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Understanding LiOH chemistry in a ruthenium-catalyzed Li-O2 battery

Understanding LiOH chemistry in a ruthenium-catalyzed Li-O2 battery
Understanding LiOH chemistry in a ruthenium-catalyzed Li-O2 battery
Non‐aqueous Li–O2 batteries are promising for next‐generation energy storage. New battery chemistries based on LiOH, rather than Li2O2, have been recently reported in systems with added water, one using a soluble additive LiI and the other using solid Ru catalysts. Here, the focus is on the mechanism of Ru‐catalyzed LiOH chemistry. Using nuclear magnetic resonance, operando electrochemical pressure measurements, and mass spectrometry, it is shown that on discharging LiOH forms via a 4 e− oxygen reduction reaction, the H in LiOH coming solely from added H2O and the O from both O2 and H2O. On charging, quantitative LiOH oxidation occurs at 3.1 V, with O being trapped in a form of dimethyl sulfone in the electrolyte. Compared to Li2O2, LiOH formation over Ru incurs few side reactions, a critical advantage for developing a long‐lived battery. An optimized metal‐catalyst–electrolyte couple needs to be sought that aids LiOH oxidation and is stable towards attack by hydroxyl radicals.
1433-7851
16057-16062
Liu, Tao
01fc84ea-a1b9-4207-a11b-dc9b6fe27824
Liu, Zigeng
5407a2de-133e-4bfb-acfa-249ab105a9d9
Kim, Gunwoo
cf5f9ada-ef75-4b69-97ad-510d6cdfb425
Frith, James T.
349b19de-36a7-4136-9f2d-af8160311d38
Garcia-Araez, Nuria
9358a0f9-309c-495e-b6bf-da985ad81c37
Grey, Clare P.
36cd015b-a910-4b25-869b-fabc62e50602
Liu, Tao
01fc84ea-a1b9-4207-a11b-dc9b6fe27824
Liu, Zigeng
5407a2de-133e-4bfb-acfa-249ab105a9d9
Kim, Gunwoo
cf5f9ada-ef75-4b69-97ad-510d6cdfb425
Frith, James T.
349b19de-36a7-4136-9f2d-af8160311d38
Garcia-Araez, Nuria
9358a0f9-309c-495e-b6bf-da985ad81c37
Grey, Clare P.
36cd015b-a910-4b25-869b-fabc62e50602

Liu, Tao, Liu, Zigeng, Kim, Gunwoo, Frith, James T., Garcia-Araez, Nuria and Grey, Clare P. (2017) Understanding LiOH chemistry in a ruthenium-catalyzed Li-O2 battery. Angewandte Chemie International Edition, 56 (50), 16057-16062. (doi:10.1002/anie.201709886).

Record type: Article

Abstract

Non‐aqueous Li–O2 batteries are promising for next‐generation energy storage. New battery chemistries based on LiOH, rather than Li2O2, have been recently reported in systems with added water, one using a soluble additive LiI and the other using solid Ru catalysts. Here, the focus is on the mechanism of Ru‐catalyzed LiOH chemistry. Using nuclear magnetic resonance, operando electrochemical pressure measurements, and mass spectrometry, it is shown that on discharging LiOH forms via a 4 e− oxygen reduction reaction, the H in LiOH coming solely from added H2O and the O from both O2 and H2O. On charging, quantitative LiOH oxidation occurs at 3.1 V, with O being trapped in a form of dimethyl sulfone in the electrolyte. Compared to Li2O2, LiOH formation over Ru incurs few side reactions, a critical advantage for developing a long‐lived battery. An optimized metal‐catalyst–electrolyte couple needs to be sought that aids LiOH oxidation and is stable towards attack by hydroxyl radicals.

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Accepted/In Press date: 19 October 2017
e-pub ahead of print date: 23 October 2017
Published date: 11 December 2017

Identifiers

Local EPrints ID: 415279
URI: http://eprints.soton.ac.uk/id/eprint/415279
ISSN: 1433-7851
PURE UUID: 855f64ee-7910-4f42-bf4e-2ff8543f9e82
ORCID for Nuria Garcia-Araez: ORCID iD orcid.org/0000-0001-9095-2379

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Date deposited: 06 Nov 2017 17:30
Last modified: 07 Oct 2020 04:48

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Contributors

Author: Tao Liu
Author: Zigeng Liu
Author: Gunwoo Kim
Author: James T. Frith
Author: Clare P. Grey

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