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Incorporation of Fe3+ into MnO2 birnessite for enhanced energy storage: Impact on the structure and the charge storage mechanisms

hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorINVERNIZZI, Ronan
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorKOVRUGIN, Vadim
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorMOLINIÉ, Louise
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
dc.contributor.authorIADECOLA, Antonella
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorDUTTINE, Mathieu
hal.structure.identifierInstitut des Sciences Moléculaires [ISM]
dc.contributor.authorBOURGEOIS, Lydie
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
hal.structure.identifierAdvanced Lithium Energy Storage Systems - ALISTORE-ERI [ALISTORE-ERI]
dc.contributor.authorOLCHOWKA, Jacob
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierRéseau sur le stockage électrochimique de l'énergie [RS2E]
hal.structure.identifierAdvanced Lithium Energy Storage Systems - ALISTORE-ERI [ALISTORE-ERI]
dc.contributor.authorGUERLOU-DEMOURGUES, Liliane
dc.date.issued2024
dc.identifier.issn2050-7488
dc.description.abstractEnBirnessite δ-MnO2, with its low cost, high theoretical capacity, and stable cycling performance in aqueous electrolytes, holds promise as an electrode material for high-power and cost-effective electrochemical energy storage devices. To address its poor electronic conductivity, we incorporated environmentally friendly iron into birnessite and conducted a comprehensive study on its influence on crystal structure, electrochemical reaction mechanisms, and energy storage performance. In this study, a series of birnessite samples with varying iron content (δ-Mn1-xFexO2 with 0 ≤ x ≤ 0.20) were synthesized using solid-state reactions, resulting in well-crystallized particles with micrometric platelet morphology. Through X-ray absorption and Mössbauer spectroscopies, we clearly demonstrated that Fe replaces Mn in the metal oxide layer, while X-ray diffraction revealed that iron content significantly affects interlayer site symmetry and the resulting polytype. The sample with the lowest iron content (δ-Mn0.96Fe0.04O2) exhibits a monoclinic birnessite structure with an O-type interlayer site, while increasing iron content leads to hexagonal symmetry with P-type interlayer sites. Electrochemical investigations indicated that these P-type sites facilitate the diffusion of partially hydrated alkaline ions and exhibit superior rate capabilities compared to the O-type phase. Furthermore, operando XAS revealed that Fe is electrochemically inactive and that the charge storage in birnessite-type phases in a 0.5M K2SO4 electrolyte primarily relies on the redox reaction of Mn. Finally, we determined that P-type δ-Mn0.87Fe0.13O2 achieved the best compromise between enhancing electrical conductivity and maintaining a maximum content of electrochemically active Mn cations.
dc.description.sponsorshipLaboratory of excellency for electrochemical energy storage - ANR-10-LABX-0076
dc.description.sponsorshipSpectromètre EXAFS Rapide pour Cinétiques Chimiques - ANR-10-EQPX-0045
dc.language.isoen
dc.publisherRoyal Society of Chemistry
dc.title.enIncorporation of Fe3+ into MnO2 birnessite for enhanced energy storage: Impact on the structure and the charge storage mechanisms
dc.typeArticle de revue
dc.identifier.doi10.1039/D3TA04544G
dc.subject.halChimie/Matériaux
bordeaux.journalJournal of Materials Chemistry A
bordeaux.page3373-3385
bordeaux.volume12
bordeaux.issue6
bordeaux.peerReviewedoui
hal.identifierhal-04184429
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-04184429v1
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Journal%20of%20Materials%20Chemistry%20A&rft.date=2024&rft.volume=12&rft.issue=6&rft.spage=3373-3385&rft.epage=3373-3385&rft.eissn=2050-7488&rft.issn=2050-7488&rft.au=INVERNIZZI,%20Ronan&KOVRUGIN,%20Vadim&MOLINI%C3%89,%20Louise&IADECOLA,%20Antonella&DUTTINE,%20Mathieu&rft.genre=article


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