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Molecules 2020, 25, 1712 19 of 44 1357 mA cm−2 for the composite membranes with filler of 10, 20, and 50% titanium oxide nanotube (TNT) content and recast Nafion, respectively. Molecules 2020, 25, x 19 of 44 Molecules 2020, 25, x 20 of 44 (121 mS cm−1) having slightly decreased conductivity. The composite membranes also outperformed the pristine Nafion at variable RH. Fuel cell experiments at 80 °C and 100% RH (Figure 5) show that the composite membranes perform much better than the recast membrane, with current densities at Figure 4. Polarization (I–V) curves for the (a,b) TP25, (c,d) TMP, and (e,f) titanium oxide nanotube Figure 4. Polarization (I–V) curves for the (a,b) TP25, (c,d) TMP, and (e,f) titanium oxide nanotube ◦ −2 0.6 V o(fTN17T7) 7co,m1p6o0s9i,te1s4m9e8asaunred 1at38507amndA13c0m°C; rfeoprotdhuececdowmitphopseirtmeismsioenmfrborman[1e5s4]w. ith filler of 10, 20, and (TNT) composites measured at 80 and 130 C; reproduced with permission from [154]. 50% titanium oxide nanotube (TNT) content and recast Nafion, respectively. Zhengbang et al. [155] synthesised titanium oxide nanowires as a filler material in Nafion for PEMFCs operating at a higher temperature in addition to reinforcing the mechanical properties of the membrane. Addition of the nanowires led to a subsequent drop in water uptake and swelling, with increasing loading leading to increased reductions. The reduced swelling would help maintain mechanical integrity at higher operating temperatures. Fuel cell testing at 90 °C showed that the composite membrane experienced a smaller drop in polarisation when the humidity was reduced, in comparison to Nafion where the change in polarisation was much greater. Humidity stress tests revealed that the composite membrane had less stress (which becomes smaller with increased loading) than the recast Nafion, which experienced a high level of humidity related stress indicating lower lifetime. Ketpang et al. [156] further developed their idea of tubular inorganic fillers by studying the effect of titanium oxide nanotubes as a filler. The composite membranes had a higher water uptake compared to recast Nafion, with recast Nafion achieving 21.8%, Nafion-TiNT-10 33.7%, Nafion-TiNT-20 31.3% and the Nafion composite with 50% titanium oxide nanotubes achieving a water uptake of 29.6%. In addition, FT-IR analysis after drying the membranes at 110 °C revealed that the composite membranes still had water (from electrostatic interaction) through peaks that corresponded to -OH stretching (3455 cm−1) and –HOH- (1625 cm−1) bending vibration. Proton conductivity measurements at 80 °C and 100% RH confirmed that the filler improved the proton conductivity compared to recast Nafion (97 mS cm−1). The highest proton conductivity measurement Figure 5. Polarization plots of Nafion 212 (black), recast Nafion (pink), Nafion TNT 10% (blue), Figure 5. Polarization plots of Nafion 212 (black), recast Nafion (pink), Nafion TNT 10% (blue), Nafion was achieved by the composite with 10% filler (155 mS cm−1), with the 20% (142 mS cm−1) and 50% ◦ Nafion TNT 20% (red), Nafion TNT 50% (green) at 80°C and 100% RH; reproduced with permission TNT20%(red),NafionTNT50%(green)at80 Cand100%RH;reproducedwithpermissionfrom[156]. from [156]. The OCV also ranged from 0.97 to 1.03 V, indicating low crossover. Similar to the zirconium oxide nanotube, the titanium oxide nanotube composite displayed greater current densities at lower voltages. A 100 h stability test at 0.5 V, 80 °C and 18% RH showed that the composite membrane’s maximum power density decreased from 470 to 442 mW cm−2, whereas Nafion 212 only managed toPDF Image | Composite Polymers for Electrolyte Membrane Technologies
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