Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment
Abstract
Lithium-rich transition metal oxide (Li1+XM1–XO2) cathodes have high energy density above 900 Wh kg–1 due to hybrid anion- and cation-redox (HACR) contributions, but critical issues such as oxygen release and voltage decay during cycling have prevented their application for years. Here we show that a molten molybdate-assisted LiO extraction at 700 °C creates lattice-coherent but depth (r)-dependent Li1+X(r)M1–X(r)O2 particles with a Li-rich (X ≈ 0.2) interior, a Li-poor (X ≈ –0.05) surface and a continuous gradient in between. The gradient Li-rich single crystals eliminate the oxygen release to the electrolyte and, importantly, still allow stable oxygen redox contributions within. Here, both the metal valence states and the crystal structure are well maintained during cycling. The gradient HACR cathode displays a specific density of 843 Wh kg–1 after 200 cycles at 0.2C and 808 Wh kg–1 after 100 cycles at 1C, with very little oxygen release and consumption of electrolyte. This high-temperature immunization treatment can be generalized to leach other elements to avoid unexpected surface reactions in batteries.
- Authors:
-
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
- OSTI Identifier:
- 1593263
- Report Number(s):
- BNL-213531-2020-JAAM
Journal ID: ISSN 2058-7546
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Energy
- Additional Journal Information:
- Journal Volume: 4; Journal Issue: 12; Journal ID: ISSN 2058-7546
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Zhu, Zhi, Yu, Daiwei, Yang, Yang, Su, Cong, Huang, Yimeng, Dong, Yanhao, Waluyo, Iradwikanari, Wang, Baoming, Hunt, Adrian, Yao, Xiahui, Lee, Jinhyuk, Xue, Weijiang, and Li, Ju. Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment. United States: N. p., 2019.
Web. doi:10.1038/s41560-019-0508-x.
Zhu, Zhi, Yu, Daiwei, Yang, Yang, Su, Cong, Huang, Yimeng, Dong, Yanhao, Waluyo, Iradwikanari, Wang, Baoming, Hunt, Adrian, Yao, Xiahui, Lee, Jinhyuk, Xue, Weijiang, & Li, Ju. Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment. United States. https://doi.org/10.1038/s41560-019-0508-x
Zhu, Zhi, Yu, Daiwei, Yang, Yang, Su, Cong, Huang, Yimeng, Dong, Yanhao, Waluyo, Iradwikanari, Wang, Baoming, Hunt, Adrian, Yao, Xiahui, Lee, Jinhyuk, Xue, Weijiang, and Li, Ju. Thu .
"Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment". United States. https://doi.org/10.1038/s41560-019-0508-x. https://www.osti.gov/servlets/purl/1593263.
@article{osti_1593263,
title = {Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment},
author = {Zhu, Zhi and Yu, Daiwei and Yang, Yang and Su, Cong and Huang, Yimeng and Dong, Yanhao and Waluyo, Iradwikanari and Wang, Baoming and Hunt, Adrian and Yao, Xiahui and Lee, Jinhyuk and Xue, Weijiang and Li, Ju},
abstractNote = {Lithium-rich transition metal oxide (Li1+XM1–XO2) cathodes have high energy density above 900 Wh kg–1 due to hybrid anion- and cation-redox (HACR) contributions, but critical issues such as oxygen release and voltage decay during cycling have prevented their application for years. Here we show that a molten molybdate-assisted LiO extraction at 700 °C creates lattice-coherent but depth (r)-dependent Li1+X(r)M1–X(r)O2 particles with a Li-rich (X ≈ 0.2) interior, a Li-poor (X ≈ –0.05) surface and a continuous gradient in between. The gradient Li-rich single crystals eliminate the oxygen release to the electrolyte and, importantly, still allow stable oxygen redox contributions within. Here, both the metal valence states and the crystal structure are well maintained during cycling. The gradient HACR cathode displays a specific density of 843 Wh kg–1 after 200 cycles at 0.2C and 808 Wh kg–1 after 100 cycles at 1C, with very little oxygen release and consumption of electrolyte. This high-temperature immunization treatment can be generalized to leach other elements to avoid unexpected surface reactions in batteries.},
doi = {10.1038/s41560-019-0508-x},
journal = {Nature Energy},
number = 12,
volume = 4,
place = {United States},
year = {2019},
month = {12}
}
Web of Science
Works referenced in this record:
Intercalation-conversion hybrid cathodes enabling Li–S full-cell architectures with jointly superior gravimetric and volumetric energy densities
journal, March 2019
- Xue, Weijiang; Shi, Zhe; Suo, Liumin
- Nature Energy, Vol. 4, Issue 5
Anion-redox nanolithia cathodes for Li-ion batteries
journal, July 2016
- Zhu, Zhi; Kushima, Akihiro; Yin, Zongyou
- Nature Energy, Vol. 1, Issue 8
A high-energy-density and long-life lithium-ion battery via reversible oxide–peroxide conversion
journal, October 2019
- Qiao, Yu; Jiang, Kezhu; Deng, Han
- Nature Catalysis, Vol. 2, Issue 11
One-Pot Synthesis of Lithium-Rich Cathode Material with Hierarchical Morphology
journal, November 2016
- Luo, Kun; Roberts, Matthew R.; Hao, Rong
- Nano Letters, Vol. 16, Issue 12
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
High-energy ‘composite’ layered manganese-rich cathode materials via controlling Li2MnO3 phase activation for lithium-ion batteries
journal, January 2012
- Yu, Haijun; Kim, Hyunjeong; Wang, Yarong
- Physical Chemistry Chemical Physics, Vol. 14, Issue 18
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
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
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
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
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
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
Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging
journal, July 2018
- Singer, A.; Zhang, M.; Hy, S.
- Nature Energy, Vol. 3, Issue 8
Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release
journal, July 2018
- Hu, Enyuan; Yu, Xiqian; Lin, Ruoqian
- Nature Energy, Vol. 3, Issue 8
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
Mechanisms Associated with the “Plateau” Observed at High Voltage for the Overlithiated Li 1.12 (Ni 0.425 Mn 0.425 Co 0.15 ) 0.88 O 2 System
journal, August 2008
- Tran, N.; Croguennec, L.; Ménétrier, M.
- Chemistry of Materials, Vol. 20, Issue 15
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
Surface coating of lithium–manganese-rich layered oxides with delaminated MnO2 nanosheets as cathode materials for Li-ion batteries
journal, January 2014
- Guo, Shaohua; Yu, Haijun; Liu, Pan
- Journal of Materials Chemistry A, Vol. 2, Issue 12
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
The Effects of Acid Treatment on the Electrochemical Properties of 0.5 Li2MnO3 ∙ 0.5 LiNi0.44Co0.25Mn0.31O2 Electrodes in Lithium Cells
journal, January 2006
- Kang, S.-H.; Johnson, C. S.; Vaughey, J. T.
- Journal of The Electrochemical Society, Vol. 153, Issue 6, p. A1186-A1192
Li–O2 and Li–S batteries with high energy storage
journal, January 2012
- Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J.
- Nature Materials, Vol. 11, Issue 1, p. 19-29
Reactions in the Rechargeable Lithium–O 2 Battery with Alkyl Carbonate Electrolytes
journal, May 2011
- Freunberger, Stefan A.; Chen, Yuhui; Peng, Zhangquan
- Journal of the American Chemical Society, Vol. 133, Issue 20
Solvents’ Critical Role in Nonaqueous Lithium–Oxygen Battery Electrochemistry
journal, May 2011
- McCloskey, B. D.; Bethune, D. S.; Shelby, R. M.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 10, p. 1161-1166
Nanostructured high-energy cathode materials for advanced lithium batteries
journal, October 2012
- Sun, Yang-Kook; Chen, Zonghai; Noh, Hyung-Joo
- Nature Materials, Vol. 11, Issue 11
Advanced Concentration Gradient Cathode Material with Two-Slope for High-Energy and Safe Lithium Batteries
journal, June 2015
- Lim, Byung-Beom; Yoon, Sung-Jun; Park, Kang-Joon
- Advanced Functional Materials, Vol. 25, Issue 29
Defect chemical studies on oxygen release from the Li-rich cathode material Li 1.2 Mn 0.6 Ni 0.2 O 2−δ
journal, January 2019
- Nakamura, Takashi; Gao, Hongze; Ohta, Kento
- Journal of Materials Chemistry A, Vol. 7, Issue 9
A New Type of Protective Surface Layer for High-Capacity Ni-Based Cathode Materials: Nanoscaled Surface Pillaring Layer
journal, February 2013
- Cho, Yonghyun; Oh, Pilgun; Cho, Jaephil
- Nano Letters, Vol. 13, Issue 3
Manganese valence imaging in Mn minerals at the nanoscale using STEM-EELS
journal, January 2007
- Loomer, D. B.; Al, T. A.; Weaver, L.
- American Mineralogist, Vol. 92, Issue 1
Interface and Surface Cation Stoichiometry Modified by Oxygen Vacancies in Epitaxial Manganite Films
journal, June 2012
- Li, Zhipeng; Bosman, Michel; Yang, Zhen
- Advanced Functional Materials, Vol. 22, Issue 20
Nanoscale Coating of LiMO 2 (M = Ni, Co, Mn) Nanobelts with Li + -Conductive Li 2 TiO 3 : Toward Better Rate Capabilities for Li-Ion Batteries
journal, January 2013
- Lu, Jun; Peng, Qing; Wang, Weiyang
- Journal of the American Chemical Society, Vol. 135, Issue 5
Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi 0.5 Mn 1.5 O 4 Electrodes
journal, November 2015
- Qiao, Ruimin; Wray, L. Andrew; Kim, Jung-Hyun
- The Journal of Physical Chemistry C, Vol. 119, Issue 49
Anion Redox Chemistry in the Cobalt Free 3d Transition Metal Oxide Intercalation Electrode Li[Li 0.2 Ni 0.2 Mn 0.6 ]O 2
journal, August 2016
- Luo, Kun; Roberts, Matthew R.; Guerrini, Niccoló
- Journal of the American Chemical Society, Vol. 138, Issue 35
Direct observation of reversible oxygen anion redox reaction in Li-rich manganese oxide, Li 2 MnO 3 , studied by soft X-ray absorption spectroscopy
journal, January 2016
- Oishi, Masatsugu; Yamanaka, Keisuke; Watanabe, Iwao
- Journal of Materials Chemistry A, Vol. 4, Issue 23
High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions
journal, February 2019
- Dai, Kehua; Wu, Jinpeng; Zhuo, Zengqing
- Joule, Vol. 3, Issue 2
Direct evidence of gradient Mn(II) evolution at charged states in LiNi0.5Mn1.5O4 electrodes with capacity fading
journal, January 2015
- Qiao, Ruimin; Wang, Yuesheng; Olalde-Velasco, Paul
- Journal of Power Sources, Vol. 273
Redox Processes of Manganese Oxide in Catalyzing Oxygen Evolution and Reduction: An in Situ Soft X-ray Absorption Spectroscopy Study
journal, August 2017
- Risch, Marcel; Stoerzinger, Kelsey A.; Han, Binghong
- The Journal of Physical Chemistry C, Vol. 121, Issue 33
Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy
journal, September 2016
- Li, Qinghao; Qiao, Ruimin; Wray, L. Andrew
- Journal of Physics D: Applied Physics, Vol. 49, Issue 41
Phase Relationships and Structural and Chemical Stabilities of Charged Li[sub 1−x]CoO[sub 2−δ] and Li[sub 1−x]Ni[sub 0.85]Co[sub 0.15]O[sub 2−δ] Cathodes
journal, January 2003
- Venkatraman, S.; Shin, Y.; Manthiram, A.
- Electrochemical and Solid-State Letters, Vol. 6, Issue 1
Origin of Carbon Dioxide Evolved during Cycling of Nickel-Rich Layered NCM Cathodes
journal, October 2018
- Hatsukade, Toru; Schiele, Alexander; Hartmann, Pascal
- ACS Applied Materials & Interfaces, Vol. 10, Issue 45
Oxidative Electrolyte Solvent Degradation in Lithium-Ion Batteries: An In Situ Differential Electrochemical Mass Spectrometry Investigation
journal, January 1999
- Imhof, Roman
- Journal of The Electrochemical Society, Vol. 146, Issue 5
Oxygen Release and Its Effect on the Cycling Stability of LiNi x Mn y Co z O 2 (NMC) Cathode Materials for Li-Ion Batteries
journal, January 2017
- Jung, Roland; Metzger, Michael; Maglia, Filippo
- Journal of The Electrochemical Society, Vol. 164, Issue 7
CO 2 and O 2 Evolution at High Voltage Cathode Materials of Li-Ion Batteries: A Differential Electrochemical Mass Spectrometry Study
journal, June 2014
- Wang, Hongsen; Rus, Eric; Sakuraba, Takahito
- Analytical Chemistry, Vol. 86, Issue 13
Chemical, Structural, and Electronic Aspects of Formation and Degradation Behavior on Different Length Scales of Ni‐Rich NCM and Li‐Rich HE‐NCM Cathode Materials in Li‐Ion Batteries
journal, April 2019
- de Biasi, Lea; Schwarz, Björn; Brezesinski, Torsten
- Advanced Materials, Vol. 31, Issue 26
Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging
text, January 2018
- Singer, A.; Zhang, M.; Hy, S.
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Chemical, Structural, and Electronic Aspects of Formation and Degradation Behavior on Different Length Scales of Ni‐Rich NCM and Li‐Rich HE‐NCM Cathode Materials in Li‐Ion Batteries
text, January 2019
- De Biasi, Lea; Schwarz, Björn; Brezesinski, Torsten
- Karlsruhe
Works referencing / citing this record:
Li gradients for Li-rich cathodes
journal, December 2019
- Toney, Michael F.
- Nature Energy, Vol. 4, Issue 12