Unraveling the multivalent Aluminium-ion redox mechanism in 3,4,9,10-Perylenetetracarboxylic dianhydride (PTCDA)

Abstract: Rechargeable Aluminium-organic batteries are an exciting emerging energy storage technology owing to their low cost and promising high performance, thanks to the ability to allow multiple-electron redox chemistry and multivalent Al-ion intercalation. In this work, we use a combination of Density Functional Theory (DFT) calculations and experimental methods to examine the mechanism behind the charge-discharge reaction of the organic dye 3,4,9,10-Perylenetetracarboxylic dianhydride (PTCDA) in the 1,3-ethylmethylimidazolium (EMIm$^+$) chloroaluminate electrolyte. We conclude that, contrary to previous reports claiming the intercalation of trivalent Al$^{3+}$, the actual ionic species involved in the redox reaction is the divalent AlCl$^{2+}$. While a less-than-ideal scenario, this mechanism still allows a theoretical transfer of four electrons per formula unit, corresponding to a remarkable specific capacity of 273 mAh g$^{-1}$. However, the poor reversibility of the reaction and low cycle life of the PTCDA-based cathode, due to its solubility in the electrolyte, make it an unlikely candidate for a commercial application.