Highlights

  • Analysis of the gas and organic by-products after batteries incineration.
  • Incineration of LiCoO2, LiMn2O4, and LiNiO2 with graphite addition.
  • Thermodynamic modeling for LiCoO2, LiMn2O4, and LiNiO2 reduction.
  • Reduction products: CoO, Co3O4, NiO, Mn3O4, MnO2 Li2O, and Li2CO3.
  • Fluorine behavior during thermal treatment and its presence in oil by-products.

Abstract

In several industrial Lithium-ion batteries recycling processes, a thermal treatment with oxidative atmosphere is used to separate the battery components and to remove the organic components. This method is often combined with hydrometallurgical processes with the aim to increase the metal recovery rate or to improve the efficiency of the existing processes. Despite such efforts, the effects of a thermal treatment in an oxidative atmosphere on the microstructure and composition on cathode and anode materials has not been explored.

In this manuscript, spent batteries which cathode active material has the composition Li(NixMnyCoz)Oz, i.e. NMC-LiBs, were subjected to thermal treatment at 400º, 500º, 600º, and 700°C for 30, 60, and 90 min. The microstructure and the composition were studied using XRD and ICP-OES. Thermodynamic calculations were performed to forecast the trend of the carbothermic reduction of active materials. It was observed the formation of gas and organic oil by-products from the decomposition of the polypropylene separator and the polyvinylidene fluoride binder. The identification of the composition of these by-products has great importance since they have a corrosive and toxic behavior. It was observed the fluorine behavior during the thermal treatment and its presence in the oil by-products.