TY - JOUR
T1 - Study on the structural phase transitions in NaSICON-type compounds using Ag3Sc2(PO4)3as a model system
AU - Redhammer, Günther J.
AU - Tippelt, Gerold
AU - Stahl, Quirin
AU - Benisek, Artur
AU - Rettenwander, Daniel
N1 - Publisher Copyright:
© 2021 International Union of Crystallography. All rights reserved.
PY - 2021/2/1
Y1 - 2021/2/1
N2 - 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.
AB - 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.
KW - AgSc(PO)
KW - Ion conductivity
KW - NaSICON-type compound
KW - Order-disorder
KW - Scandium
KW - Structural phase transition
UR - http://www.scopus.com/inward/record.url?scp=85110888240&partnerID=8YFLogxK
U2 - 10.1107/S2052520620014870
DO - 10.1107/S2052520620014870
M3 - Article
AN - SCOPUS:85110888240
SN - 2052-5192
VL - 77
SP - 10
EP - 22
JO - Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials
JF - Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials
ER -