ABSTRACT
In order to examine the effect of excessive sulfate in the leachate of spent Li-ion batteries (LIBs), LiNi1/3Co1/3Mn1/3O2 (pristine NCM) and sulfate-containing LiNi1/3Co1/3Mn1/3O2 (NCMS) are prepared by a co-precipitation method. The crystal structures, morphology, surface species, and electrochemical performances of both cathode active materials are studied by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and charge-discharge tests. The XRD patterns and XPS results identify the presence of sulfate groups on the surface of NCMS. While pristine NCM exhibits a very dense surface in SEM images, NCMS has a relatively porous surface, which could be attributed to the sulfate impurities that hinder the growth of primary particles. The charge-discharge tests show that discharge capacities of NCMS at C-rates, which range from 0.1 to 5 C, are slightly decreased compared to pristine NCM. In dQ/dV plots, pristine NCM and NCMS have the same redox overvoltage regardless of discharge C-rates. The omnipresent sulfate due to the sulfuric acid leaching of spent LIBs has a minimal effect on resynthesized NCM cathode active materials as long as their precursors are adequately washed.
ABSTRACT
As the explosive growth of the electric vehicle market leads to an increase in spent lithium-ion batteries (LIBs), the disposal of LIBs has also made headlines. In this study, we synthesized the cathode active materials Li[Ni1/3Mn1/3Co1/3]O2 (NMC) and Li[Ni1/3Mn1/3Co1/3Fe0.0005Al0.0005]O2 (NMCFA) via hydroxide co-precipitation and calcination processes, which simulate the resynthesis of NMC in leachate containing trace amounts of iron and aluminum from spent LIBs. The effects of iron and aluminum on the physicochemical and electrochemical properties were investigated and compared with NMC. Trace amounts of iron and aluminum do not affect the morphology, the formation of O3-type layered structures, or the redox peak. On the other hand, the rate capability of NMCFA shows high discharge capacities at 7 C (110 mAh g-1) and 10 C (74 mAh g-1), comparable to the values for NMC at 5 C (111 mAh g-1) and 7 C (79 mAh g-1), respectively, due to the widened interslab thickness of NMCFA which facilitates the movement of lithium ions in a 2D channel. Therefore, iron and aluminum, which are usually considered as impurities in the recycling of LIBs, could be used as doping elements for enhancing the electrochemical performance of resynthesized cathode active materials.
ABSTRACT
Solvent extraction (SX) separation of Al from Ni sulphate leach liquor (LL) of spent Raneynickel catalyst containing 0.12 M Al and 1.448 M Ni using organophosphorus extractants has been investigated. Optimization of process conditions includes aqueous pH, extractant concentration, phase ratio, and stripping. Comparison of Al extraction efficiency with 0.45 M extractant concentration for TOPS 99, PC 88 A, and Cyanex 272 at an equilibrium pH of 2.23 was 81.8%, 98.6%, and 75%, respectively. The corresponding coextraction of Ni was 0.65, 0.6, and 0.9. Among the three extractants screened, PC 88A showed better extraction efficiency for Al at lower pH values than the others. Using 0.45 M PC 88 A, extraction isotherm was obtained at an aqueous-to-organic (A : O) phase ratio of 1 : 1-3 and O : A ratio of 1 : 1-5, which predicted possible separation of Al in 2 stages at A/O ratio of 2. Quantitative stripping was achieved by H(2)SO(4).
