A Catalytic Path for Electrolyte Reduction in Lithium-Ion Cells Revealed by in Situ Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy

Feifei Shi; Philip N. Ross; Hui Zhao; Gao Liu; Gabor A. Somorjai; Kyriakos Komvopoulos

doi:10.1021/ja5128456

A Catalytic Path for Electrolyte Reduction in Lithium-Ion Cells Revealed by in Situ Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy

Feifei Shi, Philip N. Ross, Hui Zhao, Gao Liu, Gabor A. Somorjai, Kyriakos Komvopoulos

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

90 Scopus citations

Abstract

© 2015 American Chemical Society. Although controlling the interfacial chemistry of electrodes in Li-ion batteries (LIBs) is crucial for maintaining the reversibility, electrolyte decomposition has not been fully understood. In this study, electrolyte decomposition on model electrode surfaces (Au and Sn) was investigated by in situ attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. Simultaneously obtained ATR-FTIR spectra and cyclic voltammetry measurements show that lithium ethylene dicarbonate and lithium propionate form on the Au electrode at 0.6 V, whereas diethyl 2,5-dioxahexane dicarboxylate and lithium propionate form on the Sn electrode surface at 1.25 V. A noncatalytic reduction path on the Au surface and a catalytic reduction path on the Sn surface are introduced to explain the surface dependence of the overpotential and product selectivity. This represents a new concept for explaining electrolyte reactions on the anode of LIBs. The present investigation shows that catalysis plays a dominant role in the electrolyte decomposition process and has important implications in electrode surface modification and electrolyte recipe selection, which are critical factors for enhancing the efficiency, durability, and reliability of LIBs.

Original language	English (US)
Pages (from-to)	3181-3184
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	137
Issue number	9
DOIs	https://doi.org/10.1021/ja5128456
State	Published - Feb 25 2015
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Freedom CAR and Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02 O5CH1123. The last author (K.K.) also acknowledges the funding provided for this work by the UCB-KAUST Academic Excellence Alliance (AEA) Program. The IR instrumentation was purchased with funding from the Director, Office of Basic Energy Sciences, Materials Science and Engineering Division of the U.S, Department of Energy.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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10.1021/ja5128456

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title = "A Catalytic Path for Electrolyte Reduction in Lithium-Ion Cells Revealed by in Situ Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy",

abstract = "{\textcopyright} 2015 American Chemical Society. Although controlling the interfacial chemistry of electrodes in Li-ion batteries (LIBs) is crucial for maintaining the reversibility, electrolyte decomposition has not been fully understood. In this study, electrolyte decomposition on model electrode surfaces (Au and Sn) was investigated by in situ attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. Simultaneously obtained ATR-FTIR spectra and cyclic voltammetry measurements show that lithium ethylene dicarbonate and lithium propionate form on the Au electrode at 0.6 V, whereas diethyl 2,5-dioxahexane dicarboxylate and lithium propionate form on the Sn electrode surface at 1.25 V. A noncatalytic reduction path on the Au surface and a catalytic reduction path on the Sn surface are introduced to explain the surface dependence of the overpotential and product selectivity. This represents a new concept for explaining electrolyte reactions on the anode of LIBs. The present investigation shows that catalysis plays a dominant role in the electrolyte decomposition process and has important implications in electrode surface modification and electrolyte recipe selection, which are critical factors for enhancing the efficiency, durability, and reliability of LIBs.",

author = "Feifei Shi and Ross, {Philip N.} and Hui Zhao and Gao Liu and Somorjai, {Gabor A.} and Kyriakos Komvopoulos",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Freedom CAR and Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02 O5CH1123. The last author (K.K.) also acknowledges the funding provided for this work by the UCB-KAUST Academic Excellence Alliance (AEA) Program. The IR instrumentation was purchased with funding from the Director, Office of Basic Energy Sciences, Materials Science and Engineering Division of the U.S, Department of Energy. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

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AU - Liu, Gao

AU - Somorjai, Gabor A.

AU - Komvopoulos, Kyriakos

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Freedom CAR and Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02 O5CH1123. The last author (K.K.) also acknowledges the funding provided for this work by the UCB-KAUST Academic Excellence Alliance (AEA) Program. The IR instrumentation was purchased with funding from the Director, Office of Basic Energy Sciences, Materials Science and Engineering Division of the U.S, Department of Energy. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2015/2/25

Y1 - 2015/2/25

N2 - © 2015 American Chemical Society. Although controlling the interfacial chemistry of electrodes in Li-ion batteries (LIBs) is crucial for maintaining the reversibility, electrolyte decomposition has not been fully understood. In this study, electrolyte decomposition on model electrode surfaces (Au and Sn) was investigated by in situ attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. Simultaneously obtained ATR-FTIR spectra and cyclic voltammetry measurements show that lithium ethylene dicarbonate and lithium propionate form on the Au electrode at 0.6 V, whereas diethyl 2,5-dioxahexane dicarboxylate and lithium propionate form on the Sn electrode surface at 1.25 V. A noncatalytic reduction path on the Au surface and a catalytic reduction path on the Sn surface are introduced to explain the surface dependence of the overpotential and product selectivity. This represents a new concept for explaining electrolyte reactions on the anode of LIBs. The present investigation shows that catalysis plays a dominant role in the electrolyte decomposition process and has important implications in electrode surface modification and electrolyte recipe selection, which are critical factors for enhancing the efficiency, durability, and reliability of LIBs.

AB - © 2015 American Chemical Society. Although controlling the interfacial chemistry of electrodes in Li-ion batteries (LIBs) is crucial for maintaining the reversibility, electrolyte decomposition has not been fully understood. In this study, electrolyte decomposition on model electrode surfaces (Au and Sn) was investigated by in situ attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. Simultaneously obtained ATR-FTIR spectra and cyclic voltammetry measurements show that lithium ethylene dicarbonate and lithium propionate form on the Au electrode at 0.6 V, whereas diethyl 2,5-dioxahexane dicarboxylate and lithium propionate form on the Sn electrode surface at 1.25 V. A noncatalytic reduction path on the Au surface and a catalytic reduction path on the Sn surface are introduced to explain the surface dependence of the overpotential and product selectivity. This represents a new concept for explaining electrolyte reactions on the anode of LIBs. The present investigation shows that catalysis plays a dominant role in the electrolyte decomposition process and has important implications in electrode surface modification and electrolyte recipe selection, which are critical factors for enhancing the efficiency, durability, and reliability of LIBs.

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A Catalytic Path for Electrolyte Reduction in Lithium-Ion Cells Revealed by in Situ Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy

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