2,5‐Dimercapto‐1,3,4‐Thiadiazole (DMCT)‐Based Polymers for Rechargeable Metal–Sulfur Batteries

Abstract

Organosulfur materials are a sustainable alternative to the present‐day layered oxide cathodes in lithium‐based batteries. One such organosulfur material that was intensely explored from the 1990s to early 2010s is 2,5‐dimercapto‐1,3,4‐thiadiazole (DMCT). However, research interest declined as the electrode reactions with DMCT were assumed to be too sluggish to be practical. Armed with the advances in metal–sulfur batteries, we revisit DMCT‐based materials in the form of poly[tetrathio‐2,5‐(1,3,4‐thiadiazole)], referred to as pDMCT‐S. With an appropriate choice of electrode design and electrolyte, pDMCT‐S cathode paired with a Li‐metal anode shows a capacity of 715 mA h g−1 and a Coulombic efficiency of 97.7% at a C/10 rate, thus quelling the concerns of sluggish reactions. Surprisingly, pDMCT‐S shows significantly improved long‐term cyclability compared to a sulfur cathode. Investigations into the origin of the stability reveals that the discharge product Li‐DMCT in its mesomeric form can strongly bind to polysulfides, preventing their dissolution into the electrolyte and shuttling. This unique mechanism solves a critical problem faced by sulfur cathodes. Encouragingly, this mechanism results in a stable performance of pDMCT‐S with Na‐metal cells as well. This study opens the potential for exploring other organic materials that have inherent polysulfide sequestering capabilities, enabling long‐life metal–sulfur batteries.