Correlation of Local Structure and Diffusion Pathways in the Modulated Anisotropic Oxide Ion Conductor CeNbO4.25

Handle URI:
http://hdl.handle.net/10754/624955
Title:
Correlation of Local Structure and Diffusion Pathways in the Modulated Anisotropic Oxide Ion Conductor CeNbO4.25
Authors:
Pramana, Stevin S.; Baikie, Tom; An, Tao; Tucker, Matthew G.; Wu, Ji; Schreyer, Martin K.; Wei, Fengxia; Bayliss, Ryan D.; Kloc, Christian L.; White, Timothy J.; Horsfield, Andrew P.; Skinner, Stephen J.
Abstract:
CeNbO is reported to exhibit fast oxygen ion diffusion at moderate temperatures, making this the prototype of a new class of ion conductor with applications in a range of energy generation and storage devices. To date, the mechanism by which this ion transport is achieved has remained obscure, in part due to the long-range commensurately modulated structural motif. Here we show that CeNbO forms with a unit cell 12 times larger than the stoichiometric tetragonal parent phase of CeNbO as a result of the helical ordering of Ce and Ce ions along z. Interstitial oxygen ion incorporation leads to a cooperative displacement of the surrounding oxygen species, creating interlayer NbO connectivity by extending the oxygen coordination number to 7 and 8. Molecular dynamic simulations suggest that fast ion migration occurs predominantly within the xz plane. It is concluded that the oxide ion diffuses anisotropically, with the major migration mechanism being intralayer; however, when obstructed, oxygen can readily move to an adjacent layer along y via alternate lower energy barrier pathways.
Citation:
Pramana SS, Baikie T, An T, Tucker MG, Wu J, et al. (2016) Correlation of Local Structure and Diffusion Pathways in the Modulated Anisotropic Oxide Ion Conductor CeNbO4.25. Journal of the American Chemical Society 138: 1273–1279. Available: http://dx.doi.org/10.1021/jacs.5b11373.
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
Issue Date:
15-Jan-2016
DOI:
10.1021/jacs.5b11373
Type:
Article
ISSN:
0002-7863; 1520-5126
Sponsors:
We gratefully acknowledge the support of the EPSRC for the award of a doctoral training account studentship for R.D.B. Additionally, we acknowledge the support of King Abdullah University of Science and Technology, who partially funded this work (S.S.P. and J.W.). We further thank STFC for the award of neutron powder diffraction beam time at the Rutherford Appleton Laboratory (ISIS) under award RB1120177. We also acknowledge the Institut Laue-Langevin (ILL) for the award of Easy access on the D2B beamline and Diamond Light Source Ltd., U.K., for access to the I11 powder diffraction beamline.
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Full metadata record

DC FieldValue Language
dc.contributor.authorPramana, Stevin S.en
dc.contributor.authorBaikie, Tomen
dc.contributor.authorAn, Taoen
dc.contributor.authorTucker, Matthew G.en
dc.contributor.authorWu, Jien
dc.contributor.authorSchreyer, Martin K.en
dc.contributor.authorWei, Fengxiaen
dc.contributor.authorBayliss, Ryan D.en
dc.contributor.authorKloc, Christian L.en
dc.contributor.authorWhite, Timothy J.en
dc.contributor.authorHorsfield, Andrew P.en
dc.contributor.authorSkinner, Stephen J.en
dc.date.accessioned2017-06-12T13:52:07Z-
dc.date.available2017-06-12T13:52:07Z-
dc.date.issued2016-01-15en
dc.identifier.citationPramana SS, Baikie T, An T, Tucker MG, Wu J, et al. (2016) Correlation of Local Structure and Diffusion Pathways in the Modulated Anisotropic Oxide Ion Conductor CeNbO4.25. Journal of the American Chemical Society 138: 1273–1279. Available: http://dx.doi.org/10.1021/jacs.5b11373.en
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.doi10.1021/jacs.5b11373en
dc.identifier.urihttp://hdl.handle.net/10754/624955-
dc.description.abstractCeNbO is reported to exhibit fast oxygen ion diffusion at moderate temperatures, making this the prototype of a new class of ion conductor with applications in a range of energy generation and storage devices. To date, the mechanism by which this ion transport is achieved has remained obscure, in part due to the long-range commensurately modulated structural motif. Here we show that CeNbO forms with a unit cell 12 times larger than the stoichiometric tetragonal parent phase of CeNbO as a result of the helical ordering of Ce and Ce ions along z. Interstitial oxygen ion incorporation leads to a cooperative displacement of the surrounding oxygen species, creating interlayer NbO connectivity by extending the oxygen coordination number to 7 and 8. Molecular dynamic simulations suggest that fast ion migration occurs predominantly within the xz plane. It is concluded that the oxide ion diffuses anisotropically, with the major migration mechanism being intralayer; however, when obstructed, oxygen can readily move to an adjacent layer along y via alternate lower energy barrier pathways.en
dc.description.sponsorshipWe gratefully acknowledge the support of the EPSRC for the award of a doctoral training account studentship for R.D.B. Additionally, we acknowledge the support of King Abdullah University of Science and Technology, who partially funded this work (S.S.P. and J.W.). We further thank STFC for the award of neutron powder diffraction beam time at the Rutherford Appleton Laboratory (ISIS) under award RB1120177. We also acknowledge the Institut Laue-Langevin (ILL) for the award of Easy access on the D2B beamline and Diamond Light Source Ltd., U.K., for access to the I11 powder diffraction beamline.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleCorrelation of Local Structure and Diffusion Pathways in the Modulated Anisotropic Oxide Ion Conductor CeNbO4.25en
dc.typeArticleen
dc.identifier.journalJournal of the American Chemical Societyen
dc.contributor.institutionDepartment of Materials, Imperial College London, Exhibition Road, London, SW7 2AZ, , United Kingdomen
dc.contributor.institutionEnergy Research Institute, NTU, Research Technoplaza, Nanyang Technological University, Nanyang Drive, Singapore, , Singaporeen
dc.contributor.institutionDivision of Materials Science and Engineering, Nanyang Technological University, Nanyang Drive, Singapore, , Singaporeen
dc.contributor.institutionISIS Facility, Rutherford Appleton Laboratory, Didcot, OX11 0QX, , , United Kingdomen
dc.contributor.institutionDiamond Light Source, Chilton, Oxfordshire, OX11 0DE, , United Kingdomen
dc.contributor.institutionInstitute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, , , Singaporeen
dc.contributor.institutionInstitute of Materials Research and Engineering, 3 Research Link, Singapore, , Singaporeen
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