Characterizing pulse reverse-pulse uranium recovery in molten LiCl-KCl with intermittent electrochemical impedance spectroscopy

Eakin, Jeffrey; Ivory, Cornelius

doi:10.1016/j.rechem.2023.101068

Characterizing pulse reverse-pulse uranium recovery in molten LiCl-KCl with intermittent electrochemical impedance spectroscopy

Journal Article · Tue Aug 22 00:00:00 EDT 2023 · Results in Chemistry

DOI:https://doi.org/10.1016/j.rechem.2023.101068· OSTI ID:1996924

^[1]; Ivory, Cornelius ^[2]

Washington State University, Pullman, WA (United States); University of Notre Dame
Washington State University, Pullman, WA (United States)

In this work, EIS was applied to characterize the temporal recovery of uranium from UCl₄ onto a tungsten electrode in molten LiCl-KCl salt between sets of pulse reverse-pulse (PRP) deposition steps. Impedance measurements were fitted to an equivalent circuit (EC) model of the electrode interface using Simplex optimization to calculate the double layer capacitance, charge transfer resistance, Warburg impedance, and CPE-restricted diffusion. Diffusion of uranium towards the electrode surface dominated the surface interactions for the first 80 cycles, followed by a transition to kinetic control for the remaining 520 cycles. A decrease in the Warburg impedance showed depletion of uranium from the bulk melt, which was confirmed to be a 52.5% reduction through ICP-OES. Reduction in the phasance from CPE-restricted diffusion suggested the formation of pores in the uranium deposits, which was confirmed through SEM characterization.

View Accepted Manuscript (DOE)

Research Organization:: University of Notre Dame, IN (United States)

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

Grant/Contract Number:: NA0003763

OSTI ID:: 1996924

Journal Information:: Results in Chemistry, Journal Name: Results in Chemistry Vol. 6; ISSN 2211-7156

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (55)

Towards Size‐Controlled Deposition of Palladium Nanoparticles from Polyoxometalate Precursors: An Electrochemical Scanning Tunneling Microscopy Study Bock, Nicolas; De Clercq, Astrid; Seidl, Lukas ChemElectroChem, Vol. 8, Issue 7 https://doi.org/10.1002/celc.202100131	journal	February 2021
Copper Deposition on Au(111) in a Deep Eutectic Solvent: An In Situ STM Study** Tan, Zhuo; Liu, Shuai; Wu, Jiedu ChemElectroChem, Vol. 9, Issue 4 https://doi.org/10.1002/celc.202101412	journal	January 2022
Exhaustive electrolysis for recovery of actinides from molten LiCl–KCl using solid aluminium cathodes Souček, P.; Malmbeck, R.; Mendes, E. Journal of Radioanalytical and Nuclear Chemistry, Vol. 286, Issue 3 https://doi.org/10.1007/s10967-010-0739-6	journal	August 2010
Electrochemical behavior and electrowinning of uranium(IV) from FLiNaK molten salt Jiang, Feng; Huang, Wei; Zheng, Haiyang Journal of Radioanalytical and Nuclear Chemistry, Vol. 311, Issue 3 https://doi.org/10.1007/s10967-016-5160-3	journal	January 2017
Conversion of UO2 to UCl3 using AlCl3 in LiCl–KCl eutectic melt in presence of lanthanide (Nd, Pr, Ce, La) oxides: a spectroscopic study Samanta, Nibedita; Maji, S.; Kumar, Satendra Journal of Radioanalytical and Nuclear Chemistry, Vol. 331, Issue 12 https://doi.org/10.1007/s10967-022-08664-9	journal	December 2022
Kinetic properties and electro-separation of U on binary liquid Ga–Al eutectic alloy cathode Yang, Da-Wei; Jiang, Shi-Lin; Liu, Ya-Lan Journal of Radioanalytical and Nuclear Chemistry, Vol. 332, Issue 4 https://doi.org/10.1007/s10967-023-08782-y	journal	January 2023
Impedance of constant phase element (CPE)-blocked diffusion in film electrodes Bisquert, J.; Garcia-Belmonte, G.; Bueno, P. Journal of Electroanalytical Chemistry, Vol. 452, Issue 2 https://doi.org/10.1016/S0022-0728(98)00115-6	journal	July 1998
Evaluation of stainless steel–zirconium alloys as high-level nuclear waste forms McDeavitt, S. M.; Abraham, D. P.; Park, J. Y. Journal of Nuclear Materials, Vol. 257, Issue 1 https://doi.org/10.1016/S0022-3115(98)00433-4	journal	September 1998
Imaging the reduction of chromium(VI) on magnetite surfaces using in situ electrochemical AFM Walker, Sarah M.; Marcano, Maria C.; Bender, Will M. Chemical Geology, Vol. 429 https://doi.org/10.1016/j.chemgeo.2016.02.025	journal	July 2016
An experimental study of deposition of suspended magnetite in high temperature-high pressure boiler type environments Raman, Balaji; Hall, Derek M.; Shulder, Stephen J. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 508 https://doi.org/10.1016/j.colsurfa.2016.08.018	journal	November 2016
Pyrochemical Reprocessing of Spent Fuel by Electrochemical Techniques Using Solid Aluminium Cathodes Souček, P.; Malmbeck, R.; Nourry, C. Energy Procedia, Vol. 7 https://doi.org/10.1016/j.egypro.2011.06.052	journal	January 2011
Electrochemical studies on the redox mechanism of uranium chloride in molten LiCl–KCl eutectic Prabhakara Reddy, B.; Vandarkuzhali, S.; Subramanian, T. Electrochimica Acta, Vol. 49, Issue 15 https://doi.org/10.1016/j.electacta.2004.02.002	journal	June 2004
Electrochemical behaviour of LaCl3 at tungsten and aluminium cathodes in LiCl–KCl eutectic melt Vandarkuzhali, S.; Gogoi, Nibedita; Ghosh, Suddhasattwa Electrochimica Acta, Vol. 59 https://doi.org/10.1016/j.electacta.2011.10.062	journal	January 2012
Electrochemical separation of Th from ThO2 and Eu2O3 assisted by AlCl3 in molten LiCl–KCl Liu, Ya-Lan; Yan, Yong-De; Han, Wei Electrochimica Acta, Vol. 114 https://doi.org/10.1016/j.electacta.2013.09.154	journal	December 2013
Thermodynamics of separation of uranium from neodymium between the gallium-indium liquid alloy and the LiCl-KCl molten salt phases Smolenski, V.; Novoselova, A.; Osipenko, A. Electrochimica Acta, Vol. 133 https://doi.org/10.1016/j.electacta.2014.04.042	journal	July 2014
Investigation on the electrochemical behavior of neodymium chloride at W, Al and Cd electrodes in molten LiCl-KCl eutectic Vandarkuzhali, S.; Chandra, Manish; Ghosh, Suddhasattwa Electrochimica Acta, Vol. 145 https://doi.org/10.1016/j.electacta.2014.08.069	journal	November 2014
In situ scanning tunneling microscopy (STM), atomic force microscopy (AFM) and quartz crystal microbalance (EQCM) studies of the electrochemical deposition of tantalum in two different ionic liquids with the 1-butyl-1-methylpyrrolidinium cation Carstens, Timo; Ispas, Adriana; Borisenko, Natalia Electrochimica Acta, Vol. 197 https://doi.org/10.1016/j.electacta.2015.07.178	journal	April 2016
Mean-Field Theory of Electrical Double Layer In Ionic Liquids with Account of Short-Range Correlations Goodwin, Zachary A. H.; Feng, Guang; Kornyshev, Alexei A. Electrochimica Acta, Vol. 225 https://doi.org/10.1016/j.electacta.2016.12.092	journal	January 2017
Measurement and Analysis of Exchange Current Density for U/U3+ Reaction in LiCl-KCl Eutectic Salt via Various Electrochemical Techniques Yoon, Dalsung; Phongikaroon, Supathorn Electrochimica Acta, Vol. 227 https://doi.org/10.1016/j.electacta.2017.01.011	journal	February 2017
In situ investigation of copper corrosion in acidic chloride solution using atomic force—scanning electrochemical microscopy Izquierdo, J.; Eifert, A.; Kranz, C. Electrochimica Acta, Vol. 247 https://doi.org/10.1016/j.electacta.2017.07.042	journal	September 2017
Direct separation of uranium from lanthanides (La, Nd, Ce, Sm) in oxide mixture in LiCl-KCl eutectic melt Liu, Yalan; Liu, Kui; Luo, Lixia Electrochimica Acta, Vol. 275 https://doi.org/10.1016/j.electacta.2018.04.140	journal	June 2018
Electrical double layer in molten salts taking into account Lennard-Jones potential Kłos, Jacek; Lamperski, Stanisław Electrochimica Acta, Vol. 337 https://doi.org/10.1016/j.electacta.2020.135747	journal	March 2020
Electrocrystallization of UO2 on nanoporous WO3/W electrode in LiCl-KCl melts Li, Haiming; Liu, Rugeng; Han, Wei Electrochimica Acta, Vol. 400 https://doi.org/10.1016/j.electacta.2021.139474	journal	December 2021
Electrochemical deposition of Al–Mg alloys on tungsten wires from AlCl3–NaCl–KCl melts Li, Yaling; Zhao, Peng; Dai, Yinhai Fusion Engineering and Design, Vol. 103 https://doi.org/10.1016/j.fusengdes.2015.11.053	journal	February 2016
A study on the electrochemical deposition behavior of uranium ion in a LiCl–KCl molten salt on solid and liquid electrode Kim, Gha-Young; Yoon, Dalseong; Paek, Seungwoo Journal of Electroanalytical Chemistry, Vol. 682 https://doi.org/10.1016/j.jelechem.2012.07.025	journal	August 2012
Electrochemical behaviour of LiCl-KCl eutectic melts containing moisture as impurity. Part II: Uranium electrode Swain, Litun; Pakhui, Gurudas; Jain, Ashish Journal of Electroanalytical Chemistry, Vol. 907 https://doi.org/10.1016/j.jelechem.2021.115969	journal	February 2022
Electrode processes and electrochemical formation of Dy-Ga and Dy-Cd alloys in molten LiCl–KCl–CsCl eutectic Novoselova, Alena; Smolenski, Valeri; Volkovich, Vladimir A. Journal of Electroanalytical Chemistry, Vol. 906 https://doi.org/10.1016/j.jelechem.2022.116012	journal	February 2022
Electrochemical behaviour of LiCl-KCl eutectic melts containing moisture as impurity. Part I: Inert tungsten electrode Swain, Litun; Pakhui, Gurudas; Jain, Ashish Journal of Electroanalytical Chemistry, Vol. 910 https://doi.org/10.1016/j.jelechem.2022.116125	journal	April 2022
Separation of actinides from irradiated An–Zr based fuel by electrorefining on solid aluminium cathodes in molten LiCl–KCl Souček, P.; Murakami, T.; Claux, B. Journal of Nuclear Materials, Vol. 459 https://doi.org/10.1016/j.jnucmat.2014.12.103	journal	April 2015
Effect of cathode material on the electrorefining of U in LiCl-KCl molten salts Lee, Chang Hwa; Kim, Tack-Jin; Park, Sungbin Journal of Nuclear Materials, Vol. 488 https://doi.org/10.1016/j.jnucmat.2017.03.023	journal	May 2017
Transient modeling of spent nuclear fuel electrorefining with liquid metal electrode Seo, Seungjin; Choi, Sungyeol; Park, Byung Gi Journal of Nuclear Materials, Vol. 491 https://doi.org/10.1016/j.jnucmat.2017.04.053	journal	August 2017
Galvanic reduction of uranium(III) chloride from LiCl-KCl eutectic salt using gadolinium metal Bagri, Prashant; Zhang, Chao; Simpson, Michael F. Journal of Nuclear Materials, Vol. 493 https://doi.org/10.1016/j.jnucmat.2017.06.007	journal	September 2017
Recovery of actinides from actinide-aluminium alloys by chlorination: Part III - Chlorination with HCl(g) Meier, Roland; Souček, Pavel; Walter, Olaf Journal of Nuclear Materials, Vol. 498 https://doi.org/10.1016/j.jnucmat.2017.09.045	journal	January 2018
Optimization of UCl 3 and MgCl 2 separation from molten LiCl-KCl eutectic salt via galvanic drawdown with sacrificial Gd anode Bagri, Prashant; Ong, Joshua; Zhang, Chao Journal of Nuclear Materials, Vol. 505 https://doi.org/10.1016/j.jnucmat.2018.04.011	journal	July 2018
Electrorefining of irradiated experimental metallic fuel at high lanthanides concentration in the LiCl–KCl electrolyte Souček, P.; Uruga, K.; Murakami, T. Journal of Nuclear Materials, Vol. 526 https://doi.org/10.1016/j.jnucmat.2019.151743	journal	December 2019
The dendrite growth, morphology control and deposition properties of uranium electrorefining Liu, Kui; tan, Tan; Zhou, Xuanpu Journal of Nuclear Materials, Vol. 555 https://doi.org/10.1016/j.jnucmat.2021.153110	journal	November 2021
In-situ monitoring of polyelectrolytes adsorption kinetics by electrochemical impedance spectroscopy: Application in fabricating nanofiltration membranes via layer-by-layer deposition Liang, Yuanzhe; Gao, Fei; Wang, Li Journal of Membrane Science, Vol. 619 https://doi.org/10.1016/j.memsci.2020.118747	journal	February 2021
Separation of uranium from lanthanides (La, Sm) with sacrificial Li anode in LiCl-KCl eutectic salt Wang, Dong-Dong; Liu, Ya-Lan; Yang, Da-Wei Separation and Purification Technology, Vol. 292 https://doi.org/10.1016/j.seppur.2022.121025	journal	July 2022
The Role of Ion–Ion Correlations for the Differential Capacitance of Ionic Liquids Downing, Rachel; Bossa, Guilherme Volpe; May, Sylvio The Journal of Physical Chemistry C, Vol. 122, Issue 50 https://doi.org/10.1021/acs.jpcc.8b09756	journal	November 2018
Real-Time Observation of Li Deposition on a Li Electrode with Operand Atomic Force Microscopy and Surface Mechanical Imaging Kitta, Mitsunori; Sano, Hikaru Langmuir, Vol. 33, Issue 8 https://doi.org/10.1021/acs.langmuir.6b04651	journal	February 2017
Electrochemical Impedance Spectroscopy (EIS) Based Characterization of Mineral Deposition from Precipitation Reactions Li, Heng; Dzombak, David; Vidic, Radisav Industrial & Engineering Chemistry Research, Vol. 51, Issue 7 https://doi.org/10.1021/ie201802n	journal	February 2012
In situ Real-time Monitoring of Electrochemical Ag Deposition on a Reconstructed Au(111) Surface Studied by Scanning Tunneling Microscopy Takakusagi, Satoru; Kitamura, Ken; Uosaki, Kohei The Journal of Physical Chemistry C, Vol. 112, Issue 8 https://doi.org/10.1021/jp709916m	journal	February 2008
Convenient Synthesis, Structure, and Reactivity of (C ₅ Me ₅ )U(CH ₂ C ₆ H ₅ ) ₃ : A Simple Strategy for the Preparation of Monopentamethylcyclopentadienyl Uranium(IV) Complexes Kiplinger, Jaqueline L.; Morris, David E.; Scott, Brian L. Organometallics, Vol. 21, Issue 26 https://doi.org/10.1021/om0206610	journal	December 2002
A detailed Raman and X-ray study of UO _2+x oxides and related structure transitions Elorrieta, J. M.; Bonales, L. J.; Rodríguez-Villagra, N. Physical Chemistry Chemical Physics, Vol. 18, Issue 40 https://doi.org/10.1039/C6CP03800J	journal	January 2016
The growth mechanism of calcareous deposits under various hydrostatic pressures during the cathodic protection of carbon steel in seawater Li, C. J.; Du, M. RSC Advances, Vol. 7, Issue 46 https://doi.org/10.1039/C7RA03709K	journal	January 2017
Nanoscale electrochemical 3D deposition of cobalt with nanosecond voltage pulses in an STM Reiser, Alain; Schuster, Rolf; Spolenak, Ralph Nanoscale, Vol. 14, Issue 14 https://doi.org/10.1039/D1NR08409G	journal	January 2022
Progress in Electrometallurgical Treatment of Spent Nuclear Fuel Benedict, Robert; Goff, Michael; Teske, Gregory Journal of Nuclear Science and Technology, Vol. 39, Issue sup3 https://doi.org/10.1080/00223131.2002.10875575	journal	November 2002
Double Layer in Ionic Liquids: Overscreening versus Crowding Bazant, Martin Z.; Storey, Brian D.; Kornyshev, Alexei A. Physical Review Letters, Vol. 106, Issue 4 https://doi.org/10.1103/PhysRevLett.106.046102	journal	January 2011
Electrochemical Behavior and Some Thermodynamic Properties of UCl[sub 4] and UCl[sub 3] Dissolved in a LiCl-KCl Eutectic Melt Kuznetsov, S. A.; Hayashi, H.; Minato, K. Journal of The Electrochemical Society, Vol. 152, Issue 4 https://doi.org/10.1149/1.1864532	journal	January 2005
Electrochemical Deposition with Redox Replacement of Lanthanum with Uranium in Molten LiCl-KCl Eakin, Jeffrey; Molina, Daniel; Guo, Xiaofeng Journal of The Electrochemical Society, Vol. 170, Issue 3 https://doi.org/10.1149/1945-7111/acc09c	journal	March 2023
Electrochemical and Spectroscopic Monitoring of Interactions of Oxide Ion with U (III) and Ln (III) (Ln = Nd, Ce, and La) in LiCl-KCl Melts Choi, Suhee; Bae, Sang-Eun; Park, Tae-Hong Journal of The Electrochemical Society, Vol. 164, Issue 8 https://doi.org/10.1149/2.0071708jes	journal	January 2017
Evaluation of the Electroextractions of Ce and Nd from LiCl-KCl Molten Salt Using Liquid Ga Electrode Liu, Kui; Liu, Ya-Lan; Chai, Zhi-Fang Journal of The Electrochemical Society, Vol. 164, Issue 4 https://doi.org/10.1149/2.0511704jes	journal	January 2017
A Description of the Ceramic Waste Form Production Process from the Demonstration Phase of the Electrometallurgical Treatment of EBR-II Spent Fuel Simpson, Michael F.; Goff, K. Michael; Johnson, Stephen G. Nuclear Technology, Vol. 134, Issue 3 https://doi.org/10.13182/NT01-A3200	journal	June 2001
Electrochemical Atomic Force Microscopy Study on the Dynamic Evolution of Lithium Deposition Shi, Xixiu; Yang, Jingru; Wang, Wenyang Materials, Vol. 16, Issue 6 https://doi.org/10.3390/ma16062278	journal	March 2023
The Influence of Oxide Ions on the Electrochemical Behavior of UCl₄ and UCl₃ in a LiCl-KCl Eutectic Melt Kuznetsov, Sergey A.; Hayashi, Hirokazu; Minato, Kazuo Electrochemistry, Vol. 73, Issue 8 https://doi.org/10.5796/electrochemistry.73.630	journal	August 2005

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Characterizing pulse reverse-pulse uranium recovery in molten LiCl-KCl with intermittent electrochemical impedance spectroscopy

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