中文摘要：

利用动电位极化和循环伏安法对全钒液流电池阳极VO2＋/VO2＋电偶的氧化反应的动力学行为进行了研究。动电位极化曲线的分析表明：在η〈0．130V时电荷转移步骤为电极过程的控制步骤；在0．130V〈η〈0．330V时电极过程受电荷转移和扩散步骤混合控制；当η〉0．330V时扩散步骤为电极过程的控制步骤。利用动电位极化和循环伏安法的实验结果计算出25℃时实验溶液中VO2＋/VO2＋氧化反应的相关参数：交换电流密度为5．34×10^-5 A／cm2；平衡电极电位0．717V：电荷传递电阻为462．8Ω·cm2；电荷传递系数0．57；VO2＋的扩散系数3．52×10^-11 cm／s；反应平衡常数6．71×10^-7。分析VO孙的氧化反应历程，实验证明了VO乱的氧化反应为单电子不可逆反应。并具有随后可逆化学反应的电化学反应的特征。

英文摘要：

The mechanism and kinetics of the oxidation process of VO2＋/VO2＋ redox couple on graphite electrode in sulfuric acid solution was studied by dynamic polarization and cyclic voltammetry method. By the polarization curve analysis, it is known that the anodic oxidation process is controlled by the electrochemical step when η〈0.130 V and by the diffusion process 0.330 V〈η. According to the results of the polarization and cyclic voltammetry, the exchange current density is calculated as 5.34 × 10^-5 A/cm2; the equilibrium electrode potential is 0.717 V; the charger transfer resistance is 462.8Ω.cm2; the charge transfer coefficient is 0.57; the diffusion coefficient of VO2＋ ion is 3.52 × 10^-11 cm/s and the reaction equilibdum constant is 6.71 ×10^-7. The cyclic voltammetry results indicate that the mechanism of VO2＋ oxidation is a one-electron transfer reaction followed by reversible chemical process.