INVESTIGATION OF ANION EXCHANGE MEMBRANES FOR ELECTROCHEMICAL ENERGY CONVERSION AND STORAGE SYSTEMS

The alkaline stability of poly (arylene ether) backbones in anion exchange membranes (AEMs) derivatized with quaternary benzyl N, N- dimethylhexylammmonium (DMH+) and trimethylammonium (TMA+) cation groups were investigated in poly (2,6- dimethyl 1,4-phenylene) oxide (PPO) and Udel® polysulfone (PSF) polymers. Previous studies have demonstrated that quaternary ammonium and phosphonium groups trigger backbone degradation in commercially available poly (arylene ether)-based AEMs, despite the base polymers’ resilience to alkaline solutions. Herein, I demonstrate that the electron withdrawing or donating character in the poly (arylene ether) backbone ultimately dictates whether the prepared AEMs will become brittle in alkaline media due to cation-triggered backbone degradation (Arges, Parrondo, Johnson, Nadhan, & Ramani, 2012a; Christopher G. Arges, Lihui Wang, Javier Parrondo, & Vijay Ramani, 2013). Mitigation of cation-triggered backbone degradation was only achieved when electron withdrawing substituents (not including the cation), such as sulfone or bromine, were eliminated from the polymer backbone (or, alternately, when electron donating groups were present). Hence, PPO AEMs prepared through chloromethylation, rather than free radical bromination, were resistant to backbone hydrolysis in alkaline media because each cation-functionalized repeat unit had two electron-donating methyl groups rather than a single methyl group. This study presents some design rules for preparing mechanically stable poly (arylene ether) AEMs from low cost, commercially available polymers for alkaline electrochemical devices.Ph.D. in Chemical Engineering, May 201