Proton Self‐Limiting Effect of Solid Acids Boosts Electrochemical Performance of Zinc‐ion Batteries

Abstract At present, aqueous rechargeable Zn–MnO 2 batteries have attracted widespread attention as green potential application for renewable energy storage devices. MnO 2 cathode has great potential for application, but its proton reaction results in side reactions of cathode, electrolyte consumption, and dramatic pH value changes, suffering from capacity degradation. To address the issues caused by proton deficit, a proton–limited domain strategy is proposed by integrating solid acids (Sulfonic acid type polystyrene–divinylbenzene, SATP) with proton exchange reactions into MnO 2 . SATP can act as a new proton source increasing the amount of H + and reducing the generation of zinc hydroxide sulfate, by–product of proton at the cathode interface, via proton exchange reactions of ‐HSO 3 – group. As a result, Zn–MnO 2 /SATP battery delivered with excellent rate performance (218.4 mAh g –1 at 2 A g –1 ) and high cycling stability (the retained capacity of 115.8 mAh g –1 after 500 cycles at a current density of 1 A g –1 . This work provides an innovative strategy for high performance aqueous Zn–MnO 2 batteries.