Assessing Ni<sub>2</sub>(dobpdc) Anchoring for Mitigating\nLithium Polysulfide Dissolution in Lithium–Sulfur Batteries

In this work, we have explored sulfur loading, the anchoring\nability\nof lithium polysulfides (LiPSs), and the formation mechanism of a\nnet-like Li<sub>2</sub>S structure in a Ni<sub>2</sub>(dobpdc) metal–organic\nframework (MOF) using density functional theory (DFT) calculations\nand molecular dynamics (MD) simulations. The MD results reveal a net-like\nstructure of (Li<sub>2</sub>S)<sub><i>n</i></sub> covering\nthe Ni<sub>2</sub>(dobpdc) MOF surface when the S<sub>8</sub> cluster\nis transformed into short-chain LiPS molecules at a high level of\nlithiation. Further, the LiPS molecules adsorbed on the Ni<sub>2</sub>(dobpdc) MOF surface (in the presence of a solvent) have been considered.\nBased on the electron distribution analysis of the three-dimensional\nreference interaction site model (3D-RISM) results, 1,3-dioxolane\n(DOL) can hinder LiPS dissolution owing to its weak binding strength\nwith the LiPS molecules. In contrast, the ethylene carbonate (EC)\nsolvent significantly decreases the adsorption strength of the long-chain\nLiPS molecules, leading to a severe shuttling effect of the LiPSs\nin Ni<sub>2</sub>(dobpdc). Our findings indicate that the shuttling\neffect of the LiPSs is highly dependent on the dielectric constant\nof solvents, suggesting that solvents with a strong polarizability,\nsuch as EC, should be avoided. The present findings also offer comprehensive\ninsights into the impact of various solvents on LiPS adsorption in\nNi<sub>2</sub>(dobpdc), paving the way for developing innovative cathode\nmaterials for next-generation Li–S batteries.