Department of Chemistry and the Lise Meitner-Minerva Center of Computational Quantum Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel.
J Am Chem Soc. 2011 Apr 27;133(16):6270-8. doi: 10.1021/ja1098512. Epub 2011 Apr 1.
We present a rigorous analysis of unique, wide electrochemical window solutions for rechargeable magnesium batteries, based on aromatic ligands containing organometallic complexes. These solutions are comprised of the transmetalation reaction products of Ph(x)MgCl(2-x) and Ph(y)AlCl(3-y) in different proportions, in THF. In principle, these reactions involve the exchange of ligands between the magnesium and the aluminum based compounds, forming ionic species and neutral molecules, such as Mg(2)Cl(3)(+)·6THF, MgCl(2)·4THF, and Ph(y)AlCl(4-y)(-) (y = 0-4). The identification of the equilibrium species in the solutions is carried out by a combination of Raman spectroscopy, multinuclear NMR, and single-crystal XRD analyses. The association of the spectroscopic results with explicit identifiable species is supported by spectral analyses of specially synthesized reference compounds and DFT quantum-mechanical calculations. The correlation between the identified solution equilibrium species and the electrochemical anodic stability window is investigated. This study advances both development of new nonaqueous solution chemistry and possible development of high-energy density rechargeable Mg batteries.
我们提出了一种针对可充电镁电池的独特、宽电化学窗口溶液的严格分析，该溶液基于含有有机金属配合物的芳族配体。这些溶液由 Ph(x)MgCl(2-x)和 Ph(y)AlCl(3-y)在不同比例的四氢呋喃中的转金属化反应产物组成。原则上，这些反应涉及镁和铝基化合物之间配体的交换，形成离子物种和中性分子，如 Mg(2)Cl(3)(+)·6THF、MgCl(2)·4THF 和 Ph(y)AlCl(4-y)(-)（y = 0-4）。通过拉曼光谱、多核 NMR 和单晶 XRD 分析相结合，对溶液中的平衡物种进行了鉴定。光谱分析特别合成的参考化合物和 DFT 量子力学计算支持了光谱结果与明确可识别物种之间的关联。研究了所确定的溶液平衡物种与电化学阳极稳定性窗口之间的关系。这项研究推进了新型非水溶剂化学的发展和高能密度可充电镁电池的可能发展。
