A green process for phosphorus recovery from spent LiFePO₄ batteries by transformation of delithiated LiFePO₄ crystal into NaFeS₂

Recovery of high-content and valuable elements including phosphorus (P) is critical for recycling of spent LiFePO₄ battery, but P recovery is challengeable due to the poor solubility of lithium phosphate and iron phosphate. This study compared two strategies to recover P by adopting sulfide salt to induce P dissolution, i.e., recovery of P directly from LiFePO₄, and step-by-step recovery of Li then P. The results revealed that the second strategy was more efficient because of the higher recovering efficiency and selectivity. Accordingly, an acid-free process to recover P was successfully demonstrated. Li-recovery efficiency of 97.5 % was reached at a leaching time of 65 min, and nearly 100 % P-recovery efficiency was reached at 5 h. Mechanism analysis revealed that the transforming of delithiated LiFePO₄ crystal to NaFeS₂ was mainly responsible for P dissolution. Thermodynamic analysis and density functional theory calculation further proved the transformation reaction, and a stepwise-transformation mechanism was proposed. In addition, P was reclaimed in the form of soluble phosphate salts. The process is especially appealing due to its environmental and economic benefits for recycling spent LiFePO₄ batteries.