Akeel A. Shah

Recent progress and continuing challenges in bio-fuel cells. Part I: Enzymatic cells

Recent developments in bio-fuel cell technology are reviewed. A general introduction to bio-fuel cells, including their operating principles and applications, is provided. New materials and methods for the immobilisation of enzymes and mediators on electrodes, including the use of nanostructured electrodes are considered. Fuel, mediator and enzyme materials (anode and cathode), as well as cell configurations are discussed. A detailed summary of recently developed enzymatic fuel cell systems, including performance measurements, is conveniently provided in tabular form. The current scientific and engineering challenges involved in developing practical bio-fuel cell systems are described, with particular emphasis on a fundamental understanding of the reaction environment, the performance and stability requirements, modularity and scalability. In a companion review (Part II), new developments in microbial fuel cell technologies are reviewed in the context of fuel sources, electron transfer mechanisms, anode materials and enhanced O(2) reduction.

Recent progress and continuing challenges in bio-fuel cells. Part II: microbial

Recent key developments in microbial fuel cell technology are reviewed. Fuel sources, electron transfer mechanisms, anode materials and enhanced O(2) reduction are discussed in detail. A summary of recently developed microbial fuel cell systems, including performance measurements, is conveniently provided in tabular form. The current challenges involved in developing practical bio-fuel cell systems are described, with particular emphasis on a fundamental understanding of the reaction environment, the performance and stability requirements, modularity and scalability. This review is the second part of a review of bio-fuel cells. In Part 1 a general introduction to bio-fuel cells, including their operating principles and applications, was provided and enzymatic fuel cell technology was reviewed.

Modeling and Simulation of the Degradation of Perfluorinated Ion-Exchange Membranes in PEM Fuel Cells

A polymer-electrolyte membrane fuel cell model that incorporates chemical degradation in perlfluorinated sulfonic acid membranes is developed. The model is based on conservation principles and includes a detailed description of the transport phenomena. A degradation sub-model describes the formation of hydrogen peroxide \/\it via\/ distinct mechanisms in the cathode and anode, together with the subsequent formation of radicals \/\it via\/ Fenton reactions involving metal-ion impurities. The radicals participate in the decomposition of reactive end groups to form carboxylic acid, hydrogen fluoride and CO_2. Degradation proceeds through unzipping of the polymer backbone and cleavage of the side chains. Simulations are presented and the numerical code is shown to be extremely time efficient. Known trends with respect to operating conditions are qualitatively captured and the exhibited behaviour is shown to be robust to changes in the rate constants. The feasibility of a chemical degradation mechanism based on peroxide and radical formation is discussed.

A Dynamic Unit Cell Model for the All-Vanadium Flow Battery

In this paper, a mathematical model for the all-vanadium battery is presented and analytical solutions are derived. The model is based on the principles of mass and charge conservation, incorporating the major resistances, the electrochemical reactions and recirculation of the electrolyte through external reservoirs. Comparisons between the model results and experimental data show good agreement over practical ranges of the vanadium concentrations and the flow rate. The model is designed to provide accurate, rapid solutions at the unit-cell scale, which can be used for control and monitoring purposes. Crucially, the model relates the process time and process conditions to the state of charge via vanadium concentrations.

A Mathematical Model for the Soluble Lead-Acid Flow Battery

The soluble lead-acid battery is a redox flow cell that uses a single reservoir to store the electrolyte and does not require a microporous separator or membrane, allowing a simpler design and a substantial reduction in cost. In this paper, a transient model for a reversible, lead-acid flow battery incorporating mass and charge transport and surface electrode reactions is developed. The charge–discharge behavior is complicated by the formation and subsequent oxidation of a complex oxide layer on the positive electrode surface, which is accounted for in the model. The full charge/discharge behavior over two cycles is simulated for many cases. Experiments measuring the cell voltage during repeated charge–discharge cycles are described, and the simulation results are compared to the laboratory data, demonstrating good agreement. The model is then employed to investigate the effects of variations in the current density on the performance of the battery.

Flame balls with thermally sensitive intermediate kinetics

Spherical flame balls are studied using a model for the chemical kinetics which involves a non-exothermic autocatalytic reaction, describing the chain-branching generation of a chemical radical and an exothermic completion reaction, the rate of which does not depend on temperature. When the chain-branching reaction has a large activation temperature, an asymptotic structure emerges in which the branching reaction generates radicals and consumes fuel at a thin flame interface, although heat is produced and radicals are consumed on a more distributed scale. Another model, based more simply, but less realistically, on the generation of radicals by decomposition of the fuel, provides exactly the same leading order matching conditions. These can be expressed in terms of jump conditions across a reaction sheet that are linear in the dependent variables and their normal gradients. Using these jump conditions, a reactive–diffusive model with linear heat loss then leads to analytical solutions that are multivalued for small enough levels of heat loss, having either a larger or a smaller radius of the interface where fuel is consumed. The same properties are found, numerically, to persist as the activation temperature of the branching reaction is reduced to values that seem to be typical for hydrocarbon chemistry. Part of the solution branch with larger radius is shown to become stable for low enough values of the Lewis number of the fuel.

Membrane-less organic–inorganic aqueous flow batteries with improved cell potential

A membrane-less organic-inorganic flow battery based on zinc and quinone species is proposed. By virtue of the slow dissolution rate of the deposited anode (<11.5 mg h-1 cm-2), the battery has a cell voltage of ca. 1.52 V with an average energy efficiency of ca. 73% at 30 mA cm-2 over 12 cycles.

Stability of a Spherical Flame Ball in a Porous Medium

Gaseous flame balls and their stability to symmetric disturbances are studied numerically and asymptotically, for large activation temperature, within a porous medium that serves only to exchange heat with the gas. Heat losses to a distant ambient environment, affecting only the gas, are taken to be radiative in nature and are represented using two alternative models. One of these treats the heat loss as being constant in the burnt gases and linearizes the radiative law in the unburnt gas (as has been studied elsewhere without the presence of a solid). The other does not distinguish between burnt and unburnt gas and is a continuous dimensionless form of Stefans law, having a linear part that dominates close to ambient temperatures and a fourth power that dominates at higher temperatures. Numerical results are found to require unusually large activation temperatures in order to approach the asymptotic results. The latter involve two branches of solution, a smaller and a larger flame ball, provided heat losses are not too high. The two radiative heat loss models give completely analogous steady asymptotic solutions, to leading order, that are also unaffected by the presence of the solid which therefore only influences their stability. For moderate values of the dimensionless heat-transfer time between the solid and gas all flame balls are unstable for Lewis numbers greater than unity. At Lewis numbers less than unity, part of the branch of larger flame balls becomes stable, solutions with the continuous radiative law being stable over a narrower range of parameters. In both cases, for moderate heat-transfer times, the stable region is increased by the heat capacity of the solid in a way that amounts, simply, to decreasing an effective Lewis number for determining stability, just as if the heat-transfer time was zero.

The Ignition of Low-Exothermicity Solids by Local Heating

In this paper we bring together a number of recent studies associated with the burning of low-exothermicity porous materials that are inadvertently, or otherwise, exposed to a maintained heat source (hotspot). Additionally, we provide some new results in the form of dimensionless ignition criteria, which allow us to generalize previous results to a broader class of materials and to larger sample sizes. It is shown that systems of the type described can be represented by a hierarchy of mathematical models, depending on whether oxygen is in limited supply, is not required (as in the case of thermal decomposition), and/or a significant volume of gaseous products is present. We summarize the behaviour of systems in which gas motion through the solid pores has a negligible effect, including cases where the burning is dependent on a limited supply of oxygen. The effects of geometry and initial-boundary conditions are discussed. Finally, for reactions involving gaseous products, we present numerical solutions to a system of equations that incorporates the gas motion through the solid pores by employing Darcys law. In comparison with the previous cases, it is demonstrated that ignition of low-exothermicity materials is more difficult to achieve (a larger hotspot heat-flux is required), essentially because of transportation of heat by advection towards the unburnt solid, and, consequently, increased reactant depletion. Furthermore, ignition will always take place away from the hot-spot surface; this is in complete contrast to highly exothermic materials, in which reactant depletion is negligible during the early stages of ignition, and in which ignition occurs at the hotspot boundary.

High order effects in one step reaction sheet jump conditions for premixed flames

The differences need to be understood between the leading order jump conditions, often assumed at a flame sheet in combustion theory, and the actual effect of a one step chemical reaction governed by Arrhenius kinetics. These differences are higher order in terms of a large activation temperature analysis and can be estimated using an asymptotic approach. This paper derives one order of asymptotic correction to the leading order jump conditions that are normally used for describing premixed laminar combustion, providing additional contributions that are due to curvature, flow through the flame sheet and the temperature gradient into the burnt gas. As well as offering more accurate asymptotic results, these can be used to estimate the errors that are inherent in adopting only the leading order version and they can point towards major qualitative changes that can occur at finite activation temperatures in some cases. Applied to steady non-adiabatic flame balls it is found that the effect of a non-zero temperature gradient in the burnt gas provokes the most serious deficiency in the asymptotic approach.