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

Stevin S. Pramana; Tom Baikie; Tao An; Matthew G. Tucker; Ji Wu; Martin K. Schreyer; Fengxia Wei; Ryan D. Bayliss; Christian L. Kloc; Timothy J. White; Andrew P. Horsfield; Stephen J. Skinner

doi:10.1021/jacs.5b11373

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

Stevin S. Pramana, Tom Baikie, Tao An, Matthew G. Tucker, Ji Wu, Martin K. Schreyer, Fengxia Wei, Ryan D. Bayliss, Christian L. Kloc, Timothy J. White, Andrew P. Horsfield, Stephen J. Skinner

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37 Scopus citations

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.

Original language	English (US)
Pages (from-to)	1273-1279
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	138
Issue number	4
DOIs	https://doi.org/10.1021/jacs.5b11373
State	Published - Jan 25 2016
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: 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.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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10.1021/jacs.5b11373

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Pramana, S. S., Baikie, T., An, T., Tucker, M. G., Wu, J., Schreyer, M. K., Wei, F., Bayliss, R. D., Kloc, C. L., White, T. J., Horsfield, A. P., & Skinner, S. J. (2016). Correlation of Local Structure and Diffusion Pathways in the Modulated Anisotropic Oxide Ion Conductor CeNbO4.25. Journal of the American Chemical Society, 138(4), 1273-1279. https://doi.org/10.1021/jacs.5b11373

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

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.",

author = "Pramana, {Stevin S.} and Tom Baikie and Tao An and Tucker, {Matthew G.} and Ji Wu and Schreyer, {Martin K.} and Fengxia Wei and Bayliss, {Ryan D.} and Kloc, {Christian L.} and White, {Timothy J.} and Horsfield, {Andrew P.} and Skinner, {Stephen J.}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

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AU - Pramana, Stevin S.

AU - Baikie, Tom

AU - An, Tao

AU - Tucker, Matthew G.

AU - Wu, Ji

AU - Schreyer, Martin K.

AU - Wei, Fengxia

AU - Bayliss, Ryan D.

AU - Kloc, Christian L.

AU - White, Timothy J.

AU - Horsfield, Andrew P.

AU - Skinner, Stephen J.

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2016/1/25

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N2 - 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.

AB - 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.

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JF - Journal of the American Chemical Society

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ER -

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

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