Reactions in the Rechargeable Lithium-O2 Battery with Alkyl Carbonate Electrolytes

Stefan A. Freunberger; Yuhui Chen; Zhangquan Peng; John M. Griffin; Laurence J. Hardwick; Fanny Barde; Petr Novak; Peter G. Bruce

doi:10.1021/ja2021747

Reactions in the Rechargeable Lithium-O₂ Battery with Alkyl Carbonate Electrolytes

Stefan A. Freunberger, Yuhui Chen, Zhangquan Peng, John M. Griffin, Laurence J. Hardwick, Fanny Barde, Petr Novak, Peter G. Bruce

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

Abstract

The nonaqueous rechargeable lithium–O₂ battery containing an alkyl carbonate electrolyte discharges by formation of C₃H₆(OCO₂Li)₂, Li₂CO₃, HCO₂Li, CH₃CO₂Li, CO₂, and H₂O at the cathode, due to electrolyte decomposition. Charging involves oxidation of C₃H₆(OCO₂Li)₂, Li₂CO₃, HCO₂Li, CH₃CO₂Li accompanied by CO₂ and H₂O evolution. Mechanisms are proposed for the reactions on discharge and charge. The different pathways for discharge and charge are consistent with the widely observed voltage gap in Li–O₂ cells. Oxidation of C₃H₆(OCO₂Li)₂ involves terminal carbonate groups leaving behind the OC₃H₆O moiety that reacts to form a thick gel on the Li anode. Li₂CO₃, HCO₂Li, CH₃CO₂Li, and C₃H₆(OCO₂Li)₂ accumulate in the cathode on cycling correlating with capacity fading and cell failure. The latter is compounded by continuous consumption of the electrolyte on each discharge.

Original language	English
Pages (from-to)	8040-8047
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	133
Issue number	20
DOIs	https://doi.org/10.1021/ja2021747
Publication status	Published - 25 May 2011

Keywords

LI-AIR BATTERIES
SUPEROXIDE ION
LITHIUM/OXYGEN BATTERY
PROPYLENE CARBONATE
OXYGEN BATTERIES
APROTIC MEDIA
DISPROPORTIONATION
DECOMPOSITION
ELECTRODES
DISCHARGE

Access to Document

10.1021/ja2021747

Platform Grant Renewal: Platform Grant Renewal - Materials for Lithium Batteries
Bruce, FRS, P. (PI)
EPSRC
1/09/11 → 31/08/16
Project: Standard
Crossing Boundaries in Energy Storage: Crossing Boundaries in Energy Storage
Bruce, FRS, P. (PI)
EPSRC
1/08/11 → 31/07/15
Project: Standard
An O2 Electrode for a Rechargeable Batte: An O2 Electrode for a Rechargeable Lithium Battery
Bruce, FRS, P. (PI)
EPSRC
1/07/07 → 30/06/11
Project: Standard

Cite this

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title = "Reactions in the Rechargeable Lithium-O2 Battery with Alkyl Carbonate Electrolytes",

abstract = "The nonaqueous rechargeable lithium–O2 battery containing an alkyl carbonate electrolyte discharges by formation of C3H6(OCO2Li)2, Li2CO3, HCO2Li, CH3CO2Li, CO2, and H2O at the cathode, due to electrolyte decomposition. Charging involves oxidation of C3H6(OCO2Li)2, Li2CO3, HCO2Li, CH3CO2Li accompanied by CO2 and H2O evolution. Mechanisms are proposed for the reactions on discharge and charge. The different pathways for discharge and charge are consistent with the widely observed voltage gap in Li–O2 cells. Oxidation of C3H6(OCO2Li)2 involves terminal carbonate groups leaving behind the OC3H6O moiety that reacts to form a thick gel on the Li anode. Li2CO3, HCO2Li, CH3CO2Li, and C3H6(OCO2Li)2 accumulate in the cathode on cycling correlating with capacity fading and cell failure. The latter is compounded by continuous consumption of the electrolyte on each discharge. ",

keywords = "LI-AIR BATTERIES, SUPEROXIDE ION, LITHIUM/OXYGEN BATTERY, PROPYLENE CARBONATE, OXYGEN BATTERIES, APROTIC MEDIA, DISPROPORTIONATION, DECOMPOSITION, ELECTRODES, DISCHARGE",

author = "Freunberger, {Stefan A.} and Yuhui Chen and Zhangquan Peng and Griffin, {John M.} and Hardwick, {Laurence J.} and Fanny Barde and Petr Novak and Bruce, {Peter G.}",

year = "2011",

month = may,

day = "25",

doi = "10.1021/ja2021747",

language = "English",

volume = "133",

pages = "8040--8047",

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AU - Freunberger, Stefan A.

AU - Chen, Yuhui

AU - Peng, Zhangquan

AU - Griffin, John M.

AU - Hardwick, Laurence J.

AU - Barde, Fanny

AU - Novak, Petr

AU - Bruce, Peter G.

PY - 2011/5/25

Y1 - 2011/5/25

N2 - The nonaqueous rechargeable lithium–O2 battery containing an alkyl carbonate electrolyte discharges by formation of C3H6(OCO2Li)2, Li2CO3, HCO2Li, CH3CO2Li, CO2, and H2O at the cathode, due to electrolyte decomposition. Charging involves oxidation of C3H6(OCO2Li)2, Li2CO3, HCO2Li, CH3CO2Li accompanied by CO2 and H2O evolution. Mechanisms are proposed for the reactions on discharge and charge. The different pathways for discharge and charge are consistent with the widely observed voltage gap in Li–O2 cells. Oxidation of C3H6(OCO2Li)2 involves terminal carbonate groups leaving behind the OC3H6O moiety that reacts to form a thick gel on the Li anode. Li2CO3, HCO2Li, CH3CO2Li, and C3H6(OCO2Li)2 accumulate in the cathode on cycling correlating with capacity fading and cell failure. The latter is compounded by continuous consumption of the electrolyte on each discharge.

AB - The nonaqueous rechargeable lithium–O2 battery containing an alkyl carbonate electrolyte discharges by formation of C3H6(OCO2Li)2, Li2CO3, HCO2Li, CH3CO2Li, CO2, and H2O at the cathode, due to electrolyte decomposition. Charging involves oxidation of C3H6(OCO2Li)2, Li2CO3, HCO2Li, CH3CO2Li accompanied by CO2 and H2O evolution. Mechanisms are proposed for the reactions on discharge and charge. The different pathways for discharge and charge are consistent with the widely observed voltage gap in Li–O2 cells. Oxidation of C3H6(OCO2Li)2 involves terminal carbonate groups leaving behind the OC3H6O moiety that reacts to form a thick gel on the Li anode. Li2CO3, HCO2Li, CH3CO2Li, and C3H6(OCO2Li)2 accumulate in the cathode on cycling correlating with capacity fading and cell failure. The latter is compounded by continuous consumption of the electrolyte on each discharge.

KW - LI-AIR BATTERIES

KW - SUPEROXIDE ION

KW - LITHIUM/OXYGEN BATTERY

KW - PROPYLENE CARBONATE

KW - OXYGEN BATTERIES

KW - APROTIC MEDIA

KW - DISPROPORTIONATION

KW - DECOMPOSITION

KW - ELECTRODES

KW - DISCHARGE

U2 - 10.1021/ja2021747

DO - 10.1021/ja2021747

M3 - Article

SN - 0002-7863

VL - 133

SP - 8040

EP - 8047

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 20

ER -

Reactions in the Rechargeable Lithium-O2 Battery with Alkyl Carbonate Electrolytes

Abstract

Keywords

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Projects

Platform Grant Renewal: Platform Grant Renewal - Materials for Lithium Batteries

Crossing Boundaries in Energy Storage: Crossing Boundaries in Energy Storage

An O2 Electrode for a Rechargeable Batte: An O2 Electrode for a Rechargeable Lithium Battery

Cite this

Reactions in the Rechargeable Lithium-O₂ Battery with Alkyl Carbonate Electrolytes