Fluoride Action Network

Transformation and migration mechanism of fluorine-containing pollutants in the pyrolysis process of spent lithium-ion battery.

Source: Journal of Hazardous Materials, 435:128974. | April 20th, 2022 | Authors: Huang H, Liu C, Sun Z.
Location: International
Industry type: Batteries Incineration


  • Adsorption of electrodes to electrolyte can lead to fluorine-containing residues.
  • Melting PVDF prevents the deep removal of fluorine-containing pollutants.
  • A synergistic transformation mechanism of fluorine during pyrolysis is proposed.


Pyrolysis is an effective method to remove organics (e.g. electrolytes and binders) from spent lithium-ion battery (LIB). In this study, the co-pyrolysis characteristics of fluorine-containing substances and active materials from LIB were investigated using thermogravimetric-differential scanning calorimetry (TG-DSC), infrared spectroscopy (IR), and mass spectrometry (MS) analysis. Associated with the pyrolysis, active materials adsorb the residues of electrolyte on the surface and into the pores (20-200 °C), while polyvinylidene fluoride (PVDF) forms a liquid film to cover the local surface of active materials (400-500 °C). These interactions prevent deep removal of organics, leaving fluorine-containing contaminants in active materials. The barrier effect of PVDF liquid mesophase on the removal of organics with secondary liquidous phase formation during pyrolysis was confirmed by in situ optical observation. The migration behavior of fluorine element during the pyrolysis of black mass (BM) from spent LIB was also investigated. With pyrolysis temperature increasing from 100 °C to 600 °C, the dissociable fluorine content in pyrolyzed BM increased from 1.4 wt% to 3.7 wt%. The fluorine-containing contaminants in BM cannot be removed completely by simply increasing pyrolysis temperature. This study provides a better understanding on the transformation of fluorine-containing pollutants during the pyrolysis of BM.

Graphical Abstract


*Original abstract online at https://www.sciencedirect.com/science/article/abs/pii/S0304389422007634?via%3Dihub