A comprehensive comparison of fuel options for fuel cell vehicles in China

Fuel cell vehicles (FCVs) offer the potential of ultra-low emissions combined with high efficiency. Proton exchange membrane (PEM) fuel cells being developed for vehicles require hydrogen as a fuel. Due to the various pathways of hydrogen generation, both onboard and off-board, the question about which fuel option is the most competitive for fuel cell vehicles is of great current interest. In this paper, a life-cycle assessment (LCA) model was made to conduct a comprehensive study of the energy, environmental, and economic (3E) impacts of FCVs from well to wheel (WTW). In view of the special energy structure of China and the timeframe, 10 vehicle/fuel systems are chosen as the study projects. The results show that methanol is the most suitable fuel to serve as the ideal hydrogen source for fuel cell vehicles in the timeframe and geographic regions of this study. On the other hand, gasoline and pure hydrogen can also play a role in short-term and regional applications, especially for local demonstrations of FCV fleets. (c) 2004 Elsevier B.V All rights reserved.

Structure and chemical composition of supported Pt-Sn electrocatalysts for ethanol oxidation

Carbon supported PtSn alloy and PtSnOx particles with nominal Pt:Sn ratios of 3:1 were prepared by a modified polyol method. High resolution transmission electron microscopy (HRTEM) and X-ray microchemical analysis were used to characterize the composition, size, distribution, and morphology of PtSn particles. The particles are predominantly single nanocrystals with diameters in the order of 2.0-3.0 nm. According to the XRD results, the lattice constant of Pt in the PtSn alloy is dilated due to Sn atoms penetrating into the Pt crystalline lattice. While for PtSnOx nanoparticles, the lattice constant of Pt only changed a little. HRTEM micrograph of PtSnOx clearly shows that the change of the spacing of Pt (111) plane is neglectable, meanwhile, SnO2 nanoparticles, characterized with the nominal 0.264 nm spacing of SnO2 (10 1) plane, were found in the vicinity of Pt particles. In contrast, the HRTEM micrograph of PtSn alloy shows that the spacing of Pt (111) plane extends to 0.234 nm from the original 0.226 nm. High resolution energy dispersive X-ray spectroscopy (HR-EDS) analyses show that all investigated particles in the two PtSn catalysts represent uniform Pt/Sn compositions very close to the nominal one. Cyclic voltammograms (CV) in sulfuric acid show that the hydrogen ad/desorption was inhibited on the surface of PtSn alloy compared to that on the surface of the PtSnOx catalyst. PtSnOx catalyst showed higher catalytic activity for ethanol electro-oxidation than PtSn alloy from the results of chronoamperometry (CA) analysis and the performance of direct ethanol fuel cells (DEFCs). It is deduced that the unchanged lattice parameter of Pt in the PtSnOx catalyst is favorable to ethanol adsorption and meanwhile, tin oxide in the vicinity of Pt nanoparticles could offer oxygen species conveniently to remove the CO-like species of ethanolic residues to free Pt active sites. (C) 2005 Elsevier Ltd. All rights reserved.

Design, fabrication and characterisation of components for microfluidic enzymatic biofuel cells

The concept of a biofuel cell takes inspiration from the natural capability of biological systems to catalyse the conversion of organic matter with a subsequent release of electrical energy. Enzymatic biofuel cells are intended to mimic the processes occurring in nature in a more controlled and efficient manner. Traditional fuel cells rely on the use of toxic catalysts and are often not easily miniaturizable making them unsuitable as implantable power sources. Biofuel cells however use highly selective protein catalysts and renewable fuels. As energy consumption becomes a global issue, they emerge as important tools for energy generation. The microfluidic platforms developed are intended to maximize the amount of electrical energy extracted from renewable fuels which are naturally abundant in the environment and in biological fluids. Combining microfabrication processes, chemical modification and biological surface patterning these devices are promising candidates for micro-power sources for future life science and electronic applications. This thesis considered four main aspects of a biofuel cell research. Firstly, concept of a miniature compartmentalized enzymatic biofuel cell utilizing simple fuels and operating in static conditions is verified and proves the feasibility of enzyme catalysis in energy conversion processes. Secondly, electrode and microfluidic channel study was performed through theoretical investigations of the flow and catalytic reactions which also improved understanding of the enzyme kinetics in the cell. Next, microfluidic devices were fabricated from cost-effective and disposable polymer materials, using the state-of-the-art micro-processing technologies. Integration of the individual components is difficult and multiple techniques to overcome these problems have been investigated. Electrochemical characterization of gold electrodes modified with Nanoporous Gold Structures is also performed. Finally, two strategies for enzyme patterning and encapsulation are discussed. Several protein catalysts have been effectively immobilized on the surface of commercial and microfabricated electrodes by electrochemically assisted deposition in sol-gel and poly-(o-phenylenediamine) polymer matrices and characterised with confirmed catalytic activity.

Origin of Low CO2 Selectivity on Platinum in the Direct Ethanol Fuel Cell

Calculated answer: First-principles calculations have been applied to calculate the energy barrier for the key step in CO formation on a Pt surface (see picture; Pt blue, Pt atoms on step edge yellow) to understand the low CO2 selectivity in the direct ethanol fuel cell. The presence of surface oxidant species such as O (brown bar) and OH (red bar) led to an increase of the energy barrier and thus an inhibition of the key step. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

A quantitative research on S- and SO2-poisoning Pt/Vulcan carbon fuel cell catalyst

A quantitative research on S and SO2 poisoning Pt/Vulcan carbon (Pt/VC) catalysts for fuel cells was conducted by the three-electrode method. Pt/VC electrodes were contaminated by submersion in a SO2- containing solution made up of 0.2 mM Na2SO3 and 0.5 M H2SO4 for different periods of time, and held at 0.05 V (vs. RHE) in 0.5 M H2SO4 solutions in order to gain zero-valence sulfur (S0) poisoned electrodes. The sulfur coverage of Pt was determined from the total charge consumed as the sulfur was oxidized from S0 at 0.05 V (vs. RHE) to sulfate at >1.1 V (vs. RHE). The summation of initial coverage of S0 (S) and coverage of H (H) are approximately equal to 1 (H + S = 1) when 0.5

Measuring oxygen reduction/evolution reactions on the nanoscale

The efficiency of fuel cells and metal-air batteries is significantly limited by the activation of oxygen reduction and evolution reactions. Despite the well-recognized role of oxygen reaction kinetics on the viability of energy technologies, the governing mechanisms remain elusive and until now have been addressable only by macroscopic studies. This lack of nanoscale understanding precludes optimization of material architecture. Here, we report direct measurements of oxygen reduction/evolution reactions and oxygen vacancy diffusion on oxygen-ion conductive solid surfaces with sub-10 nm resolution. In electrochemical strain microscopy, the biased scanning probe microscopy tip acts as a moving, electrocatalytically active probe exploring local electrochemical activity. The probe concentrates an electric field in a nanometre-scale volume of material, and bias-induced, picometre-level surface displacements provide information on local electrochemical processes. Systematic mapping of oxygen activity on bare and platinum-functionalized yttria-stabilized zirconia surfaces is demonstrated. This approach allows direct visualization of the oxygen reduction/evolution reaction activation process at the triple-phase boundary, and can be extended to a broad spectrum of oxygen-conductive and electrocatalytic materials.

The Role of Water and Adsorbed Hydroxyls on Ethanol Electrochemistry on Pd: New Mechanism, Active Centers and Energetics for Direct Ethanol Fuel Cell Running in Alkaline Medium

First principles calculations with molecular dynamics are
utilized to simulate a simplified electrical double layer formed in the
active electric potential region during the electrocatalytic oxidation of
ethanol on Pd electrodes running in an alkaline electrolyte. Our
simulations provide an atomic level insight into how ethanol oxidation
occurs in fuel cells: New mechanisms in the presence of the simplified
electrical double layer are found to be different from the traditional
ones; through concerted-like dehydrogenation paths, both acetaldehyde
and acetate are produced in such a way as to avoid a variety of
intermediates, which is consistent with the experimental data obtained
from in situ FTIR spectroscopy. Our work shows that adsorbed OH on
the Pd electrode rather than Pd atoms is the active center for the
reactions; the dissociation of the C−H bond is facilitated by the
adsorption of an OH− anion on the surface, resulting in the formation
of water. Our calculations demonstrate that water dissociation rather than H desorption is the main channel through which
electrical current is generated on the Pd electrode. The effects of the inner Helmholtz layer and the outer Helmholtz layer are
decoupled, with only the inner Helmholtz layer being found to have a significant impact on the mechanistics of the reaction. Our
results provide atomic level insight into the significance of the simplified electrical double layer in electrocatalysis, which may be
of general importance.

An improved TLBO with elite strategy for parameters identification of PEM fuel cell and solar cell models

Clean and renewable energy generation and supply has drawn much attention worldwide in recent years, the proton exchange membrane (PEM) fuel cells and solar cells are among the most popular technologies. Accurately modeling the PEM fuel cells as well as solar cells is critical in their applications, and this involves the identification and optimization of model parameters. This is however challenging due to the highly nonlinear and complex nature of the models. In particular for PEM fuel cells, the model has to be optimized under different operation conditions, thus making the solution space extremely complex. In this paper, an improved and simplified teaching-learning based optimization algorithm (STLBO) is proposed to identify and optimize parameters for these two types of cell models. This is achieved by introducing an elite strategy to improve the quality of population and a local search is employed to further enhance the performance of the global best solution. To improve the diversity of the local search a chaotic map is also introduced. Compared with the basic TLBO, the structure of the proposed algorithm is much simplified and the searching ability is significantly enhanced. The performance of the proposed STLBO is firstly tested and verified on two low dimension decomposable problems and twelve large scale benchmark functions, then on the parameter identification of PEM fuel cell as well as solar cell models. Intensive experimental simulations show that the proposed STLBO exhibits excellent performance in terms of the accuracy and speed, in comparison with those reported in the literature.

Preliminary Investigation on the Electrochemical Activity of Butanol Isomers as Potential Fuel for Direct Alcohol Fuel Cell

A preliminary investigation of electrocatalytic oxidation activity ofbutanol isomers has been carried out to study their potential asfuels for direct alcohol fuel cells. The electrochemical study wascarried out on Pt and Pd electrodes using a three electrode cell setup in alkaline media. The primary alcohol isomers of butanol wereobserved to behave similarly in their electrochemical reactionswhereas 2-butanol showed completely different oxidation featureson both catalysts. For example, no poisoning effects were observedfor 2- butanol unlike for the primary butanol isomers. In contrast,tert-butanol did not show any oxidation reaction on Pt and Pdelectrodes. Furthermore, Pd was not active at all in acidic mediafor butanol oxidation. The reactivity of butanol isomers were foundto be in the order n-butanol>iso-butanol>2-butanol>tert-butanolbased on the oxidation current density values.

Enhanced bio-decolourisation of acid orange 7 by Shewanella oneidensis through co-metabolism in a microbial fuel cell

The decolourisation of acid orange 7 (AO7) (C.I.15510) through co-metabolism in a microbial fuel cell by Shewanella oneidensis strain 14063 was investigated with respect to the kinetics of decolourisation, extent of degradation and toxicity of biotransformation products. Rapid decolourisation of AO7 (>98% within 30 h) was achieved at all tested dye concentrations with concomitant power production. The aromatic amine degradation products were recalcitrant under tested conditions. The first-order kinetic constant of decolourisation (k) decreased from 0.709 ± 0.05 h−1 to 0.05 ± 0.01 h−1 (co-substrate – pyruvate) when the dye concentration was raised from 35 mg l−1 to 350 mg l−1. The use of unrefined co-substrates such as rapeseed cake, corn-steep liquor and molasses also indicated comparable or better AO7 decolourisation kinetic constant values. The fully decolourised solutions indicated increased toxicity as the initial AO7 concentration was increased. This work highlights the possibility of using microbial fuel cells to achieve high kinetic rates of AO7 decolourisation through co-metabolism with concomitant electricity production and could potentially be utilised as the initial step of a two stage anaerobic/aerobic process for azo dye biotreatment.

Molecular aluminum hydrides identified by inelastic neutron scattering during H-2 regeneration of catalyst-doped NaAlH4

Catalyst-doped sodium aluminum hydrides have been intensively studied as solid hydrogen carriers for onboard proton-exchange membrane (PEM) fuel cells. Although the importance of catalyst choice in enhancing kinetics for both hydrogen uptake and release of this hydride material has long been recognized, the nature of the active species and the mechanism of catalytic action are unclear. We have shown by inelastic neutron scattering (INS) spectroscopy that a volatile molecular aluminum hydride is formed during the early stage of H-2 re-eneration of a depleted, catalyst-doped sodium aluminum hydride. Computational modeling of the INS spectra suggested the formation of AlH3 and oligomers (AlH3)(n) (Al2H6, Al3H9, and Al4H12 clusters), which are pertinent to the mechanism of hydrogen storage. This paper demonstrates, for the first time, the existence of these volatile species.

Doped sodium aluminium hydrides as hydrogen storage materials: characterizations and mechanistic insights

The dehydriding and rehydriding of sodium aluminium hydride, NaAlR4, is kinetically enhanced and rendered reversible in the solid state upon doping with a small amount of catalyst species, such as titanium, zirconium or tin. The catalyst doped hydrides appear to be good candidates for development as hydrogen carriers for onboard proton exchange membrane (PEM) fuel cells because of their relatively low operation temperatures (120-150 degrees C) and high hydrogen carrying capacities (4-5 wt.%). However, the nature of the active catalyst species and the mechanism of catalytic action are not yet known. In particular, using combinations of Ti and Sri compounds as dopants, a cooperative catalyst effect of the metals Ti and Sn in enhancing the hydrogen uptake and release kinetics is hereby reported. In this paper, characterization techniques including XRD, XPS, TEM, EDS and SEM have been applied on this material. The results suggest that the solid state phase changes during the hydriding and dehydriding processes are assisted through the interaction of a surface catalyst. A mechanism is proposed to explain the catalytic effect of the Sn/Ti double dopants on this hydride.

Classification and fault detection methods for fuel cell monitoring and quality control

In this paper, various types of fault detection methods for fuel cells are compared. For example, those that use a model based approach or a data driven approach or a combination of the two. The potential advantages and drawbacks of each method are discussed and comparisons between methods are made. In particular, classification algorithms are investigated, which separate a data set into classes or clusters based on some prior knowledge or measure of similarity. In particular, the application of classification methods to vectors of reconstructed currents by magnetic tomography or to vectors of magnetic field measurements directly is explored. Bases are simulated using the finite integration technique (FIT) and regularization techniques are employed to overcome ill-posedness. Fisher's linear discriminant is used to illustrate these concepts. Numerical experiments show that the ill-posedness of the magnetic tomography problem is a part of the classification problem on magnetic field measurements as well. This is independent of the particular working mode of the cell but influenced by the type of faulty behavior that is studied. The numerical results demonstrate the ill-posedness by the exponential decay behavior of the singular values for three examples of fault classes.