Ether Cleavage Decreases the Ion Exchange Capacity of Anion Exchange Membranes

Erimban, Shakkira; Factorovich, Matias H.; Bombau, Ignacio J.; Karnes, John J.; Gadea, Esteban D.; Schwartz, Johanna J.; Molinero, Valeria

doi:10.1021/acs.chemmater.5c00273

Ether Cleavage Decreases the Ion Exchange Capacity of Anion Exchange Membranes

Journal Article · Fri Apr 11 00:00:00 EDT 2025 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.5c00273· OSTI ID:2585299

Erimban, Shakkira ^[1]; Factorovich, Matias H. ^[2]; Bombau, Ignacio J. ^[2]; ^[3]; Gadea, Esteban D. ^[1]; Schwartz, Johanna J. ^[3]; ^[1]

Univ. of Utah, Salt Lake City, UT (United States)
Univ. of Utah, Salt Lake City, UT (United States); Univ. of Buenos Aires (Argentina)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Anion exchange membranes (AEMs) are integral to fuel cells and water electrolysis systems but suffer from poor durability under alkaline conditions. Ether cleavage is an important failure pathway of poly(arylene ether)-based AEMs that compromises both mechanical stability and ion transport. While this degradation pathway is often studied in terms of polymer fragmentation, the role of newly formed hydrophilic groups has been largely overlooked. Here, we show that polymer scission leads to reduced mechanical rigidity, while the introduction of hydrophilic groups partially mitigates this loss. Under alkaline conditions, phenoxide groups formed during ether cleavage neutralize the polymer cations, leading to a previously unreported loss of ion exchange capacity (IEC). This IEC loss mechanism exacerbates the reduction in ionic conductivity, emphasizing the severity of ether cleavage as a degradation pathway. Recognizing that ether cleavage introduces significant chemical changes beyond polymer fragmentation provides critical insights into its interplay with other degradation mechanisms, such as the direct reduction of cationic sites by E2 and S_N2, and provides molecular-level interpretations for the concurrent effects of polymer scission and increased hydrophilicity on membrane performance.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 2585299

Report Number(s):: LLNL--JRNL-2002380

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 8 Vol. 37; ISSN 1520-5002; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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