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Polymers 2021, 13, 359 6 of 11 Figure 2. In-plane vs. through-plane proton conductivities of (a) Nafion recast, (b) Nafion 212; (c) Nafion un crystallized and (d) Nafion 117 as received and Nafion 117 oriented membranes as a function of temperature (20–120 ◦C) at 90% RH%. (The error bars are not reported because they are smaller than the size of the symbols). Table 1. Proton conductivity [mS cm−1], @ RH 90% and for three temperature values, of the PFSA membranes (along with the standard deviation resulting from three independent measurements). 40 ◦C 80 ◦C 120 ◦C Membranes Nafion 117 Nafion 212 Nafion recast Nafion uncrystallized Nafion 117 oriented In-Plane 40.0 ± 0.8 74.1 ± 1.5 54.8 ± 1.2 31.2 ± 1.1 11.07 ± 0.6 Through- Plane 36.7 ± 1.2 76.1 ± 1.6 58.7 ± 1.3 30 ± 0.9 5.1 ± 0.3 In-Plane 76.5 ± 1.7 157.0 ± 2.1 119.7 ± 1.9 52.1 ± 1.1 16.0 ± 0.8 Through- Plane 63.6 ± 1.3 153.1 ± 2.1 113.3 ± 1.8 56.1 ± 1.4 8.08 ± 0.3 In-Plane 118.4 ± 1.7 220.0 ± 2.1 151.0 ± 2.0 71.3 ± 1.3 21.0 ± 0.8 Through- Plane 100.6 ± 1.6 213.1 ± 2.2 149.1 ± 1.9 76.1 ± 1.6 14.09 ± 0.7 Our findings are consistent with the outcome described by Holdcroft et al., as all the solution-cast membranes (Nafion recast, 212, and uncrystallized) exhibited isotropic conductivity, confirming the absence of any particular orientation in their polymer chains and/or in their ionic clusters. At the same time, a relatively small anisotropy was observed in the case of Nafion 117, with the conductivity parallel to the extruding direction (σIP) ~ 20% higher than the through-plane. It is worth noting that the in-plane to through-plane anisotropy increased to almost 106% when Nafion 117 oriented. This suggests that the ion-conducting clusters are mostly oriented along the plane of the membrane’s surface, inducing a strong directionality to the proton transport. This is expected to greatly affect the performance of the electrolyte in the PEMFC, where the σTP is crucial. In particular, while the through-plane conductivity of Nafion 212, recast, 117, and partially uncrystallized membranes still match the requirements for PEMFC application, the low σTP of Nafion 117 oriented makes it unsuitable for practical application; for this reason, its formationPDF Image | Morphology of Nafion-Based Membranes Affects Proton Transport
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