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Title: Suppressed oxygen extraction and degradation of LiNi xMn yCo zO 2 cathodes at high charge cut-off voltages

The capacity degradation mechanism in lithium nickel–manganese–cobalt oxide (NMC) cathodes (LiNi 1/3Mn 1/3Co 1/3O 2 (NMC 333) and LiNi 0.4Mn 0.4Co 0.2O 2 (NMC 442)) during high-voltage (cut-off of 4.8 V) operation has been investigated. In contrast to NMC 442, NMC 333 exhibits rapid structural changes including severe micro-crack formation and phase transformation from a layered to a disordered rock-salt structure, as well as interfacial degradation during high-voltage cycling, leading to a rapid increase of the electrode resistance and fast capacity decline. The fundamental reason behind the poor structural and interfacial stability of NMC 333 was found to be correlated to its high Co content and the significant overlap between the Co 3+/4+ t 2g and O 2- 2p bands, resulting in oxygen removal and consequent structural changes at high voltages. In addition, oxidation of the electrolyte solvents by the extracted oxygen species generates acidic species, which then attack the electrode surface and form highly resistive LiF. These findings highlight that both the structural and interfacial stability should be taken into account when tailoring cathode materials for high voltage battery systems.
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [2] ;  [2] ;  [1] ;  [1] ;  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Nano Research
Additional Journal Information:
Journal Volume: 10; Journal Issue: 12; Journal ID: ISSN 1998-0124
Publisher:
Springer
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Office of Vehicle Technology
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Li-ion battery; high-voltage cycling; interfacial stability; layered structure; material composition; structural stability
OSTI Identifier:
1423450

Zheng, Jianming, Yan, Pengfei, Zhang, Jiandong, Engelhard, Mark H., Zhu, Zihua, Polzin, Bryant J., Trask, Steve, Xiao, Jie, Wang, Chongmin, and Zhang, Jiguang. Suppressed oxygen extraction and degradation of LiNixMnyCozO2 cathodes at high charge cut-off voltages. United States: N. p., Web. doi:10.1007/s12274-017-1761-6.
Zheng, Jianming, Yan, Pengfei, Zhang, Jiandong, Engelhard, Mark H., Zhu, Zihua, Polzin, Bryant J., Trask, Steve, Xiao, Jie, Wang, Chongmin, & Zhang, Jiguang. Suppressed oxygen extraction and degradation of LiNixMnyCozO2 cathodes at high charge cut-off voltages. United States. doi:10.1007/s12274-017-1761-6.
Zheng, Jianming, Yan, Pengfei, Zhang, Jiandong, Engelhard, Mark H., Zhu, Zihua, Polzin, Bryant J., Trask, Steve, Xiao, Jie, Wang, Chongmin, and Zhang, Jiguang. 2017. "Suppressed oxygen extraction and degradation of LiNixMnyCozO2 cathodes at high charge cut-off voltages". United States. doi:10.1007/s12274-017-1761-6. https://www.osti.gov/servlets/purl/1423450.
@article{osti_1423450,
title = {Suppressed oxygen extraction and degradation of LiNixMnyCozO2 cathodes at high charge cut-off voltages},
author = {Zheng, Jianming and Yan, Pengfei and Zhang, Jiandong and Engelhard, Mark H. and Zhu, Zihua and Polzin, Bryant J. and Trask, Steve and Xiao, Jie and Wang, Chongmin and Zhang, Jiguang},
abstractNote = {The capacity degradation mechanism in lithium nickel–manganese–cobalt oxide (NMC) cathodes (LiNi1/3Mn1/3Co1/3O2 (NMC333) and LiNi0.4Mn0.4Co0.2O2 (NMC442)) during high-voltage (cut-off of 4.8 V) operation has been investigated. In contrast to NMC442, NMC333 exhibits rapid structural changes including severe micro-crack formation and phase transformation from a layered to a disordered rock-salt structure, as well as interfacial degradation during high-voltage cycling, leading to a rapid increase of the electrode resistance and fast capacity decline. The fundamental reason behind the poor structural and interfacial stability of NMC333 was found to be correlated to its high Co content and the significant overlap between the Co3+/4+ t2g and O2- 2p bands, resulting in oxygen removal and consequent structural changes at high voltages. In addition, oxidation of the electrolyte solvents by the extracted oxygen species generates acidic species, which then attack the electrode surface and form highly resistive LiF. These findings highlight that both the structural and interfacial stability should be taken into account when tailoring cathode materials for high voltage battery systems.},
doi = {10.1007/s12274-017-1761-6},
journal = {Nano Research},
number = 12,
volume = 10,
place = {United States},
year = {2017},
month = {9}
}