Combined Modification of Dual-Phase Li₄Ti₅O₁₂–TiO₂ by Lithium Zirconates to Optimize Rate Capabilities and Cyclability

The low electrical conductivity and ordinary lithium-ion transfer capability of Li4Ti5O12 restrict its application to some degree. In this work, dual-phase Li4Ti5O12–TiO2 (LTOT) was modified by composite zirconates of Li2ZrO3, Li6Zr2O7 (LZO) to boost the rate capabilities and cyclability. When the homogeneous mixture of LiNO3, Zr(NO3)4·5H2O and LTOT was roasted at 700 °C for 5 h, the obtained composite achieved a superior reversible capacity of 183.2 mAh g–1 to the pure Li4Ti5O12 after cycling at 100 mA g–1 for 100 times due to the existence of a scrap of TiO2. Meanwhile, when the composite was cycled by consecutively doubling the current density between 100 and 1600 mA g–1, the corresponding reversible capacities are 183.2, 179.1, 176.5, 173.3, and 169.3 mAh g–1, signifying the prominent rate capabilities. Even undergoing 1400 charge/discharge cycles at 500 mA g–1, a reversible capacity of 144.7 mAh g–1 was still attained, denoting splendid cyclability. From a series of comparative experiments and systematic characterizations, the formation of LZO meliorated both the Li+ migration kinetics and electrical conductivity on account of the concomitant superficial Zr4+ doping, responsible for the comprehensive elevation of the electrochemical performance.