Suppressed oxygen extraction and degradation of LiNixMnyCozO2 cathodes at high charge cut-off voltages

Zheng, Jianming; Yan, Pengfei; Zhang, Jiandong; Engelhard, Mark H.; Zhu, Zihua; Polzin, Bryant J.; Trask, Steve; Xiao, Jie; Wang, Chongmin; Zhang, Jiguang

doi:10.1007/s12274-017-1761-6

Title: Suppressed oxygen extraction and degradation of LiNi_xMn_yCo_zO₂ cathodes at high charge cut-off voltages

Journal Article · Fri Sep 01 00:00:00 EDT 2017 · Nano Research

DOI:https://doi.org/10.1007/s12274-017-1761-6· OSTI ID:1423450

Zheng, Jianming ^[1]; Yan, Pengfei ^[1]; Zhang, Jiandong ^[1]; Engelhard, Mark H. ^[1]; Zhu, Zihua ^[1]; Polzin, Bryant J. ^[2]; Trask, Steve ^[2]; Xiao, Jie ^[1]; Wang, Chongmin ^[1]; Zhang, Jiguang ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

The capacity degradation mechanism in lithium nickel–manganese–cobalt oxide (NMC) cathodes (LiNi_1/3Mn_1/3Co_1/3O₂ (NMC₃₃₃) and LiNi_0.4Mn_0.4Co_0.2O₂ (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 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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Office of Vehicle Technology

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1423450

Journal Information:: Nano Research, Vol. 10, Issue 12; ISSN 1998-0124

Publisher:: SpringerCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Suppressed oxygen extraction and degradation of LiNixMnyCozO2 cathodes at high charge cut-off voltages

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Title: Suppressed oxygen extraction and degradation of LiNi_xMn_yCo_zO₂ cathodes at high charge cut-off voltages