Redox-Active Supramolecular Polymer Binders for Lithium-Sulfur Batteries That Adapt Their Transport Properties in Operando

π-Stacked perylene bisimide (PBI) molecules are implemented here as highly networked, redox-active supramolecular polymer binders in sulfur cathodes for lightweight and energy-dense Li-S batteries. We show that the in operando reduction and lithiation of these PBI binders sustainably reduces Li-S cell impedance relative to nonredox active conventional polymer binders. This lower impedance enables high-rate cycling in Li-S cells with excellent durability, a critical step toward unlocking the full potential of Li-S batteries for electric vehicles and aviation.