Lithiated Defect Sites in Zr Metal-Organic Framework for Enhanced Sulfur Utilization in Li-S Batteries

Lithium sulfur (Li-S) battery technology is one of the most promising candidates for next-generation energy storage devices; however, it is still hindered by limited capacity yield and poor long-term stability. The complexity of these devices has hindered efforts to study electrochemical determinants of battery performance, impeding advancement of the field. Due to the ease of functionalization, metal-organic frameworks (MOFs) are unique platforms to explore such reactions, where integration of defects into the crystalline structure provides a convenient method for introducing synthetic handles. In Zr-based MOFs such as UiO-66, the engineered defect sites contain acidic protons that can be replaced with lithium ions, transforming defected MOFs into a range of materials with tunable lithium content. Our results demonstrate the capability of this facile lithiation procedure to create novel cathode additives and evaluate their influence on Li-S battery performance. By improving ionic conductivity and dispersion of sulfur species, lithiated MOFs enhance both sulfur utilization and capacity retention at a variety of cycling rates compared to the as-synthesized MOFs. Our general synthetic strategy has the potential to be applied to technologies beyond MOFs, including polymeric and inorganic materials. Ultimately, we illustrate that defected MOFs can be used to systematically control lithiation, currently unprecedented in conventional inorganic materials, and provide a window to examine heterogeneous reactions relevant to energy conversion and storage.