N. F. Nikol’skaya

Porous structure and hydrophilic-hydrophobic properties of gas diffusion layers of the electrodes in proton-exchange membrane fuel cells

The porous structure and hydrophilic-hydrophobic properties of the gas diffusion layers (GDL) of electrodes on a substrate of carbon paper in proton-exchange membrane fuel cells have been investigated with the methods of standard porosimetry and of pycnometry. GDL containing various fluoroplast concentrations were impregnated with water, and this process has been investigated at 20 and 80°C. The impregnation rate is significantly higher for untreated carbon paper than for teflonated GDL and also increases significantly with increasing temperature. With teflonization of the carbon paper, hydrophilic porosity decreases, while hydrophobic porosity increases. This increase, however, ceases at high fluoroplast concentrations. The concept of hydrophobization effectiveness of the porous carbon substrate of GDL is introduced. It has been established that hydrophobization effectiveness decreases with increasing fluoroplast concentration and depends on the type of suspension. Curves of the angle of wetting of GDL by water versus the pore radius exhibit a minimum. Different values of the angle of wetting of GDL by water in different pores are explained by nonuniform distributions of both fluoroplast particles and hydrophilic surface groups in pores of different dimensions.

Hydrophilic-hydrophobic and sorption properties of the catalyst layers of electrodes in a proton-exchange membrane fuel cell: A stage-by-stage study

In the electrodes of a proton-exchange membrane fuel cell, the hydrophilic-hydrophobic properties of the catalyst layers (CL), which contain a carbon substrate (CS), an ionomer in the form of Nafion resin, and a platinum catalyst, are investigated with standard contact porosimetry. Regularities in the influence of ionomer on the hydrophilic-hydrophobic properties of ten different CS, including Vulcan XC-72 carbon black, are investigated. The following plots are obtained: pore distribution curves with respect to radii, water desorption isotherms, moisture content distribution curves with respect to capillary pressure and to the free energy of binding water to material, and the wetting angle of water for the samples under investigation as a function of pore radius. It is established that both a hydrophobic effect and a hydrophilic effect occur in CL as a result of ionomer application to the CS under investigation. It is concluded that these different effects are determined by the orientation of the sulfonate groups (inside and outside) in the resin particles. This orientation depends on the extent of the binding of sulfonate groups to the CS surface by adsorption. CS surface properties are determined by the type and concentration of surface groups. Thus, the phenomenon of ionogenic-group inversion is established. When platinum is applied to CS, the CL become partially hydrophilic.

Carbon nanotubes as a support for Pt-and Pt-Ru-catalysts of reactions proceeding in fuel cells

Comparative study of two types of single-wall carbon nanotubes and standard carbon black Vulcan XC-72 as supports for catalysts of reactions proceeding in fuel cells is carried out. The nanotubes were prepared by arc method; they differed in the degree of their purifying from amorphous carbon and metal impurities. The structure and hydrophobic-hydrophilic properties of these carbon supports are studied by etalon porosimetry. The effect of the supports’ specific surface area on the deposited catalyst particles size and specific surface area is studied. The catalysts (Pt-Ru and Pt) were deposited from aqueous solutions of their salts. Platinum was also deposited by thermal decomposition of ethoxy clusters. It is shown that in methanol oxidation reaction at the Pt-Ru catalysts the current values per unit true surface area do not depend on the support nature, provided the catalyst loading is equal and the particle size is similar. When oxygen is reduced at platinum deposited onto purified nanotubes and the carbon black Vulcan XC-72, specific kinetic currents also are close to each other. It is shown that the degree of nanotubes purification and their structure affect the kinetics of this reaction significantly.

Study of the porous structure of a monolayer carbon-ceramic composite material of the C-SiC composition

Samples of a monolayer carbon-ceramic composite material (composite) of the C-SiC composition are obtained as a result of the compaction of porous substrates made of a thin carbonized carbon fiber-reinforced plastic based on one layer of a carbon cloth with silicon carbide deposited from the gas phase of methylsilane. At each step of preparation of this material, its density, porosity, and specific pore surface are determined by standard contact porosimetry. Based on the obtained distributions of the specific volume and specific surfaces of pores by their radii, changes in the porous structure of samples are considered. The necessity of high-temperature annealing as a technological step in making the composite leading to the disappearance of microporosimety within the composite is shown. The microstructure of the composite under study is also studied with the use of scanning electronic microscopy.

Porous structure of the catalyst layers of electrodes in a proton-exchange membrane fuel cell: A stage-by-stage study

Porous structure is studied by standard contact porosimetry after each stage in the preparation of a catalyst layer, which contains a carbon substrate (CS), an ionomer in the form of Nafion resin, and a platinum catalyst. The influence of the ionomer on the porous structure of ten different CS is investigated. The structure of these samples is studied over the maximum range of their pore radii r ∼ 0.3–105 nm. Pores of main volume within particles of the CS under investigation are mainly distributed over the maximum range of their radii from r ≤ 1 to ∼ 50 nm. Ionomer introduction into all the CS under investigation leads to an increase in the integral porosity due to the porosity of the intergranular structure. The change in porosity of the intragranular structure is caused by ionomer blocking small pores in the CS. In most CS, ionomer blocks pores of different sizes, from micropores with radii r ≤ 1 nm and up to r ∼ 1000 nm. It is concluded that the extent of blockage of CS pores is largely determined by the surface properties of the CS and Nafion resin and, more precisely, by the difference in resin adhesion to the CS surface because of the presence of different surface groups on the CS surface. When platinum is applied to CS, this leads to an increase in the specific volume of the micropores. The smallest dimensions of platinum particles are estimated to be on the order of 1 nm.

Irreversible processes during the lithium intercalation into graphite: the passive film formation

Comparative studies of three type of carbonaceous materials—the modified oxidized graphite, thermoexpanded graphite, and carbon paper—prior to and after galvanostatic cycling in 1 M LiClO4 solution in propylene carbonate-dimethoxyethane mixture are carried out using standard porosimetry. It was shown that the mean (effective) thickness of the passive film [solid electrolyte interface (SEI)] at the electrodes of the modified oxidized graphite and thermoexpanded graphite equals a few nanometers. The comparison of porosimetric and electrochemical data shows that the passive film comprises both lithium carbonate and alkylcarbonates. Additionally, this comparison allows corroborating the concept on the formation of polymer (or oligomer) component of the passive film at least at the thermoexpanded graphite electrodes.

Porous structure of carbon-carbon friction composites studied by gas adsorption and standard contact porosimetry techniques

Using low-temperature nitrogen adsorption measurements and standard contact porosimetry, we determined parameters of the pore structure of a carbon-carbon friction composite: specific surface area, total pore volume, and pore volume-size distribution. The results demonstrate that the material is macroporous, with predominant pore radii in the range 1 to 100 μm. Using two saturating fluids, octane and water, we established distinctions between the hydrophilic properties of the surface of different groups of pores in the composite material.

Thin-film positive electrode based on vanadium oxides for lithium-ion accumulators

The results of the experiments on the development of positive thin-film electrodes for lithium-ion accumulators based on vanadium oxides are presented. The deposition modes and controlling methods of the structure and phase composition of the films, diagnostics methods of the structure and phase composition, and the results of the electrochemical tests of the positive electrodes are described.

Thin film negative electrode based on silicon composite for lithium-ion batteries

The experimental results concerning the elaboration of the technology used to manufacture thin film negative electrodes for lithium-ion batteries based on Si–O–Al–Zn composites have been presented. The regimes of sputtering and the possibilities of controlling the structure and phase composition of the films, the methods used for the diagnostics of the structure and phase composition of the films, and the results of the electrochemical tests of the negative electrodes have been described.