Plating of magnesium from organic solvents

Lossius, Lorentz Petter; Emmenegger, Franzpeter

doi:10.1016/0013-4686(95)00326-6

Cited by 62 publications

(49 citation statements)

References 3 publications

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“…50 Another peculiarity of the Mg(TFSI) 2 /G2 electrolyte is the debated instability of plating/stripping overpotentials at different salt concentrations and current densities. 28,50,51 In pursuit of understanding the Mg(TFSI) 2 electrolyte behavior and its potential improvement, extensive computational studies were carried out. 5,6,27,31 Using a combination of classical MD simulations and quantum chemistry calculations hybridized with implicit solvent models, 52 it was shown that the solvent donor strength and its chelating ability largely determine the solubility of Mg(TFSI) 2 and the ion-pair solvation structure.…”

Section: ■ Introductionmentioning

confidence: 99%

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)₂ in Diglyme: Implications for Multivalent Electrolytes

2016

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We reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitals are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI)2)/diglyme) and its singly charged ion pair, MgTFSI+. In particular, we found that both stable (MgTFSI)+ and (MgTFSI)0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This implies that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI)+ ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. The obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.

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Section: ■ Introductionmentioning

confidence: 99%

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)₂ in Diglyme: Implications for Multivalent Electrolytes

2016

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“…One of the most serious issues is on the Mg negative electrode, i.e., the reversible Mg plating and stripping hardly realized in the various electrolyte solutions, because of the formation of insulating surface film. [2][3][4][5] Although the Grignard reagent based solutions can achieve the high reversible Mg plating and stripping reaction, 1,6,7 the solutions have critical disadvantages, such as low ionic conductivity, poor chemical and electrochemical stability. Recently, however, it was reported that the reversible Mg plating and stripping was achieved with Mg(N(CF 3 SO 2 ) 2 ) 2 (Mg(TFSA) 2 ) dissolved in triethyleneglycol dimethyl ether (triglyme) based solutions.…”

Section: Introductionmentioning

confidence: 99%

The Effect of the Cyclic Ether Additives to the Ethereal Electrolyte Solutions for Mg Secondary Battery

et al. 2016

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The effect of crown ether additives for the electrolyte solution containing Mg(N(CF 3 SO 2 ) 2 ) 2 (Mg(TFSA) 2 ) was studied. Mg(TFSA) 2 salt hardly dissolved in tetrahydrofuran, while 1 mol dm −3 solution was obtained by 18-crown-6 (18C6) ether addition and the 10 −3 S cm −1 order of ionic conductivity was achieved. From the FT-IR spectrum, the predominantly coordination between Mg 2+ -ion and 18C6 was indicated. Cyclic voltammogram showed the redox current, which indicated that the reversible Mg plating and stripping reaction took place, while the clear redox current did not appear in the additive-free solution. From the results, we concluded the specific solvation structure of Mg 2+ -ion by 18C6 ether would play the effective role for the reversible Mg plating and stripping reaction.

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“…Early studies indicated that although offering high charge density by the Mg 2+ ion, simple Mg salts such as Mg(ClO4)2 or Mg(PF6)2 failed to work in Mg batteries as the respective anions decomposed on, and passivated the Mg metal surface. 300,301 Interestingly, nearly 100 years ago, the Grignard reagent was studied as an electrolyte that allowed etching of the passivating oxide coating, and hence reversible deposition and dissolution of Mg on the negatrode. 302 However, Grignard reagents (RMgX, where R is an alkyl or aryl group, and X is Cl or Br) cannot be used in batteries due to its intrinsic reducing power.…”

Section: Magnesium Batteriesmentioning

confidence: 99%

Electrolytes for electrochemical energy storage

Xia

et al. 2017

Mater. Chem. Front.

225

116

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A note on versions:The version presented here may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the repository url above for details on accessing the published version and note that access may require a subscription.For more information, please contact eprints@nottingham.ac.uk Journal NameThis journal is © The Royal Society of Chemistry 20xxJ. Name., 2013, 00, 1-3 | 1 Electrolyte is a key component of electrochemical energy storage (EES) devices and its properties greatly affect the energy capacity, rate performance, cyclability and safety of all EES devices. This article offers a critical review of recent progresses and challenges in electrolyte research and development particularly for supercapacitors and supercapatteries, recharegable batteries (such as lithium-ion and sodium-ion batteries), and redox flow batteries (including fuel cells in a broad sense). The review will focus on liquid electrolytes, particularly aqueous and organic electrolytes, ionic liquids and molten salts. Influences of electrolyte properties on the performances of different EES devices are discussed in detail.

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Plating of magnesium from organic solvents

Cited by 62 publications

References 3 publications

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)₂ in Diglyme: Implications for Multivalent Electrolytes

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)₂ in Diglyme: Implications for Multivalent Electrolytes

The Effect of the Cyclic Ether Additives to the Ethereal Electrolyte Solutions for Mg Secondary Battery

Electrolytes for electrochemical energy storage

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Plating of magnesium from organic solvents

Cited by 62 publications

References 3 publications

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)2 in Diglyme: Implications for Multivalent Electrolytes

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)2 in Diglyme: Implications for Multivalent Electrolytes

The Effect of the Cyclic Ether Additives to the Ethereal Electrolyte Solutions for Mg Secondary Battery

Electrolytes for electrochemical energy storage

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Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)₂ in Diglyme: Implications for Multivalent Electrolytes

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)₂ in Diglyme: Implications for Multivalent Electrolytes