The kinetics process of a Pb(<scp>ii</scp>)/Pb(0) couple and selective fabrication of Li–Pb alloys in LiCl–KCl melts

Abstract

The electrode reaction of Pb(ii) and co-reduction of Li(i) and Pb(ii) were investigated on a tungsten electrode in LiCl-KCl eutectic melts by a range of electrochemical techniques. From cyclic voltammetry and square wave voltammetry measurements, the reduction of Pb(ii) was found to be a one-step diffusion-controlled reversible process with the exchange of 2 electrons. The diffusion coefficients of Pb(ii) were computed, and they obey the Arrhenius law. Using the linear polarization technique, the kinetic parameters, such as exchange current intensity (<i>j</i> ₀), standard rate constant (<i>k</i> ⁰) and charge transfer resistance (<i>R</i> _ct) for the Pb(ii)/Pb(0) couple on a tungsten electrode were studied at different temperatures, and the activation energy is 27.32 kJ mol^-1, smaller than the one for diffusion of Pb(ii), which further confirmed that the reduction of Pb(ii) was controlled by diffusion. A depolarisation effect for Li(i) reduction was observed from the results of cyclic voltammetry, square wave voltammetry and chronopotentiometry due to the formation of Li-Pb alloys by co-reduction of Li(i) and Pb(ii). Furthermore, five Li-Pb intermetallic compounds, LiPb, Li₈Pb₃, Li₃Pb, Li₁₀Pb₃ and Li₁₇Pb₄ characterized by scanning electronic microscopy and X-ray diffraction, were selectively prepared by potentiostatic electrolysis on a tungsten electrode and galvanostatic electrolysis on a liquid Pb electrode, respectively.