Electrochemical measurements of diffusion coefficients and activity coefficients for MnCl2 in molten eutectic LiCl-KCl

Horváth, Dávid; Rappleye, Devin; Bagri, Prashant; Simpson, Michael F.

doi:10.1016/j.jnucmat.2017.06.015

Cited by 8 publications

(12 citation statements)

References 21 publications

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“…A possible mechanism for this interdependency is detailed below based on the concept of "sacrificial protection". During the corrosion process, Mn atoms at the surface will have the highest driving force to deplete and dissolve into molten salt since the salt redox potential, fixed by the europium redox couple, is higher than that of MnCl 2 , [16,30] and the Gibbs free energy of MnCl 2 /Mn is the lowest compared to other three element constituents of the printed alloys (Fe, Cr, and Ni). Following the dissolution, vacancies will be injected in the alloy subsurface (see Figure 4c).…”

Section: Discussionmentioning

confidence: 99%

“…However, a few studies [18,19] performed electrochemical test of FeCl 2 in LiCl-KCl molten salt at 500 °C to study the diffusion coefficient of Fe 2+ at different concentrations up to 5000 ppm and no salt saturation was observed. Electrochemical study of MnCl 2 in LiCl-KCl molten salt at 500 °C was conducted by Simpson et al [20] at different concentrations up to 8100 ppm and no salt saturation was observed as well. The concentrations of Fe 2+ and Mn 2+ in LiCl-KCl molten salt reported in these studies [18][19][20] are much higher than the total concentrations of corrosion products obtained by ICP-MS (Figure 4b) in this study.…”

Section: Htp Materials/molten Salt Compatibility Testmentioning

confidence: 99%

“…Electrochemical study of MnCl 2 in LiCl-KCl molten salt at 500 °C was conducted by Simpson et al [20] at different concentrations up to 8100 ppm and no salt saturation was observed as well. The concentrations of Fe 2+ and Mn 2+ in LiCl-KCl molten salt reported in these studies [18][19][20] are much higher than the total concentrations of corrosion products obtained by ICP-MS (Figure 4b) in this study. Based on these literature inputs, it is unlikely that salt saturation occurred in the HTP corrosion experiment.…”

Section: Htp Materials/molten Salt Compatibility Testmentioning

confidence: 99%

See 2 more Smart Citations

Integrated High‐Throughput and Machine Learning Methods to Accelerate Discovery of Molten Salt Corrosion‐Resistant Alloys

et al. 2022

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Insufficient availability of molten salt corrosion-resistant alloys severely limits the fruition of a variety of promising molten salt technologies that could otherwise have significant societal impacts. To accelerate alloy development for molten salt applications and develop fundamental understanding of corrosion in these environments, here an integrated approach is presented using a set of high-throughput (HTP) alloy synthesis, corrosion testing, and modeling coupled with automated characterization and machine learning. By using this approach, a broad range of Cr-Fe-Mn-Ni alloys are evaluated for their corrosion resistances in molten salt simultaneously demonstrating that corrosion-resistant alloy development can be accelerated by 2 to 3 orders of magnitude. Based on the obtained results, a sacrificial protection mechanism is unveiled in the corrosion of Cr-Fe-Mn-Ni alloys in molten salts which can be applied to protect the less unstable elements in the alloy from being depleted, and provided new insights on the design of high-temperature molten salt corrosion-resistant alloys.

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Section: Discussionmentioning

confidence: 99%

Section: Htp Materials/molten Salt Compatibility Testmentioning

confidence: 99%

Section: Htp Materials/molten Salt Compatibility Testmentioning

confidence: 99%

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Integrated High‐Throughput and Machine Learning Methods to Accelerate Discovery of Molten Salt Corrosion‐Resistant Alloys

et al. 2022

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“…Conventional direct current (DC) techniques for measuring D, such as chronopotentiometry (CP), cyclic voltammetry (CV), and chronoamperometry (CA), induce significant changes in potential or current flow, resulting in notable alterations in electrode surface characteristics during the electrodeposition. [4][5][6] In contrast, electrochemical impedance spectroscopy (EIS) employs small, transient potential perturbations, specifically superimposed alternating current (AC), thereby mitigating the impact of deposition and dissolution on the electrode surface. 7,8 Additionally, the inherent attributes of AC techniques facilitates a distinct discrimination between capacitive and Faradaic currents, potentially improving the accuracy of D determination.…”

mentioning

confidence: 99%

Determination of the Diffusion Coefficient in Electrodeposition Reactions by Electrochemical Impedance Spectroscopy: A Case Study of Cobalt in Molten LiCl-KCl Salt

Cha,

Park,

Yun

2024

J. Electrochem. Soc.

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Compared to direct current (DC) techniques, electrochemical impedance spectroscopy (EIS) allows for a more accurate determination of the diffusion coefficient of metal ions in electrodeposition reactions. However, its actual application has been less attempted due to the difficulty in determining complex parameters, such as the concentration of deposited species in the electrode matrix. Here, we introduce a simplified approach to facilitate the EIS application to electrodeposition reactions, using the Co(II)/Co(0) reaction in molten LiCl-KCl salt as a case study. The working electrode surface area was determined by the photography of the electrochemical cell taken in situ. The diffusion coefficients of Co(II) in the LiCl-KCl salt, determined by EIS, were found to be (3.56±0.49)×10-5 cm2/s and (1.61±0.12)×10-5 cm2/s for the tungsten and liquid bismuth electrodes, respectively. The possible reasons for the observed discrepancy in the diffusion coefficients of Co(II) obtained from the two different electrodes are discussed.

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“…In molten chloride salts, it is not uncommon to find studies in which diffusion coefficient values calculated from electrodeposition peaks in CV measurements differ significantly from those calculated from other electrochemical methods. [21][22][23][24][25][26][27][28][29][30][31][32] This is partly due to the application of B-D equation when a foreign substrate and/or digital staircase is used.…”

mentioning

confidence: 99%

Bringing the Analysis of Electrodeposition Signals in Voltammetry Out of the Shadows

Rappleye

Fuller

2023

J. Electrochem. Soc.

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Voltammetry studies of electrodeposition are growing rapidly. Yet, relations for the analysis of electrodeposition reactions in voltammetry remain relatively obscure in the literature. The existing cyclic and square wave voltammetry relations for electrodeposition and their limitations are discussed to increase awareness. A retrospective analysis is performed to demonstrate the impact of model selection in improving the analysis of electrodeposition behavior with voltammetric data. A repository for voltammetry models of electrodeposition is proposed to further increase familiarity and application of the most appropriate models, which would support a rapidly growing area of research and technological development.

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Electrochemical measurements of diffusion coefficients and activity coefficients for MnCl2 in molten eutectic LiCl-KCl

Cited by 8 publications

References 21 publications

Integrated High‐Throughput and Machine Learning Methods to Accelerate Discovery of Molten Salt Corrosion‐Resistant Alloys

Integrated High‐Throughput and Machine Learning Methods to Accelerate Discovery of Molten Salt Corrosion‐Resistant Alloys

Determination of the Diffusion Coefficient in Electrodeposition Reactions by Electrochemical Impedance Spectroscopy: A Case Study of Cobalt in Molten LiCl-KCl Salt

Bringing the Analysis of Electrodeposition Signals in Voltammetry Out of the Shadows

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