Domain Formation in Lithium-Rich Manganese-Nickel-Cobalt-Oxide Epitaxial Thin Films and Implications for Interpretation of Electrochemical Behavior.

Due to the directional dependence of physical properties, it is advantageous to grow and then study materials in specific orientations. Films of battery materials grown in epitaxy offers the possibility to gain new insight into the role of physical structure on electrochemical behaviors. Here we demonstrate the growth, testing, and characterization of monoclinic-phase (space group C2/m) Li-Mn-Ni-Co-O epitaxial films. The monoclinic phase is a layered structure and as such lithium diffusion is favored along specific crystallographic directions. Films were grown by pulsed laser deposition onto SrRuO3/SrTiO3 substrates with (001) and (111) orientations. Cyclic voltammetry measured the response of these positive electrode materials, while the film structure was characterized using scanning transmission electron microscopy. A combination of imaging and diffraction identifies the presence of orientational variants. Variants disrupt the orientation anisotropy expected of these layered materials when grown in epitaxy, thereby masking differences in electrochemical behavior as a function of substrate orientation. Learning to control the domain structure now presents itself as a challenge to realize the potential of low symmetry battery materials grown in epitaxy on high symmetry substrates.