The Hall–Héroult aluminum production process generates lithium-rich waste barrier materials, which are challenging to process using conventional acid leaching due to the environmental risks posed by hydrofluoric acid (HF) emissions. This research introduces a two-stage water–HCl sequential leaching (WHSL) approach to recover lithium while reducing these environmental impacts. The method evaluates key factors, such as the liquid–solid ratio, temperature, duration, rotation speed, and HCl concentration, and compares its efficacy with traditional HCl leaching using XRD, FTIR, DBP, and SEM techniques. The findings indicate that initial water leaching dissolves NaF salts, creating surface grooves and cracks. Subsequent HCl leaching selectively extracts lithium from aluminum and silicon, forming silica gel while preserving the nepheline phase due to its structural integrity. The process produces a porous residue with smaller particles, reduced surface potential, and promotes colloidal aggregation. This two-step process achieves efficient lithium recovery while reducing acid consumption and minimizing hydrogen fluoride (HF) emissions.

The comprehensive recycling of aluminum electrolysis cell waste barrier material is urgent. This study focuses on the sulfuric acid leaching of waste barrier material, systematically examining the effects of factors such as reaction temperature, liquid-to-solid ratio, sulfuric acid concentration, and reaction time on the leaching of elements like lithium, aluminum, sodium, and silicon. The experimental results show that under the conditions of 0.9 mol/L sulfuric acid concentration, a liquid-to-solid ratio of 20:1, a reaction temperature of 90 °C, and a reaction time of 1.5 h, the leaching rates were 84.5% for lithium, 85.6% for aluminum, 98.5% for sodium, and 4.8% for silicon. The sulfuric acid leaching process of the waste barrier material follows a shrinking core model and is controlled by internal diffusion. The apparent activation energies for the leaching reactions of lithium, aluminum, and sodium were 4.29 kJ/mol, 8.99 kJ/mol, and 9.11 kJ/mol, respectively. The selective leaching of lithium, sodium, and aluminum from silicon was successfully achieved in the sulfuric acid leaching of the waste barrier material.