First-principles calculation studies of metal-organic frameworks and their derivatives for electrochemical energy conversion and storage

Abstract

Researchers are increasingly focusing on seeking for advanced electrode materials for high-performance secondary batteries and electrocatalysis. One effective method involves the density functional theory-based first-principles calculations, which is used to design and fabricate novel electrode materials. This computational approach predicts electronic structures, chemical bonding, and electrochemical properties at the atomic scale to evaluate their energy storage and conversion performance. Among all energy materials, metal-organic frameworks (MOFs) and their derivatives exhibit significant advantages over traditional electrode materials. These advantages include cost-effective synthesis, high specific surface area, tunable porosity, customizable functionality, electrochemical stability, and their potential to form elaborate heterostructures. First-principles calculations effectively predict the electronic structures of MOF-based materials and the mechanisms of energy conversion and storage. This review pays close attention to the adsorption and diffusivity of metal ions within the porous structures of MOFs and their derivatives, as well as their electrocatalytic behavior and structural stability under varying electrochemical conditions. The discussion begins with the significance of first-principles computation methods in electrochemistry, followed by their application in the study of the electrochemical behaviors of MOFs and derivatives in lithium-ion, sodium-ion, potassium-ion, and lithium‑sulfur batteries, supercapacitors, electrocatalysis, and other battery systems. Finally, we provide mechanistic insights and demonstrate the predictive potential of first-principles calculations for the proper development and optimization of MOF-based materials for diverse energy applications.