Fuel cells, as devices for direct conversion of the chemical energy of a fuel into electricity by electrochemical reactions, are among the key enabling technologies for the transition to a hydrogen-based economy. Of several different types of fuel cells under development today, polymer electrolyte fuel cells (PEFCs) have been recognized as a potential future power source for zero-emission vehicles. However, to become commercially viable, PEFCs have to overcome the barrier of high catalyst cost caused by the exclusive use of platinum and platinum-based catalysts in the fuel-cell electrodes. Here we demonstrate a new class of low-cost (non-precious metal)/(heteroatomic polymer) nanocomposite catalysts for the PEFC cathode, capable of combining high oxygen-reduction activity with good performance durability. Without any optimization, the cobalt-polypyrrole composite catalyst enables power densities of about 0.15 W cm(-2) in H2-O2 fuel cells and displays no signs of performance degradation for more than 100 hours. The results of this study show that heteroatomic polymers can be used not only to stabilize the non-precious metal in the acidic environment of the PEFC cathode but also to generate active sites for oxygen reduction reaction.

A class of non-precious metal composite catalysts for fuel cells

Introduction Technology for electrical power generation using enzyme catalysts, established four decades ago, has recently received increased attention associated with demand for micro-scale and implantable power supplies. The main challenges, namely the fragility of enzyme molecules, characteristic low current density, and poor fundamental understanding of redox biocatalysis, are currently being addressed from a variety of research perspectives, to take advantage of enzyme selectivity, low temperature and moderate pH activity, and manufacturability in small-scale devices. Such an effort benefits from four decades of multidisciplinary research in biosensors and related bioelectrochemical fields. This review paper summarizes the current state of enzymatic biofuel cell research in the context of foreseeable applications and assesses the future prospects of the technology. Emphasis is placed on device performance and engineering aspects, with a view toward practical portable power devices based on enzymatic biofuel cells. Research in biocatalytically modified electrodes, particularly for sensor applications, has provided a significant technological underpinning for current biofuel cell development. There exists significant overlap in technical requirements between sensors and biofuel cells, including chemical and mechanical stability, selectivity, and cost of materials. However, these two technologies diverge in the areas of current density, cell potential and stability. There exists extensive review literature in the area of biological fuel cells. Notably, Palmore and Whitesides summarized biological fuel cell concepts and performance up until about 1992. More recently, Katz and Willner discussed recent progress in novel electrode chemistries for both microbial and enzymatic fuel cells. We do not duplicate these valuable contributions, but instead focus on the strengths and weaknesses of state-of-art materials in the context of specific classes of applications, and point to areas where additional knowledge is currently needed to exploit biological fuel cells. With some exceptions, we focus on contributions made after 1992. Biofuel cells have traditionally been classified according to whether the catalytic enzymes were located inside or outside of living cells. If living cells are involved the system is considered to be microbial, and if not it is considered enzymatic. Although microbial fuel cells posses unique features unmatched by enzymatic cells, such as long-term stability and fuel efficiency, the power densities associated with such devices are typically much lower owing to resistance to mass transfer across cell membranes. Thus, microbial fuel cells are expected to find limited application in smallscale electronic devices. This review will focus on enzymatic biofuel cells. While such cells typically demonstrate reduced stability due to the limited lifetime of extracellular enzymes, and are typically unable to fully oxidize fuels, they allow for substantial concentration of catalysts and removal of mass transfer barriers and provide higher current and power densities, approaching the range of applicability to microand mini-scale electronics applications. Applications and Requirements The range of possible applications for biofuel cells may be broken down into three main subclasses: 1. Implantable power, such as micro-scale cells implanted in human or animal tissue, or larger cells implanted in blood vessels. 2. Power derived from ambient fuels or oxidants, mainly plant saps and juices, but extending to sewage and other waste streams. 3. Power derived from conventional fuels including hydrogen, methanol or higher alcohols. Classes 1 and 2 are closely related. The fuels available for implantable power, such as blood borne glucose or lactate, are ambient in the sense that they are present in a physiological environment in the absence of a fuel cell device. One major distinction between these two classes is that the ambient-fueled cell need not be implanted, and focuses on plantor waste-derived fuels, whereas the implantable cell focuses on animal-derived fuels and is present within the physiological system. Class 3 is unique in that this class competes with well-established conventional fuel cell technology. To a greater or lesser extent, all three classes share the fundamental technical requirements of high power density and high activity.

Enzymatic biofuel cells for implantable and microscale devices.

This article introduces the radical approach of applying alkaline anion-exchange membranes (AAEMs) to meet the current challenges with regards to direct methanol fuel cells (DMFCs). A review of the literature is presented with regards to the testing of fuel cells with alkaline membranes (fuelled with hydrogen or methanol) and also to candidate alkaline anion-exchange membranes for such an application. A brief review of the directly related patent literature is also included. Current and future research challenges are identified along with potential strategies to overcome them. Finally, the advantages and challenges with the direct electrochemical oxidation of alternative fuels are discussed, along with how the application of alkaline membranes in such fuel cells may assist in improving performance and fuel efficiency.

https://epubs.surrey.ac.uk/1696/1/fulltext.pdf

Prospects for Alkaline Anion-Exchange Membranes in Low Temperature Fuel Cells†

Multiwalled carbon nanotube-supported Pt (Pt/MWNT) nanocomposites were prepared by both the aqueous solution reduction of a Pt salt (HCHO reduction) and the reduction of a Pt ion salt in ethylene glycol solution. For comparison, a Pt/XC-72 nanocomposite was also prepared by the EG method. The Pt/MWNT catalyst prepared by the EG method has a high and homogeneous dispersion of spherical Pt metal particles with a narrow particle-size distribution. TEM images show that the Pt particle size is in the range of 2-5 nm with a peak at 2.6 nm, which is consistent with 2.5 nm obtained from the XRD broadening calculation. Surface chemical modifications of MWNTs and water content in EG solvent are found to be the key factors in depositing Pt particles on MWNTs. In the case of the direct methanol fuel cell (DMFC) test, the Pt/MWNT catalyst prepared by EG reduction is slightly superior to the catalyst prepared by aqueous reduction and displays significantly higher performance than the Pt/XC-72 catalyst. These differences in catalytic performance between the MWNT-supported or the carbon black XC-72-supported catalysts are attributed to a greater dispersion of the supported Pt particles when the EG method is used, in contrast to aqueous HCHO reduction and to possible unique structural and higher electrical properties when contrasting MWNTs to carbon black XC-72 as a support.

Preparation and Characterization of Multiwalled Carbon Nanotube-Supported Platinum for Cathode Catalysts of Direct Methanol Fuel Cells

3.8.2. Temperature Distribution Measurements 4749 3.8.3. Two-Phase Visualization 4750 3.8.4. Experimental Validation 4751 3.9. Modeling the Catalyst Layer at Pore Level 4751 3.10. Summary and Outlook 4752 4. Direct Methanol Fuel Cells 4753 4.1. Technical Challenges 4754 4.1.1. Methanol Oxidation Kinetics 4754 4.1.2. Methanol Crossover 4755 4.1.3. Water Management 4755 4.1.4. Heat Management 4756 4.2. DMFC Modeling 4756 4.2.1. Needs for Modeling 4756 4.2.2. DMFC Models 4756 4.3. Experimental Diagnostics 4757 4.4. Model Validation 4758 4.5. Summary and Outlook 4760 5. Solid Oxide Fuel Cells 4760 5.1. SOFC Models 4761 5.2. Summary and Outlook 4762 6. Closing Remarks 4763 7. Acknowledgments 4763 8. References 4763

Fundamental models for fuel cell engineering.

Recent advances in direct methanol fuel cells at Los Alamos National Laboratory

Direct methanol fuel cells: progress in cell performance and cathode research

The ionomer content in catalyst layers has a marked influence on direct methanol fuel cell (DMFC) performance. In an anode which contains unsupported PtRu as the catalyst, the recast ionomer may not always be necessary because the protonic conductivity of hydrous RuOx, the presence of which is inferred from the X‐ray diffraction pattern, may be sufficient to allow effective utilization of catalyst sites. To examine interpenetration of catalyst and membrane material as a possible explanation for the lack of an apparent need of added ionomer, ultramicrotomed thin sections of the membrane‐electrode assembly (MEA) were examined by scanning electron microscopy. Microscopic examination of such MEA cross sections revealed significant porosity in layers made by mixing unsupported catalysts with recast ionomer. Images of such sections did not reveal significant interpenetration, supporting the interpretation that hydrous RuOx may by itself provide sufficient protonic conductivity in PtRu catalyst layers prepared with no added ionomer. In contrast we show that the presence of recast ionomer in DMFC cathodes based on unsupported Pt as the catalyst is essential for optimum DMFC performance, because the recast ionomer is the primary source of protonic conductivity in the latter case. Having shown its potential function as proton conductor, we stress that Ru oxide is apparently not the key for maximizing DMFC anodic activity. © 1999 The Electrochemical Society. All rights reserved.

https://iopscience.iop.org/article/10.1149/1.1392642/pdf

Influence of Ionomer Content in Catalyst Layers on Direct Methanol Fuel Cell Performance

Abstract: Primary hyperparathyroidism (PHPT) usually presents with one of the classical symptoms of hypercalcemia - painful bones, psychic moans, abdominal groans or renal stones. It is well known that many a times PHPT can be asymptomatic. Asymptomatic parathyroid disease is identified on screening, when calcium is found elevated or when bone density is found to be unusually low. Impacted fish bone being a reason for neck imaging and thereby leading on to a diagnosis of PHPT is uncommon. Here we present the unusual way in which a left inferior parathyroid adenoma was diagnosed in a 51 year old lady. Keywords: Parathyroid adenoma, Hypercalcemia, Hyperparathyroidism, Foreign body, Fishbone. 

Sharon C Thomas

Papers

Recent advances in direct methanol fuel cells at Los Alamos National Laboratory

Direct methanol fuel cells: progress in cell performance and cathode research

Influence of Ionomer Content in Catalyst Layers on Direct Methanol Fuel Cell Performance

Fish Bone that Hooked an Adenoma-Primary Hyperparathyroidism