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Full-Text Articles in Engineering
Hydrogen Peroxide Formation Rates In A Pemfc Anode And Cathode: Effect Of Humidity And Temperature, Vijay A. Sethuraman, John W. Weidner, Andrew T. Haug, Sathya Motupally, Lesia V. Protsailo
Hydrogen Peroxide Formation Rates In A Pemfc Anode And Cathode: Effect Of Humidity And Temperature, Vijay A. Sethuraman, John W. Weidner, Andrew T. Haug, Sathya Motupally, Lesia V. Protsailo
Faculty Publications
Hydrogen peroxide (H2O2) formation rates in a proton exchange membrane fuel cell (PEMFC) anode and cathode were estimated as a function of humidity and temperature by studying the oxygen reduction reaction (ORR) on a rotating ring disk electrode. Fuel cell conditions were replicated by depositing a film of Pt/Vulcan XC-72 catalyst onto the disk and by varying the temperature, dissolved O2 concentration, and the acidity levels in hydrochloric acid (HClO4). The HClO4 acidity was correlated to ionomer water activity and hence fuel cell humidity. The H2O2 formation rates showed …
Development Of Ruthenium-Based Catalysts For Oxygen Reduction Reaction, Lingyun Liu, Hansung Kim, Jong-Won Lee, Branko N. Popov
Development Of Ruthenium-Based Catalysts For Oxygen Reduction Reaction, Lingyun Liu, Hansung Kim, Jong-Won Lee, Branko N. Popov
Faculty Publications
A process was developed to synthesize ruthenium-based chelate (RuNx) electrocatalysts for the oxygen reduction reaction, using RuCl3 and propylene diammine as the Ru and N precursors, respectively. High-temperature pyrolysis has a critical role in the formation of the catalytic Ru–N sites for oxygen reduction. The RuNx catalyst modified in the presence of nitrogen-containing organic exhibited comparable catalytic activity and selectivity for oxygen reduction to the carbon-supported Pt catalyst in acidic media. The catalyst generates less than 2% hydrogen peroxide during oxygen reduction.
Development Of Method For Synthesis Of Pt–Co Cathode Catalysts For Pem Fuel Cells, Xuguang Li, Héctor R. Colón-Mercado, Gang Wu, Jong-Won Lee, Branko N. Popov
Development Of Method For Synthesis Of Pt–Co Cathode Catalysts For Pem Fuel Cells, Xuguang Li, Héctor R. Colón-Mercado, Gang Wu, Jong-Won Lee, Branko N. Popov
Faculty Publications
A procedure was developed to synthesize a platinum–cobalt (Pt–Co) alloy electrocatalyst for oxygen reduction using Co/C composite as a support. The Pt–Co/C catalysts were synthesized through: (i) chemical oxidation of carbon black, (ii) Co deposition on the oxidized carbon using a chelation method, (iii) chemical treatment in an acidic medium to remove excess of Co on the carbon surface, (iv) Pt deposition onto the Co/C support, and (v) postheat treatment to form the Pt–Co alloy catalyst. The synthesized Pt–Co/C catalyst showed improved activity and long-term stability in polymer electrolyte membrane …
Simulation Of Polarization Curves For Oxygen Reduction Reaction In 0.5 M H2So4 At A Rotating Ring Disk Electrode, Qingbo Dong, Shriram Santhanagopalan, Ralph E. White
Simulation Of Polarization Curves For Oxygen Reduction Reaction In 0.5 M H2So4 At A Rotating Ring Disk Electrode, Qingbo Dong, Shriram Santhanagopalan, Ralph E. White
Faculty Publications
A cylindrical two-dimensional model based on the Nernst–Planck equations, the Navier–Stokes equation, and the continuity equation is used to simulate the oxygen reduction reaction in 0.5MH2SO4 at a rotating ring disk electrode. Concentration distributions and a potential profile are obtained as a function of the axial and radial distances from the center of the electrode surface. Polarization curves are simulated to interpret experimental results by studying various reaction mechanisms, i.e., the four-electron-transfer reduction of oxygen, the two-electron-transfer reduction of oxygen, a combination of the above two reactions, mechanisms with reduction of peroxide to water, and/or the heterogeneous …
Simulation Of The Oxygen Reduction Reaction At An Rde In 0.5 M H2So4 Including An Adsorption Mechanism, Qingbo Dong, Shriram Santhanagopalan, Ralph E. White
Simulation Of The Oxygen Reduction Reaction At An Rde In 0.5 M H2So4 Including An Adsorption Mechanism, Qingbo Dong, Shriram Santhanagopalan, Ralph E. White
Faculty Publications
Oxygen reduction on the surface of a rotating disk electrode (RDE) in 0.5 M H2SO4 is simulated by including mass transfer, adsorption, and charge transfer. A generalized model for the adsorption and reaction of several species is introduced. The oxygen reduction reaction is simulated as a limiting case where oxygen is the only species adsorbed, and oxygen reduction is the only reaction that takes place on the surface of the electrode. The model is based on the Nernst–Planck equations for mass transfer and the Butler–Volmer equation for electrochemical kinetics. The simulated polarization curves capture the change in …
Development Of First Principles Capacity Fade Model For Li-Ion Cells, P. Ramadass, Bala Haran, Parthasarathy M. Gomadam, Ralph E. White, Branko N. Popov
Development Of First Principles Capacity Fade Model For Li-Ion Cells, P. Ramadass, Bala Haran, Parthasarathy M. Gomadam, Ralph E. White, Branko N. Popov
Faculty Publications
A first principles-based model has been developed to simulate the capacity fade of Li-ion batteries. Incorporation of a continuous occurrence of the solvent reduction reaction during constant current and constant voltage (CC-CV) charging explains the capacity fade of the battery. The effect of parameters such as end of charge voltage and depth of discharge, the film resistance, the exchange current density, and the over voltage of the parasitic reaction on the capacity fade and battery performance were studied qualitatively. The parameters that were updated for every cycle as a result of the side reaction were state-of-charge of the electrode materials …
Cycle Life Modeling Of Lithium-Ion Batteries, Gang Ning, Branko N. Popov
Cycle Life Modeling Of Lithium-Ion Batteries, Gang Ning, Branko N. Popov
Faculty Publications
A first-principles-based charge-discharge model was developed to simulate the capacity fade of Li-ion batteries. The model is based on the loss of active lithium ions due to solvent reduction reaction and on the rise of the anode film resistance. The effect of parameters such as exchange current density, depth of discharge (DOD), end of charge voltage, film resistance, and the overvoltage of parasitic reaction were studied quantitatively. The model controls the required DOD by controlling the discharge time and estimates the end of discharge voltages as a function of cycle number.
Parameter Estimates For A Pemfc Cathode, Qingzhi Guo, Vijay A. Sethuraman, Ralph E. White
Parameter Estimates For A Pemfc Cathode, Qingzhi Guo, Vijay A. Sethuraman, Ralph E. White
Faculty Publications
Five parameters of a model of a polymer electrolyte membrane fuel cell (PEMFC) cathode (the volume fraction of gas pores in the gas diffusion layer, the volume fraction of gas pores in the catalyst layer, the exchange current density of the oxygen reduction reaction, the effective ionic conductivity of the electrolyte, and the ratio of the effective diffusion coefficient of oxygen in a flooded spherical agglomerate particle to the square of that particle radius) were determined by least-squares fitting of experimental polarization curves. The values of parameters obtained in this work indicate that ionic conduction and gas-phase transport are two …
Synthesis And Characterization Of Mno2-Based Mixed Oxides As Supercapacitors, Hansung Kim, Branko N. Popov
Synthesis And Characterization Of Mno2-Based Mixed Oxides As Supercapacitors, Hansung Kim, Branko N. Popov
Faculty Publications
Mn/Pb and Mn/Ni mixed oxide were prepared at ambient temperature by reduction of KMnO4 with Mn, Pb, and Ni salts. This low-temperature approach provides amorphous structure of the active material. The specific capacitance of pure MnO2 was estimated to be 166 F/g and increased to 210 and 185 F/g for Mn/Ni and Mn/Pb oxides, respectively. The carbon loading was optimized at 20 wt %. Based on a single electrode, the Mn/Ni mixed oxide showed a high rate capability of 3.12 Wh/kg at constant power discharge of 1 kW/kg.
The Role Of Oxygen At The Second Discharge Plateau Of Nickel Hydroxide, Sathya Motupally, Mukul Jain, Venkat Srinivasan, John W. Weidner
The Role Of Oxygen At The Second Discharge Plateau Of Nickel Hydroxide, Sathya Motupally, Mukul Jain, Venkat Srinivasan, John W. Weidner
Faculty Publications
It was shown that the appearance of a secondary discharge plateau approximately 400 mV below the primary plateau can result from the reduction of oxygen. During the galvanostatic discharge of planar nickel-hydroxide films at room temperature and in 3 weight percent KOH solutions, the second discharge plateau was observed only in the presence of dissolved oxygen in the electrolyte. When the solution was deoxygenated, no residual capacity could be extracted from the films even at low discharge rates or from overcharged films. In addition, the duration of the second plateau is inversely proportional to the square of the discharge current, …
Linear Algebra Used To Determine Independent Half‐Cell Equations, D. H. Coleman, Ralph E. White
Linear Algebra Used To Determine Independent Half‐Cell Equations, D. H. Coleman, Ralph E. White
Faculty Publications
No abstract provided.
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 …
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 …
Reduction Of Chromium (Vi) When Solar Selective Black Chromium Is Deposited In The Presence Of Organic Additive, Branko N. Popov, Ralph E. White, D. Slavkov, Z. Koneska
Reduction Of Chromium (Vi) When Solar Selective Black Chromium Is Deposited In The Presence Of Organic Additive, Branko N. Popov, Ralph E. White, D. Slavkov, Z. Koneska
Faculty Publications
Electrochemical dc methods were used to study the reduction of chromium (VI) in the presence of organic additives. It is shown that F–, thiourea, and citric acid are essential to enable deposition of black chrome from concentrated chromic acid solutions. A new formulation of the plating bath is defined. The optimum operating conditions under which spectrally selective surface of black chrome is deposited have been determined.
A Mathematical Model Of A Sealed Nickel-Cadmium Battery, Deyuan Fan, Ralph E. White
A Mathematical Model Of A Sealed Nickel-Cadmium Battery, Deyuan Fan, Ralph E. White
Faculty Publications
A mathematical model for the charge and discharge of a sealed nickel-cadmium (Ni-Cd) battery is presented. The model is used to study the effect of transport properties of the electrolyte and kinetic parameters of the electrode reactions on the cell performance during the charge and discharge period. The model can also be used to demonstrate the changes of cell performance during cycling. Some comparisons between model predictions and experimental results indicate that the model predictions appear to fit the experimental data well. Sensitivity analyses illustrate that the sealed nickel-cadmium battery operates under activation control. It is also shown theoretically that …
Electrode Kinetics Of Oxygen Reduction In Lithium Carbonate Melt: Use Of Impedance Analysis And Cyclic Voltammetric Techniques To Determine The Effects Of Partial Pressure Of Oxygen, Bhasker B. Davé, Ralph E. White, Supramanian Srinivasan, A. John Appleby
Electrode Kinetics Of Oxygen Reduction In Lithium Carbonate Melt: Use Of Impedance Analysis And Cyclic Voltammetric Techniques To Determine The Effects Of Partial Pressure Of Oxygen, Bhasker B. Davé, Ralph E. White, Supramanian Srinivasan, A. John Appleby
Faculty Publications
The effects of the partial pressure of oxygen and temperature on the oxygen reduction on a submerged gold electrode in a lithium carbonate melt were investigated using cyclic voltammetry and impedance analysis. The values for the mass-transfer parameters, DCO, obtained from cyclic voltammetry and impedance analysis were in good agreement. The reaction orders for oxygen at 800°C were calculated to be about 0.3 for the exchange current density and 0.5 for the product DCO; these values are consistent with the mechanism proposed in the literature for oxygen reduction in Li2CO3 melt.
A Computer Simulation Of The Oxygen Reduction Reaction In Carbonate Melts, P. K. Adanuvor, Ralph E. White, A. J. Appleby
A Computer Simulation Of The Oxygen Reduction Reaction In Carbonate Melts, P. K. Adanuvor, Ralph E. White, A. J. Appleby
Faculty Publications
A computer simulation of the oxygen reduction reaction in various carbonate melts has been carried out under steady-state conditions on the basis of a proposed kinetic model which takes into consideration the autocatalytic reaction involving oxygen and other reducible oxygen species in the melt, and the neutralization of oxide ions by dissolved carbon dioxide. A simulation of the presence of (physically) dissolved oxygen, in the diffusion layer region of the melt, corresponding to the possible situation in porous electrodes, causes a significant enhancement in the polarization curves, particularly in the mass-transfer control region. On the other hand, high levels of …
Oxygen Reduction In A Proton Exchange Membrane Test Cell, S. J. Ridge, Ralph E. White, Y. Tsou, R. N. Beaver, G. A. Eisman
Oxygen Reduction In A Proton Exchange Membrane Test Cell, S. J. Ridge, Ralph E. White, Y. Tsou, R. N. Beaver, G. A. Eisman
Faculty Publications
Oxygen reduction in a gas-fed porous electrode attached to a proton exchange membrane is discussed. Experimental data and a mathematical model are presented for the test cell used. Various membrane and electrode assemblies were tested at different levels of platinum loading and Teflon® content. The model accounts for the diffusion and reaction of oxygen and the diffusion and reaction of hydrogen ions. Sulfuric acid was placed above the membrane in the test cell reservoir to provide a source of protons for the reduction of oxygen at the cathode. Based upon model predictions, it is shown that the transport of the …
Oxygen Reduction On Silver In 6.5 Molar Caustic Soda Solution, Prosper K. Adanuvor, Ralph E. White
Oxygen Reduction On Silver In 6.5 Molar Caustic Soda Solution, Prosper K. Adanuvor, Ralph E. White
Faculty Publications
No abstract provided.
Oxygen Reduction On Silver In 6.5m Caustic Soda Solution, Prosper K. Adanuvor, Ralph E. White
Oxygen Reduction On Silver In 6.5m Caustic Soda Solution, Prosper K. Adanuvor, Ralph E. White
Faculty Publications
The cathodic reduction of oxygen in 6.5M membrane-grade caustic soda solution has been studied experimentally at a silver rotating disk electrode at 25°C. The results can be approximated by the parallel mechanism for oxygen reduction with catalytic decomposition of peroxide. Further analysis of this mechanism indicates that the sequential process with catalytic decomposition of peroxide predominates over the direct 4e– process. Direct application of the sequential mechanism to the data indicates that the latter mechanism with catalytic decomposition of peroxide much more accurately reflects the experimental results. The relevant kinetic parameters are calculated on the basis of …
Electrochemical Production And Corrosion Testing Of Amorphous Ni-P, Jose L. Carbajal, Ralph E. White
Electrochemical Production And Corrosion Testing Of Amorphous Ni-P, Jose L. Carbajal, Ralph E. White
Faculty Publications
Ni-P alloys were prepared by electrodeposition under different conditions on a rotating disk electrode. A variety of alloys were prepared ranging from Ni-15P to Ni-25P. An indirect reduction of species in solution involving several steps appears to be favored over the direct reduction at the electrode based on the low P content in the alloy. Energy dispersion x-ray microanalysis was used to determine composition of the alloy. Transmission electron microscopy and x-ray diffraction corroborated the amorphous nature of the structure. The physical and chemical homogeneity of the metallic glasses produced electrochemically is substantiated by the absence of electrochemical localized attack. …
Simulation Of The Polarization Curves For Oxygen Reduction At A Rotating Disk Electrode, P. K. Adanuvor, Ralph E. White
Simulation Of The Polarization Curves For Oxygen Reduction At A Rotating Disk Electrode, P. K. Adanuvor, Ralph E. White
Faculty Publications
The electrochemical reduction of oxygen in 1M NaOH solution is simulated at a rotating disk electrode. Steady-state polarization curves are presented for possible reaction schemes for the reduction process. The effect of changes in the kinetic parameters on the polarization curves is demonstrated and special attention is focused on the production of hydrogen peroxide.
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–) …
Extension Of Darby's Model Of A Hydrophylic Gas Fed Porous Electrode, Ralph E. White, M. A. Nicholson, L. G. Kleine, J. Van Zee, R. Darby
Extension Of Darby's Model Of A Hydrophylic Gas Fed Porous Electrode, Ralph E. White, M. A. Nicholson, L. G. Kleine, J. Van Zee, R. Darby
Faculty Publications
A model presented previously by one of the authors (1,2) is reviewed and extended. Aspects of this model which were not previously available in the open literature are considered, and the model is extended to include previously neglected terms in the governing differential equations, fractional reaction orders in the current density-overpotential expression, and mass-transfer coefficients to account for mass-transfer resistance of the reactants to the faces of the porous electrode. The model is used to predict quantities of interest for oxygen reduction in an acidic aqueous solution in a porous carbon electrode.
An Analysis Of A Back Fed Porous Electorde For The Br2/Br- Redox Reaction, John W. Van Zee, Ralph E. White
An Analysis Of A Back Fed Porous Electorde For The Br2/Br- Redox Reaction, John W. Van Zee, Ralph E. White
Faculty Publications
No abstract provided.
An Analysis Of A Back Fed Porous Electrode For The Br2/Br Reaction, John Van Zee, Ralph E. White
An Analysis Of A Back Fed Porous Electrode For The Br2/Br Reaction, John Van Zee, Ralph E. White
Faculty Publications
An experimental analysis of the Br2/Br– redox reaction in a porous back fed ruthenium-coated titanium electrode is described. A mathematical model of the steady-state process is presented. Nonlinear regression of the model against the experimental data gives physically meaningful parameter estimates; these parameters and the model provide a design equation for the porous electrode current as a function of specific surface area, bulk Br2 concentration, average total overpotential, and the Reynolds number. The design equation shows that the back fed electrode could reduce the loss of Br2 across the separator and the ohmic loss in …
Electrochemical Reduction Of Molybdenum(Vi) Compounds In Molten Lithium Chloride-Potassium Chloride Eutectic, Branko N. Popov, H. A. Laitinen
Electrochemical Reduction Of Molybdenum(Vi) Compounds In Molten Lithium Chloride-Potassium Chloride Eutectic, Branko N. Popov, H. A. Laitinen
Faculty Publications
Molybdenum (VI) oxide reacts with molten LiCl-KCl eutectic at 450° to form MoO2CI2, which probably is present as an anion MoO2Cl4=, and pyromolybdate, Mo2O7=. Both of these species are electrochemically reduced to MoO2, which can be reoxidized to MoO2Cl2 by current reversal. A second reduction step, observed whether MoO3 or Mo2O72− is added to the melt, can be attributed to the reduction of MoO4−−, formed as a secondary reaction product in the first …
Electrochemical Reduction Of Chromate In The Presence Of Nickel Chloride In Molten Lithium Chloride-Potassium Chloride Eutectic, Branko N. Popov, H. A. Laitinen
Electrochemical Reduction Of Chromate In The Presence Of Nickel Chloride In Molten Lithium Chloride-Potassium Chloride Eutectic, Branko N. Popov, H. A. Laitinen
Faculty Publications
Chronopotentiometry of chromate in the presence of NiCl2 in molten LiCl-KCl eutectic reveals a diffusion controlled, three electron reduction step. In the presence of excess NiCl2, chromate is reduced at −0.35V vs. Pt(II)/Pt reference electrode and the electroactive species responsible for the chrono-potentiometric wave is estimated to have a diffusion coefficient of 1.06 · 10−5 cm2 sec−1 at 450°C. The stoichiometry of the reduction product depends mainly on the temperature at which the deposit is formed. At 500°C the deposit approaches the composition LiNi2CrO4. X-ray powder diffraction shows the deposit …