Effect of gas-phase transport in molten carbonate fuel cell

Electrode reaction characteristics involving gas-phase transport effect have been investigated with several 100 cm 2 class molten carbonate fuel cells (MCFCs). Although the MCFCs operate on gas-phase reactants at relatively high temperature, most of studies on the electrode reaction kinetics have been confined within kinetic-control and liquid-phase mass-transfer regions. To evaluate the gas-phase transport effect in the MCFC, an inert gas step addition (ISA) method was devised in this work. The ISA varies reactant flow rate for an electrode by adding an inert gas, which results in an overpotential shift. Since gas-phase mass-transfer resistance should be a function of reactant flow rate, correlation of the overpotential shifts with the reactant flow rates yields valuable information regarding the gas-phase transport effect in the electrode. The ISA was performed at both the anode and cathode with respect to reactant gas flow rates, addition amounts of inert gas, inert gas species, and currents applied to the cell. The overpotential shifts for both the anode and cathode were found to be inversely proportional to the square root of the reactant flow rate, indicating gas-phase mass-transfer control of both these electrodes. Especially, the overpotential shift values for the anode are much larger than those for the cathode, which suggests that the anode is under severe gas-phase mass-transfer control. From the partial pressure dependence of the overpotential shifts in the cathode, the cathode was found to be a combined gas and liquid-phase mass-transfer control system. # 2002 Elsevier Science B.V. All rights reserved.

[1]  Hiroshi Morita,et al.  Model of Cathode Reaction Resistance in Molten Carbonate Fuel Cells , 1998 .

[2]  A. Appleby,et al.  Reduction of oxygen in alkali carbonate melts , 1977 .

[3]  H. R. Kunz,et al.  The Effect of Thickness on the Performance of Molten Carbonate Fuel Cell Cathodes , 1982 .

[4]  P. Tomczyk,et al.  Kinetics of the oxygen electrode reaction in molten Li + Na carbonate eutectic: Part 3. Quantitative analysis of the linear scan voltammetric curves for the first reduction process at Au electrodes , 1991 .

[5]  M. Cassir,et al.  Stability and Characterization of Oxygen Species in Alkali Molten Carbonate: A Thermodynamic and Electrochemical Approach , 1993 .

[6]  Robert E. Wilson,et al.  Fundamentals of momentum, heat, and mass transfer , 1969 .

[7]  J. Selman,et al.  Gas Electrode Reactions in Molten Carbonate Media Part V . Electrochemical Analysis of the Oxygen Reduction Mechanism at a Fully Immersed Gold Electrode , 1990 .

[8]  J. R. Selman,et al.  Porous‐Electrode Modeling of the Molten‐Carbonate Fuel‐Cell Electrodes , 1992 .

[9]  J. Selman,et al.  Characterization of fuel cell electrode processes by AC impedance , 1988 .

[10]  Allen J. Bard,et al.  Electrochemical Methods: Fundamentals and Applications , 1980 .

[11]  I. Uchida,et al.  Gas electrode reactions in molten carbonate media Part I. Exchange current density of oxygen reduction in (Li + K)CO3 eutectic at 650°C , 1986 .

[12]  Tatsuo Nishina,et al.  Characterization of a 100 cm2 Class Molten Carbonate Fuel Cell with Current Interruption , 1998 .

[13]  Gas Electrode Reactions in Molten Carbonate Media IV . Electrode Kinetics and Mechanism of Hydrogen Oxidation in Eutectic , 1990 .

[14]  O. Levenspiel Chemical Reaction Engineering , 1972 .

[15]  G. Rosen The mathematical theory of diffusion and reaction in permeable catalysts , 1976 .

[16]  Impedance Analysis for Oxygen Reduction in a Lithium Carbonate Melt , 1991 .

[17]  G. Mordarski Kinetics of the oxygen electrode reaction in molten Li + Na carbonate eutectic: Part 4. Quantitative analysis of the potential-step chronoamperometric curves at Au electrodes , 1991 .

[18]  D. Inman Electrochemistry of molten and solid electrolytes : Vol. 3, edited by A.N. baraboshkin, English translation, Consultants Bureau, New York, 1966, pages viii+133, $17.50. , 1967 .

[19]  K. Kobe,et al.  Chemical engineering kinetics , 1956 .

[20]  K. Hemmes,et al.  A Comparative Study of NiO ( Li ) , LiFeO2, and LiCoO2 Porous Cathodes for Molten Carbonate Fuel Cells , 1994 .

[21]  J. Selman,et al.  Electrode kinetics of oxygen reduction on gold in molten carbonate , 1992 .

[22]  Gerald Wilemski Simple Porous Electrode Models for Molten Carbonate Fuel Cells , 1983 .

[23]  G. Lindbergh,et al.  Experimental Investigation of the Porous Nickel Anode in the Molten Carbonate Fuel Cell , 2001 .

[24]  I. Uchida,et al.  Gas electrode reactions in molten carbonate media: Part III. Temperature dependence of oxygen reduction kinetics in (Li + K)CO3 eutectic , 1986 .

[25]  L. J. Bregoli,et al.  Studies of the Reduction of Oxygen on Gold in Molten Li2 CO 3 ‐ K 2 CO 3 at 650°C , 1983 .

[26]  P. Tomczyk,et al.  Kinetics of the oxygen electrode reaction in molten Li + Na carbonate eutectic , 1991 .

[27]  A. Appleby,et al.  The reduction of oxygen in molten lithium carbonate , 1974 .

[28]  A. F. Sammells,et al.  Influence of Electrolyte Composition on Electrode Kinetics in the Molten Carbonate Fuel Cell , 1980 .

[29]  L. Bieniasz Kinetics of the oxygen electrode reaction in molten Li + Na carbonate eutectic: Part 2. Theory of linear scan voltammetry and potential-step chronoamperometry for the reaction m O + n e− ⇌ q R initially at equilibrium , 1991 .

[30]  J. R. Selman,et al.  Polarization of the Molten Carbonate Fuel Cell Anode and Cathode , 1984 .

[31]  Edward L Cussler,et al.  Diffusion: Mass Transfer in Fluid Systems , 1984 .

[32]  J. R. Selman,et al.  The Polarization of Molten Carbonate Fuel Cell Electrodes II . Characterization by AC Impedance and Response to Current Interruption , 1991 .

[33]  J. R. Selman,et al.  The Polarization of Molten Carbonate Fuel Cell Electrodes I . Analysis of Steady‐State Polarization Data , 1991 .

[34]  Reduction of oxygen in lithium-potassium carbonate melt , 1980 .

[35]  Ralph E. White,et al.  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 , 1991 .