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@ARTICLE{Maus:1007410,
author = {Maus, Oliver and Agne, Matthias T. and Fuchs, Till and
Till, Paul S. and Wankmiller, Björn and Gerdes, Josef
Maximilian and Sharma, Rituraj and Heere, Michael and
Jalarvo, Niina and Yaffe, Omer and Hansen, Michael Ryan and
Zeier, Wolfgang G.},
title = {{O}n the {D}iscrepancy between {L}ocal and {A}verage
{S}tructure in the {F}ast ${N}a^+$ {I}onic {C}onductor
${N}a_{2.9}{S}b_{0.9}{W}_{0.1}{S}_{4}$},
journal = {Journal of the American Chemical Society},
volume = {145},
number = {13},
issn = {0002-7863},
address = {Washington, DC},
publisher = {ACS Publications},
reportid = {FZJ-2023-02065},
pages = {7147 - 7158},
year = {2023},
abstract = {Aliovalent substitution is a common strategy to improve the
ionic conductivity of solid electrolytes for solid-state
batteries. The substitution of SbS43– by WS42– in
Na2.9Sb0.9W0.1S4 leads to a very high ionic conductivity of
41 mS cm–1 at room temperature. While pristine Na3SbS4
crystallizes in a tetragonal structure, the substituted
Na2.9Sb0.9W0.1S4 crystallizes in a cubic phase at room
temperature based on its X-ray diffractogram. Here, we show
by performing pair distribution function analyses and static
single-pulse 121Sb NMR experiments that the short-range
order of Na2.9Sb0.9W0.1S4 remains tetragonal despite the
change in the Bragg diffraction pattern.
Temperature-dependent Raman spectroscopy revealed that
changed lattice dynamics due to the increased disorder in
the Na+ substructure leads to dynamic sampling causing the
discrepancy in local and average structure. While showing no
differences in the local structure, compared to pristine
Na3SbS4, quasi-elastic neutron scattering and solid-state
23Na nuclear magnetic resonance measurements revealed
drastically improved Na+ diffusivity and decreased
activation energies for Na2.9Sb0.9W0.1S4. The obtained
diffusion coefficients are in very good agreement with
theoretical values and long-range transport measured by
impedance spectroscopy. This work demonstrates the
importance of studying the local structure of ionic
conductors to fully understand their transport mechanisms, a
prerequisite for the development of faster ionic
conductors.},
cin = {IEK-12},
ddc = {540},
cid = {I:(DE-Juel1)IEK-12-20141217},
pnm = {1221 - Fundamentals and Materials (POF4-122)},
pid = {G:(DE-HGF)POF4-1221},
typ = {PUB:(DE-HGF)16},
pubmed = {36946557},
UT = {WOS:000967981500001},
doi = {10.1021/jacs.2c11803},
url = {https://juser.fz-juelich.de/record/1007410},
}