Condition dependence of Zr electrochemical reactions and morphological evolution of Zr deposits in molten salt

Abstract

This work presents a comprehensive study for the electrochemical behaviors of zirconium in LiCl-KCl eutectic. The effects of stirring, temperature and Zr concentration on the electrode reactions, the ZrCl4 sublimation from the melt, microcosmic morphologies of Zr deposits (ZrCl and Zr) obtained at different potential and temperature have been investigated. The behaviors of Zr(IV), on a large concentration range from 0.13% to 2.28% in melt, show a multiple-step reaction involving Zr(IV), Zr(II), ZrCl and Zr species. Temperature plays a crucial role on the changes of Zr(IV) reduction behavior on the solid electrode. The Zr(IV)/ZrCl couple is more easily observed at lower temperature and gradually diminishes with the increase of temperature. The Zr(IV)/Zr(II) and Zr(II)/Zr reactions are predominant on the W electrode at higher temperatures. At 673 K, a layered structure of insoluble ZrCl formed by potentiostatic electrolyses at 1.1 V was visualized by scanning electron microscopy-energy dispersive X-ray (SEM-EDS), while only Zr metal particles was observed at higher temperature than 773 K. An evolution of the Zr-based structure and size corresponding to the ZrCl and Zr metal based on different potentiostatic electrolysis was observed. The average particle size of the Zr metalparticles increases with the increase of temperature.