Electrochemical Deposition and Dissolution of Magnesium Metal in Various Ether-Based Electrolytes

Yasui, Ryohei; Asaka, Keisuke; Miyazaki, Kohei; Fukutsuka, Tomokazu; Abe, Takeshi; Nishio, Koji; Uchimoto, Yoshiharu

doi:10.1149/ma2013-02/6/463

Meet. Abstr.

2013

DOI: 10.1149/ma2013-02/6/463

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Electrochemical Deposition and Dissolution of Magnesium Metal in Various Ether-Based Electrolytes

Ryohei Yasui

Keisuke Asaka

Kohei Miyazaki

et al.

Abstract: not Available.

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Cited by 3 publications

(3 citation statements)

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“…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.…”

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confidence: 99%

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: 99%

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Kitada

Kang

Matsumoto

et al. 2015

J. Electrochem. Soc.

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“…Deposition of elemental Mg without THF and/or RMgX has been reported. [18][19][20][21][22][23][24] Cheek et al showed Mg deposition redox behavior at room temperature in an IL dissolving Mg(ClO 4 ) 2 or MgCl 2 , although their reduction currents were significantly lower than that in RMgX-containing ILs. 18 Abe et al demonstrated the reversible deposition/dissolution cycle of Mg with high coulombic efficiency in 2Me-THF where MgBr 2 dissolved.…”

mentioning

confidence: 99%

“…19 In addition, they also showed that some kinds of glyme solution, where MgCl 2 and AlCl 3 were dissolved, gave reversible deposition/dissolution behavior at room temperature. 20 Nevertheless, the abovementioned Mg salts contain halide anions, which can form halogen gas through anodic oxidization. 18 Because halogen gases carry a high environmental burden, non-halide anion electrolytes such as Mg(Tf 2 N) 2 are favorable.…”

mentioning

confidence: 99%

Room-Temperature Electrodeposition of Mg Metal from Amide Salts Dissolved in Glyme-Ionic Liquid Mixture

Kitada

Kang

Uchimoto

et al. 2013

J. Electrochem. Soc.

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The electrodeposition of Mg metal from an ionic liquid-glyme mixture was investigated at room temperature. The mixture contains a glyme, a simple amide salt Mg(Tf 2 N) 2 (Tf = SO 2 CF 3), and a quaternary-ammonium Tf 2 N ionic liquid. Using the mixture bath, substantial cathodic electrodeposition of Mg at a large current density (∼10 mA cm −2) was observed, suggesting a change in coordination geometry around Mg 2+ cation together with improved conductivity. By mixing diglyme, the conductivity increased by an order of magnitude (2.5-2.6 mS cm −1) compared to the glyme-free ionic liquid (0.35 mS cm −1) and the viscosity became as low as that of pure glyme. Additionally, potentiostatic electrolysis resulted in a non-dendritic thin film of elemental Mg with metallic luster.

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AlCl3-dissolved Diglyme as Electrolyte for Room-Temperature Aluminum Electrodeposition

et al. 2014

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We first report an AlCl 3 -containing diglyme electrolyte for room temperature Al electrodeposition, which have relatively low volatilities and low cost. With the molar ratio of AlCl 3 :diglyme = 1:5, the diglyme solution enabled deposition and dissolution of Al, which required relatively small overpotentials at room temperature. The deposits were not dendritic, indicating potential applications for Al plating or Al ion batteries.

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Electrochemical Deposition and Dissolution of Magnesium Metal in Various Ether-Based Electrolytes

Abstract: not Available.

Cited by 3 publications

References 3 publications

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Room-Temperature Electrodeposition of Mg Metal from Amide Salts Dissolved in Glyme-Ionic Liquid Mixture

AlCl3-dissolved Diglyme as Electrolyte for Room-Temperature Aluminum Electrodeposition

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