Effect of Soluble Corrosion Products on Electrical Double Layer in LiCl-KCl Molten Salts

Guo, Yanjun; Chen, Dongliang; Kim, Hojong; Shi, Feifei

doi:10.1149/1945-7111/ae1b42

Effect of Soluble Corrosion Products on Electrical Double Layer in LiCl-KCl Molten Salts

Journal Article · Wed Nov 12 19:00:00 EST 2025 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/1945-7111/ae1b42· OSTI ID:3012189

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Pennsylvania State University, University Park, PA (United States)

Corrosion in molten salts greatly hampers the application for renewable energy applications like molten salt reactors. To develop effective strategies for corrosion mitigation, understanding the interfacial structures and properties such as specific ion adsorption and electrical double layer capacitance are crucial. Using cyclic voltammetry and electrochemical impedance spectroscopy, we systematically studied the interfaces on various model electrodes including W (solid), Bi (liquid), and the stainless steel 316 in LiCl-KCl eutectic molten salts with the addition of corrosion species CrCl₂ and FeCl₂. Both Cr²⁺ and Fe²⁺ ions increased electrical double layer capacitance, with Cr²⁺ showing specific adsorption behavior and shifting the potential of zero charge, while Fe²⁺ had minimal effect on point of zero charge. Two-working electrode measurements revealed increasing open-circuit potential and electrical double layer capacitance during the exposure of stainless steel 316, indicating its progressive corrosion and ion accumulation at the interface. X-ray photoelectron spectroscopy and Raman confirmed Cr enrichment at the interface. This work highlights the strong correlation between electrical double layer behavior and corrosion dynamics in molten salts and suggests electrical double layer capacitance as a sensitive, in situ indicator for corrosion monitoring.

View Accepted Manuscript (DOE)

Research Organization:: Pennsylvania State University, University Park, PA (United States)

Sponsoring Organization:: USDOE; National Science Foundation (NSF)

Grant/Contract Number:: NE0009286

OSTI ID:: 3012189

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 11 Vol. 172; ISSN 1945-7111; ISSN 0013-4651

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

Ueber einige Gesetze der Vertheilung elektrischer Ströme in körperlichen Leitern, mit Anwendung auf die thierisch-elektrischen Versuche (Schluss.) Helmholtz, H. Annalen der Physik und Chemie, Vol. 165, Issue 7 https://doi.org/10.1002/andp.18531650702	journal	January 1853
Zur Theorie der Elektrolytischen Doppelschicht Stern, Otto Zeitschrift für Elektrochemie und angewandte physikalische Chemie, Vol. 30, Issue 21-22 https://doi.org/10.1002/bbpc.192400182	journal	November 1924
Surface Defects, Ni³⁺ Species, Charge Transfer Resistance, and Surface Area Dictate the Oxygen Evolution Reaction Activity of Mesoporous NiCo₂O₄ Thin Films Dubai, Erik; Wu, Qingyang; Lauterbach, Stefan ChemNanoMat, Vol. 10, Issue 11 https://doi.org/10.1002/cnma.202400242	journal	October 2024
Multi-scale computational study of the molten salt based recycling of spent nuclear fuels: Computational study of recycling spent nuclear fuels Kwak, Dohyun; Noh, Seunghyo; Han, Byungchan International Journal of Energy Research, Vol. 38, Issue 15 https://doi.org/10.1002/er.3210	journal	May 2014
Investigation of the electric double layer in salt melts Ukshe, E. A.; Bukun, N. G.; Leikis, D. I. Electrochimica Acta, Vol. 9, Issue 4 https://doi.org/10.1016/0013-4686(64)80049-9	journal	April 1964
Zero-point potentials of metals in molten alkali halides and their binary mixtures Smirnov, M. V.; Stepanov, V. P. Electrochimica Acta, Vol. 24, Issue 6 https://doi.org/10.1016/0013-4686(79)87047-4	journal	June 1979
XPS and IR investigations of FeCl3-doped polyphenylacetylene: the solvent effect Russo, M. V.; Polzonetti, G.; Furlani, A. Synthetic Metals, Vol. 39, Issue 3 https://doi.org/10.1016/0379-6779(91)91755-Y	journal	January 1991
Double layer capacitance on a rough metal surface: Surface roughness measured by “Debye ruler” Daikhin, L. I.; Kornyshev, A. A.; Urbakh, M. Electrochimica Acta, Vol. 42, Issue 19 https://doi.org/10.1016/S0013-4686(97)00106-0	journal	January 1997
The capacitance of the electric double layer of electrodes in molten salts Kisza, Adolf Journal of Electroanalytical Chemistry, Vol. 534, Issue 2 https://doi.org/10.1016/S0022-0728(02)01148-8	journal	October 2002
The electrical double layer in molten salts Graves, A. D. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 25, Issue 3 https://doi.org/10.1016/S0022-0728(70)80097-3	journal	May 1970
The electrical double layer in molten salts Graves, A. D.; Inman, D. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 25, Issue 3 https://doi.org/10.1016/S0022-0728(70)80098-5	journal	May 1970
The analysis of electrode impedances complicated by the presence of a constant phase element Brug, G. J.; van den Eeden, A. L. G.; Sluyters-Rehbach, M. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 176, Issue 1-2 https://doi.org/10.1016/S0022-0728(84)80324-1	journal	September 1984
Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials Yamashita, Toru; Hayes, Peter Applied Surface Science, Vol. 254, Issue 8 https://doi.org/10.1016/j.apsusc.2007.09.063	journal	February 2008
Specific adsorption induced electric double layer on gallium-based liquid metal electrode Gao, Xiongfei; Zhang, Lu-Wen; Liew, K. M. Applied Surface Science, Vol. 636 https://doi.org/10.1016/j.apsusc.2023.157804	journal	November 2023
Defining the nature of adventitious carbon and improving its merit as a charge correction reference for XPS Grey, Lauren H.; Nie, Heng-Yong; Biesinger, Mark C. Applied Surface Science, Vol. 653 https://doi.org/10.1016/j.apsusc.2024.159319	journal	April 2024
A promising fuel for fast neutron spectrum Molten Salt Reactor: NaCl-ThCl4-PuCl3 Dumaire, T.; Ocádiz-Flores, J. A.; Konings, R. J. M. Calphad, Vol. 79 https://doi.org/10.1016/j.calphad.2022.102496	journal	December 2022
Review of the molten salt technology and assessment of its potential to achieve an energy efficient heat management in a decarbonized chemical industry de Figueiredo Luiz, Debora; Boon, Jurriaan; Otero Rodriguez, Gustavo Chemical Engineering Journal, Vol. 498 https://doi.org/10.1016/j.cej.2024.155819	journal	October 2024
The capacitance of the diffuse layer of electric double layer of electrodes in molten salts Kisza, Adolf Electrochimica Acta, Vol. 51, Issue 11 https://doi.org/10.1016/j.electacta.2005.03.093	journal	February 2006
Physical interpretation of cyclic voltammetry for measuring electric double layer capacitances Wang, Hainan; Pilon, Laurent Electrochimica Acta, Vol. 64 https://doi.org/10.1016/j.electacta.2011.12.118	journal	March 2012
Discrete Helmholtz charge distribution at liquid-liquid interfaces: Electrocapillarity, capacitance and non-linear spectroscopy studies Gschwend, Grégoire C.; Girault, Hubert H. Journal of Electroanalytical Chemistry, Vol. 872 https://doi.org/10.1016/j.jelechem.2020.114240	journal	September 2020
Corrosion assessment of 9Cr-1Mo steel in molten LiCl-KCl eutectic salt by electrochemical methods Rao, Ch. Jagadeeswara; Venkatesh, P.; Ningshen, S. Journal of Nuclear Materials, Vol. 514 https://doi.org/10.1016/j.jnucmat.2018.11.014	journal	February 2019
Corrosion in the molten fluoride and chloride salts and materials development for nuclear applications Guo, Shaoqiang; Zhang, Jinsuo; Wu, Wei Progress in Materials Science, Vol. 97 https://doi.org/10.1016/j.pmatsci.2018.05.003	journal	August 2018
Electrochemical and kinetic analysis of Ce recovery using Ga electrode in LiCl-KCl melt Ding, Li; Yang, Shanxin; Yan, Yongde Separation and Purification Technology, Vol. 323 https://doi.org/10.1016/j.seppur.2023.124492	journal	October 2023
Corrosion of stainless steel 316 in eutectic molten salts for thermal energy storage Sarvghad, Madjid; Steinberg, Theodore A.; Will, Geoffrey Solar Energy, Vol. 172 https://doi.org/10.1016/j.solener.2018.03.053	journal	September 2018
Corrosion of stainless steels and low-Cr steel in molten Ca(NO3)2–NaNO3–KNO3 eutectic salt for direct energy storage in CSP plants Fernández, A. G.; Galleguillos, H.; Fuentealba, E. Solar Energy Materials and Solar Cells, Vol. 141 https://doi.org/10.1016/j.solmat.2015.05.004	journal	October 2015
A eutectic salt high temperature phase change material: Thermal stability and corrosion of SS316 with respect to thermal cycling Liu, Ming; Bell, Stuart; Segarra, Mercè Solar Energy Materials and Solar Cells, Vol. 170 https://doi.org/10.1016/j.solmat.2017.05.047	journal	October 2017
Corrosion of steel alloys in molten NaCl + Na2SO4 at 700 °C for thermal energy storage Sarvghad, Madjid; Will, Geoffrey; Steinberg, Theodore A. Solar Energy Materials and Solar Cells, Vol. 179 https://doi.org/10.1016/j.solmat.2017.11.017	journal	June 2018
Electrochemical impedance spectroscopy (EIS): An efficient technique for monitoring corrosion processes in molten salt environments in CSP applications Encinas-Sánchez, V.; de Miguel, M. T.; Lasanta, M. I. Solar Energy Materials and Solar Cells, Vol. 191 https://doi.org/10.1016/j.solmat.2018.11.007	journal	March 2019
In Situ Corrosion Monitoring of the T91 Alloy in a Molten Chloride Salt Using a Miniaturized Electrochemical Probe for High-Throughput Applications Wang, Yafei; Goh, Bonita; Sridharan, Kumar Analytical Chemistry, Vol. 94, Issue 9 https://doi.org/10.1021/acs.analchem.1c05196	journal	February 2022
Understanding the Electric Double-Layer Structure, Capacitance, and Charging Dynamics Wu, Jianzhong Chemical Reviews, Vol. 122, Issue 12 https://doi.org/10.1021/acs.chemrev.2c00097	journal	May 2022
Structure of the Electrical Double Layer Revisited: Electrode Capacitance in Aqueous Solutions Khademi, Mahmoud; Barz, Dominik P. J. Langmuir, Vol. 36, Issue 16 https://doi.org/10.1021/acs.langmuir.0c00024	journal	March 2020
Calculated electrocapillary curve for a molten salt Goodisman, J.; Amokrane, S. The Journal of Physical Chemistry, Vol. 86, Issue 25 https://doi.org/10.1021/j100222a031	journal	December 1982
Double-Layer in Ionic Liquids: Paradigm Change? Kornyshev, Alexei A. The Journal of Physical Chemistry B, Vol. 111, Issue 20 https://doi.org/10.1021/jp067857o	journal	May 2007
Electrical Double-Layer Capacitance in Room Temperature Ionic Liquids: Ion-Size and Specific Adsorption Effects Lauw, Y.; Horne, M. D.; Rodopoulos, T. The Journal of Physical Chemistry B, Vol. 114, Issue 34 https://doi.org/10.1021/jp105317e	journal	August 2010
Low-Temperature Carbonization and More Effective Degradation of Carbohydrates Induced by Ferric Trichloride Xia, Juan; Song, Le Xin; Dang, Zheng The Journal of Physical Chemistry B, Vol. 116, Issue 26 https://doi.org/10.1021/jp303041v	journal	June 2012
Relationship between the Origin of Constant-Phase Element Behavior in Electrochemical Impedance Spectroscopy and Electrode Surface Structure Córdoba-Torres, Pedro; Mesquita, Thiago J.; Nogueira, Ricardo P. The Journal of Physical Chemistry C, Vol. 119, Issue 8 https://doi.org/10.1021/jp512063f	journal	February 2015
Specific ion effects at graphitic interfaces Zhan, Cheng; Cerón, Maira R.; Hawks, Steven A. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12854-7	journal	October 2019
Emerging oxidized and defective phases in low-dimensional CrCl₃ Mastrippolito, Dario; Ottaviano, Luca; Wang, Jing Nanoscale Advances, Vol. 3, Issue 16 https://doi.org/10.1039/D1NA00401H	journal	January 2021
Electrolytic reduction of CrF₃ and Cr₂O₃ in molten fluoride salt Ji, Nan; Jiang, Fangling; Peng, Hao RSC Advances, Vol. 13, Issue 25 https://doi.org/10.1039/D3RA02926C	journal	January 2023
Sur la constitution de la charge électrique à la surface d'un électrolyte Gouy, M. Journal de Physique Théorique et Appliquée, Vol. 9, Issue 1 https://doi.org/10.1051/jphystap:019100090045700	journal	January 1910
Grand canonical Monte Carlo investigations of electrical double layer in molten salts Lamperski, Stanisław; Kłos, Jacek The Journal of Chemical Physics, Vol. 129, Issue 16 https://doi.org/10.1063/1.2933434	journal	October 2008
Electrical double layers and differential capacitance in molten salts from density functional theory Frischknecht, Amalie L.; Halligan, Deaglan O.; Parks, Michael L. The Journal of Chemical Physics, Vol. 141, Issue 5 https://doi.org/10.1063/1.4891368	journal	August 2014
Analysis of electrical double layer structure in molten salts Kłos, Jacek; Lamperski, Stanisław The Journal of Chemical Physics, Vol. 150, Issue 6 https://doi.org/10.1063/1.5082561	journal	February 2019
The differential capacitance as a probe for the electric double layer structure and the electrolyte bulk composition Cats, Peter; van Roij, René The Journal of Chemical Physics, Vol. 155, Issue 10 https://doi.org/10.1063/5.0064315	journal	September 2021
LI. A contribution to the theory of electrocapillarity Chapman, David Leonard The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, Vol. 25, Issue 148 https://doi.org/10.1080/14786440408634187	journal	April 1913
Fiftieth Anniversary: Mathematical Theory of the Faradaic Admittance Grahame, David C. Journal of The Electrochemical Society, Vol. 99, Issue 12 https://doi.org/10.1149/1.2779638	journal	January 1952
Molecular Dynamics Simulations of Metal Electrode/Molten LiCl-KCl-UCl ₃ Mixtures Interface Yang, Yang; Lan, Jianhui; Liang, Bo Journal of The Electrochemical Society, Vol. 169, Issue 3 https://doi.org/10.1149/1945-7111/ac579a	journal	March 2022
Electrochemical Behaviors and Thermodynamic Properties of Ce on Liquid Bi, Sn, and Zn Electrodes in Molten LiCl-KCl Salt Park, Jun Woo; Cha, Han Lim; Yun, Jong-Il Journal of The Electrochemical Society, Vol. 169, Issue 4 https://doi.org/10.1149/1945-7111/ac63f1	journal	April 2022
A New Model of the Electric Double Layer at Electrodes in Molten Salts Kisza, Adolf ECS Proceedings Volumes, Vol. 2002-19, Issue 1 https://doi.org/10.1149/200219.0399PV	journal	January 2002
Analysis of Corrosion of Hastelloy-N, Alloy X750, SS316 and SS304 in Molten Salt High-Temperature Environment Sandhi, Ketan Kumar; Szpunar, Jerzy Energies, Vol. 14, Issue 3 https://doi.org/10.3390/en14030543	journal	January 2021
A Potential-Induced Transformation in the Double Electrical Layer on the Rhenium Electrode in Alkali Chloride Melts Kirillova, Ekaterina V.; Stepanov, Victor P. Materials, Vol. 14, Issue 20 https://doi.org/10.3390/ma14206009	journal	October 2021
Voltammetry of Constant Phase Elements: Analyzing Scan Rate Effects Je, Hyeonsu; Chow, Kwok-Fan; Chang, Byoung-Yong Journal of Electrochemical Science and Technology, Vol. 15, Issue 3 https://doi.org/10.33961/jecst.2024.00318	journal	August 2024
Determination of Constant Phase Element Parameters under Cyclic Voltammetry Conditions Using a Semi-theoretical Equation Charoen-Amornkitt, Patcharawat; Suzuki, Takahiro; Tsushima, Shohji Electrochemistry, Vol. 87, Issue 4 https://doi.org/10.5796/electrochemistry.18-00082	journal	July 2019

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