Improved electrochemical properties of LiMn2O4 with the Bi and La co-doping for lithium-ion batteries

Abstract

A series of LiBi_xLa_xMn_2−2xO₄ (x = 0, 0.002, 0.005, 0.010, 0.020) samples were synthesized by solution combustion synthesis in combination with calcination. The phase structure and morphology of the products were characterized by X-ray diffraction, scanning electron microscopy, and transition electron microscopy. The results demonstrated that a single-phase LiMn₂O₄ spinel structure was obtained for the LiBi_xLa_xMn_2−2xO₄ (x = 0, 0.002, 0.005) samples, whereas impurities were observed for the LiBi_xLa_xMn_2−2xO₄ (x = 0.010, 0.020) samples as a result of the doping limit. The electrochemical properties were investigated by galvanostatic charge–discharge cycling and cycling voltammetry in a voltage range of 3.2–4.4 V. The substitution of Mn³⁺ by equimolar Bi³⁺ and La³⁺ could significantly improve the structural stability and suppress the Jahn–Teller distortion, thereby resulting in improved electrochemical properties for the Bi and La co-doped samples in contrast with the pristine LiMn₂O₄ sample. In particular, the LiBi_0.005La_0.005Mn_1.99O₄ sample delivered a high initial discharge capacity of 130.2 mA h g⁻¹ at 1C, and following 80 cycles, the capacity retention was as high as 95.0%. Moreover, it also presented the best rate capability among all the samples, in which a high discharge capacity of 98.3 mA h g⁻¹ was still maintained at a high rate of 7C compared with that of 75.8 mA h g⁻¹ for the pristine LiMn₂O₄ sample.