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At least 595 records · Page 33

Durability of Polymer Electrolyte Membrane Fuel Cells Operated at Subfreezing Temperatures

The structure, composition, and interfaces of membrane electrode assemblies (MEA) and gas-diffusion layers (GDLs) have a significant effect on the performance of single-proton-exchange-membrane (PEM) fuel cells operated isothermally at subfreezing temperatures. During isothermal constant-current operation at subfreezing temperatures, water forming at the cathode initially hydrates the membrane, then forms ice in the catalyst layer and/or GDL. This ice formation results in a gradual decay in voltage. High-frequency resistance initially decreases due to an increase in membrane water content and then increases over time as the contact resistance increases. The water/ice holding capacity of a fuel cell decreases with decreasing subfreezing temperature (-10°C vs. -20°C vs. -30°C) and increasing current density (0.02 A cm -2 vs. 0.04 A cm -2 ). Ice formation monitored using in-situ high-resolution neutron radiography indicated that the ice was concentrated near the cathode catalyst layer at low operating temperatures (≈-20°C) and high current densities (0.04 A cm -2 ). Significant ice formation was also observed in the GDLs at higher subfreezing temperatures (≈-10°C) and lower current densities (0.02 A cm -2 ). These results are in good agreement with the long-term durability observations that show more severe degradation at lower temperatures (-20°C and -30°C).

30 DIRECT ENERGY CONVERSION↗

Near-ambient solid polymer fuel cell

Fuel cells are extremely attractive for extraterrestrial and terrestrial applications because of their high energy conversion efficiency without noise or environmental pollution. Among the various fuel cell systems the advanced polymer electrolyte membrane fuel cells based on sulfonated fluoropolymers (e.g., Nafion) are particularly attractive because they are fairly rugged, solid state, quite conductive, of good chemical and thermal stability and show good oxygen reduction kinetics due to the low specific adsorption of the electrolyte on the platinum catalyst. The objective of this program is to develop a solid polymer fuel cell which can efficiently operate at near ambient temperatures without ancillary components for humidification and/or pressurization of the fuel or oxidant gases. During the Phase 1 effort we fabricated novel integral electrode-membrane structures where the dispersed platinum catalyst is precipitated within the Nafion ionomer. This resulted in electrode-membrane units without interfacial barriers permitting unhindered water diffusion from cathode to anode. The integral electrode-membrane structures were tested as fuel cells operating on H2 and O2 or air at 1 to 2 atm and 10 to 50 C without gas humidification. We demonstrated that cells with completely dry membranes could be self started at room temperature and subsequently operated on dry gas for extended time. Typical room temperature low pressure operation with unoptimized electrodes yielded 100 mA/cm(exp 2) at 0.5V and maximum currents over 300 mA/cm(exp 2) with low platinum loadings. Our results clearly demonstrate that operation of proton exchange membrane fuel cells at ambient conditions is feasible. Optimization of the electrode-membrane structure is necessary to assess the full performance potential but we expect significant gains in weight and volume power density for the system. The reduced complexity will make fuel cells also attractive for smaller and portable power supplies and as replacement for batteries.

Holleck, G. L.↗

Degradation & Performance Studies of ALD-Stabilized Nano-Composite SOFC Cathodes

This work showed, definitively, for the first time, that zirconia Atomic Layer Deposited (ALD) overcoats improve the stability of Solid Oxide Fuel Cell (SOFC) cathodes by chemically gettering interfacial Sr that has segregated out of lanthanum strontium cobalt iron oxide (LSCF). The optimum ALD ZrO 2 overcoat thickness was found to be ≥5 nm and <10 nm. Gadolinium doped ceria (GDC) pre-infiltration was also shown, for the first time, to improve SOFC cathode stability through the chemical getting of Sr at the LSCF-backbone and LSCF-gas interfaces. Due to the fact that it can be performed easily in air on large-area electrodes, GDC pre-infiltration is likely more commercially viable than ALD ZrO 2 overcoating as an interfacial Sr gettering technique. Combining ZrO 2 overcoating with GDC pre-infiltration was not successful because the GDC nano-particles gettered the ZrO 2 overcoat instead of the interfacial Sr.

30 DIRECT ENERGY CONVERSION↗

Intermetallic PtCo Catalysts with Enhanced Performance and Stability [Slides]

Pt-based catalysts need systematic modifications to be adapted to different applications (LDV or HDV). L1 0 -CoPt particles have been demonstrated as highly active and durable cathode materials for fuel cells. Colloidal synthesis can generate catalysts with highly uniform particles size but the removal of surfactants is challenging. Acid leaching warrants a Pt shell with certain thickness, which mitigates the Co leaching. Controlling the size of L1 0 -CoPt particles is a robust method to alter their catalytic behaviours and tailor the function of catalysts. Modifying the carbon features (e.g. porosity and graphitization) is an effective method to regulate the performance and stability of catalysts to adapt the catalysts to different applications.

30 DIRECT ENERGY CONVERSION↗

Modeling Hierarchical Non-Precious Metal Catalyst Cathodes for PEFCs Using Multi-Scale X-ray CT Imaging

This paper reports the development of a model for simulating polymer electrolyte fuel cells (PEFCs) with non-precious metal catalyst (NPMC) cathodes. NPMCs present an opportunity to dramatically reduce the cost of PEFC electrodes by removing the costly Pt catalyst. To address the significant transport losses in thick NPMC cathodes (ca. >60 µm), we developed a hierarchical electrode model that resolves the unique structure of the NPMCs we studied. A unique feature of the approach is the integration of the model with morphology data extracted from nano-scale resolution X-ray computed tomography (nano-CT) imaging of the electrodes. A notable finding is the impact of the liquid water accumulation in the electrode and the significant performance improvement possible if electrode flooding is mitigated.

30 DIRECT ENERGY CONVERSION↗

Electrochemical device for converting carbon dioxide to a reaction product

An electrochemical device converts carbon dioxide to a reaction product. The device includes an anode and a cathode, each comprising a quantity of catalyst. The anode and cathode each has reactant introduced thereto. A polymer electrolyte membrane is interposed between the anode and the cathode. At least a portion of the cathode catalyst is directly exposed to gaseous carbon dioxide during electrolysis. The average current density at the membrane is at least 20 mA/cm.sup.2, measured as the area of the cathode gas diffusion layer that is covered by catalyst, and CO selectivity is at least 50% at a cell potential of 3.0 V. In some embodiments, the polymer electrolyte membrane comprises a polymer in which a constituent monomer is (p-vinylbenzyl)-R, where R is selected from the group consisting of imidazoliums, pyridiniums and phosphoniums. In some embodiments, the polymer electrolyte membrane is a Helper Membrane comprising a polymer containing an imidazolium ligand, a pyridinium ligand, or a phosphonium ligand.

30 DIRECT ENERGY CONVERSION↗

Demonstration of Electroreduction Technology to Convert GNF Uranium Oxide Powder to Metal

Global Nuclear Fuel – Americas LLC (GNF) has partnered with Argonne National Laboratory to demonstrate electroreduction of uranium oxides produced by deconversion of UF 6 to uranium metal through the Gateway for Accelerated Innovation in Nuclear (GAIN) program under the U.S. Department of Energy to accelerate the domestic production of metallic advanced reactor fuels. Electroreduction of uranium oxide was first demonstrated and patented by Argonne in the early 2000s as a technology to convert used oxide nuclear fuel from light water reactors to metal for further fuel reprocessing. More recently, electroreduction has been proposed as a front-end technology for metallization of uranium oxides produced by deconversion of UF 6 and for scrap recovery of oxide materials. During the electroreduction process, UO 2 powder is contained in a stainless-steel mesh basket with a cathode lead located in the center of the UO 2 bed. The basket is immersed in lithium chloride molten salt electrolyte containing 1 wt% lithium oxide along with a platinum anode and a nickel/nickel oxide (Ni/NiO) reference electrode. Current is applied to the cell between the cathode and anode to reduce the UO 2 to metallic uranium via a solid-state reduction reaction. Oxide ions released from the UO 2 during reduction are transported through the salt to the anode where oxygen gas is evolved. Once reduction is complete, the basket containing the metallicized uranium is removed from the salt and can be processed to remove the salt and consolidate the uranium into an ingot for use in metallic fuel fabrication. This project was performed to provide evidence of the electroreduction technology readiness level for metallization of UO 2 powder, identify and retire technical risks for industrialization of electroreduction, and accelerate the path to commercialization for metallic fast reactor fuel production. To that end, five electroreduction tests were performed with UO 2 provided by GNF and the resulting product was analyzed for the extent of conversion to metal and for impurity contents of the metal product to verify that electroreduction does not introduce impurities that would prevent use of the product in metallic fuel fabrication.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Multicoordination Control Strategy Performance in Hybrid Power Systems

This paper evaluates a state-space methodology of a multi-input multi-output (MIMO) control strategy using a 2 × 2 tightly coupled scenario applied to a physical gas turbine fuel cell hybrid power system. A centralized MIMO controller was preferred compared to a decentralized control approach because previous simulation studies showed that the coupling effect identified during the simultaneous control of the turbine speed and cathode airflow was better minimized. The MIMO controller was developed using a state-space dynamic model of the system that was derived using first-order transfer functions empirically obtained through experimental tests. The controller performance was evaluated in terms of disturbance rejection through perturbations in the gas turbine operation, and setpoint tracking maneuver through turbine speed and cathode airflow steps. The experimental results illustrate that a multicoordination control strategy was able to mitigate the coupling of each actuator to each output during the simultaneous control of the system, and improved the overall system performance during transient conditions. On the other hand, the controller showed different performance during validation in simulation environment compared to validation in the physical facility, which will require a better dynamic modeling of the system for the implementation of future multivariable control strategies.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Explosion behavior investigation and safety assessment of large-format lithium-ion pouch cells

We report large-format lithium-ion (Li-ion) batteries with high energy density for electric vehicles are prone to thermal runaway (or even explosion) under abusive conditions. In this study, overcharge induced explosion behaviors of large-format Li-ion pouch cells with Li[Ni 0.8 Co 0.1 Mn 0.1 ]O 2 cathode at different current rates (C-rates) (0.5C, 1C, 2C) were investigated. The explosion characteristics of the cells were elucidated by discussing the evolution of the cell voltage, the surface temperature and the shock wave pressure. Generally, the whole overcharge process could be divided into four stages according to the evolution of several key parameters and the overcharge behaviors; the overcharge C-rate has a great influence on cells’ thermal behaviors. The experimental results showed that the thermal runaway process of Li-ion cells caused by overcharging consisted of two kinds of explosions, physical explosion and chemical explosion. The existence of observable negative pressure zone in the pressure curves indicated that the Li-ion cells are not a self-supplying oxygen system during the explosion. Further, the explosion dynamics parameters were matched. An explosion TNT-equivalent conversion strategy that depended on the pressure of the shock wave was utilized to evaluate the released energy and its hazards. In addition, with respect to the overcharge of Li-ion pouch cells, a safety assessment method and a safety management method were proposed based on the explosion behaviors. From the perspective of battery safety, this study is of great significance for the safety design of Li-ion cells and can provide guidance for engineers to optimize the safety function of battery packs.

25 ENERGY STORAGE↗

Electrochemical Carbon Monoxide Reduction on Polycrystalline Copper: Effects of Potential, Pressure, and pH on Selectivity toward Multicarbon and Oxygenated Products

Here by understanding the surface reactivity of CO, which is a key intermediate during electrochemical CO 2 reduction, is crucial for the development of catalysts that selectively target desired products for the conversion of CO 2 to fuels and chemicals. In this study, a custom-designed electrochemical cell is utilized to investigate planar polycrystalline copper as an electrocatalyst for CO reduction under alkaline conditions. Seven major CO reduction products have been observed including various hydrocarbons and oxygenates which are also common CO 2 reduction products, strongly indicating that CO is a key reaction intermediate for these further-reduced products. A comparison of CO and CO 2 reduction demonstrates that there is a large decrease in the overpotential for C–C coupled products under CO reduction conditions. The effects of CO partial pressure and electrolyte pH are investigated; we conclude that the aforementioned large potential shift is primarily a pH effect. Thus, alkaline conditions can be used to increase the energy efficiency of CO and CO 2 reduction to C–C coupled products, when these cathode reactions are coupled to the oxygen evolution reaction at the anode. Further analysis of the reaction products reveals common trends in selectivity that indicate both the production of oxygenates and C–C coupled products are favored at lower overpotentials. These selectivity trends are generalized by comparing the results on planar Cu to current state-of-the-art high-surface-area Cu catalysts, which are able to achieve high oxygenate selectivity by operating at the same geometric current density at lower overpotentials. Combined, these findings outline key principles for designing CO and CO 2 electrolyzers that are able to produce valuable C–C coupled products with high energy efficiency.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Metal-Supported Ceria Electrolyte-based SOFC Stack for Scalable, Low-Cost, High-Efficiency and Robust Stationary Power Systems (Final Report)

This is the end of project report for the DOE Project DE-FE-0027844 “Metal-Supported Ceria Electrolyte-based SOFC Stack for Scalable, Low-Cost, High-Efficiency and Robust Stationary Power Systems”. The objectives of the project were to develop several technologies required for the mass adoption of Solid Oxide Fuel Cell systems for medium to large power generation applications. The key achievements of this project were: 1) Development of fuel cells with complete internal fuel reforming capability. 2) Fuel cell power scale up with production of cells with larger active areas. 3) Assembly of an integrated 5 kW modular stack platform capable of installation into medium to large power systems. 4) Demonstration of a 10 kW Fuel Cell Power System utilizing the integrated 5 kW modular stack platform. 5) Cost modelling to show system cost of $1,500/kW are achievable at production volumes. 6) Development of cathode air poison getters for reduced degradation and extended fuel cell life. 7) Assessment of fuel poison on anode degradation, particularly poisons frequently produced from the process of gasification of coal. The Cummins led Voice of Customer (VOC) work identified several significant markets for natural gas powered fuel cell systems, where the end customer is interested in reducing energy consumption and emissions, or increasing reliability of electrical supply. Data centers and truck Auxiliary Power Units (APU) were highlighted as 2 key future markets for fuel cell systems.

30 DIRECT ENERGY CONVERSION↗

In-line monitoring of Li-ion battery electrode porosity and areal loading using active thermal scanning - modeling and initial experiment

This work focuses on a new technique called active thermal scanning for in-line monitoring of porosity and areal loading of Li-ion battery electrodes. In this technique a moving battery electrode is subjected to thermal excitation and the induced temperature rise is monitored using an infra-red camera. Static and dynamic experiments with speeds up to 1.5 m min -1 are performed on both cathodes and anodes and a combined micro- and macro-scale finite element thermal model of the system is developed. It is shown experimentally and through simulations that during thermal scanning the temperature profile generated in an electrode depends on both coating porosity (or area loading) and thickness. Here, it is concluded that by inverting this relation the porosity (or areal loading) can be determined, if thermal response and thickness are simultaneously measured.

25 ENERGY STORAGE↗

Effect of System Contaminants on the Performance of a Proton Exchange Membrane Fuel Cell

The performance loss and recovery of the fuel cell due to Balance of Plant (BOP) contaminants was identified via a combination of experimental data and a mathematical model. The experiments were designed to study the influence of organic contaminants (e.g. those from BOP materials) on the resistance of the catalyst, ionomer and membrane, and a mathematical model was developed that allowed us to separate these competing resistances from the data collected on an operating fuel cell. For this reason, based on the functional groups, four organic contaminants found in BOP materials, diethylene glycol monoethyl ether (DGMEE), diethylene glycol monoethyl ether acetate (DGMEA), benzyl alcohol (BzOH) and 2,6-diaminotoluene (2,6-DAT) were infused separately to the cathode side of the fuel cell. The cell voltage and high frequency impedance resistance was measured as a function of time. The contaminant feed was then discontinued and voltage recovery was measured. It was determined that compounds with ion exchange properties like 2,6-DAT can cause voltage loss with non-reversible recovery, so this compound was studied in more detail. Finally, the degree of voltage loss increased with an increase in concentration, and/or infusion time, and increased with a decrease in catalyst loadings.

30 DIRECT ENERGY CONVERSION↗

Effect of Concentration, Temperature, and Interelectrode Gap on the Voltage Drop in an Electrochemical System of GdCl{sub 3}-LiCl-KCl

One of the most common conversations for those in the nuclear field and the public when discussing nuclear power is the issue of nuclear waste. When used nuclear fuel (UNF) is removed from a reactor, it contains fission products, some of which are long lived isotopes that will continue to irradiate for hundreds of years. One of several solutions to this issue is reprocessing, a process where minor actinides and other fission products are separated from still fissile and fertile materials. In the United States, there is no reprocessing of UNF at an industrial scale; however, one of the methods that universities and national labs are currently researching is known as pyro-processing. Pyro-processing utilizes electrochemistry in a molten salt environment to treat UNF and remove uranium and plutonium. The heart of the pyro-processing system is an electrorefining process, where most of the U in the UNF is selectively collected on a solid cathode in molten lithium-potassium chloride (LiCl-KCl) at high temperatures (723 K - 773 K). To model the behavior of materials in the electro-refiner, small bench-scale electrochemical experiments are being performed at many research universities and national labs to better understand material behavior. Within the electrochemical cell, there is a small resistance to current between the cathode and anode. This results in a voltage drop, which can affect the results of the experiments. This voltage drop varies based upon concentration of the salt, the temperature, the distance between the anode and cathode, and the scan rate. For this study, cyclic voltammetry will be performed on GdCl{sub 3}-LiCl-KCl at various temperatures (723 K - 798 K), various sample concentrations (1, 5, and 10 wt%), various scan rates (50, 100, 200, and 300 mV/s), and two different electrode spacing configurations. The resulting cyclic voltammograms will be compared for both electrode configurations to see the impact of interelectrode gap on the voltage drop.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Anolyte Enhances Catalyst Utilization and Ion Transport Inside a CO 2 Electrolyzer Cathode

Electrochemical CO 2 reduction is a promising technology to capture and convert CO 2 to valuable chemicals. High Faradaic efficiencies of CO 2 reduction products are achieved with zero-gap alkaline CO 2 electrolyzers with a supporting electrolyte at the anode (anolyte). Herein, we investigate the effect of anolyte on the electrode properties such as catalyst utilization, ionic accessibility etc. of a CO 2 reduction cathode using electrochemical techniques and cell configurations that avoid the complexities related to co-electrolysis. Using 1M KOH as the anolyte and a Cu gas-diffusion-electrode with low Nafion content as the model CO 2 reduction electrode, we find that electrode capacitance (proxy for electrochemically active surface area) and ionic conductivity inside the cathode increase approximately 4 and 447 times, respectively, in presence of KOH. Liquid anolyte wets the electrode’s pore structure more efficiently than capillary condensation of feed water vapor. The ionomer coverage is very low, and its distribution inside the electrode is highly fragmented. Surface ion conduction mechanisms inside the electrode are orders of magnitude lower than the bulk ion conduction in presence of anolyte. This study shows that when an anolyte (e.g., KOH) is used, catalyst utilization and ionic accessibility inside the electrode increase significantly.

30 DIRECT ENERGY CONVERSION↗

Layered materials with improved magnesium intercalation for rechargeable magnesium ion cells

Electrochemical devices which incorporate cathode materials that include layered crystalline compounds for which a structural modification has been achieved which increases the diffusion rate of multi-valent ions into and out of the cathode materials. Examples in which the layer spacing of the layered electrode materials is modified to have a specific spacing range such that the spacing is optimal for diffusion of magnesium ions are presented. An electrochemical cell comprised of a positive intercalation electrode, a negative metal electrode, and a separator impregnated with a nonaqeuous electrolyte solution containing multi-valent ions and arranged between the positive electrode and the negative electrode active material is described.

25 ENERGY STORAGE↗

Pyroprocessing of oxidized sodium-bonded fast reactor fuel - An experimental study of treatment options for degraded EBR-II fuel

An experimental study was conducted to assess pyrochemical treatment options for degraded EBR-II fuel. As oxidized material, the degraded fuel would need to be converted back to metal to enable electrorefining within an existing electro-metallurgical treatment process. A lithium-based electrolytic reduction process was studied to assess the efficacy of converting oxide materials to metal with a particular focus on the impact of zirconium oxide and sodium oxide on this process. Bench-scale electrolytic reduction experiments were performed in LiCl-Li{sub 2}O at 650 C. degrees with combinations of manganese oxide (used as a surrogate for uranium oxide), zirconium oxide, and sodium oxide. In the absence of zirconium or sodium oxide, the electrolytic reduction of MnO showed nearly complete conversion to metal. The electrolytic reduction of a blend of MnO-ZrO{sub 2} in LiCl - 1 wt% Li{sub 2}O showed substantial reduction of manganese, but only 8.5% of the zirconium was found in the metal phase. The electrolytic reduction of the same blend of MnO-ZrO{sub 2} in LiCl - 1 wt% Li{sub 2}O - 6.2 wt% Na{sub 2}O showed substantial reduction of manganese, but zirconium reduction was even less at 2.4%. This study concluded that ZrO{sub 2} cannot be substantially reduced to metal in an electrolytic reduction system with LiCl - 1 wt% Li{sub 2}O at 650 C. degrees due to the perceived preferential formation of lithium zirconate. This study also identified a possible interference that sodium oxide may have on the same system by introducing a parasitic and cyclic reaction of dissolved sodium metal between oxidation at the anode and reduction at the cathode. When applied to oxidized sodium-bonded EBR-II fuel (e.g., U-10Zr), the prescribed electrolytic reduction system would not be expected to substantially reduce zirconium oxide, and the accumulation of sodium in the electrolyte could interfere with the reduction of uranium oxide, or at least render it less efficient.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Fuel cell and membrane therefore

A fuel cell includes first and second flow field plates, and an anode electrode and a cathode electrode between the flow field plates. A polymer electrolyte membrane (PEM) is arranged between the electrodes. At least one of the flow field plates influences, at least in part, an in-plane anisotropic physical condition of the PEM that varies in magnitude between a high value direction and a low value direction. The PEM has an in-plane physical property that varies in magnitude between a high value direction and a low value direction. The PEM is oriented with its high value direction substantially aligned with the high value direction of the flow field plate.

30 DIRECT ENERGY CONVERSION↗