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At least 1,081 records · Page 60

Determination of the “NiOOH” charge and discharge mechanisms at ideal activity

Here, optimization of electrodeposition conditions produced Ni(OH) 2 deposits chargeable up to 1.84 ± 0.02 e – per Ni on and the resulting nickel oxide/hydroxide active material could subsequently deliver 1.58 ± 0.02 e – per Ni ion (462 mA h/g) over a potential range <0.2 V. The ability of the “NiOOH” active material to deliver an approximately ideal charge and discharge facilitated a coulometric and thermodynamic analysis through which the charge/discharge mechanisms were determined from known enthalpies of formation. The (dis)charge states were confirmed with in situ Raman spectroscopy. The mechanisms were additionally evaluated with respect to pH and potential dependence, charge quantities, hysteresis, and fluoride ion partial inhibition of the charge mechanism. The results indicate that the “NiOOH” (dis)charges as a solid-state system with mechanisms consistent with known nickel and oxygen redox reactions. A defect chemistry mechanism known for the LiNiO 2 system also occurs for “NiOOH” to cause both high activity and hysteresis. Similar to other cation insertion nickel oxides, the activity of the “NiOOH” mechanism is predominantly due to oxygen redox activity and does not involve the Ni4 + oxidation state. The “NiOOH” was produced from cathodic electrodeposition of Ni(OH) 2 from nickel nitrate solutions onto highly oriented pyrolytic graphite at ideal electrodeposition current efficiencies and the deposition mechanism was also characterized.

30 DIRECT ENERGY CONVERSION↗

Fracture strength and elastic modulus as a function of porosity for hydroxyapatite and other brittle materials Part I

Porous brittle materials are used as filters, catalyst supports, solid oxide fuel cells and biomedical materials. However the literature on the Weibull modulus, m, versus volume fraction porosity, P, is extremely limited despite the importance of m as a gauge of mechanical reliability. In Part I of this study, m is determined for 441 sintered hydroxyapatite (HA) specimens fractured in biaxial flexure for 0.08 P 0.62. In this study, we analyze a combined data set collected from the literature that represents work from a total of 17 different research groups (including the present authors), eight different materials and more than 1560 oxide and non-oxide specimens, the m versus P plot is Ushaped with a wide band of m values for P < 0.1 (Region I) and P > 0.55 (Region III), and a narrower band of m values in the intermediate porosity region of 0.1 < P < 0.55 (Region II). The limited range of m ( 4 < m < 11) in Region II has important implications since Region II includes the P range for the majority of the applications of porous brittle materials. Part II of this study focuses on the P dependence of the mean fracture strength,< f >, and the Young s modulus E for the HA specimens tested in Part I along with literature data for other brittle materials. Both < f > and E are power law functions of the degree of densification, , where = 1 P/PG and PG is the green (unfired) porosity.

30 DIRECT ENERGY CONVERSION↗

Understanding activity engagement across weekdays and weekend days: A multivariate multiple discrete-continuous modeling approach

This paper is motivated by the increasing recognition that modeling activity-travel demand for a single day of the week, as is done in virtually all travel forecasting models, may be inadequate in capturing underlying processes that govern activity-travel scheduling behavior. The considerable variability in daily travel suggests that there are important complementary relationships and competing tradeoffs involved in scheduling and allocating time to various activities across days of the week. Both limited survey data availability and methodological challenges in modeling week-long activity-travel schedules have precluded the development of multi-day activity-travel demand models. With passive and technology-based data collection methods increasingly in vogue, the collection of multi-day travel data may become increasingly commonplace in the years ahead. This paper addresses the methodological challenge associated with modeling multi-day activity-travel demand by formulating a multivariate multiple discrete-continuous probit (MDCP) model system. The comprehensive framework ties together two MDCP model components, one corresponding to weekday time allocation and the other to weekend activity-time allocation. By tying the two MDCP components together, the model system also captures relationships in activity-time allocation between weekdays on the one hand and weekend days on the other. Model estimation on a week-long travel diary data set from the United Kingdom shows that there are significant inter-relationships between weekdays and weekend days in activity-travel scheduling behavior. In conclusion, the model system presented in this paper may serve as a higher-level multi-day activity scheduler in conjunction with existing daily activity-based travel models.

30 DIRECT ENERGY CONVERSION↗

Thermoelectrics: From longitudinal to transverse

Thermoelectric power generation is a promising technology to realize a sustainable society because it directly converts thermal energy into electricity in a solid. Conventional thermoelectric generation is driven by the Seebeck effect, discovered by T.J. Seebeck in 1821, in which a charge current J c is generated in the direction parallel to a temperature gradient ∇T, the longitudinal geometry. Here, the ratio between the generated longitudinal electromotive force and applied ∇T is defined as the Seebeck coefficient. As shown in Figure 1A, a thermoelectric module based on the Seebeck effect typically consists of many pairs (128 for a 12V unit) of p-type and n-type conductors alternately arranged and connected in series. Since the Seebeck coefficient of a p-type (n-type) conductor is positive (negative), the thermopower in each element adds to the total output in the Seebeck module. This configuration is needed to achieve a practical voltage because each element only supplies millivolts but limits the use of thermoelectric generators. The efficiency of thermoelectric generators is characterized by the thermoelectric figure of merit, zT. Despite a 3-fold improvement in zT resulting from materials research over the last two decades, little progress has been made in their practical use; this is ascribed to the technological challenges in contact technology. The contacts on the hot side are subject to thermal degradation. All contacts (512 for a 12V unit) add electrical and thermal contact resistances that reduce the device efficiency to a fraction of that promised by the materials.

30 DIRECT ENERGY CONVERSION↗

Micelle-Like Bulk Structure of Localized High-Concentration Electrolytes

In the recent article by Efaw et al. published in Nature Materials, a unique micelle-like bulk structure of localized high-concentration electrolytes (LHCEs) is revealed to provide beneficial characteristics with respect to solid electrolyte interphase (SEI) stability on lithium metal anodes. This work adds to the pertinent discussions on design rules of LHCE, providing tangible guidelines for its improvement.

DIRECT ENERGY CONVERSION↗

Conformal high-entropy oxide coatings enable fast and durable surface oxygen reactions

Developing active and durable air electrodes for efficient oxygen reactions is challenging for protonic ceramic cells (PCCs), especially at temperatures below 550°C. Here, in this study, we report a rationally designed conformal coating with a high-entropy PrNi 0.2 Mn 0.2 Co 0.2 Fe 0.2 Cu 0.2 O 3−δ (PNMCFC) perovskite structure on the surface of a state-of-the-art PrBaCo 2 O 5+δ (PBC) air electrode. The formed hybrid air electrode (PNMCFC-PBC) shows faster surface oxygen kinetics and a more stable phase structure in high-humidity air than the bare PBC electrode. Further density functional theory calculations suggest that the conformal coating mitigates Ba segregation at the interface and improves oxygen-related reactions, enhancing overall stability and electrocatalytic performance. The cells with the developed hybrid electrodes show encouraging electrochemical performance at 550°C: a polarization resistance of 0.72 Ω cm 2 , a peak power density of 1.30 W cm −2 , an electrolysis current density of −1.36 A cm −2 at 1.3 V, and reasonable operating stabilities (∼200 h at 550°C).

30 DIRECT ENERGY CONVERSION↗

Tungsten Carbide Modified High Surface Area Carbon as Fuel Cell Catalyst Support

Phase pure WC nanoparticles were synthesized on high surface area carbon black (800 m{sup 2} g{sup -1}) by a temperature programmed reaction (TPR) method. The particle size of WC can be controlled under 30 nm with a relatively high coverage on the carbon surface. The electrochemical testing results demonstrated that the corrosion resistance of carbon black was improved by 2-fold with a surface modification by phase pure WC particles. However, the WC itself showed some dissolution under potential cycling. Based on the X-ray diffraction (XRD) and inductively coupled plasma (ICP) analysis, most of the WC on the surface was lost or transformed to oxides after 5000 potential cycles in the potential range of 0.65-1.2 V. The Pt catalyst supported on WC/C showed a slightly better ORR activity than that of Pt/C, with the Pt activity loss rate for Pt/WC/C being slightly slower compared to that of Pt/C. The performance and decay rate of Pt/WC/C were also evaluated in a fuel cell.

30 DIRECT ENERGY CONVERSION↗

Extended reaction zone of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 cathode for solid oxide fuel cell

The oxygen reduction reaction at the cathode of solid oxide fuel cell (SOFC) is a complicated process which involves the interaction of oxygen molecules, electrons, and oxygen ions. Therefore, it can only proceed at locations where gas, electronic conductor, and an oxygen ion conductor meet. Although the extension of the reaction zone beyond the traditional so-called triple-phase-boundary (TPB) is widely accepted for a mixed ionically and electronically conductive cathode, work in this area has yet to reach a consensus on how far the reaction zone can be extended. In this study, anode-supported fuel cells with a variety of LSCF cathode thicknesses were fabricated and tested in two cathode environments, flowing oxygen and flowing air. In flowing oxygen, the cell performance increased with LSCF cathode thickness over the entire range investigated (from 5 to 33 μm). In flowing air, the cell performance also increased with the LSCF cathode thickness from 5 to 13 μm, but then remained almost constant with further increase in cathode thickness. In flowing oxygen, since there was no concentration polarization related to oxygen diffusion, the polarization resistance of oxygen reduction decreased with the LSCF cathode thickness because of the increased number of reaction sites. A linear relationship was established between the reciprocal of the polarization resistance and the cathode thickness, which was explained by a model developed for aqueous gas diffusion electrodes.

30 DIRECT ENERGY CONVERSION↗

Compliant alkali silicate sealing glass for solid oxide fuel cell applications: Combined stability in isothermal ageing and thermal cycling with YSZ coated ferritic stainless steels

An alkali-containing silicate glass (SCN-1) is currently being evaluated as a candidate sealing glass for solid oxide fuel cell (SOFC) applications. The glass contains about 17 mole% alkalis (K+Na) and has low glass transition and softening temperatures. It remains vitreous and compliant around 750-800oC after sealing without substantial crystallization, as contrary to conventional glass-ceramic sealants, which experience rapid crystallization after the sealing process. The glassy nature and low characteristic temperatures can reduce residual stresses and result in the potential for crack healing. In a previous study, the glass was found to have good thermal cycle stability and was chemically compatible with YSZ coating during short term testing. In the current study, the compliant glass was further evaluated in a more realistic way in that the sealed glass couples were first isothermally aged for 1000h followed by thermal cycling. High temperature leakage was measured. The chemical compatibility was also investigated with powder mixtures at 700 and 800oC to enhance potential interfacial reaction. In addition, interfacial microstructure was examined with scanning electron microscopy and evaluated with regard to the leakage and chemical compatibility results.

30 DIRECT ENERGY CONVERSION↗

Effects of Operating Conditions on Internal Resistances in Enzyme Fuel Cells Studied via Electrochemical Impedance Spectroscopy

Enzyme fuel cells (EFCs) offer some advantages over traditional precious-metal-catalyzed fuel cells, such as polymer electrolyte membrane fuel cells (PEMFCs). However, EFCs exhibit far less power output than PEMFCs and have relatively short life spans before materials must be replaced. In this work, electrochemical impedance spectroscopy (EIS) is used to analyze the internal resistances throughout the EFC at a variety of operating conditions. EIS analysis is focused primarily on the resistances of the anode, solution/membrane, and cathode. Increased enzyme loading results in improved power output and reductions in internal resistance. Conditions are identified for which enzyme loading does not limit the EFC performance. EIS experiments are also reported for EFCs operated continuously for 2 days; power output declines sharply over time, while all internal resistances increase. Drying of the cathode and enzyme/mediator degradation are believed to have contributed to this behavior. Finally, experiments are performed at varying air-humidification temperatures. Little effect on internal resistances or power output is observed. However, it is anticipated that increased air humidification can improve longevity by delivering more water to the cathode. Improvements to the enzymatic cathode are needed for EFC development. These improvements need to focus on improving transport rather than increasing enzyme loading.

30 DIRECT ENERGY CONVERSION↗

Performance of Ni-Fe/gadolinium-doped CeO{sub2} anode supported tubular solid oxide fuel cells using steam reforming of methane

Iron nanoparticles (Fe{sub 2}O{sub 3}) were added to NiO/gadolinium-doped CeO{sub 2} (GDC) anode supported solid oxide fuel cell (SOFC) for the direct methane-water fuel operation. The cell was co-sintered at 1400 C, and the anode porosity is 31.8%. The main size corresponding to peak volume is around 1.5 {mu}m. When steam and methane directly fed to the cell, the power density is about 0.57 W cm{sup -2} at 650 C. It is the familiar performance for H{sub 2} operation (4 times of flow rate) with same fuel utilization. Compare with the testing temperature of 600 and 650 C, there is almost no carbon fiber deposition at 700 C with steam/methane (S/C) of 5. At the same time, fuel operation of high value of S/C (=3.3) resulted in fiber-like deposition and degradation of power performance based on loading test results.

03 NATURAL GAS↗

Demonstration of a Highly Efficient Solid Oxide Fuel Cell Power System Using Adiabatic Steam Reforming and Anode Gas Recirculation

Solid oxide fuel cells (SOFC) are currently being developed for a wide variety of applications because of their high efficiency at multiple power levels. Applications for SOFCs encompass a large range of power levels including 1-2 kW residential combined heat and power applications, 100-250 kW sized systems for distributed generation and grid extension, and MW-scale power plants utilizing coal. This paper reports on the development of a highly efficient, small-scale SOFC power system operating on methane. The system uses adiabatic steam reforming of methane and anode gas recirculation to achieve high net electrical efficiency. The anode exit gas is recirculated and all of the heat and water required for the endothermic reforming reaction are provided by the anode gas emerging from the SOFC stack. Although the single-pass fuel utilization is only about 55%, because of the anode gas recirculation the overall fuel utilization is up to 93%. The demonstrated system achieved gross power output of 1650 to 2150 watts with a maximum net LHV efficiency of 56.7% at 1720 watts. Overall system efficiency could be further improved to over 60% with use of properly sized blowers.

01 COAL, LIGNITE, AND PEAT↗

A Damage Model for Degradation in the Electrodes of solid oxide fuel cells: Modeling the effects of sulfur and antimony in the anode

Over their designed lifetime, high temperature electrochemical devices, such as solid oxide fuel cells (SOFCs), can experience degradation in their electrochemical performance due to environmental conditions, operating conditions, contaminants, and other factors. Understanding the different degradation mechanisms in SOFCs and other electrochemical devices is essential to reducing performance degradation and increasing the lifetime of these devices. In this paper SOFC degradation mechanisms are discussed and a damage model is presented which describes performance degradation in SOFCs due to damage or degradation in the electrodes of the SOFC. A degradation classification scheme is presented that divides the various SOFC electrode degradation mechanisms into categories based on their physical effects on the SOFC. The application of the damage model and the classification method is applied to sulfur poisoning and antimony poisoning which occur in the anode of SOFCs. For sulfur poisoning the model is able to predict the degradation in SOFC performance based on the operating temperature and voltage of the fuel cell and the concentration of gaseous sulfur species in the anode. For antimony poisoning the effects of nickel removal from the anode matrix is investigated.

30 DIRECT ENERGY CONVERSION↗

Performance of Anode-Supported Solid Oxide Fuel Cell with Thin Bi-Layer Electrolyte by Pulsed Laser Deposition

Anode-supported yttria stabilized zirconia (YSZ)/samaria doped ceria (SDC) bi-layer electrolytes with uniform thickness and high density were fabricated by pulsed laser deposition at 1000 degrees C. Fuel cells with such bi-layer electrolytes were fabricated and tested, yielding open circuit voltages from 0.94 to 1.0 V at 600-700 degrees C. Power densities from 0.4 to 1.0 W cm{sup -2} at 0.7 V were achieved in air at temperatures of 600-700 degrees C. Cell performance was improved in flowing oxygen, with an estimated peak power density of over 2 W cm{sup -2} at 650 degrees C, assuming the same overall resistance over the entire range of current density. The high cell performance was attributed to the very low ohmic resistance of the fuel cell, owing to the small thickness of the electrolyte. Stable performance was also demonstrated in that the voltage of the fuel cell showed very little change at a constant current density of 1 A cm{sup -2} during more than 400 hours of operation at 650 degrees C in flowing oxygen. SEM analysis of the fuel cell after testing showed that the bi-layer electrolyte had retained its chemical and mechanical integrity.

30 DIRECT ENERGY CONVERSION↗

A reduced temperature solid oxide fuel cell with three-dimensionally ordered macroporous cathode

Three-dimensionally ordered macroporous cathode was fabricated for a zirconia based micro-tubular solid oxide fuel cells (SOFCs). Three different cathodes (cathode A, no pore former; cathode B, with pore former (1.5 {micro}m in diameter); cathode C, with pore former (0.8 {micro}m in diameter)) were compared to investigate how the microstructure of it affected the cell performance at various operating temperatures. Micro-sized pores were well distributed within cathode B and C. The total porosity of cathode A is 35%, while it respectively reached 42 and 50% for cathodes B and C. At the same time, the specific surface area of them was 28.8 and 52.0% larger than that of the cathode A. As a result, the peak power density of the zirconia based cell, with cathode C, was 0.25 and 0.56 W cm{sup -2} at 550 and 600 C, while the respective value was just 0.11 and 0.30 W cm{sup -2} for the cell with cathode A. Thus, optimizing microstructure of cathode should be one of the best approaches for lowering the operating temperature for SOFCs.

30 DIRECT ENERGY CONVERSION↗

Performance of solid oxide fuel cells operated with coal syngas provided directly from a gasification process

Solid oxide fuel cells (SOFCs) are presently being developed for gasification integrated power plants that generate electricity from coal at 50+% efficiency. The interaction of trace metals in coal syngas with the Ni-based SOFC anodes is being investigated through thermodynamic analyses and in laboratory experiments, but direct test data from coal syngas exposure are sparsely available. This research effort evaluates the significance of SOFC performance losses associated with exposure of a SOFC anode to direct coal syngas. SOFC specimen of industrially relevant composition are operated in a unique mobile test skid that was deployed to the research gasifier at the National Carbon Capture Center (NCCC) in Wilsonville, AL. The mobile test skid interfaces with a gasifier slipstream to deliver hot syngas (up to 300°C) directly to a parallel array of 12 button cell specimen, each of which possesses an active area of approximately 2 cm2. During the 500 hour test period, all twelve cells were monitored for performance at four discrete operating current densities, and all cells maintained contact with a data acquisition system. Of these twelve, nine demonstrated good performance throughout the test, while three of the cells were partially compromised. Degradation associated with the properly functioning cells was attributed to syngas exposure and trace material attack on the anode structure that was accelerated at increasing current densities. Cells that were operated at 0 and 125 mA/cm² degraded at 9.1 and 10.7% per 1000 hours, respectively, while cells operated at 250 and 375 mA/cm² degraded at 18.9 and 16.2% per 1000 hours, respectively. Post-trial spectroscopic analysis of the anodes showed carbon, sulfur, and phosphorus deposits; no secondary Ni-metal phases were found.

Environmental Molecular Sciences Laboratory↗