Fuel Cells

Vladimir S. Bagotsky is an acclaimed scientist in the field of electrochemical phenomena. A former department head at the Moscow Power Sources Institute, where he supervised the development of fuel cells for various national and international projects, including the Sputnik satellites, Dr. Bagotsky also spent twenty years as a department head and principal scientist at the A. N. Frumkin Institute of Physical Chemistry and Electrochemistry. He has published more than 400 papers in scientific journals and in 2010 was acknowledged by the ECS for his sixty-five years spent working in theoretical electrochemistry, electrocatalysis, and applied electrochemistry.

• PREFACE xi PREFACE TO THE FIRST EDITION xiiiSYMBOLS xvABBREVIATIONS AND ACRONYMS xviiPART I INTRODUCTION 1Introduction 3What Is a Fuel Cell? Definition of the Term, 3Significance of Fuel Cells for the Economy, 31 The Working Principles of a Fuel Cell 51.1 Thermodynamic Aspects, 51.2 Schematic Layout of Fuel Cell Units, 91.3 Types of Fuel Cells, 131.4 Layout of a Real Fuel Cell: The Hydrogen–Oxygen Fuel Cell with Liquid Electrolyte, 131.5 Basic Parameters of Fuel Cells, 18Reference, 242 The Long History of Fuel Cells 252.1 The Period Prior to 1894, 252.2 The Period from 1894 to 1960, 282.3 The Period from 1960 to the 1990s, 312.4 The Period After the 1990s, 37References, 38PART II MAJOR TYPES OF FUEL CELLS 413 Proton-Exchange Membrane Fuel Cells 433.1 History of the PEMFC, 443.2 Standard PEMFC Version from the 1990s, 473.3 Special Features of PEMFC Operation, 513.4 Platinum Catalyst Poisoning by Traces of CO in the Hydrogen, 543.5 Commercial Activities in Relation to PEMFCs, 563.6 Future Development of PEMFCs, 573.7 Elevated-Temperature PEMFCs, 64References, 674 Direct Liquid Fuel Cells 71Part A: Direct Methanol Fuel Cells, 714.1 Methanol as a Fuel for Fuel Cells, 714.2 Current-Producing Reactions and Thermodynamic Parameters, 724.3 Anodic Oxidation of Methanol, 724.4 Milestones in DMFC Development, 744.5 Membrane Penetration by Methanol (Methanol Crossover), 744.6 Varieties of DMFCs, 774.7 Special Operating Features of DMFCs, 794.8 Practical Models of DMFCs and Their Features, 814.9 Problems to Be Solved in Future DMFCs, 83Part B: Direct Liquid Fuel Cells, 854.10 The Problem of Replacing Methanol, 854.11 Fuel Cells Using Organic Liquids as Fuels, 864.12 Fuel Cells Using Inorganic Liquids as Fuels, 91References, 945 Phosphoric Acid Fuel Cells 995.1 Early Work on Phosphoric Acid Fuel Cells, 995.2 Special Features of Aqueous Phosphoric Acid Solutions, 1005.3 Construction of PAFCs, 1015.4 Commercial Production of PAFCs, 1025.5 Development of Large Stationary Power Plants, 1035.6 The Future of PAFCs, 1035.7 Importance of PAFCs for Fuel Cell Development, 104References, 1056 Alkaline Fuel Cells 1076.1 Hydrogen–Oxygen AFCs, 1086.2 Alkaline Hydrazine Fuel Cells, 1156.3 Anion-Exchange (Hydroxyl Ion–Conducting) Membranes, 1186.4 Methanol Fuel Cells with Anion-Exchange Membranes, 1196.5 Methanol Fuel Cell with an Invariant Alkaline Electrolyte, 1206.6 Direct Ammonia Fuel Cell with an Anion-ExchangeMembrane, 121References, 1217 Molten Carbonate Fuel Cells 1237.1 Special Features of High-Temperature Fuel Cells, 1237.2 Structure of Hydrogen–Oxygen MCFCs, 1247.3 MCFCs with Internal Fuel Reforming, 1267.4 Development of MCFC Work, 1287.5 The Lifetime of MCFCs, 129References, 1318 Solid-Oxide Fuel Cells 1338.1 Schematic Design of Conventional SOFCs, 1348.2 Tubular SOFCs, 1368.3 Planar SOFCs, 1408.4 Monolithic SOFCs, 1438.5 Varieties of SOFCs, 1448.6 Utilization of Natural Fuels in SOFCs, 1468.7 Interim-Temperature SOFCs, 1488.8 Low-Temperature SOFCs, 1528.9 Factors Influencing the Lifetime of SOFCs, 154References, 1569 Other Types of Fuel Cells 1599.1 Redox Flow Cells, 1599.2 Biological Fuel Cells, 1629.3 Semi-Fuel Cells, 1679.4 Direct Carbon Fuel Cells, 169References, 17410 Fuel Cells and Electrolysis Processes 17710.1 Water Electrolysis, 17710.2 Chlor-Alkali Electrolysis, 18210.3 Electrochemical Synthesis Reactions, 185References, 187PART III INHERENT SCIENTIFIC AND ENGINEERING PROBLEMS 18911 Fuel Management 19111.1 Reforming of Natural Fuels, 19211.2 Production of Hydrogen for Autonomous Power Plants, 19611.3 Purification of Technical Hydrogen, 19911.4 Hydrogen Transport and Storage, 202References, 20512 Electrocatalysis 20712.1 Fundamentals of Electrocatalysis, 20712.2 Putting Platinum Catalysts on the Electrodes, 21112.3 Supports for Platinum Catalysts, 21412.4 Platinum Alloys and Composites as Catalysts for Anodes, 21712.5 Nonplatinum Catalysts for Fuel Cell Anodes, 22012.6 Electrocatalysis of the Oxygen Reduction Reaction, 22112.7 Stability of Electrocatalysts, 227References, 22813 Membranes 23313.1 Fuel Cell–Related Membrane Problems, 23413.2 Work to Overcome Degradation of Nafion Membranes, 23513.3 Modification of Nafion Membranes, 23513.4 Membranes Made from Polymers Without Fluorine, 23713.5 Membranes Made from Other Materials, 23913.6 Matrix-Type Membranes, 23913.7 Membranes with Hydroxyl Ion Conduction, 240References, 24114 Structural and Wetting Properties of Fuel Cell Components 243Coauthor: Yurij M. Volfkovich14.1 Methods for Investigating Porous Materials, 24414.2 A New Method: The Method of Standard Contact Porosimetry, 24514.3 Catalysts Used in Fuel Cells, 24814.4 The Catalytic Layer, 25214.5 The Gas-Diffusion Layer, 25414.6 Membranes, 25714.7 Influence of Structural and Wetting Properties on Fuel Cell Performance, 262References, 26415 Mathematical Modeling of Fuel Cells 267Felix N. B¨uchi15.1 Zero-Dimensional Models, 27015.2 One-Dimensional Models, 27015.3 Two-Dimensional Models, 27115.4 Three-Dimensional Models, 27215.5 Time Domain, 27315.6 Concluding Remarks, 273References, 27416 Experimental Methods for Investigating Fuel Cell Stacks 27516.1 Methods Developed Before 2007, 27716.2 Optical, X-Ray, and EM Methods, 27816.3 Neutron Beam–Based Methods, 28116.4 Electrochemical Methods, 28316.5 Miscellaneous Methods, 286References, 28817 Small Fuel Cells for Portable Devices 29117.1 Special Operating Features of Mini-Fuel Cells, 29217.2 Flat Mini-Fuel Batteries, 29317.3 Silicon-Based Mini-Fuel Cells, 29617.4 PCB-Based Mini-Fuel Cells, 29817.5 Mini-Solid-Oxide Fuel Cells, 29917.6 The Problem of Air-Breathing Cathodes, 30017.7 Prototypes of Power Units with Mini-Fuel Cells, 30117.8 Concluding Remarks, 304References, 30518 Nonconventional Design Principles for Fuel Cells 30718.1 Conventional Design Principles and Their Drawbacks, 30718.2 The Principle of Mixed-Reactant Supply: Mixed-Reactant Fuel Cells, 30818.3 Coplanar Fuel Cell Design: Strip Cells, 31018.4 The Flow-Through Electrode Principle, 31218.5 Single-Chamber SOFCs, 31318.6 Microfluidic Fuel Cells, 319References, 321PART IV COMMERCIALIZATION OF FUEL CELLS 32519 Applications 32719.1 Large Stationary Power Plants, 32719.2 Small Stationary Power Units, 33219.3 Fuel Cells for Transport Applications, 33519.4 Portables, 34119.5 Military Applications, 34519.6 Handicaps Preventing a Broader Commercialization of Fuel Cells, 347References, 34820 Fuel Cell Work in Various Countries 35120.1 Driving Forces for Fuel Cell Work, 35120.2 Fuel Cells and the Hydrogen Economy, 35320.3 Activities in North America, 35520.4 Activities in Europe, 35620.5 Activities in other Countries, 35720.6 The Volume of Published Fuel Cell Work, 35920.7 Legislation and Standardization in the Field of Fuel Cells, 361References, 36221 Outlook 36321.1 Periods of Alternating Hope and Disappointment, 36321.2 Some Misconceptions, 364Klaus Müller21.3 Ideal Fuel Cells, 36621.4 Projected Future of Fuel Cells, 368References, 369GENERAL BIBLIOGRAPHY 371AUTHOR INDEX 373SUBJECT INDEX 379

“I enjoyed reading the book. From an academician point of view, the content and amount of material covered in this book makes it an ideal choice for a beginner-level undergraduate text.”  (Nanomaterials and Energy,6 November 2012)