Highly active electrolytes for rechargeable Mg batteries based on a [Mg2(μ-Cl)2](2+) cation complex in dimethoxyethane.

A novel [Mg2(μ-Cl)2](2+) cation complex, which is highly active for reversible Mg electrodeposition, was identified for the first time in this work. This complex was found to be present in electrolytes formulated in dimethoxyethane (DME) through dehalodimerization of non-nucleophilic MgCl2 by reacting with either Mg salts (such as Mg(TFSI)2, TFSI = bis(trifluoromethane)sulfonylimide) or Lewis acid salts (such as AlEtCl2 or AlCl3). The molecular structure of the cation complex was characterized by single crystal X-ray diffraction, Raman spectroscopy and NMR. The electrolyte synthesis process was studied and rational approaches for formulating highly active electrolytes were proposed. Through control of the anions, electrolytes with an efficiency close to 100%, a wide electrochemical window (up to 3.5 V) and a high ionic conductivity (>6 mS cm(-1)) were obtained. The understanding of electrolyte synthesis in DME developed in this work could bring significant opportunities for the rational formulation of electrolytes of the general formula [Mg2(μ-Cl)2][anion]x for practical Mg batteries.

[1]  A. Manivannan,et al.  Rechargeable Magnesium Battery: Current Status and Key Challenges for the Future , 2014 .

[2]  A. Manivannan,et al.  A study of a fluorine substituted phenyl based complex as a 3 V electrolyte for Mg batteries , 2014 .

[3]  Yuyan Shao,et al.  Facile Synthesis of Chevrel Phase Nanocubes and Their Applications for Multivalent Energy Storage , 2014 .

[4]  Yuyan Shao,et al.  High performance batteries based on hybrid magnesium and lithium chemistry. , 2014, Chemical communications.

[5]  J. Mueller,et al.  Novel transmetalation reaction for electrolyte synthesis for rechargeable magnesium batteries , 2014 .

[6]  Jaephil Cho,et al.  Magnesium(II) bis(trifluoromethane sulfonyl) imide-based electrolytes with wide electrochemical windows for rechargeable magnesium batteries. , 2014, ACS applied materials & interfaces.

[7]  Yuyan Shao,et al.  A facile approach using MgCl2 to formulate high performance Mg2+ electrolytes for rechargeable Mg batteries , 2014 .

[8]  Yuyan Shao,et al.  Electrochemically stable cathode current collectors for rechargeable magnesium batteries , 2014 .

[9]  Yuyan Shao,et al.  Highly reversible Mg insertion in nanostructured Bi for Mg ion batteries. , 2014, Nano letters.

[10]  Doron Aurbach,et al.  Novel, electrolyte solutions comprising fully inorganic salts with high anodic stability for rechargeable magnesium batteries. , 2014, Chemical communications.

[11]  Bingkun Guo,et al.  Highly soluble alkoxide magnesium salts for rechargeable magnesium batteries , 2014 .

[12]  Yuyan Shao,et al.  Coordination Chemistry in magnesium battery electrolytes: how ligands affect their performance , 2013, Scientific Reports.

[13]  Doron Aurbach,et al.  Mg rechargeable batteries: an on-going challenge , 2013 .

[14]  Fuminori Mizuno,et al.  A high energy-density tin anode for rechargeable magnesium-ion batteries. , 2013, Chemical communications.

[15]  E. Matsubara,et al.  Electrochemical Stability of Magnesium Battery Current Collectors in a Grignard Reagent-Based Electrolyte , 2013 .

[16]  Ayyakkannu Manivannan,et al.  A Scientific Study of Current Collectors for Mg Batteries in Mg(AlCl2EtBu)2/THF Electrolyte , 2013 .

[17]  S. Hirano,et al.  A novel electrolyte system without a Grignard reagent for rechargeable magnesium batteries. , 2012, Chemical communications.

[18]  Fan Zhang,et al.  Boron-based electrolyte solutions with wide electrochemical windows for rechargeable magnesium batteries , 2012 .

[19]  Ruigang Zhang,et al.  α-MnO2 as a cathode material for rechargeable Mg batteries , 2012 .

[20]  Allen G. Oliver,et al.  Electrolyte roadblocks to a magnesium rechargeable battery , 2012 .

[21]  Timothy S. Arthur,et al.  Electrodeposited Bi, Sb and Bi1-xSbx alloys as anodes for Mg-ion batteries , 2012 .

[22]  W. Marsden.  I and J , 2012 .

[23]  Jiulin Wang,et al.  MWNT/C/Mg1.03Mn0.97SiO4 hierarchical nanostructure for superior reversible magnesium ion storage , 2011 .

[24]  Allen G. Oliver,et al.  Structure and compatibility of a magnesium electrolyte with a sulphur cathode , 2011, Nature communications.

[25]  Doron Aurbach,et al.  Structural analysis of electrolyte solutions for rechargeable Mg batteries by stereoscopic means and DFT calculations. , 2011, Journal of the American Chemical Society.

[26]  Hua Ma,et al.  Rechargeable Mg Batteries with Graphene‐like MoS2 Cathode and Ultrasmall Mg Nanoparticle Anode , 2011, Advanced materials.

[27]  D. Aurbach,et al.  Electrolyte Solutions with a Wide Electrochemical Window for Rechargeable Magnesium Batteries , 2008 .

[28]  D. Aurbach,et al.  Improved Electrolyte Solutions for Rechargeable Magnesium Batteries , 2006 .

[29]  C. Peters,et al.  Decomposition of ionic liquids in electrochemical processing , 2006 .

[30]  D. Aurbach,et al.  Alkyl Group Transmetalation Reactions in Electrolytic Solutions Studied by Multinuclear NMR , 2004 .

[31]  M. Armand,et al.  Issues and challenges facing rechargeable lithium batteries , 2001, Nature.

[32]  D. Aurbach,et al.  On the mechanisms of reversible magnesium deposition processes , 2001 .

[33]  E. Levi,et al.  Prototype systems for rechargeable magnesium batteries , 2000, Nature.

[34]  V. Terskikh,et al.  27Al MAS NMR study of the interaction of supported Ziegler–Natta catalysts with organoaluminium co-catalyst in the presence of donors , 2000 .

[35]  D. Aurbach,et al.  On the electrochemical behavior of magnesium electrodes in polar aprotic electrolyte solutions , 1999 .

[36]  B. Conway,et al.  27Al NMR spectroscopy studies on speciation of Al complex ions in AlCl3 + LiAlH4 solutions in tetrahydrofuran for electroplating of Al , 1998 .

[37]  W. R. Carper,et al.  27Al NMR relaxation studies of molten salts containing ethylaluminum dichloride , 1993 .

[38]  T. Gregory,et al.  Nonaqueous Electrochemistry of Magnesium Applications to Energy Storage , 1990 .

[39]  A. I. Popov,et al.  Magnesium-25 NMR studies of magnesium salts and complexes in nonaqueous solvents , 1979 .

[40]  R. Stephenson.  A and V , 1962, The British journal of ophthalmology.