The effect of the parasitic current on the Direct Ethanol PEM Fuel Cell Operation

In the present work the effect of the parasitic or leakage current, Ip, which is the result of the ethanol crossover through the polymer electrolyte membrane (PEM) from the anode to the cathode side of the cell, on both the cathode activation overpotential and the fuel cell operation is investigated. A one-dimensional (1-D), isothermal mathematical model is developed in order to describe the operation of a Direct Ethanol PEM Fuel Cell (DE-PEMFC) in steady state. The equations used describe the mass transport of both ethanol and humidified oxygen at the anode and the cathode compartment of the cell respectively. The mathematical model is validated against experimental data and a relatively good agreement between the model predictions and the experimental results is found. The direct correlation that exists between the ethanol crossover rate and the parasitic current formation is graphically depicted. Moreover, when the parasitic current is enabled and disabled, the calculation of the cathode activation overpotential shows that the mixed overpotential for a DE-PEMFC poses a serious problem hindering the fuel cell operation. According to the model results, the parasitic current is greater at low current density values due to the greater amounts of the crossovered ethanol. Finally, the effect of both the oxygen feed concentration and the parasitic current formation on the fuel cell operation is also presented and discussed.

[1]  Robert F. Savinell,et al.  Evaluation of Ethanol, 1‐Propanol, and 2‐Propanol in a Direct Oxidation Polymer‐Electrolyte Fuel Cell A Real‐Time Mass Spectrometry Study , 1995 .

[2]  T. Zhao,et al.  Simultaneous oxygen-reduction and methanol-oxidation reactions at the cathode of a DMFC: A model-based electrochemical impedance spectroscopy study , 2007 .

[3]  J. Smith,et al.  Introduction to chemical engineering thermodynamics , 1949 .

[4]  T. Iwasita,et al.  A sniftirs study of ethanol oxidation on platinum , 1989 .

[5]  Kai Sundmacher,et al.  A model for the liquid feed direct methanol fuel cell , 1999 .

[6]  A. Kulikovsky,et al.  Analytical model of the anode side of DMFC: the effect of non-Tafel kinetics on cell performance , 2003 .

[7]  Keith Scott,et al.  Performance and modelling of a direct methanol solid polymer electrolyte fuel cell , 1997 .

[8]  Shimshon Gottesfeld,et al.  Electro‐osmotic Drag of Water in Ionomeric Membranes New Measurements Employing a Direct Methanol Fuel Cell , 1997 .

[9]  G. Lindbergh,et al.  Investigation of Mass-Transport Limitations in the Solid Polymer Fuel Cell Cathode I. Mathematical Model , 2002 .

[10]  William H. Press,et al.  Numerical Recipes 3rd Edition: The Art of Scientific Computing , 2007 .

[11]  Ralph E. White,et al.  Methanol Fuel Cell Model: Anode , 1999 .

[12]  Qin Xin,et al.  Direct methanol fuel cells: The effect of electrode fabrication procedure on MEAs structural properties and cell performance , 2005 .

[13]  Panagiotis Tsiakaras,et al.  PtM/C (M = Sn, Ru, Pd, W) based anode direct ethanol–PEMFCs: Structural characteristics and cell performance , 2007 .

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

[15]  Claude Lamy,et al.  A kinetic analysis of the electro-oxidation of ethanol at a platinum electrode in acid medium , 1994 .

[16]  Shuqin Song,et al.  Ethanol/water mixture permeation through a Nafion® based membrane electrode assembly , 2007 .

[17]  George Andreadis,et al.  Ethanol crossover and direct ethanol PEM fuel cell performance modeling and experimental validation , 2006 .

[18]  T. Springer,et al.  Polymer Electrolyte Fuel Cell Model , 1991 .

[19]  Satoru Kato,et al.  Permeation rates of aqueous alcohol solutions in pervaporation through Nafion membranes , 1992 .

[20]  Weijiang Zhou,et al.  Ethanol crossover phenomena and its influence on the performance of DEFC , 2005 .

[21]  Tianshou Zhao,et al.  Two-phase, mass-transport model for direct methanol fuel cells with effect of non-equilibrium evaporation and condensation , 2007 .

[22]  E. Gonzalez,et al.  Effect of temperature on the mechanism of ethanol oxidation on carbon supported Pt, PtRu and Pt3Sn electrocatalysts , 2006 .

[23]  C. Lamy,et al.  Recent progress in the direct ethanol fuel cell: development of new platinum–tin electrocatalysts , 2004 .

[24]  Panagiotis Tsiakaras,et al.  Recent progress in direct ethanol proton exchange membrane fuel cells (DE-PEMFCs) , 2006 .

[25]  Shuqin Song,et al.  How Far Are Direct Alcohol Fuel Cells From Our Energy Future , 2007 .

[26]  S. F. Lee,et al.  Modeling the catalyst layer of a PEM fuel cell cathode using a dimensionless approach , 2004 .

[27]  Claude Lamy,et al.  Electrocatalytic oxidation of aliphatic alcohols: Application to the direct alcohol fuel cell (DAFC) , 2001 .

[28]  Roger Dougal,et al.  Mathematical Model of a Direct Methanol Fuel Cell , 2004, 2003.04083.

[29]  S. Jiang,et al.  Kinetics of ethanol electrooxidation at Pd electrodeposited on Ti , 2007 .

[30]  Q. Xin,et al.  High performance direct ethanol fuel cell with double-layered anode catalyst layer , 2008 .

[31]  Christophe Coutanceau,et al.  Direct ethanol fuel cell (DEFC): Electrical performances and reaction products distribution under operating conditions with different platinum-based anodes , 2006 .

[32]  G. Yin,et al.  Investigation of ethanol electrooxidation on a Pt-Ru-Ni/C catalyst for a direct ethanol fuel cell , 2006 .

[33]  Tianshou Zhao,et al.  Effect of methanol crossover on the cathode behavior of a DMFC: A half-cell investigation , 2007 .

[34]  M. Verbrugge,et al.  Mathematical model of a gas diffusion electrode bonded to a polymer electrolyte , 1991 .

[35]  Qin Xin,et al.  Direct ethanol fuel cells based on PtSn anodes: the effect of Sn content on the fuel cell performance , 2005 .

[36]  Christophe Coutanceau,et al.  Recent advances in the development of direct alcohol fuel cells (DAFC) , 2002 .

[37]  R. A. Rightmire,et al.  Ethyl Alcohol Oxidation at Platinum Electrodes , 1964 .

[38]  Anil Verma,et al.  Experimental evaluation and mathematical modeling of a direct alkaline fuel cell , 2007 .

[39]  Claude Lamy,et al.  Optimization of platinum dispersion in Pt–PEM electrodes: application to the electrooxidation of ethanol , 1998 .

[40]  Tianshou Zhao,et al.  A two-dimensional, two-phase mass transport model for liquid-feed DMFCs , 2007 .

[41]  N. S. Vlachos,et al.  A three-dimensional CFD model of direct ethanol fuel cells: Anode flow bed analysis , 2006 .

[42]  Weijiang Zhou,et al.  Bi- and tri-metallic Pt-based anode catalysts for direct ethanol fuel cells , 2004 .

[43]  Shuqin Song,et al.  Direct alcohol fuel cells: A novel non-platinum and alcohol inert ORR electrocatalyst , 2008 .

[44]  Sarwan S. Sandhu,et al.  Prediction of methanol and water fluxes through a direct methanol fuel cell polymer electrolyte membrane , 2005 .

[45]  E. Gonzalez,et al.  Effect of Ru addition on the structural characteristics and the electrochemical activity for ethanol oxidation of carbon supported Pt–Sn alloy catalysts , 2007 .

[46]  Ken-Ming Yin An algebraic model on the performance of a direct methanol fuel cell with consideration of methanol crossover , 2007 .

[47]  Van P. Carey,et al.  The properties of gases & liquids: 4th Edition. Robert C. Reid, John M. Prausnitz, and Bruce E. Poling, McGraw-Hill Book Company, New York, NY, 1987, 741 pages, $49.50. , 1988 .

[48]  C. R. Martin,et al.  Investigations of the O sub 2 reduction reaction at the platinum/Nafion interface using a solid-state electrochemical cell. Technical report , 1991 .

[49]  Masahiro Watanabe,et al.  Electrocatalysis by ad-atoms: Part II. Enhancement of the oxidation of methanol on platinum by ruthenium ad-atoms , 1975 .

[50]  E. Antolini Catalysts for direct ethanol fuel cells , 2007 .

[51]  Hubert A. Gasteiger,et al.  Determination of Catalyst Unique Parameters for the Oxygen Reduction Reaction in a PEMFC , 2006 .

[52]  Chao-Yang Wang,et al.  Mathematical Modeling of Liquid-Feed Direct Methanol Fuel Cells , 2003 .

[53]  P. Kauranen,et al.  Mixed methanol oxidation/oxygen reduction currents on a carbon supported Pt catalyst , 1996 .

[54]  Y. Çengel,et al.  Thermodynamics : An Engineering Approach , 1989 .

[55]  A. O. Neto,et al.  Co-catalytic effect of nickel in the electro-oxidation of ethanol on binary Pt-Sn electrocatalysts , 2005 .

[56]  Kai Sundmacher,et al.  Dynamics of the direct methanol fuel cell (DMFC): experiments and model-based analysis , 2001 .

[57]  Hubert A. Gasteiger,et al.  Handbook of fuel cells : fundamentals technology and applications , 2003 .

[58]  Nigel M. Sammes,et al.  Fuel cell technology : reaching towards commercialization , 2006 .

[59]  Tsung-Kuang Yeh,et al.  A mathematical model for simulating methanol permeation and the mixed potential effect in a direct methanol fuel cell , 2006 .

[60]  Jeremy P. Meyers,et al.  Simulation of the Direct Methanol Fuel Cell II. Modeling and Data Analysis of Transport and Kinetic Phenomena , 2002 .

[61]  Xianguo Li,et al.  Composition and performance modelling of catalyst layer in a proton exchange membrane fuel cell , 1999 .

[62]  Jeremy P. Meyers,et al.  Simulation of the Direct Methanol Fuel Cell I. Thermodynamic Framework for a Multicomponent Membrane , 2002 .

[63]  G. Naterer,et al.  Fuel cell entropy production with ohmic heating and diffusive polarization , 2006 .

[64]  Weijiang Zhou Pt based anode catalysts for direct ethanol fuel cells , 2003 .

[65]  K. Jeng,et al.  Modeling and simulation of a direct methanol fuel cell anode , 2002 .

[66]  A. Kulikovsky,et al.  The voltage–current curve of a direct methanol fuel cell: “exact” and fitting equations , 2002 .

[67]  Alexandra M.F.R. Pinto,et al.  A comparative study of approaches to direct methanol fuel cells modelling , 2007 .

[68]  J. M. Smith Chemical Engineering Kinetics , 1980 .

[69]  Jeremy P. Meyers,et al.  Simulation of the Direct Methanol Fuel Cell III. Design and Optimization , 2002 .

[70]  E. Gonzalez,et al.  Ethanol oxidation on a carbon-supported Pt75Sn25 electrocatalyst prepared by reduction with formic acid: Effect of thermal treatment , 2007 .