On the Incompatibility of lithium–O₂ Battery Technology with CO₂

When solubilized in a hexacarboxamide cryptand anion receptor, the peroxide dianion reacts rapidly with CO₂ in polar aprotic organic media to produce hydroperoxycarbonate (HOOCO₂- ) and peroxydicarbonate (-O₂ COOCO₂-). Peroxydicarbonate is subject to thermal fragmentation into two equivalents of the...

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Main Authors: Chow, Gary K., Lopez, Nazario, Britt, David R., Nocera, Daniel G., Zhang, Shiyu, Nava, Matthew Jordan, Wu, Gang, Cummins, Christopher C
Other Authors: Massachusetts Institute of Technology. Department of Chemistry
Format: Article
Published: Royal Society of Chemistry (RSC) 2018
Online Access:http://hdl.handle.net/1721.1/113277
https://orcid.org/0000-0002-9239-7505
https://orcid.org/0000-0003-2568-3269
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author Chow, Gary K.
Lopez, Nazario
Britt, David R.
Nocera, Daniel G.
Zhang, Shiyu
Nava, Matthew Jordan
Wu, Gang
Cummins, Christopher C
author2 Massachusetts Institute of Technology. Department of Chemistry
author_facet Massachusetts Institute of Technology. Department of Chemistry
Chow, Gary K.
Lopez, Nazario
Britt, David R.
Nocera, Daniel G.
Zhang, Shiyu
Nava, Matthew Jordan
Wu, Gang
Cummins, Christopher C
author_sort Chow, Gary K.
collection MIT
description When solubilized in a hexacarboxamide cryptand anion receptor, the peroxide dianion reacts rapidly with CO₂ in polar aprotic organic media to produce hydroperoxycarbonate (HOOCO₂- ) and peroxydicarbonate (-O₂ COOCO₂-). Peroxydicarbonate is subject to thermal fragmentation into two equivalents of the highly reactive carbonate radical anion, which promotes hydrogen atom abstraction reactions responsible for the oxidative degradation of organic solvents. The activation and conversion of the peroxide dianion by CO₂ is general. Exposure of solid lithium peroxide (Li₂ O₂) to CO₂ in polar aprotic organic media results in aggressive oxidation. These findings indicate that CO₂ must not be introduced in conditions relevant to typical lithium-O₂ cell configurations, as production of HOOCO₂ - and -O₂COOCO₂-during lithium-O₂ cell cycling will lead to cell degradation via oxidation of organic electrolytes and other vulnerable cell components.
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spelling mit-1721.1/1132772022-10-01T08:05:41Z On the Incompatibility of lithium–O₂ Battery Technology with CO₂ Chow, Gary K. Lopez, Nazario Britt, David R. Nocera, Daniel G. Zhang, Shiyu Nava, Matthew Jordan Wu, Gang Cummins, Christopher C Massachusetts Institute of Technology. Department of Chemistry Zhang, Shiyu Nava, Matthew Jordan Wu, Gang Cummins, Christopher C When solubilized in a hexacarboxamide cryptand anion receptor, the peroxide dianion reacts rapidly with CO₂ in polar aprotic organic media to produce hydroperoxycarbonate (HOOCO₂- ) and peroxydicarbonate (-O₂ COOCO₂-). Peroxydicarbonate is subject to thermal fragmentation into two equivalents of the highly reactive carbonate radical anion, which promotes hydrogen atom abstraction reactions responsible for the oxidative degradation of organic solvents. The activation and conversion of the peroxide dianion by CO₂ is general. Exposure of solid lithium peroxide (Li₂ O₂) to CO₂ in polar aprotic organic media results in aggressive oxidation. These findings indicate that CO₂ must not be introduced in conditions relevant to typical lithium-O₂ cell configurations, as production of HOOCO₂ - and -O₂COOCO₂-during lithium-O₂ cell cycling will lead to cell degradation via oxidation of organic electrolytes and other vulnerable cell components. 2018-01-23T16:36:51Z 2018-01-23T16:36:51Z 2017-06 2017-03 2018-01-18T18:29:25Z Article http://purl.org/eprint/type/JournalArticle 2041-6520 2041-6539 http://hdl.handle.net/1721.1/113277 Zhang, Shiyu, et al. “On the Incompatibility of lithium–O₂ Battery Technology with CO₂.” Chemical Science 8, 9 (2017): 6117–6122 © 2017 The Royal Society of Chemistry https://orcid.org/0000-0002-9239-7505 https://orcid.org/0000-0003-2568-3269 http://dx.doi.org/10.1039/C7SC01230F Chemical Science Creative Commons Attribution 3.0 Unported license http://creativecommons.org/licenses/by/3.0/ application/pdf Royal Society of Chemistry (RSC) Royal Society of Chemistry
spellingShingle Chow, Gary K.
Lopez, Nazario
Britt, David R.
Nocera, Daniel G.
Zhang, Shiyu
Nava, Matthew Jordan
Wu, Gang
Cummins, Christopher C
On the Incompatibility of lithium–O₂ Battery Technology with CO₂
title On the Incompatibility of lithium–O₂ Battery Technology with CO₂
title_full On the Incompatibility of lithium–O₂ Battery Technology with CO₂
title_fullStr On the Incompatibility of lithium–O₂ Battery Technology with CO₂
title_full_unstemmed On the Incompatibility of lithium–O₂ Battery Technology with CO₂
title_short On the Incompatibility of lithium–O₂ Battery Technology with CO₂
title_sort on the incompatibility of lithium o₂ battery technology with co₂
url http://hdl.handle.net/1721.1/113277
https://orcid.org/0000-0002-9239-7505
https://orcid.org/0000-0003-2568-3269
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