Microelectrode studies of reversible Mg deposition in THF solutions containing complexes of alkylaluminum chlorides and dialkylmagnesium

Viestfrid, Yu.; Levi, M. D.; Gofer, Yosef; Aurbach, Doron

doi:10.1016/j.jelechem.2004.09.034

Cited by 74 publications

(66 citation statements)

References 24 publications

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“…The anodic stability tends to improve using TFSI − and PF 6 − anions. However, the reversible deposition-dissolution of magnesium cannot be obtained in the solutions of BMImPF 6 or BMMImTFSI containing Mg(CF 3 SO 3 ) 2 .…”

Section: Resultsmentioning

confidence: 99%

“…It is known that electrochemical Mg deposition is impossible from solutions containing simple ionic Mg salts (such as MgCl 2 , Mg(ClO 4 ) 2 , etc.) in commonly used aprotic solvents (such as alkyl carbonates, esters, and acetonitrile) [6,7]. However, magnesium can be reversibly deposited electrochemically in the systems without the passivating phenomena, such as ethereal solutions of Grignard reagents (RMgX, R = alkyl, aryl groups; X = halide: Cl, Br) [7][8][9][10], amidomagnesium halides [11,12], Mg(BR 2 R 2 ) 2 (R = alkyl and R = aryl group) [2,11], Mg(AX 4−n R n R n ) 2 (A = Al, B; X = Cl, Br; R, R = alkyl or aryl groups, and n + n = n) [13,14], and PhMgCl-AlCl 3 [15].…”

Section: Introductionmentioning

confidence: 99%

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Reversible Deposition and Dissolution of Magnesium from Imidazolium-Based Ionic Liquids

Zhao

Nuli

Nasiman

et al. 2012

International Journal of Electrochemistry

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The electrochemical performance of six imidazolium cation-based ionic liquids (ILs) containing 0.3 mol L −1 Mg(CF 3 SO 3 ) 2 as the electrolytes for magnesium deposition-dissolution was examined by cyclic voltammogramms and constant current dischargecharge techniques. Scanning electron microscopy and energy dispersive X-ray spectroscopy measurements were conducted to characterize the morphologies and components of the deposits. The cathodic satiability of imidazolium cations can be improved by increasing the length of alkyls at the 1-position and introducing methyl group at the 2-position of the imidazolium cations. A reversible magnesium deposition-dissolution can be achieved at room temperature. After adding appreciate amount of tetrahydrofuran (THF) organic solvent, the conductivity and the peak currents for Mg deposition and dissolution can be significantly improved. The potential polarization of deposition-dissolution process is decreased using Mg powder electrode.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Reversible Deposition and Dissolution of Magnesium from Imidazolium-Based Ionic Liquids

Zhao

Nuli

Nasiman

et al. 2012

International Journal of Electrochemistry

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“…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%

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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“…[46] In 2014, Doe et al resumed this combination and demonstrated that the DME solution of MgCl 2 -AlCl 3 , the so called "MACC" in a ratio of 3 : 2 offers an anodic stability of 3.1 V versus Mg, Coulombic efficiency of 99% and conductivity of 2 mS/cm (25°C). [47] As a full inorganic electrolyte, the MACC electrolyte has drawn much attention in the community, and has been extensively studied in recent years.…”

Section: Combinations Of Magnesium Chloride With Aluminum-based Lewismentioning

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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Microelectrode studies of reversible Mg deposition in THF solutions containing complexes of alkylaluminum chlorides and dialkylmagnesium

Cited by 74 publications

References 24 publications

Reversible Deposition and Dissolution of Magnesium from Imidazolium-Based Ionic Liquids

Reversible Deposition and Dissolution of Magnesium from Imidazolium-Based Ionic Liquids

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Magnesium-sulfur battery: its beginning and recent progress

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