Incorporation of Fe3+ into MnO2 birnessite for enhanced energy storage: Impact on the structure and the charge storage mechanisms
hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
dc.contributor.author | INVERNIZZI, Ronan | |
hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
dc.contributor.author | KOVRUGIN, Vadim | |
hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
dc.contributor.author | MOLINIÉ, Louise | |
hal.structure.identifier | Réseau sur le stockage électrochimique de l'énergie [RS2E] | |
dc.contributor.author | IADECOLA, Antonella | |
hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
dc.contributor.author | DUTTINE, Mathieu | |
hal.structure.identifier | Institut des Sciences Moléculaires [ISM] | |
dc.contributor.author | BOURGEOIS, Lydie | |
hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
hal.structure.identifier | Réseau sur le stockage électrochimique de l'énergie [RS2E] | |
hal.structure.identifier | Advanced Lithium Energy Storage Systems - ALISTORE-ERI [ALISTORE-ERI] | |
dc.contributor.author | OLCHOWKA, Jacob | |
hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
hal.structure.identifier | Réseau sur le stockage électrochimique de l'énergie [RS2E] | |
hal.structure.identifier | Advanced Lithium Energy Storage Systems - ALISTORE-ERI [ALISTORE-ERI] | |
dc.contributor.author | GUERLOU-DEMOURGUES, Liliane | |
dc.date.issued | 2024 | |
dc.identifier.issn | 2050-7488 | |
dc.description.abstractEn | Birnessite 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.sponsorship | Laboratory of excellency for electrochemical energy storage - ANR-10-LABX-0076 | |
dc.description.sponsorship | Spectromètre EXAFS Rapide pour Cinétiques Chimiques - ANR-10-EQPX-0045 | |
dc.language.iso | en | |
dc.publisher | Royal Society of Chemistry | |
dc.title.en | Incorporation of Fe3+ into MnO2 birnessite for enhanced energy storage: Impact on the structure and the charge storage mechanisms | |
dc.type | Article de revue | |
dc.identifier.doi | 10.1039/D3TA04544G | |
dc.subject.hal | Chimie/Matériaux | |
bordeaux.journal | Journal of Materials Chemistry A | |
bordeaux.page | 3373-3385 | |
bordeaux.volume | 12 | |
bordeaux.issue | 6 | |
bordeaux.peerReviewed | oui | |
hal.identifier | hal-04184429 | |
hal.version | 1 | |
hal.popular | non | |
hal.audience | Internationale | |
hal.origin.link | https://hal.archives-ouvertes.fr//hal-04184429v1 | |
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