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 LiNi x Mn y Co 1– x – y O 2 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 (∼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) LiCoO 2 (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 ∼2 nm from the LCO surface. Additionally, we observe layering of Al and O atoms at the LCO-film interface that extends for ∼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 [4] Al is the prevailing coordination environment, significant amounts of [6] Al exist at the interface between the LiCoO 2 surface and the film. Taken together, these principal findings point to a pseudomorphic Li–Al–O overlayer that approximates the underlying layered LiCoO 2 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 LiNi x Mn y Co 1– x – y O 2 materials because of their shared crystal structure with LiCoO 2 . 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.