Ab initio molecular dynamics study of AlCl4- adsorption on PEDOT conducting polymer chains

In the search for alternatives to lithium batteries, aluminium makes a promising negative electrode due to its high theoretical specific energy and energy density. One battery chemistry making use of an aluminium negative electrode is the aluminium-poly(3,4-ethylenedioxythiophene) (PEDOT) battery, which has been shown to have long cycle life and specific energy comparable to other aluminium rechargeable batteries. The battery stores AlCl4- anions in the PEDOT cathode when charged. However, the storage mechanism is not well understood. Here, ab initio molecular dynamics simulations (AIMD) are used to help understand the optimum (relaxed) configuration of AlCl4- anions when stored on a single chain of PEDOT. Two main conclusions arise. Firstly, it is generally not stable to have two anions adsorbed to one monomer unit, and this configuration can be avoided for future work. Secondly, AIMD does not find lower energy configurations for the PEDOT/AlCl4- system than DFT geometry relaxation, providing that the starting geometry does not have two anions on the same monomer unit. Based on our results, we believe it is likely that similar behaviour will be observed in other conducting polymer systems. (C) 2021 The Authors. Published by Elsevier Ltd.

Automated summary

Aluminum shows promising potential as a negative electrode in terms of energy and specific energy; the aluminum-PEDOT battery demonstrates long cycle life and comparable specific energy; it is unstable to have two AlCl4- anions adsorbed on one monomer unit, providing insights for future research.