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Title: Synthesis, crystal structure, electrical properties, and sodium transport pathways of the new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6}

Abstract

A new sodium cobalt (II) arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} has been synthesized by a solid-state reaction and its crystal structure determined from single crystal X-ray diffraction data. It crystallizes in the monoclinic system, space group C2/m, with a=10.7098(9) Å, b=14.7837(9) Å, c=6.6845(7) Å, and β=105.545(9)°. The structure is described as a three-dimensional framework built up of corner-edge sharing CoO{sub 6}, CoO{sub 4} and AsO{sub 4} polyhedra, with interconnecting channels along [100] in which the Na{sup +} cations are located. The densest ceramics with relative density of 94% was obtained by ball milling and optimization of sintering temperature, and its microstructure characterized by scanning electron microscopy. The electrical properties of the ceramics were studied over a temperature interval from 280 °C to 560 °C using the complex impedance spectroscopy over the range of 13 MHz–5 Hz. The ionic bulk conductivity value of the sample at 360 °C is 2.51 10{sup −5} S cm{sup −1} and the measured activation energy is Ea=1 eV. The sodium migration pathways in the crystal structure were investigated computationally using the bond valence site energy (BVSE) model and classical molecular dynamics (MD) simulations. - Graphical abstract: Correlation between crystal structure, microstructure and ionic conductivity .more » Display Omitted - Highlights: • A new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} was prepared by solid state reaction. • Its crystal structure was determined by powder X-ray diffraction. • Na{sup +} ionic conductivity was probed by complex impedance spectroscopy. • Na{sup +} conduction pathways were modeled by bond-valence method and molecular dynamics.« less

Authors:
;  [1];  [2];  [3];  [3];  [4]; ;  [1]
  1. Université de Tunis El Manar, Laboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, Campus Universitaire, 2092 Manar II, Tunis (Tunisia)
  2. Université Grenoble Alpes, Laboratoire d’Electrochimie et de Physicochimie des Matériaux et des Interfaces LEPMI, F-38000 Grenoble (France)
  3. Bragg Institute, Australian Nuclear Science and Technology Organisation (ANSTO), New Illawarra Road, Lucas Heights, New South Wales 2234 (Australia)
  4. (Australia)
Publication Date:
OSTI Identifier:
22584138
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 239; Other Information: Copyright (c) 2016 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACTIVATION ENERGY; ARSENATES; CATIONS; CERAMICS; COBALT OXIDES; ELECTRON SCANNING; IONIC CONDUCTIVITY; MHZ RANGE; MICROSTRUCTURE; MOLECULAR DYNAMICS METHOD; MONOCLINIC LATTICES; MONOCRYSTALS; SCANNING ELECTRON MICROSCOPY; SODIUM; SOLIDS; SPACE GROUPS; SPECTROSCOPY; SYNTHESIS; X RADIATION; X-RAY DIFFRACTION

Citation Formats

Ben Smida, Youssef, Marzouki, Riadh, Georges, Samuel, Kutteh, Ramzi, Avdeev, Maxim, School of Chemistry, University of Sydney, Sydney, New South Wales 2006, Guesmi, Abderrahmen, and Zid, Mohamed Faouzi. Synthesis, crystal structure, electrical properties, and sodium transport pathways of the new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6}. United States: N. p., 2016. Web. doi:10.1016/J.JSSC.2016.04.005.
Ben Smida, Youssef, Marzouki, Riadh, Georges, Samuel, Kutteh, Ramzi, Avdeev, Maxim, School of Chemistry, University of Sydney, Sydney, New South Wales 2006, Guesmi, Abderrahmen, & Zid, Mohamed Faouzi. Synthesis, crystal structure, electrical properties, and sodium transport pathways of the new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6}. United States. doi:10.1016/J.JSSC.2016.04.005.
Ben Smida, Youssef, Marzouki, Riadh, Georges, Samuel, Kutteh, Ramzi, Avdeev, Maxim, School of Chemistry, University of Sydney, Sydney, New South Wales 2006, Guesmi, Abderrahmen, and Zid, Mohamed Faouzi. Fri . "Synthesis, crystal structure, electrical properties, and sodium transport pathways of the new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6}". United States. doi:10.1016/J.JSSC.2016.04.005.
@article{osti_22584138,
title = {Synthesis, crystal structure, electrical properties, and sodium transport pathways of the new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6}},
author = {Ben Smida, Youssef and Marzouki, Riadh and Georges, Samuel and Kutteh, Ramzi and Avdeev, Maxim and School of Chemistry, University of Sydney, Sydney, New South Wales 2006 and Guesmi, Abderrahmen and Zid, Mohamed Faouzi},
abstractNote = {A new sodium cobalt (II) arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} has been synthesized by a solid-state reaction and its crystal structure determined from single crystal X-ray diffraction data. It crystallizes in the monoclinic system, space group C2/m, with a=10.7098(9) Å, b=14.7837(9) Å, c=6.6845(7) Å, and β=105.545(9)°. The structure is described as a three-dimensional framework built up of corner-edge sharing CoO{sub 6}, CoO{sub 4} and AsO{sub 4} polyhedra, with interconnecting channels along [100] in which the Na{sup +} cations are located. The densest ceramics with relative density of 94% was obtained by ball milling and optimization of sintering temperature, and its microstructure characterized by scanning electron microscopy. The electrical properties of the ceramics were studied over a temperature interval from 280 °C to 560 °C using the complex impedance spectroscopy over the range of 13 MHz–5 Hz. The ionic bulk conductivity value of the sample at 360 °C is 2.51 10{sup −5} S cm{sup −1} and the measured activation energy is Ea=1 eV. The sodium migration pathways in the crystal structure were investigated computationally using the bond valence site energy (BVSE) model and classical molecular dynamics (MD) simulations. - Graphical abstract: Correlation between crystal structure, microstructure and ionic conductivity . Display Omitted - Highlights: • A new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} was prepared by solid state reaction. • Its crystal structure was determined by powder X-ray diffraction. • Na{sup +} ionic conductivity was probed by complex impedance spectroscopy. • Na{sup +} conduction pathways were modeled by bond-valence method and molecular dynamics.},
doi = {10.1016/J.JSSC.2016.04.005},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 239,
place = {United States},
year = {Fri Jul 15 00:00:00 EDT 2016},
month = {Fri Jul 15 00:00:00 EDT 2016}
}