Synthesis and electrochemistry of cubic rocksalt Li–Ni–Ti–O compounds in the phase diagram of LiNiO2–LiTiO2–Li[Li1/3Ti2/3]O2

On the basis of extreme similarity between the triangle phase diagrams of LiNiO2–LiTiO2–Li[Li1/3Ti2/3]O2 and LiNiO2–LiMnO2–Li[Li1/3Mn2/3]O2, new Li–Ni–Ti–O series with a nominal composition of Li1+z/3Ni1/2−z/2Ti1/2+z/6O2 (0 ≤ z ≤ 0.5) was designed and attempted to prepare via a spray-drying method. XRD identified that new Li–Ni–Ti–O compounds had cubic rocksalt structure, in which Li, Ni and Ti were evenly distributed on the octahedral sites in cubic closely packed lattice of oxygen ions. They can be considered as the solid solution between cubic LiNi1/2Ti1/2O2 and Li[Li1/3Ti2/3]O2 (high temperature form). Charge–discharge tests showed that Li–Ni–Ti–O compounds with appropriate compositions could display a considerable capacity (more than 80 mAh g−1 for 0.2 ≤ z ≤ 0.27) at room temperature in the voltage range of 4.5–2.5 V and good electrochemical properties within respect to capacity (more than 150 mAh g−1 for 0 ≤ z ≤ 0.27), cycleability and rate capability at an elevated temperature of 50 °C. These suggest that the disordered cubic structure in some cases may function as a good host structure for intercalation/deintercalation of Li+. A preliminary electrochemical comparison between Li1+z/3Ni1/2−z/2Ti1/2+z/6O2 (0 ≤ z ≤ 0.5) and Li6/5Ni2/5Ti2/5O2 indicated that charge–discharge mechanism based on Ni redox at the voltage of >3.0 V behaved somewhat differently, that is, Ni could be reduced to +2 in Li1+z/3Ni1/2−z/2Ti1/2+z/6O2 while +3 in Li6/5Ni2/5Ti2/5O2. Reduction of Ti4+ at a plateau of around 2.3 V could be clearly detected in Li1+z/3Ni1/2−z/2Ti1/2+z/6O2 with 0.27 ≤ z ≤ 0.5 at 50 °C after a deep charge associated with charge compensation from oxygen ion during initial cycle.