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Transferring lithium ions in the nanochannels of flexible metal-organic frameworks featuring superchaotropic metallacarborane guests: mechanism of ionic conductivity at atomic resolution
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SYSNO ASEP 0533405 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Transferring lithium ions in the nanochannels of flexible metal-organic frameworks featuring superchaotropic metallacarborane guests: mechanism of ionic conductivity at atomic resolution Author(s) Brus, Jiří (UMCH-V) RID, ORCID
Czernek, Jiří (UMCH-V) RID
Urbanová, Martina (UMCH-V) RID, ORCID
Rohlíček, Jan (FZU-D) RID, ORCID
Plecháček, T. (CZ)Source Title ACS Applied Materials and Interfaces. - : American Chemical Society - ISSN 1944-8244
Roč. 12, č. 42 (2020), s. 47447-47456Number of pages 10 s. Language eng - English Country US - United States Keywords metal-organic frameworks ; lithium metallacarborane salts ; all-solid-state electrolytes Subject RIV CD - Macromolecular Chemistry OECD category Polymer science Subject RIV - cooperation Institute of Physics - Solid Matter Physics ; Magnetism R&D Projects GA20-01233S GA ČR - Czech Science Foundation (CSF) GA18-12925S GA ČR - Czech Science Foundation (CSF) LM2018110 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) Research Infrastructure e-INFRA CZ - 90140 - CESNET, zájmové sdružení právnických osob
CERIT-SC - 90085 - Masarykova univerzita
CzechNanoLab - 90110 - Vysoké učení technické v BrněMethod of publishing Open access Institutional support UMCH-V - RVO:61389013 ; FZU-D - RVO:68378271 UT WOS 000584489800029 EID SCOPUS 85094219898 DOI 10.1021/acsami.0c12293 Annotation Metal–organic frameworks (MOFs), owing to their unique architecture, attract consistent attention in the design of high-performance Li battery materials. Here, we report a new category of ion-conducting crystalline materials for all-solid-state electrolytes based on an MIL53(Al) framework featuring a superchaotropic metallacarborane (Li+CoD–) salt and present the first quantitative data on Li+ ion sites, local dynamics, chemical exchange, and the formation of charge-transfer pathways. We used multinuclear solid-state nuclear magnetic resonance (ss-NMR) spectroscopy to examine the mechanism of ionic conductivity at atomic resolution and to elucidate order–disorder processes, framework–ion interactions, and framework breathing during the loading of Li+CoD– species and transfer of Li+ ions. In this way, the MIL53(Al)@LiCoD framework was found to adopt an open-pore conformation accompanied by a minor fraction of narrow-pore channels. The inserted Li+ ions have two states (free and bound), which both exhibit extensive motions. Both types of Li+ ions form mutually communicating chains, which are large enough to enable efficient long-range charge transfer and macroscopic conductivity. The superchaotropic anions undergo high-amplitude uniaxial rotation motions supporting the transfer of Li+ cations along them, while the fluctuations of MOF aromatic linkers support the penetration of Li+ through the channel walls. Our findings provide a detailed atomic-resolution insight into the mechanism of ionic conductivity and thus have significant implications for the design of the next generation of energy-related materials. Workplace Institute of Macromolecular Chemistry Contact Eva Čechová, cechova@imc.cas.cz ; Tel.: 296 809 358 Year of Publishing 2021 Electronic address https://pubs.acs.org/doi/10.1021/acsami.0c12293
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