
Energy Storage
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Ralph Zito, PhD, was a pioneer in the field of electrical energy for over 30 years. With more than 40 patents and 60 papers to his credit, his resume is a virtual who's who of energy companies, such as GE, Westinghouse, and Sylvania, to name a few. He taught at the Carnegie Institute, where he obtained his doctorate, and did research at New York University, where he received his baccalaureate. Ralph Zito passed away in 2012.
Haleh Ardebili, PhD, is currently the Bill D. Cook Associate Professor of Mechanical Engineering at the University of Houston. She also holds a joint appointment in Materials Science and Engineering Program. She received her B.S. Honors degree in Engineering Science and Mechanics from Pennsylvania State University (1994), M.S. in Mechanical Engineering at the Johns Hopkins University (1996), and a Ph.D. in Mechanical Engineering from the University of Maryland at College Park (2001). Ardebili was a research scientist at General Electric R&D, and later a postdoctoral fellow at Rice University in 2010 before joining University of Houston. Her current research work focuses on materials for energy storage and topics include flexible and stretchable lithium ion batteries, next-generation polymer nanocomposite electrolytes among others. She has several publications and patents in the areas of energy storage and electronics. Her awards and honors include the NSF CAREER, Texas Space Grants Consortium New Investigators Program, and the Kittinger award for teaching. She is a regular contributor to the National Public Radio Show, "Engines of Our Ingenuity".
Content
Preface to Second Edition xi
Acknowledgements to First Edition xv
Acknowledgements to Second Edition xvi
1 Introduction 1
1.1 The Energy Problem 1
1.1.1 Increasing Population and Energy Consumption 2
1.1.2 The Greenhouse Effect 3
1.1.3 Energy Portability 4
1.2 The Purposes of Energy Storage 5
1.3 Types of Energy Storage 6
1.4 Sources of Energy 10
1.5 Overview of this Book 12
2 Fundamentals of Energy 15
2.1 Classical Mechanics and Mechanical Energy 15
2.1.1 The Concept of Energy 15
2.1.2 Kinetic Energy 19
2.1.3 Gravitational Potential Energy 26
2.1.4 Elastic Potential Energy 27
2.2 Electrical Energy 28
2.3 Chemical Energy 31
2.3.1 Nucleosynthesis and the Origin of Elements 31
2.3.2 Breaking and Forming the Chemical Bonds 35
2.3.3 Chemical vs. Electrochemical Reactions 36
2.3.4 Hydrogen 37
2.4 Thermal Energy 39
2.4.1 Temperature 39
2.4.2 Thermal Energy Storage Types 40
2.4.3 Phase Change Materials 42
3 Conversion and Storage 43
3.1 Availability of Solar Energy 46
3.2 Conversion Processes 48
3.2.1 Photovoltaic Conversion Process 49
3.2.2 Thermoelectric Effects: Seebeck and Peltier 49
3.2.3 Multiple P-N Cell Structure Shown with Heat 50
3.2.4 Early Examples of Thermoelectric Generators 50
3.2.5 Thermionic Converter 51
3.2.6 Thermogalvanic Conversion 51
3.3 Storage Processes¿ 54
3.3.1 Redox Full-Flow Electrolyte Systems 54
3.3.2 Full Flow and Static Electrolyte System Comparisons 55
4 Practical Purposes of Energy Storage 59
4.1 The Need for Storage 59
4.2 The Need for Secondary Energy Systems 62
4.2.1 Comparisons and Background Information 63
4.3 Sizing Power Requirements of Familiar Activities 64
4.3.1 Examples of Directly Available Human Manual Power Mechanically Unaided 66
4.3.1.1 Arm Throwing 66
4.3.1.2 Vehicle Propulsion by Human Powered Leg Muscles 66
4.3.1.3 Mechanical Storage: Archer's Bow and Arrow 67
4.4 On-the-Road Vehicles 69
4.4.1 Land Vehicle Propulsion Requirements Summary 69
4.5 Rocket Propulsion Energy Needs Comparison 70
5 Competing Storage Methods 71
5.1 Problems with Batteries 72
5.2 Hydrocarbon Fuel: Energy Density Data 75
5.3 Electrochemical Cells 77
5.4 Metal-Halogen and Half-Redox Couples 78
5.5 Full Redox Couples 83
5.6 Possible Applications 85
6 The Concentration Cell 89
6.1 Colligative Properties of Matter 89
6.2 Electrochemical Application of Colligative Properties 91
6.2.1 Compressed Gas 93
6.2.2 Osmosis 94
6.2.3 Electrostatic Capacitor 95
6.2.4 Concentration Cells: CIR (Common Ion Redox) 96
6.3 Further Discussions on Fundamental Issues 101
6.4 Adsorption and Diffusion Rate Balance 107
6.5 Storage by Adsorption and Solids Precipitation 109
6.6 Some Interesting Aspects of Concentration Cells 113
6.7 Concentration Cell Storage Mechanisms that Employ Sulfur 116
6.8 Species Balance 118
6.9 Electrode Surface Potentials 119
6.10 Further Examination of Concentration Ratios 120
6.11 Empirical Results with Small Laboratory Cells 122
6.12 Iron/Iron Concentration Cell Properties 126
6.13 The Mechanisms of Energy Storage Cells 127
6.14 Operational Models of Sulfide Based Cells 132
6.15 Storage Solely in Bulk Electrolyte 134
6.16 More on Storage of Reagents in Adsorbed State 137
6.17 Energy Density 140
6.18 Observations Regarding Electrical Behavior 141
6.19 Concluding Comments 143
6.20 Typical Performance Characteristics 145
6.21 Sulfide/Sulfur Half Cell Balance 145
6.22 General Cell Attributes 146
6.23 Electrolyte Information 146
6.24 Concentration Cell Mechanism and Associated Mathematics 149
6.25 Calculated Performance Data 150
6.26 Another S/S-2 Cell Balance Analysis Method 153
6.27 A Different Example of a Concentration Cell, Fe+2/ Fe+3 155
6.28 Performance Calculations Based on Nernst Potentials 156
6.28.1 Constant Current Discharge 157
6.28.2 Constant Power Discharge 158
6.29 Empirical Data 160
7 Thermodynamics of Concentration Cells 163
7.1 Thermodynamic Background 163
7.2 The CIR Cell 166
8 Polysulfide - Diffusion Analysis 175
8.1 Polarization Voltages and Thermodynamics 176
8.2 Diffusion and Transport Processes at the (-) Electrode Surface 177
8.3 Electrode Surface Properties, Holes, and Pores 179
8.4 Electric (Ionic) Current Density Estimates 183
8.5 Diffusion and Supply of Reagents 184
8.6 Cell Dynamics 186
8.6.1 Electrode Processes Analyses 186
8.6.2 Polymeric Number Change 186
8.7 Further Analysis of Electrode Behavior 198
8.7.1 Flat Electrode with Some Storage Properties 198
8.8 Assessing the Values of Reagent Concentrations 206
8.9 Solving the Differential Equations 207
8.10 Cell and Negative Electrode Performance Analysis 219
8.11 General Comments 225
9 Design Considerations 227
9.1 Examination of Diffusion and Reaction Rates and Cell Design 227
9.2 Electrodes 228
9.3 Physical Spacing in Cell Designs 229
9.3.1 Electrode Structures 229
9.4 Carbon-Polymer Composite Electrodes 233
9.4.1 Particle Shapes and Sizes 235
9.4.2 Metal to Carbon Resistance 235
9.4.3 Cell Spacing 236
9.5 Resistance Measurements in Test Cells 237
9.6 Electrolytes and Membranes 239
9.7 Energy and Power Density Compromises 240
9.8 Overcharging Effects on Cells 244
9.9 Imbalance Considerations 244
10 Electrolytes, Separators, and Membranes 245
10.1 Electrolyte Classifications 246
10.2 Ionic Conductivity 247
10.2.1 Measurement Techniques 247
10.2.2 Nyquist Plot Circuit Fitting 249
10.3 Ion Conduction Theory 251
10.3.1 Ion Conduction in Liquid Electrolytes 252
10.3.2 Ion Conduction in Polymer Electrolytes 256
10.3.3 Ion Conduction in Ceramic Electrolytes 260
10.4 Factors Affecting Ion Conductivity 262
10.5 Transference Number 263
10.6 Electrolytes for Lithium Ion Batteries 264
10.6.1 Liquid Electrolytes 264
10.6.1.1 Non-Aqueous Electrolytes 264
10.6.1.2 Aqueous Electrolytes 268
10.6.2 Solid and Quasi-Solid Electrolytes 270
10.6.2.1 Polymer Electrolytes 270
10.6.2.2 Ceramic Electrolytes 272
10.7 Electrolytes for Supercapacitors 272
10.8 Electrolytes for Fuel Cells 276
10.9 Fillers and Additives 282
11 Single Cell Empirical Data 283
11.1 Design and Construction of Cells and the Materials Employed 283
11.2 Experimental Data 287
12 Conclusions and Future Trends 289
12.1 Future of Energy Storage 289
12.2 Flexible and Stretchable Energy Storage Devices 290
12.3 Self-Charging Energy Storage Devices 294
12.4 Recovering Wasted Energy 295
12.5 Recycling Energy Storage Devices 298
12.6 New Chemistry for Electrochemical Cells 300
12.7 Non-Electrochemical Energy Storage 301
12.8 Concentration Cells 302
12.8.1 Pros and Cons of Concentration Cells 303
12.8.2 Future Performance and Limitations 304
Appendix 1 307
Appendix 2 323
Bibliography 335
Index 341
Chapter 1
Introduction
Billions of years ago, during the Big Bang nucleosynthesis, chemical energy was stored in the chemical elements. We now store electrochemical energy in our modern-day batteries. Over the estimated 14 billion years life of our universe, energy storage has been and will continue to be an essential part of all things in existence.
In the last few decades, we have become dramatically more dependent on reliable and long-lasting energy storage. Several reasons have contributed to this increased reliance, including the widespread use of modern portable or wearable devices, significant growth of human population, and the rising demands of the 21st century lifestyle. Meanwhile, there are other driving factors at play. Our conventional sources of energy like non-renewable fossil fuels continue to decline, and the environmental, economic and political concerns surrounding the generation and use of energy are growing, leading to a wide range of energy challenges and concerns.
To resolve and manage the unique energy challenges of the 21st century, much effort has been directed toward identifying the most efficient, effective and durable energy storage solutions that can adequately meet our multifaceted life requirements. In this book, we will address a wide range of energy storage methods with emphasis on their basic mechanisms. In this chapter, we will first discuss the "energy problem" and the motivation underpinning the development of efficient approaches to store energy. We'll then classify, compare and discuss various methods of energy storage. In the final section, an overview of this book will be provided.
1.1 The Energy Problem
All the discussions and dire announcements in technical literature during recent years have certainly made everyone aware of the "energy problem." There is not much doubt that we are confronted with a real problem of domestic and international importance. The critical issues concerning the availability of energy sources and their efficient use are rapidly becoming vitally important. Increasing population, in conjunction with the greater-than-ever energy and materials demands that people are making in order to increase their comfort, travel, and other lifestyle choices is indeed causing greater stress. All of these require not only an increased availability of energy but also more effective ways of utilizing what is available.
1.1.1 Increasing Population and Energy Consumption
Human population is growing at a rapid rate. The world population is projected to reach about 9 billion by 2040, as depicted in Figure 1.1. Consequently, energy consumption has risen significantly due to the increasing human dependency on various technologies and the power and energy they require.
Figure 1.1 World population increase.
According to the 2016 International Energy Outlook (IEO) by U.S. Energy Information Administration (EIA), the total world energy consumption is projected to surpass 900 quadrillion Btu by 2040. British thermal unit (Btu) is defined as approximately 1,055 Joules. The electrical power and industrial sectors are projected to each increase over 300 quadrillion Btu by 2040. The measured and projected total delivered energy consumption per sector is shown in Figure 1.2. Clearly, we must seek sustainable and global energy solutions to combat the significantly large energy consumption demands of the 21st century.
Figure 1.2 World energy consumption by sector type.
The main efforts of research and development have been directed toward the development of new alternatives or finding more primary sources of energy. For the present, and until the discovery of a new class of phenomena, we have a fairly good idea of what can be accomplished. We know what alternative sources are possible - alternative presumably to petroleum products. Yet none of them are nearly as attractive for portable or motive power unless we significantly lower our criteria.
It would appear that sources of energy are plentiful on planet Earth. However, they are often locally unavailable, too bulky, too unpredictable (solar and wind), and/or too dangerous to be portable. An effective method for storing energy would greatly reduce the problem and would provide low-cost energy for everyone. It seems that not nearly as much attention or support has been directed toward the problem of storage as that which has been directed toward generation. Perhaps this difference is due to the absence of many promising approaches to accomplishing the latter. This book presents a different approach and aims to stimulate additional efforts toward the search and development of better storage.
1.1.2 The Greenhouse Effect
The Earth is believed to be approximately 5 billion years old. For a relatively long time, life could not be sustained outside the ocean. This is mainly due to the absence of a properly formed atmosphere that could protect life from lethal radiations. Several billions of years later (about 600 million years ago) the Earth's atmosphere, capable of protecting life, was formed.
For millions of years, the atmosphere and the surface of Earth have effectively reflected the solar radiation to Space, and the consequent infrared (IR) radiation has passed through the atmosphere back to Space as depicted in Figure 1.3. However, it is believed that more recently, some of the IR radiation has been absorbed by the greenhouse gases below the Earth's atmosphere and the absorbed IR radiation is re-emitted back to Earth. This phenomenon is commonly referred to as the "Greenhouse Effect". It can be mainly attributed to the use of fossil fuels and the human industrial evolution. The greenhouse effect presents yet another major reason for the global community to actively move toward environmentally friendly and renewable energy harvesting, conversion and storage.
Figure 1.3 (1) Solar rays radiated toward Earth, (2) some reflected by Earth's atmosphere, (3) some reflected by Earth's surface, (4) infrared radiation passes through the atmosphere and out to Space, and (5) some of the infrared radiation is absorbed and re-emitted back to Earth by the greenhouse gases.
1.1.3 Energy Portability
Energy portability is another major challenge. We cannot carry windmills around - they are huge and dangerous. A waterfall, due to topographical considerations, is not available everywhere, and its size is immense for the intermittent power and energy produced. Solar cells can be designed to be portable but their usage is confined to the available sunny days and limited daytime hours. There are really not too many attractive choices for portable energy harvesting and storage.
Batteries and supercapacitors are the least obtrusive and the most predictable limited secondary sources, but they are not practical as large-scale primary or secondary sources. Windmills and photovoltaic cells are almost useless without either storage or the assistance of an electric utility power grid, which operates on nuclear power or coal fuel. It would appear that the energy source trap has merely changed shape.
Ideally, high energy and power density "batteries" of some sort that are charged by nuclear or fossil fuel would be a good solution for smoothing the irregularities in the distribution and availability for the planet's population. The term "batteries" used here only refers to some mechanism for practical storage. So far, the most promising is probably an electrochemical method. Compressed air, metal springs, flywheels, etc., all have very serious drawbacks. Most generating facilities are not portable, nor would most people wish to live with them in their midst.
1.2 The Purposes of Energy Storage
Storing energy in its many forms in nature is a vital part of all processes as well as life itself on Earth. As we explore these processes and their importance to us, we can gradually make observations that lead to some revealing conclusions.
One of our purposes is to examine the general area of energy storage and to identify the key mechanisms that have significant roles in nature and civilization. Then we will develop a description and a reasonably detailed understanding of why we need to store energy and how the various mechanisms we employ work to satisfy these needs. Most of this book is devoted to electrochemical processes and, in particular, full flow electrolyte cells that are frequently referred to as redox batteries.
In a very general sense, there are only three purposes for the storage of energy: to make an energy supply portable from essentially non-portable sources, to store from an ongoing source for use at a later time, and to change the ratio of power-to-energy, as accomplished by flywheels, capacitors, etc.
All applications of energy storage can be put into one or more of these categories. Certainly, if we wish to power a portable power tool or an electric automobile, a hydroelectric plant is hardly practical. However, if we use the energy produced by the hydroelectric station and store part of what is not immediately needed in an electric battery, it becomes a pragmatic concern for the electric vehicle. Nuclear energy sources are hardly portable on a small scale. But in similar fashion, as for non-portable hydroelectric stations, storing portions of the generated energy in some sort of device such as a battery could become useful in mobile electric vehicles.
In the second instance, we might have the need to...
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