RESUMO
Carbothermal reduction of cathode materials is an effective method to selectively extract lithium carbonate, both mechanical activation and microwave heating can enhance thermal reduction of mixed electrode materials. However, the mechanism of enhanced lithium extraction has not been fully revealed. This study attempts to uncover the synergistic strengthening mechanisms of mechanical activation-microwave reduction from the aspects of material structure, dielectric properties, reduction kinetics and lithium recovery rate. Mechanical activation induces amorphization and structural defects. The enhanced dielectric properties of materials and the induced hotspots/arc plasmas are also responsible for the enhancement of the reduction reaction. The average dissociation activation energy in the activated sample is 18.0 kJ·mol-1, which is 20.3 kJ·mol-1 lower than that of unactivated sample. The model-free method reveals that the carbothermic reduction process can be divided into three stages: (I) initial stage (α < 0.4(0.6)): the activation energy gradually decreases with the formation of strong microwave acceptor-reduction products; (II) transitional stage (0.4(0.6) < α < 0.7): the increase in mass transfer resistance leads to gradual increase in activation energy. Mechanical activation shortens the transitional reaction stage; (III) later reaction stage (α > 0.7), the decrease in activation energy may be attributed to the enhanced microwave absorption and CO reduction. The model-fitting method reveals that after mechanical activation, the reaction kinetic changes from reaction-order model to Ginstling-Brounshtein diffusion model. The optimized lithium extraction process parameters were: activation 300 rpm for 1.5 h, reduction temperature 550 °C. The research results can provide theoretical support for the enhanced extraction of cathode materials.