One‐Pot Synthesis of High‐Capacity Sulfur Cathodes via In‐Situ Polymerization of a Porous Imine‐Based Polymer

Abstract Lithium‐ion batteries, essential for electronics and electric vehicles, predominantly use cathodes made from critical materials like cobalt. Sulfur‐based cathodes, offering a high theoretical capacity of 1675 mAh g −1 and environmental advantages due to sulfur's abundance and lower toxicity, present a more sustainable alternative. However, state‐of‐the‐art sulfur‐based electrodes do not reach the theoretical capacities, mainly because conventional electrode production relies on mixing of components into weakly coordinated slurries. Consequently, sulfur‘s mobility leads to battery degradation—an effect known as the “sulfur‐shuttle”. This study introduces a solution by developing a microporous, covalently‐bonded, imine‐based polymer network grown in situ around sulfur particles on the current collector. The polymer network (i) enables selective transport of electrolyte and Li‐ions through pores of defined size, and (ii) acts as a robust host to retain the active component of the electrode (sulfur species). The resulting cathode has superior rate performance from 0.1 C (1360 mAh g −1 ) to 3 C (807 mAh g −1 ). Demonstrating a high‐performance, sustainable sulfur cathode produced via a simple one‐pot process, our research underlines the potential of microporous polymers in addressing sulfur diffusion issues, paving the way for sulfur electrodes as viable alternatives to traditional metal‐based cathodes.