Journal of the American Chemical Society, volume 144, issue 4, pages 1795-1812
Opening Diffusion Pathways through Site Disorder: The Interplay of Local Structure and Ion Dynamics in the Solid Electrolyte Li6+xP1–xGexS5I as Probed by Neutron Diffraction and NMR
Katharina Hogrefe
1
,
Nicoló Minafra
2
,
Isabel Hanghofer
1
,
Ananya Banik
2
,
Wolfgang G. Zeier
2, 3
,
Martin Wilkening
1
Publication type: Journal Article
Publication date: 2022-01-20
Quartile SCImago
Q1
Quartile WOS
Q1
Impact factor: 15
ISSN: 00027863, 15205126
General Chemistry
Catalysis
Biochemistry
Colloid and Surface Chemistry
Abstract
Solid electrolytes are at the heart of future energy storage systems. Li-bearing argyrodites are frontrunners in terms of Li+ ion conductivity. Although many studies have investigated the effect of elemental substitution on ionic conductivity, we still do not fully understand the various origins leading to improved ion dynamics. Here, Li6+xP1-xGexS5I served as an application-oriented model system to study the effect of cation substitution (P5+ vs Ge4+) on Li+ ion dynamics. While Li6PS5I is a rather poor ionic conductor (10-6 S cm-1, 298 K), the Ge-containing samples show specific conductivities on the order of 10-2 S cm-1 (330 K). Replacing P5+ with Ge4+ not only causes S2-/I- anion site disorder but also reveals via neutron diffraction that the Li+ ions do occupy several originally empty sites between the Li rich cages in the argyrodite framework. Here, we used 7Li and 31P NMR to show that this Li+ site disorder has a tremendous effect on both local ion dynamics and long-range Li+ transport. For the Ge-rich samples, NMR revealed several new Li+ exchange processes, which are to be characterized by rather low activation barriers (0.1-0.3 eV). Consequently, in samples with high Ge-contents, the Li+ ions have access to an interconnected network of pathways allowing for rapid exchange processes between the Li cages. By (i) relating the changes of the crystal structure and (ii) measuring the dynamic features as a function of length scale, we were able to rationalize the microscopic origins of fast, long-range ion transport in this class of electrolytes.
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1 publication, 2.04%
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- We do not take into account publications without a DOI.
- Statistics recalculated only for publications connected to researchers, organizations and labs registered on the platform.
- Statistics recalculated weekly.
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Hogrefe K. et al. Opening Diffusion Pathways through Site Disorder: The Interplay of Local Structure and Ion Dynamics in the Solid Electrolyte Li6+xP1–xGexS5I as Probed by Neutron Diffraction and NMR // Journal of the American Chemical Society. 2022. Vol. 144. No. 4. pp. 1795-1812.
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Hogrefe K., Minafra N., Hanghofer I., Banik A., Zeier W. G., Wilkening M. Opening Diffusion Pathways through Site Disorder: The Interplay of Local Structure and Ion Dynamics in the Solid Electrolyte Li6+xP1–xGexS5I as Probed by Neutron Diffraction and NMR // Journal of the American Chemical Society. 2022. Vol. 144. No. 4. pp. 1795-1812.
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TY - JOUR
DO - 10.1021/jacs.1c11571
UR - https://doi.org/10.1021/jacs.1c11571
TI - Opening Diffusion Pathways through Site Disorder: The Interplay of Local Structure and Ion Dynamics in the Solid Electrolyte Li6+xP1–xGexS5I as Probed by Neutron Diffraction and NMR
T2 - Journal of the American Chemical Society
AU - Minafra, Nicoló
AU - Hanghofer, Isabel
AU - Banik, Ananya
AU - Hogrefe, Katharina
AU - Zeier, Wolfgang G.
AU - Wilkening, Martin
PY - 2022
DA - 2022/01/20 00:00:00
PB - American Chemical Society (ACS)
SP - 1795-1812
IS - 4
VL - 144
SN - 0002-7863
SN - 1520-5126
ER -
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@article{2022_Hogrefe,
author = {Nicoló Minafra and Isabel Hanghofer and Ananya Banik and Katharina Hogrefe and Wolfgang G. Zeier and Martin Wilkening},
title = {Opening Diffusion Pathways through Site Disorder: The Interplay of Local Structure and Ion Dynamics in the Solid Electrolyte Li6+xP1–xGexS5I as Probed by Neutron Diffraction and NMR},
journal = {Journal of the American Chemical Society},
year = {2022},
volume = {144},
publisher = {American Chemical Society (ACS)},
month = {jan},
url = {https://doi.org/10.1021/jacs.1c11571},
number = {4},
pages = {1795--1812},
doi = {10.1021/jacs.1c11571}
}
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Hogrefe, Katharina, et al. “Opening Diffusion Pathways through Site Disorder: The Interplay of Local Structure and Ion Dynamics in the Solid Electrolyte Li6+xP1–xGexS5I as Probed by Neutron Diffraction and NMR.” Journal of the American Chemical Society, vol. 144, no. 4, Jan. 2022, pp. 1795-1812. https://doi.org/10.1021/jacs.1c11571.