Application of First Principles Computations Based on Density Functional Theory (DFT) in Cathode Materials of Sodium-Ion Batteries

Abstract

Sodium-ion batteries (SIBs) have been widely explored by researchers because of their abundant raw materials, uniform distribution, high-energy density and conductivity, low cost, and high safety. In recent years, theoretical calculations and experimental studies on SIBs have been increasing, and the applications and results of first-principles calculations have aroused extensive interests worldwide. Herein, the authors review the applications of density functional (DFT) theory in cathode materials for SIBs, summarize the applications of DFT in transition-metal oxides/chalcogenides, polyanionic compounds, Prussian blue, and organic cathode materials for SIBs from three aspects: diffusion energy barrier and diffusion path, energy calculation and structure, and electronic structure. The relationship between the structure and performance of the battery material will be comprehensively understood by analyzing the specific working principle of battery material through theoretical calculation and combining with high-precision experimental characterization technologies. Selecting materials with good performance from a large number of electrode materials through theoretical calculation can avoid unnecessary complex experiments and instrument characterizations. With the gradual deepening of research, the DFT calculation will play a greater role in the sodium-ion battery electrode field.

Facilitating Layered Oxide Cathodes Based on Orbital Hybridization for Sodium‐Ion Batteries: Marvelous Air Stability, Controllable High Voltage, and Anion Redox Chemistry

“…[153] DFT calculations (Figure 12m,n) show that Cu 3d orbital overlap more with O 2p near the E F and the Mn─O bond length tends to average out, indicating that Cu substitution can modulate the electronic structure around the Mn─O bond (Figure 12o,p), thus alleviating the anisotropic coupling between oxidized O 2− and Mn 4+ . [154,155] Therefore, it is clear that Cu substitution inhibits the phase transition and the structure of P'2 transforms into the OP4 phase during the Na + extraction process. [156] The overall electrochemical properties are further improved.…”

“…Thirdly, the application of theoretical calculations has been extensively explored in recent years to analyze the kinetics of elec-trochemical reactions at the atomic scale and hence the mechanism for storing energy. [154,203] The relationship between structure and performance can be further explored through high precision experimental characterization approaches. [204] It has been shown that first-principles calculations of the energy levels of electrode materials can theoretically assess whether or not the cathode design is appropriate.…”

Basic guidelines of first-principles calculations for suitable selection of electrochemical Li storage materials: a review

“…Hence, computations have evolved into a fundamental pillar of research related to batteries, offering valuable insights into underlying processes. Computational investigations of specic battery materials have recently been reviewed by Ceder et al, 17 Kuganathan, 18 Chen et al, 19 Zou et al, 20 Kowalski et al 21 and many others. [22][23][24][25][26] Li 6 -SiO 4 Cl 2 is a candidate electrolyte material which was recently characterized by Kuganathan using both experimental and computational techniques.…”

“…18 DFT theory is also applied to transition-metal oxides/chalcogenides, polyanionic compounds, Prussian blue, and organic cathode materials for SIBs in three ways: diffusion energy barrier and diffusion path, energy calculation and structure, and electronic structure. 19 Kowalski et al discussed correct computation of electronic structures, oxidation states and related redox reactions, phase transformation in doped oxides and challenges in the computation of surface chemical reactions on oxides and metal surfaces in the presence of electrolyte. 21 DFT has significant potential to aid understanding of advanced LIB technology by enabling material discovery, understanding electrochemical reactions, optimizing electrolytes, studying interfaces, analyzing stress and strain, exploring new materials, elucidating energy storage mechanisms, reducing costs, and accelerating research and development.…”

Advances in data‐assisted high‐throughput computations for material design

“…Batteries utilize different kinds of materials to achieve specific electrochemical reactions and energy storage. Many researchers were dedicated to developing new materials to improve properties of batteries such as energy density, cycle life, charge–discharge rate, and safety [280–282] . While these descriptors can be obtained via usual DFT calculations, the HTC strategy may significantly improve the efficiency in computational design and screening for battery materials.…”