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Nanoarchitectonics
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Nanoarchitectonics
Edited by
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Contents
Preface xvii
1 Electrodes for Flexible Integrated Supercapacitors 1
Sajid ur Rehman and Hong Bi
1.1 Introduction and Overview of Supercapacitors 2
1.2 Electrode Materials for Flexible Supercapacitors 4
1.2.1 Carbon Materials 4
1.2.1.1 Activated Carbon 4
1.2.1.2 Carbon Nanotubes 5
1.2.1.3 Graphene 6
1.2.1.4 Carbon Aerogels 8
1.2.1.5 Graphene Hydrogel 8
1.2.2 Conducting Polymers 10
1.2.3 Metal Compounds 13
1.2.3.1 Ruthenium Oxide (RuO2) Electrode Material 14
1.2.3.2 Nickel Oxide (NiO) Electrode Material 15
1.2.3.3 Copper Oxide (CuO) Electrode Material 16
1.2.3.4 Composite Electrode Materials 17
1.3 Device Architecture of Flexible Supercapacitor 18
1.4 Integration of Flexible Supercapacitors 19
1.5 Conclusion 21
References 22
2 Flexible Supercapacitors Based on Fiber-Shape Electrodes 27
Faiza Bibi, Muhammad Inam Khan, Abdur Rahim,
Nawshad Muhammad and Lucas S.S. Santos
2.1 Introduction 27
2.2 Supercapacitors 29
2.2.1 Electrochemical Supercapacitor 29
2.2.2 Flexible Supercapacitors 30
2.3 Shape Dependent Flexible Electrodes 31
2.3.1 Porous 3D Flexible Electrodes 32
v
vi Contents
2.3.2 Flexible Paper Electrodes 32

2.3.3 Flexible Fiber Electrodes 33
2.4 Fiber Shape Electrodes (FE/FSC) 34
2.4.1 Wrapping Fiber Shape Electrode/Supercapacitors 34
2.4.2 Coaxial Fiber Shape Electrode/Supercapacitor 35
2.4.3 Parallel Fiber Shape Electrode/Supercapacitor 36
2.4.4 Twisted Fiber Shape Electrode/Supercapacitor 37
2.4.5 Rolled Fiber Shape Electrode/Supercapacitors 38
2.5 Conclusion 39
References 40
3 Graphene-Based Electrodes for Flexible Supercapacitors 43
Jyoti Raghav, Sapna Raghav and Pallavi Jain
3.1 Introduction 43
3.2 Type of SCs 44
3.2.1 EDLC 44
3.2.2 PCs 45
3.2.3 Flexible Graphene-Based Nano Composites 45
3.3 Fabrication Techniques for the Electrode Materials 46
3.3.1 Electrodeposition 46
3.3.2 Direct Coating (DC) 46
3.3.3 Chemical Vapor Deposition (CVD) 48
3.3.4 Hydrothermal 48
3.4 Substrate Materials for the Flexible SCs 48
3.5 Graphene Nanocomposite-Based Electrode Materials 49
3.5.1 Additives/Graphene Electrodes 49
3.5.2 Binder/Graphene Electrodes 49
3.5.3 Pure Graphene Electrode 50
3.5.4 Conductive Polymers/Graphene Composites Electrode 50
3.5.5 Metal or Metal Oxides (MOs) Composite Electrodes 51
3.6 NSs for the Flexible SC 52
3.7 Conclusion 53
Acknowledgment 54
References 54
4 Polymer-Based Flexible Substrates for Flexible Supercapacitors 59
Zul Adlan Mohd Hir, Shaari Daud, Hartini Ahmad Rafaie,
Nurul Infaza Talalah Ramli and Mohamad Azuwa Mohamed
4.1 Introduction 60
4.2 Polymers-Based Flexible Materials for Flexible
Supercapacitors 61
Contents vii
4.3 Synthesis and Fabrication Approach of the Polymer-Based

Electrode 62
4.3.1 Preparation of Polymer-Based Electrode Materials 62
4.3.1.1 Polyaniline (PANI) 63
4.3.1.2 Polypyrrole (PPy) 65
4.3.1.3 Poly (3,4-ethylenedioxythiophene) (PEDOT) 66
4.3.2 Electrode Fabrication 69
4.4 Physicochemical Characterization of Flexible Supercapacitors 70
4.4.1 Scanning Electron Microscopy 70
4.4.2 Transmission Electron Microscopy 71
4.4.3 X-Ray Diffraction 73
4.4.4 Surface Area Analysis by BET (Brunauer, Emmett
and Teller) 75
4.4.5 X-Ray Photoelectron Spectroscopy (XPS) 78
4.5 Recent Findings on the Performance of Flexible
Supercapacitors 79
4.5.1 Electrochemical Double-Layer Capacitor (EDLC) 80
4.5.2 Pseudocapacitor 81
4.5.3 Hybrid Supercapacitor 83
4.6 Conclusion 86
References 87
5 Carbon Substrates for Flexible Supercapacitors and Energy
Storage Applications 95
Seyyed Mojtaba Mousavi, Seyyed Alireza Hashemi,
Najmeh Parvin, Chin Wei Lai, Sonia Bahrani,
Wei-Hung Chiang and Sargol Mazraedoost
5.1 Introduction 96
5.2 Overview of the Energy Storage System 98
5.3 Capacitors Modeling 109
5.3.1 Equivalent Circuit Models 120
5.3.2 Intelligent Models 121
5.3.3 Self-Discharge 122
5.3.4 Fractional-Order Models 122
5.3.5 Thermal Modeling 123
5.4 Industrial Applications of Capacitors 124
5.4.1 Power Electronics 124
5.4.2 Uninterruptible Power Supplies 125
5.4.3 Hybrid Energy Storage 126
5.5 Conclusions 127
References 127
viii Contents
6 Organic Electrolytes for Flexible Supercapacitors 143

Younus Raza Beg, Gokul Ram Nishad and Priyanka Singh
6.1 Introduction 143
6.2 Organic Electrolytes 145
6.3 Solid and Quasi-Solid-State Electrolytes 150
6.3.1 PVA-Based Gel Electrolytes 154
6.3.2 PEG-Based Gel Electrolytes 156
6.3.3 PVDF-Based Gel Electrolytes 157
6.4 Ionic Liquids-Based Electrolytes 159
6.5 Redox Active Electrolytes 165
6.6 Conclusion 167
References 170
7 Carbon-Based Electrodes for Flexible Supercapacitors
Beyond Graphene 177
Sunil Kumar and Rashmi Madhuri
7.2 Materials Used to Prepare Flexible Supercapacitors 179
7.2.1 Carbon Materials 180
7.2.1.1 Activated Carbon (AC) 180
7.2.1.2 Carbon Nanotubes (CNTs) 180
7.2.1.3 Graphene 181
7.2.1.4 Carbon Aerogel 181
7.2.2 Conducting Polymer 181
7.2.3 Metal Oxide 182
7.3 The Carbon-Based Electrode Used for Flexible
Supercapacitors 182
7.3.1 Carbon Nanotube (CNT)-Based Materials 182
7.3.1.1 CNT-Conducting Polymer Composite
as Supercapacitors 182
7.3.1.2 CNT–Metal Oxide Composite as
Supercapacitors 185
7.3.2 Activated Carbon-Based Materials 191
7.3.2.1 Activated Carbon-Conducting Polymer
Composite as a Supercapacitor 191
7.3.2.2 Activated Carbon–Metal Oxide Composite
as a Supercapacitor 195
7.4. Conclusion 201
References 201
Contents ix
8 Biomass-Derived Electrodes for Flexible Supercapacitors 211

Selvasundarasekar Sam Sankar and Subrata Kundu
8.1.1 Electrode Materials for Flexible Supercapacitors 213
8.2 Biomass-Derived Carbon Materials 214
8.2.1 Activation 214
8.2.1.1 Physical Activation 215
8.2.1.2 Chemical Activation 215
8.2.1.3 Other Activation 218
8.2.2 Carbonization 218
8.2.2.1 Hydrothermal Method 218
8.2.2.2 Pyrolysis Method 219
8.3 Incorporation of Biomass-Based Electrodes in Flexible
Supercapacitors 220
8.4 Challenges for Using Biomass-Derived Materials 222
8.5 Conclusion 224
References 225
9 Conducting Polymer Electrolytes for Flexible Supercapacitors 233
Aqib Muzaffar, M. Basheer Ahamed and Kalim Deshmukh
9.2 Components of a Supercapacitor 236
9.2.1 Electrodes 236
9.2.2 Electrolytes 237
9.2.3 Separator 238
9.2.4 Current Collectors 239
9.2.5 Sealants 239
9.3 Configuration of a Supercapacitor 240
9.4 Conducting Polymer Electrolytes 241
9.4.1 Gel Conducting Polymer Electrolytes 243
9.4.2 Ionic Liquid-Based Conducting Polymer 246
9.4.3 OH− Ion Conducting Polymers 247
9.5 Conclusion 252
References 252
10 Inorganic Electrodes for Flexible Supercapacitor 263
Muhammad Inam Khan, Faiza Bibi, Muhammad
Mudassir Hassan, Nawshad Muhammad, Muhammad Tariq
and Abdur Rahim
10.2 Flexible Inorganic Electrode Based on Carbon
Nanomaterial 265
x Contents
10.2.1 Carbonaceous Material 265

10.2.1.1 Graphene 266
10.2.1.2 Graphene Oxide-Based Electrodes 268
10.2.1.3 Carbon Nanotubes 269
10.2.1.4 Carbon Films/Textiles 271
10.3 Conclusion 272
References 273
11 New-Generation Materials for Flexible Supercapacitors 277
P.E. Lokhande, U.S. Chavan, Suraj Bhosale, Amol Kalam
and Sonal Deokar
11.2 Taxonomy of Supercapacitor 278
11.3 Fundamentals of Supercapacitor 280
11.4 Flexible Supercapacitor 282
11.4.1 Graphene-Based Flexible Supercapacitor 282
11.4.2 Metal Oxide/Hydroxide-Based Flexible
Supercapacitor 284
11.4.3 Conducting Polymer-Based Flexible
Supercapacitor 290
11.5 Outlook and Perspectives 298
Acknowledgement 303
References 303
12 Asymmetric Flexible Supercapacitors: An Overview of
Principle, Materials and Mechanism 315
Sabina Yeasmin and Debajyoti Mahanta
12.1 Introduction: Why Store Energy? 316
12.2 Supercapacitor: A Green Approach Towards Energy
Storage 316
12.3 Flexible Supercapacitors 319
12.3.1 Solid Electrolytes 320
12.3.2 Flexible Electrodes 322
12.3.3 Cell Designs for Flexible Supercapacitor 324
12.4 Asymmetric Supercapacitor 325
12.4.1 Principle, Material and Mechanism 325
12.4.2 Performance Evaluation in Asymmetric
Supercapacitor 330
12.5 Recent Advances in Flexible Asymmetric Supercapacitors 333
12.6 Conclusion 335
References 335
Contents xi
13 Aqueous Electrolytes for Flexible Supercapacitors 349

Dipanwita Majumdar
13.1.1 Influence of Electrolytes on Performance
of Supercapacitors 352
13.1.2 What is an Ideal Electrolyte? 354
13.1.3 Classes of Electrolytes for Supercapacitors 355
13.2 Electrolyte Performance-Controlling Parameters
for Designing Flexible Supercapacitors 357
13.2.1 Large Electrochemical Stability 357
13.2.2 High Ionic Conductivity 357
13.2.3 Nature of Electrolyte 358
13.2.4 Dielectric Constant and Viscosity of Solvent 358
13.2.5 Low Melting and High Boiling Points 359
13.2.6 High Chemical Stability 360
13.2.7 High Flash Point 360
13.2.8 Low Cost and Availability 360
13.2.9 Influence of Pressure 360
13.2.10 Influence of Binder 361
13.3 Why Aqueous Electrolytes? 362
13.4 Acid Electrolytes 363
13.4.1 EDLC and Pseudocapacitor Electrode Materials
Employing H2SO4 Aqueous Electrolyte 375
13.4.2 H2SO4 Electrolyte-Based Nanocomposite
Electrode Material Supercapacitors 377
13.4.3 H2SO4 Electrolyte-Based Hybrid Supercapacitors 377
13.5 Alkaline Electrolytes 378
13.5.1 Alkaline Electrolyte-Based EDLC and
Pseudocapacitors 379
13.5.2 Alkaline Electrolyte-Based Nanocomposite
Supercapacitors 381
13.5.3 Alkaline Electrolyte-Based Hybrid Supercapacitors 383
13.6 Neutral Electrolyte 383
13.6.1 Neutral Salt Aqueous Electrolyte-Based EDLC
and Pseudocapacitors 384
13.6.2 Neutral Salt Aqueous Electrolyte-Based
Nanocomposite Supercapacitors 387
13.6.3 Neutral Electrolyte-Based Hybrid Supercapacitors 388
13.7 Comparative Electrochemical Performances in Different
Aqueous Electrolytes 388
xii Contents
13.8 Water-in-Salt Electrolytes for Flexible Supercapacitors 394

13.9 Conclusion and Future Prospects 395
Acknowledgements 396
References 396
14 Electrodes for Flexible Micro-Supercapacitors 413
Subrata Ghosh, Jiacheng Wang, Gustavo Tontini
and Suelen Barg
14.2 Electrode Configurations 414
14.2.1 Sandwich µSCs 414
14.2.2 Fiber or Wire µSC 415
14.2.2.1 Parallel 416
14.2.2.2 Twisted or Two-Ply 417
14.2.2.3 Coaxial 417
14.2.2.4 Rolled 417
14.2.2.5 All-in-One 418
14.2.3 Interdigitated µSCs 418
14.3 Manufacturing Techniques 421
14.3.1 Photolithography 421
14.3.2 Electrodeposition 422
14.3.3 Laser Direct-Writing 422
14.3.3.1 Laser Carving 423
14.3.3.2 Laser Scribing 423
14.3.3.3 Laser Transfer Method 424
14.3.4 Printing 425
14.3.4.1 Screen Printing 426
14.3.4.2 Inkjet Printing 427
14.3.4.3 3D Printing 428
14.4 State-of-the-Art Electrode Materials 431
14.4.1 Nanocarbons 431
14.4.2 MXenes 433
14.4.3 Transition-Metal Chalcogenides 435
14.4.4 Metal-Based Materials 435
14.4.5 Conducting Polymers 438
14.4.6 Composites or Hybrid Structures 440
14.4.7 Symmetric vs Asymmetric 441
14.5 Conclusion and Outlook 445
Acknowledgement 446
References 447
Contents xiii
15 Electrodes for Flexible Self-Healable Supercapacitors 461

Ayesha Taj, Rabisa Zia, Sumaira Younis, Hunza Hayat,
Waheed S. Khan and Sadia Z. Bajwa
15.1.1 Supercapacitors 463
15.1.2 Electric Double Layer Capacitors (EDLCs) 464
15.1.3 Hybrid Capacitors 467
15.2 Self-Healable Nanomaterials 468
15.2.1 Metallic Nanomaterials 468
15.2.2 Non-Metallic/Carbon-Based Nanomaterials 470
15.2.3 Conducting Polymer-Based Nanomaterials 471
15.3 Nanomaterials-Based Interfaces for Supercapacitors 472
15.3.1 Metal Nanomaterials-Based Interfaces
for Supercapacitors 473
15.3.2 Graphene-Based Interfaces for Self-Healable
Supercapacitors 474
15.3.3 CNT/GO/PANI Composites Supercapacitors 478
15.4 Conclusion 479
References 480
16 Electrodes for Flexible–Stretchable Supercapacitors 485
Ravi Arukula, Pawan K. Kahol and Ram K. Gupta
16.1.1 Supercapacitors and Energy Storage Mechanisms 487
16.1.2 Flexible/Stretchable Supercapacitors 489
16.2 Electrodes for Flexible/Stretchable Supercapacitors 490
16.2.1 Metal Oxide-Based Flexible/Stretchable
Supercapacitors 491
16.2.1.1 Vanadium-Based Flexible Electrodes 493
16.2.1.2 Manganese-Based Flexible/Stretchable
Electrodes 494
16.2.1.3 Ruthenium-Based Flexible Electrodes 496
16.2.1.4 Other Metal Oxides-Based Flexible
Electrodes 498
16.2.2 2D Materials-Based Flexible/Stretchable
Supercapacitors 499
16.2.3 Carbon-Based Flexible/Stretchable Supercapacitors 504
16.2.4 Conductive Polymer-Based Flexible/Stretchable
Supercapacitors 505
16.2.5 Hybrid Composites-Based Flexible/Stretchable
Supercapacitors 507
xiv Contents
16.3 Conclusion and Future Remarks 511

References 512
17 Fabrication Approaches of Energy Storage Materials
for Flexible Supercapacitors 533
Mohan Kumar Anand Raj, Rajasekar Rathanasamy,
Prabhakaran Paramasivam and Santhosh Sivaraj
Abbreviations 533
17.1 Intoduction 534
17.2 Classification of Flexible Supercapacitors 536
17.2.1 Materials 536
17.2.1.1 Carbon 536
17.2.1.2 Metal Oxides 537
17.2.1.3 Conducting Polymers 537
17.2.1.4 Composites 537
17.2.2 Fabrication Methods 538
17.2.2.1 Electro-Chemical Deposition Method 538
17.2.2.2 Chemical Bath Deposition (CBD)
Process 539
17.2.2.3 Inkjet Printing 540
17.2.2.4 Spray Deposition Method 541
17.2.2.5 Sol–Gel Technique 542
17.2.2.6 Direct Writing Method 543
17.3 Conclusion 544
References 545
18 Nature-Inspired Electrodes for Flexible Supercapacitors 549
Aqib Muzaffar, M. Basheer Ahamed and Kalim Deshmukh
18.2 Energy Storing Mechanism of Supercapacitors 552
18.2.1 Electrostatic Double Layer Capacitor (EDLC) 554
18.2.2 Pseudocapacitor 555
18.2.3 Hybrid Supercapacitor 556
18.3 Flexible Supercapacitors 557
18.4 Essential Parameters of Supercapacitors 560
18.4.1 Energy Density Parameter 560
18.4.2 Power Density Parameter 561
18.5 Natural Flexible Supercapacitors 561
18.6 Conclusion 565
References 565
Contents xv
19 Ionic Liquid Electrolytes for Flexible Supercapacitors 575

Udaya Bhat K. and Devadas Bhat Panemangalore
Abbreviations 575
19.2 Mobile Energy Storage Systems and Supercapacitors 578
19.3 Flexible Supercapacitors: Need and Challenges 580
19.4 Developments in the Design of a Supercapacitor 581
19.5 Electrolytes for Flexible Supercapacitors 583
19.5.1 Aqueous Electrolytes 583
19.5.2 Solid Electrolytes 584
19.5.3 Liquid Electrolytes 584
19.5.4 Ionic Liquid (IL) Electrolytes 585
19.6 Gel Polymer Electrolytes (GPEs) 586
19.7 Development in ILEs 588
19.8 Design Flexibility With IL Electrolytes 594
19.9 Electrolyte–Electrode Hybrid Design 596
19.10 Ionic Liquid Electrolytes and Problem of Leakage 597
19.11 Mechanical Stability of ILs 597
19.12 Conclusions 598
References 598
20 Conducting Polymer-Based Flexible Supercapacitor Devices 611
Anand I. Torvi, Satishkumar R. Naik, Sachin N. Hegde,
Mohemmedumar Mulla, Ravindra R. Kamble,
Geoffrey R. Mitchell and Mahadevappa Y. Kariduraganavar
20.2 Principles of Supercapacitor 612
20.3 Classification of Supercapacitors 613
20.3.1 Electrochemical Double-Layer Capacitors 613
20.3.2 Pseudocapacitors 613
20.3.2.1 Conducting Polymers 614
20.4 Conducting Polymer-Based Flexible Supercapacitors 615
20.4.1 Polyaniline-Based Flexible Supercapacitors 616
20.4.2 Polypyrrole-Based Flexible Supercapacitors 618
20.4.3 Polythiophene and its Derivatives-Based Flexible
Supercapacitors 621
20.5 Electrolytes for Flexible Supercapacitors 624
20.6 Conclusions and Future Perspectives 626
Acknowledgements 626
References 626
Index 635
Preface
The tremendous demand for energy for miniaturized portable and wear-
able electronic devices has inspired intense research on lightweight, flexible
energy storage devices for commercial applications such as smartwatches,
mobile phones, flexible displays, electronic skin and implantable medical
devices. The speedy progress in ﬂexible electronics has sparked wide-rang-
ing endeavors in exploring coordinating power sources as ﬂexible super-
capacitor devices. Flexible supercapacitors are flexible, wearable devices
that deliver high-power density, high specific capacitance, fast charge/
discharge processes, long cycle life, low cost, and environmental friendli-
ness. They hold enormous potential to meet the rapidly expanding market
for portable and wearable electronics. Designing flexible supercapacitors
requires essential architectures such as electrodes, electrolytes, and sub-
strate materials that become robust, flexible, and durable under mechan-
ical deformations without sacrificing the electrochemical performance.
These flexible supercapacitors are promising energy technologies that can
supplement or even substitute batteries in portable and flexible electronics;
however, research and development (R&D) studies need to be conducted
for their large-scale commercialization. Therefore, awareness and knowl-
edge of flexible supercapacitors is crucial for advanced energy research.
This book presents a comprehensive overview of flexible supercapacitors
using engineering nanoarchitectures mediated by functional nanomateri-
als and polymers as electrodes, electrolytes, separators, etc., for advanced
energy applications. Various aspects of flexible supercapacitors, including
capacitor electrochemistry, evaluating parameters, operating conditions,
characterization techniques, different types of electrodes, electrolytes, and
flexible substrates are covered. Since it is probably the first book of its type
to systematically describe the recent developments and progress in flexible
supercapacitor technology, it will help readers understand fundamental
issues and solve problems. This book is the result of the commitment of top
researchers with various backgrounds and expertise in the flexible power
sources field. Those working in science, research, industry, or academia
xvii
xviii Preface
will benefit from the information archived herein relating to the fields of
flexible power sources, solid-state electrochemistry, advanced energy stor-
age material science, energy, electronics, advanced materials, and wearable
science. It will be a very helpful reference source for generating innovative
ideas in the field of energy storage material for wearable/flexible industry
applications and also useful in resolving current industry issues. A sum-
mary of the information included in the 21 chapters is given below.
Chapter 1 discusses the types of electrode materials and the role they
play in the high performance of flexible supercapacitors. Device prepara-
tion is described as well as the integration of flexible supercapacitors in
various applications.
Chapter 2 highlights flexible fiber-shaped electrodes for flexible super-
capacitors. Supercapacitors have an incredible impact on electrochemical
devices in energy storage systems. To meet the rapid consumer demand for
wearable and portable devices a new class of energy devices employ flexible
fibrous electrodes/supercapacitors. These fiber-shaped flexible electrodes
have garnered great attention for use in miniaturized microscale devices
and the modern textile industry.
Chapter 3 discusses recent developments in graphene-based flexible
supercapacitors, the structural morphology of flexible graphene-based
electrodes and methods used to fabricate them, and the electrochemical
performance of the devices.
Chapter 4 mainly discusses the preparation of polymer-based electrode
materials. Also highlighted are the various prominent characterization
techniques to elucidate the intercorrelation between physicochemical and
performance properties of polymer-based electrode materials. The new
reinforced polymer-based electrode materials for flexible supercapacitor
applications are also discussed.
Chapter 5 thoroughly reviews the energy storage system and types of
capacitor modeling. The structure, types of flexible supercapacitors and
industrial applications are introduced.
Chapter 6 discusses the types of electrolytes for flexible supercapacitors
and their salient features. Various electrolytes such as polyethylene gly-
col, polyvinylidene fluoride, ionic liquid and redox-active materials-based
electrolytes are discussed along with their effect on the performance of
flexible supercapacitors.
Chapter 7 discusses the preparation and properties of carbon-derived
composite materials such as CNT-conducting polymer, CNT-metal oxide,
activated carbon-conducting polymer, and activated carbon-metal oxide.
The main focus of this chapter is to provide an overview of the latest prog-
ress in the development of flexible supercapacitors beyond graphene.
Preface xix
Chapter 8 highlights the various synthesis processes for making biomass-

derived electrode materials, their recent developments and the associated chal-
lenges for the near future. After a brief general introduction, the chapter moves
on to discuss various electrode materials used for flexible supercapacitors;
biomass-derived carbon materials and their different activation processes like
physical, chemical and other activations; and carbonization processes using
the hydrothermal method, pyrolysis method, etc. The possible incorporation
of biomass-based electrodes in flexible supercapacitors and the challenges for
using biomass-derived materials in the near future are also discussed in detail.
Chapter 9 portrays the importance and applicability of conducting poly-
mer electrolytes, especially in flexible supercapacitors. The components of
supercapacitors and their configurations are discussed in detail along with
the role of conducting polymer-based electrolytes and their significance
in the performance of flexible supercapacitors. The essential enhancing
parameters of such electrolytes, including their consequences and electro-
chemical activity, are also elaborated.
Chapter 10 discusses the various inorganic electrode materials used in
flexible supercapacitors. These flexible inorganic-based electrodes have
great potential in the field of stretchable, lightweight and intrinsic fast
charging and discharging performance.
Chapter 11 focuses on different new generation materials used for flexible
supercapacitor electrodes. Also, in order to predict future trends, the direction
towards developing new materials exhibiting superior electrochemical perfor-
mance and their feasibility in practical applications are discussed.
Chapter 12 briefly describes flexible supercapacitors and their flexible
components with a concise outline of innovative cell designs. Additionally,
there is an overview of the principle behind the energy-storage mechanism
and the anode and cathode materials used for asymmetric supercapacitors.
Chapter 13 provides detailed insights into the gradual development and latest
accomplishments achieved with aqueous electrolyte-based flexible supercapac-
itors. Advantages of low production costs, eco-friendliness, non-flammability,
and many other attractive factors have motivated scientists to design these
smart devices to meet the high rising energy demands of modern society.
Chapter 14 presents systematic evaluations of different kinds of
micro-supercapacitor configurations, possible strategies of fabrication,
and state-of-the-art electrode materials. Discussions on designing asym-
metric micro-supercapacitors and the influence of electrolytes on enhanc-
ing charge-storage properties are also provided. Finally, the challenges of
current technologies and possible solutions are highlighted.
Chapter 15 discusses the categories of supercapacitors and their mode of
action. Different types of nanomaterials, including metallic, non-metallic
xx Preface
and graphene-based hybrid, are discussed in detail for their self-healable

properties to modify the electrodes in supercapacitors. The major focus is
given to those nanomaterials that increase the self-healing properties of
supercapacitors with enhanced capacitance.
Chapter 16 discusses the recent advancements for the fabrication of
flexible and stretchable electrode supercapacitors using metal oxides, 2D
materials, carbon, conductive polymers, and various hybrid nanocompos-
ites. Moreover, possible applications of flexible/stretchable supercapacitors
using these electrode materials, along with upcoming opportunities and
challenges in this emerging field, are also discussed.
Chapter 17 discusses the classification of flexible supercapacitors and
various superconducting materials. Additionally, different fabrication
methods, namely, electrochemical deposition, chemical bath deposition
(CBD), inkjet printing spray deposition, sol-gel technique, and direct writ-
ing method are discussed in detail.
Chapter 18 deals with the fundamental aspects of flexible supercapacitors
with naturally inspired electrodes for energy storage systems. The mechanisms
and principle behind energy storage in supercapacitors along with its essential
parameters are presented. The use of common and naturally occurring mate-
rials and their electrochemical behavior is also discussed.
Chapter 19 focuses on advances in the field of high-performance ionic
liquid electrolytes for flexible supercapacitors. After a brief discussion of
the fundamentals, developments in the field of ionic liquids are presented.
Design perspectives like electrolyte-electrode hybridization, challenges in
encapsulation and mechanical stability are also presented.
Chapter 20 describes various types of conducting polymer-based flex-
ible supercapacitors. Special emphasis is given to the fabrication methods
employed for flexible supercapacitor devices. The different electrolytes,
which play a significant role in flexible supercapacitors, are also discussed.
The chapter concludes with perspectives on flexible supercapacitors.
Inamuddin, Mohd Imran Ahamed,

Rajender Boddula and Tariq Altalhi
March 2021
1
Electrodes for Flexible
Integrated Supercapacitors
Sajid ur Rehman1,2 and Hong Bi1*
1
School of Chemistry and Chemical Engineering, Anhui University, Hefei, China
2
High Magnetic Field Laboratory, Key Laboratory of High Magnetic Field
and Ion Beam Physical Biology, Hefei Institutes of Physical Science,
Chinese Academy of Sciences, Hefei, China
Abstract
Supercapacitor, as a new type of energy storage device lying in-between battery
and traditional capacitor, owns many advantages such as fast charge and dis-
charge time, high power density, environmental-friendly and long cycle life. It has
become one of the hot research topics in the field of energy storage. Electrode
materials play a vital role in flexible supercapacitors, the common electrode
materials include carbon materials, conducting polymers and transition metal
oxides. In order to exploit flexible high-performance supercapacitors, new high-
performance electrode materials need to be developed. Metal oxides are prom-
ising supercapacitor electrode materials due to their low cost, good chemical
stability, high theoretical specific capacitance and environmental friendliness.
However, cycling stability and rate performance of metal oxides based superca-
pacitor still can’t meet the requirements of practical applications. Therefore, the
research on electrode materials are not limited to single-component material, and
nanocomposites can synergistically enhance the intrinsic properties of each com-
ponent to exhibit more outstanding electrochemical properties. In this chapter,
we discuss the electrode materials for flexible supercapacitors in detail and also
describes the device preparation as well as the integration of the flexible superca-
pacitors in various applications.
Keywords: Flexible electrodes, carbon, metal oxides, supercapacitors, EDLC,

pseudo-capacitors, hybrid electrodes, electrolytes
*Corresponding author: bihong@ahu.edu.cn
Inamuddin, Mohd Imran Ahamed, Rajender Boddula and Tariq Altalhi (eds.) Flexible Supercapacitor
Nanoarchitectonics, (1–26) © 2021 Scrivener Publishing LLC
1
2 Flexible Supercapacitor Nanoarchitectonics
1.1 Introduction and Overview of Supercapacitors

In today’s world, coal, oil, natural gas and other traditional nonrenewable
fossil energy are gradually exhausted, as the demand and consumption
of energy are increasing day by day, which have been difficult to main-
tain for the sustainable development of human society and economy.
Supercapacitor, also known as an electrochemical capacitor, is a new
type of energy storage device between the battery and traditional capac-
itor, which is based on the principle of electric double-layer capacitance
(EDLC) or pseudocapacitance. Because of its fast charge and discharge
rate, high power density, environment-friendly and long cycle life, it has
attracted increasing attention [1].
Supercapacitor is mainly composed of current collector, electrode active
material, diaphragm and electrolyte (see Figure 1.1) [2]. Among them,
electrode materials play an important role in improving electrochemical
performance. The collector usually has good conductivity, does not react
with the electrolyte, can exist stably in it, and has little contribution to the
specific capacity of the capacitor. Different metal materials, such as nickel
foam and aluminum foam, are used according to the electrolyte. An ideal
electrode material should have the characteristics of large specific surface
area, good conductivity, unique porous structure, high catalytic activity,
good chemical stability and low manufacturing cost [2, 3]. Supercapacitors
are commonly categorized into three sets based on the mechanism of
charge storage: (1) EDLCs that store charge statically at interface of carbon
electrode with large specific surface area; (2) Faraday pseudocapacitors that
store electric energy electrochemically through electron transfer during
reversible redox reaction, usually based on metal oxides and conduct-
ing polymer; (3) hybrid supercapacitor composed of special hybrid elec-
trode or asymmetric electrode, which has significant carbon double-layer
Charging
Discharging
Separator Active materials

Current collector and electrolyte
Figure 1.1 Schematic illustration of charge storage in supercapacitors [13]. Copyright ©

2013 Elsevier Ltd. Reproduced with permission from Elsevier.
Electrodes for Flexible Supercapacitors 3
capacitance and pseudocapacitance of conducting polymer or transition

metal oxide [4, 5].
Starting from the theory of interface double electric layer proposed by
Helmholtz, a German physicist, EDLCs began to be developed gradually.
When two electrodes are inserted into the electrolyte, the positive and
negative ions in the electrolyte will move towards the two poles rapidly
under the action of the electric field, and attach to the electrode surface,
forming a compact double electric layer [6]. As shown in Figure 1.1 [7], in
the charging process, the applied electric field releases electrons, and the
direction of electrons is from the negative electrode to the positive elec-
trode. At this time, the ions present in the electrolyte will transport towards
the respective electrodes respectively, so as to adsorb on the electrode sur-
face and form a stable voltage. In the process of discharge, electrons flow
through the conductor to generate current, at this time, the anion and cat-
ion on the electrode surface will be released into the electrolyte. In this
process, the electrode material will not react with the electrolyte, only the
adsorption and desorption of anions and cations in the electrolyte on the
electrode surface [8, 9].
Hybrid supercapacitor (HSC) includes a composite symmetrical super-
capacitor, battery supercapacitor mixer and asymmetric supercapacitor
(ASCs). The structure of ASCs is shown in Figure 1.5 [10], which is usually
assembled by two different materials as anode and cathode. In the process
of charging and discharging, oxidation–reduction (Faraday) reaction usu-
ally takes place at the positive electrode, while adsorption and desorption
of the negative electrode mainly take place at the double electric layer. In
fact, EDLC can achieve fast and stable charge storage but provide relatively
low specific capacitance, while the pseudocapacitor can obtain high spe-
cific capacitance but has poor multiplier performance and low cycle sta-
bility. The hybrid supercapacitor, which combines the advantages of EDLC
and pseudocapacitor, has become a new hotspot in capacitor research area.
It can achieve high energy and power density as well as good cycle stabil-
ity in one device. However, the performance of all these supercapacitors
depends on the properties of their active materials, the fabrication of elec-
trodes, the selection of electrolytes and the geometry of devices [11, 12].
Throughout the development of supercapacitors, electrode materials
have always played an important role in the electrochemical performance.
Generally, the ideal electrode material should have the characteristics of
large specific surface area, good conductivity, unique porous structure,
high mechanical strength, good chemical stability and low manufacturing
cost. Among them, carbon materials, metal oxides, conductive polymers
and other electrode materials are the main research objects.
1.2 Electrode Materials for Flexible Supercapacitors

1.2.1 Carbon Materials
As electrode material of flexible supercapacitors (FSCs), carbon-based
materials are beneficial due to their low cost, large specific surface area, sta-
ble electrochemical performance, better electrical and thermal conductiv-
ity, and mature synthesis process. At present, the commonly used carbon
materials include activated carbon [14], carbon nanotubes [15], graphene
[16], and carbon aerogel [17]. Their specific surface area, pore size and dis-
tribution, conductivity and heteroatom doping have certain effects on the
electrochemical performance of [18].
1.2.1.1 Activated Carbon

Activated carbon is the first electrode material used in supercapacitors.
Due to its advantages of low price, wide source of raw materials and stable
physical and chemical properties, it has been widely used in commercial
supercapacitors. So far, it still has a broad market [19]. After activated by
KOH, the specific surface area of activated carbon can reach as high as
2,000 m2 g–1. However, the specific surface area of the active carbon elec-
trode material is not directly proportional to the specific capacitance. The
main reason is that the activated carbon has not been fully explored in
terms of specific surface area, and the diameters of various electrolyte
ions are required to be different for different pore diameters in the acti-
vated carbon, so some micropores do not play the role of storing electric
charge, resulting in the available effective specific surface area becom-
ing smaller, affecting its electrochemical performance [20]. As shown in
Figure 1.2 [21], when the porous carbon has large pores (>50 nm), the
electrode surface can rapidly adsorb electrolyte ions. Because the pore size
is large, its specific surface area is reduced, resulting in a small effective
adsorption area and poor capacitance performance. When the pore is a
mesopore (2–50 nm), the inner surface of the pore can also rapidly adsorb
electrolyte ions, and the mesopore also results in a large specific surface
area and specific surface area. When the porous carbon is microporous
(<2 nm), the size of ions is larger than that of the pore size, so, it cannot enter
into the inner part of the pore, and the ion adsorption is reduced, resulting
in the reduction of effective adsorption area. Therefore, in order to improve
the electrochemical properties of the materials, in addition to improving
the specific surface area of the activated carbon, the doping of hetero
atoms, pore size control and the addition of surface functional groups
+ ∆V –
Nanoporous Carbon
Supercapacitors
εr ε0 A
C=
d
> 50 nm De 2π εr ε0 L δ–
cre C= δ– δ–
as In(b/a)
ing
Po δ– δ–
re
Siz δ– δ–
e
2 – 50 nm 2π εr ε0 L δ–
C=
In(b/a0)
< 2 nm
Figure 1.2 Schematic illustration of charge adsorption in porous carbon materials

with different sizes in double-layer capacitors [24]. Copyright 2016. Reproduced with
permission from John Wiley & Sons.
can also be used. Zhou et al. [22] reported N-doped porous carbon with
pore size classification by activating m-aminophenol formaldehyde resin
with KOH, which has a high specific surface area of 1,847.5 m2 g−1 and
thus a specific capacitance of 114 F g−1. Bleda Martine et al. [23] obtained
oxygen-containing functional groups on the activated carbon through
HNO3 peroxidation and subsequent heat treatment in N2 atmosphere,
which not only improved the wettability of the surface of the activated car-
bon to the electrolyte but also generated additional pseudocapacitance to
improve the specific capacitance.
1.2.1.2 Carbon Nanotubes

Carbon nanotubes (CNTs) are a kind of tubular carbon material made
of single or multi-layer graphite curled. Its structure is very perfect, with
seamless porous structure connected by hexagonal carbon atoms [25].
CNTs can be categorized into single-walled carbon nanotubes (SWCNTs,
single layer) and multi-walled carbon nanotubes (MWCNTs, two or more
layers). Single-walled carbon nanotubes have a higher specific surface area,
(a) S-720 (b) S-800
500 nm 500 nm
3
(c) S-720 (d) S-800
2 1
1
Current, mA
0 Current, mA 0
–1
–1
–2
20 mV s–1 1 M H2SO4 20 mV s–1 1 M H2SO4
–3 –2
0 200 400 600 800 1000 0 200 400 600 800 1000
Voltage, mV Voltage, mV
Figure 1.3 (a, b) HRTEM images of multi-walled carbon nanotube (MWNTs)

synthesized at different temperatures, (c–d) CV curves at 20 mV s−1 rate in 1 M H2SO4
aqueous electrolyte, respectively [30]. Copyright 2016. Reproduced with permission from
John Wiley & Sons.
but it is more difficult to prepare and purify. CNTs have excellent physical
and chemical properties. Due to its unique hollow porous structure, large
specific surface area, and good conductivity, it is considered to be an ideal
electrode material for supercapacitors [26–29]. As shown in Figures 1.3(a, b)
carbon nanotubes can form a network structure when they are entangled
with each other. Most of the pore diameter is more than 2 nm, which is
conducive to the penetration of electrolyte ions. Therefore, their specific
surface area utilization ratio is high. Popvo et al. [30] have synthesized the
MWCNTs at different temperatures and study the influence on superca-
pacitance properties. As shown in Figures 1.3(c, d), they found an increase
in double-layer capacitance because of the larger surface area as well as the
improvement in pseudocapacitance owing to the larger oxygenated groups
grown on the exterior of nanotubes.
1.2.1.3 Graphene
Graphene is a kind of two-dimensional crystal plane material [31, 32]
which is composed of sp2-hybridized carbon atoms tightly stacked and
connected, in which the covalent bond between carbon atoms is formed,
presenting a hexagonal ring honeycomb shape. It has a unique two-

dimensional (2D) structure and many attractive characteristics and is
widely used in electrochemical energy storage devices, as shown in Figure
1.4 [33]. Graphene is one of the allotropes of carbon, and it is also the basic
unit of other dimensional carbon materials. A single layer of graphene has
only one carbon atom thickness (0.335 nm).
Graphene has a large specific surface area, better electrical and ther-
mal conductivity, excellent mechanical strength and chemical stability. Its
surface is easy to show a three-dimensional (3D) fold structure, which is
conducive to the transmission of electrons on the surface and the diffu-
sion of ions in the material. It has great potential to apply it to electrode
materials of supercapacitors. In fact, graphene itself is easy to aggregate,
making its specific surface area far away from the theoretical value, thus
limiting its electrochemical performance [34–36]. Therefore, it is very
important to modify the surface of graphene or composite it with other
materials. Si et al. [37] combined Pt particles with graphene, which made
Pt nanoparticles deposit on graphene sheets. Pt played a role of separation,
prevented the aggregation of graphene sheets face to face, mechanically
peeled off graphene effectively. As a result, the embedded Pt@graphene
had a highly expanded layered structure and retained the characteristics
of 2D graphene hexagonal carbon network with large specific surface area.
The specific surface area of Pt@graphene composite was 862 m2 g−1, and
the specific capacitance of Pt@graphene composite was increased to 269 F
g−1. Zhu et al. [38] reported that porous graphene oxide prepared by KOH
chemical activation has a specific surface area of up to 3,100 m2 g−1, accom-
panied with high conductivity and low hydrogen and oxygen content, and
the sp2-bonded carbon has a continuous highly curved three-dimensional
0.14 nm
Covalent bonds
Carbon atoms
Van der Waals

bonds
0.34 nm
Figure 1.4 Schematic diagram of the Origin (illustrating the transformations) of

graphene from graphite and peculiar structure of graphite and graphene [33]. Open access
article under Creative Commons CC BY license copyright © 2020, Elsevier.
network, forming a hole with a width of 0.6–5 nm. Using organic and ionic
liquid electrolytes, the double electrode supercapacitor made of this kind
of carbon can obtain 3.5 V working voltage and 167 F g−1 specific capaci-
tance (5.7 A g−1 current density), and the energy density can reach 70 Wh
kg−1. In addition, the electrochemical properties of graphene can also be
improved by combining graphene with other pseudocapacitor materials
(such as transition metal oxides (NiO, MnO2, etc.) or conducting polymers
(polyaniline, polypyrrole, etc.).
1.2.1.4 Carbon Aerogels

Carbon aerogel is a lightweight, porous, amorphous three-dimensional
carbon nanostructured material. Because of its large specific surface area,
abundant mesoporous and wide range of density variation, it is considered
as an ideal electrode material for supercapacitors. In 1989, Pekala used
resorcinol and formaldehyde as raw materials and sodium carbonate as
catalyst. It is found that the carbon aerogel has the specific surface area of
400–800 m2 g−1 and the ultrafine pore size (<100 nm), and the specific capac-
itance of the 5 mol L−1 KOH solution is 45 F g−1. Subsequently, the research
on carbon aerogels in supercapacitors has attracted more and more atten-
tion. Lin et al. [39] synthesized a series of carbon aerogels with a bimodal
(microporous and mesoporous) structure by using iron-based ionic liquids
as a solvent ionic thermal carbonization method and pore-forming agent.
It has a high specific surface area up to 1,200 m2 g−1 and pore volume of 0.8
cm3 g−1, and a specific capacitance reaching as high as 245 F g−1. Carbon
aerogels have certain advantages in the application of supercapacitors, but
their shortcomings have seriously restricted their industrialization, such as
expensive raw materials, long-time synthetic process, high equipment cost
and difficulty to achieve a large-scale production.
1.2.1.5 Graphene Hydrogel

The effective specific area of graphene is greatly reduced due to the stack-
ing and agglomeration of graphene layers. Therefore, the researchers have
envisaged the connection and integration of 2D structure and designed
various kinds of graphene, such as graphene hydrogel, aerogel, foam and
sponge, to develop and utilize the properties of graphene in various 3D
network structures. Its preparation methods are various, mainly including
self-assembly, template oriented, new 3D printing and ultrasonic-assisted

technology. Although the structures and properties of these 3D graphene
materials are different, they all have the common characteristics of high
specific surface area and porosity, low bulk density, high conductivity and
so on. Therefore, they have been widely studied and applied in adsorption,
catalysis, sensing, energy storage and conversion, biomedicine and other
fields [40].
Graphene hydrogel is a 3D solid structure cross-linked by 2D graphene,
which can be prepared by freeze-drying or supercritical drying to remove
moisture. It has both the intrinsic properties of graphene nanosheet and
3D porous material and shows better performance than the graphene
nanosheet in the electrochemical application. Graphene hydrogel has
interconnected porous structure, large specific surface area, low mass
density and strong mechanical properties, making it widely used in elec-
trode materials of the supercapacitor. As a high volume capacitor mate-
rial, the large pores interconnected in the frame become unimpeded ion
transmission channels, which is conducive to shortening the diffusion
distance from the external electrolyte to the internal surface, thereby
enhancing the ion transmission; while the graphene sheet in the frame is
conducive to promoting the electron transmission on the electrode surface
[12, 39]. Huang et al. [41] reported the elastic carbon aerogels and
graphene as 3-D Matrix for supercapacitance properties. The schematic
diagram as illustrated in Figures 1.5(a, b) demonstrates the interconnected
macropores which exhibit high elasticity, improved surface area along with
charge-transfer efficiency owing to the excessive interconnections between
graphene flakes and carbon nanofiber ribs, which reveals prominent
capacitive performance as supercapacitor electrode as shown in Figures
1.5(d–e). Xu et al. [42], using hydroquinone as both reductive and func-
tionalized molecules, synthesized functional graphene hydrogels through
a simple one-step reduction method, showing excellent electrochemical
properties. Graphene hydrogel as a negative electrode can effectively pre-
vent the aggregation of graphene nanosheets, provide large active surface
area, and promote the transmission of electrolyte ions. Gao et al. [43] used
graphene hydrogels with 3D interconnected pores as negative electrodes,
and vertically aligned MnO2 nanosheets loaded on nickel foam as posi-
tive electrodes, successfully produced asymmetrical supercapacitors with
high energy and power density. The potential window could reach 2.0 V,
and the energy density achieved 23.2 wh kg−1 while the power density was
1.0 kW kg−1.
(a)
Mixing and
co-assembling Carbonization
Freeze-drying
oPAN dispersion GO suspension GO/oPAN aerogel GCA
(b) Cyclisation (c)

CN CN CN CN CN N N N N
Dehydrogenation
N N N N
O
O H H O O
C H
O C
100 µm
(d) 20 (e) 0.0

1 A g–1
15
2 A g–1
–0.2
10 5 A g–1
10 A g–1
Current (mA)
5 –0.4 15 A g–1
Voltage (V)
20 A g–1
0
–0.6
–5
–10 20 mV s–1 –0.8

5 mV s–1 50 mV s–1
–15 10 mV s–1 100 mV s–1
–1.0
–20
–1.0 –0.8 –0.6 –0.4 –0.2 0.0 0 50 100 150 200 250 300 350 400 450 500
Potential (V) vs. Ag/AgCl Time (s)
Figure 1.5 (a) Schematic presentation of graphene/carbon nanofiber (CNF) composite

aerogels (GCA) by co-assembly and carbonization. (b) Illustration of the pre-oxidation
process of polyacrylonitrile (PAN) nanofibers and hydrogen bondings between GO
and pre-oxidized PAN. (c) SEM image showing the graphene/carbon composite aerogel
(GCA). (d) CV curves at different scan rates in 6 M KOH aqueous electrolyte.
(e) Galvanostatic charge/discharge curves at different current densities [41]. Open access
article under Creative Commons CC BY license copyright © 2016, Springer Nature.
1.2.2 Conducting Polymers

In 2000, the Nobel Prize in chemistry was awarded to Heeger A.J.,
MacDiarmid A.G. of the United States and Yingshu Shirakawa of Japan
for their contributions to the field of conducting polymers [44]. Through
their research, they have proved that people usually think that insulating
polymer materials can also have conductivity under certain conditions,
breaking the traditional concept that polymers are insulators. Since then,
more and more attention has been paid to this field, and researchers have
developed many conductive polymers such as polyacetylene, polyaniline,
polypyrrole, thiophene and their derivatives. Their structures are shown in

Table 1.1.
Common conductive polymer electrode materials are prepared by
chemical oxidation and electrochemical oxidation. Conductive polymers
have been widely used as electrode materials for supercapacitors because
of their low cost, good conductivity and wide electrochemical window.
When oxidation occurs, the conductive polymer can be p-doped with
anions, while in the reduction process, it will be n-doped with cations. The
simplified charging process equation is as follows:
p-Type doping: CP → CPn+ ( A– )n + ne – (1.1)
n-Type doping: CP + ne – (C + )n + CPn– (1.2)
The discharge time is contrary to the above process. The conducting

polymer will be p-type or n-type doped, so it can store more charge and
obtain higher Faraday pseudocapacitance.
There are three kinds of devices for supercapacitor assembled only by
conducting polymer materials [45] namely, polyaniline, polypyrrole, poly-
thiophene and derivatives of polythiophene, as well as composites of these
materials with carbon nanotubes and inorganic battery materials. Various
treatments of the conducting polymer materials to improve their proper-
ties are considered and comparisons are made with other supercapacitor
Table 1.1 Several common conducting polymers.

Polymers Structural formula
Polyacetylene
CH CH
n
Polyaniline
NH
n
Polypyrrole
N n
H
Polythiophene
S n
materials such as carbon and with inorganic battery materials. Conducting

polymers are pseudo-capacitive materials, which means that the bulk of the
material undergoes a fast redox reaction to provide the capacitive response
and they exhibit superior specific energies to the carbon-based super-
capacitors (double-layer capacitors: type I (symmetric), using the same
p-type doped conducting polymer for positive and negative materials; type
II (asymmetric), p-type doped conducting polymer with different electric
activity ranges for positive and negative materials; type III (symmetric), for
two electrodes the same polymer is used, in which p-type doping is used
as positive electrode and n-type doping is used as negative electrode. In
addition, a conductive polymer can be used as a positive electrode and a
carbon material as a negative electrode to construct an asymmetric device.
Among them, the type III device based entirely on conductive polymer is
the most attractive, because it is highly conductive in the charged state and
has high capacitance performance, but due to the difficulty of n-type dop-
ing, the performance of these types of conductive polymer supercapacitor
devices is not as good as expected [46]. Wang et al. [47] demonstrated the
excellent performance of N-graphene doped polyacrylic acid/polyaniline
composites flexible solid-state carbon cloth supercapacitors. Figure 1.6(a)
shows the image of aqueous nitrogen-doped graphene (NG) enhanced
polyacrylic acid/polyaniline (NG-PAA/PANI) composites suspension
containing 32 wt.% PANI and 1.3 wt.% NG. Figure 1.6(b) demonstrates
the flexibility of the carbon cloth electrode and Figure 1.6(c) shows the
SEM image of carbon fiber. The optimal performance of electrode (CC@
NG-PAA/PANI) has been achieved with a high capacitance of 521 F g−1 at
0.5 A g−1.
Carbon materials generally have excellent cycle stability, but the capac-
ity of conducting polymers usually starts to decrease in less than 1,000
cycles. This is because, in the process of charge and discharge test, ions
are continuously doped/de-doped (embedded/de-embedded) into the
doped polymer under the action of electric field, its physical structure will
change, which to a certain extent, aggravates the expansion and contrac-
tion of the skeleton chain, destroys the stability of the material, leading to
its cycle stability decay. In addition, some conducting polymers undergo
incomplete reversible redox reactions [48, 49]. Therefore, the specific
capacitance and cycle stability of the conductive polymer can be greatly
improved by forming a composite electrode material between the conduc-
tive polymer and other materials such as carbon materials (graphene, car-
bon nanotubes, etc.) and metal oxides (NiO, CoO, etc.). Zhang et al. [49]
synthesized graphene and polypyrrole composites (GNS/PPy) by in-situ
polymerization of pyrrole monomers in the presence of graphene under
(a) (b)
(c)
NG-PAA/PANI
20µm
(d) (e) 0.8

45 5 mV/s
10 mV/s 10 A/g
30 20 mV/s 5.0 A/g
0.6
50 mV/s 3.0 A/g
1.0 A/g
Current (A/g)
Potential (V)
15 100 mV/s
0.5 A/g
0 0.4
–15
–30 0.2
–45
0.0
–0.2 –0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0 500 1000 1500 2000
Potential (V) Time (sec)
Figure 1.6 Photo of (a) the aqueous nitrogen-doped graphene (NG) enhanced
polyacrylic acid/polyaniline (NG-PAA/PANI) composites suspension containing 32 wt.%
PANI and 1.3 wt.% NG, (b) a single bent carbon cloth (CC) electrode. (c) SEM images
of single carbon fibers coated by PAA/PANI, (d) CV curves at different scan rates, and
(e) Galvanostatic charge/discharge curves at different current densities [47]. Open access
article under Creative Commons CC BY license copyright © 2016, Springer Nature.
acidic conditions. The specific capacitance of GNS/PPy was 482 F g−1 at the
current density of 0.5 A g−1, and the attenuation of specific capacity was less
than 5% after 1,000 charge–discharge cycles, indicating that the composite
had excellent cycling stability.
1.2.3 Metal Compounds

The metal-oxides used as electrode material of supercapacitor are mainly
based on the Faraday pseudocapacitance which is produced by the
reversible oxidation–reduction reaction at the interface of electrode and
solution. Compared to carbon based materials, Faraday’s reaction can
provide higher specific capacitance and energy density; compared with
conductive polymers, it can obtain better electrochemical stability, so it
has attracted extensive interest and favor of researchers. Transition metal
oxides are often used as electrode materials for supercapacitors, includ-
ing noble metal oxides (RuO2, IrO2, etc.) and non-noble metal oxides
(MnO2, NiO, CuO, CoO, etc.). Due to the limited resources and high
cost of precious metals, their large-scale production and application are
limited. Thus, it is essential to discover alternative materials with com-
parable performance and low price. The emphasis of electrode materi-
als has gradually shifted from precious metal oxides to non-precious
metal oxides.
1.2.3.1 Ruthenium Oxide (RuO2) Electrode Material

In the early stage of supercapacitor research, RuO2 is the most popular
and researched noble metal oxide electrode material because of its good
conductivity and high specific capacitance. Hu et al. [50] successfully pre-
pared RuO2·× H2O nanotube array electrode by using membrane template
synthesis route and anode deposition technology, while maintaining the
(a)
Glass plate (b) (c)
SEBS
Twisting
(d) (e)
Stretching
MWCNTs wrapping
50 µm 500 µm 50 µm 500 µm
RuO2 or MnO2 dry painting/MWCNT wrapping

(f) 0.3 (g)60
0.2 RuO2 + MnO2
50
MnO2
Repeat dry painting and MWCNT wrapping 0.1 40
C60 (G g–1)
I (A g–1)
0.0 30
–0.1 20 RuO2
MWCNT sheet RuO2
MnO2 layer –0.2 RuO2 + MnO2 10 MnO2
RuO2 layer –0.3 0
SEBS core –0.2 0.0 0.2 0.4 0.6 0.8
E (V vs. Ag/AgCl)
Figure 1.7 (a) Schematic structure and Fabrication method of stretchable

pseudocapacitor. Where highly stretchable stylene-ethylene/butylene-stylene (SEBS)
is used as the supporting elastomeric core. SEM images of (b) as-prepared stretchable
pseudocapacitor, (c) after a 1,000 times of repeated stretching by 200%; (d) magnified
image of the as-prepared and (e) magnified image of the stretched pseudocapacitor.
(f) Cyclic voltammograms of variously prepared yarn type pseudocapacitors using 1 M
Na2SO4 as electrolyte. (g) Bar graphs showing the decrease in specific capacitance of the
pseudocapacitors: green and red bars denote graphs obtained before and after stretching
the pseudocapacitor yarn a thousand times, respectively [51]. Open access article under
Creative Commons CC BY license copyright © 2016, Springer Nature.
permeability of electrolyte, the simplicity of proton exchange/diffusion and

the metal conductivity of RuO2 crystal. Its power density and energy den-
sity were up to 4,320 kW kg−1 and 7.5 Whkg−1. Lee et al. [51] synthesized
(Figure 1.7(a)) the stretchable yarn-based pseudocapacitor. They applied
dry painting of RuO2 and MnO2 on the soft SEBS surface. As shown in
Figures 1.7(b–e), the yarn-type pseudocapacitor comprised of eight-
layered MWCNTs, three-layered RuO2, and two-layered MnO2, presented
specific capacitance of 25 F g−1 (shown in Figures 1.7(f–g)). The electro-
chemical pseudocapacitor yarn retained its electrical capacity after 200%
stretching.
1.2.3.2 Nickel Oxide (NiO) Electrode Material

Among the transition metal oxides, nickel oxide has been widely used in
supercapacitors, catalysts, sensors, magnetic materials and other fields
[52–55]. Among them, due to its advantages of high theoretical capaci-
tance, wide sources, easy preparation and environmental friendliness, it is
considered to be the most likely alternative to RuO2 as an ideal supercapac-
itor electrode material. It has excellent reversibility and stability in alkaline
solution. The oxidation-reduction reaction of Faraday pseudocapacitance
usually formed is as follows:
NiO + OH- ↔ NiOOH + e- (1.3)
NiO, as electrode material of supercapacitor, has been widely studied.

Wang et al. [56] synthesized NiO with ordered mesoporous structure by
duplicating SBA-15 template and studied its electrochemical capacitance
characteristics in 2 M KOH electrolyte solution for the first time. The
ordered mesoporous structure can greatly improve the utilization of NiO.
Its specific capacitance was 120 F g−1, and it had good rate performance.
However, when single-phase NiO is utilized as an electrode material, its
cycle stability is not good, because its volume structure will be expanded
and contracted to a certain extent in the process of continuous charging
and discharging. Therefore, researchers began to focus on the formation of
composite electrode materials with NiO and carbon materials (graphene,
carbon nanotubes, etc.) or other pseudo capacitor materials (CoO, PPy,
etc.). Fang et al. [57] reported the hybrid NiO–CuO mesoporous nano
wire arrangement with excessive oxygen vacancies as a high-performance
supercapacitor electrode material. Figure 1.8(a) shows the scheme of syn-
thesis where Figures 1.8(b, c) show the SEM and TEM images of urchin-
like hollow structure with abundant nails of CuO–NiO heterostructures
(a)
NiO
CuO
+ Urea Hydrothermal Annealing
(Ni, Cu)2CO3(OH)2 NiO-CuO
(d) 160
(b) Ni : Cu=1:1 (c) NiO-CuO 30 mV s–1
120 25 mV s–1
Current density (mA cm–2)

20 mV s–1
80 15 mV s–1
40 10 mV s–1
5 mV s–1
0
–40
–80
1 µm 50 nm –120
5 nm
0.0 0.2 0.4 0.6

Potential (V vs. SCE)
(e) 0.5
(f)
2 mA cm–2
3 mA cm–2 NiO
0.4 K+ CuO
Potential/V (vs SCE)
5 mA cm–2 OH–
10 mA cm–2 – e–
e e–
0.3 15 mA cm–2
20 mA cm–2
0.2 electrolyte
0.1
Ni foam Ni foam
0.0
0 500 1000 1500 2000 2500
Time (s)
Figure 1.8 (a) Schematic illustration of the synthesis of urchin-like NiO–CuO hollow
architectures, (b) SEM image and (c) TEM image of the NiO–CuO sample, the inset in
(c) is the magnified image of NiO–CuO. (d) CVs and (e) GCDs of the electrode of NiO–
CuO with Ni:Cu = 1:1. (f) The charge transfer mechanism of the electrode based on NiO–
CuO [57]. Copyright 2019. Reprinted with permission from Royal Society of Chemistry.
on the surface. The hybrid NiO–CuO exhibited an excellent supercapaci-

tance performance (shown in Figures 1.8(d, e)). The 3D hollow structure
of NiO–CuO facilitated the electrolyte penetration, increased the contact
area of the electrode/electrolyte interface and provided a large number of
active sites for electrochemical reactions, as shown in Figure 1.8(f).
1.2.3.3 Copper Oxide (CuO) Electrode Material

CuO, as a common transition metal oxide has the characteristics of low
cost synthesis, rich sources, simple preparation method, high theoret-
ical specific capacitance and excellent chemical stability, and has gradu-
ally attracted attention in the field of supercapacitor electrode materials
[58–60]. CuO has a variety of micromorphology, which has a certain
influence on its capacitance performance. Mosavifard et al. [59] synthe-

sized 3D highly ordered nanoporous CuO by using nanoporous silica as
template. Its specific capacitance was 431 F g−1 at 0.35 mA cm−1current
density, having outstanding performance and cycle life. Dubal et al. [61]
synthesized well dispersed cauliflower-like CuO on stainless steel substrate
by a simple and effective electrodeposition method. It had a high specific
capacitance of 179 F g−1 in Na2SO4 electrolyte, and the capacity retention
rate was 81% after 2,000 cycles. However, when only single-phase CuO is
used as electrode material of supercapacitor, its specific capacitance is far
from ideal, so a series of CuO composite materials have also been stud-
ied. Qian et al. [62] directly synthesized CuO/polypyrrole core-shell nano
sheet array by electrochemical co-deposition on interdigital electrode.
1.2.3.4 Composite Electrode Materials

There have been three kinds of electrode materials of supercapacitor are
introduced above, which have both advantages and disadvantages when
applied to the electrode materials of supercapacitor. The specific capac-
itance of carbon material is far less than that of conducting polymer
and transition metal oxide. The structure of conducting polymer will be
destroyed after multiple cycles of charging and discharging, and the cycle
stability is poor. In addition, as electrode materials, transition-metal oxides
have the benefits of great specific capacitance, high energy density, rich
sources, easy preparation, electrochemical stability, etc., but most of them
have low intrinsic conductivity, increased electrode resistance, and poor
cycle stability. Therefore, researchers are committed to the study of com-
posite electrode materials (composed of two or more materials). Composite
electrode materials can take advantage of the advantages of every single
component to play a synergistic role to obtain electrode materials with
better performance than single materials. Common composite materials
include: (1) the composite of carbon-based materials and pseudo capacitor
materials (transition metal oxides or conductive polymers), which can not
only improve the specific capacitance of carbon-based materials but also
improve the cycle stability of transition metal oxides or conductive poly-
mers. For example, Zhao et al. [63] made nickel ions adsorbed on both sides
of GO through the electrostatic interaction of two substances, forming a
single graphene/NiO sheet, which greatly increased the surface area of the
composite and can maintain a capacity retention rate of 95.4% after 1,000
cycles. Liu et al. [64] prepared graphene oxide/polypyrrole (GO/PPy) com-
posite by simple electrochemical deposition technology, and the specific
capacitance reached 358 F g−1, after 1,000 charges and discharges cycles at a
(a) (b) (c)
2 µm 200 nm
Coat MWCNT Electrodeposite MnO2 Coat electrolyte Assemble

(d)
Assembled flexible
bare textiles MWCNT ink dipped Electrodeposite MnO2 PVA-H2SO4 solid-state supercapacitor
Figure 1.9 (a) Photograph of prepared hybrid supercapacitor, (b, c) SEM images of
MnO2/CNTs, (d) Scheme of the fabrication process of the honeycomb MnO2/CNT
textile-based flexible solid-state supercapacitors [66]. Open access article under Creative
Commons CC BY license copyright © 2016, Springer Nature.
scanning rate of 10 mV s−1, the capacitance showed only 7.1% attenuation.

(2) The composite of two kinds of pseudocapacitor materials can obtain
new morphology and structure, so as to obtain better performance. For
example, Li et al. [65] used low-temperature hydrothermal in-situ growth
process to grow three-dimensional MnO2 nanowire/ZnO nanorods array
composite electrode materials on carbon cloth without binder. With the
support of ZnO nanorods array, the electrochemical performance of MnO2
nanowire can be greatly improved. Yinko et al. [66] prepared porous hon-
eycomb structures from interconnected MnO2 sheets on CNT-coated sub-
strates. Figure 1.9(a) shows the photograph of prepared flexible hybrid
supercapacitor. The morphology of the produced MnO2/CNT composites
was studied by SEM at different magnifications, as presented in Figures
1.9(b, c). The 3D honeycomb (MnO2/CNT) minimizes the accumulation
of the MnO2 layers, improving the electrolyte-accessible area and enables
easy approach of ions inside the electrodes. The honeycomb-like MnO2/
CNT textiles were straightly applied as the binder-free electrodes for the
production of bendable solid-state supercapacitors shown in Figure 1.9(d).
1.3 Device Architecture of Flexible Supercapacitor

Electrochemical functioning of supercapacitors depends not only on the
performance of the materials used in each component, but also on the
design, matching, and combination of these components in order to make

a device which meets the performance needs [59, 62, 63].
The early all-solid-state flexible supercapacitor (FSCs) used a tradi-
tional sandwich like design with {a current collector|electrode|electrolyte|
electrode|current collector} layered structure. This design has appealed the
consideration of scientists due to its simple configuration and quite sim-
ple manufacturing procedure. Though, increased ion transmission paths
result in limitations to ion transmission severely when stiffer electrodes are
needed [60, 63]. Also, not only the portable electronic devices needs to be
flexible, but they should also be thin and smaller size. Therefore, the large
sandwich structure is not compatible with the planar microstructure of
micro-electronics and is not feasible to meet the requirements of electronic
circuits.
To solve this drawback, a new device structure (Figure 1.6(b)) [59]
has been developed into a flat design, which intersects multiple micro-
electrodes (for one electrode) on an elastic substrate, such as p-benzene
ethylene glycol diformate (PET) or polyimide (PI) layer or paper (cross
design). The preparation of the interdigital microelectrode usually requires
an extra micro-patterning step prior or post thin film electrode deposition.
Such type of planar interdigital structure has the advantage of space saving,
shorter ion transmission better diffusion of electrolyte ions and appropri-
ate integration in electronic systems.
Use of elastic substrate for supporting electrodes is another technique
for the fabrication of flexible solid-state supercapacitor. Plastics such as
polyethylene terephthalate (PET) being flexible, lightweight and thin
thickness are reported as the supporting substrates for FSCs. Kaempgen
et al. [67] demonstrated thin film supercapacitor built on spray coated
SWCNT nets.
1.4 Integration of Flexible Supercapacitors

In the beginning, mostly FSCs were utilized for the supply power to basic
electronic devices, for example, LEDs or clocks [66, 68, 69]. So as to accom-
plish the current or voltage prerequisites of electronics, FSCs are typically
utilized in series and/or parallel arrangement. Scientists and engineers
keep on investigating the handy utilizations of FSCs in practical applica-
tions. Lu et al. [70] utilized a series combination of three asymmetric FSCs
made of MnO2/Fe2O3 electrodes and arranged them to charge cell phones
(HTC, A320e). Kim et al. [71] prepared a waterproof wire type of FSCs
(a) (b)
15cm 12 Scan rate: 0.5 V/s
Current density (mA/cm2)

1cm 3cm 5cm
8 10cm 15cm
5cm
4
1cm
0
–4
800µm 3cm 0.25cm
–8
10cm 2 cm 2 cm –12
0.0 0.5 1.0 1.5
Voltage (V)
(c) MSC array
Red LED
2cm
Figure 1.10 (a) Optical images of CF/MWNT/V2O5 NW (CMV) electrode and wire-
type supercapacitors (WSCs) with varying length, (b) CV curves of WSCs with various
lengths at scan rate of 0.5 V s−1, (c) wire-type supercapacitors array and LED array on
T-shirts [71]. Copyright © 2017 Elsevier Ltd. Reproduced with permission from Elsevier.
(shown in Figure 1.10(a)) to supply power a gas sensor (NO2) shown in

Figure 1.10(c). The sensor have ability to detect NO2 gas for 50 min after
completely charging the MSCs.
Shi et al. [72] prepared different shaped flexible asymmetric superca-
pacitors on ultrathin 2D nanosheets demonstrating good mechanical flexi-
bility and excellent optical transparency as shown in Figure 1.11 (a-c). The
flexible supercapacitor achieved a high specific capacitance of 774 F g−1
even after 10,000 cycles. The asymmetric supercapacitors exhibited a very
high energy density with less than 3% capacitance loss following 10,000
cycles in aqueous electrolyte Figure 1.11 (d-f). This study on electrode
materials for FSCs shows that there have been still a void space for an out-
standing material or nano composite to fill for the high power density and
high energy density simultaneously.
0.5×0.5 1.5×1.5 flexible

(mm)
picture
word
Tsinghua University
or letter magnify visible
pattern
Tsinghua University
wooden chopsticks
(a) (b) (c)

1.2
Capacitance Retention (%)

straight 100 MS-GA 120 MS-MS
bended Energy Density (Wh/kg) MS-MS
0.8 MS-GA
Ref 100
bended
Current (mA)
0.4
80 MS GA MS MS
0.0
60
–0.4 MS-GA MS-MS
40
–0.8 10
20
–1.2 electrolyte
0
0.0 0.5 1.0 1.5 2.0 10 100 1000 10000 0 2000 4000 6000 8000 10000
Voltage (V) Power Density (W/kg) Cycle number
(d) (e) (f)
Figure 1.11 (a) Photographs of the screen-printed electrodes of several designs;

(b) Photographs of electrodes demonstrating good mechanical flexibility. (c) Photograph
of the ‘‘panda’’ asymmetric MS/GA supercapacitor lighting up a red light emitting diode.
(d) CV curves of straight and bended supercapacitor at 20 mV. (e) Ragone plots of MS/GA
and MS/MS supercapacitor compared with other MnO2 based asymmetric supercapacitors
(f) Cycle performance and schematic illustration of screen-printed supercapacitor [72]. Open
access article under Creative Commons CC BY license copyright © 2013, Springer Nature.
1.5 Conclusion
The urgent need for efficient energy storage and conversion promotes the
research of new energy storage devices such as supercapacitors. The elec-
trode materials, which are essential to supercapacitors have been widely
concerned and studied. Despite the progress in all-solid-state manufactur-
ing of flexible supercapacitor with sandwich-like and interdigital structure,
to achieve full commercialization, much tasks remain to be done. Further
work needs in electrodes, manufacturing technology and equipment
integration.
More research work is required to acquire flexible electrode materials
to enhance the performance of FSCs. Therefore, it is mandatory to explore
bendable electrodes that combine the advantages such as good conduc-
tivity, close-packed structure and enhanced ion contact area. In addition,
an outstanding electrochemical stability is quiet one of the core research
goals.
At the end, it is very important to build combinations of FSCs with

new electronics (such as photodetectors, TENGs, solar cells and oth-
ers) in smart devices. Besides the research on electrodes, manufacturing
the integrated wearable devices like thermal supercapacitors and photo-
supercapacitors are worth exploring.
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am living in a modest room on the upper floor) at half-past five,
thinking it best to see them as far as the harbour myself. The
appointed time has come, but not a carrier is to be seen. I wait till a
quarter to six, and am becoming somewhat uneasy, when I am aware
of the gradual approach of so frightful a din that there cannot be the
slightest doubt as to who is causing it. But have the twenty-four been
suddenly multiplied by three? A closely-packed crowd roars and
surges in the square beneath me; the bass voices of the men, the
shrill, vibrating cries of the women make up a pandemonium of
sound; but no disorderly actions take place—in fact I had not
expected any. The crowd follows me in a confused mass for the few
hundred paces down to the harbour, where the ferry-boat is waiting.
“Bwana, I would rather stay here,” says Kazi Ulaya, the handsome,
with a tender look at the fair one beside him. “Do what thy heart
prompts, my son,” I reply mildly. “And this is my boy, sir,” says Pesa
mbili II, of Manyema, who has by this time recovered his plumpness.
But he refrains from introducing to me the bibi, who, in some
embarrassment, is hiding behind his broad back.
“Now sing those fine songs of yours once more.”
The men are standing round me in a serried circle. “Kuya
mapunda” goes very well; the pleasing melody rises in full volume of
sound above the voice of the rushing Lukuledi. In “Dasige
Murumba” too, the singers acquit themselves fairly well; but when
the standard song, “Yooh nderule” begins, the circle seems full of
gaps, and my eye can distinguish in the twilight various couples
scattered here and there among the bushes by the bank. “Ah!
farewell scenes,” I think to myself, but soon perceive that I am
mistaken; no tender sentiments are being discussed, but my matter-
of-fact fellows are throwing themselves like wolves on the last repast
prepared for them by loving hands before the voyage. I wish them,
sotto voce, a good appetite, and make a note of the fact that the heart
of the native, like that of the European, can be reached through his
stomach.
The ferryman shouts impatiently to hurry them up, and I drive the
unattached contingent of the singers down into the shallow water.
Splashing and laughing they wade towards the boat; the darkness
has come on rapidly, and I can only just distinguish the white figures
as they clamber on board. “Yooh nderule, yooh nderule, bwana
mkubwa nderule”—the familiar sounds, long drawn out, ring over
the water in Pesa mbili’s voice—“kuba sumba na wogi nderulewa,
yooh nderule”—the chorus dies away. The boat has disappeared in
the darkness, and I turn my steps towards the mess-room, and the
principal meal of the day, where I am once more claimed by
civilization. The Weule Expedition is at an end.
ENTERING THE RED SEA
CHAPTER XIX
FROM LINDI TO TANGA
On Board the ss. König, in the Mediterranean, off the

Mouths of the Nile, January 20, 1907.
A few hours ago, in losing sight of the palms of Port Said, we left the
last of Africa behind us. The flat, sandy shore of the Egyptian Delta
has now vanished from our view, and a grey waste of waters lies
before the vessel as she fights her way with increasing difficulty
against the rising north-west gale. The Mediterranean in winter is
not inviting. No trace in reality of the ever-cloudless sky we have
been taught to look for; and Captain Scharf, who certainly ought to
know, says that he has never experienced any other weather here at
this time of year. This season is always cold and stormy, forming no
pleasant transition between the delightful temperature of the Red
Sea in winter and the sub-Arctic climate of the Atlantic and the
North Sea. We shall have to steam along the coast of Crete and to
pass close enough to the southern extremity of Greece, to catch sight
of the snow-covered peaks of the Spartan mountains; so much does
the head-wind retard the course of our broad-bowed, somewhat old-
fashioned boat, which, for a first-class steamer, makes wonderfully
little way. The traveller has all the more leisure to retire, in the
comfortable smoking-saloon, into the solitude of his own thoughts,
and take stock of all that he has seen, heard and learnt in the last
nine months.
The evening of the 2nd of December passed very pleasantly on
board the Kanzler in Lindi roadstead. One could scarcely make out
where so many white-clad Europeans came from, all at once. One of
the passengers attributed this influx to the iced Pilsener which
Ewerbeck and I lavished in unlimited quantities in the high spirits of
departure; but this suggestion is scarcely to be taken seriously. The
presence of a German steamer in the harbour is in these latitudes
always a festival, celebrated by most people whenever it comes
round. And quite rightly so, for nothing is more deadening than the
monotony of workaday life in Africa.
The trip which had taken the Rufiji three days of hard work was
performed by the swift Kanzler in one day. Early on the morning of
the fourth, Ewerbeck and I landed at Dar es Salam: Ewerbeck, in
order to take his final leave of the Protectorate, and I, to give account
to the Government of the financial and administrative side of my
expedition. For a new-comer like myself a change of place made no
difference; but the Imperial District Commissioner was visibly
moved by sad and serious thoughts. He had spent the best part of his
life, over fifteen years, in the development of this very part of
German East Africa; and, in such a case, a man does not leave the
scene of his labours with a light heart.
Dar es Salam was still more delightful than in June. At this time of
year it abounds in mangoes of every size and every variety. The
mango-tree was long ago imported from India, and is now found
wherever Indians are settled in East Africa, whether in British,
German, or Portuguese territory. It is certainly a pleasanter
immigrant than the low-caste Indian; it somewhat resembles our
linden tree in its mode of growth, and gives a pleasant look of home
to a settlement. The fruit, sometimes as large as a child’s head, is
served on ice at every meal, and is almost equal in flavour to the
pine-apple.
Into this pleasant, easy life the news of the events of December
13th came like a bolt from the blue. An excellent hotel, the
“Kaiserhof,” had been opened just before my return to Dar es Salam,
and I had the great pleasure of being one of its first guests. We were
almost suffocated with comfort: electric light, a broad, shady
verandah outside every room, a comfortable bath-room attached to
each apartment, and a more than luxurious table were, together,
almost too much of a good thing, after our lean months in the bush.
Fortunately, however, man becomes accustomed to every thing, even
to good living.
I have seldom seen so many long faces as in those days, when the
news of the sudden dissolution of the Reichstag burst like a bomb in
the comfortable, well-to-do official circles of the town. It seemed as
though every single European, down to the lowest subordinate, had
been personally affected by the event; all the mess-rooms were loud
with the dismal prognostications of the croakers as to the black
future—or rather the want of any future—before the colony, whose
inglorious end seemed placed beyond doubt,
as each of us foresaw that the General Election
in January would admit at least a hundred
Socialists to the Reichstag. “And of course it is
all up with the railways,” was the stereotyped
refrain of all these lamentations, which the
mourners duly drowned in a sea of whisky and
soda. Personally I am convinced that things
will not be as bad as that, but that the next
Reichstag will show at least as much feeling
for the colonies as its predecessor, or, indeed,
it is to be hoped, still more. On January 25th
our steamer is to arrive at Genoa; on that date
the elections will be over, and on the following
day we shall be able to get a general survey of
THE AUTHOR IN the results, and form some idea as to the fate
BUSH COSTUME of our colonies in the immediate future.
I left Dar es Salam on December 20th by the
Admiral, a splendid boat, almost new, and rolling far less even than
the Prinzregent. It was also more comfortable than the latter; it was
no wonder, therefore, that all the cabins were full. We had still more
English on board than in the spring; many from Cape Town, and still
more from Johannesburg. Accordingly, the prevailing style of dress
was noticeably luxurious. This time I was able to go ashore at Tanga,
and even see something of the Usambara railway. Captain Doherr,
with his usual foresight, had (probably remembering the managerial
functions which he had been called upon to perform a few months
previously, in the service of the eight Deputies) arranged for a special
train to be ready for the passengers, or at least for such as wished to
avail themselves of it. With this we made the run to Muhesa, where
the expedition was brought to a halt by means of enormous dishes of
sandwiches and trays of whiskies and sodas. Something is really
being done in the north-east of the colony, as one can see even from
the train; it is true that not all the land is yet under cultivation, but
every bit of it is already in the hands of a permanent owner, even far
beyond the rail-head.
There were grand doings at Tanga in the evening. This town enjoys
a whole series of advantages. In the first place, it is the nearest to the
mother country of all our East African ports, and thus constitutes the
gateway to the colony. In the second place, the harbour is tolerably
good; the bay, indeed, is not land-locked to the same extent as that of
Dar es Salam, but, like the latter, it has sufficient anchorage within a
short distance of the shore. The most important point, however, is its
nearness to Usambara, the choicest part of our territory as regards
climate and soil. Usambara has but one fault: it is not large enough
to accommodate all would-be settlers. It is said that even now the
available land has been allotted, and there is no chance for later
applicants. Many of these are now staying at Tanga, or on their way
south to seek new fields for their energies: in fact, the boom at Lindi
was in great part caused by the congestion in the north. The
economic centre of gravity, therefore, for our whole colonial activity
lies at present in this north-eastern district. This, by the bye, is
evident from the whole aspect of European life at Tanga. After
passing many months on end in the Usambara mountains, with no
opportunities for social intercourse, the planter suddenly feels the
need of society, and in a few hours’ time we may behold him seated
in the club at Tanga.
Where there are Germans, there is also music. Dar es Salam enjoys
the advantage of two bands—that of the sailors from the two cruisers,
and that of the askari. Both are under official patronage, but I
cannot say much for the proficiency of the native performers: in any
case, their music was accompanied by a great deal of noise. At Tanga
it is not in economic matters only that the residents assert their
independence—even the Boys’ Band of that town is a purely private
enterprise. Tanga is a scholastic centre par excellence, hundreds of
native children being instructed in the elements of European
knowledge and initiated into the mysteries of the German tongue,
which, indeed, one finds that all the little black imps can speak after
a fashion. The more intelligent, in whom their teachers discover, or
think they discover, any musical gift, are admitted to the famous
Boys’ Band. This is just now in excellent training. When the
passengers from the Admiral presented themselves in the evening on
the square in front of the Club, the band turned out to welcome
them, and the playing was really remarkably good.
CHAPTER XX
RETROSPECT
At the Entrance to the Red Sea.
Christmas and New Year’s Eve were passed at sea, with the usual
festivities; the latter, on which the dancing was kept up with equal
enthusiasm and energy by German and English passengers, was also
the eve of our arrival at Suez.
About noon on the first day of January, 1907, I set foot on the soil
of Egypt, which I have only just left, after a stay of nearly three
weeks. I had a great desire to study the relics of ancient Egyptian
culture on the spot, and therefore left Cairo and its neighbourhood as
speedily as possible for Upper Egypt—Luxor, Karnak and Deir el
Bahri. From a climatic point of view, also, Cairo was not well adapted
for an intermediate station between the tropics and the winter of
Northern Europe. One after another of our passengers remaining
behind for a tour in Egypt became indisposed. Some, therefore, took
the next boat for Germany, arguing that their colds “would cost less
at home,” while others made off up the Nile by train de luxe, in order
to accustom themselves slowly and carefully in the glorious desert air
of Assuan to the sub-arctic climate of Ulaya.
The Assuan dam is historically a piece of Vandalism, technically a
meritorious piece of engineering, economically a truly great
achievement. The narrow-gauge railway winds up the Nile in sharp
curves between Luxor and Assuan. Sometimes the Nile flows in
immediate proximity to the track—sometimes there is a narrow strip
of alluvial level between the sacred stream and the new unholy iron
road. All this time one is oppressed by the narrowness of the country;
it seems as if the first high wind must blow the sand right across it
and bury it altogether. Suddenly the bare hills on the left retreat: a
wide plain opens out before us, only bounded in the far distance by
the sharp contours of the hills in the Arabian Desert. The plain itself,
too, is a desert—but how long will it remain so? Turn to the right and
consider the great block of buildings which meets your eye. It is
neither Egyptian nor Arabian, there is none of the dirt of Fellah
barbarism about it; on the contrary, it represents the purest Anglo-
American factory style. The tall chimney crowning the whole, and
emitting a dense cloud of smoke, forms an incongruous contrast with
its surroundings—the silver Nile with its border of green fields,
running like a ribbon across the boundless sands of the desert to east
and west. Look before you at the straight canal crossing the plain and
lost to sight in the distance and the ditches and channels by which it
distributes the Nile water in all directions, with perfect regularity.
The building is a pumping-station, established to restore the desert
plain by irrigation to its former fertility. Now it is still perfectly bare:
in a few months’ time, it will be a sea of waving corn with stalks
bearing fruit a hundredfold.
The economic exploitation of the Upper Nile Valley is an example
which ought to be followed by our own colonial administration.
Without a resolute purpose, without capital, and without accurate
knowledge of the country and its resources, even that English or
American company could do nothing. We need all three factors, if we
want to make any progress, whether in Eastern or in South-Western
Africa, in Kamerun or in Togo. There is only one small point of
difference—the alluvial soil of the Nile Valley, accumulated through
many myriads of years needs nothing but irrigation to once more
make it into arable soil of the first quality. The Nile, wisely regulated,
is the magic wand which will, almost instantaneously, change the
desert into a fruitful field. This transforming agency is absent in the
bush and steppes of German East Africa. It is true that that country
possesses numerous streams, but at present their volume of water is
subject to no regulation, and none of them is navigable on the same
imposing scale as the Nile. In the course of years, no doubt, the
Pangani will become an artery of traffic, as also the Rufiji, and
perhaps our frontier stream, the Rovuma; but it will not be within
the lifetime of the present generation.
The soil of German East Africa, too, cannot be compared with that
of Egypt; it is no alluvial deposit, rich in humus, but in general a
tolerably poor one, produced by the weathering of the outcropping
rocks and not to be rendered fertile by moisture alone. Nevertheless,
so far as I am able to judge, the water question remains the cardinal
one in our colonial agriculture. At Saadani they have begun at once
to do things on the grand scale, breaking up large areas with steam-
ploughs, in the hope that wholesale cotton cultivation may put an
end to the American monopoly. So far this is very good; the
temperature is favourable, and the soil quite suitable for such a crop.
One factor only is uncertain: German East Africa, like India, is never
able to reckon on a normal amount of atmospheric moisture—and, if
the rains fail, what then?
The Dark Continent has often been compared to an inverted plate.
The land slopes gently upwards from the sea-shore, the angle of
inclination gradually becoming greater, till we have a bordering
range of mountains of considerable height. But it is only as seen from
the coast that this range can be said to have a mountainous
character; once he has crossed it, the traveller finds that, as on the
heights of the Harz or the Rhenish slate mountains, he is on a plain
almost level with its summit. To carry out the comparison with the
plate, we may say that he has now crossed the narrow ledge at the
bottom, and is now walking over the horizontal surface within that
ledge.
This peculiar conformation has to be taken into account by those
engaged in developing our colonies, i.e., in the first place, it is
responsible for the fact that the rivers are navigable only to a very
slight degree, if at all. In the second place, the greater part of the
rainfall is precipitated on the seaward slope of the range, while its
other side is almost rainless, which accounts for the arid character of
Ugogo and the neighbouring districts. Yet the greater part even of
this interior has a soil on which any crops which can be cultivated at
all in Equatorial Africa are well able to thrive. The planter there is
fortunate in being able to count on the vivifying influence of the
tropical sun, which, throughout the year, conjures flourishing fields
out of the merest sand. In the south I was able, day after day, to
convince myself of the truth of this assertion.
The South has hitherto been the Cinderella of our colonial
districts, and I fear it is likely to remain so. The prejudice as to its
barrenness has deterred both official and private enterprise. It is true
that neither the Mwera Plateau nor the Makonde highlands, nor the
wide plains extending behind these two upland areas, between the
Rovuma in the south and the Mbemkuru or the Rufiji in the north,
can be called fertile. Sand and loam, loam and sand, in the one case,
and quartz detritus in the other, are the dominant note of the whole.
Yet we have absolutely no reason to despair of this country, for if the
native can make a living out of the soil, without manuring and with
none of the appliances of our highly-developed intensive farming—if
this same native is in a position to export an appreciable fraction of
his produce in the shape of sesamum, ground-nuts, rubber, wax,
cereals and pulse—it would surely be strange if the white man could
not make much more out of the same ground.
One thing, indeed, must never be forgotten: neither this district
nor Africa in general is a pays de Cocagne where roast pigeons will
fly of their own accord into people’s mouths; work, unceasing,
strenuous work, is just as much an indispensable condition of
progress as in less happy climates. We have had sufficient
opportunity to observe and appreciate this persevering industry in
the case of the Makonde, the Yaos, and the Makua. And we may be
sure of one thing, that the European planter, whether in the north or
the south, on the coast or in the interior, will not have a much easier
time than these people. That, however, will do him no harm; on the
contrary, the harder the struggle for existence, the more vigorous has
been the development of a colony throughout the whole course of
human history. The United States of to-day are the standing proof of
this assertion; the South African colonies, now developing in a most
satisfactory manner, speak no less clearly, and other cases in point
might easily be adduced.
The waves are running higher, the König having more breadth of
beam than depth, does not roll, but cannot help shipping more seas
than she would like. Ought I, in face of this grand spectacle, to let
myself be absorbed in useless forecasts of the future? My friend
Hiram Rhodes’s taunt about “political childhood” was cruel—yet
there was some truth in it, and not as regards the Zanzibar treaty
only. We Germans have begun colonizing three hundred years later
than other nations, and yet Dick, Tom and Harry are raising an
outcry because our colonies, acquired fully twenty years ago, do not
yet produce a surplus. The honest fellows think that “South-West”
alone ought to be in a position to relieve them from the necessity of
paying any taxes whatever. One could tear one’s hair at such folly
and such utter lack of the historic sense. Most books are printed in
Germany—none are bought, and but few read there. Among these
few we can scarcely include any works on colonial history, otherwise
it would be impossible that even colonial experts should know so
little of those thousand conflicts, difficulties and reverses
experienced to their cost by the English in India, in the South Seas,
in Africa, and in America, and which over and over again might well
have disgusted the Dutch, the Spaniards, and the Portuguese with
their extensive colonial possessions. Unconsciously influenced by the
wealth of England and the affluence of Holland, both in great part
arising from their foreign possessions, we are apt to forget that three
centuries are a period fifteen times as long as our own colonial era,
and that at least ten generations of English and Dutch have won by
hard, unceasing work what we expect to receive without effort on our
part. I am firmly convinced that we shall never learn to appreciate
our really splendid possessions till a more thorough system of
instruction has supplied the want above referred to—doubly
inexcusable in a nation whose intellectual pre-eminence is
everywhere acknowledged.
Such historic sense is to be gained by putting two kinds of capital
into the colonies—the blood shed for their preservation and
development, and the hard cash spent on the utilization of their
resources.
To illustrate the extent of the British Colonial Empire and its
distribution throughout the world, it is often pointed out that the
mother country is seldom without a colonial war of some kind. This
is true in the present, and it has also been true in the past: England
has in fact always had to fight for her dominions beyond sea.
Undoubtedly, this three hundred years’ struggle for possession,
which, under her special circumstances has often been for England a
struggle for existence, is the principal ground for the peculiarly close
and intimate relation between the mother country and the daughter
states. Hardly a family but has dear ones buried in Indian or African
soil. This fact at first attaches to the country a painful interest, which
very soon gives rise to an interest of another sort. The truth of this
doctrine has been illustrated in the saddest way for us by the
sanguinary war in South Western Africa.
The other kind of capital—the monetary—cannot be discussed in
the case of our colonies without touching on the railway question.
What complaints have been made of the invincible reluctance of
German capitalists to engage in colonial undertakings! I am not
myself a wealthy man, but, if I had a million to lose, I should
nevertheless hesitate before investing it in a country without means
of communication, being entirely devoid of natural ones, while
artificial ones are as yet only in the elementary stage. At home, every
one is now expecting great things from the new driver of our colonial
chariot. Herr Dernburg is a trained financier, and he, perhaps, can
succeed where others have failed—in the completion of the great
railway system projected long ago, and in procuring the no less
necessary financial resources.
Lastly, the native is not without an important bearing on the future
of our East African colony. As an ethnographer, I am in a better
position to form an opinion about him than with respect to other
questions, in which the outsider like myself has only common sense
to guide him. The black man is pronounced by some, “an untrained
child;” by others, “utterly depraved and incurably lazy.” There is yet a
third party who are inclined to leave him at least one or two small
virtues, but these are steadily shouted down. It is true that the native
population of the Coast towns have a horror of any serious work, and
look down on it as a lowering of themselves; but I think we may be
permitted to entertain a better opinion as to the great mass of the
people in German East Africa. The most numerous tribe in the whole
colony are the Wanyamwezi, who are estimated at about four million
souls, and occupy the whole central area east of the Great Rift Valley.
No one has yet ventured to doubt their industry or their capacity for
progress; they are excellent agriculturists, and at the same time they
were, for a whole century, the mainstay of the caravan trade between
the coast and the heart of the continent. Before long this traffic must
in the nature of things cease, but we have no right to suppose that the
Wanyamwezi will therefore become superfluous. A glance over the
reports of the Uganda Railway will show us how fortunate we are in
possessing such an element in the social structure as this vigorous
tribe. Let us then be wise enough to encourage and develop this
economic force for the native’s own benefit, and above all to get the
full advantage of it ourselves. What is true of the Wanyamwezi is also
true of many other tribes. Even now, I cannot forget the impression
made on me by the high average of the farming which I saw among
my friends in the Rovuma Valley. People who, however often they
have been displaced, still cling so firmly to the soil, must certainly
have great potentialities for good, or all the teachings of racial
psychology and history are falsified. This unexpectedly high stage of
culture can only be explained by an evolution extending over a
period of incalculable length. There is nothing to disprove the great
antiquity of agriculture among the Bantu; they are conservative, as
their continent is conservative; the few alien elements still in the
economic stage of the collector and hunter—the Bushmen in the
most arid parts of the south, and the Pygmies in the most
inaccessible forests of Central and West Africa—must have been
crowded out by them many centuries ago.
The farming of our natives is done entirely with the hoe—that
implement-of-all-work, with the heavy transverse blade which serves
alike for breaking up and cleaning the ground, for sowing the crops,
and, to a certain extent, for reaping them. We are too much inclined
to think of this mode of cultivation as something primitive and
inferior, and, in fact, in so far as it dispenses with domestic animals,
whether for work or for the supply of manure, it is really very far
behindhand. But we must also take into account that some parts of
our colonies are infested with the tsetse-fly, and that the system of
cultivating narrow strips of ground entirely with the hoe really marks
a very high stage of farming. The best proof of this is the retention of
the narrow bed in our gardens, where the cultivation can scarcely be
said to be of a more elementary description than that of our fields. It
is significant, too, that for the more intensive forms of culture when
carried on in the open fields, e.g., flower-growing, as near Erfurt,
Quedlinburg, Haarlem, etc., and market-gardening as in the
neighbourhood of Brunswick, Hanover, Mainz, and other large
towns, the long, narrow bed is most in favour. Moreover, it is
difficult to see how the native could cope with the weeds—the
principal danger to his crops—were it not that his narrow beds are
easily reached from all sides.
The native mode of agriculture, therefore, need not be interfered
with: it has been tested and found excellent.
Another question is, how shall we, on this basis, make our black
fellow-subjects useful to ourselves? In my opinion, there are two
ways, as to both of which the pros and cons are about equal. Both
have been in operation for some time, so that we have a standard to
guide us in forecasting the ultimate development of the whole
colony. In the one, the native is not encouraged to advance in his
own home and on his own holding, but is trained as a labourer on the
plantation of a European master—plantations being laid out
wherever suitable soil and tolerable climate promise a good return
for outlay. The other method has the progress of the native himself in
view, and aims at increasing his economic productivity by
multiplying and improving the crops grown by him on his own
account, teaching him new wants and at the same time increasing his
purchasing power. In this way it is hoped that he will exchange his
exports for ours.
The future must show whether the German people will decide for
one of these ways to the exclusion of the other, or whether, as
heretofore, both will be retained. For the mother country their value
is about equal and depends on the degree of activity shown in
colonial affairs as a whole. But the second is decidedly to the
advantage of the native himself. As a plantation labourer he is and
remains a mshenzi; as a peasant proprietor he is able to advance. At
the same time we must not forget that our colonies were founded in
the expectation of providing homes for our surplus population, and
that if the native is to claim the most fertile parts of his own country
for himself, nothing can come of that ver sacrum. It also depends on
the general direction of our policy whether the numerical increase
and physical improvement of the native are to our interest or not.
Some primitive peoples have almost or entirely disappeared under
the influence of civilization; the Tasmanians belong to history; the
Maoris of New Zealand and the Kanakas of Hawaii are rapidly
diminishing, and we have lately heard of the last Vedda in Ceylon.
The negro race does not belong to these candidates for extinction; on
the contrary, wherever it has come in contact with the white, it has
grown stronger in every respect; there is therefore no fear of its dying
out. But shall we go further and, by artificial selection, deliberately
raise their coefficient of multiplication? Certainly we ought to do so,
for a numerous resident population is under all circumstances a
benefit to us. It solves the labour problem for the planter, and, on the
other hand, the European manufacturer and merchant will, of
course, prefer a large number of customers to a small one. How is
this improvement to be initiated? I have nothing further to add to the
remarks which, à propos of the various diseases and other scourges
of this continent, occur in the preceding pages.
In Europe some people are stupid, others of moderate capacity,
and yet others decidedly clever. The huge lip-ornaments of the
Makonde and Makua women sometimes produce the impression of a
simian type of face, and small boys occasionally suggest by their
features a not remote kinship with the missing link, but this exhausts
the list of excuses I could have alleged for looking down from a
superior height on the people in question. In all the months spent
among the natives of the Rovuma Valley, I never discovered any
reason why we should, as we are so fond of doing, associate the idea
of absurdity with the African. On the contrary, the behaviour, not
only of the elders, but of the liveliest of the young people in their
intercourse with Knudsen and myself, was characterized by a quiet
dignity which might well have served as an example to many a
European of similar social position. My personal experiences will not
allow me to believe in the dogma of the negro’s incapacity for
development. It cannot be denied that he has achieved a certain
intellectual progress, even in North America, though the obstacles
there are greater than the facilities. Why, therefore, should he not
rise, as soon as the opportunity is offered to him in such a way that
he can take advantage of it? Only we must not expect this advance to
take place overnight, any more than we can expect a rapidity of
economic progress at variance with every law of historical
probability.
It is now quite dark; the boat must have changed her course, for
the gale no longer meets us in front, but comes from the port side, so
that no doubt we are approaching Crete. To-morrow, or the day after,
we shall pass the coast of Greece. I must confess that I am looking
forward to a sight of this country, though I do not regard its classic
age with the same unbounded and uncritical enthusiasm as many of
our countrymen, to whom the ancient Greek is the embodiment of all
historical and cultural virtues. One thing only even the blackest envy
cannot deny to the Hellenes of old—a courage in colonial enterprise
which we should do well to imitate both now and in the future.
This future is still shrouded in mystery. Will our East African
colony become a second India? I do not doubt for a moment that it
will, and my mind’s eye sees the whole country traversed by railway
lines. One of these follows the old caravan road from the coast to
Tanganyika. The iron horse has superseded the old carrier-transport,
and the clattering train now bears the carriers themselves, as well as
bulky goods which could never have been put on the market under
the old system. One line runs to the Victoria Nyanza and another to
distant Nyasa; we are able to link up with the British network of
railways in South Africa, with the communications of the Congo
State, with the Nile Valley. Thirty years ago Stanley’s march to the
Lake Region and his boat-voyage down the Congo were epoch-
making achievements. We of to-day may perhaps live to make the
trip by train de luxe from the Cape to Cairo, and from Dar es Salam
to Kamerun.
INDEX
Abdallah bin Malim, Wali of Mahuta, 352 et seq.;

his noisy devotions, 399–400
Achmed bar Shemba, song by, 31
Adams, Pater, on the Makonde, 259–60
African continent, conformation of in relation to Colonization, 415
race, original home, question of, 12
African Fund, the, 9, 10
Age-classes, 304
Akundonde, Yao chief, information from, 140, 184
settlement of, 212,
visit to, 213 et seq.
Alum, as water-clarifier, 153–4
Ancestor-worship, 326
Antelope-hunting, 200–1
Anthropology, difficulties of, in G.E. Africa, 53
Artistic aptitudes of Natives (see also Drawings), 36
Asiatic origin of African races, discussed, 12, 13
Assuan dam, the, lessons from for Germany, 413–5
Astronomical beliefs and customs, Yao, 184–5
Atlantic Ocean, historical density, 6
Axes, etc., bewitched, 210–12
Babies, see Children & Infants
Bagamoyo roadstead, 2
Bakeri of Zanzibar, 140, 142–3
Bangala river, Camp at mouth of, 208
Bantu imitation of the Masai, 118
origin, tribes of, 12, 53, 139
Baraza, the, 65,
described, 135
Bards, 170, 175
Bark-cloth, ceremonial uses of, 276–7, 313
manufacture of, 274 et seq.
Barnabas as artist, 367–8
Birth customs
Makonde, 281, 283
Yao (as to twins), 283
Black race, distribution of, explanation of, 13
Boots, question of, 71
Bornhardt on the geology of German East Africa, 66, 67–8
Botanical features (see also Bush), Masasi region, 69
Bows and arrows, 74
methods of using, 75–6
as toys, 285
Boys’ initiation ceremonies, see Lupanda, and Unyago
Brass-founding, native, 267–70
British Colonial Empire, comments on, 417
Burial customs,
Makua, 132
Yao, 194 & note
Bush and Scrub vegetation, 51, 52, 60
Bush-burning, 58–61, 255, 257
Bwalo, the, 231 & note
Calico, as dower, 306

over graves, 194, 214
Camp life, 83–4
sleeping discomforts, 119, 163, 164
Cape Banura, 24, 25
Guardafui, 14, 15
“Cape rubies,” 209, 210
Carnon, Archdeacon of Masasi, 45
hospitality of, 74
Carriers, see also Wanyamwezi,
difficulties with, 393
paying off of, and farewell to, 393–4, 400, 405–7
Cattle, Matola’s, 138,
stampede by, 164
Central Lukuledi Valley, lions in, 245
Chain-gangs, 28, 44,
native drawing of, 371
Charms (Dawa), 129;
used in Majimaji rebellion, 51
“Cherchez la femme!” 397–9
Child-life, native, G.E. Africa, 157–8 & note, 284 et seq.
Children, native, characteristics of, and aspect, 148
Chingulungulu, author’s stay at, 104 et seq.
description of, 134 et seq.
diseases noted at, 192
meaning of name, 104 note
native amusements at, 169
characteristics, 106
route to, from Mkululu, 126–7
water-supply at, 150–2

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Flexible Supercapacitor

Supra-Materials Nanoarchitectonics 1st Edition

Applied Soil Chemistry Inamuddin

Materials for Supercapacitor Applications 1st Edition

Biosensors Nanotechnology, 2nd Edition Inamuddin

Flexible Bronchoscopy 4th Edition Ko-Pen Wang

Proton Exchange Membrane Fuel Cells Inamuddin

Biofuel Cells: Materials and Challenges Inamuddin

Biodegradable Materials and Their Applications

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2.3.2 Flexible Paper Electrodes 32

4.3 Synthesis and Fabrication Approach of the Polymer-Based

6 Organic Electrolytes for Flexible Supercapacitors 143

8 Biomass-Derived Electrodes for Flexible Supercapacitors 211

10.2.1 Carbonaceous Material 265

13 Aqueous Electrolytes for Flexible Supercapacitors 349

13.8 Water-in-Salt Electrolytes for Flexible Supercapacitors 394

15 Electrodes for Flexible Self-Healable Supercapacitors 461

16.3 Conclusion and Future Remarks 511

19 Ionic Liquid Electrolytes for Flexible Supercapacitors 575

Chapter 8 highlights the various synthesis processes for making biomass-

and graphene-based hybrid, are discussed in detail for their self-healable

Inamuddin, Mohd Imran Ahamed,

Keywords: Flexible electrodes, carbon, metal oxides, supercapacitors, EDLC,

*Corresponding author: bihong@ahu.edu.cn

1.1 Introduction and Overview of Supercapacitors

Separator Active materials

Figure 1.1 Schematic illustration of charge storage in supercapacitors [13]. Copyright ©

capacitance and pseudocapacitance of conducting polymer or transition

1.2 Electrode Materials for Flexible Supercapacitors

1.2.1.1 Activated Carbon

Figure 1.2 Schematic illustration of charge adsorption in porous carbon materials

1.2.1.2 Carbon Nanotubes

(a) S-720 (b) S-800

Figure 1.3 (a, b) HRTEM images of multi-walled carbon nanotube (MWNTs)

presenting a hexagonal ring honeycomb shape. It has a unique two-

Van der Waals

Figure 1.4 Schematic diagram of the Origin (illustrating the transformations) of

1.2.1.4 Carbon Aerogels

1.2.1.5 Graphene Hydrogel

self-assembly, template oriented, new 3D printing and ultrasonic-assisted

oPAN dispersion GO suspension GO/oPAN aerogel GCA

(b) Cyclisation (c)

(d) 20 (e) 0.0

–10 20 mV s–1 –0.8

Figure 1.5 (a) Schematic presentation of graphene/carbon nanofiber (CNF) composite

1.2.2 Conducting Polymers

polypyrrole, thiophene and their derivatives. Their structures are shown in

p-Type doping: CP → CPn+ ( A– )n + ne – (1.1)

n-Type doping: CP + ne – (C + )n + CPn– (1.2)

The discharge time is contrary to the above process. The conducting

Table 1.1 Several common conducting polymers.

materials such as carbon and with inorganic battery materials. Conducting

(d) (e) 0.8

1.2.3 Metal Compounds

1.2.3.1 Ruthenium Oxide (RuO2) Electrode Material

RuO2 or MnO2 dry painting/MWCNT wrapping

Figure 1.7 (a) Schematic structure and Fabrication method of stretchable

permeability of electrolyte, the simplicity of proton exchange/diffusion and