Revealing the Local pH Value Changes of Acidic Aqueous Zinc Ion Batteries with a Manganese Dioxide Electrode during Cycling

The research on aqueous zinc ion batteries (AZIB) is getting more attention as the energy transition continues to develop and the need for inexpensive and safe stationary storage batteries is growing. As the detailed reaction mechanisms are not conclusively revealed, we want to take an alternative approach to investigate the importance of pH value changes during cycling. By adding a pH-indicator to the electrolyte (2 M ZnSO4 + 0.1 M MnSO4), the local pH-value change during operation is visualized in operando. The overall pH value was found to increase during cycling whereas a major temporary pH drop in close proximity of the manganese dioxide electrode surface occurs. Additionally, this pH value change was quantified locally by in operando measurements with a pH micro electrode. Different electrolyte compositions with additives (sodium dodecyl sulfate (SDS), sulfuric acid (H2SO4)) and operation voltages were tested. The pH-potential-diagrams of manganese and zinc reveal pH value and potential limits, leading to active material dissolution at lower pH values and oxygen gas evolution at higher potentials >1.7 V. The procedure of combining a pH indicator, pH microelectrode measurements and pH-potential diagrams can be seen as an appropriate method to determine the recommendable working window of aqueous batteries.