Impact of the metal centre (Al 3+ , Fe 3+ ) on the post-synthetic lithiation of functionalized MIL-53s and the electrochemical properties of lithiated derivatives - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Molecular Systems Design & Engineering Année : 2023

Impact of the metal centre (Al 3+ , Fe 3+ ) on the post-synthetic lithiation of functionalized MIL-53s and the electrochemical properties of lithiated derivatives

Résumé

Metal-organic frameworks (MOFs) combining both organic and inorganic redox-active moieties have recently drawn interest in the field of electrochemical energy storage. Here we focused our attention on MIL-53(M) (M = Al, Fe) analogues based on 2,5-dioxo-1,4-benzenedicarboxylate, as this ligand was already found to present an interesting electrochemical activity based on the quinone/phenolate redox couple in the solid state. We described here our attempts to chemically lithiate the title solids. Various synthetic paths were explored, and the resulting solids were characterized by a broad set of techniques, including X-ray diffraction, MAS NMR spectroscopy, transmission electron microscopy, inductively coupled plasma-atomic emission spectroscopy and total X-ray scattering experiments, among others. We showed that although the lithiation was accompanied by a loss of the long-range order whatever the synthetic conditions and the trivalent cation, the reactivity strongly differed for M = Al and Fe. Eventually, the electrochemical extraction/uptake of Li+ in the lithiated derivatives was evaluated in Li-half cells. Although their storage capacities are moderate, we found that the presence of even a minor amount of M3+ cations not only impacts the working potential of the ligand but also improves their long term capacity retention.
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hal-04085374 , version 1 (13-06-2023)

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Morgane Denis, Hubert Chevreau, Pablo Salcedo-Abraira, Philippe Moreau, Nicolas Dupré, et al.. Impact of the metal centre (Al 3+ , Fe 3+ ) on the post-synthetic lithiation of functionalized MIL-53s and the electrochemical properties of lithiated derivatives. Molecular Systems Design & Engineering, 2023, 8 (8), pp.1030. ⟨10.1039/d3me00030c⟩. ⟨hal-04085374⟩
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