Rational Design Toward Advanced Non‐Flow Aqueous Zinc‐Bromine Systems Boosted by Alkaline‐Neutral Decoupling Electrolytes

Abstract Non‐flow aqueous zinc‐bromine batteries (AZBBs) are highly attractive owing to their lightweight construction and largely reduced cost compared with the flow ones. Yet, their development is restricted by the sluggish reaction kinetics of Br 2 /Br − , the shuttle of soluble polybromide species (Br n − , n is odd), and the poor stability of Zn‐based anode. Herein, an effective alkaline‐neutral electrolyte decoupling system is constructed to mitigate these issues, where nitrogen‐doped carbon felt with high catalytic activity to Br 2 /Br − reaction is developed for cathode, a cost‐effective cation exchange membrane (CEM) of polyethersulfone/sulfonated polyether ether ketone (PES/SPEEK‐M) that can stop Br n − is used as separator, and glucose that can inhibit dendrites is introduced as anolyte additive. The constructed flowless AZBB mainly consists of two separate redox couples, including Zn/Zn(OH) 4 2− in alkaline anolyte and Br 2 /Br − in neutral media, where non‐cations (e.g. OH − , Zn(OH) 4 2− , H 2 O, and Br n − ) can be restricted to their respective chamber by the PES/SPEEK‐M while cations can pass by. In the optimized system, good electrochemical performance is achieved, mainly including a surprising discharge voltage of 2.01 V, a high average Coulombic efficiency of 96.7%, and a good cycling life of ≈1000 cycles without obvious capacity decay at a fixed charge capacity of 2 mAh cm −2 .