On the electrochemical behavior of magnesium electrodes in polar aprotic electrolyte solutions

Lu, Zhonghua; Schechter, Alex; Moshkovich, M.; Aurbach, Doron

doi:10.1016/s0022-0728(99)00146-1

Cited by 472 publications

(470 citation statements)

References 33 publications

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“…However, as previously mentioned, the presence of such a film may have other undesirable side effects, such as limited conductivity for Mg ions. [19][20] Interactions with the battery's cathode control the oxidative stability of the electrolyte. This is due to the fact that the HOMO position is much closer to the redox level of the cathode, µ C , than to the Mg 0 /Mg 2+ level.…”

Section: Ionization Energy (Ie)mentioning

confidence: 99%

“…10 The stability of the anode/electrolyte interface also remains a point of concern: In contrast to Li-ion systems, where the formation of an SEI limits the rate of electrode corrosion and electrolyte decomposition, the existence and desirability of an SEI on the surface of a Mg anode remains a matter of debate. [11][12][18][19][20] Aurbach has argued that an SEI is undesirable in Mg batteries since the resulting film is not amenable to facile Mg-ion transport. 8 Figure 1 and the preceding discussion highlight the importance of the electrolyte's electronic structure (i.e., HOMO-LUMO positions) in controlling electrolyte decomposition and the tendency for SEI formation.…”

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confidence: 99%

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Interface-Induced Renormalization of Electrolyte Energy Levels in Magnesium Batteries

Kumar¹,

Siegel

2016

J. Phys. Chem. Lett.

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A promising strategy for increasing the energy density of Li-ion batteries is to substitute a multivalent (MV) metal for the commonly used lithiated carbon anode. Magnesium is a prime candidate for such a MV battery due to its high volumetric capacity, abundance, and limited tendency to form dendrites. One challenge that is slowing the implementation of Mg-based batteries, however, is the development of efficient and stable electrolytes. Computational screening for molecular species having sufficiently wide electrochemical windows is a starting point for the identification of optimal electrolytes. Nevertheless, this window can be altered via interfacial interactions with electrodes. These interactions are typically omitted in screening studies, yet they have the potential to generate large shifts to the HOMO and LUMO of the electrolyte components. The present study quantifies the stability of several common electrolyte solvents on model electrodes of relevance for Mg batteries. Many-body perturbation theory calculations based on the G 0 W 0 method were used to predict shifts in a solvent's electronic levels arising from interfacial interactions. In molecules exhibiting large dipole moments, our calculations indicate that these interactions reduce the HOMO− LUMO gap by ∼25% (compared to isolated molecules). We conclude that electrode interactions can narrow an electrolyte's electrochemical window significantly, thereby accelerating redox decomposition reactions. Accounting for these interactions in screening studies presents an opportunity to refine predictions of electrolyte stability.

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Section: Ionization Energy (Ie)mentioning

confidence: 99%

mentioning

confidence: 99%

Interface-Induced Renormalization of Electrolyte Energy Levels in Magnesium Batteries

Kumar¹,

Siegel

2016

J. Phys. Chem. Lett.

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“…12,13 There are only a handful of electrolytes known to be stable 14 during battery cycling, due to the reactivity of the Mg anode. 8,15 Lu et al considered different classes of organic solvents; 15 those containing carbonate or nitrile groups led to the formation of surface films on the anode, but ethereal solvents remained inactive. Additionally, salt anions such as ClO 4 − and BF 4 − led to the formation of passivation layers with high impedance.…”

mentioning

confidence: 99%

Exploring the Liquid Structure and Ion Formation in Magnesium Borohydride Electrolyte Using Density Functional Theory

Deetz¹,

Cao²,

Wang³

et al. 2018

J. Electrochem. Soc.

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Rechargeable magnesium batteries have attracted much interest due their high volumetric capacity, potential for safe operation, and the natural abundance of magnesium. However, the development of magnesium batteries for practical applications has been obstructed by the lack of understanding of the liquid structure of electrolytes. Herein, we use quantum density functional theory coupled with a continuum solvation model to investigate the structure of Mg(BH 4 ) 2 in two ethereal solvents: tetrahydrofuran (THF), and monoglyme (G1). The most energetically favorable clusters of Mg(BH 4 ) 2 , MgBH 4 + , and Mg 2+ , with associated solvent molecule ligands, are determined. The free energy required to generate monovalent ions in the electrolyte is positive and the formation of divalent complexes is prohibitive. Singly and doubly charged complexes are more stable in G1 than THF, which is consistent with experimental findings. From the standpoint of free energy, clusters containing multiple magnesium atoms are not favored. Theoretical 25 Mg-NMR, 11 B-NMR spectra, and infrared vibrational modes of borohydride were calculated for each cluster. The relationships between cluster charge and the signals of each spectrum are determined. These analytical descriptors could be useful to characterize the degree of ion dissociation in the electrolyte. For rechargeable batteries to become widespread in electric vehicle and grid energy storage applications, it is imperative that they are safe and low cost.1,2 These challenges have motivated researchers in recent years to consider alternatives to lithium-ion batteries, such as sodium 3,4 and multivalent 5,6 battery chemistries. Ever since the first prototypes were developed, 7,8 magnesium batteries have attracted much interest from the research community. Compared with lithiumion batteries, magnesium batteries have several advantages, such as their high volumetric capacity (3832 mAh/cm 3 ), which is a result of the divalency of magnesium. Additionally, the cycling of plating/stripping of Mg 2+ onto the magnesium metal anode does not produce dendrites, which alleviates one of safety concerns of lithium batteries. 9,10 However, magnesium batteries face crucial challenges before they can succeed in practical applications.11 In particular, the choice of the electrolyte is critical to their performance. 12,13 There are only a handful of electrolytes known to be stable 14 during battery cycling, due to the reactivity of the Mg anode. that an electrolyte consisting of magnesium borohydride in an ethereal solvent, such as tetrahydrofuran or monoglyme, could reversibly plate/strip Mg 2+ onto a magnesium metal anode. X-ray photoelectron spectroscopy 13 has shown that a Mg anode using this electrolyte did not yield signals for boron or carbon, implying that the electrolyte is electrochemically stable during charge and discharge cycles. This marked the discovery of the first stable, halide-free electrolyte for magnesium batteries. Since then, there have been a number of experimental 13,[20][21][22...

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“…are not suitable for reversible stripping an plating of Mg ions in aprotic solvents because they either react with the anode or passivate the Mg. [5,21] Gregory et al initially synthesized Mg electrolytes through the reaction of an organomagnesium with aluminum chloride (AlCl 3 ) or trialkylborane (Lewis acid) in ethereal solvents. [5] Using the same synthetic concept, Aurbach et al prepared the so-called DCC electrolytes through the reaction between Bu 2 Mg and EtAlCl 2 in tetrahydrofuran (THF) and demonstrated the first prototype rechargeable Mg battery.…”

Section: Challenges and Advances In The Development Of Magnesium Elecmentioning

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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On the electrochemical behavior of magnesium electrodes in polar aprotic electrolyte solutions

Cited by 472 publications

References 33 publications

Interface-Induced Renormalization of Electrolyte Energy Levels in Magnesium Batteries

Interface-Induced Renormalization of Electrolyte Energy Levels in Magnesium Batteries

Exploring the Liquid Structure and Ion Formation in Magnesium Borohydride Electrolyte Using Density Functional Theory

Magnesium-sulfur battery: its beginning and recent progress

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