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 ZnSO 4 + 0.1 M MnSO 4 ), 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 (H 2 SO 4 )) 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.
The reaction mechanisms (RM) during cycling of aqueous rechargeable Zn//MnO2 batteries (ARZIBs) are still controversially discussed. The present study of different acidic electrolyte compositions (0.9 mM H2SO4, 0.5 M MnSO4, 2 M ZnSO4, 2 M ZnSO4+0.5 M MnSO4) and their pH behaviour is therefore designed as an alternative approach to investigate the RM. In operando pH tracking during cycling shows periodic pH changes for each electrolyte, highlighting the role of the pH‐relevant ions OH− and H+ in the chemical processes, the major influence of MnO2 deposition/dissolution mechanisms and the buffering behaviour of the zinc hydroxide sulphate (ZHS) precipitation. Innovative coupled cyclic voltammetry (CV) and pH measurements can link CV redox peaks to a pH change and a corresponding chemical reaction. It was found that a Zn2+ (de‐)intercalation has little or no influence on the capacity. The cycling of the SO42−‐free electrolyte 2 M Zn(CF3SO3)2 underlines the pH‐dependant behaviour of the chemical processes. The results can contribute to the debate of RMs in ARZIBs and other aqueous battery chemistries by introducing a novel measurement technique.
Aqueous zinc ion batteries are considered to be one of the most promising battery types for stationary energy storage applications. Due to their aqueous electrolyte, they are inherently safe concerning flammability and environmentally friendly. In this work, the strong influence of the particle size of manganese sesquioxide on the performance of the battery is investigated. Ball milling was used to decrease the particle diameter. The resulting powders were used as active material for the cathodes, which were assembled in coin cells as full cells together with zinc foil anodes and aqueous electrolyte. It was shown that about one third of the original particle size can nearly triple the initial capacity when charged with constant current and constant end-of-charge voltage. Additionally, smaller particles were found to be responsible for the collapse of capacity at high current densities. By means of electrochemical impedance spectroscopy, it was shown that particle size also has a large impact on the internal resistance. Initially, the internal resistance of the cells with small particles was about half that of those with big particles, but became larger during cycling. This reveals accelerated aging processes when the reactive surface of the active material is increased by smaller particles.
Considering the literature for aqueous rechargeable Zn//MnO2 batteries with acidic electrolytes using the doctor blade coating of the active material (AM), carbon black (CB), and binder polymer (BP) for the positive electrode fabrication, different binder types with (non-)aqueous solvents were introduced so far. Furthermore, in most of the cases, relatively high passive material (CB+BP) shares ~30 wt% were applied. The first part of this work focuses on different selected BPs: polyacrylonitrile (PAN), carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR), cellulose acetate (CA), and nitrile butadiene rubber (NBR). They were used together with (non-)aqueous solvents: DI-water, methyl ethyl ketone (MEK), and dimethyl sulfoxide (DMSO). By performing mechanical, electrochemical and optical characterizations, a better overall performance of the BPs using aqueous solvents was found in aqueous 2 M ZnSO4 + 0.1 M MnSO4 electrolyte (i.e., BP LA133: 150 mAh·g−1 and 189 mWh·g−1 @ 160 mA·g−1). The second part focuses on the mixing ratio of the electrode components, aiming at the decrease of the commonly used passive material share of ~30 wt% for an industrial-oriented electrode fabrication, while still maintaining the electrochemical performance. Here, the absolute CB share and the CB/BP ratio are found to be important parameters for an application-oriented electrode fabrication (i.e., high energy/power applications).
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