The Interplay of Al and Mg Speciation in Advanced Mg Battery Electrolyte Solutions

See, Kimberly A.; Chapman, Karena W.; Zhu, Lingyang; Wiaderek, Kamila M.; Borkiewicz, Olaf J.; Barile, Christopher J.; Chupas, Peter J.; Gewirth, Andrew A.

doi:10.1021/jacs.5b10987

Cited by 189 publications

(302 citation statements)

References 52 publications

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“…Short-range atomic order, within a few Å, can be captured with local structure probes, such as pair distribution function (PDF) 1, 2 . More extended models for the atomic structure can be derived from three-dimensional configurations such as those generated through reverse Monte Carlo (RMC) modeling, whereby the PDF calculated for a large atomic configuration is optimized against the experimental PDF 3, 4 .…”

Section: Introductionmentioning

confidence: 99%

Local structure of liquid gallium under pressure

Wang

et al. 2017

Sci Rep

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In situ high energy X-ray pair distribution function (PDF) measurements, microtomography and reverse Monte Carlo simulations were used to characterize the local structure of liquid gallium up to 1.9 GPa. This pressure range includes the well-known solid-solid phase transition from Ga-I to Ga-II at low temperature. In term of previous research, the local structure of liquid gallium within this domain was suggested a mixture of two local structures, Ga I and Ga II, based on fitting experimental PDF to known crystal structure, with a controversy. However, our result shows a distinctly different result that the local structure of liquid gallium resembles the atomic arrangement of both gallium phase II and III (the high pressure crystalline phase). A melting mechanism is proposed for Ga, in which the atomic structure of phase Ι breaks up at the onset of melting, providing sufficient free volume for atoms to rearrange, to form the melt.

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Section: Introductionmentioning

confidence: 99%

Local structure of liquid gallium under pressure

Wang

et al. 2017

Sci Rep

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“…We point out that this pre-deposition compressive stress is likely induced by the adsorption of Mg 2+ /anion/solvent complexes on the surface prior to the deposition. 49,56 The comparable magnitudes of these values among the different electrolytes further suggests that qualitatively similar Mg 2+ /anion/solvent complexes are created (albeit with different anions and solvents) and that similar coverages of these adsorbate adlayers are reached on the electrode before the deposition starts.…”

Section: Discussionmentioning

confidence: 83%

Dynamic Surface Stress Response during Reversible Mg Electrodeposition and Stripping

Ha¹,

Zeng²,

Barile³

et al. 2016

J. Electrochem. Soc.

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Through the use of in situ electrochemical surface stress measurements, Mg deposition and stripping processes in electrolytes for Mg batteries are studied. We examine four electrolytes: PhMgCl+AlCl 3 /THF, (DTBP)MgCl-MgCl 2 /THF, MgCl 2 +AlCl 3 /THF, and Mg(BH 4 ) 2 +LiBH 4 /diglyme. Each of these electrolytes exhibits common surface stress response features, indicating that the mechanisms of Mg deposition and stripping are similar among the different electrolytes. Combining the measurements with density functional theory calculations, each part of the stress-potential curve is assigned to steps in the deposition and stripping reactions. The analysis suggests the following mechanism: (1) Mg 2+ /anion/solvent complexes adsorb on the substrate prior to the deposition; (2) Mg deposits as random nuclei and the deposition continues without a recrystallization process; (3) during the initial stage of Mg stripping, less coordinated Mg(0) is converted to soluble Mg(II) species and to partially oxidized species, MgO x ; (4) as the anodic reactions proceed further, Mg continues to dissolve and MgO x is removed via chemical processes; (5) due to the strong interaction between Mg and the noble metal substrate atoms, the Mg layer directly bound to the substrate are the last to be anodically converted (and desorb There is much interest in developing rechargeable Mg batteries due to the high theoretical volumetric capacity, abundance, and benign nature of Mg. Finding a suitable electrolyte for reversible Mg deposition and dissolution, however, is challenging due to the difficulty in producing soluble Mg 2+ and the formation of passivation films on the electrode surface.1-3 The first reversible Mg deposition and stripping was performed in Grignard solutions, 4-6 which suffer from low anodic stability and poor ionic conductivity. The anodic stability and the Coulombic efficiency is greatly enhanced in electrolytes based on Mg organohaloaluminate, prepared via an acid-base reaction between a MgR 2 Lewis base and an AlCl 3-n R n Lewis acid. 7 An inorganic magnesium aluminum chloride complex from MgCl 2 -and AlCl 3 -based electrolyte exhibits even higher anodic stability and a lower overpotential. 8,9 However, the corrosivity of chloride and the reactivity of Lewis acids have prompted the development of newer, less corrosive electrolytes, including Mg(BH 4 ) 2 based inorganic salts with LiBH 4 additive electrolytes 10,11 and all-magnesium phenolatebased electrolytes.12 Thus, previous work illustrates that several Mg systems exhibit promise as a battery electrolyte; however, their interfacial chemistries are complicated and need to be better understood. [8][9][10][11][12][13] Efficient electrodeposition and stripping reactions are essentials in rechargeable batteries. One of the effective in operando techniques for studying such processes is monitoring the electrochemical surface stresses developed during the deposition and dissolution of metals.14 In situ surface stress measurements are experimentally less demanding compared to oth...

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“…[47] As a full inorganic electrolyte, the MACC electrolyte has drawn much attention in the community, and has been extensively studied in recent years. [48][49][50][51][52] − . [53] The oxidative stability of 2.5 V versus Mg on Pt electrode for this electrolyte is inferior to the reported MACC solution in a pure ethereal solvent and the ionic liquid possibly contributed to the high ionic conductivity of the electrolyte (8.5 mS/ cm).…”

Section: Combinations Of Magnesium Chloride With Aluminum-based Lewismentioning

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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The Interplay of Al and Mg Speciation in Advanced Mg Battery Electrolyte Solutions

Cited by 189 publications

References 52 publications

Local structure of liquid gallium under pressure

Local structure of liquid gallium under pressure

Dynamic Surface Stress Response during Reversible Mg Electrodeposition and Stripping

Magnesium-sulfur battery: its beginning and recent progress

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