Nanowire Energy Storage Devices:

Synthesis, Characterization and

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Nanowire Energy Storage Devices
Nanowire Energy Storage Devices

Synthesis, Characterization, and Applications

Edited by Liqiang Mai

The Editor All books published by WILEY-VCH are carefully
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Prof. Liqiang Mai publisher do not warrant the information
Wuhan University of Technology contained in these books, including this book,
122 Luoshi Road to be free of errors. Readers are advised to keep
Wuhan in mind that statements, data, illustrations,
China procedural details or other items may
430070 inadvertently be inaccurate.

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Print ISBN: 978-3-527-34917-3

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 v

Contents

Preface xi

1 Nanowire Energy Storage Devices: Synthesis,

Characterization, and Applications 1
1.1 Introduction 1
1.1.1 One-Dimensional Nanomaterials 1
1.1.1.1 Nanorods 3
1.1.1.2 Carbon Nanofibers 3
1.1.1.3 Nanotubes 3
1.1.1.4 Nanobelts 5
1.1.1.5 Nanocables 6
1.1.2 Energy Storage Science and Technology 6
1.1.2.1 Mechanical Energy Storage 7
1.1.2.2 Electromagnetic Energy Storage 9
1.1.2.3 Electrochemical Energy Storage 9
1.1.3 Overview of Nanowire Energy Storage Materials and Devices 13
1.1.3.1 Si Nanowires 15
1.1.3.2 ZnO Nanowires 17
1.1.3.3 Single Nanowire Electrochemical Energy Storage Device 18
References 19

2 Fundamentals of Nanowire Energy Storage 27

2.1 Physical and Chemical Properties of Nanowires 27
2.1.1 Electronic Structure 27
2.1.2 Thermal Properties 29
2.1.2.1 Melting Point 29
2.1.2.2 Thermal Conduction 30
2.1.3 Mechanical Properties 31
2.1.4 Adsorption and Surface Activity 32
2.1.4.1 Adsorption 33
2.1.4.2 Surface Activity 33
2.2 Thermodynamics and Kinetics of Nanowires Electrode Materials 34
2.2.1 Thermodynamics 34
vi Contents

2.2.2 Kinetics 34
2.3 Basic Performance Parameters of Nanowires Electrochemical Energy
Storage Devices 35
2.3.1 Electromotive Force 36
2.3.2 Operating Voltage 36
2.3.3 Capacity and Specific Capacity 36
2.3.4 Energy and Specific Energy 37
2.3.5 Current Density and Charge–Discharge Rate 37
2.3.6 Power and Specific Power 38
2.3.7 Coulombic Efficiency 38
2.3.8 Cycle Life 38
2.4 Interfacial Properties of Nanowires Electrode Materials 38
2.4.1 Interface Between Nanowire Electrode Materials and Electrolytes 38
2.4.2 Heterogeneous Interfaces in Nanowire Electrode Materials 40
2.5 Optimization Mechanism of Electrochemical Properties of Nanowires
Electrode Materials 42
2.5.1 Mechanism of Electron/Ion Bicontinuous Transport 42
2.5.2 Self-Buffering Mechanism 44
2.6 Theoretical Calculation of Nanowires Electrode Materials 44
2.7 Summary and Outlook 48
References 49

3 Design and Synthesis of Nanowires 51

3.1 Conventional Nanowires 51
3.1.1 Wet Chemical Methods 51
3.1.1.1 Hydrothermal/Solvothermal Method 52
3.1.1.2 Sol–Gel Method 53
3.1.1.3 Coprecipitation Method 54
3.1.1.4 Ultrasonic Spray Pyrolysis Method 55
3.1.1.5 Electrospinning Method 55
3.1.2 Dry Chemical Method 57
3.1.2.1 High-Temperature Solid-State Method 57
3.1.2.2 Chemical Vapor Deposition Method 58
3.1.3 Physical Method 59
3.2 Porous Nanowires 60
3.2.1 Template Method 60
3.2.1.1 Template by Nanoconfinement 60
3.2.1.2 Template by Orientation Induction 62
3.2.2 Self-Assembly Method 63
3.2.3 Chemical Etching Method 64
3.3 Hierarchical Nanowires 65
3.3.1 Self-Assembly Method 65
3.3.2 Secondary Nucleation Growth Method 68
3.4 Heterogeneous Nanowires 69
3.4.1 Heterogeneous Nucleation 69
 Contents vii

3.4.2 Secondary Modification 71

3.5 Hollow Nanowires 73
3.5.1 Wet Chemical Method 73
3.5.2 Template Method 73
3.5.3 Gradient Electrospinning 76
3.6 Nanowire Arrays 79
3.6.1 Template Method 79
3.6.2 Wet Chemical Method 81
3.6.3 Chemical Vapor Deposition 83
3.7 Summary and Outlook 86
References 88

4 Nanowires for In Situ Characterization 95

4.1 In Situ Electron Microscopy Characterization 95
4.1.1 In Situ Scanning Electron Microscopy (SEM) Characterization 95
4.1.2 In Situ Transmission Electron Microscope (TEM) Characterization 97
4.2 In Situ Spectroscopy Characterization 101
4.2.1 In Situ X-ray Diffraction 101
4.2.2 In Situ Raman Spectroscopy 106
4.2.3 In Situ X-ray Photoelectron Spectroscopy 108
4.2.4 In Situ XAS Characterization 108
4.3 In Situ Characterization of Nanowire Devices 111
4.3.1 Nanowire Device 111
4.3.2 Nanowire Device Characterization Example 111
4.4 Other In Situ Characterization 115
4.4.1 In Situ Atomic Force Microscopy Characterization 115
4.4.2 In Situ Nuclear Magnetic Resonance 117
4.4.3 In Situ Neutron Diffraction 119
4.4.4 In Situ Time-of-Flight Mass Spectrometry 121
4.5 Summary and Outlook 123
References 124

5 Nanowires for Lithium-ion Batteries 131

5.1 Electrochemistry, Advantages, and Issues of LIBs Batteries 131
5.1.1 History of Lithium-ion Batteries 131
5.1.2 Electrochemistry of Lithium-ion Batteries 132
5.1.2.1 Theoretical Operation Potential 133
5.1.2.2 Theoretical Specific Capacity of Electrode Materials and Cells 133
5.1.2.3 Theoretical Specific Energy Density of an Electrochemical Cell 134
5.1.3 Key Materials for Lithium-ion Batteries 134
5.1.3.1 Cathode 134
5.1.3.2 Anode 135
5.1.3.3 Electrolyte 135
5.1.3.4 Separator 136
5.1.4 Advantages and Issues of Lithium-ion Batteries 137
viii Contents

5.2 Unique Characteristic of Nanowires for LIBs 138

5.2.1 Enhancing the Diffusion Dynamics of Carriers 138
5.2.2 Enhancing Structural Stability of Materials 138
5.2.3 Befitting the In Situ Characterization of Electrochemical Process 139
5.2.4 Enabling the Construction of Flexible Devices 139
5.3 Nanowires as Anodes in LIBs 139
5.3.1 Alloy-Type Anode Materials (Si, Ge, and Sn) 139
5.3.1.1 Lithium Storage in Si Nanowires 139
5.3.1.2 Lithium Storage in Ge Nanowires 142
5.3.1.3 Lithium Storage in Sn Nanowires 145
5.3.2 Metal Oxide Nanowires 146
5.3.3 Carbonaceous Anode Materials 148
5.4 Nanowires as Cathodes in LIBs 151
5.4.1 Transition Metal Oxides 151
5.4.2 Vanadium Oxide Nanowires 153
5.4.3 Iron Compounds Including Oxides and Phosphates 157
5.5 Nanowires-Based Separators in LIBs 160
5.6 Nanowires-Based Solid-State Electrolytes in LIBs 163
5.7 Nanowires-Based Electrodes for Flexible LIBs 168
5.8 Summary and Outlook 174
References 175

6 Nanowires for Sodium-ion Batteries 185

6.1 Advantages and Challenges of Sodium-ion Batteries 185
6.1.1 Development of Sodium-ion Batteries 185
6.1.2 Characteristic of Sodium-ion Batteries 186
6.1.2.1 The Working Principle of Sodium-ion Battery 186
6.1.2.2 Advantages of Sodium-ion Batteries 186
6.1.3 Key Materials for Sodium-ion Batteries 187
6.1.3.1 Cathode 188
6.1.3.2 Anode 188
6.1.3.3 Electrolyte 189
6.1.3.4 Separator 189
6.1.4 Challenges for Sodium-ion Batteries 191
6.2 Nanowires as Cathodes in Sodium-ion Batteries 193
6.2.1 Layered Oxide Nanowires 193
6.2.2 Tunnel-type Oxide Nanowires 195
6.2.3 Polyanionic Compound Nanowires 196
6.3 Nanowires as Anodes in Sodium-ion Batteries 200
6.3.1 Carbonaceous Materials and Polyanionic Compounds 200
6.3.1.1 Graphitized Carbon Materials 200
6.3.1.2 Amorphous Carbon Materials 201
6.3.1.3 Carbon Nanomaterials 201
6.3.2 Polyanionic Compounds 203
6.3.3 Metals and Metal Oxides 206
 Contents ix

6.3.3.1 Metal Nanowires 206

6.3.3.2 Transition Metal Oxide Nanowires 207
6.3.4 Metal Sulfides 215
6.3.4.1 Molybdenum Sulfide and Its Composites 216
6.3.4.2 Tungsten Sulfide and Its Composites 216
6.3.4.3 Stannic Sulfide and Its Composites 218
6.3.4.4 Nickel Sulfide, Ferrous Sulfide and Their Composites 218
6.4 Summary 220
References 220

7 Application of Nanowire Materials in Metal-Chalcogenide

Battery 229
7.1 Lithium–Sulfur Battery 230
7.1.1 Sulfur–Carbon Nanowire Composite Cathode Materials 231
7.1.2 Conductive Polymer Nanowire/Sulfur Composite Cathode
Materials 236
7.1.3 Metal Compound Nanowires/Sulfur Composite Cathode Materials 237
7.2 Sodium–Sulfur Battery and Magnesium–Sulfur Battery 243
7.2.1 Sodium–Sulfur Battery 243
7.2.2 Magnesium–Sulfur Battery 247
7.3 Lithium–Selenium Battery 249
7.3.1 Reaction Mechanism of Lithium–Selenium Battery 250
7.3.2 Selenium-Based Cathode Materials 251
7.3.3 Existing Problems and Possible Solutions 256
7.4 Summary and Outlook 257
References 258

8 Application of Nanowires in Supercapacitors 263

8.1 Nanowire Electrode Material for Electrochemical Double-Layer
Capacitor 265
8.1.1 The Application of Carbon Nanotubes in EDLCs 266
8.1.2 The Application of Carbon Nanofibers in EDLCs 267
8.2 Nanowire Electrode Materials for Pseudocapacitive
Supercapacitors 269
8.2.1 Metal Oxide Nanowire Electrode Materials 269
8.2.2 Conducting Polymer Nanowire Electrode Materials 271
8.3 Nanowire Electrode Materials of Hybrid Supercapacitors 272
8.3.1 Hybrid Supercapacitor Based on Aqueous Electrolyte 274
8.3.1.1 Carbon/Metal Oxide 274
8.3.1.2 Carbon/Conductive Nanowire Polymer 276
8.3.2 Other Electrolyte System Hybrid Supercapacitors 277
8.3.2.1 Organic Electrolyte System 277
8.3.2.2 Redox-Active Electrolyte System 278
8.3.3 Solid Electrolyte or Quasi-Solid-State Hybrid Supercapacitor 279
x Contents

8.4 Summary and Outlook 279

References 280

9 Nanowires for Multivalent-ion Batteries 285

9.1 Nanowires for Magnesium-Ion Battery 285
9.1.1 Vanadium-Based Nanowires for MIBs 286
9.1.2 Manganese-Based Nanowires for MIBs 289
9.1.3 Other Nanowires for MIBs 290
9.2 Nanowires for Calcium-Ion Batteries 292
9.3 Nanowires for Zinc-Ion Batteries 293
9.3.1 Vanadium-Based Nanowires for ZIBs 294
9.3.2 Manganese-Based Nanowires for ZIBs 295
9.4 Nanowires for Aluminum Ion Batteries 296
9.5 Summary and Outlook 298
References 299

10 Conclusion and Outlook 305

10.1 Structure Design and Performance Optimization of 1D
Nanomaterials 305
10.2 Advanced Characterization Methods for 1D Nanomaterials 308
10.3 Applications and Challenges of Nanowire Energy Storage Devices 314
10.3.1 Application of Nanowire Structures in Lithium-ion Batteries 314
10.3.2 Applications of Nanowire Structures in Na-ion Battery 315
10.3.3 Applications of Nanowire Structures in Other Monovalent-ion
Batteries 316
10.3.4 Application of Nanowires in Lithium–Sulfur Batteries 316
10.3.5 Application of 1D Nanomaterials in Supercapacitors 318
10.3.6 Nanowires for Other Energy Storage Devices 319
10.3.6.1 Metal Air Batteries 319
10.3.6.2 Multivalent-ion Battery 320
10.3.6.3 Metal Sulfur Batteries 320
References 322

Index 327
 xi

Preface

With the increasing prominence of worldwide energy crisis, materials science

and nanotechnologies have become the key to the fields of new energy storage
and utilization. With the in-depth study of nanotechnologies, nanoenergy storage
materials are in the rapid development stage. Especially, owing to their excellent
chemistry, electricity, thermal, mechanical, and other properties, nanowire mate-
rials exhibit unique electron and ion transport characterization, making them
distinctive among nanomaterials. From this perspective, nanowire energy storage
devices (ESDs) show outstanding electrochemical and energy storage characteris-
tics. And nanowire materials also have more unique advantages in the construction
of micro and nanoenergy storage devices and the assembly of flexible ESDs. To this
end, nanowire materials offer various opportunities to address the challenges of
advanced ESD, thus attracting the great attention and strong interest of the majority
of scientific researchers.
In this book, we present a comprehensive discourse on nanowire energy storage
devices (ESDs) from the perspective of synthesis, characterization, and applications.
This publication is structured into 10 chapters, each with coherent connections and
distinct focal points. Readers can read systematically or selectively, according to their
needs.
The Chapter 1 is written by Prof. Liqiang Mai and Wen Luo. Chapter 1 intends to
offer an all-sided introduction to one-dimensional nanomaterials, energy storage sci-
ence and technology, and review the nanowire energy storage materials and devices.
The Chapter 2 is written by Prof. Liqiang Mai and Chaojiang Niu. Chapter 2
summarizes the physicochemical characteristics of nanowire, the unique advan-
tages of nanowires as electrode materials, the basic performance parameters of
nanowire electrochemical ESDs, the optimization mechanism of electrochemical
performance, and briefly introduces the theoretical calculations related to nanowire
electrode materials.
The Chapter 3 is written by Prof. Liqiang Mai and Lin Xu. Chapter 3 focuses
on the common synthesis methods and growth mechanisms of various types
of nanowire materials based on the classification of nanowires with different
morphologies.
The Chapter 4 is written by Prof. Liqiang Mai and Xiaocong Tian. Chapter 4
briefly introduces various characterization methods and summarizes the progress
in the characterization of nanowires up to now. Chapter 4 will also discuss the
xii Preface

future of characterization for nanowires and give perspectives on the opportunities

of nanowires in post-lithium energy storage systems.
The Chapter 5 is written by Prof. Liqiang Mai and Ya You. Chapter 5 elaborates
the application of nanowires in lithium-ion batteries, discusses the unique charac-
teristic of nanowires for energy storage, and gives perspectives on the opportunities
of nanowires in post-lithium energy storage systems.
The Chapter 6 is written by Prof. Liqiang Mai and Ting Zhu. Chapter 6 sum-
marizes the application of nanowire cathode and anode materials in sodium-ion
batteries. The synthesis, characterization, and reaction mechanism of the nanowires
are completely demonstrated. The perspectives on the development of nanowires in
sodium-ion batteries are also discussed in this chapter.
The Chapter 7 is written by Prof. Liqiang Mai and Xu Xu. Chapter 7 expounds
the principles and applications of various new batteries from the perspective of
nanowire electrode materials and explains the characteristics and advantages of
nanowire electrode materials in new batteries.
The Chapter 8 is written by Prof. Liqiang Mai and Liang Zhou. Chapter 8 focuses
on one-dimensional nanomaterials applied to three typical capacitors, including
Electric double-layer capacitors (EDLCs), pseudocapacitive supercapacitors, and
hybrid supercapacitors. The relationship between one-dimensional structure and
performance of capacitors is explored, which could provide theoretical guidance for
the deeper improvement of nanowire-based supercapacitors.
The Chapter 9 is written by Prof. Liqiang Mai and Qinyou An. Chapter 9 intro-
duces a broader application of nanowire ESDs in the various fields of multivalent-ion
batteries, such as magnesium-ion battery, calcium-ion battery, zinc-ion battery, and
aluminum-ion batteries. In the chapter, we also give a simple summary and outlook
on nanowires for multivalent-ion batteries.
The last chapter is written by Prof. Liqiang Mai and Wen Luo. Chapter 10 provides
a systematic conclusion and outlook on nanowire ESD and gives perspectives on
the structure design, performance optimization, and advanced characterization
methods of 1D nanomaterials. Moreover, in this chapter, we also intend to present a
broad picture of micro-nano device structure optimization and fabrication process
improvement for different applications.
This book is available for institutions of higher learning and scientific research
units engaged in the development of nanomaterials and ESDs research related
researchers and practitioners to use, also can be used as institutions of higher
learning materials, chemical energy, physical and related professional teachers,
graduate, and senior undergraduate professional reference book. Overall, despite
the best efforts of the author, due to the limitations of level and time, it is inevitable
that there will be some mistakes and omissions in the book. We sincerely hope that
the readers will contact us with valuable suggestions for its continued improvement.
Finally, I would like to thank all the contributors to this book. We thank
the support of the National Key Research and Development Program of China
(2020YFA0715000), the National Natural Science Foundation of China (51832004,
52127816, 51802239, 52172233).

February 2023 Liqiang Mai

Wuhan, China
 1

Nanowire Energy Storage Devices: Synthesis,

Characterization, and Applications

1.1 Introduction
1.1.1 One-Dimensional Nanomaterials
As an important member of the large family of nanomaterials, one-dimensional
nanowire (NW) materials, including nanorods, nanotubes, nanobelts, and
nanocables, have gradually received attention from researchers (Figure 1.1). A NW
can be defined as a one-dimensional structure that is less than 100 nm in the lateral
direction (there is no limitation in the longitudinal direction). The aspect ratio of a
part of a NW is more than 1000 [1]. According to their different compositions, NWs
can be divided into different types, including metal NWs (such as Ni, Pt, and Au),
semiconductor NWs (such as InP, Si, and GaN), and insulator NWs (such as SiO2
and TiO2 ). NW materials have important implications for theoretical research and
technical applications. This kind of material has peculiar physical and chemical
properties, such as the transition from metal to insulator, super mechanical strength,
high luminous efficiency, lower laser threshold, and enhanced thermoelectric
coefficient [2].
The research on NWs can be traced to the early 1960s. In 1964, Wagner and
Ellis [3] used vapor–liquid–solid (VLS) growth to epitaxially grow Si single crys-
tal whiskers on a single crystal Si(111) substrate, creating a precedent for Si NW
research. In 1975, Givargizov [4] conducted a systematic study on the process of VLS
growth and gave a reasonable VLS growth mechanism for NWs. In 1998, Morales [5]
and Zhang et al. [6] used laser ablation deposition (LAD) to successfully grow Si
NWs. NW materials exhibit unique optical, electrical, and magnetic properties that
many bulk materials do not have. Therefore, they have an extremely important
position in the field of producing nanodevices, various sensors, microtools, micro-
electrodes, device-integrated connection lines, and next-generation EL display
devices. Current research results show that many one-dimensional nanomaterials
have demonstrated essential applications. For example, Huang et al. [7] grew ZnO
NW array with a diameter of 20–150 nm and a length of about 10 μm through
a vapor-phase transport process on a sapphire substrate, successfully preparing

Nanowire Energy Storage Devices: Synthesis, Characterization, and Applications, First Edition.
Edited by Liqiang Mai.
© 2024 WILEY-VCH GmbH. Published 2024 by WILEY-VCH GmbH.
2 1 Nanowire Energy Storage Devices: Synthesis, Characterization, and Applications

Nanorods Nanobelts

Nanocables Nanowires
Nanotubes

Nanowire arr
tworks ays
ire ne
w
no
Na

Nanowires

ers
Nanowire clust
Figure 1.1 Schematic diagram of different types of nanowires and their secondary
structures.

nanolasers in 2001. In 2007, Prof. Lieber from Harvard University and his team
developed the first single NW solar cell [8]. They reported a solar cell prepared by
a single coaxial silicon nanowire (SiNW), which adopts a p–i–n coaxial structure.
The synthesis and application of NWs have become hot spots for scientists in recent
years because of their unique advantages. Prof. Mai from Wuhan University of
Technology and his team designed and assembled the first single NW electrochem-
ical energy storage device to reveal the intrinsic mechanism of electrochemical
performance degradation in 2010 [9]. In the same year, Huang et al. [10] used in
situ TEM to observe the lithiation phenomenon of a single NW of SnO2 for the
first time. In 2012, Kouwenhoven from Delft University of Technology and his
team verified the hypothesis that Majorana fermions in NWs are coupled with
superconductors [11]. In 2014, Prof. Cheng from Monash University and his team
built a wearable pressure sensor using gold nanowires [12]. In 2019, scientists
from Cambridge University, King’s College London, Peking University, Zhejiang
University, Shanghai Jiao Tong University, and other universities developed the
first single NW spectrometer in the world [13]. In 2020, researchers from Chinese
Academy of Sciences demonstrated a new flexible dual- NW structure consisting
of a GeSn layer with Sn content of 10% heteroepitaxially grown on the sidewall
of a Ge NW by molecular beam epitaxy (MBE), which effectively suppressed
the formation of defects at the GeSn/Ge interface and greatly reduced the dark
current and static power consumption of the photodetector with GeSn/Ge dual-NW
structure [14]. NWs and devices with various structures have been continuously
developed, and their applications in scientific research and industrialization have
become increasingly extensive with the continuous progress of nanotechnology.
 1.1 Introduction 3

The important development process is shown in Figure 1.2. This book focuses on
the introduction of NW materials in electrochemical energy storage.

1.1.1.1 Nanorods
Nanorods and NWs are well-known one-dimensional nanostructures, which are
frequently used not only in nano-electromechanical systems but also in biomedical
treatments, dentistry, production of energy from solar cells, and humidity-sensitive
analysis [15]. Nanorods consist of rod-like nanoparticles. Its length is usually much
larger than its size in the two-dimensional direction and can achieve a macroscopic
magnitude. It should be noted that there is no strict distinction between NWs and
nanorods. Generally, those with a large slenderness ratio are called nanofibers,
and those with a small aspect ratio are called nanorods. The dividing line is located
at 1 μm. The preparation methods for nanorods mainly adopt VLS growth and
template-based synthesis. Nanorods can also be formed by using LAD. Pana-
sonic, the U.S. Bureau of Standards and Metrology, and the University of Florida
have done a large quantity of work in this area, using the pulsed laser method
to successfully prepare one-dimensional SiNWs and boron nitride nanotubes.
The one-dimensional nanomaterial synthesized by this method has the advantages
of high purity, large output, and uniform diameter. Researchers at the University of
Minnesota and Princeton University successfully prepared a quantum disk in 1998.
This disk is a nano-array system composed of magnetic nanorods with a density of
109 bit cm−2 .

1.1.1.2 Carbon Nanofibers

Carbon nanofibers (CNFs) are sp2 -based linear, noncontinuous filaments that are
different from carbon fibers, which are continuous with diameter of several microm-
eters [16]. They are a new type of quasi-one-dimensional carbon material that has
attracted more attention in recent years. Its diameter is generally 50–200 nm, the
length is 50–100 μm, and the aspect ratio is 100–500. Its structure and performance
are in the transition state between ordinary carbon fiber and carbon nanotubes, and
are formed by stacking nano-sized graphite sheets at different angles to the axial
direction of the fiber in space [17]. One-dimensional CNFs have many superior prop-
erties, so their application prospects are extensive. CNFs have pores on molecular
level over the surface and also have pores inside, as well as a large specific surface
area [18]. Therefore, it can absorb a large amount of gas and is a potential hydro-
gen storage material. It can also be used as a high-efficiency adsorbent, catalyst, and
catalyst carrier [19]. CNFs also have high electrical conductivity and can be used
as cathode materials for lithium-ion secondary batteries and electrodes for electric
double-layer capacitors [20].

1.1.1.3 Nanotubes
Carbon nanotubes, the one-dimensional allotropes of carbon, have attracted signif-
icant research interest ever since their discovery due to their outstanding material
properties. Carbon nanotubes are a typical representative of nanotubes. In the 1970s,
4 1 Nanowire Energy Storage Devices: Synthesis, Characterization, and Applications

Z. Di et al. demonstrate

Normalized PL
a flexible GeSn/Ge dual- 2020
nanowire structure
T. Hasan et al. developed
2019 500 550 600 650 700 the first single nanowire
Wavelength (nm)
spectrometer in the world

W. Cheng et al. buil

a wearable pressure 2014
sensor using gold
nanowires

L. P. Kouwenhoven et al. verified the

2012 hypothesis of coupling between
Majorana fermions and
superconductors of nanowires

L. Mai et al. developed a

J. Huang et al. observed the single nanowire
lithiation of a single SnO2 2010 electrochemical device
nanowire for the first time

C. M. Lieber et al.
Z. Wang et al. developed the developed a single
first nanowire generator in the 2007 silicon nanowire
world solar cell

R. R. Llinás et al. have

developed a new method of
2005 implanting platinum metal
nano-cables into human blood
vessels

Z. Wang et al. discovered and P. Yang et al.

synthesized semiconductor 2001 developed the first
oxide nanobelts nanowire laser

R. E. Smalley et al.
synthesized single-
walled carbon 1996
nanotube bundles
arranged in lines 1991

M. Endo developed carbon 1978

fiber with a diameter of 7 nm

R. S. Wagner et al. proposed “solid-

1964 liquid-gas growth mechanism”

Year

Figure 1.2 Important development history of nanowire materials. Source: Refs. [3–14].
 1.1 Introduction 5

M. Endo from the University of Orléans in France successfully synthesized carbon

fibers with a diameter of 7 nm, but he did not carefully evaluate and characterize
the structure of these carbon fibers [21]. Until 1991, Iijima [22] of the Japanese NEC
company discovered carbon nanotubes for the first time with a high-resolution elec-
tron microscope. Since then, nanomaterials have attracted widespread attention in
the global scientific research field. In 1996, the famous American Nobel Prize win-
ner Smalley and others synthesized single-walled carbon nanotube (SWNT) bundles
arranged in rows, which signifies that scientists can prepare batches of NWs in a
controlled manner [23]. Xie and coworkers [24] from Institute of Physics, Chinese
Academy of Sciences, have achieved the directional growth of carbon nanotubes and
successfully synthesized ultra-long (millimeter-level) carbon nanotubes, reported
the synthesis of strong, highly conducting, and transparent SWNT films in 2007.
Because carbon nanotubes have the advantages of large specific surface area,
good electrical conductivity, and high chemical stability, they have also been widely
used for electric double-layer supercapacitor electrodes or as conductive additives
in other electrochemical energy storage systems, such as pseudocapacitors and
metal ion batteries [25]. At the same time, the internal and surface bond states
of carbon nanotubes are different, and there is a phenomenon of incomplete
coordination of surface atoms, which leads to an increase in active sites on the
surface. These characteristics make carbon nanotubes one of the ideal catalyst
support materials [26]. In addition, carbon nanotubes are also expected to be used
for field emission tubes, field emission flat panel displays, microwave generators,
gas discharge tubes, and fluorescent lamps, and their nano-scale hollow pipes also
make them have great potential for hydrogen storage [27].

1.1.1.4 Nanobelts
It is difficult to maintain stability during large-scale industrial production of carbon
nanotubes, slowing the research of nanomaterials. In 2001, Prof. Zhonglin Wang and
his team used the high-temperature solid gas phase method to discover and synthe-
size semiconductor oxide nanobelt structures for the first time in the world [28].
Then, they successfully synthesized the ribbonlike structure of broadband semicon-
ductor systems such as zinc oxide, tin oxide, indium oxide, cadmium oxide, and
gallium oxide. The purity of these ribbonlike structure materials is as high as 95%,
and they have the advantages of large output, perfect structure, clean surface, no
internal defects, and no dislocations. In 2007, Zhonglin Wang and his team devel-
oped the first NW generator in the world [29].
The cross section of the nanobelt is a narrow rectangular structure with a band-
width of 30–300 nm, a thickness of 5–10 nm, and length of up to several millimeters.
Compared with carbon nanotubes, silicon, and compound semiconductor linear
structures, nanobelts are the only broadband semiconductor one-dimensional rib-
bon structures that have been found to have a controllable structure, be defect-free,
and have more unique and superior features of structure and physical properties
than carbon nanotubes. Although nanobelts lack the high structural strength of
cylindrical nanotubes, they can ensure the necessary stability of electronic equip-
ment and the uniformity of the material structure during mass production because
6 1 Nanowire Energy Storage Devices: Synthesis, Characterization, and Applications

of their superior performance, which is very important in nanophysics research

and nanodevice applications. This structure is an ideal system for researching the
transport processes of light, electricity, and heat in one-dimensional functional
and smart materials. It can enable scientists to use single oxide nanobelts to make
nanometer-sized gas and liquid sensors, nanofunctions, and smart optoelectronic
components, laying a solid foundation for nanooptoelectronics [30].

1.1.1.5 Nanocables
In 1997, French scientists C. Colliex and his team found a sandwich-geometry
C–BN–C tube in the product obtained by analyzing the arc discharge. Because its
geometry is similar to that of a coaxial cable and the diameter is at the nanometer
level, it is called a coaxial nanocable [31]. In 1998, Zhang et al. [32] used laser
ablation to synthesize a coaxial nanocable with a diameter of tens of nanometers
and a length of 50 μm. Their experiment shows that if the mixed powder of BN, C,
and SiO2 is used as the raw material, a single-core nanocable can be formed with
β-SiC core wire inside and amorphous SiO2 single wire outside. If Li3 N is added to
the raw materials, a coaxial nanocable with another structure can be formed, that is,
the core is SiC, the middle layer is amorphous SiO2 , and the outermost layer is BNC
with a graphite structure. At the same time, Meng et al. [33] developed a new coaxial
nanocable preparation method, which is sol–gel and carbothermal reduction with
evaporation–condensation, and successfully synthesized a coaxial nanocable with
SiC semiconductor core and SiO2 insulator on the outer layer. After 2000, people
have successfully prepared hundreds of coaxial nanocables using different synthesis
methods and different kinds of materials, such as SiGaN/SiOx Ny [34], Fe/C [35],
Ag/polypyrrole [36], GaP/ZnS [37], CdSe/TiO2 [38], and three-layer structure of
Ag/SiO2 /ppy [39] and Nd/FM (FM = Fe, Co, Ni)/PA66 [40].
Coaxial nanocables play a crucial role in the fields of biomedicine, nano-electronic
devices, nano-microprocessing, and testing technology. In terms of practical appli-
cations, the components in the ultrahigh-density-integrated circuit are mainly con-
nected by nanocable coupling; hence, the nanocable also plays an important role
in the connection line. Considering the research on solar cells, the US National
Renewable Energy Laboratory has developed a kind of solar cell with high-energy
conversion using coaxial nanocable. Respecting medical research, in 2005, scientists
in the Unites States and Japan successfully developed a new method of implant-
ing platinum metal nanocables with a diameter of 1% of human hair into human
blood vessels and hoped that one day it would help doctors treat certain human dis-
eases [41]. Nanocables can also be used as probes for miniature detectors on impor-
tant nano-resolution detectors such as field emission detectors, biological detectors,
and atomic force microscopes [42]. It is believed that with the continuous discovery
of new special properties of nanocables, coaxial nanocables will also become a new
force in the field of NW materials.

1.1.2 Energy Storage Science and Technology

The widespread application of fossil fuels (oil, coal, and natural gas) has greatly pro-
moted the rapid development of the world economy. Nowadays, the improvement
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around like a butterfly this minute, most likely,” and the young man
smiled rather bitterly.
He had come from the city to make sure a girl was not in trouble, but
the thought of her enjoying herself made him uneasy.
From the village to the “Bend” was, as he had remarked, quite a
distance. In spite of brisk walking it was nearly dark before his
destination was reached.
“That must be the place,” he thought, quickening his steps as the
white buildings of the Whittaker farm loomed up in the dusk.
“What in the world shall I do, now I’m here?” he asked himself, as he
paused in front of the house. “If she’d only come out and take back
her words it would be all right. But goodness! she’s an awful spunky
little thing when she’s once under way, and it was pretty tough for
her. It’s mighty certain it’s not in her line, but I needn’t have been
quite so hard with her. Hang it all! what am I going to do now? What
in the Dickens made me come, anyway? Only because I’m such a
fool I couldn’t keep myself away.”
He stood leaning against a tree near one of the windows. The
summer air was very still. Only occasionally the birds stirred in their
nests above his head and murmured sleepily. Once some restless
animal pounded the floor of the barn.
Suddenly a low strain of music startled him. Did it come from one of
the open windows? Timidly soft it sounded, as though fearing to let
itself be heard—weird and sad.
The man out among the shadows trembled. “Can that be she? Has
she given in?”
The music grew more abandoned. In its sorrow it seemed to have
forgotten its timidity. The long notes sobbed and moaned, now and
then dying into quieter, more entreating tones. In their tears they
paused and prayed.
The listener was a musician, and the melody reached the depths of
his soul. Facing the window, he called in a broken voice, “Gertrude.”
The music instantly ceased. A glad cry rang out, “Herman! my
Herman!”
In a second, the man had vaulted the low sill of the parlor window.
He hurriedly glanced around the room. No musical instrument could
be seen, but a trembling form was steadying itself against the
casing.
“Gertie, poor little Gertie!”
A faint voice answered, “Is it true? Can it be you? O Herman!”
Again the music rang out. Triumphant peals this time, strain after
strain of tumultuous joy, clearer and clearer, stronger and stronger,
until the notes could hardly hold their fulness.
In the parlor Gertrude and Herman stood gazing into each other’s
startled eyes.
The wild, rapturous song paused; then breaking out in steadier
notes, even and rich, it gradually mellowed and hushed until it died
away in a whispered breath.
“It ended like a prayer of thanksgiving,” said he.
Gertrude caught her breath. “Hush!” She buried her face in her
hands, whispering, “It was. I see it all now. It must have been little
Chee,—there is no one else.” Lifting her head, she added, with a
strange, new light in her eyes, “Oh, Herman, she was thanking God
for answering her prayer. I believe it.” And then, half choked with
feeling, she told what she knew of her little Indian cousin.
 CHAPTER IX.
COUSIN GERTRUDE stole up-stairs. Chee had heard good-byes a
few moments before, and was hoping, yet fearing, she might find
her.
The child sat by the window removing her stockings. Daddy Joe’s
fiddle lay on the bed.
“Birdie, how could you? Oh, how could you?”
“I don’t know,” answered Chee, in an excited voice. “I tried not to
play out loud, but I got feeling sorrier and sorrier, and wishing He
would only let me help. And I forgot to play still, and then I heard a
man’s voice, and heard you answer, and I knew everything was all
right, and I was so happy I just snatched up Daddy’s fiddle and
played out my glad. I didn’t care who heard, for a minute; and, oh,
Cousin Gertrude, I felt it—I felt it.”
“Felt what, Childie?”
“Why, the music—way down in my heart, and all over me, just like I
did at the concert. I don’t know what to call it, but it’s something, and
I’ve tried to feel it for such a long time. And now I have, and it makes
me so happy—so happy, you can’t know. It just makes me glad all
through, and I feel like crying, too.”
“I am as happy as you, my own little Bird.”
Chee’s arms were around Gertrude’s neck, as she asked, “He did
hear, didn’t He?”
“Yes, my comfort, He did hear,” answered Gertrude, tears again in
her voice, “but you helped Him.”
“I helped Him?” echoed Chee, shaking her head almost sadly. “No, I
wanted to so much, but He didn’t need me.”
After a little, Gertrude said, “Listen, while I tell you how you helped—
you’ll see He did need you, after all.
“I love the violin, too—not as you do. I wanted to play because
people expected I would. I felt too proud to say that, after years of
study, I could never be a great player, and so I kept on working with
one teacher after another. Finally, Mr. Farrar, that is my Herman, told
me I had better not spend all my time and money for that any longer.
He said I had come to a place where I could never go much beyond,
and that I wanted to play more from pride than from love—just
because my parents had decided, when I was but a child, that music
was my first gift. I had found true what he said, but it made me angry
that he should dare to tell me. I said some words back. He retorted.
We’re both sorry now, but I was so vexed then, I said I would never
touch the violin again. My temper offended him, his also rose, and he
said he would not speak to me until I took back my words.
“It was the day I had set to come here. He was just going to the
woods for his vacation, but he felt so sad he could not go, and went
back home instead. Then one night he had a horrible dream that
troubled him, so he came to see if I was really safe and well. He
says that, down in his heart, he was hoping I was ready to take back
my words.
“While he was wishing so much I would come to him—he was out
under the trees, you know—he heard music. He thought for a
moment I was playing, and when he reached me and found out I
wasn’t—well, we were both so glad to be together again we forgot
which one was to blame. It seemed very silly to have quarrelled at all
when we understood and loved each other so. Anyway, now we are
only glad to be together again and forget everything. Can’t you see
how it might never have come right if you had not played when you
did?”
Chee made no answer, her heart was full.
“Of course,” she continued, “if he had stopped to think he would
have known it never could have been my playing,—he knows me so
well,—but he was anxious and didn’t realize. It seemed to him, he
said, the music must be mine, he wanted so much I should take back
my words.
“You did help, my Birdie, but you sha’n’t be left to sing alone any
longer. Oh!” a new light dawning, “now I know why you love to think
Opechee means a song-bird,” and she kissed the silent child with
new fondness.
“We are going to ride in the morning, my Herman and I, and when
we return perhaps we will have something to tell you. But oh, my
precious cousin, you can never, never know all you have done for
us.”
Chee only answered with a grave little shake of her head, “It wasn’t
me, ’twas only Our Father, and”—she added tenderly—“Daddy Joe’s
fiddle.”
 CHAPTER X.
IN the morning, as he had promised, Mr. Farrar came to take Cousin
Gertrude to drive.
“Chee! Chee! Nut-Brown Maiden, where are you?” Stepping to the
stairway, Gertrude called, more earnestly, “Birdie, I want you.”
A shy little face peered over the railing, “Please, Cousin Gertrude,
have I got to come down?”
“Why, Chee, wouldn’t you like to? There is some one here I want you
to see.”
“Yes, I know, but I’d rather look at him through the parlor blinds.”
Gertrude showed her disappointment. Chee watched her and
yielded, exclaiming, “Well, you must be awful proud of him to feel so
bad. I suppose I’d ought to come.”
Cousin Gertrude’s cheeks grew pinker, but she did not look
displeased; she only held out her hand to Chee. Wondering what
she might say to put the little girl more at ease, she led her to the
veranda.
A gentleman was standing by the carriage block, stroking the mane
of a horse. At sight of Chee he quickly removed his hat, as though to
some fine lady. “So this is little Chee,” said he, “our sweet singer,
only she doesn’t really sing, she plays. Good morning, my dear.”
“Good morning. I don’t know just what to call you yet. It doesn’t seem
quite kind to say ‘Mr. Farrar,’ when you are Cousin Gertrude’s best
friend, does it? She calls you ‘my Herman,’ but I’m afraid she’d
rather I wouldn’t say that, too.”
Mr. Farrar was pleased with this artlessness, characteristic of Chee,
so unlike any boldness, so like open confidence in one she
instinctively recognized to be worthy. Her voice at such times
seemed to say, “I’ll trust you, you may trust me.”
His eyes twinkled, but he said gravely, seeming not to notice
Gertrude, “Suppose you compromise, and say ‘our Herman.’”
Chee gave a perplexed glance toward Gertrude. Suddenly a smile
brightened her face, as she exclaimed, “Oh, I’ve got it. Why didn’t we
think before? S’pose I call you ‘Cousin Herman.’” She gave no
opportunity for dissent before adding, “It’s so much more
comfortable, now I know who you are.”
Cousin Gertrude appeared somewhat confused, but her friend patted
the little girl’s head approvingly, saying, “Quite right, little Chee, the
very thing, indeed—”
“But Birdie,” hastily interrupted Gertrude, “we haven’t thanked you
yet.” The child cast furtive glances toward the house. Her
companions changed the conversation. Their eyes, following hers,
had seen others, steel blue, peering through a lace curtain.
“Is Aunt Mean busy?” asked Gertrude.
After a discreet silence Aunt Mean appeared in the front doorway. A
brief introduction had scarcely passed before she said, aside to
Gertrude, in low but decidedly distinct tones, “A very likely young
man, my dear, very likely. You showed good taste. I persume there
ain’t a better looking in our neighborhood,” adding, reflectively, “It’s a
mighty serious business, this gittin’ a man.”
Chee wondered if Aunt Mean spoke from experience, and if it
wouldn’t have been a very serious matter indeed if Aunt Mean had
ever attempted to “git” any man other than her brother. During the
embarrassment that followed, Mr. Farrar found occasion to remark
that it was getting late, and Cousin Gertrude felt obliged to go for her
hat. But before entering the carriage she managed to whisper to
Chee, “Don’t undress when you go up-stairs to-night—we shall be
home early.”
What a long day it seemed to Chee! How anxiously she listened for
the sound of wheels on the driveway!
After all she watched in vain, for they had left the carriage before the
Bend was reached. The first she knew of their coming was a step on
the stairway—very soft, like stocking feet. She opened the door a
little. “Take off your shoes please, Chee, and come down into the
parlor awhile.”
It was fortunate that the bedrooms occupied by Miss Almeana and
her brother were at the extreme end of the house. Furthermore, both
were slightly deaf and extraordinarily sound sleepers.
In the parlor the cousins and Mr. Farrar gathered around Chee’s tin
lamp. “And so you have had no instructor but that minister,” he
began. “We saw him to-day, and, as he himself says, he doesn’t
know much about music. You can read notes, he tells me.”
“Easy music,” answered Chee, bashfully. The dreaded ordeal had
come—her secret was out.
“Well, that’s good, but how in the world did you learn to manage the
instrument? Who taught you to hold it, child?”
“I don’t know, Cousin Herman, I think perhaps I hold it just as Daddy
did, maybe I don’t, though. It’s so long since I’ve seen him I can’t be
sure.” This last was added a little wearily. “What has the way I hold
Daddy’s fiddle to do with Cousin Herman?” she wondered.
“It’s just as I say,” exclaimed Mr. Farrar, turning to Gertrude,
—“inherited talent. Probably the father was only a fair player, but
unless I’m stepping down a peg, the child’s a genius.” Chee
wondered if a genius was something nice, but, because she disliked
to show her ignorance, refrained from asking.
“Of course the child has run to weeds—it couldn’t be otherwise. I
must hear her play again, but at all odds she is a musician.” Then
turning suddenly to Chee, he asked, “Where is your violin, my dear?
You must play your best for me, then Gertrude shall tell you our
plan.”
Chee looked frightened, “Why, Cousin Herman, I couldn’t, she’d hear
me—I couldn’t for anything.”
“Who? Oh, I forgot. Well, we’ll have to fix it somehow. Where have
you been playing all this while? Up attic? What’s the harm now,
then?” So saying, Mr. Farrar proceeded to unlace his shoes.
Chee was a little tremulous over the undertaking, but Cousin
Herman was firm; so carrying her small lamp she led the way up the
front stairs, shielding the flickering flame with her hand. The light fell
full upon her excited face. Now and then she paused in the slow,
careful ascent to give whispered warning where a stair-riser might
creak—all so familiar to her. Mr. Farrar easily stepped over these
places, as did Chee, but, lest there should be any slight noise and
their stealthy journey to the attic be disclosed, he assisted Gertrude
over the treacherous places as indicated by their little Indian guide.
When the garret was reached, Gertrude seated herself on a trunk.
Mr. Farrar leaned against the chimney. Chee lingered at the railing,
anxiously listening.
 “SHE STOOD A MOMENT IN MEDITATION, THE VIOLIN
ALREADY UNDER HER CHIN”
“Chee!” they both impatiently called, at the same time glancing
curiously around.
She approached the familiar hiding-place, and very slowly drew out
the old violin box. Her cheeks were flushed, and her lips met in a
straight line. A brave determination burned in her eyes. She realized
in a vague way that much depended upon this effort, but with a
pleased, expectant look she deftly attuned the strings of her
instrument.
When this was done, she stood a moment in meditation, the violin
already under her chin, lightly tapping one foot with the bow.
It was a queer place in which to make one’s début,—that dusty
corner of the old loft. The tin lamp on a box lighted up the beams
hung with long drooping garlands of cobwebs. Not within reach of
the lamplight, or the pale moonshine coming through the curtainless
windows, huge black shadows gathered around. But the weirdness
of the aspect did not impress Chee; for her a more familiar spot
could not have been chosen. Oh, how many happy hours she had
spent in that dim little corner!
Soon her meditative position changed, she had come to a decision,
and began to play.
At first, embarrassment hindered her, but before many notes
trembled out on the stillness, she had forgotten everything except
her song.
It was only the old-fashioned air, “Annie Laurie.” The child must have
known the words, for her music told, even plainer than any words
could tell, the sentiment of the old-time refrain. Perhaps she had
guessed more of her listeners’ state of mind than they knew.
However this may have been, she had chosen well; while the song
lasted, her listeners forgot to be critics—they were only lovers.
The last strains had scarcely died away, when, close upon them,
followed the opening notes of “Nearer, My God, to Thee.” If the first
piece had been selected for her audience, this was for herself.
It was her favorite, the one she most often played. No
embarrassment now—with a far-away expression in her eyes, she
gave variation after variation of the familiar hymn. Suddenly the bow
paused—the note just begun was never finished. A slight noise came
from the stairway. After a moment of listening, Mr. Farrar crept to the
railing and looked down. Everything was still.
“It must have been only mice,” he said, but Chee was thoroughly
frightened. Nothing could induce her to continue. At the first sign of
alarm Daddy Joe’s fiddle had disappeared.
 CHAPTER XI.
AFTER Mr. Farrar had bade them good night and stolen out the front
doorway, Gertrude revealed to Chee their plan.
“We are going to have a concert,” she announced. “Mr. Green says
you haven’t had one here in town since last Christmas—and we’re
going to get people so interested the whole place will turn out.
Herman knows how, for he has gotten up several in the city.”
“Get up a concert, why, how can he?” asked Chee, incredulously.
“He will have a chorus. Every child in the village must be in that. And
he is going to send for some of his friends,—a man to play the harp,
and a lady to sing, and some others. And Herman, you know, plays
on the piano,—that’s his profession.”
“Oh!” said Chee, in a tone of new understanding.
“But wait, dear, the best part is coming. You are the best part of all.”
“Me?”
“Yes, Birdie, you. That’s what the whole thing is for. It’s Mr. Green’s
idea as much as Herman’s. It’s to be kept a surprise—I mean you
are—your name won’t appear on the programme at all.”
“My name on the programme! Cousin Gertrude, what do you mean?”
Poor Chee was thoroughly alarmed now.
“Mean? You dear little monkey, you. Why nothing at all but that you
and your violin are going to bring down the house.”
“Do you mean my secret has got to come out?”
“Of course. Isn’t it already out? More’s the pity it has been kept so
long.”
“But Aunt Mean! Why, Cousin Gertrude, what are you thinking of?
You know how she hates it, and calls it wicked.” Chee was almost in
tears.
“Dear Birdie, can’t you see that’s what the whole thing is for—to cure
Aunt Mean of her nonsense? You know how proud she is—we think
if we can only get her to the hall, that, after she has heard how
beautifully you play and how fine people think it is, she will give right
in.”
“I’m ’fraid she mightn’t—’sides, Cousin Gertrude, how could I ever
play at the hall? I never, never could do that.”
“Chee,” Gertrude’s face was earnest with pleading, “you love your
little violin, don’t you?”
“You know I love Daddy Joe’s fiddle best of everything in this world.”
“Well, if you knew that all you ever might learn about it depended
upon whether you played at the hall or not, couldn’t you do it?”
“Do you mean I could learn to make music like the man at the
concert long ago?” Chee spoke tremulously, and tears filled her eyes
as they looked up, so full of yearning entreaty.
“Yes, I think you could. If our concert was a success, so Aunt Mean
would let you go, we would take you to the city with us, where you
could study music to your heart’s content.”
“Go to the city and learn how to play all I want to!” Chee echoed.
“Can’t you get courage to play at the concert, now?” The child’s lips
compressed for a moment, then she answered in a whisper, “I don’t
believe she’d ever let me go, but I’ll try.”
“That’s a dear. Don’t you worry about Aunt Mean. Just wait until my
Nut-Brown Maiden thrills the house.”
Chee shook her head dubiously. “Aunt Mean never lets anything
make her feel as though she must fly straight to heaven. She can’t,”
said the little girl, translating Gertrude’s words into a language of her
own.
 CHAPTER XII.
BUSY weeks followed. Mr. Farrar frequently came and went—of
course to see Gertrude, but often their afternoon drive together was
only to and from the parsonage gate.
Finally the day for the concert was set. Artists from a distance were
engaged, and the children’s rehearsal commenced. Chesterfield life
had begun to lag. For the farmers it was less dull than for the
townsfolk, on account of the haying. But gossip was scarce, and the
news of a concert ahead was a genuine treat.
“Now I wouldn’t snap my fingers to hear the school youngsters holler,
but regular music fellers from the city—that’s something we don’t get
a chance at every day.”
The choir-leader made this remark with his usual nasal drawl. The
big bulletin of the coming event was being fastened against the wall
of the post-office. A little knot of men and boys had gathered around.
“Well, I don’t know as I could ’zactly afford to pay for city finery, but
as Sadie and Bill are both a-going to sing, mother ’n’ me cal’ated as
how we’d have to see they did right proper,” replied wee Sadie’s
grandpa.
“Stuff and nonsense,” growled the doctor, as he peered impatiently
at the postmistress, as though that meek little person was to blame
for the tardiness of a letter, “waste of time and money.” But the
doctor was a bachelor, and “took in the shows,” so the people said,
during his city trips. He was a gruff man, and though they had often
proved his kind-heartedness in a case of measles, or scarlet fever,
small urchins stepped aside with alacrity as he passed.
“Some on you is wrong, and some on you is maybe right,” said Bill
Saulswick, the village wag and philosopher, “but I know good tunes
when I hears ’um; just gimme the sort, be it fiddlin’, or singin’, or
drummin’,—that tells me why I’m who, and which I’m what, and when
I’m where, and I’ll sit there till the lights go out.”
While the villagers enjoyed the gossip, poor little Chee was in a whirl
of excitement. Her days seemed a series of ups and downs. At times
she could hardly wait for the great day to arrive, then in a moment
her heart would sink with terror, and she would hide herself for hours
until she had conquered the temptation to tell Cousin Gertrude she
must break her promise. But she came of a sturdy, resolute race,—to
falter would be worse than to fail, so she struggled with herself,
Gertrude claiming more and more of her time as the eventful day
drew nearer.
“It do beat all,” Aunt Mean would exclaim, as from the pantry window
she watched the girls go through the meadow lot, “what Gertrude
finds so entertainin’ about that child. She hasn’t eyes for nobody but
her, gaddin’ off every day, or ridin’ to town. I should most expect her
beau would make some kind of a row over it.”
For they did “gad off” every pleasant day, sometimes to the grove to
plan, but more often to the minister’s. There Chee would practise on
Mr. Green’s violin, while Gertrude read or talked with Mrs. Green.
A few days before the concert, Mr. Farrar met them that he might
hear, for the last time, Chee’s piece.
“Cousin Herman, if I play very well indeed, will you please say ‘yes’
to something?”
“That’s rather broad,” replied the gentleman; “suppose I can’t say
‘yes.’”
“Oh, but I know you can, just as well as not.”
“What is it about?”
Chee flushed a little, but answered, smilingly, “Clothes.”
“Ho, ho, that’s it! Well, I guess I can go it.”
Mr. Farrar considered himself an apt student of human nature. “It’s
only natural the child should have a little pride. It’s a good thing
Gertrude intends to see to a gown for her.” So said the young man to
himself, little doubting the exact nature of Chee’s request.
Satisfied with his promise to say “yes,” the little girl began to play her
chosen piece.
It had taken so long to make a selection from her old pieces, Cousin
Herman had bought several new ones—marvels of creation they
were to Chee. “Fixed up with the baby songs all in,” as she styled the
turns and trills. She had tried to play true to the notes, but it was a
hard task. To-day as she was conscientiously measuring them out,
he left the room a moment to speak with the minister. Returning, he
was surprised at the progress she had made in his absence.
Thinking his presence had hindered her, he stole softly to the door.
With a listening expression on her face, Chee was slowly pacing the
floor. The sheet of music lay on the table, face down. Undoubtedly,
as Mr. Farrar recalled the selection, it was the one she was playing—
but how changed! It seemed to have been but the framework for the
little artist to build upon.
She finished, and brushing the damp hair from her warm forehead,
looked up. Cousin Herman stood in the doorway. Chee glanced at
the neglected sheet of music with a guilty look. “I forgot, Cousin
Herman, I really did,” she explained, hurriedly.
“I guess you needn’t bother with the notes. I see you have the
melody in your head.” He tried to speak unconcernedly.
Chee was relieved. “I’m ever so glad. You don’t know how much
easier it will be.”
“After you have a teacher I suppose it will be necessary to tie you
down to accurate reading, but until then we won’t spoil your own
way.”
The minister came in just then, followed by his wife and Gertrude. “Is
the lesson over?” he asked.
“Cousin Herman has got to say ‘yes’ now.”
“Say ‘yes?’ What to?”
“That’s just what he hasn’t been told,” replied Mr. Farrar.
Going to him, Chee drew down his head, that she might whisper in
his ear. He looked perplexed. A private consultation followed, much
to the amusement of the others in the room.
At first he seemed hard to persuade, but finally yielded, and Chee
left him with a satisfied, “That’s a good Cousin Herman.”
“Gertrude,” he said at parting, “you needn’t order Chee’s dress; that
matter has already been attended to.”
Gertrude was not only astonished, she was disappointed, and
started to speak, then checked herself.
“After all, Herman must know what he is about. I’ll leave it to him.”
Gertrude had learned one lesson; it could not be forgotten soon.
 CHAPTER XIII.
THE day of the concert smilingly dawned.
At breakfast, Uncle Reuben surprised them by saying, “I’m going
over the river to-day, Mean. Don’t you want to go ’long, and stop to
George’s?”
Aunt Mean hesitated.
“You kin wear your best bunnet, so’s to stop to the concert on the
way back.”
“Reuben Whittaker! you’re not going to blow in a single cent on any
concert, and you know it. If Gertrude is foolish ’nough to go and take
Chee, that ain’t none of my business.” Aunt Mean looked toward her
nieces as she spoke, but the cousins’ eyes were fixed upon their
plates.
“Why, Mean,” said Uncle Reuben, mildly, “the minister says the hull
town is going to turn out. Even—”
“When did you see the minister?” interrupted his sister.
“Even Miss Flanigin sent for her sister to take keer of the young’ns,”
continued Uncle Reuben, without notice of any question. “I never
reckoned on our being behind the Flanigins.”
“Humph! those Flanigins,” was Aunt Mean’s only comment. But
Gertrude noticed, as they drove away, a bonnet with a purple poppy
had won the day.
“What could have possessed Uncle Reuben to take her off to-day, of
all days?” gleefully questioned Chee.
“Everything is turning out just right, that’s a fact,” replied her cousin.
A thought of half suspicion came to Chee. “You don’t suppose—”
she began, impressively, when Gertrude gave a little cry of pleasure,
saying, “If here doesn’t come Herman, the old dear, and the house
all to ourselves.”
What a day of it they had! With only her two good friends to watch
her, Chee forgot her usual reserve, and quite surprised them with her
happy chatter. Without the restraint of Aunt Mean’s practical
presence, some of the child’s queer fancies and odd expressions
crept into her talk. Until then, Gertrude had but half realized how truly
the little cousin’s nature was made up of the sensitive perceptions
and legendary instincts of her mother’s people.
Toward evening a thunder-storm threatened. The three were sitting
in Aunt Mean’s plant-room at the time.
“Grandfather is speaking,” said Chee, pleasantly, as the first distant
mutterings of thunder were heard. Cousin Herman looked up
questioningly.
“Who?” asked Gertrude.
“Grandfather—don’t you hear him?”
Just then a sharp clap rang through the air. Gertrude held her fingers
to her ears.
“That was M’dessun,” said Chee. Then noticing her companions’
bewildered glances, added, “It’s very easy to know his voice from
grandfather’s other sons’—he talks so angrily.”
The thunder still roared. Mr. Farrar closed the plant-room door. “I
guess we hadn’t better sit out here for awhile,” he said, gathering up
Gertrude’s books. “We can come back, it won’t last long, I think.”
“Don’t go! What made you shut the door? I love to hear them,” and
Chee stepped out into the rising storm fearlessly, as though the sky
had been all sunshine.
“Come in, Chee. Oh, do come in!” cried Gertrude, pale with alarm.
The child ran quickly, and throwing her arms around her cousin,
asked, “Why, are you sick? What is the matter? Don’t you like
Thunder? He is our grandfather, you know.”
“Is the girl crazy?” asked Mr. Farrar.