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Title: Anode-Dependent Impedance Rise in Layered-Oxide Cathodes of Lithium-Ion Cells

Abstract

Nickel-rich Ni-Co-Mn (NCM) or Ni-Co-Al (NCA) layered-oxide positive electrodes (cathodes) allow high-voltage operation of lithium-ion cells with increased energy density, but their long-term cycling causes gradual increase in their impedance that slows down lithiation and delithiation of the material. Here we report that pairing of these cathodes with lithium titanate (Li 4Ti 5O 12, LTO) negative electrodes (anodes) accelerates this impedance rise when compared to pairing with graphite (Gr) electrodes, during potentiostatic holds (calendar-aging) at sufficiently high (> 4.2 V vs. Li/Li +) layered-oxide potentials. Our results suggest that gases generated in the cell play an important role in this impedance rise. In the graphite cells, these gases are gradually depleted by reactions at the Gr electrode, but such reactions do not occur at the LTO electrode. The generation and buildup of gases degrades the electron conduction network within the cathode, and also leads to modifications at the oxide-electrolyte interfaces, causing the observed impedance rise. The calendar-aging also alters cell capacity, with losses observed in the Gr cells and gains observed in the LTO cells. Possible causes and consequences of these changes in the lithium-ion inventory of the cells are discussed.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1441036
Alternate Identifier(s):
OSTI ID: 1467081
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 165; Journal Issue: 9; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; crosstalk; impedance; reference electrode

Citation Formats

Rodrigues, Marco-Tulio F., Kalaga, Kaushik, Trask, Stephen E., Shkrob, Ilya A., and Abraham, Daniel P. Anode-Dependent Impedance Rise in Layered-Oxide Cathodes of Lithium-Ion Cells. United States: N. p., 2018. Web. doi:10.1149/2.0611809jes.
Rodrigues, Marco-Tulio F., Kalaga, Kaushik, Trask, Stephen E., Shkrob, Ilya A., & Abraham, Daniel P. Anode-Dependent Impedance Rise in Layered-Oxide Cathodes of Lithium-Ion Cells. United States. doi:10.1149/2.0611809jes.
Rodrigues, Marco-Tulio F., Kalaga, Kaushik, Trask, Stephen E., Shkrob, Ilya A., and Abraham, Daniel P. Thu . "Anode-Dependent Impedance Rise in Layered-Oxide Cathodes of Lithium-Ion Cells". United States. doi:10.1149/2.0611809jes.
@article{osti_1441036,
title = {Anode-Dependent Impedance Rise in Layered-Oxide Cathodes of Lithium-Ion Cells},
author = {Rodrigues, Marco-Tulio F. and Kalaga, Kaushik and Trask, Stephen E. and Shkrob, Ilya A. and Abraham, Daniel P.},
abstractNote = {Nickel-rich Ni-Co-Mn (NCM) or Ni-Co-Al (NCA) layered-oxide positive electrodes (cathodes) allow high-voltage operation of lithium-ion cells with increased energy density, but their long-term cycling causes gradual increase in their impedance that slows down lithiation and delithiation of the material. Here we report that pairing of these cathodes with lithium titanate (Li4Ti5O12, LTO) negative electrodes (anodes) accelerates this impedance rise when compared to pairing with graphite (Gr) electrodes, during potentiostatic holds (calendar-aging) at sufficiently high (> 4.2 V vs. Li/Li+) layered-oxide potentials. Our results suggest that gases generated in the cell play an important role in this impedance rise. In the graphite cells, these gases are gradually depleted by reactions at the Gr electrode, but such reactions do not occur at the LTO electrode. The generation and buildup of gases degrades the electron conduction network within the cathode, and also leads to modifications at the oxide-electrolyte interfaces, causing the observed impedance rise. The calendar-aging also alters cell capacity, with losses observed in the Gr cells and gains observed in the LTO cells. Possible causes and consequences of these changes in the lithium-ion inventory of the cells are discussed.},
doi = {10.1149/2.0611809jes},
journal = {Journal of the Electrochemical Society},
number = 9,
volume = 165,
place = {United States},
year = {2018},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1149/2.0611809jes

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Cited by: 3 works
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