Effect of Antagonistic Binder–Catalyst Interactions on Catalytic Activity in Lithium–Sulfur Batteries

ABSTRACT Lithium‐sulfur (Li‐S) batteries are a promising next‐generation energy storage solution, as they can reduce reliance on critical transition metals while offering high energy densities. However, their deployment is hindered by low sulfur utilization and the formation/diffusion of lithium polysulfides (LiPSs). While transition‐metal catalysts and polymeric binders have been independently developed to enhance redox kinetics and LiPS adsorption, their mutual compatibility has remained largely unexplored. We show here that binder‐catalyst interactions can significantly impact catalytic performance. Employing TiO 2 as a generic catalyst, the electrochemical performance is shown to depend strongly on the binder environment. TiO 2 paired with lithiated polyacrylic acid (LiPAA) shows benign interactions, resulting in enhanced cycle life. In contrast, pairing TiO 2 with protonated PAA produces antagonistic interactions that hinder Li 2 S growth. A mechanistic analysis unveils that the carboxylic H atom in PAA promotes COO − coordination to Ti sites, occupying catalytic centers and suppressing LiPS adsorption, increasing charge transfer and diffusion resistances. This phenomenon is observed across multiple catalysts, indicating that COOH‐functionalized binders may broadly hinder catalytic activity. Overall, this study underscores the need for holistic cathode design and identifies binder‐catalyst compatibility as an important parameter for high‐performance Li‐S batteries.