Polymer electrolyte fuel cell (PEFC), as an efficient hydrogen energy conversion device, has been developed for decades. Catalyst layer (CL), where the oxygen reduction reaction occurs, predominantly determines the performance of PEFC. Since 1889, the mass activity of catalyst layer has been improved for more than three orders of magnitudes, thanks to the invention of PFSA ionomer and highly dispersed catalyst on nano-sized carbon support. In recent years, introducing order into CL is bringing the CL performance to a higher level. The CLs with state-of-the-art performance feature nanofiber structures. One type of is ionomer nanofibers deposited with Pt/C catalyst on the surface, and another type is composite nanofiber containing ionomer, Pt/C catalyst, and binding polymer. Their superior performance may come from the ordered mass transport network and the size effect of nanofiber conductivity. To further improve the CL performance, the structure-property-performance relationship of ionomer nanofibers or composite nanofibers needs to be clarified.

In this work, we designed a setup to measure the proton, electron and thermal conductivity as well as the performance of a single ionomer or composite nanofiber. We developed a self-bonding method to fix the nanofiber on the micro-electrode. For proton and electron conductivity measurement, four-probe method was adopted to eliminate the electrical contact resistance and interfacial effect. For thermal conductivity measurement, Raman assisted steady state method was used to directly measure the temperature profile along the nanofiber. So, the measurement error resulting from the thermal contact resistance between the sample and the temperature sensor/heat sink can be eliminated. For performance measurement, three-electrode system was adopted using the Ag/AgCl electrode as the reference electrode and the Zn/ZnCl₂ electrode as the counter electrode. We prepared nanofibers with different size, polymer content, and cross-sectional component distribution by controlling the ink recipe and electrospinning parameters. The integrated thermo-electric measurement found that the proton and thermal conductivity of nanofiber are one order of magnitude higher than bulk properties and increases with decreasing fiber radius. This is attributed to the oriented ionic morphology along the nanofiber. Furthermore, a nanofiber model was developed to extract the catalytic activity and gas diffusion coefficient of nanofiber. These characterization and modelling work can provide guidance to the design and optimization of catalyst layer with electrospun ionomer or composite nanofibers.