In Situ ATR-FTIR Study of the Cathode–Electrolyte Interphase: Electrolyte Solution Structure, Transition Metal Redox, and Surface Layer Evolution

Bertrand J. Tremolet de Villers; Seong Min Bak; Junghoon Yang; Sang Don Han

doi:10.1002/batt.202000259

In Situ ATR-FTIR Study of the Cathode–Electrolyte Interphase: Electrolyte Solution Structure, Transition Metal Redox, and Surface Layer Evolution

Bertrand J. Tremolet de Villers, Seong Min Bak, Junghoon Yang, Sang Don Han

Department of Materials Science and Engineering

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

Abstract

We present a study of the lithium nickel manganese cobalt oxide (LiNi_0.6Mn_0.2Co_0.2O₂, NMC622) cathode-electrolyte interphase (CEI) during galvanostatic charging and discharging using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) methods to investigate the voltage dependent electrolyte solution structure changes at the interface, transition metal (TM) redox chemistry, and cathode/electrolyte interfacial layer evolution. Our in situ cell design provides both reliable electrochemical device testing and strong FTIR vibrational absorption signals near the cathode surface. Specifically, advanced spectral analysis elucidates changes of near-surface Li⁺ ion (de)solvation by solvent molecules during galvanostatic cycling. Moreover, cathode metal-oxygen vibrational absorptions, sensitive to TM redox behaviors and subsequent local structural variations, were correlated to cathode de-lithiation (and lithiation) and electrolyte solution structure changes. In addition, we have detected the formation and evolution of a CEI surface layer on the NMC622 cathode that contributes to the cell's capacity fade.

Original language	English
Pages (from-to)	778-784
Number of pages	7
Journal	Batteries and Supercaps
Volume	4
Issue number	5
DOIs	https://doi.org/10.1002/batt.202000259
Publication status	Published - 2021 May

Bibliographical note

Funding Information:
This work was authored in part by Alliance for Sustainable Energy, LLC, the manager and operator of the National Renewable Energy Laboratory (NREL) for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Support from the Vehicle Technologies Office (VTO), Hybrid Electric Systems Program, David Howell (Manager), Battery R&D, Peter Faguy (Technology Manager), at the U.S. DOE, Office of Energy Efficiency and Renewable Energy, is gratefully acknowledged. The electrode active materials used in this article were synthesized at Argonne's Cell Analysis, Modeling and Prototyping (CAMP) Facility. Funding for in situ ATR-FTIR characterization provided in part by the Laboratory Directed Research and Development (LDRD) Program at NREL. The XAS research used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory (BNL) under Contract No. DE-SC0012704. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes.

Publisher Copyright:
© 2020 Wiley-VCH GmbH

All Science Journal Classification (ASJC) codes

Energy Engineering and Power Technology
Electrical and Electronic Engineering
Electrochemistry

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10.1002/batt.202000259

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title = "In Situ ATR-FTIR Study of the Cathode–Electrolyte Interphase: Electrolyte Solution Structure, Transition Metal Redox, and Surface Layer Evolution",

abstract = "We present a study of the lithium nickel manganese cobalt oxide (LiNi0.6Mn0.2Co0.2O2, NMC622) cathode-electrolyte interphase (CEI) during galvanostatic charging and discharging using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) methods to investigate the voltage dependent electrolyte solution structure changes at the interface, transition metal (TM) redox chemistry, and cathode/electrolyte interfacial layer evolution. Our in situ cell design provides both reliable electrochemical device testing and strong FTIR vibrational absorption signals near the cathode surface. Specifically, advanced spectral analysis elucidates changes of near-surface Li+ ion (de)solvation by solvent molecules during galvanostatic cycling. Moreover, cathode metal-oxygen vibrational absorptions, sensitive to TM redox behaviors and subsequent local structural variations, were correlated to cathode de-lithiation (and lithiation) and electrolyte solution structure changes. In addition, we have detected the formation and evolution of a CEI surface layer on the NMC622 cathode that contributes to the cell's capacity fade.",

author = "{Tremolet de Villers}, {Bertrand J.} and Bak, {Seong Min} and Junghoon Yang and Han, {Sang Don}",

note = "Funding Information: This work was authored in part by Alliance for Sustainable Energy, LLC, the manager and operator of the National Renewable Energy Laboratory (NREL) for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Support from the Vehicle Technologies Office (VTO), Hybrid Electric Systems Program, David Howell (Manager), Battery R&D, Peter Faguy (Technology Manager), at the U.S. DOE, Office of Energy Efficiency and Renewable Energy, is gratefully acknowledged. The electrode active materials used in this article were synthesized at Argonne's Cell Analysis, Modeling and Prototyping (CAMP) Facility. Funding for in situ ATR-FTIR characterization provided in part by the Laboratory Directed Research and Development (LDRD) Program at NREL. The XAS research used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory (BNL) under Contract No. DE-SC0012704. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes. Publisher Copyright: {\textcopyright} 2020 Wiley-VCH GmbH",

year = "2021",

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doi = "10.1002/batt.202000259",

language = "English",

volume = "4",

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AU - Bak, Seong Min

AU - Yang, Junghoon

AU - Han, Sang Don

N1 - Funding Information: This work was authored in part by Alliance for Sustainable Energy, LLC, the manager and operator of the National Renewable Energy Laboratory (NREL) for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Support from the Vehicle Technologies Office (VTO), Hybrid Electric Systems Program, David Howell (Manager), Battery R&D, Peter Faguy (Technology Manager), at the U.S. DOE, Office of Energy Efficiency and Renewable Energy, is gratefully acknowledged. The electrode active materials used in this article were synthesized at Argonne's Cell Analysis, Modeling and Prototyping (CAMP) Facility. Funding for in situ ATR-FTIR characterization provided in part by the Laboratory Directed Research and Development (LDRD) Program at NREL. The XAS research used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory (BNL) under Contract No. DE-SC0012704. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes. Publisher Copyright: © 2020 Wiley-VCH GmbH

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N2 - We present a study of the lithium nickel manganese cobalt oxide (LiNi0.6Mn0.2Co0.2O2, NMC622) cathode-electrolyte interphase (CEI) during galvanostatic charging and discharging using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) methods to investigate the voltage dependent electrolyte solution structure changes at the interface, transition metal (TM) redox chemistry, and cathode/electrolyte interfacial layer evolution. Our in situ cell design provides both reliable electrochemical device testing and strong FTIR vibrational absorption signals near the cathode surface. Specifically, advanced spectral analysis elucidates changes of near-surface Li+ ion (de)solvation by solvent molecules during galvanostatic cycling. Moreover, cathode metal-oxygen vibrational absorptions, sensitive to TM redox behaviors and subsequent local structural variations, were correlated to cathode de-lithiation (and lithiation) and electrolyte solution structure changes. In addition, we have detected the formation and evolution of a CEI surface layer on the NMC622 cathode that contributes to the cell's capacity fade.

AB - We present a study of the lithium nickel manganese cobalt oxide (LiNi0.6Mn0.2Co0.2O2, NMC622) cathode-electrolyte interphase (CEI) during galvanostatic charging and discharging using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) methods to investigate the voltage dependent electrolyte solution structure changes at the interface, transition metal (TM) redox chemistry, and cathode/electrolyte interfacial layer evolution. Our in situ cell design provides both reliable electrochemical device testing and strong FTIR vibrational absorption signals near the cathode surface. Specifically, advanced spectral analysis elucidates changes of near-surface Li+ ion (de)solvation by solvent molecules during galvanostatic cycling. Moreover, cathode metal-oxygen vibrational absorptions, sensitive to TM redox behaviors and subsequent local structural variations, were correlated to cathode de-lithiation (and lithiation) and electrolyte solution structure changes. In addition, we have detected the formation and evolution of a CEI surface layer on the NMC622 cathode that contributes to the cell's capacity fade.

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In Situ ATR-FTIR Study of the Cathode–Electrolyte Interphase: Electrolyte Solution Structure, Transition Metal Redox, and Surface Layer Evolution

Abstract

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