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Polymer Electrolytes
Polymer Electrolytes
Characterization Techniques and Energy Applications
Edited by
Tan Winie, Abdul K. Arof, and Sabu Thomas

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v
Contents
Preface xiii
1 Polymer Electrolytes: State of the Art 1

Masashi Kotobuki
1.1 Introduction 1
1.2 Solid Polymer Electrolyte 4
1.3 Gel Polymer Electrolyte 8
1.4 Composite Polymer Electrolyte 12
1.5 Summary 17
References 17
2 Impedance Spectroscopy in Polymer Electrolyte

Characterization 23
Mohamed Abdul Careem, Ikhwan Syafiq Mohd Noor, and Abdul K. Arof
2.1 Introduction 23
2.2 IS: Principal Operation and Experimental Setup 23
2.2.1 Basic Principles of Impedance Spectroscopy 23
2.2.2 Impedance Spectroscopy (IS) Technique 25
2.2.3 Electrical Conductivity of a Sample 26
2.2.4 Conditions Necessary for IS Measurements 26
2.2.5 Impedance Plots of Simple Circuits 28
2.2.5.1 A Pure Resistance, R 28
2.2.5.2 A Pure Capacitance, C 28
2.2.5.3 R and C Connected in Series 29
2.2.5.4 R and C Connected in Parallel 30
2.2.5.5 Combined Series and Parallel Circuits 31
2.2.5.6 Impedance Spectra of Model Electrolyte Systems 32
2.2.6 Possible Conduction Processes in a Solid Electrolyte 35
2.2.7 Impedance Spectra of Real Systems 36
2.2.7.1 The Constant Phase Element (CPE) 37
2.2.7.2 Equivalent Circuits for Real Systems 37
2.2.7.3 Electrolyte/Electrode (E/E) Interface 39
2.2.7.4 Diffusion Impedance or Mass Transport Impedance 39
2.2.7.5 Warburg Impedance 40
2.2.7.6 Equivalent Circuit Representation of an E/E System 41
vi Contents
2.2.8 Impedance-Related Functions 42

2.2.8.1 Immittance Functions 43
2.2.8.2 Relationships Between Immittance Functions 43
2.2.8.3 Immittance Plots 43
2.2.8.4 Choice Between Immittance Functions 46
2.2.9 Experimental Setup 46
2.2.9.1 Sample and Cell Arrangement 47
2.2.9.2 Other Practical Details and Precautions 48
2.3 IS: Experimental Data Interpretation and Analysis 49
2.3.1 Determination of Bulk Resistance from the Impedance Plots 49
2.3.2 Impedance Data Interpretation and Analysis 50
2.3.2.1 Interpretation of Impedance Data 51
2.3.2.2 Choice of Equivalent Circuits 51
2.3.3 Determination of Transport Parameters from Impedance Data 53
2.3.3.1 Bandara–Mellander (B–M) Method 53
2.3.3.2 Nyquist Plot Fitting Method 57
2.3.4 Some Experimental Results and Analysis 59
2.3.4.1 Conductivity Calculation of Impedance Plots 59
2.3.4.2 Conductivity Determination from Fitting Equivalent Circuit 60
2.3.4.3 Evaluation of Transport Properties using Nyquist Plot Fitting
Method 60
2.4 Conclusions 63
References 64
3 Thermal Characterization of Polymer Electrolytes 65

Aparna Thankappan, Manuel Stephan, and Sabu Thomas
3.1 Introduction 65
3.2 TGA: Experimental Data Interpretation and Analysis 67
3.3 DSC: Experimental Data Interpretation and Analysis 75
3.4 DSC: Experimental Errors and Suggestion for Improvement 82
3.4.1 Transition(s) at 0 ∘ C 83
3.4.2 Apparent Melting at T g 83
3.4.3 Exothermic Peaks Below Decomposition Temperature While
Heating 84
3.4.4 Baseline Shift after Endothermic or Exothermic Peaks 86
3.4.5 Sharp Endothermic Peaks During Exothermic Reactions 86
3.5 DMA: Experimental Data Interpretation and Analysis 87
References 91
4 Energy in a Portable World 93

Noor Syuhada Zakuan, Woo Haw Jiunn, and Tan Winie
4.1 Introduction 93
4.2 History Development of Mobile Power 94
4.3 Caring for Mobile Power from Birth to Retirement 102
4.3.1 Getting the Most Out of the Primary Batteries 103
4.3.2 Getting the Most Out of the Lead-Acid Batteries 103
4.3.3 Getting the Most Out of the Nickel-Based Batteries 104
Contents vii
4.3.4 Getting the Most Out of the Lithium Ion Batteries 105
4.4 Mobile Power Recycling 106
4.4.1 Recycling Primary Batteries 106
4.4.2 Recycling Rechargeable Batteries 109
Acknowledgments 111
References 111
5 Insight on Polymer Electrolytes for Electrochemical Devices

Applications 113
Maria Manuela Silva, Verónica de Zea Bermudez, and Agnieszka Pawlicka
5.1 Introduction 113
5.2 Theory: Ionic Conductivity 117
5.3 Applications 120
5.3.1 Conventional Batteries and Transient Batteries 120
5.3.2 Fuel Cells 123
5.3.3 Supercapacitors 124
5.3.4 Electrochromic Devices 125
5.3.5 Dye-Sensitized Solar Cells 127
5.3.6 Sensors 128
5.3.7 Light-Emitting Electrochemical Cells 128
References 129
6 Polymer Electrolyte Application in Electrochemical

Devices 137
Siti Nor Farhana Yusuf and Abdul K. Arof
6.2 Properties of Polymer Electrolytes (PEs) 137
6.3 Review of Polymer Electrolytes 138
6.3.1 Dry Solid Polymer Electrolytes (SPEs) 138
6.3.2 Gel Polymer Electrolytes (GPEs) 141
6.3.2.1 Ionic Liquid Gel Polymer Electrolytes (ILGPEs) 144
6.3.2.2 Gel Polymer Electrolytes with Nanomaterials 146
6.4 Application of PEs in Electrochemical Devices 148
6.4.1 Dye-Sensitized Solar Cells (DSSCs) 148
6.4.2 Lithium Ion Batteries 150
6.4.3 Electrical Double Layer Capacitors (EDLCs) 152
6.4.4 Polymer Electrolyte Fuel Cells 156
6.4.5 Electrochromic Windows 163
6.4.6 Electrochromic Materials 164
6.4.6.1 Transition Metal Oxides 164
6.5 Challenges and Improvements 167
6.5.1 In Electrolytes 167
6.5.2 In Devices 169
6.5.2.1 DSSCs 169
6.5.2.2 Fuel Cell 170
6.5.2.3 Batteries 171
viii Contents
6.5.2.4 EDLCs 172

6.5.2.5 Electrochromic Windows (ECWs) 172
6.6 Future Aspects 173
6.6.1 Electrochromic Windows 173
6.6.2 Batteries 173
6.6.3 DSSCs 173
6.6.4 Fuel Cells 174
References 175
7 Polymer Electrolytes for Lithium Ion Batteries and Challenges:

Part I 187
Shishuo Liang, Wenqi Yan, Minxia Li, Yusong Zhu, Lijun Fu, and Yuping Wu
7.2 Classification of Polymer Electrolytes 188
7.2.1 Solid Polymer Electrolytes (SPEs) 188
7.2.2 Gel Polymer Electrolytes (GPEs) 190
7.3 Performance and Improvements 190
7.4 Application and Performance of Polymer Lithium Ion Batteries 194
7.5 Future Trends 195
Acknowledgments 196
References 197
8 Polymer Electrolytes for Lithium Ion Batteries and Challenges:

Part II 201
Siti Nor Farhana Yusuf and Abdul K. Arof
8.2 Structure and Operation of Lithium Ion Batteries 202
8.2.1 Anode Materials 204
8.2.2 Cathode Materials 205
8.2.3 Electrolytes 206
8.2.4 Li+ Ion Transport in Polymer Electrolytes 206
8.3 Polymer Electrolyte for Lithium Ion Batteries 207
8.4 Performance Characteristics of Lithium Ion Batteries 216
8.5 Challenges and Improvement 218
References 221
9 Polymer Electrolytes for Supercapacitor and Challenges 231

Safir Ahmad Hashmi, Nitish Yadav, and Manoj Kumar Singh
9.2 Principle and Working Process of Supercapacitors 232
9.2.1 Charge Storage Mechanisms in EDLCs 233
9.2.2 Charge Storage Mechanisms in Pseudocapacitors 236
9.2.2.1 Underpotential Deposition 237
9.2.2.2 Redox Pseudocapacitance 237
9.2.2.3 Intercalation Pseudocapacitance 238
Contents ix
9.3 Electrolytes for Supercapacitors 239

9.3.1 Liquid Electrolytes 239
9.3.2 Polymer-Based Electrolytes 241
9.3.2.1 Solvent-Free Solid Polymer Electrolytes (SPEs) 242
9.3.2.2 Gel Polymer Electrolytes (GPEs) 242
9.3.2.3 Porous Polymer Electrolytes 252
9.4 Performance Characteristics 255
9.4.1 Electrode Characterization 255
9.4.2 Characterization of Supercapacitors 258
9.4.2.1 Electrochemical Characterization Techniques and Important
Parameters 258
9.4.2.2 Performance of Polymer Electrolyte-Based Supercapacitors: Some
Case Studies 262
9.5 Challenges to Solid-State Supercapacitors and Future Scope of
Improvement 284
References 285
10 Polymer Electrolytes for Quantum Dot-Sensitized Solar Cells

(QDSSCs) and Challenges 299
T.M.W.J. Bandara and J.L. Ratnasekera
10.1 Demand and Supply of Energy 299
10.2 The Sun as a Potential Energy Resource 300
10.3 Advantages of Solar Cells 301
10.4 Photo-Electrochemical Solar Cells 301
10.4.1 General Mechanism of a Photo-Electrochemical Solar Cell 303
10.4.2 Mechanism of a Photo-Electrochemical Solar Cell 304
10.4.3 Semiconductor/Polymer Electrolyte Junction 308
10.4.4 Photo-sensitization of Wide Bandgap Semiconductors 308
10.5 Quantum Dot-Sensitized Solar Cells (QDSSCs) 310
10.5.1 Quantum Dots 310
10.5.2 Mechanism of a QDSSC 313
10.5.3 Quantum Dot-Sensitized Solar Cells (QDSSCs) 314
10.5.4 Polymer Electrolytes for QDSSCs 317
10.6 Performances of Different QDSSCs Assemblies Based on Polymer
Electrolytes 318
10.6.1 Quasi-Solid-State QDSSCs Based on Polyacrylamide Hydrogel
Electrolytes 318
10.6.1.1 Hydrogel Electrolyte with Polyacrylamide 318
10.6.2 CdS-Sensitized Cell with PAN and PVDF Electrolytes 319
10.6.3 ZnO-Based Quasi-Solid QDSSCs Sensitized with CdS and CdSe 323
10.6.3.1 Quasi-Solid-State Electrolyte Preparation 324
10.6.4 Natural Polysaccharide Thin Film-Based Electrolyte for Quasi-Solid
State QDSSCs 324
10.6.5 Dextran-Based Hydrogel Polysulfide Electrolyte for Quasi-Solid-State
QDSSCs 325
10.6.6 Carbon Dots Enhance Light Harvesting in a Solid-State QDSSC 326
x Contents
10.6.7 Quantum Dot-Sensitized Solar Cells Based on Oligomer Gel

Electrolytes 326
10.6.8 QDSSCs with Thiolate/Disulfide Redox Couple and
Succinonitrile-Based Electrolyte 327
10.6.9 Graphene-Implanted Polyacrylamide Gel Electrolytes for
QDSSCs 328
10.6.10 PEO and PVDF-Based Electrolyte for Solid-State Electrolytes for
QDSSCs 329
10.6.11 Hydroxystearic Acid-Based Polysulfide Hydrogel Electrolyte for
CdS/CdSe QDSSCs 329
10.6.12 QDSSCs Based on a Sodium Polyacrylate Polyelectrolyte 330
10.7 Summary 331
References 334
11 Polymer Electrolytes for Perovskite Solar Cell and

Challenges 339
Rahul Singh, Hee-Woo Rhee, Bhaskar Bhattacharya, and Pramod K. Singh
11.2 Principle and Working Process of Perovskite Solar Cell 341
11.2.1 Perovskite Materials 342
11.2.2 Perovskite Structure 344
11.2.3 Synthesis of Perovskite 349
11.2.3.1 Solution-Processed Method 349
11.2.3.2 Hot Casting Technique 352
11.2.3.3 Vapor Deposition Method 352
11.2.3.4 Thermal Evaporation Technique 352
11.3 Polymer Electrolyte for Perovskite Solar Cell 354
11.3.1 Device Fabrication 354
11.3.2 Hole Transport Layer 355
11.4 Performance Characteristics 355
11.5 Challenges and Improvement 356
11.7 Conclusion 358
Competing Interests 358
Acknowledgments 358
References 358
12 Polymer Electrolytes for Electrochromic Windows 365

Li Na Sim and Agnieszka Pawlicka
12.2 Principles and Working Process of Electrochromic Window 366
12.3 Types of Electrochromic Electrodes 367
12.4 Mechanism of ECW 368
12.5 Polymer Electrolytes for Electrochromic Windows 369
12.5.1 Background 369
12.5.2 Criteria of Polymer Electrolytes and Electrochromic Device 369
12.5.3 Types of Polymer Electrolytes Used in ECWs 370
Contents xi
12.5.3.1 Solid Polymer Electrolytes (SPEs) 370

12.5.3.2 Gel Polymer Electrolytes (GPEs) 374
12.5.3.3 Composite Polymer Electrolyte 383
12.6 Present ECDs Uses/Applications 385
References 385
Index 391
xiii
Preface
Polymer electrolytes resulting from the complexation of polymer with organic

or inorganic salts were first introduced by P.V. Wright in 1975 and proposed as
potential material for electrochemical devices by M. Armand in 1978. The poly-
meric property of polymer electrolytes gives it advantages over liquid electrolytes
in terms of leak-proof, size and shape flexibility. Polymer electrolytes are substi-
tuted for the liquid electrolyte in new generation electrochemical devices such as
batteries, supercapacitors and solar cells.
Chapter 1 of this book provides an important review of the development
of polymer electrolytes. Chapters 2 and 3 present the electrical and thermal
properties of polymer electrolytes characterized by impedance spectroscopy,
TGA and DSC, respectively. These chapters include theoretical considerations,
the know-how needed to set up the experiments and how to analyze their
results. There are also discussions on sources of errors along with suggestions
for improvement. Chapters 4 to 12 focus on applications of polymer electrolytes,
which cover the batteries, supercapacitors, solar cells and electrochromic
windows. Challenges in fabrication and performance improvement of these
devices were indentified along with suggestions for improvement.
This book brings together prestigious international authors. Novice reader will
find an outline of basic theory, experimental set up and a discussion of exper-
imental methods and data analysis, with examples and appropriate references.
Leading researchers and faculty members will find this book very valuable as an
excellent review and a comprehensive summary of the literature on the subject
with a discussion of current theoretical and experimental issues.
Finally, we wish to express our gratitude and appreciation to the chapter
contributors. Comments from reviewers are gratefully appreciated.
October 8, 2019 Tan Winie

Abdul K. Arof
Sabu Thomas
1
Polymer Electrolytes: State of the Art

Masashi Kotobuki
National University of Singapore, Department of Mechanical Engineering, 21 Lower Kent Ridge Rd.,
Singapore 119077, Singapore
Polymers are defined as large molecules or macromolecules, which consist of

repeated subunits. The polymers may be synthetic plastics or natural biopoly-
mers such as protein, DNA, and so on. In the past 20 years, polymers have been
tailored as electron or ion conductors. When appropriate salt is added into some
polymers, their ionic conductivity can be improved to the value that can be used
as electrolyte. In the past three decades, many researchers have endeavored to
develop new polymer electrolytes (PEs) due to their potential application in elec-
trochemical/electrical power generation, storage, and conversion systems. As a
result, a lot of new PEs have been found, characterized, and tried to be applied in
electrochemical/electrical devices. Particularly, Li ion-conductive PEs have been
of interest for application in Li batteries due to their high energy density. In this
chapter, the state-of-the-art development of Li ion-conductive PEs is described.
1.1 Introduction
PE was first introduced in 1973 [1]. Since then, the research on PE has been
eagerly performed by many researchers, especially in the early 1980s, due to the
recognition of PEs in industrial applications.
PE is a membrane composed of salts dissolved in a polymer [2]. Some polymer
matrixes such as polyethylene oxide (PEO) and poly(methyl methacrylate)
(PMMA) can dissolve salts and form salt–polymer complexes due to the inter-
action between oxygen atom in the polymer chain and cation in the salt. This
solvent-free and ion-conductive system has been expected to be widely applied
in electrochemical devices like rechargeable solid-state batteries, especially
rechargeable Li ion batteries. In recent years, PEs have other prospective appli-
cations in advanced electrochemical, electrochromic, and electronic devices such
as fuel cells, supercapacitors, electrochemical sensors, analog memory devices,
and electrochromic windows [3–7]. Figure 1.1 shows the structure of commercial
Li ion batteries using graphite and LiCoO2 as an anode and cathode, respectively.
Li ions only exist in the cathode side when the batteries are constructed. The Li
Polymer Electrolytes: Characterization Techniques and Energy Applications,

First Edition. Edited by Tan Winie, Abdul K. Arof, and Sabu Thomas.
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2020 by Wiley-VCH Verlag GmbH & Co. KGaA.
2 1 Polymer Electrolytes: State of the Art
Discharge Charge
Charge
Li+ Li+ Li+
Discharge
+
Li Li+ Li+
LiCoO2 Non aqueous electrolyte Graphite
Figure 1.1 Li battery.
ions move from cathode to anode in a charge process. In a discharge process, Li

ions migrate to the opposite direction. The electrolyte does not get involved in
battery reactions in the Li batteries and just acts as Li ion-conductive media. In
general, the electrodes of Li batteries are prepared by mixing three components,
i.e. active material, binder, and conductive material. Poly(vinylidene fluoride)
(PVdF) has been used as a binder thus far. As a conductive material, acetylene
black and Ketjen black have been normally employed. These three components
are mixed and added into a solvent N-methyl-2-pyrrolidone (NMP) to make a
slurry. The slurry is painted onto Cu (for anode) or Al (for cathode) foil, which
is used as a current collector. As for the electrolytes, nonaqueous electrolytes
have been used so far due to narrow electrochemical window of aqueous
electrolytes. The nonaqueous electrolytes are composed of Li salt (usually LiPF6 )
dissolved into organic solvents, which are a mixture of acyclic solvent with low
viscosity like dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC)
and cyclic solvent with high dielectric constant like ethylene carbonate (EC).
However, flammability of these nonaqueous organic solvents sometimes has
caused serious safety issues such as fire hazard and leakage of electrolyte [8–10].
Contrary to the nonaqueous electrolytes, solid polymer electrolytes (SPEs) can
solve the issue of leakage. Additionally, PEs possess much lower flammability
than the organic electrolytes due to low vapor pressure. The PEs should have the
following physical, chemical, and electrochemical properties [11]:
(1) High ionic conductivity at operating temperature (normally room tempera-
ture), while electronic conductivity can be negligible.
(2) Sufficient mechanical strength at the operating temperature for self-
supported cell.
(3) High electrochemical decomposition voltage (wide electrochemical
window).
(4) High cationic or anionic transference number.
1.1 Introduction 3
(5) Environmental benign, non-hygroscopic, low cost, and ease of preparation.

(6) Stability against chemical and electrochemical reactions with both electrodes
(cathode and anode) during preparation and operation of the battery.
(7) Thermal expansion coefficient matches with that of the electrodes to ensure
good contacts between PE and electrodes.
Table 1.1 summarizes a comparison of properties of conventional nonaqueous

electrolyte and PE. Ceramic electrolyte, which is another type of solid electrolyte,
is also compared. The ceramic electrolytes possess excellent safety due to their
nonflammable nature although structural flexibility is very low and conductiv-
ity is low because of high grain boundary resistance. PEs normally possess high
conductivity and structural flexibility as well as relatively wide electrochemical
window.
PEs can be categorized into three groups based on their physical state and
composition: (i) Solid polymer electrolyte (SPE), (ii) gel polymer electrolyte
(GPE), and (iii) composite polymer electrolyte (CPE) [12, 13]. Also, PEs can be
divided into two groups by polymer source, i.e. synthetic polymer and natural
polymer (Figure 1.2). Synthetic polymers such as PEO and polycarbonate have
been used as polymer matrix. Natural polymers like chitosan are usually low
cost, eco-friendly, biodegradable, and abundant. Therefore, researches on natural
polymer for PEs have been eagerly performed in recent years.
Table 1.1 Comparison of various properties among nonaqueous, polymer,

and ceramics electrolytes.
Nonaqueous Polymer Ceramics

electrolyte electrolyte electrolyte
Conductivity High Middle Low

Safety Low High High
Structural flexibility Middle High Low
Electrochemical window Middle Middle Wide
Based on physical state

and composition Based on source of polymers
Solid polymer Gel polymer Composite polymer Synthetic Natural

electrolyte electrolyte electrolyte polymer polymer
Figure 1.2 Classification of polymer electrolytes.

1.2 Solid Polymer Electrolyte

SPE is composed of host polymer matrix(es) and Li salts. The salts are dissolved
into the polymer matrix(es) and provide ionic conduction. The research on
SPEs commenced three decades ago [14]. The PEO-based SPE was investigated
first and has been most widely researched so far [1]. The ether oxygen atoms
in the PEO matrix complex with Li ion [15] and dissolve the Li salts. It is
widely believed that the cation transport is related to the complexing segmental
motion of PEO chain [16, 17] (Figure 1.3). Other polymer hosts such as PVdF,
poly(vinylidene fluoride–hexafluoropropylene) (PVdF–HFP), PMMA, poly(vinyl
chloride) (PVC), poly(acrylonitrile) (PAN), poly(acrylic acid) (PAA), poly(ethyl
methacrylate) (PEMA), and so on also contain oxygen, nitrogen, chlorine, or
fluorine atom, which can form a complex with Li ion, and the segmental motion
would cause ion conduction. Table 1.2 summarizes repeat unit of polymer
Polyethylene oxide (PEO) Figure 1.3 Segmental

motion-assisted Li ion
HO CH2 CH2 O H conduction in PEO-based
m polymer.
O O O
O
O
O Li+
O Li+
O O O O
O
O O
Table 1.2 Polymer host generally used in polymer electrolytes.
Ionic
conductivity
at room
Example of temperature
Polymer host Repeat unit polymer electrolyte (S cm−1 ) References
PEO –(CH2 CH2 O)n – (PEO-HBP)–LiTFSI– 2.6 × 10−4 [18]

BaTiO3
PVdF –(CH2 CF2 )n – PVdF–PEO–LiTFSI 5.4 × 10−4 [19]
PVdF-HFP –[(CH2 CF2 ) – P(VdF-HFP–SiO2 – 4.3 × 10−3 [20]
(CF2 CFCF3 )]n – LiTFSI
PMMA –[(CH2 C(–CH3 ) – PMMA–LiClO4 – 7.3 × 10−6 [21]
COOCH3 )]n – DMP–CeO2
PVC –(CH2 CHCl)n – PVC–Li2 B4 O7 –DBP 2.83 × 10−6 [22]
PAN –[CH2 CH(–CN)]n – PAN–LiClO4 –Al2 O3 5.7 × 10−4 [23]
PAA –[CH2 CH(–COOH)]n – PAA–LiClO4 –Sb2 O3 2.15 × 10−4 [24]
PEMA –[(CH2 C(–CH3 ) – PEMA–LiTf-IL 1.17 × 10−4 [25]
COOCH2 CH3 )]n –
Figure 1.4 Schematic Arrhenius plot of 40 °C

PEO–LiClO4 polymer electrolyte.
Conductivity (S cm–1)
1/T (K–1)
hosts and examples of PEs. The structural flexibility directly relates to the
ionic conductivity. In other words, the amorphous phase in the SPEs supports
ionic conduction. The continuous segmental motion of the amorphous chain
occurs above the glass transition temperature (T g ) [26]. T g of the PEs should
be lower than room temperature. Moreover, increase in the amorphous regions
with raised temperature improves the ionic conductivity. Figure 1.4 depicts
a schematic Arrhenius plot of PEO–polystyrene (PSt)-LiClO4 PE [27]. An
inflection point around 40 ∘ C can be observed in this plot. This corresponds to
a phase transition from crystalline to amorphous phase of the polymer host.
Due to the phase transition, the activation energy of ionic conduction is lowered
considerably. However, mechanical strength of the SPE system is related to
the movement of polymer chain. Increase in the amorphous regions implies
that the polymer chains move actively, which enhances the ionic conductivity,
but decreases the mechanical strength. This adverse effect leads to difficulty in
construction of self-supported polymer batteries.
In order to solve this problem, many efforts have been devoted to develop
novel polymer matrixes containing amorphous state, including blending of poly-
mers, cross-linking, copolymerization, and so on. These approaches can lower
crystallinity or T g of the SPE systems and increase the ionic conductivity and
mechanical strength [28–30].
Blend PEs are prepared by mixing two or more kinds of molecular chains
(Figure 1.5). The chains are mixed with/without any chemical bonding between
them. This blended polymer chain destroys the regularity of one polymer
chain and prevents its rearrangement, resulting in formation of amorphous
structure. Tanaka et al. prepared a polymer blend comprising of PEO and
polyethylene imine (PEI). The ionic conductivity of [(8 : 2) PEO/PEI]–LiClO4
was ∼10−4 S cm−1 at 30 ∘ C [31]. This high ionic conductivity is considered to
Polymer A Polymer B Blend polymer
Figure 1.5 Schematic image of blend polymer.

be due to mixing of PEO with PEI that hindered their crystallization and led to
more useful matrices.
Block copolymer electrolytes (BCEs) have been proposed as a novel SPE
to satisfy both the ionic conductivity and the mechanical strength [32]. The
most common structures researched are the diblock and triblock copoly-
mers. A lithium salt-solvating polymer is used to ensure continuous ionic
conduction pathways, and another polymer host, which forms a polymer
framework of the SPEs, is chosen to provide the mechanical strength to the
SPEs [33]. Polymer films with good mechanical strength can be obtained
without sacrificing the ionic conductivity. Thus, a balance of the salt-solvating
polymer and the framework polymer is important. Niitani et al. reported novel
PSt–poly(ethylene glycol) (PEG) methyl ether methacrylate (PME)–PSt–LiClO4
triblock copolymers (Figure 1.6) [34, 35]. The triblock SPE exhibited high
ionic conductivity of 2.0 × 10−4 S cm−1 without plasticizer. The PSt block was
used to improve mechanical properties, while the PEO moiety increased the
ionic conductivity. An all-solid-state battery of LiCoO2 /SPE/Li cell demon-
strated excellent charge–discharge property at room temperature. This concept
can also increase Li ion transference number. Bouchet et al. reported a
single-ion PE based on poly[lithium 4-styrenesulfonyl(trifluoromethylsulfonyl)
imide] [P(STFSILi)–PEO–P(STFSILi)] polyanionic triblock copolymers [36].
This material demonstrated high Li ion transference number (>0.85), excel-
lent mechanical strength, and good ionic conductivity (1.3 × 10−5 S cm−1
at 60 ∘ C). The battery tests exhibited good power and cycling performances
at 60 ∘ C.
Cross-linking PEs show good ionic conductivity at ambient temperature and
fully amorphous feature (Figure 1.7) [37]. However, the cross-linking polymer
generally exhibits low elasticity and brittleness as well as low processability [38].
A cross-linked high molecular weight poly(oxyethylene) has been reported as a
CH3
CH CH2 CH2 C
n
C=O m
CH2CH2O CH3
y
PSt
PEO
Figure 1.6 Schematic image of novel nanostructure-controlled SPE and its synthetic scheme.
Polymer A Polymer B Cross-linked polymer
Figure 1.7 Schematic image of the cross-linked polymer.
new SPE, which demonstrated favorable ionic conductivity and good mechanical
strength [39].
Copolymer is a polymer prepared from at least two different types of
monomers. PVdF-HFP is the most common copolymer researched as PE.
The PVdF-HFP copolymer is prepared by copolymerization of PVdF and
HFP (Figure 1.8). The copolymer exhibits better features compared with the
mono-polymers alone, which could be attributed to the synergistic effects in
the combined structure. Also, PVdF has received much attention due to good
electrochemical stability and high dielectric constant [40, 41]. The presence of
strong electron-withdrawing fluorine atoms (C–F) promotes dissociation of
salts and increases the concentration of charge carriers, leading to high ionic
conductivity. Jiang et al. reported ionic conductivity of PVdF-based SPEs of
above 10−4 S cm−1 at room temperature [41].
Other polymer hosts also have been researched. The potential of PMMA as a
polymer host was reported by Iijima et al [42]. The PMMA-based SPEs showed
low mechanical integrity and high brittleness [43]. Blending of PMMA with PVC
has also been researched [44, 45]. PVC is also an attractive polymer host due
to its low cost and easy processing. GPEs based on PVC with plasticizers have
been widely researched. Poly(vinyl alcohol) (PVA) is nontoxic and cost effec-
tive and possess good tensile strength, good mechanical strength, good optical
properties, high temperature resistance, high abrasion resistance, good flexibil-
ity, biocompatibilities, high hydrophilicity, and excellent chemical and thermal
stabilities [46–50]. PVA contains a large amount of polar hydroxyl group, lead-
ing to high hydrophilicity. This provides other advantages like ease in preparation
and high dielectric constant. Due to these superior properties, PVA has received
considerable research interest as electrolytes for fuel cells and electrical double
layer capacitors [51]. A PAN-based PE has some outstanding characteristics such
as high thermal stability and high ionic conductivity [52]. PAN is superior over
PVdF with respect to mechanical stability [53]. The –CN groups in PAN can inter-
act with cations. Structures of these polymer hosts are shown in Figure 1.9.
Additionally, natural polymer such as chitosan [54], rice starch [55], and corn
starch [56] has also been studied. These have an advantage as novel polymer hosts
due to being low cost, biodegradable, eco-friendly, and abundant.
Polymer A Polymer B Copolymer
Figure 1.8 Schematic image of the copolymer.

PVdF PVdF-HFP
F
CH2 CF2 CH2 CF2 CF2 C

n n
CF3
m
PMMA PVC PVA PAN
CH3 Cl
CH2 C CH2 C CH2 CH2 CH2 CH
COOCH3 n H OH CN
n n n
Figure 1.9 Structure of polymer hosts.
1.3 Gel Polymer Electrolyte

GPE is also known as plasticized PE, which was first introduced by Feuillade and
Perche in 1975 [57]. GPE contains a plasticizer or gelled polymer matrix, which is
swollen by addition of the plasticizers [58], and can be prepared by simply heat-
ing a mixture of polymer and Li salt with solvent. By introducing a plasticizer
and/or solvent, the ion transport is not dominated by the segmental motion of
polymer chains but occurs in the swollen gelled phase or liquid phase. In general,
when the polymer is composed of interconnected micropores, the ionic conduc-
tivity of GPEs mainly depends on the properties of trapped liquid electrolyte. On
the contrary, ion transport mainly occurs in the swollen gelled phase if the poly-
mer does not contain many interconnected pores. The GPEs should possess good
mechanical strength, capability of holding a liquid electrolyte, high ionic conduc-
tivity, and electrochemical stability toward both cathode and anode. Many kinds
of polymer matrix such as PEO [59], PMMA [60], PAN [61], PVC [62], PVdF
[63], and P(VdF-HFP) copolymer [64] have been widely studied as a framework
for GPEs.
Plasticizers, which are usually low molar-mass organics, organic solvents, or
ionic liquids (ILs), largely affect the properties of GPEs. A plasticizer can increase
the content of the amorphous phase in a PE and promote segmental motion
[65]. In addition, it can also promote dissociation of ion pairs. As a result, the
number of charge carriers is increased, leading to enhanced ionic conductivity
[59]. PEG has been widely used as a low molar-mass plasticizer. It was reported
that the ionic conductivity of PEO–LiCF3 SO3 complex increased with the
decrease of molecular weight of PEG and with the increase of PEG content [66].
However, the hydroxyl end groups in PEG react with electrode materials such
as lithium metal. Therefore, various modified forms of PEG were synthesized by
replacing active oxygen atoms in PEG with monomethoxy (MMPEG), dimethoxy
(DMPEG) groups, or lithium (LPEG) ions [67]. The LPEG plasticizer can improve
the compatibility of the PE with lithium metal anode [13]. On the contrary, in
some polymer systems such as PEO-PMMA, no significant improvement of
ionic conductivity by addition of PEG was reported. The plasticizer must be
chosen carefully depending on the polymer host used. Other low molar-mass
plasticizers such as polyethylene glycol dimethyl ether (PEGDME) [68], borate

ester such as PEG borate ester [69], tris(2-(2-methoxyethoxy)ethyl) borate
(B2 ), and tris(2-(2-(2-methoxyethoxy)ethyl borate (B3 ) [70], phthalates such as
dibutyl phthalate (DBP) [71], dimethyl phthalate (DMP) [65], dioctyl phthalate
(DOP) [72], succinonitrile (SN) [73], and so on have also been studied. The ionic
conductivity of the PEs containing these plasticizers is summarized in Table 1.3.
The organic solvents usually used as plasticizer are polar and nonvolatile sol-
vents such as EC, propylene carbonate (PC), diethyl carbonate (DEC), and DMC.
The solvents help to solvate ions and facilitate their transportation. Therefore,
high dielectric constant and low viscosity are required for the solvents. Individ-
ual solvent is difficult to meet all the requirements; thus, a mixture of the solvents
usually has been employed. The mixture of solvents is more efficient to enhance
the ionic conductivity compared with a single solvent, which is due to the com-
bined action of dielectric constant and viscosity [75]. The ionic conductivity of
some GPEs using the plasticizers is tabulated in Table 1.4. The ionic conductiv-
ity can be increased to ∼10−3 S cm−1 by the addition of suitable solvents. Choi
et al. studied the ionic conductivity of PAN polymer swollen by 1 M LiPF4 in
EC/DMC (1 : 2 wt%), EC/DMC (1 : 1), EC/EMC (1 : 1), EC/DEC (1 : 1), and
EC/DMC/DEC (1 : 1 : 1) [61]. The order of ionic conductivity was EC/DMC/DEC
(1 : 1 : 1) > EC/DMC (1 : 1) > EC/EMC (1 : 1) > EC/DEC (1 : 1) > EC/DMC (2 : 1).
ILs have attracted considerable interest as a novel plasticizer. They are room
temperature molten salts, which are composed of a bulky organic cation and a
large delocalized inorganic anion. The ILs possess some unique properties such
as high chemical and thermal stabilities, nonflammability, negligible volatility,
and high electrochemical stability [83–85]. Due to these unique properties, the
incorporation of room temperature ionic liquids (RTILs) into PEs can overcome
inherent limitations of the ionic conductivity in SPEs as proposed by Passerini
Table 1.3 Ionic conductivity of various polymer electrolytes with plasticizers.
Ionic
conductivity Temperature
Polymer (S cm−1 ) (∘ C) References
(PEO)15 /LiTFSI/10 wt% PEGDME >10−3 50 [59]

(PEO)20 /LiCF3 SO3 /50 wt% PEGDME 1.2 × 10−4 30 [68]
30 wt% PVA/10 wt% LiClO4 /60 wt% DMP 1.5 × 10−4 29 [65]
−5
17.5 wt% PVA+7.5 wt% PMMA/8 wt% 6 × 10 30 [74]
LiClO4 /67 wt% DMP
PEO/15 wt% LiCF3 SO3 /15 wt% PEG 1.7 × 10−5 RT [72]
−4
PEO/15 wt% LiCF3 SO3 /20 wt% DOP 7.6 × 10 RT [72]
(PEO)20 /LiBOB/24 mol% SN >6 × 10−4 60 [73]
PEO/13 wt% LiCF3 SO3 /10 wt% DBP 1.6 × 10−4 27 [71]
(PEO)20 /LiTFSI/100 wt% PEG borate ester 1.36 × 10−5 30 [69]
−5
PSi/15 wt% LiCF3 SO3 /40 wt% borate ester B2 3.70 × 10 RT [70]
PSi/15 wt% LiCF3 SO3 /40 wt% borate ester B3 1.60 × 10−4 RT [70]
Table 1.4 Ionic conductivity of various polymer electrolytes with organic solvents.
Ionic
conductivity Temperature
Polymer (S cm−1 ) (∘ C) References
P(VdF-HFP)/1.0 M LiPF6 /EC + DEC 1.0 × 10−3 RT [76]

P(VdF-HFP)/1.0 M LiPF6 /EC + DMC + DEC 1.43 × 10−3 RT [64]
PVdF/1.0 M LiPF6 /EC + DMC + DEC 1.0 × 10−3 RT [77]
30 wt% PVC/8 wt% LiClO4 /62 wt% PC 6.70 × 10−6 30 [62]
−5
PEO/15 wt% LiCF3 SO3 /20 wt% EC 8.12 × 10 RT [78]
(PEO)16 /LiClO4 /40 wt% EC 2.67 × 10−4 RT [79]
4.5 wt% PMMA/46.5 wt% LiClO4 /30 wt% 5.0 × 10−4 RT [80]
PC + 19 wt% EC
PAN/1 M LiPF6 /EC + DMC + DEC >1.0 × 10−3 RT [61]
PAN/1 M LiBF4 /EC + DEC 2.80 × 10−3 RT [81]
PVdF/1.0 M LiPF6/EC + DMC 1.00 × 10−3 RT [63]
−5
7.5 wt% PVC/5 wt% LiBF4 /42 wt% 8.60 × 10 RT [82]
EC + 28 wt% PC
et al. in 2003 [86]. Since then, many groups have devoted much effort to study
GPEs containing ILs. Many types of IL comprising cations based on pyridium,
imidazolium, piperidinium, quaternary ammonium, and so on and anions
based on [BF4 ]− , [PF6 ]− , [N(CF3 SO2 )2 ]− , [CF3 SO3 ]− , [C4 F9 SO3 ]− , [N(CN)2 ]− ,
[CF3 CO2 ]− , [CF3 CONCF3 SO2 ]− , and so on have been investigated. In most
cases, the ILs contain the same anion as salts such as IL containing [PF6 ]−
anion in LiPF6 . This is because the solubility of the salt into the IL incorpo-
rating the same anion is much higher than in a system of different anions.
Passerini et al. studied a series of ILs containing pyrrolidinium-based cations
and TFSI anions [87–94]. The structure of N-alkyl-N-methyl-pyrrolidium
bis(trifluoromethanesulfonyl) imide (PYR1A TFSI, A = Cn H2n+1 , 1 < n < 10)
is depicted in Figure 1.10. The commonly used ILs for PEs are PYR13 TFSI
(1-propyl-1-methylpyrrolidinium bis(fluorosulfonyl) imide) and PYR14 TFSI
(1-butyl-1-methylpyrrolidinium bis(trifluorosulfonyl) imide). The ionic conduc-
tivity of PEO/LiTFSI/PYR13 TFSI PE is ∼10−4 S cm−1 at 20 ∘ C, which is about two
orders of magnitude higher than that without the IL [86]. It was reported that the
PYR13 TFSI also improved the ionic conductivity of PVdF-based polymer. The
GPE composed of P(VdF-HFP)/LiTFSI/PYR13 TFSI showed high ionic conduc-
tivity of 2.7 × 10−4 S cm−1 [95]. Also, incorporation of PYR14 TFSI plasticizer into
P(VdF-HFP)/LiTFSI PE showed a good ionic conductivity of 4.0 × 10−4 S cm−1
and high thermal stability [96]. An interesting study was performed by Winter
et al. [83, 84]. They conducted in situ UV photoradiation of a complex of
PRO/LiTFSI/PYR14 TFSI using benzophenone as a cross-linking agent to obtain
high conductive PEs with high mechanical properties.
ILs containing 1-alkyl-3-methylimidazolium cation have also been used
as a plasticizer in GPEs. The structure of 1-alkyl-3-methylimidazolium
Figure 1.10 Structure of A= n-methyl

N-alkyl-N-methyl-pyrrolidium A= n-ethyl
+ A= n-propyl (PYR13)
bis(trifluoromethanesulfonyl) imide. N A= iso-propyl
A A= n-butyl (PYR14)
A= iso-butyl
O O A= sec-butyl
– A= tert-butyl
CF3 S N S CF3
O O
+ +
N N
PYR13 PYR14
Figure 1.11 Structure of O O

1-alkyl-3-methylimidazolium EMIm TFSI + –
N N CF3 S N S CF3
bis(trifluoromethylsulfonyl) imide.
O O
+ O O
PMIm TFSI N N –
CF3 S N S CF3
O O
O O
BMIm TFSI + –
N N CF3 S N S CF3
O O
bis(trifluoromethylsulfonyl) imide IL is depicted in Figure 1.11. The alkyl group

in the cation affects the ionic conductivity of GPEs. EMImTFSI, PMImTFSI, and
BMImTFSI were employed as plasticizers to form GPEs based on P(VdF-HFP)
matrix [97]. All these GPEs revealed a high ionic conductivity in the range
of 2.4 × 10−3 to 4.5 × 10−3 S cm−1 . The GPE containing EMImTFSI showed
the highest conductivity. Also, effects of anion on conductivity of PEO-based
GPE were studied using ILs containing BMIm cation [98]. In the study, three
different anions (TFSI− , BF4 − , and CF3 SO3 − ) and BMIm cation were employed.
The PEO/LiTFSI/BMImTFSI electrolyte showed the highest ionic conductivity
and good electrochemical stability [99].
As expected, compatibility between ILs and polymer
is critical to determine the properties of GPEs. It was n
reported that quaternary ammonium-based ILs were more O
compatible than imidazolium-based ILs with PEO-PMMA HN O
copolymer [100]. This is thought to be due to preferable
S O–Li+
interaction between IL and polymer matrix.
O
The GPEs comprising polymeric lithium salts and
ILs have been proposed as novel GPEs. Lithium Figure 1.12 Structure
poly(2-acrylamido-2-methyl propanesulfonate) (PAMP- of PAMPSLi.
SLi, Figure 1.12) is used as the polymeric lithium salt. The
PAMPSLi-PVdF copolymer was combined with 1-ethyl-3-methylimidazolium
tricyanomethanide (EMImTCM). The ionic conductivity of PAMPSLi-PVdF
CH3 CH2CH2CH3
+
N
TFSI–
C + m n
N –
CH3 N N CH3 Y O
O
N N
CH3 CH3
(a) (b) Y– = PF6– or TFSI–
Figure 1.13 Structure of (a) guanidinium IL and (b) guanidinium-based PIL.
copolymer with EMImTCM IL was 5.43 × 10−3 S cm−1 , which was four times
higher than that of homopolymer system of PAMPSLi-PVdF [101].
Also, polymeric ionic liquids (PILs) obtained by the
n polymerization of an IL monomer have attracted much
N attention as the polymer matrix in GPEs. The main
2TFSI–
advantages of the PIL-based GPEs are low flammability
+ and high anodic stability. Guanidinium-based PILs con-
N
taining different anions (PF6 − and TFSI− ) were prepared
+ by the polymerization of a guanidinium IL monomer with
N
methyl acrylate (Figure 1.13). A quaternary GPE with a
guanidinium PIL (matrix), a guanidinium IL, LiTFSI salt,
Figure 1.14 Structure and nano-SiO2 particles showed high conductivity and
of imidazolium–
wide electrochemical stability window [102]. Yin et al.
tetraalkylammonium-
based PIL. synthesized a novel dicationic PIL and employed it for the
GPE matrix (Figure 1.14) [103]. The novel GPE with dica-
tionic PIL, poly(N,N,N-trimethyl-N-(1-vinylimidazolium-3-ethyl) ammonium
bis(trifluoromethanesulfonyl)imide), 1,2-dimethyl-3-ethoxyethylimidazolium
TFSI (IM(2o2)11TFSI) IL, and LiTFSI salt exhibited a low T g (−54 ∘ C), high
thermal stability (330 ∘ C), good ionic conductivity (about 10−4 S cm−1 at
25–40 ∘ C), and high electrochemical stability. In another research using PIL,
a less flammable GPE was prepared by the in situ polymerization of an IL
monomer, 1-methyl-2-(2-acryloyloxyethyl)imidazolium tetrafluoroborate
(MAHI-BF4 ) [104].
1.4 Composite Polymer Electrolyte

CPEs were discovered in an attempt to overcome disadvantages and limitations
of PEs. Generally, the CPEs are prepared by dispersing inorganic fillers such as
insulative ceramic fillers (Al2 O3 , SiO2 , TiO2 , etc.), ferroelectric ceramic fillers
(BaTiO3 , PbTiO3 , LiNbO3 , etc.), clay, carbon nanotubes (CNTs), and powder of
fast ionic conductors into the polymer matrix [80, 105, 106], which can improve
the mechanical properties and ionic conductivity of PEs [107–109]. Also, the
fillers can increase the ionic conductivity by percolating interfacial effect, i.e.
anions adsorb on the surface of fillers due to Lewis acid–base character and then
promote dissociation of ion pairs, leading to increase interfacial ionic conductiv-

ity. Another reason for improvement of ionic conductivity by the fillers is thought
to be due to a reduction in the crystallinity of the polymer–salt system because
the nanoparticles can reduce crystallinity [110–112]. Accordingly, particle size,
content, and surface functional groups of fillers are critical factors to determine
the properties of the CPEs.
A novel PE that was PEO-based incorporated with inert ceramic fillers such as
Al2 O3 , TiO2 , and SiO2 was reported as a successful approach to enhance ionic
conductivity [113, 114]. Figure 1.15 depicts an image of the Arrhenius plots of
P(EO)8 LiClO4 + 10 wt% ceramic nanoparticle electrolyte during cooling. In the
filler-free electrolyte, an inflection point was observed around 84 ∘ C. This was
attributed to the crystallization of PEO polymer. On the contrary, the inflection
point did not appear in the electrolytes containing TiO2 or SiO2 filler. The fillers
prevented the crystallization of PEO polymer and helped to keep high conductive
amorphous phase. As a result, the filler containing PEO polymer exhibited high
ionic conductivity.
The amorphous state of PEO polymer was stable over 60 days at 30 ∘ C by the
addition of filler. The fillers stabilized the high conductive amorphous state at
ambient temperature for a long time. Similar behavior was also observed in
Al2 O3 -added PEO-LiCF3 SO3 composite electrolyte [72, 115].
The addition of fillers can also enhance the iconic conductivity of
PEO-PVdF blend PE [116]. Yoon et al. fabricated a composite electrolyte
based on PEO-PVdF–LiClO4 –2 wt% silica aerogel. Highest conductivity
of 1.7 × 10−4 S cm−1 was obtained at 30 ∘ C in the composite composed of
PEO:PVdF = 3 : 1 and polymer:salt = 6 : 1. The ionic conductivity decreased with
an increase of silica aerogel content owing to degradation of mobility caused
by the aggregation of silica aerogel particles. The surface functional groups
on the fillers affect properties of the CPEs. It was reported that addition of
acid-modified nano-SiO2 reduced the interfacial resistance and prevented
dendrite formation of Li metal significantly [117].
Among the nanosized ceramic fillers, TiO2 was thought to be the best
candidate for the CPEs. Lin et al. studied the effects of particle size of TiO2
on ion transport properties of PEO-based composite electrolytes [118]. It was
Figure 1.15 Arrhenius plots of the ionic 84 °C

conductivity of P(EO)8 LiClO4 .
Conductivity
With filler
Without filler
1/T
found that the ionic conductivity increased with a decrease in the particle size
of TiO2 . The conductivity of 1.40 × 10−4 S cm−1 was obtained for PEO–10 wt%
LiClO4 –5 wt% TiO2 (3.7 nm) electrolyte. The transference number also increased
from 0.21 to 0.51 by the addition of TiO2 . This result indicated that nanosized
TiO2 particles in the PEO-LiClO4 matrix formed a new pathway for Li ion trans-
port. It is thought that TiO2 –Li+ interaction changed the Li ion environment
and provided a fast Li ion-conducting pathway at the interface between the
fillers and the polymer [119].
A highly conductive layer on the surface of filler particles is created by an
interaction between the filler and cations. Therefore, ferroelectric ceramic fillers
are expected to interact with the cations easily owing to the permanent dipole of
the ferroelectric ceramic materials, resulting in enhancement in ionic conductiv-
ity [120]. Sun et al. studied electrochemical properties of composite electrolytes
based on PEO, Li salts (LiClO4 , LiBF4 , LiCF3 SO3 , and LiN(CF3 SO2 )2 ), and
ferroelectric ceramic materials (BaTiO3 , PbTiO3 , and LiNbO3 ) [121]. The results
showed that the ionic conductivity was greatly enhanced by only a small amount
of ferroelectric filler addition. The highest ionic conductivity was obtained for
2 wt% ferroelectric BaTiO3 addition. Also, it was found that the enhancement
in ionic conductivity was affected by anions of the Li salt. The enhancement
in conductivity was highest in ClO4 − anion. On the contrary, no enhancement
was observed in the composite with LiCF3 SO3 salt. This enhancement of
conductivity can be explained by the association tendency of anions with Li
ions and the spontaneous polarization of the ferroelectric ceramics due to their
particular crystal structure.
The usage of layered clays such as montmorillonite (MMT) and hecorite
as fillers has also been reported [122, 123]. The layered clay can contain
cations due to intercalation reaction. It was reported that the ionic conduc-
tivity of PEO–LiTFSI composite containing 10 wt% MMT was 3.22 × 10−4
and 2.75 × 10−5 S cm−1 at 60 and 25 ∘ C, respectively [124]. Li-intercalated clay
(bentonite) also increased the ionic conductivity about one order of magni-
tude when it was incorporated into PEO-based PE [125]. CNT has also been
researched as fillers to enhance the ionic conductivity of PEs. The strong affinity
between CNT’s electron cloud and cation promotes salt dissociation, resulting
in high conductivity. However, compositing CNTs with the PE may enhance the
electronic conductivity due to high electronic conductivity of CNTs. Therefore,
Tang et al. prepared CNT packaged in insulating clay for nanofiller. This hybrid
nanofiller can block electron conduction in CNT and eliminate the risk of
increased electronic conductivity of CPEs. This hybrid filler could increase the
ionic conductivity of PEO-LiClO4 electrolyte (Figure 1.16) [126]. The highest
conductivity was obtained for PEO-LiClO4 containing 10 wt% clay–CNT hybrid
filler.
Inorganic ceramic solid electrolytes, namely, fast ceramic ionic conductors, are
also considered as promising fillers because it can provide another pathway for
ionic transport (Figure 1.17).
The CPEs with many Na superionic conductor (NASICON) type ionic
conductors with the general formula of LiM2 (PO4 )3 (M = Ti, Ge, Sr, Zr, Sn,
etc.) (Figure 1.18) have been investigated in the past decade [127]. Among the
–2.5
Without filler
–3 5% clay
10% clay
–3.5 5% clay-CNT
10% clay-CNT
Log σ (S cm−1)
–4 15% clay-CNT
–4.5
–5
–5.5
–6
–6.5
2.8 3 3.2 3.4
(a) 1000/T (K)
1.0E–4
Ionic conductivity at 25 °C
1.0E–5
(S cm−1)
1.0E–6
1.0E–7
0 2 4 6 8 10 12 14 16
(b) Clay-CNT content (%)
Figure 1.16 (a) Ionic conductivity of PEO-based composite electrolytes and (b) ionic
conductivity of PEO-based composite electrolyte with various contents of the hybrid filler.
Polymer Ceramic soild

electrolyte Interfacial ionic
electrolyte filler
conduction
M+ Ion conduction in
Ion conduction in solid electrolyte
amorphous polymer
M+ M+
Filler surface
Figure 1.17 Three conduction pathway in composite electrolyte with inorganic solid
electrolyte filler.
Figure 1.18 Crystal structure of

NASICON-type solid electrolyte.
a
b
NASICON-type ionic conductors, Li1.5 Al0.5 Ge1.5 (PO4 )3 (LAGP) has been of par-
ticular interest because of its wide electrochemical window and relatively high
ionic conductivity. Solvent-free composite electrolyte comprising LAGP and
PEO–LiClO4 has been studied [128]. The electrolyte possessed high mechanical
strength and is free standing. By addition of ion-conductive LAGP powder into
the PEO-LiClO4 PE, the ionic conductivity was improved. The all-solid-state
LiFePO4 /Li cell assembled with the composite electrolyte demonstrated a good
cycle stability at 55 ∘ C. Garnet-type solid electrolytes, Li7 La3 Zr2 O12 (LLZ),
and its derivatives have also been paid much attention as composite for solid
electrolyte due to their high chemical stability, high ionic conductivity, and
wide electrochemical window [129–131]. The structure of LLZ is depicted
in Figure 1.19. The framework of LLZ garnet is composed of dodecahedral
LaO8 and octahedral ZrO6 . The CPEs composed of LLZ and PEO–LiClO4
ZrO6 Figure 1.19 Structure of

LLZ.
c b LaO8
Li
References 17
matrix showed high ionic conductivity of 4.42 × 10−4 S cm−1 [132]. Furthermore,
the charge and discharge properties of Li/LiNi0.6 Co0.2 Mn0.2 O2 cell using the
composite electrolyte were better than those of pure PEO membrane.
The sulfide electrolytes have extra high ionic conductivity and wide electro-
chemical window. The addition of sulfide electrolytes into the polymer matrix
has also been studied. Li10 GeP2 S12 (LGPS) was incorporated into PEO-LiTFSI
matrix [133]. The composite electrolyte with 1 wt% LGPS exhibited the highest
conductivity of 1.21 × 10−3 and 1.18 × 10−5 S cm−1 at 80 and 25 ∘ C, respectively.
1.5 Summary
Recent researches on PEs for Li battery are described. The battery using PEs has a
lot of advantages such as their structural flexibility and high safety. The researches
on PEs have focused on the increase in ionic conductivity and improving mechan-
ical strength, but a compatibility of the PEs with electrode materials, which is
another critical property, has not been extensively studied. The compatibility,
particularly the interface between electrode materials and the PEs during elec-
trochemical reactions, should be studied in nanoscale. The characterization of
the interface and a development of the characterization technique for this type
of study will promote the development of Li batteries using PEs.
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23
Impedance Spectroscopy in Polymer Electrolyte

Characterization
Mohamed Abdul Careem 1 , Ikhwan Syafiq Mohd Noor 2 , and Abdul K. Arof 1
1 Centre for Ionics University of Malaya, Department of Physics, Faculty of Science, University of Malaya,
50603 Kuala Lumpur, Malaysia

2
Physics Division, Centre of Foundation Studies for Agricultural Science, Universiti Putra Malaysia, 43400 UPM
Serdang, Selangor Darul Ehsan, Malaysia
2.1 Introduction
The resistance to the passage of an alternating current (ac) in a material is gen-
erally called electrical impedance or simply impedance. The impedance concept
was first introduced by Oliver Heaviside in the 1880s in respect of electrical cir-
cuits [1]. The concept was further developed by A.E. Kennelley with the use of
vector diagrams and complex number representations [2]. Impedance is depen-
dent on frequency of the applied alternating signal. The impedance response of a
system can be measured as a function of frequency and represented in a complex
plane with frequency as an implicit variable similar to Argand diagrams in math-
ematics. Hence, the term impedance spectroscopy (IS) can be used for analysis of
impedance of a system as a function of frequency. The IS as a technique to study
electrochemical behavior of materials was introduced in the early 1900s [3]. The
technique is still being developed and has gained wide acceptance now. Since its
introduction, IS technique has undergone tremendous progressive evolution. It
has become an important tool in multidisciplinary areas ranging from materials
science, agriculture, and medical fields. IS is a powerful technique in materials
research and for studying electrochemical systems and processes.
2.2 IS: Principal Operation and Experimental Setup

2.2.1 Basic Principles of Impedance Spectroscopy
According to Ohm’s law, electrical resistance in the circuit element is the ratio
between the voltage applied and the current flow across that element. This widely
known relationship is limited to only ideal resistor that is independent on fre-
quency. In reality, the circuit elements are more complex that limits the function
Polymer Electrolytes: Characterization Techniques and Energy Applications,

First Edition. Edited by Tan Winie, Abdul K. Arof, and Sabu Thomas.
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2020 by Wiley-VCH Verlag GmbH & Co. KGaA.
24 2 Impedance Spectroscopy in Polymer Electrolyte Characterization
of direct current (dc). Therefore the use of impedance is more convenient to

determine the electrical resistance of a material.
Impedance spectroscopy is based on measuring the impedance “feedback” of
a material or an electrochemical system or process to a small ac signal. Since
the ac signal is frequency dependent, the resulting impedance response also will
be frequency dependent. Impedance is a complex quantity and therefore can be
written in terms of its real and imaginary parts. The real and imaginary parts can
be calculated from the phase shift between the applied signal and the current
through the material and magnitude of the impedance. From the phase shift, it is
possible to know how resistive, capacitive, or inductive the material, system, or
process can be.
In the IS technique, a small alternating (e.g. sinusoidal) voltage of a few mil-
livolts is applied across a sample. Current through the sample is measured. The
small applied signal v(t) ensures that the current response i(t) to the alternating
voltage is linear or pseudo-linear. Thus, the frequency of is also the same as
that of the voltage applied, but is phase shifted. The voltage to current ratio,
i.e. v(t)/i(t), is the complex impedance of the sample and noted as Z. Since v(t)
and i(t) differ with frequency, impedance is therefore frequency (f ) or angular
frequency (𝜔) dependent. A spectrum of Z versus f (𝜔) can be obtained for the
frequency of choice.
Suppose a small ac voltage represented by Eq. (2.1) is applied to a sample sand-
wiched between two electrodes as shown in Figure 2.1.
v(t) = vo sin 𝜔t (2.1)
Here vo is the maximum voltage and 𝜔 = 2𝜋f is the angular frequency of the ac
signal.
The resulting ac current flowing through the sample is given by
i(t) = io sin(𝜔t + 𝜃) (2.2)
where 𝜃 is a phase difference between i(t) and v(t). Here the current is ahead of
voltage by 𝜃 as shown in Figure 2.2.
The impedance of the sample is given by
v(t) vo sin 𝜔t
Z= = (2.3)
i(t) io sin(𝜔t + 𝜃)
Z is a function of frequency and has a magnitude of
v
|Z| = o = Zo (2.4)
io
and a phase angle 𝜃. Both Zo and 𝜃 are frequency-dependent quantities.
v(t) Figure 2.1 A sample with an ac signal

applied across.
~
i(t)
Sample
Figure 2.2 Pictorial v(t)

representations of an ac
voltage and an ac current. i(t)
Here the current is ahead of t
the voltage with a phase
difference of 𝜃.
θ = phase shift
Figure 2.3 Complex impedance plot. y
Imaginary Z
|Z|
Z′′
θ
x
Z′ Real Z
Generally ac impedances are represented by Z(𝜔), which is a complex quantity.

Hence, impedance has real Z′ (𝜔) and an imaginary Z′′ (𝜔) component. Then
√
Z(𝜔) = Z′ (𝜔) + jZ′′ (𝜔), j = −1 (2.5)
Here the real part, Z′ (𝜔), and imaginary part, Z′′ (𝜔) of Z(𝜔), are respectively given
by
Z′ (𝜔) = |Z| cos 𝜃 and Z′′ (𝜔) = |Z| sin 𝜃 (2.6)
The phase angle of Z(𝜔) is given by
[ ′′ ]
Z (𝜔)
𝜃 = tan−1 (2.7)
Z′ (𝜔)
The magnitude of Z(𝜔) is given by
√
|Z| = [Z ′ (𝜔)]2 + [Z′′ (𝜔)]2 (2.8)
All these quantities are pictorially illustrated in Figure 2.3. Some people prefer to
use Zr and Zi to represent the real part Z′ and imaginary part Z′′ , respectively.
2.2.2 Impedance Spectroscopy (IS) Technique

The conventional IS technique involves the measuring Z as a function of fre-
quency f (𝜔 = 2𝜋f ) over a wide frequency range for a sample and plotting of Z(f )
against f in the form of Z′′ (f ) against Z′ (f ) for various f . The resulting graph is
called a complex impedance plane plot or an impedance plot. Sometimes the plot
is erroneously referred as a Nyquist plot, a term strictly applicable to electronic
circuits. Such a plot can be used to evaluate the electrical or electrochemical
parameters/processes of the system under study.
8 Figure 2.4 A typical impedance plot.
6
–Z′′ (k Ω)
R
0
0 2 4 6 8
Z′ (k Ω)
If Z(𝜔) has a magnitude |Z| and phase angle −𝜃, it can be as a complex function
in the form
Z(𝜔) = |Z|e−j𝜃 = |Z|[cos 𝜃 − j sin 𝜃] = Z′ (𝜔) − jZ′′ (𝜔) (2.9)
′′ ′
Then −Z (𝜔) is plotted against Z (𝜔) to obtain the impedance or Nyquist plot.
An example of such a plot is shown in Figure 2.4.
In Figure 2.4, the horizontal axis represents the real impedance, Z′ (𝜔). The ver-
tical axis represents the imaginary impedance, Z′′ (𝜔). The intercept of the plot
with the Z′ axis corresponds to the resistance R of the sample. The vertical axis
corresponds to the reactance X of the sample. The plot shown in Figure 2.4 corre-
sponds to simple systems. Some systems may have more complicated impedance
plots as will be discussed later on.
2.2.3 Electrical Conductivity of a Sample

For a sample in the form of a disc, cylinder, or film, the resistance can be written as
L
R=𝜌 (2.10)
A
where 𝜌 represents the resistivity of the material, L is the length or thickness
of the sample, and A is the cross-sectional area of the sample. The electrical
conductivity, 𝜎 of the sample is given by
L∕A
1
𝜎= = (2.11)
𝜌 R
where L/A is the cell constant. Since R can be obtained from IS plot and L and A
are known, thus 𝜎 can be determined.
2.2.4 Conditions Necessary for IS Measurements

From the experimental point of view, three fundamental conditions must be ful-
filled in order for the impedance measurement data to be valid.
0
Current (×10–4 A)
Current (×10–4 A)
–2
–4
–6
–8
10 20 30 7.42 9.35
Potential (mV) Potential (mV)
Figure 2.5 Example of a small signal that fulfills the linearity condition of an I–V response.
(i) Linearity:
The system under study must behave linearly under measuring conditions.
For this, the applied ac amplitude must be small so that the response of the
sample is linear or assumed to be linear.
The size of signal used depends on the sample under investigation. Signal
must be small enough to produce a linear response and at the same time it
must be big enough to measure the response. An example is illustrated in
Figure 2.5 in which the solid curve represents the I–V response of a sample
and the superimposed small signal that can be assumed to be linear is applied
at a dc bias voltage. Usually ac signals of around 10–20 mV are used. For most
IS measurements, signals are applied with no dc bias.
Whether the ac signal chosen for a particular measurement has satisfied
the linearity condition or not can be tested practically by changing the
magnitude of the signal applied and making sure that the impedance
measured remains same. Theoretically the linearity can be checked using
Kramers–Kronig (KK) transformation relations. On using these relations,
the real and imaginary components of impedance must transform correctly
into one another [4].
(ii) Stability:
The state of the sample or system under study should not change (signif-
icantly) during the acquisition of the data. Hence, it is essential to choose
the appropriate frequency range and measurement conditions. Generally the
experimental duration for impedance measurements is determined by the
low frequency limit chosen. Most electrochemical systems are unstable due
to corrosion of electrodes, adsorption or formation of oxides on the elec-
trodes, discharge of the device, changes in the electrochemical interface, etc.
Therefore, precautions must be taken to avoid such changes taking place dur-
ing the measuring period.
(iii) Causality:
The measured ac response of the system must be directly correlated to the
applied ac signal only. Therefore, precautions must be taken to avoid outside
interference to the sample response so that the observed response is corre-
lated to the applied ac signal only. In many situations it is necessary to shield
the sample cell to avoid interference from outside sources.
2.2.5 Impedance Plots of Simple Circuits

2.2.5.1 A Pure Resistance, R
Consider a resistor with a resistance R. Since R is a constant quantity independent
of frequency, its complex impedance Z(𝜔) will be R for all values of f or 𝜔. Hence
Z(𝜔) will have a magnitude |Z| = R and a phase angle 𝜃 = 0. Thus for all values 𝜔,
Z ′ (𝜔) = R and Z′′ (𝜔) = 0. Hence, the impedance plot is a point on the real axis
at Z′ = R as shown in Figure 2.6.
2.2.5.2 A Pure Capacitance, C

Consider a capacitor with a capacitance C. Its complex impedance Z(𝜔) is
given by
1 j
Z(𝜔) = =− (2.12)
j𝜔C 𝜔C
Hence the Z′ (𝜔) and Z′′ (𝜔) can be written as
1
Z′ (𝜔) = 0 and Z′′ (𝜔) = − (2.13)
𝜔C
Therefore, Z(𝜔) = Z′′ (𝜔), which varies with frequency. As 𝜔 increases, Z′′ (𝜔)
decreases. The impedance plot will consist of points on the Z′′ -axis with each
point corresponding to the frequency concerned. The impedance plot will be
vertical line along the Z′′ -axis as depicted in Figure 2.7. The arrow indicates the
–Z′′ Figure 2.6 Impedance plot of a resistor.

R
R
Z′
Figure 2.7 Impedance plot of a capacitor. –Z′′

C
Z′
direction of increase in frequency values. It should be noted that the Z′′ values
are negative when capacitances are involved and that is why the −Z′′ is used for
the y-axis.
2.2.5.3 R and C Connected in Series

If a resistor of resistance R and a capacitor of capacitance C are connected in
series, the total impedance of the system is obtained by adding the impedances
of R and C as
j
Z(𝜔) = R − (2.14)
𝜔C
Hence,
1
Z′ (𝜔) = R and Z′′ (𝜔) = − (2.15)
𝜔C
The resulting impedance plot will have the characteristics both of a pure resis-
tance and a pure capacitance. Hence the impedance plot becomes a vertical line
at Z ′ = R, parallel to the Z ′′ -axis as shown in Figure 2.8.
Figure 2.8 Impedance plot of a resistor and –Z′′ R C

capacitor connected in series.
Z′
2.2.5.4 R and C Connected in Parallel

If a resistor of resistance R and a capacitor of capacitance C are connected in
parallel, the total impedance of the combination Z(𝜔) is given by
1 1 1 1
= + 1 = + j𝜔C (2.16)
Z R ∕j𝜔C R
Hence,
R
Z(𝜔) =
1 + j𝜔RC
R(1 − j𝜔RC)
=
(1 + j𝜔RC)(1 − j𝜔RC)
R(1 − j𝜔RC)
=
1 + (𝜔RC)2
R j𝜔R2 C
= −
1 + 𝜔2 R2 C 2 1 + 𝜔2 R2 C 2
= Z′ (𝜔) − Z′′ (𝜔) (2.17)
Here,
R
Z′ (𝜔) = (2.18)
1 + 𝜔2 R2 C 2
and
𝜔R2 C
Z′′ (𝜔) = (2.19)
1 + 𝜔2 R2 C 2
Then,
Z′′ (𝜔)
= 𝜔RC (2.20)
Z′ (𝜔)
On eliminating 𝜔 in Eqs. (2.18) and (2.19), it can be shown Z′ and Z′′ are related
by the equation
[ ( )]2 ( )2
R R
Z′ (𝜔) − + [Z ′′ (𝜔)]2 = (2.21)
2 2
The Eq. (2.21) represents a circle of radius R/2 with the center at the point (R/2, 0).
Hence the impedance plot is a semicircle with its center at (R/2, 0) lying on the
Z′ -axis as shown in Figure 2.9.
Maximum point on the semicircle is given by
𝜔m RC = 1 (2.22)
Hence the angular frequency at the maximum point is
1
𝜔m = (2.23)
RC
Here RC is referred to the time constant or relaxation time and is usually denoted
by 𝜏. The time constant corresponds to a single relaxation process. From the value
of 𝜔m , C can be evaluated for an unknown circuit. Z′ and Z ′′ axis must have the
same scales to see the semicircular shape. In fact all plots of imaginary against
real responses must have axis with the same scale.
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ship, engined with suitable machinery. Built in London, and installed
with engines by Robert Napier (by the courtesy of whose kinsman,
Mr. James Napier, the illustration is here given), the British Queen
was considered a wonder in her day, and even exceeded the
dimensions of the famous Great Western, costing as much as
£60,000 to build. As will be seen, she is neither brig- nor ship-rigged,
but is a barque. In spite of the hideous old stern of those times and
the old-fashioned square ports, and the medieval custom of stowing
one of her anchors abreast of the fore-mast—a practice which
survived until well into the nineteenth century—her appearance
shows that she was an advance on what had gone before. She had
about seven beams to her length, and her bow gives evidence that
the old Dutch influence was at last being forsaken: it is, in fact, the
transition stage before the clippers modified it still more. The same
long space which we noted in an earlier ship, extending between the
fore- and main-mast to afford room for the engines, will here be
recognised, and the paddle-wheels, unlike those of the early river
craft, are placed about amidships. In designing her with about 40
feet greater length than the Great Western had possessed, the aim
was no doubt to attain not merely sufficient space for passengers,
cargo, engines and ample fuel, but also to be able to wrestle with the
long Atlantic waves, whose average length has been computed at
about 200 feet. Seventy years ago this British Queen was designed
to be 275 feet over all; to-day, the Lusitania is 760 feet thus
measured, and it is this appreciation of the value of length which has
a good deal to do with the evolution of the modern liner from being a
moderate-sized vessel to one of enormous proportions. In her first
voyage from Portsmouth to New York, the British Queen kept up an
average speed for one day of over ten knots, whereas the Great
Western had on her maiden voyage outward-bound averaged about
two knots less. Leaving Portsmouth on April 2nd, 1839, the British
Queen arrived in New York on April 16th, or three days quicker than
the first Royal William had done the journey in the opposite direction
under sail and steam. The British Queen consumed about 613 tons
of coal on the way.
Thus we have seen the steamship arrive at a stage very far from
being merely experimental. We have watched her gradually grow
from her infancy, when she was good only as a tug or river craft, until
now she has shown in the enthusiasm of her youth that she can
stride across the Atlantic. It will be our duty in the following chapter
to indicate how she came to be treated with entire confidence, and to
take her part in the regular routine of the world’s work.
CHAPTER IV
THE INAUGURATION OF THE LINER
It was not to be thought that the achievements which we

chronicled at the end of the preceding chapter would remain without
their immediate results. If such small vessels as the Sirius, propelled
by steam, could cross the Atlantic and return safe and sound; if still
more easily the Great Western had been able to perform the feat
and to show a substantial return on the capital laid out, surely there
was an assured future for steamship enterprise. “What man has
done, man can do,” is an old proverb, the application of which has
led to the founding of those mighty, excellently equipped fleets which
have transformed the trackless, desolate North Atlantic into a busy
thoroughfare, along whose fixed routes every day of the year are
carried thousands of passengers and tons of merchandise from one
continent to the other. Although nowadays there is scarcely a corner
of the world to which a regular line of steamships does not run, yet it
is the North Atlantic that has always been the scene of the greatest
enterprise in steamship development. We could find plenty of
reasons for this if we cared to inquire into the matter. It was not until
the advent of the transatlantic steamship that all the possibilities of
the Tudor voyages and discoveries began to be appreciated fully. A
continent, like a single country, flourishes not merely by its produce
of wealth, but by its exchange thereof. So long as it is separated by
thousands of miles, every fathom of which is fraught with danger and
has to be traversed by sailing ships whose arrival may be weeks or
months late, which may, in fact, never arrive at all, a tight restriction
is kept on the exchange of wealth; stagnation ensues, people travel
as little as possible, and remain ignorant in their own narrow
provincialism. Whereas, to-day, they take every possible advantage
of travel, of voyaging the world over, not merely to exchange wealth
but to exchange ideas, to add to their knowledge, to wipe out their
provincialism.
For this we must thank the coming of the liner.
It was that memorable year of 1838 that set all this going.
Impressed by the obvious advantages which the steamship now
showed for speed and reliability, the Lords Commissioners of the
Admiralty, to whose care was then entrusted the arrangement of
postal contracts, saw that those ancient “coffin brigs” were doomed.
Their lordships forthwith issued circulars inviting tenders for the
carrying of the American mails by steamers. It happened that one of
these circulars fell into the hands of Samuel Cunard, a prominent
merchant of Halifax, Nova Scotia. He had been anything but
disconnected with shipping, for he was the owner of a number of
sailing ships trading between Boston, Newfoundland and Bermuda,
and was agent at Halifax for the East India Company, who in their
time owned some of the very finest sailing fleets that ever put to sea.
And this Samuel Cunard had been one of the shareholders of that
first Royal William which crossed in 1833 from Pictou, Nova Scotia,
to the Isle of Wight. A man of energy and enterprise, he had already
realised that a line of steamers connecting the two continents ought
to become something real, and he had sufficient foresight to see that
this was an opportunity which does not occur many times in a
generation.
Having made up his mind, after reading this circular, the next
thing was to find the money. In Halifax it was not possible to raise the
required capital, so he crossed forthwith to London. But London is
not always ahead of the provinces, and the wealthy merchants
declined to show their financial interest in the scheme. Therefore,
armed with a letter of introduction from the secretary of the East
India Company, Mr. Cunard travelled north to Glasgow, to Mr. Robert
Napier, whose name we have already mentioned as a great Clyde
shipbuilder and engineer. Napier promised to give him all the
assistance possible, and introduced him to Mr. George Burns, and
the latter, in turn, to Mr. David MacIver. Both had an expert
knowledge of the shipping business, and to a Scotch shrewdness
united wide experience and ability to look ahead. As a result, within a
few days the necessary capital of £270,000 had been subscribed,
and an offer was made to the Admiralty for the conveyance of Her
Majesty’s mails once a fortnight between Liverpool and Halifax and
Boston. But the owners of the Great Western, with a ship all ready
for the work, were not going to let so fine a chance slip by without an
effort. They, too, competed for the privilege, though eventually the
organisation with which Cunard was connected was considered to
have made the more favourable tender. This was accepted by the
Government, and a contract for seven years was signed. The three
enterprisers went to their posts—Cunard to London, Burns to
Glasgow, and MacIver to Liverpool, but before matters had taken a
final shape the Government required that the service was to be
carried on by four ships instead of three, that fixed dates of sailings
should be adhered to, and in consideration of all this a subsidy was
eventually granted to the steamship owners of the sum of £81,000
per year. The corporation which we now know as the Cunard
Company was then called the British and North American Royal Mail
Steam Packet Company, and they proceeded to get in hand the
building of those first four steamers of which the Mauretania and
Lusitania to-day are the lineal descendants. These four, then, were
respectively the Britannia, the Acadia, the Caledonia, and the
Columbia. They were all built of wood, all propelled by paddle-
wheels, specially adapted for the transport of troops and stores in
the event of war, with an indicated horse-power of 740,
accommodation for 115 cabin passengers, a cargo capacity of 225
tons, while their dimensions and tonnage differed but slightly the one
ship from the other. Their speed averaged 8½ knots per hour on a
coal consumption of thirty-eight tons a day, the engines in each case
being not unnaturally made by that Robert Napier who had by his
introduction done so much to bring the formation of this company to
a practical conclusion. These vessels were built on the Clyde by four
different builders in the year 1840, but the Britannia was the first that
was ready for service, her measurements being 207 feet long, 34
feet 4 inches wide, and 22 feet 6 inches deep, with a tonnage of
1,154.
Before we go on to outline the marvellous growth which has
been seen under the Cunard Company’s flag, whose history is
practically a history of the Atlantic liner, varied here and there by the
happenings which other rival companies have brought about, it is
both curious and amusing to append the following letter, which has
only quite recently been made public, and which will surprise many
of those who here read it. It is evidence of the remarkable speed at
which events may happen, and men’s minds adapt themselves to
newer conditions. Although Samuel Cunard was part owner of the
first Royal William in 1833, and already three years earlier had
thought over the idea of starting a line of Atlantic steamers, yet it will
be seen that towards the end of 1829 he was not favourably inclined
to the project. Having in mind all that the Cunard Company has done
towards the inauguration of the liner, her continuous improvements,
her safety and her efficiency, it is instructive to read the reply which
was sent at this time to Messrs. Ross and Primrose, of Pictou, Nova
Scotia, who had written to Cunard and Company in regard to
steamship establishment:—
“Dear Sirs,—We have received your letter of the 22nd

inst. We are entirely unacquainted with the cost of a
steamboat, and would not like to embark in a business of
which we are quite ignorant. Must, therefore, decline taking
any part in the one you propose getting up.—We remain,
yours, etc.
S. Cunard and Company.
“Halifax, October 28th, 1829.”
The above letter is now in the possession of Mr. John M. Ross,

of Pictou.
But to return to the first sailing of the new company: the Britannia
started the mail service in no conventional manner. Not merely was
she to throw time-honoured custom to the winds by carrying the
mails by the help of steam, but she dealt another blow to sailor-
conservatism by setting forth on her maiden voyage on a Friday,
which also happened to be the fourth of July, a day commemorative
of another kind of Independence. Of course, the old-fashioned
prophesied that so flagrant a disregard for superstition would spell
disaster; but somehow the Britannia managed to arrive quite safely
at Boston, on July 18th, 1840, after a voyage of just eight hours
beyond a fortnight, though she had touched at Halifax after eleven
days, four hours. The citizens of Boston celebrated the event with
banqueting and wild enthusiasm as the forging—shall we not say?—
of the first of those stronger links which were to bind the two
countries more closely and more securely together. Four years later,
one bitter February, when this same Britannia was hemmed in,
icebound in Boston harbour, the same enthusiasts liberated her by
cutting a canal seven miles long and a hundred feet wide through the
ice, and this entirely at their own expense.
Facing page 102 will be seen an illustration of a model of this
Britannia. Old paintings show her rigged as a barque, with a couple
of ship’s boats in davits on either side, and another hung over the
stern in a manner that will be familiar to those readers who have
seen the American sailing schooners, and some of the Norwegian
craft. The space for boilers and engines still causes that long gap
between the fore- and main-mast that we mentioned earlier. The
square stern, the old-fashioned bows, and her lines generally, show
that this first Atlantic liner was hardly a thing of beauty, if even she is
to be remembered for ever as the first of a new series. Her paddle-
wheels were 28 feet in diameter, and had 21 floats, which measured
8 feet by 2.8 feet. The mean draught of this little ship was 16.8 feet.
Her engines were of the side-lever type, of course, the making of
which Napier understood so well. Steam was generated in four
boilers with twelve furnaces, and there were two cylinders. As we
have already dealt with the working of these engines we need do
little more than ask the reader to turn to the next page, where he will
find a sectional model of an engine very similar to that which was
installed in these first four Cunard liners. The non-technical reader
will find this some considerable help in following our previous
references to engines of this type, and the section of the cylinder at
the extreme left-hand of the picture will be found illustrative of the
working of the piston inside the cylinder. As we are writing the story
of the steamship, and not a history of engineering, we need not
digress from our historical continuity, and we can now pass on to two
other steamers built in 1841, for the Royal Mail Company. In the
illustration facing this page will be seen the Teviot and Clyde
respectively, the former being of 1,793 tons, the latter of 1,371 tons.
We have already spoken of the founding of the General Steam
Navigation Company, and shall speak presently of the Peninsular
and Oriental Company. Following the precedent set by the Cunard
Company, the Royal Mail Line, on March 20th, 1840, entered into an
agreement with the British Government by which the Royal Mail
Steam Packet Company were “to provide, maintain, and keep
seaworthy, and in complete repair and readiness, for the purpose of
conveying all Her Majesty’s mails, a sufficient number (not less than
fourteen) of good, substantial, and efficient steam vessels, of such
construction and strength as to be fit and able to carry guns of the
largest calibre now used on board of Her Majesty’s steam vessels of
war, each of such vessels to be always supplied with first-rate
appropriate steam engines of not less than 400 collective horse-
power, and also a sufficient number—not less than four—of good,
substantial, and efficient sailing vessels, of at least 100 tons burthen
each.” Previous to this agreement, the Government had conveyed
the mails to the West India Islands in gun-brigs, and in those days
we must not forget that the seas were not the free highways that
they are now.
THE “TEVIOT” AND “CLYDE” (1841).
From a Painting in the Victoria and Albert Museum.
SIDE-LEVER ENGINE.
From the Model in the Victoria and Albert Museum.
The contract was for ten years, and to take effect from
December 1st, 1841. The fourteen ships were all named after British
rivers, and many readers will be aware that this custom of the
company has continued ever since, although in some cases the
names of foreign rivers have also been thus employed. Some of
these vessels were built at Northfleet on the Thames, others
(including the Teviot and Clyde) were built at Greenock, others at
Dumbarton, Leith, and Cowes. The Lords of the Admiralty stipulated
that the vessels should be built under their supervision, and a naval
officer was put in charge of the mails on each steamer, and carried
out a sort of supervision of the ship’s affairs, a boat’s crew being
always at his service when the mails were being taken aboard or
disembarked. The illustration facing page 112 shows the launch of
the Forth at Leith in 1841. This picture, which is taken from a
contemporary painting, is worthy of perusal, as showing the close
resemblance between the mercantile marine and naval architecture
of the period. Strength rather than slim beauty, massiveness rather
than fineness, formed the keynote both in the steam and sailing
ships of that time. In the same year had already been launched the
Thames from Northfleet, and in the following year that vessel
inaugurated this new service, setting forth, like the older packets,
from Falmouth. The voyage from there to the West Indies took about
eighteen days, but exceptional runs were done in seventeen days.
This new steamship departure was an undoubted success, and
the Admiralty admitted that even the Government, with all its naval
resources, could not have succeeded so well as this private
company in getting together and ready for sea in so short a time so
many large and well-equipped new steamers. Financially this meant
a very large outlay, and there was not much less than a million of
money expended on this first fleet. It should be stated, however, that
the Government subsidised the concern by a grant of £240,000 per
annum. Presently Falmouth gave way to Southampton as the
headquarters of the Royal Mail fleet. To-day there are so many big
liners calling at the Hampshire port, and there is at all times of the
day so continuous a procession of all kinds of large steamships, that
it is difficult to realise that in those days this was comparatively a
small port.
It was only natural that, as soon as ever the West Indian service
should have proved itself successful, a branch should be extended
to the South American Continent. In 1846, therefore, the company
organised a means of transit by mules and canoes across the
Isthmus of Panama, which were in 1855 superseded by the Panama
Railroad. Although we are departing from our historical sequence in
the development of the steamship, it is convenient here to sketch
very rapidly the progress of the Royal Mail Line farther still, for the
evolution of a steamship company is not necessarily that of the
steamship. A small company may be famous for having one or two
ships that are always the last word in modern ship-building and
marine engineering; a large company may possess a considerable
aggregate of tonnage, but its ships may be behind the lead of others
in improvements. For the moment we are considering the enterprise
which enabled the early steamships to penetrate to distant, over-sea
territories where the Elizabethan sailors had gone in their slow-going
ships scarcely three centuries before.
LAUNCH OF THE “FORTH” (1841).

By Permission of the Royal Mail Steam Packet Co.
THE “WILLIAM FAWCETT” AND H.M.S. “QUEEN” (1829).
From the Painting by Frank Murray in the possession of the Peninsular & Oriental
Steam Navigation Co.
In 1851 the Royal Mail Line service to South America began,

and about 1869 those steamers which had stopped short at Brazil,
and served the Argentine by transfer, continued their voyage to
Buenos Ayres. In the course of time it was only to be expected that
the heavy subsidy should be reduced. It dwindled down to £85,000 a
year, and was finally allowed to vanish altogether as recently as
June, 1905. Since then the Royal Mail Company has extended its
West Indian service to New York via Jamaica. During the Crimean
War some of the vessels of this line did good service as transports,
and even more recently still during the South African War. It was on
one of the vessels of this line that, during the American Civil War, an
incident occurred which was of international importance. The ship
which was brought so prominently into notice was the Trent, that had
been launched at Northfleet. Some readers will doubtless remember
that Messrs. Slidell and Mason were forcibly taken from this vessel
by a Federal man-of-war, and that Lord Palmerston, by his action in
the matter, set forth that valuable doctrine, still recognised, that an
individual on board a British ship is as safe from foreign interference
as if he were on British soil.
It was in 1840, also, that the Pacific Steam Navigation Company
was granted its charter, and its history is, so to speak, a complement
B
of that of the Royal Mail Company. After the latter had extended its
service to the Isthmus of Panama, and established a means of
transit across to the western coast, it was evident that the Pacific
littoral was ready for the steamship, and this the Pacific Steam
Navigation Company now supplied. In the olden days the sailing ship
had been the only means of doing this, but that meant braving the
terrors of Cape Horn, as many of the surviving sailing ships do to this
day. But the enterprise of the Royal Mail Line on the one side of the
narrow neck separating North from South America, and the co-
operation of the Pacific Steam Navigation Company on the other,
together with the intervening land-journey, brought the inhabitants of
the Southern Pacific much nearer to Europe. The Panama Canal,
which is promised for opening in 1915, was thus foreshadowed.
Sending round its two steamers, the Chile and Peru, to the west
coast, the Pacific Company opened up a new sphere of commerce,
and these two steamships were the very first steam-propelled craft
that ever passed through the Straits of Magellan.
B
The Royal Mail Co. has now absorbed the
Pacific Steam Navigation Co.
The foundation of the Peninsular Company dates back as far as

1837. Even a year or two before then its ships had commenced
running to the Peninsula, but at the time mentioned a regular service
of mail packets from London to Lisbon and Gibraltar was instituted.
Here again we find the existence of a contract between the Admiralty
and a steamship company for the carrying of the mails, but it was not
until 1840 that the line was extended to Malta and Alexandria, and
was incorporated by Royal Charter under the now well-known title of
the Peninsular and Oriental Steam Navigation Company, with a view
to carrying on operations in the Far East. The lower illustration facing
page 112 shows the first steamship owned by the Peninsular
Company, a little paddle vessel of only 209 tons. This was the
William Fawcett, which was built in the year 1829. She measured 74
feet long, only 16 feet wide, developed 60 horse-power, and was
engaged in the trade between England, Lisbon, and Gibraltar. But
the first steamer which the newly incorporated company dispatched
to India, via the Cape of Good Hope, was the Hindostan, a vessel of
1,800 tons, and 500 horse-power. She began her voyage from
England in September, 1842, and her departure was a memorable
event when we consider all that was destined to follow therefrom,
and how certainly it meant the ending of the careers of those fine
East India sailing ships which had been brought to such a high state
of perfection ere steam had appeared on the sea. The Hindostan
was a three-masted vessel with a long bowsprit, “steeved” at a big
angle, setting yards on her fore-mast for fore-sail, topsail and
t’gallant, while her main and mizen were fore-and-aft rigged. She is
interesting as having not one but two funnels, the first being placed
very far forward, just abaft the fore-mast, whilst the other was
immediately in front of the main-mast. The distance between the two
funnels was great, for the purpose already indicated. The Hindostan
was followed by other steamers, and in 1844 the P. and O. Company
undertook a mail service between England and Alexandria, and so
from Suez to Ceylon, Calcutta, and China.
Of course, as yet, there was no Suez Canal, so that, in a manner
similar to that across the Isthmus of Panama, an overland route had
to be instituted for passengers, cargo, and mails across the Isthmus
of Suez. The P. and O. Company had, then, to land their passengers
at Alexandria, and just as canoes and mules had to be employed in
America, so boats and camels were requisitioned in Africa. But it
was a complicated journey, for this “overland” route was mostly an
over-water route. By means of the Mahmoudieh Canal the
passengers and goods were sent from Alexandria to the Nile,
whence they proceeded by steamer to Cairo. From there they
travelled through the desert to Suez. Three thousand camels had to
be employed for transporting a single steamer’s loading; every
package had to be subjected to three separate transfers, and the
inconvenience was indeed considerable. But for nearly twenty years
this system continued.
Steam communication was inaugurated by the company with
Australia in 1852, by means of a branch line from Singapore, and
two years later the service between Suez and Bombay was
absorbed by the P. and O. Company. This had been retained hitherto
by the East India Company in order to keep alive their navy. In 1869,
came the opening of the Suez Canal, and it was essentially the
steamship and not the sailing ship which brought this about,
although the Suez Railway preceded the canal by ten years. It is not
generally known, perhaps, that a continuous waterway had already
existed long years before. In the times of the early Egyptians there
had been a canal which connected the Nile with the Red Sea, so that
ships could circumnavigate Africa and, returning by the
Mediterranean, could come out through the Nile into the Red Sea
again. But the Suez Canal had not been demanded so long as the
steamship remained undeveloped, and even for some time after the
traffic to Australia and New Zealand was principally carried on in
those handsome clipper-ships which were representative of the
finest examples of the sailing ship. It is only by means of the
steamship that it is possible to bring across so many thousands of
miles the great quantities of frozen meat and other perishable foods
which now reach this country, and the Suez Canal certainly assisted
to make this possible. Not merely did the steamship indirectly bring
about the Canal, but the latter increased the steamship’s sphere of
usefulness.
About the time when the Suez Canal was opened the practical
adoption of the compound engine was taking place in the mercantile
marine. This idea had been introduced about 1856 by Messrs.
Randolph Elder and Company, and had been installed in the ships of
the Pacific Steam Navigation Company. In explanation of this system
we may say at once that its great advantage lay in the fact that it
reduced the coal consumption to just about half of what it had been
hitherto in the most economical engines. The principle is based on
the fact that steam possesses elastic properties which can be put to
excellent use. Put simply, the compound engine allows the steam to
enter one cylinder at high pressure, and, after it has moved the
piston, escapes into one (or more) cylinders of larger size, where it
does its work by direct expansion, and so much more work is done
at little expense. The expression “triple expansion,” which frequently
confronts the reader interesting himself in steamships, simply means
that the steam is expanded one stage further. Quadruple expansion
is the same idea pushed still another stage. When about twenty
years ago the triple expansion system was brought in, the steam
pressures were increased from 125 lb. to 160 lb. per square inch,
and so the coal consumption was reduced also. But the triple
expansion had been preceded by the compound and the low
pressure engine, just as it was followed by the quadruple.
The opening of the Suez Canal was not devoid of side issues,
for it took away that monopoly which the P. and O. had enjoyed,
since the world’s steamships now poured in and began to go
eastward and back again. There was difficulty with the Post Office,
who refused to allow the Canal route for the conveyance of mails, on
the ground that it was not so suitable as the Egyptian Railway, and it
was not until 1888, when the charge for carrying the mails had been
reduced by nearly £100,000 a year, that the accelerated mails sent
via Brindisi were transferred to the Canal route, although the heavy
mails had already been carried by it. But the P. and O. were unlucky
in another way. The Mooltan, their first ship to be installed with the
compound engine, in 1860, had proved such a success that several
other steamers of the line were thus fitted, but the result was
disappointing. Although it was quite clear that this type of engine
made for economy, yet it was found unreliable, and in some cases
had to be replaced by less complex machinery.
We have now been able to see steamship lines established and
sending their fleets regularly with passengers, cargoes, and mails to
the uttermost ends of the earth, and we have been able to look
ahead a little so that we shall be free to concentrate our attention
very shortly on that centre of steamship activity the North Atlantic.
Between 1840 and 1860 the Cunard Company had practically a
monopoly of the Atlantic trade. For a time the American clippers
hung on, but as they had ousted the old brigs, even the fastest
sailing vessels were replaced by the steamship. From 1850 to 1858
there was, indeed, some opposition from a steamship company
called the Collins Line, which had been subsidised by the American
Government. This competition was very keen, for both lines were
compelled to put forth the best steamers they could, but in the end
the Collins Line withdrew from the contest.
DESIGNS FOR SCREW PROPELLERS PRIOR TO 1850.

From the Drawing in the Victoria and Albert Museum.
But there was now another force coming in, which was to entirely
alter the character of the liner. Let us trace the evolution of the screw
propeller, which has completely banished the old-fashioned paddle-
wheel from its place in the ocean-going ship, and is rapidly having
the same effect in cross-Channel steamers. We saw that away back
in 1804 John Stevens had crossed the Hudson in a little ship that
was driven along by a screw propeller, but it was not until the year
1836 that the screw was re-introduced. In this year John Ericsson, a
Swedish engineer, obtained a patent for his invention which
consisted of two drums, on whose exteriors were seven helical
blades, the interior of each drum having the three blades which
formed the radii of the circle. Both these drums worked on one axis,
and were placed behind the rudder, and not in front of it as is the
modern propeller. If the reader will turn to the plate facing page 118,
he will see this at the beginning of the second line to the left. The
drums were made to work in opposite directions, the object being to
avoid loss due to the rotary motion already remaining in the water
discharged by a single screw.
Ericsson applied this invention to the Francis B. Ogden, which
was built in 1837. She was 45 feet long, and was driven by a two-
cylinder steam engine with a boiler pressure of 50 lb. The result of
the experiment showed that she could tow a vessel of 630 tons
burthen at 4½ knots against the tide. The following year a larger
vessel, the Robert F. Stockton, was built by Laird Brothers, and
attained a speed of thirteen knots on the Thames, with the tide in her
favour. Afterwards she crossed the Atlantic, but under canvas, and
was turned into a tug as the New Jersey, for work in New York
waters. The illustration facing page 120, which has been lent by
Messrs. Cammell, Laird and Company, Limited, of Birkenhead,
shows her rigged as a topsail schooner under sail and steam. Her
measurements were 63.4 feet long, 10 feet beam, 7 feet deep, with a
register of 33 tons, and engines of 30 horsepower. Although she was
the first screw steamer to cross the Atlantic, yet her voyage is
interesting rather as a fairly daring trip of a small sailing ship than as
proving the reliability of the screw propeller.
But at the same time that Ericsson was working at his idea,
Francis Smith, an Englishman, who was afterwards knighted, was
also engaged at the same problem, though his method of solution
was of a different nature, as will be seen by a reference to the last
illustration on the first line of the plate facing page 118. His patent
was granted in the same year as Ericsson’s, and was tried with
success the year after on the Paddington Canal. Smith was a farmer
at Hendon, and had already experimented with a model driven by
clockwork on a farm pond, just as Fulton had carried out his early
experiments with a clockwork model in a tank. The next step was to
repeat the experiment on a six-ton boat which was driven by a steam
engine, the propeller being, like those of the modern aeroplanes, of
wood. It was while thus experimenting that an interesting accident
happened, for about one-half of the screw thus shown in the
illustration was broken off, and to everyone’s surprise the boat
instantly began to leap forward at a quicker speed. Later the boat
was fitted with a screw having one turn instead of two, and made of
metal instead of wood, and in this small craft Smith cruised as far as
Folkestone. Her speed was 5½ knots.
THE “ROBERT F. STOCKTON” (1838).

Photograph supplied by Messrs. Cammell, Laird & Co., Limited, Birkenhead.
THE “ARCHIMEDES” (1839).
From a Contemporary Print.
From these satisfactory results made by the six-tonner Francis

Smith, sufficient interest was aroused to form a syndicate to test the
proposition commercially, and to purchase Smith’s patents. The
result was that the Archimedes, of 240 tons, was launched from
Limehouse in November, 1838, and fitted with Smith’s screw. It must
be recollected that the same old obstinacy was still very much alive
that had hindered other inventions connected with the ship, and it
was not until the Archimedes had toured round Great Britain, and
steamed across the Bay of Biscay and back without mishap, that
people began to believe in this new method of propulsion. To-day
everyone knows how entirely dominated by the screw the steamship
now is, and that the paddle-wheel belongs almost exclusively to the
excursion passenger steamer.
Of course, Smith’s propeller was very different in expression
from the shape in use to-day, but the last word as to the ideal shape
and size of the screw has even yet to be said. It would be interesting
to detail all the attempts which have been made by different
inventors to deal with the screw, but their name is legion, and our

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Polymer Electrolytes: Characterization

and Applications Arof

Characterization Techniques and Energy Applications

Tan Winie, Abdul K. Arof, and Sabu Thomas

© 2020 Wiley-VCH Verlag GmbH &

All rights reserved (including those of

Print ISBN: 978-3-527-34200-6

Typesetting SPi Global, Chennai, India

Printed on acid-free paper

1 Polymer Electrolytes: State of the Art 1

2 Impedance Spectroscopy in Polymer Electrolyte

2.2.8 Impedance-Related Functions 42

3 Thermal Characterization of Polymer Electrolytes 65

4 Energy in a Portable World 93

5 Insight on Polymer Electrolytes for Electrochemical Devices

6 Polymer Electrolyte Application in Electrochemical

6.5.2.4 EDLCs 172

7 Polymer Electrolytes for Lithium Ion Batteries and Challenges:

8 Polymer Electrolytes for Lithium Ion Batteries and Challenges:

9 Polymer Electrolytes for Supercapacitor and Challenges 231

9.3 Electrolytes for Supercapacitors 239

10 Polymer Electrolytes for Quantum Dot-Sensitized Solar Cells

10.6.7 Quantum Dot-Sensitized Solar Cells Based on Oligomer Gel

11 Polymer Electrolytes for Perovskite Solar Cell and

12 Polymer Electrolytes for Electrochromic Windows 365

12.5.3.1 Solid Polymer Electrolytes (SPEs) 370

Polymer electrolytes resulting from the complexation of polymer with organic

October 8, 2019 Tan Winie

Polymer Electrolytes: State of the Art

Polymers are deﬁned as large molecules or macromolecules, which consist of

Polymer Electrolytes: Characterization Techniques and Energy Applications,

Li+ Li+ Li+

LiCoO2 Non aqueous electrolyte Graphite

Figure 1.1 Li battery.

ions move from cathode to anode in a charge process. In a discharge process, Li

(5) Environmental benign, non-hygroscopic, low cost, and ease of preparation.

Table 1.1 summarizes a comparison of properties of conventional nonaqueous

Table 1.1 Comparison of various properties among nonaqueous, polymer,

Nonaqueous Polymer Ceramics

Conductivity High Middle Low

Based on physical state

Solid polymer Gel polymer Composite polymer Synthetic Natural

Figure 1.2 Classiﬁcation of polymer electrolytes.

1.2 Solid Polymer Electrolyte

Polyethylene oxide (PEO) Figure 1.3 Segmental

Table 1.2 Polymer host generally used in polymer electrolytes.

PEO –(CH2 CH2 O)n – (PEO-HBP)–LiTFSI– 2.6 × 10−4 [18]

Figure 1.4 Schematic Arrhenius plot of 40 °C

Polymer A Polymer B Blend polymer

Figure 1.5 Schematic image of blend polymer.

Polymer A Polymer B Cross-linked polymer

Figure 1.7 Schematic image of the cross-linked polymer.

Polymer A Polymer B Copolymer

Figure 1.8 Schematic image of the copolymer.

CH2 CF2 CH2 CF2 CF2 C

PMMA PVC PVA PAN

CH2 C CH2 C CH2 CH2 CH2 CH

Figure 1.9 Structure of polymer hosts.

1.3 Gel Polymer Electrolyte

plasticizers such as polyethylene glycol dimethyl ether (PEGDME) [68], borate

Table 1.3 Ionic conductivity of various polymer electrolytes with plasticizers.

(PEO)15 /LiTFSI/10 wt% PEGDME >10−3 50 [59]

P(VdF-HFP)/1.0 M LiPF6 /EC + DEC 1.0 × 10−3 RT [76]