pH buffer KH2PO4 boosts zinc ion battery performance via facilitating proton reaction of MnO2 cathode

Zinc-ion batteries (ZIBs) are rapidly emerging as safe, cost-effective, nontoxic, and environmentally friendly energy storage systems. However, mildly acidic electrolytes with depleted protons cannot satisfy the huge demand for proton reactions in MnO2 electrodes and also cause several issues in ZIBs, such as rapidly decaying cycling stability and low reaction kinetics. Herein, we propose a pH-buffering strategy in which KH2PO4 is added to the electrolyte to overcome the problems caused by low proton concentrations. This strategy significantly improves the rate and cycle stability performance of zinc-manganese batteries, delivering a high capacity of 122.5 mAh/g at a high current density of 5 A/g and enabling 9000 cycles at this current density, with a remaining capacity of 70 mAh/g. Ex-situ X-ray diffraction and scanning electron microscopy analyses confirmed the generation/dissolution of Zn3PO4·4H2O and Zn4(OH)6(SO4)·5H2O, byproducts of buffer products and proton reactions. In-situ pH measurements and chemical titration revealed that the pH change during the electrochemical process can be adjusted to a low range of 2.2-2.8, and the phosphate distribution varies with the pH range. Those results reveal that H2PO4- provides protons to the cathode through the chemical balance of HPO42-, HPO42-, and Zn3PO4·4H2O. This study serves as a guide for studying the influences and mechanisms of buffering additives in Zn-MnO2 batteries.