Electrochemical Components

Marie-Cécile Péra is Full Professor at the University of Franche-Comte in France and Deputy Director of the FEMTO-ST Institute (CNRS). Her research activities include modeling, control and diagnosis of electrical power generation systems (fuel cells – PEMFC and SOFC, supercapacities, batteries) for transportation and stationary applications.Daniel Hissel is Full Professor at the University of Franche-Comte in France and Director of the Fuel Cell Lab Research Federation (CNRS). He also leads a research team devoted to hybrid electrical systems in the FEMTO-ST Institute (CNRS).Hamid Gualous is Full Professor at the University of Caen Lower Normandy in France and director of the LUSAC laboratory. His current research interests include power electronics, electric energy storage, power and energy systems and energy management.Christophe Turpin is Full Researcher at the CNRS. He is responsible for hydrogen activities within the Laboratory LAPLACE, Toulouse, France. His research activities include the characterization and modeling of fuel cells and electrolyzers, the state of health of these components and their hybridization with other electrochemical components (ultracapacitators, batteries) within optimized energy systems for stationary and aeronautical applications.

• Preface xiChapter 1. Basic Concepts of Electrochemistry used in Electrical Engineering 11.1. Introduction 11.2. Brief description and principles of operation of electrochemical components 11.2.1. Principle of operation 11.2.2. Brief description of groups of components 41.3. Redox reaction 71.4. Chemical energy 91.4.1. Enthalpy, entropy and free energy 91.4.2. Enthalpy, entropy and free energy of formation 101.5. Potential or voltage of an electrode 101.6. Reversible potential of a cell 111.7. Faradaic current density and the Butler–Volmer equation 131.8. Butler–Volmer equation for a whole cell 151.9. From the Butler–Volmer equation to the Tafel equation 171.10. Faraday’s law 191.11. Matter transfer model: Nernst model 201.12. Concept of limit current 221.13. Expression of the polarization curve 241.14. Double-layer capacity 271.15. Electrochemical impedance 271.16. Reagents and products in the gaseous phase: total pressure, partial pressure, molar fraction and mixture 301.17. Corrected exercises 311.17.1. Calculation of the variation in enthalpy during the formation of a mole of water 311.17.2. Calculation of the variation in entropy for the formation of a mole of water 341.17.3. Calculation of the variation in free energy during the formation of a mole of water 361.17.4. Calculation of the Nernst potential for a cell in a PEM fuel cell (PEMFC) 381.17.5. Faraday equations for a Pb accumulator 391.17.6. Calculation of the mass of water consumed by an electrolysis cell  40Chapter 2. Water Electrolyzers 412.1. Introduction 412.2. Principles of operation of the main water electrolyzers 442.3. History of water electrolysis 462.4. Technological elements 512.4.1. Alkaline technology 512.4.2. PEM technology 562.4.3. SO technology 612.4.4. Comparison of the three water electrolyzer technologies 642.4.5. Specifications of a commercial electrolyzer 652.5. Theoretical approach to an electrolyzer 672.5.1. Energy-related elements 672.5.2. Electrical behavior in the quasi-static state 802.5.3. Electrical behavior in the dynamic state with a large signal 952.5.4. Electrical behavior in a dynamic state with a small signal (impedance) 1002.6. Experimental characterization of the electrical behavior of an electrolyzer 1042.6.1. Polarization curve (quasi-static characterization) 1062.6.2. Impedance spectroscopy (dynamic small-signal characterization) 1082.6.3. Current steps 1102.6.4. Current sweeping (large-signal dynamic characterization) 1112.6.5. Combining the approaches to characterization (advanced approach) 1112.7. Procedures for parameterizing the models 1122.7.1. Minimal combinatorial approach to experimental characterizations 1132.7.2. Multiple impedance spectra approach 1142.7.3. Low-frequency multi-sweeping approach 1142.7.4. Toward an optimal and systematic combinatorial exploitation of the experimental characterizations 1152.8. Combination with a fuel cell. Concept of the “hydrogen battery” 1162.8.1. General considerations 1172.8.2. Static characteristics of an H2/O2 battery 1192.8.3. Deadband of an H2/O2 battery 1202.8.4. Brief overview of situation with industrial developments 1222.9. A few examples of applications for electrolyzers 1232.9.1. Points about industrial hydrogen production by electrolysis 1242.9.2. State of the art on applications coupling solar photovoltaic and hydrogen; close examination of the French projects MYRTE, PEPITE and JANUS 1262.10. Some points about the storage of hydrogen 1352.11. Conclusions and perspectives 1372.12. Exercises 137Chapter 3. Fuel Cells 1513.1. Introduction 1513.2. Classification of fuel cell technologies 1523.2.1. Classification on the basic of the acid/basic medium 1533.2.2. Classification on the basis of the operating temperature 1543.2.3. Classification on the basis of the type of electrolyte 1543.3. Proton Exchange Membrane Fuel Cells (PEMFCs) 1573.3.1. Constitution 1573.3.2. Characteristics 1603.4. Solid Oxide Fuel Cells (SOFCs) 1683.5. Fuel-cell systems 1713.5.1. General points 1713.5.2. PEMFC systems 1733.5.3. SOFC systems 1793.6. Applications for fuel cells 1803.6.1. Mobile applications 1813.6.2. Stationary applications 1833.6.3. Applications in transport 1843.7. Corrected exercises 1903.7.1. Calculation of the cost of platinum for an electrode 1903.7.2. Dimensions of a “standard” fuel cell module 1913.7.3. Calculation of the flowrate of reactant gases entering the cell 1913.7.4. Calculation of the water content of the air upon input and output of the cell. Calculation of the dew point at the cell output 1933.7.5. Calculation of the yield of a PEMFC 1973.7.6. Autonomy of an exploration submarine 1983.7.7. Power supply to an isolated farm site 1993.7.8. Fuel-cell generator for a private vehicle 204Chapter 4. Electrical Energy Storage by Supercapacitors 2094.1. Introduction 2094.2. Operation and energy characteristics of EDLCs 2114.2.1. Structure and operation of supercapacitors 2114.2.2. Electrical and energetic characterization of supercapacitors 2144.3. Supercapacitor module sizing 2194.3.1. Power-based design 2204.3.2. Dimension design based on the energy stored by the supercapacitor 2224.3.3. Balancing the supercapacitors 2244.4. Supercapacitor modeling 2264.5. DC/DC converter associated with a supercapacitor module 2334.6. Thermal behavior of supercapacitors 2344.6.1. Thermal modeling of supercapacitors 2354.6.2. Modeling by thermal/electrical analogy 2374.7. Hybrid electricity storage device: the LIC (Lithium Ion Capacitor) 2384.8. Exercises – statements 240Chapter 5. Electrochemical Accumulators 2535.1. Introduction 2535.2. Lead accumulators 2535.2.1. Operational principle 2535.2.2. Advantages and disadvantages to this technology 2545.3. Nickel accumulators 2555.3.1. Nickel-Cadmium (Ni-Cd) accumulator 2555.3.2. Nickel Metal Hydride (Ni-MH) accumulator 2565.3.3. Nickel-Zinc accumulator 2585.4. Lithium accumulators 2595.4.1. Why lithium? 2595.4.2. Principle of their function 2595.4.3. Advantages and disadvantages to these technologies 2605.4.4. Lithium-ion technology 2615.4.5. Lithium-metal-polymer technology 2625.4.6. Other technologies 2635.5. Characteristics of an accumulator or battery 2645.5.1. Capacity 2645.5.2. Internal resistance 2665.5.3. Voltages 2675.5.4. Energy 2685.5.5. State of charge of a battery 2685.6. Modeling of a battery 2695.6.1. Thévenin model 2695.6.2. Improved Thévenin model 2705.6.3. FreedomCar model 2715.7. Aging of batteries 2725.8. Exercises 273Chapter 6. Hybrid Electrical System 2776.1. Introduction 2776.2. Definitions 2776.2.1. General points 2776.2.2. Particular case of a hybrid electric vehicle 2786.2.3. Hybrid electric system 2796.3. Advantages to hybridization 2796.3.1. Ragone plot 2806.3.2. Different types of energy? 2846.3.3. Taking account of non-energy-related criteria in the choice of a hybrid electricity storage solution 2876.4. Management of the energy flows in a hybrid system 2896.4.1. Optimization-based strategies 2906.4.2. Rule-based strategies 2916.4.3. Criteria for the supervision of the energy flows 2926.5. Example of application in the domain of transport: the ECCE platform (Evaluation des Composants d’une Chaine de traction Electrique – Evaluation of the Components in an Electric Powertrain) 2936.6. Corrected exercises 2966.6.1. Ragone plot of an ideal battery 2966.6.2. Ragone plot of an ideal capacitor 2996.6.3. Design of an electric vehicle 3026.6.4. Energy management in an electric vehicle 306Bibliography 309Index 321