Degradation of LiNi0.5Mn1.5O4 cathodes in the P111i4FSI ionic liquid electrolyte and carbonate electrolytes

LiNi0.5Mn1.5O4 (LNMO) is a promising material for the cathode of lithium-ion batteries (LiBs); however, its high operating voltage causes stability issues when used with carbonate battery electrolytes. Ionic liquids are a viable alternative to conventional carbonate solvents due to their thermal sta...

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Autores: Hamonnet, Johan, Nylund, Inger-Emma, Kontis, Paraskevas, Hua, Weicheng, Alonso-Sánchez, Pedro, Rubio Zuazo, Juan, Blanco, Maria Valeria, Svensson, Ann Mari
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/404231
Acceso en línea:http://hdl.handle.net/10261/404231
Access Level:acceso abierto
Palabra clave:High-voltage cathode
Ionic liquid electrolyte
Lithium-ion battery
Spectroscopy
Transition metal dissolution
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network_acronym_str ES
network_name_str España
repository_id_str
dc.title.none.fl_str_mv Degradation of LiNi0.5Mn1.5O4 cathodes in the P111i4FSI ionic liquid electrolyte and carbonate electrolytes
title Degradation of LiNi0.5Mn1.5O4 cathodes in the P111i4FSI ionic liquid electrolyte and carbonate electrolytes
spellingShingle Degradation of LiNi0.5Mn1.5O4 cathodes in the P111i4FSI ionic liquid electrolyte and carbonate electrolytes
Hamonnet, Johan
High-voltage cathode
Ionic liquid electrolyte
Lithium-ion battery
Spectroscopy
Transition metal dissolution
title_short Degradation of LiNi0.5Mn1.5O4 cathodes in the P111i4FSI ionic liquid electrolyte and carbonate electrolytes
title_full Degradation of LiNi0.5Mn1.5O4 cathodes in the P111i4FSI ionic liquid electrolyte and carbonate electrolytes
title_fullStr Degradation of LiNi0.5Mn1.5O4 cathodes in the P111i4FSI ionic liquid electrolyte and carbonate electrolytes
title_full_unstemmed Degradation of LiNi0.5Mn1.5O4 cathodes in the P111i4FSI ionic liquid electrolyte and carbonate electrolytes
title_sort Degradation of LiNi0.5Mn1.5O4 cathodes in the P111i4FSI ionic liquid electrolyte and carbonate electrolytes
dc.creator.none.fl_str_mv Hamonnet, Johan
Nylund, Inger-Emma
Kontis, Paraskevas
Hua, Weicheng
Alonso-Sánchez, Pedro
Rubio Zuazo, Juan
Blanco, Maria Valeria
Svensson, Ann Mari
author Hamonnet, Johan
author_facet Hamonnet, Johan
Nylund, Inger-Emma
Kontis, Paraskevas
Hua, Weicheng
Alonso-Sánchez, Pedro
Rubio Zuazo, Juan
Blanco, Maria Valeria
Svensson, Ann Mari
author_role author
author2 Nylund, Inger-Emma
Kontis, Paraskevas
Hua, Weicheng
Alonso-Sánchez, Pedro
Rubio Zuazo, Juan
Blanco, Maria Valeria
Svensson, Ann Mari
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Research Council of Norway
European Commission
European Synchrotron Radiation Facility
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv High-voltage cathode
Ionic liquid electrolyte
Lithium-ion battery
Spectroscopy
Transition metal dissolution
topic High-voltage cathode
Ionic liquid electrolyte
Lithium-ion battery
Spectroscopy
Transition metal dissolution
description LiNi0.5Mn1.5O4 (LNMO) is a promising material for the cathode of lithium-ion batteries (LiBs); however, its high operating voltage causes stability issues when used with carbonate battery electrolytes. Ionic liquids are a viable alternative to conventional carbonate solvents due to their thermal stability and electrochemical window. This work reports the performance of LNMO/Li half cells with an ionic liquid electrolyte (ILE) composed of 0.79 molal LiFSI in trimethyl isobutyl phosphonium bis-fluorosulfonyl imide (P111i4FSI). The long-term stability of the cells cycled at 25 °C in ILE is superior compared to all the other cycling conditions, as shown by the Coulombic efficiency (>99.5%) and capacity retention after 210 cycles (>87.9%). Spectroscopy measurements showed that the LNMO in the LP40 cycled cells had severe structural damage, with visible holes in the surface region of the particle, extending 15-20 nm away from the surface. On the other hand, the structure of the LNMO used in the cells with ILE was similar to that of the pristine spinel after 210 cycles, the only difference being a rock-salt layer on the surface. The surface chemistry of the LNMO particles was analyzed by electron energy-loss spectroscopy and revealed that the surface region of the LNMO cycled in LP40 adopted a (MnxNiy)3O4-type structure in the previously described holes, while the surface chemistry was nearly unaffected by cycling in ILE. XPS highlighted the influence of the electrolyte on the nature of the cathode electrolyte interface (CEI), which showed the presence of a predominantly organic CEI after cycling in LP40. The CEI formed after cycling in ILE was thinner and dominated by species like Li2CO3 and salt decomposition products. Overall, the cycling stability of LNMO with LiFSI in P111i4FSI was improved, and the structural integrity was maintained with this electrolyte, as opposed to the conventional LP40.
publishDate 2025
dc.date.none.fl_str_mv 2025
2025
2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/404231
url http://hdl.handle.net/10261/404231
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Hamonnet, Johan; Nylund, Inger-Emma; Kontis, Paraskevas; Hua, Weicheng; Alonso-Sánchez, Pedro; Rubio Zuazo, Juan; Blanco, Maria Valeria; Svensson, Ann Mari; 2025; Supporting Information: Degradation of LiNi0.5Mn1.5O4 cathodes in the P111i4FSI ionic liquid electrolyte and carbonate electrolytes [Dataset]; American Chemical Society; https://doi.org/10.1021/acsami.5c11439
https://doi.org/10.1021/acsami.5c11439
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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spelling Degradation of LiNi0.5Mn1.5O4 cathodes in the P111i4FSI ionic liquid electrolyte and carbonate electrolytesHamonnet, JohanNylund, Inger-EmmaKontis, ParaskevasHua, WeichengAlonso-Sánchez, PedroRubio Zuazo, JuanBlanco, Maria ValeriaSvensson, Ann MariHigh-voltage cathodeIonic liquid electrolyteLithium-ion batterySpectroscopyTransition metal dissolutionLiNi0.5Mn1.5O4 (LNMO) is a promising material for the cathode of lithium-ion batteries (LiBs); however, its high operating voltage causes stability issues when used with carbonate battery electrolytes. Ionic liquids are a viable alternative to conventional carbonate solvents due to their thermal stability and electrochemical window. This work reports the performance of LNMO/Li half cells with an ionic liquid electrolyte (ILE) composed of 0.79 molal LiFSI in trimethyl isobutyl phosphonium bis-fluorosulfonyl imide (P111i4FSI). The long-term stability of the cells cycled at 25 °C in ILE is superior compared to all the other cycling conditions, as shown by the Coulombic efficiency (>99.5%) and capacity retention after 210 cycles (>87.9%). Spectroscopy measurements showed that the LNMO in the LP40 cycled cells had severe structural damage, with visible holes in the surface region of the particle, extending 15-20 nm away from the surface. On the other hand, the structure of the LNMO used in the cells with ILE was similar to that of the pristine spinel after 210 cycles, the only difference being a rock-salt layer on the surface. The surface chemistry of the LNMO particles was analyzed by electron energy-loss spectroscopy and revealed that the surface region of the LNMO cycled in LP40 adopted a (MnxNiy)3O4-type structure in the previously described holes, while the surface chemistry was nearly unaffected by cycling in ILE. XPS highlighted the influence of the electrolyte on the nature of the cathode electrolyte interface (CEI), which showed the presence of a predominantly organic CEI after cycling in LP40. The CEI formed after cycling in ILE was thinner and dominated by species like Li2CO3 and salt decomposition products. Overall, the cycling stability of LNMO with LiFSI in P111i4FSI was improved, and the structural integrity was maintained with this electrolyte, as opposed to the conventional LP40.The Research Council of Norway (RCN) is acknowledged for its support to the Norwegian Micro- and Nano-Fabrication Facility, NorFab (No. 295864) and the Norwegian Laboratory for Mineral and Materials Characterization, MiMaC (No. 269842). Constantinos Hatzoglou is also acknowledged for his support with the APT facilities. Helene Lillevestre Langli is acknowledged for her help in collecting the cyclic voltammetry results. We would like to acknowledge the national projects MOZEES (No. 257653) and SUMBAT (No. 328780) for funding the postdoctoral researchers (J.H. and I.-E.N.), who carried out this research. The authors would like to acknowledge support from the Research Council of Norway through the Norwegian Center for Transmission Electron Microscopy, NORTEM (197405/F50). We would like to thank the European Synchrotron ESRF for the provision of synchrotron radiation at BM25.Peer reviewedAmerican Chemical SocietyResearch Council of NorwayEuropean CommissionEuropean Synchrotron Radiation FacilityConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202520252025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/404231reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)InglésHamonnet, Johan; Nylund, Inger-Emma; Kontis, Paraskevas; Hua, Weicheng; Alonso-Sánchez, Pedro; Rubio Zuazo, Juan; Blanco, Maria Valeria; Svensson, Ann Mari; 2025; Supporting Information: Degradation of LiNi0.5Mn1.5O4 cathodes in the P111i4FSI ionic liquid electrolyte and carbonate electrolytes [Dataset]; American Chemical Society; https://doi.org/10.1021/acsami.5c11439https://doi.org/10.1021/acsami.5c11439Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/4042312026-05-22T06:33:51Z
score 15,81155

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