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Phase-field modeling of solid-state metathesis reactions with the charge neutrality constraint

by Guanglong Huang, David Montiel, Rebecca D Mcauliffe, Gabriel M Veith, Katsuyo Thornton
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Computational Materials Science
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In this work, we present a phase-field model that captures the evolution of ionic concentrations and phase fractions during solid-state metathesis (SSM) reactions where diffusion limits the rate of transformation. The evolution of the mole fraction of each ion is obtained via governing equations that describe the reduction of a free energy, which includes an energy landscape with local minima located at compositions corresponding to stable products. We utilized two Lagrange multipliers to impose constraints of electroneutrality as well as on the sum of mole fractions, which were then eliminated to derive set of two partial differential equations that describe the dynamics of the mole fraction evolution. From these governing equations, the expressions for effective mobilities for the cations and the anions were obtained. We first study the effect of mobilities of ions on the reaction kinetics, using a simple model considering the ions with an identical absolute value of charge numbers. The simulation results show that the overall characteristic mobility, defined as the sum of the two effective ionic mobilities, provides an excellent measure of the rate at which reaction progresses and that the ratio of the effective mobilities of the anions and the cations signifies the manner by which the reaction progresses. We then generalize the model to consider ions with different charge numbers and tuned the mobility of ions based on their diffusion coefficients reported in the literature and experimental data from a thin-film experiment for the synthesis of FeS2 to demonstrate the capability of the model to predict the phase evolution during SSM reactions. In particular, the simulation predicts nonplanar phase evolution, which is recently observed in thin-film reactions for the synthesis of FeS2 via transmission electron microscopy. The approach can serve as a basis for models for phase transformations in other multiphase ionic mixtures, such as in all-solid-state batteries and in ionic liquids.