Rechargeable Batteries: History,

Progress, and Applications Rajender

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 Rechargeable Batteries

History, Progress, and Applications

Edited by
Rajender Boddula, Inamuddin,
Ramyakrishna Pothu
and Abdullah M. Asiri
This edition first published 2020 by John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA
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ISBN 9781119661191

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 Editors are honored to dedicate
this book to
Boddula Laxmibai & Laxman
(Mother & Father of Dr. B. Rajender)

v
 Contents

Preface xvii
1 Progress in Separators for Rechargeable Batteries 1
Cheng-song Yang, Dian-hui Han and Meng Zhang
1.1 Separator Overview 1
1.2 Polymer Membrane 2
1.2.1 Polyolefin Separators 2
1.2.2 PVDF 5
1.2.3 PTFE 6
1.2.4 PU 6
1.2.5 PVA 7
1.2.6 Cellulose 8
1.2.7 Other Polymer 8
1.3 Non-Woven Fabric Separator 8
1.3.1 PET 9
1.3.2 PAN 10
1.3.3 PVDF 11
1.3.4 PTFE 11
1.3.5 PVA 12
1.3.6 PI 12
1.4 Polymer Electrolyte 13
1.5 Conclusions 14
References 14
2 Pb Acid Batteries 17
Hasan Jafari and Mohammad Reza Rahimpour
2.1 History of Batteries 17
2.2 Primary Batteries 19
2.3 Secondary Batteries 20
2.4 Flow Batteries 23
2.4.1 All Vanadium Redox Flow Batteries (VRBs) 24
2.4.2 Zinc-Bromine Flow Cells 25

vii
viii Contents

2.5 Lead-Acid Batteries 26

2.5.1 Early Applications of Lead-Acid Batteries 26
2.5.2 Comparison With Other Types of Secondary Batteries 26
2.5.3 Electrochemistry of Lead-Acid Batteries 28
2.5.4 Basic Components of Lead-Acid Cells 29
2.5.5 Types of Lead-Acid Batteries 31
2.5.6 Charging 33
2.5.7 Maintenance 34
2.5.8 Failure Modes 34
List of Abbreviations 36
References 36
3 Flexible Batteries 41
Muhammad Inam Khan, Muhammad Mudassir Hassan,
Abdur Rahim and Nawshad Muhammad
3.1 Introduction 42
3.2 Battery Types 43
3.2.1 Lead-Acid Battery 44
3.2.2 Nickel Cadmium 44
3.2.3 Nickel/Hydrogen and Nickle/Metal Hydride 44
3.2.4 Lithium-Ion Batteries 45
3.3 Storage Mechanism 45
3.3.1 Flexible Electrode 47
3.3.2 Carbon Base Flexible Electrodes 47
3.4 Graphene Base Flexible Batteries 52
3.5 Metal Oxide-Based Flexible Batteries 52
3.6 Fiber-Shape Designed Flexible Batteries 53
3.7 Natural Fiber Base Flexible Batteries 55
3.8 Flexible Electrolytes 56
3.9 Conclusion 57
References 58
4 Polymer Electrolytes in Rechargeable Batteries 61
Yogesh Kumar, Meenal Gupta, Ashwani Kumar
and N. B. Singh
4.1 Introduction 61
4.2 Solid Electrolytes for Rechargeable Batteries 63
4.2.1 Solid Oxide Electrolytes 63
4.2.2 Sulfide Solid Electrolytes 63
4.2.3 Inorganic-Organic Hybrid Electrolytes 65
4.2.4 Solid Polymer Electrolytes in Rechargeable Batteries 66
 Contents ix

4.3 Polymer-Based Electrolytes 66

4.4 Classification of Polymer-Based Electrolytes 68
4.4.1 Polymer-Salt Complexes 69
4.4.2 Plasticized Polymer Electrolytes 69
4.4.3 Rubbery Electrolytes 69
4.4.4 Solvent-Swollen Polymers 69
4.4.5 Polyelectrolytes 71
4.4.6 Gel Polymer Electrolytes 72
4.4.7 Composite Polymer Electrolytes (CPEs) 74
4.4.8 Ionic Liquid Incorporated Polymer/Gel Electrolytes 75
4.5 Conclusion and Future Prospects 79
References 79
5 Advancement in Electrolytes for Rechargeable Batteries 87
Prasun Banerjee, Adolfo Franco Jr, R. Z. Xiao,
K. Chandra Babu Naidu, R. M. Rao,
Ramyakrishna Pothu and Rajender Boddula
5.1 Introduction 88
5.2 Aqueous Electrolytes 89
5.2.1 Lithium Nitrate 89
5.2.2 Saturated LiCl Electrolyte 89
5.2.3 Aqueous Sodium Salts 90
5.3 Non-Aqueous Electrolytes 90
5.4 Polymer Electrolytes 91
5.4.1 Solid Polymer Electrolytes (SPE) 91
5.4.2 Gel Polymer Electrolytes (GPE) 92
5.5 Ionic Liquids Electrolytes (ILE) 94
5.6 Hybrid Electrolytes 94
5.7 Conclusions 95
Acknowledgements 95
References 96
6 Fabrication Assembly Techniques for K-Ion Batteries 99
Praachi Kapoor, Parul Khurana, Christinee Jeyseelen,
Dinesh Kumar and Sheenam Thatai
6.1 Introduction 100
6.2 Battery and Its Types 100
6.3 Ni-Cd Batteries 100
6.4 Li-Ion Batteries 101
6.5 Advantages of Rechargeable Batteries 101
6.6 Disadvantages of Rechargeable Batteries 102
6.7 K-Ion Batteries 102
x Contents

6.8 Advantages 102

6.9 Disadvantages 103
6.10 Honeycomb Structure of K-Ion Batteries 105
6.10.1 Methods/Synthesis of Potassium Tellurates 106
6.11 Negative Electrode Materials for K-Ion Batteries 108
6.12 K-Ion Batteries Based on Patterned Electrodes 110
6.13 Conclusion 111
Acknowledgement 112
References 112
7 Recent Advances in Ni-Fe Batteries as Electrical
Energy Storage Devices 115
K. Chandra Babu Naidu, N. Suresh Kumar, H. Manjunatha,
Prasun Benerjee, D. Baba Basha, S. Naresh Kumar,
Ramyakrishna Pothu and Rajender Boddula
7.1 Introduction 116
7.2 Structure of Ni-Fe Batteries 117
7.3 Discussion on Electrochemical Parameters
of Various Materials for Ni-Fe Batteries 118
7.4 Conclusions 128
References 128
8 Nickel-Metal Hydride (Ni-MH) Batteries 131
Sandeep Arya and Sonali Verma
8.1 Introduction 131
8.2 History 132
8.3 Invention of the Rechargeable Battery 133
8.4 Metal Hydrides (MH) 134
8.5 Thermodynamics and Crystal Structures
of Ni-MH Battery Materials 135
8.5.1 Thermodynamics 135
8.5.2 Crystal Structures of Battery Materials 137
8.5.3 Crystal Structure of AB5 and AB2 Materials 139
8.5.4 Structure of AB5 Compounds 139
8.5.5 Structure of AB2 Compounds 140
8.5.6 Substitutions of A and B Components
in AB5 and AB2 140
8.5.7 Mg-Based Alloys 144
8.5.8 Rare Earth-Mg-Ni-Based Alloys 145
8.5.9 Ti-V-Based Alloys 146
8.6 Ni-MH Batteries 146
 Contents xi

8.7 Mechanism of Ni-MH Batteries 148

8.7.1 Battery Description 149
8.7.2 Principle 149
8.7.3 Negative Electrode 150
8.7.4 Positive Electrode 151
8.7.5 Electrolyte 151
8.7.6 Separator 151
8.8 Materials 151
8.9 Charging Nickel-Based Batteries 152
8.9.1 Guidelines for Charging 154
8.10 Performance 154
8.11 Factors Affecting Life 155
8.11.1 Exposure to Elevated Temperatures 155
8.11.2 Reversal 155
8.11.3 Extended Storage under Load 156
8.11.4 Limiting Mechanisms 156
8.12 Advantages 156
8.13 Applications 157
8.13.1 Electric Vehicles 157
8.13.2 Fuel Cell (FC) EVs 157
8.13.3 Pure EVs 157
8.13.4 Hybrid EVs 158
8.13.5 Applications in Traditional Portable
Electronic Devices 159
8.13.5.1 Mobile Phones 159
8.13.5.2 Digital Cameras 159
8.14 Recent Developments and Research Work 160
8.15 Shortcomings 163
References 163
9 Ni-Cd Batteries 177
Christine Jeyaseelan, Antil Jain, Parul Khurana,
Dinesh Kumar and Sheenam Thatai
9.1 Introduction 178
9.2 History 179
9.3 Characteristics 180
9.4 Construction and Working 180
9.5 Types of NiCd Batteries 183
9.6 Memory Effect 184
9.7 Maintenance and Safety 185
xii Contents

9.8 Availability and Cost 186

9.9 Applications 187
9.9.1 Transportation in Hybrid and Electric Vehicles 187
9.9.2 Aircrafts 187
9.9.3 Electronic Flash Units 187
9.9.4 Cordless Applications 188
9.9.5 Motorized Equipment 188
9.9.6 Two Ways Radios 188
9.9.7 Medical Instrumentation 188
9.9.8 Toys 188
9.10 Advantages and Disadvantages 189
9.11 Recycling of NiCd Batteries 192
9.12 Comparison With Other Batteries 192
9.13 Conclusion 192
Acknowledgement 193
References 193
10 Ca-Ion Batteries 195
Arti Jain and Ritu Payal
10.1 Introduction 196
10.2 Selection of Anodic and Cathodic Materials 199
10.2.1 Alloy Anodes 201
10.2.1.1 Choice of Cathodes for Calcium-Ion
Batteries 202
10.2.1.2 Choice of Anodes for Calcium-Ion
Batteries 204
10.3 Electrochemical Arrangement 207
10.4 Electrode Materials 207
10.5 Conclusions and Perspectives 209
References 210
11 Analytical Investigations in Rechargeable Batteries 217
Bhawana Jain, Sunita Singh, Anupama Asthana,
Ajaya Kumar Singh and Md. Abu Bin Hasan Susan
11.1 Introduction 217
11.2 Components of a Battery 219
11.3 Principle of Rechargeable Battery 220
11.4 Aging of Rechargeable Battery 221
11.5 Analysis Techniques Used for Rechargeable Batteries 222
11.5.1 X-Ray Based 223
11.5.2 Neutron Based 224
11.5.3 Optical Analysis Techniques 225
 Contents xiii

11.5.4 Electron Based 226

11.5.5 Vibrational Analysis Techniques 227
11.5.6 Magnetism Based 228
11.5.7 Gravimetric-Based Analysis Techniques 229
11.6 Conclusion 229
References 230
12 Remediation of Spent Rechargeable Batteries 237
Amal I. Hassan and Hosam M. Saleh
12.1 Introduction 237
12.2 A Brief History of Battery Origin 239
12.3 The Types of Batteries 240
12.3.1 Types of Primary Batteries 240
12.3.1.1 Types of Secondary Batteries 242
12.4 Recharge the Battery 245
12.5 Battery Life 247
12.6 A Lithium-Ion Battery (LIB) 248
12.6.1 Advantages of Li-Ion Batteries 251
12.6.2 Disadvantages of Li-Ion Batteries 251
12.7 Impact of Batteries on Health 252
12.7.1 Protection Against Battery Disadvantages 252
12.8 Mercury (Hg) 253
12.9 Remediation of Spent Rechargeable Batteries 255
12.9.1 Future and Challenges: Nanotechnology
in Batteries 255
12.10 Conclusions 257
References 257
13 Classification, Modeling, and Requirements
for Separators in Rechargeable Batteries 265
Zahra Pezeshki
Acronyms 265
13.1 Introduction and Area 267
13.2 Separators in Rechargeable Batteries 269
13.3 Classification of Separator in Rechargeable Batteries 272
13.3.1 Nonwoven Separators 273
13.3.2 Microporous Membrane Separators 277
13.3.3 Ion-Exchange Membrane Separators 287
13.3.4 Nanoporous Membrane Separators 297
13.4 Properties of Separator in Rechargeable Batteries 299
13.5 Requirements for Separator in Rechargeable Batteries 301
xiv Contents

13.6 Modeling of Separator in Rechargeable Batteries 303

13.7 Results and Discussions 307
13.8 Future Approach 307
13.9 Conclusion 308
References 308
14 Research and Development and Commercialization
in Rechargeable Batteries 315
Nelson Pynadathu Rumjit, Paul Thomas, Jishnu Naskar,
George Thomas, P.J. George, Chin Wei Lai,
Mohd Rafie Bin Johan and Elizabeth George
14.1 Introduction 316
14.1.1 Types of Rechargeable Batteries (RBs)
and Challenges Faced Towards Practical
Applications 317
14.1.1.1 Li-Ion Batteries (LIBs) 317
14.1.1.2 Na and K-Ion Batteries 317
14.1.1.3 Magnesium Rechargeable
Batteries (MgRBs) 319
14.1.1.4 Aqueous RBs 320
14.1.1.5 Pb-Acid, Ni-Cd, and Ni-MH Batteries 320
14.1.1.6 Zinc-Ion RBs 321
14.1.1.7 Metal-Air Batteries 321
14.1.1.8 Flexible RBs 322
14.1.2 Nanotechnology Interventions
in Rechargeable Batteries 323
14.2 Research and Development in Rechargeable Batteries 327
14.2.1 Zinc Rechargeable Batteries (ZnRBs) 327
14.2.2 Magnesium Rechargeable Batteries (MgRBs) 330
14.2.3 Aqueous RBs and Hybrid Aqueous RBs 330
14.2.4 Li-Based RBs 331
14.3 Commercialization Aspects of Rechargeable Batteries 339
14.4 Future Prospects of RBs 341
14.5 Conclusion 343
References 344
15 Alkaline Batteries 357
Sapna Raghav, Jyoti Raghav, Praveen Kumar Yadav
and Dinesh Kumar
15.1 Introduction 357
15.1.1 How Batteries Work 359
 Contents xv

15.2 History 361

15.3 Advantages 363
15.4 Disadvantages 365
15.4.1 Internal Resistance 365
15.4.2 Leakage and Damages 365
15.5 Spent ARBs 365
15.6 Classification of ABs 367
15.6.1 Ni/Co Batteries 367
15.6.2 Ni/Ni ARBs 368
15.7 Application of ABs 370
15.8 Conclusion 371
Acknowledgements 372
References 372
16 Advances in “Green” Ion-Batteries Using Aqueous Electrolytes 379
Chenar A. Tahir, Charu Agarwal and Levente Csóka
16.1 Introduction 379
16.2 Monovalent Ion Aqueous Batteries 380
16.2.1 Lithium Ion Aqueous Batteries (LIABs) 380
16.2.2 Sodium Ion Aqueous Batteries (SIABs) 382
16.2.3 Potassium Ion Aqueous Batteries (PIABs) 386
16.3 Multivalent Ion Aqueous Batteries 387
16.3.1 Zinc Ion Aqueous Batteries (ZIABs) 387
16.3.2 Magnesium Ion Aqueous Batteries (MIABs) 389
16.3.3 Aluminum Ion Aqueous Batteries (AIABs) 392
16.4 Summary and Outlook 394
Acknowledgements 394
References 394
17 K-Ion Batteries 403
Mohd Imran Ahamed and Naushad Anwar
17.1 Introduction 404
17.2 Fundamentals of K-Ion Batteries 406
17.3 Mechanism 406
17.3.1 Cathode Materials 409
17.3.1.1 Hexacyanoferrate 409
17.3.1.2 Prussian Blue 410
17.3.1.3 Layered Materials 413
17.3.1.4 Polyanionic Compounds 413
17.3.1.5 Organic Materials 414
17.4 Anode Materials: Graphite Anodes 415
17.5 Key Performance 415
xvi Contents

17.6 Summary and Outlook 417

References 417
18 Li-S Batteries 425
Nitin Kumar Sharma and Dinesh Kumar
18.1 What are Li-S Batteries? 425
18.2 Advances and Challenges in Carbon-Sulfur Electrodes 428
18.3 Role of Additives in Sulfur Electrodes 431
18.3.1 Chemical Absorption Method 432
18.3.2 Electrolytic Additives 433
18.3.3 Metal Fabrication in Li-S Batteries 433
18.3.4 Graphite as an Anode 433
18.3.5 Polymer-Based Electrolyte 434
18.4 Summary and Outlook 434
Acknowledgements 436
References 436
19 Aqueous Na-Air Batteries 441
Mehdi Dehghan Manshadi and Mohammad Reza Rahimpour
19.1 Introduction 441
19.2 Characteristics of Sodium 443
19.3 Electrochemical Reactions in Aqueous Na-Air Batteries 445
19.4 Main Components of Aqueous SABs 447
19.4.1 Properties and Characteristics of Sodium Anode 447
19.4.2 Properties and Characteristics of Air Electrode 453
19.4.3 Properties and Characteristics of Electrolyte 454
19.4.3.1 Effect of Sodium Salt 455
19.4.3.2 Effect of Organic Solvents and Additives 455
19.4.4 Properties and Characteristics
of Separators 455
19.5 Harmful Factors for the Aqueous SABs Stability 456
19.5.1 Carbon Dioxide Poisoning 456
19.5.2 Water Leakage/Evaporation 457
19.6 Price Comparison Among Different Types of Batteries 458
19.7 Conclusion 458
References 459
Index 465
 Preface

The gradual depletion of fossil fuels led humans to explore high-performance

continuous renewable energy sources, especially rechargeable batteries.
In 1859, French physicist Gaston Plante invented the lead acid cell as a
rechargeable battery, and since 1991, lithium-ion batteries have been intro-
duced commercially and exploited in electric vehicles as portable energy
devices. These are becoming an interesting method due to their adjust-
able shapes and sizes, high energy efficiencies and densities, pollution-free
operations, long-cycle life, and affordability as an energy-storage system. In
2019, the Nobel Prize in Chemistry was awarded for work on lithium-ion
batteries. Rechargeable battery technologies have been a milestone for
modern fossil-fuel-free society; they include groundbreaking changes in
energy storage, transportation, and electronics. Improvements in battery
electrodes and electrolytes have been a remarkable development. In the
last few years, rechargeable batteries have attracted significant interest
from scientists as they are a boon for electric vehicles, laptops and comput-
ers, mobile phones, portable electronics, and grid-level electricity storage
devices.

Rechargeable Batteries: History, Progress, and Applications describes

an up-to-date and comprehensive viewpoint of electrochemical power
sources. Rechargeable batteries have made a tremendous impact on our
society. The book discusses innovative rechargeable batteries constructed
using bounteous elements such as Li+, Na+, K+, Ca2+, Zn2+, Mg2+, Al3+, etc.,
which show countless attractive options for energy-storage devices. This
book provides a complete outline of rechargeable batteries. It is intended
for undergraduates, postgraduates, researchers, professionals, and scien-
tists working in areas such energy science, chemical engineering, material
science, and industries. Based on thematic topics, the book contains the
following nineteen chapters:

xvii
xviii Preface

Chapter 1 reviews the history and progress of separators for rechargeable

batteries, involving polymer separators, non-woven fabric separators, and
polymer electrolytes. The advantages and drawbacks of these separator
materials are discussed. A viewpoint on the state of current research and
future research directions of separators is presented.

Chapter 2 describes the improvements in secondary batteries with a focus

on Pb-Acid rechargeable batteries. In this chapter, the backgrounds, prin-
ciples, theoretical aspects, and basic components of this type of batteries
are described. Another important part of this chapter is the definition of
failure mechanisms in Pb-Acid batteries, i.e., sulfation, corrosion, and
degradation.

Chapter 3 discusses different electrode materials that are commonly

used for flexible batteries. A brief description of carbon-based flexible
nano-materials, metal oxides, graphene composites, and natural fiber-
based electrode materials as a binder is presented. Moreover, the storage
mechanism, types of batteries, and flexible electrolytes are studied.

Chapter 4 discusses solid polymer electrolytes used in rechargeable bat-

teries. Different types of solid polymer electrolytes, their classifications,
structures, and properties are discussed. It is predicted that the future
development in this area may be a combination of fast ion conductors and
polymers.

Chapter 5 discusses different types of electrolytes for rechargeable electro-

chemical batteries. The focus is especially on the aqueous, non-aqueous,
polymer, ionic, and hybrid electrolytes for the rechargeable electrochemi-
cal battery applications.

Chapter 6 deals with the introduction of ion batteries along with their types
and leading to how conventional batteries have made it possible to leave
behind the different traditional batteries like Li-ion batteries. Further, the
chapter focuses on the advantages and disadvantages of using conventional
K-ion batteries with suitable solutions to the bottlenecks listed as well as on
fabrication techniques of K-ion batteries.

Chapter 7 discusses the materials for Ni-Fe batteries and their applications
towards electrochemical performance. It also reviews the formation and
structure of Ni-Fe batteries. Also, various organic, inorganic, polymer and
 Preface xix

composite materials are extracted in order to evaluate their electrochemi-

cal performance for energy storage applications in the case of nickel-iron
batteries.

Chapter 8 deals with Ni-MH batteries. Different types of metal hydrides

and their structures are discussed in detail. In addition to the merits
and demerits, the mechanism, performance, and various applications of
Ni-MH batteries are also discussed. This chapter also focuses on recent
progress in the field of Ni-MH batteries.

Chapter 9 summarizes the history, characteristics, constructions, and

working of NiCd batteries. It also focuses on including the types of NiCd
batteries and their applications in various fields.

Chapter 10 confers the emergence of high energy density rechargeable

Ca-ion batteries as a boon for various electrical systems. Theoretical calcu-
lations have been used to select the best possible cathodes for these anodic
Ca-ion batteries (CIBs). Additionally, various pros and cons, applications,
fabrication techniques, as well as future aspects of CIBs have been scruti-
nized with respect to previously mentioned battery structures.

Chapter 11 narrates a blueprint for approaching an ageing process by

explaining various analytical techniques based on X-ray, neutron, electron,
gravimetric mass spectroscopy, and many more. This chapter begins with
the exploration of various rechargeable batteries, its ageing process and
various analytical techniques along with key scientific questions in the
sphere, followed by their successful application to answer basic questions.

Chapter 12 highlights a brief history of the origin of the battery and its
types. It also addresses the impact of batteries on health, along with the
future and challenges in the use of nanotechnology and clean chemistry
in battery manufacturing and safety requirements in manufacturing and
charging.

Chapter 13 deals with various types of separators used in rechargeable

batteries. The properties, requirements, and modeling of separators are
reviewed. The major focus is on manufacturing process according to char-
acteristics. The future approach is offered in accordance with positive and
negative properties reported in this literature review.
xx Preface

Chapter 14 presents a brief overview of the research, development, and

commercialization aspects of various rechargeable batteries. Several chal-
lenges confronted by rechargeable batteries are reviewed in detail.
Additionally, this chapter details the future outlook of rechargeable batter-
ies for wide-scale applications in electrical and electronic devices towards
a sustainable system.

Chapter 15 discusses the different alkaline batteries and the history of

the development of alkaline batteries. The chapter discusses how alkaline
rechargeable batteries (ARBs) work, advantages and disadvantages, appli-
cations, and developments in the area of alkaline batteries. In addition, Zn/
Mn alkaline batteries, Ni/Co and Ni/Ni alkaline batteries are also discussed.

Chapter 16 discusses the aqueous batteries as renewable and sustainable

energy storage devices. Aqueous batteries have cathode, anode, and aque-
ous electrolyte with a mixed metal ion charge carrier. The major focus is
given to communicate the recent advancements made in aqueous batteries,
with a focus on their mechanism of operation and working.

Chapter 17 reveals the spontaneity of KIBs anode materials and their fun-
damental properties, mechanisms, and key performance factors and their
comparison with LIBs and/or SIBs.

Chapter 18 highlights the challenges of carbon-sulfur electrodes and the

role of additives in sulfur electrodes used in Li-S batteries.

Chapter 19 counts the cons and pros of aqueous NA-Air batteries. In addi-
tion to a short discussion about historical background, a comparison is
made between this type of battery and other convenient batteries. Finally,
characteristics, main reactions, different components and harmful factors
for stability of these batteries are discussed.
 Preface xxi

Key Features
• Focuses on the wide range of energy storage materials
• Provides an understanding of electrodes, electrolytes, and
separators
• Coverage of Pb-acid batteries to modern, flexible batteries
• Emphasis on fundamental principles, mechanisms, chal-
lenges, and prospective

Editors
Rajender Boddula
Inamuddin
Ramyakrishna Pothu
Abdullah M. Asiri
 1
Progress in Separators for
Rechargeable Batteries
Cheng-song Yang, Dian-hui Han and Meng Zhang*

School of Materials Science and Engineering, Henan University of Technology,

Zhengzhou, Henan, China

Abstract
This article introduces the research progress of rechargeable battery separators. At
present, rechargeable battery separators are mainly divided into polyolefin-based
separators, non-woven separators, and ceramic composite separators. In recent
years, separators have been adopted on the basis of these three categories. Different
preparation methods and the replacement of the separator's role have led to some
new types of separators, such as polymer electrolyte separators. It is divided into
solid polymer electrolytes and gel polymer electrolytes. This electrolyte can sepa-
rate the cathode and anode to prevent short circuits, while ensuring lithium Ions
can shuttle. This article details the development of rechargeable battery separators,
including some new ones in recent years.

Keywords: Rechargeable battery separators, polyolefin-based separators, non-

woven fabric separators, composite separators, solid electrolyte separators,
electrolyte separators, gel polymer separators

1.1 Separator Overview

The separator is an important part of the battery. It separates the positive
electrode and negative electrode in the battery, prevents the positive and
negative electrodes from directly contact which may cause short circuit,
and has a porous structure to provide a passage for the lithium ions, real-
izing lithium ions transport between the positive and negative electrodes.
The separator itself does not participate in the reaction of the battery, but

*Corresponding author: meng_zhang@haut.edu.cn

Rajender Boddula, Inamuddin, Ramyakrishna Pothu and Abdullah M. Asiri (eds.) Rechargeable
Batteries: History, Progress, and Applications, (1–16) © 2020 Scrivener Publishing LLC

1
2 Rechargeable Batteries

it plays a vital role in the battery. The separator affects the battery capacity,
rate performance, cycle performance, and safety performance to a certain
extent. Currently, polyolefin separators (PP, PE) and non-woven fabric
separators are widely used commercially.
The main factors of the separator include chemical stability, mechanical
strength, porosity, wettability, and heat resistance. Considering the above fac-
tors to select the appropriate separator material, the main diaphragm materi-
als of lithium-ion batteries are polyolefin separators, non-woven membranes,
and ceramic composite separators. Through the analysis of existing diaphragm
materials, the new ideas of improving separator performance are developed.

1.2 Polymer Membrane

1.2.1 Polyolefin Separators
In polyolefin separators, the main materials are polyethylene and poly-
propylene, which have low cost, good chemical stability, excellent
mechanical properties, and high electrochemical insulation. At higher
temperatures, the holes in the diaphragm will self-close and form an
open circuit, thus ensuring the safety performance of the secondary
battery.
Polyethylene (PE) microporous films began in the early 1960s, and both
melt-stretching (dry method) and thermally induced phase separation
(wet method) methods were produced. Polypropylene (PP) microporous
membrane research began in the early 1970s and was mainly produced by
melt drawing [1].
The main preparation processes of the melt-spinning-cold stretch-
ing method include melt extrusion, heat treatment, and stretching. The
microstructure of the microporous polyolefin membranes made by dry
process is shown in Figure 1.1. In the process of melt extrusion, under
the effect of large stress field, a hard elastic precursor membrane with
a lamellar crystal structure perpendicular to the extrusion direction
is obtained. During the heat treatment, under the effect of high-stress
field at a temperature slightly lower than the melting point, annealing
is performed to increase crystallinity, and then, heat treatment can
obtain a hard elastic membrane [2]. Finally, the hard elastic membrane
is stretched to separate the lamellar crystal, and the amorphous region is
destroyed to form a large number of micro­porous structures. Stretching
is divided into two processes, firstly cold stretching, then hot stretching
at a small heating rate, and finally heat setting at a certain temperature.
According to the stretching method, the melt stretching method can be
 Separators for Rechargeable Batteries 3

Figure 1.1 Microstructure of the microporous polyolefin membranes made by dry

process. Reproduced with permission from ref [5] and American Chemical Society.

classified into uniaxial stretching and biaxial stretching. The method has
low cost and uniform pore size, but the product is slightly thick, easy to
tear, and has a high short circuit rate [3].
The main steps of the thermally induced phase separation process
include extrusion, stretching, extraction, and heat setting. The micro-
structure of the microporous polyolefin membranes made by wet process
is shown in Figure 1.2. It is mainly used to prepare PE separators. At a
temperature above the melting point of the crystalline polymer mixing PE
with a high boiling point, low molecular weight diluting agent to form a
homogeneous melt. The melt is pre-formed into a membrane. When the
temperature is lowered, the solubility of the diluting agent decreases, and
the polymer crystallizes. At this time, s­ olid-liquid or liquid-liquid phase
separation occurs. After cooling and stretching, extract with a volatile
extractant, and finally, the extractant is removed to obtain a microporous
separator [4]. This method produces a thin diaphragm, is not easy to tears,
and has a short circuit rate, but the cost is high, the environment is pol-
luted, and the heat resistance of the separator is poor [3].
Polyethylene and polypropylene have their own advantages and dis-
advantages, polyethylene is more resistant to low temperature, and
polypropylene is more resistant to high temperature. The self-closed holes
temperature of polyethylene is 135 C, and this date of polypropylene is
165 C. Celgard PP/PE/PP three-layer composite diaphragm, PE interme-
diate layer will be self-closed at 135 C. However, there is a 30 C heating
4 Rechargeable Batteries

Figure 1.2 Microstructure of the microporous polyolefin membranes made by wet

process. Reproduced with permission from ref [5] and American Chemical Society.

space from the closed hole to the separator damage, which improves the
safety of the separator [5].
There are many modification methods for PE and PP separators, the
most common of which are coating modification, coating inorganic
nanoparticles, or polymer particles for modification.
Zhang [6] et al. coated PTFE particles to both sides of the PE separator
with a diluted PTFE suspension, in order to prepare a selfbonding PTFE
separator, then modified it with a H2O2/H2SO4 solution, the hydroxyl
group is introduced, this structure has a porosity of 66%, and the elec-
trolyte absorption rate is 190.6%. The ionic conductivity is much higher
than PE separator. The PTFE particles provide good thermal stability and
excellent cycle stability.
Won-Kyung Shin [7] et al. use ultrathin nitrogen and sulfur codoped
graphene (NSG) layer deposited on a polyethylene (PE) separator by a
simple vacuum infiltration method effectively suppressed the dendritic
growth of lithium metal, compared to an uncoated separator. The ther-
mal stability is improved, and the cycle stability of the lithium battery is
effectively improved.
Zhou Xiangyang [8] et al. coated nitrogen-doped microporous carbon
from polyaspartic acid bonding on the surface of Celgard 2400, used on
Li-S battery. This method is easy to prepare and low in cost; high N doping
level promotes chemisorption of polysulfide and improves overall perfor-
mance of Li-S batteries.
 Separators for Rechargeable Batteries 5

1.2.2 PVDF
Poly(vinylidene fluoride) (PVDF) combines the characteristics of fluo-
roresin and general-purpose resin. The structure of PVDF is shown in
Figure 1.3. It has good chemical resistance, high temperature resistance,
electrical insulation, and dielectric properties. It is very suitable as a
separator material. Its molecular chain is closely arranged, and there are
strong hydrogen bonds between the molecular chains. Its oxygen index
is 46%, non-combustible, crystallinity is 65%~78%, melting point is
172 C, heat distortion temperature is 112 C~145 C, and the decompo-
sition temperature is greater than 390 C the long-term use temperature
is −40 C to 150 C. The thermal decomposition temperature is much
higher than the melting point, making it excellent in processability.
PVDF itself has high crystallinity and excellent mechanical properties,
but high crystallinity will affect the movement of molecular segment, mak-
ing it less swellable in electrolyte solution, and poor wettability, lead to
large internal resistance. Based on this, the other monomers are added to
copolymerized, PVDF-HFP was prepared by copolymerization of hexa-
fluoropropylene monomer and vinylidene fluoride [9]. It can reduce crys-
tallinity, thereby improving ion conductivity, reducing internal resistance,
and improving battery performance. In the study of RE-Sousa [10] et al.,
PVDF-CTFE separator was prepared by phase transfer in a DMF solution
by adding chlorotrifluoroethylene and vinylidene fluoride, which has good
cycle performance and rate performance. PVDF diaphragm is easy to get
out of control at high temperatures, so it has certain safety problems. In the
study of Cui [11] et al., PE microspheres were prepared and coated on the
surface of PVDF separator to prepare a separator with thermal shutdown
coating. The coating will not adversely influence the electrochemical per-
formance and it can close at high temperature.
Although the technology continues to advance, this separator still has
problems such as poor wettability and uneven pore distribution. In recent years,
the rise of non-woven fabric technology has changed this situation. PVDF is a
popular one among non-woven separators. PVDF can also be used to prepare

F F F
F

F F
F F
n

Figure 1.3 Schematic illustration of PVDF structure diagram, Plot from ChemDraw.
6 Rechargeable Batteries

a polymer gel electrolyte membrane that integrates the separator with the elec-
trolyte. PVDF can also be used as a binder for ceramic based separators.

1.2.3 PTFE
Polytetrafluoroethylene (PTFE) is a high performance material with excel-
lent heat resistance, chemical inertness, and insulation stability. The struc-
ture of PTFE is shown in Figure 1.4. Since the radius of the fluorine atom
is large, the surface of the whole polymer chain is covered by the fluorine
atoms, which is the main reason for its physicochemical properties. The
breakdown voltage, volume resistivity, and arc resistance are both higher.
The fluorine atom in PTFE is highly electronegative, and the symmetry
of the tetrafluoroethylene monomer is excellent, so that the PTFE has a
lower surface energy [12], so the PTFE separator is mainly prepared by
electrospinning, which will be described later.

1.2.4 PU
Polyurethane (PU) is a synthetic polymer material, it can be resistant to a
wide range of acids and bases and organic solvents. PU molecules consist
of a soft polyol segment and a hard diisocyanate segment. There are a large
number of ether bonds and urea bond and ester bond in the molecular
structure of the polyurethane. The bond makes it easy to form hydrogen
bonds between the polyurethane segments. The mechanical properties of
PU can be controlled; the ratio of the hard segment to the soft segment
can be controlled to obtain different properties. It also has the possibility
of theoretically controlling the balance between porosity and mechanical
properties. Polyurethane is a potential separator material.
Byung Gom Kim [13] et al. used PU separators in LI-O2 batteries to
improve the poor cycle performance. It’s working principle was shown in
Figure 1.5. The PU separators here are non-porous. This special feature

F F

F F
n

Figure 1.4 Schematic illustration of PTFE structural unit, Plot from ChemDraw.
 Separators for Rechargeable Batteries 7

(a) PE cell (b) PU cell

Generated H2O

MWNT cathode
LiOH

Li metal
&
Side Li+
Products
Crossover O2

PE PU
Li metal degradation Li metal protection

Figure 1.5 Comparative schematic illustration of Li-O2 cells with (a) conventional
polyolefin porous PE separator and (b) poreless PU separator. Reproduced with
permission from ref [13].

prevents water and oxygen from penetrating into the Li surface. The
cycle performance of the LI-O2 battery is improved, and 600 mAhg−1 can
be maintained in 200 cycles, which is far superior to the conventional
PE separator.

1.2.5 PVA
Polyvinyl alcohol (PVA) is one of the few industrially produced water-
soluble high molecular polymers that can be prepared from natural
gas. Its properties are between rubber and plastic [14]. PVA has a poly-
hydroxyl structure and strong hydrogen bonds can be formed, which
results in excellent adhesion, excellent mechanical properties, and
membrane formation. It has good biocompatibility and low toxicity, so
it is widely used in medicine, agriculture, forestry, chemical industry,
environmental protection, and other fields. PVA membrane has excel-
lent oil resistance (vegetable oil, animal oil, mineral oil) and organic
solvent resistance, it is soluble in water (above 95 C), slightly soluble in
dimethyl sulfoxide, insoluble in gasoline, kerosene, vegetable oil, ben-
zene, toluene, dichloroethane, carbon tetrachloride, acetone, ethyl ace-
tate, methanol, ethylene glycol, etc.
Xiao [15] et al. used polyvinyl alcohol as a membrane-forming material
to prepare a microporous lithium-ion battery separator by phase transfer
method. The inside of the separator was a network pore structure, and the
electrolyte had good wettability and showed good battery charge and dis-
charge performance. PVA separators are mostly prepared by electrospin-
ning, which will be described in detail later.
8 Rechargeable Batteries

1.2.6 Cellulose
The chemical structure of cellulose is a macromolecule formed by a
glucose-based unit linked by a β-1,4-glycosidic bond. Each glucose unit
has a hydroxyl group on C2, C3, and C6. At normal temperature, cellu-
lose is insoluble in water and insoluble in common organic solvents such
as alcohol, ether, acetone, benzene, etc. It is also insoluble in dilute alkali
solutions. It has good biocompatibility, is non-toxic and harmless, is easy
to degrade, and can be regenerated. It is a chemical raw material with great
application value [16].
Although cellulose itself has certain disadvantages and cannot meet
the performance requirements of the separator, cellulose contains a large
amount of polar hydroxyl groups, which leads to the modification of cel-
lulose by catalytic oxidation, hydrogenation, etherification, esterification,
etc., to get different cellulose product attributes.
Luo [17] et al. prepared cellulose acetate porous pore separator by phase
transfer method. The separator has a network pore structure, high poros-
ity, strong electrolyte affinity, good wettability, and good performance
under high temperature conditions. The electrochemical performance is
superior to that of polyolefin separators. There will be hopes for practical
application in the future.

1.2.7 Other Polymer

Fossil energy is increasingly exhausted, and the use of renewable resources as
a chemical industry has become one of the hotspots today. More and more
renewable materials in nature have been researched and applied by scientists.
Cellulose is a good example, and it is widely used in various chemical fields.
AA Izazi [18] et al. found that Red Seaweed Pulp has a small hollow fiber
structure, which theoretically has good electrolyte wettability and good ion
transport. The prepared Red Seaweed Pulp separator was used in a bat-
tery using aluminum as an anode, graphite as a cathode, and NaCl as an
electrolyte. A small current was observed and the cycle performance was
tested, proving its potential to be an environmentally friendly diaphragm.

1.3 Non-Woven Fabric Separator

Polyolefin separators have excellent chemical stability and low cost, but their
thermal stability and wettability are poor. The new non-woven membrane
effectively improves this situation. The non-woven membrane has a three-
dimensional pore structure, and the electrolyte has good wettability and
 Separators for Rechargeable Batteries 9

retention. However, the simple non-woven membrane has a large surface

area and a wide distribution range, it is easy to cause internal short circuit of
the battery by direct use. Therefore, the non-woven membrane is generally
optimized for its surface. A common method is to use a polymer coating or
ceramic powder for compounding. The preparation method of the nonwoven
fabric separator includes an electrostatic spinning method, a solution extru-
sion method, a melt blowing method, a papermaking process, etc.

1.3.1 PET
Polyethylene terephthalate (PET) is derived from the dehydration conden-
sation reaction of ethylene terephthalate. Ethylene terephthalate is obtained
by esterification of terephthalic acid and ethylene glycol. The structure of
PET is shown in Figure 1.6.
PET is a highly crystalline polymer with a smooth surface. It has excel-
lent physical and mechanical properties.
Jeong [19] et al. placed PET nonwoven fabric in PVDF-HFP/acetone
solution and prepared PVDF-HFP/PET composite separator by phase
transfer method. This method explores the effect of water content in the
system on porosity. The coated separator has a narrow pore size distribu-
tion and a small pore diameter. Its electrochemical performance is stable,
and its tensile strength and thermal stability are high.
Choi [20] et al. selected SiO2 particles with different particle sizes and
coated them on the surface of PET non-woven fabric with PVDF-HFP as
binder to investigate the effects of different particle sizes on electrochemi-
cal performance. The results show that the SiO2 particle small particle size
(40 nm) separator has superior electrochemical performance compared
to the large particle size (530 nm). The small particle size separator has a
high porosity and is available, so that the electrochemical performance is
superior.
Kun Peng [21] et al. modified the macroporous structure of PET
non-woven fabric separator by electrostatic spinning PSA nanofibers, and

O O

O O
n

Figure 1.6 Schematic illustration of PET structural unit, Plot form ChemDraw.
Another random document with
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see such a living proof. She is my little Jane as she was when a child
—my little Jane—my darling! Mrs. Lanier, will you excuse me!—the
sight of her has quite unnerved me”; and suddenly sinking into a
chair he pressed the child to his heart and hid his face on her bright
golden head.
What passed between Lady Jane and her grandfather, Mr. and
Mrs. Lanier never knew, for they slipped quietly out of the room, and
left the cold, stern man alone with the last of his family—the child of
that idolized but disobedient daughter, who had caused him untold
sorrow, and whom he had never forgiven until that moment, when he
held in his arms, close to his heart, the child, her living image.
It was some time before Mr. Chetwynd appeared, and when he did
he was as cold and self-possessed as if he had never felt a throb of
emotion, or shed a tear of sorrow on the pretty head of the child, who
held his hand, and prattled as freely and confidingly as though she
had known him always.
“What will Mother Margaret say,” she exclaimed, looking at Mrs.
Lanier with wide, glistening eyes, “when I tell her that I’ve found Tony
and my grandpapa both in one Christmas? I never saw a grandpapa
before. Pepsie read to me about one in a book, and he was very
cross; but this one isn’t. I think he’s very good, because he says that
he will give me everything I wish, and I know I shall love him a great
deal.”
“Now, Lady Jane, confess to me, and I’ll never tell,” whispered
Arthur with an air of great secrecy. “Which do you love best, Tony or
your new grandpapa?”
She raised her clear eyes to the roguish face of the boy with a little
perplexed smile, and then replied unhesitatingly: “Well, I’ve known
Tony longer, but I think I’ll love my grandpapa as well by and by,
because, you know, he’s my grandpapa.”
Arthur laughed heartily at the clever way in which she evaded the
question, and remarked to Mrs. Lanier that Lady Jane would wind
her grandfather around her little finger before a month was over.
Which prediction was likely to prove true, for Mr. Chetwynd did not
seem to have any other interest in life than to gratify every wish the
child expressed.
“She has taken complete possession of me,” he said to Mrs.
Lanier, “and now my greatest happiness will be to make her happy.
She is all I have, and I shall try to find in her the comfort her mother
deprived me of.”
In spite of his affection for the child, his feelings did not soften
toward the mother; he could not forget that she had disappointed him
and preferred a stranger to him; that she had given up wealth and
position to bury herself in obscurity with a man he hated. It was a
bitter thought, yet he would spare no pains to solve the mystery that
hung over her last days.
Money and influence together soon put the machinery of the law in
motion; therefore it was not a month after Mr. Chetwynd’s arrival in
New Orleans before everything was as clear as day. The young
widow was traced to Madame Jozain’s; there were many who
remembered her death and funeral. The physician’s certificate at the
Board of Health bore the name of Dr. Debrot, who was found, and
interviewed during one of his lucid moments; he described the young
mother and child, and even remembered the blue heron; and his
testimony, sad though it was, was still a comfort to Jane Chetwynd’s
friends. She had died of the same fever that killed her husband, and
she had been carefully nursed and decently buried. Afterward, the
Bergeron tomb was opened, the remains identified, and then sent to
New York to rest with her mother, in the stately Chetwynd tomb, in
Greenwood cemetery.
Then a careful search was made for her personal effects, but
nothing was recovered except the watch that Paichoux was fortunate
enough to secure. Mr. Chetwynd handed Paichoux a large check in
exchange for it, but the honest man refused to take any more than
he had paid Raste Jozain in order to get possession of it. However,
the millionaire proved that he was not ungrateful nor lacking in
appreciation, when he presented him with a rich, plain watch suitably
inscribed, from the donor to a most worthy friend. And when the
pretty Marie was married, she received from the same jeweler who
made the watch an exquisite silver tea-service, which was the pride
of her life, and which was cherished not only for its value, but
because it was a gift from Lady Jane’s grandpapa.
Mr. Chetwynd made a number of visits to Good Children Street in
company with Mrs. Lanier and Lady Jane, and there were a great
many long conversations between Mam’selle Diane, the millionaire,
and the banker’s wife, while Lady Jane played with her jolly little
friend, the canary, among the branches of the rose-bush. During
these conversations there was a great deal of argument and anxious
urging on the part of the visitors, and a great many excuses and
much self-depreciation on the part of the gentle, faded lady.
“I have been buried so long,” she would say pathetically, “that the
great world will appal and confuse me. I shall be like a blind person
suddenly made sensible of the light.”
“But you will soon become accustomed to the light,” urged Mrs.
Lanier.
“And I might long for seclusion again; at my age one cannot easily
change one’s habits.”
“You shall have all the seclusion you wish for,” said Mr. Chetwynd
kindly.
“Besides I am so old-fashioned,” murmured Mam’selle Diane,
blushing deeply.
“A quality which I greatly admire,” returned Mr. Chetwynd, with a
courtly bow.
“And think how Lady Jane loves you,” said Mrs. Lanier, as if to
clinch the argument.
“Yes; my love for her and hers for me are the strongest points in
the situation,” replied Mam’selle Diane reflectively; “when I think of
that I can hardly refuse to comply with your wishes.”
At that time it seem as if Lady Jane acted the part of fairy
godmother to those who had been her friends in her days of
adversity; for each one had only to express a wish and it was
gratified.
 Pepsie’s cottage in the country was about to become a reality. In
one of the charming shady lanes of Carrollton they found just such a
bowery little spot as the girl wished for, with a fine strip of land for a
garden. One day Mr. Chetwynd and Lady Jane went down to Good
Children Street and gave the deed of it to Mademoiselle Madelon
Modeste Ferri, which was Pepsie’s baptismal name, although she
had never been called by it in all her life. The little cripple was so
astonished and delighted that she could find no words of thanks; but
after a few moments of very expressive silence she exclaimed: “After
all, my cards were right, for they told me over and over that I should
go to live in the country; and now I’m going, thanks to Lady Jane.”
When little Gex was asked what he most wished for in the world,
he hesitated for a long time, and finally confessed that the desire of
his life was to go back to Paris.
“Well, you shall go, Mr. Gex,” said Lady Jane confidently, “and I
shall see you there, because I’m going to Paris with grandpapa very
soon.”
It is needless to say that Gex went, and the little shop in Good
Children Street saw him no more forever.
And Margaret—the good Margaret. What could Lady Jane do for
her? Only the noble woman and the destitute orphans could testify to
the generous aid that came yearly in the shape of a check for a large
amount from Lady Jane for dear Mother Margaret’s home.
“And Mam’selle Diane,—dear Mam’selle! what can I give her?”
asked Lady Jane eagerly.
“We have our plans for Mam’selle Diane, my dear,” said Mrs.
Lanier. “There is only one thing to do for her, and that is to take her
with you. Your grandpapa has begged her to take charge of your
education. Poor, lonely woman; she loves you dearly, and in spite of
her reluctance to leave her seclusion, I think she would go to the
world’s end with you.”
And so it was arranged that when Mr. Chetwynd and Lady Jane
left New Orleans, Mam’selle Diane d’Hautreve went with them, and
the little house and tiny garden were left to solitude, while the jolly
canary was sent to keep Tony company in Mrs. Lanier’s
conservatory.
 CHAPTER XXXIII
AS IT IS NOW

A LL this happened years ago, some ten or twelve, more or less,

and there have been many changes in that time.
In front of the iron railing where Lady Jane clung on that cold
Christmas eve, peering into the warmth and light of the Orphans’
Home, there is now a beautiful little park, with magnolias, oaks,
fragrant white jasmine, and pink flowering crape-myrtle. The grass is
green, and the trees make shadows on the pretty little pond, the tiled
bridge and shelled walks, the cactus and palmetto. Flowers bloom
there luxuriantly, the birds sing merrily, and it is a spot beloved of
children. Always their joyous laugh can be heard mingled with the
songs of birds and the distant hum of many little voices in the
Orphans’ Home a few paces away.
In the center of that square on a green mound, bordered with
flowers, stands a marble pedestal, and on that pedestal is a statue. It
is the figure of a woman, seated and holding a little orphan to her
heart. The woman has a plain, homely face, the thin hair is combed
back austerely from the broad forehead, the eyes are deep-set, the
features coarse, the mouth wide. She is no high-born dame of
delicate mold, but a woman of the people—untaught, honest, simple,
industrious. Her plain gown falls around her in scanty lines; over her
shoulders is modestly folded a little shawl; her hands, that caress the
orphan at her side, are large and rough with honest toil; but her face,
and her whole plain figure, is beautiful with purity and goodness. It is
Margaret, the orphans’ friend, who, though a destitute orphan
herself, by her own virtue and industry earned the wealth to found
homes and asylums, to feed and clothe the indigent, to save the
wretched and forsaken, and to merit the title of Mother to the
Motherless.
 And there sits her marble image, through summer’s heat and
winter’s cold, serene and gentle, under the shadow of the home she
founded, and in sound of the little voices that she loved so well; and
there she will sit when those voices are silent and those active little
forms are dust, as a monument of honest, simple virtue and charity,
as well as an enduring testimony to the nobility of the women who
erected this statue in respectful recognition of true greatness under
the homely guise of honest toil.
If one of my young readers should happen near this spot just at
the right moment on some fine evening in early spring, he or she
might chance to notice an elegant carriage drawn by two fine horses,
and driven by a sleek darky in plain livery, make the circuit of the
place and then draw up near the statue of Margaret, while its
occupants, an elderly woman of gentle and distinguished
appearance, and a beautiful young girl, study the homely, serene
face of the orphans’ friend.
Presently the girl says reverently, “Dear Mother Margaret! She was
a saint, if earth ever knew one.”
“Yes; she was a noble woman, and she came from the poor and
lowly. My dear, she is an example of a great truth, which may be
worthy of consideration. It is, that virtue and purity do not disdain to
dwell in the meanest shrine, and that all the titles and wealth of earth
could not ennoble her as her own saintly character has done.”
The occupants of the carriage are Lady Jane and Mam’selle Diane
d’Hautreve.
The beautiful child is now a beautiful girl of seventeen. Her
education is finished, and she has not disappointed the expectations
of her friends. At home and abroad she is not only known as the
Chetwynd heiress, but also for her many accomplishments, as well
as for her beauty and charitableness. And her wonderful voice, which
time has enriched and strengthened, is a constant delight to those
who hear it, although it is never heard in public, save in the service
of God, or for some work of charity. The poor and the lowly, the sick
and the dying have often been carried to the very gates of heaven on
its melodious strains, and the good sisters and grateful little orphans
in Margaret’s Home count it a day long to be remembered when
Lady Jane sits down among them and sings some of the hymns that
she loved so well in those old days when she herself was a
homeless little orphan.
Mr. Chetwynd still likes to spend part of the year in Paris; but he
has purchased a beautiful winter home in one of the lovely streets in
the garden district, not far from Mrs. Lanier, and Lady Jane and
Mam’selle Diane spend several months every spring in its delightful
seclusion.
And here Madelon comes to bring her delicious cakes, which she
now sells to private customers instead of having a stand on the Rue
Bourbon; and Tante Modeste often rattles up in her milk cart, a little
older, a little stouter, but with the same bright face; and on the same
seat where Lady Jane used to sit is one of Marie’s little ones, instead
of one of her own. “Only think, my dear,” she says proudly, “Tiburce
has graduated, and now he is studying law with Marie’s husband,
who is rising fast in his profession.”
But among all her happy hours there are none pleasanter than
those she spends with Pepsie in the pretty cottage at Carrollton,
when the bright-faced little cripple, who seems hardly a day older,
spreads out her beautiful needlework and expatiates eloquently on
the fine results she obtains from the Paris patterns and exquisite
material with which she is constantly supplied. She is a natural little
artist with the needle, her dainty work sells readily and profitably, and
she is in a fair way to become rich. “Just think,” she says with one of
her broad smiles, “I could buy a piano now myself, if I wanted to, and
perhaps I shall, so that you can play to me when you come.”
During sunny mornings, on a certain lawn in the garden district,
there is nearly always a merry party playing tennis, while a gentle-
faced woman sits near holding a book, which she seldom reads, so
interested is she in watching a golden-haired girl and a handsome
young man, who frequently interrupt the game to point out the grave
antics of a stately blue heron, that stalks majestically about the lawn
or poses picturesquely on one leg under a glossy palm.
 But we must not approach the border-land of romance. Lady Jane
is no longer a child, and Arthur Maynard is years older than the boy
who gave her the blue heron.

THE END
 Transcriber’s Notes

pg 14 Changed: if you thing it’s right

to: if you think it’s right
pg 133 Changed: LADY JANE FINDS A MUSIC-TEACHFR
to: LADY JANE FINDS A MUSIC-TEACHER
pg 152 Changed: You didn’t wear a handkerchef over your ears
to: You didn’t wear a handkerchief over your ears
pg 168 Changed: annoyed at Pespie’s air of secrecy
to: annoyed at Pepsie’s air of secrecy
*** END OF THE PROJECT GUTENBERG EBOOK LADY JANE ***

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