Sulfonation-Time-Dependent Structure–Property Relationships of Electrospun Polyketone Nanofiber Membranes for PEMFC Applications

Electrospun sulfonated polyketone (PK) nanofiber membranes were prepared to investigate the sulfonation-time-dependent structure–property relationships of hydrocarbon-based polymer electrolyte membranes for PEMFC (Polymer Electrolyte Membrane Fuel Cell) applications. NaCl addition to the electrospinning solution increased solution conductivity and enabled the formation of uniform PK nanofibers with an average diameter of approximately 270 nm. Subsequent sulfonation introduced sulfonic-acid-related groups into the PK nanofiber framework, and the resulting membrane properties were strongly governed by sulfonation time. Among the tested membranes, PK-NC16 exhibited the highest proton conductivity of 0.107 ± 0.031 S cm−1 and an ion exchange capacity of 2.82 meq g−1, exceeding or comparable to those of Nafion 115 under the tested conditions. FTIR-based analysis indicated that the relative sulfonation index increased up to 16 h, whereas extended sulfonation for 24 h generated additional sulfone/sulfonate-related bands, suggesting possible side reactions or structural changes under prolonged acid treatment. The high water uptake of PK-NC16 enhanced proton transport but also revealed a hydration-sensitive polymer network, as reflected by a voltage degradation rate of approximately −590 μV h−1 during a 100 h short-term stability constant-current test. These results demonstrate that sulfonation time is a key parameter controlling the balance among ionic functionality, hydration, mechanical response, proton conductivity, and PEMFC-relevant single-cell performance in electrospun PK nanofiber membranes.