Designing high-voltage and high-rate Li1-xNaxCoO2 by enlarging Li layer spacing

Abstract In our work, a series of Li 1-x M x CoO 2 (M = Na, x = 0–0.05) samples are synthesized by the solid-state calcination route. Electrochemical measurements show that high-rate capacities and high-voltage performances receive obvious improvements with an appropriate content of Na-doping. Specially, the capacity retentions of Li 0.97 Na 0.03 CoO 2 and LiCoO 2 are 65.6% and 62.7% after the 100 th cycle at 3.0–4.5 V, respectively. The discharge capacity of Li 0.97 Na 0.03 CoO 2 compared with the pristine electrode LiCoO 2 is greatly enhanced from 125 to 135 mAh·g −1 at the rate of 5 C and 98 to 120 mAh·g −1 at the rate of 10 C (1C = 140 mA g −1 ) respectively. With the larger radius of Na + substituted for the smaller radius of Li + , it is found that the bond length of Li O is reduced from 2.0801 A to 2.0781 A, which is helpful for stabilizing the structure of LiCoO 2 and improving the cycle capability at high voltages. At the same time, the inter-planar distance of Li slabs is expanded from 2.5904 A to 2.59511 A which can accelerate the diffusion of Li + and improve the rate capacity. Therefore, Na-doped LiCoO 2 shows outstanding high-voltage and high-rate performances, and the strategy can also be popularized and applied to other layered cathodes.

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