Issue 8, 2023

Impact of the metal centre (Al3+, Fe3+) on the post-synthetic lithiation of functionalized MIL-53s and the electrochemical properties of lithiated derivatives

Abstract

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.

Graphical abstract: Impact of the metal centre (Al3+, Fe3+) on the post-synthetic lithiation of functionalized MIL-53s and the electrochemical properties of lithiated derivatives

Supplementary files

Article information

Article type
Paper
Submitted
20 Feb 2023
Accepted
08 Mar 2023
First published
09 Mar 2023

Mol. Syst. Des. Eng., 2023,8, 1030-1039

Impact of the metal centre (Al3+, Fe3+) on the post-synthetic lithiation of functionalized MIL-53s and the electrochemical properties of lithiated derivatives

M. Denis, H. Chevreau, P. Salcedo-Abraira, P. Moreau, N. Dupré, M. Paris, P. Poizot and T. Devic, Mol. Syst. Des. Eng., 2023, 8, 1030 DOI: 10.1039/D3ME00030C

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