Modification of LiMn2O4 surfaces by controlling the Acid–Base surface chemistry of atomic layer deposition

[Display omitted] •Donghyeon Kang, Robert E. Warburton, Anil U. Mane, Jeffrey Greeley, Jeffrey W. Elam.•We examined ALD Al2O3 coating growth on LiMn2O4 surfaces using five different precursors.•Density functional theory identified precursor acidity as a key indicator of decomposition mechanisms.•Precursors with greater Lewis acidity increased concentration of surface Mn3+ ions.•Optimal ALD alumina coatings are significantly thinner than previously reported. In this combined theoretical and experimental study, we report the effects of Al precursor selection on the growth chemistry, interfacial structure, and electrochemistry of Al2O3 coatings on spinel LiMn2O4 (LMO) surfaces by atomic layer deposition (ALD). Five Al precursors, exhibiting a range of Lewis acid–base properties, were used to establish trends in the ALD Al2O3 growth chemistry on LMO powders in comparison to redox-inactive planar silicon substrates. We show that the Lewis acid–base properties of the Al precursor ligands can be used to tune both the Mn oxidation states and the Al2O3 coverage on the LMO surface. Density functional theory calculations are used to examine the reaction mechanism of each precursor on LMO surfaces, elucidating a correlation between the Lewis acidity of the ligands and the decomposition thermochemistry. In-depth X-ray photoelectron spectroscopy and in situ Fourier transform infrared spectroscopy measurements support these theoretical predictions and further reveal how different Al precursors modify the atomic and electronic structure near the LMO surface during ALD. While the Mn oxidation state is strongly influenced by the Lewis acidity of the precursor ligand, the surface coverage and thickness of the Al2O3 coating are a more representative descriptor of the electrochemical performance measured in coin cell experiments. We show how the ligand acid–base properties of ALD precursors can be used to rationally tailor atomic layer growth mechanisms, which may enable atomic level control over the structure of functionalized interfaces for various applications related to catalysis, semiconductors, and energy storage.