The global issue for proton exchange membrane fuel cell market development is a reduction in the device cost through an increase in efficiency of the oxygen reduction reaction occurring at the cathode and an extension of the service life of the electrochemical device. Losses in the fuel cell performance are due to various degradation mechanisms in the catalytic layers taking place under conditions of high electric potential, temperature, and humidity. This review is devoted to recent advances in the field of increasing the efficiency and durability of electrocatalysts and other electrode materials by introducing structured carbon components into their composition. The main synthesis methods, physicochemical and electrochemical properties of materials, and performance of devices on their basis are presented. The main correlations between the composition and properties of structured carbon electrode materials, which can provide successful solutions to the highlighted issues, are revealed.

In this study, we performed small-angle X-ray scattering (SAXS) to investigate the structure of Nafion^® membranes. The effect of freeze/thaw (F/T) cycles (from ambient temperature down to −40 °C) on the membrane nanostructure was considered for the first time. The SAXS measurements were taken for different samples: a commercial Nafion^® 212 membrane swollen in water and methanol solution, and a water-swollen silica-modified membrane. The membrane structure parameters were obtained from the measured SAXS profiles using a model-dependent approach. It is shown that the average radius of water channels (R_wc) decreases during F/T cycles due to changes in the membrane structure as a result of ice formation in the pore volume after freezing. The use of water-methanol solution (methanol content of 20 vol.%) for the membrane soaking prevents changes in the membrane structure during F/T cycles compared to the water-swollen membrane. Modification of the membrane surface with silica (SiO₂ content of 20 wt.%) led to a redistribution of water in the membrane volume and resulted in a decrease in R_wc. However, R_wc for the modified membrane did not decrease with the increasing number of F/T cycles due to the involvement of SiO₂ in the sorption of membrane water and, therefore, the prevention of ice formation.

An important stage in the development of platinum electrocatalysts on carbon support is the analysis of their basic parameters. Cyclic voltammetry is an effective tool for analyzing the structural and electrochemical properties of such electrocatalysts. Using Frumkin adsorption isotherms, the contribution of the platinum surface to the hydrogen adsorption region was well described by three peaks corresponding to different crystal structures. The screening was carried out for platinum black and platinum electrocatalysts supported by carbon black, reduced graphene oxide (RGO), carbon nanotubes (CNTs), and nanofibers (CNFs). For most samples, the peak contribution to the electrochemical surface area (ESA) and corresponding hydrogen adsorption energies had close values, but the parameters deviated for Pt black and RGO-based samples was observed. The dependence of the calculated peak parameters on the number of accelerated stress test cycles was used to evaluate the effect of the type of carbon support on the stability of the electrocatalyst and the structure of platinum nanoparticles. The experimental results indicate a high degree of stability and differences in the degradation mechanisms of electrocatalysts based on nanostructured carbon compared to carbon black, which are explained by differences in the metal-support interaction and corrosion resistance of nanostructured carbon supports.

Pt/C and Pt/x-SnO₂/C catalysts (where x is mass content of SnO₂) were synthesized using a polyol method. Their kinetic properties towards oxygen reduction reaction were studied by a rotating disk electrode (RDE) technique in a temperature range from 1 to 50 °C. The SnO₂ content of catalyst samples was 5 and 10 wt.%. A quick evaluation of the catalyst activity, electrochemical behavior and average number of transferred electrons were performed using the RDE technique. It has been shown that the use of x-SnO₂ (through modification of the carbon support) in a binary system together with Pt does not reduce the catalyst activity in the temperature range of 1–30 °C. The temperature rising up to 50 °C resulted in composite catalyst activity reduction at about 30%.

One of the most important problems in the development of proton-exchange membrane fuel cells (PEMFCs) is the selection of an efficient support material to serve as the electrocatalyst, which can ensure PEMFCs’ durability at low active metal loading, with minimal changes in the electrochemical surface and conductivity during long-term operations. Carbon nanostructures are now widely used in PEMFCs as such support materials, including carbon nanotubes (CNTs). In order to estimate the effect of the geometric parameters of a CNT-based support on the resulting size distribution of platinum nanoparticles for given synthesis conditions, in this work, we propose a semi-empirical model that assumes a random uniform distribution of platinum particles over the CNT surface. Based on the obtained distribution, the electrochemically active surface area (EASA) of the electrocatalyst is calculated and further used to evaluate the performance of the catalytic layer (CL) in the PEMFC. The applicability of the proposed model for calculating the parameters of CNT-based CLs and the output electrochemical characteristics of PEMFCs is shown.

One of the most important problems in the development of proton exchange membrane fuel cells remains the selection of an efficient electrocatalyst support capable of providing a low loading of active metal with minimal changes in the electrochemical surface, electronic conductivity, and activity. In this work, carbon nanotube arrays (CNTAs) grown directly on commercial gas diffusion layers (GDLs) are used to form electrodes of a new type. The CNTAs are used in the electrode as a microporous layer. The catalytic layer is formed in the microporous layer by a method that does not destroy the carbon support structure and consists of the controlled impregnation of CNTAs with the Pt-precursor with subsequent reduction in platinum particles in the surface volume of the layer. The resulting electrode was studied by scanning/transmission electron microscopy and Raman spectroscopy. This electrode provides increased electrical conductivity of the layer and can also improve stability and longer service life due to the enhanced adhesion of carbon materials to the GDL.