Reversible deposition and dissolution of magnesium from BMIMBF4 ionic liquid

Nuli, Yanna; Yang, Jun; Wu, Rong

doi:10.1016/j.elecom.2005.07.013

Cited by 107 publications

(71 citation statements)

References 19 publications

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“…16 Therefore, it is of special interest to investigate glyme-based electrolytes where all glymes coordinate to any cations such as metal cations and/or ammnonium cations of ILs. Notably, the reversible deposition/dissolution cycle of Mg was reported using Mg 2+ -amide-containing ILs without glymes; [22][23][24][25] this was found to be highly suspicious in subsequent studies. 8,11,16,[26][27][28] In this paper, we studied the room temperature electrochemistry of metallic Mg using relatively safe electrolytes consisting of a Mg(Tf 2 N) 2 and IL/glyme mixture.…”

mentioning

confidence: 97%

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Kitada

Kang

Matsumoto

et al. 2015

J. Electrochem. Soc.

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We prepared less volatile and halide-free electrolytes for room temperature non-dendritic magnesium (Mg) electrodeposition by mixing a Mg 2+ -amide-containing ionic liquid (IL) with equimolar glyme (Mg 2+ +IL : glyme = 1:1). Raman spectroscopy suggested that in the equimolar mixture most glyme molecules are coordinated to Mg 2+ cations and/or IL cations, which is also supported by a single crystal X-ray diffraction study. The glyme-coordinated IL electrolytes showed sizable redox currents (order of mA cm -2 ), while aging deterioration of electrochemical properties was observed for the triglyme mixture due to partial bath decomposition. The tetraglyme-coordinated IL electrolyte enabled flat electrodeposition of Mg with a metallic luster and showed with very high anodic stability (ca. +4 V vs. Mg) because of decrease in uncoordinated glymes, which can be used for high-voltage Mg ion batteries. In the last few decades elemental magnesium (Mg) has come to be viewed as one of the most interesting negative electrode materials for post lithium ion secondary batteries because of its high-theoretical capacity (3839 mAh cm -3 ), low electrode potential (-2.356 V vs. SHE), and natural abundance. The well-known electrolytes for electrodepositing Mg metal at room temperature are Grignard electrolytes comprised of an ether solvent tetrahydrofuran (THF) and alkylmagnesium halides RMgX (R = alkyl or aryl groups; X = Cl, Br). Addition of AlCl 3 makes more electroactive species of organo-halo-aluminates, giving larger current density and/or higher anodic stability.1-10 However, the highly volatile THF and the highly moisture sensitive RMgX and AlCl 3 are difficult to use practically. Safer alternatives to both solvents and solutes for Mg-ion battery electrolytes are still being sought.Several groups have reported deposition of elemental Mg without using THF or RMgX. Ionic liquids (ILs) are one of the least volatile solvents and efforts have been made to electrodeposit Mg from ILs. For example, Mg redox behavior has been observed in an IL solution of Mg(ClO 4 ) 2 or MgCl 2 , although their current densities were significantly lower than those for RMgX-dissolved ILs.11 Some organic solvents that enable redox of Mg are less volatile than THF; these include 2-methyl-tetrahydrofuran, 12 and ethyleneglycol dimethylethers (glymes), [13][14][15] where Mg halides and hydrides were dissolved. Notably, glymes have boiling points above 150• C and are relatively safe at room temperature. However, in halide or hydride solutions hazardous halogen gas or hydrogen gas may evolve through anodic oxidation. From this viewpoint amide electrolytes are quite desirable as they hardly yield dissociated halogen ions.Glyme solutions of magnesium amides such as bis [(trifluoromethyl) 16 Therefore, it is of special interest to investigate glyme-based electrolytes where all glymes coordinate to any cations such as metal cations and/or ammnonium cations of ILs. Notably, the reversible deposition/dissolution cycle of Mg was reported using Mg 2+ -amide-containi...

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mentioning

confidence: 97%

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Kitada

Kang

Matsumoto

et al. 2015

J. Electrochem. Soc.

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“…SEM and AFM images of the Mg film typically show a highly faceted film with grains on the order of 1 μm in width. [8][9][10][11] However, other morphologies with either larger 10 or smaller 12,13 features have also been observed. The most comprehensive examination of the morphology of electrodeposited Mg was conducted by Matsui,4 who examined the morphology of 1 C/cm 2 of Mg deposited at 0.5, 1, and 2 mA/cm 2 .…”

mentioning

confidence: 99%

Computational Examination of Orientation-Dependent Morphological Evolution during the Electrodeposition and Electrodissolution of Magnesium

DeWitt

Hahn

Zavadil

et al. 2015

J. Electrochem. Soc.

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A new model of electrodeposition and electrodissolution is developed and applied to the evolution of Mg deposits during anode cycling. The model captures Butler-Volmer kinetics, facet evolution, the spatially varying potential in the electrolyte, and the time-dependent electrolyte concentration. The model utilizes a diffuse interface approach, employing the phase field and smoothed boundary methods. Scanning electron microscope (SEM) images of magnesium deposited on a gold substrate show the formation of faceted deposits, often in the form of hexagonal prisms. Orientation-dependent reaction rate coefficients were parameterized using the experimental SEM images. Three-dimensional simulations of the growth of magnesium deposits yield deposit morphologies consistent with the experimental results. The simulations predict that the deposits become narrower and taller as the current density increases due to the depletion of the electrolyte concentration near the sides of the deposits. Increasing the distance between the deposits leads to increased depletion of the electrolyte surrounding the deposit. Two models relating the orientation-dependence of the deposition and dissolution reactions are presented. The morphology of the Mg deposit after one deposition-dissolution cycle is significantly different between the two orientation-dependence models, providing testable predictions that suggest the underlying physical mechanisms governing morphology evolution during deposition and dissolution. Magnesium batteries have garnered substantial attention as a successor to Li-ion batteries due to their potential for high energy density and safe operation.1-3 Metallic Mg anodes provide a substantially higher specific volumetric capacity (3833 mA h/cm 3 ) than either Ligraphite anodes (760 mA h/cm 3 ) or metallic Li anodes (2046 mA h/cm 3 ). 2 Furthermore, unlike metallic Li anodes, 5 metallic Mg anodes can be cycled without the formation of dendrites. 4 Dendrite growth poses a hazard because dendrites can grow across the separator to the cathode and short the battery, leading to thermal runaway. 5,6 Instead of forming dendrites, metallic Mg anodes form compact, faceted films, practically eliminating this risk. 4 Understanding the evolution of this Mg film during cycling is a critical factor in the development of high-performance magnesium batteries. 7Although the development of electrolytes for the efficient and reversible deposition and dissolution of Mg has been pursued extensively (see Refs. 1 and 2 for comprehensive reviews on this topic), much less attention has been given to the morphological evolution of the Mg deposits during cycling. SEM and AFM images of the Mg film typically show a highly faceted film with grains on the order of 1 μm in width. [8][9][10][11] However, other morphologies with either larger 10 or smaller 12,13 features have also been observed. The most comprehensive examination of the morphology of electrodeposited Mg was conducted by Matsui, 4 who examined the morphology of 1 C/cm 2 of Mg deposited at 0.5...

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“…The application studies of ILs have been proposed varying from precious metal processing [29][30][31][32][33][34][35][36][37][38][39][40] to mineral leaching [41][42][43][44]; however, very few have come to practical fruition although several are at a pilot scale [45][46][47]. Except some technical diiculties that are hard to solve at our present state of knowledge [48], the relatively prohibitive high cost of ILs is also a main reason for delaying their industrial application [44].…”

Section: Why Use Ils As Electrodeposition Additives and Corrosion Inhmentioning

confidence: 99%

Ionic Liquids as Electrodeposition Additives and Corrosion Inhibitors

Zhang¹,

Ye²

2017

Progress and Developments in Ionic Liquids

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Ionic liquids (ILs) are molten salts with a melting point of 100°C or below and solely consist of cations and anions. As a kind of novel green solvent, ILs have been obtained broad and deep investigations, and enormous progresses in various ields have been made during the recent 20 years. Despite the fact that the application studies of ILs have been proposed in various ields, no processes have yet been developed to an industrial scale. However, the main interests are still focused on their industrial applications. In this chapter, two perspective applications of ILs in electrochemical ields including additives for metal electrodeposition and inhibitors for metal anti-corrosion were introduced.

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Reversible deposition and dissolution of magnesium from BMIMBF4 ionic liquid

Cited by 107 publications

References 19 publications

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Computational Examination of Orientation-Dependent Morphological Evolution during the Electrodeposition and Electrodissolution of Magnesium

Ionic Liquids as Electrodeposition Additives and Corrosion Inhibitors

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