Theoretical approaches to defect mechanisms and transport properties of compounds used for electrodes and solid-state electrolytes in alkali-ion batteries.

The transition from fossil fuels to cleaner energies employing different renewable sources constitutes one of the primary worldwide challenges. The search for appropriate solutions is becoming more urgent in view of the severe consequences of climate change. As for a perspective, stationary energy storage, alkali-ion batteries and hybrid supercapacitors are, among others, considered as efficient and affordable solutions. Alkali-ion batteries have proved to be the most investigated products in the past decade including optimizations for cost, energy density and safety. In this Perspective, a computational approach and its applicability in the inverse material design are presented. This approach includes density functional theory calculations, force field-based determinations and both static and molecular dynamics simulations. As for an illustration, the main properties of a selected series of battery materials, including oxides and sulfides Li 2 SiO 3 , Li 2 SnO 3 , SrSnO 3 , and A 2 B 6 X 13 (A = Li + , Na + , K + ; B = Ti 4+ , Sn 4+ ; X = O 2- , S 2- ), and mixed halide antiperovskite A 3 OX (A = Li + , Na + ; X = Cl - , Br - ) are explored in depth using these theoretical approaches. Doping strategies, new dopant incorporation mechanism, treatment with alkali insertion/de-insertion cycle in electrodes, transport properties, as well as thermodynamic stability, are discussed. Theoretical approaches reveal that the oxygen-sulfur exchange in alkali hexatitanates and hexastannates induces remarkable improvement of the required properties for electrode and electrolyte materials. In addition, doping of Li 2 SiO 3 with low Na-concentration enhances the room temperature Li-diffusivity by a reduction of the activation energy. The effects of transition-metal and divalent dopants on the defect chemistry and transport properties of Li 2 SnO 3 are also disclosed. The interstitial trivalent doping mechanism is a friendly synthesis strategy to improve the large-scale diffusion in Li 2 SnO 3 . The potential of SrSnO 3 as an anode in alkali-ion batteries, and the influence of a particular grain boundary in nanocrystalline antiperovskite A 3 OX are also revealed by using advanced atomistic simulations. The computational approaches described here provide us with a convenient tool for the determination of the properties of battery materials with high accuracy and for the prediction of characteristics of a new generation of alkali battery materials that could be used in improved technologies.