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Results for “Solid Acid Fuel Cell”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Hydrogen oxidation kinetics on platinum-palladium bimetallic thin films for solid acid fuel cells

Solid acid fuel cells (SAFCs) based on the proton-conductive electrolyte CsH 2 PO 4 have shown promising power densities at an intermediate operating temperature of ~250 °C. However, Pt loadings in SAFCs remain higher than desirable, and the electrocatalysis mechanisms in these devices are still unknown. Here, hydrogen oxidation kinetics on Pt and Pt-Pd bimetallic thin film electrodes on CsH 2 PO 4 have been evaluated to establish the potential for a beneficial role of Pd in SAFC anodes. Symmetric cells fabricated by depositing a metal film on both sides of electrolyte discs are characterized for studying hydrogen electro-oxidation across the gas|metal|CsH 2 PO 4 structure. It was found that Pd reacts with CsH 2 PO 4 , forming palladium phosphide at the metal-electrolyte interface. Accordingly, the activity of Pd was examined in a bilayer geometry of Pd|Pt|CsH 2 PO 4 |Pt|Pd. The bilayer Pt|Pd films showed much higher activity for hydrogen electro-oxidation than films of Pt alone, as measured by AC impedance spectroscopy. Ex situ low energy ion scattering and scanning transmission electron microscopy revealed that Pd diffused into the Pt layer under operating conditions. The dramatic impact of Pd along with its presence throughout the film suggests that it catalyzes reactions at both the metal-gas and metal-electrolyte interfaces, as well as increasing hydrogen diffusion rates through the films.

36 MATERIALS SCIENCE↗

Solid Acid Fuel Cell Stack for APU Applications

Solid acid fuel cell technology affords the opportunity to operate at the 200-300 degree centigrade regime that would allow for more fuel flexibility, compared to polymer electrode membrane fuel cell, while avoiding the relatively more expensive and complex system components required by solid oxide fuel cell. This project addresses many factors such as MEA size scalability, fuel robustness, stability, etc., that are essential for successful commercialization of the technology.

08 HYDROGEN↗

A durable polyvinyl butyral-CsH 2 PO 4 composite electrolyte for solid acid fuel cells

We report a composite electrolyte membrane composed of polyvinyl butyral (PVB) and CsH 2 PO 4 has been prepared via a facile and cost-effective method for solid acid fuel cells. The effect of PVB content on conductivity, mechanical integrity, and fuel cell performance is investigated. A minimum amount of 3 wt% PVB in the CsH 2 PO 4 -based composite electrolyte not only offers the required mechanical integrity but also allows high conductivity (~28 mS cm -1 at 260 °C). Single cells based on the composite electrolytes demonstrate a peak power density of 108 mW cm -2 at 260 °C. Almost no degradation in electrochemical performance could be observed during the stability test for 10 h and three thermal-cycling test in H 2 /O 2 fuel cell, indicating the promising application of the composite electrolyte in solid acid fuel cells.

25 ENERGY STORAGE↗

Atomic layer deposition of Pt@CsH 2 PO 4 for the cathodes of solid acid fuel cells

Atomic layer deposition (ALD) has been used to apply continuous Pt films on powders of the solid acid CsH 2 PO 4 (CDP), in turn, used in the preparation of cathodes in solid acid fuel cells (SAFCs). The film deposition was carried out at 150 °C using trimethyl(methylcyclopentadienyl)platinum (MeCpPtMe 3 ) as the Pt source and ozone as the reactant for ligand removal. Chemical analysis showed a Pt growth rate of 0.09 ± 0.01 wt%/cycle subsequent to an initial nucleation delay of 84 ± 20 cycles. Electron microscopy revealed the contiguous nature of the films prepared using 200 or more cycles. The cathode overpotential (0.48 ± 0.02 V at a current density of 200 mA/cm 2 ) was independent of Pt deposition amount beyond the minimum required to achieve these continuous films. The cell electrochemical characteristics were moreover extremely stable with time, with the cathode overpotentials increasing by no more than 10 mV over a 100 h period of measurement. So, ALD holds promise as an effective tool in the preparation of SAFC cathodes with high activity and excellent stability.

25 ENERGY STORAGE↗

From Fundamental Interfacial Reaction Kinetics to Macroscopic Current–Voltage Characteristics: Case Study of Solid Acid Fuel Cell Limitations and Possibilities

The unique properties of solid acid electrolytes, in particular CsH 2 PO 4 , are in many ways ideal for fuel cell operation. However, the technology is constrained by high cathode overpotentials. Here a simplified cathode geometry is employed to obtain the fundamental electrochemical parameters (exchange current density and charge transfer coefficient) describing the oxygen reduction reaction (ORR) at the CsH 2 PO 4 -Pt-gas interface. The parameters are incorporated into a 1D model of the voltage–current characteristics of realistic SAFC cathodes, which reproduced the measured polarization behavior of such cathodes without recourse to fitting adjustable parameters. Following this validation, the model is utilized to evaluate the impact of changes to cathode properties, microstructure, and operating conditions. Of these, the charge transfer coefficient, measured to have a value of ≈0.6 for ORR on Pt in the SAFC cathode environment, is found to have the greatest impact on power output. Nevertheless, even without material modifications, a combination of microstructural and operational modifications are identified with projected performance metrics meeting Department of Energy targets (0.8 V at 300 mA cm –2 , and peak power density of 1 W cm –2 ), albeit at high Pt loadings. However, the analysis indicates that truly meaningful advances will likely necessitate the discovery of alternative ORR catalysts.

36 MATERIALS SCIENCE↗

Activity and Evolution of Vapor Deposited Pt-Pd Oxygen Reduction Catalysts for Solid Acid Fuel Cells

The performance of hydrogen fuel cells based on the crystalline solid proton conductor CsH2PO4 is circumscribed by the mass activity of platinum oxygen reduction catalysts in the cathode. Here we report on the first application of an alloy catalyst in a solid acid fuel cell, and demonstrate an activity 4.5 times greater than Pt at 0.8 V. These activity enhancements were obtained with platinum-palladium alloys that were vapor-deposited directly on CsH2PO4 at 210 C. Catalyst mass activity peaks at a composition of 84 at% Pd, though smaller activity enhancements are observed for catalyst compositions exceeding 50 at% Pd. Prior to fuel cell testing, Pd-rich catalysts display lattice parameter expansions of up to 2% due to the presence of interstitial carbon. After fuel cell testing, a Pt-Pd solid solution absent of lattice dilatation and depleted in carbon is recovered. The structural evolution of the catalysts is correlated with catalyst de-activation.

Papandrew, Alexander B↗

Bottom up synthesis of boron-doped graphene for stable intermediate temperature fuel cell electrodes

The high surface area and electrical conductivity of few-layered graphene would make it an ideal catalyst support and electrode in fuel cells apart from its susceptibility to oxidative corrosion. Here we report the single-step, bottom-up synthesis of oxidation-resistant boron-doped graphene and show its increased stability in the aggressive electrochemical environment of intermediate temperature solid acid fuel cells (SAFCs). Boron was shown to alter the growth mode of single walled carbon nanohorns by laser vaporization to produce high yields of thin (<20 layer) boron-doped (2–3 at.%) crystalline flakes of turbostratic graphene (B-GLF). Alternatively, adding partial pressures of hydrogen less effectively shifted the growth mode of SWCNHs toward planar, turbostratic graphene-like flakes (GLFs). Thermogravimetric analysis indicates that boron-doping enhances the oxidation resistance of few-layer GLFs by >140 °C, with large fractions of multilayered B-GLFs surviving 10 °C/min ramps to 1000 °C. These B-GLFs provided a stable Pt catalyst support and electrode over 40 h operation in SAFCs with cesium dihydrogen phosphate electrolyte operating at 250 °C, as opposed to undoped GLFs or SWCNHs which were nearly completely consumed. Furthermore, the facile synthesis and oxidation-resistant properties of boron-doped GLF appear promising for graphene applications in oxidizing environments.

25 ENERGY STORAGE↗

Nanostructured carbon electrocatalyst supports for intermediate-temperature fuel cells: Single-walled versus multi-walled structures

It is unknown if nanostructured carbons possess the requisite electrochemical stability to be used as catalyst supports in the cathode of intermediate-temperature solid acid fuel cells (SAFCs) based on the CsH2PO4 electrolyte. To investigate this application, single-walled carbon nanohorns (SWNHs) and multi-walled carbon nanotubes (MWNTs) were used as supports for Pt catalysts in SAFCs operating at 250 °C. SWNH-based cathodes display greater maximum activity than their MWNT-based counterparts at a cell voltage of 0.8 V, but are unstable in the SAFC cathode as a consequence of electrochemical carbon corrosion. MWNT-based cells are resistant to this effect and capable of operation for at least 160 h at 0.6 V and 250 °C. Cells fabricated with nanostructured carbon supports are more active (52 mA cm -1 vs. 28 mA cm -1 at 0.8 V) than state-of-the-art carbon-free formulations while simultaneously displaying enhanced Pt utilization (40 mA mgPt -1 vs. 16 mA mgPt -1 at 0.8 V). Finally, these results suggest that MWNTs are a viable support material for developing stable, high-performance, low-cost air electrodes for solid-state electrochemical devices operating above 230 °C.

25 ENERGY STORAGE↗

Spontaneous formation of nanoparticles on electrospun nanofibres

We report the spontaneous formation of nanoparticles on smooth nanofibres in a single-step electrospinning process, as an inexpensive and scalable method for producing high-surface-area composites. Layers of nanofibres, containing the proton conducting electrolyte, caesium dihydrogen phosphate, are deposited uniformly over large area substrates from clear solutions of the electrolyte mixed with polymers. Under certain conditions, the normally smooth nanofibres develop caesium dihydrogen phosphate nanoparticles in large numbers on their external surface. The nanoparticles appear to originate from the electrolyte within the fibres, which is transported to the outer surface after the fibres are deposited, as evidenced by cross-sectional imaging of the electrospun fibres. The presence of nanoparticles on the fibre surface yields composites with increased surface area of exposed electrolyte, which ultimately enhances electrocatalytic performance. Indeed, solid acid fuel cells fabricated with electrodes from processed nanofibre-nanoparticle composites, produced higher cell voltage as compared to fuel cells fabricated with state-of-the-art electrodes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Degradation and recovery of solid oxide fuel cell performance by control of cathode surface acidity: Case study – Impact of Cr followed by Ca infiltration

Solid oxide fuel cells (SOFC) have attracted attention as clean and efficient energy conversion devices with low emissions. However, several degradation mechanisms limit the electrochemical performance of current SOFCs, with cathode degradation due to Cr-poisoning from metal interconnects particularly problematic. The acidity/basicity of binary additives has been found to be a sensitive descriptor of the oxygen exchange kinetics, indicating that acidic Cr-species/basic Ca-species can be expected to deactivate/activate the cathode surface, respectively. Inspired by recent advances, the feasibility of relative acidity as a tool for reviving degraded SOFCs is demonstrated by neutralizing Cr-poisoned SOFCs by subsequent serial infiltration of Ca-species. Furthermore, a model mixed ionic and electronic conducting oxide, Pr 0.1 Ce 0.9 O 2-δ (PCO), is selected as the cathode material. Area-specific resistances (ASR) of symmetric cells obtained by electrochemical impedance spectroscopy show that Cr-infiltration results in a seven-fold increase in ASR, while subsequent infiltration of Ca-species leads to complete recovery. Performance degradation and recovery are attributed to depressed/enhanced redox properties at the PCO surface, as supported by XPS analysis. Experiments using anode-supported fuel cells show a reduction in peak power density by 26% upon Cr-infiltration, reversed following Ca-infiltration, after which no degradation is observed during subsequent operation for 100 h.

(Pr,Ce)O2-δ↗

Manufacturing Process Modeling of 100-400 kW e Combined Heat and Power Stationary Fuel Cell Systems

A one year project to examine the processes employed in the manufacture of combined heat and power stationary fuel cells operating in the 100-400kWe range was commissioned in June 2010. The results of this project would be used to inform decision makers in charge of allocating R&D resources by highlighting the most expensive steps in the manufacturing process where processing alternatives might have the greatest potential for high impact cost reduction. Three fuel cell technologies were examined: phosphoric acid (PAFC), molten carbonate (MCFC), and solid oxide (SOFC) fuel cells. Two fuel cell technologies, PAFC and MCFC, are represented by commercially available products within the study boundaries. United Technologies Corporation (UTC) offers the PureCell 400 ® , a 400 kWe combined heat and power PAFC system. FuelCell Energy (FCE) offers the DFC-300 ® , a 375 kWe combined heat and power MCFC. A combined heat and power SOFC within the study boundaries is not available in the marketplace at the time of this study. Process based cost models using 2010 dollars were developed for each fuel cell technology. For all three technologies, model boundaries encompassed all direct and indirect materials; direct and indirect labor; capital, maintenance, tooling, floor space, and energy costs associated with the manufacturing process. Cost estimates were developed with academic and patent literature, industry partners, supplier quotations, Monte Carlo simulation software, and DFMA software. Life cycle and non-manufacturing costs such as sales, administration, R&D, office floor space, and profit were not quantified. Results presented are for assumed annual production volumes of 5, 20, 50, and 500 MWe/yr, and expressed in terms of dollars per kilowatt of electrical energy. A model baseline production volume of 20 MWe/yr (similar to recent production volumes experienced by UTC and FCE) was assumed for all three technologies.

Warren, Joshua A.↗

Tuning Surface Acidity of Mixed Conducting Electrodes: Recovery of Si‐Induced Degradation of Oxygen Exchange Rate and Area Specific Resistance

Abstract Metal oxides are an important class of functional materials, and for many applications, ranging from solid oxide fuel/electrolysis cells, oxygen permeation membranes, and oxygen storage materials to gas sensors (semiconducting and electrolytic) and catalysts, the interaction between the surface and oxygen in the gas phase is central. Ubiquitous Si‐impurities are known to impede this interaction, commonly attributed to the formation of glassy blocking layers on the surface. Here, the surface oxygen exchange coefficient ( k chem ) is examined for Pr 0.1 Ce 0.9 O 2‐δ (PCO), a model mixed ionic electronic conductor, via electrical conductivity relaxation measurements, and the area‐specific resistance (ASR) by electrochemical impedance spectroscopy. It is demonstrated that even low silica levels, introduced by infiltration, depress k chem by a factor 4000, while the ASR increases 40‐fold and we attribute this to its acidity relative to that of PCO. The ability to fully regenerate the poisoned surface by the subsequent addition of basic Ca‐ or Li‐species is further shown. This ability to not only recover Si‐poisoned surfaces by tuning the relative surface acidity of an oxide surface, but subsequently outperform the pre‐poisoned response, promises to extend the operating life of materials and devices for which the catalytic oxygen/solid interface reaction is central.

30 DIRECT ENERGY CONVERSION↗

Structural and transport properties of Nafion in hydrobromic-acid solutions

Proton-exchange membranes are key solid-state ion carriers in many relevant energy technologies including flow batteries, fuel cells, and solar-fuel generators. In many of these systems, the membranes are in contact with electrolyte solutions. In this paper, we focus on the impact of different HBr, a flow-battery and exemplary acid electrolyte, external concentrations on the conductivity of Nafion, a perfluorosulfonic acid membrane that is commonly used in many energy-related applications. The peak and then decrease in conductivity is correlated with measured changes in the water and HBr content within the membrane. In addition, small-angle x-ray scattering is used to probe the nanostructure to correlate how the interactions of the bromide ion with the fixed sulfonic-acid sites impact conductivity and hydrophilic domain distance. It is also shown that membrane pretreatment has a large impact on the underlying structure/function relationship. The obtained data and results are useful for delineation of optimal operating regimes for flow batteries and similar technologies as well as in understanding underlying structure/function relationships of ionomers in electrolyte solutions. (C) 2013 Elsevier B.V. All rights reserved.

Kusoglu, A↗