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Flow Batteries
Edited by Christina Roth, Jens Noack, and
From Fundamentals to Applications
Maria Skyllas-Kazacos
Flow Batteries
Volume 1
Flow Batteries
Volume 2
Flow Batteries
Volume 3
Editors All books published by WILEY-VCH are carefully
produced. Nevertheless, authors, editors, and
Prof. Dr. Christina Roth publisher do not warrant the information
University Bayreuth contained in these books, including this book,
Electrochemical Process Engineering to be free of errors. Readers are advised to keep
Universitätsstraße 30 in mind that statements, data, illustrations,
95448 Bayreuth procedural details or other items may
Germany inadvertently be inaccurate.
Adj. Assoc. Prof. (UNSW) Dr. Jens Noack Library of Congress Card No.: applied for
Fraunhofer-Institute for Chemical
Technology British Library Cataloguing-in-Publication Data
Applied Electrochemistry A catalogue record for this book is available
Joseph-von-Fraunhofer-Str. 7 from the British Library.
76327 Pfinztal
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the Deutsche Nationalbibliothek
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© 2023 WILEY-VCH GmbH, Boschstraße 12,
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v
Contents
Volume 1
Foreword xxi
Preface xxiii
About the Editors xxvii
Part I Fundamentals 1
1 The Need for Stationary Energy Storage 3

Anthony Price
1.1 Power Systems 3
1.1.1 The Role of Electricity in Energy Supply 3
1.1.2 The Development of DC and AC Power Systems 4
1.1.3 The Early Use of Energy Storage on Power Systems 4
1.1.4 Centralised and Distributed Generation 4
1.1.5 Power System Infrastructure 5
1.1.6 Other Types of Electricity Generation and System Control 7
1.2 The Need for Electricity Storage 8
1.2.1 Operation of a Modern Power Network – The Requirement for
Operational Stability 8
1.2.2 Requirements for Storage and the Use of Alternative Technologies, such
as Demand-Side Response, Interconnectors, and Flexible Generation 8
1.2.3 Optimisation of Power Networks for Technical Performance, Economic
Efficiency, and Sustainability – The Energy Trilemma 10
1.3 Changes in Electricity Network Operation: Interconnected Systems,
Microgrids, and Standalone Systems 12
1.3.1 The Growth in Renewable Energy Generation 12
1.3.2 The Overlap Between Stationary Storage and Transportable and Mobile
Applications 12
1.4 The Parameters for Storage: Short Term, Small Scale to Long Term, Long
Duration, and Large-Scale Storage 14
1.4.1 Stationary Storage Applications 14
vi Contents
1.5 The Need for Longer-Duration Energy Storage 16

1.5.1 Market Estimates 17
1.6 Energy Storage Types 18
1.6.1 Pumped-Hydro Energy Storage 18
1.6.2 Alternatives to Pumped-Hydro Storage 19
1.6.3 Compressed Air Energy Storage 19
1.6.4 The Hydrogen Cycle 20
1.7 Battery Energy Storage Technologies 20
1.7.1 Flow Batteries 20
1.7.2 Flow Battery Ancillary Systems 21
1.7.2.1 Advantages and Benefits 22
1.8 The Deployment of Flow Battery and Energy Storage 22
1.9 A Future Outlook 24
References 26
2 History of Flow Batteries 29

Jens Noack, Maria Skyllas-Kazacos, Larry Thaller, Gerd Tomazic,
Bjorn Jonshagen, and Patrick Morrissey
2.1 Early Developments (1884–1963) 29
2.2 Fe/Cr FBs (1974 – mid-2010s) 32
2.3 Zinc/Bromine FBs (1977–mid 2010s) 34
2.4 1977–1981 35
2.5 Vanadium-Based Flow Batteries (1980s–2010) 37
2.6 Regenesys Polysulphide/Bromide Flow Battery (1984–Early 2000s) 42
2.7 Other Flow-Battery Chemistries 2000–2020 44
2.8 Organic Flow Batteries 46
2.9 Advanced Flow-Battery Concepts 47
2.10 Perspective 47
References 48
3 General Electrochemical Fundamentals of Batteries 53

Rudolf Holze
3.1 Introduction 53
3.2 Thermodynamics 55
3.3 Kinetics 61
3.4 Practical Aspects and Consequences 66
Acknowledgments 66
References 67
4 General Aspects and Fundamentals of Flow Batteries 69

Luis F. Arenas, Frank C. Walsh, and Carlos Ponce de León
4.1 Introduction 69
4.2 The Flow Battery 71
Contents vii
4.3 Main Components of a FB Energy Storage System 75

4.4 Advantages and Environmental Benefits 77
4.5 Types of FB 79
4.6 Fields of Application 84
4.7 Ideal Characteristics of a FB 85
4.8 Engineering Aspects of FBs 86
4.9 Fluid Flow Aspects of FBs 87
4.10 Typical Figures of Merit 90
4.11 Conclusions 92
Acknowledgments 93
Abbreviations 94
List of Symbols and Subscripts 94
Greek Letters 95
References 95
5 Redox-mediated Processes 99
Danick Reynard, Mahdi Moghaddam, Cedrik Wiberg, Silver Sepp,
Pekka Peljo, and Hubert H. Girault
5.1 Fundamental Theory on Redox-mediated Processes 99
5.2 Redox-mediated Processes: Various Applications for Flow Batteries 101
5.2.1 Dual-flow Circuit Flow Battery 101
5.2.2 Solid Boosters 106
5.2.2.1 Thermodynamics of Solid Boosters: Equilibrium 109
5.2.2.2 Kinetics of Solid Boosters 113
5.2.2.3 System Design 113
5.3 Conclusion 115
References 116
6 Membranes for Flow Batteries 121

Giovanni Crivellaro, Chuanyu Sun, Gioele Pagot, Enrico Negro, Keti Vezzù,
Francesca Lorandi, and Vito Di Noto
6.1 Introduction 121
6.2 Membrane Characteristics 123
6.2.1 Ion-Exchange Capacity (IEC) 124
6.2.2 Water Uptake (WU), Swelling Ratio (SR), and Water Transport 125
6.2.3 Ionic Conductivity (𝜎) 126
6.2.4 Permselectivity of Chemical Species 128
6.2.5 Chemical Stability 129
6.2.6 Thermal and Mechanical Stability 130
6.2.7 Cost of the IEMs 130
6.3 Classification of Membranes 131
6.3.1 Cation-Exchange Membranes (CEMs) 132
viii Contents
6.3.1.1 Perfluorinated Membranes 132

6.3.1.2 Non-perfluorinated Membranes 134
6.3.2 Anion-Exchange Membranes (AEMs) 137
6.3.3 Amphoteric Ion-Exchange Membranes (AIEMs) 139
6.3.4 Hybrid Membranes (HMs) 140
6.3.4.1 Hybrid Inorganic–Organic IEMs 141
6.3.4.2 Organic Polymer Blends as IEMs 142
6.3.5 Porous Membranes 143
6.4 Conclusions 144
References 146
7 Standards for Flow Batteries 155

Jens Noack
7.2 A Definition of Flow Batteries 156
7.3 International Standards for Flow Batteries 159
7.3.1 Standards of the International Electrotechnical Commission (IEC) 160
7.3.2 Standards of the Institute of Electrical and Electronics Engineers 166
7.4 Other National and International Standards, as well as Other
Documents 168
7.5 Chinese National Standards 171
7.6 Conclusions 174
Abbreviations 174
References 174
8 Safety Considerations of the Vanadium Flow Battery 175

Adam H. Whitehead
8.1 Regulatory Framework 175
8.2 Thermal Hazards 177
8.3 Chemical Hazards 178
8.4 Electrical Hazards 180
8.5 Other Considerations 187
8.6 Summary & Outlook 187
References 188
9 A Student Workshop in Sustainable Energy Technology: The

Principles and Practice of a Rechargeable Flow Battery 193
C.T. John Low, Carlos Ponce de León, Richard G.A. Wills, and Frank C. Walsh
9.2 Laboratory Experiment 193
9.2.1 Chemicals 194
9.2.2 Materials for Construction 194
Contents ix
9.3 Results and Discussion 195

9.3.1 Preparation of the Flow Battery 195
9.3.2 Electrochemical Reactions in a Soluble Lead–Acid Flow Battery 196
9.3.3 Effect of Current Density on Cell Voltage 198
9.4 Assessment of Hazards 199
9.5 Teaching Assessment and Learning Outcomes 199
9.6 Conclusions 200
Supplementary Materials 200
Acknowledgments 200
Appendix: Supplementary Information for Students 200
9.A Chemicals and Materials for the Soluble Lead Flow Battery 200
9.B Experimental Procedure 201
9.C Types of Flow Battery 202
9.D Components of Cell Voltage 202
9.E Characteristics of a Flow Battery 204
9.F The Efficiency of a Flow Battery 205
9.G Nomenclature 205
9.H Supplementary Materials for the Instructor 206
References 209
Part II Characterization of Flow Batteries and

Materials 213
10 Characterization Methods in Flow Batteries: A General

Overview 215
Christina Roth and Marcus Gebhard
10.1 General Overview 215
10.1.1 Physicochemical Methods in General 215
10.1.2 Characterization Techniques for Redox-Flow Batteries 218
10.1.2.1 Physicochemical Characterization 218
10.1.2.2 Electrochemical Characterization 221
10.1.2.3 General Observations 224
10.1.3 Further Outline of Part II 224
Acknowledgments 225
References 225
11 Electrochemical Methods 229

Jonathan Schneider, Tim Tichter, and Christina Roth
11.1 Fundamental Definitions 229
11.2 Cyclic Voltammetry 231
x Contents
11.2.1 Measuring Cyclic Voltammetry 231

11.2.2 Interpreting CV and LSV at Planar Electrodes – The Randles–Ševčík
Relations 233
11.2.3 Strategies for Simulating Cyclic Voltammetry 235
11.2.4 The Diffusion Domain Approximation Approach for Felt
Electrodes 237
11.2.5 The Real-Space Simulation Approach 240
11.2.6 Remarks on Cyclic Voltammetry 242
11.3 Electrochemical Impedance Spectroscopy 245
11.3.1 Principles and Advantages of Electrochemical Impedance
Spectroscopy 245
11.3.2 Interpreting Electrochemical Impedance Spectroscopy 246
11.3.3 Impedance of Macrohomogeneous Porous Electrodes – The Paasch
Model 248
11.3.4 The Normalization Method 248
11.3.5 The Distribution of Relaxation Times (DRT) Analysis 249
11.3.6 Characteristics of a “Good Impedance” – The Kramers–Kronig
Relations 251
11.3.7 Advanced Electroanalytical Techniques 252
11.3.7.1 Hydrodynamic Voltammetry – The Rotating Ring-Disc Electrode
(RRDE) 253
11.3.7.2 Alternating Current Cyclic Voltammetry (ACCV) 254
References 255
12 Radiography and Tomography 263

Roswitha Zeis
12.1 Working Principle 263
12.1.1 Morphology of Electrode Materials 263
12.1.2 Visualizing the Flow and Electrolyte Distribution in the Porous
Electrode 267
12.1.2.1 Injection of Electrolyte Into the Carbon Electrode (No Potential
Control) 268
12.1.2.2 Electrolyte Flow in the Carbon Electrode (Cell Potential Applied) 274
12.2 Outlook 276
References 276
13 Characterization of Carbon Materials 281

Michael Bron, Julia Melke, and Matthias Steimecke
13.2 Structure of Carbon Materials 283
Contents xi
13.2.1 Raman Spectroscopy 283

13.3 X-ray Powder Diffraction (XRD) 286
13.4 Surface Chemistry of Carbon Materials 288
13.5 Functionalization of Carbons 288
13.5.1 Thermal Methods 290
13.5.1.1 TPD 291
13.5.1.2 TPR/TPO 292
13.5.1.3 TG/TGA 292
13.6 X-ray Photoelectron Spectroscopy (XPS) 293
13.7 Infrared Spectroscopy 296
13.8 Imaging Techniques 297
13.9 Surface Area Determination and Porosity 298
13.10 Conclusion and Perspectives 299
References 300
14 Characterization of Membranes for Flow Batteries 307

Jochen Kerres, Nico Mans, and Henning Krieg
14.2 Ex situ Characterization Methods for Membranes 307
14.2.1 Ion-Exchange Capacity of Ionomer Membranes 307
14.2.2 Ion Conductivity of Ionogenic Groups in Membranes 310
14.2.3 Ion Permeability of the Ion-Exchange Membranes 311
14.2.4 Membrane Weight Loss 311
14.2.5 Molecular Weight (Degradation) of Ionomers and Ionomer
Membranes 313
14.2.6 Determination of the Thermal Stability of the Membranes 314
14.2.7 Spectroscopical Membrane Characterization 315
14.2.8 Determination of Mechanical Membrane Properties 317
14.2.9 Microscopical Membrane Characterization 317
14.2.10 Water Transfer Behavior 318
14.3 In situ Characterization Methods for Membranes 319
14.3.1 Charge/Discharge Cycles 319
14.3.1.1 Current, Voltage, and Energy Efficiency 320
14.3.1.2 Discharge Capacity and Capacity Retention 324
14.3.2 Open-Circuit Voltage 326
14.3.3 Electrochemical Impedance Spectroscopy (EIS) 327
14.3.4 In situ Membrane Permeability Estimation 328
14.4 Summary 329
References 329
xii Contents
Part III Modeling and Simulation 333
15 Quantum Mechanical Modeling of Flow Battery

Materials 335
Piotr de Silva
15.2 Fundamental Concepts of Molecular Quantum Mechanics 337
15.3 Density Functional Theory 339
15.4 Computational Electrochemistry at the Atomistic Scale 343
15.5 Applications to FB Materials 348
References 351
16 Mesoscale Modeling and Simulation for Flow Batteries 355

Jia Yu and Alejandro A. Franco
16.1 Mesoscale Modeling Introduction 355
16.2 Mesoscale Modeling of Electrochemical Kinetics 356
16.2.1 Electron Transfer Process 356
16.3 Mesoscale Modeling of Electrified Interfaces: Monte Carlo
Methods 360
16.3.1 Kinetic Monte Carlo Method 360
16.3.1.1 Methodology of Kinetic Monte Carlo Method 360
16.3.1.2 KMC Applications in FB and Porous Electrode Systems 361
16.3.2 Grand Canonical Monte Carlo Method 362
16.4 Mesoscale Modeling of Transport: Dissipative Particles Dynamics and
Discrete Element Method 364
16.4.1 Methodology of Dissipative Particles Dynamics 364
16.4.2 DPD Applications to FBs 366
16.4.3 Discrete Element Method 366
16.5 Lattice Boltzmann Method 367
16.5.1 Methodology of Lattice Boltzmann Method 367
16.5.2 LBM Application to FBs 369
16.6 Conclusion and Perspectives 372
References 373
17 Continuum Modelling and Simulation of Flow Batteries 379

Jakub K. Włodarczyk, Gaël Mourouga, Roman P. Schärer, and
Jürgen O. Schumacher
17.2 An Engineer’s Approach to Cell-scale Modelling 383
17.2.1 Integrating Batteries in Electric Grids 383
17.2.2 Battery Performance Models 383
17.2.2.1 Ohmic Resistance 385
17.2.2.2 Influence of the State of Charge 385
Contents xiii
17.2.2.3 Overpotentials and Mass Transport Problems 385

17.2.3 System Efficiency Modelling 387
17.2.3.1 Pumping Losses 387
17.2.3.2 Coulombic Efficiency 387
17.2.3.3 Round-trip Efficiency 388
17.2.4 Lifetime Models 388
17.2.4.1 Practical and Theoretical Capacity 388
17.2.4.2 Capacity Fade Through Membrane Transport 389
17.2.4.3 Degradation 390
17.2.5 Towards Flow-Battery Fundamentals 390
17.3 Fundamentals of Flow Batteries: A Thermodynamic Perspective 390
17.3.1 Modelling the Open-Circuit Voltage 391
Example 17.1: OCP Predictions in Hydrogen-Bromine System 393
17.3.2 Nonequilibrium Thermodynamics 396
17.3.2.1 General Balance Laws 396
17.3.2.2 Constitutive Relations 397
17.3.2.3 Concentrated Electrolyte Solutions 397
17.3.2.4 Generalised Nernst–Planck Models 398
17.3.2.5 Transport Through Membranes 399
17.4 Multiscale Modelling of Porous Electrodes 400
17.4.1 Electrochemical Interface Models 400
17.4.2 Porous Electrode Modelling 401
17.5 Discussion and Conclusions 403
References 404
18 Pore-scale Modeling of Flow Batteries 413

Amadeus Wolf, Susanne Kespe, and Hermann Nirschl
List of Symbols 413
18.2 Microstructure Characterization 415
18.2.1 Reconstruction of Experimentally-Gained Images 416
18.2.2 Stochastic Microstructure Generation 418
18.2.3 Structured Electrodes 419
18.3 Theory 419
18.3.1 Fluid Transport 420
18.3.2 Species Transport 420
18.3.3 Electrochemical Reaction 421
18.3.4 Charge Transport 422
18.3.5 Boundary and Initial Conditions 423
18.3.5.1 Boundary Conditions for Fluid Transport 423
18.3.5.2 Boundary Conditions for Species Transport 423
18.3.5.3 Boundary Conditions for Charge Transport 423
xiv Contents
18.3.6 Computational Details 424

18.4 Numerical Methods 424
18.4.1 Finite Volume Method 424
18.4.2 Taylor–Galerkin Finite Element Methods 425
18.4.3 Lattice Boltzmann Method 425
18.5 Validation of the Numerical Model 425
18.6 Simulation Study 426
18.6.1 Numerical Investigations on Structured Electrodes 426
18.6.1.1 Effect of Different Initial Concentrations 427
18.6.1.2 Effect of Electrode Active Surface Area 427
18.6.2 Numerical Investigations on Reconstructed Microstructure 430
18.7 Pore-scale Modeling Examples 434
18.7.1 Pore Network Models 434
18.7.2 Multiphase Reactive Transport Model 435
18.7.3 Model for Determination of the Mass Transfer Coefficient 436
18.7.4 Three-dimensional Pore-scale Lattice Boltzmann Model 437
18.8 Conclusion 437
Acknowledgment 438
References 439
19 Dynamic Modelling of Vanadium Flow Batteries for System

Monitoring and Control 443
Jie Bao and Yitao Yan
19.1 Dynamic Modelling of VFB 444
19.1.1 Dynamic Stack Mass Balance Model 444
19.1.1.1 Mass Balance During Normal Operation 445
19.1.1.2 Self-discharge During Standby 448
19.1.2 Dynamic Stack Thermal Model 450
19.1.3 Simulation Study on VFB 452
19.2 Battery System Monitoring and Control 456
19.2.1 Electrolyte Flowrate Control 457
19.2.2 Power Flow Control 458
Nomenclature 459
References 460
20 Techno-economic Modelling and Evaluation of Flow

Batteries 463
Christine Minke and Thomas Turek
20.2 Goal and Scope Definition of Techno-economic Assessment 463
20.2.1 Rethinking Goal Definition 464
20.2.2 Rethinking Scope Definition 466
Contents xv
20.2.2.1 Technical System Definition 466

20.2.2.2 Economic System Definition 468
20.3 Methodology of Techno-economic Modelling 468
20.3.1 Multi-level Modelling of FB 468
20.3.1.1 Electrochemical Level 469
20.3.1.2 Component Level 470
20.3.1.3 System-Level 471
20.3.2 Economic Modelling Methods 472
20.3.2.1 Capital Costs 472
20.3.2.2 Total Cost of Storage 473
20.4 Data Basis and Quality 474
20.4.1 Input Data 475
20.4.2 Primary and Secondary Data 475
20.4.3 Uncertainty 476
20.5 Meta-analysis of Techno-economic Modelling and Evaluation
Studies 476
20.5.1 Review and Classification of Techno-economic Modelling
Approaches 477
20.5.1.1 Goal and Scope Definitions in Literature 477
20.5.1.2 Techno-economic Modelling and Data in Literature 478
20.5.2 Results of Techno-economic Evaluation in Literature 480
20.5.2.1 Cost Structure of VFB 480
20.5.2.2 Capital Costs of VFB 480
20.5.2.3 LCOS of VFB 481
20.6 Conclusions 482
References 483
21 Machine Learning for FB Electrolyte Screening 487

Laura-Sophie Berg, Jan Hamaekers, and Astrid Maass
21.2 Data-Driven Models 489
21.2.1 Training Data 490
21.2.2 Computed Data Sets 490
21.2.2.1 Experimental Data Sets 491
21.2.3 Representation and Features 491
21.2.4 Machine-Learning Techniques 493
21.3 FB Application 494
21.3.1 Standard Potential 494
21.3.2 Solubility 496
21.4 Conclusion and Outlook 499
Acknowledgement 500
References 500
xvi Contents
Volume 2
Foreword xvii
Preface xix
About the Editors xxiii
Part IV Vanadium Flow Batteries 507
22 The History of the UNSW All-Vanadium Flow Battery

Development 509
23 Vanadium Electrolytes and Related Electrochemical

Reactions 539
Nataliya V. Roznyatovskaya, Karsten Pinkwart, and Jens Tübke
24 Electrodes for Vanadium Flow Batteries (VFBs) 563

D.N. Buckley, A. Bourke, N. Dalton, M. Alhajji Safi, D. Oboroceanu,
V. Sasikumar, and R.P. Lynch
25 Membranes for Vanadium Flow Batteries 589

Purna Chandra Ghimire, Arjun Bhattaraj, Nyunt Wai, and Tuti Mariana Lim
26 Advanced Flowfield Architecture for Vanadium Flow

Batteries 607
Yasser Ashraf Gandomi, D. Aaron, and M.M. Mench
27 State-of-Charge Monitoring for Vanadium Redox Flow

Batteries 627
Yifeng Li
28 Rebalancing/Regeneration of Vanadium Flow Batteries 641

Nicola Poli, Andrea Trovò, and Massimo Guarnieri
29 Life Cycle Analysis of Vanadium Flow Batteries 659

Carmen M. Fernández-Marchante, María Millán, and Justo Lobato
Contents xvii
30 Next-Generation Vanadium Flow Batteries 673

Chris Menictas and Maria Skyllas-Kazacos
31 Asymmetric Vanadium-based Aqueous Flow Batteries 689

Soowhan Kim, Litao Yan, and Wei Wang
Part V Other Important Inorganic Flow Battery

Technologies 709
32 Zn/Br Battery – Early Research and Development 711

Gerd Tomazic
33 Iron–Chromium Flow Battery 741

Huan Zhang and Chuanyu Sun
34 An Overview of the Polysulfide/Bromine Flow Battery 765

Patrick Morrissey
35 Fe/Fe Flow Battery 791

Robert F. Savinell, Nicholas Sinclair, Xiaochen Shen, Julia Song, and
Jesse S. Wainright
36 Zinc–Cerium and Related Cerium-Based Flow Batteries:

Progress and Challenges 819
37 Undivided Copper–Lead Dioxide Flow Battery Based on

Soluble Copper and Lead in Aqueous Methanesulphonic
Acid 837
R.C. Tangirala, F.C. Walsh, and C. Ponce de León
38 All-copper Flow Batteries 855

Laura Sanz, Wouter D. Badenhorst, Giampaolo Lacarbonara,
Luigi Faggiano, David Lloyd, Pertti Kauranen, Catia Arbizzani, and
Lasse Murtomäki
39 Hydrogen-Based Flow Batteries 875

Douglas I. Kushner and Adam Z. Weber
xviii Contents
Volume 3
Foreword xvii
Preface xix
Part VI Organic Flow Batteries 895
40 Aqueous Organic Flow Batteries 897

Yan Jing, Roy G. Gordon, and Michael J. Aziz
41 Metal Coordination Complexes for Flow Batteries 923

Benjamin D. Silcox, Curt M. Wong, Xiaoliang Wei, Christo Sevov, and
Levi T. Thompson
42 Organic Redox Flow Batteries: Lithium-Ion-based FBs 951

Feifei Zhang and Qing Wang
43 Nonaqueous Metal-Free Flow Batteries 975

Kathryn Toghill and Craig Armstrong
44 Polymeric Flow Batteries 1007

Oliver Nolte, Martin D. Hager, and Ulrich S. Schubert
Part VII Industrial and Commercialization Aspects of Flow

Batteries 1025
45 Inverter Interfacing and Grid Behaviour 1027

John Fletcher and Jiacheng Li
46 Flow-Battery System Topologies and Grid Connection 1041

Thomas Lüth, Thorsten Seipp, and David Kienbaum
47 Vanadium FBESs installed by Sumitomo Electric

Industries, Ltd 1055
Toshio Shigematsu and Toshikazu Shibata
48 Industrial Applications of Flow Batteries 1079

Pavel Mardilovich and Martin Harrer
49 Applications of VFB in Rongke Power 1099

Huamin Zhang
Contents xix
50 Metal-Free Flow Batteries Based on TEMPO 1115

Tobias Janoschka and Olaf Conrad
51 Commercialization of All-Iron Redox Flow-Battery

Systems 1127
Julia Song
52 Application of Hydrogen–Bromine Flow Batteries: Technical

Paper 1145
Wiebrand Kout and Yohanes A. Hugo
53 Some Notes on Zinc/Bromine Flow Batteries 1153

Bjorn Hage
54 Mobile Applications of the ZBB 1171

Gerd Tomazic
Index 1201
v
Contents
Volume 1
Foreword xxi
Preface xxiii

Anthony Price


Rudolf Holze



Jens Noack
vi Contents

Adam H. Whitehead

C.T. John Low, Carlos Ponce de León, Richard G.A. Wills, and
Frank C. Walsh

Materials 213

Overview 215


Roswitha Zeis



Materials 335
Piotr de Silva


Contents vii



Batteries 463

Volume 2
Foreword xvii
Preface xix

Development 509
22.2 Initial Electrolyte Studies at UNSW and First All-Vanadium Redox Cell
Patent 509
22.3 First Licence 512
22.4 Low-Cost Electrolyte Process Breakthrough 512
22.5 Further Licencing and Early Field Trials and Demonstrations 513
22.6 Sale of UNSW VFB Patents 516
22.7 UNSW Vanadium Flow Cell Research Highlights 518
22.7.1 Electrolyte Characterisation and Optimisation 519
22.7.2 Electrode Material Screening and Development 523
22.7.3 Electrocatalysis of Graphite Electrodes for Increased Cell
Performance 524
22.7.4 Electrode Substrate Materials and Bipolar Electrode Development 525
22.7.5 Membrane Screening, Evaluation, and Modification 527
22.7.6 Studies of Water Transfer Processes Across Ion Exchange Membranes in
the VFB 528
viii Contents
22.7.7 Flow Rate Control and Battery Management 529

22.8 Summary 531
References 531

Reactions 539
23.1 Electrolyte Composition 539
23.1.1 Vanadium Speciation 542
23.2 Physicochemical Properties of VFB Electrolytes 544
23.3 Electrochemical Reactions in VFB 547
23.4 Types of VFB Electrolyte Degradation and Mitigation Strategies 550
23.5 Electrolyte Production 554
23.6 Summary 559
References 559

24.2 Electrode Requirements and Materials 563
24.2.1 Carbon and Graphite Felts 564
24.2.2 Carbon Papers 565
24.2.3 Novel Electrode Materials 566
24.2.4 Bipolar Plates 567
24.2.5 Thermal and Chemical Pretreatments of Electrodes 567
24.3 Electrode Kinetics and Mechanism of the VII /VIII and VIV /VV Redox
Reactions 568
24.3.1 Studies of Electrode Kinetics on Carbon in Conventional
Three-Electrode Cells 570
24.3.2 Effects of Electrochemical Pretreatment on Electrode Kinetics 571
24.3.3 Other Studies of Electrochemical and Thermal Pretreatment 575
24.3.4 Mechanisms of Reactions and Surface Processes 576
24.4 Effects of Electrodes on the Long-Term Performance of VFBs 578
24.4.1 Side Reactions at VFB Electrodes 578
24.4.2 Carbon Corrosion 579
24.4.3 Degradation of Electrode Performance 580
24.5 Summary 581
References 582

Purna Chandra Ghimire, Arjun Bhattaraj, Nyunt Wai, and Tuti Mariana Lim
25.2 Membranes for Vanadium Flow Battery 590
Contents ix
25.2.1 Nomenclatures and Types of Membranes 590

25.2.1.1 Cation-Exchange Membrane (CEM) 590
25.2.1.2 Anion Exchange Membrane (AEM) 593
25.2.1.3 Amphoteric-Ion Exchange Membranes (AIEM) 594
25.2.1.4 Nonionic Porous Membrane 595
25.2.2 Membrane Preparation Methods 596
25.2.2.1 Casting Method 596
25.2.2.2 Extrusion Process 596
25.2.2.3 Graft Polymerization 597
25.2.2.4 Layer-to-Layer Self-Assembled Method 597
25.2.3 Membrane Characteristics and Measurement 597
25.2.3.1 Ion Exchange Capacity (IEC) 597
25.2.3.2 Water Uptake (WU) and Swelling Ratio (SR) 597
25.2.3.3 Water Transport Measurement 598
25.2.3.4 Area-Specific Resistance 598
25.2.3.5 Ion Permeability Measurement 598
25.2.3.6 Chemical Stability 599
25.2.4 Performance in Flow Batteries 599
25.3 Recent Developments and Future Directions 600
Acknowledgment 602
References 602

Batteries 607
26.1.1 Prior Efforts in Electrochemical Reactor Design for VRFBs 610
26.1.2 Cell-Based Performance of VRFBs: Energy Efficiency Comparison 615
26.2 Principles of Reactor Design 615
26.2.1 High Performance 616
26.2.2 Capacity Retention 619
26.2.3 Enhanced Electrolyte Utilization (Higher Depth of
Charge/Discharge) 620
26.2.4 Lower Parasitic Losses 622
26.3 Outlook 623
References 625

Batteries 627
Yifeng Li
27.2 SOC Monitoring Based on Electrolyte Properties 628
27.2.1 Open-Circuit Potential 628
x Contents
27.2.2 Half-cell Potential 630

27.2.3 Electrolyte Conductivity 632
27.2.4 Electrolyte Density and Viscosity 634
27.2.5 Spectroscopic Methods 634
27.2.6 Ultrasonic Methods 635
27.3 Model-Based SOC Estimation 636
27.3.1 Coulomb Counting 636
27.3.2 State Observer-Based Estimation 637
27.4 Summary 637
References 638

28.2 Electrolyte Imbalance 642
28.3 Rebalancing Processes 647
28.3.1 Physical Regeneration Process 647
28.3.2 Chemical Regeneration Process 649
28.3.3 Electrochemical Regeneration Process 650
28.4 Summary 653
References 654

29.2 The LCA Methodology 660
29.3 Definition of Boundaries for the VFB 661
29.4 LCA of VFB 663
29.5 Comparison with Other Batteries 664
References 669

30.2 Generation 1 All-Vanadium Flow Battery 675
30.3 Generation 2 Vanadium Bromide Flow Battery 678
30.4 Generation 3 VFB with H2 SO4 and HCI Mixed Acid Electrolyte 681
30.5 Generation 4 Vanadium Oxygen Fuel Cell 682
30.6 Conclusion 685
References 685
Contents xi

31.2 V–Fe Flow Battery 690
31.2.1 V–Fe Electrolyte 691
31.2.2 Low-cost Hydrocarbon Membranes 693
31.3 V–H2 Flow Battery 694
31.3.1 Electrode for V–H2 FBs 698
31.3.2 Advantages of V–H2 FB 698
31.4 V–Ce FB 700
31.5 V–Mn and V–Co FBs 702
31.6 Summary 704
References 705

Technologies 709

Gerd Tomazic
32.2 Exxon-Zn/Br-Design at Project Start in 1983 712
32.2.1 The Bipolar Stack 713
32.2.2 Stack Assembly 715
32.2.2.1 Preparing for Shunt Current Protection. Step C 716
32.2.2.2 Stack Sealing (Step D) 718
32.2.2.3 The Stacking Procedure 718
32.2.3 Reservoir and Periphery 720
32.2.4 Main Problems Encountered 721
32.2.4.1 Warpage of Stack Components 721
32.2.4.2 Internal and External Leakage 722
32.2.4.3 Shunt Current Protection 723
32.2.4.4 Collector 723
32.3 Design Development at SEA 723
32.3.1 Electrode Development 723
32.3.2 Separator Development 723
32.3.3 Collector Development 724
32.3.4 Stack Welding Development 724
32.3.5 Development of Electrolyte Loop Periphery 728
32.3.5.1 Stack Connector 730
32.3.6 Handling of Shunt Current 730
xii Contents
32.3.6.1 Shunt Current Interruption (SCI) 732

32.3.6.2 Spider Principle Development 734
32.3.7 Reservoir Development 735
32.3.7.1 Bromine Reservoir 736
32.3.7.2 Zinc Reservoir 736
32.3.8 Battery Types 736
32.3.9 Summary and Conclusions 736

33.1 Characteristics of ICFB 742
33.2 Fundamental Principles of Operation for ICFB 743
33.3 Research Status of Key Components in ICFBs 745
33.3.1 Electrolyte 745
33.3.2 Carbon-Based Electrodes 747
33.3.2.1 Graphite Felt (GF)/Carbon Felt (CF)/Carbon Paper (CP) 749
33.3.2.2 Activation Treatment 752
33.3.2.3 Catalyst 753
33.3.3 Membranes 754
33.4 Other Recent Research Results in ICFBs 756
33.5 Summary 758
References 758

Patrick Morrissey
34.1 Introduction – Technology Drivers 765
34.2 Polysulfide/Bromine FB Components 766
34.2.1 Electrolytes 766
34.2.1.1 Polysulfide Electrolyte 766
34.2.1.2 Bromine Electrolyte 768
34.2.1.3 Polysulfide/Bromine Electrochemical Couple 770
34.2.1.4 Self-Discharge Reaction 771
34.2.2 Plant/Electrolyte Management System (EMS) 773
34.2.3 Module 779
34.2.3.1 Membrane 781
34.2.3.2 Electrode 782
34.2.3.3 Frame 783
34.2.4 System/Plant 785
34.3 Summary 786
Acknowledgments 787
References 787
Contents xiii

Jesse S. Wainright
35.2 The All-Iron Flow Battery Chemistry 792
35.3 IFB Background 794
35.3.1 Electrolyte Factors in an IFB 796
35.3.2 Membrane Factors in an IFB 800
35.4 IFB Economics 803
35.5 Hybrid Flow Battery Performance 807
35.6 Slurry Iron Flow Battery Concept and Performance 809
35.7 Summary 813
References 813

36.2 The Cerium, Positive Electrode Reaction 820
36.2.1 Cerium Redox Reactions in MSA Electrolytes 820
36.2.2 Electrode Materials 821
36.3 Types of Cerium-Based FBs and Their Performance 823
36.3.1 Zinc–Cerium 823
36.3.2 Undivided Zinc–Cerium 826
36.3.3 Vanadium–Cerium 827
36.3.4 Hydrogen–Cerium 828
36.3.5 Lead–Cerium 828
36.3.6 Titanium–Cerium 829
36.3.7 Recent Trends 829
36.4 Summary 830
36.5 Recommendations for Further R&D 831
References 832

Acid 837
37.2 Experimental Details 838
37.2.1 Voltammetry 838
37.2.2 Flow Cell and Electrolyte Circulation 838
37.2.3 Deposition of Materials in a Hull Cell 841
xiv Contents
37.2.4 Methodology 841

37.3 Results and Discussion 842
37.3.1 Voltammetry 842
37.3.2 Hull Cell Deposition Experiments 846
37.3.3 Charge–Discharge Experiments 847
Acknowledgements 852
References 853

Lasse Murtomäki
38.1 All-copper Flow Batteries (CuFB) 855
38.2 Chemistry 856
38.3 Cell Components 858
38.3.1 Electrolytes 858
38.3.2 Electrodes 864
38.3.3 Separators 866
38.4 Stack Configuration 868
38.5 Economy and Sustainability of the Solution 870
References 871

39.2 Cell Architecture 877
39.3 Considerations and Governing Phenomena 880
39.3.1 Thermodynamics 882
39.3.2 Kinetics 882
39.3.3 Transport Processes 883
39.3.4 Durability 884
39.4 Chemistry and Cell Performance 884
39.4.1 H2 /Metal Ion 888
39.4.2 H2 /Halogen 889
39.4.3 H2 /O2 890
39.5 Concluding Remarks 891
References 891
Volume 3
Foreword xvii
Preface xix
Contents xv


Levi T. Thompson




Batteries 1025





Huamin Zhang


Systems 1127
Julia Song
Application of Hydrogen–Bromine Flow Batteries: Technical
Some Notes on Zinc/Bromine Flow Batteries 1153
Mobile Applications of the ZBB 1171

Gerd Tomazic
Paper 1145
Index 1201
Bjorn Hage
Contents
52
53
54
xvi
v
Contents
Volume 1
Foreword xxi
Preface xxiii

Anthony Price


Rudolf Holze



Jens Noack
vi Contents

Adam H. Whitehead

C.T. John Low, Carlos Ponce de León, Richard G.A. Wills, and
Frank C. Walsh

Materials 213

Overview 215


Roswitha Zeis



Materials 335
Piotr de Silva


Contents vii



Batteries 463

Volume 2
Foreword xvii
Preface xix

Development 509

Reactions 539


Purna Chandra Ghimire, Arjun Bhattaraj, Nyunt Wai, and
Tuti Mariana Lim

Batteries 607
viii Contents

Batteries 627
Yifeng Li





Technologies 709

Gerd Tomazic


Patrick Morrissey

Jesse S. Wainright


Acid 837
Contents ix

Lasse Murtomäki

Volume 3
Foreword xvii
Preface xix

40.1 Advantages 898
40.2 Challenges and Opportunities 900
40.2.1 Solubility 900
40.2.2 Viscosity 900
40.2.3 Crossover 901
40.2.4 Lifetime 901
40.2.5 Analytic Methods 903
40.2.6 Molecular Engineering 904
40.2.7 Cost 905
40.2.8 Membrane 906
40.2.9 pH Imbalance 907
40.2.10 Toxicity 907
40.3 Classes of Aqueous Organic Redox Actives 908
40.3.1 Redox Aromatic Carbonyl Compounds (Quinones, Fluorenones) 908
40.3.2 Aza-/Azo-Aromatics (Alloxazines, Phenazines, Azobenzenes, and
Viologens) 910
40.3.3 Nitroxide Radicals 910
40.3.4 Metal Coordination Complexes 911
40.4 Properties of Aqueous Organic Redox Actives 912
40.4.1 Range of Redox Potential 912
40.4.2 Range of Solubility 912
40.4.3 Range of Fade Rate 913
40.4.4 General Decomposition Mechanisms 913
x Contents
40.4.5 Range of Operational pH 913

40.4.6 Recomposition of Redox-active Molecules 915
40.5 Performance of AOFBs 915
40.6 Outlook for AOFBs 918
Acknowledgments 919
References 919

Levi T. Thompson
41.1.1 Background 923
41.1.2 Overview of Metal Coordination Complexes in Flow Batteries 924
41.1.3 Chapter Overview 925
41.2 Aqueous Metal Coordination Complex Based Flow Batteries 926
41.2.1 Catholyte Chemistries 926
41.2.1.1 Ferrocene Complexes 926
41.2.1.2 Ferro/ferricyanide Complexes 929
41.2.1.3 Fe Oligo-Aminocarboxylate Complexes 930
41.2.1.4 Co-Based Complexes 931
41.2.2 Anolyte Chemistries 931
41.2.2.1 Fe-Based Complexes 931
41.2.2.2 Cr-Based Complexes 933
41.3 Non-Aqueous Metal Coordination Complex Based Flow Batteries 933
41.3.1 Chalcogen (M–O/S) Chemistries 933
41.3.1.1 Acetylacetonate Complexes 933
41.3.1.2 Amino-Alcohol Complexes 937
41.3.1.3 Tunable Oxo Complexes 937
41.3.2 Pyridyl Chemistries 938
41.3.3 Metallocene Chemistries 941
41.4 Conclusion 941
References 941

42.2 Semi-solid Electroactive Materials for LFBs 951
42.2.1 Electroactive Materials Based on Li+ Insertion-Extraction
Chemistry 953
42.2.2 Electroactive Materials Based on Precipitation-Dissolution
Chemistry 955
42.2.3 Electroactive Materials Based on Multiple Redox Reactions 959
42.3 Redox Targeting-based LFBs 960
42.3.1 Principles of Redox Targeting-based LFBs 960
42.3.2 Development of Redox Targeting-based LFBs 961
Contents xi
42.3.3 Redox Targeting-based Lithium–Sulfur Flow Batteries 965

42.3.4 Redox Targeting-based Lithium–Oxygen Flow Batteries 966
42.4 Challenges and Outlook 968
References 969

Preamble 975
43.2 Catholytes 979
43.2.1 Nitroxyl Radical 979
43.2.2 Dialkoxybenzene Derivatives 980
43.2.3 Phenothiazine and Phenazine 980
43.2.4 Cyclopropenium Derivatives 981
43.2.5 Amines 982
43.3 Anolytes 982
43.3.1 Phthalimide (N-MP) 982
43.3.2 Benzophenone (BP) 984
43.3.3 Benzothiadiazole (BTZ) 984
43.3.4 Nitrobenzene (NB) 984
43.3.5 Fluorenone (FL) 985
43.3.6 Pyridine Derivatives (Py and BPy) 985
43.3.7 Viologen 986
43.3.8 Quinones and Quinoxaline 987
43.4 Symmetric and Bipolar Redox Materials 987
43.5 Limitations and Challenges 989
43.5.1 Electrolyte Stability 989
43.5.2 Electrolyte Conductivity 992
43.5.3 Membrane Incompatibility 993
43.5.4 Electrolyte Cost 993
43.5.5 Solubility and Energy Density 995
43.5.6 Outlook – Transitional Developments 996
43.5.7 Conclusions 997
References 998

44.2 Basic Organic Redox Moieties 1008
44.3 Oligomers and Polymers 1010
44.4 Examples of Polymeric FBs 1014
44.5 Countering the Challenges 1017
44.6 Conclusion and Outlook 1018
References 1019
xii Contents

Batteries 1025

45.2 The Six-Switch, Three-Phase Inverter Circuit 1027
45.2.1 The Inverter DC-Link Model 1031
45.2.2 Three-Phase Inverter and Pulse-Width Modulation 1031
45.2.3 Inverter Control Schemes – Grid Feeding 1033
45.3 Inverter Control Modes for Energy Storage Applications 1035
45.3.1 Fault Response 1037
45.3.2 Single-phase Inverters 1037
45.3.3 Inverters for Flow Battery Energy Storage 1038
Reference 1039

46.1.1 Power-Conditioning System (PCS) 1041
46.1.2 Shunt Currents 1042
46.1.3 Reliability 1042
46.1.4 SoC Band Limitation 1043
46.1.5 Modularity/Flexibility 1043
46.1.6 System Size 1043
46.2 Topologies 1044
46.2.1 Low-Voltage Parallel Connection (LV-P) 1044
46.2.2 Low-Voltage System with Several Inverters (LV-DC/AC) 1045
46.2.3 Low-Voltage System with Several DC/DC Converters and One Central
Inverter (LV-DC/DC) 1046
46.2.4 High-Voltage System with One Tank Pair (HV-1T) 1046
46.2.5 High-Voltage System with Multiple Tank Pairs (HV–MT) 1048
46.2.6 Mixed Parallel-Series High-Voltage System (HV-MIX) 1049
46.3 Evaluation of the Topologies 1050
46.4 Summary 1052
References 1052

47.1 Historical Overview [1–3] 1055
47.2 Typical Vanadium FBESs Delivered by Sumitomo Electric 1058
Contents xiii
47.2.1 1990s 1058

47.2.2 2000s 1059
47.2.2.1 A 500 kW×10 hours Vanadium FBES with Underground Tanks Installed
at a University [2001–2011] 1059
47.2.2.2 A 1.5 MW × 1 hours Vanadium FBES with Momentary Voltage Drop
Compensation Function in a Factory [2001–2007] 1059
47.2.2.3 A 4 MW × 1.5 hour Vanadium FBES Installed in a Wind Farm
[2003–2007] 1061
47.2.3 Recent Vanadium FBESs Since 2010 1065
47.2.3.1 A Vanadium FBES for Optimal Energy Management in a Factory with
Photovoltaic Power Generation (in Operation Since 2012) 1065
47.2.3.2 Operation Example of Grid Control (2015–2018 Demonstration,
2019 ∼ Practical Operation) 1067
47.2.3.3 Operation Example of Wholesale Market [2017∼] 1070
47.2.3.4 Microgrid Operation [2018∼] 1072
47.2.3.5 Operation in an Off-grid Area [2019∼] 1074
47.3 Summary 1076
References 1076

48.1 Company History: How Funktionswerkstoffe Forschungs und
Entwicklung GmbH Became Enerox, and What Is CellCube 1079
48.2 Elephant in the Room: Can Flow Batteries Deliver the Duration They
Promise? 1085
48.3 Anatomy of A Project: What Does It Take to Put in a MW-Plus Battery in
the Field? 1088
48.4 I’m on a Boat!: Innovation at CellCube 1095
48.5 Sunny Upside: An Egg Pun or a Realistic Outlook? 1096
Acknowledgements 1097
Reference 1098

Huamin Zhang
49.1 Development and Application of Core Materials for VFB 1100
49.1.2 Bipolar Plate 1101
49.1.3 Ion-Conducting Membrane 1102
49.1.3.1 Excellent Ion Conductivity 1103
49.1.3.2 High ion Selectivity 1103
49.1.3.3 Outstanding Mechanical and Chemical Stability 1103
49.1.3.4 Low Cost for Large-Scale Commercial Application 1103
xiv Contents
49.1.4 Key Technologies of Stack and Energy Storage System of VFB in

RKP–DICP Team 1105
49.1.5 Applications of VFB Technology 1107
49.1.5.1 VPower 1107
49.1.5.2 TPower 1108
49.1.5.3 ReFlex 1108
References 1112

50.2 Properties, Synthetic Procedures, and Redox Reactions 1115
50.2.1 TEMPO 1115
50.2.2 Viologen 1118
50.3 TEMPO Flow Batteries – Selected Examples 1120
50.3.1 Fundamental Research 1120
50.3.2 Scale-up 1122
50.4 Raw Materials Outlook and Summary 1124
References 1124

Systems 1127
Julia Song
51.2 Background 1128
51.3 Key IFB Technology Breakthroughs and IFB System
Commercialization 1131
51.3.1 The Proton Pump 1131
51.3.2 IFB Power Module 1134
51.3.3 System Optimization and LCOS 1138
References 1143
52 Application of Hydrogen–Bromine Flow Batteries: Technical

Paper 1145
52.2 Energy Domain 1145
52.2.2 Hydrogen 1146
52.3 Power Domain 1147
52.3.1 Membrane Electrode Assembly 1147
Another random document with
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The clatter of my hoofs made both Mr. England and Martin glance
back. They saw Missy coming after, pulling me in with might and
main, and fairly standing in her stirrups. Mr. England gave Martin the
reins and sprang to the ground. The trap was turned squarely across
the drive. And I came bouncing into it, Mr. England catching at my
bridle.
Missy dismounted, breathing hard.
“Thank you, thank you,” she said. “What possessed you, Hector?
Oh, there’s something the matter with the darling!”
At that Thunderbolt turned his head. “Overfeeding,” he snickered.
The hide-bound spavin!
“I think,” Mr. England was saying, “that you’d better not ride to the
stable. Martin will drive you home, and I’ll take charge of this chap.
He’s still excited.”
(I was only out of temper with Thunderbolt.)
But poor Missy! She lowered the nigh stirrup quick as a wink. “No,
no, it really isn’t necessary,” she said; “Really it isn’t. I wouldn’t for
the world let Hector think he’d scared me. It would spoil him. I must
ride him right away, and conquer him.” And she mounted.
Martin had turned the trap by now, for other vehicles were passing.
But Mr. England did not get up.
“You’re right, of course,” he answered. “If he thinks he beat you out,
he’ll only bully you every chance he gets after this. But still I must
insist on taking you to the stable. We’ll go slowly, and you put his
nose close behind the rumble and keep it there.”
I felt the reins tremble dreadfully. It wasn’t fear, either. Then Missy
bent over, speaking low.
“Mr. England,” she said earnestly, “not Martin. Won’t you send him
home with Thunderbolt? Please.”
Mr. England saw that she was troubled about something and he
gave her her head. “Martin,” he called to the groom, “you take the
trap in. And attend to that thong on the whiffletree—it doesn’t hold
the trace.”
Thunderbolt went trotting off. Mr. England turned back to Missy.
“Hector seems a little quieter now,” he said.
Then I saw that Missy wasn’t going to let Mr. England come with her
any more than she had Martin. “There isn’t any reason for your
coming,” she said. “Hector’s like a lamb.”
For a second, I thought he hesitated. But I settled that. With a little
squeal and a shake of my head, I reared—just a trifle.
Quick as a fly, Mr. England had my reins. “He isn’t over his tantrum
yet, you see,” he said quietly, but very decidedly. “I can’t think of
letting you take him in alone.”
Well, Missy protested. But he was firm. And we started for the
entrance, with him at my bridle.
As soon as I saw he was really coming, I hung my head and went
along like a case of chest-founder. When we reached the street, he
took to the sidewalk, watching me every instant though, and
watching poor Missy. She was hanging her head, too.
At a corner, Mr. England turned north, expecting us to follow. For that
was the way to Hawley’s. Missy reined me up and called to him, and
he came back.
I could see her face was dreadfully pale. But she was just as straight
in her saddle as she could be. “Not that way, Mr. England,” she said.
He didn’t show the least surprise. (He is a thoroughbred, too.) “You
lead,” he said; “I’ll follow.”
And so we went on—to the wagon-yard, Mr. England looking at the
sidewalk, Missy looking straight ahead.
The gate was open. I went in, not stopping till I reached the door of
my shanty. There, Missy got down. She was standing beside me as
Mr. England came around the corner, and leaning a little upon me,
one gloved hand reached up to the saddle.
Mr. England strode close up to her, and they stood for a moment, her
face raised bravely to his, his eyes searching her.
“Oh, little woman!” he said, and his voice shook; “oh, little woman!”
She took her under lip in her teeth. “There’s—there’s no reason for
me to conceal anything,” she said. “Matters were a little tight at
home, and I had to be economical.”
He was looking at her as if he was bewildered. “Matters tight—at
home——” he repeated. Then, of a sudden, he seemed to know
what it all meant, and his face got as white as Missy’s. “Your father—
then, your father——?” he began, almost chokingly.
Missy looked straight back at him, and there was no more leaning
against me. “Yes. And now you know why I didn’t want you to come
here. It wasn’t because I was ashamed of this. It was because I
knew you’d find out. And then you might think—might think that I felt
there was something personal about it. You see, I realise there
wasn’t. Father made contracts to deliver. Afterward, wool went up
——”
Mr. England groaned. “To think it reached you! That you had to
suffer.”
“But I haven’t suffered. Work was offered me here,—work in an art
line. I have felt no hardship from it. In fact, there is happiness in
earning a living. I am learning so much. The only disappointment I’ve
had was about Hector. He’s not been quite as comfortable——” She
stopped and caressed my shoulder tenderly.
Something got into my wind-pipe then, and I had to mouth my bits to
keep from coughing.
“And where do you live?” asked Mr. England. “Not where you did. I
went there—more than once.”
“Well,—no-o—. But in a very nice place. I take my meals across from
the store.”
“The store?”
“Yes. I am painting Christmas things—cards and so on. It’s pleasant
work. And my room looks out on the side of a church. And there’s a
stained-glass window there, and ivy all over the church wall.”
Mr. England began again, low and deep and earnestly. “Once in a
lifetime,” he said, “a man meets a girl like you—sweet and sensible
and good, that can take a blow like this without a word, find her feet
again, and begin her fight bravely, doing without things that are
second nature to her, and going without comforts for a friend, even
when that friend is only a horse!”
“But I couldn’t do without Hector,” Missy declared. “I love him too
much.”
(I rubbed my nose against her sleeve.)
“Sometimes I’ve had a terrible thought,” she said, half in a whisper.
“It was that I might be forced to part with him. And—and I’ve
wondered—oh, you’ll forgive me, I hope—if I have to, you’ll take him,
Mr. England? He’s a perfect lady’s saddler.”
“You mean,—I may need a lady’s saddler?”
“Well, you—you might.”
“I shall—if I have my way about it.”
Dear Missy turned to me again, and put her arms about my neck.
“I’m not brave about this,” she whispered, and hid her face in my
mane.
All of a sudden he pulled her hands free and turned her toward him.
“You love him,” he said. “I wonder if there’s room in your heart for
anyone else, dear little woman?”
And just at that moment that ragamuffin of a stable-boy popped into
sight. Of course, I was led away.
I don’t know how I ever lived through the next few days. No Missy,
no dainties, nothing but a short airing each morning to take me out of
that terrible shanty. Ah, I knew what had happened to me this time. I
was out of the Sanborn family. I was somebody else’s lady’s saddler!
Then, one morning, when the boy led me out through the gate, he
started off south along the Boulevard. I had on my dress-blanket and
hood. Behind me came another boy, carrying my saddle and bridle
and the rest of my clothes. This was going somewhere.
“They can’t find any place in New York worse than that shanty,” I said
to myself. And for the first time since leaving California, I completely
lost heart. I put my head down and just stumbled long.
And then—I suddenly found that we had passed the Circle, turned
east, and were in front of Hart’s! We mounted the runway. And there
it was—the roomy box-stall across from Thunderbolt’s, deep with
sweet bedding, and matted in Peter’s best style. And there was
Missy, looking so pink and pretty! And there was Mr. England,
smiling so hard he couldn’t talk!
“Dear Hector!” cried Missy. “Oh, Martin, be very good to him while
we’re away!”
“Yes, mum,” said Martin.
“And to Thunderbolt, too,” said Missy.
Martin bobbed, and tugged at his cap.
Then Missy reached up and pulled my head down close to her.
“Darling Hector!” she whispered. “We’re home to stay!” And she
kissed the star in my forehead.
THE GENEVIEVE EPIDEMIC
“I ’M homely,” said Sue, smiling and pulling the grey pony down to a
walk; “I’m the homeliest girl to be found at the Brampton Country
Club. Why, even plain young married women ask me to their houses
on protracted visits.”
As he reined his own horse, Philip Rawson turned upon her a look of
reproof. “Ridiculous!” he exclaimed. “The first time a fellow meets
you, maybe he only does remember your hair or your eyes. You’ve
got awfully attractive eyes, Sue. But the second time he sees how
nice you are. And the third time he’s sure to look forward to meeting
you again. But by the fourth or fifth time! Well, by gad! by the fourth
or fifth time there’s no half-way about it—he thinks you’re a dandy!”
Sue laughed teasingly. “You’ve grown up with those ideas,” she
declared. “Do you remember that once—you were twelve, Phil,—you
gave Len Hammond the nosebleed because he called me ‘cotton-
top’?”
“Your hair is stunning,” said Phil defensively. “And no girl could look
better than you do on a horse.”
“But imagine riding a horse to a dance,” said Sue.
“Who wants to go to dances?” demanded Phil. “The idea of wasting
hours getting togged for a confounded silly affair and then more
hours attending it—when there’s all outdoors to enjoy!”
“Don’t scold,” said Sue. “It’s been ages since I’ve ‘wasted hours’ at a
dance. And yesterday I wore out two horses.”
Phil suddenly brightened. “Let’s go to Wheaton Hill some afternoon,”
he suggested. “And up to Hadbury another day. I want to see the
polo-field. Brampton’s going to play Hadbury soon. And there’s a
new litter of collies at the St. Ives kennels. We’ll canter over and see
’em.”
“How I’ve missed you these two years!” said Sue. “I’ve ridden a lot,
of course. But my tennis has suffered. And not a single fish have I
caught. The other men—even Bob and Courtney and Len, too—all
wait on me when I ride with them or fish. I hate that: I hate being
treated like a drawing-room ornament. Now, you, Phil,——”
“Can be pretty nearly as rude and selfish as a brother,” broke in Phil.
“You’re more like a—a chum,” said Sue. “And so I’m awfully glad to
get you back, not a bit spoiled, and not—married.”
Phil stared. “Married!” he repeated. “Me?”
“Hillcrest needs a mistress, Phil.”
“Suppose I were to pull a long face and say: ‘Sue, Arbor Lodge
needs a master’?” He drew off his cap and stuffed it into the front of
his shirt, shook his head vigorously, so that the morning wind could
catch at his hair, and rolled his sleeves up to his elbow, showing two
stout arms as brown as the pony under him.
“I’m so homely,” said Sue, “that I’m marriage-proof.”
“Sue,”—very earnestly—“I didn’t see a single girl on the other side
that I could fall in love with. I guess it’ll have to be an American that
takes my mother’s place.”
Sue waved her whip. “Down with foreign alliances!”
“Oh, there wasn’t anything patriotic about it,” said Phil. “I just didn’t
see the girl.”
“You’re calloused,” asserted Sue. “You’ve played polo so long that
you’ve got a basswood ball for a heart. Here you are, twenty-six,
handsome——”
“Loyalty, thy name is Sue Townsend!”
“And wholesome and good and awfully popular; and rich, too, with
such a place, such woods and streams!”
“And such a blarney of a little friend,” added Phil.
“It’s not blarney,” Sue declared. “No; I leave all that for Larry. Phil,
where did you pick him up?”
Phil gave a quick glance round at the red-cheeked, red-haired groom
riding at the prescribed distance behind. “He was born in Dublin,”
said he, grinning, “and I got him in Hongkong. He hasn’t been twenty
feet away from me since. The fellows call him my ‘shadow.’”
“But, of course, you’re sure to meet your fate some day,” went on
Sue. “And your kind, when they do fall in love, get fearfully hard hit.”
“Huh!”
Sue nodded wisely. “I don’t believe you’ll even survive what’s in store
for you this very week,” she declared.
“No? What is it?”
“She’s coming to The Lilacs to-day to stay a month—Mrs. Vander
Laan knew her mother. Last year she visited me. She’s tall and
slender, and has the most beautiful eyes, and hair, and nose, and
mouth, and complexion——”
“Hold! Hold!” cried Phil, in mock alarm.
“She’s perfect, in fact. Let’s take this dapply road.”
“Haven’t time—the fellows expect me at practice. Go on about the
goddess.”
“She is a goddess. And everybody worships at her shrine. You’ve
heard of faces that haunt?”
“Creditors?” suggested Phil.
“I met her first at Miss Pendleton’s. She ruled the school, she was so
beautiful. No man’s ever seen her without capitulating.”
“Number one,” announced Phil, pointing at his chest. “What’s her
name?”
“Genevieve.”
“I never cared for it.” He looked at his watch. “If I get to the field in
time I’ll have to turn now. Want to come along?”
“I’m afraid I can’t.” Sue wheeled the grey. “Grandmamma hasn’t
been well lately. I shall stay with her to-day. Let’s race home.”
Galloping level, the grey and the brown made back along the shaded
road, with the wind tugging harder than ever at Phil’s hair, and
blowing out wisps against Sue’s pink cheeks. At the wide, stone gate
of Arbor Lodge they drew rein.
“See you to-morrow?” he asked.
“Telephone me,” said Sue. “Meanwhile, you may meet Genevieve.
And I warn you——”
“Rubbish!” said Phil.
The polo enthusiasts of the Brampton Country Club were in despair;

in particular, three members of the team reserved for the Hadbury
game were pulling their hair wildly. But the fourth member was
apparently indifferent to the awfulness of the situation—a situation of
which he was himself the cause. And the reason for his indifference
was not far to seek. The majority of the club knew it quite as well as
if he had put up blue-and-white enameled signs beside the
advertisements of automobile tires on every fence in that part of the
country, and on the signs one line: The Brampton’s Captain is——
But wait.
In their anxiety, the trio who were to go against Hadbury called in
solemn conclave upon Sue Townsend. Not that Sue was in any way
implicated—Sue had never been concerned in an affair of this
particular sort. The three players wished to state the case to her and
ask her immediate aid.
“We shan’t keep you a minute,” began Leonard Hammond, when
Sue greeted her visitors in the library at Arbor Lodge, “I see you’re
going out. But”—his tone was mournful—“it’s something horribly
serious.” (Mr. Hammond had constituted himself the first spokesman
because, playing Number One in the team, he realised his Captain’s
value.)
Sue was very smart in a linen habit, and she gave the three glum
faces an encouraging and hospitable smile. “Oh, it won’t matter in
the least if you keep me a few minutes,” she declared, shaking
hands warmly. “Do sit down.” She indicated the library couch. “You
see, I’m only going for a ride, and Phil hasn’t come yet.” She took a
plump chair which was in front of the couch and leaned back to
recover breath after her tripping rush down the stairs.
“Phil!” repeated the three in chorus, and dropped rather precipitately
upon the couch. Then: “We are just in time!”—this from Mr.
Hammond.
Sue leaned forward suddenly. Her eyes were dark-blue and heavy-
lashed, and now they looked her solicitude. “Is something—wrong
with Phil?” she asked.
Mr. Courtney Graves, Second Forward of the team, almost stared at
her. “Wrong?” he repeated. “Haven’t you heard?”
“No.” She looked from one to another, the colour going from her
cheeks. “Bob! What is it?”
Mr. Robert St. Ives, Half-back, began: “It’s a mess, Sue, hanged if it
isn’t!—a confounded mess. Phil was to play against the Hadbury
team, you know, and reserved us for the game.”
“Yes.” With one hand Sue smoothed a round gold locket that hung
between the lapels of her coat.
“Now,” continued Mr. St. Ives, biting each word short to give it full
significance, “—now, all at once, he’s dropped off in his practice,
says he doesn’t want to go to Hadbury, wants me to be captain—rot!
And he spends his time in his car, while his ponies hammer their legs
to pieces in their boxes. We got that much from Larry.”
She leaned back once more, relieved and smiling. “Why has Phil
changed?” she inquired in mild surprise.
“Because he wants to stay at Brampton,” answered Mr. St. Ives
forcibly, “and motor when he can, or hang out on the club veranda
when she won’t motor. That’s why.”
“She?” said Sue, under her breath. “Who?”
Mr. Courtney Graves stood up and pointed, first to the fireplace, then
to a writing-desk, last of all to a panel between two bookcases.
Above the fireplace, on the carved mantel, was the full-length portrait
of a beautiful girl—a dark, imperious, queenly girl in ball dress. On
the writing-desk, in delicate frames of hand-wrought silver, were two
other photographs of the same girl. One of these showed her in a
trailing carriage-coat, with furs; the other was a lake scene, and she
was seated in a drifting boat, with a ruffled parasol shading her
lovely face. In the panel between the bookcase was a fourth picture
of the selfsame subject—an etching done with great skill and
effectiveness. The dark girl, gowned in clinging white, was shown
against a massed background. A flowered hat rested upon her
poised head; one hand was outstretched to feed a fawn.
“He has it!” announced Mr. Graves portentously; “he’s another added
to the epidemic. Sue, Phil Rawson’s in love with Genevieve Unger.”
Whereupon he sank between his companions.
Sue did not speak, but sat regarding them from the depths of her
chair.
“It’s a particularly bad case,” said Mr. Hammond, “and we fear the
worst.”
“The worst?” questioned Sue in a low voice.
“You know Miss Unger. Is she going to let Hillcrest slip through her
fingers? Hang these visiting girls, anyhow! They always create
trouble.”
Sue put up a gloved hand quickly. “Please don’t criticise Genevieve
to me, Len,” she said. “She’s my friend.”
“Just the same, you know what she’ll do,” persisted Mr. Hammond.
“She’ll keep Phil dangling as long as she can—perhaps one month,
perhaps two—then she’ll haughtily accept him. Meanwhile, what’ll he
be good for? Polo? And the Hadbury game comes off in just ten
days. We’ll lose it without him.” He nursed a knee disconsolately.
“We thought,” began Mr. Graves, taking up the matter where Mr.
Hammond had left off, “that you might be able to shorten the period
of agony—the dangling period, I mean. If Miss Unger imagined there
was the least danger that she’d lose him, why, she’d grab him.”
“Yes, she would,” declared Mr. St. Ives. “Her visit at The Lilacs is up
pretty soon. Where’ll she go next?”
“Here,” said Sue quietly, “—if anyone is speaking unkindly of her.”
“That’s lucky for her,” went on Mr. Graves. “Your hospitality isn’t to be
sneezed at by a girl who likes to spend all of her income on her
duds.”
Sue rose. “Really,” she said, “I can’t listen any longer. Genevieve is
the handsomest girl in the State of New York. She’s a darling to boot.
And you gentlemen”—this with studied candor—“would have less to
say if each and every one of you had not been given your—your
——”
“Mitten?” suggested Mr. St. Ives politely.
“—Last year,” concluded Sue. “I’m sorry I’ve listened to a single
unkind thing about her. I insist that you talk of something else while
you remain.”
“We’d better go, then,” said Mr. Hammond, his face eloquent of woe.
“We came to talk about just that, you see. There isn’t a dashier
player, or a stronger hitter, or a better shot at goal in Westchester
County. Of course, there’s Tommy Watts. He could sub. But none of
us want Tommy, he’s so wild with that whippy stick of his. Oh, why—
why——”
“I haven’t seen Phil for nearly two weeks,” said Sue. “Grandmamma
has been quite ill.”
“How is Mrs. Townsend?” inquired Mr. St. Ives. “Pardon our
forgetting to ask. We’re so confounded worried——”
“Phil’s happiness must come before polo,” went on Sue very
decidedly. “Surely you didn’t think that I would conspire against him.”
“Oh, nothing of the sort!” cried Mr. Graves. “Our hope wasn’t that you
would butt in—that is, interfere unpleasantly—and break things up.
On the contrary, we wanted you to—er—well, to sort of stampede
Genevieve so that she’d say ‘Yes’ at once, or maybe elope. Oh, if
Phil only had an old cat of a mother who would oppose the match!”
Sue looked down at her boots. Then, after a moment’s thought: “If
you like Phil, and think so badly of Genevieve,” she argued, “why
should you wish to see them marry? I refuse to be the cat.”
“The Hadbury game!” cried Mr. Hammond. “Sue, we want to win that
game!”
“Well,” she said, “if Phil really loves Genevieve, and if Genevieve
loves Phil, I’ll try my best to—to—but I make you no promise. I shall
think only of their happiness, of course.”
The three filed to the door. There they turned. “Point out to
Genevieve,” suggested Mr. St. Ives, “that Hillcrest is an ideal place
for entertaining.”
“And mention,” added Mr. Graves, “that Phil’s income is in the first
flight—oh, don’t omit that.”
“But, above all things, cut down the dangling,”—this from Mr.
Hammond. They shook hands with her impressively and filed out into
the hall.
Sue returned to the plump chair and sat down. Directly before her
was the writing-desk with its pair of silver-bordered photographs.
She studied the pictures earnestly for a while. And when she turned
from them it was to go to a mirror and look at her own reflection—
long and keenly and with honest eyes. There were her horseback
freckles, dotting her nose as the stars dot the sky, and her square,
little, undimpled chin, and her sunburned cheeks, roughened by all
the winds of spring. “Ah,” she said at last, “she is so beautiful. I love
her for her beauty, too. I don’t blame anybody for loving her.” Then
she left the mirror and went back to the chair before the couch.
Many another person had contrasted the two. And not a few of the
Country Club members openly asserted—and with wrath—that
Genevieve Unger’s desire for Sue Townsend’s society lay in the fact
that Sue, with her wisp of a figure and her irregular little face, served
as a contrast to the other girl’s stateliness and radiant beauty. But
there were other striking contrasts between the girls, apart from the
one of looks. As one club wag put it, a mere comparison of their
footwear accounts for the year presented the essential difference
between them. During the season, Sue wore out two pairs of riding-
boots, tan; one pair of riding-boots, black; one pair of boots for
climbing; three pairs of stout shoes for morning wear; six pairs of
sandals suitable for use in the surf; ten pairs of tennis shoes, and
two pairs of slippers; while Genevieve’s list for the same length of
time included six pairs of boudoir slippers; six pairs of carriage shoes
—to match as many gowns; one pair of high-heeled shoes
unsuitable for street wear; and twenty-two pairs of slippers in velvet,
satin and kid.
But to Sue, ready for her ride forty minutes ahead of the appointed
time, only one contrast appeared. And when Mr. Rawson was
announced she sprang from her chair, bade the servant tell him that
she would be down in one moment, and fled up the stairs to her
dressing-room, where she dabbed a bit of powder upon the
offending nose, fluffed out her hair at either temple, and donned a
white chiffon veil.
But Phil barely glanced at her as she came out to her horse. His
eyes, blue like her own, had a far-away expression in them, and he
answered her greeting absent-mindedly. When he had put her up
and mounted his own pony he rode away beside her at a walk, his
look fixed ahead of him eagerly but unseeing; his lips parted in a
faint smile. Behind them, at the prescribed distance, followed the
red-cheeked, red-haired groom.
Sue said nothing, letting her companion have all his thoughts for
himself. Every now and then she gave him a quick, inquiring glance.
When he broke silence at last he spoke musingly—almost as if to
himself. “What a day to be at the dentist’s,” he said. “I hope he won’t
hurt her.”
“Dentist’s?” inquired Sue. “Who’s gone?”
“Why—Miss Unger.” He coloured self-consciously.
“Oh, has she?” went on Sue, surprised. “Are you sure? I thought this
was the date for that lawn fête at the Fanshaws’—Greenwich, you
know—for the benefit of something or other. Genevieve telephoned
me she’d promised to go and sell fudge.”
“But she went to town instead,”—this with finality.
At this point, Sue thought of Messrs. Hammond, Graves and St.
Ives, and of the oncoming contest at Hadbury. “Did you play this
morning?” she asked. “I suppose the team is getting splendidly
drilled.”
“I suppose so,” he answered vaguely. He was looking far ahead
once more.
“I think I’ll ask Genevieve to drive to Hadbury with me the day of the
game,” resumed Sue.
He turned toward her, then, undisguised pleasure brightening his
face: “How you always think of doing nice things for others!” he said.
“Go, Sue. It’ll be a corking match.”
“I wouldn’t miss it for anything. And, of course, I’d take Genevieve.
One can’t help doing nice things for her. Isn’t she beautiful, Phil!”
She said it earnestly.
“So beautiful that most of the girls aren’t especially kind to her,” Phil
answered. “Just this morning Elizabeth Carlton had to throw out
something—a nasty hint, you understand. It was about Valentine,
that English chap who’s been at the club so much lately.”
“I really don’t know him,” returned Sue. “But I’ve heard——”
“Yes, and I’ll wager it’s all true,” went on Phil hotly. “He isn’t the sort
of a man you’d like to see her marry.”
“Phil, you’ve fallen a victim, too,” said Sue gently.
“Oh, I don’t know.”
“Well, I told you you would.”
After that the conversation was still of Genevieve, until the gates of
Arbor Lodge were passed again—of Genevieve, the queenly;
Genevieve, the faultless; and (with a little embarrassment on Phil’s
part) of Genevieve, the trampler of hearts.
“You’ll be at practice to-morrow morning, won’t you?” asked Sue,
from the terrace steps. “Let me know when you can ride again. I hate
going out alone.”
Phil headed his horse toward home. “Oh, yes, I’ll play in the
morning,” he answered; “but I’ll take a car out in the afternoon,
probably. Good-bye, Sue.” And with Larry following hard on his
tracks he galloped away.
Sue drove over to The Lilacs immediately after breakfast, the day of
the Hadbury game—to find Genevieve still in a soft dressing-gown of
cobwebby lace and pink ribbons, lazily sipping her chocolate. She
held up a satin cheek to be kissed.
“I’m on time, you see,” laughed Sue. “But don’t hurry. I’ve got the
Lenox wagon and the bay ponies, and we’ll go a-zipping. How did
the lawn fête turn out?”
Genevieve did not look up, but broke her toast with tapering fingers.
“I didn’t go,” she said carelessly, after a moment of silence.
“Oh!” Sue’s tone was one of relief. “So you went to town, after all—
Phil said you had. We hoped the dentist didn’t hurt you.”
A shade of annoyance crossed the face of the other girl. Then, “He
didn’t, thank you,” she said shortly, and got up to make ready for the
drive.
The two arrived at Hadbury in plenty of time. It was a perfect
morning—the sun warm, the air soft and still, the sky cloudless—and
the scene at the polo-field was a gay one. On one side of the
rectangle rose the “ladies’ stand,” a grassy slope occupied by little
groups of people who had come on foot; on the other side, at a
discreet distance, was a line of vehicles. Sue guided her scampering
ponies midway of the line, between two other teams. Phil came over
to them for a moment. Others gathered, too, until there was a man
for every spoke of the nigh front wheel, and dark-eyed Genevieve
held a little court.
There were no callers at the off wheel, and Sue had all her attention
for the lines. So she protested to Phil against his having sent the red-
haired, red-cheeked Shadow to stand at her horses’ heads. “I don’t
need him,” she said, “and it makes the ponies cross to be held.”
“Larry came of his own accord,” whispered Phil. “He’s an obliging
lad, and he likes you.”
At that, Sue brightened and observed the red-haired lad pleasantly.
But Larry did not see her kindly glance. Standing straight, with heel
to heel and a hand at either bit, his gaze was fixed in open,
undisguised wonderment upon the beautiful Miss Unger.
Soon the match began—and went superbly. To quote Mr. Hammond,
it was “the greatest ever since the Persians played polo, by Jove!”
Upon the vivid green of the field went the teams, playing a hard-
galloping, hard-hitting game, in which Phil particularly distinguished
himself. He rode the brown pony, and his sleeves were rolled up, his
head was bare, despite the heavy sticks that described circles about
him, his hair flew in the wind like a young Indian’s. Now his orders
rang out sharp and clear—“Take the ball!” or “Back-hander there!” or
“Ride the man and leave the ball!” And his mount sped up and down;
his square-headed stick did skilful work.
“It’s an education to watch him,” declared Sue enthusiastically, as a
rousing bravo from a group of onlooking men went up, for Phil had
just dashed in, changed places with Number Three and made a
brilliant stroke.
Genevieve did not answer. She was talking to a tall man with a face
the approximate shade of Larry’s. “May I present Mr. Valentine?” she
asked presently, with some affectation, “—late of the English Army,
you know.”
Sue bowed.
“Churmed,” observed Mr. Valentine, in what was to Sue an entirely
new British mode of pronunciation.
At the end of the first period Phil came over to the wagon a second
time and chatted with Genevieve, who was looking particularly
handsome in a mauve linen and a tailored hat—so handsome that
Sue, dressed in less striking colours, seemed white and tired in
comparison. Again a group was gathered at Genevieve’s side of the
wagon, but Sue, more quiet than was her wont, had no smiles for
them. She looked away between the paper goal-posts that, painted
in wide cream-and-blue bands, loomed up near by like giant sticks of
candy.
“This afternoon he’ll motor”—it was Mr. St. Ives who was talking; he
was standing beside Phil. “To-morrow afternoon he’ll motor. The next
afternoon he’ll go out in his car.” Then he made a wry face and
reached over the back of the seat to seize Sue’s fingers and
squeeze them gratefully under a pretext of shaking hands.
“Will you go this afternoon, Miss Unger?” asked Phil. “My ten
minutes are nearly up, aren’t they, Sue?”
“Sue’s only got her locket,” said Miss Unger with a lazy smile.
“Well, what’s the time by your locket, Sue?” demanded Mr. St. Ives,
and reached for it.
Sue slipped the locket inside her shirtwaist.
“Say yes, Miss Unger,” urged Phil.
“I’m fearfully sorry—I really can’t go this afternoon.” Genevieve gave
a quick glance past Phil to the man behind him—Valentine. “I have
an engagement.”
At that, Phil fell back, his face suddenly grave, lifted a hand in a gay
salute and strode away.
But throughout the remainder of the game he played harder than
ever, and with such coolness, resource and accuracy that there was
frequent hand-clapping from the line of vehicles, and even Hadbury
parasols were waved from the ladies’ stand; while to one side, where
the extra ponies waited, groom leaned to groom, commenting
excitedly. But when the match was done, with the Brampton team
victors, he disappeared, and Sue did not see him again. She got
away as soon as she could manage it, and turned the bays
homeward at top speed.
“Don’t you think Mr. Valentine handsome?” asked Genevieve, as
they rolled along. “Soldierly, I think.”
“Bob doesn’t believe the man has ever been in the army,” said Sue.
“And he says Mr. Valentine owes everyone in Brampton.”
Genevieve opened her eyes. “Why, Sue!” she exclaimed. “I’ve never
heard you repeat things against anyone before. Mr. Valentine has
plenty of money. And shopkeepers always gossip to curry favor with
servants.”
“And Bob says he gambles,” persisted Sue. “I like you too well to see
him claim any of your attention.”
“Don’t all men gamble?” demanded Genevieve.
“Not professionally—that’s common.”
Genevieve put up her pretty chin. “It’s hardly any commoner than
gossip,” she answered. “However, I’ve noticed that if a man is
distinguished he gets a lot of criticism. But”—with a shrug—“one
never minds the criticism of kids.”
Sue said nothing.
She left Genevieve at The Lilacs and went home. But she had only
arrived when she was summoned to the telephone. As she took the
receiver she could hear sobbing. Then, “Sue!” wailed a voice—
Genevieve’s; “l-look in the wagon, Sue. I—I lost my p-purse this
morning.” She began to sob again.
Sue gave a prompt order. “Dear Genevieve,” she answered back,
“don’t worry. The purse is sure to turn up.” A few minutes later she
was in the carriage-house, dressed for riding. And when she learned
that no purse had been found, telephoned Genevieve again before
mounting the grey to ride to The Lilacs.
Genevieve was gone to Hadbury when Sue arrived, Phil having
urged that an advertisement be placed at once in the Star, together
with the offer of a suitable reward.
“Then Phil came, after all,” said Sue. She was walking to and fro in
the old-fashioned drawing-room.
“I called him,” answered Mrs. Vander Laan, who was a little old lady
with an enthusiastic liking for young people. “When he got here he
telephoned to have the field searched; then started. The reward is to
be one hundred dollars.”
“That much?” asked the girl. “The purse must have contained a good
deal.”
“Exactly seven hundred,” said Mrs. Vander Laan; “all of her month’s
allowance. Wasn’t she foolish to be carrying so much about with her!
But the sweet child was so pretty as she wept.”
“Seven hundred!” exclaimed Sue. “Has she any idea where she lost
it?”
“She thinks it was when she was just starting for home. She
remembers having the purse when she was still at the polo-field. She
says you drove so rapidly——”
“I did,” admitted Sue, conscience-stricken. “Oh, I sha’n’t let her lose
it, Mrs. Vander Laan. It was my fault. Why didn’t she deposit it in a
bank that day she went into town?”
Mrs. Vander Laan was embroidering. Now she suddenly stopped
and looked up at Sue. “But she hasn’t been to town,” she declared.
“Not to the dentist’s?” asked Sue, “—the day of the Fanshaw garden
fête?”
“No, dear. She went driving with Mr. Valentine.”
“Oh.” Sue began to walk the floor again.
She was still walking when Genevieve and Phil came in. “Genevieve,
I’m so sorry,” she cried, giving her hand to the other girl. “Tell me
something to do.”
Genevieve met her sympathy ungraciously. “Oh, don’t bother,” she
said with a little irritation. “I’d rather not have such a fuss made about
it.” Then, to Mrs. Vander Laan: “May we have tea, mütterchen? Sue,
take Mr. Rawson home with you and jolly him up with some tennis.”
But Phil did not look like a candidate for “jollying up.” He turned to
Sue. “To think that Miss Unger carried the money all around New
York that afternoon in a hand-bag that anybody might have
grabbed,” he said, “and then lost it at the polo match.”

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Flow Batteries: From Fundamentals to

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1 The Need for Stationary Energy Storage 3

1.5 The Need for Longer-Duration Energy Storage 16

2 History of Flow Batteries 29

3 General Electrochemical Fundamentals of Batteries 53

4 General Aspects and Fundamentals of Flow Batteries 69

4.3 Main Components of a FB Energy Storage System 75

6 Membranes for Flow Batteries 121

6.3.1.1 Perfluorinated Membranes 132

7 Standards for Flow Batteries 155

8 Safety Considerations of the Vanadium Flow Battery 175

9 A Student Workshop in Sustainable Energy Technology: The

9.3 Results and Discussion 195

Part II Characterization of Flow Batteries and

10 Characterization Methods in Flow Batteries: A General

11 Electrochemical Methods 229

11.2.1 Measuring Cyclic Voltammetry 231

12 Radiography and Tomography 263

13 Characterization of Carbon Materials 281

13.2.1 Raman Spectroscopy 283

14 Characterization of Membranes for Flow Batteries 307

Part III Modeling and Simulation 333

15 Quantum Mechanical Modeling of Flow Battery

16 Mesoscale Modeling and Simulation for Flow Batteries 355

17 Continuum Modelling and Simulation of Flow Batteries 379

17.2.2.3 Overpotentials and Mass Transport Problems 385

18 Pore-scale Modeling of Flow Batteries 413

18.3.6 Computational Details 424

19 Dynamic Modelling of Vanadium Flow Batteries for System

20 Techno-economic Modelling and Evaluation of Flow

20.2.2.1 Technical System Definition 466

21 Machine Learning for FB Electrolyte Screening 487

Part IV Vanadium Flow Batteries 507

22 The History of the UNSW All-Vanadium Flow Battery

23 Vanadium Electrolytes and Related Electrochemical

24 Electrodes for Vanadium Flow Batteries (VFBs) 563

25 Membranes for Vanadium Flow Batteries 589

26 Advanced Flowﬁeld Architecture for Vanadium Flow

27 State-of-Charge Monitoring for Vanadium Redox Flow

28 Rebalancing/Regeneration of Vanadium Flow Batteries 641

29 Life Cycle Analysis of Vanadium Flow Batteries 659

30 Next-Generation Vanadium Flow Batteries 673

31 Asymmetric Vanadium-based Aqueous Flow Batteries 689

Part V Other Important Inorganic Flow Battery

32 Zn/Br Battery – Early Research and Development 711

33 Iron–Chromium Flow Battery 741

34 An Overview of the Polysulﬁde/Bromine Flow Battery 765

35 Fe/Fe Flow Battery 791

36 Zinc–Cerium and Related Cerium-Based Flow Batteries: