Transition metal carbides are a class of materials widely known for both their interesting physical properties and catalytic activity. In this work, we have used plane-wave DFT methods to study the interaction with increasing amounts of molecular hydrogen on the low-index surfaces of four major carbides – TiC, VC, ZrC and NbC. Adsorption is found to be generally exothermic and occurs predominantly on the surface carbon atoms. We identify trends over the carbides and their surfaces for the energetics of the adsorption as a function of their electronic and geometrical characteristics. An ab initio thermodynamics formalism is used to study the properties of the slabs as the hydrogen coverage is increased.

Solid electrolytes have shown superior behavior and many advantages over liquid electrolytes, including simplicity in battery design. However, some chemical and structural instability problems arise when solid electrolytes form a direct interface with the negative Li-metal electrode. In particular, it was recognized that the interface between the β-Li₃PS₄ crystal and lithium anode is quite unstable and tends to promote structural defects that inhibit the correct functioning of the device. As a possible way out of this problem, we propose a material, Li₂S, as a passivating coating for the Li/β-Li₃PS₄ interface. We investigated the mutual affinity between Li/Li₂S and Li₂S/β-Li₃PS₄ interfaces by DFT methods and investigated the structural stability through the adhesion energy and mechanical stress. Furthermore, a topological analysis of the electron density identified preferential paths for the migration of Li ions.

We present a computational study of the activity and selectivity of early transition-metal carbides as carbon dioxide reduction catalysts. We analyze the effects of the adsorption of CO₂ and H₂ on the (001), (011), and metal-terminated (111) surfaces of TiC and ZrC, as carbon dioxide undergoes either dissociation to CO or hydrogenation to COOH or HCOO. The relative stabilities of the three reduction intermediates and the activation energies for their formation allow the identification of favored pathways on each surface, which are examined as they lead to the release of CO, HCOOH, CH₃OH, and CH₄, thereby also characterizing the activity and selectivity of the two materials. Reaction energetics implicate HCO as the key common intermediate on all surfaces studied and rule out the release of formaldehyde. Surface hydroxylation is shown to be highly selective toward methane production as the formation of methanol is hindered on all surfaces by its barrierless conversion to CO.

In the roadmap toward designing new and improved materials for Lithium ion batteries, the ability to estimate the diffusion coefficient of Li atoms in electrodes, and eventually solid-state electrolytes, is key. Nevertheless, as of today, accurate prediction through computational tools remains challenging. Its experimental measurement does not appear to be much easier. In this work, we devise a computational protocol for the determination of the Li-migration energy barrier and diffusion coefficient, focusing on a common cathode material such as LiNiO₂, which represents a prototype of the widely adopted NMC (LiNi_1-x-y Mn _x Co _y O₂) class of materials. Different methodologies are exploited, combining ab initio metadynamics, path sampling, and density functional theory. Furthermore, we propose a novel, fast, and simple 1D approximation for the estimation of the effective frequency. The outlined computational protocol aims to be generally applicable to Lithium diffusion in other materials and components for batteries, including anodes and solid electrolytes.