Intercalation of Lithium Ions from Gaseous Precursors into β-MnO2 Thin Films Deposited by Atomic Layer Deposition

LiMn2O4 is a promising candidate for a cathode material in lithium-ion batteries because of its ability to intercalate lithium ions reversibly through its three-dimensional manganese oxide network. One of the promising techniques for depositing LiMn2O4 thin-film cathodes is atomic layer deposition (ALD). Because of its unparalleled film thickness control and film conformality, ALD helps to fulfill the industry demands for smaller devices, nanostructured electrodes, and all-solid-state batteries. In this work, the intercalation mechanism of Li+ ions into an ALD-grown beta-MnO2 thin film was studied. Samples were prepared by pulsing (LiOBu)-Bu-t and H2O for different cycle numbers onto about 100 nm thick MnO2 films at 225 degrees C and characterized with X-ray absorption spectroscopy, X-ray diffraction, X-ray reflectivity, time-of-flight elastic recoil detection analysis, and residual stress measurements. It is proposed that for <100 cycles of LiOtBu/H2O, the Li+ ions penetrate only to the surface region of the beta-MnO2 film, and the samples form a mixture of beta-MnO2 and a lithium-deficient nonstoichiometric spinel phase Li,Mn2O4 (0 < x < 0.5). When the lithium concentration exceeds x approximate to 0.5 in LixMn(2)O(4) (corresponding to 100 cycles of LiOtBu/H2O), the crystalline phase of manganese oxide changes from the tetragonal pyrolusite to the cubic spinel, which enables the Li+ ions to migrate throughout the whole film. Annealing in N-2 at 600 degrees C after the lithium incorporation seemed to convert the films completely to the pure cubic spinel LiMn2O4.