Deconvoluting sources of failure in lithium metal batteries containing NMC and PEO-based electrolytes

W. Blake Hawley; Zhijia Du; Alexander J. Kukay; Nancy J. Dudney; Andrew S. Westover; Jianlin Li

doi:10.1016/j.electacta.2021.139579

Deconvoluting sources of failure in lithium metal batteries containing NMC and PEO-based electrolytes

W. Blake Hawley, Zhijia Du, Alexander J. Kukay, Nancy J. Dudney, Andrew S. Westover, Jianlin Li

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

16 Scopus citations

Abstract

Solid-state lithium metal batteries (SSLMBs) containing polyethylene oxide (PEO)-derived polymer electrolytes and high-voltage (> 4 V vs. Li/Li⁺) cathode materials suffer from three sources of failure: (1) instability between the polymer electrolyte and cathode at high voltage, (2) instability of the polymer electrolyte with Li metal, and (3) poorly-designed cathodes. In this study, these three sources of failure are deconvoluted by studying Ni-rich LiNi_xMn_yCo_1-x-yO₂ (NMC, x ≥ 0.6) cathodes and a gel polymer electrolyte (GPE) derived from PEO. Initial cycling data reveals that rapid capacity fade occurs regardless of whether soft short circuits form due to Li dendrites. Cyclic voltammetry scans on cells featuring a Li metal electrode, GPE, and a NMC811 electrode free of additives suggest that there are no runaway reactions between the GPE and NMC811 up to 4.5 V vs. Li/Li⁺. Cathode/cathode symmetric cell cycling demonstrates that Li metal reactivity is a prime source of failure, though a poorly-designed cathode leads to subpar performance. A cathode with single-crystal NMC particles was demonstrated to achieve better initial capacity and longer cycle life, indicating room for improvement in SSLMB cathode design. Therefore, the sources of failure as enumerated may be ranked as follows from most to least concerning: 2 > 3 > 1.

Original language	English
Article number	139579
Journal	Electrochimica Acta
Volume	404
DOIs	https://doi.org/10.1016/j.electacta.2021.139579
State	Published - Feb 1 2022

Funding

This research is sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory (ORNL), managed by UT-Battelle, LLC for the U.S. Department of Energy under Contract No. DE-AC0500OR22725. SEM imaging of cathode materials was conducted at Oak Ridge National Laboratory's Center for Nanophase Materials Sciences (CNMS), which is a DOE Office of Science User Facility. The authors acknowledge Ritu Sahore (ORNL) for her assistance with revising the manuscript. This research is sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory (ORNL), managed by UT-Battelle, LLC for the U.S. Department of Energy under Contract No. DE-AC0500OR22725. SEM imaging of cathode materials was conducted at Oak Ridge National Laboratory's Center for Nanophase Materials Sciences (CNMS), which is a DOE Office of Science User Facility. The authors acknowledge Ritu Sahore (ORNL) for her assistance with revising the manuscript. This manuscript has been authored in part by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE 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
U.S. Department of Energy	DE-AC0500OR22725
Office of Science
Oak Ridge National Laboratory
UT-Battelle

Keywords

Cyclic voltammetry
Dust electrode
High-voltage cathode
Single-crystal cathode
Solid-state battery
Symmetric cell

UN SDGs

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

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10.1016/j.electacta.2021.139579

Cite this

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title = "Deconvoluting sources of failure in lithium metal batteries containing NMC and PEO-based electrolytes",

abstract = "Solid-state lithium metal batteries (SSLMBs) containing polyethylene oxide (PEO)-derived polymer electrolytes and high-voltage (> 4 V vs. Li/Li+) cathode materials suffer from three sources of failure: (1) instability between the polymer electrolyte and cathode at high voltage, (2) instability of the polymer electrolyte with Li metal, and (3) poorly-designed cathodes. In this study, these three sources of failure are deconvoluted by studying Ni-rich LiNixMnyCo1-x-yO2 (NMC, x ≥ 0.6) cathodes and a gel polymer electrolyte (GPE) derived from PEO. Initial cycling data reveals that rapid capacity fade occurs regardless of whether soft short circuits form due to Li dendrites. Cyclic voltammetry scans on cells featuring a Li metal electrode, GPE, and a NMC811 electrode free of additives suggest that there are no runaway reactions between the GPE and NMC811 up to 4.5 V vs. Li/Li+. Cathode/cathode symmetric cell cycling demonstrates that Li metal reactivity is a prime source of failure, though a poorly-designed cathode leads to subpar performance. A cathode with single-crystal NMC particles was demonstrated to achieve better initial capacity and longer cycle life, indicating room for improvement in SSLMB cathode design. Therefore, the sources of failure as enumerated may be ranked as follows from most to least concerning: 2 > 3 > 1.",

keywords = "Cyclic voltammetry, Dust electrode, High-voltage cathode, Single-crystal cathode, Solid-state battery, Symmetric cell",

author = "Hawley, {W. Blake} and Zhijia Du and Kukay, {Alexander J.} and Dudney, {Nancy J.} and Westover, {Andrew S.} and Jianlin Li",

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doi = "10.1016/j.electacta.2021.139579",

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T1 - Deconvoluting sources of failure in lithium metal batteries containing NMC and PEO-based electrolytes

AU - Hawley, W. Blake

AU - Du, Zhijia

AU - Kukay, Alexander J.

AU - Dudney, Nancy J.

AU - Westover, Andrew S.

AU - Li, Jianlin

PY - 2022/2/1

Y1 - 2022/2/1

N2 - Solid-state lithium metal batteries (SSLMBs) containing polyethylene oxide (PEO)-derived polymer electrolytes and high-voltage (> 4 V vs. Li/Li+) cathode materials suffer from three sources of failure: (1) instability between the polymer electrolyte and cathode at high voltage, (2) instability of the polymer electrolyte with Li metal, and (3) poorly-designed cathodes. In this study, these three sources of failure are deconvoluted by studying Ni-rich LiNixMnyCo1-x-yO2 (NMC, x ≥ 0.6) cathodes and a gel polymer electrolyte (GPE) derived from PEO. Initial cycling data reveals that rapid capacity fade occurs regardless of whether soft short circuits form due to Li dendrites. Cyclic voltammetry scans on cells featuring a Li metal electrode, GPE, and a NMC811 electrode free of additives suggest that there are no runaway reactions between the GPE and NMC811 up to 4.5 V vs. Li/Li+. Cathode/cathode symmetric cell cycling demonstrates that Li metal reactivity is a prime source of failure, though a poorly-designed cathode leads to subpar performance. A cathode with single-crystal NMC particles was demonstrated to achieve better initial capacity and longer cycle life, indicating room for improvement in SSLMB cathode design. Therefore, the sources of failure as enumerated may be ranked as follows from most to least concerning: 2 > 3 > 1.

AB - Solid-state lithium metal batteries (SSLMBs) containing polyethylene oxide (PEO)-derived polymer electrolytes and high-voltage (> 4 V vs. Li/Li+) cathode materials suffer from three sources of failure: (1) instability between the polymer electrolyte and cathode at high voltage, (2) instability of the polymer electrolyte with Li metal, and (3) poorly-designed cathodes. In this study, these three sources of failure are deconvoluted by studying Ni-rich LiNixMnyCo1-x-yO2 (NMC, x ≥ 0.6) cathodes and a gel polymer electrolyte (GPE) derived from PEO. Initial cycling data reveals that rapid capacity fade occurs regardless of whether soft short circuits form due to Li dendrites. Cyclic voltammetry scans on cells featuring a Li metal electrode, GPE, and a NMC811 electrode free of additives suggest that there are no runaway reactions between the GPE and NMC811 up to 4.5 V vs. Li/Li+. Cathode/cathode symmetric cell cycling demonstrates that Li metal reactivity is a prime source of failure, though a poorly-designed cathode leads to subpar performance. A cathode with single-crystal NMC particles was demonstrated to achieve better initial capacity and longer cycle life, indicating room for improvement in SSLMB cathode design. Therefore, the sources of failure as enumerated may be ranked as follows from most to least concerning: 2 > 3 > 1.

KW - Cyclic voltammetry

KW - Dust electrode

KW - High-voltage cathode

KW - Single-crystal cathode

KW - Solid-state battery

KW - Symmetric cell

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Deconvoluting sources of failure in lithium metal batteries containing NMC and PEO-based electrolytes

Abstract

Funding

Keywords

UN SDGs

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