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Novel Electrochemical Energy Storage Devices
Novel Electrochemical Energy Storage
Devices
Materials, Architectures, and Future Trends
Feng Li
Lei Wen
Hui-ming Cheng
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10 9 8 7 6 5 4 3 2 1
v
Contents
Preface xiii
Abbreviations xv
1 Introduction 1
1.1 Energy Conversion and Storage: A Global Challenge 1
1.2 Development History of Electrochemical Energy Storage 3
1.3 Classification of Electrochemical Energy Storage 4
1.4 LIBs and ECs: An Appropriate Electrochemical Energy
Storage 6
1.5 Summary and Outlook 10
References 10
2 Materials and Fabrication 15

2.1 Mechanisms and Advantages of LIBs 15
2.1.1 Principles 15
2.1.2 Advantages and Disadvantages 16
2.2 Mechanisms and Advantages of ECs 18
2.2.1 Categories 18
2.2.2 EDLCs 18
2.2.3 Pseudocapacitor 20
2.2.4 Hybrid Capacitors 21
2.3 Roadmap of Conventional Materials for LIBs 22
2.4 Typical Positive Materials for LIBs 23
2.4.1 LiCoO2 Materials 23
2.4.2 LiNiO2 and Its Derivatives 25
2.4.3 LiMn2 O4 Material 26
2.4.4 LiFePO4 Material 27
vi Contents
2.4.5 Lithium–Manganese-rich Materials 28

2.4.6 Commercial Status of Main Positive Materials 28
2.5 Typical Negative Materials for LIBs 29
2.5.1 Graphite 29
2.5.2 Soft and Hard Carbon 31
2.6 New Materials for LIBs 33
2.6.1 Nanocarbon Materials 33
2.6.2 Alloy-Based Materials 35
2.6.3 Metal Lithium Negative 39
2.7 Materials for Conventional ECs 39
2.7.1 Porous Carbon Materials 40
2.7.2 Transition Metal Oxides 41
2.7.3 Conducting Polymers 42
2.8 Electrolytes and Separators 42
2.8.1 Electrolytes 42
2.8.2 Separators 45
2.9 Evaluation Methods 46
2.9.1 Evaluation Criteria for LIBs 46
2.9.2 Theoretical Gravimetric and Volumetric Energy
Density 46
2.9.3 Practical Energy and Power Density of LIBs 47
2.9.4 Cycle Life 48
2.9.5 Safety 48
2.9.6 Evaluation Methods for ECs 49
2.10 Production Processes for the Fabrication 50
2.10.1 Design 50
2.10.2 Mixing, Coating, Calendering, and Winding 51
2.10.3 Electrolyte Injecting and Formation 51
2.11 Perspectives 51
References 53
3 Flexible Cells: Theory and Characterizations 67

3.1 Limitations of the Conventional Cells 67
3.1.1 Mechanical Properties of Conventional Materials 67
3.1.2 Limitations of Conventional Architectures 68
3.1.3 Limitations of Electrolytes 69
Contents vii
3.2 Mechanical Process for Bendable Cells 69

3.2.1 Effect of Thickness 70
3.2.2 Effect of Flexible Substrates and Neutral Plane 71
3.3 Mechanics of Stretchable Cells 72
3.3.1 Wavy Architectures by Small Deformation Buckling
Process 72
3.3.2 Wavy Architectures by Large Deformation Buckling
Process 74
3.3.3 Island Bridge Architectures 75
3.4 Static Electrochemical Performance of Flexible Cells 76
3.5 Dynamic Performance of Flexible Cells 77
3.5.1 Bending Characterization 78
3.5.2 Stretching Characterization 78
3.5.3 Conformability Test 79
3.5.4 Stress Simulation by Finite Element Analysis 79
3.5.5 Dynamic Electrochemical Performance During
Bending 83
3.5.6 Dynamic Electrochemical Performance During
Stretching 85
3.6 Summary and Perspectives 90
References 90
4 Flexible Cells: Materials and Fabrication

Technologies 95
4.1 Construction Principles of Flexible Cells 95
4.2 Substrate Materials for Flexible Cells 95
4.2.1 Polymer Substrates 96
4.2.2 Paper Substrate 97
4.2.3 Textile Substrate 98
4.3 Active Materials for Flexible Cells 98
4.3.1 CNTs 98
4.3.2 Graphene 99
4.3.3 Low-Dimensional Materials 99
4.4 Electrolytes for Flexible LIBs 101
4.4.1 Inorganic Solid-state Electrolytes for Flexible LIBs 102
4.4.2 Solid-state Polymer Electrolytes for Flexible LIBs 104
viii Contents
4.5 Electrolytes for Flexible ECs 104

4.6 Nonconductive Substrates-Based Flexible Cells 107
4.6.1 Paper-Based Flexible Cells 108
4.6.2 Textiles-Based Flexible Cells 112
4.6.3 Polymer Substrates-Based Flexible Cells 117
4.7 CNT and Graphene-Based Flexible Cells 121
4.7.1 Free-standing Graphene and CNTs Films for SCs 121
4.7.2 Free-standing Graphene and CNT Films for LIBs 122
4.7.3 Flexible CNTs/Graphene Composite Films for the
Cells 125
4.8 Construction of Stretchable Cells by Novel
Architectures 127
4.8.1 Stretchable Cells Based on Wavy Architecture 127
4.8.2 Stretchable Cells Based on Island-Bridge
Architecture 129
4.9 Conclusion and Perspectives 130
4.9.1 Mechanical Performance Improvement 131
4.9.2 Innovative Architecture for Stretchable Cells 132
4.9.3 Electrolytes Development 132
4.9.4 Packaging and Tabs 132
4.9.5 Integrated Flexible Devices 133
References 133
5 Architectures Design for Cells with High Energy

Density 147
5.1 Strategies for High Energy Density Cells 147
5.2 Gravimetric and Volumetric Energy Density of
Electrodes 149
5.3 Classification of Thick Electrodes: Bulk and Foam
Electrodes 151
5.4 Design and Fabrication of Bulk Electrodes 153
5.4.1 Advantages of Bulk Electrodes 153
5.4.2 Low Tortuosity: The Key for Bulk Electrodes 155
5.5 Characterization and Numerical Simulation of
Tortuosity 157
5.5.1 Characterization of Tortuosity by X-ray Tomography 157
Contents ix
5.5.2 Numerical Simulation of Tortuosity on Rates by

Commercial Software 158
5.6 Fabrication Methods for Bulk Electrodes 159
5.7 Thick Electrodes with Random Pore Structure 160
5.7.1 Pressure-less High-temperature Sintering Process 160
5.7.2 Cold Sintering Process 161
5.7.3 Spark Plasma Sintering Technology 162
5.7.4 Brief Summary for Sintering Technologies 165
5.8 Thick Electrodes with Directional Pore Distribution 165
5.8.1 Iterative Extrusion Method 165
5.8.2 Magnetic-Induced Alignment Method 168
5.8.3 Carbonized Wood Template Method 168
5.8.4 Ice Templates Method 172
5.8.5 3D-Printing for Thick Electrodes 173
5.8.6 Brief Summary for Bulk Electrodes 175
5.9 Carbon-Based Foam Electrodes with High Gravimetric
Energy Density 178
5.9.1 Graphene Foam 179
5.9.2 CNTs Foam 181
5.9.3 CNT/Graphene Foam 181
5.10 Carbon-Based Thick Electrodes 182
5.10.1 Low Electronic Conductive Material/Carbon Foam 182
5.10.2 Large Volume Variation Materials/Carbon Foam 186
5.10.3 Compact Graphene Electrodes 188
5.10.4 Summary for Carbon Foam Electrodes 189
5.11 Thick Electrodes Based on the Conductive Polymer
Gels 191
References 195
6 Miniaturized Cells 205
6.1 Introduction 205
6.1.1 Definition of the Miniaturized Cells and Their
Applications 205
6.1.2 Classification of Miniaturized Cells 206
6.1.3 Development Trends of the Miniaturized Cells 207
6.2 Evaluation Methods for the Miniaturized Cells 209
x Contents
6.2.1 Evaluation Methods for Electric Double-layer m-ECs 210

6.2.2 Evaluation methods for m-LIBs and m-ECs 211
6.3 Architectures of Various Miniaturized Cells 212
6.4 Materials for the Miniaturized Cells 213
6.4.1 Electrode Materials 213
6.4.2 Electrolytes for the Miniaturized Cells 214
6.5 Fabrication Technologies for Miniaturized Cells 215
6.5.1 Fabrication of Miniaturized Cells with 2D Parallel Plate
Configuration 216
6.6 Fabrication Technologies for 2D Interdigitated Cells 220
6.7 Printing Technologies for 2D Interdigitated Cells 222
6.7.1 Advantages of Printing Technologies 222
6.7.2 Classification of Printing Techniques 222
6.7.3 Screen Printing for Miniaturized Cells 224
6.7.4 Inkjet Printing 228
6.8 Electrochemical Deposition Method for 2D Interdigitated
Cells 228
6.9 Laser Scribing for 2D Interdigitated Cells 231
6.10 In Situ Electrode Conversion for 2D Interdigitated
Cells 234
6.11 Fabrication Technologies for 3D In-plane Miniaturized
Cells 236
6.11.1 3D Printing for 3D Interdigitated Configuration Cells 236
6.11.2 3D Interdigitated Configuration by Electrodeposition 239
6.12 Fabrication of Miniaturized Cells with 3D Stacked
Configuration 240
6.12.1 3D Stacked Configuration by Template Deposition 241
6.12.2 3D Stacked Configuration by Microchannel-Plated
Deposition Methods 245
6.13 Integrated Systems 247
References 250
7 Smart Cells 263

7.1 Definition of Smart Materials and Cells 263
7.1.1 Definition of Smart Cells 263
Contents xi
7.1.2 Definition of Smart Materials 263

7.2 Type of Smart Materials 264
7.2.1 Self-healing Materials 264
7.2.2 Shape-memory Alloys 265
7.2.3 Thermal-responding PTC Thermistors 266
7.2.4 Electrochromic Materials 267
7.3 Construction of Smart Cells 268
7.3.1 Self-healing Silicon Anodes 268
7.3.2 Aqueous Self-healing Electrodes 271
7.3.3 Liquid-alloy Self-healing Electrode Materials 273
7.3.4 Thermal-responding Layer 274
7.3.5 Thermal-responding Electrodes Based on the PTC
Effect 276
7.3.6 Ionic Blocking Effect-Based Thermal-responding
Electrodes 278
7.4 Application of Shape-memory Materials in LIBs and
ECs 280
7.4.1 Self-adapting Cells 280
7.4.2 Shape-memory Alloy-Based Thermal Regulator 281
7.5 Self-heating and Self-monitoring Designs 282
7.5.1 Self-heating 283
7.5.2 Self-monitoring 285
7.6 Integrated Electrochromic Architectures for Energy
Storage 286
7.6.1 Integration Possibilities 286
7.6.2 Integrated Electrochromic ECs 287
7.6.3 Integrated Electrochromic LIBs 289
References 292
Index 301
xiii
Preface
Electrochemical energy storage in the cells (here these are lithium ion batteries
(LIBs) and electrochemical capacitors (ECs)) has been recognized as the most
promising technology for portable electronics as well as stationary and vehicle
applications. Existing technologies still face performance and cost challenges,
including barriers in specific energy, energy density, service life, and energy effi-
ciency at high rates. Over the past decades, portable electronics have been used in
every aspect of our daily life. One of the key components of future portable devices
is the compatible cell with an ultrahigh energy density and specific features (e.g.
miniaturization, integration, flexibility, and smart functions).
Developing advanced cells always requires the discovery of new materials, new
electrochemistry, and an increased understanding of the processes on which the
devices depend. The overall performance of the cells is limited by the fundamen-
tal behavior of the used materials, including electrode active materials, electrolytes,
separators, and other components. Unfortunately, the conventional fabrication tech-
nology and architectures of electrodes based on these materials have almost reached
their limits, which cannot satisfy future requirements. Therefore, for the coming era
of portable electronics, we urgently need to reconsider how we rationally design and
intelligently fabricate advanced and intelligent cells. We need to not only construct
novel configurations of materials, electrolytes, separators, and, as results, the cells
to meet the desired criteria but also develop smart technologies to fabricate these
electrochemical energy storage devices in an economically viable and time-efficient
manner.
In this book, we will present a comprehensive introduction of the developments of
innovative materials, architectures and design considerations in the electrode, and
cell configurations, together with the recent technologies used to achieve these novel
designs. As we wanted to write a book for researchers, engineers, and students, we
try our best to understand the current application of the cells in portable electronic
products.
The writing of this book was completed by Prof. Feng Li and Dr. Lei Wen, and
Prof. Hui-ming Cheng revised it. The origin of this book is from the meeting of Prof.
Li and Dr. Zai Yu in ChinaNano2017 at Beijing. Dr. Yu wished that we can write a
book about our research. It is a hard work for us and new chance to think about
our research insight. In 2018, we wrote an outline of the book and passed it to the
xiv Preface
reviewers for approval. After that, we began writing the book. Although Dr. Zai Yu
has left Wiley, Ms. Aruna Pragasam is very happy to continue to contact and help
us. On one occasion, Prof. Li went to Tsinghua University and talked with Prof.
Qiang Zhang and Prof. Jiaqi Huang. We know that Dr. Shaoyu Qian is responsible
for author of China region. She answered our questions with patience during the
writing.
Finally, we would like to thank all scientists who have been helpful in the prepa-
ration of this book and all colleagues who kindly devoted their time and efforts to
contribute chapters and discussions. We thank Dr. Hongze Luo, from Council for
Scientific and Industrial Research (CSIR), South Africa, for preparing the draft of
Chapter 6; Dr. Zhigang Zhao, from Suzhou Institute of Nano-tech and Nano-Bionics
(SINANO), China, for his help in the preparation of Electrochromic Cells section
in Chapter 7; Drs. Ji Liang and Hou Feng, Mrs Hao Li, Nan Li, and Miss Pengyi
Lu from Tianjin University, China, for their helpful discussion and initial drafting
of Chapters 3 and 4; and Dr. Liqun Wang, Tianjin Normal University, for the help-
ful discussion in drafting Chapter 6. We would like to thank Mr. Haorui Shen and
Huicong Yang, PhD candidates in our lab. Mr. Shen helped in the plotting of figures.
Mr. Huicong Yang is the first reader of this book and gave valuable advices toward
the entire book.
We also thank the financial support from National Natural Science Foundation of
China (Nos. 51525206, 51927803, 52020105010, 51972313, 52072378 and 51902316),
MOST (2016YFA0200102 and 2016YFB0100100), the Strategic Priority Research
Program of the Chinese Academy of Sciences (XDA22010602), Liaoning Revitaliza-
tion Talents Program (No. XLYC1908015), Youth Innovation Promotion Association
of the Chinese Academy of Sciences (No. Y201942) and China Petrochemical
Cooperation (No. 218025). The Bureau of Industry and Information Technology of
Shenzhen for the “2017 Graphene Manufacturing Innovation Center Project” (No.
201901171523).
xv
Abbreviations
AAO anodized aluminum oxide

AC activated carbon, alternative current
AGV automated guided vehicles
ALD atomic layer deposition
CAS Chinese Academy of Sciences
CCCD constant current charge and discharge
CMC sodium carboxymethyl cellulose
CNF cellulose nanofiber
CNT carbon nanotubes
CV cyclic voltammetry
CVD chemical vapor deposition
DEC diethyl carbonate
DMC dimethyl carbonate
DME dimethoxyethane
DOE Department of Energy
DOL 1,3-dioxolane
EBID electron beam-induced deposition
EC electrochemical capacitors, ethylene carbonate
EDLC electric double-layer capacitors
EG exfoliated graphene
EIS electrochemical impedance spectroscopy
ELD electrolytic deposition
EMC ethyl methyl carbonate
EPD electrophoretic deposition
ETPTA ethoxylated trimethylolpropane triacrylate
EV electric vehicle
EVA ethylene vinyl acetate
FTO fluorine-doped tin oxide
GCE gel composite electrolyte
GCP graphene-coated paper
GIC graphite intercalation compound
GNS graphene nanosheet
GO graphene oxide
xvi Abbreviations
HEV hybrid electric vehicle

HFP hexafluoropropylene
IDC International Data Corporation
IHP inner Helmholtz plane
IoT Internet of Things
IREA International Renewable Energy Agency
ITO indium tin oxide
LBL layer-by-layer
LCO LiCoO2
LDH layer double hydroxides
LFP LiFePO4
LIB lithium ion battery
LIBOB lithium bis(oxalato)borate
LIPON lithium phosphorus oxynitrides
LLZO Li7 La3 Zr2 O12
LMO LiMn2 O4
LTO Li4 Ti5 O12
m-LIBs micro lithium ion batteries
m-ECs micro electrochemical capacitors
MCMB mesocarbon microbeads
mtoe million ton oil equivalent
NASICON sodium super ionic conductor
NCA LiNix Coy Al1−x−y O2
NEDO New Energy and Industrial Technology Development Organization
NiCd nickel cadmium
NiMH nickel metal hydride
NMC LiNix Mny Co1−x−y O2
NMP N-methyl-2-pyrrolidone
NW nano wire
OHP outer Helmholtz plane
P3DT poly(3-decylthiophene)
P3OT poly(3-octylthiophene-2,5-diyl)
P3OPy PSS poly(3-octylpyrrole) poly(styrenesulfonate)
PAA polyacrylic acid
PAAm polyacrylamide
PANI polyaniline
PC propylene carbonate
PDA polydopamine
PDMS polydimethylsiloxane
PE polyethylene
PEDOT poly(3,4-ethylenedioxythiophene)
PEO polyoxyethylene
PEG polyethylene glycol
PEN polyethylene naphthalate
PES polyethersulfone
Abbreviations xvii
PET polyethylene terephthalate

PI polyimide
PMMA polymethyl methacrylate
PP polypropylene
PPO propylene oxide
PPY polypyrrole
PSS poly(styrenesulfonate)
PTC positive temperature coefficient
PTFE polytetrafluoroethylene
PU polyurethane
PVA polyvinyl alcohol
PVDF polyvinylidene difluoride
PVP polyvinylpyrrolidone
rGO reduced graphene oxide
RF radio frequency
RTIL room-temperature ionic liquid
SE solid electrolyte
SEBS styrene–ethylene–butylene–styrene
SEI solid electrolyte interphase
SEM scanning electron microscope
SHE standard hydrogen electrode
SHP self-healing polymer
SPE solid polymer electrolyte
SPRP Strategic Priority Research Program
TEABF4 tetraethylammonium tetrafluoroborate
TEM transmission electron microscope
TMO transition metal oxides
MWCNTs multi-walled carbon nanotubes
UPy ureidopyrimidinone
UV ultraviolet
1
Introduction
The world is witnessing increasing requirements for energy to meet the needs of
modern society. Due to the drastic climate warming around the world, developing
innovative sustainable clean energy (wind, tidal, solar energy, etc.) with high energy
efficiency is extremely important. However, various renewable energy to electricity
are quite fluctuating over time, and developing reliable energy storage systems is
an important way to solve these challenges. Therefore, to satisfy the increasing
social and industrial demands, better electrochemical energy storage devices should
be used.
On this point, searching for novel electrochemical energy storage system with
exceptional electrochemical properties for energy storage is essential. In this chapter,
we will first give a brief introduction toward various electrochemical energy storage
devices, including electrochemical capacitors (ECs) and lithium ion batteries (LIBs).
1.1 Energy Conversion and Storage: A Global Challenge

Nobel chemistry prize winner Richard Smalley had said: “Energy is the single most
important problem facing humanity today and energy is the largest enterprise on
Earth” [1]. Nowadays, the energy generation still mainly relies on fossil fuels (oil,
coal, and gas), which occupy 80% of total energy needs in the world. On the other
hand, the fossil fuels are still to be the dominant primary energy resources for many
years in the future. Therefore, limited supplies of the fossil fuels make it impera-
tive that combustion-based energy sources should be replaced by clean and renew-
able energy [2]. These sustainable energies mainly include hydropower, solar, wind,
geothermal, and tidal energy.
Figure 1.1 shows the global energy consumption. In 2018, the growth rate of global
energy consumption is 2.9%, which was the highest rate since 2010. Although fossil
energy still occupies the most energy consumption around the world, the renew-
able energy also made a significant increase in recent years [4]. Gas and renewables
have the most obvious increase among various energy sources since 2010 [3].
More importantly, the renewable energy sector also has significant social and eco-
nomic impact. In 2018, at least 11 million people were employed in the renewable
energy sector around the world. Compared with the data in 2016, the growth rate
Novel Electrochemical Energy Storage Devices: Materials, Architectures, and Future Trends,
First Edition. Feng Li, Lei Wen, and Hui-ming Cheng.
© 2021 WILEY-VCH GmbH. Published 2021 by WILEY-VCH GmbH.
2 1 Introduction
160 00
World energy consumption (MTOE) Coal
Renewables
Hydroelectricity
12 000 Nuclear energy
Natural gas
Oil
8000
4000
0
1996 2000 2004 2008 2012 2016
Years
Figure 1.1 Amounts of global energy consumption.
Solar
photovoltaic 3605
Off-grid solar for
Liquid biofuels 2063 energy access
Hydropower
2054
Wind energy
1160
Solar heating/
cooling 801
Solid biomass 787
Biogas
334
Geothermal
energy 94
Municipal and
industrial waste 41
CSP 34
Tide, wave and
1
ocean energy
0 500 1000 1500 2000 2500 3000 3500 4000
Jobs (thousands)
Figure 1.2 Global renewable energy employment indexed by technology. Source:

International Renewable Energy Agency [4]. © 2018, IRENA - International Renewable
Energy Agency.
of employment was 5.3% [4]. As shown in Figure 1.2, the top five employment in
the renewable energy sector on the list includes solar photovoltaic, liquid biofuels,
hydropower, wind energy, and solar heating.
Electricity has been considered as the most effective way to explore and utilize
various renewable energies effectively. Compared with other forms of energy,
electricity has many obvious advantages as follows [5]: (i) Convenience: electricity
can be easily transformed into the desired forms of energy, such as heat, light, and
mechanical energy. (ii) Easy control: electricity can simply be operated and tuned.
1.2 Development History of Electrochemical Energy Storage 3
Mobile devices Robots, AGV
Electric vehicles Aerospace
Renewable energy Industry
Figure 1.3 Application of electrochemical energy storage, AGV (automated guided

vehicles).
(iii) Flexibility: electricity can be easily transferred by transmission line. (iv) Cheap:
compared with other forms of energy, electricity is an economical form, which has
been widely used for domestic and industrial applications. (v) Low transmission
loss: electricity can be easily transmitted with high efficiency from the power plant
to the user.
Although electricity has many advantages, the renewable energy-based electricity
is quite fluctuating over time. For example, the clouds constantly alter the output of
solar energy systems and wind cannot blow at a fixed speed. Unfortunately, grid has
a fixed frequency of 50 Hz, which was determined by turbines in power plants. These
must be matched to avoid the fluctuation of grid. Therefore, the clean energy-based
electricity requires to be stored and delivered for commercial usage.
As a result, renewable energy calls for the development of electricity storage
devices. Among these various electrochemical energy storage systems, ECs and
various batteries have showed great potential not only in the powering portable
electronics but also in the transportation sector.
As shown in Figure 1.3, various electrochemical energy storage has been widely
used in every aspect in our daily life, such as aerospace (satellites, rockets, and air-
crafts), transportation (cars, trains, and ships), portable electronic gadgets (mobile
phones, laptops, and digital cameras), and industry fields [6]. The ever-growing
advancement of electrochemical energy storage technology has greatly promoted
the development of human society. It can be anticipated that electrochemical
energy storage materials and technology play more important role in human life.
1.2 Development History of Electrochemical Energy

Storage
As shown in Figure 1.4, the first electrochemical energy storage chemistry in history
is Baghdad battery, which consisted of a ceramic pot, a tube of copper, a rod of iron,
and vinegar electrolyte. This ancient battery has ∼2.0 volts of electricity [8].
4 1 Introduction
Baghdad battery
Iron head
Asphalt seal
Clay case
13.5 cm
Electrolyte chamber
Internal copper cylinder
www.aquiziam.com (C)
Figure 1.4 Replica of Baghdad battery found in Iraq. Source: Aquiziam [7].
The first modern battery was invented by the Italian scientist Volta in 1799, which
was called as “Volta pile.” This battery was a stack of Ag and Zn disks, and the metal
disks were separated by salt water-soaked cloth [9]. Volta found that the single pile
could only produce 1.0–2.0 volts of electricity. To increase the voltage output, several
“Volta piles” could be constructed side by side. The processes that occur in the device
were later demonstrated by Humphry Davy and Michael Faraday, which described
that it is the occurrence of chemical reactions that is responsible for the production
of electricity [9].
This finding marked the emergence of the electrochemistry. Consequently,
the research and development of various electrochemical energy storage systems
became active in the nineteenth and twentieth centuries.[10] The simple history of
electrochemical energy storage is shown in Figure 1.5.
1.3 Classification of Electrochemical Energy Storage

The electrochemical energy storage has almost penetrated every aspect in our daily
life, which can efficiently store and convert energy reversibly between chemical
energy and electrical energy in an environmentally friendly way.
There are many requirements that electrochemical energy storage needs to fulfill
for various application fields, such as portable electronics, electric vehicles (EVs),
and power tools. The main requirements for different electrochemical energy
storage include high gravimetric/volumetric energy density, long cycle life, low
cost, safety, and easy fabrication [11]. These attributes are mainly determined by the
intrinsic properties of the materials and chemistry constituting the electrochemical
1.3 Classification of Electrochemical Energy Storage 5
Figure 1.5 Development of various electrochemical energy storage.
Figure 1.6 Classification of

Electrochemical energy systems
electrochemical energy storage. EDLC,
electric double-layer capacitors.
Electrochemical
Batteries
capacitors
EDLC Primary batteries
Pseudocapacitors Secondary batteries
energy storage [12]. Based on the charge storage mechanism, the electrochemical
energy storage technology has two main categories: ECs and batteries, as shown in
Figure 1.6.
As shown in Figure 1.6, ECs have two mechanisms to store electricity: double-layer
capacitance and pseudocapacitance. Double-layer capacitance is based on ionic
adsorption, whereas pseudocapacitance is an electrochemical process. Electro-
chemical batteries have two broad categories, primary and secondary batteries. A
primary battery is one that cannot easily be recharged after one use. An example of
a primary battery is the dry cell, which was commonly used to power remotes and
clocks. In such cells, a Zn container acts as the negative and a carbon rod acts as
the positive. A secondary battery can be recharged to their original pre-discharge
status, such as LIBs, NiCd, and NiMH batteries.
6 1 Introduction
1.4 LIBs and ECs: An Appropriate Electrochemical

Energy Storage
Batteries can store energy through reversible redox reactions in the bulk phase elec-
trodes, whereas ECs can store amounts of energy at the electrolyte–electrode inter-
face or through redox reactions on the surface of electrode [13, 14]. As shown in
Figure 1.7, a battery usually deliver higher energy density and lower power density
than that of ECs, whereas ECs are advantageous and potential candidates in a wide
range of applications due to their high power densities (>10 kW kg−1 ), exceptional
reversibility (90–95%), and ultra-long life span (>100 000 cycles) [15].
Among various secondary batteries, such as Pb-acid, Ni-Cd, and NiMH batteries,
LIBs possess higher energy density and cycle life and have reasonably attracted the
biggest commercial and research interest. LIBs have been widely used to power the
portable electronics and have also enabled the rapid development of EVs and renew-
able energy sources. Compared with other secondary batteries, LIBs show many
outstanding properties, such as high voltage and energy density, better cycle life,
light weight, and low self-discharge rate [16]. Therefore, the development of LIBs
has been a hotspot both in industry and in academy. In 2019, the Noble Prize in
Chemistry rewards the study of the LIBs to Drs. M. Stanley Whittingham, John B.
Goodenough, and Akira Yoshino.
The LIBs concept emerged in the 1970s and was finally commercialized by Sony
in the 1990s [17, 18]. The foundation of LIB began during the oil crisis by Stanley
Whittingham, who found that TiS2 can accommodate lithium ions at a molecular
level [19–21].
107
Capacitors
106
105
Power density (W kg–1)
104
103 Electrochemical
capacitors
102
Batteries Fuel
10 cells
1
10–2 10–1 1 10 102 103
Energy density (Wh kg–1)
Figure 1.7 Power density as a function of energy density for various electrochemical
energy storage. Source: Libich et al. [13].
1.4 LIBs and ECs: An Appropriate Electrochemical Energy Storage 7
Lithium is the lightest metal (relative atomic weight is 6.94), and it has the lowest
potential (−3.04 vs. standard hydrogen electrode, SHE); this property enables LIBs
with higher energy density than that of other secondary battery [22]. Since 1970s,
metallic lithium has been used as the negative material for lithium primary batteries.
Unfortunately, metallic lithium is not suitable for secondary lithium batteries due to
the uncontrolled lithium dendrite during cycling, which can pierce the separators to
cause inner short-circuit, eventually causing smoking, firing, and explosion [23, 24].
The basic concept of “Rocking chair battery” was proposed in the late 1970s,
which used a layer compound to replace the common lithium metal as negative
electrode [16, 25]. In this configuration, lithium exists in an ionic state rather
than a metal state; the lithium deposition can be greatly suppressed during
the electrochemical process. Therefore, the safety of battery can be remarkably
improved. According to this concept, Megahed and Scrosati [26] used LiWO2 as
the negative, V2 O5 as the positive, and 1 mol l−1 LiClO4 /PC (propylene carbonate)
as the electrolyte to confirm this rocking chair battery concept. However, the
obtained LIB still showed low specific capacity and poor cycling, which failed
to be commercialized. When a metal oxide rather than a metal sulfide acted as
the positive, Dr. John Goodenough predicted that the positive may have greater
potential. After a systematic investigation, he showed that LiCoO2 can produce as
high as four volts potential in 1980 [27]. The finding of LiCoO2 was a revolutionary
breakthrough and would result in more powerful batteries. In 1986, Auborn and
Barberio [28] also assembled an LIB with LiCoO2 as the positive electrode, MoO2 as
the negative electrode, and 1 mol l−1 LiPF6 /PC as the organic electrolyte. However,
this battery has the intrinsic problems, such as low operating voltage and sluggish
diffusion of lithium ions in the negative electrode.
In the following years, the research and development of LIBs did not make
significant progress. Until 1985, with the positive of Goodenough as a basis, Akira
Yoshino constructed the first commercial LIB. Rather than the reactive metal
lithium as the negative, petroleum coke was used as the negative electrode and
LiCoO2 acted as the positive electrode to construct a new, high-voltage LIB [16].
This combination of positive and negative materials greatly extended the cycle life
of LIBs and significantly improved its safety and voltage. This innovative design
opened the door for the large-scale commercialization of LIBs, which has been
regarded as a milestone in the history.
Since its commercialization in 1991, LIBs have entered every aspect in our daily
life and are the foundation of a wireless, fossil fuel-free society. The better LIBs have
been an ongoing goal to satisfy future demands ranging from small-scale consumer
electronics to large-scale EVs and grid storage. As shown in Figure 1.8, the energy
density of 18 650 cylindrical cells slowly increased from ∼70 to ∼300 Wh kg−1 [29].
Nowadays, LIBs of 240–300 Wh kg−1 level have been commercialized and widely
used in EVs. To develop better LIBs, major countries in the world have been
invested lots of resources to conduct extensive and in-depth research in this
field. For example, the “Battery 500” project was supported by the Department of
Energy of United States to set a goal to achieve 500 Wh kg−1 in 2021. The “New Gen-
eration Battery” plan was also funded by New Energy and Industrial Technology
8 1 Introduction
Figure 1.8 The history, current status, and development of LIBs. (NEDO, The New Energy
and Industrial Technology Development Organization; GP, graphite; LFP, LiFePO4 ; NCM333,
LiNi1/3 Co1/3 Mn1/3 O2 ; CATL, Contemporary Amperex Technology, Co. Ltd., Ningde, China; BYD,
BYD Company Limited, Shenzhen, China; SKI, SK Innovation Co., LTD., Korea.)
Development Organization (NEDO) of Japan and planned to achieve 500 Wh kg−1

in 2030. In China, “Strategic Priority Research Program for Electric Vehicles with
long range” was released by the Chinese Academy of Sciences (CAS). “Made
in China 2025” project launched by the Chinese government set a goal to
achieve 300 and 400 Wh kg−1 of LIBs in 2020 and 2025, respectively (as shown in
Figure 1.8) [29].
In summary, a better volumetric/gravimetric energy density, lower cost, better
safety, and cycle life are still important requirements to power mobile devices and
improve the driving range of EVs. On the other hand, various renewable energies
also require to be stored and delivered for commercial applications. In summary,
these two problems call for developing appropriate LIBs to meet these requirements.
Figure 1.9 shows the general trends for the present automobile battery research
and development objectives with respect to the employed materials of negative, elec-
trolyte, and positive. As shown in Figure 1.9, the energy density of first-generation
LIBs for EVs is ∼130 Wh kg−1 , which is based on LiCoO2 , LiFePO4 , LiMn2 O4 ,
and graphite materials. By far, the second-generation LIBs, which are based on
the high-capacity LiNix Mny Coz O2 (NMC) or LiNi0.8 Co0.15 Al0.05 O2 (NCA)-positive
[31] and graphite materials, normally show practical energy densities up to c.
240 Wh kg−1 and was subsequently commercialized in TESLA Model S, shown
in Figure 1.9. According to both Department of Energy (DOE) and SPRP (Strate-
gic Priority Research Program) projects, a 400 Wh kg−1 is the roof-top in the
third-generation LIBs due to the limitation in the capacity of conventional LIBs
configuration. To achieve higher energy density, post LIBs chemistry has also been
investigated, such as Li-S, Li-Air, and other systems.
ECs are another important electrochemical energy storage devices, which first
appeared in the middle of the twentieth century. Generally, ECs can be regarded as
a complementary role for LIBs. In 1957, the first type of ECs was invented by Becker
of General Electric. It was found that its capacitance is considerably higher than
1.4 LIBs and ECs: An Appropriate Electrochemical Energy Storage 9
DOE: US department of energy

SPRP goals
SPRP: Strategic priority research program,
Chinese academy of sciences
DOE goals
Next generation batteries: Post LIBs

Post Li-ion battery (Li-O2 or Li-S): > 3000 wh kg–1, > 3000 wh l–1 (Li-O2, DOE Expected)
: 560 wh kg–1 (Li-S); 526 wh kg–1 (Li-O2) SPRP 2016 2020-203X
ca. 400 wh kg–1
Si/C anode with High-Voltage Si/C anode with High-voltage 3rd Generation–LIBs
cathode energy density: 300–400 cathode energy density: 300 wh kg–1
wh kg–1, 800–1200 wh l–1 (cell) / 2000 cycles Under research 2018–2020
Graphite/NCA or NMC Graphite/NCA 2nd Generation LIBs

Energy density: Energy density: 180 wh kg–1, (cell)/
220 wh kg–1, 600 wh l–1 150 wh kg–1 (Package) Achieved by 2014–2015
Tesla model S
Graphite/Spinel or Phosphate 1st Generation LIBs

Energy density:
130 wh kg–1 Achieved by 2012–2013
Nissan LEAF BYD e6
Figure 1.9 Progress of battery technologies based on DOE and SPRP projects. Source:
Hong et al. [30]. Reproduced with permission of Wiley.
conventional capacitor due to the high specific surface area of porous carbon [13].
In 1969, a non-aqueous electrolyte was used in porous carbon-based ECs by Sohio,
which enhanced the upper potential to 3 V [32]. Then in 1971, the capacitance behav-
ior of RuO2 films was investigated by Trasatti and Buzzanca et al. [33]. In 1980s,
Conway et al. [32, 34, 35] also conducted lots of investigations on the RuO2 type of
EC, which shows a surface-redox pseudocapacitance. This field has been very active
since about 1990s. Among various materials, carbon materials with high specific
surface area, including activated carbons (ACs), carbon aerogels, carbon nanotubes
(CNTs), and graphene, are unique class of materials for electric double-layer capac-
itors (EDLC)-type ECs and have been applied and investigated [36–38].
The energy storage mechanism in ECs takes place through either ion adsorption
at the electrode/electrolyte interface or reversible faradaic reactions [13, 32, 39].
Based on their mechanisms of charge storage, ECs are classified into four broad
categories. The first type includes electric double-layer capacitors or so-called
EDLC ECs. The second type is pseudocapacitors or Faradaic ECs, which is based on
reversible Faradic reactions. The third is called hybrid ECs. Hybrid ECs combines
both previous EDLC and pseudocapacitors. The fourth category represents hybrid
EC-LIBs devices, which is based on the combination of ECs, reversible faradic
reactions, and LIB-type materials [40].
In Chapter 2, we will also give a brief introduction toward the mechanism of ECs.
Table 1.1 shows summarization and comparisons of the important performances
between LIBs and ECs. The important performances include energy and power
density, self-discharge rate, cycle life, and the working temperatures. ECs can
produce ultra-high power density and cycle performances, whereas LIBs usually
possess higher gravimetric/volumetric energy density.
10 1 Introduction
Table 1.1 Comparison between ECs and LIBs.
Performances ECs LIBs

EDLC EC Pseudo EC Hybrid EC
Charge time (s) 1–10 1–10 100 600

Cycle performance 1 000 000 100 000 500 000 500–2000
Cell voltage (V) 0–2.7 2.3–2.8 2.3–2.8 3.6
Energy density (Wh kg−1 ) 3–5 10 180 250
Price (USD/kWh) –10 000 –10 000 –140
Operating temperature (∘ C) −40–65 −40–65 −40–65 −20–60
Self-discharge per month (%) 60 60 4
Electrolytes Aprotic/protic Protic Aprotic Aprotic
Source: Libich et al. [13].
Based on Table 1.1, ECs and LIBs can provide unique solution to the electro-
chemical energy storage and could be considered as complementary technologies.
Therefore, LIBs and ECs are the dominant electrochemical energy storage systems
in modern society.
Performances of LIBs and ECs strongly linked with the electrode materials used.
With the booming development of materials, the performance of LIBs and ECs has
also been progressing rapidly. In Chapter 2, the main part will be focused on mate-
rials of LIBs and ECs as the current advanced electrochemical energy storage.
1.5 Summary and Outlook

Renewable energy sources, such as wind, solar tide, and geothermal, become
extremely important in our modern society. Renewable energy sources must be first
converted to secondary electricity before utilization. Therefore, developing elec-
tricity storage systems can be available to meet demand whenever needed would
be the breakthrough in electricity distribution. Among electrochemical energy
storage systems, ECs and LIBs have displayed great potential not only in portable
electronics but also in the renewable energy transportation sector. ECs and LIBs
have their own advantages; ECs can produce ultra-high power density and cycle
life, whereas LIBs usually possess higher gravimetric/volumetric energy density.
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15
Materials and Fabrication
As stated in Chapter 1, lithium ion batteries (LIBs) and electrochemical capacitors

(ECs) have been widely investigated and utilized as power sources for various appli-
cations. The innovative materials and fabrications are crucial and required for devel-
oping and manufacturing next-generation high-performance LIBs and ECs. In this
chapter, we present a comprehensive introduction for the developments of innova-
tive materials, architectures, and design considerations in the electrode and cell con-
figurations of LIBs and ECs, together with the recent technologies used to achieve
these novel designs.
2.1 Mechanisms and Advantages of LIBs

2.1.1 Principles
A LIB consists of two electrodes, the negative and the positive, which are separated
by a polymer separator soaked in liquid electrolytes with lithium salt, as shown in
Figure 2.1. The principle of LIBs can be summarized as follows: (i) During charg-
ing process, Li+ is deintercalated from the positive material, then passed through
the liquid electrolyte, and inserted into the negative; (ii) during the discharge pro-
cess, Li+ is removed from the negative and then reinserted into the positive. That
is to say, the rocking-chair-type LIB is a Li+ concentration gradient battery. Dur-
ing charging/discharging process, the Li+ continuously shuttles between the high
concentration and the low concentration part. The positive and negative electrodes
undergo redox reaction, respectively, which is shown in Figure 2.1. Take a typical
LiCoO2 ||C system as an example, the overall electrochemical reaction is as follows:
Positive reaction ∶ LiCoO2 = CoO2 + x Li+ + xe−
Negative reaction ∶ 6C + x Li+ + x e− = Lix C6
All reaction ∶ 6C + LiCoO2 = Li1−x CoO2 + Lix C6
In a typical LIB with LiCoO2 positive, the total electrochemical reaction is
usually reversible for a portion of lithium, which limits the depth of discharge.
The LIB chemistry was first developed by Sony in 1990s. It can be seen from the
Novel Electrochemical Energy Storage Devices: Materials, Architectures, and Future Trends,
First Edition. Feng Li, Lei Wen, and Hui-ming Cheng.
© 2021 WILEY-VCH GmbH. Published 2021 by WILEY-VCH GmbH.
16 2 Materials and Fabrication
e–
– +
Cu AI
Li+
Separator
Anode Electrolyte Cathode

(graphite) (LiCoO2)
Figure 2.1 Mechanisms of a LIB (LiCoO2 | Li+ electrolyte | graphite). Source: Goodenough
and Park [1].
aforementioned reaction that the energy density of a LIB is determined by the Gibbs
free energy change during the entire reaction. Therefore, the choice of suitable
materials is the basis for the development of high-performance LIBs.
As shown in Figure 2.2, currently, the commercial cells mostly include cylindrical
cells, prismatic cells, and pouch cells. The cylindrical cells with the standard size
18650 are the typical products in the market. 18650 stands for the cell with 18 mm
in diameter by 65 mm in length, and 0 means the shape of the cells is cylindrical.
The prismatic and pouch-type LIBs are also widely used in various applications
due to their small inactive volume and high design freedom at the module level.
Compared with the cylindrical cells, the size of prismatic and pouch cells is easy
to customize for the final product. As depicted in Figure 2.2, inside the cell,
negative–separator–positive are stacked or wound together to yield the core, in
which the negative material and positive material are coated on both sides of
current collectors, respectively [2].
2.1.2 Advantages and Disadvantages

Similar to other batteries, the electrode materials determine the performance of
LIBs, such as capacity, power density, and safety. For example, LIBs based on
LiCoO2 positive provide higher capacity but poor safety due to its poor thermal
stability. LiFePO4 is another important positive material for LIBs, which has
4–5 times longer cycle lifetimes, 8–10 times power density, and wider operating
temperature range compared with LiCoO2 [3].
Although the properties of LIB vary from material to material, LIB has some
common characteristics. Their main advantages compared with other rechargeable
batteries are: (i) high energy density, which makes LIBs more practical in portable
electronic devices. (ii) Low self-discharge rate (∼1.5% per month), which means that
2.1 Mechanisms and Advantages of LIBs 17
Separators Cathode
Separators
Anode
Can Cathode Anode Can
(a) Cylindrical (b) Prismatic
Exterior 300 mm
m m 265 mm
0m m
10 90
Thickness: 10 mm
Pouch
n Stacks of
Separator
anode–separator–cathode
Cathode
Separator
Anode
Pouch
(c) Pouch
Figure 2.2 Three typical cell architectures. (a) Cylindrical cell, (b) prismatic cell, and (c)
pouch cell. Source: Choi et al. [2].
the cell has a longer shelf life. (iii) Low memory effect: LIB has almost zero memory
effect, which is a well-known phenomenon observed in Ni–Cd and NiMH batteries.
Ni–Cd or NiMH batteries may gradually lose usable capacity when repeatedly
recharged after being only partially discharged. (iv) Quick charging speed: LIBs has
obvious higher charger rates compared with other secondary battery systems. (v)
High working voltage: The open-circuit voltage of LIB is higher than other aqueous
batteries, such as lead acid, NiCd, and NiMH batteries. (vi) Long life span: LIB can
be charged/discharged over hundreds of cycles, and the LIBs can be 80% of their
original capacity even after several thousand cycles.
Disadvantages of LIBs are as follows: (i) Expensive: Generally, LIB is more expen-
sive than the other batteries due to its complexity of manufacture and additional
on-board circuitry. (ii) Sensitive to temperature: For LIB, heat usually causes the
cells to degrade faster than they normally would be. Although LIBs have a wide
working temperature range (−20 to 65 ∘ C), the recommended working and storing
temperature for the most LIBs is around 15–25 ∘ C. For example, LiFePO4 batteries
must not be charged at temperatures below zero due to sluggish ionic kinetics,
and LiMn2 O4 batteries must not be worked at higher than 55 ∘ C due to severe
capacity fading caused by manganese dissolution. (iii) Aging effect: LIB is able
to operate several thousand charge/discharge cycles. However, an unused LIB is
not completely durable because it starts the degradation after manufacturing. (iv)
Safety issues: LIB can be fired or exploded under overheating, overcharging, short
circuit, or other abuse condition.
2.2 Mechanisms and Advantages of ECs

2.2.1 Categories
Generally, ECs also consist of two electrodes, which are separate by a membrane
separator within the electrolyte. The performance of EC is mainly determined by the
electrode materials [4]. The energy storage mechanism in ECs takes place through
either ion adsorption at the electrode–electrolyte interface or reversible Faradaic
processes on the surface [5]. Based on the mechanisms of charge storage, as stated
in Chapter 1, ECs are classified into four broad categories. The first category of
ECs includes electric double-layer capacitors or the so-called electric double layer
capacitors (EDLCs). The second category includes pseudocapacitors or Faradaic
ECs, which is based on reversible Faradic reactions. The third includes hybrid ECs.
The fourth category represents hybrid EC-LIBs devices, which is based on the com-
bination of ECs, reversible Faradic reactions, and intercalation-type materials [4].
2.2.2 EDLCs
EDLCs store charge through adsorption of ions by making use of an electrical double
layer of charge developed at the electrode/electrolyte interface [6].
This kind of charge storage involves only nanometer distances and interaction
allowing EDLCs to charge or discharge fully in seconds [7]. It is generally believed
that the electrode materials for EDLCs require the highly accessible specific surface
area with high electrical conductivity. The most investigated and favorable materials
for EDLCs are mainly porous carbon materials, such as carbon nanotubes (CNTs),
activated carbon, and graphenes [8].
Figure 2.3 illustrates three models in order to explain EDLs. As shown in
Figure 2.3a, Helmholtz model is the simplest model to explain the spatial charge
distribution on the interface between two layers. The charge of the solid electronic
conductor is neutralized by oppositely charged ions at a d distance from the surface
to the center of the ions. Gouy and Chapman developed theories of the diffuse
layer, in which the ion concentration in the solution near the surface follows the
Boltzmann distribution [9]. Combining both previous models, Stern improved
the model showing that the ions have a finite size, giving an internal Stern layer
(Helmholtz layer) and an outer diffuse layer (Gouy–Chapman layer). In Figure 2.3b,
– – –
Ψ0 + Ψ0 + – Ψ0 +
+ – + + –
– –
POSITIVELY CHARGED SURFACE

+ – + +
+
+Ψ – + – + –
+ – + +
– – + –
+ – + +
–
+ – + – – + – –
+ – + – +
–
+ – + + + +
Ψ
+ – + +
– +
+ – + – – + – –
+ – + – +
+ – + – – + + –
– Ψ –
+ + +
– –
+ – + + + –
–
– IHP OHP
d Diffuse layer Stern layer Diffuse layer
(a) (b) (c)
+ Solvated cation – Anion
Figure 2.3 EDL models. (a) Helmholtz, (b) Gouy–Chapman, and (c) Stern models . Source:
Zhang and Zhao [8].
c, ψ is the potential, ψ 0 is the electrode potential, IHP is the inner Helmholtz plane,
and OHP is the outer Helmholtz plane explained in the Stern model [8, 10].
Nowadays, Stern model has been considered as a typical description for EDL
inside the solid/liquid electrode interface. Recently, this model was further mod-
ulated to be available for the solid/solid interfacial one by our group [11]. A
solid/solid electrode interface often exists in the organic electrolyte-based systems
due to the decomposition products of electrolyte or additive depositing on electrode
surface. The formation of the solid/solid interface can effectively widen the stable
voltage window of electrode. The modulated EDL is shown in the Figure 2.4, which
has the same structure as Stern model that is composed of an internal Helmholtz
layer and an outer diffuse layer. However, because of the ionic conduction and
electronic insulation of solid electrolyte interface layer, this EDL is established by
desolvated ions. This model can successfully explain the phenomenon that: First,
the capacitance of electrodes increases after the solid/solid interface was formed,
which is attributed to a shorter separated distance (d) of Helmholtz layer inside this
interface; second, self-discharge rate of electrodes also decreases after a solid/solid
interface was formed due to the stronger interaction force between the electrode
surface and electrolyte ions inside this interface [11].
EDLC uses a liquid ion electrolyte instead of a solid insulating dielectric as the
dielectric layer to store electric charges by forming an EDL on the surface of the
electrode/electrolyte. In the simplest configuration, an EDLC consists of two elec-
trodes immersed into an electrolyte and separated by separators.
Figure 2.4 EDL model inside a solid/solid

electrode interface. Source: Wang et al. [11].
Electrode
Helmholtz Diffusion
layer (H) layer (D)
PF6– Li+ Solvents
Charge storage mechanism in the EDLC is non-Faradaic. EDLC exhibits high

energy density compared with conventional capacitors due to their very small
charge separation distances and maximum effective surface space.
2.2.3 Pseudocapacitor
Owing to the electrostatic type of charge storage at the interfaces, EDLCs show excel-
lent cyclic stability, which is useful in various applications ranging from hybrid vehi-
cles to portable electronics [12]. However, EDLCs can still not satisfy the require-
ments for high energy density. The most common strategy to increase their energy
storage capability is the integration of electrode materials that utilize fast Faradaic
redox reactions, such as transition metal compounds, redox-active polymers, and
hydroxides [13]. It was found that reversible redox reactions at the surface of appro-
priate materials show EDLC-like electrochemical features [14, 15]. Pseudocapacitor
(or Faradaic capacitor) has totally different energy storage mechanism with EDLC.
It involves reversible redox reactions on the electrode surface without bulk phase
transformation. Generally, pseudocapacitors develop a different type of capacitance
at the electrodes where the Faradaic charge depends linearly on the applied voltage
exhibiting a capacitor-like behavior known as “pseudocapacitance,” which resem-
bles a battery behavior but is different from the capacitive behavior of EDLCs [16].
Pseudocapacitive materials show the potential to obtain battery-level energy density
combined with the power density and cycle life of EDLCs [15].
The characteristic behavior of different energy storage materials was summa-
rized by Lukatskaya et al. [17]. As shown in Figure 2.5a, carbon-based EDLC
shows nearly rectangular cyclic voltammetry (CV) curves and linear galvanostatic
charge/discharge profiles.
Unlike EDLCs, the phase transformation of the active material usually occurs
during charge/discharge in the batteries, which can be characterized by distinct
peaks in the CV and voltage plateaus in the charge/discharge curves as shown in
Figure 2.5d. In contrast, without the phase transition, the pseudocapacitive mate-
rials present a continuous, highly reversible change in the oxidation state during
charge/discharge, characterized by CVs with either significantly broadened peaks
(intercalation pseudocapacitance, for example: T-Nb2 O5, Figure 2.5c) and little sep-
aration in peak position during charge/discharge or almost perfectly rectangular
CVs (surface redox due to adsorption and/or fast intercalation of ions (for example:
Electrical double Surface redox Intercalation

Battery
layer capacitor Pseudocapacitor
Current (i)
Current (i)
Current (i)
Current (i)
Potential (V) Potential (V) Potential (V) Potential (V)
Potential (V)
Potential (V)
Potential (V)
Potential (V)
50 nm 50 nm 50 nm 5 nm
Bulk
Bulk Bulk Bulk
0 0.5 1 Q/Qmax 0 0.5 1 Q/Qmax 0 0.5 1 Q/Qmax 0 0.5 1 Q/Qmax
Mechanism
No phase change No phase change No phase change Phase change
Continuous change in Intercalation + change in Intercalation + change in
Reversible ion adsorption
oxidation state oxidation state oxidation state
Intrinsic kinetics
i~v i~v i~v i~v0.5
Typical systems
High specific surface area Transition metal

Transition metal
materials. chemistry; specific High theoretical capacity.
chemistry, large
Example: Porous carbons structures. Example: LiCoO2, Si,
channeled structures.
(CDC, activated cabon), Example: RuO2 (hydrated), LiFePO4
Examples: T-Nb2O5
graphene, carbon onions birnessite MnO2, 2D Ti3C2
Porous carbon Birnessite MnO2 T-Nb2O5 LiFePO4
Challenges: Rapid ion access to each active site
(a) (b) (c) (d)
Figure 2.5 Characteristic behaviors, such as CV, galvanostatic curves, mechanisms of

typical materials. Source: Lukatskaya et al. [17]. Licensed under CC-BY-4.0.
hydrated RuO2 , birnessite MnO2 and MXene Ti3 C2 , Figure 2.5b) [18, 19]. It must be
noted that pseudocapacitance is commonly associated with surface or near-surface
reversible redox reactions. However, it was recently demonstrated that a pseudoca-
pacitive mechanism often occurs when conventional battery materials are down-
sized to nanosized particles, even for the typical LiCoO2 positive [20].
2.2.4 Hybrid Capacitors

Figure 2.6 shows the charge storage mechanisms of different hybrid capacitors.
Figure 2.6a shows the plot of the electrode potentials (V+ and V− ) and cell potential
(V) vs. specific capacity for symmetric (blue lines) and hybrid (red lines) configura-
tions. Figure 2.6b is the typical symmetric configuration with activated carbon as
both positive and negative electrodes. Figure 2.6c is the example of hybrid device
consisting of an insertion metal oxide (MeO) negative combined with a high surface
area of activated carbon positive (AC in the figure) [21].
The hybrid capacitors, which are the combination of EDLC and pseudo-
capacitor, have more enhanced performance. Contrary to the EDLC and the
5
Oxidative decomposition of electrolyte
+ –
+ –
+ –
4 AC +
–
+
–
+
Potential (V vs. Li/Li+)
–
–
+
3
AC AC
2 AC
Li
Li+
– –
Li+ –
Li+ –
Li+ –
Li+
Li4Ti5O12 (1.55 V) Li+
– –
1 Li+
Li+ – –
Reductive decomposition of electrolyte Li+ –
Li4Ti5O12 AC
0
0 10 20 30 40
Specific capacity (mAh g–1)
Figure 2.6 Hybrid capacitors and symmetric ECs, AC, activated carbon; Source: Naoi et al.
[21].
pseudocapacitor using symmetric design, the hybrid capacitor with asymmetric

electrode configuration delivers higher specific capacitance associated with differ-
ent storage mechanisms [21]. The two electrodes work with different mechanisms,
which can effectively improve the working voltage range (Figure 2.6a), obviously
improve the electrochemical performance, especially the energy density. In a typical
hybrid capacitor, one of the electrodes is typically a pseudocapacitor electrode or
battery-type electrode providing high energy density (Figure 2.6c).
The hybrid capacitor is referred to as a lithium ion capacitor when the LIB-type
electrolyte is used. Lithium ion capacitor combines the advantages of both LIB and
EC. However, it is still a great challenge to balance the reaction kinetics between
capacitive materials and intercalation-type electrodes [22, 23]. Due to the excellent
electrochemical performances of graphene, the dual-graphene-based lithium ion
capacitor has attracted wide attention. Recently, a dual-graphene-based lithium ion
capacitor was proposed by charge injection strategy to maximize the energy density
[24]. The hybrid capacitor showed the great potential for practical applications due
to its energy density as battery with high power output and long cycle ability.
In comparison to the present LIBs, the ECs, including EDLC, pseudocapacitor,
and hybrid EC can deliver much greater power density and cycle life.
2.3 Roadmap of Conventional Materials for LIBs

Like any other batteries, there are four core components inside a LIB, including pos-
itive and negative to supply and store Li+ , respectively, an electrolyte to transfer Li+ ,
and a polymer separator to keep the electrodes electronically separate.
Figure 2.7 indicates the current material status of LIBs. The upper section above
the dash line corresponds to positive materials, while the lower part contains various
5
LiMn2O4 NMC/NCA
4 LiCoO2
Voltage (V vs. Li+Li)
LiFePO4
3
2
Li4Ti5O12 Metal oxides
1 Si
Graphite Metal Li
0
0 200 400 3400 3600 3800
Specific capacity (mAhg–1)
Figure 2.7 Specific capacities and working voltages of different materials.
negative materials. For example, the potential of LiFePO4 and Li4 Ti5 O12 is ∼3.5V
and ∼1.5V, respectively. Therefore, the voltage of a LiFePO4 //Li4 Ti5 O12 battery
is 2.0V. The positive materials (LiCoO2 , LiMn2 O4 , LiFePO4 , LiNix Coy Mn1−x−y O2 ,
etc.) currently applied in commercial batteries allow for a nominal voltage of
∼4 V [25]. The upper limit of the electrochemical window of the electrolyte (alkyl
carbonates/LiPF6 ) is about 5.0 V (vs. Li/Li+ ). While the negative materials in
Figure 2.7 indicate four most promising groups: (i) graphite, (ii) tin and Si-based
composites, (iii) metal oxides, and (iv) Li4 Ti5 O12 electrodes. Due to its flat voltage
potential, graphite has been widely used for commercial LIBs. In the following
section, we give a brief introduction toward various materials for LIBs.
2.4 Typical Positive Materials for LIBs

As a key component of LIBs, the ideal positive material should have the following
properties: (i) higher redox potential to ensure higher operating voltage; (ii) high
lithium storage capacity; (iii) stable crystal structure to maintain long cycle life; (iv)
high electronic and ionic conductivity to reduce the polarization; (v) good chemical
stability and electrolyte compatibility; (vi) simple fabrication process, rich source
of raw materials, and pollution-free. Currently, the dominant commercial positive
materials mainly include LiCoO2 , LiNiO2 , LiMn2 O4 , LiFePO4 , LiNix Coy Mn1−x−y O2 ,
and their derivatives [26].
2.4.1 LiCoO2 Materials

The layered rock-salt structured LiCoO2 was recognized as the first viable positive
material by Goodenough et al. [27, 28] in 1980, then successfully commercialized by
Sony in 1991. Until now, LiCoO2 is still the most preferred positive active material
Figure 2.8 Crystal lattice structure of layered

LiCoO2 and LiNiO2 with R3m group.
a b
due to its superior cycle stability, excellent reversibility, high capacity, high volume
energy density, and easy preparation.
In the layered structured LiCoO2 , the Co ions are surrounded by six oxygen ions.
The Li and Co ions are located in alternating planes, separated by oxygen layers as
shown in Figure 2.8. The layered LiCoO2 possesses R3m space group and is indexed
to a hexagonal crystal-type structure [28]. LiCoO2 has excellent electrochemical
cycling performance between 3.5 and 4.2 V and possesses high theoretical capacity
up to 274 mAh g−1 [28]. However, the practical capacity can only reach half the
theoretical capacity because the reversible delithiation is limited to 0.5Li per LiCoO2
for safety reasons [29].
As shown in Figure 2.9, LiCoO2 has gradual phase transitions from H1 to H2, M1,
H3, M2, and O1 phases. These phase transitions cause large anisotropic expansion
14.5
H3 H2
M1 H1 4.5
14.0
4.2
13.5
M2 H2
M1/M2 3.9
H1
a (Å)
c (Å)
LiCoO2 LixCoO2
13.0 O1 E
Co3+(4s0: a*1g) (4p0: t*1u)–O2–(2p6) 3.6
Evac Evac
eϕLCO=
12.5 5.0 ± 0.1 eV
Co3+(d 6: e*g)–O2–(2p6)
1.3 ± 0.1 eV
μ=EF Δμ
ΔE=0.2 eV
3.3
1.1 ± 0.1 eV μ=EF(4.2 V)
Co3+(d 6: t2g) 0.8 ± 0.1 eV
Co3+/4+(t2g)
O2–(2p6) O2–(2p6)
12.0 3.0
O1 H3 N (ε) N (ε)
11.5 2.7
0.0 0.2 0.4 0.6 0.8 1.0
x in LixCoO2
Figure 2.9 The variations in the a and c lattice parameters and phase transitions during
Li+ extraction from LiCoO2 . Source: Wang et al. [27].
and contraction [30]. As a result, the anisotropic dimensional change causes uneven
stress and mechanical fracture within the particles.
Therefore, the excessive deintercalation of Li+ over 0.5 per LiCoO2 leads to the
crystal instability of LiCoO2 structure, which causes the cobalt atoms to migrate from
the plane to the neighboring plane where the lithium atoms are located.
In order to improve the crystal stability and increase the upper voltage limit, many
strategies have been used [27]. For example, a La–Al co-doping was used to solve the
issue of instability and increase the capacity of LiCoO2 at 4.5 V [31]. The dopants are
found to reside in the crystal lattice of LiCoO2 , where La works as a pillar to increase
the c-axis distance. Al acts as a positively charged center, which facilitates Li+ diffu-
sion, stabilizes the structure, and suppresses the phase transition during cycling at
4.5 V. In another work, the trace Ti–Mg–Al codoping improved the cycling perfor-
mance of LiCoO2 at 4.6 V (vs. Li/Li+ ) [32]. Mg and Al doping inhibits the undesired
phase transition at voltages above 4.5 V. Even in trace doping, Ti can segregate obvi-
ously at the grain boundaries and modify the microstructure of the particles.
Generally, the commercial LiCoO2 is prepared via a solid-state reaction between
Co3 O4 and Li2 CO3 at high temperatures. To improve the electrochemical perfor-
mance, many modification methods have been used, which mainly include elemen-
tal doping, surface, and coating [27, 33, 34]. Some of the major obstacles for its wide
application in EV and hybrid electric vehicle (HEV) field are its high cost, poor safety,
limited cobalt resources on earth, and toxicity [35].
2.4.2 LiNiO2 and Its Derivatives

Due to their high energy densities, the nickel-rich positive materials have been dom-
inated in EV market [36].
LiNiO2 has layered structure similar to LiCoO2 with R3m space group, as shown
in Figure 2.8 [37]. Compared with LiCoO2 , LiNiO2 has a higher theoretical capacity
with lower cost, which was actively investigated as a high-capacity positive material
to replace LiCoO2 for LIBs since 1990s [38]. The actual capacity of LiNiO2 can reach
190–210 mAh g−1 between 2.5 and 4.1 V. However, LiNiO2 also has severe issues,
such as low thermal stability, difficult to synthesize, and less ordered structure, com-
pared to LiCoO2 . LiNiO2 also has poorer cycle performance when it was charged to
the higher voltage of above 4.3 V [39]. Cationic mixing also usually takes place in the
LiNiO2 crystal structure, where Li layers are occupied by Ni2+ . This Li+ /Ni2+ mix-
ing usually results in sluggish Li+ transportation kinetics during the electrochemical
reaction [38].
To reduce the capacity fading during cycling, the nickel in LiNiO2 was sub-
stituted by manganese and cobalt to yield LiNix Mny Co1−x−y O2 [40]. One of the
most successful candidates of this group is LiNi0.8 Mn0.1 Co0.1 O2 positive, which
was called NCM811. In LiNix Coy Mnz O2 , the valency of the nickel, cobalt, and
manganese cation is usually divalent, trivalent, and tetravalent, respectively. The
electrochemically inert tetravalent manganese provides acceptable safety during
charge/discharge. Trivalent cobalt can ensure the high electric conductivity and
alleviate cation disorder. The redox couple of Ni2+ /4+ and Co3+ /4+ can achieve
the capacity over 200 mAh g−1 at 4.3 V [36]. This material not only delivers higher
Another random document with
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plenty of evidence that the object of the burglary was to secure a
sight of this will.”
Jimmy was unperturbed at the scarcely-veiled charge, and if he
moved it was only with the object of taking up an easier position in
the chair. Not even the shocked eyes of the girl that looked
appealingly toward him caused him any apparent uneasiness.
“Go on,” he said, as the lawyer paused as though waiting for an
admission. He was quietly amused. He knew very well now who this
considerate burglar was.
“By copying this will the burglar or burglars obtained an unfair
advantage over the other legatee or legatees.”
The stiff paper crackled noisily as he unfolded the document in his
hand.
“I will formally read the will and afterwards explain it to such of you
as need the explanation,” Spedding resumed.
The girl listened as the lawyer began to read. Confused by the legal
terminology, the endless repetitions, and the chaotic verbiage of the
instrument, she yet realized as the reading went on that this last will
and testament of old Reale was something extraordinary. There was
mention of houses and estates, freeholds and bonds ... “... and all
the residue of any property whatsoever and wheresoever absolutely”
that went to somebody. To whom she could not gather. Once she
thought it was to herself, “to Francis Corydon Kent, Esquire, or the
heirs of his body;” once it sounded as though this huge fortune was
to be inherited by “James Cavendish Fairfax Stannard, Baronet of
the United Kingdom.” She wondered if this was Jimmy, and
remembered in a vague way that she had heard that the ninth
baronet of that name was a person of questionable character. Then
again it seemed as if the legatee was to be “Patrick George Connor.”
There was a doggerel verse in the will that the lawyer gabbled
through, and something about the great safe, then the lawyer came
to an end. In the conventional declaration of the witnesses lay a sting
that sent a dull red flush to Connor’s cheek and again provoked
Jimmy’s grim smile.
The lawyer read:—
“Signed by the above James Ryan Reale as his last will and
testament (the word ‘thief’ after ‘James Cavendish Fairfax Stannard,
Baronet of the United Kingdom,’ and the word ‘thief’ after ‘Patrick
George Connor,’ in the twentieth and twenty-third lines from the top
hereof, having been deleted), in the presence of us....”
The lawyer folded the will perversely and put it in his pocket. Then
he took four slips of paper from an envelope.
“It is quite clear to you gentlemen.” He did not wait for the men’s
reply, but went on addressing the bewildered girl.
“To you, Miss Kent, I am afraid the will is not so clear. I will explain it
in a few words. My late client was the owner of a gambling
establishment. Thus he amassed a huge fortune, which he has left to
form, if I may so put it, a large prize fund. The competitors are
yourselves. Frankly, it is a competition between the dupes, or the
heirs of the dupes, who were ruined by my late client, and the men
who helped in the fleecing.”
The lawyer spoke dispassionately, as though expounding some
hypothesis, but there was that in his tone which made Connor wince.
“Your father, my dear young lady, was one of these dupes many
years ago—you must have been at school at the time. He became
suddenly a poor man.”
The girl’s face grew hard.
“So that was how it happened,” she said slowly.
“That is how it happened,” the lawyer repeated gravely. “Your father’s
fortune was one of four great fortunes that went into the coffers of
my late client.” The formal description of Reale seemed to lend him
an air of respectability. “The other three have long since died, neither
of them leaving issue. You are the sole representative of the victims.
These gentlemen are—let us say—in opposition. This safe,” he
waved his hand toward the great steel room that crowned the granite
column, “contains the fortune. The safe itself is the invention of my
late client. Where the lock should be are six dials, on each of which
are the letters of the alphabet. The dials are ranged one inside the
other, and on one side is a steel pointer. A word of six letters opens
the safe. By turning the dials so that the letters come opposite the
pointer, and form this word, the door is opened.”
He stopped to wipe his forehead, for in the energy of his explanation
he had become hot. Then he resumed—
“What that word is, is for you to discover. My late client, who had a
passion for acrostics and puzzles and inventions of every kind, has
left a doggerel verse which he most earnestly assured me contained
the solution.”
He handed a slip first to the girl and then to the others. For a
moment the world swam before Kathleen’s eyes. All that hinged
upon that little verse came home to her. Carefully conning each
word, as if in fear of its significance escaping her, she read:—
“Here’s a puzzle in language old,
Find my meaning and get my gold.
Take one Bolt—just one, no more—
Fix it on behind a Door.
Place it at a river’s Mouth
East or west or north or south.
Take some Leaves and put them whole
In some water in a Bowl.
I found this puzzle in a book
From which some mighty truths were took.”
She read again and yet again, the others watching her. With every
reading she seemed to get further from the solution of the mystery,
and she turned in despair to Angel.
“I can make nothing of it,” she cried helplessly, “nothing, nothing,
nothing.”
“It is, with due respect to my late client, the veriest doggerel,” said
the lawyer frankly, “and yet upon that the inheritance of the whole of
his fortune depends.”
He had noticed that neither Connor nor Jimmy had read the slips he
had handed to them.
“The paper I have given you is a facsimile reproduction of the
original copy, and that may be inspected at any time at my office.”
The girl was scanning the rhyme in an agony of perplexity.
“I shall never do it,” she said in despair.
Angel took the paper gently from her hand.
“Don’t attempt it,” he said kindly. “There is plenty of time. I do not
think that either of your rival competitors have gained anything by the
advantage they have secured. I also have had in my possession a
copy of the rhyme for the past week.”
The girl’s eyes opened wide in astonishment.
“You?” she said.
Angel’s explanation was arrested by a singular occurrence.
Connor sat at one end of the row of chairs moodily eying the paper.
Jimmy, thoughtfully stroking his beard at the other end, suddenly
rose and walked to where his brooding confederate sat. The man
shrunk back as he approached, and Jimmy, seating himself by his
side, bent forward and said something in a low voice. He spoke
rapidly, and Angel, watching them closely, saw a look of incredulous
surprise come into Connor’s face. Then wrath and incredulity
mingled, and Connor sprang up, striking the back of the chair with
his fist.
“What?” he roared. “Give up a chance of a fortune? I’ll see you——”
Jimmy’s voice never rose, but he gripped Connor’s arm and pulled
him down into his chair.
“I won’t! I won’t! D’ye think I’m going to throw away——”
Jimmy released the man’s arm and rose with a shrug of his
shoulders.
He walked to where Kathleen was standing.
“Miss Kent,” he said, and hesitated. “It is difficult for me to say what I
have to say; but I want to tell you that so far as I am concerned the
fortune is yours. I shall make no claim to it, and I will afford you every
assistance that lies in my power to discover the word that is hidden
in the verse.”
The girl made no reply. Her lips were set tight, and the hard look that
Angel had noticed when the lawyer had referred to her father came
back again.
Jimmy waited a moment for her to speak, but she made no sign, and
with a slight bow he walked toward the door.
“Stop!”
It was Kathleen that spoke, and Jimmy turned and waited.
“As I understand this will,” she said slowly, “you are one of the men
to whom my father owed his ruin.”
His eyes met hers unfalteringly.
“Yes,” he said simply.
“One of the men that I have to thank for years of misery and sorrow,”
she continued. “When I saw my father slowly sinking, a broken-
hearted man, weighed down with the knowledge of the folly that had
brought his wife and child to comparative poverty; when I saw my
father die, crushed in spirit by his misfortunes, I never thought I
should meet the man who brought his ruin about.”
Still Jimmy’s gaze did not waver. Impassive, calm and imperturbable,
he listened unmoved to the bitter indictment.
“This will says you were a man of my father’s own class, one who
knew the tricks by which a gentle, simple man, with a childish faith in
such men as you, might be lured into temptation.”
Jimmy made no reply, and the girl went on in biting tones—
“A few days ago you helped me to escape from men whom you
introduced with an air of superiority as thieves and blackmailers.
That it was you who rendered me this service I shall regret to the
end of my days. You! You! You!” She flung out her hand scornfully. “If
they were thieves, what are you? A gambler’s tout? A decoy? A
harpy preying on the weakness of your unfortunate fellows?”
She turned to Connor.
“Had this man offered me his help I might have accepted it. Had he
offered to forego his claim to this fortune I might have been
impressed by his generosity. From you, whom God gave advantages
of birth and education, and who utilized them to bring ruin and
disaster on such men as my father, the offer is an insult!”
Jimmy’s face was deadly pale, but he made no sign. Only his eyes
shone brighter, and the hand that twisted the point of his beard
twitched nervously.
The girl turned to Angel wearily. Her outburst and the tension of the
evening had exhausted her.
“Will you take me home, Mr. Angel?” she said.
She offered her hand to the lawyer, who had been an interested
observer of the scene, and ignoring the two men, she turned to go.
Then Jimmy spoke.
“I do not attempt to excuse myself, Miss Kent,” he said evenly; “for
my life and my acts I am unaccountable to man or woman. Your
condemnation makes it neither easier nor harder to live my life. Your
charity might have made a difference.”
He held out a detaining hand, for Kathleen had gathered up her
skirts to move away.
“I have considered your question fairly. I am one of the men to whom
your father owed his ruin, insomuch as I was one of Reale’s
associates. I am not one of the men, insomuch as I used my every
endeavor to dissuade your father from taking the risks he took.”
The humor of some recollection took hold of him, and a grim little
smile came into his face.
“You say I betrayed your father,” he said in the same quiet tone. “As
a fact I betrayed Reale. I was at trouble to explain to your father the
secret of Reale’s electric roulette table; I demonstrated the futility of
risking another farthing.” He laughed. “I have said I would not excuse
myself, and here I am pleading like a small boy, ‘If you please, it
wasn’t me,’” he said a little impatiently; and then he added abruptly,
“I will not detain you,” and walked away.
He knew instinctively that she waited a moment hesitating for a reply,
then he heard the rustle of her dress and knew she had gone. He
stood looking upward to where the graven granite set marked the
ashes of Reale, until her footsteps had died away and the lawyer’s
voice broke the silence.
“Now, Sir James——” he began, and Jimmy spun round with an
oath, his face white with passion.
“Jimmy,” he said in a harsh voice, “Jimmy is my name, and I want to
hear no other, if you please.”
Mr. Spedding, used as he was to the wayward phases of men, was a
little startled at the effect of his words, and hastened to atone for his
blunder.
“I—I beg your pardon,” he said quickly. “I merely wished to say——”
Jimmy did not wait to hear what he said, but turned upon Connor.
“I’ve got a few words to say to you,” he said. His voice had gone
back to its calm level, but there was a menace in its quietness.
“When I persuaded Angel to give you a chance to get away on the
night the ‘Borough Lot’ was arrested, I hoped I could get you to
agree with me that the money should be handed to Miss Kent when
the word was found. I knew in my inmost heart that this was a forlorn
hope,” he went on, “that there is no gold in the quartz of your
composition. You are just beast all through.”
He paced the floor of the hall for a minute or two, then he stopped.
“Connor,” he said suddenly, “you tried to take my life the other night.
I have a mind to retaliate. You may go ahead and puzzle out the
word that unlocks that safe. Get it by any means that suggest
themselves to you. Steal it, buy it—do anything you wish. The day
you secure the key to Reale’s treasure I shall kill you.”
He talked like a man propounding a simple business proposition, and
the lawyer, who in his early youth had written a heavy little paper on
“The Congenital Criminal,” listened and watched, and, in quite a
respectable way, gloated.
Jimmy picked up his hat and coat from a chair, and nodding to the
lawyer, strolled out of the hall.
In the vestibule where the one commissionaire had been were six.
Every man was a non-commissioned officer, and, as was apparent
from his medals, had seen war service. Jimmy noted the belt about
each man and the dangling revolver holster, and approved of the
lawyer’s precaution.
“Night guard, sergeant-major?” he asked, addressing one whose
crowned sleeve showed his rank.
“Day and night guard, sir,” replied the officer quietly.
“Good,” said Jimmy, and passed out into the street.
And now only the lawyer and Connor remained, and as Jimmy left,
they too prepared for departure.
The lawyer was mildly interested in the big, heavy criminal who
walked by his side. He was a fairly familiar type of the bull-headed
desperado.
“There is nothing I can explain?” asked Spedding, as they stood
together in the vestibule.
Connor’s eyes were on the guard, and he frowned a little.
“You don’t trust us very much,” he said.
“I don’t trust you at all,” said the lawyer.
CHAPTER VI
THE RED ENVELOPE
Mr. Spedding, the admirable lawyer, lived on Clapham Common,

where he owned the freehold of that desirable residence, “High Holly
Lodge.”
He was a bachelor, with a taste for bridge parties and Madeira.
Curious neighbors would have been mystified if they had known that
Mr. Spedding’s repair bill during the first two years of his residence
was something well over three thousand pounds. What they did
know was that Mr. Spedding “had the builders in” for an
unconscionable time, that they were men who spoke in a language
entirely foreign to Clapham, and that they were housed during the
period of renovation in a little galvanized iron bungalow erected for
the purpose in the grounds.
A neighbor on visiting terms expressed his opinion that for all the
workmen had done he could discern no material difference in the
structure of the house, and from his point of view the house
presented the same appearance after the foreign builders left, as it
did before their advent. Mr. Spedding met all carelessly-applied
questions concerning the extent of the structural alterations with
supreme discretion. He spoke vaguely about a new system of
ventilation, and hinted at warmth by radiation.
Suburbia loves to show off its privately conceived improvements to
property, but Mr. Spedding met veiled hints of a desire to inspect his
work with that comfortable smile which was so valuable an asset of
his business.
It was a few evenings after the scene in the Lombard Street Deposit
that Mr. Spedding sat in solitude before his modest dinner at
Clapham.
An evening newspaper lay by the side of his chair, and he picked it
up at intervals to read again the paragraph which told of the release
of the “Borough Lot.” The paragraph read:—
“The men arrested in connection with the gambling raid at
Poplar were discharged to-day, the police, it is understood,
failing to secure sufficient evidence to justify a
prosecution.”
The lawyer shook his head doubtfully.
“I rather like Angel Esquire’s definition,” he said with a wry smile. “It
is a neat method of saving the face of the police, but I could wish
that the ‘Borough Lot’ were out of the way.”
Later he had occasion to change his opinion.
A tap at the door preceded the entry of a sedate butler. The lawyer
looked at the card on the tray, and hesitated; then, “Show him in,” he
said.
Jimmy came into the room, and bowed slightly to the elder man, who
rose at his entrance.
They waited in silence till the servant had closed the door behind
him.
“To what am I indebted?” began the lawyer, and motioned his visitor
to a seat.
“May I smoke?” asked Jimmy, and Mr. Spedding nodded.
“It is in the matter of Reale’s millions,” said Jimmy, and allowed his
eyes to follow the cloud of smoke he blew.
“I thought it was understood that this was a subject which might only
be discussed at my office and in business hours?” said the lawyer
sharply, and Jimmy nodded again.
“You will confess, Mr. Spedding,” he said easily, “that the Reale will is
sufficiently unconventional to justify any departure from established
custom on the part of the fortunate or unfortunate legatees.”
Mr. Spedding made an impatient movement of his hand.
“I do not inquire into your business,” Jimmy went on smoothly
enough, “and I am wholly incurious as to in what strange manner you
became acquainted with your late client, or what fees you received
to undertake so extraordinary a commission; but I am satisfied that
you are recompensed for such trifling inconveniences as—say an
after-dinner visit from myself.”
Jimmy had a way of choosing his words, hesitating for the exact
expression that would best convey every shade of his meaning. The
lawyer, too, recognized the logic of the speech, and contented
himself with a shrug which meant nothing.
“I do not inquire into your motives,” Jimmy resumed; “it pleases me
to believe that they are entirely disinterested, that your attitude is the
ideal one as between client and agent.”
His pause was longer this time, and the lawyer was piqued into
interjecting an impatient—
“Well?”
“Well,” said Jimmy slowly, “believing all this, let us say, I am at a loss
to know why at the reading of the will you gave us no indication of
the existence of a key to this mysterious verse.”
“There is no key,” said the lawyer quickly, and added, “so far as I
know.”
“That you did not tell us,” Jimmy went on, as though unconscious of
any interruption, “of the big red envelope——”
Spedding sprang to his feet white as death.
“The envelope,” he stammered angrily, “what do you know—what
envelope?”
Jimmy’s hand waved him to his seat.
“Let us have no emotions, no flights, no outraged honor, I beg of you,
dear Mr. Spedding. I do not suggest that you have any sinister
reasons for withholding information concerning what my friend Angel
would call the ‘surprise packet.’ In good time I do not doubt you
would have disclosed its existence.”
“I know of no red envelope,” said the lawyer doggedly.
“I rather fancied you would say that,” said Jimmy, with a touch of
admiration in his tone. “You are not the sort of fox to curl up and howl
at the first bay of the hound—if you will permit the simile—indeed,
you would have disappointed me if you had.”
The lawyer paced the room.
“Look here,” he said, coming to a halt before the semi-recumbent
form that lay behind a haze of cigarette smoke in the arm-chair,
“you’ve spent a great deal of your time telling me what I am,
describing my many doubtful qualities, and hinting more or less
broadly that I am a fairly representative scoundrel. May I ask what is
your ultimate object? Is it blackmail?” he demanded harshly.
“No,” said Jimmy, by no means disconcerted by the brutality of the
question.
“Are you begging, or borrowing, or——”
“Stealing?” murmured Jimmy lazily.
“All that I have to say to you is, finish your business and go.
Furthermore, you are at liberty to come with me to-morrow morning
and search my office and question my clerks. I will accompany you
to my banks, and to the strong-room I rent at the deposit. Search for
this red envelope you speak about, and if you find it, you are at
liberty to draw the worst deductions you will.”
Jimmy pulled gently at his cigarette with reflective eyes cast upward
to the ceiling.
“Do you speak Spanish?” he asked.
“No,” said the other impatiently.
“It’s a pity,” said Jimmy, with a note of genuine regret. “Spanish is a
very useful language—especially in the Argentine, for which
delightful country, I understand, lawyers who betray their trust have
an especial predilection. My Spanish needs a little furbishing, and
only the other day I was practising with a man whose name, I
believe, is Murrello. Do you know him?”
“If you have completed your business, I will ring for the servant,” said
the lawyer.
“He told me—my Spaniard, I mean—a curious story. He comes from
Barcelona, and by way of being a mason or something of the sort,
was brought to England with some other of his fellow-countrymen to
make some curious alterations to the house of a Señor in—er—
Clapham of all places in the world.”
The lawyer’s breath came short and fast.
“From what I was able to gather,” Jimmy went on languidly, “and my
Spanish is Andalusian rather than Catalonian, so that I missed some
of his interesting narrative, these alterations partook of the nature of
wonderfully concealed strong-rooms—steel doors artfully covered
with cheap wood carving, vaults cunningly constructed beneath
innocent basement kitchens, little stairways in apparently solid walls
and the like.”
The levity went out of his voice, and he straightened himself in his
chair.
“I have no desire to search your office,” he said quietly, “or perhaps I
should say no further desire, for I have already methodically
examined every hole and corner. No,” he checked the words on
Spedding’s lips, “no, it was not I who committed the blundering
burglary you spoke of. You never found traces of me, I’ll swear. You
may keep the keys of your strong-room, and I shall not trouble your
bankers.”
“What do you want?” demanded the lawyer shortly.
“I want to see what you have got downstairs,” was the reply, and
there was no doubting its earnestness, “and more especially do I
want to see the red envelope.”
The lawyer bent his brows in thought. His eyes were fixed
unwaveringly on Jimmy’s.
“Suppose,” he said slowly, “suppose that such an envelope did exist,
suppose for the sake of argument these mysterious vaults and
secret chambers are, as you suggest, in existence, what right have
you, more than any other one of the beneficiaries under the will, to
demand a private examination? Why should I give you an unfair
advantage over them?”
Jimmy rose to his feet and stretched himself before replying.
“There is only one legatee whom I recognize,” he said briefly, “that is
the girl. The money is hers. I do not want a farthing. I am equally
determined that nobody else shall touch a penny—neither my young
friend Connor”—he stopped to give emphasis to the next two words
—“nor yourself.”
“Sir!” said the outraged Mr. Spedding.
“Nor yourself, Mr. Spedding,” repeated Jimmy with conviction. “Let
us understand each other thoroughly. You are, as I read you, a fairly
respectable citizen. I would trust you with ten or a hundred thousand
pounds without experiencing the slightest anxiety. I would not trust
you with two millions in solid cash, nor would I trust any man. The
magnitude of the sum is calculated to overwhelm your moral sense.
The sooner the red envelope is in the possession of Angel Esquire
the better for us all.”
Spedding stood with bent head, his fingers nervously stroking his
jaw, thinking.
“An agile mind this,” thought Jimmy; “if I am not careful there will be
trouble here.”
He watched the lawyer’s face, and noticed the lines suddenly
disappear from the troubled face, and the placid smile returning.
“Conciliation and partial confession,” judged Jimmy, and his
diagnosis was correct.
“Well, Mr. Jimmy,” said Spedding, with some show of heartiness,
“since you know so much, it may be as well to tell you more. As you
have so cleverly discovered, my house to a great extent is a strong-
room. There are many valuable documents that I could not with any
confidence leave deposited at my office. They are safer here under
my eye, so to speak. The papers of the late Mr. Reale are, I confess,
in this house; but—now mark me—whether the red envelope you
speak of is amongst these I do not know. There is a multitude of
documents in connection with the case, all of which I have had no
time to go through. The hour is late, but——”
He paused irresolutely.
“——If you would care to inspect the mysteries of the basement”—
he smiled benevolently, and was his old self—“I shall be happy to
have your assistance in a cursory search.”
Jimmy was alert and watchful and to the point.
“Lead the way,” he said shortly, and Spedding, after a moment’s
hesitation, opened the door and Jimmy followed him into the hall.
Contrary to his expectations, the lawyer led him upstairs, and
through a plainly furnished bedroom to a small dressing-room that
opened off. There was a conventional wardrobe against the wall, and
this Spedding opened. A dozen suits hung from hooks and
stretchers, and the lawyer groped amongst these for a moment.
Then there was a soft click, and the back of the wardrobe swung
back.
Spedding turned to his visitor with a quizzical smile.
“Your friend Angel’s method of gaining admittance to the haunt of the
‘Borough Lot’ was not original. Come.”
Jimmy stepped gingerly through into the darkness. He heard the
snap of a button, and a soft glow of light revealed a tiny chamber, in
which two men might comfortably stand upright. The back of the
wardrobe closed, and they were alone in a little room about as large
as an average cupboard.
There was a steel lever on one side of the walls, and this the lawyer
pulled cautiously. Jimmy felt a sinking sensation, and heard a faint,
far-off buzzing of machinery.
“An electric lift, I take it,” he said quietly.
“An electric lift,” repeated the lawyer.
Down, down, down they sank, till Jimmy calculated that they must be
at least twenty feet below the street level. Then the lift slowed down
and stopped at a door. Spedding opened this with a key he took from
his pocket, and they stepped out into a chill, earthy darkness.
“There’s a light here,” said the lawyer, and groped for the switch.
They were in a large vaulted apartment lit from the roof. At one end a
steel door faced them, and ranged about the vault on iron racks a
number of black japanned boxes.
Jimmy noted the inscriptions, and was a little surprised at the extent
and importance of the solicitor’s practice. Spedding must have read
his thoughts, for he turned with a smile.
“Not particularly suggestive of a defaulting solicitor,” he said
ironically.
“Two million pounds,” replied Jimmy immediately, “that is my answer
to you, Mr. Spedding. An enormous fortune for the reaching. I
wouldn’t trust the Governors of the Bank of England.”
Spedding may have been annoyed as he walked to the door in the
wall and opened it, but he effectively concealed his annoyance.
As the door fell backward, Jimmy saw a little apartment, four feet by
six feet, with a roof he could touch with his hand. There was a fresh
current of air, but from whence it came he could not discover. The
only articles of furniture in the little cell were a writing table and a
swing chair placed exactly beneath the electric lamp in the roof.
Spedding pulled open a drawer in the desk.
“I do not keep my desks locked here,” he said pleasantly enough.
It was characteristic of him that he indulged in no preamble, no
apologetic preliminaries, and that he showed no sign of
embarrassment as he slipped his hand into the drawer, and drawing
forth a bulky red envelope, threw it on to the desk.
You might have forgotten that his last words were denials that the
red envelope had existed. Jimmy looked at him curiously, and the
lawyer returned his gaze.
“A new type?” he asked.
“Hardly,” said Jimmy cheerfully. “I once knew a man like you in the
Argentine—he was hanged eventually.”
“Curious,” mused the lawyer, “I have often thought I might be
hanged, but have never quite seen why——” He nearly added
something else, but checked himself.
Jimmy had the red envelope in his hand and was examining it
closely. It was heavily sealed with the lawyer’s own seal, and bore
the inscription in Reale’s crabbed, illiterate handwriting, “Puzzle
Ideas.” He weighed it and pinched it. There was a little compact
packet inside.
“I shall open this,” said Jimmy decisively. “You, of course, have
already examined it.”
The lawyer made no reply.
Jimmy broke the seal of the envelope. Half his mind was busy in
speculation as to its contents, the other half was engaged with the
lawyer’s plans. Jimmy was too experienced a man to be deceived by
the complaisance of the smooth Mr. Spedding. He watched his every
move. All the while he was engaged in what appeared to be a
concentrated examination of the packet his eyes never left the
lawyer. That Spedding made no sign was a further proof in Jimmy’s
eyes that the coup was to come.
“We might as well examine the envelope upstairs as here,” said the
lawyer. The other man nodded, and followed him from the cell.
Spedding closed the steel door and locked it, then turned to Jimmy.
“Do you notice,” he said with some satisfaction, “how skilfully this
chamber is constructed?” He waved his hand round the larger vault,
at the iron racks and the shiny black boxes.
Jimmy was alert now. The lawyer’s geniality was too gratuitous, his
remarks a trifle inapropos. It was like the lame introduction to a story
which the teller was anxious to drag in at all hazards.
“Here, for instance,” said the lawyer, tapping one of the boxes, “is
what appears to be an ordinary deed box. As a matter of fact, it is an
ingenious device for trapping burglars, if they should by any chance
reach the vault. It is not opened by an ordinary key, but by the
pressure of a button, either in my room or here.”
He walked leisurely to the end of the vault, Jimmy following.
For a man of his build Spedding was a remarkably agile man. Jimmy
had underrated his agility.
He realized this when suddenly the lights went out. Jimmy sprang for
the lawyer, and struck the rough stone wall of the vault. He groped
quickly left and right, and grasped only the air.
“Keep quiet,” commanded Spedding’s calm voice from the other end
of the chamber, “and keep cool. I am going to show you my burglar
catcher.”
Jimmy’s fingers were feeling along the wall for the switch that
controlled the lights. As if divining his intention, the lawyer’s voice
said—
“The lights are out of control, Jimmy, and I am fairly well out of your
reach.”
“We shall see,” was Jimmy’s even reply.
“And if you start shooting you will only make the atmosphere of this
place a little more unbreathable than it is at present,” Spedding went
on.
Jimmy smiled in the darkness, and the lawyer heard the snap of a
Colt pistol as his captive loaded.
“Did you notice the little ventilator?” asked the lawyer’s voice again.
“Well, I am behind that. Between my unworthy body and your nickel
bullets there are two feet of solid masonry.”
Jimmy made no reply, his pistol went back to his hip again. He had
his electric lamp in his pocket, but prudently kept it there.
“Before we go any further,” he said slowly, “will you be good enough
to inform me as to your intentions?”
He wanted three minutes, he wanted them very badly; perhaps two
minutes would be enough. All the time the lawyer was speaking he
was actively employed. He had kicked off his shoes when the lights
went out, and now he stole round the room, his sensitive hands
flying over the stony walls.
“As to my intentions,” the lawyer was saying, “it must be fairly
obvious to you that I am not going to hand you over to the police.
Rather, my young friend, in the vulgar parlance of the criminal
classes, I am going to ‘do you in,’ meaning thereby, if you will forgive
the legal terminology, that I shall assist you to another and, I hope,
though I am not sanguine, a better world.”
He heard Jimmy’s insolent laugh in the blackness.
“You are a man after my own heart, Jimmy,” he went on regretfully. “I
could have wished that I might have been spared this painful duty;
but it is a duty, one that I owe to society and myself.”
“You are an amusing person,” said Jimmy’s voice.
“I am glad you think so. Jimmy, my young friend, I am afraid our
conversation must end here. Do you know anything of chemistry?”
“A little.”
“Then you will appreciate my burglar catcher,” said Spedding, with
uncanny satisfaction. “You, perhaps, noticed the japanned box with
the perforated lid? You did? Good! There are two compartments, and
two chemicals in certain quantities kept apart. My hand is on the key
now that will combine them. When cyanide of potassium is combined
with sulphuric acid, do you know what gas is formed?”
Jimmy did not reply. He had found what he had been searching for.
His talk with the Spanish builder had been to some purpose. It was a
little stony projection from the wall. He pressed it downward, and
was sensible of a sensation of coldness. He reached out his hand,
and found where solid wall had been a blank space.
“Do you hear, Jimmy?” asked the lawyer’s voice.
“I hear,” replied Jimmy, and felt for the edge of the secret door. His
fingers sliding down the smooth surface of the flange encountered
the two catches.
“It is hydrocyanic acid,” said the lawyer’s smooth voice, and Jimmy
heard the snap of the button.
“Good-by,” said the lawyer’s voice again, and Jimmy reeled back
through the open doorway swinging the door behind him, and
carrying with him a whiff of air heavily laden with the scent of
almonds.

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Novel Electrochemical Energy Storage Devices Materials Architectures and Future Trends 1St Edition Feng Li Full Chapter

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Novel Electrochemical Energy Storage

Devices: Materials, Architectures, and

Materials, Architectures, and Future Trends

All rights reserved (including those of

Print ISBN: 978-3-527-34579-3

Typesetting SPi Global, Chennai, India

Printed on acid-free paper

2 Materials and Fabrication 15

2.4.5 Lithium–Manganese-rich Materials 28

3 Flexible Cells: Theory and Characterizations 67

3.2 Mechanical Process for Bendable Cells 69

4 Flexible Cells: Materials and Fabrication

4.5 Electrolytes for Flexible ECs 104

5 Architectures Design for Cells with High Energy

5.5.2 Numerical Simulation of Tortuosity on Rates by

6.2.1 Evaluation Methods for Electric Double-layer m-ECs 210

7 Smart Cells 263

7.1.2 Definition of Smart Materials 263

AAO anodized aluminum oxide

HEV hybrid electric vehicle

PET polyethylene terephthalate

1.1 Energy Conversion and Storage: A Global Challenge

Figure 1.1 Amounts of global energy consumption.

Figure 1.2 Global renewable energy employment indexed by technology. Source:

Mobile devices Robots, AGV

Electric vehicles Aerospace

Renewable energy Industry

Figure 1.3 Application of electrochemical energy storage, AGV (automated guided

1.2 Development History of Electrochemical Energy

Internal copper cylinder

1.3 Classiﬁcation of Electrochemical Energy Storage

Figure 1.5 Development of various electrochemical energy storage.

Figure 1.6 Classiﬁcation of

EDLC Primary batteries

Pseudocapacitors Secondary batteries

1.4 LIBs and ECs: An Appropriate Electrochemical

Development Organization (NEDO) of Japan and planned to achieve 500 Wh kg−1

DOE: US department of energy

Next generation batteries: Post LIBs

ca. 400 wh kg–1

Graphite/NCA or NMC Graphite/NCA 2nd Generation LIBs

Graphite/Spinel or Phosphate 1st Generation LIBs

Table 1.1 Comparison between ECs and LIBs.

Performances ECs LIBs

Charge time (s) 1–10 1–10 100 600

Source: Libich et al. [13].

1.5 Summary and Outlook

3 BP Company (2019). BP Statistical Review of World Energy, 68e. UK: BP Com-

39 Conway, B.E. (1991). Transition from supercapacitor to battery behavior in

Materials and Fabrication

As stated in Chapter 1, lithium ion batteries (LIBs) and electrochemical capacitors

2.1 Mechanisms and Advantages of LIBs

Anode Electrolyte Cathode

2.1.2 Advantages and Disadvantages

Can Cathode Anode Can

(a) Cylindrical (b) Prismatic

2.2 Mechanisms and Advantages of ECs

POSITIVELY CHARGED SURFACE

POSITIVELY CHARGED SURFACE

(a) (b) (c)

+ Solvated cation – Anion

Figure 2.4 EDL model inside a solid/solid

Charge storage mechanism in the EDLC is non-Faradaic. EDLC exhibits high