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Title: Cycling behavior of NCM523/graphite lithium-ion cells in the 3–4.4 V range: Diagnostic studies of full cells and harvested electrodes

Abstract

Energy density of full cells containing layered-oxide positive electrodes can be increased by raising the upper cutoff voltage above the current 4.2 V limit. In this article we examine aging behavior of cells, containing LiNi 0.5Co 0.2Mn 0.3O 2 (NCM523)-based positive and graphite-based negative electrodes, which underwent up to ~400 cycles in the 3-4.4 V range. Electrochemistry results from electrodes harvested from the cycled cells were obtained to identify causes of cell performance loss; these results were complemented with data from X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS) measurements. Our experiments indicate that the full cell capacity fade increases linearly with cycle number and results from irreversible lithium loss in the negative electrode solid electrolyte interphase (SEI) layer. The accompanying electrode potential shift reduces utilization of active material in both electrodes and causes the positive electrode to cycle at higher states-of-charge. Here, full cell impedance rise on aging arises primarily at the positive electrode and results mainly from changes at the electrode-electrolyte interface; the small growth in negative electrode impedance reflects changes in the SEI layer. Our results indicate that cell performance loss could be mitigated by modifying the electrode-electrolyte interfaces through use of appropriate electrode coatingsmore » and/or electrolyte additives.« less

Authors:
; ; ; ; ; ; ;
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)
OSTI Identifier:
1337947
Grant/Contract Number:
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 164; Journal Issue: 1; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
30 DIRECT ENERGY CONVERSION

Citation Formats

Gilbert, James A., Bareño, Javier, Spila, Timothy, Trask, Stephen E., Miller, Dean J., Polzin, Bryant J., Jansen, Andrew N., and Abraham, Daniel P. Cycling behavior of NCM523/graphite lithium-ion cells in the 3–4.4 V range: Diagnostic studies of full cells and harvested electrodes. United States: N. p., 2016. Web. doi:10.1149/2.0081701jes.
Gilbert, James A., Bareño, Javier, Spila, Timothy, Trask, Stephen E., Miller, Dean J., Polzin, Bryant J., Jansen, Andrew N., & Abraham, Daniel P. Cycling behavior of NCM523/graphite lithium-ion cells in the 3–4.4 V range: Diagnostic studies of full cells and harvested electrodes. United States. doi:10.1149/2.0081701jes.
Gilbert, James A., Bareño, Javier, Spila, Timothy, Trask, Stephen E., Miller, Dean J., Polzin, Bryant J., Jansen, Andrew N., and Abraham, Daniel P. 2016. "Cycling behavior of NCM523/graphite lithium-ion cells in the 3–4.4 V range: Diagnostic studies of full cells and harvested electrodes". United States. doi:10.1149/2.0081701jes. https://www.osti.gov/servlets/purl/1337947.
@article{osti_1337947,
title = {Cycling behavior of NCM523/graphite lithium-ion cells in the 3–4.4 V range: Diagnostic studies of full cells and harvested electrodes},
author = {Gilbert, James A. and Bareño, Javier and Spila, Timothy and Trask, Stephen E. and Miller, Dean J. and Polzin, Bryant J. and Jansen, Andrew N. and Abraham, Daniel P},
abstractNote = {Energy density of full cells containing layered-oxide positive electrodes can be increased by raising the upper cutoff voltage above the current 4.2 V limit. In this article we examine aging behavior of cells, containing LiNi0.5Co0.2Mn0.3O2 (NCM523)-based positive and graphite-based negative electrodes, which underwent up to ~400 cycles in the 3-4.4 V range. Electrochemistry results from electrodes harvested from the cycled cells were obtained to identify causes of cell performance loss; these results were complemented with data from X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS) measurements. Our experiments indicate that the full cell capacity fade increases linearly with cycle number and results from irreversible lithium loss in the negative electrode solid electrolyte interphase (SEI) layer. The accompanying electrode potential shift reduces utilization of active material in both electrodes and causes the positive electrode to cycle at higher states-of-charge. Here, full cell impedance rise on aging arises primarily at the positive electrode and results mainly from changes at the electrode-electrolyte interface; the small growth in negative electrode impedance reflects changes in the SEI layer. Our results indicate that cell performance loss could be mitigated by modifying the electrode-electrolyte interfaces through use of appropriate electrode coatings and/or electrolyte additives.},
doi = {10.1149/2.0081701jes},
journal = {Journal of the Electrochemical Society},
number = 1,
volume = 164,
place = {United States},
year = 2016,
month = 9
}

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Free Publicly Available Full Text
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Cited by: 4works
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  • The electrochemical performance of cells with a Li 1.03(Ni 0.5Co 0.2Mn 0.3) 0.97O 2 (NCM523) positive electrode and a blended silicon-graphite (Si-Gr) negative electrode are investigated using various electrolyte compositions and voltage cycling windows. Voltage profiles of the blended Si-Gr electrode show a superposition of graphite potential plateaus on a sloped Si profile with a large potential hysteresis. The effect of this hysteresis is seen in the cell impedance versus voltage data, which are distinctly different for the charge and discharge cycles. We confirm that the addition of compounds, such as vinylene carbonate (VC) and fluoroethylene carbonate (FEC) to themore » baseline 1.2 M LiPF 6 in ethylene carbonate (EC): ethyl methyl carbonate (EMC) (3:7 w/w) electrolyte, improves cell capacity retention with higher retention seen at higher additive contents. We show that reducing the lower cutoff voltage (LCV) of full cells to 2.5 V increases the Si-Gr electrode potential to 1.12 V vs. Li/Li +; this relatively-high delithiation potential correlates with the lower capacity retention displayed by the cell. Hence, we show that raising the upper cutoff voltage (UCV) can increase cell energy density without significantly altering capacity retention over 100 charge discharge cycles.« less
  • Here, tris(trimethylsilyl) phosphite (TMSPi) has emerged as an useful electrolyte additive for lithium ion cells. This work examines the use of TMSPi and a structurally analogous compound, triethyl phosphite (TEPi), in LiNi 0.5Mn 0.3Co 0.2O 2-graphite full cells, containing a (baseline) electrolyte with 1.2 M LiPF6 in EC: EMC (3:7 w/w) and operating between 3.0-4.4 V. Galvanostatic cycling data reveal a measurable difference in capacity fade between the TMSPi and TEPi cells. Furthermore, lower impedance rise is observed for the TMSPi cells, because of the formation of a P-and O-rich surface film on the positive electrode that was revealed bymore » X-ray photoelectron spectroscopy data. Elemental analysis on negative electrodes harvested from cycled cells show lower contents of transition metal (TM) elements for the TMSPi cells than for the baseline and TEPi cells. Our findings indicate that removal of TMS groups from the central P-O core of the TMSPi additive enables formation of the oxide surface film. This film is able to block the generation of reactive TM-oxygen radical species, suppress hydrogen abstraction from the electrolyte solvent, and minimize oxidation reactions at the positive electrode-electrolyte interface. In contrast, oxidation of TEPi does not yield a protective positive electrode film, which results in inferior electrochemical performance.« less
  • No abstract prepared.
  • Lithium-ion batteries are a candidate for the energy storage system onboard low-earth-orbit satellites. Terrestrial experiments are able to capture the performance degradation of cells in orbit, therefore providing the opportunity for lifetime investigations. The lifetime performance of 3 Ah commercial Li{sub x}Mn{sub 2}O{sub 4}-based pouch cells was evaluated in a matrix of different cycling depths-of-discharge (DODs: 0, 20, 40%) and temperatures (25, 45 C). Aged cells were disassembled and the electrochemical performance of harvested electrodes investigated with two- and three-electrode pouch cells. The positive electrode had a larger decrease in capacity than the negative electrode. Both the positive and negativemore » electrode contributed to the increase of cell impedance measured at high states-of-charge (SOCs). The data at low SOCs indicated that the increase of cell impedance was associated with the positive electrode, which showed a significant increase in the magnitude of the high-frequency semi-circle. This SOC-dependence was observed for cells cycled for either extended periods of time or at higher temperatures with a 40% DOD swing. Low-current cycling of positive electrodes revealed a change in the second potential plateau, possibly reflecting a structural change of the Li{sub x}Mn{sub 2}O{sub 4}. This could impact on the electrode kinetics and provide a possible explanation for the SOC-dependent change of the impedance.« less