Local structure and conductivity behaviour in Bi7WO13.5

Anna Borowska-Centkowska , Marzena Leszczyńska - Redek , Franciszek Krok , Marcin Małys , Wojciech Wróbel , S. Hull , I. Abrahams

Abstract

The structure and electrical properties of the oxide ion conductor Bi7WO13.5 have been examined as a function of temperature using neutron diffraction, differential thermal analysis and a.c. impedance spectroscopy. At room temperature, Bi7WO13.5 exhibits the type Ib tetragonally ordered fluorite structure, with tungsten distributed over two of the six cation sites. Reverse Monte Carlo (RMC) analysis of total neutron scattering data reveals a more realistic picture of the tungsten coordination environment than obtained by the average crystallographic analysis, with tungsten in predominantly tetrahedral coordination and an average bismuth coordination number of around 5. At 893 °C on heating Bi7WO13.5 undergoes a phase transition to a cubic δ-Bi2O3 type phase. The total scattering analysis of this phase reveals significant detail of the local environments of the cations. In particular, a bimodal distribution is found for Bi–O correlations, which has been used to guide the crystallographic analysis. Even in the type Ib phase Bi7WO13.5 shows relatively high conductivity in the intermediate temperature range and measurements of the oxide ion transference number confirm this to be virtually pure ionic in nature. Analysis of the oxide ion vacancy distributions shows a preference for 〈100〉 vacancy pair alignment in both phases. Evidence for a second order phase transition at around 400 °C is discussed.
Author Anna Borowska-Centkowska (FP / SSID)
Anna Borowska-Centkowska,,
- Solid State Ionics Division
, Marzena Leszczyńska - Redek (FP / SSID)
Marzena Leszczyńska - Redek,,
- Solid State Ionics Division
, Franciszek Krok (FP / SSID)
Franciszek Krok,,
- Solid State Ionics Division
, Marcin Małys (FP / SSID)
Marcin Małys,,
- Solid State Ionics Division
, Wojciech Wróbel (FP / SSID)
Wojciech Wróbel,,
- Solid State Ionics Division
, S. Hull - [ISIS Facility]
S. Hull,,
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, I. Abrahams - [School of Biological and Chemical Sciences Queen Mary University of London]
I. Abrahams,,
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Journal seriesJournal of Materials Chemistry A: materials for energy and sustainability, ISSN 2050-7488, [2050-7496], (A 40 pkt)
Issue year2018
Vol13
No6
Pages5407-5418
Publication size in sheets0.55
ASJC Classification2500 General Materials Science; 2105 Renewable Energy, Sustainability and the Environment; 1600 General Chemistry
DOIDOI:10.1039/C7TA09225C
URL http://pubs.rsc.org/en/Content/ArticleLanding/2018/TA/C7TA09225C#!divAbstract
Languageen angielski
Score (nominal)40
ScoreMinisterial score = 40.0, 13-08-2019, ArticleFromJournal
Publication indicators Scopus Citations = 1; WoS Citations = 1; Scopus SNIP (Source Normalised Impact per Paper): 2016 = 1.468; WoS Impact Factor: 2017 = 9.931 (2) - 2017=9.531 (5)
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