Electroanalytical Measurements of Oxide Ions in Molten CaCl2 on W electrode

Zhang, Chao; Rappleye, Devin; Nelson, Art; Simpson, Scott; Simpson, Michael

doi:10.1149/1945-7111/ac208e

Electroanalytical Measurements of Oxide Ions in Molten CaCl₂ on W electrode

Journal Article · Thu Sep 02 00:00:00 EDT 2021 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/1945-7111/ac208e· OSTI ID:1829586

^[1]; ^[2]; Nelson, Art ^[3]; ^[3]; ^[4]

Univ. of Utah, Salt Lake City, UT (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Brigham Young Univ., Provo, UT (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Univ. of Utah, Salt Lake City, UT (United States)

The electrochemical interaction of oxide ions with tungsten electrodes in molten calcium chloride (CaCl₂) was analyzed by combining electroanalytical techniques with X-ray photoelectron spectroscopy. During a cyclic voltammetry (CV) scan, the oxide ions appear to interact with the tungsten working electrode via a multi-step oxidation and reduction process. The overall redox peaks behave reversibly up to 750 mV s^-1. This electrochemical process enables the oxide ion concentration to be correlated to CV oxidation peaks. Lastly, the resulting correlation agrees well (8.8% difference) with back titration measurements and can be used to monitor oxide content in the salt in real-time during CaCl₂ based pryoprocesses.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1829586

Report Number(s):: LLNL-JRNL--811812; 1018091

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 9 Vol. 168; ISSN 0013-4651

Publisher:: IOP Publishing - The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (45)

The crystallisation of alkaline-earth metal tungstates (molybdates, chromates, and sulphates) from metal chloride melts Packter, A.; Roy, B. N. Kristall und Technik, Vol. 6, Issue 1 https://doi.org/10.1002/crat.19710060106	journal	January 1971
Hydrolysis of fused calcium chloride at high temperature Kondo, H.; Asaki, Z.; Kondo, Y. Metallurgical Transactions B, Vol. 9, Issue 4 https://doi.org/10.1007/BF02654424	journal	December 1978
Electrochemical deoxidation of titanium Okabe, T. H.; Nakamura, M.; Oishi, T. Metallurgical and Materials Transactions B, Vol. 24, Issue 3 https://doi.org/10.1007/BF02666427	journal	June 1993
A new concept for producing Ti sponge: Calciothermic reduction Ono, Katsutoshi; Suzuki, Ryosuke O. JOM, Vol. 54, Issue 2 https://doi.org/10.1007/BF02701078	journal	February 2002
Effect and measurement of residual water in CaCl2 intended for use as electrolyte in molten salt electrochemical processing Faulkner, Emma; Monreal, Marisa; Jackson, Matt Journal of Radioanalytical and Nuclear Chemistry, Vol. 326, Issue 2 https://doi.org/10.1007/s10967-020-07413-0	journal	October 2020
Electrochemical Reduction of Tungsten Compounds to Produce Tungsten Powder Erdoğan, Metehan; Karakaya, İshak Metallurgical and Materials Transactions B, Vol. 41, Issue 4 https://doi.org/10.1007/s11663-010-9374-4	journal	April 2010
On the Electrochemical Reduction Mechanism of CaWO4 to W Powder Erdoğan, Metehan; Karakaya, İshak Metallurgical and Materials Transactions B, Vol. 43, Issue 4 https://doi.org/10.1007/s11663-012-9689-4	journal	June 2012
Direct electrochemical reduction of solid vanadium oxide to metal vanadium at low temperature in molten CaCl2-NaCl Cai, Zhuo-fei; Zhang, Zhi-mei; Guo, Zhan-cheng International Journal of Minerals, Metallurgy, and Materials, Vol. 19, Issue 6 https://doi.org/10.1007/s12613-012-0586-2	journal	June 2012
Characterization of Nernstian square-wave voltammograms Aoki, Koichi; Maeda, Kazunobu; Osteryoung, Janet Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 272, Issue 1-2 https://doi.org/10.1016/0022-0728(89)87065-2	journal	November 1989
Role of CaCl2 in the reduction of PuO2 Perry, George S.; Macdonald, Lindsay G. Journal of Nuclear Materials, Vol. 130 https://doi.org/10.1016/0022-3115(85)90312-5	journal	February 1985
Review of major plutonium pyrochemical technology Moser, W. Scott; Navratil, James D. Journal of the Less Common Metals, Vol. 100 https://doi.org/10.1016/0022-5088(84)90062-6	journal	July 1984
Semidifferential electroanalysis Goto, Masashi; Ishii, Daido Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 61, Issue 3 https://doi.org/10.1016/S0022-0728(75)80237-3	journal	June 1975
Electrochemical behaviour of erbium in the eutectic LiCl–KCl at W and Al electrodes Castrillejo, Y.; Bermejo, M. R.; Barrado, E. Electrochimica Acta, Vol. 51, Issue 10 https://doi.org/10.1016/j.electacta.2005.07.004	journal	February 2006
Electrochemistry of terbium in the eutectic LiCl–KCl Bermejo, M. R.; Gómez, J.; Martínez, A. M. Electrochimica Acta, Vol. 53, Issue 16 https://doi.org/10.1016/j.electacta.2008.02.058	journal	June 2008
Electrochemical reduction of cerium oxide into metal Claux, Benoît; Serp, Jérôme; Fouletier, Jacques Electrochimica Acta, Vol. 56, Issue 7 https://doi.org/10.1016/j.electacta.2010.12.040	journal	February 2011
CO2 gas decomposition to carbon by electro-reduction in molten salts Otake, Koya; Kinoshita, Hiroshi; Kikuchi, Tatsuya Electrochimica Acta, Vol. 100 https://doi.org/10.1016/j.electacta.2013.02.076	journal	June 2013
Preparation and characterization of tungsten powder through molten salt electrolysis in a CaWO4–CaCl2–NaCl system Xu, Wang; Chunfa, Liao International Journal of Refractory Metals and Hard Materials, Vol. 31 https://doi.org/10.1016/j.ijrmhm.2011.11.004	journal	March 2012
Direct electrochemical production of Ti–10W alloys from mixed oxide preform precursors Dring, K.; Bhagat, R.; Jackson, M. Journal of Alloys and Compounds, Vol. 419, Issue 1-2 https://doi.org/10.1016/j.jallcom.2005.10.029	journal	August 2006
The electrochemistry of gadolinium in the eutectic LiCl–KCl on W and Al electrodes Bermejo, M. R.; Gómez, J.; Medina, J. Journal of Electroanalytical Chemistry, Vol. 588, Issue 2 https://doi.org/10.1016/j.jelechem.2005.12.031	journal	March 2006
On the use of electrochemical techniques to monitor free oxide content in molten fluoride media Massot, L.; Cassayre, L.; Chamelot, P. Journal of Electroanalytical Chemistry, Vol. 606, Issue 1 https://doi.org/10.1016/j.jelechem.2007.04.005	journal	August 2007
Electrochemical studies on the redox behaviour of zirconium in molten LiCl–KCl eutectic Ghosh, Suddhasattwa; Vandarkuzhali, S.; Venkatesh, P. Journal of Electroanalytical Chemistry, Vol. 627, Issue 1-2 https://doi.org/10.1016/j.jelechem.2008.12.011	journal	March 2009
Determination of activity coefficient of lanthanum chloride in molten LiCl-KCl eutectic salt as a function of cesium chloride and lanthanum chloride concentrations using electromotive force measurements Bagri, Prashant; Simpson, Michael F. Journal of Nuclear Materials, Vol. 482 https://doi.org/10.1016/j.jnucmat.2016.10.006	journal	December 2016
CaO solubility and activity coefficient in molten salts CaCl2–x (x=0, NaCl, KCl, SrCl2, BaCl2 and LiCl) Wang, Shulan; Zhang, Fusheng; Liu, Xuan Thermochimica Acta, Vol. 470, Issue 1-2 https://doi.org/10.1016/j.tca.2008.02.007	journal	April 2008
Reversible hydration behavior of CaCl2 at high H2O partial pressures for thermochemical energy storage Molenda, Margarethe; Stengler, Jana; Linder, Marc Thermochimica Acta, Vol. 560 https://doi.org/10.1016/j.tca.2013.03.020	journal	May 2013
Peak shapes in semidifferential electroanalysis Dalrymple-Alford, Penny.; Goto, Masashi.; Oldham, Keith B. Analytical Chemistry, Vol. 49, Issue 9 https://doi.org/10.1021/ac50017a025	journal	August 1977
DC Voltammetry of Electro-deoxidation of Solid Oxides Abdelkader, A. M.; Kilby, K. Tripuraneni; Cox, A. Chemical Reviews, Vol. 113, Issue 5 https://doi.org/10.1021/cr200305x	journal	January 2013
CaCl2-rich region of the CaCl2-CaF2-CaO system Wenz, Donald A.; Johnson, Irving; Wolson, Raymond D. Journal of Chemical & Engineering Data, Vol. 14, Issue 2 https://doi.org/10.1021/je60041a027	journal	April 1969
Direct electrochemical reduction of titanium dioxide to titanium in molten calcium chloride Fray, Derek J.; Chen, George Zheng; Farthing, Tom W. Nature, Vol. 407, Issue 6802, p. 361-364 https://doi.org/10.1038/35030069	journal	September 2000
Capture and electrochemical conversion of CO ₂ to ultrathin graphite sheets in CaCl ₂ -based melts Hu, Liwen; Song, Yang; Ge, Jianbang Journal of Materials Chemistry A, Vol. 3, Issue 42 https://doi.org/10.1039/C5TA05127D	journal	January 2015
Electrochemical synthesis and characterization of a NdCo5 permanent magnet Abdelkader, A. M.; Hyslop, D. J. S.; Cox, A. Journal of Materials Chemistry, Vol. 20, Issue 29 https://doi.org/10.1039/c0jm00096e	journal	January 2010
769. The thermal dissociation of calcium hydroxide Halstead, P. E.; Moore, A. E. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9570003873	journal	January 1957
Mechanisms of electroreduction and electroplating of VI-A group metal coatings from ionic melts Malyshev, V. V. Protection of Metals and Physical Chemistry of Surfaces, Vol. 45, Issue 4 https://doi.org/10.1134/S2070205109040017	journal	July 2009
Voltammetric Studies of the Oxygen-Titanium Binary System in Molten Calcium Chloride Chen, George Z.; Fray, Derek J. Journal of The Electrochemical Society, Vol. 149, Issue 11 https://doi.org/10.1149/1.1513985	journal	January 2002
Voltammetry of Titanium Dioxide in Molten Calcium Chloride at 900°C Dring, K.; Dashwood, R.; Inman, D. Journal of The Electrochemical Society, Vol. 152, Issue 3 https://doi.org/10.1149/1.1860515	journal	January 2005
Electrochemical Reduction of UO[sub 2] in Molten CaCl[sub 2] or LiCl Sakamura, Yoshiharu; Kurata, Masaki; Inoue, Tadashi Journal of The Electrochemical Society, Vol. 153, Issue 3 https://doi.org/10.1149/1.2160430	journal	January 2006
Production of Ti–W Alloys from Mixed Oxide Precursors via the FFC Cambridge Process Bhagat, R.; Jackson, M.; Inman, D. Journal of The Electrochemical Society, Vol. 156, Issue 1 https://doi.org/10.1149/1.2999340	journal	January 2009
Application of Voltammetry for Quantitative Analysis of Actinides in Molten Salts Tylka, M. M.; Willit, J. L.; Prakash, J. Journal of The Electrochemical Society, Vol. 162, Issue 12 https://doi.org/10.1149/2.0281512jes	journal	January 2015
Preliminary Study of Optimization of Normal Pulse Voltammetry for Actinide Measurement in Molten Salt Electrorefiners Using LiCl-KCl-UCl ₃ -MgCl ₂ as a Surrogate Salt Zhang, Chao; Rappleye, Devin; Simpson, Michael Journal of The Electrochemical Society, Vol. 164, Issue 8 https://doi.org/10.1149/2.0321708jes	journal	January 2017
Method Development for Quantitative Analysis of Actinides in Molten Salts Tylka, M. M.; Willit, J. L.; Prakash, J. Journal of The Electrochemical Society, Vol. 162, Issue 9 https://doi.org/10.1149/2.0401509jes	journal	January 2015
Electroanalytical Measurements of Binary-Analyte Mixtures in Molten LiCl-KCl Eutectic: Gadolinium(III)- and Lanthanum(III)-Chloride Rappleye, Devin; Jeong, Sang-Mun; Simpson, Michael Journal of The Electrochemical Society, Vol. 163, Issue 9 https://doi.org/10.1149/2.1011609jes	journal	January 2016
Production of Fine Tungsten Powder by Electrolytic Reduction of Solid CaWO ₄ in Molten Salt Tang, Dingding; Xiao, Wei; Yin, Huayi Journal of The Electrochemical Society, Vol. 159, Issue 6 https://doi.org/10.1149/2.113206jes	journal	January 2012
Direct electrochemical conversion of metal oxides to metal by molten salt electrolysis: a review Mohandas, K. S. Mineral Processing and Extractive Metallurgy, Vol. 122, Issue 4 https://doi.org/10.1179/0371955313Z.00000000069	journal	December 2013
Direct reduction of vanadium oxide in molten CaCl ₂ Suzuki, R. O.; Ishikawa, H. Mineral Processing and Extractive Metallurgy, Vol. 117, Issue 2 https://doi.org/10.1179/174328508X290894	journal	June 2008
Thermodynamic calculation and reference electrode calibration for high temperature molten salts Zhang, W.; Pulham, C. R.; Mount, A. R. Energy Materials, Vol. 3, Issue 2 https://doi.org/10.1179/174892408X394254	journal	June 2008
Application of Voltammetry to Measurement of Concentrations of Multiple Lanthanide Ions in Molten LiCl-KCl Rappleye, Devin; Jeong, Sang-Mun; Gonzalez, Mario Journal of Nuclear Fuel Cycle and Waste Technology, Vol. 13, Issue Special https://doi.org/10.7733/jnfcwt.2015.13.S.29	journal	November 2015

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