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

Kitada, Atsushi; Kang, Yuu; Uchimoto, Yoshiharu; Murase, Kuniaki

doi:10.1149/2.011403jes

Cited by 48 publications

(50 citation statements)

References 38 publications

(54 reference statements)

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“…Compared to the case of Ref. 16 the concentration of Mg 2+ is three times larger and the viscosity is about ten times larger while the conductivity is almost the same. Thus the present electrolyte has larger mobility of Mg 2+ .…”

Section: Bath Properties-mentioning

confidence: 60%

“…7a, at -1.0 V vs. Mg the CV for G2 mixture showed sizable reduction currents up to about 6 mA cm -2 , 1.5 times larger than the previous report on diglymerich mixture. 16 Because the Mg complexes as cationic species in the solution which was revealed by the Raman results, they can more easily access the cathode surface due to the electrostatic attractions with cathode, giving the large current densities. Compared to the case of Ref.…”

Section: Bath Properties-mentioning

confidence: 99%

“…[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. In these Mg 2+ -amide-containing glyme solutions, however, sizable amounts of free glyme molecules exists, as in IL-free glyme electrolytes, and thus all the reported electrolytes are either volatile and/or have limited anodic stability to some extent.…”

mentioning

confidence: 92%

“…Furthermore, we speculate that glymes can coordinate the ammonium cations of ILs since macrocyclic polyethers and openchain polyethers can coordinate alkylammonium cations through hydrogen bonding, 21 and in fact no phase separation occurred in our previous study. 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.…”

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: Bath Properties-mentioning

confidence: 60%

Section: Bath Properties-mentioning

confidence: 99%

mentioning

confidence: 92%

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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“…[42][43][44][45] In this case, Mg metal was used as the counter electrode, and Li metal immersed in 0. Fig.…”

Section: N M'mentioning

confidence: 99%

EQCM Analysis of Redox Behavior of CuFe Prussian Blue Analog in Mg Battery Electrolytes

Yagi

Fukuda

Ichitsubo

et al. 2015

J. Electrochem. Soc.

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A wide variety of ions and molecules can be accommodated in the framework structure of Prussian blue (PB) and its analogs (PBAs). Mono-and polyvalent ions accommodated in the PB framework structure and PBAs can be extracted or re-inserted by redox reactions of transition metal ions composing the framework for charge compensation. In the present work, we report the detailed mechanism of the electrochemical inseration/extraction of Mg 2+ ions and the effect of anions on the redox chemistry of a PBA composed of Cu and Fe ions by electrochemical quartz crystal microbalance and X-ray absorption spectroscopy. Furthermore, we evaluated the PBA as an active material using aqueous and organic electrolytes for Mg battery systems, and clarified that the redox potential of CuFe-PBA is approximately 3 V vs. Mg/Mg 2+ in both aqueous and organic electrolytes. Rechargeable Mg batteries have received intensive attention as affordable rechargeable batteries with high electromotive force, high energy density, and high safety because of the following superb properties of Mg; Mg possesses two valence electrons and has the lowest standard electrode potential (ca. −2.36 V vs. SHE) among the airstable metals; 1,2 Mg metal can be used as an active material because Mg metal hardly forms dendrites; 3-6 and Mg is a lightweight and abundant element widely spread in the world. However, the slow diffusion of Mg 2+ ions in solid crystals prevents the realization of active materials for Mg rechargeable batteries at room temperature. Although some complex oxides have been reported to work as active materials at higher temperatures, [7][8][9][10] Chevrel compounds are still the gold standards, which work at room temperature.11,12 However, the working voltage of the magnesium battery using a Chevrel compound for the positive electrode is only ca. 1.2 V, which is far below that of lithium ion batteries (3-5 V). Nevertheless, Chevrel compounds have the significant advantage that a relatively large space exists in the crystal structure, which allows for fast Mg 2+ ion diffusion. On the other hand, since Neff first reported the redox behavior of a Prussian blue (PB)-modified electrode with rapid color change, 13 the structures, electronic and optical properties, and redox behaviors of PB and its analogs (PBAs) have been thoroughly investigated. [14][15][16][17][18][19][20][21][22][23][24][25] As shown in Fig. 1 2+ ions? Why do several peaks appear in voltammograms of these compounds? In the present study, to answer these questions, we investigated the insertion and extraction behavior of Mg 2+ ions in a CuFe-PBA using electrochemical quartz crystal microbalance (EQCM) and X-ray absorption spectroscopy (XAS). This work is expected to provide guidance for choosing framework compounds as active materials for Mg 2+ batteries. * Electrochemical Society Active Member. z E-mail: s-yagi@21c.osakafu-u.ac.jp ExperimentalSynthesis of a Prussian blue analog CuFe-PBA.-All chemicals for the synthesis of CuFe-PBA and electrochemical tests in aqueous electrolytes wer...

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Experimental and Computational Investigation of NonaqueousMg/O₂Batteries

Smith

Vardar

Monroe

et al. 2018

Metal‐Air Batteries

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

Cited by 48 publications

References 38 publications

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

EQCM Analysis of Redox Behavior of CuFe Prussian Blue Analog in Mg Battery Electrolytes

Experimental and Computational Investigation of NonaqueousMg/O₂Batteries

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

Cited by 48 publications

References 38 publications

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

EQCM Analysis of Redox Behavior of CuFe Prussian Blue Analog in Mg Battery Electrolytes

Experimental and Computational Investigation of NonaqueousMg/O2Batteries

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Experimental and Computational Investigation of NonaqueousMg/O₂Batteries