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Full-Text Articles in Engineering
Quantifying Individual Potential Contributions Of The Hybrid Sulfur Electrolyzer, John A. Staser, Maximilian B. Gorensek, John W. Weidner
Quantifying Individual Potential Contributions Of The Hybrid Sulfur Electrolyzer, John A. Staser, Maximilian B. Gorensek, John W. Weidner
Faculty Publications
The hybrid sulfur cycle has been investigated as a means to produce clean hydrogen efficiently on a large scale by first decomposing H2SO4 to SO2, O2, and H2O and then electrochemically oxidizing SO2 back to H2SO4 with the cogeneration of H2. Thus far, it has been determined that the total cell potential for the hybrid sulfur electrolyzer is controlled mainly by water transport in the cell. Water is required at the anode to participate in the oxidation of SO2 to H2SO4 …
Analytical Expression For The Impedance Response For A Lithium-Ion Cell, Godfrey Sikha, Ralph E. White
Analytical Expression For The Impedance Response For A Lithium-Ion Cell, Godfrey Sikha, Ralph E. White
Faculty Publications
An analytical expression to predict the impedance response of a dual insertion electrode cell (insertion electrodes separated by an ionically conducting membrane) is presented. The expression accounts for the reaction kinetics and double-layer adsorption processes at the electrode-electrolyte interface, transport of electroactive species in the electrolyte phase, and insertion of species in the solid phase of the insertion electrodes. The accuracy of the analytical expression is validated by comparing the impedance response predicted by the expression to the corresponding numerical solution. The analytical expression is used to predict the impedance response of a lithium-ion cell consisting of a porous LiCoO …
Development Of A Novel Co Tolerant Proton Exchange Membrane Fuel Cell Anode, Andrew T. Haug, Ralph E. White, John W. Weidner, Wayne Huang
Development Of A Novel Co Tolerant Proton Exchange Membrane Fuel Cell Anode, Andrew T. Haug, Ralph E. White, John W. Weidner, Wayne Huang
Faculty Publications
Typically Pt is alloyed with metals such as Ru, Sn, or Mo to provide a more CO-tolerant, high-performance proton exchange membrane fuel cell (PEMFC) anode. In this work, a layer of carbon-supported Ru is placed between the Pt catalyst and the anode flow field to form a filter. When oxygen is added to the fuel stream, it was predicted that the slow H2 kinetics of Ru in this filter would become an advantage compared to Pt and Pt:Ru alloy anodes, allowing a greater percentage of O2 to oxidize adsorbed CO to CO2. With an anode feed …
Using Sputter Deposition To Increase Co Tolerance In A Proton-Exchange Membrane Fuel Cell, Andrew T. Haug, Ralph E. White, John W. Weidner, Wayne Huang, Steven Shi, Narender Rana, Stephan Grunow, Timothy C. Stoner, Alain E. Kaloyeros
Using Sputter Deposition To Increase Co Tolerance In A Proton-Exchange Membrane Fuel Cell, Andrew T. Haug, Ralph E. White, John W. Weidner, Wayne Huang, Steven Shi, Narender Rana, Stephan Grunow, Timothy C. Stoner, Alain E. Kaloyeros
Faculty Publications
Placing a layer of Ru atop a Pt anode increases the carbon monoxide tolerance of proton-exchange membrane fuel cells when oxygen is added to the fuel stream. Sputter-deposited Ru filter anodes composed of a single Ru layer and three Ru layers separated by Nafion-carbon ink, respectively, were compared to Pt, Pt:Ru alloy, and an ink-based Ru filter anodes. The amount of Pt in each anode was 0.15 mg/cm2 and the amount of Ru in each Ru-containing anode was 0.080 mg/cm2. For an anode feed consisting of hydrogen, 200 ppm CO, and 2% O2 (in the form …
Increasing Power Density Of Lsgm-Based Solid Oxide Fuel Cells Using New Anode Materials, Kevin Huang, Jen-Hau Wan, John B. Goodenough
Increasing Power Density Of Lsgm-Based Solid Oxide Fuel Cells Using New Anode Materials, Kevin Huang, Jen-Hau Wan, John B. Goodenough
Faculty Publications
Chemical reactions between the superior perovskite oxide-ion conductor Sr- and Mg-doped LaGaO3 (LSGM), CeO2, and NiO have been studied by powder X-ray diffraction. The results showed that an extensive reactivity occurs as a result of La migration driven by a gradient of La chemical activity. La migration across the LSGM/electrode interfaces in a fuel cell leads to the formation of resistive phases at the interface, either LaSrGa3O7 or LaSrGaO4. Use of 40 mol % La2O3 -doped CeO2 as an interlayer between anode and electrolyte as well as in …
Electrochemical Investigations Of Cobalt-Doped Limn2O4 As Cathode Material For Lithium-Ion Batteries, P. Arora, Branko Popov, Ralph E. White
Electrochemical Investigations Of Cobalt-Doped Limn2O4 As Cathode Material For Lithium-Ion Batteries, P. Arora, Branko Popov, Ralph E. White
Faculty Publications
A wide range (y = 0.05–0.33) of Co-doped LiCoyMn2–yO4 spinels were synthesized and electrochemically characterized. These Co-doped spinels showed improved specific capacity and capacity retention over pure spinels. Electrochemical impedance spectroscopy and the linear polarization resistance technique were used to determine the transport and electrochemical kinetic parameters of Co-doped spinels. The presence of Co in the spinel inhibits the passivation process occurring on the surface of the cathode. Also, Co increases the exchange current density and facilitates the charge-transfer reaction of the active material. The lower self-discharge observed for Co-doped spinels was attributed …
Characterization Of Hydrogen Permeation Through Zinc-Nickel Alloys Under Corroding Conditions: Mathematical Model And Experimental Study, M. Ramasubramanian, Branko N. Popov, Ralph E. White
Characterization Of Hydrogen Permeation Through Zinc-Nickel Alloys Under Corroding Conditions: Mathematical Model And Experimental Study, M. Ramasubramanian, Branko N. Popov, Ralph E. White
Faculty Publications
A mathematical model was developed for the characterization of hydrogen permeation into metals and alloys under corroding conditions. The model requires a knowledge of the corrosion rate of the given metal or alloy in solutions of various H+ concentrations. It provides quantitative values of rate constants of the hydrogen discharge, recombination, and adsorption reactions. This model can serve as a diagnostic criterion for determining the effectiveness of various metals and alloys as hydrogen permeation inhibitors and can be used for evaluation of hydrogen entry inhibition efficiency. Experiments were carried out to study the effectiveness of thin layers of electrodeposited …
Theoretical Analysis Of Metal Hydride Electrodes: Studies On Equilibrium Potential And Exchange Current Density, Bala S. Haran, Branko N. Popov, Ralph E. White
Theoretical Analysis Of Metal Hydride Electrodes: Studies On Equilibrium Potential And Exchange Current Density, Bala S. Haran, Branko N. Popov, Ralph E. White
Faculty Publications
A theoretical model for the metal hydride electrode has been developed assuming that hydrogen diffusion in the alloy and charge-transfer at the surface control the discharge process. Theoretical equations for the dependence of equilibrium potential and exchange current density on the surface hydrogen concentration have been derived. These parameters have been used to correlate experimental data with the theoretical electrode discharge model. Analysis of both the experimental and theoretical discharge curves reveals a potential plateau determined by the magnitude of the interactions between the hydrogen in the alloy and the unhydrided metal. Neglecting these hydrogen-metal site interactions results in simulations …
A Multiphase Mathematical Model Of A Nickel/Hydrogen Cell, Pauline De Vidts
A Multiphase Mathematical Model Of A Nickel/Hydrogen Cell, Pauline De Vidts
Faculty Publications
No abstract provided.
Mathematical Modeling Of A Nickel-Cadmium Cell: Proton Diffusion In The Nickel Electrode, Pauline De Vidts, Ralph E. White
Mathematical Modeling Of A Nickel-Cadmium Cell: Proton Diffusion In The Nickel Electrode, Pauline De Vidts, Ralph E. White
Faculty Publications
In this paper we present a mathematical model of a sealed nickel-cadmium cell that includes proton diffusion and ohmic drop through the active material in the nickel electrode. The model is used to calculate sensitivity coefficients for various parameters in the model. These calculations show that the discharge voltage of the cell is affected mostly by the kinetics of the nickel reaction. Toward the end of discharge, proton diffusion also becomes important, because the proton diffusion process affects the active material utilization significantly. During charge, the cell voltage is mainly affected by the kinetics of the nickel reaction until the …
The Effect Of Current And Nickel Nitrate Concentration On The Deposition Of Nickel Hydroxide Films, Christopher C. Streinz, Andrew P. Hartman, Sathya Motupally, John W. Weidner
The Effect Of Current And Nickel Nitrate Concentration On The Deposition Of Nickel Hydroxide Films, Christopher C. Streinz, Andrew P. Hartman, Sathya Motupally, John W. Weidner
Faculty Publications
An electrochemical quartz crystal nanobalance (EQCN) has been utilized to measure the mass of Ni(OH)2 films electrochemically deposited from Ni(NO3)2 solutions. The objective of this work was to quantify electrochemical deposition as a function of deposition conditions. The changing mass recorded on the EQCN was demonstrated to be the result of Ni(OH)2 deposition. Deposited mass was observed to increase proportionally with applied charge as suggested by previous investigators. Most significantly, the rate of deposition was found to decrease more than an order of magnitude as the Ni(NO3)2 concentration increased from 0.2 to …
The Role Of Thallium As A Hydrogen Entry Promoter On Cathodically Polarized Hy-130 Steel, G. Zheng, Branko N. Popov, Ralph E. White
The Role Of Thallium As A Hydrogen Entry Promoter On Cathodically Polarized Hy-130 Steel, G. Zheng, Branko N. Popov, Ralph E. White
Faculty Publications
Hydrogen permeation experiments were carried out to investigate the effect of thallium on hydrogen entry into HY-130steel. These experiments show that the presence of thallium ions in an electrolyte drastically increase the hydrogen entry rate. The hydrogen entry efficiency and hydrogen surface coverage were increased by a factor of 10 and 6, respectively. In order to fit the permeation experimental data, the Iyer-Pickering-Zamanzadeh (I-P-Z) hydrogen permeation model was modified by including a mass-transfer term in the discharging equation. The relationship between hydrogen permeation and the hydrogen evolution reaction were investigated and new relationships were obtained.
Impedance Analysis For Oxygen Reduction In A Lithium Carbonate Melt: Effects Of Partial Pressure Of Carbon Dioxide And Temperature, Bhasker B. Dave, Ralph E. White, Supramaniam Srinivasan, A. John Appleby
Impedance Analysis For Oxygen Reduction In A Lithium Carbonate Melt: Effects Of Partial Pressure Of Carbon Dioxide And Temperature, Bhasker B. Dave, Ralph E. White, Supramaniam Srinivasan, A. John Appleby
Faculty Publications
Effects of partial pressure of carbon dioxide and temperature on oxygen reduction kinetics on a gold electrode in a lithium carbonate melt were examined using electrochemical impedance spectroscopic (EIS) and linear sweep voltammetric techniques. The impedance spectra were analyzed by a complex nonlinear least squares method, using the Randles-Ershler equivalent circuit model, to determine the electrode-kinetic and the mass-transfer parameters such as the charge-transfer resistance and the Warburg coefficient. The cyclic voltammetric measurements indicated that the oxygen reduction process in lithium carbonate melt is "reversible" up to 200 mV/s. The product DC0 determined by cyclic voltammetry agreed well …
A Mathematical Model Of A Cuo/Cu Vaporvolt Cell, Makoto Kawanami, Trung V. Nguyen, Ralph E. White
A Mathematical Model Of A Cuo/Cu Vaporvolt Cell, Makoto Kawanami, Trung V. Nguyen, Ralph E. White
Faculty Publications
A new battery named "Vaporvolt"b cell is in the early stage of its development. A mathematical model of a CuO/CuVaporvolt cell is presented that can be used to predict the potential and the transport behavior of the cell during discharge.A sensitivity analysis of the various transport and electrokinetic parameters indicates which parameters have the mostinfluence on the predicted energy and power density of the Vaporvolt cell. This information can be used to decide whichparameters should be optimized or determined more accurately through further modeling or experimental studies. Theoptimal thicknesses of electrodes and separator, the concentration of the electrolyte, and …
Parameter Sensitivity And Optimization Predictions Of A Hydrogen/Oxygen Alkaline Fuel Cell Model, Michael C. Kimble, Ralph E. White
Parameter Sensitivity And Optimization Predictions Of A Hydrogen/Oxygen Alkaline Fuel Cell Model, Michael C. Kimble, Ralph E. White
Faculty Publications
A mathematical model is used to predict parameter sensitivities and optimal design parameters for a hydrogen/oxygen alkaline fuel cell. A sensitivity analysis of the various transport and electrode kinetic parameters indicates which parameters have the most influence on the predicted current density and over which range of potentials these parameters affect the fuel-cell performance the most. This information can be used to decide which parameters should be optimized or determined more accurately through further modeling or experimental studies. The effect of various design parameters on the limiting current density are investigated to determine if optimal values exist for the parameters. …
The Self-Discharge Of The Niooh/Ni(Oh)2 Electrode Constant Potential Study, Z. Mao, Ralph E. White
The Self-Discharge Of The Niooh/Ni(Oh)2 Electrode Constant Potential Study, Z. Mao, Ralph E. White
Faculty Publications
Hydrogen oxidation currents at a NiOOH/Ni(OH)2 electrode were measured directly at constant potentials for various hydrogen pressures and states of charge. It was found that the hydrogen oxidation current is linearly proportional to the hydrogen pressure at all electrode potentials and that the logarithm of the anodic current is a linear function of electrode potential. It was also found that hydrogen oxidation on the nickel substrate material was strongly inhibited by the presence of nickel hydroxide on the substrate surface. By comparing the currents for hydrogen oxidation and oxygen evolution on the NiOOH/Ni(OH)2 electrode and on a nickel …
Current Distribution In A Horizon® Lead-Acid Battery During Discharge, Z. Mao, Ralph E. White, B. Jay
Current Distribution In A Horizon® Lead-Acid Battery During Discharge, Z. Mao, Ralph E. White, B. Jay
Faculty Publications
A simple mathematical model is presented and used to analyze the potential and current distributions in a HORIZON® sealed lead-acid battery. It was found that an increase in the thickness of an electrode would not enhance the discharge rate of that electrode; instead, it causes the transfer current distribution to be less uniform in the electrode. Also, the ohmic drop across the separator would decrease with a decrease in the thickness of the separator more rapidly when the thickness is small than when it is large. In addition, it was found that efficient high-capacity, high-rate electrodes must consider the electrode …
Effect Of Ohmic, Mass-Transfer, And Kinetic Resistances On Linear-Sweep Voltammetry In A Cylindrical-Pore Electrode, John W. Weidner, Peter S. Fedkiw
Effect Of Ohmic, Mass-Transfer, And Kinetic Resistances On Linear-Sweep Voltammetry In A Cylindrical-Pore Electrode, John W. Weidner, Peter S. Fedkiw
Faculty Publications
Extracting quantitative kinetic information from linear-sweep voltammograms (LSV) on porous electrodes is more difficult than on planar electrodes since the electrode surface is not uniformly accessible to the bulk supply of reactant or the counterelectrode. We present here a means to account for the effect of ohmic, mass-transfer, and kinetic resistances on LSV by modeling a pore in a porous matrix as a cylindrical-pore electrode, and solving the mass and charge conservation equations in the context of this geometry for the simply redox reaction O + ne– <=> R where both O and R are soluble species. Both analytical …
A Mathematical Model Of A Lithium/Thionyl Chloride Primary Cell, T. I. Evans, T. V. Nguyen, Ralph E. White
A Mathematical Model Of A Lithium/Thionyl Chloride Primary Cell, T. I. Evans, T. V. Nguyen, Ralph E. White
Faculty Publications
A one-dimensional mathematical model for the lithium/thionyl chloride primary cell has been developed to investigate methods of improving its performance and safety. The model includes many of the components of a typical lithium/thionyl chloride cell such as the porous lithium chloride film which forms on the lithium anode surface. The governing equations are formulated from fundamental conservation laws using porous electrode theory and concentrated solution theory. The model is used to predict one-dimensional, time dependent profiles of concentration, porosity, current, and potentialas well as cell temperature and voltage. When a certain discharge rate is required, the model can be used …
Estimation Of Electrode Kinetic Parameters Of The Lithium/Thionyl Chloride Cell Using A Mathematical Model, T. I. Evans, Ralph E. White
Estimation Of Electrode Kinetic Parameters Of The Lithium/Thionyl Chloride Cell Using A Mathematical Model, T. I. Evans, Ralph E. White
Faculty Publications
A one-dimensional mathematical model for the lithium/thionyl chloride primary cell is used in conjunction with a parameter estimation technique, in order to estimate the electrode kinetic parameters of this electrochemical system. The electrode kinetic parameters include the anodic transfer coefficient and exchange current density of the lithium oxidation, a,1 and i0,1,ref; the cathodic transfer coefficient and the effective exchange current density of the thionyl chloride reduction, c,4 and a0i0,4,ref, and a morphology parameter, . The parameter estimation is performed on simulated data first in order to gain confidence in the method. Data reported in …
Analysis Of Electrokinetic Data By Parameter Estimation And Model Discrimination Techniques, Prosper K. Adanuvor, Ralph E. White
Analysis Of Electrokinetic Data By Parameter Estimation And Model Discrimination Techniques, Prosper K. Adanuvor, Ralph E. White
Faculty Publications
An alternative approach to classical methods of electrochemical data analysis is presented. This alternative method is based on nonlinear parameter estimation and model discrimination techniques. The method is used to obtain the relevant kinetic and transport parameters and to elucidate the kinetic mechanism of O2 reduction at carbon and silver electrodes in alkaline electrolytes.
Modeling The Rotating Disk Electrode For Studying The Kinetics Of Electrochemical Reactions, P K. Adanuvor, Ralph E. White, S E. Lorimer
Modeling The Rotating Disk Electrode For Studying The Kinetics Of Electrochemical Reactions, P K. Adanuvor, Ralph E. White, S E. Lorimer
Faculty Publications
A general mathematical model for studying the kinetics of electrochemical reactions at a rotating disk electrode under steady-state potentiostatic conditions is presented. The model, apart from predicting the net and partial current densities at given values of the applied potential, the ohmic potential drop, and the concentration and potential profiles in the solution, also accounts for homogeneous reactions of any order in the solution and noncharge transfer reactions at the electrode surface. The versatility of the model is demonstrated by the application of the model to a variety of complex reaction schemes.
The Effect Of The Tribromide Complex Reaction On The Oxidation/Reduction Current Of The Br2/Br– Electrode, P K. Adanuvor, Ralph E. White, S. E. Lorimer
The Effect Of The Tribromide Complex Reaction On The Oxidation/Reduction Current Of The Br2/Br– Electrode, P K. Adanuvor, Ralph E. White, S. E. Lorimer
Faculty Publications
The Br2/Br– electrode reaction with tribromide complex formation reaction in the solution, a chemical-electrochemical (C-E) type reaction, has been investigated in order to determine the effect of the chemical reaction on the electrode kinetics. It is shown that the chemical reaction has little effect on the electrode kinetics at very slow homogeneous reaction rates, but has a more drastic effect on the electrode kinetics at faster homogeneous reaction rates. Also, the kinetics at the electrode are affected by changes in the concentrations of the active species (Br2, Br–, and Br3–) …
A Mathematical Model For A Parallel Plate Electrochemical Reactor, Cstr, And Associated Recirculation System, T V. Nguyen, C W. Walton, Ralph E. White
A Mathematical Model For A Parallel Plate Electrochemical Reactor, Cstr, And Associated Recirculation System, T V. Nguyen, C W. Walton, Ralph E. White
Faculty Publications
A mathematical model is presented for a system comprised of a parallel plate electrochemical reactor (PPER) and a continuous, stirred-tank reactor (CSTR) under both total and partial recycle. The model is used to predict the time dependent behavior of the electrowinning of copper from an aqueous, hydrochloric acid solution. The model includes many important aspects of a PPER/CSTR system which have been neglected previously. These aspects are the kinetics of electrode reactions, the electroneutrality condition, three mass transfer processes for ionic species in the electrolyte (diffusion, ionic migration, and convection) and the electrode gap in the PPER, and the inclusion …