The electrodeposition of magnesium using solutions of organomagnesium halides, amidomagnesium halides and magnesium organoborates

Liebenow, C.; Yang, Zhen; Lobitz, P.

doi:10.1016/s1388-2481(00)00094-1

Cited by 135 publications

(112 citation statements)

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“…2 -glyme complex.-Batterygrade G2, G3, G4 and Mg(Tf 2 N) 2 from Kishida Kagaku were used as reagents. Each glyme of 1.5 cm 3 and Mg(Tf 2 N) 2 was mixed at a molar ratio of 3:1, heated to 90…”

Section: Journal Of the Electrochemical Society 162 (8) D389-d396 (2mentioning

confidence: 99%

“…Addition of AlCl 3 makes more electroactive species of organo-halo-aluminates, giving larger current density and/or higher anodic stability. [1][2][3][4][5][6][7][8][9][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.…”

mentioning

confidence: 99%

“…Glyme solutions of magnesium amides such as bis[(trifluoromethyl)sulfonyl] amide Mg(Tf 2 N) 2 , where Tf denotes (trifluoromethyl)sulfonyl or CF 3 SO 2 , have recently been reported to show successful electrodeposition of Mg metal. [16][17][18][19] We have also reported an amide-containing glyme-IL solution with which room temperature electrodeposition of Mg metal was successfully demonstrated.…”

mentioning

confidence: 99%

“…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. Addition of equimolar glyme to Mg 2+ -containing ILs gave high stabilities toward oxidation of glymes, all of which seems to be coordinated to Mg 2+ or IL cations.…”

mentioning

confidence: 99%

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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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Section: Journal Of the Electrochemical Society 162 (8) D389-d396 (2mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 2 more Smart Citations

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Kitada

Kang

Matsumoto

et al. 2015

J. Electrochem. Soc.

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“…The reversible Mg deposition of the non-nucleophilic Hauserbase hexamethyldisilazide magnesium chloride (HMDSMgCl) was first reported by Liebenow et al, [27] and the electrolyte showed superior electrochemical properties compared with those of Grignard reagent-based electrolytes. Later, Muldoon and co-workers applied the previously established strategy from Aurbach by adding AlCl 3 to the solution of Liebenow's electrolyte HMDSMgCl and observed an increased current density for Mg plating/stripping.…”

Section: Non-nucleophilic Magnesium Electrolytes Hauser Base-based Elmentioning

confidence: 99%

Magnesium-sulfur battery: its beginning and recent progress

Zhao‐Karger

Fichtner

2017

MRS Communications

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Rechargeable magnesium (Mg) battery has been considered as a promising candidate for future battery generations because of its potential high-energy density, its safety features and low cost. The challenges lying ahead for the realization of Mg battery in general are to develop proper electrolytes fulfilling a multitude of requirements and to discover cathode materials enabling high-energy Mg batteries. The combination of Mg anode with a sulfur cathode is one of the promising electrochemical couples due to its advantages of safety, low costs, and a high theoretical energy density of over 3200 Wh/L. However, the research on magnesium-sulfur (Mg-S) battery is just at its beginning and the development of suitable electrolytes has been the key challenge for further improvement, and, thus, in the focus of recent research. In this review, we highlight the recent progress achieved in Mg electrolytes and Mg-S batteries and discuss the major technical issues, which must be resolved for the improvement of Mg-S batteries.

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Electrochemistry of Organomagnesium Compounds

Jaworski

2009

Patai's Chemistry of Functional Groups

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Introduction Electrochemical Synthesis of Organomagnesium Compounds Conductivity of Solutions of Organomagnesium Compounds Anodic Oxidation of Organomagnesium Compounds Cathodic Reduction of Organomagnesium Compounds Organomagnesium Compounds as Intermediates in Electrode Reactions Concluding Remarks: Electrochemical Data in the Elucidation of Reactivity of G rignard Reagents

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The electrodeposition of magnesium using solutions of organomagnesium halides, amidomagnesium halides and magnesium organoborates

Cited by 135 publications

References 8 publications

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Magnesium-sulfur battery: its beginning and recent progress

Electrochemistry of Organomagnesium Compounds

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