Effect of microstructure change on resistance of spherical LiCoO2 to electrode degradation for proton intercalation

Abstract

Lithium cobalt oxide (LCO) with layered crystal structure suffers the structural proton intercalation in aqueous electrolytes of low pH values, little information is available about the effect of microstructure change on the cycling stability of LCO in response to the proton intercalation. In this work, electrochemical properties of three kinds of LCO spheres with different microstructures are studied in neutral aqueous 0.5 M Li2SO4 solution. The investigated materials were obtained by calcining the spherical LCO precursors at various temperatures, which were synthesized via a modified solid phase method for lithiation of spherical Co3O4. Structure and morphology of materials were characterized by X-ray diffraction (XRD) and field emission scanning electron microscope (FE-SEM). The spherical LCO prepared at lower temperature shows more superior electrochemical stability. Herein, the resistance of spherical LCO with a particular microstructure to the electrode degradation for the proton intercalation can be measured by the frequency of occurrences of greater-than-100% coulombic efficiencies during cycling. Meanwhile, the capability of retaining the capacity contribution from the order-to-disorder transformation of lithium ions on the hexagonal lattice of host site after the first-order phase transition was proposed to compare and investigate the cyclability of the three kinds of spherical LCO with different microstructures.