Abstract
The influence of water concentration on the electrochemical behavior of Al anodes in Al/active-non-aqueous electrolytes is investigated. Normally passive, Al exhibits facile electrochemical oxidation in both AlCl 3/γ-butyrolactone (AlCl 3/BLA) and (C 2H 5) 4NCl acetonitrile (TEAC/ACN) electrolytes. However, in these two electrolytes, the influence of water on Al oxidation shows opposite effects. Incremental increase from 0 to 1.5 M H 2O (0 to 3% water by volume) hinders Al oxidation in 1 M AlCl 3/BLA, increasing polarization loss from 100 to 400 mV cm 2 mA −1. Yet in 0.3 M TEAC/ACN, Al is passive in the absence of water, exhibiting currents only in the μA cm −2 domain, equivalent to oxidative polarization losses of over 1000 mV cm 2 mA −1. This polarization loss is alleviated by water addition, and decreases from 20 to 7 mV cm 2 mA −1 as water is increased from 0.3 to 1.5 M. FT-IR spectroscopy, linear voltammetry, galvanostatic reduction, surface microscopy and electrolytic conductivity measurements were conducted to probe competing water activation or water passivation effects on organic-phase Al electrochemistry.
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