Boron-based electrolyte solutions with wide electrochemical windows for rechargeable magnesium batteries

Guo, Yongsheng; Zhang, Fan; Yang, Jun; Wang, Feifei; Nuli, Yanna; Hirano, Shin‐ichi

doi:10.1039/c2ee22509c

Cited by 198 publications

(202 citation statements)

References 28 publications

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“…313 Very recently, the first inorganic compound, magnesium aluminium chloride complex (MACC), was synthesised via the acid-base reaction of MgCl2 with Lewis acidic compounds such as AlCl3, which demonstrated a high coulombic efficiency (up to 99 %), low deposition overpotential (<200 mV), and good anodic stability (3.1 V vs. Mg/Mg 2+ ). Despite of the good performance achieved with all the above reported electrolytes, corrosion of aluminium and stainless steel current collectors posed by the presence of halide ions had hampered the commercialisation of these batteries.…”

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confidence: 99%

Electrolytes for electrochemical energy storage

Xia

et al. 2017

Mater. Chem. Front.

234

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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confidence: 99%

Electrolytes for electrochemical energy storage

Xia

et al. 2017

Mater. Chem. Front.

234

116

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“…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.…”

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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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“…Anodic stabilities of electrolytes exceeding 3 V vs. Mg/Mg 2+ have been demonstrated recently. [5][6][7] However, until now all electrolytes for Mg batteries with good electrochemical performance (i.e. large voltage window, compatibility with metallic Mg and high ionic conductivity) contain chlorine, which was found to cause severe corrosion of current collectors made from Cu, Al, Ti and stainless steel.…”

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confidence: 99%

Corrosion Resistance of Current Collector Materials in Bisamide Based Electrolyte for Magnesium Batteries

Wall

Zhao‐Karger

Fichtner

2014

ECS Electrochemistry Letters

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The compatibility of Ti, Cr, Ni, Fe, Al, steel type 304, Inconel 625, Hastelloy B and carbon coated current collectors with bisamide based electrolyte for Mg-batteries was investigated. Pitting corrosion of current collectors made from 3d-transition metals and steel type 304 was observed at potentials between 2.2-3.1 V vs. Mg/Mg 2+ . Anodic stability up to 3.8 V and resistance against corrosion for 48 h at a potential of 2.5 V vs. Mg/Mg 2+ and above was found for Inconel 625, Hastelloy B, graphite and carbon coated Al foil. © The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org. [DOI: 10.1149/2.0111501eel] All rights reserved.Manuscript submitted October 9, 2014; revised manuscript received November 10, 2014. Published November 18, 2014 Recently Mg batteries have gained large interest due to the high theoretical energy density of Mg (2233 mAh g −1 and 3832 mAh cm −3 , respectively) but also because of the comparable low price, high abundance and the non-toxic properties of Mg.1,2 In contrast to metallic Li, no dendrite formation has been observed during electrochemical cycling of Mg.3,4 Thus, the technical application of metallic Mg anodes for secondary batteries with liquid electrolyte is not hampered by safety concerns as they exist for metallic Li. As the energy density of a battery is determined by the capacity of the electrode materials and by the potential difference between the anode and the cathode, both should be as high as possible. However, high operation potentials increase the driving force for oxidative decomposition of the electrolyte as well as for corrosion of the current collector at the cathode. Anodic stabilities of electrolytes exceeding 3 V vs. Mg/Mg 2+ have been demonstrated recently. [5][6][7] However, until now all electrolytes for Mg batteries with good electrochemical performance (i.e. large voltage window, compatibility with metallic Mg and high ionic conductivity) contain chlorine, which was found to cause severe corrosion of current collectors made from Cu, Al, Ti and stainless steel. 2,8,9Recently we developed a synthesis for bisamide based electrolytes with unprecedented anodic stability by reaction of magnesiumbis(hexamethyldisilazide) [(HMDS) 2 Mg] with AlCl 3 in different aprotic solvents, which are compatible with sulfur cathodes. 5,10 In order to utilize such electrolytes for magnesium batteries, we have now studied the corrosion behavior of various metals and steels and investigated if corrosion can be mitigated by a carbon coating. ExperimentalChronoamperometry and linear sweep voltammetry of current collectors was conducted vs. Mg foil, (Goodfellow, 99.99 %) in two...

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Boron-based electrolyte solutions with wide electrochemical windows for rechargeable magnesium batteries

Cited by 198 publications

References 28 publications

Electrolytes for electrochemical energy storage

Electrolytes for electrochemical energy storage

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

Corrosion Resistance of Current Collector Materials in Bisamide Based Electrolyte for Magnesium Batteries

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