Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping
Abstract
Here, lithium cobalt oxides (LiCoO2) possess a high theoretical specific capacity of 274 mAh/g. However, cycling LiCoO2-based batteries to voltages greater than 4.35 V vs. Li/Li+ causes significant structural instability and severe capacity fade. Consequently, commercial LiCoO2 exhibits a maximum capacity of only ~165 mAh/g. Here we develop a doping technique to tackle this long-standing issue of instability and thus increase the capacity of LiCoO2. La and Al are concurrently doped into Co-containing precursors, followed by high-temperature calcination with lithium carbonate. The dopants are found to reside in the crystal lattice of LiCoO2, where La works as a pillar to increase the c-axis distance and Al as a positively charged center, facilitating Li+ diffusion, stabilizing the structure and suppressing the phase transition during cycling, even at a high cut-off voltage of 4.5 V. This doped LiCoO2 displays an exceptionally high capacity of 190 mAh/g, cyclability with 96% capacity retention over 50 cycles and significantly enhanced rate capability.
- Authors:
-
- Argonne National Lab. (ANL), Argonne, IL (United States); City Univ. of Hong Kong, Hong Kong (China)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Huawei Technologies, Shenzhen (China)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
- OSTI Identifier:
- 1487027
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Energy
- Additional Journal Information:
- Journal Volume: 3; Journal Issue: 11; Journal ID: ISSN 2058-7546
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Liu, Qi, Su, Xin, Lei, Dan, Qin, Yan, Wen, Jianguo, Guo, Fangmin, Wu, Yimin A., Rong, Yangchun, Kou, Ronghui, Xiao, Xianghui, Aguesse, Frederic, Bareño, Javier, Ren, Yang, Lu, Wenquan, and Li, Yangxing. Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping. United States: N. p., 2018.
Web. doi:10.1038/s41560-018-0180-6.
Liu, Qi, Su, Xin, Lei, Dan, Qin, Yan, Wen, Jianguo, Guo, Fangmin, Wu, Yimin A., Rong, Yangchun, Kou, Ronghui, Xiao, Xianghui, Aguesse, Frederic, Bareño, Javier, Ren, Yang, Lu, Wenquan, & Li, Yangxing. Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping. United States. https://doi.org/10.1038/s41560-018-0180-6
Liu, Qi, Su, Xin, Lei, Dan, Qin, Yan, Wen, Jianguo, Guo, Fangmin, Wu, Yimin A., Rong, Yangchun, Kou, Ronghui, Xiao, Xianghui, Aguesse, Frederic, Bareño, Javier, Ren, Yang, Lu, Wenquan, and Li, Yangxing. Mon .
"Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping". United States. https://doi.org/10.1038/s41560-018-0180-6. https://www.osti.gov/servlets/purl/1487027.
@article{osti_1487027,
title = {Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping},
author = {Liu, Qi and Su, Xin and Lei, Dan and Qin, Yan and Wen, Jianguo and Guo, Fangmin and Wu, Yimin A. and Rong, Yangchun and Kou, Ronghui and Xiao, Xianghui and Aguesse, Frederic and Bareño, Javier and Ren, Yang and Lu, Wenquan and Li, Yangxing},
abstractNote = {Here, lithium cobalt oxides (LiCoO2) possess a high theoretical specific capacity of 274 mAh/g. However, cycling LiCoO2-based batteries to voltages greater than 4.35 V vs. Li/Li+ causes significant structural instability and severe capacity fade. Consequently, commercial LiCoO2 exhibits a maximum capacity of only ~165 mAh/g. Here we develop a doping technique to tackle this long-standing issue of instability and thus increase the capacity of LiCoO2. La and Al are concurrently doped into Co-containing precursors, followed by high-temperature calcination with lithium carbonate. The dopants are found to reside in the crystal lattice of LiCoO2, where La works as a pillar to increase the c-axis distance and Al as a positively charged center, facilitating Li+ diffusion, stabilizing the structure and suppressing the phase transition during cycling, even at a high cut-off voltage of 4.5 V. This doped LiCoO2 displays an exceptionally high capacity of 190 mAh/g, cyclability with 96% capacity retention over 50 cycles and significantly enhanced rate capability.},
doi = {10.1038/s41560-018-0180-6},
journal = {Nature Energy},
number = 11,
volume = 3,
place = {United States},
year = {Mon Jun 11 00:00:00 EDT 2018},
month = {Mon Jun 11 00:00:00 EDT 2018}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Effect of Mn-substitution for Co on the crystal structure and acid delithiation of LiMnyCo1−yO2 solid solutions
journal, November 1994
- Stoyanova, R.; Zhecheva, E.; Zarkova, L.
- Solid State Ionics, Vol. 73, Issue 3-4
X-ray diffraction, 57Fe Mössbauer and step potential electrochemical spectroscopy study of LiFeyCo1−yO2 compounds
journal, September 1999
- Alcántara, R.; Jumas, J. C.; Lavela, P.
- Journal of Power Sources, Vol. 81-82
Lithium Batteries and Cathode Materials
journal, October 2004
- Whittingham, M. Stanley
- Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302
Effects of MgO Coating on the Structural and Electrochemical Characteristics of LiCoO 2 as Cathode Materials for Lithium Ion Battery
journal, April 2014
- Shim, Jae-Hyun; Lee, Sanghun; Park, Sung Soo
- Chemistry of Materials, Vol. 26, Issue 8
Electrochemical properties of LiMxCo1−xO2 [M = Mg, Zr] prepared by sol–gel process
journal, November 2004
- Kim, Hyung-Sun; Ko, Tae-Kon; Na, Byung-Ki
- Journal of Power Sources, Vol. 138, Issue 1-2
Issues and challenges facing rechargeable lithium batteries
journal, November 2001
- Tarascon, J.-M.; Armand, M.
- Nature, Vol. 414, Issue 6861, p. 359-367
Effect of Cr dopant on the cathodic behavior of LiCoO2
journal, December 2002
- Madhavi, S.; Subba Rao, G. V.; Chowdari, B. V. R.
- Electrochimica Acta, Vol. 48, Issue 3
First-Principles Prediction of Vacancy Order-Disorder and Intercalation Battery Voltages in
journal, July 1998
- Wolverton, C.; Zunger, Alex
- Physical Review Letters, Vol. 81, Issue 3
High-capacity battery cathode prelithiation to offset initial lithium loss
journal, January 2016
- Sun, Yongming; Lee, Hyun-Wook; Seh, Zhi Wei
- Nature Energy, Vol. 1, Issue 1
Sol–gel synthesis and electrochemical characterization of Mg-/Zr-doped LiCoO2 cathodes for Li-ion batteries
journal, January 2012
- Nobili, F.; Croce, F.; Tossici, R.
- Journal of Power Sources, Vol. 197
Significant improvement of high voltage cycling behavior AlF3-coated LiCoO2 cathode
journal, May 2006
- Sun, Y.; Han, J.; Myung, S.
- Electrochemistry Communications, Vol. 8, Issue 5, p. 821-826
On the LixCo1−yMgyO2 system upon deintercalation: electrochemical, electronic properties and 7Li MAS NMR studies
journal, November 2002
- Levasseur, S.; Ménétrier, M.; Delmas, C.
- Journal of Power Sources, Vol. 112, Issue 2
Challenges in the development of advanced Li-ion batteries: a review
journal, January 2011
- Etacheri, Vinodkumar; Marom, Rotem; Elazari, Ran
- Energy & Environmental Science, Vol. 4, Issue 9
Kinetics of non-equilibrium lithium incorporation in LiFePO4
journal, July 2011
- Malik, Rahul; Zhou, Fei; Ceder, G.
- Nature Materials, Vol. 10, Issue 8
A manganese oxyiodide cathode for rechargeable lithium batteries
journal, November 1997
- Kim, Jaekook; Manthiram, Arumugam
- Nature, Vol. 390, Issue 6657
Phase Transitions and High-Voltage Electrochemical Behavior of LiCoO[sub 2] Thin Films Grown by Pulsed Laser Deposition
journal, January 2007
- Xia, H.; Lu, L.; Meng, Y. S.
- Journal of The Electrochemical Society, Vol. 154, Issue 4
Identification of cathode materials for lithium batteries guided by first-principles calculations
journal, April 1998
- Ceder, G.; Chiang, Y. -M.; Sadoway, D. R.
- Nature, Vol. 392, Issue 6677
Nanoscale Surface Modification of Lithium-Rich Layered-Oxide Composite Cathodes for Suppressing Voltage Fade
journal, September 2015
- Zheng, Fenghua; Yang, Chenghao; Xiong, Xunhui
- Angewandte Chemie International Edition, Vol. 54, Issue 44
CoO2, The End Member of the LixCoO2 Solid Solution
journal, January 1996
- Amatucci, G. G.; Tarascon, J. M.; Klein, L. C.
- Journal of The Electrochemical Society, Vol. 143, Issue 3, p. 1114-1123
Influence of the PVdF binder on the stability of LiCoO2 electrodes
journal, December 2005
- Markevich, E.; Salitra, G.; Aurbach, D.
- Electrochemistry Communications, Vol. 7, Issue 12
Staging Phase Transitions in Li[sub x]CoO[sub 2]
journal, January 2002
- Chen, Zhaohui; Lu, Zhonghua; Dahn, J. R.
- Journal of The Electrochemical Society, Vol. 149, Issue 12
First-principles investigation of phase stability in
journal, August 1998
- Van der Ven, A.; Aydinol, M. K.; Ceder, G.
- Physical Review B, Vol. 58, Issue 6
Cobalt dissolution in LiCoO2-based non-aqueous rechargeable batteries
journal, January 1996
- Amatucci, G. G.; Tarascon, J. M.; Klein, L. C.
- Solid State Ionics, Vol. 83, Issue 1-2, p. 167-173
Li-ion battery materials: present and future
journal, June 2015
- Nitta, Naoki; Wu, Feixiang; Lee, Jung Tae
- Materials Today, Vol. 18, Issue 5
Improving the Capacity Retention of LiCoO[sub 2] Cycled to 4.5 V by Heat-Treatment
journal, January 2004
- Chen, Zhaohui; Dahn, J. R.
- Electrochemical and Solid-State Letters, Vol. 7, Issue 1
In Situ XRD Investigation and Thermal Properties of Mg Doped LiCoO 2 for Lithium Ion Batteries
journal, January 2012
- Yin, Ri-Zhu; Kim, Yang-Soo; Shin, Se-Jong
- Journal of The Electrochemical Society, Vol. 159, Issue 3
Advances in lithium–sulfur batteries based on multifunctional cathodes and electrolytes
journal, September 2016
- Pang, Quan; Liang, Xiao; Kwok, Chun Yuen
- Nature Energy, Vol. 1, Issue 9
Electrochemical and In Situ X‐Ray Diffraction Studies of Lithium Intercalation in LixCoO2
journal, January 1992
- Reimers, Jan N.; Dahn, J. R.
- Journal of The Electrochemical Society, Vol. 139, Issue 8, p. 2091-2097
Neutron diffraction studies on structural effect for Ni-doping in LiCo1−xNixO2
journal, September 2014
- Adipranoto, Dyah S.; Ishigaki, Toru; Hoshikawa, Akinori
- Solid State Ionics, Vol. 262
Synergistic effects of coating and doping for lithium ion battery cathode materials: synthesis and characterization of lithium titanate-coated LiCoO2 with Mg doping
journal, December 2015
- Shim, Jae-Hyun; Lee, Jaehan; Han, Sang Yun
- Electrochimica Acta, Vol. 186
LixCoO2 (0<x<-1): A new cathode material for batteries of high energy density
journal, June 1980
- Mizushima, K.; Jones, P. C.; Wiseman, P. J.
- Materials Research Bulletin, Vol. 15, Issue 6
High Capacity Surface-Modified LiCoO[sub 2] Cathodes for Lithium-Ion Batteries
journal, January 2003
- Kannan, A. M.; Rabenberg, L.; Manthiram, A.
- Electrochemical and Solid-State Letters, Vol. 6, Issue 1
Synthesis and electrochemical performance of tetravalent doped LiCoO2 in lithium rechargeable cells
journal, April 2003
- Gopukumar, S.
- Solid State Ionics, Vol. 159, Issue 3-4
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
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries
journal, March 2014
- Lin, Feng; Markus, Isaac M.; Nordlund, Dennis
- Nature Communications, Vol. 5, Issue 1
Lithium Batteries and Cathode Materials
journal, December 2004
- Whittingham, M. Stanley
- ChemInform, Vol. 35, Issue 50
Works referencing / citing this record:
Tuning Anionic Redox Activity and Reversibility for a High‐Capacity Li‐Rich Mn‐Based Oxide Cathode via an Integrated Strategy
journal, March 2019
- Li, Qingyuan; Zhou, Dong; Zhang, Lijuan
- Advanced Functional Materials, Vol. 29, Issue 10
Ultralong‐Life Chloride Ion Batteries Achieved by the Synergistic Contribution of Intralayer Metals in Layered Double Hydroxides
journal, November 2019
- Yin, Qing; Luo, Jianeng; Zhang, Jian
- Advanced Functional Materials, Vol. 30, Issue 5
Unveiling Nickel Chemistry in Stabilizing High‐Voltage Cobalt‐Rich Cathodes for Lithium‐Ion Batteries
journal, November 2019
- Yoon, Moonsu; Dong, Yanhao; Yoo, Youngbin
- Advanced Functional Materials, Vol. 30, Issue 6
Dopant Segregation Boosting High‐Voltage Cyclability of Layered Cathode for Sodium Ion Batteries
journal, September 2019
- Wang, Kuan; Wan, Hui; Yan, Pengfei
- Advanced Materials, Vol. 31, Issue 46
Uniform Na + Doping‐Induced Defects in Li‐ and Mn‐Rich Cathodes for High‐Performance Lithium‐Ion Batteries
journal, May 2019
- He, Wei; Liu, Pengfei; Qu, Baihua
- Advanced Science, Vol. 6, Issue 14
A Novel Bifunctional Self‐Stabilized Strategy Enabling 4.6 V LiCoO 2 with Excellent Long‐Term Cyclability and High‐Rate Capability
journal, April 2019
- Wang, Longlong; Ma, Jun; Wang, Chen
- Advanced Science, Vol. 6, Issue 12
Commercialization of Lithium Battery Technologies for Electric Vehicles
journal, June 2019
- Zeng, Xiaoqiao; Li, Matthew; Abd El‐Hady, Deia
- Advanced Energy Materials, Vol. 9, Issue 27
Realizing Reversible Conversion‐Alloying of Sb(V) in Polyantimonic Acid for Fast and Durable Lithium‐ and Potassium‐Ion Storage
journal, November 2019
- Wang, Boya; Deng, Zhiwen; Xia, Yuting
- Advanced Energy Materials, Vol. 10, Issue 1
Exploiting Mechanistic Solvation Kinetics for Dual‐Graphite Batteries with High Power Output at Extremely Low Temperature
journal, November 2019
- Holoubek, John; Yin, Yijie; Li, Mingqian
- Angewandte Chemie, Vol. 131, Issue 52
Exploiting Mechanistic Solvation Kinetics for Dual‐Graphite Batteries with High Power Output at Extremely Low Temperature
journal, December 2019
- Holoubek, John; Yin, Yijie; Li, Mingqian
- Angewandte Chemie International Edition, Vol. 58, Issue 52
Reduced Lithium/Nickel Disorder Degree of Sodium‐Doped Lithium‐Rich Layered Oxides for Cathode Materials: Experiments and Calculations
journal, December 2019
- Hu, Yongyuan; Qin, Zhongzheng; Pei, Jian
- ChemElectroChem, Vol. 7, Issue 1
The critical role of carbon in marrying silicon and graphite anodes for high‐energy lithium‐ion batteries
journal, September 2019
- Wu, Jingxing; Cao, Yinliang; Zhao, Haimin
- Carbon Energy, Vol. 1, Issue 1
Surface Modification of Li 1.144 Ni 0.136 Co 0.136 Mn 0.544 O 2 by Hybrid Protection Layer with Enhanced Rate Capability
journal, January 2020
- Liao, Yingling; Li, Jianbin; Deng, Bangwei
- Energy Technology, Vol. 8, Issue 5
Transformation of Polyoxometalate into 3D Porous Li‐Containing Oxide: A Case Study of γ‐LiV 2 O 5 for High‐Performance Cathodes of Li‐Ion Batteries
journal, April 2019
- Bayaguud, Aruuhan; Zhang, Zhibo; Geng, Maoning
- Small Methods, Vol. 3, Issue 10
In Situ Probing Multiple-Scale Structures of Energy Materials for Li-Ion Batteries
journal, May 2019
- Zhu, He; Huang, Yalan; Zhu, Hekang
- Small Methods
Manipulating Interfacial Nanostructure to Achieve High‐Performance All‐Solid‐State Lithium‐Ion Batteries
journal, April 2019
- Wang, Changhong; Li, Xia; Zhao, Yang
- Small Methods, Vol. 3, Issue 10
Recent progress on lithium-ion batteries with high electrochemical performance
journal, February 2019
- Lu, Yong; Zhang, Qiu; Chen, Jun
- Science China Chemistry, Vol. 62, Issue 5
Boron-doped single crystal LiNi0.6Mn0.2Co0.2O2 with improved electrochemical performance for lithium-ion batteries
journal, July 2019
- Huang, Bing; Yang, Xiaowei; Xu, Guodong
- Ionics, Vol. 25, Issue 12
Boosting fast energy storage by synergistic engineering of carbon and deficiency
journal, January 2020
- Deng, Shengjue; Zhu, He; Wang, Guizhen
- Nature Communications, Vol. 11, Issue 1
Building ultraconformal protective layers on both secondary and primary particles of layered lithium transition metal oxide cathodes
journal, May 2019
- Xu, Gui-Liang; Liu, Qiang; Lau, Kenneth K. S.
- Nature Energy, Vol. 4, Issue 6
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
Constraining CO coverage on copper promotes high-efficiency ethylene electroproduction
journal, November 2019
- Li, Jun; Wang, Ziyun; McCallum, Christopher
- Nature Catalysis, Vol. 2, Issue 12
Monitoring the evolution of local oxygen environments during LiCoO 2 charging via ex situ 17 O NMR
journal, January 2019
- Geng, Fushan; Shen, Ming; Hu, Bei
- Chemical Communications, Vol. 55, Issue 52
Improving the specific capacity of nickel hydroxide nanocrystals via yttrium doping for application in hybrid supercapacitors
journal, January 2019
- Zhu, Yuanyi; An, Shengli; Cui, Jinlong
- CrystEngComm, Vol. 21, Issue 27
An inorganic-framework proton exchange membrane for direct methanol fuel cells with increased energy density
journal, January 2020
- Yan, Xiaohui; Li, Haozhen; Lin, Chen
- Sustainable Energy & Fuels, Vol. 4, Issue 2
A new dual-ion hybrid energy storage system with energy density comparable to that of ternary lithium ion batteries
journal, January 2020
- He, Shenggong; Wang, Shaofeng; Chen, Hedong
- Journal of Materials Chemistry A, Vol. 8, Issue 5
Unveiling the origin of high reversible capacity in Li-rich layered oxide in Li-ion batteries
journal, September 2019
- Hu, Huicong; Zhang, Maolin; Zhang, Dongyan
- Materials Research Express, Vol. 6, Issue 11
Structuring Al3+-doped LiNi1∕3Co1∕3Mn1∕3O 2 by 3D-birdnest-shaped MnO 2
journal, August 2019
- Zhu, Jiping; Yan, Jiawei; Chen, Jun
- Functional Materials Letters, Vol. 12, Issue 04
(De)Lithiation Mechanism of Hierarchically Layered LiNi 1/3 Co 1/3 Mn 1/3 O 2 Cathodes during High-Voltage Cycling
journal, November 2018
- Hua, Weibo; Schwarz, Björn; Knapp, Michael
- Journal of The Electrochemical Society, Vol. 166, Issue 3
Realization of Ti Doping by Electrostatic Assembly to Improve the Stability of LiCoO 2 Cycled to 4.5 V
journal, January 2019
- Sun, Liwei; Zhang, Zeshu; Hu, Xuefeng
- Journal of The Electrochemical Society, Vol. 166, Issue 10
Improved Cycling Stability of LiCoO2 at 4.5 V via Surface Modification of Electrodes with Conductive Amorphous LLTO Thin Film
journal, May 2020
- Song, Shipai; Peng, Xiang; Huang, Kai
- Nanoscale Research Letters, Vol. 15, Issue 1
(De)Lithiation Mechanism of Hierarchically Layered LiNi$_{1/3}$Co$_{1/3}$Mn$_{1/3}$O$_{2}$ Cathodes during High-Voltage Cycling
text, January 2019
- Hua, Weibo; Schwarz, Björn; Knapp, Michael
- Karlsruhe
Figures / Tables found in this record: