Engineering the d-Orbital Energy of Metal-Organic Frameworks-Based Solid-State Electrolytes for Lithium-Metal Batteries.
basic_science · Level V
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- Record sourced from PubMed, PMID 38295105.
- Also identified by DOI 10.1021/acs.nanolett.3c04654.
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Abstract
Having an orbital-level understanding of the relationship between the electronic state of a central metal in metal-organic frameworks (MOFs) as solid-state electrolytes (SSEs) and Li<sup>+</sup> ion conductivity is crucial <i>yet</i> challenging for lithium-metal batteries (LMBs). In this study, we report the synthesis of functionalized UiO-66 as a model system to investigate the relationship between the d-band energy of Zr 3d orbitals and Li<sup>+</sup> ion conductivity. Specifically, the NO<sub>2</sub> group in electron-withdrawing NO<sub>2</sub>-decorated UiO-66 (NO<sub>2</sub>-UiO-66) can capture electron from ZrO<sub>8</sub> sites, resulting the increased energy in 3d<sub><i>z</i><sup>2</sup></sub> and 3d<sub><i>xz</i><i>/yz</i></sub> orbitals of Zr atom. The high-energy 3d<sub><i>z</i><sup>2</sup></sub> and 3d<sub><i>xz</i><i>/yz</i></sub> orbitals of Zr in NO<sub>2</sub>-UiO-66 hybridize with the 2p<sub><i>z</i></sub> and 2p<sub><i>x/y</i></sub> orbitals of O in ClO<sub>4</sub><sup>-</sup>, leading to decreased antibonding orbital energy and resulting in a strong adsorption, ultimately immobilizing the anions and enhancing ion conductivities. Establishing the correlation between the d-orbital energy and Li<sup>+</sup> ion conductivity may create a descriptor for designing efficient SSEs for LMBs.