Evaluation of Nucleation and Growth Kinetics of Li₃PO₄ Reactive Crystallization from Low-Concentration Lithium-Rich...

Li₃PO₄ is a promising raw material for the low-cost synthesis of high-performance LiFePO₄. Reactive crystallization from low-concentration lithium-rich brine is a key process for the efficient preparation of high-quality Li₃PO₄ products. The effect of operating conditions (temperature/supersaturation/impurities/ultrasonic) on the induction time was investigated using a focused beam reflectance measurement. The evaluation of the primary nucleation, growth kinetics, and parameters for the extraction of Li₃PO₄ from low-concentration lithium-rich brine was conducted using an induction time method. The dominant mechanisms at different stages were inferred through online monitoring of the particle size distribution during the Li₃PO₄ crystallization process. Results show that induction time decreases with increasing operating conditions (temperature/supersaturation/ultrasonic frequency), indicating that their increases all promote nucleation. Impurities (NaCl/KCl) did not significantly affect the induction time, whereas Na₂SO₄ and Na₂B₄O₇ significantly increased it, with Na₂B₄O₇ showing the most notable effect. Classical nucleation theory was applied to determine kinetic parameters (nucleation activation energy/interfacial tension/contact angle/critical nucleus size/surface entropy factor). Results indicate that Li₃PO₄ mainly nucleates through heterogeneous nucleation, with a temperature increase weakening the role of heterogeneous nucleation. Fitted models indicate that Li₃PO₄ predominantly follows the secondary nucleation and spiral growth mechanism. Our findings are crucial for crystallization design and control in producing high-quality Li₃PO₄ from lithium-rich brines.