Nanocrystalline carbon films, which consist of graphite-like nanocrystals within an amorphous carbon matrix, have recently attracted extensive theoretical and experimental attention. Understanding the electronic transport and corrosion mechanisms of graphite-like nanocrystalline carbon films (GNCFs) is essential for their application in proton-exchange membrane fuel cells (PEMFCs). So far, limited progress has been made on the electronic or atomistic understanding of how the degree of structural order and grain boundaries affect the electronic transport and corrosion behaviors of GNCFs. In this work, using the Landauer-Büttiker formula merged with first-principles density functional theory, the conductance of GNCFs is presented as a function of their crystallinity. As the crystallinity decreases, the electron states around the Fermi level are found to be more spatially localized, thus hindering the electronic transport of GNCFs. Additionally, a systemic picture of the chemical reactivity of nanostructured surface in GNCFs toward typical particles existing in PEMFCs is drawn by ab initio molecular dynamics simulations. Systemic experimental investigations on the corrosion mechanisms of GNCFs used in PEMFCs have been conducted in this work. Compared with pure amorphous carbon films, the GNCFs exhibit higher corrosion current densities due to the preferential corrosion in the larger slit pores at the grain boundaries, but their stability in interfacial contact resistance is significantly improved by the embedded graphite-like nanocrystals, which have high levels of resistance to oxygen chemical adsorptions and act as high-speed ways to transport electrons.
Keywords: PEMFCs; degree of order; durability enhancement; electronic transport; first-principles calculations; nanocrystalline carbon films.