Enhanced lithium storage and chemical diffusion in metal-LiF nanocomposites: Experimental and theoretical results
An extra storage of Li has been observed experimentally at low potential in Me/LiF nanocomposites where Me refers to transition metals such as Cu, Co, etc., with a pseudocapacitive behavior characterized by a high rate performance. To understand the mechanistic details of the lithium storage anomaly, we have performed comparative ab initio calculations on the atomic and electronic structure of the nonpolar Cu/ LiF001 and model Li/ LiF001 interfaces. For this aim, we inserted extra Li atoms at several possible sites of the periodic two-dimensional Me/LiF Me= Cu, Li interfaces. The energetically most favorable site for extra Li atom is
Evidence for Interfacial-Storage Anomaly in Nanocomposites for Lithium Batteries from First-Principles Simulations
We present theoretical support for a mass storage anomaly proposed for nanocomposites in the context of lithium batteries which forms the transition between an electrostatic capacitive mechanism and an electrode mechanism. Ab initio atomic and electronic structure calculations, performed on the Ti(0001)/Li2O(111) model interface, indicate the validity of the phenomenological model of interfacial Li storage and provide a deeper insight into the local situation. Beyond the specific applicability to storage devices, the possibility of a two-phase effect on mass storage generally highlights the availability of novel degrees of freedom in materials research when dealing with nanocomposites.
Enhanced interfacial lithium storage in nanocomposites of transition metals with LiF and Li2O: Comparison of DFT calculations and experimental studies
Abstract Me/LiX nanocomposites (Me – transition metal and X = F or O) exhibit extra lithium storage, with pseudo-capacitive behavior and high-rate performance. While LiX surface layers or the interfacial core serves as hosts for extra Li, atoms of contacting transition metal serve as electron sinks, depending on Me electronegativity. To verify the mechanism, we have performed comparative DFT-LCAO calculations on the polar Ti|Li|Li2O(111) and non-polar Cu|Li|LiF(001) interfaces with extra Li atoms inserted inside both 2D interfaces, gradually changing their concentration. Theoretical calculations confirm validity of this interfacial model for explanation of the extra storage capacity at low …