期刊
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
卷 7, 期 5, 页码 4619-4624出版社
AMER CHEMICAL SOC
DOI: 10.1021/acssuschemeng.8b06254
关键词
Metal-organic frameworks; Sulfonate ligand; Naphthalenediimide; Lithium ion; Electrical conductivity; Ionic conductivity; Impedance spectroscopy
资金
- National Science Foundation [DMR-1809092, CHE-1660329]
- Clemson University
Lithium ion-conducting metal-organic frameworks (MOFs) are rapidly gaining interest because of their potential application as ion-permeable, robust electrode separators in rechargeable batteries, arguably the most ubiquitous portable clean energy storage devices developed to date. A novel, water-stable 2D sheet-like neutral Cu(I)-sulfonate MOF featuring pi-acidic naphthalenediimide (NDI) ligands that can simultaneously bind guest lithium ions with its carbonyl and uncoordinated sulfonate oxygen atoms and charge diffuse perchlorate anions through anion-it interaction has been constructed. While the pristine MOF pellets displayed poor intrinsic electrical conductivity (4.65 X 10(-10) S/m) at room temperature due to inadequate charge carrier density and electron delocalization pathway, upon infiltration of LiClO4, its ionic conductivity surged almost million times to 2.3 X 10(-4) S/m, and the activation energy for charge carrier transport dropped to a mere 0.167 eV. In contrast, the conductivity of Bu4NClO4-treated MOF remained practically unchanged from its original value possibly due to size exclusion and/or facile removal of large uncoordinated Bu4N+ cations, revealing the positive impact of Li+ ion infiltration and binding. Thus, this report presents a rare, if not the first, example of significant lithium ion conductivity of a neutral, practically solvent-free, not post-synthetically modified MOF and offers new strategy to develop ion-conducting sulfonate MOFs for potential battery applications.
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