New Magnesium-ion Conductive Electrolyte Solution Based on Triglyme for Reversible Magnesium Metal Deposition and Dissolution at Ambient Temperature

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

doi:10.1246/cl.140704

Cited by 62 publications

(81 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…According to the above definition, the decomposition potential of the 0.5 mol dm -3 Mg(Tf 2 N) 2 /G3 solution locates at around +3.4 V vs. Mg QRE with the same sweep rate. 19 Such an improvement in anodic stability due to a lack of free glymes has also been reported in LiTf 2 N/glyme solution. 20 Therefore, it is concluded that the IL/glyme mixtures have higher anodic stability than the IL-free Mg(Tf 2 N) 2 /G3 solution.…”

Section: 19mentioning

confidence: 60%

“…The viscosity of each glyme mixture is about 25-26 mPa s, one order of magnitude higher than that of the previously reported glyme-rich mixture (2.32 mPa s; Mg 2+ :IL:G2 = 1:7:56 by mole). 16 However, the conductivities shown in Table III 16,17,19 although slightly smaller than typical lithium-ion conductive electrolyte solutions. Notably, the bulk bath properties were fairly similar within 7 days for each IL/glyme mixture (see Fig.…”

Section: Resultsmentioning

confidence: 89%

“…7b were five times smaller than those in 0.5 mol dm -3 Mg 2+ in G3 solution. 19 Although the viscosity of the pure G3 solution is not presented, the viscosity can be one order of magnitude lower than the IL/G3 mixed solution, and both the concentration and conductivity are similar to those of the IL/G3. Thus similar mobility of Mg 2+ should be present in the pure G3 and the IL/G3 solutions.…”

Section: Bath Properties-mentioning

confidence: 99%

“…Without ILs, the G3 solution of Mg(Tf 2 N) 2 shows as large current density as IL/G2 or IL/G4 mixture. 18,19 Moreover, the IL/G3 sample kept in a glove box for 7 days after mixing changed to yellowish from colorless while the others remained fairly colorless (see Fig. 8).…”

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: 94%

See 4 more Smart Citations

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Kitada

Kang

Matsumoto

et al. 2015

J. Electrochem. Soc.

View full text Add to dashboard Cite

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...

show abstract

Section: 19mentioning

confidence: 60%

Section: Resultsmentioning

confidence: 89%

Section: Bath Properties-mentioning

confidence: 99%

Section: Bath Properties-mentioning

confidence: 99%

mentioning

confidence: 94%

See 3 more Smart Citations

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Kitada

Kang

Matsumoto

et al. 2015

J. Electrochem. Soc.

View full text Add to dashboard Cite

show abstract

Structure Design of Long‐Life Spinel‐Oxide Cathode Materials for Magnesium Rechargeable Batteries

et al. 2021

View full text Add to dashboard Cite

Development of metal‐anode rechargeable batteries is a challenging issue. Especially, magnesium rechargeable batteries are promising in that Mg metal can be free from dendrite formation upon charging. However, in case of oxide cathode materials, inserted magnesium tends to form MgO‐like rocksalt clusters in a parent phase even with another structure, which causes poor cyclability. Here, a design concept of high‐performance cathode materials is shown, based on: i) selecting an element to destabilize the rocksalt‐type structure and ii) utilizing the defect‐spinel‐type structure both to avoid the spinel‐to‐rocksalt reaction and to secure the migration path of Mg cations. This theoretical and experimental work substantiates that a defect‐spinel‐type ZnMnO3 meets the above criteria and shows excellent cycle performance exceeding 100 cycles upon Mg insertion/extraction with high potential (≈2.5 V vs Mg2+/Mg) and capacity (≈100 mAh g−1). Thus, this work would provide a design guideline of cathode materials for various multivalent rechargeable batteries.

show abstract

Intercalation and Push‐Out Process with Spinel‐to‐Rocksalt Transition on Mg Insertion into Spinel Oxides in Magnesium Batteries

et al. 2015

View full text Add to dashboard Cite

On the basis of the similarity between spinel and rocksalt structures, it is shown that some spinel oxides (e.g., MgCo2O4, etc) can be cathode materials for Mg rechargeable batteries around 150 °C. The Mg insertion into spinel lattices occurs via “intercalation and push‐out” process to form a rocksalt phase in the spinel mother phase. For example, by utilizing the valence change from Co(III) to Co(II) in MgCo2O4, Mg insertion occurs at a considerably high potential of about 2.9 V vs. Mg2+/Mg, and similarly it occurs around 2.3 V vs. Mg2+/Mg with the valence change from Mn(III) to Mn(II) in MgMn2O4, being comparable to the ab initio calculation. The feasibility of Mg insertion would depend on the phase stability of the counterpart rocksalt XO of MgO in Mg2X2O4 or MgX3O4 (X = Co, Fe, Mn, and Cr). In addition, the normal spinel MgMn2O4 and MgCr2O4 can be demagnesiated to some extent owing to the robust host structure of Mg1−xX2O4, where the Mg extraction/insertion potentials for MgMn2O4 and MgCr2O4 are both about 3.4 V vs. Mg2+/Mg. Especially, the former “intercalation and push‐out” process would provide a safe and stable design of cathode materials for polyvalent cations.

show abstract

New Magnesium-ion Conductive Electrolyte Solution Based on Triglyme for Reversible Magnesium Metal Deposition and Dissolution at Ambient Temperature

Cited by 62 publications

References 20 publications

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Room Temperature Magnesium Electrodeposition from Glyme-Coordinated Ammonium Amide Electrolytes

Structure Design of Long‐Life Spinel‐Oxide Cathode Materials for Magnesium Rechargeable Batteries

Intercalation and Push‐Out Process with Spinel‐to‐Rocksalt Transition on Mg Insertion into Spinel Oxides in Magnesium Batteries

Contact Info

Product

Resources

About