TY  - JOUR
AU  - Helm, Bianca
AU  - Minafra, Nicolò
AU  - Wankmiller, Björn
AU  - Agne, Matthias T.
AU  - Li, Cheng
AU  - Senyshyn, Anatoliy
AU  - Hansen, Michael Ryan
AU  - Zeier, Wolfgang G.
TI  - Correlating Structural Disorder to $Li^+$ Ion Transport in $Li_{4–x}Ge_{1–x}Sb_xS_4$ (0 ≤ x ≤ 0.2)
JO  - Chemistry of materials
VL  - 34
IS  - 12
SN  - 0897-4756
CY  - Washington, DC
PB  - American Chemical Society
M1  - FZJ-2022-02367
SP  -  5558–5570
PY  - 2022
AB  - Strong compositional influences are known to affect the ionic transport within the thio-LISICON family, however, a deeper understanding of the resulting structure - transport correlations have up until now been lacking. Employing a combination of high-resolution neutron diffraction, impedance spectroscopy and nuclear magnetic resonance spectroscopy, together with bond valence site energy calculations and the maximum entropy method for determining the underlying Li+ scattering density distribution of a crystal structure, this work assesses the impact of the Li+ substructure and charge carrier density on the ionic transport within the Li4-xGe1-xSbxS4 substitution series. By incorporating Sb5+ into Li4GeS4, an anisometric expansion of the unit cell is observed. An additional Li+ position is found as soon as (SbS4)3− polyhedra are present, leading to a better local polyhedral connectivity and a higher disorder in the Li+ substructure. Here, we are able to relate structural disorder to an increase in configurational entropy, together with a two order-of-magnitude increase in ionic conductivity. This result reinforces the typically believed paradigm that structural disorder leads to improvements in ionic transport.
LB  - PUB:(DE-HGF)16
UR  - <Go to ISI:>//WOS:000819657500001
DO  - DOI:10.1021/acs.chemmater.2c00608
UR  - https://juser.fz-juelich.de/record/908088
ER  -