Hydrophobized oxygen cathode of a fuel cell with a liquid electrolyte: Calculating overall currents and thicknesses

The mechanism governing operation of hydrophobized cathodes is discussed. A model is proposed for the active-layer structure. The model consists of equidimensional hydrophobic (agglomerates of polytetrafluoroethylene particles) and hydrophilic (agglomerates of carbon black particles with the catalyst on them) grains. The percolation characteristics of the model are calculated: the presence of a gas cluster and an ionic cluster is established, the specific area of contact between these clusters is determined, the magnitude of ionic conductivity is assayed, and so forth. The “model of cylindrical gas pores” is selected for calculating the overall current. Formulas for the bulk current density are determined. The overall characteristics of a cathode with a platinum catalyst on a carbonaceous carrier (on carbon black) in 7 M KOH at a temperature of 60°C are calculated with allowance made for the fact that the Tafel plots for the process of reduction of oxygen on platinum have two segments with different slopes.     

Performance of a polymer electrolyte fuel cell with long oxygen channel

Along-the-channel analytical model of a polymer electrolyte fuel cell is developed. The model takes into account oxygen diffusion in backing layer, diffusion and electroosmotic transport of water in membrane and oxygen depletion in a feed channel. Voltage current curve of a cell, which takes into account all these processes is obtained and expression for limiting current density is derived. The latter shows, that cell performance is described by design parameters, which are combinations of geometrical and working parameters. The region of optimal cell performance on the plane of the design parameters is determined.     

Hydrogen-oxygen (air) fuel cell with nafion and platinum: Calculating overall characteristics,comparing the performance of a cathode with polymeric electrolyte with a hydrophobized cathode with liquid electrolyte

Results of calculating the major overall characteristics of both an individual cathode and the whole hydrogen-oxygen (air) fuel cell with Nafion and platinum are shown. The effect of varying the parameters of both the active layer and the polymeric-electrolyte membrane on the overall characteristics of such a fuel cell is analyzed. The mechanisms of operation of active layers of hydrophobized cathodes and cathodes containing Nafion are compared. These two electrode types demonstrate a qualitative difference in the current generation mechanisms. As a result, the current in cathodes with Nafion increases more actively with the increase in over-potential (in proportion with exp [η₀/2], where η₀ is the cathodic overpotential) as compared with the case of hydrophobized cathodes (here the current ～ exp[η₀/4]). This explains the fact that a fuel cell with Nafion demonstrates so high power characteristics as compared with a fuel cell with hydrophobized electrodes and liquid electrolyte.     

Microfluidic synthesis of chitosan-based nanoparticles for fuel cell applications

A microfluidic platform is developed for the synthesis of monodisperse, 100 nm, chitosan based nanoparticles using nanogelation with ATP. The resulting nanoparticles tuned and enhanced transport and electrochemical properties of Nafion based nanocomposite membranes, which is highly favorable for fuel cell applications.     

Catalysts of ethanol anodic oxidation for ethanol-air fuel cell with a proton-conducting polymer electrolyte

Synthesis techniques for binary PtSn, PdM (M = Sn, V, Mo) and ternary PtSnNi, PtRuSn catalysts of ethanol electrooxidation on highly dispersed carbon materials are suggested. The highest activity in the 0.5 M H₂SO₄ solution containing 1 M C₂H₅OH corresponds to the system of PtSn (3: 1, 40 wt % Pt) with the particle size of 2–4 nm and tin content in the alloy with platinum of about 6%. It was shown that the catalyst efficiency as regards ethanol oxidation depth decreases in the series of Pt > PtRu ≈ PtSn, and the catalyst activity by current forms the series of PtSn > PtRu > Pt. The membrane-electrode assembly (MEA) with the anodes on the basis of the PtSn (3: 1, 40 wt % Pt) catalyst had stable characteristics for 220 h at the current density of ∼50 mA/cm².     

A Li-air fuel cell with recycle aqueous electrolyte for improved stability

A lithium-air fuel cell with a new designed cell structure for improved stability is proposed. The cell consists of two subunits: an energy conversion unit that employs a cation exchange membrane and a reaction-product recycling unit that collects/removes LiOH and thus protects the LISICON plate from corrosion under strong alkaline conditions. The aqueous electrolyte recycling system allows the newly structured Li-air fuel cell to attain higher theoretical energy density, and hence potential application as an alternative energy source for transportation.     

Electrocatalysts and membrane for direct ethanol-oxygen fuel cell with alkaline electrolyte

Results of studies of anodic (RuNi/C) and cathodic (PtCo/C; CoN₄/C) catalysts, polybenzimidazole membrane, and membrane-electrode assemblies on their basis for alkaline ethanol-oxygen fuel cell are presented. It is shown that the anodic catalyst RuNi/C optimized in its composition (Ru: Ni = 68: 32 in atomic percent) and the metal mass on carbonaceous support (15–20%) is sufficiently effective with respect to ethanol oxidation; it is well superior to commercial Pt/C- and RuPt/C-catalysts when calculated per unit mass of the precious metal. The effect of electrolyte composition, electrode potential, and temperature on the CO₂ yield is studied by chromatographic analysis of the ethanol oxidation products. It is shown that the highest CO₂ yield (the process involves the C-C bond break) is achieved at low electrolysis overvoltage and elevated temperature. The mean number of electrons given up by C₂H₅OH molecule approaches 10 at temperatures over 60°C. The studied cathodic catalysts form the following series of their specific activity in the oxygen reduction reaction: (20 wt % Pt) E-TEK ≥ (7.3 wt % Pt) PtCo/C > CoN₄/C; however, in the presence of alcohol the activity series is reversed. On this reason fuel cell cathodes were prepared by using synthesized CoN₄/C-catalyst. For the alkali-doped polybenzimidazole membrane the conductivity and ethanol crossover were determined. A membrane-electrode assembly for platinum-free alkaline ethanol-oxygen fuel cell is designed. It comprised anodic (RuNi/C) and cathodic (CoN₄/C) catalysts and polybenzimidazole membrane. The period of service of the fuel cell exceeded 100 h at a voltage of 0.5 V and current of 100 mA/cm².     

Direct ethanol oxidation fuel cell with anionite membrane and alkaline electrolyte

A number of cathode catalysts were synthesized from nitrogen-containing organic complexes on XC-72R carbon black for an alkaline electrolyte. The catalysts were studied by the rotating disc electrode (RDE) technique. The polyacrilonitrile (PAN), phthalocyanine (Pc), and cobalt tetra(methoxyphenyl)porphyrin (CoTMPP) systems showed the highest activity. The slope of the oxygen polarization curves in the first region in 1 M KOH was 35–40 mV; this corresponds to concentration polarization in an alkaline solution in the O₂-HO₂⁻ system. A cyclic voltammetry study demonstrated that the catalytic systems with the highest corrosion stability were Pc + Co + Fe/XC-72R and CoTMPP/XC-72R pyropolymer. The activity of the catalysts decreased by 20–25% compared with the initial current densities on average. An ethanol-oxygen fuel cell with a Fumasep FAA anionite membrane and nonplatinum catalysts was tested. The maximum power density was 32 mW/cm² at 40°C. The stability test of the fuel cell showed that the materials used for the membrane-electrode assembly allowed more than 100 h of continuous operation with constant working characteristics.     

Numerical simulation of a new operational regime for a polymer electrolyte fuel cell

A quasi-3D (Q3D) numerical simulation of a gas feed direct methanol fuel cell is performed. On both sides of the cell the flow field is formed by three parallel meander-like channels. It is shown that reduction of pressure in the middle channel on the cathode side leads to significant flux of water vapor to this channel without degradation of cell performance. At high current densities the channel with reduced pressure serves as collector of excessive water, which may prevent cell flooding.     

Effect of convective channel-to-channel mass flow in a polymer electrolyte fuel cell

The effect of convective channel-to-channel mass flow on the local performance of a polymer electrolyte fuel cell (PEFC) air cathode is determined experimentally by using submillimeter resolved current density distribution measurements in channel and land areas. A special cell is employed, where the two parallel channels of the cathode flow field can be operated at different pressure. For isobaric operation of the channels (Δp = 0 mbar), the lateral current density distribution shows a distinct minimum in the land area between the channels as diffusive mass transport becomes limiting at a higher cell polarization. Toward higher Δp, the local cell performance in the land area improves initially as a result of an improving convective channel-to-channel mass flow. However, as the pressure difference exceeds a value of 10 mbar, no noteworthy additional benefit is observed with further increasing Δp. Under these conditions, the convective mass flow provides an abundant reactant supply in the land area and, since reactant depletion is no longer limiting, the lateral current density distribution is primarily governed by the local ohmic resistance. As a result, the current density exhibits a maximum in the land area, where the local ohmic resistance shows a minimum.     

Gelation of a liquid electrolyte with aniline for use in a quasi-solid-state dye-sensitized solar cell

A new kind of gel electrolyte containing only organic solvents and an iodide salt-namely 3-methoxypropionitrile(MPN),aniline and AlI 3 -has been prepared.Gel formation results from the Lewis acid-base interaction between the Lewis acid ionic conductor AlI 3 and the Lewis base organic solvent aniline and no additional gelling agent is required.The AlI 3-aniline complex acts both as an ionic conductor and as a gelling agent.The differences between the peaks characteristic of the-NH 2 group and aromatic ring in the FTIR spectra of free aniline and the AlI 3-aniline hybrid confirm the formation of the AlI 3-aniline complex.The photovoltaic performance and long-term stability of dye-sensitized solar cells can be greatly enhanced by the addition of aniline to the AlI 3-MPN liquid electrolyte.     

Performance assessment of a spiral methanol to hydrogen fuel processor for fuel cell applications

A novel design of plate-type microchannel reactor has been developed for fuel cell-grade hydrogen production.Commercial Cu/Zn/Al2O3 was used as catalyst for the reforming reaction,and its effectiveness was evaluated on the mole fraction of products,methanol conversion,hydrogen yield and the amount of carbon monoxide under various operating conditions.Subsequently,0.5 wt% Ru/Al2O3 as methanation catalyst was prepared by impregnation method and coupled with MSR step to evaluate the capability of methanol processor for CO reduction.Based on the experimental results,the optimum conditions were obtained as feed flow rate of 5mL/h and temperature of 250℃,leading to a low CO selectivity and high H2 yield.The designed reformer with catalyst coated layer was compared with the conventional packed bed reformer at the same operating conditions.The constructed fuel processor had a good performance and excellent capability for on-board hydrogen production.     

一种不含胶凝剂的凝胶电解质在准固态染料敏化太阳能电池中的应用

报道了一种不含胶凝剂的凝胶电解质的制备及在准固态染料敏化太阳能电池中的应用.这种新型凝胶电解质仅含有机溶剂和碘盐,即3-甲氧基丙腈、苯胺、三碘化铝和碘.上述混合物通过路易斯酸性三碘化铝离子导体和路易斯碱性苯胺有机溶剂间的路易斯酸-碱相互作用形成凝胶,无需额外添加传统凝胶电解质的关键组分—胶凝剂.形成的三碘化铝-苯胺复合物在凝胶电解质中能同时发挥离子导体和胶凝剂的作用.红外光谱图中苯胺的氨基和苯环特征峰的变化证实了三碘化铝-苯胺复合物的形成.含这种新型凝胶电解质的准固态染料敏化太阳能电池光电性能和稳定性与含三碘化铝-3-甲氧基丙腈液体电解质的染料敏化太阳能电池相比有很大提高.     

Platinum-palladium catalysts for hydrogen fuel cell electrodes

Five series of Pt–Pd/C catalysts were prepared with different total metal loading and different atomic composition in Pt and Pd. The activity in electrooxidation of hydrogen were measured for all these catalysts. Electrooxidation of hydrogen is a structure insensitive reaction on platinum and a structure sensitive reaction on palladium. For bimetallic catalysts, curves of activity as a function of the composition of the catalyst can exhibit a maximum. Yet, metal loading can alter the atomic composition at which activities are maxima.

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Pt–Pd/C Pt Pd. . - - . . , .

     

Electrochemical noise of a hydrogen-air polymer electrolyte fuel cell operating at different loads

The electrochemical noise of a polymer membrane hydrogen-air fuel cell operating at different load currents was measured in serial experiments. Spectral power densities of the noise are shown to be divided into three regions. At frequencies greater than 3–10 Hz, the spectrum dependence has a constant slope of ??2 in the bilogarithmic coordinates. At frequencies 0.3–5 Hz, there is a horizontal plateau in which length is determined by the value of a load. At frequencies less than 0.3 Hz, the dependence of spectral power density has a slope of ??2. Medium-frequency plateau and high-frequency slope of spectral power densities of the noise were approximated by model RC circuits. The values of Faradic resistance and double-layer capacitance connected in parallel were obtained from the electrochemical impedance data. At load voltages higher 0.5 V, the height of the plateau was shown to be proportional to the 2.68 power of the load current value.     

Water transport coefficient distribution through the membrane in a polymer electrolyte fuel cell

The net water transport coefficient through the membrane, defined as the ratio of the net water flux from the anode to cathode to the protonic flux, is used as a quantitative measure of water management in a polymer electrolyte fuel cell (PEFC). In this paper we report on experimental measurements of the net water transport coefficient distribution for the first time. This is accomplished by making simultaneous current and species distribution measurements along the flow channel of an instrumented PEFC via a multi-channel potentiostat and two micro gas chromatographs. The net water transport coefficient profile along the flow channels is then determined by a control-volume analysis under various anode and cathode inlet relative humidity (RH) at 80 °C and 2 atm. It is found that the local current density is dominated by the membrane hydration and that the gas RH has a large effect on water transport through the membrane. Very small or negative water transport coefficients are obtained, indicating strong water back diffusion through the 30 μm Gore-Select^® membrane used in this study.     

Proton-conducting solid oxide fuel cell (SOFC) with Y-doped BaZrO3 electrolyte

Y-doped BaZrO₃ (BZY) electrolyte films are successfully fabricated by utilizing the driving force from the anode substrate, aiming to circumvent the refractory nature of BZY materials. The BZY electrolyte film on the high shrinkage anode becomes dense after sintering even though no sintering aid is added, while the BZY electrolyte remains porous on the conventional anode substrate after the same treatment. The resulting BZY electrolyte shows a high conductivity of 4.5 × 10^− 3 S cm^− 1 at 600 °C, which is 2 to 20 times higher than that for most of BZY electrolyte films in previous reports. In addition, the fuel cell with this BZY electrolyte generates a high power output of 267 mW cm^− 2 at 600 °C. These results suggest the strategy presented in this study provides a promising way to prepare BZY electrolyte films for fuel cell applications.