Density Functional Theory for Battery Materials

Abstract

Batteries are the most widely used energy storage devices, and the lithium‐ion battery is the most heavily commercialized and most widely used battery type in the industry. However, the current rapid development of society requires a major advancement in battery materials to achieve high capacity, long life cycle, low cost, and reliable safety. Therefore, many new efficient energy storage materials and battery systems are being developed and explored, and their working mechanisms must be clearly understood before industrial application. In recent years, density functional theory (DFT) has been employed in the energy storage field and has made significant contributions to the understanding of electrochemical reaction mechanisms and to virtual screening of promising energy storage materials. In this review, the applications of DFT to battery materials are summarized and exemplified by some representative and up‐to‐date studies in the literature. The main focuses in this review include the following: 1) structural stability estimation by cohesive energy, formation energy, Gibbs free energy, and phonon dispersion spectra calculations; 2) the Gibbs free energy calculations for electrochemical reactions, corresponding open‐circuit voltage, and theoretical capacity predictions of batteries; 3) the analyses of molecule orbitals, band structures, density of states (DOS), and charge distribution of battery materials; 4) ion transport kinetics in battery materials; 5) simulations of adsorption processes. We conclude the review with the discussion of the assessments and validation of the popular functionals against several benchmarks, and a few suggestions have been given for the selection of density functionals for battery material systems.

Dendrites in Zn‐Based Batteries

“…This chemisorption computation can effectively depict the diffusion pathway and the accompanied energy-barrier distribution of zinc ions migrating in the matrix of solid-state electrolytes and the artificial interface layer. [227,228] Distinct from the electric field simulation proceeding after the zinc nucleation step, chemisorption computation is mainly employed at the ion diffusion stage before plating, at which point the diffusion direction can be subtly guided. Recently, chemisorption energy calculations were conducted to screen out appropriate conductive substrates from copper, CuZn 5 alloy, brass, nickel, graphene nanoribbon, zinc, and PAM chains for dendrite-free substrate design.…”

Na‐Ion Batteries—Approaching Old and New Challenges

“…Currently, there is a vast toolbox to determine the significance of the solvation shell and the desolvation kinetics at the electrode/electrolyte interface, the strength of the cation‐anion interactions in the Na salts, or the effect of the additives. [ 118–121 ] Simulation and modeling studies are not only limited to elucidation of conduction mechanisms, but also provide fundamental information on the ability of different Na + ‐conducting materials to create a stable SEI. The combination of experimental studies with theoretical calculations is essential for the development of the next generation of high‐performance battery systems, reducing time‐to‐market.…”

Graphene Derivatives and Graphene Composite Electrocatalysts for N2 Reduction Reaction

“…The formation energy is expressed as Equation (14). [ 47 ] where E f is formation energy (eV); n and m are the number of reactants of A and B , respectively; E ( A ) and E ( B ) are the energies (eV) of A and B , respectively; E ( A n B m ) is the energy (eV) of the product A n B m . Generally, the structure is more stable when the E f is more negative.…”

“…[46] The bandgap in the density of states (DOS) profiles commonly is used to determine conductivity. [47][48][49] The DOS represents the number of electrons per unit energy range (E À E þ ΔE), which can effectively discriminate the types of materials (insulator, semiconductor, and conductor). Figure 4 is used as a case to illustrate the role of DOS to analyze the conductivity of materials.…”