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Structural Investigation of Monoclinic‐Rhombohedral Phase Transition in Na 3 Zr 2 Si 2 PO 12 and Doped NASICON
Author(s) -
Jolley Adam G.,
Taylor Daniel D.,
Schreiber Nathaniel J.,
Wachsman Eric D.
Publication year - 2015
Publication title -
journal of the american ceramic society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.9
H-Index - 196
eISSN - 1551-2916
pISSN - 0002-7820
DOI - 10.1111/jace.13692
Subject(s) - monoclinic crystal system , materials science , crystallography , differential scanning calorimetry , yttrium , phase transition , zirconium , fast ion conductor , doping , x ray crystallography , crystal structure , analytical chemistry (journal) , diffraction , chemistry , condensed matter physics , thermodynamics , metallurgy , electrolyte , physics , optoelectronics , electrode , chromatography , oxide , optics
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.