Engineering p‐Band Center of Oxygen Boosting H+ Intercalation in δ‐MnO2 for Aqueous Zinc Ion Batteries

Abstract In aqueous zinc ion batteries (ZIBs), the H+ intercalation possesses superior electrochemical kinetics with excellent rate capability, however, precisely modulating H+ intercalation has been still challenging. Herein, a critical modification of pre‐intercalating metal ions in the MnO2 interlayer (M−MnO2) with controllable p‐band center (ϵp) of O is reported to modulate the H+ intercalation. The modulation of metal‐O bond type and covalency degree on the average charge of O atom results in optimized ϵp and H+ adsorption energy for M−MnO2, thus promoting the balance between H+ adsorption and desorption, which plays a determinant role on H+ intercalation. The optimized Cu−MnO2 delivers superior rate capability with the capacity of 153 mAh g−1 at a high rate of 3 A g−1 after 1000 cycles. This work demonstrates that ϵp could be a significant descriptor for H+ intercalation, and tuning ϵp effectively increases H+ intercalation contribution with excellent rate capability in ZIBs.