Intrinsic Kinetic Limitations in Substituted Lithium-Layered Transition-Metal Oxide Electrodes

Antonin Grenier, Philip J. Reeves, Hao Liu, Ieuan D. Seymour, Katharina Märker, Kamila M. Wiaderek, Peter J. Chupas, Clare P. Grey, Karena W. Chapman*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

73 Citations (Scopus)


Substituted Li-layered transition-metal oxide (LTMO) electrodes such as LixNiyMnzCo1-y-zO2 (NMC) and LixNiyCo1-y-zAlzO2 (NCA) show reduced first cycle Coulombic efficiency (90-87% under standard cycling conditions) in comparison with the archetypal LixCoO2 (LCO; ∼98% efficiency). Focusing on LixNi0.8Co0.15Al0.05O2 as a model compound, we use operando synchrotron X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) spectroscopy to demonstrate that the apparent first-cycle capacity loss is a kinetic effect linked to limited Li mobility at x > 0.88, with near full capacity recovered during a potentiostatic hold following the galvanostatic charge-discharge cycle. This kinetic capacity loss, unlike many capacity losses in LTMOs, is independent of the cutoff voltage during delithiation and it is a reversible process. The kinetic limitation manifests not only as the kinetic capacity loss during discharge but as a subtle bimodal compositional distribution early in charge and, also, a dramatic increase of the charge-discharge voltage hysteresis at x > 0.88. 7Li NMR measurements indicate that the kinetic limitation reflects limited Li transport at x > 0.86. Electrochemical measurements on a wider range of LTMOs including Lix(Ni,Fe)yCo1-yO2 suggest that 5% substitution is sufficient to induce the kinetic limitation and that the effect is not limited to Ni substitution. We outline how, in addition to a reduction in the number of Li vacancies and shrinkage of the Li-layer size, the intrinsic charge storage mechanism (two-phase vs solid-solution) and localization of charge give rise to additional kinetic barriers in NCA and nonmetallic LTMOs in general.

Original languageEnglish
Pages (from-to)7001-7011
Number of pages11
JournalJournal of the American Chemical Society
Issue number15
Early online date21 Mar 2020
Publication statusPublished - 15 Apr 2020

Bibliographical note

Funding Information:
This work was supported as a part of NECCES, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award No. DE-SC0012583. This research used resources of the Advanced Photon Source, a U.S. Department of Energy Office of Science User Facility operated for the Department of Energy Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.


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