For enhancing hydroxide ion conductivity, alkaline stability, and fuel cell performance of quaternaized aromatic/perfluoroaklyl copolymer (QPAF) membranes, ammonium groups attached to the polymer backbone have been investigated. The ammonium groups included dimethylbutylamine (DMBA), dimethylhexylamine (DMHA), and 1,2-dimethylimidazole (DMIm) groups in comparison to the trimethylammonium (TMA) group. DMBA turned to be the optimum ammonium group for QPAF membranes in terms of its high hydroxide ion conductivity based on well-connected and larger phase-separated morphology than that of QPAF-TMA with similar ion exchange capacity (IEC) value. QPAF-DMBA (IEC = 1.33 mequiv g–1) exhibited the highest hydroxide ion conductivity among the tested membranes up to 152 mS cm–1 in water at 80 °C, which was 1.6 times higher than that of QPAF-TMA (95 mS cm–1). In addition, QPAF-DMBA exhibited reasonable alkaline stability in 1 M KOH at 60 °C for 1000 h. The remaining conductivity was 44 mS cm–1 (58%) for QPAF-DMBA, while that for QPAF-TMA was 1.0 mS cm–1 (1%). QPAF-DMBA (IEC = 1.09 mequiv g–1) exhibited excellent stability in 1 M KOH at 80 °C without change in the ion conductivity (22 mS cm–1) for 500 h. The post-test membranes exhibited a minor degradation in QPAF-DMBA as suggested by FT-IR spectra and DMA analyses. An H2/O2 fuel cell was operated with the QPAF-DMBA membrane to achieve the maximum power density of 167 mW cm–2 at the current density of 0.42 A cm–2, which was higher than that (138 mW cm–2) for QPAF-TMA membrane under the same operating conditions.
For improving the alkaline stability and other properties of aromatic semiblock copolymer [QPE-bl-11a(C1)] membranes containing benzyltrimethylammonium groups, several novel hydrophilic monomers with different side-chain lengths and substitution positions were designed and synthesized for the polymerization. The pendant-type preaminated copolymers PE-bl-11s were quaternized using iodomethane to obtain the target QPE-bl-11s with well-defined chemical structure. In TEM analyses, QPE-bl-11a(C3) and QPE-bl-11a(C5) membranes with propyl and pentyl side-chains, respectively, showed more developed phase-separated morphology with greater hydrophilic domains (ca. 10–20 nm in width) than that of the C1 equivalent. The phase separation was more distinct and larger for the QPE-bl-11a membranes linked with p-phenylene groups in the hydrophilic part than for the QPE-bl-11b membranes with m-phenylene groups. In particular, QPE-bl-11b(C5) membrane exhibited considerably smaller hydrophilic/hydrophobic domains compared to those of the other membranes. After the alkaline stability test in 1 M KOH aqueous solution at 60 °C for 1000 h, the remaining conductivity was better as increasing the side-chain length: 34% for QPE-bl-11a(C1), 54% for QPE-bl-11a(C3), and 72% for QPE-bl-11a(C5) at 60 °C. The results suggest that the pendant alkyl chains could improve the alkaline stability and the main-chain bond position could improve morphology, water utilization, and mechanical properties of QPE-bl-11 membranes. An H2/O2 fuel cell with QPE-bl-11 membrane showed 139 mW cm–2 of the maximum power density at 0.28 A cm–2 of the current density.
Novel anion-conductive polymers containing perfluoroalkyl and ammonium-functionalized fluorene groups were synthesized and characterized. The quaternized polymers synthesized using a dimethylaminated fluorene monomer had a well-defined chemical structure in which each fluorenyl group was substituted with two ammonium groups at specific positions. The resulting polymers had a high molecular weight ( M n = 8.9–13.8 kDa, M w = 13.7–24.5 kDa) to provide bendable thin membranes with the ion-exchange capacity (IEC) ranging from 0.7 to 1.9 mequiv g –1 by solution casting. Both transmission electron microscopy images and small-angle X-ray scattering patterns suggested that the polymer membranes possessed a nanoscale phase-separated morphology based on the hydrophilic/hydrophobic differences in the polymer components. Unlike typical anion-exchange membranes found in the literature, hydroxide ion conductivity of the membranes did not increase with increasing IEC because of their high swelling capability in water. The membrane with IEC = 1.2 mequiv g –1 showed balanced properties of high hydroxide ion conductivity (81 mS cm –1 at 80 °C in water) and mechanical strength (>100% elongation and 14 MPa maximum stress at 80 °C, 60% relative humidity). The polymer main chains were stable in 4 M KOH for 1000 h, whereas the trimethylbenzyl-type ammonium groups degraded under the conditions to cause loss in the hydroxide ion conductivity. An H 2 /O 2 fuel cell with the membrane with IEC = 1.2 mequiv g –1 exhibited a maximum power density of 242 mW cm –2 at 580 mA cm –2 current density.
Piperidinium functionalized partially fluorinated copolymers with varying alkyl spacer length were synthesized and evaluated as anion exchange membranes to achieve improved performance in alkaline fuel cells.
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