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 (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.
- Publication Date:
- Research Org.:
- Argonne National Laboratory (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)
- 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 Name: Journal of the Electrochemical Society 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. https://doi.org/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. https://doi.org/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 = {Thu Jun 07 00:00:00 EDT 2018},
month = {Thu Jun 07 00:00:00 EDT 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1149/2.0611809jes
https://doi.org/10.1149/2.0611809jes
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 38 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes: I. Nickel-Rich, LiNi
journal, December 2016
- Schipper, Florian; Erickson, Evan M.; Erk, Christoph
- Journal of The Electrochemical Society, Vol. 164, Issue 1
Observation of Microstructural Evolution in Li Battery Cathode Oxide Particles by In Situ Electron Microscopy
journal, May 2013
- Miller, Dean J.; Proff, Christian; Wen, J. G.
- Advanced Energy Materials, Vol. 3, Issue 8
Editors' Choice—Growth of Ambient Induced Surface Impurity Species on Layered Positive Electrode Materials and Impact on Electrochemical Performance
journal, January 2017
- Faenza, Nicholas V.; Bruce, Lejandro; Lebens-Higgins, Zachary W.
- Journal of The Electrochemical Society, Vol. 164, Issue 14
Lithium diffusion mechanisms in layered intercalation compounds
journal, July 2001
- Van der Ven, A.; Ceder, G.
- Journal of Power Sources, Vol. 97-98
Theoretical examination of reference electrodes for lithium-ion cells
journal, December 2007
- Dees, Dennis W.; Jansen, Andrew N.; Abraham, Daniel P.
- Journal of Power Sources, Vol. 174, Issue 2
Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells
journal, December 2016
- Gilbert, James A.; Shkrob, Ilya A.; Abraham, Daniel P.
- Journal of The Electrochemical Society, Vol. 164, Issue 2
Alternating Current Impedance Electrochemical Modeling of Lithium-Ion Positive Electrodes
journal, January 2005
- Dees, Dennis; Gunen, Evren; Abraham, Daniel
- Journal of The Electrochemical Society, Vol. 152, Issue 7
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries
journal, March 2014
- Lin, Feng; Markus, Isaac M.; Nordlund, Dennis
- Nature Communications, Vol. 5, Issue 1
Gassing in Li4Ti5O12-based batteries and its remedy
journal, December 2012
- He, Yan-Bing; Li, Baohua; Liu, Ming
- Scientific Reports, Vol. 2, Issue 1
First-cycle irreversibility of layered Li–Ni–Co–Mn oxide cathode in Li-ion batteries
journal, December 2008
- Kang, Sun-Ho; Abraham, Daniel P.; Yoon, Won-Sub
- Electrochimica Acta, Vol. 54, Issue 2
Viable Mechanisms of Hydrogen Embrittlement—A Review
conference, January 2006
- Sofronis, P.
- HYDROGEN IN MATTER: A Collection from the Papers Presented at the Second International Symposium on Hydrogen in Matter (ISOHIM), AIP Conference Proceedings
Evolution of the Electrode–Electrolyte Interface of LiNi 0.8 Co 0.15 Al 0.05 O 2 Electrodes Due to Electrochemical and Thermal Stress
journal, January 2018
- Lebens-Higgins, Zachary W.; Sallis, Shawn; Faenza, Nicholas V.
- Chemistry of Materials, Vol. 30, Issue 3
Overview of the Oxygen Behavior in the Degradation of Li 2 MnO 3 Cathode Material
journal, September 2017
- Cho, Eunseog; Kim, Kihong; Jung, Changhoon
- The Journal of Physical Chemistry C, Vol. 121, Issue 39
Origin of H 2 Evolution in LIBs: H 2 O Reduction vs. Electrolyte Oxidation
journal, January 2016
- Metzger, Michael; Strehle, Benjamin; Solchenbach, Sophie
- Journal of The Electrochemical Society, Vol. 163, Issue 5
Electrode Behavior RE-Visited: Monitoring Potential Windows, Capacity Loss, and Impedance Changes in Li 1.03 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.97 O 2 /Silicon-Graphite Full Cells
journal, January 2016
- Klett, Matilda; Gilbert, James A.; Trask, Stephen E.
- Journal of The Electrochemical Society, Vol. 163, Issue 6
Understanding Irreversible Capacity in Li[sub x]Ni[sub 1−y]Fe[sub y]O[sub 2] Cathode Materials
journal, January 2000
- Mueller-Neuhaus, J. R.; Dunlap, R. A.; Dahn, J. R.
- Journal of The Electrochemical Society, Vol. 147, Issue 10
TREOR, a semi-exhaustive trial-and-error powder indexing program for all symmetries
journal, October 1985
- Werner, P. E.; Eriksson, L.; Westdahl, M.
- Journal of Applied Crystallography, Vol. 18, Issue 5
Connecting Particle Fracture with Electrochemical Impedance in Li X Mn 2 O 4
journal, January 2017
- McGrogan, Frank P.; Bishop, Sean R.; Chiang, Yet-Ming
- Journal of The Electrochemical Society, Vol. 164, Issue 14
Capacity Fade and Its Mitigation in Li-Ion Cells with Silicon-Graphite Electrodes
journal, September 2017
- Bareño, Javier; Shkrob, Ilya A.; Gilbert, James A.
- The Journal of Physical Chemistry C, Vol. 121, Issue 38
Interactions between Positive and Negative Electrodes in Li-Ion Cells Operated at High Temperature and High Voltage
journal, January 2016
- Xiong, D. J.; Petibon, R.; Nie, M.
- Journal of The Electrochemical Society, Vol. 163, Issue 3
Surface changes on LiNi0.8Co0.2O2 particles during testing of high-power lithium-ion cells
journal, August 2002
- Abraham, D. P.; Twesten, R. D.; Balasubramanian, M.
- Electrochemistry Communications, Vol. 4, Issue 8
Tris(trimethylsilyl) Phosphite (TMSPi) and Triethyl Phosphite (TEPi) as Electrolyte Additives for Lithium Ion Batteries: Mechanistic Insights into Differences during LiNi 0.5 Mn 0.3 Co 0.2 O 2 -Graphite Full Cell Cycling
journal, January 2017
- Peebles, Cameron; Sahore, Ritu; Gilbert, James A.
- Journal of The Electrochemical Society, Vol. 164, Issue 7
Chemical Weathering of Layered Ni-Rich Oxide Electrode Materials: Evidence for Cation Exchange
journal, January 2017
- Shkrob, Ilya A.; Gilbert, James A.; Phillips, Patrick J.
- Journal of The Electrochemical Society, Vol. 164, Issue 7
Understanding the Degradation Mechanisms of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode Material in Lithium Ion Batteries
journal, August 2013
- Jung, Sung-Kyun; Gwon, Hyeokjo; Hong, Jihyun
- Advanced Energy Materials, Vol. 4, Issue 1
Application of a lithium–tin reference electrode to determine electrode contributions to impedance rise in high-power lithium-ion cells
journal, October 2004
- Abraham, Daniel P.; Poppen, Steven D.; Jansen, Andrew N.
- Electrochimica Acta, Vol. 49, Issue 26
Exploring Electrochemistry and Interface Characteristics of Lithium-Ion Cells with Li 1.2 Ni 0.15 Mn 0.55 Co 0.1 O 2 Positive and Li 4 Ti 5 O 12 Negative Electrodes
journal, January 2015
- Li, Yan; Bettge, Martin; Bareño, Javier
- Journal of The Electrochemical Society, Vol. 162, Issue 13
Aging characteristics of high-power lithium-ion cells with LiNi0.8Co0.15Al0.05O2 and Li4/3Ti5/3O4 electrodes
journal, October 2005
- Abraham, D. P.; Reynolds, E. M.; Sammann, E.
- Electrochimica Acta, Vol. 51, Issue 3
Li-ion battery materials: present and future
journal, June 2015
- Nitta, Naoki; Wu, Feixiang; Lee, Jung Tae
- Materials Today, Vol. 18, Issue 5
Computer simulation of hydrogen embrittlement in metals
journal, April 1993
- Zhong, W.; Cai, Y.; Tománek, D.
- Nature, Vol. 362, Issue 6419
Understanding Long-Term Cycling Performance of Li 1.2 Ni 0.15 Mn 0.55 Co 0.1 O 2 –Graphite Lithium-Ion Cells
journal, January 2013
- Li, Y.; Bettge, M.; Polzin, B.
- Journal of The Electrochemical Society, Vol. 160, Issue 5
Nickel-Rich Layered Cathode Materials for Automotive Lithium-Ion Batteries: Achievements and Perspectives
journal, December 2016
- Myung, Seung-Taek; Maglia, Filippo; Park, Kang-Joon
- ACS Energy Letters, Vol. 2, Issue 1
Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: Methodology, insights and novel approaches
journal, February 2015
- Hausbrand, R.; Cherkashinin, G.; Ehrenberg, H.
- Materials Science and Engineering: B, Vol. 192
Insight into the Gassing Problem of Li-ion Battery
journal, December 2014
- Zhang, Sheng S.
- Frontiers in Energy Research, Vol. 2
Evaluating electrolyte additives for lithium-ion cells: A new Figure of Merit approach
journal, October 2017
- Tornheim, Adam; Peebles, Cameron; Gilbert, James A.
- Journal of Power Sources, Vol. 365
Quantifying, Understanding and Evaluating the Effects of Gas Consumption in Lithium-Ion Cells
journal, January 2017
- Ellis, L. D.; Allen, J. P.; Thompson, L. M.
- Journal of The Electrochemical Society, Vol. 164, Issue 14
On the Localized Nature of the Structural Transformations of Li 2 MnO 3 Following Electrochemical Cycling
journal, September 2015
- Phillips, Patrick J.; Bareño, Javier; Li, Yan
- Advanced Energy Materials, Vol. 5, Issue 23
Oxygen Release and Its Effect on the Cycling Stability of LiNi x Mn y Co z O 2 (NMC) Cathode Materials for Li-Ion Batteries
journal, January 2017
- Jung, Roland; Metzger, Michael; Maglia, Filippo
- Journal of The Electrochemical Society, Vol. 164, Issue 7
Operando Monitoring of Early Ni-mediated Surface Reconstruction in Layered Lithiated Ni–Co–Mn Oxides
journal, June 2017
- Streich, Daniel; Erk, Christoph; Guéguen, Aurelie
- The Journal of Physical Chemistry C, Vol. 121, Issue 25
Rechargeability of Li–air cathodes pre-filled with discharge products using an ether-based electrolyte solution: implications for cycle-life of Li–air cells
journal, January 2013
- Meini, Stefano; Tsiouvaras, Nikolaos; Schwenke, K. Uta
- Physical Chemistry Chemical Physics, Vol. 15, Issue 27
Rapid Impedance Growth and Gas Production at the Li-Ion Cell Positive Electrode in the Absence of a Negative Electrode
journal, January 2016
- Xiong, D. J.; Ellis, L. D.; Nelson, K. J.
- Journal of The Electrochemical Society, Vol. 163, Issue 14
Cycling Behavior of NCM523/Graphite Lithium-Ion Cells in the 3–4.4 V Range: Diagnostic Studies of Full Cells and Harvested Electrodes
journal, September 2016
- Gilbert, James A.; Bareño, Javier; Spila, Timothy
- Journal of The Electrochemical Society, Vol. 164, Issue 1
Study of the Failure Mechanisms of LiNi 0.8 Mn 0.1 Co 0.1 O 2 Cathode Material for Lithium Ion Batteries
journal, January 2015
- Li, Jing; Downie, Laura E.; Ma, Lin
- Journal of The Electrochemical Society, Vol. 162, Issue 7
CMPR – a powder diffraction toolkit
journal, November 2005
- Toby, Brian H.
- Journal of Applied Crystallography, Vol. 38, Issue 6
Recent progress in Li-rich layered oxides as cathode materials for Li-ion batteries
journal, January 2014
- Yan, Jianhua; Liu, Xingbo; Li, Bingyun
- RSC Adv., Vol. 4, Issue 108