Reaction mechanisms for electrolytic manganese dioxide in rechargeable aqueous zinc-ion batteries

This study reports the phase transformation behaviour associated with electrolytic manganese dioxide (EMD) utilized as the positive electrode active material for aqueous zinc-ion batteries. Electrochemical techniques, including galvanostatic charge–discharge and rotating ring-disk electrode measurements, and microstructural techniques, using X-ray powder diffraction, scanning electron microscopy, and transmission/scanning transmission electron microscopy, were utilized to characterize the positive electrode at different stages of discharge and charge of zinc-ion cells. The results indicate that, during discharge, a fraction of EMD undergoes a transformation to ZnMn2O4 (spinel-type) and Zn2+ is intercalated into the tunnels of the γ- and ε-MnO2 phases, forming ZnxMnO2 (tunnel-type). When a critical concentration of Mn3+ in the intercalated ZnxMnO2 species is reached, a disproportionation/dissolution reaction is triggered leading to the formation of soluble Mn2+ and hydroxide (OH–) ions; the latter precipitates as zinc hydroxide sulfate (ZHS, Zn4(OH)6(SO4)·5H2O) by combination with the ZnSO4/H2O electrolyte. During charge, Zn2+ is reversibly deintercalated from the intergrown tunneled phases (γ-/ε-ZnxMnO2), Mn2+ is redeposited as layered chalcophanite (ZnMn3O7·3H2O), and ZHS is decomposed by protons (H+) formed during the electrochemical deposition of chalcophanite.

Hydrometallurgical Production of Electrolytic Manganese Dioxide (EMD) from Furnace Fines

The ferromanganese (FeMn) alloy is produced through the smelting-reduction of manganese ores in submerged arc furnaces. This process generates large amounts of furnace dust that is environmentally problematic for storage. Due to its fineness and high volatile content, this furnace dust cannot be recirculated through the process, either. Conventional MnO2 production requires the pre-reduction of low-grade ores at around 900 °C to convert the manganese oxides present in the ore into their respective acid-soluble forms; however, the furnace dust is a partly reduced by-product. In this study, a hydrometallurgical route is proposed to valorize the waste dust for the production of battery-grade MnO2. By using dextrin, a cheap organic reductant, the direct and complete dissolution of the manganese in the furnace dust is possible without any need for high-temperature pre-reduction. The leachate is then purified through pH adjustment followed by direct electrowinning for electrolytic manganese dioxide (EMD) production. An overall manganese recovery rate of >90% is achieved.

Mechanistic investigation of redox processes in Zn–MnO2 battery in mild aqueous electrolytes

We present a deep fundamental understanding of the electrolytic manganese dioxide cathode energy storage mechanism using a series of advanced characterization techniques.

An overview on potential hydrometallurgical processes for separation and recovery of manganese

With rapid economic progress worldwide, the search for new resources for materials has become a priority due to mineral resource depletion. Enhanced requirements for manganese alloys and compounds for several commercial applications created a desperate demand for manganese recovery technologies from primary as well as secondary resources. The future demand for manganese alloys and compounds is expected to increase. The growing need of electrolytic manganese dioxide (EMD) for different battery usage in automobile and energy sectors could create a gap in the supply and demand of manganese. There is an urgent necessity for eco-friendly and efficient technologies to boost the production of manganese from low-grade ores as well as post-consumer products. The framework of effective leaching processes and proper solvent extraction techniques for the recovery of manganese could be a novel pathway to get a clean, green and healthy environment for a sustainable future in the automotive and energy segment where this metal has a significant contribution.