【摘要】 基于固体Al阴极分离锕系元素（An）与裂变产物（FP）的电解精炼技术是极具前景的干法后处理流程之一。本研究采用暂态电化学法系统研究了Pu³⁺在固体Al阴极上的电化学行为。循环伏安法（CV）和方波伏安法（SWV）研究结果表明，Pu³⁺在Al阴极上可一步还原为合金，且该反应为不可逆，Pu³⁺与Al形成合金的电位与温度的关系式为E^■,*(Pu³⁺/PuAl_n)（vs. Cl^-/Cl₂）=-2.944+9.84×10^-4T。开路计时电位法（OCP）结合相图表明，Pu³⁺在固体Al阴极上可生成Pu₃Al、PuAl、PuAl₂、PuAl₃和PuAl₄五种合金化合物，且计算得到了不同温度时PuAl₄的Gibbs生成自由能。更多还原

【Abstract】 The electrolytic separation of actinides（An） from fission products（FPs） on solid Al cathode is one of the most promising pyrochemical reprocessing processes. In this work, the electrochemical behaviour of Pu³⁺ on active Al solid cathode was studied through the transient electrochemical method. Based on the results of cyclic voltammetry（CV） and square wave voltammetry（SWV）, Pu³⁺ can be reduced into alloy through a one-step three-electrons transfer process on Al cathode, and the reaction is irreversible. The relationship between the reduction potential of the alloy formed by Pu³⁺ with Al and temperature is E^■,*(Pu³⁺/PuAl_n)（vs. Cl^-/Cl₂）=-2.944+9.84×10^-4T. Five Pu alloys（involving Pu₃Al, PuAl, PuAl₂, PuAl₃, and PuAl₄） are formed according to the results of open circuit chronopotentiometry（OCP） together with phase diagrams of Pu-Al. Furthermore, the formation Gibbs free energies of PuAl₄ at different temperature are calculated.更多还原