Functionalization of poly(4‐chloromethylstyrene) with anthraquinone pendants for organic anode‐active materials

Abstract

Condensation of anthraquinone‐2‐carboxylic acid with poly(4‐chloromethylstyrene) afforded a high‐density redox polymer containing the anthraquinone pendants with reversible charge storage capability at negative potentials near −1 V versus Ag/AgCl. Electrochemically reversible redox response of the polymer, which was ascribed to the reduction of the pendant group to the anion radical and the dianion, suggested that the polymer was sufficiently robust in these redox states for charge storage application. Immobilizing the anthraquinone groups on current collectors was accomplished by the use of the polymer which was swellable and yet insoluble in both aqueous and nonaqueous electrolyte solutions. Such properties allowed the accommodation of external cations from the electrolyte solution to permeate through the polymer layer for electroneutralization of the negative charge produced at the reduced state, which led to the repeatable charging and discharging cycles without degradation of the charge storage capacity. Exploration of the aqueous electrochemistry of anthraquinone, which had been inaccessible by the lack of the solubility of the conjugated and fused‐ring molecule in H2O, became feasible by virtue of the swelling property of the polymer layer in the aqueous electrolyte. While negative charge was relatively difficult to be stored with redox polymers compared to the positive charge due to the enhanced reactivity in their reduced states and small varieties of the appropriate redox sites, the present polymer was characterized as the excellent organic electrode‐active materials that operated at sufficiently negative potentials which was essential for the fabrication of entirely organic batteries. Copyright © 2011 John Wiley & Sons, Ltd.