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FUEL CELL FUNDAMENTALS

Third Edition

RYAN 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 The G.W.C. Whiting School of Engineering, and The Energy, Environment, Sustainability and Health Institute The Johns Hopkins University Gaia Energy Research Institute [Doctorate, Engineering Science, The University of Oxford]

FRITZ B. PRINZ R.H. Adams Professor of Engineering Departments of Mechanical Engineering and Material Science and Engineering Stanford University

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Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

To the parents who nurtured us.

To the teachers who inspired us.

CONTENTS

PREFACE xi

ACKNOWLEDGMENTS xiii

NOMENCLATURE xvii

I FUEL CELL PRINCIPLES

1 Introduction 3

1.1 What Is a Fuel Cell? / 3 1.2 A Simple Fuel Cell / 6 1.3 Fuel Cell Advantages / 8 1.4 Fuel Cell Disadvantages / 11 1.5 Fuel Cell Types / 12 1.6 Basic Fuel Cell Operation / 14 1.7 Fuel Cell Performance / 18 1.8 Characterization and Modeling / 20 1.9 Fuel Cell Technology / 21 1.10 Fuel Cells and the Environment / 21 1.11 Chapter Summary / 22

Chapter Exercises / 23

v

vi CONTENTS

2 Fuel Cell Thermodynamics 25

2.1 Thermodynamics Review / 25

2.2 Heat Potential of a Fuel: Enthalpy of Reaction / 34

2.3 Work Potential of a Fuel: Gibbs Free Energy / 37

2.4 Predicting Reversible Voltage of a Fuel Cell under Non-Standard-State Conditions / 47

2.5 Fuel Cell Efficiency / 60

2.6 Thermal and Mass Balances in Fuel Cells / 65

2.7 Thermodynamics of Reversible Fuel Cells / 67

2.8 Chapter Summary / 71

Chapter Exercises / 72

3 Fuel Cell Reaction Kinetics 77

3.1 Introduction to Electrode Kinetics / 77

3.2 Why Charge Transfer Reactions Have an Activation Energy / 82

3.3 Activation Energy Determines Reaction Rate / 84

3.4 Calculating Net Rate of a Reaction / 85

3.5 Rate of Reaction at Equilibrium: Exchange Current Density / 86

3.6 Potential of a Reaction at Equilibrium: Galvani Potential / 87

3.7 Potential and Rate: Butler–Volmer Equation / 89

3.8 Exchange Currents and Electrocatalysis: How to Improve Kinetic Performance / 94

3.9 Simplified Activation Kinetics: Tafel Equation / 97

3.10 Different Fuel Cell Reactions Produce Different Kinetics / 100

3.11 Catalyst–Electrode Design / 103

3.12 Quantum Mechanics: Framework for Understanding Catalysis in Fuel Cells / 104

3.13 The Sabatier Principle for Catalyst Selection / 107

3.14 Connecting the Butler–Volmer and Nernst Equations (Optional) / 108

3.15 Chapter Summary / 112

Chapter Exercises / 113

4 Fuel Cell Charge Transport 117

4.1 Charges Move in Response to Forces / 117

4.2 Charge Transport Results in a Voltage Loss / 121

4.3 Characteristics of Fuel Cell Charge Transport Resistance / 124

4.4 Physical Meaning of Conductivity / 128

4.5 Review of Fuel Cell Electrolyte Classes / 132

CONTENTS vii

4.6 More on Diffusivity and Conductivity (Optional) / 153

4.7 Why Electrical Driving Forces Dominate Charge Transport (Optional) / 160

4.8 Quantum Mechanics–Based Simulation of Ion Conduction in Oxide Electrolytes (Optional) / 161

4.9 Chapter Summary / 163

Chapter Exercises / 164

5 Fuel Cell Mass Transport 167

5.1 Transport in Electrode versus Flow Structure / 168

5.2 Transport in Electrode: Diffusive Transport / 170

5.3 Transport in Flow Structures: Convective Transport / 183

5.4 Chapter Summary / 199

Chapter Exercises / 200

6 Fuel Cell Modeling 203

6.1 Putting It All Together: A Basic Fuel Cell Model / 203

6.2 A 1D Fuel Cell Model / 206

6.3 Fuel Cell Models Based on Computational Fluid Dynamics (Optional) / 227

6.4 Chapter Summary / 230

Chapter Exercises / 231

7 Fuel Cell Characterization 237

7.1 What Do We Want to Characterize? / 238

7.2 Overview of Characterization Techniques / 239

7.3 In Situ Electrochemical Characterization Techniques / 240

7.4 Ex Situ Characterization Techniques / 265

7.5 Chapter Summary / 268

Chapter Exercises / 269

II FUEL CELL TECHNOLOGY

8 Overview of Fuel Cell Types 273

8.1 Introduction / 273

8.2 Phosphoric Acid Fuel Cell / 274

8.3 Polymer Electrolyte Membrane Fuel Cell / 275

8.4 Alkaline Fuel Cell / 278

8.5 Molten Carbonate Fuel Cell / 280

viii CONTENTS

8.6 Solid-Oxide Fuel Cell / 282

8.7 Other Fuel Cells / 284

8.8 Summary Comparison / 298

8.9 Chapter Summary / 299

Chapter Exercises / 301

9 PEMFC and SOFC Materials 303

9.1 PEMFC Electrolyte Materials / 304

9.2 PEMFC Electrode/Catalyst Materials / 308

9.3 SOFC Electrolyte Materials / 317

9.4 SOFC Electrode/Catalyst Materials / 326

9.5 Material Stability, Durability, and Lifetime / 336

9.6 Chapter Summary / 340

Chapter Exercises / 342

10 Overview of Fuel Cell Systems 347

10.1 Fuel Cell Subsystem / 348

10.2 Thermal Management Subsystem / 353

10.3 Fuel Delivery/Processing Subsystem / 357

10.4 Power Electronics Subsystem / 364

10.5 Case Study of Fuel Cell System Design: Stationary Combined Heat and Power Systems / 369

10.6 Case Study of Fuel Cell System Design: Sizing a Portable Fuel Cell / 383

10.7 Chapter Summary / 387

Chapter Exercises / 389

11 Fuel Processing Subsystem Design 393

11.1 Fuel Reforming Overview / 394

11.2 Water Gas Shift Reactors / 409

11.3 Carbon Monoxide Clean-Up / 411

11.4 Reformer and Processor Efficiency Losses / 414

11.5 Reactor Design for Fuel Reformers and Processors / 416

11.6 Chapter Summary / 417

Chapter Exercises / 419

CONTENTS ix

12 Thermal Management Subsystem Design 423

12.1 Overview of Pinch Point Analysis Steps / 424

12.2 Chapter Summary / 440

Chapter Exercises / 441

13 Fuel Cell System Design 447

13.1 Fuel Cell Design Via Computational Fluid Dynamics / 447

13.2 Fuel Cell System Design: A Case Study / 462

13.3 Chapter Summary / 476

Chapter Exercises / 477

14 Environmental Impact of Fuel Cells 481

14.1 Life Cycle Assessment / 481

14.2 Important Emissions for LCA / 490

14.3 Emissions Related to Global Warming / 490

14.4 Emissions Related to Air Pollution / 502

14.5 Analyzing Entire Scenarios with LCA / 507

14.6 Chapter Summary / 510

Chapter Exercises / 511

A Constants and Conversions 517

B Thermodynamic Data 519

C Standard Electrode Potentials at 25∘C 529

D Quantum Mechanics 531

D.1 Atomic Orbitals / 533

D.2 Postulates of Quantum Mechanics / 534

D.3 One-Dimensional Electron Gas / 536

D.4 Analogy to Column Buckling / 537

D.5 Hydrogen Atom / 538

D.6 Multielectron Systems / 540

D.7 Density Functional Theory / 540

x CONTENTS

E Periodic Table of the Elements 543

F Suggested Further Reading 545

G Important Equations 547

H Answers to Selected Chapter Exercises 551

BIBLIOGRAPHY 555

INDEX 565

PREFACE

Imagine driving home in a fuel cell car with nothing but pure water dripping from the tailpipe. Imagine a laptop computer that runs for 30 hours on a single charge. Imagine a world where air pollution emissions are a fraction of that from present-day automobiles and power plants. These dreams motivate today’s fuel cell research. While some dreams (like cities chock-full of ultra-low-emission fuel cell cars) may be distant, others (like a 30-hour fuel cell laptop) may be closer than you think.

By taking fuel cells from the dream world to the real world, this book teaches you the science behind the technology. This book focuses on the questions “how” and “why.” Inside you will find straightforward descriptions of how fuel cells work, why they offer the potential for high efficiency, and how their unique advantages can best be used. Emphasis is placed on the fundamental scientific principles that govern fuel cell operation. These principles remain constant and universally applicable, regardless of fuel cell type or technology.

Following this philosophy, the first part, “Fuel Cell Principles,” is devoted to basic fuel cell physics. Illustrated diagrams, examples, text boxes, and homework questions are all designed to impart a unified, intuitive understanding of fuel cells. Of course, no treatment of fuel cells is complete without at least a brief discussion of the practical aspects of fuel cell technology. This is the aim of the second part of the book, “Fuel Cell Technology.” Informative diagrams, tables, and examples provide an engaging review of the major fuel cell technologies. In this half of the book, you will learn how to select the right fuel cell for a given application and how to design a complete system. Finally, you will learn how to assess the potential environmental impact of fuel cell technology.

xi

xii PREFACE

Comments or questions? Suggestions for improving the book? Found a typo, think our explanations could be improved, want to make a suggestion about other important con- cepts to discuss, or have we got it all wrong? Please send us your feedback by emailing us at fcf3@yahoogroups.com. We will take your suggestions into consideration for the next edition. Our website http://groups.yahoo.com/group/fcf3 posts these discussions, fliers for the book, and additional educational materials. Thank you.

ACKNOWLEDGMENTS

The authors would like to thank their friends and colleagues at Stanford University and the former Rapid Prototyping Laboratory (RPL), now the Nano-Prototyping Laboratory (NPL), for their support, critiques, comments, and enthusiasm.Without you, this text would not have been written! The beautiful figures and illustrations featured in this textbook were crafted primarily by Marily Mallison, with additional illustrations by Dr. Michael Sanders—their artistic touch is greatly appreciated!

The authors would like to thank the Deans of the Stanford School of Engineering, Jim Plummer and Channing Robertson, and John Bravman, Vice Provost Undergraduate Educa- tion, for the support that made this book possible.Wewould also like to acknowledgeHonda R&D, its representatives J. Araki, T. Kawanabe, Y. Fujisawa, Y. Kawaguchi, Y. Higuchi, T. Kubota, N. Kuriyama, Y. Saito, J. Sasahara, and H. Tsuru, and Stanford’s Global Climate and Energy Project (GCEP) community for creating an atmosphere conducive to studying and researching new forms of power generation. All members of RPL/NPL are recog- nized for stimulating discussions. Special thanks to Dr. Tim Holme for his innumerable contributions, including his careful review of the text, integration work, nomenclature and equation summaries, and the appendixes. Thanks also to Professor Rojana Pornprasertsuk, who developed the wonderful quantum simulation images for Chapter 3 and Appendix D. The authors are grateful to Professor Yong-il Park for his help in the literature survey of Chapter 9 and Rami Elkhatib for his significant contributions in writing this section. Profes- sor Juliet Risner deserves gratitude for her beautiful editing job, and Professor Hong Huang deserves thanks for content contribution. Dr. Jeremy Cheng, Dr. Kevin Crabb, Professor Turgut Gur, Shannon Miller, Masafumi Nakamura, and A. J. Simon also provided signifi- cant editorial advice. Thanks to Dr. Young-Seok Jee, Dr. Daeheung Lee, Dr. Yeageun Lee,

xiii

xiv ACKNOWLEDGMENTS

Dr. Wonjong Yu, and Dr. Yusung Kim for their contributions to Chapters 6 and 13. Spe- cial thanks to Rusty Powell and Derick Reimanis for their careful editing contributions to the second edition. Finally, thanks to colleagues at the Colorado School of Mines (CSM), including Bob Kee and Neal Sullivan for their helpful discussions and for a decade’s worth of students at CSM for catching typos and identifying areas in need for clarification for this third edition.

We would like to extend our gratitude to Professor Stephen H. Schneider, Professor Terry Root, Dr. Michael Mastrandrea, Mrs. Patricia Mastrandrea, Dr. Gerard Ketafani, and Dr. Jonathan Koomey. We would also like to thank the technical research staff within the U.S. Department of Energy (DOE) complex, including researchers at DOE national lab- oratories [Sandia National Laboratories (SNL), Lawrence Berkeley National Laboratory (LBNL), Argonne National Laboratory (ANL), the National Renewable Energy Laboratory (NREL), and Lawrence Livermore National Laboratory (LLNL), among others]. We would also like to thank research participants within the International Energy Agency (IEA) Sta- tionary Fuel Cell Annex, the American Institute of Chemical Engineers (AICHE) Transport and Energy Processes Division (TEP), and the National Academy of Engineering (NAE) Frontiers of Engineering (FOE) program.

For intellectually stimulating discussions on energy system design, we also would like to thank Dr. Salvador Aceves (LLNL), Dr. Katherine Ayers (ProtonOnsite Inc.), Professor Nigel Brandon (Imperial College London), Mr. Tom Brown (California State University Northridge), Dr. Viviana Cigolotti [Energy and Sustainable Economic Development (ENEA)], Professor Peter Dobson [University of Oxford (Oxon)], Dr. Elango Elangovan (Ceramatec Inc.), Professor Ferhal Erhun, Dr. Angelo Esposito (European Institute for Energy Research), Dr. Hossein Ghezel-Ayagh [FuelCell Energy Inc. (FCE)], Dr. Lorenz Gubler [Paul Scherrer Institut (PSI)], Dr. Monjid Hamdan (Giner Inc.), Dr. Joseph J. Hartvigsen (Ceramatec Inc.), Professor Michael Hickner (The Pennsylvania State University), Professor Ben Hobbs (Johns Hopkins University), Professor Daniel M. Kammen [University of California at Berkeley (UCB)], Professor Jon Koomey, Dr. Scott Larsen (New York State Energy Research and Development Authority), Mr. Bruce Lin (EnerVault Inc.), Dr. Ludwig Lipp (FCE), Dr. Bernard Liu (National Cheng Kung University), Professor V. K. Mathur (University of New Hampshire), Dr. Marianne Mintz (ANL), Professor Catherine Mitchell (University of Exeter), Dr. Cortney Mittelsteadt (Giner Inc.), Dr. Yasunobu Mizutani (ToHo Gas Co. Ltd.), John Molburg (Argonne National Laboratory), Dr. Angelo Moreno [Italian National Agency for New Technologies, Energy and Sustainable Economic Development (ENEA)], Professor Vincenzo Mulone (University of Rome Tor Vergata), Dr. Jim O’Brien (Idaho National Laboratory), Professor Joan Ogden (University of California at Davis), Dr. Pinakin Patel (FCE), Dr. Randy Petri (Versa Power Inc.), Professor Bruno Pollet (University of Ulster), Dr. Peter Rieke [Pacific Northwest National Laboratory (PNNL)], Dr. Subhash C. Singhal (PNNL), Professor Colin Snowdon (Oxon), Professor Robert Socolow (Princeton University), Mr. Keith Spitznagel (KAS Energy Services LLC), Professor Robert Steinberger-Wilckens (University of Birmingham), Dr. Jeffry Stevenson (PNNL), Professor Richard Stone (Oxon), Professor Etim Ubong (Kettering University), Professor Eric D. Wachsman (University of Maryland), Professor Xia Wang (Oakland University), and Professor Yingru Zhao (Xiamen University).

ACKNOWLEDGMENTS xv

Fritz B. Prinz wants to thank his wife, Gertrud, and his children, Marie-Helene and Benedikt, for their love, support, and patience.

Whitney G. Colella would like to thank her friends and family, especially the Bakers, Birchards, Chens, Colellas, Culvers, Efthimiades, Hoffmans, Jaquintas, Judges, Louies, Mavrovitis, Omlands, Pandolfis, Panwalkers, Qualtieris, Scales, Smiths, Spielers, Tepers, Thananarts, Tragers, Wasleys, and Wegmans.

Suk-Won Cha wishes to thank Unjung, William, and Sophia for their constant support, love, and understanding.

Ryan O’Hayre sends his thanks and gratitude to Lisa for her friendship, encouragement, confidence, support, and love. Thanks also to Kendra, Arthur, Morgan, little Anna, and little Robert. Ryan has always wanted to write a book … probably something about dragons and adventure. Well, things have a funny way of working out, and although he ended up writing about fuel cells, he had to put the dragons in somewhere.…

NOMENCLATURE

Symbol Meaning Common Units

A Area cm2

Ac Catalyst area coefficient Dimensionless a Activity Dimensionless ASR Area specific resistance Ω ⋅ cm2 C Capacitance F Cdl Double-layer capacitance F c∗ Concentration at reaction surface mol∕cm2 c Concentration mol∕m3 c Constant describing how mass transport affects

concentration losses V

cp Heat capacity J∕mol ⋅ K D Diffusivity cm2∕s E Electric field V∕cm E Thermodynamic ideal voltage V Ethermo Thermodynamic ideal voltage V ET Temperature-dependent thermodynamic voltage at

reference concentration V

F Helmholtz free energy J, J∕mol F Faraday constant 96, 485 C∕mol Fk Generalized force N f Reaction rate constant Hz, s−1

f Friction factor Dimensionless

xvii

xviii NOMENCLATURE

Symbol Meaning Common Units

G, g Gibbs free energy J, J∕mol g Acceleration due to gravity m∕s2 ΔG‡ Activation energy barrier J∕mol, J ΔGact Activation energy barrier J∕mol, J H Heat J H, h Enthalpy J, J∕mol HC Gas channel thickness cm HE Diffusion layer thickness cm h Planck’s constant 6.63 × 10−34 J ⋅ s ℏ Reduced Planck constant, h∕2𝜋 1.05 × 10−34 J ⋅ s hm Mass transfer convection coefficient m∕s i Current A J Molar flux, molar reaction rate mol∕cm2 ⋅ s Ĵ Mass flux g∕cm2 ⋅ s, kg∕m2 ⋅ s JC Convective mass flux kg∕m2 ⋅ s j Current density A∕cm2 j0 Exchange current density A∕cm2 j00 Exchange current density at reference

concentration A∕cm2

jL Limiting current density A∕cm2 jleak Fuel leakage current A∕cm2 k Boltzmann’s constant 1.38 × 10−23 J∕K L Length m M Molar mass g∕mol, kg∕mol M Mass flow rate kg∕s Mik Generalized coupling coefficient between

force and flux Varies

m Mass kg mcp Heat capacity flow rate kW∕kg ⋅ ∘C N Number of moles Dimensionless NA Avogadro’s number 6.02 × 1023 mol−1 n Number of electrons transferred in the reaction Dimensionless ng Number of moles of gas Dimensionless P Power or power density W or W∕cm2 P Pressure bar, atm, Pa Q Heat J, J∕mol Q Charge C Qh Adsorption charge C∕cm2 Qm Adsorption charge for smooth catalyst surface C∕cm2 q Fundamental charge 1.60 × 10−19 C R Ideal gas constant 8.314 J∕mol ⋅ K R Resistance Ω Rf Faradaic resistance Ω

NOMENCLATURE xix

Symbol Meaning Common Units

Re Reynolds number Dimensionless S, s Entropy J∕K, J∕mol ⋅ K S∕C Steam-to-carbon ratio Dimensionless Sh Sherwood number Dimensionless T Temperature K, ∘C t Thickness cm U Internal energy J, J∕mol u Mobility cm2∕V ⋅ s ū Mean flow velocity cm∕s, m∕s V Voltage V V Volume L, cm3

V Reaction rate per unit area mol∕cm2 ⋅ s 𝑣 Velocity cm∕s 𝑣 Hopping rate s−1, Hz 𝑣 Molar flow rate mol∕s, mol∕min W Work J, J∕mol X Parasitic power load W x Mole fraction Dimensionless x𝑣 Vacancy fraction mol vacancies∕mol sites yx Yield of element X Dimensionless Z Impedance Ω z Height cm

Greek Symbols

Symbol Meaning Common Units

𝛼 Charge transfer coefficient Dimensionless 𝛼 Coefficient for CO2 equivalent Dimensionless 𝛼∗ Channel aspect ratio Dimensionless 𝛽 Coefficient for CO2 equivalent Dimensionless 𝛾 Activity coefficient Dimensionless Δ Denotes change in quantity Dimensionless 𝛿 Diffusion layer thickness m, cm 𝜀 Efficiency Dimensionless 𝜀FP Efficiency of fuel processor Dimensionless 𝜀FR Efficiency of fuel reformer Dimensionless 𝜀H Efficiency of heat recovery Dimensionless 𝜀O Efficiency overall Dimensionless 𝜀R Efficiency, electrical Dimensionless 𝜀 Porosity Dimensionless �̇� Strain rate s−1

xx NOMENCLATURE

Symbol Meaning Common Units

𝜂 Overvoltage V 𝜂act Activation overvoltage V 𝜂conc Concentration overvoltage V 𝜂ohmic Ohmic overvoltage V λ Stoichiometric coefficient Dimensionless λ Water content Dimensionless 𝜇 Viscosity kg ⋅ m/s 𝜇 Chemical potential J, J/mol �̃� Electrochemical potential J, J/mol 𝜌 Resistivity Ω cm 𝜌 Density kg∕cm3, kg∕m3 𝜎 Conductivity S∕cm, (Ω ⋅ cm)−1 𝜎 Warburg coefficient Ω∕s0.5 𝜏 Mean free time s 𝜏 Shear stress Pa 𝜑 Electrical potential V 𝜑 Phase factor Dimensionless 𝜔 Angular frequency (𝜔 = 2𝜋f ) rad/s

Superscripts

Symbol Meaning

0 Denotes standard or reference state eff Effective property

Subscripts

Symbol Meaning

diff Diffusion E, e, elec Electrical (e.g., Pe,Welec) f Quantity of formation (e.g., ΔHf ) (HHV) Higher heating value (LHV) Lower heating value i Species i P Product P Parasitic R Reactant rxn Change in a reaction (e.g., ΔHrxn) SK Stack SYS System

Nafion is a registered trademark of E.I. du Pont de Nemours and Company. PureCell is a registered trademark of UTC Fuel Cells, Inc. Honda FCX is a registered trademark of Honda Motor Co., Ltd. Home Energy System is a registered trademark of Honda Motor Co., Ltd. Gaussian is a registered trademark of Gaussian, Inc.

PART I

FUEL CELL PRINCIPLES

CHAPTER 1

INTRODUCTION

You are about to embark on a journey into the world of fuel cells and electrochemistry. This chapter will act as a roadmap for your travels, setting the stage for the rest of the book. In broad terms, this chapter will acquaint you with fuel cells: what they are, how they work, and what significant advantages and disadvantages they present. From this starting point, the subsequent chapters will lead you onward in your journey as you acquire a fundamental understanding of fuel cell principles.

1.1 WHAT IS A FUEL CELL?

You can think of a fuel cell as a “factory” that takes fuel as input and produces electricity as output. (See Figure 1.1.) Like a factory, a fuel cell will continue to churn out product (electricity) as long as raw material (fuel) is supplied. This is the key difference between a fuel cell and a battery. While both rely on electrochemistry to work their magic, a fuel cell is not consumed when it produces electricity. It is really a factory, a shell, which transforms the chemical energy stored in a fuel into electrical energy.

Viewed this way, combustion engines are also “chemical factories.” Combustion engines also take the chemical energy stored in a fuel and transform it into useful mechanical or electrical energy. So what is the difference between a combustion engine and a fuel cell?

In a conventional combustion engine, fuel is burned, releasing heat. Consider the sim- plest example, the combustion of hydrogen:

H2 + 1 2 O2 ⇌ H2O (1.1)

3

4 INTRODUCTION

Electricity

Fuel cell H2O(1/g)O2(g)

H2(g)

Figure 1.1. General concept of a (H2–O2) fuel cell.

On the molecular scale, collisions between hydrogen molecules and oxygen molecules result in a reaction. The hydrogen molecules are oxidized, producing water and releasing heat. Specifically, at the atomic scale, in amatter of picoseconds, hydrogen–hydrogen bonds and oxygen–oxygen bonds are broken, while hydrogen–oxygen bonds are formed. These bonds are broken and formed by the transfer of electrons between themolecules. The energy of the product water bonding configuration is lower than the bonding configurations of the initial hydrogen and oxygen gases. This energy difference is released as heat. Although the energy difference between the initial and final states occurs by a reconfiguration of electrons as they move from one bonding state to another, this energy is recoverable only as heat because the bonding reconfiguration occurs in picoseconds at an intimate, subatomic scale. (See Figure 1.2.) To produce electricity, this heat energy must be converted into mechanical energy, and then the mechanical energy must be converted into electrical energy. Going through all these steps is potentially complex and inefficient.

Consider an alternative solution: to produce electricity directly from the chemical reac- tion by somehow harnessing the electrons as they move from high-energy reactant bonds

Reaction progress

P ot

en tia

l e ne

rg y

Products (H2O)

Reactants (H2/O2)

1

32 41

4

3

2

H2 H2

H2O

H2O O2

Figure 1.2. Schematic of H2–O2 combustion reaction. (Arrows indicate the relative motion of the molecules participating in the reaction.) Starting with the reactant H2–O2 gases (1), hydrogen–hydrogen and oxygen–oxygen bondsmust first be broken, requiring energy input (2) before hydrogen–oxygen bonds are formed, leading to energy output (3, 4).

WHAT IS A FUEL CELL? 5

to low-energy product bonds. In fact, this is exactly what a fuel cell does. But the question is, how do we harness electrons that reconfigure in picoseconds at subatomic length scales? The answer is to spatially separate the hydrogen and oxygen reactants so that the electron transfer necessary to complete the bonding reconfiguration occurs over a greatly extended length scale. Then, as the electrons move from the fuel species to the oxidant species, they can be harnessed as an electrical current.

BONDS AND ENERGY

Atoms are social creatures. They almost always prefer to be together instead of alone. When atoms come together, they form bonds, lowering their total energy. Figure 1.3 shows a typical energy–distance curve for a hydrogen–hydrogen bond. When the hydro- gen atoms are far apart from one another (1), no bond exists and the system has high energy. As the hydrogen atoms approach one another, the system energy is lowered until the most stable bonding configuration (2) is reached. Further overlap between the atoms is energetically unfavorable because the repulsive forces between the nuclei begin to dominate (3). Remember:

• Energy is released when a bond is formed. • Energy is absorbed when a bond is broken.

For a reaction to result in a net release of energy, the energy released by the formation of the product bonds must be more than the energy absorbed to break the reactant bonds.

1

2

3

Internuclear distance (pm)

P ot

en tia

l e ne

rg y

(K J/

m ol

)

20010074

–100

–200

–300

–400 –436

–500

Figure 1.3. Bonding energy versus internuclear separation for hydrogen–hydrogen bond: (1) no bond exists; (2) most stable bonding configuration; (3) further overlap unfavorable due to inter- nuclear repulsion.

6 INTRODUCTION

1.2 A SIMPLE FUEL CELL

In a fuel cell, the hydrogen combustion reaction is split into two electrochemical half reac- tions:

H2 ⇌ 2H + + 2e− (1.2)

1 2 O2 + 2H+ + 2e− ⇌ H2O (1.3)

By spatially separating these reactions, the electrons transferred from the fuel are forced to flow through an external circuit (thus constituting an electric current) and do useful work before they can complete the reaction.

Spatial separation is accomplished by employing an electrolyte. An electrolyte is a mate- rial that allows ions (charged atoms) to flow but not electrons. At a minimum, a fuel cell must possess two electrodes, where the two electrochemical half reactions occur, separated by an electrolyte.

Figure 1.4 shows an example of an extremely simple H2–O2 fuel cell. This fuel cell consists of two platinum electrodes dipped into sulfuric acid (an aqueous acid electrolyte). Hydrogen gas, bubbled across the left electrode, is split into protons (H+) and electrons following Equation 1.2. The protons can flow through the electrolyte (the sulfuric acid is like a “sea” of H+), but the electrons cannot. Instead, the electrons flow from left to right through a piece of wire that connects the two platinum electrodes. Note that the resulting current, as it is traditionally defined, is in the opposite direction. When the electrons reach the right electrode, they recombinewith protons and bubbling oxygen gas to producewater following Equation 1.3. If a load (e.g., a light bulb) is introduced along the path of the electrons, the flowing electrons will provide power to the load, causing the light bulb to glow. Our fuel cell

H2 O2

e–

H+

Figure 1.4. A simple fuel cell.

A SIMPLE FUEL CELL 7

is producing electricity! The first fuel cell, invented by William Grove in 1839, probably looked a lot like the one discussed here.

ENERGY, POWER, ENERGY DENSITY, AND POWER DENSITY

To understand how a fuel cell compares to a combustion engine or a battery, several quantitative metrics, or figures of merit, are required. The most common figures of merit used to compare energy conversion systems are power density and energy density.

To understand energy density and power density, you first need to understand the difference between energy and power:

Energy is defined as the ability to do work. Energy is usually measured in joules (J) or calories (cal).

Power is defined as the rate at which energy is expended or produced. In other words, power represents the intensity of energy use or production. Power is a rate. The typical unit of power, the watt (W), represents the amount of energy used or produced per second (1 W = 1 J∕s).

From the above discussion, it is obvious that energy is the product of power and time:

Energy = power × time (1.4)

Although the International System of Units (SI) uses the joule as the unit of energy, you will often see energy expressed in terms of watt-hours (Wh) or kilowatt-hours (kWh). These units arise when the units of power (e.g., watts) are multiplied by a length of time (e.g., hours) as in Equation 1.4. Obviously, watt-hours can be converted to joules or vice versa using simple arithmetic:

1Wh × 3600s∕h × 1 (J∕s)∕W = 3600J (1.5)

Refer to Appendix A for a list of some of the more common unit conversions for energy and power. For portable fuel cells and other mobile energy conversion devices, power density and energy density are more important than power and energy because they provide information about how big a system needs to be to deliver a certain amount of energy or power. Power density refers to the amount of power that can be produced by a device per unit mass or volume. Energy density refers to the total energy capacity available to the system per unit mass or volume.

Volumetric power density is the amount of power that can be supplied by a device per unit volume. Typical units are W∕cm3 or kW∕m3.

Gravimetric power density (or specific power) is the amount of power that can be sup- plied by a device per unit mass. Typical units are W/g or kW/kg.

8 INTRODUCTION

Volumetric energy density is the amount of energy that is available to a device per unit volume. Typical units are Wh∕cm3 or kWh∕m3.

Gravimetric energy density (or specific energy) is the amount of energy that is available to a device per unit mass. Typical units are Wh∕g or kWh∕kg.

1.3 FUEL CELL ADVANTAGES

Because fuel cells are “factories” that produce electricity as long as they are supplied with fuel, they share some characteristics in common with combustion engines. Because fuel

(a)

1

2 3

4

Fuel cell, battery

Combustion engine

Chemical energy

Mechanical energy

Heat energy

Electrical energy

Battery

Fuel tank

Fuel cell or combustion

engine

Work out

Work out

(b)

Figure 1.5. Schematic comparison of fuel cells, batteries, and combustion engines. (a) Fuel cells and batteries produce electricity directly from chemical energy. In contrast, combustion engines first convert chemical energy into heat, then mechanical energy, and finally electricity (alternatively, the mechanical energy can sometimes be used directly). (b) In batteries, power and capacity are typically intertwined—the battery is both the energy storage and the energy conversion device. In contrast, fuel cells and combustion engines allow independent scaling between power (determined by the fuel cell or engine size) and capacity (determined by the fuel tank size).

FUEL CELL ADVANTAGES 9

cells are electrochemical energy conversion devices that rely on electrochemistry to work their magic, they share some characteristics in common with primary batteries. In fact, fuel cells combine many of the advantages of both engines and batteries.

Since fuel cells produce electricity directly from chemical energy, they are often far more efficient than combustion engines. Fuel cells can be all solid state and mechanically ideal, meaning no moving parts. This yields the potential for highly reliable and long-lasting systems. A lack of moving parts also means that fuel cells are silent. Also, undesirable products such as NOx, SOx, and particulate emissions are virtually zero.

Unlike batteries, fuel cells allow easy independent scaling between power (determined by the fuel cell size) and capacity (determined by the fuel reservoir size). In batteries, power and capacity are often convoluted. Batteries scale poorly at large sizes, whereas fuel cells scale well from the 1-W range (cell phone) to the megawatt range (power plant). Fuel cells offer potentially higher energy densities than batteries and can be quickly recharged by refu- eling, whereas batteries must be thrown away or plugged in for a time-consuming recharge. Figure 1.5 schematically illustrates the similarities and differences between fuel cells, bat- teries, and combustion engines.

FUEL CELLS VERSUS SOLAR CELLS VERSUS BATTERIES

Fuel cells, solar cells, and batteries all produce electrical power by converting either chemical energy (fuel cells, batteries) or solar energy (solar cells) to a direct-current (DC) flow of electricity. The key features of these three devices are compared in Figure 1.6 using the analogy of buckets filled with water. In all three devices, the electrical output power is determined by the operating voltage (the height of water in the bucket) and current density (the amount of water flowing out the spigot at the bottom of the bucket).

Fuel cells and solar cells can be viewed as “open” thermodynamic systems that oper- ate at a thermodynamic steady state. In other words, the operating voltage of a fuel cell (or a solar cell) remains constant in time so long as it is continually supplied with fuel (or photons) from an external source. In Figure 1.6, this is shown by the fact that the water in the fuel cell and solar cell buckets is continually replenished from the top at the same rate that it flows out the spigot in the bottom, resulting in a constant water level (constant operating voltage).

In contrast, most batteries are closed thermodynamic systems that contain a finite and exhaustible internal supply of chemical energy (reactants). As these reactants deplete, the voltage of the battery generally decreases over time. In Figure 1.6, this is shown by the fact that the water in the battery bucket is not replenished, resulting in a decreasing water level (decreasing operating voltage) with time as the battery is discharged. It is important to point out that battery voltage does not decrease linearly during discharge. During discharge, batteries pass through voltage plateaus where the voltage remains more or less constant for a significant part of the discharge cycle. This phenomenon is captured by the strange shape of the battery “bucket.”

10 INTRODUCTION

Figure 1.6. Fuel cells versus solar cells versus batteries. This schematic diagram provides another way to look at the similarities and differences between three common energy conversion technologies that provide electricity as an output.

FUEL CELL DISADVANTAGES 11

In addition to the thermodynamic operating differences between fuel cells, solar cells, and batteries, Figure 1.6 also shows that fuel cells typically operate at much higher cur- rent densities than solar cells or batteries. This characteristic places great importance on using low-resistance materials in fuel cells to minimize ohmic (“IR”) losses. We will learn more about minimizing ohmic losses in Chapter 4 of this textbook!

1.4 FUEL CELL DISADVANTAGES

While fuel cells present intriguing advantages, they also possess some serious disadvan- tages. Cost represents a major barrier to fuel cell implementation. Because of prohibitive costs, fuel cell technology is currently only economically competitive in a few highly spe- cialized applications (e.g., onboard the Space Shuttle orbiter). Power density is another significant limitation. Power density expresses how much power a fuel cell can produce per unit volume (volumetric power density) or per unit mass (gravimetric power density). Although fuel cell power densities have improved dramatically over the past decades, fur- ther improvements are required if fuel cells are to compete in portable and automotive applications. Combustion engines and batteries generally outperform fuel cells on a volu- metric power density basis; on a gravimetric power density basis, the race is much closer. (See Figure 1.7.)

Fuel availability and storage pose further problems. Fuel cells work best on hydrogen gas, a fuel that is not widely available, has a low volumetric energy density, and is difficult

10

100

1000

10000

0.01 0.1 1 10

G ra

vi m

et ri

c p

o w

er d

en si

ty (

W /k

g )

Fuel cell (portable) IC engines

(automotive)

Lead-acid battery

IC engine (portable)

Li-ion battery

Fuel cell (automotive)

Volumetric Power Density (kW/L) IC = Internal Combustion

Figure 1.7. Power density comparison of selected technologies (approximate ranges).

12 INTRODUCTION

0

5

10

15

20

25

30

35

40

45

50

0 5 10 15 20 25 30 35

Volumetric Energy Density (MJ/L)

G ra

vi m

et ri

c en

er g

y d

en si

ty (

M J/

kg )

Hydrogen, 7500PSI (including system) Hydrogen, liquid

(including system)

Hydrogen, metal hydride (low)

Hydrogen, metal hydride (high)

Methanol

Ethanol

Gasoline

Hydrogen, 3500PSI (including system)

Figure 1.8. Energy density comparison of selected fuels (lower heating value).

to store. (See Figure 1.8.) Alternative fuels (e.g., gasoline, methanol, formic acid) are dif- ficult to use directly and usually require reforming. These problems can reduce fuel cell performance and increase the requirements for ancillary equipment. Thus, although gaso- line looks like an attractive fuel from an energy density standpoint, it is not well suited to fuel cell use.

Additional fuel cell limitations include operational temperature compatibility concerns, susceptibility to environmental poisons, and durability under start–stop cycling. These sig- nificant disadvantages will not be easy to overcome. Fuel cell adoption will be severely limited unless technological solutions can be developed to hurdle these barriers.

1.5 FUEL CELL TYPES

There are five major types of fuel cells, differentiated from one another by their electrolyte:

1. Phosphoric acid fuel cell (PAFC)

2. Polymer electrolyte membrane fuel cell (PEMFC)

3. Alkaline fuel cell (AFC)

4. Molten carbonate fuel cell (MCFC)

5. Solid-oxide fuel cell (SOFC)

FUEL CELL TYPES 13

TABLE 1.1. Description of Major Fuel Cell Types

PEMFC PAFC AFC MCFC SOFC

Polymer Liquid H3PO4 Liquid KOH Molten Electrolyte membrane (immobilized) (immobilized) carbonate Ceramic

Charge carrier H+ H+ OH− CO3 2− O2−

Operating temperature

80∘C 200∘C 60–220∘C 650∘C 600–1000∘C

Catalyst Platinum Platinum Platinum Nickel Perovskites (ceramic)

Cell components Carbon based Carbon based Carbon based Stainless based

Ceramic based

Fuel compatibility H2, methanol H2 H2 H2, CH4 H2, CH4, CO

While all five fuel cell types are based on the same underlying electrochemical princi- ples, they all operate at different temperature regimens, incorporate different materials, and often differ in their fuel tolerance and performance characteristics, as shown in Table 1.1. Most of the examples in this book focus on PEMFCs or SOFCs. We will briefly contrast these two fuel cell types.

• PEMFCs employ a thin polymermembrane as an electrolyte (the membrane looks and feels a lot like plastic wrap). The most common PEMFC electrolyte is a membrane material called NafionTM. Protons are the ionic charge carrier in a PEMFCmembrane. As we have already seen, the electrochemical half reactions in an H2–O2 PEMFC are

H2 → 2H + + 2e−

1 2 O2 + 2H+ + 2e− → H2O

(1.6)

PEMFCs are attractive for many applications because they operate at low temperature and have high power density.

• SOFCs employ a thin ceramic membrane as an electrolyte. Oxygen ions (O2–) are the ionic charge carrier in an SOFC membrane. The most common SOFC electrolyte is an oxide material called yttria-stabilized zirconia (YSZ). In an H2–O2 SOFC, the electrochemical half reactions are

H2 + O2− → H2O + 2e−

1 2 O2 + 2e− → O2−

(1.7)

To function properly, SOFCs must operate at high temperatures (>600∘C). They are attractive for stationary applications because they are highly efficient and fuel flexible.

14 INTRODUCTION

Note how changing the mobile charge carrier dramatically changes the fuel cell reaction chemistry. In a PEMFC, the half reactions are mediated by the movement of protons (H+), and water is produced at the cathode. In a SOFC, the half reactions are mediated by the motion of oxygen ions (O2–), and water is produced at the anode. Note in Table 1.1 how other fuel cell types use OH– or CO3

2– as ionic charge carriers. These fuel cell types will also exhibit different reaction chemistries, leading to unique advantages and disadvantages.

Part I of this book introduces the basic underlying principles that govern all fuel cell devices. What you learn here will be equally applicable to a PEMFC, a SOFC, or any other fuel cell for that matter. Part II discusses thematerials and technology-specific aspects of the five major fuel cell types, while also delving into fuel cell system issues such as stacking, fuel processing, control, and environmental impact.

1.6 BASIC FUEL CELL OPERATION

The current (electricity) produced by a fuel cell scales with the size of the reaction area where the reactants, the electrode, and the electrolyte meet. In other words, doubling a fuel cell’s area approximately doubles the amount of current produced.

Although this trend seems intuitive, the explanation comes from a deeper understanding of the fundamental principles involved in the electrochemical generation of electricity. As we have discussed, fuel cells produce electricity by converting a primary energy source (a fuel) into a flow of electrons. This conversion necessarily involves an energy transfer step, where the energy from the fuel source is passed along to the electrons constituting

Anode

Electrolyte

Cathode

Hydrogen

Oxygen

Figure 1.9. Simplified planar anode–electrolyte–cathode structure of a fuel cell.

BASIC FUEL CELL OPERATION 15

the electric current. This transfer has a finite rate and must occur at an interface or reaction surface. Thus, the amount of electricity produced scales with the amount of reaction surface area or interfacial area available for the energy transfer. Larger surface areas translate into larger currents.

To provide large reaction surfaces that maximize surface-to-volume ratios, fuel cells are usually made into thin, planar structures, as shown in Figure 1.9. The electrodes are highly porous to further increase the reaction surface area and ensure good gas access. One side of the planar structure is provisioned with fuel (the anode electrode), while the other side is provisioned with oxidant (the cathode electrode). A thin electrolyte layer spatially separates the fuel and oxidant electrodes and ensures that the two individual half reactions occur in isolation from one another. Compare this planar fuel cell structure with the simple fuel cell discussed earlier in Figure 1.4. While the two devices look quite different, noticeable similarities exist between them.

ANODE = OXIDATION; CATHODE = REDUCTION

To understand any discussion of electrochemistry, it is essential to have a clear concept of the terms oxidation, reduction, anode, and cathode.