Organic Chemistry

Lithium-Conducting Self-Assembled Organic Nanotubes

Abstract

Supramolecular polymers are compelling platforms for the design of stimuli-responsive materials with emergent functions. Here, we report the assembly of an amphiphilic nanotube for Li-ion conduction that exhibits high ionic conductivity, mechanical integrity, electrochemical stability, and solution processability. Imine condensation of a pyridine-containing diamine with a triethylene glycol functionalized isophthalaldehyde yields pore-functionalized macrocycles. Atomic force microscopy, scanning electron microscopy, and in solvo X-ray diffraction reveal that macrocycle protonation under their mild synthetic conditions drives assembly into high-aspect ratio (>103) nanotubes with three interior triethylene glycol groups. Electrochemical impedance spectroscopy demonstrates that lithiated nanotubes are efficient Li+ conductors, with an activation energy of 0.42 eV and a peak room temperature conductivity of 3.91 × 10-5 S cm-1. 7Li NMR and Raman spectroscopy demonstrate that lithiation occurs exclusively within the nanotube interior and implicates the glycol groups in facilitating efficient Li+ transduction. Linear sweep voltammetry and galvanostatic lithium plating-stripping tests reveal that this nanotube-based electrolyte is stable over a wide potential range and supports long-term cyclability. These findings demonstrate how coupling synthetic design and supramolecular structural control can yield high-performance ionic transporters that are amenable to device relevant fabrication. More broadly, these results demonstrate the technological potential of chemically designed self-assembled nanotubes.

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Supplementary material

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Strauss2021 Nanotubes Lithium Conductivity ChemRxiv SI
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Strauss2021 Nanotubes Lithium Conductivity ChemRxiv TOC