Engineering the d-Orbital Energy of Metal-Organic Frameworks-Based Solid-State Electrolytes for Lithium-Metal Batteries.
Nano Lett
; 24(6): 2033-2040, 2024 Feb 14.
Article
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| MEDLINE
| ID: mdl-38295105
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+ ion conductivity is crucial yet 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+ ion conductivity. Specifically, the NO2 group in electron-withdrawing NO2-decorated UiO-66 (NO2-UiO-66) can capture electron from ZrO8 sites, resulting the increased energy in 3dz2 and 3dxz/yz orbitals of Zr atom. The high-energy 3dz2 and 3dxz/yz orbitals of Zr in NO2-UiO-66 hybridize with the 2pz and 2px/y orbitals of O in ClO4-, 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+ ion conductivity may create a descriptor for designing efficient SSEs for LMBs.
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2024
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