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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
Authors All books published by Wiley-VCH
are carefully produced. Nevertheless,
Feng Li authors, editors, and publisher do not
Institute of Metal Research warrant the information contained in
Chinese Academy of Sciences these books, including this book, to
72 Wenhua Road be free of errors. Readers are advised
Shenyang 110016 to keep in mind that statements, data,
China illustrations, procedural details or other
items may inadvertently be inaccurate.
Lei Wen
Institute of Metal Research Library of Congress Card No.:
Chinese Academy of Sciences applied for
72 Wenhua Road
Shenyang 110016 British Library Cataloguing-in-Publication
China Data
A catalogue record for this book is
Hui-ming Cheng available from the British Library.
Institute of Metal Research
Chinese Academy of Sciences Bibliographic information published by
72 Wenhua Road the Deutsche Nationalbibliothek
Shenyang 110016 The Deutsche Nationalbibliothek lists
China this publication in the Deutsche
Nationalbibliografie; detailed
Cover bibliographic data are available on the
Cover Image: © TarikVision/Getty Internet at <http://dnb.d-nb.de>.
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© 2021 WILEY-VCH GmbH, Boschstr.
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transmitted or translated into a
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permission from the publishers.
Registered names, trademarks, etc.
used in this book, even when not
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be considered unprotected by law.
Print ISBN: 978-3-527-34579-3

ePDF ISBN: 978-3-527-82104-4
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Typesetting SPi Global, Chennai, India

Printing and Binding
Printed on acid-free paper
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
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avec leurs pieds, sans repos, sans pensée, absorbées par l’incessant travail
monotone et dur. Leurs membres musclés sont beaux et leurs corps sont
parfaits, malgré les faces bestiales qui repoussent.
Le tourneur auquel nous venons commander les hautes jarres à
provisions, où l’on conserve l’huile et les grains, est un artisan chenu.
Complaisant, mais peu loquace, il travaille en silence devant nous, et
tire, de son bloc de glaise, les plus surprenants objets.
—Il est le maître des maîtres,—nous dit un de ses compagnons, Allah le
conserve et le dédommage! C’est le père de Saïd, ce petit que vous avez
chez vous.
—Comment, son père?... Saïd nous a dit qu’il était mort avant sa
naissance...
Le vieux tourneur se met à rire:
—Saïd vous a menti. Vous ne savez pas encore toute sa malice! Que le
Seigneur m’en décharge!... Si vous voulez le prendre, je vous le donne.
Nous nous taisons, stupéfaits... Cet homme qui, si naïvement, abandonne
son enfant!... et puis l’étonnant mensonge de Saïd, la longue histoire
combinée par un tout petit être...
—Écoute, ô hakem, continue le potier, Saïd ne vaut rien. Le diable lui
parle et il l’écoute. J’ai voulu lui faire porter les briques, il les cassait toutes,
par méchanceté. Alors je l’ai placé, comme les enfants de son âge, chez un
tailleur de djellabas, pour dévider les fils. Saïd s’est sauvé de chez son
maître, après avoir mis le trouble dans le quartier. Et, l’autre jour, il m’a
quitté, en me volant deux réaux, à moi qui ne suis qu’un pauvre artisan!...
Les gens m’ont dit qu’il était chez toi, je ne suis pas allé le chercher... je
suis las, je suis vieux et j’avais peur qu’il n’eût déjà commis bien des
méfaits dans ta maison... vous feriez mieux de ne pas le garder! Par le
Prophète! ô seigneur hakem, je te supplie de ne pas faire retomber sur moi
le mal qu’il vous causera!
Nous rassurons le père, très contents en somme de garder l’enfant auquel
nous nous sentons attachés déjà. Comment ce gosse pourrait-il nous nuire?
Le bonhomme, trop rude, n’aura pas su redresser cette petite nature,
mauvaise, mais bien drôle.
Dès notre retour, nous interrogeons Saïd.
—Qu’est cela? Pourquoi nous as-tu dit que ton père était mort?
—Allah l’ait en sa Miséricorde! répond le gamin avec componction.
—Tu mens! C’est Sellam le tourneur. Nous l’avons va, tu le sais bien.
C’est pourquoi tu n’as pas voulu venir avec nous chez les potiers.
—J’avais trop peur de lui, avoue Saïd. Il me battait, alors je me suis
sauvé.
—Et ton maître, le tailleur de djellabas?
—Il me battait aussi, affirme Saïd, l’air tellement innocent que nous le
croyons presque, malgré ses premiers mensonges.
Et puis, qu’importe?... Déjà nous n’avons plus d’illusions! Nous voulons
en avoir.
15 octobre.
Accroupi sur une natte, au milieu de ses pots remplis de couleur,
Larfaoui Jenjoul, le maître Larfaoui, décore un coffre ciselé. Ses pinceaux
en poils d’âne se hérissent comme de petits balais (c’est ainsi qu’il les
nomme du reste), et l’on s’étonne qu’il trace des rinceaux si déliés, des
courbes si parfaites, avec de tels instruments.
Larfaoui possède les belles traditions léguées par les anciens. Il en
remontrerait même au célèbre Hammadi et à sa nièce Khdija Temtam, dont,
un jour, il me conta l’histoire. Mais un peintre italien,—Allah le confonde!
—dérouta quelque peu les conceptions millénaires de notre décorateur, en
travaillant jadis à ses côtés, dans le palais du Sultan Mouley Abdelaziz.
Larfaoui subit ainsi la fâcheuse influence européenne. Il arrive parfois
que son caprice fasse éclore des bouquets aux airs penchés, aux fleurs
presque naturelles, sur des fonds roses, bleu pâle, ou gris.
Grâce à Dieu! Larfaoui réserve ces innovations pour les demeures des
marchands enrichis, tel ce tager Ben Melih qui n’a point le goût des belles
peintures symétriques où s’enchevêtrent les lignes.
Larfaoui sait que nous, Nazaréens, apprécions le vieux style. Même il a
pour moi certaine considération, parce que j’en connais à présent la
technique, et ne laisse passer aucun décor moderne sans le repérer aussitôt
parmi les entrelacs, telle une vipère dans les branches.
J’aime à faire travailler Larfaoui chez moi, pour la jouissance de le voir
peindre. Il ignore la mélancolie. Ses pensées ont la nuance joyeuse et
changeante des couleurs qu’il manie. Il excelle à balancer les verts, les
jaunes, les rouges et les bleus, à créer des rapprochements où le regard se
plaît. C’est un maître! Il en a le sentiment et l’orgueil. Nul peintre au monde
ne saurait lui être comparé.
—Pourtant, il y a Mohammed Doukkali...
—Le Doukkali!... qu’est-ce que cela? Mets son travail auprès du mien,
on ne l’apercevra même pas.
—Et Temtam?
—Tu plaisantes! Quand il doit exécuter un ornement compliqué, je le lui
dessine.
—Les peintres de Fès?
—Ceux de Fès! Les Sultans les avaient dans leur ombre, et ils me
faisaient venir de Meknès pour décorer leurs palais.
—Soit, personne donc ne t’égale ni te dépasse?
—Si, Allah! Il a peint les Cherekrek[62] au plumage d’azur...
Un sourire d’enfantine vanité éclaire son intelligent visage noir, et, pour
me convaincre pleinement, Larfaoui, du bout de son pinceau, décrit une
série de lignes qui s’enlacent en un réseau inextricable, mais harmonieux.
Avec une affolante rapidité, le panneau est couvert, terminé. D’un vase
gracile, s’élève l’étrange épanouissement symétrique et compliqué d’un
bouquet.
Cela semble le travail de plusieurs jours, et Larfaoui l’a fait éclore en
moins d’un quart d’heure.
Mais, à présent, il flâne, il gratte doucement ses minerais jaunes, casse à
petits coups les œufs dont les coquilles jonchent les mosaïques, se complaît
à une lente et minutieuse préparation. Puis il va boire à la fontaine, cueille
une orange, considère le ciel que le crépuscule ne rosit pas encore, hélas!...
et se réaccroupit sans enthousiasme devant le coffre commencé!
Larfsaoui est un artiste, et je me sens pleine d’indulgence pour sa
paresse. Parfois, il abandonne son travail durant plusieurs jours, car c’est
«la fête du soleil». Alors il s’en va, une cage à la main, dans une arsa
fleurie. Étendu sous un arbre, il écoute l’oiseau, sirote une tasse de thé,
respire le parfum des roses... Il jouit.
Après ces fugues, il ne manque pas de m’apporter un bouquet ou un
fruit, qu’il m’offre avec un large rire. Larfaoui me désarme et m’enchante.
Saïd s’est installé auprès de lui et considère son œuvre. S’il plaît à Dieu!
Saïd lui aussi sera peintre, il perpétuera les traditions qui ont créé tant de
merveilles.
—Quel est cet enfant? demande Larfaoui.
—Un petit abandonné que nous élèverons.
—Allah vous récompense! D’où vient-il?
—C’est le fils de Sellam le potier.
—Ah! fait Larfaoui, d’un air singulier. Va me chercher un verre d’eau,
dit-il au bambin, et, dès que celui-ci disparaît, il ajoute:
—On ne t’a donc pas dit qu’il a deux sœurs, des prostituées, hachek?
(sauf ton respect).
—Je sais. Mais ce n’est pas la faute de l’enfant. Avec l’aide d’Allah nous
en ferons un honnête et bon Musulman.
—Tu as connu El Hadi, le tisserand?
—Oui... qu’a-t-il à faire en ceci?
—Il est mort il y a deux mois.
—Dieu l’accueille en sa Clémence!
—Par le serment! je vais te dire une chose vraie. El Hadi fréquentait ces
chiennes, il leur avait prêté de l’argent. Vint l’échéance, elles lui dirent:
«Donne-nous un délai.» Il l’accorda, et, pour l’en remercier, elles lui
envoyèrent un couscous. Dès qu’il en eut mangé, son ventre lui fit mal,
jusqu’à en mourir... Certes il fut empoisonné!
—O Puissant!... A-t-on prévenu la justice?
—A quoi bon? Il était mort... Mais je te conseille, méfie-toi de l’enfant.
En grandissant, le louveteau ne saurait devenir qu’un loup.
Saïd arrive à petits pas, tenant avec précaution le verre plein d’eau. Son
visage s’arrondit déjà, la mèche d’Aïssaoui se balance drôlement au côté du
crâne bien rasé... Non, nous ne le rejetterons pas au vice. Qu’Allah nous
accorde son assistance!
6 novembre.
«L’Achoura vient.».... En cette attente, Meknès a pris son visage le plus
riant; toutes les préoccupations, toutes les querelles restent suspendues, rien
ne pouvant égaler l’importance d’une fête qui se renouvelle, identique,
chaque année.
Puissance des fêtes sur les enfants et les peuples simples qui leur
ressemblent.
Nous ne savons plus en jouir comme eux. Qui nous rendra les liesses de
jadis, pour Noël et pour Pâques? Nos jours enfiévrés fuient d’une allure
uniforme.
Mais ici, grâce à Dieu! les fêtes gardent tout leur prestige. Saïd en parle
abondamment. Il sait déjà prévoir le nombre de roues qui tourneront sur la
place de Bab Berdaine.
—On dit, ô ma mère, qu’il y en aura dix mille! Combien plus que l’an
dernier!...
Toujours, bien entendu, la fête qui vient surpassera les précédentes.
Depuis une semaine, Saïd a été presque sage. Il n’a point menti, ni volé,
ni fait d’affreuses colères. Il mérite aujourd’hui de revêtir le selham de satin
émeraude, dont le capuchon encadre sa face de ouistiti.
Les petites filles suivent, fières et gauches dans leurs caftans de drap
neuf et leurs tfinat en mousseline raide. Mais on ne distingue de leurs
splendeurs que de très estimables babouches, car elles se voilent
pudiquement dans leurs haïks. Rabha, elle-même, a voulu enrouler son
visage de linges qui écrasent son petit nez.
A mesure que nous approchons de la place, la foule se fait très dense et
Kaddour a bien de la peine à nous frayer un passage. Foule éclatante,
colorée, sans une tache d’étoffe sombre. Pas de femmes, ou presque, à part
quelques hétaïres et des femmes berbères au profil sauvage, mais des
tirailleurs, des artisans, de jeunes bourgeois, et surtout des enfants.
C’est la fête des petits. Il y en a de tous les âges, de toutes les tailles,
importants et raides en leurs beaux habits. Ceux qui ne marchent pas encore
sont portés sur les bras. Tous les crânes des garçons reluisent, fraîchement
rasés; une mèche se balance au sommet, à droite ou à gauche, selon la
confrérie à laquelle on les a voués. Les selhams, de velours et de soie,
miroitent au soleil. Les fillettes ont des nattes minuscules, enchevêtrées
avec art et régularité, tout autour de la tête. Elles se parent de ferronnières,
de lourds anneaux d’oreilles et de colliers prêtés par leurs mamans. La
plupart circulent à visage découvert, le port du haïk n’étant de rigueur qu’au
moment où l’enfant devient nubile, et alors les sorties se font très rares...
Celles qui voulurent, ainsi que les nôtres, prendre des allures de dames, se
trouvent fort embarrassées de leurs voiles, sur cette place où l’on s’amuse.
Les marchands de sucreries, très entourés, se tiennent derrière leurs
frêles étalages qui attirent les guêpes. Ils vendent des bonbons roses et
blancs, des nougats empoussiérés, des pains de millet au miel, des beignets,
des grenades et de jolies arbouses écarlates et veloutées.
La foule s’agite dans un brouillard doré, poussière et soleil.
Un immense grincement domine le tumulte des voix, acide, exaspérant,
grincement de bois et de ferraille, grincement des roues, à sièges suspendus,
qui tournent en hauteur, au moyen d’un mécanisme ingénieusement simple.
Ces roues,—il y en a une quinzaine,—sont le plus couru des
divertissements, et les amateurs attendent, avec impatience, leur tour de
monter dans les grinçantes machines. Mais ceux qui déjà y sont accroupis,
ne se rassasient point d’un tel plaisir et paient guirch sur guirch pour le
prolonger. Ils jouissent aussi de se trouver en mire à tous les yeux, ils rient
très haut et s’efforcent de faire tourner leurs sièges sur eux-mêmes, sens
dessus dessous, tandis que la roue continue à les emporter, de son propre
mouvement.
Parmi les tirailleurs et les jeunes hommes, trois belles sont montées dans
une roue, et font sensation. Les voiles ne laissent apercevoir de leurs
visages que les yeux peints, allongés jusqu’aux tempes, mais les djellabas,
impudemment ouvertes, révèlent de clinquants colliers et l’éclat des étoffes,
tandis que les jambes s’agitent, avec ostentation, chaque fois que le siège
bascule.
—Par Allah! s’écria Rabha. Regarde, ô ma mère, c’est Mouley El Fadil
qui rit avec ces femmes! Un chérif d’entre les chorfas!...
Je partage l’indignation de la petite. Il faut, en vérité, que Mouley El
Fadil ait perdu la raison pour s’exposer avec des courtisanes, aux populaires
réjouissances d’Achoura!...
Installé dans le quatrième siège de la roue, il semble s’amuser à
l’extrême limite de l’amusement, bascule, pieds par-dessus tête, virevolte,
lance aux belles de plaisantes apostrophes.
Dès ce soir, Lella Oum Keltoum sera certainement informée de ce
scandale, et les colporteuses de nouvelles insisteront, avec perfidie, sur les
ébats du «fils de son oncle».
—Il est fou de cette Drissia, tu vois, la plus salée, celle au caftan
«cardon»... Les hommes ne valent rien, formule Rabha en faisant une moue
attristée.
Que ne m’eût-elle appris, la petite fille, si la «carroussa» n’était, à ce
moment, passée près de nous. Rabha fut saisie d’un intense désir d’y
prendre place. Haïk et mines de femme sont vite rejetés. Pour un sou, la
voici logée dans la boîte, prison roulante qui bute, cahote et grince, où les
enfants s’entassent jusqu’à l’étouffement. Un homme traîne, deux autres
poussent et s’efforcent d’activer les roues qui ne marchent pas...
Pendant ce temps, Saïd savoure les joies d’un autre sport. Sur ce poteau,
fiché dans le sol, des barres en croix tournent horizontalement. Au bout de
chaque poutre, deux cordes soutiennent un siège fait de quatre planches
peintes et parfois décorées de colonnettes. Si les enfants placés vis-à-vis
sont d’un poids égal, et si les gamins chargés de tirer sur les cordes
accomplissent leur tâche, le système s’ébranle. Entraînés par la force
centrifuge, les sièges s’éloignent du poteau central, dans une envolée qui
force l’entourage à s’écarter. Saïd ne veut plus quitter la passionnante
machine, ses menottes s’agrippent aux cordes, son selham vert balaye
l’assistance. Il est heureux!
Nous accédons à ses supplications et le confions à Kaddour qui s’amuse
autant que lui. Les petites filles, déjà lasses, inhabituées aux sorties, ne
demandent qu’à rentrer. Mais tout le reste du jour, elles ressassent, avec
excitation, les plaisirs de la fête.
Vers le mohgreb, Kaddour est revenu, seul et la mine soucieuse. Il porte
sur son bras le selham de satin vert.
—Où est Saïd?
—C’est un vaurien, fils de vaurien!... Il s’est sauvé de moi, tandis que
nous étions devant un marchand de bonbons. Voici des heures que je le
cherche!... La foule était si compacte qu’une sauterelle, tombant sur la
place, n’aurait pu se poser à terre...
Saïd n’est pas beaucoup plus gros qu’une sauterelle, mais le vert de son
selham l’emporte, quant à l’éclat, sur celui de ces bestioles.
—Dans ma pensée, reprend Kaddour, il s’en est justement débarrassé
afin que je ne puisse plus le reconnaître. Un homme me l’a remis tout
piétiné. Un selham de satin!...
—As-tu été chez le Pacha?...
—J’ai vu le Pacha, j’ai vu le Mohtasseb, j’ai vu le chef du quartier!... Il
n’y a pas de lieu au monde où je ne sois allé. Maintenant j’ai lâché les
crieurs publics, ils parcourent la ville. Écoute...
La voix sonore, au rythme connu, s’enfle et décroît, tout au long de la
rue, derrière nos murs, mais elle ne proclame point la perte ordinaire d’une
sacoche ou d’un âne:
O les gens de religion!

O les braves gens!
Un enfant a disparu!
Un garçon de trois ans,
Possesseur d’un petit caftan rose,
Celui qui peut donner de ses nouvelles
Fera le bien et recevra sa récompense.
Le crieur chante en courant, la voix s’éloigne:
O les gens de religion!

O les braves gens...
Toute la ville va s’occuper du méchant gamin, et je ne doute point qu’on

ne le ramène ici. Qui donc, sauf nous, voudrait garder Saïd?...
Pourtant la nuit s’avançait lorsqu’un Mokhazni du Pacha, tenant l’enfant
endormi dans ses bras, vint heurter à notre porte.
—Il était sous l’auvent de la grande mosquée. Une femme qui avait
entendu le crieur est venue me prévenir.
—Sur elle et sur toi, la bénédiction d’Allah! Voici des réaux que vous
partagerez.
Saïd, posé à terre et mal réveillé, ouvre des yeux hagards.
Il parle, parle, d’une bizarre petite voix haletante:
—Mes sœurs m’ont dit: «Prends-leur des gâteaux, il y en a chez eux...
prends-leur du sucre que tu nous apporteras, et du petit argent si tu en
trouves...» Il y avait des hommes et des femmes. Nous nous sommes bien
réjouis, nous avons bu et nous avons mangé... nous avons parfumé nos
vêtements... Mes sœurs, ce ne sont que des p... de Sidi Nojjar, mais elles
m’ont donné des bonbons.
—O méchant! pourquoi t’es-tu sauvé de Kaddour? Tes sœurs étaient
donc à la fête? Nous t’avions défendu de les voir jamais, tu le sais bien.
L’enfant rit sans répondre, puis il entonne une chanson obscène, vacille
et tombe accroupi sur les mosaïques. Son haleine, empestée de mahia[63],
confirme ce que déjà nous avions deviné.
Saïd est ivre, épouvantablement!...
12 novembre.
Les vapeurs qui s’étendaient sur le ciel, comme le tfina de mousseline
dont la transparence atténue l’éclat d’un caftan, se sont accumulées, cette
nuit, et deviennent d’épaisses nuées menaçantes.
Elles accourent de l’ouest, se poursuivent, se bousculent, se confondent
en un conflit tragique et muet. Plus haute et subitement hostile, la chaîne du
Zerhoun barre l’horizon d’un rempart indigo foncé; les ruines
s’abandonnent, très grises; il semble que la ville se soit écroulée davantage.
En cette atmosphère de tristesse et d’hiver, ce n’est plus qu’un lamentable
tas de décombres.
Quelques gouttes s’écrasent lentement dans la poussière en y traçant des
étoiles... Leur rythme s’accentue, se précipite, et Meknès disparaît sous le
voile rayé de la pluie.
Elle tombe! Elle tombe! impétueuse, irrésistible, dévastatrice. On dirait
qu’elle veut se venger de son long exil. Elle tombe avec rage, avec férocité.
Elle noie les demeures, transperce les murs, flagelle les arbres et les plantes.
La rue tout entière est un torrent qui dégringole; certains patios en contre-
bas de la chaussée se remplissent d’eau, l’inondation gagne les chambres et
en chasse les habitants... J’aperçois des voisines réfugiées sur la terrasse de
leur pauvre masure. Elles sont trois, blotties les unes contre les autres, telles
des oiseaux frileux, résistant mal au déluge et au vent qui les cingle.
Kaddour apporte une échelle. Il doit opérer un véritable sauvetage pour les
amener dans la cuisine où elles se sécheront.
Mais nous n’avons point le temps de nous apitoyer sur les malheurs
d’autrui. Les petites filles, très excitées, nous signalent nos propres
désastres. L’eau ruisselle dans le salon à travers la coupole précieusement
ciselée... elle suinte le long des murs sous le haïti[64] de velours... elle
envahit le vestibule... En hâte on déménage les pièces, on sauve les anciens
tapis de Rabat, on décloue les tentures et les broderies.
C’est bien notre faute! A cette époque nos terrasses devraient être
refaites, nouvellement blanchies à la chaux, pour affronter la mauvaise
saison. Mais la nonchalance des Musulmans nous a gagnés. Comme eux
nous remettons de jour en jour les plus urgents travaux; comme eux nous
voilà surpris par ces pluies tardives, et, comme eux aussi, nous nous
précipiterons, à la première éclaircie, chez les «blanchisseurs de terrasses»
que toute la ville se disputera...
On en a vite assez de la pluie!...
Il fait froid, on grelotte dans ces immenses salles revêtues de mosaïques.
Un vent glacial filtre sous les portes et les croisées mal jointes; le riadh est
transformé en un bassin au milieu duquel, imperturbable et fier, le jet d’eau,
sans attrait, continue à s’élancer.
Privée de tous ses reflets, notre demeure prend un air lugubre de prison;
les ors, les faïences, les vitraux se sont éteints...
Il n’y a plus de soleil!... Toutes ces choses d’Orient ne vivent que de
soleil. Elles n’ont été conçues que pour le soleil. Elles ne signifient rien
sans soleil...
Sa première fureur apaisée, la pluie se fait régulière et monotone; elle
s’installe...
Les rues s’emplissent de boue. Il y a des flaques profondes où l’on
s’enlise, des pentes que l’on ne saurait gravir sans glisser, des ruisseaux
gluants épais et bruns...
Au pas de sa mule, un notable éclabousse les murs et les passants. Des
négrillons barbotent avec ivresse, maculant leur peau de taches blanchâtres.
Les Marocains ont chaussé de hautes socques en bois qui pointent à
l’avant du pied. Enveloppés de leur burnous de drap sombre, aux capuchons
dressés, ils ressemblent à des gnomes. Eux aussi ont perdu tout leur charme
de belles draperies et d’allures majestueuses. Mais ils ne s’abordent qu’avec
des airs réjouis et ils se congratulent comme pour une fête:
—Quel est ton état par ce temps? Allah le prolonge!
—Certes! il promet l’abondance et la prospérité.
—L’orge, ainsi que le poisson, aime l’eau...
—Louange à Dieu qui nous accorde la pluie!
—Bénie soit-elle! les récoltes seront heureuses...
Le jour oscille et s’abîme dans la nuit. Une nuit mate, épaisse, absolue...
Aucune lueur ne descend du ciel, ces ténèbres n’ont pas d’étoiles. Seules,
des lanternes errantes éclairent le sol de reflets en zigzag.
21 novembre.
Quelques paroles de Saïd.
Je ferme les boutons à pression de ma robe. L’enfant écoute
attentivement leur petit bruit sec:
—Ils claquent, dit-il, comme des poux sous l’ongle.
Mon mari achève une épure. Saïd s’approche de lui et désigne le
compas:
—O mon père! voici donc l’instrument des Nazaréens pour saisir le
mauvais œil?
La pluie:
—Bénédiction! s’écrie Saïd. Il pleut des prunes et des raisins.
30 novembre.
Deux Européennes sont entrées dans la demeure éblouissante où l’on
célèbre les noces de Lella Khdija, fille d’un ancien vizir...
Elles ont un air à la fois hardi et apeuré, au milieu des Musulmanes dont
elles ne comprennent ni le langage, ni les coutumes, et qu’elles méprisent
avec curiosité... On nous avait prévenues, ce sont des étrangères de passage;
l’une, femme d’un officier, habite Casablanca; l’autre vient de Paris et visite
le Maroc. Elles avaient envie de connaître les fêtes d’un mariage et Si
Mohammed ben Daoud, pressenti, n’a pu répondre que par une invitation.
Elles restent interdites dans le patio. Les esclaves s’agitent pour leur
trouver des sièges et apportent enfin un vieux fauteuil et une chaise,
qu’elles disposent à l’entrée de la salle, devant le divan où nous sommes
accroupies.
La Parisienne arbore un impertinent face-à-main, son œil furète à droite,
à gauche, dans tous les coins. On dirait qu’elles regardent une comédie.
Elles échangent leurs impressions à voix haute, sûres de n’être point
comprises. Je me rends compte que cette Parisienne est une femme de
lettres faisant un «voyage d’études». A tout propos elle dit:
—Tel détail est caractéristique, je le signalerai à mes lecteurs... Quel
spectacle curieux! Voilà un beau sujet d’article.
Sa compagne remarque surtout nos toilettes.
C’est le soir de la suprême cérémonie, le départ de la mariée pour la
maison nuptiale. Aussi l’excitation, les parures, les chants atteignent-ils le
paroxysme de l’intensité. Toutes les invitées resplendissent à l’envi.
Combien ces Européennes élégantes, certainement habituées au monde,
apparaissent mesquines et ternes avec leurs costumes tailleurs, leurs bottes
lacées, leurs chapeaux inesthétiques! Gauches aussi, parmi les femmes,
chargées de brocarts et de bijoux, aux mouvements lents et rituels... Le
cadre trop somptueux ne convient point à leur frêle beauté. La moindre
négresse a plus d’allure que ces jolies dames, qui auraient beaucoup de
succès dans un salon.
Elles me considèrent à présent; je continue à battre des mains au rythme
de la musique, tout en chantant comme les autres:
—La paix, ô Lella!

La paix en notre demeure!
Elles ne me devinent pas. Elles ne peuvent pas me deviner sous le fard,

le kohol et les parures... Cependant c’est vers moi que leurs regards
convergent avec insistance... peut-être parce que je suis la plus éblouissante.
Lella Fatima-Zohra ne manque pas, chaque fois que je vais à des noces,
de me prêter quelques-uns de ses extraordinaires joyaux. Des rangs
d’émeraudes et de perles s’enroulent autour de mon turban, et les colliers de
la sultane Aïcha Mbarka étincellent sur mon caftan noir broché d’or. Mais
ce n’est pas seulement cette magnificence qui intrigue les jolies dames: mes
yeux trop pâles, mes yeux bleus, ont une étrange douceur au milieu des
sombres prunelles ardentes de mes amies...
Les chants ont cessé, nous reprenons nos attitudes d’idoles, échangeant à
peine de rares paroles. Les Européennes quittent leurs chaises et viennent
s’accroupir gauchement auprès de nous. Elles voudraient être aimables et
répètent le seul mot qu’elles sachent:
—Mesiane! Mesiane! (joli).
Ainsi la conversation ne peut aller fort loin. Je doute que la femme de
lettres pénètre beaucoup l’âme musulmane. Elle touche le brocart de ma
robe:
—Mesiane! dit-elle encore.
Une idée traverse mon esprit: je ne connais pas ces dames, je ne les
reverrai jamais, nulle ne se doutera de la mystification.
—Comment trouvez-vous notre fête? leur demandé-je.
Elles me regardent, interloquées.
—Tu parles français?
—Un peu.
—Très bien même, presque sans accent! s’étonne la Parisienne. Où l’as-
tu appris?
—Ma grand’mère était Française.
—Ah! c’est donc pour cela que tu as les yeux bleus!... Comment a-t-elle
épousé un Musulman?
—Je ne sais pas, dis-je, subitement hostile.
Elles comprennent qu’il ne faut point poser certaines questions. Pourtant
le désir de m’interroger les tourmente, surtout la femme de lettres, ravie
d’une si rare aubaine.
—Comme tu es belle! reprend-elle en examinant mes parures. Ces
bracelets d’or sont anciens?
—Non! m’écrié-je avec orgueil, ils sont tout neufs!
Les Européennes échangent de petits coups d’œil ironiques. La femme
de lettres exulte. C’est tout juste si elle ne dit pas: «Je noterai cela pour mes
lecteurs.»
Elle s’enquiert de mille détails saugrenus. Elle n’est pas bête cependant;
je la croirais même intelligente, mais si incompréhensive de tout ce qui
n’est pas sa civilisation, ses habitudes, sa culture! Elle est venue avec une
idée toute faite sur les odalisques lascives, alanguies, fumant le narghileh, à
moitié nues dans l’enroulement des gazes lamées d’or ou d’argent. Et aussi
les désenchantées qui aspirent à la liberté et se meurent de ne pouvoir sortir
ni fréquenter les hommes.
Elle rencontre ici des Musulmanes très graves, hiératiques, vêtues de
lourdes soieries qui ne laissent même pas deviner la silhouette de leur corps,
des femmes aux rigides allures de statues... Cela dérange sa conception, elle
y tient et veut la retrouver. Toutes ses questions tendent vers ce but:
—Sais-tu danser? me demande-t-elle. Y aura t-il des danses aujourd’hui?
—Chez nous les femmes ne dansent pas, seulement les fillettes ou les
négresses.
—La danse du ventre? la danse des poignards?
—Non, elles ne connaissent pas ces danses à vous, mais les nôtres...
Celle-ci, dis-je en désignant Kenza qui, justement, esquisse quelques
mouvements harmonieux et lents, avec l’air inspiré, presque religieux d’une
prêtresse.
—Et c’est tout! interrogent les jolies dames fort déçues.
Je sais bien ce qu’elles attendaient: la figuration de l’amour, le drame de
la volupté... Mais la danse ici n’est qu’un rite, le plus grave, le plus pudique
des rites. La petite danseuse se rassied, une esclave lui succède, dont le
visage noir s’ennoblit tandis que sa croupe ondule lentement sous le
caftan...
Les chants ont pris un rythme de psaumes, ce sont les plaintes de la
mariée songeant au départ:
Oh! qu’y a-t-il en moi, ma mère!

O dame! qu’y a-t-il en moi?...
Elles sont parties, mes compagnes,
Elles ne m’ont point avisée!
Elles m’abandonnent, hélas!
Qu’y a-t-il en moi?...
Bientôt, bientôt Dieu aura pitié de ma peine,

Je retrouverai tout ce qui m’a quittée.
Je ne me séparerai plus de toi, ma mère!
O beauté! je ne partirai pas!
Même si je dois mourir, ô chef!
Même si l’on me charge de chaînes
Et que le collier en soit neuf!
Jeunes filles nous nous tenions au bord de la fontaine

Et l’on est venu me prendre parmi elles!
—Quelle est, disaient-ils, la vierge au bandeau?
Ils m’emmenèrent... quel trouble!
Qu’y a-t-il en moi, ô dame?
O beauté! Qu’y a-t-il en moi?
Garde, ô Seigneur, les cherifat

Filles du Prophète, du Choisi!
Impassibles et silencieuses les femmes écoutent le chant nuptial, tandis

que la petite mariée sanglote derrière les tentures du ktaa.
Mais la Parisienne ne sait pas se taire, et elle me presse de questions:
—Tu portes toujours des robes comme celle-ci?
—Non, madame, c’est mon costume pour les noces.
—Dans ta maison, en temps habituel, que mets-tu?
—J’ai un caftan de drap et une tfina de mousseline.
—L’été, lorsqu’il fait chaud, ou que tu attends ton mari, n’as-tu pas
seulement des robes de gaze?
—Certes non! ce n’est pas notre coutume.
—Que fais-tu chez toi, tout le jour?
—Je dirige mes esclaves, je m’occupe de mes enfants.
—Et tu ne t’ennuies jamais?
—Pourquoi m’ennuierais-je?
—Tu n’as pas envie de sortir, de voyager comme nous?
—Si l’on voulait me faire sortir, je pleurerais pour rentrer, dis-je,
répétant la réponse qu’une Musulmane me fit à moi-même, au temps où je
ne comprenais pas encore.
—N’aimerais-tu pas voir les hommes, causer avec eux?
—Quelle honte! m’écrié-je convaincue.
La Parisienne est visiblement troublée; je jouis de son désarroi. Elle
croyait trouver des courtisanes et des rebelles en ces somptueuses barbares.
Je lui laisse entrevoir des femmes très près d’elle, tout en étant si loin, très
semblables, à part quelques différences de coutumes.—Des femmes
adaptées à leur existence et qui n’en souffrent pas plus que nous, d’être
clouées au sol, quand nous voyons passer des avions... Mais les apparences
seules frappent son esprit; elle a des étonnements excessifs pour les
cérémonies de ces noces et ne fait pas de retour sur les nôtres. Elle n’en
soupçonne point le sens profond. L’étrangeté du décor, le pittoresque de
quelques détails suffisent à la dérouter...
Nos mariées, vêtues de blanc et couronnées d’oranger, qui s’avancent
avec un traditionnel air pudique, sont pourtant les sœurs de cette aroussa
«pleine de honte», chargée de bijoux et de voiles. L’étalage des cadeaux,
accompagnés de la carte des donateurs, ne le cède en rien à leur
présentation par la neggafa. La musique, les cierges, les parures, les festins
forment le thème de nos fêtes aussi bien que de celle-ci... Vestiges des rites
millénaires qui apparentent tous les humains et dont les symboles survivent
incompris à travers les religions et les races. Ils m’apparaissent et
m’émeuvent davantage au contact de ces curiosités superficielles.
Et soudain, j’ai la poignante impression d’être étrangère à toutes, dans
cette fête. Si loin des Européennes qui ne peuvent comprendre les âmes vers
lesquelles je me suis inclinée! si loin! plus loin encore des Marocaines que
ne chercheront jamais à comprendre la mienne...
Cependant je sens mieux que, toutes, nous sommes des sœurs.
Il faut intimement connaître les Musulmanes pour ne plus voir en elles
des créatures à part, mais de simples femmes animées des sentiments les
plus naturels: des coquettes, des jalouses, des frivoles, des mères aussi,
d’excellentes maîtresses de maison... Elles s’intéressent aux toilettes, aux
histoires d’esclaves et d’amour. Cela me semble identique aux questions de
chiffons, de domestiques et d’intrigues qui passionnent tant d’Européennes.
Même l’ennui, l’inconscient ennui qui forme la trame de leurs existences
monotones et recluses, n’est guère plus accablant que celui dont languissent
nos petites bourgeoises, condamnées à vivre dans un fastidieux cercle
restreint, hors duquel, si souvent, elles ne soupçonnent rien...
Je voudrais dire tout cela et tant d’autres choses à cette femme de lettres
qui cherche à découvrir les Musulmanes. Mais je me tais, puisque
aujourd’hui j’en suis une... Car jamais aucune d’entre elles n’analysa ses
sentiments. Et c’est là surtout ce qui les différencie tellement de nos âmes
occidentales, et forme tout le secret de leur paisible bonheur.
13 décembre.
Coucher de soleil vert et rose, au dehors des murs. Étrange atmosphère
irréelle, voluptueuse et changeante, par la magie de ces deux couleurs qui se
cherchent, s’opposent, s’exaspèrent puis doucement s’atténuent et se
fondent en un crépuscule dont les cendres apaisent la dernière flambée du
jour.
Le bled, où les jeunes orges étendent leurs prairies d’un vert acide, va
rejoindre par de larges ondulations, vert-bleu, vert-mauve, vert-gris, les
montagnes lointaines et proches à la fois, nettement découpées sur la
transparence du ciel abricot.
Une route sinue, rose et dorée, à travers les champs d’où reviennent les
troupeaux roux. Des milliers d’oiseaux les accompagnent, avec un grand
tourbillonnement dans l’air calme, une palpitation d’ailes et de cris; de ces
ibis blancs, appelés «serviteurs des bœufs», qui vivent avec les bestiaux et
les quittent seulement aux portes de la ville. Quelques minutes encore, ils
tracent dans le ciel des méandres agités, tandis que la terre, à mes pieds, se
bariole de leurs fugitives ombres vertes. Puis ils s’abattent sur un bosquet,
et les arbres au sombre feuillage sont fleuris tout à coup, comme des
magnolias, d’innombrables fleurs d’un rose laiteux.
Le cimetière de Sidi Ben Aïssa dort à l’ombre des oliviers, très solitaire
et paisible à cette heure. Mais, de l’autre côté de ses murs, s’adossent
accroupis, en petits tas de haillons dorés, des Arabes et des Chleuhs qui
projettent leurs belles ombres vertes sur ces murs très roses, et, recueillis,
écoutent les discours d’un charmeur de serpents.
Agile et svelte en sa courte tunique, l’homme évolue au milieu de son
auditoire, ses yeux hallucinants fixent tour à tour chacun des spectateurs.
Au sommet de son crâne rasé, s’épanouit la mèche des Aïssaouas que le
soleil fait flamber comme du cuivre rouge. Un petit orchestre, accroupi dans
la poussière, accompagne ses gestes et scande ses discours. Ce jongleur,
parfois, a l’air d’un saint en extase, et les gens ne démêlent pas très bien
s’ils assistent à des tours habiles et récréants, ou participent aux miracles
que renouvelle, chaque jour, sur cette place, le charmeur de serpents. Car
l’homme ne brave les reptiles et ne s’en joue que par la protection des saints
dont il proclame la baraka.
Mouley Abdelkader! O Mouley Abdelkader!
Allah lui a conféré sa grâce!
Quand un disciple l’appelle, le maître accourt vers lui,
Il agite ses manches et vole comme l’oiseau.
Ris et sois joyeux! Chasse de ton cœur le souci!

L’assurance de la richesse
Mouley Abdelkader te la donne.
Et quand il l’a donnée
Il ne revient pas sur sa parole,
Notre Seigneur Dieu s’en est porté garant.
Moi je suis tien, O illustre!

Je n’ai d’autre recours que toi,
Accorde-moi ta protection, ne tarde pas!
Mouley Abdelkader,
O Sauveur des patrons de vaisseaux!
Galope! Il te suffit pour cela d’un roseau.
Moi je suis tien, O illustre!
Et les assistants supplient en chœur:

O Mouley Abdelkader!
O Sidi Ben Aïssa!
Protecteurs des gens en péril!
O ceux par qui l’on ne craint pas!
L’imploration, peu à peu, se fait plus pressante, les musiciens martèlent

avec rage leurs tambourins. Soudain, les sons stridents d’une flûte percent
les notes ronronnantes et graves, et deux serpents, lancés à toute volée d’on
ne sait où, s’abattent au milieu du cercle. L’homme les saisit par l’extrémité
de la queue. Au bout de ses bras, les serpents tombent, allongés et minces,
presque inertes. L’un a le ventre rosâtre, du rose délicat d’un pétale, l’autre
le ventre couleur d’absinthe. Après quelques moments, ils se raniment; un
frissonnement coule tout du long de leur peau, les têtes plates se redressent
avec effort et se dardent l’une vers l’autre en agitant des langues aiguës. Ils
se défient, s’abordent et s’enroulent étroitement. De cette corde vivante,
l’homme cingle l’air au-dessus des gens effarés:
Enlève de ton âme la crainte,
Pourquoi t’effrayer?
Celui qui tient la hache
A-t-il besoin de chercher la jointure?
Il frappe où il veut,
Il possède l’acier puissant.
Moi, j’ai appelé la bénédiction de Mouley Abdelkader,
Moi, j’implore le secours de Sidi Ben Aïssa.
Tout en chantant, l’homme abandonne les reptiles enlacés et s’accroupit

en face de cylindres en peau, sortes d’outres rigides, au col serré d’un lien.
Il plonge ses mains dans les profondeurs des outres et les retire pleines
de serpents qu’il jette négligemment sur le sol: petits serpents luisants,
lisses et blanchâtres, molles couleuvres aux écailles vert sombre, serpents
épais, ronds et lourds, qui déroulent leurs anneaux avec pesanteur et
semblent quitter à regret la retraite d’où ils sont extraits. Comment ces deux
outres, d’apparence médiocre, pouvaient elles recéler un tel nombre de
serpents?
Quelques-uns se sont éloignés du tas répugnant, et sinuent, dans la
poussière, vers la foule qui se débande. Mais le jongleur les a vite rattrapés,
et il les fixe par les bouts de leurs queues, serrés entre ses orteils. Ainsi
maintenus, les serpents s’écartent sur le sol, en éventail aux branches
inégales. Seul, le plus grand, que l’homme a jeté sur ses épaules, entoure
son cou et pend, sans entraves, jusqu’au bas de sa tunique.
Parmi les petits serpents déployés à terre, le disciple des saints choisit le
plus vif, le plus frétillant. Il le pince au milieu du corps, entre le pouce et
l’index, et l’élève à la hauteur de son visage.
Le petit serpent nerveux s’est crispé, sa queue se tortille, d’un raide
mouvement, sa tête fine se tend, gueule béante, vers le charmeur.
Va, marche au milieu des serpents!
Va! Chasse dans la forêt, O toi qui crains!
Dans la forêt entre les oueds,
Sur la colline de Mzara
Où le fusil est braqué.
Si Ben Aïssa le protège,
Pour te trancher un seul poil
Mille coups ne suffiraient.
Hypnotisées mutuellement, les têtes se sont rapprochées, celle de

l’homme et celle du reptile, les bouches se sont ouvertes, et, tandis que les
yeux se fascinent, étincelants, la langue tendue de l’Aïssaoui disparaît dans
la gueule du petit serpent. Ils restent là, fixés l’un à l’autre avec de pareils
airs d’extase.....
O Mouley Abdelkader!
O Sidi Ben Aïssa!
Protecteurs des gens en péril,
O ceux par qui l’on ne craint pas!
Les dernières lueurs du moghreb s’éteignent, les serpents verts ne

forment plus qu’un tas noir aux pieds du charmeur, tous les roses du ciel et
de la terre sont absorbés par la nuit.
Lorsque l’homme retira sa langue de la gueule du petit serpent, deux
gouttes sombres tombèrent dans la poussière, sans qu’on en distinguât la
rougeur sanglante.
24 décembre.
Discret, timide et si décent, le maître de Saïd m’aborde. Il parle bas,
d’une voix enrouée, monotone, comme s’il dévidait quelque verset du
Coran. L’enseignement sacré, qu’il distribue depuis trente ans à des
générations de petits Marocains, n’a pas été sans l’affaisser un peu. Il
n’entre jamais dans notre demeure qu’avec une secrète appréhension, car la
vue du hakem paralyse sa langue, experte aux récitations pieuses. Il ne se
plaît qu’au milieu des enfants dont il a gardé l’âme simple.
—Quelles sont les nouvelles du lettré? lui demandai-je. La fête fut-elle
réussie?

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Novel Electrochemical Energy Storage

Devices: Materials, Architectures, and

Recent Advancements in Polymeric Materials for

Lead Free Piezoelectric Materials 1st Edition Jing Feng

Antenna Architectures for Future Wireless Devices Koul

Energy Storage and Conversion Devices: Supercapacitors,

Energy Storage Devices for Renewable Energy-Based

Electrode Materials for Energy Storage and Conversion

Polymer Electrolytes for Energy Storage Devices: Volume

Biomaterials and Materials for Medicine: Innovations in

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