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Research Article

Electrochemistry of Hf (IV) in NaCl-KCl-NaF-K2HfF6 molten salts

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  • Received: 19 March 2020Revised: 21 April 2020Accepted: 26 April 2020Available online: 30 April 2020
  • In order to obtain the purified dendritic hafnium metal, the cathodic redution mechanism of Hf (IV) ions in NaCl-KCl-NaF-K2HfF6 fused salt system were studied in various NaF concentrations at 1073 K. The results of cyclic voltammetry and square wave voltammetry indicate that the reduction process is two steps of Hf (IV)→Hf (II) and Hf (II) →Hf at lower NaF concentrations (0<[F-/Hf4+]<17.39), and one step Hf (IV) →Hf at higher NaF concentrations (17.39< [F-/Hf4+] <23.27). The structure and morphology of the deposits obtained by potentiostatic electrolysis at one step reduction process were analysised and verifyed by XRD, SEM and EDS. At one-step reduction process, the disproportionation reaction between hafnium metal and hafnium complex ions was inhibited, and large dendrite hafnium metal was achieved in molten salt electrorefining.
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Electrochemistry of Hf (IV) in NaCl-KCl-NaF-K2HfF6 molten salts

  • Corresponding author:

    Yan-ke Wu    E-mail: luckwyk@163.com

  • GRINM Resources and Environment Tech. Co., Ltd, Beijing 101407, China

Abstract: In order to obtain the purified dendritic hafnium metal, the cathodic redution mechanism of Hf (IV) ions in NaCl-KCl-NaF-K2HfF6 fused salt system were studied in various NaF concentrations at 1073 K. The results of cyclic voltammetry and square wave voltammetry indicate that the reduction process is two steps of Hf (IV)→Hf (II) and Hf (II) →Hf at lower NaF concentrations (0<[F-/Hf4+]<17.39), and one step Hf (IV) →Hf at higher NaF concentrations (17.39< [F-/Hf4+] <23.27). The structure and morphology of the deposits obtained by potentiostatic electrolysis at one step reduction process were analysised and verifyed by XRD, SEM and EDS. At one-step reduction process, the disproportionation reaction between hafnium metal and hafnium complex ions was inhibited, and large dendrite hafnium metal was achieved in molten salt electrorefining.

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