Understanding the correlation between ionic motion and crystal structure is crucial for improving solid electrolyte conductivities. Several substitution series in the Li
GeP
S
structure have shown a ...favorable impact on the ionic conductivity,
the replacement of P(+V) by Sb(+V) in Li
GeP
S
. However, here the interplay between the structure and ionic motion remains elusive. X-Ray diffraction, high-resolution neutron diffraction, Raman spectroscopy and potentionstatic impedance spectroscopy are employed to explore the impact of Sb(+V) on the Li
GeP
S
structure. The introduction of antimony elongates the unit cell in the
-direction and increases the M(1)/P(1) and Li(2) polyhedral volume. Over the solid solution range, the Li
distribution remains similar, an inductive effect seems to be absent and the ionic conductivity is comparable for all compositions. The effect of introducing Sb(+V) in Li
GeP
S
cannot be corroborated.
Understanding the correlation between ionic motion and crystal structure is crucial for improving solid electrolyte conductivities. Several substitution series in the Li10GeP2S12 structure have shown ...a favorable impact on the ionic conductivity, e.g. the replacement of P(+V) by Sb(+V) in Li10GeP2S12. However, here the interplay between the structure and ionic motion remains elusive. X-Ray diffraction, high-resolution neutron diffraction, Raman spectroscopy and potentionstatic impedance spectroscopy are employed to explore the impact of Sb(+V) on the Li10GeP2S12 structure. The introduction of antimony elongates the unit cell in the c-direction and increases the M(1)/P(1) and Li(2) polyhedral volume. Over the solid solution range, the Li+ distribution remains similar, an inductive effect seems to be absent and the ionic conductivity is comparable for all compositions. The effect of introducing Sb(+V) in Li10GeP2S12 cannot be corroborated.
Understanding the correlation between ionic motion and crystal structure is crucial for improving solid electrolyte conductivities. Several substitution series in the Li
10
GeP
2
S
12
structure have ...shown a favorable impact on the ionic conductivity,
e.g.
the replacement of P(+V) by Sb(+V) in Li
10
GeP
2
S
12
. However, here the interplay between the structure and ionic motion remains elusive. X-Ray diffraction, high-resolution neutron diffraction, Raman spectroscopy and potentionstatic impedance spectroscopy are employed to explore the impact of Sb(+V) on the Li
10
GeP
2
S
12
structure. The introduction of antimony elongates the unit cell in the
c
-direction and increases the M(1)/P(1) and Li(2) polyhedral volume. Over the solid solution range, the Li
+
distribution remains similar, an inductive effect seems to be absent and the ionic conductivity is comparable for all compositions. The effect of introducing Sb(+V) in Li
10
GeP
2
S
12
cannot be corroborated.
Sb(+V) substitution in Li
10
GeP
2
S
12
has only a minor effect on the structure and ionic transport.
Exploration of sulfidic sodium solid electrolytes and their design contributes to advances in solid-state sodium batteries. Such a design is guided by a better understanding of fast sodium transport, ...for instance, in the herein studied Na11Sn2PS12-type materials. By using Rietveld refinements against synchrotron X-ray diffraction and electrochemical impedance spectroscopy, the influence of aliovalent substitution on the structure and transport in Na11+x Sn2P1–x M x S12 with M = Ge and Sn is investigated. Although Sn induces stronger structural changes than Ge, the influence on the sodium sublattice and the ionic transport properties is comparable. Overall, a reduced in-grain activation energy of Na+ transport can be found with the reducing Na+ vacancy concentration. This work explores previously unreported phases in the Na11Sn2PS12 structure type based on their determined properties revealing Na+ vacancy concentrations to be an important factor providing a further understanding of Na11Sn2PS12-type materials.
Sulfidic sodium ion conductors are currently investigated for the possible use in all-solid-state sodium ion batteries. The design of high-performing electrolytes in terms of temperature-dependent ...ionic transport is based upon the fundamental understanding of structure–transport relationships within the given structural phase boundaries inherent to the investigated materials class. In this work, the Na+ superionic structural family of Na11Sn2PS12 is explored by using the systematic antimony substitution with phosphorus in Na11+x Sn2+x (Sb1–y P y )1–x S12. A combination of Rietveld refinements against X-ray synchrotron diffraction data with electrochemical impedance spectroscopy is used to monitor the changes in the anionic framework, the Na+ substructure, and the ionic transport. A new simplified descriptor for the average Na+ diffusion pathways, the average Na+ polyhedral volume, is introduced, which is used to correlate the contraction of the overall lattice and the found activation barriers in the system. This study exemplifies how substitution affects diffusion pathways in ionic conductors and widens the knowledge about the related structural motifs and their influence on the ionic transport in this novel class of ionic conductors.
