Dual-function additive enables a self-regulatory mechanism to balance cathode-anode interface demands in Zn‖MnO2 batteries.

The poor reversibility of the zinc (Zn) anodes and the irreversible deposition/dissolution of Mn2+/MnO2 significantly impede the commercialization of Zn-Mn aqueous batteries (ZMABs). In reducing the difference between the desired interfacial reaction environments of the cathode and anode, we found that they face the same problem of interference-the generation of irreversible corrosion products. Herein, we have introduced a novel self-regulatory mechanism. This mechanism involves the addition of sodium dihydrogen phosphate, which shifts from passive protection to active regulation. It effectively captures OH- ions, prevents corrosion product formation, and facilitates the in situ generation of a solid electrolyte interface (SEI) film. This modification also homogenizes Zn ion flow and improves the reversibility of Zn plating and stripping. Furthermore, a stable and slightly acidic environment has been established to stabilize the pH at the cathodic interface, mitigate corrosion product formation, and enhance the reversible deposition and dissolution of Mn2+/MnO2. With the optimal electrolyte, Zn‖Zn symmetric cells demonstrate stable operation for over 3000 hours at 1 mA cm-2, 1 mA h cm-2. Additionally, the Zn‖Cu cells maintain high reversibility after 1000 cycles, achieving an average coulombic efficiency (CE) of 99.76%. The assembled Zn‖MnO2 full cells exhibit exceptional cycling stability and rate performance. This work adopts the approach of seeking common ground and emphasizing the balance of cathode and anode interfacial requirements, which represents a new and significant insight for design of ZMABs with high reversibility and high cyclability.