Room temperature electrodeposition of metallic magnesium from ethylmagnesium bromide in tetrahydrofuran and ionic liquid mixtures

Lu Chen, Shufeng Zhao, Yuping Liu, Mike Horne, Alan Bond, Jie Zhang

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The redox processes, nucleation-growth mechanisms and magnesium (Mg) speciation associated with the room temperature electrodeposition of metallic Mg on an aluminum (Al) electrode are described from mixed deposition media composed of 0.095 M ethylmagnesium bromide (EtMgBr)/tetrahydrofuran (THF) and 0.54 M ionic liquid including: 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([Py14][FAP]), 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Py14][TFSI]), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide ([Py14][FSI]), 1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide ([Pip][TFSI]), ethyldimethylpropylammonium bis(trifluoromethylsulfonyl)imide ([N1123][TFSI]) and diethylmethyl (2-methoxyethyl) ammonium bis(trifluoromethylsulfonyl)imide ([DEME][TFSI]). Cyclic voltammetric results show a chemically reversible Mg/Mg2+ process in the case of [FAP]- and [TFSI]- based ionic liquids, but not for the [FSI]- based one, ascribed to ionic liquid dependent Mg speciation. Analysis of chronoamperometric data reveal that in the presence of [Py14][FAP] and [Pip][TFSI], Mg nucleation follows a 3D instantaneous nucleation and diffusion controlled semi-spherical growth model. However, in the case of [Py14][TFSI], [DEME][TFSI] and [N1123][TFSI], deviations from this model are evident. The influence of deposition parameters, such as current density and deposition time, on appearance, crystallite size and preferred orientation of Mg are also reported in a deposition medium containing 90% 1 M EtMgBr/THF and 10% ionic liquid (v/v ratio). [Py14][FAP] was found to be the most favourable ionic liquid for electrodepositon of Mg.

Original languageEnglish
Pages (from-to)H3043-H3051
Number of pages9
JournalJournal of the Electrochemical Society
Volume163
Issue number4
DOIs
Publication statusPublished - 2016

Cite this

@article{2b0dd646535046e991a8418689263a15,
title = "Room temperature electrodeposition of metallic magnesium from ethylmagnesium bromide in tetrahydrofuran and ionic liquid mixtures",
abstract = "The redox processes, nucleation-growth mechanisms and magnesium (Mg) speciation associated with the room temperature electrodeposition of metallic Mg on an aluminum (Al) electrode are described from mixed deposition media composed of 0.095 M ethylmagnesium bromide (EtMgBr)/tetrahydrofuran (THF) and 0.54 M ionic liquid including: 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([Py14][FAP]), 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Py14][TFSI]), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide ([Py14][FSI]), 1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide ([Pip][TFSI]), ethyldimethylpropylammonium bis(trifluoromethylsulfonyl)imide ([N1123][TFSI]) and diethylmethyl (2-methoxyethyl) ammonium bis(trifluoromethylsulfonyl)imide ([DEME][TFSI]). Cyclic voltammetric results show a chemically reversible Mg/Mg2+ process in the case of [FAP]- and [TFSI]- based ionic liquids, but not for the [FSI]- based one, ascribed to ionic liquid dependent Mg speciation. Analysis of chronoamperometric data reveal that in the presence of [Py14][FAP] and [Pip][TFSI], Mg nucleation follows a 3D instantaneous nucleation and diffusion controlled semi-spherical growth model. However, in the case of [Py14][TFSI], [DEME][TFSI] and [N1123][TFSI], deviations from this model are evident. The influence of deposition parameters, such as current density and deposition time, on appearance, crystallite size and preferred orientation of Mg are also reported in a deposition medium containing 90{\%} 1 M EtMgBr/THF and 10{\%} ionic liquid (v/v ratio). [Py14][FAP] was found to be the most favourable ionic liquid for electrodepositon of Mg.",
author = "Lu Chen and Shufeng Zhao and Yuping Liu and Mike Horne and Alan Bond and Jie Zhang",
year = "2016",
doi = "10.1149/2.0051604jes",
language = "English",
volume = "163",
pages = "H3043--H3051",
journal = "Journal of the Electrochemical Society",
issn = "0013-4651",
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Room temperature electrodeposition of metallic magnesium from ethylmagnesium bromide in tetrahydrofuran and ionic liquid mixtures. / Chen, Lu; Zhao, Shufeng; Liu, Yuping; Horne, Mike; Bond, Alan; Zhang, Jie.

In: Journal of the Electrochemical Society, Vol. 163, No. 4, 2016, p. H3043-H3051.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Room temperature electrodeposition of metallic magnesium from ethylmagnesium bromide in tetrahydrofuran and ionic liquid mixtures

AU - Chen, Lu

AU - Zhao, Shufeng

AU - Liu, Yuping

AU - Horne, Mike

AU - Bond, Alan

AU - Zhang, Jie

PY - 2016

Y1 - 2016

N2 - The redox processes, nucleation-growth mechanisms and magnesium (Mg) speciation associated with the room temperature electrodeposition of metallic Mg on an aluminum (Al) electrode are described from mixed deposition media composed of 0.095 M ethylmagnesium bromide (EtMgBr)/tetrahydrofuran (THF) and 0.54 M ionic liquid including: 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([Py14][FAP]), 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Py14][TFSI]), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide ([Py14][FSI]), 1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide ([Pip][TFSI]), ethyldimethylpropylammonium bis(trifluoromethylsulfonyl)imide ([N1123][TFSI]) and diethylmethyl (2-methoxyethyl) ammonium bis(trifluoromethylsulfonyl)imide ([DEME][TFSI]). Cyclic voltammetric results show a chemically reversible Mg/Mg2+ process in the case of [FAP]- and [TFSI]- based ionic liquids, but not for the [FSI]- based one, ascribed to ionic liquid dependent Mg speciation. Analysis of chronoamperometric data reveal that in the presence of [Py14][FAP] and [Pip][TFSI], Mg nucleation follows a 3D instantaneous nucleation and diffusion controlled semi-spherical growth model. However, in the case of [Py14][TFSI], [DEME][TFSI] and [N1123][TFSI], deviations from this model are evident. The influence of deposition parameters, such as current density and deposition time, on appearance, crystallite size and preferred orientation of Mg are also reported in a deposition medium containing 90% 1 M EtMgBr/THF and 10% ionic liquid (v/v ratio). [Py14][FAP] was found to be the most favourable ionic liquid for electrodepositon of Mg.

AB - The redox processes, nucleation-growth mechanisms and magnesium (Mg) speciation associated with the room temperature electrodeposition of metallic Mg on an aluminum (Al) electrode are described from mixed deposition media composed of 0.095 M ethylmagnesium bromide (EtMgBr)/tetrahydrofuran (THF) and 0.54 M ionic liquid including: 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([Py14][FAP]), 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Py14][TFSI]), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide ([Py14][FSI]), 1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide ([Pip][TFSI]), ethyldimethylpropylammonium bis(trifluoromethylsulfonyl)imide ([N1123][TFSI]) and diethylmethyl (2-methoxyethyl) ammonium bis(trifluoromethylsulfonyl)imide ([DEME][TFSI]). Cyclic voltammetric results show a chemically reversible Mg/Mg2+ process in the case of [FAP]- and [TFSI]- based ionic liquids, but not for the [FSI]- based one, ascribed to ionic liquid dependent Mg speciation. Analysis of chronoamperometric data reveal that in the presence of [Py14][FAP] and [Pip][TFSI], Mg nucleation follows a 3D instantaneous nucleation and diffusion controlled semi-spherical growth model. However, in the case of [Py14][TFSI], [DEME][TFSI] and [N1123][TFSI], deviations from this model are evident. The influence of deposition parameters, such as current density and deposition time, on appearance, crystallite size and preferred orientation of Mg are also reported in a deposition medium containing 90% 1 M EtMgBr/THF and 10% ionic liquid (v/v ratio). [Py14][FAP] was found to be the most favourable ionic liquid for electrodepositon of Mg.

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U2 - 10.1149/2.0051604jes

DO - 10.1149/2.0051604jes

M3 - Article

VL - 163

SP - H3043-H3051

JO - Journal of the Electrochemical Society

JF - Journal of the Electrochemical Society

SN - 0013-4651

IS - 4

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