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 and the film resistance, both estimated at the end of CC-CV charging. The effect of rate of solvent reduction reaction and the conductivity of the film formed were also studied. © 2004 The Electrochemical Society. All rights reserved.

A model for the simulation of the steady-state impedance response of a polymer electrolyte membrane fuel cell (PEMFC) cathode is presented. The catalyst layer of the electrode is assumed to consist of many flooded spherical agglomerate particles surrounded by a small volume fraction of gas pores. Stefan-Maxwell equations are used to describe the multicomponent gas-phase transport occurring in both the gas diffusion layer and the catalyst layer of the electrode. Liquid-phase diffusion of O-2 is assumed to take place in the flooded agglomerate particles. Newman s porous electrode theory is applied to determine over-potential distributions. (C) 2004 The Electrochemical Society.

An easy-to-use variant of the finite difference method (FDM), the polynomial finite difference method (PFDM), for the numerical solution of ordinary differential equations (ODEs) and differential-algebraic equations (DAEs), is presented. Compared to the traditional implementation of the FDM, the PFDM approach has two major advantages: straightforward implementation, and easily adjustable accuracy order. Some examples are presented to compare the numerical solutions of the PFDM to those of other popular ODEs/DAEs methods. These examples show that the PFDM also has the following good features: feasible for ODEs/DAEs in the implicit form, capable of self-starting in high orders, and applicable to stiff problems. © 2003 Elsevier Ltd. All rights reserved.

A macrohomogeneous model is presented for a porous electrode that includes coupled potential and concentration gradients with linear kinetics. The equations are solved to obtain an analytical expression for the impedance of a porous electrode. Complex plane plots are presented that illustrate two well-defined arcs: a kinetic arc and a diffusion arc with their time constants far apart. The effects of parameters such as exchange current density, porosity, diffusion coefficient, thickness, and interfacial area on the impedance spectra are presented. The usefulness of the analytical solution in investigating the effect of solution phase diffusion is also presented.

Transient analytical solutions are presented for the overpotential and the voltage for a porous electrode that includes both double-layer charging and a faradaic reaction. In addition, a simplified dynamic model is developed for the same process based on a second order, three-parameter polynomial approximate model. The effects of the parameters such as dimensionless exchange current density, conductivity ratio and applied current density on the voltage and overpotential distribution are presented. Also, using the exact transient solution an expression for the dimensionless interfacial current density is derived and the effects of the parameters mentioned above are presented. © 2004 Elsevier B.V. All rights reserved.

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 processes significantly influencing the performance of PEMFC air cathodes. While ionic conduction influences cathode performance over a wide range of current densities, gas-phase transport influences cathode performance only at high current densities. © 2004 The Electrochemical Society. All rights reserved.

A mathematical model is presented to predict the performance of a lithium-ion battery, It includes the changes in the porosity of the material due to the reversible intercalation processes and the irreversible parasitic reaction, The model was also extended to predict the capacity fade in a lithium-ion battery based on the unwanted parasitic reaction that consumes Li + along with the changes in the porosities of the electrodes with cycling due to the continuous parasitic side reaction. The model can be used to predict the drop in the voltage profile, change in the state of charge, and the effects of charge and discharge rates during cycling. © 2004 The Electrochemical Society. All rights reserved.

A one-dimensional, isothermal model for a direct methanol fuel cell (DMFC) is presented. This model accounts for the kinetics of the multi-step methanol oxidation reaction at the anode. Diffusion and crossover of methanol are modeled and the mixed potential of the oxygen cathode due to methanol crossover is included. Kinetic and diffusional parameters are estimated by comparing the model to data from a 25 cm 2 DMFC. This semi-analytical model can be solved rapidly so that it is suitable for inclusion in real-time system level DMFC simulations. Copyright © 2004 by ASME.

A capacity fade prediction model has been developed for Li-ion cells based on a semi-empirical approach. Correlations for variation of capacity fade parameters with cycling were obtained with two different approaches. The first approach takes into account only the active material loss, while the second approach includes rate capability losses too. Both methods use correlations for variation of the film resistance with cycling. The state of charge (SOC) of the limiting electrode accounts for the active material loss. The diffusion coefficient of the limiting electrode was the parameter to account for the rate capability losses during cycling. © 2003 Elsevier Science B.V. All rights reserved.

A theoretical model for the molten carbonate fuel cell was developed based on the three-phase homogeneous approach. Using this model, the contribution of different cell components to losses in cell performance has been studied, In general, at low current densities, the electrolyte matrix contributed to the major fraction of potential losses. Mass transfer effects became important at high current densities and were more prominent at the cathode. Electrolyte conductivity and cathode exchange current density seemed to play a limiting role in determining cell performance. Using the model, the maximum power density from a single cell for different cell thicknesses was determined. © 2003 The Electrochemical Society. All rights reserved.