Blow-Spinning Enabled Precise Doping and Coating for Improving High-Voltage Lithium Cobalt Oxide Cathode Performance.

Abstract

Lithium cobalt oxide (LiCoO2) possesses an attractive theoretical specific capacity (274 mAh g-1) and high discharge voltage (∼4.2 V vs Li+/Li). However, only a half of the theoretical capacity of LiCoO2 is available in commercialized lithium ion batteries because of the intrinsic structural instability and detrimental interface of LiCoO2 at the charging voltage over 4.2 V. Here, a facile blow-spinning synthetic method is developed to realize precise doping and simultaneous self-assembly coating of LiCoO2 particles, achieving a record performance among present LiCoO2 cathodes. Owing to the spatial confinement effect of microfibers fabricated by blow-spinning, homogeneously Mn and La doped in the LiCoO2 host and uniformly Li-Ti-O segregated at the LiCoO2 surface can be realized in every batch of samples. It is demonstrated that the Mn and La codoping can suspend the intrinsic instability and increase the Li+ diffusivity of the LiCoO2 host, and the Ti-based coating can stabilize the interface of LiCoO2 particles at the charging voltage up to 4.5 V. As a result, the obtained comodified LiCoO2 cathode shows the best rate performance (1.85 mAh cm-2 at 2C) and longest cycling stability under an areal capacity of 2.04 mAh cm-2 (83% capacity retention over 300 cycles at 0.3C), in comparison to previously reported LiCoO2 cathodes.