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Title: The preparation, structure, and conductivity of scandium-substituted NASICONs

Abstract

A series of NASICON type compounds was prepared in which Sc(III) partially replaced Zr(IV). By simultaneously correlating the extent of this substitution with the amount of Si(IV) replacement o P(V) it was possible to obtain a series with a constant amount (3 mole) of sodium ion. All of the rhombohedral members of this series exhibited similar conductivities and activation energies over the temperature range 30-350/sup 0/C. Transformation to the monoclinic phase occurred at a composition of Na/sub 3/ Sc /SUB 0.5/ Zr /SUB 1.5/ Si /SUB 1.5/ P /SUB 1.5/ O/sub 12/ and was accompanied by a threefold increase in conductivity. Activation energies of the monoclinic (room temperature) phases in the temperature range 200-300/sup 0/C were 0.2-0.23 eV. Crystal structures of the rhombohedral phase of composition Na/sub 3/ScZrSiP/sub 2/O/sub 12/ and the monoclinic phase, Na/sub 3/ Sc /SUB 0.5/ Zr /SUB 1.5/ Si /SUB 1.5/ P /SUB 1.5/ O/sub 12/, were carried out by Rietveld refinement of their X-ray powder patterns. The structures confirmed those presented by Hong, and also confirmed the stoichiometry of these phases as evidenced from site occupancy refinement. These results were compared with the structure of a nonstoichiometric phase, Na /SUB 3.20/ Zr /SUB 1.68/ Simore » /SUB 1.84/ P /SUB 1.16/ O /SUB 11.54/ , prepared by hydrothermal route. In the latter case it was shown that the low Zr content is due to Na/sup +/ substitution for Zr/sup 4 +/. No such substitution occurred in the scandium containing phases, and it is suggested that when Sc/sup 3 +/ substitution for zirconium takes place it prevents the sodium ion from occupying these sites.« less

Authors:
; ;
Publication Date:
Research Org.:
Department of Chemistry, Texas AandM University, College Station, Texas
OSTI Identifier:
5954961
Resource Type:
Journal Article
Journal Name:
J. Solid State Chem.; (United States)
Additional Journal Information:
Journal Volume: 60:2
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; PHOSPHORUS OXIDES; CRYSTAL STRUCTURE; ELECTRIC CONDUCTIVITY; HYDROTHERMAL SYNTHESIS; SCANDIUM OXIDES; SILICON OXIDES; SODIUM OXIDES; ZIRCONIUM OXIDES; ACTIVATION ENERGY; CRYSTAL-PHASE TRANSFORMATIONS; STOICHIOMETRY; ALKALI METAL COMPOUNDS; CHALCOGENIDES; ELECTRICAL PROPERTIES; ENERGY; OXIDES; OXYGEN COMPOUNDS; PHASE TRANSFORMATIONS; PHOSPHORUS COMPOUNDS; PHYSICAL PROPERTIES; SCANDIUM COMPOUNDS; SILICON COMPOUNDS; SODIUM COMPOUNDS; SYNTHESIS; TRANSITION ELEMENT COMPOUNDS; ZIRCONIUM COMPOUNDS; 360202* - Ceramics, Cermets, & Refractories- Structure & Phase Studies; 360201 - Ceramics, Cermets, & Refractories- Preparation & Fabrication

Citation Formats

Subramanian, M A, Clearfield, A, and Rudolf, P R. The preparation, structure, and conductivity of scandium-substituted NASICONs. United States: N. p., 1985. Web. doi:10.1016/0022-4596(85)90109-4.
Subramanian, M A, Clearfield, A, & Rudolf, P R. The preparation, structure, and conductivity of scandium-substituted NASICONs. United States. https://doi.org/10.1016/0022-4596(85)90109-4
Subramanian, M A, Clearfield, A, and Rudolf, P R. Fri . "The preparation, structure, and conductivity of scandium-substituted NASICONs". United States. https://doi.org/10.1016/0022-4596(85)90109-4.
@article{osti_5954961,
title = {The preparation, structure, and conductivity of scandium-substituted NASICONs},
author = {Subramanian, M A and Clearfield, A and Rudolf, P R},
abstractNote = {A series of NASICON type compounds was prepared in which Sc(III) partially replaced Zr(IV). By simultaneously correlating the extent of this substitution with the amount of Si(IV) replacement o P(V) it was possible to obtain a series with a constant amount (3 mole) of sodium ion. All of the rhombohedral members of this series exhibited similar conductivities and activation energies over the temperature range 30-350/sup 0/C. Transformation to the monoclinic phase occurred at a composition of Na/sub 3/ Sc /SUB 0.5/ Zr /SUB 1.5/ Si /SUB 1.5/ P /SUB 1.5/ O/sub 12/ and was accompanied by a threefold increase in conductivity. Activation energies of the monoclinic (room temperature) phases in the temperature range 200-300/sup 0/C were 0.2-0.23 eV. Crystal structures of the rhombohedral phase of composition Na/sub 3/ScZrSiP/sub 2/O/sub 12/ and the monoclinic phase, Na/sub 3/ Sc /SUB 0.5/ Zr /SUB 1.5/ Si /SUB 1.5/ P /SUB 1.5/ O/sub 12/, were carried out by Rietveld refinement of their X-ray powder patterns. The structures confirmed those presented by Hong, and also confirmed the stoichiometry of these phases as evidenced from site occupancy refinement. These results were compared with the structure of a nonstoichiometric phase, Na /SUB 3.20/ Zr /SUB 1.68/ Si /SUB 1.84/ P /SUB 1.16/ O /SUB 11.54/ , prepared by hydrothermal route. In the latter case it was shown that the low Zr content is due to Na/sup +/ substitution for Zr/sup 4 +/. No such substitution occurred in the scandium containing phases, and it is suggested that when Sc/sup 3 +/ substitution for zirconium takes place it prevents the sodium ion from occupying these sites.},
doi = {10.1016/0022-4596(85)90109-4},
url = {https://www.osti.gov/biblio/5954961}, journal = {J. Solid State Chem.; (United States)},
number = ,
volume = 60:2,
place = {United States},
year = {1985},
month = {11}
}