Structural and electrochemical properties of LiCoO₂ and LiAl_yCo_1−yO₂ (y=0.1 and 0.2) oxides: A comparative study of electrodes prepared by the citrate precursor route

Abstract

We present the characterization and electrode behavior of LiCoO₂ and Al-doped LiAl_yCo_1−yO₂ (y=0.1 and 0.2) oxides prepared by wet-chemical method from the citrate precursor route. We study the phase evolution as a function of the aluminum substitution and the modification on the intercalation and deintercalation of Li ions. Characterization methods include XRD, SEM, and FTIR. X-ray diffraction patterns show that samples belong to the LiCoO₂-LiAlO₂ solid solution and have the layered α-NaFeO₂ structure. FT-infrared vibrational spectroscopy indicates the slight modification in the local structure related to the short-range environment of oxygen coordination around the cations in oxide lattices. The frequencies and relative intensities of the bands are sensitive to the covalency of the (Al, Co)O₂ slabs. The overall electrochemical capacity of the LiAl_yCo_1−yO₂ oxides have been reduced due to the sp metal substitution, however, a more stable charge-discharge cycling performances have been observed when electrodes are charged to 4.3 V as compared to the performances of the native oxide. Differences and similarities between LiCoO₂ and Al-substituted oxides are discussed therefrom.