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(Nd/Pr)2NiO4+δ: reaction intermediates and redox behavior explored by in situ neutron powder diffraction during electrochemical oxygen intercalation

hal.structure.identifierInstitut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier [ICGM]
dc.contributor.authorCERETTI, Monica
hal.structure.identifierInstitut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier [ICGM]
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorWAHYUDI, Olivia
hal.structure.identifierLaboratoire Léon Brillouin [LLB - UMR 12]
dc.contributor.authorANDRÉ, Gilles
hal.structure.identifierRheinisch-Westfälische Technische Hochschule Aachen University [RWTH]
dc.contributor.authorMEVEN, Martin
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorVILLESUZANNE, Antoine
hal.structure.identifierInstitut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier [ICGM]
dc.contributor.authorPAULUS, Werner
dc.date.issued2018
dc.identifier.issn0020-1669
dc.description.abstractEnOxygen intercalation/deintercalation in Pr2NiO4+δ and Nd2NiO4+δ was followed by in situ neutron powder diffraction during electrochemical oxidation/reduction, in a dedicated reaction cell at room temperature. For both systems three phases, all showing the same line width, were identified. The starting phases Pr2NiO4.23 and Nd2NiO4.24, considered with an average orthorhombic Fmmm symmetry, although both show a slight monoclinic distortion, get reduced in a two-phase reaction step to tetragonal intermediate phases with 0.07 ≤ δ ≤ 0.10 and P42/ ncm space group, which on further reduction transform, again in a two-phase reaction step, toward the respective stoichiometric (Pr/Nd)2NiO4.0 phases, with Bmab space group. Electrochemical oxidation does, however, not proceed fully reversibly for both cases: while the reoxidation of Nd2NiO4+δ is limited to the tetragonal intermediate phase with δ = 0.10, the homologous Pr2NiO4+δ can be reoxidized up to δ = 0.17, showing orthorhombic symmetry. For the intermediate tetragonal phase, we were able to establish for Pr2NiO4.09 a complex anharmonic displacement behavior of the apical oxygen atoms, as analyzed by single-crystal neutron diffraction and maximum entropy analysis, in agreement with a low- T diffusion pathway for oxygen ions, activated by lattice dynamics.
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.subject.enNon-Stoichiometric Oxides
dc.subject.enin-situ
dc.subject.enneutron diffraction
dc.subject.enelectrochemistry
dc.subject.enoxygen ionic conductors
dc.subject.enRuddlesden-Popper oxides
dc.title.en(Nd/Pr)2NiO4+δ: reaction intermediates and redox behavior explored by in situ neutron powder diffraction during electrochemical oxygen intercalation
dc.typeArticle de revue
dc.identifier.doi10.1021/acs.inorgchem.8b00393
dc.subject.halChimie/Chimie inorganique
dc.subject.halChimie/Autre
bordeaux.journalInorganic Chemistry
bordeaux.page4657–4666
bordeaux.volume57
bordeaux.issue8
bordeaux.peerReviewedoui
hal.identifierhal-01760591
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-01760591v1
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