Improve First-Cycle Efficiency and Rate Performance of Layered-Layered Li 1.2 Mn 0.6 Ni 0.2 O 2 Using Oxygen Stabilizing Dopant

Li, Jinfeng; Zhan, Chun; Lu, Jun; Yuan, Yifei; Shahbazian-Yassar, Reza; Qiu, Xinping; Amine, Khalil

doi:10.1021/acsami.5b04343

Improve First-Cycle Efficiency and Rate Performance of Layered-Layered Li _1.2 Mn _0.6 Ni _0.2 O ₂ Using Oxygen Stabilizing Dopant

Journal Article · Tue Jul 14 04:00:00 EDT 2015 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.5b04343· OSTI ID:1391669

Li, Jinfeng ^[1]; Zhan, Chun ^[2]; Lu, Jun ^[2]; Yuan, Yifei ^[3]; Shahbazian-Yassar, Reza ^[4]; Qiu, Xinping ^[1]; Amine, Khalil ^[2]

Key Laboratory of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China
Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, United States
Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, United States; Department of Materials Science and Engineering, Michigan Technological University, 1400 Townsend Drive, Houghton, Michigan 49931, United States
Department of Materials Science and Engineering, Michigan Technological University, 1400 Townsend Drive, Houghton, Michigan 49931, United States

The poor first-cycle Coulombic efficiency and rate performance of the Li-rich layered-layered oxides are associated with oxygen gas generation in the first activation charging and sluggish charge transportation along the layers. In this work, we report that barium doping improves the first-cycle efficiency of Li-rich layered-layered Li1.2Mn0.6Ni0.2O2 via suppression of the oxidation of O2– ions in the first charging. This effect can be attributed to the stabilizing effect of the barium cations on the oxygen radical intermediates generated during the oxidation of O2–. Meanwhile, because the stabilized oxygen radicals likely facilitate the charge transportation in the layered-layered structure, the barium-doped Li1.2Mn0.6Ni0.2O2 exhibits significant improvement in rate performance. Stabilizing the oxygen radicals could be a promising strategy to improve the electrochemical performance of Li-rich layered-layered oxides.

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES); Argonne National Laboratory (ANL)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1391669

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 29 Vol. 7; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

References (31)

Electrochemical and Structural Investigations on ZnO Treated 0.5 Li ₂ MnO ₃ -0.5LiMn _0.5 Ni _0.5 O ₂ Layered Composite Cathode Material for Lithium Ion Battery Singh, Gurpreet; Thomas, R.; Kumar, Arun Journal of The Electrochemical Society, Vol. 159, Issue 4 https://doi.org/10.1149/2.100204jes	journal	January 2012
Electrochemical Activities in Li[sub 2]MnO[sub 3] Yu, Denis Y. W.; Yanagida, Katsunori; Kato, Yoshio Journal of The Electrochemical Society, Vol. 156, Issue 6 https://doi.org/10.1149/1.3110803	journal	January 2009
Accommodation of Excess Oxygen in Group II Monoxides Middleburgh, Simon C.; Lagerlof, Karl Peter D.; Grimes, Robin W. Journal of the American Ceramic Society, Vol. 96, Issue 1 https://doi.org/10.1111/j.1551-2916.2012.05452.x	journal	September 2012
Investigation of the Irreversible Capacity Loss in the Lithium-Rich Oxide Li[Li1/5Ni1/5Mn3/5]O2 van Bommel, Andrew; Krause, L. J.; Dahn, J. R. Journal of The Electrochemical Society, Vol. 158, Issue 6 https://doi.org/10.1149/1.3579418	journal	January 2011
Conductive Surface Modification with Aluminum of High Capacity Layered Li[Li _0.2 Mn _0.54 Ni _0.13 Co _0.13 ]O ₂ Cathodes Liu, Jun; Reeja-Jayan, B.; Manthiram, Arumugam The Journal of Physical Chemistry C, Vol. 114, Issue 20 https://doi.org/10.1021/jp102050s	journal	May 2010
The Effects of Acid Treatment on the Electrochemical Properties of 0.5 Li₂MnO₃ ∙ 0.5 LiNi_0.44Co_0.25Mn_0.31O₂ Electrodes in Lithium Cells Kang, S.-H.; Johnson, C. S.; Vaughey, J. T. Journal of The Electrochemical Society, Vol. 153, Issue 6, p. A1186-A1192 https://doi.org/10.1149/1.2194764	journal	January 2006
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
High-Power Nanostructured LiMn ₂ _- _x Ni _x O ₄ High-Voltage Lithium-Ion Battery Electrode Materials: Electrochemical Impact of Electronic Conductivity and Morphology Kunduraci, Muharrem; Al-Sharab, Jafar F.; Amatucci, Glenn G. Chemistry of Materials, Vol. 18, Issue 15 https://doi.org/10.1021/cm060729s	journal	July 2006
Critical Role of Oxygen Evolved from Layered Li–Excess Metal Oxides in Lithium Rechargeable Batteries Hong, Jihyun; Lim, Hee-Dae; Lee, Minah Chemistry of Materials, Vol. 24, Issue 14 https://doi.org/10.1021/cm3005634	journal	July 2012
Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: A joint experimental and theoretical study Xu, Bo; Fell, Christopher R.; Chi, Miaofang Energy & Environmental Science, Vol. 4, Issue 6 https://doi.org/10.1039/c1ee01131f	journal	January 2011
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
Electrochemical Behavior of Cr- Doped Composite Li ₂ MnO ₃ -LiMn _0.5 Ni _0.5 O ₂ Cathode Materials Singh, Gurpreet; Thomas, R.; Kumar, Arun Journal of The Electrochemical Society, Vol. 159, Issue 4 https://doi.org/10.1149/2.059204jes	journal	January 2012
Cathode materials for next generation lithium ion batteries Xu, Jiantie; Dou, Shixue; Liu, Huakun Nano Energy, Vol. 2, Issue 4 https://doi.org/10.1016/j.nanoen.2013.05.013	journal	July 2013
Capacity-controllable Li-rich cathode materials for lithium-ion batteries Ye, Delai; Ozawa, Kiyoshi; Wang, Bei Nano Energy, Vol. 6 https://doi.org/10.1016/j.nanoen.2014.03.013	journal	May 2014
Local structure and composition studies of Li1.2Ni0.2Mn0.6O2 by analytical electron microscopy Lei, C. H.; Bareño, J.; Wen, J. G. Journal of Power Sources, Vol. 178, Issue 1 https://doi.org/10.1016/j.jpowsour.2007.11.077	journal	March 2008
Asynchronous Crystal Cell Expansion during Lithiation of K ⁺ -Stabilized α-MnO ₂ Yuan, Yifei; Nie, Anmin; Odegard, Gregory M. Nano Letters, Vol. 15, Issue 5 https://doi.org/10.1021/nl5048913	journal	April 2015
The electrochemical properties of Fe- and Ni-cosubstituted Li2MnO3 via combustion method Liu, Guo-Biao; Liu, Heng; Wang, Yan Journal of Solid State Electrochemistry, Vol. 17, Issue 9 https://doi.org/10.1007/s10008-013-2127-y	journal	May 2013
Overcharging manganese oxides: Extracting lithium beyond Mn4+ Armstrong, A. R.; Robertson, A. D.; Bruce, P. G. Journal of Power Sources, Vol. 146, Issue 1-2 https://doi.org/10.1016/j.jpowsour.2005.03.104	journal	August 2005
Understanding the Effect of Co ³⁺ Substitution on the Electrochemical Properties of Lithium-Rich Layered Oxide Cathodes for Lithium-Ion Batteries Xiang, Xingde; Knight, James C.; Li, Weishan The Journal of Physical Chemistry C, Vol. 118, Issue 38 https://doi.org/10.1021/jp506731v	journal	September 2014
Design of surface protective layer of LiF/FeF3 nanoparticles in Li-rich cathode for high-capacity Li-ion batteries Zhao, Taolin; Li, Li; Chen, Renjie Nano Energy, Vol. 15 https://doi.org/10.1016/j.nanoen.2015.04.013	journal	July 2015
Oxygen Nonstoichiometry in Li ₂ MnO ₃ : An Alternative Explanation for Its Anomalous Electrochemical Activity Pasero, D.; McLaren, V.; de Souza, S. Chemistry of Materials, Vol. 17, Issue 2 https://doi.org/10.1021/cm040186r	journal	January 2005
Influence of cationic substitutions on the first charge and reversible capacities of lithium-rich layered oxide cathodes Wang, Chih-Chieh; Manthiram, Arumugam Journal of Materials Chemistry A, Vol. 1, Issue 35 https://doi.org/10.1039/c3ta11703k	journal	January 2013
Comments on the structural complexity of lithium-rich Li_1+xM_1−xO₂ electrodes (M=Mn, Ni, Co) for lithium batteries Thackeray, M. M.; Kang, S.-H.; Johnson, C. S. Electrochemistry Communications, Vol. 8, Issue 9, p. 1531-1538 https://doi.org/10.1016/j.elecom.2006.06.030	journal	September 2006
Composites of porous Co ₃ O ₄ grown on Li ₂ MnO ₃ microspheres as cathode materials for lithium ion batteries Wang, Faxing; Chang, Zheng; Wang, Xiaowei Journal of Materials Chemistry A, Vol. 3, Issue 9 https://doi.org/10.1039/C4TA06309K	journal	January 2015
Mechanism of Electrochemical Activity in Li ₂ MnO ₃ Robertson, Alastair D.; Bruce, Peter G. Chemistry of Materials, Vol. 15, Issue 10 https://doi.org/10.1021/cm030047u	journal	May 2003
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
Electrochemical and Ex Situ X-Ray Study of Li(Li[sub 0.2]Ni[sub 0.2]Mn[sub 0.6])O[sub 2] Cathode Material for Li Secondary Batteries Kang, S. -H.; Sun, Y. K.; Amine, K. Electrochemical and Solid-State Letters, Vol. 6, Issue 9 https://doi.org/10.1149/1.1594411	journal	January 2003
Enhancing the rate capability of high capacity xLi₂MnO₃ · (1−x)LiMO₂ (M=Mn, Ni, Co) electrodes by Li–Ni–PO₄ treatment Kang, Sun-Ho; Thackeray, Michael M. Electrochemistry Communications, Vol. 11, Issue 4, p. 748-751 https://doi.org/10.1016/j.elecom.2009.01.025	journal	April 2009
High-Energy Cathode Materials (Li ₂ MnO ₃ –LiMO ₂ ) for Lithium-Ion Batteries Yu, Haijun; Zhou, Haoshen The Journal of Physical Chemistry Letters, Vol. 4, Issue 8 https://doi.org/10.1021/jz400032v	journal	March 2013
Improved electron/Li-ion transport and oxygen stability of Mo-doped Li2MnO3 Gao, Yurui; Ma, Jun; Wang, Xuefeng Journal of Materials Chemistry A, Vol. 2, Issue 13 https://doi.org/10.1039/c3ta15236g	journal	January 2014
Atomic Structure of Li ₂ MnO ₃ after Partial Delithiation and Re-Lithiation Wang, Rui; He, Xiaoqing; He, Lunhua Advanced Energy Materials, Vol. 3, Issue 10 https://doi.org/10.1002/aenm.201200842	journal	June 2013

Cited By (7)

Li-Rich Layered/Spinel Cathode Composite 3/4[Li ₂ MnO ₃ ·LiCxO ₂ ]·1/4[LiCxMnO ₄ ] (Cx = Cr _1-y Co _y ) for Li-Ion Batteries Ma, Zhijie; Li, Dan; Han, Yan Journal of The Electrochemical Society, Vol. 166, Issue 3 https://doi.org/10.1149/2.0111903jes	journal	November 2018
Understanding the effect of an in situ generated and integrated spinel phase on a layered Li-rich cathode material using a non-stoichiometric strategy Zhang, Jicheng; Gao, Rui; Sun, Limei Physical Chemistry Chemical Physics, Vol. 18, Issue 36 https://doi.org/10.1039/c6cp03683j	journal	January 2016
New insights into the modification mechanism of Li-rich Li _1.2 Mn _0.6 Ni _0.2 O ₂ coated by Li ₂ ZrO ₃ Zhang, Jicheng; Zhang, Heng; Gao, Rui Physical Chemistry Chemical Physics, Vol. 18, Issue 19 https://doi.org/10.1039/c6cp01366j	journal	January 2016
Self-standing Li _1.2 Mn _0.6 Ni _0.2 O ₂ /graphene membrane as a binder-free cathode for Li-ion batteries Puheng, Yang; Wenxu, Wang; Xiaoliang, Zhang RSC Advances, Vol. 8, Issue 69 https://doi.org/10.1039/c8ra06086j	journal	January 2018
Lithium diffusion study in Li ₂ MnO ₃ and Li _1.17 Ni _0.17 Mn _0.67 O ₂ : a combined experimental and computational approach Sarkar, Tanmay; Prakasha, Kunkanadu R.; Bharadwaj, Mridula Dixit Physical Chemistry Chemical Physics, Vol. 19, Issue 47 https://doi.org/10.1039/c7cp06458f	journal	January 2017
Core–shell and concentration-gradient cathodes prepared via co-precipitation reaction for advanced lithium-ion batteries Hou, Peiyu; Zhang, Hongzhou; Zi, Zhongyue Journal of Materials Chemistry A, Vol. 5, Issue 9 https://doi.org/10.1039/c6ta10297b	journal	January 2017
Mitigating oxygen release in anionic-redox-active cathode materials by cationic substitution through rational design Wynn, Thomas A.; Fang, Chengcheng; Zhang, Minghao Journal of Materials Chemistry A, Vol. 6, Issue 47 https://doi.org/10.1039/c8ta06296j	journal	January 2018

Similar Records

Improve First-Cycle Efficiency and Rate Performance of Layered-Layered Li_1.2Mn_0.6Ni_0.2O₂ Using Oxygen Stabilizing Dopant

Journal Article · Sun Jun 28 20:00:00 EDT 2015 · ACS Applied Materials and Interfaces · OSTI ID:1370832

Revisiting the role of Zr doping in Ni-rich layered cathodes for lithium-ion batteries

Journal Article · Sun Aug 01 20:00:00 EDT 2021 · Journal of Materials Chemistry. A · OSTI ID:1845107

Uncovering the Critical Role of Ni on Surface Lattice Stability in Anionic Redox Active Li_1.2Ni_0.2Mn_0.6O₂

Journal Article · Tue Mar 18 20:00:00 EDT 2025 · Carbon Energy · OSTI ID:2553921

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Barium doping
Layered-layered Li1.2Mn0.6Ni0.2O2
Lithium ion battery
Oxygen releasing
Stabilizing oxygen radicals