Study on the structural phase transitions in NaSICON-type compounds using Ag3Sc2(PO4)(3) as a model system

Author(s)
Christian Lengauer, Martin Ende, Gerold Tippelt, Günther J. Redhammer
Abstract

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 Na3Sc2(PO4)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 [Sc2(PO4)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.

Organisation(s)
Department of Mineralogy and Crystallography
External organisation(s)
Paris-Lodron Universität Salzburg
Volume
77
Pages
10-22
No. of pages
13
DOI
https://doi.org/10.1107/S2052520620014870
Publication date
02-2021
Austrian Fields of Science 2012
104011 Materials chemistry, 105113 Crystallography
Keywords
ASJC Scopus subject areas
Electronic, Optical and Magnetic Materials, Metals and Alloys, Materials Chemistry, Atomic and Molecular Physics, and Optics
Portal url
https://ucrisportal.univie.ac.at/en/publications/84952f36-7b44-47b5-8306-bedabffe19d0