Wen Xiaoyu, Liu Yuhang, Xu Da, Zhao Yifan, Lake Roger K, Guo Juchen
Department of Chemical and Environmental Engineering , University of California , Riverside , California 92521 , United States.
Department of Electrical and Computer Engineering , University of California , Riverside , California 92521 , United States.
J Phys Chem Lett. 2020 Feb 20;11(4):1589-1593. doi: 10.1021/acs.jpclett.0c00256. Epub 2020 Feb 12.
The coordination mechanism of chloroaluminate species in aluminum chloride (AlCl) solutions in γ-butyrolactone (GBL) is investigated using electrochemical, spectroscopic, and computational methods. The liquid-state Al NMR spectroscopy shows a sequence of new species generated in the AlCl-GBL solutions with increasing AlCl/GBL ratio. Ab initio molecular dynamics simulation reveals the dynamic coordination process between GBL and AlCl, and the resultant chloroaluminate species are identified as [AlCl·(GBL)], AlCl, AlCl·GBL, and AlCl. The species are further confirmed by surface enhanced Raman spectroscopy combined with calculated Raman spectra from methods based on density functional theory. Electrochemical deposition of Al is achieved from the AlCl-GBL solution containing AlCl, which is one of the few noneutectic electrolytes for room-temperature Al deposition reported to date.
采用电化学、光谱学和计算方法研究了氯化铝（AlCl）在γ-丁内酯（GBL）溶液中氯铝酸盐物种的配位机制。液态铝核磁共振光谱表明，随着AlCl/GBL比例的增加，AlCl-GBL溶液中会生成一系列新物种。从头算分子动力学模拟揭示了GBL与AlCl之间的动态配位过程，生成的氯铝酸盐物种被确定为[AlCl·(GBL)]、AlCl、AlCl·GBL和AlCl。通过表面增强拉曼光谱结合基于密度泛函理论方法计算的拉曼光谱进一步证实了这些物种。从含有AlCl的AlCl-GBL溶液中实现了铝的电化学沉积，这是迄今为止报道的少数几种用于室温铝沉积的非共晶电解质之一。
