Paving the Way towards Highly Stable and Practical Electrolytes for Rechargeable Magnesium Batteries

Tutusaus, Oscar; Mohtadi, Rana

doi:10.1002/celc.201402207

Cited by 73 publications

(100 citation statements)

References 51 publications

(66 reference statements)

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“…While commercially practical electrolytes may not be a reality yet, researchers have made tremendous progress in the electrolyte in the last fifteen years [104,107]. Notably, a recent trend to reduce chlorine content in electrolytes has enabled the discovery of noncorrosive electrolytes with good conductivity (>1 mS cm −1 ), efficient Mg dissolution/deposition (>98% Coulombic efficiency) and anodic stability well beyond 3 V [110,[112][113][114].…”

Section: Science China Materialsmentioning

confidence: 99%

Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

2015

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to develop and install renewable energy harvesting technologies [3]. However, their successful implementation will be dependent on reliable and robust storage devices since harvesting solar and wind energy is inherently intermittent and the majority of consumption targets cannot be readily tethered to the grid.As energy storage devices, batteries possess high portability, high energy density, high Coulombic efficiency, and long cycle life. They are ideal power sources for portable devices, automobiles, and backup power supplies; accordingly, batteries power nearly all of our mobile electronics and are used to improve the efficiency of hybrid electric vehicles [4,5]. Unfortunately, considerable improvements in performance are still required in order to meet the demands of advanced portable devices and achieve energy sustainability (e.g., through smart grid and electric vehicle technologies) [6]. These enduring needs have driven intensive research investments. While efforts have been successful, there is still significant room for improvement regarding the development and understanding of electrode materials [7]. The overall capacity and potential cycling window of many electrode materials are limited to prevent degradation over long term cycling. In addition to exploring new electrode materials, there have been strong efforts to improve those that are already utilized. Expense reduction is a priority as approximately 23% and 8% of the overall battery pack costs stem from the respective cathode and anode active materials alone [8].An alkali-ion battery consists of several electrochemical cells connected in parallel and/or in series to provide a designated current or voltage. Each electrochemical cell has two electrodes separated by an electrolyte that is electrically insulating but ionically conductive. During discharge, when the alkali-ion battery operates as a galvanic cell, alkali ions exit the negative electrode (typically carbon) and insert themselves into the positive electrode while electronsThe need for economical and sustainable energy storage drives battery research today. While Li-ion batteries are the most mature technology, scalable electrochemical energy storage applications benefit from reductions in cost and improved safety. Sodium-and magnesium-ion batteries are two technologies that may prove to be viable alternatives. Both metals are cheaper and more abundant than Li, and have better safety characteristics, while divalent magnesium has the added bonus of passing twice as much charge per atom. On the other hand, both are still emerging fields of research with challenges to overcome. For example, electrodes incorporating Na + are often pulverized under the repeated strain of shuttling the relatively large ion, while insertion and transport of Mg 2+ is often kinetically slow, which stems from larger electrostatic forces. This review provides an overview of cathode and anode materials for sodium-ion batteries, and a comprehensive summary of research on cathodes for magnesium-ion batteries. In additi...

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Section: Science China Materialsmentioning

confidence: 99%

Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

2015

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“…21 Recently, a whole new promising family of halide-free salts containing the B-H motif z E-mail: nlyn@sjtu.edu.cn expanded the portfolio of Mg-compatible electrolytes. 22 Carboranebased electrolytes display non-corrosive nature and permit standardized methods of high-voltage cathode testing in a typical coin cell. 23,24 Magnesium borohydride Mg(BH 4 ) 2 , with LiBH 4 shows unprecedented reversible Mg deposition-dissolution in tetrahydrofuran (THF), dimethoxyethane (DME) and DGM (diglyme) solvents.…”

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confidence: 99%

Magnesium Borohydride-Based Electrolytes Containing 1-butyl-1-methylpiperidinium bis(trifluoromethyl sulfonyl)imide Ionic Liquid for Rechargeable Magnesium Batteries

Nuli

Wang

et al. 2016

J. Electrochem. Soc.

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The electrolytes containing halide-free inorganic magnesium salt Mg(BH 4 ) 2 dissolved in ether solvents have shown reversible Mg deposition-dissolution performance. Herein, we improved the anodic stability of the electrolytes on non-inert stainless-steel electrode by mixing PP 14 TFSI ionic liquid with tetraglyme (TG) and dimethoxyethane (DME) ether solvents. The effect of mixing ratios and salt concentrations on the electrochemical behavior of the electrolyte were investigated. High anodic stability, good ionic conductivity, excellent cycling efficiency, feasibility of the preparation and good compatibility toward Mo 6 S 8 and TiO 2 insertion cathode make the electrolytes promising for the potential application in rechargeable magnesium batteries. 3-5 The development of magnesium electrolytes is considered as the most important challenge for the commercial application of rechargeable magnesium batteries because electrolyte properties govern battery performance and determine the class of cathodes to be utilized. 6 The significant progress is the reports of 0.25 mol L −1 Mg(AlCl 2 BuEt) 2 /THF (Bu=butyl, Et=ethyl) electrolyte 7,8 and 0.4 mol L −1 (PhMgCl) 2 -AlCl 3 /THF electrolyte, 9,10 which have high anodic stability (2.5 V and 3.3 V vs. Mg RE on inert Pt electrode, respectively) and reversibility of Mg deposition-dissolution. Recently, a family of novel boron based electrolytes with high ionic conductivity, excellent Mg deposition reversibility as well as high anodic potential were proposed.11,12 On the other hand, phenolate-based 13 and alkoxide-based 14 electrolytes exhibit air insensitive character and excellent magnesium depositiondissolution performance. Meanwhile, inorganic magnesium salt solutions synthesized by the acid-base reaction of MgCl 2 and Lewis acidic compounds such as AlCl 3 show high coulombic efficiency, low overpotential for magnesium deposition-dissolution and good anodic stability. [15][16][17][18] However, these electrolytes may corrode non-inert current collectors at lower anodic potentials duo to the presence of halides in the cation and anion components of the electrolytes, although some of these electrolytes have shown impressive stability against electrochemical oxidation.19 Hence, it is still necessary to find electrolytes with high stabilities on non-inert current collectors for a practical rechargeable Mg battery system. Nelson et al. showed that decreasing the chloride content in Mg electrolytes by switching the Lewis acid from AlCl 3 to Al(OPh) 3 greatly improves the anodic stability up to 5 V on both Pt and stainless steel electrodes.20 Ha et al. proposed a new class of electrolytes based on magnesium (II) bis(trifluoromethane sulfonyl)imide (Mg[N-(SO 2 CF 3 ) 2 ] 2 , Mg(TFSI) 2 ) dissolved in glymebased solvents with unique characteristics such as highly reduced corrosive nature toward the current collector, low volatility, high solvating power, and the ability to form an appropriate solvation sheath structure for Mg deposition-dissolution. 21 Recently, a whole new promisi...

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“…7,10 Conductivity, deposition overpotentials, and oxidative stabilities were similar whether an aryloxymagnesium chloride 13 or a diaryloxymagnesium precursor was used, suggesting that similar electroactive species are generated on adding AlCl 3 . The conductivity of the Mg(OiPr) 2 :AlCl 3 solution was measured to be lower than that of either the Mg(OPh) 2 :AlCl 3 or Mg(OtBu) 2 :AlCl 3 ones ( Figure 4); conductivity is not simply related to aryloxy vs. alkoxy coordination.…”

Section: Resultsmentioning

confidence: 91%

“…6 As such, the development of other, more suitable electrolytes for reversible magnesium electrodeposition is paramount. Most studies focus on modifying the Lewis acid component of the electrolyte mixture, either by modifying the anion 7 or the metal center; [8][9][10] in contrast, we focus on the magnesium species.…”

mentioning

confidence: 99%

Structural Effects of Magnesium Dialkoxides as Precursors for Magnesium-Ion Electrolytes

Herb

Nist-Lund

Schwartz

et al. 2015

ECS Electrochemistry Letters

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A challenge for magnesium ion battery research is the development of electrolytes that are capable of reversible magnesium electrodeposition through multiple cycles. Magnesium alkoxide chlorides and aryloxide chlorides are known magnesium ion electrolytes when used in conjunction with aluminum chloride. Herein we report the effects of structural variation in several dialkoxy and diaryloxy magnesium complex aggregates with aluminum chloride, Mg(OR) 2 :AlCl 3 (R = iPr, t-Bu, phenyl), on electrochemical characteristics of their solutions and on compositions of the magnesium-containing deposits they yield. We also report the synthesis of a magnesium phenoxide-based electrolyte directly from magnesium metal. © The Author Nonaqueous magnesium ion batteries that use a metallic magnesium anode are attractive due to their high theoretical volumetric energy density and comparatively low cost of materials compared to lithium ion systems.1,2 Studies incorporating Grignard-based electrolytes for magnesium electrodeposition date back to the early twentieth century, 3 but their use as electrolytes for magnesium batteries became of interest only as recently as 1990.4 Aurbach et al. 5 studied electrolyte solutions that were synthesized by reacting an alkylmagnesium halide or a dialkylmagnesium species with a Lewis acid of general structure R x AlCl 3-x . The complex species that result are capable of reversible magnesium electrodeposition, yet Barile et al. showed that these types of adducts decompose as a function of cycle count, based on NMR and GC-MS of the electrolyte and on SEM-EDS analysis of the electrodeposited metal.6 As such, the development of other, more suitable electrolytes for reversible magnesium electrodeposition is paramount. Most studies focus on modifying the Lewis acid component of the electrolyte mixture, either by modifying the anion 7 or the metal center; 8-10 in contrast, we focus on the magnesium species.It is known that phenoxymagnesium chloride 11 and alkoxymagnesium chloride 12 solutions react with aluminum chloride to generate electrolytes with good deposition overpotentials and acceptable conductivity. Nelson et al. studied phenol-based systems by modifying substituents on the aromatic ring; electron-withdrawing substituents showed higher oxidative stability of ca. 0.4 V more positive than the parent phenol.13 Magnesium alkoxides have also been employed as additives for magnesium electrolyte systems, 14 as have thiols 15 and amides. [16][17][18] For example, Zhao-Karger et al. found that magnesium bisamide compounds in combination with aluminum chloride showed comparable electrochemical performance in a variety of ethereal solvents to species derived from Grignard reagents, yet were easier to handle. 18 Here we report that magnesium dialkoxides and diaryloxidebased electrolyte solutions can be used for reversible magnesium electrodeposition whose properties are a function of ligand structure; we also show that an active complex can be prepared directly from magnesium metal. ExperimentalDi-n-butylma...

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Paving the Way towards Highly Stable and Practical Electrolytes for Rechargeable Magnesium Batteries

Cited by 73 publications

References 51 publications

Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

Magnesium Borohydride-Based Electrolytes Containing 1-butyl-1-methylpiperidinium bis(trifluoromethyl sulfonyl)imide Ionic Liquid for Rechargeable Magnesium Batteries

Structural Effects of Magnesium Dialkoxides as Precursors for Magnesium-Ion Electrolytes

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