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Sodium Ion Conductivity in Superionic IL-Impregnated Metal-Organic Frameworks: Enhancing Stability Through Structural Disorder

preprint
submitted on 16.08.2019 and posted on 19.08.2019 by Vahid Nozari, Courtney Calahoo, Joshua M. Tuffnell, Philipp Adelhelm, Katrin Wondraczek, Siân E. Dutton, Thomas Bennett, Lothar Wondraczek

Metal—organic frameworks (MOFs) are intriguing host materials in composite electrolytes due to their ability for tailoring host-guest interactions by chemical tuning of the MOF backbone. Here, we introduce particularly high sodium ion conductivity into the zeolitic imidazolate framework ZIF-8 by impregnation with the sodium-salt-containing ionic liquid (IL) (Na0.1¬EMIM0.9)TFSI. We demonstrate an ionic conductivity exceeding 2×10-4 S ⋅cm-1 at room temperature, with an activation energy as low as 0.26 eV, i.e., the highest reported performance for room temperature Na+-related ion conduction in MOF-based composite electrolytes to date. Partial amorphization of the ZIF-backbone by ball-milling results in significant enhancement of the composite stability, reflecting in persistent and stable ionic conductivity during exposure to ambient air over up to 20 days. While the introduction of network disorder decelerates IL exudation and interactions with ambient contaminants, the ion conductivity is only marginally affected, decreasing linearly with decreasing crystallinity but still maintaining superionic behavior. This highlights the general importance of 3D networks of interconnected pores for efficient ion conduction in MOF/IL blends, whereas pore symmetry is a presumably less stringent condition.

Funding

H2020 ERC CoG UTOPES 681652

NanoDTC ESPSRC Grant EP/L015978/1

Royal Society University Research Fellowship UF150021

History

Email Address of Submitting Author

lothar.wondraczek@uni-jena.de

Institution

University of Jena

Country

Germany

ORCID For Submitting Author

0000-0002-0747-3076

Declaration of Conflict of Interest

The authors declare no conflict of interest.

Version Notes

Version 1.0

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