Lithium Intercalation Mechanism and Critical Role of Structural Water in Layered H2V3O8 High-Capacity Cathode Material for Lithium-Ion Batteries

H2V3O8 (HVO) is a promising high-capacity cathode material for lithium-ion batteries (LIBs). It allows reversible two-electron transfer during electrochemical lithium cycling processes, yielding a very attractive theoretical capacity of 378 mAh g–1. While an abundant number of research works exclusi...

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Autores: Kuhn, Alois, Perez-Flores, Juan Carlos, Prado Gonjal, Jesús de la Paz, Morán Miguélez, Emilio, Hoelzel, Markus, Díez-Gómez, Virginia, Sobrados, Isabel, Sanz, Jesús, García Alvarado, Flaviano
Tipo de recurso: artículo
Fecha de publicación:2022
País:España
Institución:Universidad Complutense de Madrid (UCM)
Repositorio:Docta Complutense
Idioma:inglés
OAI Identifier:oai:docta.ucm.es:20.500.14352/94336
Acceso en línea:https://hdl.handle.net/20.500.14352/94336
Access Level:acceso abierto
Palabra clave:Baterias de ion litio
H2V3O8
Electroquímica
Química inorgánica (Química)
Materiales
2210.28 Química del Estado Sólido
2303 Química Inorgánica
2210.05 Electroquímica
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spelling Lithium Intercalation Mechanism and Critical Role of Structural Water in Layered H2V3O8 High-Capacity Cathode Material for Lithium-Ion BatteriesKuhn, AloisPerez-Flores, Juan CarlosPrado Gonjal, Jesús de la PazMorán Miguélez, EmilioHoelzel, MarkusDíez-Gómez, VirginiaSobrados, IsabelSanz, JesúsGarcía Alvarado, FlavianoBaterias de ion litioH2V3O8ElectroquímicaQuímica inorgánica (Química)Materiales2210.28 Química del Estado Sólido2303 Química Inorgánica2210.05 ElectroquímicaH2V3O8 (HVO) is a promising high-capacity cathode material for lithium-ion batteries (LIBs). It allows reversible two-electron transfer during electrochemical lithium cycling processes, yielding a very attractive theoretical capacity of 378 mAh g–1. While an abundant number of research works exclusively proved the outstanding electrochemical lithium storage properties of H2V3O8, structural changes during the intercalation process have not been scrutinized, and the crystallographic positions occupied by the guest species have not been revealed yet. However, an in-depth understanding of structural changes of cathode materials is essential for developing new materials and improving current materials. Aimed at providing insights into the storage behavior of HVO, in this work, we employed a combination of high-resolution synchrotron X-ray and neutron diffraction to accurately describe the crystal structures of both pristine and lithiated H2V3O8. In HVO, hydrogen is located on one single-crystallographic site in a waterlike arrangement, through which bent asymmetric hydrogen bonds across adjacent V3O82– chains are established. The role played by water in network stabilization was further examined by density functional theory (DFT) calculations. Easy hydrogen-bonding switch of structural water upon lithium intercalation not only allows better accommodation of intercalated lithium ions but also enhances Li-ion mobility in the crystal host, as evidenced by magic-angle spinning (MAS) NMR spectroscopy. Facile conduction pathways for Li ions in the structure are deduced from bond valence sum difference mapping. The hydrogen bonds mitigate the volume expansion/contraction of vanadium layers during Li intercalation/deintercalation, resulting in improved long-term structural stability, explaining the excellent performance in rate capability and cycle life reported for this high-energy cathode in LIBs. This study suggests that many hydrated materials can be good candidates for electrode materials in not only implemented Li technology but also emerging rechargeable batteries.Universidad Complutense de Madrid20222022-01-0120222022-01-01journal articlehttp://purl.org/coar/resource_type/c_6501info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/20.500.14352/94336reponame:Docta Complutenseinstname:Universidad Complutense de Madrid (UCM)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:docta.ucm.es:20.500.14352/943362026-06-02T12:44:21Z
dc.title.none.fl_str_mv Lithium Intercalation Mechanism and Critical Role of Structural Water in Layered H2V3O8 High-Capacity Cathode Material for Lithium-Ion Batteries
title Lithium Intercalation Mechanism and Critical Role of Structural Water in Layered H2V3O8 High-Capacity Cathode Material for Lithium-Ion Batteries
spellingShingle Lithium Intercalation Mechanism and Critical Role of Structural Water in Layered H2V3O8 High-Capacity Cathode Material for Lithium-Ion Batteries
Kuhn, Alois
Baterias de ion litio
H2V3O8
Electroquímica
Química inorgánica (Química)
Materiales
2210.28 Química del Estado Sólido
2303 Química Inorgánica
2210.05 Electroquímica
title_short Lithium Intercalation Mechanism and Critical Role of Structural Water in Layered H2V3O8 High-Capacity Cathode Material for Lithium-Ion Batteries
title_full Lithium Intercalation Mechanism and Critical Role of Structural Water in Layered H2V3O8 High-Capacity Cathode Material for Lithium-Ion Batteries
title_fullStr Lithium Intercalation Mechanism and Critical Role of Structural Water in Layered H2V3O8 High-Capacity Cathode Material for Lithium-Ion Batteries
title_full_unstemmed Lithium Intercalation Mechanism and Critical Role of Structural Water in Layered H2V3O8 High-Capacity Cathode Material for Lithium-Ion Batteries
title_sort Lithium Intercalation Mechanism and Critical Role of Structural Water in Layered H2V3O8 High-Capacity Cathode Material for Lithium-Ion Batteries
dc.creator.none.fl_str_mv Kuhn, Alois
Perez-Flores, Juan Carlos
Prado Gonjal, Jesús de la Paz
Morán Miguélez, Emilio
Hoelzel, Markus
Díez-Gómez, Virginia
Sobrados, Isabel
Sanz, Jesús
García Alvarado, Flaviano
author Kuhn, Alois
author_facet Kuhn, Alois
Perez-Flores, Juan Carlos
Prado Gonjal, Jesús de la Paz
Morán Miguélez, Emilio
Hoelzel, Markus
Díez-Gómez, Virginia
Sobrados, Isabel
Sanz, Jesús
García Alvarado, Flaviano
author_role author
author2 Perez-Flores, Juan Carlos
Prado Gonjal, Jesús de la Paz
Morán Miguélez, Emilio
Hoelzel, Markus
Díez-Gómez, Virginia
Sobrados, Isabel
Sanz, Jesús
García Alvarado, Flaviano
author2_role author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Universidad Complutense de Madrid
dc.subject.none.fl_str_mv Baterias de ion litio
H2V3O8
Electroquímica
Química inorgánica (Química)
Materiales
2210.28 Química del Estado Sólido
2303 Química Inorgánica
2210.05 Electroquímica
topic Baterias de ion litio
H2V3O8
Electroquímica
Química inorgánica (Química)
Materiales
2210.28 Química del Estado Sólido
2303 Química Inorgánica
2210.05 Electroquímica
description H2V3O8 (HVO) is a promising high-capacity cathode material for lithium-ion batteries (LIBs). It allows reversible two-electron transfer during electrochemical lithium cycling processes, yielding a very attractive theoretical capacity of 378 mAh g–1. While an abundant number of research works exclusively proved the outstanding electrochemical lithium storage properties of H2V3O8, structural changes during the intercalation process have not been scrutinized, and the crystallographic positions occupied by the guest species have not been revealed yet. However, an in-depth understanding of structural changes of cathode materials is essential for developing new materials and improving current materials. Aimed at providing insights into the storage behavior of HVO, in this work, we employed a combination of high-resolution synchrotron X-ray and neutron diffraction to accurately describe the crystal structures of both pristine and lithiated H2V3O8. In HVO, hydrogen is located on one single-crystallographic site in a waterlike arrangement, through which bent asymmetric hydrogen bonds across adjacent V3O82– chains are established. The role played by water in network stabilization was further examined by density functional theory (DFT) calculations. Easy hydrogen-bonding switch of structural water upon lithium intercalation not only allows better accommodation of intercalated lithium ions but also enhances Li-ion mobility in the crystal host, as evidenced by magic-angle spinning (MAS) NMR spectroscopy. Facile conduction pathways for Li ions in the structure are deduced from bond valence sum difference mapping. The hydrogen bonds mitigate the volume expansion/contraction of vanadium layers during Li intercalation/deintercalation, resulting in improved long-term structural stability, explaining the excellent performance in rate capability and cycle life reported for this high-energy cathode in LIBs. This study suggests that many hydrated materials can be good candidates for electrode materials in not only implemented Li technology but also emerging rechargeable batteries.
publishDate 2022
dc.date.none.fl_str_mv 2022
2022-01-01
2022
2022-01-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/20.500.14352/94336
url https://hdl.handle.net/20.500.14352/94336
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:Docta Complutense
instname:Universidad Complutense de Madrid (UCM)
instname_str Universidad Complutense de Madrid (UCM)
reponame_str Docta Complutense
collection Docta Complutense
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300724

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