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Diagnostic Mathematical Models for Fuel Cell Poisoning - Eche 401 Case Western Reserve University ECHE 401
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  • Title: Diagnostic Mathematical Models for Fuel Cell Poisoning - Eche 401
  • Type: Notes
  • School: Case Western Reserve University
  • Course: ECHE 401
  • Term: Fall

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Mathematical Diagnostic Models for Fuel Cell Poisoning Tom Greszler, Vladimir Gurau, T.A. Zawodzinski Outline Background Fuel Cells in General Fuel Cell Problems/Issues Purpose Proposed Research Experimentation Modeling Budget & Timeline Conclusions PEM Fuel Cell - Overview Anodic Reaction (hydrogen electrode) 2H2 4H+ + 4eCathodic Reaction (oxygen electrode) 4H+ + 4e- + O2 2H2O Overall Reaction 2H2 + O2 2H2O + Energy Animation from H-Power corporation website PEM Fuel Cell - Components Nafion: Problems/Issues System Economics Hydrogen Storage/Production Reforming? Membrane Materials Stack Design System Water Balance Seals Durability Component Degradation External Contamination Research Focus! Purpose To develop mathematical models that accurately predict the effect of external contaminants on the performance of PEM fuel cells and to use these models as tools for diagnosing PEM performance degradation. External Contaminants Adsorptive Poisons Ionic Poisons Surface Property Modifiers Each type affects the fuel cell in a fundamentally different way Adsorptive Poisons Cell Voltage (V) Anything that binds to the catalyst Blocks sites Relatively Well Studied with CO Models Exist 0 ppm CO 50 ppm CO Current Density (A/cm2) Experimentation and Modeling Needed for Additional Poisons: H2S, SOx, NOx, etc. Developed at Los Alamos by Springer, et al. Models the entire anode side of the fuel cell GDL Diffusion with Stefan-Maxwell Equations Catalyst Layer Fickian diffusion with reaction kinetics CO Model CO + v co bfc*kfc kfh kfc H 2 + 2 v 2 H bfh*kfh H H + + e + V H 2O + co V + CO2 + 2 H + + 2e One-Dimensional, but captures most experimental data kec keh Adsorptive Poisons Concentrate on H2S Poisoning Preliminary work completed at Los Alamos Need additional data with operating fuel cell Polarization Curves, Cyclic Voltammetry Modeling will use Los Alamos CO Model as base Adjust kinetic parameters and isotherms Energy Saturated Hydrogen Saturated Nitrogen Saturated Air Saturated Nitrogen Adsorptive Poison Water Fuel Cell H2S Poisoning .4 1 H S on 2 1 .2 1 0 .8 0 .6 0 .4 0 .2 0 3 ppm Current Density (A/c H S off 2 1 ppm H S off 2 0 5 1 0 1 5 2 0 2 5 t i m e / hour More Advanced Model Study CO/ H2S bonding in 3-D CFD Suggest new fabrication techniques CO hot spots? Gas flow channels? Study transient poisoning CO level spiking Still based on Los Alamos model Ionic Poisons Cations replace protons in membrane Iron, Sodium, Ammonia, etc. Three effects: Decrease membrane ionic conductivity Decrease electrode kinetics Screw up water balance Decrease diffusion coefficient Increase electro-osmotic drag Each needs to be explored Ionic Conductivity AC impedance Ionic Poisoning Contaminated Nafion Contaminated Catalyst Layers Kinetics RDE coated with contaminated Nafion Micro-Electrodes Fuel Cell Testing CV, Tafel Water Balance Diffusion rate through membrane Electro-Osmotic Drag Streaming potential NMR, Streaming potential As Functions of Water & Poison Content Modeling Technique Need complete fuel cell model Start with water balance model of Springer, Zawodzinski, et al. Add complexity Catalyst layers Update Experimental Data Add Ionic Poison Data Surface Property Modifiers GDL Carefully engineered properties Optimum water balance Contaminants coat surface Cause clogging Destroy properties Examine surface tension effects Fuel cell testing Modeling CFD Water Balance Model Diagnostics Using data and models Develop diagnostics for each type of poison Polarization curve based Operational fuel cell Aid for industry Budget ~$105,000 No major equipment purchases Mostly personnel costs Timeline May-June 2003 Literature Survey CO Model Ionic Poisoning Experiments Adsorbtive Poisoning Experiments "Clogging" Poisoning Experiments Data Analysis Formulate New Models Thesis Preparation July-Aug 2003 Sep-Oct 2003 Nov-Dec 2003 Jan-Feb 2004 Mar-Apr 2004 May-June 2004 Conclusions Develop Models for External Contaminants Accurate, experimentally based Determine mechanisms of degradation Develop Diagnostics Identification of performance degradation Expertise and Equipment in place Questions?

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