Frank C. Walsh

Electrochemical corrosion of unalloyed copper in chloride media––a critical review

The literature dealing with the electrochemical corrosion characteristics of unalloyed copper in aqueous chloride media is examined. The enormous quantity of polarisation and mixed/corrosion potential data that has been made available in the literature over the last 50 years has been compiled and discussed in a comprehensive review. For a wide range of electrode geometries, the importance of the chloride ion and the mass transport of anodic corrosion products on the corrosion behaviour of copper are made clear for both freshly polished and ‘filmed’ surfaces.

Ionic Conductivity of an Extruded Nafion 1100 EW Series of Membranes

The proton conductivity of a series of extruded Nafion membranes @of equivalent weight ~EW! of 1100 and nominal dry thickness of 51, 89, 127, and 178 mm# has been studied. Measurements were made in 1 M H2SO4 at 298 K using a four-electrode, dc technique. The membrane area resistance increases with thickness, as expected, from 0.07 to 0.16 V cm2 for Nafion 112 and Nafion 117, respectively. However, in contrast to the published literature, after correcting for the membrane thickness, the conductivity of the membranes decreases with decreasing membrane thickness. For example, values of 0.083 and 0.16 S cm21 were obtained for Nafion 112 and 117 membranes, respectively. In situ current-interrupt measurements in a proton exchange membrane fuel cell confirmed the relatively poor conductivity of the membrane electrode assemblies ~MEAs! based on the thinner membranes. While a high contact resistance to the electrodes may have contributed to the in situ MEA resistance, water balance measurements over the MEA showed that the high resistance was not due to a low water content or to an uneven water distribution in the MEAs. The implications of the findings for the understanding of the membrane properties are discussed.

Progress in redox flow batteries, remaining challenges and their applications in energy storage

Redox flow batteries, which have been developed over the last 40 years, are used to store energy on the medium to large scale, particularly in applications such as load levelling, power quality control and facilitating renewable energy deployment. Various electrode materials and cell chemistries have been proposed; some of the successful systems have been demonstrated on a large-scale in the range of 10 kW–10 MW. Enhanced performance is attributable to the improvements in electrodes, separator materials and an increasing awareness of cell design. This comprehensive review provides a summary of the overall development of redox flow battery technology, including proposed chemistries, cell components and recent applications. Remaining challenges and directions for further research are highlighted.

Electrodes based on Magnéli phase titanium oxides: the properties and applications of Ebonex® materials

Magnéli phases are a range of substoichiometric oxides of titanium of the general formula TinO2n−1, (where n is between 4 and 10) produced from high temperature reduction of titania in a hydrogen atmosphere. These blue/black ceramic materials exhibit a conductivity comparable to that of graphite and can be produced in a number of forms, such as tiles, rods, fibres, foams and powders. While these materials have been studied for many years, they have only recently received interest for use as ceramic electrode materials, commercially termed ‘Ebonex®’, and are beginning to challenge precious metal coated anodes for some applications in aggressive electrolytes. Other uses for these materials include electrowinning, electroplating, battery materials, impressed current cathodic protection anodes, electrochemical soil remediation, oxidation of organic wastes, flexible cable materials and electrophoresis. The scope of this review considers the structure and properties of Magnéli phase titanium oxide materials, together with their electrochemical behaviour and applications.

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.

The electrochemistry of l-cystine and l-cysteine: Part 1: Thermodynamic and kinetic studies

Abstract Thermodynamic and kinetic aspects of the electrochemistry Of l -cystine reduction and l -cysteine oxidation are reviewed. Both mercury and a range of solid electrodes are considered. In the former case, cysteinate complex formation occurs; in the case of solid electrodes, reactant adsorption is a complicating factor. At both types of electrode, the kinetics of electron transfer and mass transport of reactant can become an important rate-determining step. The implications of thermodynamic and kinetic studies on the electrosynthesis of l -cysteine are highlighted.

Energy and Battery Management of a Plug-In Series Hybrid Electric Vehicle Using Fuzzy Logic

Fuzzy logic is used to define a new quantity called the battery working state (BWS), which is based on both battery terminal voltage and state of charge (SOC), to overcome the problem of battery over-discharge and associated damage resulting from inaccurate estimates of the SOC. The BWS is used by a fuzzy logic energy-management system of a plug-in series hybrid electric vehicle (HEV) to make a decision on the power split between the battery and the engine, based on the BWS and vehicle power demand, while controlling the engine to work in its fuel economic region. The fuzzy logic management system was tested in real time using an HEV simulation test bench with a real battery in the loop. Simulation results are presented to demonstrate the performance of the proposed fuzzy logic energy-management system under different driving conditions and battery SOCs. The results indicate that the fuzzy logic energy-management system using the BWS was effective in ensuring that the engine operates in the vicinity of its maximum fuel efficiency region while preventing the battery from over-discharging.

Electrodeposited lead dioxide coatings

Lead dioxide coatings on inert substrates such as titanium and carbon now offer new opportunities for a material known for 150 years. It is now recognised that electrodeposition allows the preparation of stable coatings with different phase structures and a wide range of surface morphologies. In addition, substantial modification to the physical properties and catalytic activities of the coatings are possible through doping and the fabrication of nanostructured deposits or composites. In addition to applications as a cheap anode material in electrochemical technology, lead dioxide coatings provide unique possibilities for probing the dependence of catalytic activity on layer composition and structure (critical review, 256 references).

Plasma electrolytic oxidation (PEO) for production of anodised coatings on lightweight metal (Al, Mg, Ti) alloys

Abstract The introduction of plasma electrolytic oxidation (PEO) as a surface finishing technique has enabled a range of hard, dense oxide coatings to be produced on aluminium, magnesium, titanium and other lightweight alloy substrates. As with all surface coating technologies, successful development of PEO coatings requires adequate attention to substrate pretreatment together with careful control of electrolyte conditions and process variables. The principles and applications of the PEO coating process are considered, including the fundamentals of oxide deposition, the technology involved and the typical characteristics of the coatings. Industrial applications are considered together with their coating requirements. Plasma electrolytic oxidation coating is a specialised but well developed process. Suitable control of electrolyte and process conditions can realise a novel range of coatings having technologically attractive physical and chemical properties. The development of PEO technology over the last decade has provided coatings having controlled appearance, hardness, corrosion resistance and other tribological properties across an extending range of industrial sectors. Continuing developments are concisely reviewed and the PEO process is illustrated by the characterisation of anodised coatings on an AZ91 magnesium alloy surface.

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.