Hydrometallurgical processing of spent lithium ion batteries (LIBs) in the presence of a reducing agent with emphasis on kinetics of leaching

Abstract In this study, sulfuric acid leaching was applied to recover lithium, cobalt, nickel and manganese from the cathodic active material of spent LIBs in presence of a reducing agent, sodium bisulfite. The conditions for the dissolution of valuable metals were optimized while varying the parameters such as acid concentration, leaching time, temperature and pulp density. It was found that with 1 M H2SO4 and 0.075 M NaHSO3 as reducing agent ∼96.7% Li, 91.6% Co, 96.4% Ni and 87.9% Mn were recovered in 4 h at 368 K and a pulp density of 20 g/L. Kinetic data for the dissolution of the metals such as Li, Co and Ni in the temperature range 308–368 K showed best fit to the kinetic model governed by the empirical logarithmic rate law. Leaching of the metals proceeded through the diffusion of lixiviant on the surface of the substrate particles, which was corroborated by XRD phase analyses and SEM–EDS of the untreated sample and the leach residues. From the leach liquor, >98% Co was recovered as cobalt oxalate (CoC2O4·2H2O) by precipitation with oxalic acid. MnCO3, NiCO3 and Li2CO3 were precipitated from the cobalt depleted solution. By this process, high recovery of Li and Co could be achieved in the solution and then in the form of carbonate and oxalate, respectively along with the recovery of Mn and Ni as their carbonates.

[1]  S. Shin,et al.  Recovery of Cobalt in Sulfuric Acid Leaching Solution Using Oxalic Acid , 2006 .

[2]  Feng Wu,et al.  Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries. , 2010, Waste management.

[3]  Jinki Jeong,et al.  Hydrometallurgical process for recovery of cobalt from waste cathodic active material generated during manufacturing of lithium ion batteries , 2007 .

[4]  Li Yong-jia,et al.  Hydrometallurgical process for recovery and synthesis of LiCoO2 from spent lithium-ion batteries , 2011, 2011 International Conference on Electric Technology and Civil Engineering (ICETCE).

[5]  Bruno Scrosati,et al.  A laboratory-scale lithium-ion battery recycling process , 2001 .

[6]  B. D. Pandey,et al.  Leaching kinetics of copper from waste printed circuit boards by electro-generated chlorine in HCl solution , 2011 .

[7]  G. Civelekoglu,et al.  Acidic leaching and precipitation of zinc and manganese from spent battery powders using various reductants. , 2010, Journal of hazardous materials.

[8]  Marcelo Borges Mansur,et al.  A study of the separation of cobalt from spent Li-ion battery residues , 2007 .

[9]  Jin-Gu Kang,et al.  Recovery of cobalt sulfate from spent lithium ion batteries by reductive leaching and solvent extraction with Cyanex 272 , 2010 .

[10]  Tao Zhou,et al.  Hydrometallurgical process for the recovery of metal values from spent lithium-ion batteries in citric acid media , 2014, Waste management & research : the journal of the International Solid Wastes and Public Cleansing Association, ISWA.

[11]  O. Burheim,et al.  Recovery of metallic values from spent Li ion secondary batteries , 2006 .

[12]  O. Levenspiel Chemical Reaction Engineering , 1972 .

[13]  B. D. Pandey,et al.  Extraction of lithium from primary and secondary sources by pre-treatment, leaching and separation: A comprehensive review , 2014 .

[14]  Young Han Kim,et al.  Development of a metal recovery process from Li-ion battery wastes , 2005 .

[15]  Kang-In Rhee,et al.  Reductive leaching of cathodic active materials from lithium ion battery wastes , 2003 .

[16]  Li Li,et al.  Preparation of LiCoO2 films from spent lithium-ion batteries by a combined recycling process , 2011 .

[17]  B. D. Pandey,et al.  Recovery of valuable metals from cathodic active material of spent lithium ion batteries: Leaching and kinetic aspects. , 2015, Waste management.

[18]  M. A. H. Shuva,et al.  Hydrometallurgical Recovery of Value Metals from Spent Lithium Ion Batteries , 2013 .

[19]  Junmin Nan,et al.  Recovery of metal values from spent lithium-ion batteries with chemical deposition and solvent extraction , 2005 .

[20]  Zhiwen Zeng,et al.  Process for the recovery of cobalt oxalate from spent lithium-ion batteries , 2011 .

[21]  M. Bahgat,et al.  A novel approach for synthesis of nanocrystalline γ-LiAlO2 from spent lithium-ion batteries , 2007 .

[22]  Feng Wu,et al.  Recovery of cobalt and lithium from spent lithium ion batteries using organic citric acid as leachant. , 2010, Journal of hazardous materials.

[23]  Katsutoshi Inoue,et al.  Hydrometallurgical process for recovery of metal values from spent lithium-ion secondary batteries , 1998 .

[24]  Kang-In Rhee,et al.  Preparation of LiCoO2 from spent lithium-ion batteries , 2002 .

[25]  Keqiang Qiu,et al.  Organic oxalate as leachant and precipitant for the recovery of valuable metals from spent lithium-ion batteries. , 2012, Waste management.