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

Lamuel David; Debasish Mohanty; Linxiao Geng; Rose E. Ruther; Athena S. Sefat; Ercan Cakmak; Gabriel M. Veith; Harry M. Meyer; Hsin Wang; David L. Wood

doi:10.1002/celc.201901338

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

Lamuel David, Debasish Mohanty, Linxiao Geng, Rose E. Ruther, Athena S. Sefat, Ercan Cakmak, Gabriel M. Veith, Harry M. Meyer, Hsin Wang, David L. Wood

Research output: Contribution to journal › Article › peer-review

17 Scopus citations

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. This study identifies 4.5 V (vs. graphite) as the optimum upper cutoff voltage (UCV) for a Ni-rich NCA cathode [LiNi_0.8Co_0.15Al_0.05O₂]. 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. Our results show a change in transition metal oxidation states and an onset of structural ordering occurs when the UCV is 4.7 V.

Original language	English
Pages (from-to)	5571-5580
Number of pages	10
Journal	ChemElectroChem
Volume	6
Issue number	22
DOIs	https://doi.org/10.1002/celc.201901338
State	Published - Nov 18 2019

Funding

D.M. pursued the idea, L.D and D.W. lead this research. L.D. and L.G. performed electrochemical and structural characterization and analyzed the data and wrote the manuscript. A.S. performed the magnetization experiment and was involved in the technical discussions. E.C. did X‐ray diffraction and was involved in diffraction analysis and discussion. H.M.M. performed the XPS experiments and was involved in XPS data analysis. H.W. performed DSC experiments. D.W. was also involved in the technical discussions and manuscript preparation. This manuscript has been authored by UT‐Battelle, LLC under Contract No. DE‐AC05‐00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non‐exclusive, paid‐up, irrevocable, world‐wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe‐public‐access‐plan).

Funders	Funder number
DOE BES
DOE Basic Energy Sciences
U.S. Department of Energy	DE‐AC05‐00OR22725
Battelle
Office of Energy Efficiency and Renewable Energy
Basic Energy Sciences
Oak Ridge National Laboratory
Vehicle Technologies Office
Division of Materials Sciences and Engineering

Keywords

Li-ion battery
Ni-rich cathodes
electrochemistry
in situ XRD
magnetic susceptibility

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/celc.201901338

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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. This study identifies 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. Our results show a change in transition metal oxidation states and an onset of structural ordering occurs when the UCV is 4.7 V.",

keywords = "Li-ion battery, Ni-rich cathodes, electrochemistry, in situ XRD, magnetic susceptibility",

author = "Lamuel David and Debasish Mohanty and Linxiao Geng and Ruther, {Rose E.} and Sefat, {Athena S.} and Ercan Cakmak and Veith, {Gabriel M.} and Meyer, {Harry M.} and Hsin Wang and Wood, {David L.}",

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AU - Geng, Linxiao

AU - Ruther, Rose E.

AU - Sefat, Athena S.

AU - Cakmak, Ercan

AU - Veith, Gabriel M.

AU - Meyer, Harry M.

AU - Wang, Hsin

AU - Wood, David L.

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N2 - 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. This study identifies 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. Our results show a change in transition metal oxidation states and an onset of structural ordering occurs when the UCV is 4.7 V.

AB - 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. This study identifies 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. Our results show a change in transition metal oxidation states and an onset of structural ordering occurs when the UCV is 4.7 V.

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

Abstract

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Keywords

UN SDGs

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