Two-Dimensional Substitution: Toward a Better Understanding of the Structure-Transport Correlations in the Li-Superionic Thio-LISICONs

Nicolò Minafra, Katharina Hogrefe, Federico Barbon, Bianca Helm, Cheng Li, H. Martin R. Wilkening, Wolfgang G. Zeier

Research output: Contribution to journalArticlepeer-review

22 Scopus citations

Abstract

A deeper understanding of the relationships among composition-structure-transport properties in inorganic solid ionic conductors is of paramount importance to develop highly conductive phases for future employment in solid-state Li-ion battery applications. To shed light on the mechanisms that regulate these relationships, in this work, we perform a "two-dimensional"substitution series in the thio-LISICON family Li4Ge1-xSnxS4-ySey. The structural modifications brought up by the elemental substitutions were investigated via Rietveld refinements against high-resolution neutron diffraction data that allowed a precise characterization of the anionic framework and lithium substructure. The analyses show that the anionic and cationic substitutions influence the polyhedral and unit cell volumes in different fashions and that the size of the polyanionic groups alone is not enough to describe lattice expansion in these materials. Moreover, we show that the lithium disorder that is crucial to achieve fast ionic mobility may be correlated to the lithium polyhedral volumes. The correlation of these structural modifications with the transport properties, investigated via electrochemical impedance spectroscopy and 7Li nuclear magnetic resonance spin-lattice relaxation measurements, shows a nonmonotonic behavior of the ionic conductivity and activation energy against the lithium polyhedral volumes, hinting to an optimal size of the conduction pathways for the ionic diffusion. Ultimately, the results obtained in this work will help to establish new guidelines for the optimization of solid electrolytes and gain a more profound understanding of the influence of the substituents on the structure and transport properties of Li-ion conductors.

Original languageEnglish
Pages (from-to)727-740
Number of pages14
JournalChemistry of Materials
Volume33
Issue number2
DOIs
StatePublished - Jan 26 2021

Funding

The research was supported by the Deutsche Forschungsgemeinschaft (DFG) under grant number ZE 1010/4-1. This research used resources at the Spallation Neutron Source (IPTS-22924.1), operated by the Oak Ridge National Laboratory. Furthermore, the authors are thankful for financial support from the FFG (Austrian Research Promotion Agency) in the frame of the competence project “safe battery”.

FundersFunder number
Deutsche ForschungsgemeinschaftZE 1010/4-1
Österreichische Forschungsförderungsgesellschaft

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