The capacity decay of layered cathodes in high-voltage
applications
underscores the need to utilize accurate and precise techniques to
understand the underlying mechanisms. Here, we use well-defined epitaxial
LiCoO2 (LCO) films on SrRuO3/SrTiO3 (SRO/STO) with controlled orientations and defect structures along
with in situ electrochemical atomic force microscopy
to probe the structural and morphological evolutions during the charge
and overcharge processes. We quantitatively show the morphological
changes in both the reversible delithiation regime and the irreversible
over-delithiation regime and correlate the overall electrochemical
behaviors to atomic scale defect evolutions in the films. We also
observe a significantly lower charging capacity for LCO/SRO/STO(111)
compared to that of LCO/SRO/STO(001) films of the same thickness,
which is ascribed to different types of atomic scale defects formed
during the film growth process. Our high-resolution scanning transmission
electron microscopy (STEM) and electron energy loss spectroscopy (EELS)
studies reveal that the antiphase boundaries in LCO/SRO/STO(111) act
as viable channels for Li migration but are more susceptible to irreversible
phase transitions, which then block subsequent Li diffusion. The failure
mechanisms developed here may provide insight into the design of future
cathode materials.