Cathodes
journal, February 2015

  • Dogan, Fulya; Long, Brandon R.; Croy, Jason R.
  • Journal of the American Chemical Society, Vol. 137, Issue 6
  • DOI: 10.1021/ja511299y

Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: A joint experimental and theoretical study
journal, January 2011

  • Xu, Bo; Fell, Christopher R.; Chi, Miaofang
  • Energy & Environmental Science, Vol. 4, Issue 6
  • DOI: 10.1039/c1ee01131f

A novel electrochemical cell for in situ neutron diffraction studies of electrode materials for lithium-ion batteries
journal, July 2008

  • Rosciano, Fabio; Holzapfel, Michael; Scheifele, Werner
  • Journal of Applied Crystallography, Vol. 41, Issue 4
  • DOI: 10.1107/S0021889808018025

New in-situ neutron diffraction cell for electrode materials
journal, February 2014


Lithium Migration in Li 4 Ti 5 O 12 Studied Using in Situ Neutron Powder Diffraction
journal, March 2014

  • Pang, Wei Kong; Peterson, Vanessa K.; Sharma, Neeraj
  • Chemistry of Materials, Vol. 26, Issue 7
  • DOI: 10.1021/cm5002779

An In-Situ Electrochemical Cell for Neutron Diffraction Studies of Phase Transitions in Small Volume Electrodes of Li-Ion Batteries
journal, January 2014

  • Vadlamani, B.; An, K.; Jagannathan, M.
  • Journal of The Electrochemical Society, Vol. 161, Issue 10
  • DOI: 10.1149/2.0951410jes

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

A new O3-type layered oxide cathode with high energy/power density for rechargeable Na batteries
journal, January 2015

  • Liu, Haodong; Xu, Jing; Ma, Chuze
  • Chemical Communications, Vol. 51, Issue 22
  • DOI: 10.1039/C4CC09760B

Understanding the Role of NH 4 F and Al 2 O 3 Surface Co-modification on Lithium-Excess Layered Oxide Li 1.2 Ni 0.2 Mn 0.6 O 2
journal, August 2015

  • Liu, Haodong; Qian, Danna; Verde, Michael G.
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 34
  • DOI: 10.1021/acsami.5b04932

In situ investigations of a Li-rich Mn–Ni layered oxide for Li-ion batteries
journal, January 2012

  • Simonin, Loïc; Colin, Jean-François; Ranieri, Vincent
  • Journal of Materials Chemistry, Vol. 22, Issue 22
  • DOI: 10.1039/c2jm31205k

Theoretical prediction of the 5 V rechargeable Li ion battery using Li 2 CoMn 3 O 8 as a cathode
journal, August 2015


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

Electrochemical and Structural Study of the Layered, “Li-Excess” Lithium-Ion Battery Electrode Material Li[Li 1/9 Ni 1/3 Mn 5/9 ]O 2
journal, July 2009

  • Jiang, Meng; Key, Baris; Meng, Ying S.
  • Chemistry of Materials, Vol. 21, Issue 13
  • DOI: 10.1021/cm900279u

Uncovering the roles of oxygen vacancies in cation migration in lithium excess layered oxides
journal, January 2014

  • Qian, Danna; Xu, Bo; Chi, Miaofang
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 28
  • DOI: 10.1039/C4CP01799D

First In Situ Lattice Strains Measurements Under Load at VULCAN
journal, October 2010

  • An, Ke; Skorpenske, Harley D.; Stoica, Alexandru D.
  • Metallurgical and Materials Transactions A, Vol. 42, Issue 1
  • DOI: 10.1007/s11661-010-0495-9

EXPGUI , a graphical user interface for GSAS
journal, April 2001


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


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


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


Generalized gradient approximation for the exchange-correlation hole of a many-electron system
journal, December 1996


    Works referencing / citing this record:

    Feasibility of Cathode Surface Coating Technology for High-Energy Lithium-ion and Beyond-Lithium-ion Batteries
    journal, March 2017