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@ARTICLE{Schuett:1025018,
author = {Schuett, Judith and Schillings, Johanna and
Neitzel-Grieshammer, Steffen},
title = {{I}nterstitial or interstitialcy: effect of the cation size
on the migration mechanism in {N}a{SICON} materials},
journal = {Physical chemistry, chemical physics},
volume = {26},
number = {3},
issn = {1463-9076},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {FZJ-2024-02612},
pages = {2190 - 2204},
year = {2024},
abstract = {Sodium superionic conductors (NaSICONs) with general
formula NaM2A3O12 have attracted significant attention as
solid electrolytes for all solid-state batteries owing to
their remarkable room temperature ionic conductivity in the
order of 10−3 S cm−1. Their flexible structural
framework, which allows the incorporation of various
aliovalent cations, affects the Na+ ion transport. However,
establishing a straightforward correlation between Na+
mobility and NaSICON composition proves challenging due to
competing influences such as framework alteration and
stoichiometric changes of the cation substituents and thus
the mobile Na+ ions. Therefore, we systematically
investigate the NaSICON system across various
Na1+xM2SixP3−xO12 compositions. We unravel and examine
independently two key aspects impacting the Na+ ion
transport in NaSICONs: structural factors determined by
introduced M4+ framework cations and the substitution level
(x). By employing DFT calculations, we explore the
interstitial- and interstitialcy-like migration mechanisms,
revealing that these mechanisms and the associated migration
energies are primarily influenced by metastable transient
states traversed during the Na+ ion migration. The stability
of these transient states, in turn, depends on the spatial
arrangement of the Na+ ions, the size of the M4+ cations
defining the structural framework, and x. This study
enhances our fundamental understanding of Na+ ion migration
within NaSICONs across a wide range of compositions. The
findings offer valuable insights into the microscopic
aspects of NaSICON materials and provide essential guidance
for prospective studies in this field.},
cin = {IEK-12},
ddc = {540},
cid = {I:(DE-Juel1)IEK-12-20141217},
pnm = {1221 - Fundamentals and Materials (POF4-122) / DFG project
452855747 - Bestimmung der ionischen Leitfähigkeit von
kationenleitenden Elektrolyten mittels Kinetik Monte Carlo
Simulationen (452855747)},
pid = {G:(DE-HGF)POF4-1221 / G:(GEPRIS)452855747},
typ = {PUB:(DE-HGF)16},
pubmed = {38164803},
UT = {WOS:001134532100001},
doi = {10.1039/D3CP05089K},
url = {https://juser.fz-juelich.de/record/1025018},
}