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Are Redox‐Active Organic Small Molecules Applicable for High‐Voltage (>4 V) Lithium‐Ion Battery Cathodes?

While organic batteries have attracted great attention due to their high theoretical capacities, high‐voltage organic active materials (> 4 V vs Li/Li(+)) remain unexplored. Here, density functional theory calculations are combined with cyclic voltammetry measurements to investigate the electroch...

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Autores principales: Katsuyama, Yuto, Kobayashi, Hiroaki, Iwase, Kazuyuki, Gambe, Yoshiyuki, Honma, Itaru
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9036039/
https://www.ncbi.nlm.nih.gov/pubmed/35266645
http://dx.doi.org/10.1002/advs.202200187
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author Katsuyama, Yuto
Kobayashi, Hiroaki
Iwase, Kazuyuki
Gambe, Yoshiyuki
Honma, Itaru
author_facet Katsuyama, Yuto
Kobayashi, Hiroaki
Iwase, Kazuyuki
Gambe, Yoshiyuki
Honma, Itaru
author_sort Katsuyama, Yuto
collection PubMed
description While organic batteries have attracted great attention due to their high theoretical capacities, high‐voltage organic active materials (> 4 V vs Li/Li(+)) remain unexplored. Here, density functional theory calculations are combined with cyclic voltammetry measurements to investigate the electrochemistry of croconic acid (CA) for use as a lithium‐ion battery cathode material in both dimethyl sulfoxide and γ‐butyrolactone (GBL) electrolytes. DFT calculations demonstrate that CA dilitium salt (CA–Li(2)) has two enolate groups that undergo redox reactions above 4.0 V and a material‐level theoretical energy density of 1949 Wh kg(–1) for storing four lithium ions in GBL—exceeding the value of both conventional inorganic and known organic cathode materials. Cyclic‐voltammetry measurements reveal a highly reversible redox reaction by the enolate group at ≈4 V in both electrolytes. Battery‐performance tests of CA as lithium‐ion battery cathode in GBL show two discharge voltage plateaus at 3.9 and 3.1 V, and a discharge capacity of 102.2 mAh g(–1) with no capacity loss after five cycles. With the higher discharge voltages compared to the known, state‐of‐the‐art organic small molecules, CA promises to be a prime cathode‐material candidate for future high‐energy‐density lithium‐ion organic batteries.
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spelling pubmed-90360392022-04-27 Are Redox‐Active Organic Small Molecules Applicable for High‐Voltage (>4 V) Lithium‐Ion Battery Cathodes? Katsuyama, Yuto Kobayashi, Hiroaki Iwase, Kazuyuki Gambe, Yoshiyuki Honma, Itaru Adv Sci (Weinh) Research Articles While organic batteries have attracted great attention due to their high theoretical capacities, high‐voltage organic active materials (> 4 V vs Li/Li(+)) remain unexplored. Here, density functional theory calculations are combined with cyclic voltammetry measurements to investigate the electrochemistry of croconic acid (CA) for use as a lithium‐ion battery cathode material in both dimethyl sulfoxide and γ‐butyrolactone (GBL) electrolytes. DFT calculations demonstrate that CA dilitium salt (CA–Li(2)) has two enolate groups that undergo redox reactions above 4.0 V and a material‐level theoretical energy density of 1949 Wh kg(–1) for storing four lithium ions in GBL—exceeding the value of both conventional inorganic and known organic cathode materials. Cyclic‐voltammetry measurements reveal a highly reversible redox reaction by the enolate group at ≈4 V in both electrolytes. Battery‐performance tests of CA as lithium‐ion battery cathode in GBL show two discharge voltage plateaus at 3.9 and 3.1 V, and a discharge capacity of 102.2 mAh g(–1) with no capacity loss after five cycles. With the higher discharge voltages compared to the known, state‐of‐the‐art organic small molecules, CA promises to be a prime cathode‐material candidate for future high‐energy‐density lithium‐ion organic batteries. John Wiley and Sons Inc. 2022-03-10 /pmc/articles/PMC9036039/ /pubmed/35266645 http://dx.doi.org/10.1002/advs.202200187 Text en © 2022 The Authors. Advanced Science published by Wiley‐VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Research Articles
Katsuyama, Yuto
Kobayashi, Hiroaki
Iwase, Kazuyuki
Gambe, Yoshiyuki
Honma, Itaru
Are Redox‐Active Organic Small Molecules Applicable for High‐Voltage (>4 V) Lithium‐Ion Battery Cathodes?
title Are Redox‐Active Organic Small Molecules Applicable for High‐Voltage (>4 V) Lithium‐Ion Battery Cathodes?
title_full Are Redox‐Active Organic Small Molecules Applicable for High‐Voltage (>4 V) Lithium‐Ion Battery Cathodes?
title_fullStr Are Redox‐Active Organic Small Molecules Applicable for High‐Voltage (>4 V) Lithium‐Ion Battery Cathodes?
title_full_unstemmed Are Redox‐Active Organic Small Molecules Applicable for High‐Voltage (>4 V) Lithium‐Ion Battery Cathodes?
title_short Are Redox‐Active Organic Small Molecules Applicable for High‐Voltage (>4 V) Lithium‐Ion Battery Cathodes?
title_sort are redox‐active organic small molecules applicable for high‐voltage (>4 v) lithium‐ion battery cathodes?
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9036039/
https://www.ncbi.nlm.nih.gov/pubmed/35266645
http://dx.doi.org/10.1002/advs.202200187
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