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Structural Investigation of Monoclinic‐Rhombohedral Phase Transition in Na 3 Zr 2 Si 2 PO 12 and Doped NASICON

Journal Article · · Journal of the American Ceramic Society
DOI:https://doi.org/10.1111/jace.13692· OSTI ID:1400713
 [1];  [1];  [1];  [1];
  1. University of Maryland Energy Research Center Department of Materials Science and Engineering University of Maryland, College Park Maryland 20742

Aliovalent doping of the zirconium site in Na 3 Zr 2 Si 2 PO 12 ( NASICON ) was performed with a range of +3 (Al, Y, Fe) and +2 (Co, Ni, Zn) valent cations. The monoclinic‐rhombohedral phase transition was analyzed with high‐temperature in situ X‐ray diffraction, and differential scanning calorimetry ( DSC ). From the lattice parameters extracted at room temperature up to 300°C it was determined that the high‐temperature rhombohedral phase distorts to the low‐temperature monoclinic phase through a shear deformation of the unit cell. DSC confirmed the phase transition and demonstrated that the phase transition temperature was lowered by doping the NASICON structure. Furthermore, the distortion of the lattice was less severe for all doped samples. Ultimately aliovalent substitution for zirconium stabilized the higher symmetry rhombohedral phase of NASICON , with yttrium doping providing the lowest phase transition temperature and the smallest distortion of the lattice through the phase change.

Sponsoring Organization:
USDOE
OSTI ID:
1400713
Journal Information:
Journal of the American Ceramic Society, Journal Name: Journal of the American Ceramic Society Journal Issue: 9 Vol. 98; ISSN 0002-7820
Publisher:
Wiley-BlackwellCopyright Statement
Country of Publication:
United States
Language:
English

References (12)

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Crystal structures and crystal chemistry in the system Na1+xZr2SixP3−xO12 journal February 1976
Fast Na+-ion transport in skeleton structures journal February 1976
Phase transition in nasicon (Na3Zr2Si2PO12) journal October 1979
Compositional dependence of the electrochemical and structural parameters in the Nasicon system (Na1+xSixZr2P3−xO12) journal August 1981
Sintering and characterization of alkaline-earth-doped and zirconium-defficient Na3Zr2Si2PO12 journal September 1983
Orientational disorder, glass/crystal transition and superionic conductivity in nasicon journal September 1986
Phase transition in, thermal history and expansion of NASICON, solid solution and lithium derivative ceramics and of SiC (mullite) fibers-NASICON composites journal November 1994
Influence of microstructure on the electrical properties of NASICON materials journal March 2001
Processing and electrical properties of NASICON prepared from yttria-doped zirconia precursors journal June 2001

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