Two-dimensional square metal organic framework as promising cathode material for lithium-sulfur battery with high theoretical energy density

Lithium-sulfur (Li-S) batteries are considered as new generation of energy storage which offer cost-effectiveness and high energy density. However, their commercialization is restricted due to a host of challenges associated with the cathode material which usually contains sulfur with several drawbacks, including a low electronic conductivity of sulfur, the 'shuttle effect', and a large volume expansion during discharge. Herein, a novel two-dimensional porphyrin-like square metal organic framework (MOF) was explored as a promising cathode material using first principles density function theory (DFT) assisted by genetic global search. The DFT results show that, among 7 kinds of transition-metal organic framework (TM-MOF), only V-MOF and Ru-MOF is found to possess considerable chemical interactions with S8 and lithium polysulfides (LiPSs) in both vacuum and in electrolytic solvents, demonstrating distinguishable anchoring performance. The genetic global search and further DFT calculations indicate that the lithiation process on V-MOF exhibited a nearly constant open-circuit voltage of about 1.92 V to 1.95 V, and the theoretical energy density could reach up to 1469 Wh kg-1 when lithiation of S8 is considered on both sides of the substrate. The volume expansion of V-MOF during discharge is found to be about 34%, much smaller than 80% for solid sulfur. The band structure and density of states of V-MOF suggest metallic properties or a small band gap for bare surface or during the lithiation process. These results indicate that two-dimensional (2D) V-MOFs can serve as high-performance cathode material with distinguished anchoring performance to block polysulfide dissolution and thereby reduce the 'shuttle effect', and help attain ultra-high energy density. Our work points the way for designing and providing experimental realization of 2D layered materials applied in cathode with high energy density and stability.