RESUMO
P2 layered oxides have attracted more and more attention as cathode materials of high-power sodium-ion batteries (SIBs). During the charging process, the release of sodium ions leads to layer slip, which leads to the transformation of P2 phase into O2 phase, resulting in a sharp decline in capacity. However, many cathode materials do not undergo P2 -O2 transition during charging and discharging, but form a "Z" phase. It is proved that the iron-containing compound Na0.67 Ni0.1 Mn0.8 Fe0.1 O2 formed the "Z" phase of the symbiotic structure of the P phase and O phase during high-voltage charging through ex-XRD and HAADF-STEM. During the charging process, the cathode material undergoes a structural change of P2 -OP4 -O2 . With the increase of charging voltage, the O-type superposition mode increases to form an ordered OP4 phase, and the P2 -type superposition mode disappears after further charging to form a pure O2 phase. 57 Fe-Mössbauer spectroscopy revealed that no migration of Fe ions is detected. The O-Ni-O-Mn-Fe-O bond formed in the transition metal MO6 (M = Ni, Mn, Fe) octahedron can inhibit the elongation of the Mn-O bond and improve the electrochemical activity so that P2-Na0.67 Ni0.1 Mn0.8 Fe0.1 O2 has an excellent capacity of 172.4 mAh g-1 and a coulombic efficiency close to 99% at 0.1C.
RESUMO
A new environmentally friendly and economical recycling process for extracting metals from spent lithium-ion batteries (LIBs) using sulfuric acid and malonic acid as leaching agents is proposed. By applying Box-Behnken design (BBD) and response surface methodology (RSM) optimization techniques, the global optimal solution of the maximum leaching rate of metals in spent LIBs is realized. The results show that under the optimal conditions of 0.93 M H2SO4, 0.85 M malonic acid, and a liquid/solid ratio of 61 g·L-1, a temperature of 70 °C and 5 vol % of 30% H2O2, 99.79% Li, 99.46% Ni, 97.24% Co, and 96.88% Mn are recovered within 81 min. The error between the theoretical value and the actual value of the metal leaching rate predicted by the regression model is less than 1.0%. Additionally, the study of leaching kinetics reveals that the leaching process of Li, Ni, Co, and Mn in spent cathode materials was affected by the synergistic effect of interfacial mass transfer and solid product layer diffusion. Economic analysis reveals that evaluation index should be fully considered when formulating recovery processes for different metals. This process can reduce the environmental risks of heavy metal disposal and allow the reuse of metals recovered from spent LIBs.
