Springer Handbook of Electrochemical Energy (eBook)

Cornelia Breitkopf is a Full Professor of in the Department of Mechanical Engineering and Chair of Technical Thermodynamics at the Technical University in Dresden, Germany. Her main research interests are transient methods for the evaluation of transport and sorption parameters of gases in porous media accompanied with the modeling of complex transport phenomena, the theoretical determination of property data, the characterization of solid porous materials, and modeling of silicon wafer structures.She received her diploma in Chemistry from the Martin-Luther-University Halle-Wittenberg where she continued her research to earn a PhD in theoretical physical chemistry. After a postdoctoral position at the Birkbeck College/University of London, she joined also as postdoc the Environmental Research Center in Leipzig. She was a Guest Researcher at the Environmental Science Center in Peterborough, Canada and at the University of Wisconsin, USA. Following her habilitation, which was part of a priority program of the German Science Foundation (DFG), she was Professor for Chemical Reaction Engineering in Leipzig and Freiberg and then worked as a Senior Scientist at the Technical University of Munich before she was appointed Full Professor in Dresden in 2010. Karen Swider-Lyons  is a Head of the Alternative Energy Section in the Chemistry Division of the Naval Research Laboratory in Washington D.C.  She currently leads research programs on advanced battery materials, low-cost catalysts for use in polymer fuel cells, and is studying how fuel cells can be used for long-endurance, energy-efficient unmanned air and undersea vehicles. Karen Swider-Lyons  obtained a PhD in Materials Science and Engineering from the University of Pennsylvania for her work on mixed conducting materials for solid oxide fuel cells. She also holds a BS in Chemistry from Haverford College. In 2010, she received the Dr. Delores M. Etter Top Scientist Award from the US Navy for her work on the long-endurance Ion Tiger Fuel Cell unmanned air vehicle. She has authored 72 papers in refereed journals, 95 technical articles/chapters and holds 14 patents.  She is a member of the Materials Research Society and Electrochemical Society (ECS) and serves as a technical advisor to the Defense Advanced Research Projects Agency and the Office of Naval Research.

Preface 6
About the Editors 8
List of Authors 9
Contents 14
List of Abbreviations 20
1 Electrochemical Science – Historial Review 27
References 35
2 Modern Electrochemistry 36
2.1 Fundamental Components of Electrochemistry 36
2.2 Thermodynamics 39
2.3 Kinetics 42
2.4 Mass Transport 44
2.5 The Charged Electrode Interface/Electrochemical Double Layer 46
2.6 Ionic and Electronic Resistance 48
2.7 Experimentation 49
2.8 Subtopics in Electrochemistry 51
2.9 Summary 53
References 54
Part A Thermodynamics 56
3 Thermodynamical Aspects of Electrochemical Reactions 57
3.1 Electrochemical Reactions for Energy Conversion 57
3.2 Electrochemical Reactions and Energy Transformation 78
References 91
4 Thermodynamicsof Electrochemical Systems 92
4.1 Scope and Premises 92
4.2 Thermodynamic Properties of the Total Cell 95
4.3 Example Cells 96
4.4 Entropy Production in Three- and Two-Dimensions 97
4.5 Alternative Variable Sets 98
4.6 Cell Potentials 103
4.7 The Polymer Electrolyte Fuel Cell 110
4.8 Transport at Interfaces. Perspectives and Conclusion 113
References 114
5 Multiscale Modeling of Solvation 117
5.1 Integral Equation Theory of Molecular Liquids 118
5.2 Statistical–Mechanical, Molecular Theory of Solvation 121
5.3 Multiscale Coupling of the 3D-RISM-KH Molecular Theory 135
5.4 Multi-Time-Step Molecular Dynamics of Biomolecules 138
5.5 Electrical Double Layer in Nanoporous Materials 145
5.6 Replica Formalism for Fluid Sorbedin a Disordered Matrix 145
5.7 Replica DRISM-KH-VM for Electrolyte Solution Sorbed in Nanoporous Material 146
5.8 Conclusions 155
References 156
Part B Electrodes and Electrode Processes 162
6 Highly Ordered Macroporous Electrodes 163
6.1 Macroporous Electrodes by Infiltrationof Colloidal Templates 164
6.2 Macroporous Materials with a Gradient in Pore Diameter 192
6.3 Macroporous Microelectrodeswith Cylindrical Geometry 201
6.4 Applicationsof Macroporous Electrodes 208
6.5 Conclusion 217
References 217
7 Ion-Sensitive Electrodes 227
7.1 Fundamentals of Potentiometry 227
7.2 Application of ISE 246
7.3 Amperometric and Voltammetric Methods 247
References 257
8 Transport in Liquid-Phase Electrochemical Devices 258
8.1 A General Transport Model for Liquid-Fed Electrochemical Cells 259
8.2 Practical Considerations 265
8.3 Example Cell: Direct Borohydride–Hydrogen Peroxide Fuel Cell 267
8.4 Conclusions 275
8.5 Nomenclature 275
References 275
9 Catalyst Layer Modeling 278
9.1 Gas Diffusion Electrodes 278
9.2 Catalyst Layer Physical Structure 280
9.3 Governing Equations 281
9.4 Macroscale Models 292
9.5 Conclusions and Outlook 301
References 302
10 Water Management in Proton Exchange Fuell Cells 305
10.1 Water Management in PEMFC 305
10.2 Thermodynamics and Electrochemistry 307
10.3 Polarization Curve 308
10.4 Gas Humidification 312
10.5 Sensorless Humidification 320
References 329
11 Calculations in Li-Ion Battery Materials 331
11.1 Using DFT to Calculate the Voltage of Layered Materials 333
11.2 PDOS Calculations of Oxygen Stability and Cycling Safety 341
11.3 Summary 344
References 345
Part C Electrochemistry Probes 347
12 Electrochemical Energy Generationand Storageas Seen by In-Situ NMR 348
12.1 Spatially-Resolved 195Pt NMR Spectroscopyof Pt-Based Electrocatalysts 353
12.2 NMR/MRI Studies of Energy Storage (Batteries) Materials 359
12.3 MRI of Water Distribution in Fuel Cells 369
12.4 Conclusion and Future Perspectives:Sensitivity, Sensitivity and Sensitivity 374
References 377
13 Spectroscopy of Electrochemical Systems 381
13.1 General Experimental Considerations 382
13.2 Electronic Spectroscopy 384
13.3 Spectroelectrochemistry of the Excited State 401
13.4 Vibrational Spectroelectrochemistry 409
13.5 Raman Spectroelectrochemistry 420
13.6 Sum Frequency Generation Spectroelectrochemistry 429
13.7 Conclusions and Outlook 430
References 431
14 Kinetic Activity in Electrochemical Cells 438
14.1 Evaluation of Pt/VC Electrocatalysts for the ORR 443
14.2 Electrochemical Characterization of the Pt/VC ElectrocatalystThin-Film Electrodes by RDE and RRDE 450
14.3 Electrochemical Characterization of Mn_xO_y Thin-Film Electrodes 455
14.4 Conclusions 458
References 459
Part D Energy Conversion and Storage 461
15 Lithium-Ion Batteries and Materials 462
15.1 Overview – Electrochemical Evaluation of Li-Ion Batteries 462
15.2 Evaluation of Materials and Components in Li-Ion Batteries 464
15.3 Evaluation at the Cell–Battery Level 494
15.4 Beyond Li-Ion 500
15.5 Conclusions 503
References 504
16 Materials for Electrochemical Capacitors 508
16.1 Batteries and Electrochemical Capacitors – Basic Concepts 509
16.2 Carbon 517
16.3 Manganese Dioxide 523
16.4 Ruthenium Oxide 536
16.5 Other Pseudocapacitive Materials 542
16.6 Electrolytes 542
16.7 Applications of Electrochemical Capacitors 550
16.8 Electrochemical Capacitor Prospective View 556
References 558
17 Electrochemical Capacitors 575
17.1 The Nature of Capacitance 575
17.2 Test Methods 580
17.3 Configuration 590
17.4 Further Practical Concerns 596
17.5 Summary and Conclusions 598
17.6 Symbols 598
References 599
18 Kinetics of Fast Redox Systems for Energy Storage 602
18.1 Overview and Introduction 602
18.2 Flow Batteries – Basic Components 608
18.3 Redox Reactions and their Kinetics 609
18.4 Acceleration of Redox Reactions 611
18.5 Materials for Electrodes in Flow Batteries 612
18.6 Catalysis and Surface Enlargement Effects 616
18.7 Future Directions 617
References 617
19 Modern Fuel Cell Testing Laboratory 622
19.1 Fuel Cell Laboratory Evolution 622
19.2 Safety and Test Stations 625
19.3 Fuel Cell Stack Components and Assembly 632
19.4 Testing and Diagnostic Techniques 637
19.5 Conclusion 651
References 652
20 Polymer Electrolyte Fuel Cells 659
20.1 Experimental Methods 660
20.2 H_2/O_2 or Air Fuel Cell Performance Testing 672
20.3 Application of a Fuel Cell Empirical Model 689
20.4 Fuel Crossover and Electrochemical Surface Area 693
20.5 Impedance Spectroscopy of PEM Fuel Cells 699
References 720
21 Next-Generation Electrocatalysts 722
21.1 Oxygen-Reduction Reaction – Cathodes 722
21.2 Methanol-Oxidation Reaction – Anodes 733
References 747
22 Methods in Biological Fuel Cells 751
22.1 Bioelectrocatalysis 752
22.2 Spectroscopic Methods 754
22.3 Electrochemical Methods 757
22.4 Engineering Considerations 760
22.5 Conclusions 761
References 761
23 Energy Conversion Based on Bio(electro)catalysts 764
23.1 Working Principles of Bioelectrochemical Systems 765
23.2 Bioelectrochemical Systems in Cell-Free Systems 765
23.3 General Aspects 767
23.4 Biotransformationwith Redox Enzymes 777
23.5 Conclusions and Outlook 781
References 781
24 Photoelectrochemical Conversion Processes 785
24.1 Overview and Historical Perspective 785
24.2 Photoelectrochemical Processes 786
24.3 State-of-the-Art and Emerging Technologies 801
24.4 Summary 802
References 802
Part E Electrochemical Processes 805
25 Advanced Extractive Electrometallurgy 806
25.1 Conventional Extractive Metallurgy 806
25.2 Innovative Electrolytic Extraction Techniques for Titanium 813
25.3 Direct Electroreduction of Solid Metal Oxides to Metals:The FFC Cambridge Process 819
25.4 Summary 834
References 835
26 Electrodeposition of Nanomaterials 840
26.1 Processes for Electrodeposition of Nanomaterials 841
26.2 Electrodeposited Nanomaterials for Energy Storage/Conversion Devices 870
26.3 Conclusions and Prospects 887
References 887
27 Electrochemical Hydrogen Production 901
27.1 Theoretical Aspects of Electrochemical Hydrogen Production 903
27.2 Electrochemical Hydrogen Production Methods 909
27.3 Development Perspectives 933
27.4 Conclusions 937
References 938
28 Electrochemical Machining 945
28.1 Introduction and History 946
28.2 Fundamentals of Electrochemical Machining 947
28.3 Experimental Techniques 950
28.4 The Interface Process During ECM 952
28.5 Classification of ECM Processes 956
28.6 Surface Topography, Crystallographic Effects and Surface Quality 956
28.7 Oxygen Evolution 962
28.8 Pulse ECM 963
28.9 Too Difficult-to-Machine: Hard Metals, Carbides and Nitrides 966
References 971
About the Authors 976
Detailed Contents 987
Subject Index 1000