Bromine-based flow batteries receive wide attention in large-scale energy storage because of their attractive features, such as high energy density and low cost. However, the Br diffusion and relatively low activity of Br /Br hinder their further application. Herein, a cage-like porous carbon (CPC) with specific pore structure combining superhigh activity and Br -complex-entrapping capability is designed and fabricated. According to the results of density functional theory (DFT) calculation, the pore size of the CPC (1.1 nm) is well designed between the size of Br (4.83 Å), MEP (9.25 Å), and Br complex (MEPBr 12.40 Å), wherein Br is oxidized to Br , which forms a Br complex with the complexing agent immediately and is then entrapped in the cage via pore size exclusion. In addition, the active sites produced during the carbon dioxide activation process dramatically accelerate the reaction rate of Br /Br . In this way, combining a high Br -entrapping-capability and high specific surface areas, the CPC shows very impressive performance. The zinc bromine flow battery assembled with the prepared CPC shows a Coulombic efficiency of 98% and an energy efficiency of 81% at the current density of 80 mA cm , which are among the highest values ever reported.

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