Electron Delocalization and Electrochemical Potential Distribution Phenomena in Faradaic Electrode Materials for Understanding Electrochemical Behavior

Electrochemical energy storage devices are built upon the foudations of batteries and supercapacitors. In the past decade, new pseudocapacitor-like electrodes are intensively developed to obtain superior energy storage performance. Pseudocapacitive matarials store charge through Faradaic processes, while the electrochemical signal remains like electrochemical double-layer capacitors (EDLCs). To address this controversy, an analytical model is introduced for evaluating the voltammograms of electrode materials. Given this, the work focuses on understanding the origin of the pseudocapacitive phenomena in the cyclic voltammetry (CV) electrochemical signal. Based on electron transfer mechanism and tunnelling effect within the atomic structure, pseudocapacitive matarials possess a high electron delocalization possibility related to the redox centers number and initiates the electrochemical potential distribution among neighboring redox sites, which is consequently observed in the electrochemical signal as the plateau feature in CV, like EDLC. First, the determination of the capacitive tendency of various electrode materials is proposed, which turns out to be relative to the redox centers number (n) and total charge (Z). Here, when this number is large, electron hopping will very likely happen. The developed model is versatile to predict rate/potential regimes for the maximum faradaic storage, and then well differentiates the pseudocapacitive and battery materials. Electrochemical energy storage devices, like batteries and supercapacitors, have distinct charge-storage systems resulting in varied energy and power densities. Understanding this phenomenon is challenging due to the lack of a comprehensive analytical model. This article discusses electron transfer mechanisms, highlighting differences between battery and pseudocapacitive materials. It demonstrates that both exhibit electron delocalization, leading to a wide redox potential distribution. image