This content will become publicly available on Sat Aug 17 00:00:00 EDT 2024
Facile Room-Temperature Electrodeposition of Rare Earth Metals in a Fluorine-Free Task-Specific Electrolyte
Abstract
Electrochemical deposition of rare earth metals at room temperature has attracted increasing interest due to its advantage in energy efficiency over traditional hydrometallurgical and pyrometallurgical processes. Recent progress has been made with fluorinated electrolyte systems; however, the formation of an electrode-passivating fluoride layer by electrolyte decomposition is often overlooked. Such a passivation layer causes significant and rapid decay of the deposition current and significantly hinders practical application. To address this issue, we demonstrate a fluorine (F)-free task-specific electrolyte utilizing the borohydride anion for the efficient electrodeposition of rare earth metals. By eliminating the passivation effect, the deposition process exhibits a stable current and accumulates a thick neodymium deposit on the electrode. Raman spectroscopy of the electrolyte reveals a synergetic effect between rare earth borohydride and lithium borohydride which promotes the dissociation of both borohydride salts, resulting in significantly increased ionic conductivity and electrochemical performance. Cyclic voltammetry and in-depth X-ray photoelectron spectroscopy of the deposits suggest that the electrodeposition of rare earth metals could undergo a Li-mediated reduction process. Finally, quantitative analysis of the deposits reveals that the overall concentration of the rare earth elements reaches 75% which contains 40–48% metallic phase.
- Authors:
-
[3];
[3];
[4];
[1]
- University of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- University of Tennessee, Knoxville, TN (United States)
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Idaho National Laboratory (INL), Idaho Falls, ID (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Idaho National Laboratory (INL), Idaho Falls, ID (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Materials & Manufacturing Technologies Office (AMMTO)
- OSTI Identifier:
- 1999029
- Alternate Identifier(s):
- OSTI ID: 2204968
- Report Number(s):
- INL/JOU-23-74834-Rev000
Journal ID: ISSN 2168-0485
- Grant/Contract Number:
- AC07-05ID14517; AC05-00OR22725; AL-12-350-001
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Sustainable Chemistry & Engineering
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 34; Journal ID: ISSN 2168-0485
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; rare earth elements; electrodeposition; passivation effect; neodymium; dysprosium; passivation effect,
Citation Formats
Yuan, Yating, Gaugler, James, Fan, Juntian, Thapaliya, Bishnu Prasad, Luo, Huimin, Atifi, Abderrahman, Diaz, Luis A., and Dai, Sheng. Facile Room-Temperature Electrodeposition of Rare Earth Metals in a Fluorine-Free Task-Specific Electrolyte. United States: N. p., 2023.
Web. doi:10.1021/acssuschemeng.3c01519.
Yuan, Yating, Gaugler, James, Fan, Juntian, Thapaliya, Bishnu Prasad, Luo, Huimin, Atifi, Abderrahman, Diaz, Luis A., & Dai, Sheng. Facile Room-Temperature Electrodeposition of Rare Earth Metals in a Fluorine-Free Task-Specific Electrolyte. United States. https://doi.org/10.1021/acssuschemeng.3c01519
Yuan, Yating, Gaugler, James, Fan, Juntian, Thapaliya, Bishnu Prasad, Luo, Huimin, Atifi, Abderrahman, Diaz, Luis A., and Dai, Sheng. Thu .
"Facile Room-Temperature Electrodeposition of Rare Earth Metals in a Fluorine-Free Task-Specific Electrolyte". United States. https://doi.org/10.1021/acssuschemeng.3c01519.
@article{osti_1999029,
title = {Facile Room-Temperature Electrodeposition of Rare Earth Metals in a Fluorine-Free Task-Specific Electrolyte},
author = {Yuan, Yating and Gaugler, James and Fan, Juntian and Thapaliya, Bishnu Prasad and Luo, Huimin and Atifi, Abderrahman and Diaz, Luis A. and Dai, Sheng},
abstractNote = {Electrochemical deposition of rare earth metals at room temperature has attracted increasing interest due to its advantage in energy efficiency over traditional hydrometallurgical and pyrometallurgical processes. Recent progress has been made with fluorinated electrolyte systems; however, the formation of an electrode-passivating fluoride layer by electrolyte decomposition is often overlooked. Such a passivation layer causes significant and rapid decay of the deposition current and significantly hinders practical application. To address this issue, we demonstrate a fluorine (F)-free task-specific electrolyte utilizing the borohydride anion for the efficient electrodeposition of rare earth metals. By eliminating the passivation effect, the deposition process exhibits a stable current and accumulates a thick neodymium deposit on the electrode. Raman spectroscopy of the electrolyte reveals a synergetic effect between rare earth borohydride and lithium borohydride which promotes the dissociation of both borohydride salts, resulting in significantly increased ionic conductivity and electrochemical performance. Cyclic voltammetry and in-depth X-ray photoelectron spectroscopy of the deposits suggest that the electrodeposition of rare earth metals could undergo a Li-mediated reduction process. Finally, quantitative analysis of the deposits reveals that the overall concentration of the rare earth elements reaches 75% which contains 40–48% metallic phase.},
doi = {10.1021/acssuschemeng.3c01519},
journal = {ACS Sustainable Chemistry & Engineering},
number = 34,
volume = 11,
place = {United States},
year = {Thu Aug 17 00:00:00 EDT 2023},
month = {Thu Aug 17 00:00:00 EDT 2023}
}
Free Publicly Available Full Text
This content will become publicly available on August 17, 2024
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Understanding Ca Electrodeposition and Speciation Processes in Nonaqueous Electrolytes for Next-Generation Ca-Ion Batteries
journal, May 2019
- Ta, Kim; Zhang, Ruixian; Shin, Minjeong
- ACS Applied Materials & Interfaces, Vol. 11, Issue 24
The Role of Surface Adsorbed Cl – Complexes in Rechargeable Magnesium Batteries
journal, June 2020
- Attias, Ran; Chae, Munseok S.; Dlugatch, Ben
- ACS Catalysis, Vol. 10, Issue 14
Review—Reference Electrodes in Li-Ion and Next Generation Batteries: Correct Potential Assessment, Applications and Practices
journal, December 2021
- Cengiz, Elif Ceylan; Rizell, Josef; Sadd, Matthew
- Journal of The Electrochemical Society, Vol. 168, Issue 12
Tris((hexamethyldisilyl)amido)uranium(III): preparation and coordination chemistry
journal, June 1979
- Andersen, Richard A.
- Inorganic Chemistry, Vol. 18, Issue 6
From Metal Hydrides to Metal Borohydrides
journal, August 2018
- Richter, Bo; Grinderslev, Jakob B.; Møller, Kasper T.
- Inorganic Chemistry, Vol. 57, Issue 17
Trends in Synthesis, Crystal Structure, and Thermal and Magnetic Properties of Rare-Earth Metal Borohydrides
journal, April 2019
- Grinderslev, Jakob B.; Møller, Kasper T.; Bremholm, Martin
- Inorganic Chemistry, Vol. 58, Issue 9
Electrochemical reaction of lithium alanate dissolved in diethyl ether and tetrahydrofuran
journal, January 2007
- Senoh, Hiroshi; Kiyobayashi, Tetsu; Kuriyama, Nobuhiro
- Journal of Power Sources, Vol. 164, Issue 1, p. 94-99
Toward the Circular Economy of Rare Earth Elements: A Review of Abundance, Extraction, Applications, and Environmental Impacts
journal, June 2021
- Dang, Duc Huy; Thompson, Karen A.; Ma, Lan
- Archives of Environmental Contamination and Toxicology, Vol. 81, Issue 4
The story of rare earth elements (REEs): Occurrences, global distribution, genesis, geology, mineralogy and global production
journal, July 2020
- Dushyantha, Nimila; Batapola, Nadeera; Ilankoon, I. M. S. K.
- Ore Geology Reviews, Vol. 122
Review of Emerging Concepts in SEI Analysis and Artificial SEI Membranes for Lithium, Sodium, and Potassium Metal Battery Anodes
journal, October 2020
- Liu, Wei; Liu, Pengcheng; Mitlin, David
- Advanced Energy Materials, Vol. 10, Issue 43
Coordination Chemistry in magnesium battery electrolytes: how ligands affect their performance
journal, November 2013
- Shao, Yuyan; Liu, Tianbiao; Li, Guosheng
- Scientific Reports, Vol. 3, Issue 1
Solubilities of LiBH4 and LiH in Diethyl Ether.
journal, October 1962
- Brandreth, D. A.; Molstad, M. C.
- Journal of Chemical & Engineering Data, Vol. 7, Issue 4
Electrochemical analysis of diffusion behavior and nucleation mechanism for Dy(II) and Dy(III) in phosphonium-based ionic liquids
journal, December 2013
- Kazama, Ryo; Matsumiya, Masahiko; Tsuda, Nanae
- Electrochimica Acta, Vol. 113
Fluorine-free ionic liquid electrolytes for sustainable neodymium recovery using an electrochemical approach
journal, January 2021
- Periyapperuma, Kalani; Pringle, Jennifer M.; Sanchez-Cupido, Laura
- Green Chemistry, Vol. 23, Issue 9
Electrodeposition of a Rare‐Earth Iron Alloy from an Ionic‐Liquid Electrolyte
journal, April 2019
- Xu, Xuan; Sturm, Saso; Zavasnik, Janez
- ChemElectroChem, Vol. 6, Issue 11
Attempts to the electrodeposition of Nd from ionic liquids at elevated temperatures
journal, April 2012
- Kondo, Hitomi; Matsumiya, Masahiko; Tsunashima, Katsuhiko
- Electrochimica Acta, Vol. 66
Rare earth elements: A review of applications, occurrence, exploration, analysis, recycling, and environmental impact
journal, July 2019
- Balaram, V.
- Geoscience Frontiers, Vol. 10, Issue 4
Influence of Li-Salt Concentration on Redox Potential of Lithium Metal and Electrochemistry of Ferrocene in DMSO-Based Electrolytes
journal, January 2019
- Kottam, P. K. R.; Kalkan, D.; Wohlfahrt-Mehrens, M.
- Journal of The Electrochemical Society, Vol. 166, Issue 8
New Li Ion Conductors and Solid State Hydrogen Storage Materials: LiM(BH 4 ) 3 Cl, M = La, Gd
journal, September 2012
- Ley, Morten B.; Boulineau, Sylvain; Janot, Raphaël
- The Journal of Physical Chemistry C, Vol. 116, Issue 40
Plating and stripping calcium in an organic electrolyte
journal, November 2017
- Wang, Da; Gao, Xiangwen; Chen, Yuhui
- Nature Materials, Vol. 17, Issue 1
From M(BH 4 ) 3 (M = La, Ce) Borohydride Frameworks to Controllable Synthesis of Porous Hydrides and Ion Conductors
journal, September 2016
- Ley, Morten Brix; Jørgensen, Mathias; Černý, Radovan
- Inorganic Chemistry, Vol. 55, Issue 19
Surface-enhanced Raman study of organic sulfides adsorbed on silver
journal, November 1987
- Joo, Tai Ha; Kim, Kwan; Kim, Myung Soo
- Journal of Molecular Structure, Vol. 162, Issue 3-4
Progress on Electrodeposition of Rare Earth Metals and Their Alloys
journal, September 2021
- Zhou, Jian; Meng, Xianghai; Zhang, Rui
- Electrocatalysis, Vol. 12, Issue 6
The origin of anode–electrolyte interfacial passivation in rechargeable Mg-metal batteries
journal, January 2023
- Zhang, Jinlei; Liu, Jing; Wang, Min
- Energy & Environmental Science, Vol. 16, Issue 3
Critical materials in global low-carbon energy scenarios: The case for neodymium, dysprosium, lithium, and cobalt
journal, November 2020
- Junne, Tobias; Wulff, Niklas; Breyer, Christian
- Energy, Vol. 211
Novel solvates M(BH 4 ) 3 S(CH 3 ) 2 and properties of halide-free M(BH 4 ) 3 (M = Y or Gd)
journal, January 2014
- Ley, Morten B.; Paskevicius, Mark; Schouwink, Pascal
- Dalton Trans., Vol. 43, Issue 35
Magnesium Borohydride: From Hydrogen Storage to Magnesium Battery
journal, August 2012
- Mohtadi, Rana; Matsui, Masaki; Arthur, Timothy S.
- Angewandte Chemie International Edition, Vol. 51, Issue 39, p. 9780-9783
Understanding the nature of the passivation layer enabling reversible calcium plating
journal, January 2020
- Forero-Saboya, Juan; Davoisne, Carine; Dedryvère, Rémi
- Energy & Environmental Science, Vol. 13, Issue 10
Vibrational spectra and a valence force field for conformers of diethyl ether and deuterated analogues
journal, August 1968
- Wieser, H.; Laidlaw, W. G.; Krueger, P. J.
- Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 24, Issue 8
Water Interplays during Dysprosium Electrodeposition in Pyrrolidinium Ionic Liquid: Deconvoluting the Pros and Cons for Rare Earth Metallization
journal, October 2021
- Orme, Kennalee; Baek, Donna L.; Fox, Robert V.
- ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 43
Covalent transition metal, lanthanide, and actinide tetrahydroborate complexes
journal, April 1977
- Marks, Tobin J.; Kolb, John R.
- Chemical Reviews, Vol. 77, Issue 2
Liquid‐Phase Synthesis of Highly Reactive Rare‐Earth Metal Nanoparticles
journal, June 2021
- Bartenbach, Daniel; Wenzel, Olivia; Popescu, Radian
- Angewandte Chemie International Edition, Vol. 60, Issue 32
Electroplating of Dysprosium, Electrochemical Investigations, and Study of Magnetic Properties
journal, January 2006
- Lodermeyer, J.; Multerer, M.; Zistler, M.
- Journal of The Electrochemical Society, Vol. 153, Issue 4
Vibrational dephasing and frequency shifts of polyatomic molecules in solution
journal, March 1982
- Schweizer, Kenneth S.; Chandler, David
- The Journal of Chemical Physics, Vol. 76, Issue 5
Rare Earth Metal Production by Molten Salt Electrolysis
book, January 2014
- Zhu, Hongmin
- Encyclopedia of Applied Electrochemistry
Tailoring Coordination in Conventional Ether‐Based Electrolytes for Reversible Magnesium‐Metal Anodes
journal, June 2022
- Zhao, Wanyu; Pan, Zhenghui; Zhang, Yijie
- Angewandte Chemie International Edition, Vol. 61, Issue 30
Solvation sheath reorganization enables divalent metal batteries with fast interfacial charge transfer kinetics
journal, October 2021
- Hou, Singyuk; Ji, Xiao; Gaskell, Karen
- Science, Vol. 374, Issue 6564
Charge Transfer and Blue Shifting of Vibrational Frequencies in a Hydrogen Bond Acceptor
journal, May 2013
- Wright, Ashley M.; Howard, Austin A.; Howard, J. Coleman
- The Journal of Physical Chemistry A, Vol. 117, Issue 26
The Coupling between Stability and Ion Pair Formation in Magnesium Electrolytes from First-Principles Quantum Mechanics and Classical Molecular Dynamics
journal, February 2015
- Rajput, Nav Nidhi; Qu, Xiaohui; Sa, Niya
- Journal of the American Chemical Society, Vol. 137, Issue 9, p. 3411-3420
Rare Earth Reduction: A Technological Overview of State-of-the-Art Technology and Novel Developments
book, January 2023
- Rush, Robert G.; Taylor, Patrick R.
- The Minerals, Metals & Materials Series
Electrodeposition of rare earth metals Y, Gd, Yb in ionic liquids
journal, December 2009
- Glukhov, L. M.; Greish, A. A.; Kustov, L. M.
- Russian Journal of Physical Chemistry A, Vol. 84, Issue 1
An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries
journal, May 2015
- Tutusaus, Oscar; Mohtadi, Rana; Arthur, Timothy S.
- Angewandte Chemie International Edition, Vol. 54, Issue 27
Concentration-Dependent Hydrogen-Bonding Effects on the Dimethyl Sulfoxide Vibrational Structure in the Presence of Water, Methanol, and Ethanol
journal, December 2009
- Noack, Kristina; Kiefer, Johannes; Leipertz, Alfred
- ChemPhysChem, Vol. 11, Issue 3
Solid Electrolyte Interphases on Sodium Metal Anodes
journal, September 2020
- Bao, Changyuan; Wang, Bo; Liu, Peng
- Advanced Functional Materials, Vol. 30, Issue 52
Solvent and cation dependence of the tetrahydroborate, BH4-, Raman spectrum
journal, September 1973
- Shirk, A. E.; Shriver, D. F.
- Journal of the American Chemical Society, Vol. 95, Issue 18
Metal borohydrides and derivatives – synthesis, structure and properties
journal, January 2017
- Paskevicius, Mark; Jepsen, Lars H.; Schouwink, Pascal
- Chemical Society Reviews, Vol. 46, Issue 5
Material and Energy Requirement for Rare Earth Production
journal, August 2013
- Talens Peiró, Laura; Villalba Méndez, Gara
- JOM, Vol. 65, Issue 10
Reduction of Light Rare Earths and a Proposed Process for Nd Electrorecovery Based on Ionic Liquids
journal, August 2018
- Bourbos, E.; Giannopoulou, I.; Karantonis, A.
- Journal of Sustainable Metallurgy, Vol. 4, Issue 3
Influence of Ether Solvent and Anion Coordination on Electrochemical Behavior in Calcium Battery Electrolytes
journal, July 2020
- Hahn, Nathan T.; Driscoll, Darren M.; Yu, Zhou
- ACS Applied Energy Materials, Vol. 3, Issue 9
The Preparation of Sodium Borohydride by the High Temperature Reaction of Sodium Hydride with Borate Esters 1
journal, January 1953
- Schlesinger, H. I.; Brown, Herbert C.; Finholt, A. E.
- Journal of the American Chemical Society, Vol. 75, Issue 1
Designer Ionic Liquids for Reversible Electrochemical Deposition/Dissolution of Magnesium
journal, January 2016
- Watkins, Tylan; Kumar, Ashok; Buttry, Daniel A.
- Journal of the American Chemical Society, Vol. 138, Issue 2
Effect of Chinese policies on rare earth supply chain resilience
journal, March 2019
- Mancheri, Nabeel A.; Sprecher, Benjamin; Bailey, Gwendolyn
- Resources, Conservation and Recycling, Vol. 142
Electrodeposition of metals from non-aqueous solutions
journal, September 2009
- Simka, Wojciech; Puszczyk, Dagmara; Nawrat, Ginter
- Electrochimica Acta, Vol. 54, Issue 23
LiNO3-Supported Electrodeposition of Metallic Nd from Nd-Containing Solvate Ionic Liquid
journal, September 2021
- Zhang, Baoguo; Wang, Li; Pan, Kefeng
- The Journal of Physical Chemistry C, Vol. 125, Issue 38
Electrodeposition of Dysprosium in pyrrolidinium triflate ionic liquid at ambient temperature: Unraveling system efficiency and impact of solvation interplays on the reduction process
journal, May 2021
- Atifi, Abderrahman; Baek, Donna L.; Fox, Robert V.
- Electrochimica Acta, Vol. 378
Passivation Layer Formation of Magnesium Metal Negative Electrodes for Rechargeable Magnesium Batteries
journal, January 2017
- Kuwata, Hiroko; Matsui, Masaki; Imanishi, Nobuyuki
- Journal of The Electrochemical Society, Vol. 164, Issue 13
A Review of Solid Electrolyte Interphases on Lithium Metal Anode
journal, November 2015
- Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi
- Advanced Science, Vol. 3, Issue 3
Toggling Calcium Plating Activity and Reversibility through Modulation of Ca 2+ Speciation in Borohydride-Based Electrolytes
journal, January 2022
- Melemed, Aaron M.; Skiba, Dhyllan A.; Gallant, Betar M.
- The Journal of Physical Chemistry C, Vol. 126, Issue 2