To mitigate the dependence on fossil fuels and the associated global warming issues, numerous studies have focused on the development of eco-friendly energy conversion devices such as polymer electrolyte membrane fuel cells (PEMFCs) that directly convert chemical energy into electrical energy. As one of the key components in PEMFCs, polymer electrolyte membranes (PEMs) should have high proton conductivity and outstanding physicochemical stability during operation. Although the perfluorinated sulfonic acid (PFSA)-based PEMs and some of the hydrocarbon-based PEMs composed of rationally designed polymer structures are found to meet these criteria, there is an ongoing and pressing need to improve and fine-tune these further, to be useful in practical PEMFC operation. Incorporation of organic/inorganic fillers into the polymer matrix is one of the methods shown to be effective for controlling target PEM properties including thermal stability, mechanical properties, and physical stability, as well as proton conductivity. Functionalization of organic/inorganic fillers is critical to optimize the filler efficiency and dispersion, thus resulting in significant improvements to PEM properties. This review focused on the structural engineering of functionalized carbon and silica-based fillers and comparisons of the resulting PEM properties. Newly constructed composite membranes were compared to composite membrane containing non-functionalized fillers or pure polymer matrix membrane without fillers.

Polymer electrolyte membrane fuel cell (PEMFC) is an eco-friendly energy conversion device that can convert chemical energy into electrical energy without emission of harmful oxidants such as nitrogen oxides (NO_x) and/or sulfur oxides (SO_x) during operation. Nafion^®, a representative perfluorinated sulfonic acid (PFSA) ionomer-based membrane, is generally incorporated in fuel cell systems as a polymer electrolyte membrane (PEM). Since the PFSA ionomers are composed of flexible hydrophobic main backbones and hydrophilic side chains with proton-conducting groups, the resulting membranes are found to have high proton conductivity due to the distinct phase-separated structure between hydrophilic and hydrophobic domains. However, PFSA ionomer-based membranes have some drawbacks, including high cost, low glass transition temperatures and emission of environmental pollutants (e.g., HF) during degradation. Hydrocarbon-based PEMs composed of aromatic backbones with proton-conducting hydrophilic groups have been actively studied as substitutes. However, the main problem with the hydrocarbon-based PEMs is the relatively low proton-conducting behavior compared to the PFSA ionomer-based membranes due to the difficulties associated with the formation of well-defined phase-separated structures between the hydrophilic and hydrophobic domains. This study focused on the structural engineering of sulfonated hydrocarbon polymers to develop hydrocarbon-based PEMs that exhibit outstanding proton conductivity for practical fuel cell applications.