Innovative and sustainable separation and recovery of valuable metals in spent CIGS materials

Abstract

In recent years, the rapid development of copper indium gallium selenide (GIGS) solar cells makes it necessary to recycle spent CIGS in order to realize circular economy. In this work, a novel and efficient method for comprehensive recovery valuable metals in spent CIGS materials was investigated, mainly including three steps: (1) leaching of spent CIGS with nitric acid to separate indium; (2) precipitating to obtain copper gallium selenite mixture with magnesium oxide as precipitant; (3) calcination of the residue and the precipitation to recover selenium. X-ray photoelectron spectroscopy (XPS) analysis indicates that the valence state of selenium was converted from negative divalent to positive tetravalent after oxidative leaching. In addition, the results of X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR) and scanning electron microscope/energy dispersive spectrometer (SEM/EDS) shows that the dissolution of metals in CIGS during leaching were significantly different. Copper and gallium were almost completely leached, while indium entered the slag phase as indium selenite, which achieved the separation of indium. Moreover, the reaction mechanism of leaching was analyzed from the perspective of thermodynamics. After leaching, copper, gallium and selenium can be completely recovered from the leach liquor using magnesium oxide as precipitant. Subsequently, the separation of Se in the residue and precipitates can be achieved at 800 °C for 90 min. Finally, the recovery yields of Cu, In, Ga and Se were 99.23%, 96.82, 98.08% and 96.38% respectively. This research represents an important innovation from the perspective of circular economy and provides a new idea for comprehensive utilization of secondary solar cells.