Optimizing ionic transport in argyrodites: a unified view on the role of sulfur/halide distribution and local environments.

Autor: Lavrinenko AK; Storage of Electrochemical Energy, Department of Radiation Science and Technology, Faculty of Applied Sciences, Delft University of Technology Mekelweg 15 2629JB Delft The Netherlands m.wagemaker@tudelft.nl a.vasileiadis@tudelft.nl., Famprikis T; Storage of Electrochemical Energy, Department of Radiation Science and Technology, Faculty of Applied Sciences, Delft University of Technology Mekelweg 15 2629JB Delft The Netherlands m.wagemaker@tudelft.nl a.vasileiadis@tudelft.nl., Quirk JA; Chemistry - School of Natural and Environmental Sciences, Newcastle University Newcastle upon Tyne NE1 7RU UK., Landgraf V; Storage of Electrochemical Energy, Department of Radiation Science and Technology, Faculty of Applied Sciences, Delft University of Technology Mekelweg 15 2629JB Delft The Netherlands m.wagemaker@tudelft.nl a.vasileiadis@tudelft.nl., Groszewicz PB; Storage of Electrochemical Energy, Department of Radiation Science and Technology, Faculty of Applied Sciences, Delft University of Technology Mekelweg 15 2629JB Delft The Netherlands m.wagemaker@tudelft.nl a.vasileiadis@tudelft.nl.; Helmholtz Zentrum Berlin für Materialien und Energie Hahn-Meitner-Platz 1 14109 Berlin Germany., Heringa JR; Storage of Electrochemical Energy, Department of Radiation Science and Technology, Faculty of Applied Sciences, Delft University of Technology Mekelweg 15 2629JB Delft The Netherlands m.wagemaker@tudelft.nl a.vasileiadis@tudelft.nl., Smeets S; Netherlands eScience Center Science Park 402 1098 XH Amsterdam The Netherlands., Azizi V; Netherlands eScience Center Science Park 402 1098 XH Amsterdam The Netherlands., Ciarella S; Netherlands eScience Center Science Park 402 1098 XH Amsterdam The Netherlands., Dawson JA; Chemistry - School of Natural and Environmental Sciences, Newcastle University Newcastle upon Tyne NE1 7RU UK., Wagemaker M; Storage of Electrochemical Energy, Department of Radiation Science and Technology, Faculty of Applied Sciences, Delft University of Technology Mekelweg 15 2629JB Delft The Netherlands m.wagemaker@tudelft.nl a.vasileiadis@tudelft.nl., Vasileiadis A; Storage of Electrochemical Energy, Department of Radiation Science and Technology, Faculty of Applied Sciences, Delft University of Technology Mekelweg 15 2629JB Delft The Netherlands m.wagemaker@tudelft.nl a.vasileiadis@tudelft.nl.
Jazyk: angličtina
Zdroj: Journal of materials chemistry. A [J Mater Chem A Mater] 2024 Sep 09; Vol. 12 (39), pp. 26596-26611. Date of Electronic Publication: 2024 Sep 09 (Print Publication: 2024).
DOI: 10.1039/d4ta04628e
Abstrakt: Understanding diffusion mechanisms in solid electrolytes is crucial for advancing solid-state battery technologies. This study investigates the role of structural disorder in Li 7- x PS 6- x Br x argyrodites using ab initio molecular dynamics, focusing on the correlation between key structural descriptors and Li-ion conductivity. Commonly suggested parameters, such as configurational entropy, bromide site occupancy, and bromine content, correlate with Li-ion diffusivity but do not consistently explain conductivity trends. We find that a uniform distribution of bromine and sulfur ions across the 4a and 4d sublattices is critical for achieving high conductivity by facilitating optimal lithium jump activation energies, anion-lithium distances, and charge distribution. Additionally, we introduce the ionic potential as a simple descriptor that predicts argyrodite conductivity by assessing the interaction strength between cations and anions. By analyzing the correlation between ionic potential and conductivity for a range of argyrodite compositions published over the past decade, we demonstrate its broad applicability. Minimizing and equalizing ionic potentials across both sublattices enhances conductivity by reducing the strength of anion-lithium interactions. Our analysis of local environments coordinating Li jumps reveals that balancing high and low-energy pathways is crucial for enabling macroscopic diffusion, supported by investigating percolating pathways. This study highlights the significance of the anionic framework in lithium mobility and informs the design of solid electrolytes for improved energy storage systems.
Competing Interests: There are no conflicts to declare.
(This journal is © The Royal Society of Chemistry.)
Databáze: MEDLINE
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