Lithium permeation within lithium niobate multilayers with ultrathin chromium, silicon and carbon spacer layers

Abstract

Li permeation through ultrathin Cr, Si and C layers and interfaces is of interest in the optimization of lithium ion batteries with respect to the control of Li flux. Twenty-one LiNbO₃ layers (9 nm), which serve as solid state Li reservoirs, were sputter deposited in an alternating sequence of enriched ⁶Li or ⁷Li isotope fractions spaced with (8 nm) thin Cr, Si and C layers. The Li isotope contrast was used to measure Li permeation using depth profiling by secondary ion mass spectrometry and neutron reflectometry on a nanometer scale. Extremely low Li permeation for Cr and Si at room temperature exemplifies the effective blocking of Li movement at least for five years. However, Li permeation through C layers was found to be faster than through Cr and Si layers. With temperature, the Li permeation is enhanced through Cr as compared to that through Si layers. Furthermore, material characterisation shows amorphous LiNbO₃, C and Si layers and polycrystalline Cr layers (with 80% elemental bcc chromium and 20% chromium-oxide situated at Cr/LiNbO₃ interfaces). Annealing in air at 100 °C (373 K) does not oxidize the Cr layers any further. A stress of 12 GPa, which was measured in Cr spacer layers at room temperature, remains unchanged upon annealing. The origin of a weak ferromagnetic order measured at room temperature (300 K) was attributed to some traces of Cr and Si inside LiNbO₃.