Theoretical Analysis for Faradaic and Non-Faradaic Processes at Solid/Liquid Interface

准确理解固/液界面相中所发生的电化学现象的本质对正确把握界面区的储能和电荷传递行为至关重要。本文从多相体系的热力学基本公式出发，推导出了带电界面相Gibbs自由能的通用型表达式，并依据该公式探讨了理想不可极化电极体系、理想可极化电极体系的不同电化学行为。此外，还估算了离子双电层中剩余电荷的覆盖度，阐述了界面相的电容、电阻行为在伏安曲线中的表现形式。上述研究工作有助于帮助电化学研究者从理论深层了解和掌握不同条件下带电界面相的电化学特征。Having a good understanding of inherent property of electrochemical phenomena taking place at solid-liquid interphases plays a crucial role in grasping the essence of energy storage and charge transfer. Herein the general expression of Gibbs free energy of interfacial phases was derived based on the basic thermodynamic equations of multiphase systems, by means of which the electrochemical behavior and characteristics of the ideally non-polarizable and polarizable electrode systems were interpreted. Meanwhile, the coverage of residual charge in electric double layer and the representations of capacitive and resistive behavior in voltammetric curves were also presented. The present theoretical analyses are very helpful for the researchers in the field of electrochemistry to understand the electrochemical characteristics at a charged interface under different conditions.