Molecular Engineering of Hydroxide Conducting Polymers for Anion Exchange Membranes in Electrochemical Energy...

Anion exchange membranes (AEMs) based on hydroxide-conducting polymers (HCPs) are a key component for anion-based electrochemical energy technology such as fuel cells, electrolyzers, and advanced batteries. Although these alkaline electrochemical applications offer a promising alternative to acidic proton exchange membrane electrochemical devices, access to alkaline-stable and high-performing polymer electrolyte materials has remained elusive until now. Despite vigorous research of AEM polymer design, literature examples of high-performance polymers with good alkaline stability at an elevated temperature are uncommon. Traditional aromatic polymers used in AEM applications contain a heteroatomic backbone linkage, such as an aryl ether bond, which is prone to degradation via nucleophilic attack by hydroxide ion. In this Account, we highlight some of the progress our group has made in the development of advanced HCPs for applications in AEMs and electrode ionomers. We propose that a synthetic polymer design with an all C-C bond backbone and a flexible chain-tethered quaternary ammonium group provides an effective solution to the problem of alkaline stability. Because of the critical demand for such a polymer system, we have established new synthetic strategies for polymer functionalization and polycondensation using an acid catalyst. The first approach is to graft a cationic tethered alkyl group to pre-existing, commercially available styrene-based block copolymers. The second approach is to synthesize high-molecular-weight aromatic backbone polymers using acid-catalyzed polycondensation of arene monomers and a functionalized trifluoromethyl ketone substrate. Both strategies involve a simple two-step reaction process and avoid the use of expensive metal-based catalysts and toxic chemicals, thereby making the synthetic processes easily scalable to large industrial quantities. Both polymer systems were found to have excellent alkaline stability, confirmed by the preservation of ion exchange capacity and ion conductivity of the membrane after an alkaline test under conditions of 1 M NaOH at 80-95 °C. In addition, the advantage of good solvent processability and convenient scalability of the reaction process generates considerable interest in these polymers as commercial standard AEM candidates. AEM fuel cell and electrolyzer tests of some of the developed polymer membranes showed excellent performance, suggesting that this new class of HCPs opens a new avenue to electrochemical devices with real-world applications.