Quantifying the Capacity Contributions during Activation of Li2MnO3
Abstract
Though Li2MnO3 was originally considered to be electrochemically inert, its observed activation has spawned a new class of Li-rich layered compounds that deliver capacities beyond the traditional transition-metal redox limit. Despite progress in our understanding of oxygen redox in Li-rich compounds, the underlying origin of the initial charge capacity of Li2MnO3 remains hotly contested. To resolve this issue, we review all possible charge compensation mechanisms including bulk oxygen redox, oxidation of Mn4+, and surface degradation for Li2MnO3 cathodes displaying capacities exceeding 350 mAh g–1. Using elemental and orbital selective X-ray spectroscopy techniques, we rule out oxidation of Mn4+ and bulk oxygen redox during activation of Li2MnO3. Quantitative gas-evolution and titration studies reveal that O2 and CO2 release accounted for a large fraction of the observed capacity during activation with minor contributions from reduced Mn species on the surface. Lastly, these studies reveal that, although Li2MnO3 is considered critical for promoting bulk anionic redox in Li-rich layered oxides, Li2MnO3 by itself does not exhibit bulk oxygen redox or manganese oxidation beyond its initial Mn4+ valence.
- Authors:
-
- Binghamton Univ., NY (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Binghamton Univ., NY (United States). NorthEast Center for Chemical Energy Storage (NECCES)
- Univ. of Muenster (Germany). MEET Battery Research Center, Institute of Physical Chemistry
- Helmholtz-Institute Muenster (Germany)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Binghamton Univ., NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1596994
- Grant/Contract Number:
- SC0012583; AC02-05CH11231; SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Energy Letters
- Additional Journal Information:
- Journal Volume: 5; Journal Issue: 2; Journal ID: ISSN 2380-8195
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Rana, Jatinkumar, Papp, Joseph K., Lebens-Higgins, Zachary, Zuba, Mateusz, Kaufman, Lori A., Goel, Anshika, Schmuch, Richard, Winter, Martin, Whittingham, M. Stanley, Yang, Wanli, McCloskey, Bryan D., and Piper, Louis F. J. Quantifying the Capacity Contributions during Activation of Li2MnO3. United States: N. p., 2020.
Web. doi:10.1021/acsenergylett.9b02799.
Rana, Jatinkumar, Papp, Joseph K., Lebens-Higgins, Zachary, Zuba, Mateusz, Kaufman, Lori A., Goel, Anshika, Schmuch, Richard, Winter, Martin, Whittingham, M. Stanley, Yang, Wanli, McCloskey, Bryan D., & Piper, Louis F. J. Quantifying the Capacity Contributions during Activation of Li2MnO3. United States. doi:https://doi.org/10.1021/acsenergylett.9b02799
Rana, Jatinkumar, Papp, Joseph K., Lebens-Higgins, Zachary, Zuba, Mateusz, Kaufman, Lori A., Goel, Anshika, Schmuch, Richard, Winter, Martin, Whittingham, M. Stanley, Yang, Wanli, McCloskey, Bryan D., and Piper, Louis F. J. Mon .
"Quantifying the Capacity Contributions during Activation of Li2MnO3". United States. doi:https://doi.org/10.1021/acsenergylett.9b02799. https://www.osti.gov/servlets/purl/1596994.
@article{osti_1596994,
title = {Quantifying the Capacity Contributions during Activation of Li2MnO3},
author = {Rana, Jatinkumar and Papp, Joseph K. and Lebens-Higgins, Zachary and Zuba, Mateusz and Kaufman, Lori A. and Goel, Anshika and Schmuch, Richard and Winter, Martin and Whittingham, M. Stanley and Yang, Wanli and McCloskey, Bryan D. and Piper, Louis F. J.},
abstractNote = {Though Li2MnO3 was originally considered to be electrochemically inert, its observed activation has spawned a new class of Li-rich layered compounds that deliver capacities beyond the traditional transition-metal redox limit. Despite progress in our understanding of oxygen redox in Li-rich compounds, the underlying origin of the initial charge capacity of Li2MnO3 remains hotly contested. To resolve this issue, we review all possible charge compensation mechanisms including bulk oxygen redox, oxidation of Mn4+, and surface degradation for Li2MnO3 cathodes displaying capacities exceeding 350 mAh g–1. Using elemental and orbital selective X-ray spectroscopy techniques, we rule out oxidation of Mn4+ and bulk oxygen redox during activation of Li2MnO3. Quantitative gas-evolution and titration studies reveal that O2 and CO2 release accounted for a large fraction of the observed capacity during activation with minor contributions from reduced Mn species on the surface. Lastly, these studies reveal that, although Li2MnO3 is considered critical for promoting bulk anionic redox in Li-rich layered oxides, Li2MnO3 by itself does not exhibit bulk oxygen redox or manganese oxidation beyond its initial Mn4+ valence.},
doi = {10.1021/acsenergylett.9b02799},
journal = {ACS Energy Letters},
number = 2,
volume = 5,
place = {United States},
year = {2020},
month = {1}
}
Web of Science
Works referenced in this record:
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
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
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
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
Phase Transitions in Li2MnO3 Electrodes at Various States-of-Charge
journal, March 2014
- Amalraj, S. Francis; Burlaka, Luba; Julien, Christian M.
- Electrochimica Acta, Vol. 123
Solid State NMR Studies of Li 2 MnO 3 and Li-Rich Cathode Materials: Proton Insertion, Local Structure, and Voltage Fade
journal, November 2014
- Dogan, Fulya; Croy, Jason R.; Balasubramanian, Mahalingam
- Journal of The Electrochemical Society, Vol. 162, Issue 1
Direct synthesis of oxygen-deficient Li2MnO3−x for high capacity lithium battery electrodes
journal, October 2012
- Kubota, Kei; Kaneko, Takayuki; Hirayama, Masaaki
- Journal of Power Sources, Vol. 216
On the Localized Nature of the Structural Transformations of Li 2 MnO 3 Following Electrochemical Cycling
journal, September 2015
- Phillips, Patrick J.; Bareño, Javier; Li, Yan
- Advanced Energy Materials, Vol. 5, Issue 23
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
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
Electrochemical and Structural Properties of xLi2M‘O3 ·(1− x )LiMn0.5Ni0.5O2 Electrodes for Lithium Batteries (M‘ = Ti, Mn, Zr; 0 ≤ x ⩽ 0.3)
journal, May 2004
- Kim, Jeom-Soo; Johnson, Christopher S.; Vaughey, John T.
- Chemistry of Materials, Vol. 16, Issue 10, p. 1996-2006
The significance of the Li2MnO3 component in ‘composite’ xLi2MnO3·(1−x)LiMn0.5Ni0.5O2 electrodes
journal, October 2004
- Johnson, C. S.; Kim, J-S.; Lefief, C.
- Electrochemistry Communications, Vol. 6, Issue 10, p. 1085-1091
Lithium Extraction Mechanism in Li-Rich Li 2 MnO 3 Involving Oxygen Hole Formation and Dimerization
journal, September 2016
- Chen, Hungru; Islam, M. Saiful
- Chemistry of Materials, Vol. 28, Issue 18
The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials
journal, May 2016
- Seo, Dong-Hwa; Lee, Jinhyuk; Urban, Alexander
- Nature Chemistry, Vol. 8, Issue 7
Probing the Degradation Mechanism of Li 2 MnO 3 Cathode for Li-Ion Batteries
journal, January 2015
- Yan, Pengfei; Xiao, Liang; Zheng, Jianming
- Chemistry of Materials, Vol. 27, Issue 3
Anomalous capacity and cycling stability of xLi2MnO3·(1−x)LiMO2 electrodes (M=Mn, Ni, Co) in lithium batteries at 50°C
journal, April 2007
- Johnson, Christopher S.; Li, Naichao; Lefief, Christina
- Electrochemistry Communications, Vol. 9, Issue 4, p. 787-795
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
On the structural integrity and electrochemical activity of a 0.5Li2MnO3·0.5LiCoO2 cathode material for lithium-ion batteries
journal, January 2014
- Rana, Jatinkumar; Kloepsch, Richard; Li, Jie
- Journal of Materials Chemistry A, Vol. 2, Issue 24
Structural Changes in a Li-Rich 0.5Li 2 MnO 3 * 0.5LiMn 0.4 Ni 0.4 Co 0.2 O 2 Cathode Material for Li-Ion Batteries: A Local Perspective
journal, January 2016
- Rana, Jatinkumar; Kloepsch, Richard; Li, Jie
- Journal of The Electrochemical Society, Vol. 163, Issue 6
Oxygen Release and Surface Degradation of Li- and Mn-Rich Layered Oxides in Variation of the Li 2 MnO 3 Content
journal, January 2018
- Teufl, Tobias; Strehle, Benjamin; Müller, Philipp
- Journal of The Electrochemical Society, Vol. 165, Issue 11
Manganese oxidation as the origin of the anomalous capacity of Mn-containing Li-excess cathode materials
journal, July 2019
- Radin, Maxwell D.; Vinckeviciute, Julija; Seshadri, Ram
- Nature Energy, Vol. 4, Issue 8
Gas–solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries
journal, July 2016
- Qiu, Bao; Zhang, Minghao; Wu, Lijun
- Nature Communications, Vol. 7, Issue 1
Synthesis of Li-Rich NMC: A Comprehensive Study
journal, November 2017
- Pimenta, Vanessa; Sathiya, Mariyappan; Batuk, Dmitry
- Chemistry of Materials, Vol. 29, Issue 23
Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen
journal, March 2016
- Luo, Kun; Roberts, Matthew R.; Hao, Rong
- Nature Chemistry, Vol. 8, Issue 7
Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides
journal, December 2017
- Gent, William E.; Lim, Kipil; Liang, Yufeng
- Nature Communications, Vol. 8, Issue 1
Elucidating anionic oxygen activity in lithium-rich layered oxides
journal, March 2018
- Xu, Jing; Sun, Meiling; Qiao, Ruimin
- Nature Communications, Vol. 9, Issue 1
Distinction between Intrinsic and X-ray-Induced Oxidized Oxygen States in Li-Rich 3d Layered Oxides and LiAlO 2
journal, May 2019
- Lebens-Higgins, Zachary W.; Vinckeviciute, Julija; Wu, Jinpeng
- The Journal of Physical Chemistry C, Vol. 123, Issue 21
Excess Lithium in Transition Metal Layers of Epitaxially Grown Thin Film Cathodes of Li 2 MnO 3 Leads to Rapid Loss of Covalency during First Battery Cycle
journal, November 2019
- Massel, Felix; Hikima, Kazuhiro; Rensmo, Håkan
- The Journal of Physical Chemistry C, Vol. 123, Issue 47
Revisiting the charge compensation mechanisms in LiNi 0.8 Co 0.2−y Al y O 2 systems
journal, January 2019
- Lebens-Higgins, Zachary W.; Faenza, Nicholas V.; Radin, Maxwell D.
- Materials Horizons, Vol. 6, Issue 10
Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode
journal, October 2019
- Li, Ning; Sallis, Shawn; Papp, Joseph K.
- ACS Energy Letters, Vol. 4, Issue 12
Crystallographic and magnetic structure of Li2MnO3
journal, July 1988
- Strobel, Pierre; Lambert-Andron, Bernadette
- Journal of Solid State Chemistry, Vol. 75, Issue 1
Structure of Li2MnO3 with different degrees of defects
journal, January 2010
- Boulineau, A.; Croguennec, L.; Delmas, C.
- Solid State Ionics, Vol. 180, Issue 40
Quantum many-body effects in x-ray spectra efficiently computed using a basic graph algorithm
journal, May 2018
- Liang, Yufeng; Prendergast, David
- Physical Review B, Vol. 97, Issue 20
Anionic and cationic redox and interfaces in batteries: Advances from soft X-ray absorption spectroscopy to resonant inelastic scattering
journal, June 2018
- Yang, Wanli; Devereaux, Thomas P.
- Journal of Power Sources, Vol. 389
Quantification of Surface Oxygen Depletion and Solid Carbonate Evolution on the First Cycle of LiNi 0.6 Mn 0.2 Co 0.2 O 2 Electrodes
journal, April 2019
- Renfrew, Sara E.; McCloskey, Bryan D.
- ACS Applied Energy Materials, Vol. 2, Issue 5
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013
- Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy
- APL Materials, Vol. 1, Issue 1
Isotope effects in the bonds of α-CrOOH and α-CrOOD
journal, August 1977
- Christensen, A. Nørlund; Hansen, P.; Lehmann, M. S.
- Journal of Solid State Chemistry, Vol. 21, Issue 4
Assignment of pre-edge peaks in K-edge x-ray absorption spectra of 3d transition metal compounds: electric dipole or quadrupole?
journal, November 2008
- Yamamoto, Takashi
- X-Ray Spectrometry, Vol. 37, Issue 6
Electronic structure modification and Fermi level shifting in niobium-doped anatase titanium dioxide thin films: a comparative study of NEXAFS, work function and stiffening of phonons
journal, January 2016
- Gautam, Subodh K.; Das, Arkaprava; Ojha, S.
- Physical Chemistry Chemical Physics, Vol. 18, Issue 5
Singlet oxygen evolution from layered transition metal oxide cathode materials and its implications for lithium-ion batteries
journal, October 2018
- Wandt, Johannes; Freiberg, Anna T. S.; Ogrodnik, Alexander
- Materials Today, Vol. 21, Issue 8
Reaction Heterogeneity in LiNi 0.8 Co 0.15 Al 0.05 O 2 Induced by Surface Layer
journal, August 2017
- Grenier, Antonin; Liu, Hao; Wiaderek, Kamila M.
- Chemistry of Materials, Vol. 29, Issue 17
Evolution of the Electrode–Electrolyte Interface of LiNi 0.8 Co 0.15 Al 0.05 O 2 Electrodes Due to Electrochemical and Thermal Stress
journal, January 2018
- Lebens-Higgins, Zachary W.; Sallis, Shawn; Faenza, Nicholas V.
- Chemistry of Materials, Vol. 30, Issue 3
The cathode–electrolyte interface in the Li-ion battery
journal, November 2004
- Edström, K.; Gustafsson, T.; Thomas, J. O.
- Electrochimica Acta, Vol. 50, Issue 2-3
The Effect of Vinylene Carbonate Additive on Surface Film Formation on Both Electrodes in Li-Ion Batteries
journal, January 2009
- El Ouatani, L.; Dedryvère, R.; Siret, C.
- Journal of The Electrochemical Society, Vol. 156, Issue 2
Electron Transfer Mechanisms upon Lithium Deintercalation from LiCoO 2 to CoO 2 Investigated by XPS
journal, January 2008
- Dahéron, L.; Dedryvère, R.; Martinez, H.
- Chemistry of Materials, Vol. 20, Issue 2
Surface Reactivity of Li 2 MnO 3 : First-Principles and Experimental Study
journal, December 2017
- Quesne-Turin, Ambroise; Flahaut, Delphine; Croguennec, Laurence
- ACS Applied Materials & Interfaces, Vol. 9, Issue 50
The origin of electrochemical activity in Li2MnO3
journal, October 2002
- Robertson, Alastair D.; Bruce, Peter G.
- Chemical Communications, Issue 23
Trace doping of multiple elements enables stable battery cycling of LiCoO2 at 4.6 V
journal, June 2019
- Zhang, Jie-Nan; Li, Qinghao; Ouyang, Chuying
- Nature Energy, Vol. 4, Issue 7
Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries
journal, December 2015
- McCalla, E.; Abakumov, A. M.; Saubanere, M.
- Science, Vol. 350, Issue 6267
Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries
journal, January 2017
- Xie, Y.; Saubanère, M.; Doublet, M. -L.
- Energy & Environmental Science, Vol. 10, Issue 1
Local structure adaptability through multi cations for oxygen redox accommodation in Li-Rich layered oxides
journal, January 2020
- Zhao, Enyue; Zhang, Minghao; Wang, Xuelong
- Energy Storage Materials, Vol. 24