End-of-life Zn–MnO₂ batteries: electrode materials characterization

Abstract

Physical and chemical characterization of several sizes and shapes of alkaline and saline spent Zn–MnO₂ batteries was carried out, aiming at contributing for a better definition of the applicable recycling processes. The characterization essays included the mass balance of the components, cathode and anode elemental analysis, the identification of zinc and manganese bearing phases and the morphology analysis of the electrode particles. The electrode materials correspond to 64–79% of the total weigh of the batteries, with the cathodes having clearly the highest contribution (usually more than 50%). The steel components, mainly from the cases, are also important (17–30%). Elemental analysis showed that the electrodes are highly concentrated in zinc (from 48–87% in anodes) and manganese (from 35–50% in cathodes). X-Ray powder diffraction allowed for identifying several phases in the electrodes, namely zinc oxide, in the anodes of all the types of saline and alkaline batteries tested, while zinc hydroxide chloride and ammine zinc chloride only appear in some types of saline batteries. The manganese found in the cathode materials is present as two main phases, MnO·Mn₂O₃ and ZnO·Mn₂O₃, the latter corroborating that zinc migration from anode to cathode occurs during the batteries lifespan. A unreacted MnO₂ phase was also found presenting a low crystalline level. Leaching trials with diluted HCl solutions of alkaline and saline battery samples showed that all zinc species are reactive attaining easily over than 90% leaching yields, and about 30% of manganese, present as Mn(ii/iii) forms. The MnO₂ phase is less reactive and requires higher temperatures to achieve a more efficient solubilization.

Keywords:

• Spent Zn–MnO₂ batteries
• recycling
• electrode materials
• characterization
• leaching

Acknowledgements

Financial support made by Fundação para a Ciência e Tecnologia – Project POCTI/CTA/46315/2002 and PTDC/AMB/66921/2006, is greatly acknowledged by the authors.