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Title: High-Voltage Performance of Ni-Rich NCA Cathodes: Linking Operating Voltage with Cathode Degradation

Abstract

High-voltage Ni-rich cathodes have been studied as a possible way to achieve high energy density in Li-ion batteries. However, capacity fade due to structural changes at high voltages has limited their applications. In this study, we identify 4.5 V (vs. graphite) as the optimum upper cutoff voltage (UCV) for a Ni-rich NCA cathode [LiNi0.8Co0.15Al0.05O2]. At this UCV, NCA delivers a 12 % increase in reversible capacity (when discharged to 2.5 V) and retains 92 % of its initial capacity after 100 cycles at 1C/-1C cycling when compared to 4.2 V as UCV. By increasing UCV to 4.7 V, the discharge capacity can be raised to >200 mAh/g. However, the rate of capacity fade is greater when compared to 4.5 V as UCV. This increased rate of capacity fade, at higher UCV, is related to irreversible lattice contractions that leads to structural rearrangement at charged states during high-voltage cycling. Lastly, our results show a change in transition metal oxidation states and an onset of structural ordering occurs when the UCV is 4.7 V.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (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). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1561675
Alternate Identifier(s):
OSTI ID: 1558680
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ChemElectroChem
Additional Journal Information:
Journal Volume: 6; Journal Issue: 22; Journal ID: ISSN 2196-0216
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Li-ion battery; Ni-rich cathodes; electrochemistry; magnetic susceptibility; in situ XRD

Citation Formats

David, Lamuel Abraham, Mohanty, Debasish, Geng, Linxiao, Ruther, Rose E., Sefat, Athena Safa, Cakmak, Ercan, Veith, Gabriel M., Meyer, III, Harry M., Wang, Hsin, and Wood, III, David L. High-Voltage Performance of Ni-Rich NCA Cathodes: Linking Operating Voltage with Cathode Degradation. United States: N. p., 2019. Web. doi:10.1002/celc.201901338.
David, Lamuel Abraham, Mohanty, Debasish, Geng, Linxiao, Ruther, Rose E., Sefat, Athena Safa, Cakmak, Ercan, Veith, Gabriel M., Meyer, III, Harry M., Wang, Hsin, & Wood, III, David L. High-Voltage Performance of Ni-Rich NCA Cathodes: Linking Operating Voltage with Cathode Degradation. United States. doi:10.1002/celc.201901338.
David, Lamuel Abraham, Mohanty, Debasish, Geng, Linxiao, Ruther, Rose E., Sefat, Athena Safa, Cakmak, Ercan, Veith, Gabriel M., Meyer, III, Harry M., Wang, Hsin, and Wood, III, David L. Fri . "High-Voltage Performance of Ni-Rich NCA Cathodes: Linking Operating Voltage with Cathode Degradation". United States. doi:10.1002/celc.201901338. https://www.osti.gov/servlets/purl/1561675.
@article{osti_1561675,
title = {High-Voltage Performance of Ni-Rich NCA Cathodes: Linking Operating Voltage with Cathode Degradation},
author = {David, Lamuel Abraham and Mohanty, Debasish and Geng, Linxiao and Ruther, Rose E. and Sefat, Athena Safa and Cakmak, Ercan and Veith, Gabriel M. and Meyer, III, Harry M. and Wang, Hsin and Wood, III, David L.},
abstractNote = {High-voltage Ni-rich cathodes have been studied as a possible way to achieve high energy density in Li-ion batteries. However, capacity fade due to structural changes at high voltages has limited their applications. In this study, we identify 4.5 V (vs. graphite) as the optimum upper cutoff voltage (UCV) for a Ni-rich NCA cathode [LiNi0.8Co0.15Al0.05O2]. At this UCV, NCA delivers a 12 % increase in reversible capacity (when discharged to 2.5 V) and retains 92 % of its initial capacity after 100 cycles at 1C/-1C cycling when compared to 4.2 V as UCV. By increasing UCV to 4.7 V, the discharge capacity can be raised to >200 mAh/g. However, the rate of capacity fade is greater when compared to 4.5 V as UCV. This increased rate of capacity fade, at higher UCV, is related to irreversible lattice contractions that leads to structural rearrangement at charged states during high-voltage cycling. Lastly, our results show a change in transition metal oxidation states and an onset of structural ordering occurs when the UCV is 4.7 V.},
doi = {10.1002/celc.201901338},
journal = {ChemElectroChem},
number = 22,
volume = 6,
place = {United States},
year = {2019},
month = {8}
}

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