Diffusion coefficient and nucleation density studies on electrochemical deposition of aluminum from chloroaluminate ionic liquid electrolytes

Peng, Yuxiang; Shinde, Pravin S.; Reddy, Ramana G.

doi:10.1016/j.jelechem.2021.115363

Title: Diffusion coefficient and nucleation density studies on electrochemical deposition of aluminum from chloroaluminate ionic liquid electrolytes

Journal Article · Sun May 16 00:00:00 EDT 2021 · Journal of Electroanalytical Chemistry

DOI:https://doi.org/10.1016/j.jelechem.2021.115363· OSTI ID:2222902

Peng, Yuxiang ^[1]; Shinde, Pravin S. ^[1]; Reddy, Ramana G. ^[1]

University of Alabama, Tuscaloosa, AL (United States)

In this study, aluminum was electrodeposited from ionic liquids comprising a melt of alkyl imidazolium chlorides and aluminum chloride (AlCl₃). The ionic liquids utilized in this study were 1-ethyl-3-methyl-imidazolium chloride (EMIC)-AlCl₃, 1-butyl-3-methylimidazolium chloride (BMIC)-AlCl₃, and 1-hexyl-3-methyl-imidazolium chloride (HMIC)-AlCl₃ at the AlCl₃ mole fraction of 0.667 (molar ratio of 1:2). The electrochemical behavior of chloroaluminate species in the three ionic liquids was investigated by cyclic voltammetry (CV) and chronoamperometry (CA) techniques at different temperatures. The cyclic voltammograms indicated that the reduction of Al₂Cl₇ ^– species to metallic aluminum followed a diffusion-controlled phenomenon. Moreover, even at a less negative applied potential, the higher current density was obtained for EMIC-AlCl₃ ionic liquid. That indicates that EMIC-AlCl₃ favors less energy consumption during the electrodeposition. The chronoamperometric analysis revealed that the onset of aluminum deposition from such ionic liquids proceeds via a three-dimensional instantaneous nucleation process. The concentrations of Al₂Cl₇ ^– ions in the ionic liquids were calculated based on the thermodynamic data, which were 2520, 2271, and 2035 mol m^–3 for EMIC-AlCl₃, BMIC-AlCl₃, and HMIC-AlCl₃, respectively. The diffusion coefficient (D) values of Al₂Cl₇ ^– species in such ionic liquids were also calculated at various temperatures. The D values determined from the CA technique at 363 K are 2.16 × 10^–11, 1.03 × 10^–11, and 0.87 × 10^–11 m² s^–1 for EMIC-AlCl₃, BMICAlCl₃, and HMIC-AlCl₃, respectively. In addition, the D value increased as temperature increased and decreased as the hydrocarbon group in the ionic liquid increased. As a result, the calculated grain sizes of nucleation range from 2 to 4 μm for these ionic liquids and are in good agreement with experimental data obtained from SEM micrographs.

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Research Organization:: RAPID Manufacturing Institute, New York, NY (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: EE0007888

OSTI ID:: 2222902

Journal Information:: Journal of Electroanalytical Chemistry, Vol. 895; ISSN 1572-6657

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (39)

Electrochemistry of the Hall-Heroult process for aluminum smelting Haupin, W. E. Journal of Chemical Education, Vol. 60, Issue 4 https://doi.org/10.1021/ed060p279	journal	April 1983
Dendrite-Free Aluminum Electrodeposition from AlCl3-1-Ethyl-3-Methyl-Imidazolium Chloride Ionic Liquid Electrolytes Pradhan, Debabrata; Reddy, Ramana G. Metallurgical and Materials Transactions B, Vol. 43, Issue 3 https://doi.org/10.1007/s11663-011-9623-1	journal	January 2012
Electrodeposition of aluminium from ionic liquids: Part II - studies on the electrodeposition of aluminum from aluminum chloride (AICl₃) - trimethylphenylammonium chloride (TMPAC) ionic liquids Jiang, T.; Chollier Brym, M. J.; Dubé, G. Surface and Coatings Technology, Vol. 201, Issue 1-2, p. 10-18 https://doi.org/10.1016/j.surfcoat.2005.12.024	journal	September 2006
Electrodeposition of aluminum on magnesium alloy in aluminum chloride (AlCl3)–1-ethyl-3-methylimidazolium chloride (EMIC) ionic liquid and its corrosion behavior Chang, Jeng-Kuei; Chen, Su-Yau; Tsai, Wen-Ta Electrochemistry Communications, Vol. 9, Issue 7 https://doi.org/10.1016/j.elecom.2007.03.009	journal	July 2007
Mechanistic study of Al electrodeposition from EMIC–AlCl3 and BMIC–AlCl3 electrolytes at low temperature Pradhan, Debabrata; Reddy, Ramana G. Materials Chemistry and Physics, Vol. 143, Issue 2 https://doi.org/10.1016/j.matchemphys.2013.09.033	journal	January 2014
Ionic liquids: How well do we know them? Reddy, Ramana G. Journal of Phase Equilibria and Diffusion, Vol. 27, Issue 3 https://doi.org/10.1361/154770306X110087	journal	June 2006
Electrochemical Kinetics of Reduction of Zinc Oxide to Zinc Using 2:1 Urea/ChCl Ionic Liquid Yang, Haoxing; Reddy, Ramana G. Electrochimica Acta, Vol. 178 https://doi.org/10.1016/j.electacta.2015.08.050	journal	October 2015
Electrodeposition of Cobalt‐Aluminum Alloys from Room Temperature Chloroaluminate Molten Salt Carlin, Richard T.; Trulove, Paul C.; De Long, Hugh C. Journal of The Electrochemical Society, Vol. 143, Issue 9 https://doi.org/10.1149/1.1837102	journal	September 1996
The Electrochemical Behavior of Aluminum in the Low Temperature Molten Salt System n Butyl Pyridinium Chloride: Aluminum Chloride and Mixtures of This Molten Salt with Benzene Robinson, J.; Osteryoung, R. A. Journal of The Electrochemical Society, Vol. 127, Issue 1 https://doi.org/10.1149/1.2129601	journal	January 1980
Electrodeposition of aluminium in aluminium chloride/1-methyl-3-ethylimidazolium chloride Lai, P. K.; Skyllas-Kazacos, M. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 248, Issue 2, p. 431-440 https://doi.org/10.1016/0022-0728(88)85103-9	journal	July 1988
Electrochemical production of Ti–Al alloys using TiCl4–AlCl3–1-butyl-3-methyl imidazolium chloride (BmimCl) electrolytes Pradhan, D.; Reddy, R. G. Electrochimica Acta, Vol. 54, Issue 6 https://doi.org/10.1016/j.electacta.2008.10.022	journal	February 2009
Acidity of Neutral Buffered 1-Ethyl-3-methylimidazolium Chloride−AlCl ₃ Ambient-Temperature Molten Salts Koronaios, Peter; King, Dawn; Osteryoung, Robert A. Inorganic Chemistry, Vol. 37, Issue 8 https://doi.org/10.1021/ic971345u	journal	April 1998
Recycling of aluminum metal matrix composite using ionic liquids: Kamavaram, V.; Mantha, D.; Reddy, R. G. Electrochimica Acta, Vol. 50, Issue 16-17 https://doi.org/10.1016/j.electacta.2004.12.002	journal	May 2005
Electrorefining of aluminum alloy in ionic liquids at low temperatures Kamavaram, V.; Mantha, D.; Reddy, R. G. Journal of Mining and Metallurgy, Section B: Metallurgy, Vol. 39, Issue 1-2 https://doi.org/10.2298/JMMB0302043K	journal	January 2003
Low-temperature Electrolysis of Aluminium from 1-Butyl-3-methylimidazolium Chloroaluminate Ionic Liquids with Inert Anode Zheng, Yong; Peng, Conghu; Zheng, Yongjun International Journal of Electrochemical Science, Vol. 11, Issue 7 https://doi.org/10.20964/2016.07.02	journal	July 2016
Electrodeposition of aluminium from ionic liquids: Part I—electrodeposition and surface morphology of aluminium from aluminium chloride (AlCl₃)–1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) ionic liquids Jiang, T.; Chollier Brym, M. J.; Dubé, G. Surface and Coatings Technology, Vol. 201, Issue 1-2, p. 1-9 https://doi.org/10.1016/j.surfcoat.2005.10.046	journal	September 2006
Effects of lithium bis(oxalato)borate on electrochemical stability of [Emim][Al2Cl7] ionic liquid for aluminum electrolysis Lang, Haiyan; Zhang, Junling; Kang, Yanhong Ionics, Vol. 23, Issue 4 https://doi.org/10.1007/s11581-016-1889-5	journal	November 2016
Optimization of pulsed electrodeposition of aluminum from AlCl3-1-ethyl-3-methylimidazolium chloride ionic liquid Tang, Jinwei; Azumi, Kazuhisa Electrochimica Acta, Vol. 56, Issue 3 https://doi.org/10.1016/j.electacta.2010.10.056	journal	January 2011
Determination of equilibrium constants for the tetrachloroaluminate ion dissociation in ambient-temperature ionic liquids Karpinski, Zenon J.; Osteryoung, Robert A. Inorganic Chemistry, Vol. 23, Issue 10 https://doi.org/10.1021/ic00178a039	journal	May 1984
Rechargeable aluminum batteries: effects of cations in ionic liquid electrolytes Zhu, Guanzhou; Angell, Michael; Pan, Chun-Jern RSC Advances, Vol. 9, Issue 20 https://doi.org/10.1039/C9RA00765B	journal	January 2019
Pulse current electrodeposition of Al from an AlCl3-EMIC ionic liquid Li, Bing; Fan, Chunhua; Chen, Yan Electrochimica Acta, Vol. 56, Issue 16 https://doi.org/10.1016/j.electacta.2011.03.047	journal	June 2011
Platinum as a Reference Electrode in Electrochemical Measurements Kasem, By Kasem K.; Jones, Stephanie Platinum Metals Review, Vol. 52, Issue 2 https://doi.org/10.1595/147106708X297855	journal	April 2008
Room-Temperature Electrodeposition of Aluminum via Manipulating Coordination Structure in AlCl₃ Solutions Wen, Xiaoyu; Liu, Yuhang; Xu, Da The Journal of Physical Chemistry Letters, Vol. 11, Issue 4 https://doi.org/10.1021/acs.jpclett.0c00256	journal	February 2020
Electrodeposition of aluminium from room temperature AlCl3-TMPAC molten salts Zhao, Yuguang; VanderNoot, T. J. Electrochimica Acta, Vol. 42, Issue 11 https://doi.org/10.1016/S0013-4686(96)00271-X	journal	January 1997
Electrodeposition of Pb from PbO in urea and 1-butyl-3-methylimidazolium chloride deep eutectic solutions Liu, Aimin; Shi, Zhongning; Reddy, Ramana G. Electrochimica Acta, Vol. 251 https://doi.org/10.1016/j.electacta.2017.08.011	journal	October 2017
Electrochemical deposition of zinc from zinc oxide in 2:1 urea/choline chloride ionic liquid Yang, Haoxing; Reddy, Ramana G. Electrochimica Acta, Vol. 147 https://doi.org/10.1016/j.electacta.2014.09.137	journal	November 2014
Theoretical and experimental studies of multiple nucleation Scharifker, Benjamin; Hills, Graham Electrochimica Acta, Vol. 28, Issue 7 https://doi.org/10.1016/0013-4686(83)85163-9	journal	July 1983
Fundamental Studies on Electrochemical Deposition of Lead from Lead Oxide in 2:1 Urea/Choline Chloride Ionic Liquids Yang, Haoxing; Reddy, Ramana G. Journal of The Electrochemical Society, Vol. 161, Issue 10 https://doi.org/10.1149/2.1161410jes	journal	January 2014
Electrodeposition of Silver on Metallic and Nonmetallic Electrodes from the Acidic Aluminum Chloride‐1‐Methyl‐3‐Ethylimidazolium Chloride Molten Salt Xu, Xiao‐Hong; Hussey, Charles L. Journal of The Electrochemical Society, Vol. 139, Issue 5 https://doi.org/10.1149/1.2069399	journal	May 1992
A Simple Approach to the Solution of the Diffusion Equation at the Microcylinder Electrode—an Inspiration from the Film Projector Fang, Yi‐Min; Sun, Jian‐Jun; Chen, Guo‐Nan ChemPhysChem, Vol. 10, Issue 14 https://doi.org/10.1002/cphc.200900404	journal	September 2009
Revisiting the Stokes-Einstein relation without a hydrodynamic diameter Costigliola, Lorenzo; Heyes, David M.; Schrøder, Thomas B. The Journal of Chemical Physics, Vol. 150, Issue 2 https://doi.org/10.1063/1.5080662	journal	January 2019
Density, Viscosity, and Conductivity of Lewis Acidic 1-Butyl- and 1-Hydrogen-3-methylimidazolium Chloroaluminate Ionic Liquids Zheng, Yong; Dong, Kun; Wang, Qian Journal of Chemical & Engineering Data, Vol. 58, Issue 1 https://doi.org/10.1021/je3004904	journal	November 2012
The influence of the size and symmetry of cations and anions on the physicochemical behavior of organic ionic plastic crystal electrolytes mixed with sodium salts Makhlooghiazad, F.; Guazzagaloppa, J.; O’Dell, L. A. Physical Chemistry Chemical Physics, Vol. 20, Issue 7 https://doi.org/10.1039/C7CP06971E	journal	January 2018
Potentiostatic studies of electrochemical nucleation Gunawardena, G. A.; Hills, G. J.; Montenegro, Irene Electrochimica Acta, Vol. 23, Issue 8 https://doi.org/10.1016/0013-4686(78)80026-7	journal	August 1978
Nucleation and Morphology Studies of Aluminum Deposited from an Ambient‐Temperature Chloroaluminate Molten Salt Carlin, Richard T.; Crawford, Wayne; Bersch, Michael Journal of The Electrochemical Society, Vol. 139, Issue 10, p. 2720-2727 https://doi.org/10.1149/1.2068970	journal	January 1992
Electrodeposition of Zinc from Zinc Oxide in 2:1 Urea/1-Butyl-3-methylimidazolium Chloride Ionic Liquid Liu, Aimin; Shi, Zhongning; Reddy, Ramana G. Journal of The Electrochemical Society, Vol. 164, Issue 9 https://doi.org/10.1149/2.1501709jes	journal	January 2017
General Mechanism for the Synchronization of Electrochemical Oscillations and Self-Organized Dendrite Electrodeposition of Metals with Ordered 2D and 3D Microstructures Fukami, Kazuhiro; Nakanishi, Shuji; Yamasaki, Haruka The Journal of Physical Chemistry C, Vol. 111, Issue 3 https://doi.org/10.1021/jp063462t	journal	December 2006
An electrochemical and spectroscopic study of some aromatic hydrocarbons in the room temperature molten salt system aluminum chloride-n-butylpyridinium chloride Robinson, J.; Osteryoung, R. A. Journal of the American Chemical Society, Vol. 101, Issue 2 https://doi.org/10.1021/ja00496a008	journal	January 1979
Aluminum Deposition and Nucleation on Nitrogen-Incorporated Tetrahedral Amorphous Carbon Electrodes in Ambient Temperature Chloroaluminate Melts Lee, Jae-Joon; Miller, Barry; Shi, Xu Journal of The Electrochemical Society, Vol. 147, Issue 9 https://doi.org/10.1149/1.1393908	journal	January 2000

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Title: Diffusion coefficient and nucleation density studies on electrochemical deposition of aluminum from chloroaluminate ionic liquid electrolytes

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