Lithium-sulfur (Li-S) batteries have emerged as a strong candidate to meet growing energy storage demands, boasting a five-fold increase in maximum capacity and significantly less expensive active materials than current Li-ion battery technology. Despite these advantages, Li-S systems suffer from dissolution of polysulfides formed in battery cycling that results in an irreversible capacity decay, poor cyclability, and safety concerns over the device lifetime. Lithium thiophosphates (Li<sub>3</sub>PS<sub>4</sub> and its derivatives) are able to reversibly bind polysulfides and exhibit high room-temperature ion conductivity, boding well for Li-S systems, but are limited in the solid state by poor stability and low surface area. To combat these issues and boost cycling performance, we incorporate lithium thiophosphates within metal-organic frameworks (MOFs). Using a family of zirconium MOFs, we successfully demonstrate chemical incorporation of thiophosphate moieties and their ability to enhance polysulfide encapsulation, improving electrochemical cyclability. Furthermore, the characteristic features of the thiophosphate are identifiable via NMR, XPS, and Raman spectroscopies, and impart a detailed understanding of phosphorous, Li-S, and MOF chemistries at play. Our combined characterization efforts provide evidence of the first sulfide guest molecule bound to the metal node, opening the door for a new area of post-synthetic modification in Zr MOFs. This study offers a unique interdisciplinary approach, spanning across previously discrete areas of inorganic chemistry and materials science to explore polysulfide, inorganic phosphate, and Li-ion chemistries in MOFs with promising implications for future studies in next generation batteries and solid electrolyte materials.

Metal-organic frameworks as a multidisciplinary platform to improve performance, safety, and fundamental understanding in lithium-sulfur batteries

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.