Anchored Mediator Enabling Shuttle-Free Redox Mediation in Lithium-Oxygen Batteries

Redox mediators (RMs) are considered an effective countermeasure to reduce the large polarization in lithium-oxygen batteries. Nevertheless, achieving sufficient enhancement of the cyclability is limited by the trade-offs of freely mobile RMs, which are beneficial for charge transport but also trigger the shuttling phenomenon. Here, we successfully decoupled the charge-carrying redox property of RMs and shuttling phenomenon by anchoring the RMs in polymer form, where physical RM migration was replaced by charge transfer along polymer chains. Using PTMA (poly(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl methacrylate)) as a polymer model system based on the well-known RM tetramethylpiperidinyloxyl (TEMPO), it is demonstrated that PTMA can function as stationary RM, preserving the redox activity of TEMPO. The efficiency of RM-mediated Li₂ O₂ decomposition remains remarkably stable without the consumption of oxidized RMs or degradation of the lithium anode, resulting in an improved performance of the lithium-oxygen cell.