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Title: Synthesis, crystal structure and electrical proprieties of new phosphate KCoP{sub 3}O{sub 9}

Abstract

Crystals of new tricyclophosphate KCoP{sub 3}O{sub 9} have been grown from solid state reaction and characterized by single crystal X-ray diffraction. KCoP{sub 3}O{sub 9} crystallizes in the hexagonal system, space group P6{sup ¯}c2, with a=6.616 (7) Å; c=9.788 (3) Å; V=371.06 (13) Å{sup 3}, Z=2. The final agreement factors are R=0.014, ωR=0.038, S(F{sup 2})=1.231. The structure of the title compound can be described as a three-dimensional framework built up of corner sharing CoO{sub 6} and PO{sub 4} polyhedra containing wide tunnels oriented along [001] direction and others, less broad, along [100] and [010] directions. The structural model was validated by bond valence sum (BVS) and charge distribution (CD) methods. Ball milling was used to reduce the particles sizes of the synthesized powder. At the optimal sintering temperature of 800 °C, a relative density of 85% was obtained. The microstructure was characterized by scanning electron microscopy. The electrical conductivity was 8.4×10{sup −7} S cm{sup −1} and 1.7×10{sup −4} S cm{sup −1} at 480 °C and 680 °C respectively. The activation energy deduced from the slope is 2.2 eV at low temperature region and 1.2 eV at high temperature region. The BVS model is extended to simulate the ionic migration pathways ofmore » alkali cations in the anionic framework. The BVS calculation shows one-dimensional pathways migration along c-axis. - Graphical abstract: 1D pathways link K atoms along c-axis with bond valence mismatch |ΔV(K)|=0.8 v.u. - Highlights: • A new single crystal KCoP{sub 3}O{sub 9} was grown by solid state reaction and its structure determined by single-crystal X-ray diffraction. • The purity polycrystalline of KCoP{sub 3}O{sub 9} sample was verified by Rietveld refinement. • The CIS measurements were optimized and the obtained spectra were fitted by electrical equivalent circuits. • The conduction pathways for the K{sup +} cations are simulated by means of the bond valence sum model.« less

Authors:
 [1];  [1];  [2];  [3];  [1]
  1. Université de Tunis El Manar, Faculté des Sciences de Tunis, Laboratoire de Matériaux et Cristallochimie, El Manar II, 2092 Tunis (Tunisia)
  2. (Tunisia)
  3. Université de Savoie – Université Joseph Fourier, Laboratoire d’Electrochimie et de Physicochimie des Matériaux et des Interfaces LEPMI, UMR 5279, CNRS – Grenoble INP-BP75, 38402 Saint Martin d’Hères (France)
Publication Date:
OSTI Identifier:
22443508
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 221; Other Information: Copyright (c) 2014 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACTIVATION ENERGY; CATIONS; COBALT OXIDES; DENSITY; ELECTRIC CONDUCTIVITY; EQUIVALENT CIRCUITS; HEXAGONAL SYSTEMS; MICROSTRUCTURE; MIGRATION; MONOCRYSTALS; PARTICLE SIZE; PHOSPHATES; POLYCRYSTALS; SCANNING ELECTRON MICROSCOPY; SIMULATION; SOLIDS; SPACE GROUPS; SYNTHESIS; THREE-DIMENSIONAL LATTICES; X-RAY DIFFRACTION

Citation Formats

Ben Smida, Y., E-mail: Youssef_smida@yahoo.fr, Guesmi, A., Université de Tunis El Manar, Institut Préparatoire aux Etudes d’Ingénieurs d’El Manar, El Manar II, 2092 Tunis, Georges, S., and Zid, M.F. Synthesis, crystal structure and electrical proprieties of new phosphate KCoP{sub 3}O{sub 9}. United States: N. p., 2015. Web. doi:10.1016/J.JSSC.2014.09.026.
Ben Smida, Y., E-mail: Youssef_smida@yahoo.fr, Guesmi, A., Université de Tunis El Manar, Institut Préparatoire aux Etudes d’Ingénieurs d’El Manar, El Manar II, 2092 Tunis, Georges, S., & Zid, M.F. Synthesis, crystal structure and electrical proprieties of new phosphate KCoP{sub 3}O{sub 9}. United States. doi:10.1016/J.JSSC.2014.09.026.
Ben Smida, Y., E-mail: Youssef_smida@yahoo.fr, Guesmi, A., Université de Tunis El Manar, Institut Préparatoire aux Etudes d’Ingénieurs d’El Manar, El Manar II, 2092 Tunis, Georges, S., and Zid, M.F. Thu . "Synthesis, crystal structure and electrical proprieties of new phosphate KCoP{sub 3}O{sub 9}". United States. doi:10.1016/J.JSSC.2014.09.026.
@article{osti_22443508,
title = {Synthesis, crystal structure and electrical proprieties of new phosphate KCoP{sub 3}O{sub 9}},
author = {Ben Smida, Y., E-mail: Youssef_smida@yahoo.fr and Guesmi, A. and Université de Tunis El Manar, Institut Préparatoire aux Etudes d’Ingénieurs d’El Manar, El Manar II, 2092 Tunis and Georges, S. and Zid, M.F.},
abstractNote = {Crystals of new tricyclophosphate KCoP{sub 3}O{sub 9} have been grown from solid state reaction and characterized by single crystal X-ray diffraction. KCoP{sub 3}O{sub 9} crystallizes in the hexagonal system, space group P6{sup ¯}c2, with a=6.616 (7) Å; c=9.788 (3) Å; V=371.06 (13) Å{sup 3}, Z=2. The final agreement factors are R=0.014, ωR=0.038, S(F{sup 2})=1.231. The structure of the title compound can be described as a three-dimensional framework built up of corner sharing CoO{sub 6} and PO{sub 4} polyhedra containing wide tunnels oriented along [001] direction and others, less broad, along [100] and [010] directions. The structural model was validated by bond valence sum (BVS) and charge distribution (CD) methods. Ball milling was used to reduce the particles sizes of the synthesized powder. At the optimal sintering temperature of 800 °C, a relative density of 85% was obtained. The microstructure was characterized by scanning electron microscopy. The electrical conductivity was 8.4×10{sup −7} S cm{sup −1} and 1.7×10{sup −4} S cm{sup −1} at 480 °C and 680 °C respectively. The activation energy deduced from the slope is 2.2 eV at low temperature region and 1.2 eV at high temperature region. The BVS model is extended to simulate the ionic migration pathways of alkali cations in the anionic framework. The BVS calculation shows one-dimensional pathways migration along c-axis. - Graphical abstract: 1D pathways link K atoms along c-axis with bond valence mismatch |ΔV(K)|=0.8 v.u. - Highlights: • A new single crystal KCoP{sub 3}O{sub 9} was grown by solid state reaction and its structure determined by single-crystal X-ray diffraction. • The purity polycrystalline of KCoP{sub 3}O{sub 9} sample was verified by Rietveld refinement. • The CIS measurements were optimized and the obtained spectra were fitted by electrical equivalent circuits. • The conduction pathways for the K{sup +} cations are simulated by means of the bond valence sum model.},
doi = {10.1016/J.JSSC.2014.09.026},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 221,
place = {United States},
year = {2015},
month = {1}
}