A Bimetallic Organic Framework with Mn in MIL-101(Cr) for Lithium-Sulfur Batteries

Lithium-sulfur batteries (LSBs) show excellent performance in terms of specific capacity and energy density. However, the cyclic stability of LSBs is compromised due to the "shuttle effect", which hinders the practical applications of LSBs. Herein, a metal-organic framework (MOF) based on Cr ions as the main body composition, commonly known as MIL-101(Cr), was utilized to minimize the shuttle effect and improve the cyclic performance of LSBs. To obtain MOFs with a certain adsorption capacity for lithium polysulfide and a certain catalytic capacity, we propose an effective strategy of incorporating sulfur-loving metal ions (Mn) into the skeleton to enhance the reaction kinetics at the electrode. Based on the oxidation doping method, Mn²⁺ was uniformly dispersed in MIL-101(Cr) to produce bimetallic Cr₂O₃/MnO_x as a novel sulfur-carrying cathode material. Then, a sulfur injection process was carried out by melt diffusion to obtain the sulfur-containing Cr₂O₃/MnO_x-S electrode. Moreover, an LSB assembled with Cr₂O₃/MnO_x-S showed improved first-cycle discharge (1285 mAh·g^-1 at 0.1 C) and cyclic performance (721 mAh·g^-1 at 0.1 C after 100 cycles), and the overall performance was much better than that of monometallic MIL-101(Cr) as a sulfur carrier. These results revealed that the physical immobilization method of MIL-101(Cr) positively affected the adsorption of polysulfides, while the bimetallic composite Cr₂O₃/MnO_x formed by the doping of sulfur-loving Mn²⁺ into the porous MOF produced a good catalytic effect during LSB charging. This research provides a novel approach for preparing efficient sulfur-containing materials for LSBs.