Lithium-Conducting Self-Assembled Organic Nanotubes
Year: 2021
Type: article
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.
DOI: 10.1021/jacs.1c08058
Institutions: Northwestern University, Seoul National University
Language: English
Subfield: Electrical and Electronic Engineering
Field: Engineering
Domain: Physical Sciences
Open Access status: green
Funders: National Science Foundation, U.S. Department of Energy, W. M. Keck Foundation, Northwestern University, National Research Foundation, Seoul National University, National Research Foundation of Korea, Office of Science, Materials Research Science and Engineering Center, Harvard University, Multidisciplinary University Research Initiative, International Institute for Nanotechnology, Northwestern University, Institute of Engineering Research, Seoul National University, National Cancer Institute, Division of Materials Research, Division of Graduate Education, Division of Electrical, Communications and Cyber Systems, Division of Chemistry, Army Research Office, Argonne National Laboratory
Awards: G1169090945, G1276186940, G1284175734, G1382277591, G1541189025, G2287885168, Graduate Research Fellowship Program (GRFP), G336680401, G3454132534, G3585770253, Upgrade of 400 MHz NMR Capabilities for Research, Education and Outreach, G4001230836, G4285583887, G4289625387, G4372147948, G4552929543, G4566764134, G4573007502, G4655342999, MRSEC: Center for Multifunctional Materials, G4912152698, G5218300437, G5385673730, G5410075560, NNCI: Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource, G6350795925, G661627239, G6627702815, G6851001538, G6895186206, G7452299184, G7461832402, Graduate Research Fellowship Program (GRFP), G7792979783, G8073314406, G8230932042
OpenAlex ID: W3164784919