Cathodic Decomposition Electrodes as Standard Reference Electrodes for Molten Salts: Example of the Lithium Eutectic Electrode for the LiCl-KCl Eutectic

Lichtenstein, Timothy; Schvaneveldt, Mark H.; Gesualdi, Jarrod; Hawthorne, Krista L.

doi:10.1149/1945-7111/ad76df

Cathodic Decomposition Electrodes as Standard Reference Electrodes for Molten Salts: Example of the Lithium Eutectic Electrode for the LiCl-KCl Eutectic

Journal Article · Wed Sep 11 00:00:00 EDT 2024 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/1945-7111/ad76df· OSTI ID:2440774

^[1]; Schvaneveldt, Mark H. ^[1]; Gesualdi, Jarrod ^[1]; ^[1]

Argonne National Laboratory (ANL), Argonne, IL (United States)

Alternatives to the widely-used standard anodic decomposition reference electrodes in molten salts are necessary to enable more easily reproduced thermochemical and electrochemical data in molten salt electrolytes. The class of standard reference electrodes called cathodic decomposition electrodes (CDEs) are easily constructed and can be used to make thermochemical measurements in molten salts more directly compared to anodic decomposition electrodes. The lithium eutectic electrode (LEE) was chosen as a sample test case for validation and was applied to thermochemical measurements of electroactive species in molten LiCl-KCl eutectic. Transient measurements were made to measure the Li⁺/Li reduction potential at zero current in pure LiCl-KCl eutectic relative to a Li-alloy reference electrode to validate the reference potential of the LEE. Literature-reported electromotive force measurements against Li-alloy reference electrodes were used to generate a relationship between the LEE and the standard chlorine electrode and this relationship was used to evaluate measured and reported formal potential measurements for the LiCl-KCl-GdCl₃ system. This work demonstrates the general framework for defining CDEs for any molten salt system and a method for calibrating external reference electrodes against a CDE standard reference electrode, improving the ease of obtaining thermochemical and electrochemical measurements in any molten salt system.

View Journal Article

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE; USDOE Office of Nuclear Energy (NE), Nuclear Fuel Cycle and Supply Chain. Fuel Cycle Research and Development Program; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2440774

Alternate ID(s):: OSTI ID: 2439500
OSTI ID: 2529381

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 9 Vol. 171; ISSN 0013-4651

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

References (25)

Thermodynamic study of liquid lithium–lead alloys using the EMF method Ga̧sior, W.; Moser, Z. Journal of Nuclear Materials, Vol. 294, Issue 1-2 https://doi.org/10.1016/S0022-3115(01)00440-8	journal	April 2001
Electrochemical formation of Pd–La alloy films in a LiF–NaF–KF–LaF3 melt Qiao, Huan; Nohira, Toshiyuki; Ito, Yasuhiko Journal of Alloys and Compounds, Vol. 359, Issue 1-2 https://doi.org/10.1016/S0925-8388(03)00203-2	journal	September 2003
Redox potential measurement of AgCl in molten LiCl-KCl salt using chronopotentiometry and potentiodynamic scan techniques Zhang, Mingyang; Ge, Jianbang; Zhang, Jinsuo Electrochemistry Communications, Vol. 105 https://doi.org/10.1016/j.elecom.2019.106498	journal	August 2019
A new method to determine AgCl(1% mol)/Ag electrode potential versus the standard chloride electrode potential in a LiCl-KCl eutectic Sun, Chenteng; Xu, Qian; Zou, Xingli Electrochemistry Communications, Vol. 130 https://doi.org/10.1016/j.elecom.2021.107111	journal	September 2021
Dynamic Reference Electrode development for redox potential measurements in fluoride molten salt at high temperature Durán-Klie, Gabriela; Rodrigues, Davide; Delpech, Sylvie Electrochimica Acta, Vol. 195 https://doi.org/10.1016/j.electacta.2016.02.042	journal	March 2016
Electrochemical technique for detecting the formation of uranium-containing precipitates in molten fluorides Peng, Hao; Shen, Miao; Zuo, Yong Electrochimica Acta, Vol. 222 https://doi.org/10.1016/j.electacta.2016.11.135	journal	December 2016
Solute- and solvent-based electromotive force cells for activity measurements of electroactive species in molten salts Lichtenstein, Timothy; Hawthorne, Krista L. Electrochimica Acta, Vol. 424 https://doi.org/10.1016/j.electacta.2022.140675	journal	August 2022
Electrochemical properties of the Ag+\|Ag and other reference electrodes in the LiCl–KCl eutectic melts Shirai, Osamu; Nagai, Takayuki; Uehara, Akihiro Journal of Alloys and Compounds, Vol. 456, Issue 1-2 https://doi.org/10.1016/j.jallcom.2007.02.104	journal	May 2008
Thermodynamic properties of Gd-Bi alloys determined by emf measurements in LiCl-KCl-GdCl3 electrolyte Baldivieso, Stephanie Castro; Smith, Nathan D.; Im, Sanghyeok Journal of Alloys and Compounds, Vol. 886 https://doi.org/10.1016/j.jallcom.2021.161229	journal	December 2021
Application of voltammetry for quantitative analysis of chromium in molten 2LiF-BeF2 (FLiBe) salt Doniger, William H.; Sridharan, Kumar Journal of Electroanalytical Chemistry, Vol. 838 https://doi.org/10.1016/j.jelechem.2019.02.048	journal	April 2019
Dynamic reference electrode for investigation of fluoride melts containing beryllium difluoride Afonichkin, Valery K.; Bovet, Andrey L.; Ignatiev, Victor V. Journal of Fluorine Chemistry, Vol. 130, Issue 1 https://doi.org/10.1016/j.jfluchem.2008.07.017	journal	January 2009
Electrochemical behaviour of gadolinium ion in molten LiCl–KCl eutectic Caravaca, C.; de Córdoba, G.; Tomás, M. J. Journal of Nuclear Materials, Vol. 360, Issue 1 https://doi.org/10.1016/j.jnucmat.2006.08.009	journal	January 2007
Measurement of europium (III)/europium (II) couple in fluoride molten salt for redox control in a molten salt reactor concept Guo, Shaoqiang; Shay, Nikolas; Wang, Yafei Journal of Nuclear Materials, Vol. 496 https://doi.org/10.1016/j.jnucmat.2017.09.027	journal	December 2017
Calculated thermodynamic properties of GdCl3 in LiCl-KCl eutectic molten salt Zhou, Wentao; Wang, Yafei; Zhang, Jinsuo Journal of Nuclear Materials, Vol. 508 https://doi.org/10.1016/j.jnucmat.2018.05.030	journal	September 2018
Thermodynamic Properties for Rare Earths and Americium in Pyropartitioning Process Solvents Fusselman, S. P. Journal of The Electrochemical Society, Vol. 146, Issue 7 https://doi.org/10.1149/1.1391974	journal	January 1999
Electrochemical Studies of LaCl[sub 3] and GdCl[sub 3] Dissolved in Fused LiCl-KCl Lantelme, Frédéric Journal of The Electrochemical Society, Vol. 146, Issue 11 https://doi.org/10.1149/1.1392604	journal	January 1999
Electrochemical Window and the Characteristics of (α + β) Al-Li Alloy Reference Electrode for a LiBr-KBr-CsBr Eutectic Melt Kasajima, Takeo; Nishikiori, Tokujiro; Nohira, Toshiyuki Journal of The Electrochemical Society, Vol. 151, Issue 11 https://doi.org/10.1149/1.1795542	journal	January 2004
The Single‐Electrode Peltier Heats of Li‐Al Alloy Electrodes in LiCl ‐ KCl Eutectic System Amezawa, Koji; Ito, Yasuhiko; Tomii, Yoichi Journal of The Electrochemical Society, Vol. 141, Issue 11 https://doi.org/10.1149/1.2059284	journal	November 1994
Thermodynamic and Mass Transport Properties of “LiAl” Wen, C. John Journal of The Electrochemical Society, Vol. 126, Issue 12 https://doi.org/10.1149/1.2128939	journal	January 1979
Some Investigations of the Ag∕AgCl in LiCl-KCl Eutectic Reference Electrode Yang, Ling; Hudson, Robert G. Journal of The Electrochemical Society, Vol. 106, Issue 11 https://doi.org/10.1149/1.2427195	journal	January 1959
Potentiodynamic Polarization of Pure Metals and Alloys in Molten LiF-NaF-KF (FLiNaK) Using the K/K⁺ Dynamic Reference Electrode Doniger, William H.; Couet, Adrien; Sridharan, Kumar Journal of The Electrochemical Society, Vol. 169, Issue 7 https://doi.org/10.1149/1945-7111/ac7a66	journal	July 2022
Electrochemistry and Electrocrystallization of Gadolinium on Mo Substrate in LiCl–KCl Eutectic Salts Tang, Hao; Pesic, Batric Journal of The Electrochemical Society, Vol. 161, Issue 9 https://doi.org/10.1149/2.0371409jes	journal	January 2014
Electrochemical Determination of the Thermodynamic Properties of Lithium-Antimony Alloys Kane, Margaret M.; Newhouse, Jocelyn M.; Sadoway, Donald R. Journal of The Electrochemical Society, Vol. 162, Issue 3 https://doi.org/10.1149/2.0671503jes	journal	December 2014
Fundamental Data Acquisition toward Silver-Silver Chloride Reference Electrode Yoon, Dalsung; Baggett, Adam; Phongikaroon, Supathorn Journal of The Electrochemical Society, Vol. 166, Issue 6 https://doi.org/10.1149/2.0721906jes	journal	January 2019
Observed Redox Potential Range of Li ₂ BeF ₄ Using a Dynamic Reference Electrode Kelleher, Brian; Dolan, Kieran; Anderson, Mark Nuclear Technology, Vol. 195, Issue 3 https://doi.org/10.13182/NT15-140	journal	September 2016

Similar Records

Solute- and solvent-based electromotive force cells for activity measurements of electroactive species in molten salts

Journal Article · Thu Jun 02 20:00:00 EDT 2022 · Electrochimica Acta · OSTI ID:1915452

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
LEE
Molten salt
Standard Reference Electrode

Cathodic Decomposition Electrodes as Standard Reference Electrodes for Molten Salts: Example of the Lithium Eutectic Electrode for the LiCl-KCl Eutectic

Citation Formats

References (25)

Similar Records

Related Subjects