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

Abstract

Substituted Li-layered transition-metal oxide (LTMO) electrodes such as LixNiy MnzCo1-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; similar to 98% efficiency). Focusing on LixNi0.8Co0.15Al0.0.5O2 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.more » In this paper, 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.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [2]; ORCiD logo [2];  [3];  [4]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Argonne National Lab. (ANL), Argonne, IL (United States); Stony Brook Univ., NY (United States)
  2. Univ. of Cambridge (United Kingdom)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Stony Brook Univ., NY (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1660430
Grant/Contract Number:  
AC02-06CH11357; SC0012583
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 142; Journal Issue: 15; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Layered Oxide; Battery

Citation Formats

Grenier, Antonin, Reeves, Philip J., Liu, Hao, Seymour, Ieuan D., Märker, Katharina, Wiaderek, Kamila M., Chupas, Peter J., Grey, Clare P., and Chapman, Karena W. Intrinsic Kinetic Limitations in Substituted Lithium-Layered Transition-Metal Oxide Electrodes. United States: N. p., 2020. Web. doi:10.1021/jacs.9b13551.
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Grenier, Antonin, Reeves, Philip J., Liu, Hao, Seymour, Ieuan D., Märker, Katharina, Wiaderek, Kamila M., Chupas, Peter J., Grey, Clare P., & Chapman, Karena W. Intrinsic Kinetic Limitations in Substituted Lithium-Layered Transition-Metal Oxide Electrodes. United States. https://doi.org/10.1021/jacs.9b13551
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Grenier, Antonin, Reeves, Philip J., Liu, Hao, Seymour, Ieuan D., Märker, Katharina, Wiaderek, Kamila M., Chupas, Peter J., Grey, Clare P., and Chapman, Karena W. Sat . "Intrinsic Kinetic Limitations in Substituted Lithium-Layered Transition-Metal Oxide Electrodes". United States. https://doi.org/10.1021/jacs.9b13551. https://www.osti.gov/servlets/purl/1660430.
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@article{osti_1660430,
title = {Intrinsic Kinetic Limitations in Substituted Lithium-Layered Transition-Metal Oxide Electrodes},
author = {Grenier, Antonin and Reeves, Philip J. and Liu, Hao and Seymour, Ieuan D. and Märker, Katharina and Wiaderek, Kamila M. and Chupas, Peter J. and Grey, Clare P. and Chapman, Karena W.},
abstractNote = {Substituted Li-layered transition-metal oxide (LTMO) electrodes such as LixNiy MnzCo1-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; similar to 98% efficiency). Focusing on LixNi0.8Co0.15Al0.0.5O2 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. In this paper, 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.},
doi = {10.1021/jacs.9b13551},
journal = {Journal of the American Chemical Society},
number = 15,
volume = 142,
place = {United States},
year = {Sat Mar 21 00:00:00 EDT 2020},
month = {Sat Mar 21 00:00:00 EDT 2020}
}
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https://doi.org/10.1021/jacs.9b13551
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