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An Introduction to Redox Polymers for
Energy-Storage Applications
An Introduction to Redox Polymers for
Energy-Storage Applications

Ulrich S. Schubert, Andreas Winter, and George R. Newkome

Authors All books published by WILEY-VCH are carefully
produced. Nevertheless, authors, editors, and
Prof. Dr. Ulrich S. Schubert publisher do not warrant the information
Friedrich Schiller University Jena contained in these books, including this book,
Germany to be free of errors. Readers are advised to keep
in mind that statements, data, illustrations,
Dr. Andreas Winter
procedural details or other items may
Friedrich Schiller University Jena
inadvertently be inaccurate.
Germany
Library of Congress Card No.: applied for
Dr. George R. Newkome
British Library Cataloguing-in-Publication Data:
Florida Atlantic University
A catalogue record for this book is available
USA
from the British Library.
Cover Design: Adam Design, Weinheim,
Bibliographic information published by the
Germany
Deutsche Nationalbibliothek
Cover Image: Polyethylene Terephthalate
The Deutsche Nationalbibliothek
© Shutterstock, Fondmotif and chip
lists this publication in the Deutsche
© Getty Images
Nationalbibliografie; detailed bibliographic
data are available on the Internet at <http://
dnb.d-nb.de>.
© 2023 Wiley‐VCH GmbH, Boschstr. 12,
69469 Weinheim, Germany
All rights reserved (including those of
translation into other languages). No part of
this book may be reproduced in any form – by
photoprinting, microfilm, or any other means –
nor transmitted or translated into a machine
language without written permission from the
publishers. Registered names, trademarks, etc.
used in this book, even when not specifically
marked as such, are not to be considered
unprotected by law.
Print ISBN: 9783527350902
ePDF ISBN: 9783527839285
ePub ISBN: 9783527839292
oBook ISBN: 9783527843466

Typesetting Straive, Chennai, India

 v

Contents

List of Abbreviations xi

1 The Emergence of “Redox Polymers” in the Field of Energy-Storage

Applications 1
Study Goals 1
1.1 An Introduction to Battery Systems 1
1.2 Redox Polymers: A Short View on Their Long History 3
1.2.1 The First Era of Redox Polymers 4
1.2.2 The Second Era of Redox Polymers 5
1.2.3 The Third Era of Redox Polymers 9
References 10

2 Polymer-Containing Batteries 17
Study Goals 17
2.1 Introduction 17
2.2 Working Principles 21
2.3 Characterization of Energy-Storage Devices 23
2.3.1 Performance Parameters 23
2.3.2 Charging/Discharging Characteristics 25
2.4 Battery Housing 27
2.5 Solid-State Batteries Incorporating Polymers, as Active Materials 30
2.5.1 Working Principle 31
2.5.2 Material Requirements 33
2.6 Capacitors Incorporating Polymers, as Active Materials 37
2.6.1 Historic Development and Working Principle 37
2.6.2 Material Requirements 41
2.7 Redox-Flow Batteries Incorporating Polymers as Active Materials 44
2.7.1 Working Principle 46
2.7.2 Materials Requirements 47
2.7.3 Aqueous pRFBs 50
2.7.4 Organic pRFBs 51
2.7.5 Suspension RFBs 53
2.8 Concluding Remarks 58
References 59
vi Contents

3 Redox Polymers: Architectures, Synthesis, and Characterization 69

Study Goals 69
3.1 Introduction 69
3.2 Polymer Architecture vs. Battery Cell Performance 70
3.3 Polymer Architectures 72
3.3.1 Homopolymers 72
3.3.2 Copolymers 73
3.3.2.1 Alternating Copolymers 74
3.3.2.2 Statistical and Gradient Copolymers 76
3.3.2.3 Block Copolymers 77
3.3.3 Miscellaneous Polymer Architectures 80
3.4 Polymerization Methods 88
3.4.1 Step-Growth Polymerizations 89
3.4.2 Chain-Growth Polymerizations 91
3.4.2.1 Free-Radical Polymerization 91
3.4.2.2 Controlled Radical Polymerization 92
3.4.2.3 Anionic Polymerization 100
3.4.2.4 Cationic Polymerizations 102
3.4.2.5 Ring-Opening Metathesis Polymerizations (ROMP) 102
3.4.3 Redox Polymerizations 103
3.5 TEMPO-Containing Redox Polymers: A Case Study on How the Backbone
Structure Influences the Polymeric Properties 105
3.6 Characterization of Redox Polymers 109
3.6.1 Cyclic Voltammetry (CV) 109
3.6.2 Electrochemical Impedance Spectroscopy (EIS) 115
3.6.3 Electrochemical Methods Coupled to Other Analytical Techniques 117
3.7 Concluding Remarks 120
References 121

4 Conjugated Polymers in the Context of Energy-Storage Applications 133

Study Goals 133
4.1 Introduction 133
4.2 The Classic Conjugated Polymers at a Glance 137
4.2.1 Polyaniline (Pani) 137
4.2.2 Polypyrrole (PPy) 141
4.2.3 Polythiophene (PT) and PEDOT:PSS 144
4.2.4 Conjugated Polymers for Energy-Storage Applications: General
Considerations 147
4.3 Conjugated Polymers, as Active Materials for Battery Systems 150
4.3.1 Polyacetylene 151
4.3.2 Polyaniline 156
4.3.3 Polypyrrole 164
4.3.4 Polythiophene, PEDOT, and Related Polymers 175
4.3.5 Beyond the “Big Three”: Miscellaneous Conjugated Polymers 182
4.3.5.1 Poly(p-phenylene) 182
 Contents vii

4.3.5.2 Polyindole 184

4.4 Concluding Remarks 187 References 188

5 Redox-Active, Sulfur-Containing Polymers 203

Study Goals 203
5.1 Introduction 203
5.2 Fundamentals of Sulfur-Containing Batteries 204
5.3 Composite Electrodes Incorporating Sulfur and Conductive Polymers
206
5.3.1 Polypyrrole, as the Matrix Polymer 207
5.3.2 Polyaniline, as the Matrix Polymer 210
5.3.3 Polythiophene, as the Matrix Polymer 214
5.3.4 Miscellaneous Matrix Polymers 216
5.4 Sulfur-Containing Polymers in Battery Applications 220
5.4.1 Polymers Containing Disulfide Moieties 220
5.4.2 Polymers Containing Oligosulfide or Polysulfide Moieties 226
5.4.3 Beyond Sulfides: Polymers Containing Other Redox-Active Organosulfur
Moieties 237
5.5 Concluding Remarks 245
References 246

6 Radical-Containing Polymers for Energy-Storage Applications 255

Study Goals 255
6.1 Introduction 255
6.2 Organic Radical Polymers 258
6.2.1 Free-Radical Moieties Used in ORPs 258
6.2.2 Influence of the Backbone Structure on the ORP Properties 262
6.2.3 Influence of the Polymer Architecture on the ORP Properties 263
6.3 TEMPO-Containing Polymers for Energy-Storage Applications 272
6.3.1 TEMPO-Containing Polymers in Solid-State Batteries 272
6.3.1.1 The Success Story of PTMA 272
6.3.1.2 Beyond PTMA: Polymers with Various Backbone Structures 279
6.3.2 TEMPO-Containing Polymers in Flow-Cell Applications 286
6.4 Beyond TEMPO: Other Nitroxyl Moieties in ORPs 292
6.5 Miscellaneous Free-Radical Moieties in ORPs 295
6.6 Concluding Remarks 299
References 301

7 Polymers Equipped with Redox-Active Quinone Moieties 309

Study Goals 309
7.1 Introduction 309
7.2 General Considerations Regarding Carbonyl Compounds, as Active
Electrode Materials 312
7.3 Quinone-Containing Polymers for Energy-Storage Applications 313
viii Contents

7.3.1 Polymers with Quinone Moieties Within the Backbone 315

7.3.2 Polymers with Quinone Moieties, as Side Chains 326
7.4 Polyketone-Containing Polymers for Energy-Storage Applications 330
7.5 Polymers, Which Contain Miscellaneous Redox-Active Carbonyl
Moieties 334
7.5.1 Side-Chain Polymers, Which Contain Redox-Active Carbonyl
Moieties 334
7.5.2 Main-Chain Polymers, Which Contain Redox-Active Carbonyl
Moieties 338
7.6 Concluding Remarks 343
References 344

8 Polyimides and Related Polymers in Battery Applications 349

Study Goals 349
8.1 Introduction 349
8.2 Conventional PIs, as Active Materials 353
8.3 Non-conventional PIs, as Active Materials 363
8.3.1 Polyimides with Non-innocent Moieties Within the Spacer 363
8.3.2 Polyimides with Substituents on the Diimide Core 371
8.4 Conjugated Polymers Incorporating the Core of Diimide Moieties 374
8.5 Multidimensional Polyimides 377
8.6 Miscellaneous Polymer Structures Incorporating Redox-Active Imide
Moieties 380
8.7 Concluding Remarks 383
References 384

9 Polymers Containing Redox-Active Viologen-Type Moieties 391

Study Goals 391
9.1 Introduction 391
9.2 Viologen-Containing Polymers for Solid-State Batteries 393
9.3 Viologen-Containing Polymers for Supercapacitors 403
9.4 Viologen-Containing Polymers for Redox-Flow Batteries 406
9.4.1 Aqueous Redox-Flow Batteries 407
9.4.2 Nonaqueous Redox-Flow Batteries 409
9.5 Concluding Remarks 413
References 414

10 Polymers: Containing Redox-Active N-Heterocyclic Moieties 419

10.1 Introduction 419
10.2 Polymers: Containing Triphenylamine Moieties 421
10.3 Polymers: Containing Redox-Active Carbazole Moieties 435
10.4 Polymers: Containing Redox-Active 5,10-Dihydrophenazine
Moieties 443
 Contents ix

10.5 Polymers: Containing Redox-Active Phenazine Moieties 450

10.6 Polymers: Containing Redox-Active Phenothiazine or Phenoxazine
Moieties 462
10.7 Concluding Remarks 470
References 471

11 Redox-Active Metallopolymers 479

Study Goals 479
11.1 Introduction 479
11.2 Applications Related to Redox-Active Metallopolymers 481
11.3 Ferrocene-Containing Polymers for Energy-Storage Applications 482
11.4 Beyond Ferrocene: Other Types of Redox-Active Metallopolymers 493
11.5 Concluding Remarks 502
References 502

12 Students’ Section: Representative Exercises on Redox Polymers and Their

Usage in Energy-Storage Applications 509
12.1 Introduction 509
12.2 Problems 509
References 519

Index 521
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 xi

List of Abbreviations

1,2‐benzenedithiolate
BHJ bulk heterojunction
BODIPY boron‐dipyrromethene (i.e.
4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene)
BOP benzoxazine polymer
BTMAPV 1,1‐bis‐[3‐(trimethylammonium)propyl]‐4,4‐bipyridinium
tetrachloride

cyclovoltammetry

energy efficiency
xii List of Abbreviations

Faraday constant (9.6485 × 104 C mol−1)

polyacetylene
PAMAM polyamidoamine
PAN polyacrylonitrile
PAni polyaniline
 List of Abbreviations xiii

polystyrene

refractive index
ROMP ring‐opening metathesis polymerization
xiv List of Abbreviations

voltage efficiency
WIS water‐in‐salt
XPS X‐ray photoelectron spectra
ZIB zinc‐ion battery
 1

The Emergence of “Redox Polymers” in the Field of

Energy-Storage Applications*

Study Goals
● Knowledge of the history and development of energy‐storage devices
● Knowledge of important redox polymers from the different eras

1.1 An Introduction to Battery Systems

In recent years, the market for stationary energy‐storage systems has experienced a
tremendous growth – a trend that is expected to continue almost undamped in the
future (Figure 1.1) [1]. Moreover, the society calls for efficient, durable batteries to
satisfy their specific wishes: electric vehicles, laptops, cell phones, wearable/
portable gadgets, Internet of things (IoT), etc. [2]. To fulfill these as well as projected
needs, worldwide research is focused on the improvement and development of
tailor‐made, energy‐storage systems. In this respect, the implementation of new
redox‐active materials represents one approach, and inter‐alia redox polymers have
gained significant attention in recent years [3–7]. Before introducing these materi-
als, the long history of energy‐storage devices will be briefly summarized.
In 1936, numerous items – a ceramic pot, a tube of copper, and a rod of iron – were
found in Khujut Rabu, Iraq. These artifacts have been assigned to the Parthian (150
BC–223 AD) or Sasanian era (224–650 AD). Though their actual meaning still
remains unclear, it has been speculated that they were used as an “energy‐storage
device” (a potential of c. 0.8 V was calculated) [8]. Far later, the term “battery” was
coined by Benjamin Franklin, who in 1748 compared multiple, simultaneously act-
ing “Leyden jars” to an artillery battery [9]. The first electrochemical cell, the
so‐called ”voltaic pile,” was constructed by Alessandro Volta in 1800 [10]. In
subsequent years, various alternatives of this original device have been created.
From these, the Daniell cell (initially reported in 1836) represents the first practical

*Parts of this chapter are taken from a review article published elsewhere: P. Rohland,
E. Schröter, O. Nolte, G. R. Newkome, M. D. Hager, U. S. Schubert, Prog. Polym. Sci.
2022, 125, article ID 101474. Reproduced with kind permission; © 2022 Elsevier B.V.

An Introduction to Redox Polymers for Energy-Storage Applications, First Edition.

Ulrich S. Schubert, Andreas Winter, and George R. Newkome.
© 2023 WILEY-VCH GmbH. Published 2023 by WILEY-VCH GmbH.
2 1 The Emergence of “Redox Polymers” in the Field of Energy-Storage Applications

60
Redox-flow
Lithium-ion (second life)

50 Lithium-ion
Hybrid
Sodium–sulfur
Cumulated number of projects

40 Lead–acid

30

20

10

0
2012 2013 2014 2015 2016 2017 2018
Year

Figure 1.1 Development of the number of large-scale energy-storage projects in Germany

according to battery technology [1]. Source: Figure reproduced with kind permission;
© 2020 Elsevier B.V.

and durable power source, which even became an industry standard and was
employed by the early British electrical telegraph networks [11]. All these batteries
were “wet cells,” which were constructed from glassware and contained liquid elec-
trolytes; however, in many cases, their fragile and dangerous nature prevented any
portable applications, and they were superseded by the portable, hence more con-
venient dry‐cell batteries. In this respect, the Leclanché cell and Gassner’s zinc–
carbon cell – the first real “dry cell” batteries – have to be explicitly named; these dry
cells offered potentials of 1.4 and 1.5 V, respectively [12]. The latter, patented in
Germany in 1886, comprised a MnO2 cathode, which was dipped into the NH4Cl/
ZnCl2 electrolyte paste; the surrounding Zn shell acted as the anode [13].
Along these primary batteries, the secondary batteries, i.e. rechargeable batteries,
were also disclosed in the second half of the nineteenth century. Credit must be given
to Gaston Planté, who in 1859 invented the lead–acid battery, which could be
recharged by applying an appropriate reverse current. This device can certainly be
considered, so far, the most successful secondary battery [14]. Similarly, the first
alkaline battery, the Ni–Cd cell, was invented in 1899 [15]. This cell, which then
entered the market in 1910, offered a much higher energy density to that of the lead–
acid battery but was by far more expensive. Research in the last century culminated
in the development of the secondary lithium‐ion batteries (LIBs) [16, 17]. Though
 1.2 ­Redox dolyRers Sdert VRew do SRVe dong Vrrtdel 3

initially studied by Lewis in 1912, LIBs were brought to market in the 1970s, and,
today, LIBs represent the leading technology in the field of secondary batteries. The
outstanding contributions in LIB research by J.B. Goodenough, M.S. Whittingham,
and A. Yoshino were honored with the Chemistry Nobel Prize in 2019 [18]. Though
LIBs feature distinguished benefits (e.g. low costs, high voltages, increased power
densities), some serious downside aspects have to be noted. Firstly, LIBs are nonelas-
tic and mechanically treated, leading to possible leakage and thus serious haz-
ards [19]. Secondly, cobalt raw materials are required for the LIB fabrication. These
materials are often mined under unsustainable mining conditions, which involve
slavery and/or children labor work [20, 21]. Policies against these unacceptable min-
ing conditions led to a significant increase in the world market prices for cobalt,
which has recently led to overproduction stagnation [22]. Finally, large battery packs
need reliable temperature‐control systems to guarantee safe conditions and to pre-
vent serious hazards, e.g. fires or explosions [23, 24]. These aspects limit the applica-
bility of LIBs, in particular with respect to small and flexible devices (e.g. smart
clothing, and packaging) or other demanding applications, such as grid stabilization
and on‐site storage [4].
Regarding their applications, redox polymers that are derived from organic raw
materials represent one promising alternative approach [3–7]. For example, organic
polymers allow the fabrication of flexible devices, and their use is almost independ-
ent from the fluctuating commodity prices of rare metals. Moreover, polymers can
be synthesized in a wide range of structures and topologies, thus facilitating the
preparation of tailor‐made materials. Today, the field of redox‐active polymers is a
result of eight decades of research, which will be briefly summed up next.

1.2 Redox Polymers: A Short View on Their

Long History

In 1920, Herman Staudinger published his famous article, in which polymers were
defined as “long chains of high molecular weight, which are comprised of cova-
lently linked repeating subunits, the self‐styled monomers” [25]. Though his pro-
posal met heavy opposition at the time, this perception represents the initial spark
that ignited modern polymer science. His fundamental research on macromolecules
and persistence was honored in 1953, when he received the Nobel Prize in
Chemistry [26, 27]. Carothers, a pioneer in the field of synthetic polyesters and poly-
amides, suggested the first classification scheme for synthetic macromolecules, tak-
ing into account the monomer subunit as well as the applied polymerization
technique [28]. This about 90‐year‐old material classification remains contempo-
rary and is still commonly used to rationalize the differences between macromole-
cules synthesized via different polymerization methods (e.g. step‐growth vs.
chain‐growth polymerization). The field of polymer chemistry has experienced a
tremendous evolution, and a range of reliable controlled/living polymerization
techniques (i.e. metathesis, ionic, and radical) has become available, thus enabling
4 1 The Emergence of “Redox Polymers” in the Field of Energy-Storage Applications

H
N
n N n n
H

Polyaniline Polypyrrole Polyphenylene

(PAni, 1834) (PPy, 1915) (PP, 1949)

n
n
S n

Polyacetylene Poly(phenylene Polythiophene

(PA, 1955) vinylidene) (PT, 1980)
(PPV, 1969)

Figure 1.2 Schematic representation of the most relevant parent conjugated polymers
along with their years of discovery. Source: [55], figure 1 (p.1413)/John Wiley & Sons.

the controlled and precise synthesis of polymers of various topologies (i.e. linear,
star‐shaped, and branched). However, Carothers’ fundamental systematics are gen-
erally obeyed in all of these cases.
Concurrent with the fast development in synthesis and characterization, the
focus of polymer research has moved away from the traditional areas of interest
(e.g. tire technology or packaging materials) toward targets, which address the spe-
cial needs of today’s society [29]. Hence, tailor‐made polymers with sophisticated
properties can be offered for a broad range of applications, which have relevance for
today’s daily life style. The long list of potential applications includes photovolta-
ics [30–32], light‐emitting devices [33, 34], electrochromic devices [35], smart coat-
ings [36, 37], self‐healing materials [38, 39], shape‐memory materials [40, 41],
bioimaging [42], carriers in drug/gene delivery [43–48], biodegradable packages
[49, 50], and, last but not least, energy storage [3, 4, 51–53].
In 2000, the Nobel Prize in Chemistry was awarded to H. Shirakawa,
A.G. MacDiarmid, and A.J. Heeger “for the discovery and development of electri-
cally conductive polymers” [18]. Though it is commonly believed that these authors’
collaborative research on polyacetylene (PA) represents the origin of conductive
polymers, their history can actually be traced back to the middle of the nineteenth
century [54]. The first, fully synthetic polymer, polyaniline (PAni), was already
reported by F.F. Runge in 1834 [54–56]. Although pyrrole was discovered in
1834 [56], its oxidative polymerization to afford polypyrrole (PPy), as another type
of conjugated polymer, was noticed by Angeli in 1915 [57]. The parent structures of
the most relevant conductive polymers, along with their years of discovery, are
shown in Figure 1.2. In general, their conductivity results from the (reversible) oxi-
dation or reduction of the parent π‐conjugated polymer.

1.2.1 The First Era of Redox Polymers

Due to the tremendous interest in these previously mentioned materials, nonconju-
gated, redox‐active polymers have been overlooked for some time. The interest in
such polymers with respect to energy‐storage applications can be traced back to the
 1.2 ­Redox dolyRers Sdert VRew do SRVe dong Vrrtdel 5

early days of ion‐exchange polymers, thus defining the first era of redox‐active poly-
mers (Figure 1.3). Cassidy proposed that polymers – in analogy to the proton‐
exchange capacity of acidic polymers – should also be able to exchange electrons, as
another “fundamental particle” [58]. Due to the chaos of the World War II era, this
conception was realized independently by H. Lauth and H.G. Cassidy. Thus, in
1944, Lauth filed a patent for poly(resorcin‐trihydroxybenzene‐formaldehyde)
redox polymers, as water deoxygenation agents [59], whereas Cassidy studied the
applicability of poly(vinyl quinone) (PVQ), as electron‐exchange polymers [60]. In
subsequent work, Cassidy et al. prepared a wide range of PVQ‐type polymers and
studied their properties as well as applicability [61–64]. The following years faced a
scientific dualism between the Cassidy and Manecke groups [65], the latter first
published a study in 1953 on “electron‐exchange polymers” [66]. These authors
mainly focused on polymers, which were equipped with 1,4‐/1,2‐benzoquinone
[67–83] or 9,10‐anthraquinone moieties [84]. These early contributions were sum-
marized by Cassidy in his seminal textbook on “oxidation–reduction polymers” [58]
as well as in numerous review articles [85]. Noteworthy, a range of other redox‐
active polymers was also investigated in this timeframe; these species however
remained virtually marginal. During the first era of redox‐active polymers, some
prominent redox‐active materials, which are commonly used nowadays, were ini-
tially published: polymers containing methylene blue [86], thiol [87], ferrocene [88,
89], indigo [90], and pyridinium or quinolinium moieties [91]. Moreover, Harwood
and Cassidy reported polypeptides, which incorporated 2,5‐dihydroxyphenylalanine
or 3,4‐dihydroxyphenylalanine (DOPA), as redox‐active sites [92]. One further nota-
ble milestone is the synthesis of the first stable, polymer‐bound free N‐radicals.
Henglein and Boysen prepared such a polymer by γ‐irradiation of a precursor poly-
mer [93]; more conveniently, Braun et al. obtained similar polymers by oxidizing the
precursor polymer with PbO2 or Ag2O2 in solution [94]. In the same context, the first
report of poly(TEMPO methacrylate) (PTMA), as a nitroxide‐containing polymer, is
worth mentioning (TEMPO: 2,2,6,6‐tetramethyl‐piperidinyloxy‐4‐yl) [95]. Today,
this polymer represents one of most used active materials in organic radical batter-
ies (ORBs) [3, 53, 96].
In summary, the time was not ready for a significant technological breakthrough
during the first era of redox‐active polymers. These materials attracted only interest
from a scientific point of view and their use was devoted mainly in water deoxy-
genation and H2O2 production [59, 97–101]. The first battery, which contained a
redox‐active polymer as an electrolyte, was invented in 1958 [102]; a few years later,
the first secondary LIB using a redox polymer, as cathode, was demonstrated [103].
However, these inventions did not promote the technological breakthrough of redox
polymers and were only on the scientific fringes for many years.

1.2.2 The Second Era of Redox Polymers

The second age of redox polymers, which appeared in the groundbreaking research
of Heeger, MacDiarmid, and Shirakawa, was dominated by the class of π‐conjugated
polymers and notably polymers from the first era almost fell into oblivion. These
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 O
H
N
1965
n
OH
First Li. vs.
1953 redox polymer battery
N N HO
n Manecke n N N

“electron 1957 n
n
OH n
HO OH
n
OH exchanger” DOPA O2N
N
•
NO2
O O
S
n
O O

N
H
N
N
OH N n •
• O
O
1944 1962
1862 Lauth 1955 First polymeric 1967 1979–1980 2003–2004
PANI First redox polymer Thiols radical PTMA PANI, PTh, PPy Radical ploymer batteries

Preliminary work First era Second era Third era

1949 1958 1965 1977 1988 2015

Cassidy First polymer Chinolines, Conductive PEDOT:PSS First PRFB
reinvention of battery pyridines n polymers S
redox polymers O O
n m n m
O O O O
OH OH O O
O NH n

1920 1954 1964 HN SO3

–
N
N
H. Staudinger n Methylene blue Indigos N O
• +
Cl
–
OH OH
“on polymerizations” OH
n m
n
n
HO
H
N +
NH
+ N N
O – –
N S N O Cl + Cl
HN
N
+
–
Cl

Figure 1.3 Timeline with the most noteworthy inventions and scientific milestones in the field of redox-active polymers [4]. Source: Figure
reproduced with kind permission; © 2021 Elsevier B.V.
 1.2 ­Redox dolyRers Sdert VRew do SRVe dong Vrrtdel 7

authors showed that (partially) oxidized PA exhibited a significantly increase in the

electric conductivity when compared to the parent all‐trans‐PA [104]. However, the
initial goal – replacement of Cu by organic polymers in electric wires – had to be
abandoned, and the focus of interest shifted toward an improvement of the poly-
mer’s properties. Recently, Rasmussen summarized the fascinating history of PA;
the reader is referred to this article for a detailed view on this topic [55]. At about the
same time, new redox‐active polymers were synthesized, and the long‐known mate-
rials were rediscovered. For example, Yamamoto et al. [105] as well as Koßmehl and
Chatzitheodorou [106] pioneered the research on polythiophene (PT, Figure 1.2).
Poly(phenylene vinylidene) (PPV) represents one further material, which – similar
to PA – can be doped to achieve electric conductivity; thus, the physical and electric
properties can be tuned via functional groups on the aromatic rings. Noteworthy,
the first polymer‐based, light‐emitting diode (LED), which used PPV as the emissive
layer, was reported in 1989 [107]. This discovery boosted the research in light‐
emitting π‐conjugated polymers for applications in electroluminescent devices.
Since then, a plethora of polymers have been prepared and utilized accordingly [108,
109]; however, a survey of these will not be given within this book. Special credit
goes to Diaz, who not only revisited PPy and PAni but also established electropoly-
merization, as a fast and reliable technique to fabricate conjugated polymer films on
conductive surfaces [110]. Finally, the studies by Diaz et al. on PPy [111–113] and
PAni [114, 115] enabled one to better understand the physical background, which,
in turn, is responsible for the observed phenomena [116–118].
Electropolymerization is a highly versatile method to prepare polymer films
directly on substrates, i.e. processing steps from solution become obsolete; however,
the latter represented a significant restriction, when aiming for post‐synthetic pro-
cessing. At that time, the common redox polymers were barely soluble (particularly
in water) and, thus far, from being easy to process. In 1991, Epstein and coworkers
showed that sulfonated PAni was readily soluble, even in water, thus facilitating its
processability; moreover, the self‐doping effect, due to intramolecular acid–base
reactions, induced electric conductivity [119]. The improved post‐synthetic process-
ability finally enabled the commercialization of redox polymers. The first genera-
tion of commercial products incorporating redox polymers was summarized by
Miller in 1993 [120, 121]. In particular, two rechargeable LIBs must be highlighted
in this context. In 1987, Bridgestone/Seiko began selling 3 V coin cells, which
contained
­ PAni and LiBF4, as cathode material and electrolyte, respectively
(Figure 1.4a) [122, 123]. The Varta/BASK coin cell contained partially oxidized (i.e.
p‐doped) PPy, as the active material [124]. Miller pointed out that these batteries
had lower energies than the conventional batteries available at that time, e.g. NiCd
batteries, but could be kept longer in the charged state, hold their charge longer, and
were environmentally more compatible [121]. However, these batteries could not
compete with e.g. the ones developed by Valence Technologies, which instead
utilized a Li+‐conductive polymer (interestingly, in 1992, Motorola ordered $108
worth of this battery [125]). At least in the case of Bridgestone/Seiko battery, their
sale was discontinued after only five years.
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