Electrode Processes in Vanadium‐Containing Chloride Melts

Polovov, Ilya B.; Tray, M. E.; Чернышов, М. В.; Volkovich, Vladimir A.; Vasin, B. D.; Rebrin, O. I.

doi:10.1002/9781118448847.ch4e

Cited by 8 publications

(20 citation statements)

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“…3) [11], because in this electrolyte system the potential of the QRE is established by the reaction V/V 2+ due to its contact to metallic V and divalent ions. It is close to the stationary potential (-1955 mV vs. Cl 2 /Cl -) of vanadium reported for NaCl-KCl at 698 °C [9].…”

Section: Electrochemical Measurementssupporting

confidence: 87%

“…Further reactions such as V 3+ / V 4+ considered by Polovov et al [9] were not observed in our experiments. As already reported elsewhere, higher oxidation states (V 4+ and V 5+ ) can be expected in the presence of oxygen [10,11].…”

Section: Electrochemical Measurementscontrasting

confidence: 67%

“…Cyclic voltammograms recorded in (LiCl-KCl) (eut.) -0.34mol% VCl 3 melt ( Figure 1, without V metal addition) exhibited current peaks, which can be attributed to the following reactions [9]: The current peaks R1 and O1 correspond to the electrodeposition of divalent ions and its anodic dissolution process (eq. 1).…”

Section: Electrochemical Measurementsmentioning

confidence: 99%

“…Literature on the nature and behaviour of vanadium metal and its ionic species in molten salts is very limited. In one recent publication [9], a study on the electrochemistry of vanadium in NaCl-KCl melts with various methods has been reported, including anodic dissolution, oxidation and reduction reactions of trivalent and divalent vanadium ions as well as the electrodeposition process. Furthermore, the structure of ionic vanadium species has been characterised in different studies [10,11] by means of absorption spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

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Effect of vanadium ion valence state on the deposition behaviour in molten salt electrolysis

et al. 2018

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The electrodeposition process of vanadium from LiCl-KCl base electrolytes was investigated by means of cyclic voltammetry, galvanostatic electrolyses and micro analytical analysis of the deposits. It is demonstrated that the valence state of the vanadium ions has a critical influence on the feasibility of performing a reproducible and stable coating process aiming to obtain compact vanadium films. When the electrolyte contained predominantly trivalent vanadium ions, the process was unstable and the deposit consisted of dendrites. In contrast, making use of a comproportionation reaction of metallic vanadium and VCl 3 to divalent vanadium ions led to a stable deposition behaviour and allowed to obtain thick deposits with high current efficiencies. The disadvantageous behaviour of melts with mostly trivalent ions is explained by the fact that deposition is interfered by the reduction of trivalent to divalent ions under limiting current conditions.

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Section: Electrochemical Measurementssupporting

confidence: 87%

Section: Electrochemical Measurementscontrasting

confidence: 67%

Section: Electrochemical Measurementsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Effect of vanadium ion valence state on the deposition behaviour in molten salt electrolysis

et al. 2018

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“…The electrochemistry of titanium ions [16][17][18] as well as the electrodeposition of titanium [19,20] is widely investigated, whereas there are only few articles about electrorefining [21][22][23][24] and the electrochemical behaviour of vanadium ions [25] in molten salts.…”

Section: Introductionmentioning

confidence: 99%

Electrodeposition of titanium–vanadium alloys from chloride-based molten salts: influence of electrolyte chemistry and deposition potential on composition, morphology and microstructure

et al. 2020

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In the present study, we demonstrate co-deposition of titanium and vanadium from a eutectic LiCl-KCl electrolyte enriched with VCl 3 and TiCl 2 at 700 K. While the addition of metallic titanium to the electrolyte caused vanadium depletion by a displacement reaction, metallic vanadium addition created and stabilized divalent vanadium ions in the melt, which are supposed to positively affect the deposition process. Various electrochemical experiments were carried out with different electrolyte concentrations, and a relationship between applied potential, electrolyte concentration and composition of the deposit was established. The composition and the morphology of the obtained deposits were strongly affected by the electrolysis conditions. Electrodeposited vanadium-rich Ti-V alloys were found to grow as dendrites, whereas the titanium-rich alloys exhibited a dense cauliflower-like surface morphology. In contrast to deposits of the single elements, which are composed of comparably large faceted crystals, the Ti-V alloys obtained in this study were very fine grained, especially those with vanadium contents around 10-15 at%. Transmission electron microscopy revealed that, depending on the composition of the deposit, either a biphasic α + β microstructure in the case of low vanadium contents or β-(V,Ti) with small amounts of ω phase for high vanadium contents were found.

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