Cyclodextrin Metal–Organic Framework Functionalized Carbon Materials with Optimized Interface Electronics and Selective Supramolecular Channels for High‐Performance Lithium–Sulfur Batteries

During the reaction process in lithium-sulfur batteries, Lewis acidic lithium polysulfides (LiPSs) affect ion distribution and overall electrolyte stability, degrading battery performance and product distribution (e.g., Li₂S). Here, a microenvironment regulation strategy with optimized interface electronics and selective supramolecular channels, is proposed to enhance LiPS reaction kinetics through Lewis basic γ-cyclodextrin metal-organic framework (γ-CDMOF). To validate this concept, γ-CDMOF is rapidly synthesized on 3D graphene foam (GF) via a microwave-assisted method, resulting in a γ-CDMOF/GF cathode for high-performance Li-S batteries. A range of analytical techniques combined with density functional theory (DFT) calculations confirm that introducing a Lewis basic supramolecular microenvironment mitigates the LiPSs shuttle effect, enhances polysulfide capture, and improves sulfur redox conversion. Additionally, COMSOL simulations reveal that the γ-CDMOF framework and oxygen sites significantly reduce volumetric expansion stress during the LiPS solid-liquid phase transition. Impressively, the γ-CDMOF/GF cathode exhibits exceptional performance, including a high specific capacity (1253.01 mAh g⁻¹ at 0.1C), excellent rate performance (589.68 mAh g⁻¹ at 5C), and long cycle life (over 1200 cycles). This study introduces a new concept of supramolecular microenvironment regulation and interfacial interaction strategy, offering a unique approach for the development of multifunctional electrode materials.