Electrochemically active species in aluminum electrodeposition baths of AlCl3/glyme solutions
Electrochemically active species in aluminum electrodeposition baths of AlCl3/glyme solutions
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DOI：
10.1016/j.electacta.2016.05.063
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发表时间：
2016-09
影响因子：
6.6
通讯作者：
A. Kitada;Kai Nakamura;Kazuhiro Fukami;K. Murase
中科院分区：
文献类型：
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作者：
A. Kitada;Kai Nakamura;Kazuhiro Fukami;K. Murase
研究了alcl3和低挥发溶剂（如glymes）在铝（Al）电沉积液中的电化学活性物质。拉曼光谱显示，所有的glyme浴均含有AlCl4 -阴离子和Al-Cl-glyme阳离子。二lyme （G2）、三lyme （G3）和四lyme （G4）熔池的室温电导率高达10−3S cm−1，而丁二lyme （butylG2）熔池的室温电导率仅为10−4S cm−1，这是由于离子种类浓度较低。令人惊讶的是，电化学测量表明，在glyme浴中，只有G2浴能够电沉积Al。因此，尽管Al- cl -glyme络合物阳离子结构相似，但只有G2络合物阳离子具有电化学活性。这表明，对于G2配合物来说，从Al-Cl-glyme阳离子中解离glyme及其随后的还原是非常容易的。
Electrochemically active species in aluminum (Al) electrodeposition baths using AlCl3and less volatile solventsi.e.glymes were investigated. Raman spectroscopy revealed that all the glyme baths contained AlCl4−anions and Al-Cl-glyme cations as ionic species. Room temperature conductivities were as high as the order of 10−3S cm−1for the diglyme (G2), triglyme (G3) and tetraglyme (G4) baths, whereas that for the butyl diglyme (butylG2) bath was only 10−4S cm−1due to a lower concentration of ionic species. Surprisingly, electrochemical measurements showed that, among the glyme baths, only the G2 bath enabled electrodeposition of Al. Consequently, despite the similar structures of Al-Cl-glyme complex cations, only the G2 complex cations are electrochemically active. This suggests that the desolvation of glymes from Al-Cl-glyme cations and their subsequent reduction is exceptionally easy for the G2 complexes.