Control of Interface Migration in Nonequilibrium Crystallization of Li₂SiO₃ from Li₂O-SiO₂ Melt by Spatiotemporal...

During liquid-solid transformation, bulk mass and thermal diffusion, along with the evolved interfacial latent heat, work in tandem to generate interfacial thermodynamic and kinetic forces, the interplay of which decides the solidification velocity and consequently the solidified phase attributes. Hence, access to interface dynamics information in dependence of bulk transfer processes is pivotal to tailor the desired quantity of solid phases of unique compositions. It finds particular application for engineering concentrated Lithium (Li) phases out of Li-ion battery slags, thus generating a high value-added product from a conventional waste process stream. However, considerable challenge exists to predict the impact of the diverse external cooling rates on the evolving internal transfer processes and thus tuning solidification routes for achieving phases of interest. Hence, in this work, a thermodynamically consistent nonequilibrium model, by considering spatiotemporal temperature and concentration fields, is developed and applied to study solidification of Li₂SiO₃ from a Li₂O-SiO₂ melt that constitutes an important subsystem of the Li containing battery-recycling slags. The approach treats the sharp solid/liquid interface as a moving heat source. In the presence of different heat extraction profiles, it evaluates the spatial temperature heterogeneity and its implicit correlation to internal material fluxes resulting from maximization of dissipation and consequently the interrelation to interface velocities. Model calculations revealed that irrespective of the external cooling rate, for an initial short time duration, the magnitude of which increased with decreasing cooling rates, the interface velocities show a reducing trajectory directly relatable to the reducing thermodynamic forces due to localized interfacial temperature rise from the generated latent heat of fusion from the initial solidification. This is followed by a thermodynamically controlled regime, whereby for each cooling rate, the interface velocities increase until a maxima, the magnitude of which decreases with decreasing cooling rates. Finally, the interface propagation speeds decrease as controlled by the kinetic regime.