FUEL CELL FUNDAMENTALS
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1 FUEL CELL FUNDAMENTALS RYAN P. O'HAYRE Department of Metallurgical and Materials Engineering Colorado School of Mines [PhD, Materials Science and Engineering, Stanford University] SUK-WON CHA School of Mechanical and Aerospace Engineering ; Seoul National University [PhD, Mechanical Engineering, Stanford University] WHITNEY G. COLELLA President Harry S. Truman Research Fellow in National Security Science & Engineering Energy, Resources & Systems Analysis Center Sandia National Laboratories FRITZ B. PRINZ R. H. Adams Professor of Engineering Departments of Mechanical Engineering and Materials Science and Engineering Stanford University WILEY JOHN WILEY & SONS, INC.
![of Mechanical and Aerospace Engineering ; Seoul National University [PhD, Mechanical Engineering, Stanford University] WHITNEY G. COLELLA President Harry S.](/docs-images/47/20740105/images/page_1.jpg "Truman Research Fellow in National Security Science & Engineering Energy, Resources & Systems Analysis Center Sandia National Laboratories FRITZ B. PRINZ R. H.")
2 PREFACE ACKNOWLEDGMENTS NOMENCLATURE xvii xix xxi I FUEL CELL PRINCIPLES 1 INTRODUCTION What is a Fuel Cell? / A Simple Fuel Cell / Fuel Cell Advantages / Fuel Cell Disadvantages / Fuel Cell Types / Basic Fuel Cell Operation / Fuel Cell Performance / Characterization and Modeling / Fuel Cell Technology / 19 ; 1.10 Fuel Cells and the Environment / 20 Chapter Summary / 21 Chapter Exercises / 21 vii
3 Viii CONTENTS FUEL CELL THERMODYNAMICS Thermodynamics Review / What Is Thermodynamics? / Internal Energy / First Law / Second Law / Thermodynamic Potentials / Molar Quantities / Standard State / Reversibility / Heat Potential of a Fuel: Enthalpy of Reaction / Calculating Reaction Enthalpies / Temperature Dependence of Enthalpy / Work Potential of a Fuel: Gibbs Free Energy / Calculating Gibbs Free Energies / Relationship between Gibbs Free Energy and Electrical Work / Relationship between Gibbs Free Energy and Reaction Spontaneity / Relationship between Gibbs Free Energy and Voltage / Standard Electrode Potentials: Computing Reversible Voltages / Predicting Reversible Voltage of a Fuel Cell Under Non-Standard-State Conditions / Reversible Voltage Variation with Temperature / Reversible Voltage Variation with Pressure / Reversible Voltage Variation with Concentration: Nernst Equation / Concentration Cells / Summary / Fuel Cell Efficiency / Ideal Reversible Fuel Cell Efficiency / Real (Practical) Fuel Cell Efficiency / Thermal and Mass Balances in Fuel Cells / 64 Chapter Summary / 67 Chapter Exercises / 68 FUEL CELL REACTION KINETICS Introduction to Electrode Kinetics / 71
4 ix.2 Electrochemical Processes Are Heterogeneous / 72.3 Current Is a Rate / 72.4 Charge Is an Amount / 73.5 Current Density Is More Fundamental Than Current / 74.6 Potential Controls Electron Energy / 74.7 Reaction Rates Are Finite / Why Charge Transfer Reactions Have an Activation Energy / Activation Energy Determines Reaction Rate / Calculating Net Rate of a Reaction / Rate of reaction at Equilibrium: Exchange current Density / Potential of a Reaction at Equilibrium: Galvani Potential / Potential and Rate: Butler-Volmer Equation / Exchange Currents and Electrocatalysis: How to Improve Kinetic Performance / 88 /' Increase Reactant Concentration / Decrease Activation Barrier / Increase Temperature / Increase Reaction Sites / Simplified Activation Kinetics: Tafel Equation / Different Fuel Cell Reactions Produce Different Kinetics / Catalyst-Electrode Design / Quantum Mechanics: Framework for Understanding Catalysis in Fuel Cells / Connecting the Butler-Volmer and Nernst Equations (Optional) / 101 Chapter Summary / 106 Chapter Exercises / 107 FUEL CELL CHARGE TRANSPORT Charges Move in Response to Forces / Charge Transport Results in a Voltage Loss / Characteristics of Fuel Cell Charge Transport Resistance / Resistance Scales with Area / Resistance Scales with Thickness / Fuel Cell Resistances Are Additive / Ionic (Electrolyte) Resistance Usually Dominates / Physical Meaning of Conductivity / Electronic versus Ionic Conductors / 123
5 4.4.2 Electron Conductivity in a Metal / Ion Conductivity in a Crystalline Solid Electrolyte / Review of Fuel Cell Electrolyte Classes / Ionic Conduction in Aqueous Electrolytes/Ionic Liquids / Ionic Conduction in Polymer Electrolytes / Ionic Conduction in Ceramic Electrolytes / Mixed Ionic-Electronic Conductors / More on Diffusivity and Conductivity (Optional) / Atomistic Origins of Diffusivity / Relationship between Conductivity and Diffusivity (1) / Relationship between Diffusivity and Conductivity (2) / Why Electrical Driving Forces Dominate Charge Transport (Optional) / Quantum Mechanics-Based Simulaton of Ion Conduction in Oxide Electrolytes (Optional) / 155 Chapter Summary / 157 Chapter Exercises / 158 FUEL CELL MASS TRANSPORT Transport in Electrode Versus Flow Structure / Transport in Electrode: Diffusive Transport / Electrochemical Reaction Drives Diffusion / Limiting Current Density / Concentration Affects Nernst Voltage / Concentration Affects Reaction Rate / Concentration Loss Explained on the j-v Curve / Summary of Fuel Cell Concentration Loss / Transport in Flow Structures: Convective Transport / Fluid Mechanics Review / Mass Transport in Flow Channels / Gas Is Depleted along Flow Channel / Flow Structure Design / 189 Chapter Summary / 192 Chapter Exercises / 194 FUEL CELL MODELING Putting It All Together: A Basic Fuel Cell Model / A ID Fuel Cell Model / Flux Balance in Fuel Cells / 200
6 Xi Simplifying Assumptions / Governing Equations / Examples / Additional Considerations / Fuel Cell Models Based on Computational Huid Dynamics (Optional) / 218 Chapter Summary / 221 Chapter Exercises / FUEL CELL CHARACTERIZATION What Do We Want to Characterize? / Overview of Characterization Techniques / In Situ Electrochemical Characterization Techniques / Fundamental Electrochemical Variables: Voltage, Current, and Time / Basic Fuel Cell Test Station Requirements / Current-Voltage Measurement / 232 /' Electrochemical Impedance Spectroscopy / Current Interrupt Measurement / Cyclic Voltammetry / Ex Situ Characterization Techniques / Porosity Determination / BET Surface Area Determination / Gas Permeability / Structure Determinations / Chemical Determinations / 256 Chapter Summary / 265 Chapter Exercises / 257 II FUEL CELL TECHNOLOGY 8 OVERVIEW OF FUEL CELL TYPES Introduction / Phosphoric Acid Fuel Cell / Polymer Electrolyte Membrane Fuel Cell / Alkaline Fuel Cell / Molten Carbonate Fuel Cell / Solid Oxide Fuel Cell / Other Fuel Cells / Direct Liquid-Fueled Fuel Cells / Biological Fuel Cells / 276
7 XM CONTENTS Membraneless Fuel Cells / Metal-Air Cells / Single-Chamber SOFC / Direct Flame SOFC / Liquid-Tin Anode SOFC / Summary Comparison / 282 Chapter Summary / 283 Chapter Exercises / 286 PEMFC AND SOFC MATERIALS PEMFC Electrolyte Materials / Perfluorinated Polymers (e.g., Nafion) / Sulfonated Hydrocarbon Polymers (e.g., Polyaryletherketone =PEEK) / Phosphoric Acid Doped Polybenzimidazole (PBI) / Pofymer-InorganicyComposite Membranes / Solid Acid Membranes / PEMFC Electrode/Catalyst Materials / The Dual-Layer (Gas-diffusion Layer/Catalyst Layer) Approach / GDL Electrode Materials / PEMFC Anode Catalysts / PEMFC Cathode Catalysts / SOFC Electrolyte Materials / Yttria-Stabilized Zirconia (YSZ) / Doped Ceria / Bismuth Oxides / Materials Based on La 2 Mo 2 O 9 (LAMOX Family) / Oxygen-Ion-Conducting Perovskite Oxides / Proton-Conducting Perovskites / SOFC Electrode/Catalyst Materials / The SOFC Dual-Layer Approach / Ni-YSZ Cermet Anode Materials / Ceria-Based Anode Materials / Perovskite Anode Materials / Other Anode Materials / 316, Cathode Materials / SOFC Interconnect Materials / SOFC Sealing Materials / 319
8 XiH 9.5 Material Stability, Durability, And Lifetime / PEMFC Materials Durability and Lifetime Issues / SOFC Materials Durability and Lifetime Issues / 322 Chapter Summary / 323 Chapter Exercises / OVERVIEW OF FUEL CELL SYSTEMS Fuel Cell Stack (Fuel Cell Subsystem) / The Thermal Management Subsystem / Fuel Delivery/Processing Subsystem / H 2 Storage / Using a H 2 Carrier / Fuel Delivery/Processing Subsystem Summary / Power Electronics Subsystem / Power Regulation / Power Inversion / 348 /' Monitoring and Control System / Power Supply Management / Case Study of Fuel Cell System Design: Stationary Combined Heat and Power Systems / Fuel Processor Subsystem / Fuel Cell Subsystem / Power Electronics Subsystem / Thermal Management Subsystem / Net Electrical and Heat Recovery Efficiencies / Case Study of Fuel Cell System Design: Sizing A Portable Fuel Cell / 363 Chapter Summary / 367 Chapter Exercises / FUEL PROCESSING SUBSYSTEM DESIGN Fuel Reforming Overview / Steam Reforming / Partial Oxidation Reforming / Autothermal Reforming (AR) / Gasification / Anaerobic Digestion (AD) / Water Gas Shift Reactors / Carbon Monoxide Clean-Up / Selective Methanation of Carbon Monoxide to Methane / 387
9 XiV ' CONTENTS Selective Oxidation of Carbon Monoxide to Carbon Dioxide /* Pressure Swing Adsorption / Palladium Membrane Separation / Reformer and Processor Efficiency Losses / Reactor Design for Fuel Reformers and Processors / 392 Chapter Summary / 392 Chapter Exercises / THERMAL MANAGEMENT SUBSYSTEM DESIGN Overview of Pinch Point Analysis Steps / Step One: Identify Hot and Cold Streams / Step Two: Identify Thermal Data / Step Three: Select Minimum Temperature Difference / Step Four: Evaluate Thermodynamic Plots / Step Five: Redes'ign Heat Exchanger Network / Step Six: Evaluate Multiple Scenarios / 409 Chapter Summary / 412 Chapter Exercises / FUEL CELL SYSTEM DESIGN Fuel Cell Design Via Computational Fluid Dynamics / Governing Equations / Building A Fuel Cell Model Geometry / Boundary and Volume Conditions / Solution Process and Results Analysis / Fuel Cell System Design: a Case Study / Design of a Portable Solid Oxide Fuel Cell System / Thermal and Mass Balance / Specifying the System Components / Design Review / 445 Chapter Summary / 447 Chapter Exercises / ENVIRONMENTAL IMPACT OF FUEL CELLS Life Cycle Assessment / Life Cycle Assessment as a Tool / Life Cycle Assessment Applied to Fuel Cells / Important Emissions For LCA / 460
10 XV 14.3 Emissions Related to Global Warming / Climate Change / Natural Greenhouse Effect / Global Warming / Evidence of Global Warming / Hydrogen as a Potential Contributor to Global Warming / Mitigating Climate Change with Low Carbon Fuels and Fuel Cells / Quantifying Environmental Impact Carbon Dioxide Equivalent / Quantifying Environmental Impact External Costs of Global Warming / Quantifying Environmental Impact-Applying the Appropriate Emission Data / Emissions Related to Air Pollution / Hydrogen as a Potential Contributor to/air Pollution / Quantifying Environmental Impact Health Effects of Air Pollution / Quantifying Environmental Impact External Costs of Air Pollution / Analyzing Entire Scenarios with LCA / Electric Power Scenario / 476 Chapter Summary / 479 Chapter Exercises / 480 APPENDIXES A CONSTANTS AND CONVERSIONS 485 B THERMODYNAMIC DATA 487 C STANDARD ELECTRODE POTENTIALS AT 25 C 497 D QUANTUM MECHANICS 499 D.I Atomic Orbitals / 501 D.2 Postulates of Quantum Mechanics / 502 D.3 One-Dimensional Electron Gas / 504 D.4 Analogy to Column Buckling / 505 D.5 Hydrogen Atom / 506
11 XVi CONTENTS E PERIODIC TABLE OF THE ELEMENTS 509 F SUGGESTED FURTHER READING 511 G IMPORTANT EQUATIONS 513 BIBLIOGRAPHY 517 INDEX 527
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