Using real-time electron microscopy to explore the effects of transition-metal composition on the local thermal stability in charged LixNiyMnzCo1-y-zO2 cathode materials
Abstract
In this study, we use in-situ transmission electron microcopy (TEM) to investigate the thermal decomposition that occurs at the surface of charged LixNiyMnzCo1-y-zO2 (NMC) cathode materials of different composition (with y, z=0.8, 0.1 and 0.6, 0.2 and 0.4, 0.3), after they have been charged to their practical upper limit voltage (4.3V). By heating these materials inside the TEM, we are able to directly characterize near surface changes in both their electronic structure (using electron energy loss spectroscopy) and crystal structure and morphology (using electron diffraction and bright-field imaging). The most Ni-rich material (y, z = 0.8, 0.1) is found to be thermally unstable at significantly lower temperatures than the other compositions – this is manifested by changes in both the electronic structure and the onset of phase transitions at temperatures as low as 100°C. Electron energy loss spectroscopy indicates that the thermally induced reduction of Ni ions drives these changes, and that this is exacerbated by the presence of an additional redox reaction that occurs at 4.2V in the y, z = 0.8, 0.1 material. Exploration of individual particles shows that there are substantial variations in the onset temperatures and overall extent of these changes. Of the compositions studied, themore »
- Authors:
-
- Korea Advanced Inst. Science and Technology (KAIST), Daejeon (Korea, Republic of); Korea Inst. of Science and Technology, Seoul (Korea, Republic of)
- Korea Inst. of Science and Technology, Wanju-gun(Korea, Republic of)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Korea Inst. of Science and Technology, Seoul (Korea, Republic of)
- Korea Advanced Inst. Science and Technology (KAIST), Daejeon (Korea, Republic of)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1214525
- Report Number(s):
- BNL-108321-2015-JA
Journal ID: ISSN 0897-4756; R&D Project: EST431; KC0207010
- Grant/Contract Number:
- SC00112704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 27; Journal Issue: 11; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Hwang, Sooyeon, Kim, Seung Min, Bak, Seong -Min, Kim, Se Young, Cho, Byung -Won, Chung, Kyung Yoon, Lee, Jeong Yong, Stach, Eric A., and Chang, Wonyoung. Using real-time electron microscopy to explore the effects of transition-metal composition on the local thermal stability in charged LixNiyMnzCo1-y-zO2 cathode materials. United States: N. p., 2015.
Web. doi:10.1021/acs.chemmater.5b00709.
Hwang, Sooyeon, Kim, Seung Min, Bak, Seong -Min, Kim, Se Young, Cho, Byung -Won, Chung, Kyung Yoon, Lee, Jeong Yong, Stach, Eric A., & Chang, Wonyoung. Using real-time electron microscopy to explore the effects of transition-metal composition on the local thermal stability in charged LixNiyMnzCo1-y-zO2 cathode materials. United States. https://doi.org/10.1021/acs.chemmater.5b00709
Hwang, Sooyeon, Kim, Seung Min, Bak, Seong -Min, Kim, Se Young, Cho, Byung -Won, Chung, Kyung Yoon, Lee, Jeong Yong, Stach, Eric A., and Chang, Wonyoung. Fri .
"Using real-time electron microscopy to explore the effects of transition-metal composition on the local thermal stability in charged LixNiyMnzCo1-y-zO2 cathode materials". United States. https://doi.org/10.1021/acs.chemmater.5b00709. https://www.osti.gov/servlets/purl/1214525.
@article{osti_1214525,
title = {Using real-time electron microscopy to explore the effects of transition-metal composition on the local thermal stability in charged LixNiyMnzCo1-y-zO2 cathode materials},
author = {Hwang, Sooyeon and Kim, Seung Min and Bak, Seong -Min and Kim, Se Young and Cho, Byung -Won and Chung, Kyung Yoon and Lee, Jeong Yong and Stach, Eric A. and Chang, Wonyoung},
abstractNote = {In this study, we use in-situ transmission electron microcopy (TEM) to investigate the thermal decomposition that occurs at the surface of charged LixNiyMnzCo1-y-zO2 (NMC) cathode materials of different composition (with y, z=0.8, 0.1 and 0.6, 0.2 and 0.4, 0.3), after they have been charged to their practical upper limit voltage (4.3V). By heating these materials inside the TEM, we are able to directly characterize near surface changes in both their electronic structure (using electron energy loss spectroscopy) and crystal structure and morphology (using electron diffraction and bright-field imaging). The most Ni-rich material (y, z = 0.8, 0.1) is found to be thermally unstable at significantly lower temperatures than the other compositions – this is manifested by changes in both the electronic structure and the onset of phase transitions at temperatures as low as 100°C. Electron energy loss spectroscopy indicates that the thermally induced reduction of Ni ions drives these changes, and that this is exacerbated by the presence of an additional redox reaction that occurs at 4.2V in the y, z = 0.8, 0.1 material. Exploration of individual particles shows that there are substantial variations in the onset temperatures and overall extent of these changes. Of the compositions studied, the composition of y, z = 0.6, 0.2 has the optimal combination of high energy density and reasonable thermal stability. The observations herein demonstrate that real time electron microscopy provide direct insight into the changes that occur in cathode materials with temperature, allowing optimization of different alloy concentrations to maximize overall performance.},
doi = {10.1021/acs.chemmater.5b00709},
journal = {Chemistry of Materials},
number = 11,
volume = 27,
place = {United States},
year = {Fri May 08 00:00:00 EDT 2015},
month = {Fri May 08 00:00:00 EDT 2015}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 87 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
An Electron Energy-Loss Spectrometry Study of Charge Compensation in LiNi 0.8 Co 0.2 O 2
journal, April 2003
- Graetz, J.; Ahn, C. C.; Yazami, R.
- The Journal of Physical Chemistry B, Vol. 107, Issue 13
Investigation of the Charge Compensation Mechanism on the Electrochemically Li-Ion Deintercalated Li 1 - x Co 1/3 Ni 1/3 Mn 1/3 O 2 Electrode System by Combination of Soft and Hard X-ray Absorption Spectroscopy
journal, December 2005
- Yoon, Won-Sub; Balasubramanian, Mahalingam; Chung, Kyung Yoon
- Journal of the American Chemical Society, Vol. 127, Issue 49
Extraction of EELS white-line intensities of manganese compounds: Methods, accuracy, and valence sensitivity
journal, March 2006
- Riedl, T.; Gemming, T.; Wetzig, K.
- Ultramicroscopy, Vol. 106, Issue 4-5
Lithium Batteries and Cathode Materials
journal, October 2004
- Whittingham, M. Stanley
- Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302
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
EELS analysis of cation valence states and oxygen vacancies in magnetic oxides
journal, October 2000
- Wang, Z. L.; Yin, J. S.; Jiang, Y. D.
- Micron, Vol. 31, Issue 5
Electronic Structure of Lithium Nickel Oxides by Electron Energy Loss Spectroscopy
journal, June 2005
- Koyama, Yukinori; Mizoguchi, Teruyasu; Ikeno, Hidekazu
- The Journal of Physical Chemistry B, Vol. 109, Issue 21
White lines and -band occupancy for the transition-metal oxides and lithium transition-metal oxides
journal, June 2004
- Graetz, Jason; Ahn, Channing C.; Ouyang, Hao
- Physical Review B, Vol. 69, Issue 23
Thermal stability of Li1−yNixMn(1−x)/2Co(1−x)/2O2 layer-structured cathode materials used in Li-Ion batteries
journal, August 2011
- Konishi, Hiroaki; Yuasa, Toyotaka; Yoshikawa, Masanori
- Journal of Power Sources, Vol. 196, Issue 16
Understanding the Degradation Mechanisms of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode Material in Lithium Ion Batteries
journal, August 2013
- Jung, Sung-Kyun; Gwon, Hyeokjo; Hong, Jihyun
- Advanced Energy Materials, Vol. 4, Issue 1
Ratios of ferrous to ferric iron from nanometre-sized areas in minerals
journal, December 1998
- Garvie, Laurence A. J.; Buseck, Peter R.
- Nature, Vol. 396, Issue 6712
Evaluation of thermal stability in Li0.2NixMn(1−x)/2Co(1−x)/2O2 (x = 1/3, 0.6, and 0.8) through X-ray absorption fine structure
journal, May 2014
- Konishi, Hiroaki; Yoshikawa, Masanori; Hirano, Tatsumi
- Journal of Power Sources, Vol. 254
Electrochemistry and Structural Chemistry of LiNiO[sub 2] (R3m) for 4 Volt Secondary Lithium Cells
journal, January 1993
- Ohzuku, Tsutomu
- Journal of The Electrochemical Society, Vol. 140, Issue 7
Electronic structural changes of the electrochemically Li-ion deintercalated LiNi0.8Co0.15Al0.05O2 cathode material investigated by X-ray absorption spectroscopy
journal, December 2007
- Yoon, Won-Sub; Chung, Kyung Yoon; McBreen, James
- Journal of Power Sources, Vol. 174, Issue 2
Electron energy-loss near-edge structure - a tool for the investigation of electronic structure on the nanometre scale
journal, August 2001
- Keast, V. J.; Scott, A. J.; Brydson, R.
- Journal of Microscopy, Vol. 203, Issue 2
Investigation of Changes in the Surface Structure of Li x Ni 0.8 Co 0.15 Al 0.05 O 2 Cathode Materials Induced by the Initial Charge
journal, December 2013
- Hwang, Sooyeon; Chang, Wonyoung; Kim, Seung Min
- Chemistry of Materials, Vol. 26, Issue 2
In-Situ X-ray Absorption Spectroscopic Study on Variation of Electronic Transitions and Local Structure of LiNi 1/3 Co 1/3 Mn 1/3 O 2 Cathode Material during Electrochemical Cycling
journal, June 2005
- Tsai, Y. W.; Hwang, B. J.; Ceder, G.
- Chemistry of Materials, Vol. 17, Issue 12
Correlating Structural Changes and Gas Evolution during the Thermal Decomposition of Charged Li x Ni 0.8 Co 0.15 Al 0.05 O 2 Cathode Materials
journal, January 2013
- Bak, Seong-Min; Nam, Kyung-Wan; Chang, Wonyoung
- Chemistry of Materials, Vol. 25, Issue 3
Investigating Local Degradation and Thermal Stability of Charged Nickel-Based Cathode Materials through Real-Time Electron Microscopy
journal, August 2014
- Hwang, Sooyeon; Kim, Seung Min; Bak, Seong-Min
- ACS Applied Materials & Interfaces, Vol. 6, Issue 17
Structural Origin of Overcharge-Induced Thermal Instability of Ni-Containing Layered-Cathodes for High-Energy-Density Lithium Batteries
journal, September 2011
- Wu, Lijun; Nam, Kyung-Wan; Wang, Xiaojian
- Chemistry of Materials, Vol. 23, Issue 17
TEM Study of Electrochemical Cycling-Induced Damage and Disorder in LiCoO[sub 2] Cathodes for Rechargeable Lithium Batteries
journal, January 1999
- Wang, Haifeng
- Journal of The Electrochemical Society, Vol. 146, Issue 2
Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]O2 (x = 1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries
journal, July 2013
- Noh, Hyung-Joo; Youn, Sungjune; Yoon, Chong Seung
- Journal of Power Sources, Vol. 233
Time-resolved XRD study on the thermal decomposition of nickel-based layered cathode materials for Li-ion batteries
journal, December 2006
- Yoon, Won-Sub; Chung, Kyung Yoon; Balasubramanian, Mahalingam
- Journal of Power Sources, Vol. 163, Issue 1
Crystal and electronic structures of superstructural Li1−x[Co1/3Ni1/3Mn1/3]O2 (0≤x≤1)
journal, June 2003
- Koyama, Yukinori; Tanaka, Isao; Adachi, Hirohiko
- Journal of Power Sources, Vol. 119-121
Structural Changes and Thermal Stability of Charged LiNi x Mn y Co z O 2 Cathode Materials Studied by Combined In Situ Time-Resolved XRD and Mass Spectroscopy
journal, December 2014
- Bak, Seong-Min; Hu, Enyuan; Zhou, Yongning
- ACS Applied Materials & Interfaces, Vol. 6, Issue 24
In situ x-ray diffraction and electrochemical studies of Li1−xNiO2
journal, December 1993
- Li, W.; Reimers, J.; Dahn, J.
- Solid State Ionics, Vol. 67, Issue 1-2
Works referencing / citing this record:
Towards deriving Ni-rich cathode and oxide-based anode materials from hydroxides by sharing a facile co-precipitation method
journal, January 2018
- Qiu, Haifa; Du, Tengfei; Wu, Junfeng
- Dalton Transactions, Vol. 47, Issue 20
Propagation topography of redox phase transformations in heterogeneous layered oxide cathode materials
journal, July 2018
- Mu, Linqin; Yuan, Qingxi; Tian, Chixia
- Nature Communications, Vol. 9, Issue 1
Understanding materials challenges for rechargeable ion batteries with in situ transmission electron microscopy
journal, August 2017
- Yuan, Yifei; Amine, Khalil; Lu, Jun
- Nature Communications, Vol. 8, Issue 1
Revealing the role of NH 4 VO 3 treatment in Ni-rich cathode materials with improved electrochemical performance for rechargeable lithium-ion batteries
journal, January 2018
- Zhang, Congcong; Liu, Siyang; Su, Junming
- Nanoscale, Vol. 10, Issue 18
Microstructure‐Controlled Ni‐Rich Cathode Material by Microscale Compositional Partition for Next‐Generation Electric Vehicles
journal, February 2019
- Kim, Un‐Hyuck; Ryu, Hoon‐Hee; Kim, Jae‐Hyung
- Advanced Energy Materials, Vol. 9, Issue 15
Ecofriendly Chemical Activation of Overlithiated Layered Oxides by DNA‐Wrapped Carbon Nanotubes
journal, January 2020
- Kim, Ju‐Myung; Park, Jae‐Ho; Jo, Eunmi
- Advanced Energy Materials, Vol. 10, Issue 9
Editors' Choice—Coating-Dependent Electrode-Electrolyte Interface for Ni-Rich Positive Electrodes in Li-Ion Batteries
journal, January 2019
- Karayaylali, Pinar; Tatara, Ryoichi; Zhang, Yirui
- Journal of The Electrochemical Society, Vol. 166, Issue 6
Propagation topography of redox phase transformations in heterogeneous layered oxide cathode materials
journal, July 2018
- Mu, Linqin; Yuan, Qingxi; Tian, Chixia
- Nature Communications, Vol. 9, Issue 1
Kinetic Stability of Bulk LiNiO 2 and Surface Degradation by Oxygen Evolution in LiNiO 2 -Based Cathode Materials
journal, November 2018
- Kong, Fantai; Liang, Chaoping; Wang, Luhua
- Advanced Energy Materials, Vol. 9, Issue 2
Surface/Interface Structure Degradation of Ni‐Rich Layered Oxide Cathodes toward Lithium‐Ion Batteries: Fundamental Mechanisms and Remedying Strategies
journal, December 2019
- Liang, Longwei; Zhang, Wenheng; Zhao, Fei
- Advanced Materials Interfaces, Vol. 7, Issue 3
Real-time monitoring of stress development during electrochemical cycling of electrode materials for Li-ion batteries: overview and perspectives
journal, January 2019
- Jangid, Manoj K.; Mukhopadhyay, Amartya
- Journal of Materials Chemistry A, Vol. 7, Issue 41
Using in situ and operando methods to characterize phase changes in charged lithium nickel cobalt aluminum oxide cathode materials
journal, January 2020
- Hwang, Sooyeon; Stach, Eric A.
- Journal of Physics D: Applied Physics, Vol. 53, Issue 11
Anti‐Oxygen Leaking LiCoO 2
journal, April 2019
- Sharifi‐Asl, Soroosh; Soto, Fernando A.; Foroozan, Tara
- Advanced Functional Materials, Vol. 29, Issue 23
Revealing electrolyte oxidation via carbonate dehydrogenation on Ni-based oxides in Li-ion batteries by in situ Fourier transform infrared spectroscopy
journal, January 2020
- Zhang, Yirui; Katayama, Yu; Tatara, Ryoichi
- Energy & Environmental Science, Vol. 13, Issue 1
Oxygen Release Degradation in Li‐Ion Battery Cathode Materials: Mechanisms and Mitigating Approaches
journal, April 2019
- Sharifi‐Asl, Soroosh; Lu, Jun; Amine, Khalil
- Advanced Energy Materials, Vol. 9, Issue 22