Recovery of High-Purity Lithium Hydroxide Monohydrate from Lithium-Rich Leachate by Anti-Solvent Crystallization: Process Optimization and Impurity Incorporation Mechanisms

The increasing demand for lithium-ion batteries (LIBs) has intensified the need for efficient lithium (Li) recovery from secondary sources. This study focuses on anti-solvent crystallization for the recovery of high-purity lithium hydroxide monohydrate (LiOH·H2O) from a Li-rich leachate, derived from the flue dust of a pilot-scale pyrometallurgical process for LIB material recycling. To optimize product yield and purity, a series of experiments were performed, focusing on the influence of parameters such as solvent type, organic-to-aqueous (O/A) volumetric ratio, crystallization time, stirring rate, and anti-solvent addition rate. Acetone was identified as the most effective anti-solvent, producing rectangular cuboid crystals with approximately 90% Li recovery and around 95% purity, under optimized conditions (O/A = 4, 3 h, 150 rpm, and solvent flow rate of 5 mL/min). The flow rate influenced crystal morphology and impurity entrapment, with 5 mL/min favoring nucleation-dominated crystallization regime, producing ~20 μm of well-dispersed crystals with reduced impurity incorporation. SEM-EDS, surface washing, and gradual dissolution of obtained LiOH·H2O crystals revealed that the impurities sodium (Na), potassium (K), aluminum (Al), calcium (Ca) and chromium (Cr) were crystallized as conglomerates. It was found that Na, K, Al, and Ca primarily crystallized as highly soluble conglomerates, while Cr was crystallized as a lowly soluble conglomerate impurity. In contrast Zn was distributed throughout the crystal bulk, suggesting either the entrapment of soluble zincate species within the growing crystals or the formation of mixed Li-Zn phase. Therefore, to achieve battery-grade purity, further purification measures are necessary.