The Relationship between the Crystal Structure and Electrical Properties of Oxide Ion Conducting Ba3W1.2Nb0.8O8.6

Kirstie S McCombie, Eve J Wildman, Clemens Ritter, Ronald I Smith, Janet M S Skakle, Abbie C Mclaughlin (Corresponding Author)

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The oxide ionic conductor Ba3W1.2Nb0.8O8.6 has been synthesised as part of an investigation into the new class of Ba3M’M’’O8.5 (M’ = W, Mo; M’’ = Nb) oxide-ion conducting hexagonal perovskite derivatives. The substitution of W6+ for Nb5+ in Ba3W1+xNb1-xO8.5+x/2 leads to an increase in the oxygen content, which enhances the low temperature ionic conductivity. However at 400 °C, the ionic conductivity of Ba3W1.2Nb0.8O8.6 is still significantly lower than the molybdenum compound Ba3MoNbO8.5. Remarkably, at 600 °C the bulk oxide ionic conductivities of Ba3MoNbO8.5, Ba3WNbO8.5 and Ba3W1.2Nb0.8O8.6 are very similar (σb = 0.0016 S cm-1, 0.0017 S cm-1 and 0.0022 S cm-1 respectively). The variable temperature neutron diffraction results reported here demonstrate that Ba3W1.2Nb0.8O8.6 undergoes a similar structural rearrangement to Ba3MoNbO8.5 above 300 °C but the ratio of (W/Nb)O4 tetrahedra to (W/Nb)O6 octahedra rises at a faster rate upon heating between 300 and 600 °C. There is a clear relationship between the ionic conductivity of Ba3M’1+xM’’1-xO8.5+x/2 (M’ = W, Mo; M’’= Nb) phases and the number of tetrahedrally coordinated M' and M" cations present within the crystal structure.
Original languageEnglish
Pages (from-to)11942-11947
Number of pages6
JournalInorganic Chemistry
Volume57
Issue number19
Early online date12 Sep 2018
DOIs
Publication statusPublished - 1 Oct 2018

Fingerprint

Ionic conductivity
Oxides
ion currents
Electric properties
Crystal structure
electrical properties
Ions
conduction
crystal structure
oxides
ions
Molybdenum compounds
molybdenum compounds
Neutron diffraction
Heating rate
tetrahedrons
neutron diffraction
Cations
Substitution reactions
conductors

Cite this

The Relationship between the Crystal Structure and Electrical Properties of Oxide Ion Conducting Ba3W1.2Nb0.8O8.6. / McCombie, Kirstie S; Wildman, Eve J; Ritter, Clemens; Smith, Ronald I; Skakle, Janet M S; Mclaughlin, Abbie C (Corresponding Author).

In: Inorganic Chemistry, Vol. 57, No. 19, 01.10.2018, p. 11942-11947.

Research output: Contribution to journalArticle

@article{e9c698a05bd24346af2fadf2f71a3dc6,
title = "The Relationship between the Crystal Structure and Electrical Properties of Oxide Ion Conducting Ba3W1.2Nb0.8O8.6",
abstract = "The oxide ionic conductor Ba3W1.2Nb0.8O8.6 has been synthesised as part of an investigation into the new class of Ba3M’M’’O8.5 (M’ = W, Mo; M’’ = Nb) oxide-ion conducting hexagonal perovskite derivatives. The substitution of W6+ for Nb5+ in Ba3W1+xNb1-xO8.5+x/2 leads to an increase in the oxygen content, which enhances the low temperature ionic conductivity. However at 400 °C, the ionic conductivity of Ba3W1.2Nb0.8O8.6 is still significantly lower than the molybdenum compound Ba3MoNbO8.5. Remarkably, at 600 °C the bulk oxide ionic conductivities of Ba3MoNbO8.5, Ba3WNbO8.5 and Ba3W1.2Nb0.8O8.6 are very similar (σb = 0.0016 S cm-1, 0.0017 S cm-1 and 0.0022 S cm-1 respectively). The variable temperature neutron diffraction results reported here demonstrate that Ba3W1.2Nb0.8O8.6 undergoes a similar structural rearrangement to Ba3MoNbO8.5 above 300 °C but the ratio of (W/Nb)O4 tetrahedra to (W/Nb)O6 octahedra rises at a faster rate upon heating between 300 and 600 °C. There is a clear relationship between the ionic conductivity of Ba3M’1+xM’’1-xO8.5+x/2 (M’ = W, Mo; M’’= Nb) phases and the number of tetrahedrally coordinated M' and M{"} cations present within the crystal structure.",
author = "McCombie, {Kirstie S} and Wildman, {Eve J} and Clemens Ritter and Smith, {Ronald I} and Skakle, {Janet M S} and Mclaughlin, {Abbie C}",
note = "This research was supported by the University of Aberdeen and EPSRC (research grant EP/L002493/1). We also acknowledge the UK Science and Technology Facilities Council (STFC) for provision of beamtime at ISIS and the ILL.",
year = "2018",
month = "10",
day = "1",
doi = "10.1021/acs.inorgchem.8b01366",
language = "English",
volume = "57",
pages = "11942--11947",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "19",

}

TY - JOUR

T1 - The Relationship between the Crystal Structure and Electrical Properties of Oxide Ion Conducting Ba3W1.2Nb0.8O8.6

AU - McCombie, Kirstie S

AU - Wildman, Eve J

AU - Ritter, Clemens

AU - Smith, Ronald I

AU - Skakle, Janet M S

AU - Mclaughlin, Abbie C

N1 - This research was supported by the University of Aberdeen and EPSRC (research grant EP/L002493/1). We also acknowledge the UK Science and Technology Facilities Council (STFC) for provision of beamtime at ISIS and the ILL.

PY - 2018/10/1

Y1 - 2018/10/1

N2 - The oxide ionic conductor Ba3W1.2Nb0.8O8.6 has been synthesised as part of an investigation into the new class of Ba3M’M’’O8.5 (M’ = W, Mo; M’’ = Nb) oxide-ion conducting hexagonal perovskite derivatives. The substitution of W6+ for Nb5+ in Ba3W1+xNb1-xO8.5+x/2 leads to an increase in the oxygen content, which enhances the low temperature ionic conductivity. However at 400 °C, the ionic conductivity of Ba3W1.2Nb0.8O8.6 is still significantly lower than the molybdenum compound Ba3MoNbO8.5. Remarkably, at 600 °C the bulk oxide ionic conductivities of Ba3MoNbO8.5, Ba3WNbO8.5 and Ba3W1.2Nb0.8O8.6 are very similar (σb = 0.0016 S cm-1, 0.0017 S cm-1 and 0.0022 S cm-1 respectively). The variable temperature neutron diffraction results reported here demonstrate that Ba3W1.2Nb0.8O8.6 undergoes a similar structural rearrangement to Ba3MoNbO8.5 above 300 °C but the ratio of (W/Nb)O4 tetrahedra to (W/Nb)O6 octahedra rises at a faster rate upon heating between 300 and 600 °C. There is a clear relationship between the ionic conductivity of Ba3M’1+xM’’1-xO8.5+x/2 (M’ = W, Mo; M’’= Nb) phases and the number of tetrahedrally coordinated M' and M" cations present within the crystal structure.

AB - The oxide ionic conductor Ba3W1.2Nb0.8O8.6 has been synthesised as part of an investigation into the new class of Ba3M’M’’O8.5 (M’ = W, Mo; M’’ = Nb) oxide-ion conducting hexagonal perovskite derivatives. The substitution of W6+ for Nb5+ in Ba3W1+xNb1-xO8.5+x/2 leads to an increase in the oxygen content, which enhances the low temperature ionic conductivity. However at 400 °C, the ionic conductivity of Ba3W1.2Nb0.8O8.6 is still significantly lower than the molybdenum compound Ba3MoNbO8.5. Remarkably, at 600 °C the bulk oxide ionic conductivities of Ba3MoNbO8.5, Ba3WNbO8.5 and Ba3W1.2Nb0.8O8.6 are very similar (σb = 0.0016 S cm-1, 0.0017 S cm-1 and 0.0022 S cm-1 respectively). The variable temperature neutron diffraction results reported here demonstrate that Ba3W1.2Nb0.8O8.6 undergoes a similar structural rearrangement to Ba3MoNbO8.5 above 300 °C but the ratio of (W/Nb)O4 tetrahedra to (W/Nb)O6 octahedra rises at a faster rate upon heating between 300 and 600 °C. There is a clear relationship between the ionic conductivity of Ba3M’1+xM’’1-xO8.5+x/2 (M’ = W, Mo; M’’= Nb) phases and the number of tetrahedrally coordinated M' and M" cations present within the crystal structure.

U2 - 10.1021/acs.inorgchem.8b01366

DO - 10.1021/acs.inorgchem.8b01366

M3 - Article

VL - 57

SP - 11942

EP - 11947

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 19

ER -