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      Structure and compatibility of a magnesium electrolyte with a sulphur cathode

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          Abstract

          Magnesium metal is an ideal rechargeable battery anode material because of its high volumetric energy density, high negative reduction potential and natural abundance. Coupling Mg with high capacity, low-cost cathode materials such as electrophilic sulphur is only possible with a non-nucleophilic electrolyte. Here we show how the crystallization of the electrochemically active species formed from the reaction between hexamethyldisilazide magnesium chloride and aluminum trichloride enables the synthesis of a non-nucleophilic electrolyte. Furthermore, crystallization was essential in the identification of the electroactive species, [Mg 2(μ-Cl) 3·6THF] +, and vital to improvements in the voltage stability and coulombic efficiency of the electrolyte. X-ray photoelectron spectroscopy analysis of the sulphur electrode confirmed that the electrochemical conversion between sulphur and magnesium sulfide can be successfully performed using this electrolyte.

          Abstract

          Magnesium is an ideal rechargeable battery anode material, but coupling it with a low-cost sulphur cathode, requires a non-nucleophilic electrolyte. Kim et al. prepare a non-nucleophilic electrolyte from hexamethyldisilazide magnesium chloride and aluminium trichloride, and show its compatibility with a sulphur cathode.

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          Nonaqueous liquid electrolytes for lithium-based rechargeable batteries.

          Kang Xu (2004)
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            Prototype systems for rechargeable magnesium batteries.

            The thermodynamic properties of magnesium make it a natural choice for use as an anode material in rechargeable batteries, because it may provide a considerably higher energy density than the commonly used lead-acid and nickel-cadmium systems. Moreover, in contrast to lead and cadmium, magnesium is inexpensive, environmentally friendly and safe to handle. But the development of Mg batteries has been hindered by two problems. First, owing to the chemical activity of Mg, only solutions that neither donate nor accept protons are suitable as electrolytes; but most of these solutions allow the growth of passivating surface films, which inhibit any electrochemical reaction. Second, the choice of cathode materials has been limited by the difficulty of intercalating Mg ions in many hosts. Following previous studies of the electrochemistry of Mg electrodes in various non-aqueous solutions, and of a variety of intercalation electrodes, we have now developed rechargeable Mg battery systems that show promise for applications. The systems comprise electrolyte solutions based on Mg organohaloaluminate salts, and Mg(x)Mo3S4 cathodes, into which Mg ions can be intercalated reversibly, and with relatively fast kinetics. We expect that further improvements in the energy density will make these batteries a viable alternative to existing systems.
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              Nonaqueous magnesium electrochemistry and its application in secondary batteries.

              A revolution in modern electronics has led to the miniaturization and evolution of many portable devices, such as cellular telephones and laptop computers, since the 1980s. This has led to an increasing demand for new and compatible energy storage technologies. Furthermore, a growing awareness of pollution issues has provided a strong impetus for the science and technology community to develop alternatives with ever-higher energy densities, with the ultimate goal of being able to propel electric vehicles. Magnesium's thermodynamic properties make this metal a natural candidate for utilization as an anode in high-energy-density, rechargeable battery systems. We report herein on the results of extensive studies on magnesium anodes and magnesium insertion electrodes in nonaqueous electrolyte solutions. Novel, rechargeable nonaqueous magnesium battery systems were developed based on the research. This work had two major challenges: one was to develop electrolyte solutions with especially high anodic stability in which magnesium anodes can function at a high level of cycling efficiency; the other was to develop a cathode that can reversibly intercalate Mg ions in these electrolyte systems. The new magnesium batteries consist of Mg metal anodes, an electrolyte with a general structure of Mg(AlX(3-n)R(n)R')(2) (R',R = alkyl groups, X = halide) in ethereal solutions (e.g., tetrahydrofuran, polyethers of the "glyme" family), and Chevrel phases of MgMo(3)S(4) stoichiometry as highly reversible cathodes. With their practical energy density expected to be >60 Wh/Kg, the battery systems can be cycled thousands of times with almost no capacity fading. The batteries are an environmentally friendly alternative to lead-acid and nickel-cadmium batteries and are composed of abundant, inexpensive, and nonpoisonous materials. The batteries are expected to provide superior results in large devices that require high-energy density, high cycle life, a high degree of safety, and low-cost components. Further developments in this field are in active progress. Copyright 2003 The Japan Chemical Journal Forum and Wiley Periodicals, Inc., Chem Rec 3: 61-73; 2003: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.10051
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                Author and article information

                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Pub. Group
                2041-1723
                09 August 2011
                : 2
                : 427
                Affiliations
                [1 ]simpleToyota Research Institute of North America , 1555 Woodridge Avenue, Ann Arbor, Michigan 48105, USA.
                [2 ]simpleSynthonix , 2713 Connector Drive, Wake Forest, North Carolina 2758, USA.
                [3 ]simpleUniversity of Notre Dame , Notre Dame, Indiana 46556, USA.
                [4 ]simpleEvans Analytical Group , 18705 Lake Drive East, Chanhassen, Minnesotta 55317, USA.
                Author notes
                Article
                ncomms1435
                10.1038/ncomms1435
                3266610
                21829189
                bf2d11e3-be76-4970-bb60-1b4edbcf9747
                Copyright © 2011, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved.

                This work is licensed under a Creative Commons Attribution-NonCommercial-Share Alike 3.0 Unported License. To view a copy of this license, visit http://creativecommons.org/licenses/by-nc-sa/3.0/

                History
                : 18 March 2011
                : 14 July 2011
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