Correlating Local Structure with Electrochemical Activity in Li2MnO3
Abstract
Li2MnO3 is of interest as one component of the composite lithium-rich oxides, which are under development for high capacity, high voltage cathodes in lithium ion batteries. Despite such practical importance, the mechanism of electrochemical activity in Li2MnO3 is contested in the literature, as are the effects of long-term electrochemical cycling. Here, Raman spectroscopy and mapping are used to follow the chemical and structural changes that occur in Li2MnO3. Both conventional slurry electrodes and thin films are studied as a function of the state of charge (voltage) and cycle number. Thin films have similar electrochemical properties as electrodes prepared from slurries, but allow for spectroscopic investigations on uniform samples without carbon additives. Spectral changes correlate well with electrochemical activity and support a mechanism whereby capacity is lost upon extended cycling due to the formation of new manganese oxide phases. Raman mapping of both thin film and slurry electrodes charged to different voltages reveals significant variation in the local structure. Poor conductivity and slow kinetics associated with a two-phase reaction mechanism contribute to the heterogeneity.
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1210144
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 119; Journal Issue: 32; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE
Citation Formats
Nanda, Jagjit, Sacci, Robert L., Veith, Gabriel M., Dixit, Hemant M., Cooper, Valentino R., Pezeshki, Alan M., and Ruther, Rose E. Correlating Local Structure with Electrochemical Activity in Li2MnO3. United States: N. p., 2015.
Web. doi:10.1021/acs.jpcc.5b03900.
Nanda, Jagjit, Sacci, Robert L., Veith, Gabriel M., Dixit, Hemant M., Cooper, Valentino R., Pezeshki, Alan M., & Ruther, Rose E. Correlating Local Structure with Electrochemical Activity in Li2MnO3. United States. https://doi.org/10.1021/acs.jpcc.5b03900
Nanda, Jagjit, Sacci, Robert L., Veith, Gabriel M., Dixit, Hemant M., Cooper, Valentino R., Pezeshki, Alan M., and Ruther, Rose E. Fri .
"Correlating Local Structure with Electrochemical Activity in Li2MnO3". United States. https://doi.org/10.1021/acs.jpcc.5b03900. https://www.osti.gov/servlets/purl/1210144.
@article{osti_1210144,
title = {Correlating Local Structure with Electrochemical Activity in Li2MnO3},
author = {Nanda, Jagjit and Sacci, Robert L. and Veith, Gabriel M. and Dixit, Hemant M. and Cooper, Valentino R. and Pezeshki, Alan M. and Ruther, Rose E.},
abstractNote = {Li2MnO3 is of interest as one component of the composite lithium-rich oxides, which are under development for high capacity, high voltage cathodes in lithium ion batteries. Despite such practical importance, the mechanism of electrochemical activity in Li2MnO3 is contested in the literature, as are the effects of long-term electrochemical cycling. Here, Raman spectroscopy and mapping are used to follow the chemical and structural changes that occur in Li2MnO3. Both conventional slurry electrodes and thin films are studied as a function of the state of charge (voltage) and cycle number. Thin films have similar electrochemical properties as electrodes prepared from slurries, but allow for spectroscopic investigations on uniform samples without carbon additives. Spectral changes correlate well with electrochemical activity and support a mechanism whereby capacity is lost upon extended cycling due to the formation of new manganese oxide phases. Raman mapping of both thin film and slurry electrodes charged to different voltages reveals significant variation in the local structure. Poor conductivity and slow kinetics associated with a two-phase reaction mechanism contribute to the heterogeneity.},
doi = {10.1021/acs.jpcc.5b03900},
journal = {Journal of Physical Chemistry. C},
number = 32,
volume = 119,
place = {United States},
year = {Fri Jul 31 00:00:00 EDT 2015},
month = {Fri Jul 31 00:00:00 EDT 2015}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 26 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
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
Atomic Structure of a Lithium-Rich Layered Oxide Material for Lithium-Ion Batteries: Evidence of a Solid Solution
journal, August 2011
- Jarvis, Karalee A.; Deng, Zengqiang; Allard, Lawrence F.
- Chemistry of Materials, Vol. 23, Issue 16
Li 1.20 Mn 0.54 Co 0.13 Ni 0.13 O 2 with Different Particle Sizes as Attractive Positive Electrode Materials for Lithium-Ion Batteries: Insights into Their Structure
journal, June 2012
- Koga, Hideyuki; Croguennec, Laurence; Mannessiez, Philippe
- The Journal of Physical Chemistry C, Vol. 116, Issue 25
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
Effect of Cooling Rates on Phase Separation in 0.5Li 2 MnO 3 ·0.5LiCoO 2 Electrode Materials for Li-Ion Batteries
journal, May 2014
- Long, Brandon R.; Croy, Jason R.; Dogan, Fulya
- Chemistry of Materials, Vol. 26, Issue 11
Voltage Fade of Layered Oxides: Its Measurement and Impact on Energy Density
journal, January 2013
- Bettge, Martin; Li, Yan; Gallagher, Kevin
- Journal of The Electrochemical Society, Vol. 160, Issue 11
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
Electrochemical Characterization of Lithium and Manganese Rich Composite Material for Lithium Ion Batteries
journal, January 2013
- Lu, Wenquan; Wu, Qingliu; Dees, Dennis W.
- Journal of The Electrochemical Society, Vol. 160, Issue 6
Manganese oxides for lithium batteries
journal, January 1997
- Thackeray, Michael M.
- Progress in Solid State Chemistry, Vol. 25, Issue 1-2
Lithium metal rechargeable cells using Li2MnO3 as the positive electrode
journal, July 1999
- Kalyani, P.; Chitra, S.; Mohan, T.
- Journal of Power Sources, Vol. 80, Issue 1-2
Synthesis, Electrochemistry, and Structural Studies of Lithium Intercalation of a Nanocrystalline Li 2 MnO 3 -like Compound
journal, June 2005
- Jain, Gaurav; Yang, Jingsi; Balasubramanian, Mahalingam
- Chemistry of Materials, Vol. 17, Issue 15
Study of the nanosized Li2MnO3: Electrochemical behavior, structure, magnetic properties, and vibrational modes
journal, May 2013
- Amalraj, S. Francis; Sharon, Daniel; Talianker, Michael
- Electrochimica Acta, Vol. 97
Electrochemical activation of Li2MnO3 at elevated temperature investigated by in situ Raman microscopy
journal, October 2013
- Lanz, Patrick; Villevieille, Claire; Novák, Petr
- Electrochimica Acta, Vol. 109
Electrochemical Activities in Li[sub 2]MnO[sub 3]
journal, January 2009
- Yu, Denis Y. W.; Yanagida, Katsunori; Kato, Yoshio
- Journal of The Electrochemical Society, Vol. 156, Issue 6
The origin of electrochemical activity in Li2MnO3
journal, October 2002
- Robertson, Alastair D.; Bruce, Peter G.
- Chemical Communications, Issue 23
Mn L 2,3 -edge X-ray absorption spectroscopic studies on charge-discharge mechanism of Li 2 MnO 3
journal, February 2014
- Kubobuchi, Kei; Mogi, Masato; Ikeno, Hidekazu
- Applied Physics Letters, Vol. 104, Issue 5
Structural Changes in Li 2 MnO 3 Cathode Material for Li-Ion Batteries
journal, December 2013
- Rana, Jatinkumar; Stan, Marian; Kloepsch, Richard
- Advanced Energy Materials, Vol. 4, Issue 5
Understanding the Anomalous Capacity of Li / Li [ NixLi ( 1 / 3 − 2x / 3 ) Mn ( 2 / 3 − x / 3 ) ] O2 Cells Using In Situ X-Ray Diffraction and Electrochemical Studies
journal, January 2002
- Lu, Zhonghua; Dahn, J. R.
- Journal of The Electrochemical Society, Vol. 149, Issue 7, p. A815-A822
Overcapacity of Li[Ni[sub x]Li[sub 1/3−2x/3]Mn[sub 2/3−x/3]]O[sub 2] Electrodes
journal, January 2004
- Robertson, Alastair D.; Bruce, Peter G.
- Electrochemical and Solid-State Letters, Vol. 7, Issue 9
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
Structural and Chemical Evolution of the Layered Li-Excess Li x MnO 3 as a Function of Li Content from First-Principles Calculations
journal, June 2014
- Lee, Eunseok; Persson, Kristin A.
- Advanced Energy Materials, Vol. 4, Issue 15
Mechanism of Electrochemical Activity in Li 2 MnO 3
journal, May 2003
- Robertson, Alastair D.; Bruce, Peter G.
- Chemistry of Materials, Vol. 15, Issue 10
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
Structural Analysis of Li2MnO3 and Related Li-Mn-O Materials
journal, January 2011
- Yu, Denis Y. W.; Yanagida, Katsunori
- Journal of The Electrochemical Society, Vol. 158, Issue 9
Study of the electrochemical behavior of the “inactive” Li2MnO3
journal, September 2012
- Francis Amalraj, S.; Markovsky, Boris; Sharon, Daniel
- Electrochimica Acta, Vol. 78
Raman Microspectrometry Applied to the Study of Electrode Materials for Lithium Batteries
journal, March 2010
- Baddour-Hadjean, Rita; Pereira-Ramos, Jean-Pierre
- Chemical Reviews, Vol. 110, Issue 3
In situ Raman spectroscopy of layered solid solution Li2MnO3–LiMO2 (M = Ni, Mn, Co)
journal, November 2012
- Singh, Gurpreet; West, W. C.; Soler, J.
- Journal of Power Sources, Vol. 218
Ex situ and in situ Raman microscopic investigation of the differences between stoichiometric LiMO2 and high-energy xLi2MnO3·(1–x)LiMO2 (M = Ni, Co, Mn)
journal, June 2014
- Lanz, Patrick; Villevieille, Claire; Novák, Petr
- Electrochimica Acta, Vol. 130
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
Raman Microscopy of Lithium-Manganese-Rich Transition Metal Oxide Cathodes
journal, November 2014
- Ruther, Rose E.; Callender, Andrew F.; Zhou, Hui
- Journal of The Electrochemical Society, Vol. 162, Issue 1
A Raman-Based Investigation of the Fate of Li 2 MnO 3 in Lithium- and Manganese-Rich Cathode Materials for Lithium Ion Batteries
journal, January 2015
- Wu, Qingliu; Maroni, Victor A.; Gosztola, David J.
- Journal of The Electrochemical Society, Vol. 162, Issue 7
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
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Lattice vibrations of materials for lithium rechargeable batteries III. Lithium manganese oxides
journal, June 2003
- Julien, C. M.; Massot, M.
- Materials Science and Engineering: B, Vol. 100, Issue 1
Reinvestigation of Li 2 MnO 3 Structure: Electron Diffraction and High Resolution TEM
journal, September 2009
- Boulineau, A.; Croguennec, L.; Delmas, C.
- Chemistry of Materials, Vol. 21, Issue 18
High-resolution X-ray diffraction, DIFFaX, NMR and first principles study of disorder in the Li2MnO3–Li[Ni1/2Mn1/2]O2 solid solution
journal, September 2005
- Bréger, Julien; Jiang, Meng; Dupré, Nicolas
- Journal of Solid State Chemistry, Vol. 178, Issue 9, p. 2575-2585
Raman study of layered rock-salt LiCoO2 and its electrochemical lithium deintercalation
journal, August 1997
- Inaba, Minoru; Iriyama, Yasutoshi; Ogumi, Zempachi
- Journal of Raman Spectroscopy, Vol. 28, Issue 8
In situ Raman spectroscopic studies of electrochemical intercalation in LixMn2O4-based cathodes
journal, September 1999
- Huang, Weiwei; Frech, Roger
- Journal of Power Sources, Vol. 81-82
Raman and FTIR Spectroscopic Study of Li[sub x]FePO[sub 4] (0≤x≤1)
journal, January 2004
- Burba, Christopher M.; Frech, Roger
- Journal of The Electrochemical Society, Vol. 151, Issue 7
Vibrational spectroscopic study of lithium intercalation into LiTi2(PO4)3
journal, July 2006
- Burba, C.; Frech, R.
- Solid State Ionics, Vol. 177, Issue 17-18
Local structure in the Li-ion battery cathode material Lix(MnyFe1−y)PO4 for 0
journal, October 2007
- Burba, Christopher M.; Frech, Roger
- Journal of Power Sources, Vol. 172, Issue 2
In situ Characterization of a Graphite Electrode in a Secondary Lithium-Ion Battery Using Raman Microscopy
journal, October 1999
- Panitz, J. -C.; Joho, F.; Novák, P.
- Applied Spectroscopy, Vol. 53, Issue 10
In Situ Raman Microscopy of Individual LiNi 0.8 Co 0.15 Al 0.05 O 2 Particles in a Li-Ion Battery Composite Cathode
journal, January 2005
- Lei, Jinglei; McLarnon, Frank; Kostecki, Robert
- The Journal of Physical Chemistry B, Vol. 109, Issue 2
Studying lithium intercalation into graphite particles via in situ Raman spectroscopy and confocal microscopy
journal, August 2004
- Migge, S.; Sandmann, G.; Rahner, D.
- Journal of Solid State Electrochemistry, Vol. 9, Issue 3
Reprint of “Studies of local degradation phenomena in composite cathodes for lithium-ion batteries”
journal, December 2007
- Kerlau, Marie; Marcinek, Marek; Srinivasan, Venkat
- Electrochimica Acta, Vol. 53, Issue 3
Effects of Inhomogeneities—Nanoscale to Mesoscale—on the Durability of Li-Ion Batteries
journal, February 2013
- Harris, Stephen J.; Lu, Peng
- The Journal of Physical Chemistry C, Vol. 117, Issue 13
Multiscale Phase Mapping of LiFePO 4 -Based Electrodes by Transmission Electron Microscopy and Electron Forward Scattering Diffraction
journal, November 2013
- Robert, Donatien; Douillard, Thierry; Boulineau, Adrien
- ACS Nano, Vol. 7, Issue 12
Heterogeneous behaviour of the lithium battery composite electrode LiFePO4
journal, May 2013
- Ouvrard, Guy; Zerrouki, Miloud; Soudan, Patrick
- Journal of Power Sources, Vol. 229
Local State-of-Charge Mapping of Lithium-Ion Battery Electrodes
journal, July 2011
- Nanda, Jagjit; Remillard, Jeffrey; O'Neill, Ann
- Advanced Functional Materials, Vol. 21, Issue 17
Lithium Batteries and Cathode Materials
journal, October 2004
- Whittingham, M. Stanley
- Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302
Conditions for a unique solution in factor analysis of overlapped Raman spectra of two components.
journal, January 1987
- Ozeki, Toru; Kihara, Hiroshi; Hikime, Seiichiro
- Analytical Sciences, Vol. 3, Issue 4
Microscopic Raman Line-Imaging with Principal Component Analysis
journal, September 1995
- Drumm, Charlene A.; Morris, Michael D.
- Applied Spectroscopy, Vol. 49, Issue 9
Lattice vibrations of manganese oxides
journal, February 2004
- Julien, C. M.; Massot, M.; Poinsignon, C.
- Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 60, Issue 3
Lattice vibrations of materials for lithium rechargeable batteries V. Local structure of Li0.3MnO2
journal, June 2003
- Banov, B.; Momchilov, A.; Massot, M.
- Materials Science and Engineering: B, Vol. 100, Issue 1
Preparation of Plate-Form Manganese Oxide by Selective Lithium Extraction from Monoclinic Li 2 MnO 3 under Hydrothermal Conditions
journal, November 2000
- Tang, Weiping; Kanoh, Hirofumi; Yang, Xiaojing
- Chemistry of Materials, Vol. 12, Issue 11
Morphology Modification and Delithiation Mechanisms of LiMn2 O 4 and Li2MnO3 by Acid Digestion
journal, January 1998
- Shao‐Horn, Y.; Ein‐Eli, Y.; Robertson, A. D.
- Journal of The Electrochemical Society, Vol. 145, Issue 1
In situ visualization of Li/Ag2VP2O8 batteries revealing rate-dependent discharge mechanism
journal, January 2015
- Kirshenbaum, K.; Bock, D. C.; Lee, C. -Y.
- Science, Vol. 347, Issue 6218
Raman spectra of birnessite manganese dioxides
journal, April 2003
- Julien, C.
- Solid State Ionics, Vol. 159, Issue 3-4
Electrode Performance of Sodium and Lithium-Type Romanechite
journal, January 2003
- Tsuda, Masayuki; Arai, Hajime; Nemoto, Yasue
- Journal of The Electrochemical Society, Vol. 150, Issue 6
Works referencing / citing this record:
Simply Constructing Li 1.2 Mn 0.6 Ni 0.2 O 2 /C Composites for Superior Electrochemical Performance and Thermal Stability in Li-Ion Battery
journal, December 2018
- Chen, Dandan; Xie, Dongjiu; Li, Guangshe
- ChemistrySelect, Vol. 3, Issue 48
Applications of Conventional Vibrational Spectroscopic Methods for Batteries Beyond Li-Ion
journal, March 2018
- Deng, Yuanfu; Dong, Shengyang; Li, Zhifei
- Small Methods, Vol. 2, Issue 8
Direct observation of layered-to-spinel phase transformation in Li 2 MnO 3 and the spinel structure stabilised after the activation process
journal, January 2017
- Shimoda, Keiji; Oishi, Masatsugu; Matsunaga, Toshiyuki
- Journal of Materials Chemistry A, Vol. 5, Issue 14
Composite-Structure Material Design for High-Energy Lithium Storage
journal, July 2018
- Wang, Lin; Shi, Ji-Lei; Su, Heng
- Small, Vol. 14, Issue 34