• Citric acid achieved >97% leaching efficiencies for Li, Ni, Co, and Mn from industrial pyrolytic black powder under optimized conditions.
• Response surface methodology systematically optimized the leaching process, demonstrating practical applicability for industrial-scale recycling.
• Kinetic analysis revealed internal diffusion control with low apparent activation energies (15.21–23.14 kJ/mol), indicating a facile and energy-efficient extraction process.
• FePO4 precipitation was identified as the primary inhibitor of iron dissolution, providing mechanistic insights for selective metal recovery.