4.7 Article

Lithium ion battery active material dissolution kinetics in Fe(II)/Fe(III) catalyzed Cu-H2SO4 leaching system

Journal

SEPARATION AND PURIFICATION TECHNOLOGY
Volume 236, Issue -, Pages -

Publisher

ELSEVIER
DOI: 10.1016/j.seppur.2019.116305

Keywords

Kinetics; Leaching; LiCoO2; Iron reductant-oxidant

Funding

  1. Business Finland - Academy of Finland [4853/31/2018]

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In mechanical recycling and separation of waste lithium-ion batteries (LIBs), Cu from electrode materials and Fe from battery casings may partially end up into the fine black mass fraction, rich in oxides such as LiCoO2. Herein the kinetics of LiCoO2-H2SO4-Fe-Cu- system was investigated by leaching studies in a 500 cm(3) glass reactor at T = 30 degrees C, with 2 M H2SO4 under N-2(g) purging (0.5 dm(3)/min). Design of experiments (DOE) was utilized as a supporting tool in investigation of the effect of copper (Cu/2LiCoO(2) = 0.5-1.5 mol/mol,) and iron (Fe/LiCoO2 = 0.01-0.11 mol/mol) to the measured LiCoO2 dissolution rate constants at initial phase of leaching (0-30 min) and at final phase of leaching (30-120 min). Analysis of variance showed that the kinetic rate constant models are statistically significant (p = 0.002 and p < 0.000, respectively), furthermore, the models describe real effects (coefficient of determination, R-2 = 0.920 for < 30 min model and R-2 = 0.9895 for > 30 min model). The results suggest that Cu is able to relinquish electrons to ferric ions, and the resulting ferrous ions mediate the transfer of electrons enabling reduction of LiCoO2. A sufficient Co extraction (> 95%) was achieved with solution containing dissolved iron (1.06 g/L), along with 2.167 g of metallic Cu per 6.68 g of LiCoO2 (1/1 mol ratio). It was calculated that the copper present in typical spent LIB cells is enough to satisfy this requirement. This decreases the chemical consumption as there is no need for external reductant.

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