Oxygen Reactions in a Non-Aqueous Li+ Electrolyte

Zhangquan Peng, Stefan A. Freunberger, Laurence J. Hardwick, Yuhui Chen, Vincent Giordani, Fanny Barde, Petr Novak, Duncan Graham, Jean-Marie Tarascon, Peter G. Bruce

Research output: Contribution to journalArticle

366 Citations (Scopus)

Abstract

Oxygen (O2) reduction is one of the most studied reactions in chemistry.1 Widely investigated in aqueous media, O2 reduction in non-aqueous solvents, such as CH3CN, has been studied for several decades.2–7 Today, O2 reduction in non-aqueous Li+ electrolytes is receiving considerable attention because it is the reaction on which operation of the Li–air (O2) battery depends.8–29 The Li–O2 battery is generating a great deal of interest because theoretically its high energy density could transform energy storage.8, 9 As a result, it is crucial to understand the O2 reaction mechanisms in non-aqueous Li+ electrolytes. Important progress has been made using electrochemical measurements including recently by Laoire et al.29 No less than five different mechanisms for O2 reduction in Li+ electrolytes have been proposed over the last 40 years based on electrochemical measurements alone.25–29 The value of using spectroelectrochemical methods is that they can identify directly the species involved in the reaction. Here we present in situ spectroscopic data that provide direct evidence that LiO2 is indeed an intermediate on O2 reduction, which then disproportionates to the final product Li2O2. Spectroscopic studies of Li2O2 oxidation demonstrate that LiO2 is not an intermediate on oxidation, that is, oxidation does not follow the reverse pathway to reduction.
LanguageEnglish
Pages6351-6355
Number of pages5
JournalAgewandte Chemie-International Edition
Volume50
Issue number28
DOIs
Publication statusPublished - 4 Jul 2011

Fingerprint

Electrolytes
Oxygen
Oxidation
Air

Keywords

  • electrochemistry
  • lithium batteries
  • oxygen
  • reduction
  • surface enhanced Raman spectroscopy
  • ionic liquids
  • air batteries
  • raman-scattering
  • superoxide ion
  • electroreduction
  • dioxygen
  • TIC - Bionanotechnology

Cite this

Peng, Z., Freunberger, S. A., Hardwick, L. J., Chen, Y., Giordani, V., Barde, F., ... Bruce, P. G. (2011). Oxygen Reactions in a Non-Aqueous Li+ Electrolyte. Agewandte Chemie-International Edition, 50(28), 6351-6355. https://doi.org/10.1002/anie.201100879
Peng, Zhangquan ; Freunberger, Stefan A. ; Hardwick, Laurence J. ; Chen, Yuhui ; Giordani, Vincent ; Barde, Fanny ; Novak, Petr ; Graham, Duncan ; Tarascon, Jean-Marie ; Bruce, Peter G. / Oxygen Reactions in a Non-Aqueous Li+ Electrolyte. In: Agewandte Chemie-International Edition. 2011 ; Vol. 50, No. 28. pp. 6351-6355.
@article{a05971b46f144c99bc857bee7d0a4eb4,
title = "Oxygen Reactions in a Non-Aqueous Li+ Electrolyte",
abstract = "Oxygen (O2) reduction is one of the most studied reactions in chemistry.1 Widely investigated in aqueous media, O2 reduction in non-aqueous solvents, such as CH3CN, has been studied for several decades.2–7 Today, O2 reduction in non-aqueous Li+ electrolytes is receiving considerable attention because it is the reaction on which operation of the Li–air (O2) battery depends.8–29 The Li–O2 battery is generating a great deal of interest because theoretically its high energy density could transform energy storage.8, 9 As a result, it is crucial to understand the O2 reaction mechanisms in non-aqueous Li+ electrolytes. Important progress has been made using electrochemical measurements including recently by Laoire et al.29 No less than five different mechanisms for O2 reduction in Li+ electrolytes have been proposed over the last 40 years based on electrochemical measurements alone.25–29 The value of using spectroelectrochemical methods is that they can identify directly the species involved in the reaction. Here we present in situ spectroscopic data that provide direct evidence that LiO2 is indeed an intermediate on O2 reduction, which then disproportionates to the final product Li2O2. Spectroscopic studies of Li2O2 oxidation demonstrate that LiO2 is not an intermediate on oxidation, that is, oxidation does not follow the reverse pathway to reduction.",
keywords = "electrochemistry, lithium batteries, oxygen, reduction, surface enhanced Raman spectroscopy, ionic liquids, air batteries, raman-scattering, superoxide ion, electroreduction, dioxygen, TIC - Bionanotechnology",
author = "Zhangquan Peng and Freunberger, {Stefan A.} and Hardwick, {Laurence J.} and Yuhui Chen and Vincent Giordani and Fanny Barde and Petr Novak and Duncan Graham and Jean-Marie Tarascon and Bruce, {Peter G.}",
year = "2011",
month = "7",
day = "4",
doi = "10.1002/anie.201100879",
language = "English",
volume = "50",
pages = "6351--6355",
journal = "Angewandte Chemie International Edition",
issn = "1433-7851",
number = "28",

}

Peng, Z, Freunberger, SA, Hardwick, LJ, Chen, Y, Giordani, V, Barde, F, Novak, P, Graham, D, Tarascon, J-M & Bruce, PG 2011, 'Oxygen Reactions in a Non-Aqueous Li+ Electrolyte' Agewandte Chemie-International Edition, vol. 50, no. 28, pp. 6351-6355. https://doi.org/10.1002/anie.201100879

Oxygen Reactions in a Non-Aqueous Li+ Electrolyte. / Peng, Zhangquan; Freunberger, Stefan A.; Hardwick, Laurence J.; Chen, Yuhui; Giordani, Vincent; Barde, Fanny; Novak, Petr; Graham, Duncan; Tarascon, Jean-Marie; Bruce, Peter G.

In: Agewandte Chemie-International Edition, Vol. 50, No. 28, 04.07.2011, p. 6351-6355.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Oxygen Reactions in a Non-Aqueous Li+ Electrolyte

AU - Peng, Zhangquan

AU - Freunberger, Stefan A.

AU - Hardwick, Laurence J.

AU - Chen, Yuhui

AU - Giordani, Vincent

AU - Barde, Fanny

AU - Novak, Petr

AU - Graham, Duncan

AU - Tarascon, Jean-Marie

AU - Bruce, Peter G.

PY - 2011/7/4

Y1 - 2011/7/4

N2 - Oxygen (O2) reduction is one of the most studied reactions in chemistry.1 Widely investigated in aqueous media, O2 reduction in non-aqueous solvents, such as CH3CN, has been studied for several decades.2–7 Today, O2 reduction in non-aqueous Li+ electrolytes is receiving considerable attention because it is the reaction on which operation of the Li–air (O2) battery depends.8–29 The Li–O2 battery is generating a great deal of interest because theoretically its high energy density could transform energy storage.8, 9 As a result, it is crucial to understand the O2 reaction mechanisms in non-aqueous Li+ electrolytes. Important progress has been made using electrochemical measurements including recently by Laoire et al.29 No less than five different mechanisms for O2 reduction in Li+ electrolytes have been proposed over the last 40 years based on electrochemical measurements alone.25–29 The value of using spectroelectrochemical methods is that they can identify directly the species involved in the reaction. Here we present in situ spectroscopic data that provide direct evidence that LiO2 is indeed an intermediate on O2 reduction, which then disproportionates to the final product Li2O2. Spectroscopic studies of Li2O2 oxidation demonstrate that LiO2 is not an intermediate on oxidation, that is, oxidation does not follow the reverse pathway to reduction.

AB - Oxygen (O2) reduction is one of the most studied reactions in chemistry.1 Widely investigated in aqueous media, O2 reduction in non-aqueous solvents, such as CH3CN, has been studied for several decades.2–7 Today, O2 reduction in non-aqueous Li+ electrolytes is receiving considerable attention because it is the reaction on which operation of the Li–air (O2) battery depends.8–29 The Li–O2 battery is generating a great deal of interest because theoretically its high energy density could transform energy storage.8, 9 As a result, it is crucial to understand the O2 reaction mechanisms in non-aqueous Li+ electrolytes. Important progress has been made using electrochemical measurements including recently by Laoire et al.29 No less than five different mechanisms for O2 reduction in Li+ electrolytes have been proposed over the last 40 years based on electrochemical measurements alone.25–29 The value of using spectroelectrochemical methods is that they can identify directly the species involved in the reaction. Here we present in situ spectroscopic data that provide direct evidence that LiO2 is indeed an intermediate on O2 reduction, which then disproportionates to the final product Li2O2. Spectroscopic studies of Li2O2 oxidation demonstrate that LiO2 is not an intermediate on oxidation, that is, oxidation does not follow the reverse pathway to reduction.

KW - electrochemistry

KW - lithium batteries

KW - oxygen

KW - reduction

KW - surface enhanced Raman spectroscopy

KW - ionic liquids

KW - air batteries

KW - raman-scattering

KW - superoxide ion

KW - electroreduction

KW - dioxygen

KW - TIC - Bionanotechnology

UR - http://www.scopus.com/inward/record.url?scp=79959871542&partnerID=8YFLogxK

U2 - 10.1002/anie.201100879

DO - 10.1002/anie.201100879

M3 - Article

VL - 50

SP - 6351

EP - 6355

JO - Angewandte Chemie International Edition

T2 - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

SN - 1433-7851

IS - 28

ER -

Peng Z, Freunberger SA, Hardwick LJ, Chen Y, Giordani V, Barde F et al. Oxygen Reactions in a Non-Aqueous Li+ Electrolyte. Agewandte Chemie-International Edition. 2011 Jul 4;50(28):6351-6355. https://doi.org/10.1002/anie.201100879