A Practical Guide to First‐Principles Calculations for Pseudocapacitive Materials: From Electrochemical Experiments to Atomistic Understanding

We review recent computational advances in understanding the energy storage mechanisms of pseudocapacitive electrode materials, with particular emphasis on first‐principles approaches, including density functional theory (DFT), joint density functional theory (JDFT), and computational electrochemistry at electrode/electrolyte interfaces. Representative classes of pseudocapacitive materials are systematically discussed together with the theoretical foundations, practical methodologies, and representative applications of first‐principles calculations. Particular attention is devoted to quantitative descriptions of the competition between electric double‐layer formation and Faradaic redox reactions, which governs pseudocapacitive charge storage under realistic electrochemical conditions. This review also summarizes practical considerations for computational modeling, software selection, and interpretation of computational results, providing a practical guide for researchers working at the interface between computational and experimental electrochemistry. Finally, recent developments in computational electrochemistry, together with emerging methodologies that extend first‐principles calculations, including machine‐learning potential, computational electrochemistry, and emerging electrochemoinformatics, are highlighted, along with their future prospects for predictive materials design.