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Study on the structural phase transitions in NaSICON‐type compounds using Ag 3 Sc 2 (PO 4 ) 3 as a model system
Author(s) -
Redhammer Günther J.,
Tippelt Gerold,
Stahl Quirin,
Benisek Artur,
Rettenwander Daniel
Publication year - 2021
Publication title -
acta crystallographica section b
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.604
H-Index - 33
ISSN - 2052-5206
DOI - 10.1107/s2052520620014870
Subject(s) - fast ion conductor , monoclinic crystal system , ionic conductivity , ionic bonding , phase (matter) , ion , phase transition , materials science , electrolyte , ionic radius , crystallography , analytical chemistry (journal) , crystal structure , chemical physics , chemistry , thermodynamics , physics , organic chemistry , electrode , chromatography
NaSICON (Na Super‐Ionic CONducting) structured materials are among the most promising solid electrolytes for Li‐ion batteries and `beyond Li‐ion' batteries ( e.g. Na and K) due to their superior ionic conductivities. Although this material has been well known for decades, its exact phase behaviour is still poorly understood. Herein, a starting material of Na 3 Sc 2 (PO 4 ) 3 single crystals is used, grown by flux methodology, where Na is subsequently chemically replaced by Ag, in order to take advantage of the higher scattering contrast of Ag. It is found that the NaSICON‐type compound shows two phase transitions from a low‐temperature monoclinic α‐phase to a monoclinic β‐phase at about 180 K and to a rhombohedral γ‐phase at about 290 K. The framework of [Sc 2 (PO 4 ) 3 ] 3− is rigid and does not change significantly with temperature and change of symmetry. The main driving force for the phase transitions is related to order–disorder phenomena of the conducting cations. The sensitivity of the phase behaviour on the ordering of these ions suggests that small compositional changes can have a great impact on the phase behaviour and, hence, on the ionic conductivity of NaSICON‐structured materials.