Quantitative Analysis of Ionic Channel Network Variation in Nafion Under Continuous Annealing Using Current-Sensing...

Proton exchange membranes (PEMs) are essential for PEM fuel cells, with proton conductivity arising from the hydration-induced ionic channel network. PEM performance can be enhanced through pretreatments, such as annealing, which reconstruct the ionic channels. This study investigates the ionic channel network variation in Nafion 212 under continuous annealing at 90 °C using current-sensing atomic force microscopy (CSAFM). A nanoscale PEM fuel cell was formed with a Pt-coated CSAFM tip and Pt-coated Nafion surface. Topography and surface roughness analyses revealed geometrical changes from annealing. Current-sensing images and histograms qualitatively assessed local conductance and ionic channel distribution. The ionic channel network density was quantitatively evaluated using the number of protons moving through the ionic channel network (NPMI), derived from CSAFM and electrodynamics principles. NPMI directly reflects ionic channel density. From the unannealed state to 60 h, NPMI increased linearly at 1 × 10⁴ h^-1, indicating enhanced channel formation. Beyond 60 h, NPMI decreased linearly at 1.9 × 10⁵ h^-1, reflecting progressive network degradation. As the ionic channel network increases, the number of protons reaching the membrane surface also increases, whereas in the opposite case it decreases. Thus, NPMI becomes evaluation criterion for ionic channel network density. These findings systematically link nanoscale structural changes to ionic channel reconstruction and proton transport in Nafion 212, providing insight into PEM performance evolution under thermal treatment.