Enhanced long-term cyclability in Li-Rich layered oxides by electrochemically constructing a LixTM3-xO4-type spinel shell
Abstract
The poor long-term cycling stability, including the fast capacity fade and the severe voltage decay, has become the main concern hindering the practical application of Li-rich layered oxides, a promising cathode for high- energy-density Li-ion battery. Herein, we design and electrochemically construct a ~10 nm-thick LixTM3-xO4- type (TM ¼Ni, Co, Mn, 0 <1) spinel shell at the particle surface, which possesses both the good structural stability of TM3O4-type spinel phase and the good Liþconductivity of LiMn2O4-type spinel phase. Systemic structural and electrochemical analysis demonstrate that, it slows down the activation rate of Li2MnO3 component and efficiently alleviates the lattice O loss at high voltage (>4.5 V) and Mn dissolution, thereby suppressing the structural degradation from the layered phase to the spinel phase in the bulk, eventually significantly enhancing the long-term cycling stability. This study adds richness into the Mn-based spinel phase system and provides a new heterostructure design strategy to improve the electrochemical performance of Li-rich layered cathodes and beyond.
- Authors:
-
- Peking Univ., Beijing (China); Univ. of Chicago, IL (United States)
- Peking Univ., Beijing (China)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation (NSF); National Key Research and Development Program of China
- OSTI Identifier:
- 1768872
- Alternate Identifier(s):
- OSTI ID: 1809802
- Grant/Contract Number:
- AC02-06CH11357; 2016YFB0700600; ZDSYS201707281026184; NSF/CHE-1834750
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nano Energy
- Additional Journal Information:
- Journal Volume: 77; Journal ID: ISSN 2211-2855
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; Cycling stability; Li-ion batteries; Li-rich layered oxides; LixTM3-xO4-type spinel shell; Structural degradation
Citation Formats
Zhang, Mingjian, Li, Zhibo, Yu, Lei, Kong, Defei, Li, Yiwei, Cao, Bo, Zhao, Wenguang, Wen, Jianguo, and Pan, Feng. Enhanced long-term cyclability in Li-Rich layered oxides by electrochemically constructing a LixTM3-xO4-type spinel shell. United States: N. p., 2020.
Web. doi:10.1016/j.nanoen.2020.105188.
Zhang, Mingjian, Li, Zhibo, Yu, Lei, Kong, Defei, Li, Yiwei, Cao, Bo, Zhao, Wenguang, Wen, Jianguo, & Pan, Feng. Enhanced long-term cyclability in Li-Rich layered oxides by electrochemically constructing a LixTM3-xO4-type spinel shell. United States. https://doi.org/10.1016/j.nanoen.2020.105188
Zhang, Mingjian, Li, Zhibo, Yu, Lei, Kong, Defei, Li, Yiwei, Cao, Bo, Zhao, Wenguang, Wen, Jianguo, and Pan, Feng. Sun .
"Enhanced long-term cyclability in Li-Rich layered oxides by electrochemically constructing a LixTM3-xO4-type spinel shell". United States. https://doi.org/10.1016/j.nanoen.2020.105188. https://www.osti.gov/servlets/purl/1768872.
@article{osti_1768872,
title = {Enhanced long-term cyclability in Li-Rich layered oxides by electrochemically constructing a LixTM3-xO4-type spinel shell},
author = {Zhang, Mingjian and Li, Zhibo and Yu, Lei and Kong, Defei and Li, Yiwei and Cao, Bo and Zhao, Wenguang and Wen, Jianguo and Pan, Feng},
abstractNote = {The poor long-term cycling stability, including the fast capacity fade and the severe voltage decay, has become the main concern hindering the practical application of Li-rich layered oxides, a promising cathode for high- energy-density Li-ion battery. Herein, we design and electrochemically construct a ~10 nm-thick LixTM3-xO4- type (TM ¼Ni, Co, Mn, 0 <1) spinel shell at the particle surface, which possesses both the good structural stability of TM3O4-type spinel phase and the good Liþconductivity of LiMn2O4-type spinel phase. Systemic structural and electrochemical analysis demonstrate that, it slows down the activation rate of Li2MnO3 component and efficiently alleviates the lattice O loss at high voltage (>4.5 V) and Mn dissolution, thereby suppressing the structural degradation from the layered phase to the spinel phase in the bulk, eventually significantly enhancing the long-term cycling stability. This study adds richness into the Mn-based spinel phase system and provides a new heterostructure design strategy to improve the electrochemical performance of Li-rich layered cathodes and beyond.},
doi = {10.1016/j.nanoen.2020.105188},
journal = {Nano Energy},
number = ,
volume = 77,
place = {United States},
year = {Sun Jul 26 00:00:00 EDT 2020},
month = {Sun Jul 26 00:00:00 EDT 2020}
}
Works referenced in this record:
Understanding the Rate Capability of High-Energy-Density Li-Rich Layered Li 1.2 Ni 0.15 Co 0.1 Mn 0.55 O 2 Cathode Materials
journal, December 2013
- Yu, Xiqian; Lyu, Yingchun; Gu, Lin
- Advanced Energy Materials, Vol. 4, Issue 5
Review—Lithium-Excess Layered Cathodes for Lithium Rechargeable Batteries
journal, January 2015
- Hong, Jihyun; Gwon, Hyeokjo; Jung, Sung-Kyun
- Journal of The Electrochemical Society, Vol. 162, Issue 14
The characterization and electrochemical performance of Li[Li 0.2 Ni 0.4 Mn 0.4 ]O 2 material prepared by a combustion method
journal, March 2015
- Yan, Wuwei; Wen, Hua; Chen, Yuanzhen
- Journal of Power Sources, Vol. 277
Electrochemical performances of Li4Mn5O12 films prepared by spray-coated sol-gel reaction
journal, November 2018
- Alié, Christelle; Calberg, Cédric; Páez, Carlos
- Journal of Power Sources, Vol. 403
Surface structural conversion and electrochemical enhancement by heat treatment of chemical pre-delithiation processed lithium-rich layered cathode material
journal, December 2014
- Han, Shaojie; Qiu, Bao; Wei, Zhen
- Journal of Power Sources, Vol. 268
Significant improved electrochemical performance of layered Li 1.2 Mn 0.54 Co 0.13 Ni 0.13 O 2 via graphene surface modification
journal, August 2016
- Cheng, Jianliang; Li, Xinhai; He, Zhenjiang
- Materials Technology, Vol. 31, Issue 11
Cyclic deterioration and its improvement for Li-rich layered cathode material Li[Ni0.17Li0.2Co0.07Mn0.56]O2
journal, January 2010
- Ito, Atsushi; Li, Decheng; Sato, Yuichi
- Journal of Power Sources, Vol. 195, Issue 2, p. 567-573
Synthesis and electrochemical characterization of Zn-doped Li-rich layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material
journal, November 2015
- Zhao, Junkai; Wang, Zhixing; Guo, Huajun
- Ceramics International, Vol. 41, Issue 9
Understanding the Origin of Li 2 MnO 3 Activation in Li-Rich Cathode Materials for Lithium-Ion Batteries
journal, November 2015
- Ye, Delai; Zeng, Guang; Nogita, Kazuhiro
- Advanced Functional Materials, Vol. 25, Issue 48
Understanding Voltage Decay in Lithium-Rich Manganese-Based Layered Cathode Materials by Limiting Cutoff Voltage
journal, July 2016
- Yang, Jingsong; Xiao, Lifen; He, Wei
- ACS Applied Materials & Interfaces, Vol. 8, Issue 29
Superior Long-Term Energy Retention and Volumetric Energy Density for Li-Rich Cathode Materials
journal, September 2014
- Oh, Pilgun; Myeong, Seungjun; Cho, Woongrae
- Nano Letters, Vol. 14, Issue 10
Suppressing the Voltage Decay and Enhancing the Electrochemical Performance of Li 1.2 Mn 0.54 Co 0.13 Ni 0.13 O 2 by Multifunctional Nb 2 O 5 Coating
journal, October 2018
- Pan, Wei; Peng, Wenjie; Yan, Guochun
- Energy Technology, Vol. 6, Issue 11
Continuous activation of Li2MnO3 component upon cycling in Li1.167Ni0.233Co0.100Mn0.467Mo0.033O2 cathode material for lithium ion batteries
journal, January 2013
- Yu, Seung-Ho; Yoon, Taeho; Mun, Junyoung
- Journal of Materials Chemistry A, Vol. 1, Issue 8
Another Strategy, Detouring Potential Decay by Fast Completion of Cation Mixing
journal, February 2018
- Liu, Shuai; Feng, Xin; Wang, Xuelong
- Advanced Energy Materials, Vol. 8, Issue 15
Suppressing Surface Lattice Oxygen Release of Li-Rich Cathode Materials via Heterostructured Spinel Li 4 Mn 5 O 12 Coating
journal, May 2018
- Zhang, Xu-Dong; Shi, Ji-Lei; Liang, Jia-Yan
- Advanced Materials, Vol. 30, Issue 29
Structure and electrochemistry of B doped Li(Li0.2Ni0.13Co0.13Mn0.54)1-B O2 as cathode materials for lithium-ion batteries
journal, September 2016
- Pan, Lingchao; Xia, Yonggao; Qiu, Bao
- Journal of Power Sources, Vol. 327
Enhanced electrochemical properties of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 via lithium boron oxide glass surface treatment
journal, September 2016
- Bai, Maohui; Wang, Zhixing; Li, Xinhai
- Solid State Ionics, Vol. 292
Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries
journal, March 2005
- Thackeray, Michael M.; Johnson, Christopher S.; Vaughey, John T.
- Journal of Materials Chemistry, Vol. 15, Issue 23, p. 2257-2267
Effect of cycling conditions on the electrochemical performance of high capacity Li and Mn-rich cathodes for Li-ion batteries
journal, June 2016
- Nayak, Prasant Kumar; Grinblat, Judith; Levi, Elena
- Journal of Power Sources, Vol. 318
Structural evolution and the capacity fade mechanism upon long-term cycling in Li-rich cathode material
journal, January 2012
- Song, Bohang; Liu, Zongwen; Lai, Man On
- Physical Chemistry Chemical Physics, Vol. 14, Issue 37
Origin of voltage decay in high-capacity layered oxide electrodes
journal, December 2014
- Sathiya, M.; Abakumov, A. M.; Foix, D.
- Nature Materials, Vol. 14, Issue 2
High Capacity Li-Rich Positive Electrode Materials with Reduced First-Cycle Irreversible Capacity Loss
journal, January 2015
- Shunmugasundaram, Ramesh; Senthil Arumugam, Rajalakshmi; Dahn, J. R.
- Chemistry of Materials, Vol. 27, Issue 3
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
Evolutions of Li 1.2 Mn 0.61 Ni 0.18 Mg 0.01 O 2 during the Initial Charge/Discharge Cycle Studied by Advanced Electron Microscopy
journal, September 2012
- Boulineau, Adrien; Simonin, Loïc; Colin, Jean-François
- Chemistry of Materials, Vol. 24, Issue 18
Effects of Na+ contents on electrochemical properties of Li1.2Ni0.13Co0.13Mn0.54O2 cathode materials
journal, October 2013
- Qiu, Bao; Wang, Jun; Xia, Yonggao
- Journal of Power Sources, Vol. 240
A novel architecture designed for lithium rich layered Li[Li 0.2 Mn 0.54 Ni 0.13 Co 0.13 ]O 2 oxides for lithium-ion batteries
journal, January 2015
- He, Zhenjiang; Wang, Zhixing; Huang, Zimo
- Journal of Materials Chemistry A, Vol. 3, Issue 32
Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery
journal, October 2019
- Liu, Tongchao; Dai, Alvin; Lu, Jun
- Nature Communications, Vol. 10, Issue 1
Understanding the stepwise capacity increase of high energy low-Co Li-rich cathode materials for lithium ion batteries
journal, January 2014
- Ye, Delai; Wang, Bei; Chen, Yu
- J. Mater. Chem. A, Vol. 2, Issue 44
Synthesis and electrochemical study of Zr-doped Li[Li0.2Mn0.54Ni0.13Co0.13]O2 as cathode material for Li-ion battery
journal, January 2016
- Chen, Hao; Hu, Qiyang; Huang, Zimo
- Ceramics International, Vol. 42, Issue 1
Effectively suppressing dissolution of manganese from spinel lithium manganate via a nanoscale surface-doping approach
journal, December 2014
- Lu, Jun; Zhan, Chun; Wu, Tianpin
- Nature Communications, Vol. 5, Issue 1
A New Spinel-Layered Li-Rich Microsphere as a High-Rate Cathode Material for Li-Ion Batteries
journal, April 2014
- Luo, Dong; Li, Guangshe; Fu, Chaochao
- Advanced Energy Materials, Vol. 4, Issue 11
Improving the electrochemical performance of layered lithium-rich cathode materials by fabricating a spinel outer layer with Ni 3+
journal, January 2015
- Yang, Cheng; Zhang, Qian; Ding, Weixiang
- Journal of Materials Chemistry A, Vol. 3, Issue 14
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
Synchronous Tailoring Surface Structure and Chemical Composition of Li-Rich-Layered Oxide for High-Energy Lithium-Ion Batteries
journal, August 2018
- Wu, Bing; Yang, Xiukang; Jiang, Xia
- Advanced Functional Materials, Vol. 28, Issue 37
Review—Li-Rich Layered Oxide Cathodes for Next-Generation Li-Ion Batteries: Chances and Challenges
journal, January 2015
- Rozier, Patrick; Tarascon, Jean Marie
- Journal of The Electrochemical Society, Vol. 162, Issue 14
Layered Oxide Cathodes for Li-Ion Batteries: Oxygen Loss and Vacancy Evolution
journal, August 2019
- Zhang, Hanlei; May, Brian M.; Omenya, Fredrick
- Chemistry of Materials, Vol. 31, Issue 18
Li‐ and Mn‐Rich Cathode Materials: Challenges to Commercialization
journal, December 2016
- Zheng, Jianming; Myeong, Seungjun; Cho, Woongrae
- Advanced Energy Materials, Vol. 7, Issue 6
Optimal microwave-assisted hydrothermal synthesis of nanosized x Li 2 MnO 3 ·(1 − x )LiNi 1/3 Co 1/3 Mn 1/3 O 2 cathode materials for lithium ion battery
journal, February 2014
- Miao, Xiaowei; Yan, Yuan; Wang, Chunguang
- Journal of Power Sources, Vol. 247
Structural and electrochemical characterization of Mg-doped Li1.2[Mn0.54Ni0.13Co0.13]O2 cathode material for lithium ion batteries
journal, December 2015
- Huang, Zimo; Li, Xinhai; Liang, Yuhao
- Solid State Ionics, Vol. 282
High-Energy Cathode Materials (Li 2 MnO 3 –LiMO 2 ) for Lithium-Ion Batteries
journal, March 2013
- Yu, Haijun; Zhou, Haoshen
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 8
Effect of titanium addition as nickel oxide formation inhibitor in nickel-rich cathode material for lithium-ion batteries
journal, December 2015
- Nurpeissova, Arailym; Choi, Moon Ho; Kim, Jik-Soo
- Journal of Power Sources, Vol. 299
Layered/spinel heterostructured Li-rich materials synthesized by a one-step solvothermal strategy with enhanced electrochemical performance for Li-ion batteries
journal, January 2016
- Deng, Ya-Ping; Fu, Fang; Wu, Zhen-Guo
- Journal of Materials Chemistry A, Vol. 4, Issue 1
Electrochemical performance and thermal stability of Li1.18Co0.15Ni0.15Mn0.52O2 surface coated with the ionic conductor Li3VO4
journal, January 2014
- Fu, Qiang; Du, Fei; Bian, Xiaofei
- Journal of Materials Chemistry A, Vol. 2, Issue 20
Quantifying Hysteresis and Voltage Fade in xLi 2 MnO 3 ● (1-x)LiMn 0.5 Ni 0.5 O 2 Electrodes as a Function of Li 2 MnO 3 Content
journal, December 2013
- Croy, Jason R.; Gallagher, Kevin G.; Balasubramanian, Mahalingam
- Journal of The Electrochemical Society, Vol. 161, Issue 3
Synthesis, Structure, and Electrochemical Behavior of Li[Ni[sub x]Li[sub 1/3−2x/3]Mn[sub 2/3−x/3]]O[sub 2]
journal, January 2002
- Lu, Zhonghua; Beaulieu, L. Y.; Donaberger, R. A.
- Journal of The Electrochemical Society, Vol. 149, Issue 6
Layered Lithium-Rich Oxide Nanoparticles Doped with Spinel Phase: Acidic Sucrose-Assistant Synthesis and Excellent Performance as Cathode of Lithium Ion Battery
journal, February 2016
- Chen, Min; Chen, Dongrui; Liao, Youhao
- ACS Applied Materials & Interfaces, Vol. 8, Issue 7
Lithium- and Manganese-Rich Oxide Cathode Materials for High-Energy Lithium Ion Batteries
journal, August 2016
- Wang, Jun; He, Xin; Paillard, Elie
- Advanced Energy Materials, Vol. 6, Issue 21
Retarding Phase Transformation During Cycling in a Lithium‐ and Manganese‐Rich Cathode Material by Optimizing Synthesis Conditions
journal, January 2019
- Hu, Bei; Lou, Xiaobing; Li, Chao
- ChemElectroChem, Vol. 6, Issue 5
Injection of oxygen vacancies in the bulk lattice of layered cathodes
journal, April 2019
- Yan, Pengfei; Zheng, Jianming; Tang, Zhen-Kun
- Nature Nanotechnology, Vol. 14, Issue 6
Optimally designed interface of lithium rich layered oxides for lithium ion battery
journal, June 2017
- He, Zhenjiang; Ping, Jing; Yi, Zhaojun
- Journal of Alloys and Compounds, Vol. 708
Facile design and synthesis of Li-rich nanoplates cathodes with habit-tuned crystal for lithium ion batteries
journal, November 2016
- Li, Jili; Jia, Tiekun; Liu, Kai
- Journal of Power Sources, Vol. 333
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
Countering the Voltage Decay in High Capacity xLi 2 MnO 3 •(1–x)LiMO 2 Electrodes (M=Mn, Ni, Co) for Li + -Ion Batteries
journal, January 2012
- Croy, Jason R.; Kim, Donghan; Balasubramanian, Mahalingam
- Journal of The Electrochemical Society, Vol. 159, Issue 6
Oxygen Vacancies and Stacking Faults Introduced by Low-Temperature Reduction Improve the Electrochemical Properties of Li 2 MnO 3 Nanobelts as Lithium-Ion Battery Cathodes
journal, October 2017
- Sun, Ya; Cong, Hengjiang; Zan, Ling
- ACS Applied Materials & Interfaces, Vol. 9, Issue 44
Atomic Resolution Structural and Chemical Imaging Revealing the Sequential Migration of Ni, Co, and Mn upon the Battery Cycling of Layered Cathode
journal, May 2017
- Yan, Pengfei; Zheng, Jianming; Zhang, Ji-Guang
- Nano Letters, Vol. 17, Issue 6
Effects of structural defects on the electrochemical activation of Li2MnO3
journal, September 2015
- Xiao, Liang; Xiao, Jie; Yu, Xiqian
- Nano Energy, Vol. 16
Surface Doping to Enhance Structural Integrity and Performance of Li-Rich Layered Oxide
journal, October 2018
- Liu, Shuai; Liu, Zepeng; Shen, Xi
- Advanced Energy Materials, Vol. 8, Issue 31
Suppressing Manganese Dissolution from Lithium Manganese Oxide Spinel Cathodes with Single-Layer Graphene
journal, June 2015
- Jaber-Ansari, Laila; Puntambekar, Kanan P.; Kim, Soo
- Advanced Energy Materials, Vol. 5, Issue 17
Improvement of the cyclic deterioration and structural evolution of Li[Li 0.2 Ni 0.2 Mn 0.6 ]O 2 cathode material by controlling initial charging voltages
journal, January 2016
- Yan, Wuwei; Liu, Yongning; Chong, Shaokun
- RSC Advances, Vol. 6, Issue 28
Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries
journal, December 2012
- Gu, Meng; Belharouak, Ilias; Zheng, Jianming
- ACS Nano, Vol. 7, Issue 1
Lack of Cation Clustering in Li[Ni x Li 1/3 - 2 x /3 Mn 2/3 - x / 3 ]O 2 (0 < x ≤ 1 / 2 ) and Li[Cr x Li (1 - x )/3 Mn (2 - 2 x )/3 ]O 2 (0 < x < 1)
journal, August 2003
- Lu, Zhonghua; Chen, Zhaohui; Dahn, J. R.
- Chemistry of Materials, Vol. 15, Issue 16