RESUMEN
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 x Mn2O3 and ZnO x 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 HCI 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.
Asunto(s)
Equipos y Suministros Eléctricos , Compuestos de Manganeso/química , Reciclaje/métodos , Compuestos de Zinc/química , Electrodos , Ácido Clorhídrico , Concentración de Iones de Hidrógeno , Manganeso/análisis , Manganeso/química , Cloruro de Sodio/química , Difracción de Rayos X , Zinc/análisis , Zinc/químicaRESUMEN
At the end of their life, Ni-Cd batteries cause a number of environmental problems because of the heavy metals they contain. Because of this, recycling of Ni-Cd batteries has been carried out by dedicated companies using, normally, pyrometallurgical technologies. As an alternative, hydrometallurgical processes have been developed based on leaching operations using several types of leachants. The effect of factors like temperature, acid concentration, reaction time, stirring speed and grinding of material on the leaching yields of metals contained in anodic and cathodic materials (nickel, cadmium and cobalt) using sulphuric acid, is herein explained based on the structural composition of the electrode materials. The nickel, cobalt and cadmium hydroxide phases, even with a small reaction time (less than 15 minutes) and low temperature (50 degrees C) and acid concentration (1.1 M H2SO4), were efficiently leached. However, leaching of the nickel metallic phase was more difficult, requiring higher values of temperature, acid concentration and reaction time (e.g. 85 degrees C, 1.1 M H2SO4 and 5 h, respectively) in order to obtain a good leaching efficiency for anodic and cathodic materials (70% and 93% respectively). The stirring speed was not significant, whereas the grinding of electrode materials seems to promote the compaction of particles, which appears to be critical in the leaching of Ni degrees. These results allowed the identification and understanding of the relationship between the structural composition of electrode materials and the most important factors that affect the H2SO4 leaching of spent Ni-Cd battery electrodes, in order to obtain better metal-recovery efficiency.
Asunto(s)
Metalurgia/métodos , Metales Pesados/aislamiento & purificación , Reciclaje/métodos , Ácidos Sulfúricos/química , Electrodos , TemperaturaRESUMEN
The present work aimed at the chemical and physical characterization of spent sealed MONO-type Ni-Cd batteries, contributing to a better definition of the recycling process of these spent products. The electrode material containing essentially nickel, cadmium and some cobalt corresponds to approximately 49% of the weight of the batteries. The remaining components are the steel parts from the external case and the supporting grids (40%) containing Fe and Ni, the electrolyte (9%) and the plastic components (2%). Elemental quantitative analysis showed that the electrodes are highly concentrated in metals. The phase identification achieved by X-ray powder diffraction combined with chemical analysis and leaching tests allowed the authors to proceed with the composition of the electrode materials as following: cathode: 28.7% metallic Ni, 53.3% Ni(OH)2, 6.8% Cd(OH)2 and 2.8% Co(OH)2; anode: 39.4% metallic Ni and 57.0% Cd(OH)2. The morphology of the electrodes was studied by microscopic techniques and two phases were observed in the electrodes: (1) a bright metallic phase constituted of small nickel grains that acts as conductor, and (2) the main hydroxide phase of the active electrodes into which the nickel grains are dispersed. The disaggregation of the electrode particles from the supporting plates was easily obtained during the dismantling procedures, indicating that a substantial percentage of the electrodes can be efficiently separated by wet sieving after shredding the spent batteries.