反键分子轨道
锂(药物)
金属
原子轨道
分子轨道
材料科学
化学物理
离子
无机化学
化学
电子
有机化学
分子
物理
医学
量子力学
内分泌学
作者
Yin Zhang,Junjie Chen,Jing Sun,Tianshou Zhao
出处
期刊:Nano Letters
[American Chemical Society]
日期:2024-01-31
卷期号:24 (6): 2033-2040
标识
DOI:10.1021/acs.nanolett.3c04654
摘要
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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