Electrochemical Behavior of Iron and Magnesium in Ionic Liquids

Lodovico, Lucas; Martins, Vitor L.; Benedetti, Tânia M.; Torresi, Roberto M.

doi:10.5935/0103-5053.20130305

Cited by 2 publications

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“…To date, the most favorable electrolytes and electrodes for Mg electrochemistry still lack the necessary requirements to produce a viable product. Despite the advantages they might bring, ionic liquid-based electrolytes have received only a small fraction of the attention in this area. − Here, we studied the complex environment of Mg 2+ in the room temperature ionic liquid (RTIL) n -butyl- N -methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPyrTFSI or Pyr 14 TFSI) (shown in Figure ), with the effects on the electrochemical behavior in mind.…”

Section: Introductionmentioning

confidence: 99%

Determination of Mg²⁺ Speciation in a TFSI^–-Based Ionic Liquid With and Without Chelating Ethers Using Raman Spectroscopy

2015

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Raman spectroscopy was employed to assess the complex environment of magnesium salts in the n-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPyrTFSI) room-temperature ionic liquid (RTIL). At room temperature, Mg(TFSI)2 was miscible with BMPyrTFSI and formulated by [Mg(TFSI)2](x)[BMPyrTFSI](1-x) (x ≤ 0.55). Results suggest that at low concentrations of Mg(TFSI)2, anionic complexes in which Mg(2+) is surrounded by at least four TFSI(-) were formed. Above x = 0.2 an average of three TFSI(-) surround each Mg(2+). Below x = 0.12, there is a greater number of monodentate interactions between TFSI(-) oxygens and Mg(2+) cations, whereas above x = 0.12 bidentate ligands dominate. The fraction of TFSI(-) existing in the cis conformation increased with increasing Mg(2+) concentration. Mg(ClO4)2 was also studied as a Mg(2+) source. At equivalent mole fractions to those of the Mg(TFSI)2 salt, Mg(2+) from Mg(ClO4)2 was surrounded by only two TFSI(-) anions as ClO4(-) appeared to compete with TFSI(-) for coordination with Mg(2+). Similar behavior was also observed for the less soluble halide salts MgX2 (X = Cl, Br, I). Additions of chelating ligands were shown to effectively reduce the average number of TFSI(-) around Mg(2+) in a manner consistent with maintaining a sixfold oxygen coordination number around Mg(2+). Furthermore, an alternative class of ionic liquids, known as "solvate" ionic liquids, were produced. In this case glymes (Gm, m + 1 ether oxygens) were mixed with Mg(TFSI)2 so that glymes chelated Mg(2+), creating Mg(Gm)(y)(2+) complexes. The general formula was given by Mg(Gm)(y)(TFSI)2. These solvate ILs melt between 40 and 80 °C. Raman spectra clearly showed the glyme chelating ability and stronger coordination with Mg(2+) with respect to TFSI(-). Finally, linear sweep voltammograms showed the anodic stability of the glymes to improve due to coordination with Mg(2+).

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Section: Introductionmentioning

confidence: 99%

Determination of Mg²⁺ Speciation in a TFSI^–-Based Ionic Liquid With and Without Chelating Ethers Using Raman Spectroscopy

2015

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“…Mg is a very active metal and is always covered with surface films, which usually consist of oxides, halides, hydroxides, and carbonates depending on the surrounding atmospheric conditions, solvents and gases. In addition, the passivation of Mg electrodes was observed to be quite rapid even with a small amount of moisture or water in the electrolytes [ 84 ]. However, the Mg electrodes are highly reversible only in Grignard reagents, where they can be dissolved and deposited using Grignard reagent based electrolytes, and in all other cases they tend to form passivating films with the compounds listed above.…”

Section: Literature Review On Multivalent Aqueous Batteriesmentioning

confidence: 99%

A Brief Review on Multivalent Intercalation Batteries with Aqueous Electrolytes

2016

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Rapidly growing global demand for high energy density rechargeable batteries has driven the research toward developing new chemistries and battery systems beyond Li-ion batteries. Due to the advantages of delivering more than one electron and giving more charge capacity, the multivalent systems have gained considerable attention. At the same time, affordability, ease of fabrication and safety aspects have also directed researchers to focus on aqueous electrolyte based multivalent intercalation batteries. There have been a decent number of publications disclosing capabilities and challenges of several multivalent battery systems in aqueous electrolytes, and while considering an increasing interest in this area, here, we present a brief overview of their recent progress, including electrode chemistries, functionalities and challenges.

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Electrochemical Behavior of Iron and Magnesium in Ionic Liquids

Cited by 2 publications

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Determination of Mg²⁺ Speciation in a TFSI^–-Based Ionic Liquid With and Without Chelating Ethers Using Raman Spectroscopy

Determination of Mg²⁺ Speciation in a TFSI^–-Based Ionic Liquid With and Without Chelating Ethers Using Raman Spectroscopy

A Brief Review on Multivalent Intercalation Batteries with Aqueous Electrolytes

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Electrochemical Behavior of Iron and Magnesium in Ionic Liquids

Cited by 2 publications

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Determination of Mg2+ Speciation in a TFSI–-Based Ionic Liquid With and Without Chelating Ethers Using Raman Spectroscopy

Determination of Mg2+ Speciation in a TFSI–-Based Ionic Liquid With and Without Chelating Ethers Using Raman Spectroscopy

A Brief Review on Multivalent Intercalation Batteries with Aqueous Electrolytes

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Determination of Mg²⁺ Speciation in a TFSI^–-Based Ionic Liquid With and Without Chelating Ethers Using Raman Spectroscopy

Determination of Mg²⁺ Speciation in a TFSI^–-Based Ionic Liquid With and Without Chelating Ethers Using Raman Spectroscopy