The application of industrial black liquor from the Kraft pulping process as a renewable reducing agent for the enhanced leaching of spent lithium-ion batteries using H₂SO₄ is demonstrated. The addition of acidified black liquor was shown to significantly improve the leaching efficiency for a range of cathode chemistries due to the degradation of oxygenated and aromatic groups in the liquor.

Abstract

The economic advantages of H₂SO₄ make it the acid of choice for the hydrometallurgical treatment of waste lithium-ion batteries (LIBs). However, to facilitate the full dissolution of the higher valency metal oxides present in the cathode black mass, a suitable reducing agent is required. Herein, the application of industrial black liquor (BL) obtained from the Kraft pulping for papermaking is investigated as a renewable reducing agent for the enhanced leaching of transition metals from LIB powder with H₂SO₄. The addition of acidified BL to H₂SO₄ significantly improved the leaching efficiency for a range of LIB cathode chemistries, with the strongest effect observed for manganese-rich active material. Focusing on NMC₁₁₁ (LiMn_xCo_yNi_zO₂) material, a linear correlation between the BL concentration and the leaching yield of Mn was obtained, with the best overall leaching efficiencies being achieved for 2.0 mol L⁻¹ H₂SO₄ and 50 vol % of BL at 353 K. A quasi-total degradation of oxygenated and aromatic groups from the BL during NMC₁₁₁ dissolution was observed after leaching, suggesting that these chemical groups are essential for LIB reduction. Finally, the leached transition metals could be easily recovered by pH adjustment and oxalic acid addition, closing the resource loop and fostering resource efficiency.