Alkaline Stability of Quaternized Diels–Alder Polyphenylenes

Park, Eun Joo; Maurya, Sandip; Hibbs, Michael R.; Fujimoto, Cy H.; Kreuer, Klaus-Dieter; Kim, Yu Seung

doi:10.1021/acs.macromol.9b00853

Alkaline Stability of Quaternized Diels–Alder Polyphenylenes

Journal Article · Fri Jul 12 00:00:00 EDT 2019 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.9b00853· OSTI ID:1558977

^[1]; ^[1]; Hibbs, Michael R. ^[2]; Fujimoto, Cy H. ^[2]; Kreuer, Klaus-Dieter ^[3]; ^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Max-Planck-Inst. für Festkörperforschung, Stuttgart (Germany)

Alkaline stability of anion exchange membranes is an essential requirement for the practical application of alkaline membrane fuel cells. In this study, we investigate the alkaline stability of Diels-Alder polyphenylenes (DAPPs) under various stability testing conditions. Structural analysis and membrane properties of the DAPPs indicated that different chemical structural changes of quaternized DAPPs occur depending on test conditions. Benzyltrimethylammonium functionalized DAPPs degraded rapidly via nucleophilic benzyl substitution under a relatively mild condition ca. 80 °C, 4 M NaOH whereas DAPPs with hexyltrimethylammonium (HTMA DAPP) exhibited much better alkaline stability. While only crosslinking of unreacted alkyl bromides of HTMA DAPP occurred at 80 °C, we observed the degradation of the cations via β- elimination after long term testing. At higher temperature or reduced relative humidity (RH) conditions, e.g., 160 °C or RH 10%, the rapid degradation of the cation in HTMA DAPP occurred via nucleophilic methyl substitution. These results suggest that accelerated stress tests may not be a quick and straightforward alternative to prolonged alkaline stability tests of AEMs.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE). Fuel Cell Technologies Program (EE-3F)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1558977

Report Number(s):: LA-UR--19-23599

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 14 Vol. 52; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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