Analyzing the Li-Al-O Interphase of Atomic Layer-Deposited Al₂O₃ Films on Layered Oxide Cathodes Using Atomistic Simulations

Alumina surface coatings are commonly applied to layered oxide cathode particles for lithium-ion battery applications. Atomic layer deposition (ALD) is one such surface coating technique, and ultrathin alumina ALD films (<2 nm) are shown to improve the electrochemical performance of LiNixMnyCo1-x-yO2 materials, with groups hypothesizing that a beneficial Li-Al-O product is being formed during the alumina ALD process. However, the atomic structure of these films is still not well understood, and quantifying the interface of ultrathin (similar to 1 nm) ALD films is an arduous experimental task. Here, we perform molecular dynamics simulations of amorphous alumina films of varying thickness in contact with the (0001) LiCoO2 (LCO) surface to quantify the film nanostructure. We calculate elemental mass density profiles through the films and observe that the Li-Al-O interphase extends similar to 2 nm from the LCO surface. Additionally, we observe layering of Al and O atoms at the LCO-film interface that extends for similar to 1.5 nm. To access the short-range order of the amorphous film, we calculated the Al coordination numbers through the film. We find that while Al-[4] is the prevailing coordination environment, significant amounts of Al-[6] exist at the interface between the LiCoO2 surface and the film. Taken together, these principal findings point to a pseudomorphic Li-Al-O overlayer that approximates the underlying layered LiCoO2 lattice but does not exactly replicate it. Additionally, with sufficient thickness, the Li-Al-O film transitions to an amorphous alumina structure. We anticipate that our findings on the ALD-like, Li-Al-O film nanostructure can be applied to other layered LiNixMnyCo1-x-yO2 materials because of their shared crystal structure with LiCoO2. This work provides insight into the nanostructure of amorphous ALD alumina films to help inform their use as protective coatings for Li-ion battery cathode active materials.