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Conducting Polymer-Based
Energy Storage Materials
Conducting Polymer-Based
Energy Storage Materials
Edited by
Inamuddin
Rajender Boddula
Mohammad Faraz Ahmer
Abdullah M. Asiri
CRC Press
Taylor & Francis Group
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Boca Raton, FL 33487-2742
© 2019 by Taylor & Francis Group, LLC
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International Standard Book Number-13: 978-0-367-19394-2 (Hardback)
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Contents
Preface .......................................................................................................................................................................... vii
Contributors .................................................................................................................................................................. ix
Editors......................................................................................................................................................................... xiii
Chapter 1 Polythiophene-Based Battery Applications.................................................................................................. 1

Younus Raza Beg, Gokul Ram Nishad, Chittaranjan Das, and Priyanka Singh
Chapter 2 Synthetic Strategies and Significant Issues for Pristine Conducting Polymers ............................................51
Mriganka Sekhar Manna and Kalyan Gayen
Chapter 3 Conducting Polymer Derived Materials for Batteries .................................................................................65

U. Naresh, R. Jeevan Kumar, S. Ramesh, K. Chandra Babu Naidu, D. Baba Basha,
Prasun Banerjee, and K. Srinivas
Chapter 4 An Overview on Conducting Polymer-Based Materials for Battery Application ........................................79

Satyabadi Martha and Dilip Kumar Mishra
Chapter 5 Polymer-Based Binary Nanocomposites.....................................................................................................93

Pazhanivel Thangavelu, Priyadharshini Matheswaran, and Navaneethan Duraisamy
Chapter 6 Polyaniline-Based Supercapacitor Applications........................................................................................109

Nuzhat Jamil, Sadia Zafar Bajwa, Muhammad Yasir, Asma Rehman, and Waheed S. Khan
Chapter 7 Conductive Polymer-derived Materials for Supercapacitor ......................................................................123

P.E. Lokhande and U.S. Chavan
Chapter 8 Conducting Polymer-Metal Based Binary Composites for Battery Applications......................................135

Aneela Sabir, Dania Munir, Samina Saleem, Faiqa Shakeel, Muhammad Hamad Zeeshan,
Muhammad Shafiq, Rafi Ullah Khan, and Karl I Jacob
Chapter 9 Novel Conducting Polymer-Based Battery Application............................................................................145

Aneela Sabir, Faiza Altaf, Zahid Bashir, Muhammad Hassan Tariq, Muhammad Khalil,
Muhammad Shafiq, Muhammad Hamad Zeeshan, Rafi Ullah Khan, and Karl I Jacob
Chapter 10 Conducting Polymer–Carbon-Based Binary Composites for Battery Applications ..................................155

Christelle Pau Ping Wong, Joon Ching Juan, and Chin Wei Lai
Chapter 11 Polyethylenedioxythiophene-Based Battery Applications .........................................................................161

G. Nasymov, J. Swanson, A. M. Numan-Al-Mobin, C. Jahnke, and A. Smirnova
v
vi Contents
Chapter 12 Polythiophene-Based Supercapacitor Applications ..................................................................................177

Shankara S. Kalanur, Veerendra Kumar A. Kalalbandi, and Hyungtak Seo
Chapter 13 Conducting Fibers for Energy Applications .............................................................................................193

Narendra Reddy, Roshan Paul, and Asimananda Khandual
Chapter 14 Conducting Polymer-Metal-Based Binary Composites for Supercapacitor Applications .........................209

A.B.V. Kiran Kumar, Swati Chaudhary, and C.H.V.V. Ramana
Chapter 15 Polyethylenedioxythiophene (PEDOT)-Based Supercapacitor Applications.............................................235

Manoj Karakoti, Sandeep Pandey, Nanda Gopal Sahoo, Anirban Dandapat, and Suman Mahendia
Chapter 16 Electrospun Composite Separator for Li-Ion Batteries: A Short Review..................................................255

A. Dennyson Savariraj, R.V. Mangalaraja, G. Bharath, Fawzi Banat, and N. Pugazhenthiran
Chapter 17 Conducting Polymers: Properties, Synthesis, and Energy Storage Devices ...............................................267
Mohamad Azuwa Mohamed and Nadhratun Naiim Mobarak
Chapter 18 Applications of Polyethylenedioxythiophene in Photovoltaics..................................................................287

Jazib Ali, Mutayyab Afreen, Tahir Rasheed, Muhammad Zeeshan Ashfaq, and Muhammad Bilal
Chapter 19 Conducting Polymer-Based Ternary Composites for Supercapacitor Applications ..................................301

Devalina Sarmah and Ashok Kumar
Index............................................................................................................................................................................333
Preface
Electrochemical storage devices, for example, batteries and This book explores the new aspects of conducting
supercapacitors, have demonstrated extraordinary assur- polymer processing, usable properties, nanostructures,
ance in empowering the use of energy produced from wind and engineering strategies applicable to energy storage
and solar energy sources. It is necessary to think about the applications. It briefly surveys recent advances of con-
development of independent electrochemical energy stor- ducting polymers and their composites, synthetic
age systems. The most important aspect of an energy stor- approaches, and applications in all-types electrochemical
age system is the designing of active electrode materials for energy storage devices. It deliberates cutting-edge know-
excellent electrochemical performance. Among the various ledge of energy storage technology based on synthetic
materials used in energy storage systems, conducting poly- metals and presents up-to-date literature coverage on
mers have gained significant attention by researchers across a large, rapidly growing, and complex conducting poly-
the world due to their low cost, simple tunability of mer-based electrochemical energy storage system. This
arrangements, rich redox chemistry, flexibility, structure, book is planned to provide the readers a clear thought
and morphology. Thus, conducting polymers seem to be regarding the execution of conducting polymeric mater-
the alternative for next-generation electrochemical devices. ials as electrodes in electrochemical power sources. This
However, cycle stability is a bottle-neck limitation for book is a one-stop reference guide that overviews up-
practical applications of energy storage devices based on to-date literature in the field of conducting polymer-
conducting polymers. Therefore, the research for the based energy storage systems. This book is an invaluable
development of next-generation conducting polymers- guide to students, professors, scientists, and R&D indus-
driven energy storage has been in progress to get practic- trial specialists working in the field of advanced science,
ally viable technologies. The conducting polymer-based nanodevices, flexible electronics, and energy science.
energy storage devices seem to be the incredible future,
but still more research and development studies are Inamuddin, Rajender Boddula, Mohammad Faraz
needed to commercialize them at a large scale. Ahmer, and Abdullah M. Asiri
vii
Contributors
Mutayyab Afreen G. Bharath
Department of Physics Department of Chemical Engineering
University of Agriculture Khalifa University
Faisalabad, Pakistan Abu Dhabi, United Arab Emirates
Jazib Ali Muhammad Bilal

Department of Physics and Astronomy School of Life Science and Food Engineering
Shanghai Jiao Tong University Huaiyin Institute of Technology
Shanghai, China Huaian, China
Faiza Altaf Swati Chaudhary

Department of Environmental Sciences (Chemistry) Amity Institute of Nanotechnology
Fatima Jinnah women university Amity University
Rawalpindi, Pakistan Noida, India
Muhammad Zeeshan Ashfaq U. S. Chavan

Department of Physics Department of Mechanical Engineering
University of Agriculture Sinhgad Institute of Technology Lonavala
Faisalabad, Pakistan Lonavala, India
Sadia Zafar Bajwa Anirban Dandapat

Nanobiotechnology Group National Institute for Department of Chemistry
Biotechnology and Genetic Engineering (NIBGE) DSB Campus, Kumaun University
Faisalabad, Pakistan Nainital, India
Fawzi Banat Chittaranjan Das

Department of Chemical Engineering Institute of Applied Materials-Energy Storage System
Khalifa University Karlsruhe Institute of Technology
Abu Dhabi, United Arab Emirates Karlsruhe, Germany
Prasun Banerjee Navaneethan Duraisamy

Department of Physics Department of Chemistry
GITAM Deemed to be University Periyar University
Bangalore, India Salem, India
D. Baba Basha Kalyan Gayen

Department of Physics Department of Chemical Engineering
College of Computer and Information Sciences, NIT Agartala
Majmaah University West Tripura, India
Al’Majmaah, KSA
Karl I Jacob
Zahid Bashir School of Materials Science and Engineering
Department of Polymer Engineering and Technology Georgia Institute of Technology
University of the Punjab Atlanta, GA, USA
Lahore, Pakistan
C. Jahnke
Younus Raza Beg Department of Materials and Metallurgical
Department of Chemistry Engineering
Govt. Digvijay PG Autonomous College South Dakota School of Mines and Technology
Rajnandgaon, Chhattisgarh, India Rapid City, South Dakota
ix
x Contributors
Nuzhat Jamila R. Jeevan Kumar

Nanobiotechnology Group National Institute for Department of Physics
Biotechnology and GeneticEngineering (NIBGE) Sri Krishnadevaraya University
Faisalabad, Pakistan Anantapuramu, India
Joon Ching Juan A.B.V. Kiran Kumar

Nanotechnology & Catalysis Research Centre Nano world India, Buchireddy Plaem
(NANOCAT), Institute for Advanced Studies Nellore, India
University of Malaya (UM)
Amity Institute of Nanotechnology
Kuala Lumpur, Malaysia
Amity University
Noida, India
Veerendra Kumar A. Kalalbandi
Department of Chemistry, Jain College of Engineering
Chin Wei Lai
Belagavi, Karnataka, India
Nanotechnology & Catalysis Research Centre
(NANOCAT), Institute for Advanced Studies
Shankara S. Kalanur
Department of Materials Science and Engineering
Ajou University
Suwon, Republic of Korea
P. E. Lokhande
Department of Mechanical Engineering
Manoj Karakoti
Sinhgad Institute of Technology Lonavala
Prof. R. S. Nanoscience and Nanotechnology Centre
Lonavala, India
Department of Chemistry DSB Campus, Kumaun
University
Suman Mahendia
Nainital, India
Department of Physics
Kurukshetra University
Muhammad Khalil
Kurukshetra, India
Department of Polymer Engineering and Technology
University of the Punjab
R.V. Mangalaraja
Lahore, Pakistan
Advanced Ceramics and Nanotechnology Laboratory,
Department of Materials Engineering, Faculty of
Waheed S. Khan
Engineering
Nanobiotechnology Group National Institute for
University of Concepcion
Biotechnology and Genetic Engineering (NIBGE)
Concepcion, Chile
Faisalabad, Pakistan
Technological Development Unit (UDT)
Rafi Ullah Khan University of Concepcion
Department of Polymer Engineering and Technology Coronel, Chile
Lahore, Pakistan Mriganka Sekhar Manna
Department of Chemical Engineering
Institute of Chemical Engineering and Technology
NIT Agartala
(ICET)
West Tripura, India
Lahore, Pakistan
Satyabadi Martha
Government (SSD) +2 Science College (HSS),
Asimananda Khandual
Badabharandi
Department of Textile Engineering
Umerkote, India
College of Engineering & Technology (BPUT)
Bhubaneswar, India
Priyadharshini Matheswaran
Smart Materials Interface Laboratory, Department of
Ashok Kumar
Physics
Periyar University
Napaam, Tezpur
Salem, India
Assam, India
Contributors xi
Dilip Kumar Mishra Roshan Paul

Department of Physics, Faculty of Engineering and Department of Textile Science and Technology
Technology (ITER) University of Beira Interior
Siksha ‘O’ Anusandhan Deemed to be University Covilha, Portugal
Bhubaneswar, India
N. Pugazhenthiran
Nadhratun Naiim Mobarak Laboratorio de Tecnologías Limpias, Faculty of
Centre for Advanced Materials and Renewable Engineering
Resources (CAMARR) Faculty of Science and University of Concepcion
Technology Concepcion, Chile
Universiti Kebangsaan Malaysia
Selangor, Malaysia Tahir Rasheed
Department of Chemistry and Chemical Engineering
Mohamad Azuwa Mohamed Shanghai Jiao Tong University
Centre for Advanced Materials and Renewable Shanghai, China
Resources (CAMARR) Faculty of Science and
Technology C.H.V.V. Ramana
Universiti Kebangsaan Malaysia Department of Electrical and Electronics Engineering
Selangor, Malaysia Science
University of Johannesburg, Auckland Park Campus
Dania Munir Johannesburg, South Africa
University of the Punjab S. Ramesh
Lahore, Pakistan Department of Physics
GITAM Deemed to be University
K. Chandra Babu Naidu Bangalore, India
GITAM Deemed to be University Narendra Reddy
Bangalore, India Center for Incubation, Innovation, Research and
Consultancy
U. Naresh Jyothy Institute of Technology
Department of Physics Bengaluru, India
Sri Krishnadevaraya University
Anantapuramu, India Asma Rehman
Nanobiotechnology Group National Institute for
G. Nasymov Biotechnology and Genetic Engineering
Department of Materials and Metallurgical Engineering (NIBGE)
South Dakota School of Mines and Technology Faisalabad, Pakistan
Rapid City, South Dakota
Aneela Sabir
Gokul Ram Nishad Department of Polymer Engineering and Technology
Department of Chemistry University of the Punjab
Govt. Digvijay PG Autonomous College Lahore, Pakistan
Rajnandgaon, Chhattisgarh, India
Nanda Gopal Sahoo
A. M. Numan-Al-Mobin Prof. R. S. Nanoscience and Nanotechnology Centre
Department of Materials and Metallurgical Engineering Department of Chemistry DSB Campus, Kumaun
South Dakota School of Mines and Technology University
Rapid City, South Dakota Nainital, India
Sandeep Pandey Samina Saleem

Prof. R. S. Nanoscience and Nanotechnology Centre Department of Polymer Engineering and
Department of Chemistry DSB Campus, Kumaun Technology
University University of the Punjab
Nainital, India Lahore, Pakistan
xii Contributors
Devalina Sarmah K. Srinivas

Department of Physics Department of Physics
Napaam, Tezpur GITAM Deemed to be University
Assam, India Bangalore, India
A. Dennyson Savariraj J. Swanson

Advanced Ceramics and Nanotechnology Laboratory, Department of Materials and Metallurgical Engineering
Department of Materials Engineering, Faculty of South Dakota School of Mines and Technology
Engineering Rapid City, South Dakota
University of Concepcion
Concepcion, Chile Muhammad Hassan Tariq
Department of Polymer Engineering and
Hyungtak Seo Technology
Department of Materials Science and Engineering University of the Punjab
Ajou University Lahore, Pakistan
Pazhanivel Thangavelu
Department of Energy Systems Research
Smart Materials Interface Laboratory, Department
Ajou University
of Physics
Periyar University
Salem, India
Muhammad Shafiq
Christelle Pau Ping Wong
Nanotechnology & Catalysis Research Centre
Lahore, Pakistan
(NANOCAT), Institute for Advanced Studies
Faiqa Shakeel
Muhammad Yasir
Lahore, Pakistan
Department of Chemistry
University of Lahore
Priyanka Singh
Lahore, Pakistan
Govt. Digvijay PG Autonomous College
Muhammad Hamad Zeeshan
Institute of Chemical Engineering and Technology
(ICET)
A. Smirnova
Department of Materials and Metallurgical Engineering
Lahore, Pakistan
South Dakota School of Mines and Technology
Rapid City, South Dakota
Editors
Dr. Inamuddin is currently working as Assistant Professor King Fahd University of Petroleum and Minerals, Saudi
in the Chemistry Department, Faculty of Science, King Arabia, in the field of polymer electrolyte membrane fuel
Abdulaziz University, Jeddah, Saudi Arabia. He is a cells and computational fluid dynamics of polymer electro-
permanent faculty member (Assistant Professor) at the lyte membrane fuel cells. He is a life member of the Journal
Department of Applied Chemistry, Aligarh Muslim of the Indian Chemical Society. His research interest
University, Aligarh, India. He obtained master of science includes ion exchange materials, a sensor for heavy metal
degree in organic chemistry from Chaudhary Charan ions, biofuel cells, supercapacitors, and bending actuators.
Singh (CCS) University, Meerut, India, in 2002. He
received his master of philosophy and Ph.D. degrees in Dr. Mohammad Faraz Ahmer is presently working as
Applied Chemistry from Aligarh Muslim University Assistant Professor in the Department of Electrical
(AMU), India, in 2004 and 2007, respectively. He has Engineering, Mewat Engineering College, Nuh, Haryana,
extensive research experience in multidisciplinary fields India, since 2012 after working as Guest Faculty in
of analytical chemistry, materials chemistry, and electro- University Polytechnic, Aligarh Muslim University Aligarh,
chemistry and, more specifically, renewable energy and India, during 2009–2011. He completed M.Tech. (2009)
environment. He has worked on different research projects and bachelor of engineering (2007) degrees in electrical
as project fellow and senior research fellow funded by engineering from Aligarh Muslim University, Aligarh, in
University Grants Commission (UGC), Government of the first division. He obtained a Ph.D. degree in 2016 on
India, and Council of Scientific and Industrial Research his thesis entitled “Studies on Electrochemical Capacitor
(CSIR), Government of India. He has received Fast Electrodes.” He has published six research papers in
Track Young Scientist Award from the Department of reputed scientific journals. He has edited two books with
Science and Technology, India, to work in the area of Materials Science Forum, LLC (USA). His scientific inter-
bending actuators and artificial muscles. He has completed ests include electrospun nanocomposites and supercapaci-
four major research projects sanctioned by University tors. He has presented his work at several conferences. He
Grant Commission, Department of Science and Technol- is actively engaged in searching of new methodologies
ogy, Council of Scientific and Industrial Research, and involving the development of organic composite materials
Council of Science and Technology, India. He has pub- for energy storage systems.
lished 147 research articles in international journals of
repute and eighteen book chapters in knowledge-based Prof. Abdullah M. Asiri is the Head of the Chemistry
book editions published by renowned international pub- Department at King Abdulaziz University since October
lishers. He has published 60 edited books with Springer 2009, and he is the Founder and the Director of the Center
(U.K.), Elsevier, Nova Science Publishers, Inc. (U.S.A.), of Excellence for Advanced Materials Research (CEAMR)
CRC Press Taylor & Francis Asia Pacific, Trans Tech since 2010 till date. He is a Professor of organic photo-
Publications Ltd. (Switzerland), IntechOpen Limited chemistry. He graduated from King Abdulaziz University
(U.K.), and Materials Research Forum LLC (U.S.A). He (KAU) with a B.Sc. in chemistry in 1990 and received a
is a member of various journals’ editorial boards. He is Ph.D. degree from University of Wales, College of Cardiff,
also serving as Associate Editor for journals (Environ- Wales, in 1995. His research interest covers color chemis-
mental Chemistry Letter, Applied Water Science and try, synthesis of novel photochromic and thermochromic
Euro-Mediterranean Journal for Environmental Integra- systems, synthesis of novel coloring matters and dyeing of
tion, Springer-Nature), Frontiers Section Editor (Current textiles, materials chemistry, nanochemistry and nano-
Analytical Chemistry, Bentham Science Publishers), technology, and polymers and plastics. Prof. Asiri is the
Editorial Board Member (Scientific Reports-Nature), Editor principal supervisor of more than 20 M.Sc. and six Ph.D.
(Eurasian Journal of Analytical Chemistry), and Review theses. He is the main author of ten books of different
Editor (Frontiers in Chemistry, Frontiers, U.K.) He also chemistry disciplines. Prof. Asiri is the Editor-in-Chief of
serves as guest editor for various special thematic special King Abdulaziz University Journal of Science. His major
issues to the journals of Elsevier, Bentham Science Pub- achievement is the research of tribochromic compounds,
lishers, and John Wiley & Sons, Inc. He has attended as a new class of compounds that change from slightly col-
well as chaired sessions in various international and national ored or colorless to deep colored when subjected to small
conferences. He has worked as a Postdoctoral Fellow, pressure or when ground. This discovery was introduced
leading a research team at the Creative Research Initiative to the scientific community as a new terminology pub-
Center for Bio-Artificial Muscle, Hanyang University, lished by International Union of Pure and Applied Chem-
South Korea, in the field of renewable energy, especially istry (IUPAC) in 2000. This discovery was awarded a
biofuel cells. He has also worked as a Postdoctoral Fellow patent from European Patent office and from UK patent.
at the Center of Research Excellence in Renewable Energy, Prof. Asiri has involved in many committees at both KAU
xiii
xiv Editors
level and national level. He played a major role in identi- Dr. Rajender Boddula is currently working for Chinese
fying the national plan for science and technology when Academy of Sciences President’s International Fellow-
he was part of the Advanced Materials Committee work- ship Initiative (CAS-PIFI) at National Center for
ing for King Abdulaziz City for Science and Technology Nanoscience and Technology (NCNST, Beijing). His
(KACST) in 2007 and in advancing the chemistry educa- academic honors includes University Grants Commis-
tion and research in KAU. He has been awarded the best sion National Fellowship and many merit scholarships,
researchers from KAU for the past five years. He also and CAS-PIFI. He has published many scientific articles
received the Young Scientist Award from the Saudi Chem- in international peer-reviewed journals and has authored
ical Society in 2009 and the first prize for the distinction twenty book chapters. He is also serving as an editorial
in science from the Saudi Chemical Society in 2012. He board member and a referee for reputed international
also received a recognition certificate from the American peer-reviewed journals. He has published edited books
Chemical Society (Gulf Region Chapter) for the advance- with Springer (UK), Elsevier, Materials Science Forum
ment of chemical science in the Kingdome. He received a LLC (USA) and CRC Press Taylor & Francis Asia
Scopus certificate for the most publishing scientist in Pacific, Trans Tech Publications Ltd. (Switzerland). His
Saudi Arabia in chemistry in 2008. He is also a member specialized areas of research are energy conversion and stor-
of the editorial board of various journals of international age, which include sustainable nanomaterials, graphene,
repute. He is the Vice-President of Saudi Chemical Society polymer composites, heterogeneous catalysis for organic
(Western Province Branch). He holds four US patents, transformations, environmental remediation technologies,
more than one thousand publications in international jour- photoelectrochemical water-splitting devices, biofuel cells,
nals, several book chapters, and edited books. batteries, and supercapacitors.
1 Polythiophene-Based Battery
Applications
Younus Raza Beg and Gokul Ram Nishad
Chittaranjan Das
Institute of Applied Materials-Energy Storage System
Karlsruhe Institute of Technology
Karlsruhe, Germany
Priyanka Singh
CONTENTS
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.1 Electrochemical Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.2 Chemical Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3 Battery Applications of PTs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.3.1 PTs as Cathodic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.3.1.1 PTs as Active Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.3.1.2 PTs as Binder. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .22
1.3.1.3 PTs as Conduction-Promoting Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .26
1.3.2 PTs as Air Cathode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .26
1.3.2.1 Li–Air Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .26
1.3.2.2 Aluminum–Air Battery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .27
1.3.2.3 Zinc–Air Battery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .28
1.3.3 PTs as Anodic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .28
1.3.3.1 PTs as Active Materials for Anode. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .28
1.3.3.2 PTs as Binders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .34
1.3.3.3 PTs as Conduction Promoting Agents (CPAs). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .37
1.3.4 PTs as Battery Separators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .37
1.3.4.1 Li-Ion Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .37
1.3.4.2 Li–S Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .39
1.3.4.3 Li–O2 Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .39
1.3.5 PTs as Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .42
1.3.6 PTs as Coin-cell Cases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .42
1.3.7 PTs as Li–O2 Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .43
1.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
1
2 Conducting Polymer-Based Energy Storage Materials
1.1 INTRODUCTION temperature stability [1] and very high electrical conduct-
ivity of PT films make it a highly desirable material.
An electrochemical cell that converts stored chemical energy
Their optical properties depend on environmental stimuli.
into electrical energy is known as a battery. Conventionally,
Remarkable color shifts are observed in response to
it consists of a cathode as the positive electrode and an
changes in solvent, temperature, potential applied, and
anode as the negative electrode, a separator and an electro-
binding to other molecules.
lyte which undergoes electrochemical reaction and allows
Among different PT derivatives, the most widely used
the flow of ions, thus conducting current. We will discuss the
one is poly(3,4-ethylene dioxythiophene) (PEDOT) (Figure
application of polythiophenes (PTs) and their derivatives in
1.2). It was first prepared by Bayer while attempting to fab-
the battery technology as electrode, binder, conduction-
ricate an easily oxidized and stable conducting polymer
promoting agents, separator, electrolyte, coin-cell cases, and
without undesirable α–β′ couplings, often found in PT. But
Li–O2 catalyst. Until now, a lot would have been discussed
about battery along with composition and functions of con- PEDOT films did possess high conductivity (3 × 104 S m–1)
ductive polymers. Therefore, we would directly deal with the and were found to be cathodically coloring and almost
prime focus of this chapter, i.e., PTs. PTs are the polymers of transparent in the oxidized state [2]. A water-soluble poly-
a sulfur heterocycle, thiophene, that becomes conductive electrolyte [poly(styrene sulfonate), PSS] was incorporated
upon oxidation. Alan J. Heeger, Alan MacDiarmid, and as the counter-ion in the doped state to yield the product
Hideki Shirakawa received the 2000 Nobel Prize in Chemis- poly(3,4-ethylene dioxythiophene):poly(styrenesulfonate)
try for the discovery and development of conductive poly- (PEDOT:PSS) (Figure 1.2) [3] in order to tackle its insolu-
mers. PTs are also conductive polymers and their electrical bility issues. PEDOT:PSS consists of a component, PSS,
conductivity is due to the delocalization of electrons along with deprotonated sulfonyl groups carrying negative
the polymer backbone. Therefore, the conducting polymers charge and PEDOT carrying positive charges. PEDOT and
are also known as “synthetic metals.” PEDOT:PSS play key role as organic semiconductors in
Molecular structure is a major physical property that electronics because they are p- and n-dopable as they can
determines factor for conducting polymers. Synthesis of transport either holes or electrons [4]. Several derivatives of
these materials helps in determining the magnitude of PEDOT have been synthesized to produce high-contrast,
p overlap along the backbone and thus eliminating the fast-switching polymer films. It can withstand 200ºC tem-
structural defects. Interchain overlap and dimensionality perature without being degraded. Hence, it has superior
depend on the material assembly and/or processing. Per- thermal properties in ambient air as well as good electro-
formance can be enhanced by planarization of the back- chemical stability, charge capacity, and ionic conductivity
bone and assembly of the backbone in the form of [5,6]. It offers optical transparency in thin and oxidized
p stacks through improvement of the electronic and pho- films with very high stability, reasonable bandgap, and low
tonic properties of the resultant materials. A lot of work redox potential [7]. PT is used in nonlinear optics, electrical
has been done on the selective engineering of the proper- supercapacitor, polymeric light-emitting diode (PLED)s,
ties of PTs (Figure 1.1) through synthesis and assembly. eletrochromics, antistatic coatings, sensors, batteries, solar
Although processability is difficult, the probable high- cells, memory devices, transistors, and a lot more [8].
P P
FIGURE 1.1 Chemical structure of PT and its derivatives.

Polythiophene-Based Battery Applications 3
FIGURE 1.2 Chemical structure of PEDOT and PEDOT:PSS.
1.2 SYNTHESIS potential required for the oxidation of monomer depends on

the electron density of thiophene ring π-system. The
PTs can be synthesized by either of the following methods:
required oxidation potential is lowered due to the pres-
ence of electron-donating groups, but it gets increased in
1) Electrochemical polymerization: it involves the appli-
case of electron-withdrawing groups. Table 1.1 deals with
cation of potential across a solution of the monomer.
the reaction conditions for electrochemical synthesis of
2) Chemical polymerization: it involves the use of oxi-
PTs from monomers and their conductances.
dants or cross-coupling catalysts.
Both the methods will be discussed below along with 1.2.2 CHEMICAL SYNTHESIS
their advantages and disadvantages.
Linear alkyl-substituted polymers have been studied
extensively due to their ease of synthesis. Unsubstituted
1.2.1 ELECTROCHEMICAL POLYMERIZATION PTs were chemically prepared for the first time in 1980
Thiophene and an electrolyte solution produce a conductive by Yamamoto et al. (1980) and Lin and Dudek (1980)
PT film on the anode in electrochemical polymerization. [17,18]. Both of them synthesized PT through metal-
One of the advantages of electrochemical polymerization is catalyzed polycondensation polymerization of 2,5-dibro-
its convenient nature because the polymer does not need to mothiophene. Since PT is insoluble in tetrahydrofuran
be isolated and purified. Its limitation is the formation of (THF) even at low molecular weights, its precipitation
polymers with undesirable alpha–beta linkages and varying under the proposed reaction conditions [17,18] limits the
degrees of regioregularity. Oxidation of a monomer (educt) formation of higher-molecular-weight PTs.
by removal of one electron produces a radical cation Sugimoto et al. (1986) reported the FeCl3 method for
(polaron). It couples with another radical cation to form polymerization of polyalkylthiophenes (PATs) [19]. But
a dication dimer (Figure 1.3). The radical cation can also this method gives variable results. Pomrantz et al. (1991)
couple with another monomer to produce a radical cation have studied the reproducibility of this reaction [20].
dimer followed by removal of a proton. This process is Still, it is the most widely used method for the prepar-
repeated to give the polymer. The polymer chains are also ation of PT and its derivatives, in spite of its limitations.
oxidized that obtain electrical neutrality due to the presence Pomerantz et al. (1995) reported the Ullmann coupling
of counter-ion from the electrolyte. The resulting polymer is for the synthesis of carboxylate derivatives of PTs [21].
a good conductor of electricity and acts as a new electrode. Table 1.2 deals with the reaction conditions for the synthe-
Polymerization conditions are responsible for the growth of sis of some of the PT derivatives that are being widely
either long, flexible chains or shorter and more crosslinked used in battery technology and various other fields. PTs
chains through deposition of long and well-ordered chains are used in different fields after mixing with different
onto the electrode surface. organic or inorganic additives to give nanoparticles [24],
The quality of electrochemically prepared PT film nanocomposites [25–27], nanowires [28,29], nanotubes
depends on electrode material, current density, temperature, [30], nanofibers [31,32], nanosheets [33,34], hybrid
solvent, electrolyte, presence of water, monomer concentra- materials [35], etc. These different forms of PTs have
tion, monomer structure, and applied potential [8]. The been compared in Table 1.3.
FIGURE 1.3 Initial steps involved in the electrochemical polymerization of thiophenes [8].
TABLE 1.1
Reaction conditions for electrochemical synthesis of PTs from monomers and their conductances
[Monomer] (M) Solvent Electrolyte Electrical condition σ (Sm−1) Reference
Thiophene
0.01 CH3CN Bu4NClO4 1.6 V/SCE 1 × 103–1 × 104 Tourillon and Gamier (1982) [9]
4 −2
0.2 Propylene carbonate Et4NPF6 1 × 10 mA m 2.7 × 104 Sato et al. (1985) [10]
0.1 PhNO2 Bu4NPF6 2.0 × 104 mA m−2 3.7 × 104 Roncali et al. (1989) [11]
Methyl thiophene
0.01 CH3CN Et4NPF6 1.7 V/SCE 1.0 × 102 Waltman et al. (1983) [12]
- CH3CN Bu4NSO3CF3 1.5 V/SCE 3.0 × 103–1.0 × 105 Tourillon and Gamier (1983) [13]
0.05 PhNO2 Bu4NPF6 1.5 × 104 mA cm−2 1.975 × 105 Roncali et al. (1988) [14]
Yassar et al. (1989) [15]
Bithiophene
0.1 CH3CN HSO4− 1.17 V/SCE 1.0 × 10−1 Waltman et al. (1983) [12]
Trithiophene
0.002 CH3CN Et4NPF6 1.7 V/SCE 1.0 × 101–1.0 Inganas et al. (1985) [16]
SCE: Standard calomel electrode.

TABLE 1.2
Various routes for the chemical synthesis of PTs along with the reaction conditions
S. no. Route Reactant Reagent and Product Reference
reaction condition
1 Mg/THF/Ni(biyp)Cl2 Yamamoto et al.

Yamamoto route
(1980) [17]
n
2 Lin and Dudek Mg/THF/M(acac)n Lin and Dudek

route where M = Pd, Ni, (1980) [18]
Co or Fe n
3 Sugimoto route FeCl3/CHCl3 Sugimoto et al.

(1986) [19]
n
4 Demercuration Cu/PdCl2/pyridine/Δ Yamamoto et al.

polymerization (1992) [22]
n
5 Souto Maior FeCl3 or R. M. Souto Maior

route for electrochemical et al. (1990) [23]
synthesis of method
n
HH−TT PATs
6 Souto Maior FeCl3 or R. M. Souto Maior

route for electrochemical et al. (1990) [23]
synthesis of method n
TT−HH PATs
7 Ullmann 1. Br2/AcOH Pomerantz et al.

coupling route 2. SOCl2 (1995) [21]
3. ROH, pyridine n
4. Cu, DMF/150ºC,
7 days
HH−TT PATs: head−head tail−tail polyalkylthiophenes.

TT−HH PATs: tail−tail head−head polyalkylthiophenes.
THF: tetrahydrofuran.
6
TABLE 1.3
Method of preparation of various PT-based polymeric materials along with their important properties
S. no. Polymeric materials Monomer Method of preparation/oxidant Properties Reference
Nanoparticles
1 Spherical PT nanoparticles Thiophene COP in the presence of SDS and • Regular spherical morphology Wang et al.
H2O2/cupric nitrate, cupric sulfate • Relatively low surface resistivities and (2010a) [24]
and cupric chloride • High thermal stability
Nanocomposites
2 Nanophotoadduct of pentaammine Thiophene COP/FeCl3 • Acts as a Schottky diode material Najar and
chlorocobalt(III) chloride with hexamine and • Increases the conductance and thermal stability of Majid (2013)
PT PT [25]
• Operates at relatively high temperatures in electrical
appliances
3 PT/TiO2 nanocomposites Thiophene COP/FeCl3 • Amorphous structures Uygun et al.
• Semiconductor property was observed for PT/TiO2- (2009) [26]
anionic system
4 Graphene/Fe3O4@PT Thiophene Oxidative chemical polymerization/ • Magnetic nanocomposite Mehdinia
FeCl3 • An adsorbent with the excellent extraction properties et al. (2014)
• Simple, fast, and efficient extraction technique for [254]
trace analysis of Polycyclic aromatic hydrocarbons
(PAHs) in the seawater samples
Nanowires
5 Poly(3-hexylthiophene)-block-poly(3-(3- 2,5-Dibromo-3-hexylthiophene solvent-induced crystallization/ • Capable of maintaining their structural integrity in Hammer
thioacetylpropyl)oxymethylthiophene) and 2,5-dibromo-3-(3-bromopropyl) FeCl3 solvents that normally dissolve the polymers et al. (2014)
(P3HT)-b-(P3TT) diblock copolymers oxylmethylthiophene • Could be reduced to the fully solvated polymer [28]
6 Azide-functionalized poly(3-hexylthiophene) 3-(Azidohexyl)thiophene and Photo-crosslinking and click-func- • Water-processable PT nanowires Kim et al.
(P3HTazide) NWs 3-hexylthiophene tionalization/– (2015) [29]
Nanotubes
7 Nanotube composites consisting of metal Terthiophene-functionalized metal EOP/− • Recyclable highly effective catalysts for the carbon– Umeda et al.
nanoparticles and PT (Au, Pd) nanoparticles carbon coupling reaction (2008) [30]
• Hybrid nanomaterials with controllable surface
chemistry
Conducting Polymer-Based Energy Storage Materials
Nanofibers
8 Poly(3-alkylthiophene) (P3AT) nanofibers Regioregular Whisker method using anisole solv- • Anisotropic cross-section Samitsu et al.
poly(3-butylthiophene-2,5-diyl; ent/– • Low-cost and mass production of nanofibers (2008) [31]
P3BT), poly(3-hexylthiophene-2,5-
diyl; P3HT), poly(3-octylthio-
Polythiophene-Based Battery Applications
phene-2,5-diyl; P3OT), poly(3-

decylthiophene-2,5-diyl; P3DT),
Regiorandom
poly(3-hexylthiophene-2,5-diyl;
RRa-P3HT)
9 PT nanofibers and carbonaceous PT Thiophene Surfactant-assisted dilute polymer- • Used as electrode materials for asymmetric superca- Balakrishnan
nanofibers ization method/FeCl3 pacitor applications et al. (2014)
[32]
Nanosheets
10 Graphene oxide–PT derivative hybrid Thiophene and benzaldehyde In situ polymerization method/– • Enhances the performance of supercapacitor Alabadi et al.
nanosheets • Long-term stability (2016) [33]
• Larger energy density, up to 1.48 × 102 Wh kg–1 at
a power density of 4.16 × 101 W kg–1
11 PT-coated ultrathin MnO2 nanosheets Thiophene Nanopainting with a thin layer of • Exhibits enhanced capacity retention upon high-rate Xiao et al.
conducting polymer/– charge/discharge cycling (2010) [34]
Hybrid materials
12 Regioregular PT/gold nanoparticle hybrid Poly(3-hexylthiophene) One-pot synthesis/– • Narrow size distribution Zhai et al.
materials • May find applications in single-electron tunneling (2004) [35]
studies as well as field effect transistors
PT: polythiophene.
COP: chemical oxidative polymerization.
EOP: electrochemical oxidative polymerization.
7
1.3 BATTERY APPLICATIONS OF PTs results prove that the PT coating decreases the charge
transfer resistance of LiFePO4 electrodes significantly.
1.3.1 PTS AS CATHODIC MATERIALS Charge/discharge testing was done to test the electrochem-
PTs have been used as the cathodic materials for batter- ical performance and study Li insertion and extraction.
ies in various forms that will be discussed below. Electro- Enhanced reversible capacity and better cycling ability
chemical performance of the batteries is characterized by were observed in comparison to the bare LiFePO4.
the charge/discharge test, cyclic voltammetry (CV), elec- Trinh et al. (2013) successfully prepared free-standing
trochemical impedance spectroscopic (EIS) studies, and PEDOT–LiFePO4 composite films by dynamic three-
galvanostatic intermittent titration technique (GITT). phase interline electropolymerization (D3PIE) and used
Use of PT enhances the electrical conductivity, cycling as the positive electrode in standard LIBs without fur-
performance, and Li diffusion coefficient (in Li-ion bat- ther modifications [40]. All the electrochemically inactive
teries) along with decrease in the charge transfer resist- materials—such as carbon, polymer binder, and current
ance. PTs have generally been prepared by facile in-situ collector—used in conventional composite cathodes were
chemical oxidation polymerization (COP) method. Typ- eliminated. A discharge capacity of 7.5 × 104 mAh kg–1
ically, a cathode is made up of and high capacity retention were obtained. Xing et al.
(2013) prepared a LiFePO4/C composite having three-
• active materials, dimensional (3D) carbon network [41]. Cetyltrimethyl
• conductive additives to ensure electrical conductiv- ammonium bromide (CTAB) and starch were used as
ity, and carbon sources. It consisted of a full and uniform
• binder supporting matrix. carbon coating having a continuous carbon film frame-
work that acted as a good conductive path, thus improv-
ing the electron transfer efficiency. The porous structure
1.3.1.1 PTs as Active Materials facilitates diffusion of Li+ ions that ultimately lead to
high ionic and electrical conductivities. An excellent elec-
1.3.1.1.1 Li-Ion Batteries (LIBs) trochemical performance with high-rate cyclic perform-
Lithium-ion batteries (LIBs) are the most promising and ance was obtained. A capacity of 9.5 × 104 mAh kg−1 at
advanced secondary rechargeable devices due to high a current density of 3.4 × 103 A kg−1 (20 C) and
energy density (2.50 × 102 Wh kg–1) [36]. Li ions move a discharge capacity of 7.4 × 104 mAh kg−1 was obtained
from the negative to the positive electrode during dis- even after 1200 cycles. Capacity retention was observed to
charge and back while charging. LIBs use intercalated be 80%. This electrode system shows better cyclic perform-
Li compound as one electrode material. LIBs find ver- ance than reported in previous works.
satile applications from small portable electronic devices Lithium orthosilicate, Li2MSiO4 (where M = Fe, Mn
to electric vehicles or heavy electric vehicles. Handheld and Co), based cathodic materials offer high theoretical
electronics use LIBs based on lithium cobalt oxide capacity (4.330 × 106 mAh kg–1) along with high ther-
(LiCoO2) with high energy density and safety risks mal stability due to the presence of strong Si–O bond
upon damage [37]. Electric tools, medical equipment, [42]. They are safe, cost effective, ecofriendly, and easy
etc., use lithium iron phosphate (LiFePO4), lithium-ion to synthesize but have poor conductivity that hampers
manganese oxide battery (LiMn2O4, Li2MnO3), and its application in practical cells. While comparing with
lithium nickel manganese cobalt oxide (LiNiMnCoO2) LiFePO4, orthosilicates have about three to five times
which possess comparatively low energy density but lower electronic conductivities. Kempaiah et al. (2012)
offer longer lives and are safer. Life extension, energy synthesized monodispersed Li2MnSiO4 nanoparticles
density, charge/discharge capacity, safety, cost reduc- through supercritical solvothermal method [42]. Upon
tion, and charging speed improvement are the major coating it with PEDOT, discharge capacity of 3.13 × 105
research areas for LIBs. Therefore, a lot of work is mAh kg–1 was achieved. Figure 1.4 depicts the powder
being done in order to improve the electrochemical per- X-ray diffraction pattern and Figure 1.5 shows the trans-
formance of LIBs. Renewable organic electrodes based mission electron microscopy (TEM) and high-resolution
on organosulfur compounds, organic radical polymers, transmission electron microscopy (HRTEM) images as
organic carbonyl compounds, and conducting polymers well as particle size distribution of Li2MnSiO4 and
have been worked upon [38]. PEDOT/Li2MnSiO4 nanoparticles which reveal that as-
Olivine–lithium iron phosphates are inexpensive, eco- synthesized and PEDOT-coated particles exhibit non-
friendly, stable, and naturally abundant electrode mater- aggregated spherical morphology of diameter 5–20 nm
ials and offer relatively large theoretical capacity (1.70 × (Figure 1.5a and b), with majority of particles around 10
105 mAh kg−1) [39], but suffer from poor electrical con- nm (Figure 1.5c).
ductivity. Bai et al. (2010) synthesized a series of The lithium vanadium oxide (LiV3O8) is safe, cost
LiFePO4/PT composites through in-situ polymerization effective, and offers high-specific capacity and structural
of thiophene monomers on the surface of LiFePO4 par- stability [43,44]. Its nanomaterials have been tested
ticles [39]. Electrochemical impedance spectra (EIS) extensively as it provides short diffusion pathways for
FIGURE 1.4 Powder X-ray diffraction pattern of as-synthesized Li2MnSiO4 and PEDOT/Li2MnSiO4 nanoparticles by supercritical
method (Reprinted with permission from Royal Society of Chemistry, London, Great Britain) [42].
FIGURE 1.5 (a, b) TEM and HRTEM images of as-synthesized Li2MnSiO4 and PEDOT/Li2MnSiO4 nanoparticles, (c) particle
size distribution, and (d) HRTEM image showing PEDOT-coated Li2MnSiO4 nanoparticles (Reprinted with permission from Royal
Society of Chemistry, London, Great Britain) [42].
Li-ion insertion and extraction reactions. It also has high for bare LiV3O8 due to phase transformation during cyc-
specific surface area that increases contact between the ling and dissolution of small quantity of LiV3O8 in the
active material and electrolyte [45]. Poor rate capability electrolyte [46]. Hence, structural modification through
and capacity that fade during cycling have been observed coating has been tried to enhance its electrochemical
performance. Guo et al. (2014) chemically synthesized composite electrode material based on an aromatic PI
LiV3O8/PT composite through in-situ oxidative polymer- and electron conductive PT [38]. Both PI and PT possess
ization [47]. The composite shows a single phase in the common aromatic structure that allows intimate contacts
X-ray diffraction (XRD) pattern, but Fourier transform with highly reversible redox reactions, good structural
infrared spectroscopy (FTIR) spectra confirm the exist- stability, and high electronic conductivity. PI composite
ence of PT. Initial discharge capacities for 15 wt.% LiV3 material with 30 wt.% PT coating (PI30PT) shows opti-
O8/PT composite are 2.133 × 105 and 2.003 × 105 mal combination with good conductivity and fast Li
mAh kg−1, with nearly no capacity retention after 50 reaction kinetics, resulting into a high reversible capacity
cycles at current densities of 3.00 × 105 and 9.00 × 105 of 2.168 × 105 mAh kg−1 along with high-rate cycling
mA kg−1, respectively. stability. Capacity retention of 94% was obtained after
Conversion-reaction cathodes have the potential to 1000 cycles.
increase the energy density of current LIBs by twofold. Figure 1.6 shows the scanning electron microscopy
But, low energy efficiency, power density, and cycling sta- (SEM) image of PI30PT, its total and individual EDS
bility hamper their application to LIBs [48]. Fan et al. mappings of elements C, N, O, and S along with EDS
(2015) used core-shell FeOF@PEDOT nanorods having spectra of PT, PI, PI10PT, PI30PT, and PI50PT. Nitro-
fluorine partially substituted with oxygen in FeF3 in gen and oxygen peaks are clearly seen in the PI sample
a conversion-reaction cathode in order to increase reac- which are hardly observed in other composite samples.
tion kinetics and reduction of potential hysteresis [48]. However, sulfur peak in the PI@PT composites increases
Nanolayer PEDOT coating facilitates fast electronic con- with an increase in the content of PT. Figure 1.7 repre-
nection and prevents side reactions. A capacity of 5.60 × sents the cyclic voltammograms (CVs) and charge–dis-
105 mAh kg−1 was delivered at 1.0 × 104 mA kg−1 with charge profiles of PI, PI10PT, PI30PT, and PI50PT. The
an energy density of higher than 1.10 × 103 Wh kg–1. PI30PT electrode shows two pairs of well-resolved redox
Inorganic oxides, sulfides, and graphite allow intercal- peaks with two reduction peaks at 2.39 and 2.58 V and
ation of guests into this host using suitable procedures corresponding oxidation peaks at 2.52 and 2.77 V,
[49,50]. Different two-dimensional (2D) lamellar nano- respectively (Figure 1.7a). The appearance of doublets
composites have also been chemically synthesized confirms a reversible two-electron redox reaction during
through delamination of a layered host into molecular both lithiation and de-lithiation processes, related to
single layers [51,52]. Transition metal dichalcogenides stepwise formation of radical anion and dianion. How-
having lamellar structures are amenable to intercalation ever, corresponding doublets for both PI and PI10PT are
[53]. For example, MoS2 has been employed as an inor- not well defined, owing to their low electronic conductiv-
ganic host for polymers to be used as battery cathodes ity caused by zero or lower concentration of highly con-
[54] and encapsulating support for magnetic materials ductive PT coating which results in slow charge transfer
[55]. Insertion of conducting polymers into layered host kinetics between the radical anion and the dianion.
materials has been adopted for preparing hybrid mater- Higher potential during discharge and lower potential
ials with enhanced properties. Murugan et al. (2006) during charge for the PI30PT electrode were observed
used exfoliation-induced PEDOT nanoribbon formed suggesting that it has the lowest polarization among
between the layers of MoS2 nanosheets as cathode these polymeric electrodes, resulting in high utilization
material for LIBs [56]. Significant improvement in the efficiency of polymer cathode and high specific capacity
discharge capacity (1 × 105 mAh kg−1) was observed as (Figure 1.7b). The composition and electrochemical
compared to MoS2 (4 × 104 mAh kg−1). properties of different PT-based cathodes have been
Organic electrodes such as aromatic polyimides (PIs) tabulated for LIBs in Table 1.4.
with theoretical capacity of about 400 mAh g–1 and Organosulfur compounds with multiple thiol groups
working voltage of 2.5 V vs. Li/Li+ have also been used or disulfide moieties also possess high theoretical cap-
[38]. Discharging/lithium intake by aromatic polyimides acity, chemical tunability, and redox system to capture
involves acceptance of two electrons, thus forming Li ions during discharge [64,65]. Despite of low cost and
a delocalized radical anion and dianion [57]. However, it globally abundant nature of sulfur, these compounds
has low redox potential and poor structural stability, have low electronic conductivity and sluggish kinetics of
restricting its use [58,59]. Lithium storage mechanism is redox reactions at room temperature [66,67]. 2,5-Dimer-
a simple redox reaction in aromatic polyimide [60]. capto1,3,4-thiadiazole (DMcT) is a promising organosul-
Additives such as graphene or carbon nanotubes have fur compound as cathode and Kiya et al. (2006) used
been used to overcome this intrinsic electrical insulation DMcT–PEDOT composite cathodes for LIBs [68].
of aromatic polyimides [61,62]. A polyimide derivative
obtained from condensation polymerization of pyromelli-
tic dianhydride and 2,6-diaminoanthraquinone (PMAQ) 1.3.1.1.2 Li–S Batteries
and single-walled carbon nanotube network (SWNT) Low energy density of conventional LIBs cannot fulfill
delivered capacity of 1.90 × 105 mAh kg–1 at a current the high energy requirement. Therefore, LSBs possessing
rate of 0.1 C [63]. Lyu et al. (2017) prepared an organic high theoretical capacity (1.675 × 106 mAh kg−1) and
(a)
1 μm
C N O S
(b)
PT
Intensity (a.u.)
PI50PT
PI30PT
PI10PT
PI
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Energy (keV)
FIGURE 1.6 (a) SEM image of PI30PT, its total and individual EDS mappings of elements C, N, O, and S; (b) EDS spectra of PT,
PI, PI10PT, PI30PT, and PI50PT (Reprinted with permission from Royal Society of Chemistry, London, Great Britain) [38].
0.15
3.2
(a) (b)
0.10 3.0
2.8
0.05
E / V vs. Li/Li+
j (mA cm )
-2
2.6
0.00
2.4
PI
-0.05 PI10PT PI
2.2
PI30PT PI10PT
PI50PT PI30PT
-0.10 2.0
PI50PT
1.8
-0.15
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 0 50 100 150 200
+
E / V vs. Li/Li Capacity (mAh g-1)
FIGURE 1.7 Cyclic voltammograms (CVs) of (a) PI, PI10PT, PI30PT, and PI50PT at a scan rate of 0.05 mV s−1; charge–discharge
profiles of (b) PI, PI10PT, PI30PT, and PI50PT at a current rate of C/10 (Reprinted with permission from Royal Society of Chemis-
try, London, Great Britain) [38].
TABLE 1.4
12
Composition and electrochemical properties of PT-based cathodes for Li-ion batteries (LIBs)
S. no. Working electrode (cathodic material) Counter Electrolyte/ Method of Working Specific Charge Reversible Coulombic Reference
electrode/ Solvent preparation/ voltage (V) capacity capacity/ capacity/ efficiency
Active material Conductive Binder
Separator Oxidant (mAhkg–1)/ discharge irreversible (%)/capacity
additive
current capacity capacity retention
density (mAh kg–1) (mAh kg–1) (%)/stable
(mA kg–1) cycle life
1 60 wt.% Polyimi- 30 wt.% 10 wt.% Li foil/Celgard LiPF6/EC: In-situ chemical 1.8–3.2 –/8.0 × 106 a –/– 2.168 × 100/94/1000 Lyu et al.
de@PT composites C45 PVDF 2320 DEC: DMC oxidation 105/– (2017) [38]
(1:1:1 v/v/v) polymerization/–
2 75 wt.% 20 wt.% 5 wt.% Li foil/Celgard LiClO4/EC: In-situ 2.5–4.1 1.569 × 105/ –/4.998 × 104 –/– –/–/– Bai (2010)
LiFePO4/PT Acetylene PTFE 2400 microporous DMC (1:1 v/v) polymerization/ 3.4 × 104 b [39]
composites black membrane FeCl3
3 PEDOT–LiFePO4 – – RVC foam/Celgard LiPF6/EC: D3PIE/– 2.2–4.0 –/– –/1.6 × 105 –/– –/69/>75 Trinh et al.
films 2500 DMC (1:1 v/v) (2013) [40]
4 80 wt.% LiFePO4/C 10 wt.% 10 wt.% Li foil/polypropyl- LiPF6/EC: Surfactant– 2.3–4.5 9.5 × 104/ –/1.66 × 105 –/– 100/86/1200 Xing et al.
composite powders acetylene PVDF ene (Celgard 2500) EMC:DEC mediated 1.7 × 104 (2013) [41]
black (1:1:1 v/v/v) electropolymeriza-
tion/–
5 PEDOT/Li2MnSiO4 – – Li/– LiClO4/EC and Supercritical 1.5–4.5 –/2.165 × –/3.13 × 105 –/– 100/42/20 Kempaiah
nanoparticles DMC solvothermal 105 c et al. (2012)
method/– [42]
6 85 wt.% LiV3O8/PT 10 wt.% 5 wt.% Li/Celgard 2300 LiPF6/EC: In situ oxidative 1.8–4.0 –/3.0 × 105 –/2.133 × 105 –/– –/–/50 Guo et al.
composite Carbon PVDF film DMC (1:1 v/v) polymerization/ (2014) [47]
black FeCl3
7 FeOF@PEDOT – – Li/– – In-situ 1.2–4.0 8.85 x 105 –/5.50 × 105 –/– 100/94/>150 Fan et al.
nanorods polymerization/– /1.0 × 104 (2015) [48]
8 Nanoribbon of Carbon PTFE Li foil/– LiClO4/E: Refluxing 2.0–4.4 –/1.5 × 104 –/1.0 × 105 –/– –/–/– Murugan
PEDOT/MoS2 black DMC (1:1 v/v) followed by et al. (2006)
nanocomposite acidification/FeCl3 [56]
PT: polythiophene.
PEDOT: poly(3,4-ethylene dioxythiophene).
DMcT: 2,5-dimercapto-1,3,4-thiadiazole.
PTFE: polytetrafluoroethylene.
PVDF: poly(vinylidene)fluoride.
D3PIE: dynamic three-phase interline electropolymerization.
EC: ethylene carbonate.
DEC: diethyl carbonate.
EMC: ethylmethyl carbonate.
DMC: dimethyl carbonate.
na: Unit conversion has been done by following the relation, 1 C = 4.00 × 105 mA kg–1 [38].
nb: Unit conversion has been done by following the relation, 1 C = 1.70 × 105 mA kg–1 [39].
nc: Unit conversion has been done by following the relation, 1 C = 4.33 × 105 mA kg–1 [42].
energy density (2.567 × 103 Wh kg−1) have gained atten- Abundant nanopores and large surface area of aPG pro-
tion of the scientific community as new-generation vide intimate contact and strong interaction with S species.
energy-storage devices [69,70]. However, LSBs face sev- High specific discharge capacity (1.198 × 106 mAh kg−1 at
eral issues such as 0.1 C) in the first cycle, excellent rate capability, and good
cycling stability were obtained with reversible capacity of
• low sulfur utilization, 8.45 × 105 mAh kg−1 after 200 cycles.
• poor long-term cycling stability due to the low con- Raman spectra and thermogravimetric curves of
ductivity of sulfur, sulfur, S@aPG, PEDOT/S@aPG, aPG, and PEDOT–
• lithium polysulfide shuttle effect, PSS have been presented in Figures 1.8 and 1.9, respect-
• polysulfide corrosion, ively. Elemental sulfur shows three sharp peaks (155,
• large volume change during discharge–charge 220, and 476 cm−1) and the S@aPG composite shows
processes, the characteristic peaks of elemental sulfur and the aPG
• Li dendrite growth, and (G band at 1590 cm−1 and D band at 1353 cm−1) and
• less reactivity with liquid electrolytes than Li metal. additional three new peaks at 318, 374, and 394 cm−1
attributable to C–S in plane bending, C–S deformation,
Conductive polymers act as capable matrices for confine- and S–S stretching vibrations, respectively (Figure 1.8b).
ment of lithium polysulfides. The role of different con- However, the S@aPG composite only shows characteris-
ductive polymers on electrochemical performances of tic peaks of the aPG (1590 and 1353 cm–1) only and the
S electrode is still poorly understood due to its vastly dif- peaks in the range of 150–500 cm–1 are not obvious due
ferent structural configurations. The conductive polymer to the coating of PEDOT–PSS thin layer on the surface
layer facilitates charge transport and prevents the dissol- of S@aPG. Figure 1.9 indicates the existence of close
ution of polysulfides. PEDOT composites achieve excel- interactions between sulfur and aPG. PEDOT/S@aPG
lent reversibility, good stability, and fast kinetics. Li et al. composite shows the weight loss peak of sulfur that
(2013) systematically investigated the influence of three of shifts to higher temperature range of 150–320ºC with
the most well-known conductive polymers—polyaniline, a much lower evaporation rate indicating strong confine-
polypyrrole, and PEDOT—on sulfur cathode based on ment effect due to incorporation of PEDOT–PSS for
polymer-coated hollow sulfur nanospheres with high uni- improving the stability of sulfur, and the sulfur loading
formity [71]. Experimental observations and theoretical of PEDOT/S@aPG is 60.1%.
simulations revealed that the capability of these three Oschmann et al. (2015) reported the copolymerization
polymers in improving long-term cycling stability and of sulfur- and allyl-terminated poly(3-hexylthiophene-
high-rate performance of sulfur cathode decreased in the 2,5-diyl) (P3HT) for the first time through Grignard
order PEDOT > polypyrrole > polyaniline. Table 1.5 pre- metathesis polymerization [74]. Homogeneous composite
sents a comparison of the composition and electrochem- of S-P3HT forms a framework of interconnected charge
ical properties of different PT-based cathodes for LSBs. transfer channels, and its assembly into electrodes
Porous carbon support is very important in carbon– increases the performance of LSBs. Nuclear magnetic
sulfur composite cathode materials for LSBs, but it is resonance (NMR) spectroscopy, size exclusion chroma-
electrochemically inactive, thus lowering the specific cap- tography, and near-edge X-ray absorption fine spectros-
acity and overall energy density. Sulfur nanoparticles copy confirm the formation of a C−S bond in the
(SNPs) have been used to overcome the electrical insulat- copolymer. Even though P3HT is incompatible with
ing issue without any other supporting materials because elementary sulfur, S-P3HT copolymer can be well dis-
SNPs offer high specific surface area, abundant electron persed in sulfur on the sub-micrometeric level. Enhanced
transport active sites and require short electron transfer cycling performance was obtained for S-P3HT copoly-
distance. Chen et al. (2013) reported the synthesis of mer (7.99 × 105 mAh kg−1) as compared to simple mix-
ultrafine SNPs having diameter 10–20 nm through mem- ture lacking covalent link between sulfur and P3HT
brane-assisted precipitation technique followed by (5.44 × 105 mAh kg−1) after 100 cycles at 0.5 C.
PEDOT coating to form S/PEDOT core/shell nanoparti- Sulfur is stored in the large interstitial sites of Prus-
cles [72]. Ultrasmall size of SNPs assists in electrical con- sian blue analogs (PBAs), and efficient reversible inser-
duction and increases sulfur utilization. Conducting tion/extraction of both Li+ and electrons takes place due
PEDOT shell encapsulation restricts polysulfide diffusion to the presence of well-trapped mobile dielectron redox
and lessens self-discharging as well as shuttle effect, thus centers in LSBs. Na2Fe[Fe(CN)6] possesses a large open
enhancing the cycling stability. Initial discharge capacity framework. As a cathode, it can store sulfur and act as
of 1.117 × 106 mAh kg−1 and stable capacity of 9.30 × a polysulfide diffusion inhibitor depending on the Lewis
105 mAh kg−1 after 50 cycles were obtained. Li et al. acid–base bonding effect. S@Na2Fe[Fe(CN)6]@PEDOT
(2014) prepared PEDOT–PSS-coated sulfur@activated composite prepared by Su et al. (2017) has excellent elec-
porous graphene composite (PEDOT/S@aPG) by trochemical properties due to the internal transport of
impregnation of S with aPG followed by encapsulation Li+/e−, thus maximizing the use of sulfur [75]. The
with PEDOT–PSS and used it as cathode for LSBs [73]. open metal centers serve as Lewis acid sites with high
14
TABLE 1.5
Composition and electrochemical properties of PT-based cathodes for Li–S batteries (LSBs) and LPB
S. Working electrode (cathodic material) Counter- Electrolyte/ Method of Working Specific Charge Reversible Coulombic Reference
no. electrode/ solvent preparation/ voltage (V) capacity capacity/ capacity/ efficiency
Active material Conductive Binder
Separator oxidant (mAh kg–1)/ discharge irreversible (%)/capacity
additive
current capacity capacity retention
density (mAh kg–1) (mAh kg–1) (%)/stable
(mA kg–1) cycle life
Li-S batteries
1 Hollow sulfur nano- – – Li/– LITSFI/DME: COP/(NH4)2S2 2.5–4 –/– –/1.285 × 106 1.071 × 106 –/83 (after 100 Li et al.
spheres@PEDOT DOL (1:1 v/v) O8 (after 100 cycles)/ – (2013) [71]
LiNO3 (1 wt.%) as cycles)/ –
an additive
2 70 wt.% S/PEDOT 20 wt.% 10 wt.% LA- Li foil/porous LiTFSI/DOL: Membrane- 1.0–2.8 9.3 × 105/ –/1.117 × 106 9.3 × 105 90/–/50 Chen et al.
core/shell carbon 132 latex polypropyl- DME (1:1 v/v) assisted pre- 4.0 × 105 (after 50 (2013) [72]
nanoparticles black ene cipitation and cycles)/ –
COP/FeCl3
3 80 wt.% PEDOT– 10 wt.% 10 wt.% Li foil/porous LiTFSI/DME: Ultrasonic 1.5–3.0 1.198 × 106/ –/1.180 × 106 8.45 × 105 99/43.6/200 Li et al.
PSS-coated sulfur@- acetylene LA132 in polypropyl- DOL (1:1 v/v) stirring/– 1.675 × 105 a (after 200 (2014) [73]
activated porous gra- black deionized ene mem- with 1% LiNO3 cycles)/–
phene composite water–ethanol brane (Cel- as an additive
solution gard 2400)
4 70 wt.% S-P3HT 25 wt.% 5 wt.% Li foil/ LiTFSI and Grignard 1.7–2.8 1.154 × 106/ –/– –/– –/–/– Oschmann
copolymer carbon polyethylene polyethylene LiNO3/DOL: metathesis 8.375 × 105 a et al.
(Super P) DME (1:1 polymerization/ (2015) [74]
v/v) –
5 S@Na2Fe[Fe(CN)6] – – –/– – Solution 1.7–2.7 1.291 × 106/ –/1.020 × 106 7.7 × 105 –/–/– Su et al.
@PEDOT composite method and 1.675 × 106 a (after 100 (2017) [75]
PEDOT layer cycles)/ –
coating/–
6 PEDOT-coated dia- – – Li foil/porous LiTFSI/DOL: PEDOT coat- 1.5–3.0 –/1.675 × –/1.52 × 106 –/– –/76 (after 250 Zhang
mond-shaped sulfur/ polypropyl- DME (1:1 v/v) ing through 105 a cycles)/ – et al.
SWCNT composite ene mem- with 0.1 centrifugation/ (2017a)
brane (Cel- M LiNO3 as an – [76]
gard 2400) additive
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strange that a dispensation so cruel should visit them; when, in
reality, it was an occasion for joy, that they should thus be made, in
suffering, partakers of the glory of Christ, won in like manner. He
moreover warns them to keep a constant watch over their conduct,
to be prudent and careful, because “the accusing prosecutor” was
constantly prowling around them, seeking to attack some one of
them with his devouring accusations. Him they were to meet, with a
solid adherence to the faith, knowing as they did, that the
responsibilities of their religious profession were not confined within
the narrow circle of their own sectional limits, but were shared with
their brethren in the faith throughout almost the whole world.
From all these particulars the conclusion is inevitable, that there

was in the condition of the Christians to whom he wrote, a most
remarkable crisis just occurring,――one too of no limited or local
character; and that throughout Asia Minor and the whole empire, a
trying time of universal trouble was immediately beginning with all
who owned the faith of Jesus. The widely extended character of the
evil, necessarily implies its emanation from the supreme power of
the empire, which, bounded by no provincial limits, would sweep
through the world in desolating fury on the righteous sufferers; nor is
there any event recorded in the history of those ages, which could
thus have affected the Christian communities, except the first
Christian persecution, in which Nero, with wanton malice, set the
example of cruel, unfounded accusation, that soon spread
throughout his whole empire, bringing suffering and death to
thousands of faithful believers.
Accusing prosecutor.――The view which Hug takes of the scope of the epistle, throws
new light on the true meaning of this passage, and abundantly justifies this new translation,
though none of the great New Testament lexicographers support it. The primary, simple
senses of the words also, help to justify the usage, as well as their similar force in other
passages. A reference to any lexicon will show that elsewhere, these words bear a meaning
accordant with this version. The first noun never occurs in the New Testament except in a
legal sense. The Greek is Ὁ αντιδικος ὑμων διαβολος, (1 Peter v. 8,) in which the last word
(diabolos) need not be construed as a substantive expression, but may be made an
adjective, belonging to the second word, (antidikos.) The last word, under these
circumstances, need not necessarily mean “the devil,” in any sense; but referring directly to
the simple sense of its primitive, must be made to mean “calumniating,” “slanderous,”
“accusing,”――and in connection with the technical, legal term, αντιδικος, (whose primary,
etymological sense is uniformly a legal one, “the plaintiff or prosecutor in a suit at law,”) can
mean only “the calumniating (or accusing) prosecutor.” The common writers on the epistle,
being utterly ignorant of its general scope, have failed to apprehend the true force of this
expression; but the clear, critical judgment of Rosenmueller, (though he also was without
the advantage of a knowledge of its history,) led him at once to see the greater justice of the
view here given; and he accordingly adopts it, yet not with the definite, technical application
of terms justly belonging to the passage. He refers vaguely to others who have taken this
view, but does not give names.
The time when this epistle was written is very variously fixed by the different writers to
whom I have above referred. Lardner dating it at Rome, concludes that the time was
between A. D. 63 and 65, because he thinks that Peter could not have arrived at Rome
earlier. This inference depends entirely on what he does not prove,――the assertion that by
Babylon, in the date, is meant Rome. The proofs of its being another place, which I have
given above, will therefore require that it should have been written before that time, if Peter
did then go to Rome. And Michaelis seems to ground upon this notion his belief, that it “was
written either not long before, or not long after, the year 60.” But the nobly impartial Hug
comes to our aid again, with the sentence, which, though bearing against a fiction most
desirable for his church, he unhesitatingly passes on its date. From his admirable detail of
the contents and design of the epistle, he makes it evident that it was written (from Babylon)
some years after the time when Peter is commonly said to have gone to Rome, never to
return. This is the opinion which I have necessarily adopted, after taking his view of the
design of the epistle.
Another series of passages in this epistle refers to the remarkable

fact, that the Christians were at that time suffering under an
accusation that they were “evil-doers,” malefactors, criminals liable
to the vengeance of the law; and that this accusation was so
general, that the name, Christian, was already a term denoting a
criminal directly liable to this legal vengeance. This certainly was a
state of things hitherto totally unparalleled in the history of the
followers of Christ. In all the accounts previously given of the nature
of the attacks made on them by their enemies, it is made to appear
that no accusation whatever was sustained or even brought against
them, in reference to moral or legal offences; but they were always
presented in the light of mere religious dissenters and sectaries. At
Corinth, the independent and equitable Gallio dismissed them from
the judgment-seat, with the upright decision that they were
chargeable with no crime whatever. Felix and Festus, with king
Agrippa II., also, alike esteemed the whole procedure against Paul
as a mere theological or religious affair, relating to doctrines and not
to moral actions. At Ephesus, even one of the high officers of the city
did not hesitate to declare, in the face of a mob raging against Paul
and his companions, that they were innocent of all crime. And even
as late as the seventh year of Nero, the name of Christian had so
little of an odious or criminal character, that Agrippa II. did not
disdain to declare himself almost persuaded to assume the name
and character. And the whole course of their history abundantly
shows, that so far from the idea of attacking the Christian
brotherhood in a mass, as guilty of legal offenses, and making their
very name nearly synonymous with criminal, no trace whatever of
such an attack appears, until three years after the last mentioned
date, when Nero charged the Christians, as a sect, with his own
atrocious crime, the dreadful devastation by fire of his own capital;
and on this ground, every where instituted a cruel persecution
against them. In connection with this procedure, the Christians are
first mentioned in Roman history, as a new and peculiar class of
people, called Christiani, from their founder, Christus; and in
reference to this matter, abusive charges are brought against them.
Evil doers.――These passages are in ii. 12, iii. 16, iv. 15, where the word in Greek is
κακοποιοι, (kakopoioi,) which means a malefactor, as is shown in John xviii. 30, where the
whole point of the remark consists in the fact, that the person spoken of was considered an
actual violator of known law; so that the word is evidently limited throughout, to those who
were criminals in the eye of the law.
The name Christian denoting a criminal.――This is manifest from iv. 16, where they are
exhorted to suffer for this alone, and to give no occasion whatever for any other criminal
accusation.
BETHLEHEM, AT NIGHT.
A third characteristic of the circumstances of those to whom this

epistle is addressed, is, that they were obliged to be constantly on
their guard against accusations, which would expose them to capital
punishment. They were objects of scorn and obloquy, and were to
expect to be dragged to trial as thieves, murderers, and as wretches
conspiring secretly against the public peace and safety; and to all
this they were liable in their character as Christians. The apostle,
therefore, in deep solicitude for the dreadful condition and liabilities
of his friends, warns those who, in spite of innocence, are thus made
to suffer, to consider all their afflictions as in accordance with the
wise will of God, and, in an upright course of conduct, to commit the
keeping of their souls to him, as a faithful guardian, who would not
allow the permanent injury of the souls which he had created. Now,
not even a conjecture can be made, much less, any historical proof
be brought, that beyond Palestine any person had ever yet been
made to suffer death on the score of religion, or of any stigma
attaching to that sect, before the time when Nero involved them in
the cruel charge just mentioned. The date of the first instances of
such persecutions was the eleventh year of the reign of Nero, under
the consulships of Caius Lecanius Bassus, and Marcus Licinius
Crassus, according to the Roman annals. The commencement of the
burning of Rome, which was the occasion of this first attack on the
Christians, was in the last part of the month of July; but the
persecution did not begin immediately. After various contrivances to
avert the indignation of the people from their imperial destroyer, the
Christians were seized as a proper expiatory sacrifice, the choice
being favored by the general dislike with which they were regarded.
This attack being deferred for some time after the burning, could not
have occurred till late in that year. The epistle cannot have been
written before its occurrence, nor indeed until some time afterwards;
because a few months must be allowed for the account of it to
spread to the provinces of Asia, and it must have been still later
when the news of the difficulty could reach the apostle, so as to
enable him to appreciate the danger of those Christians who were
under the dominion of the Romans. It is evident, then, that the epistle
was not written in the same year in which the burning occurred; but
in the subsequent one, the twelfth of Nero’s reign, and the sixty-fifth
of the Christian era. By that time the condition and prospects of the
Christians throughout the empire were such as to excite the deepest
solicitude in the great apostle, who, though himself residing in the
great Parthian empire, removed from all danger of injury from the
Roman emperor, was by no means disposed to forget the high
claims the sufferers had on him for counsel and consolation. This
dreadful event was the most important which had ever yet befallen
the Christians, and there would certainly be just occasion for
surprise, if it had called forth no consolatory testimony from the
founders of the faith, and if no trace of it could be found in the
apostolic records.
Committing the keeping of their souls to God.――This view of the design of the epistle
gives new force to this passage, (iv. 19.)
First mentioned in Roman history.――This is by Tacitus, (Annals xv. 44,) who thus
speaks of them:――“Nero condendae urbis novae et cognomento suo appellandae gloriam
quaerere, et sic jussum incendium credebatur. Ergo abolendo rumori subdidit reos, et
quaesitissimis poenis affecit, quos per flagitia invisos, vulgus Christianos appellabat,”
&c.――“It was believed that Nero, desirous of building the city anew, and of calling it by his
surname, had thus caused its burning. To get rid of this general impression, therefore, he
brought under this accusation, and visited with the most exquisite punishments, a set of
persons, hateful for their crimes, commonly called Christians. The name was derived from
Christus, who, in the reign of Tiberius, was seized and punished by Pontius Pilate, the
procurator. The ruinous superstition, though checked for a while, broke out again, not only
in Judea, the source of the evil, but also in the city, (Rome.) Therefore those who professed
it were first seized, and then, on their confession, a great number of others were convicted,
not so much on the charge of the arson, as on account of the universal hatred which existed
against them. And their deaths were made amusing exhibitions, as, being covered with the
skins of wild beasts, they were torn to pieces by dogs, or were nailed to crosses, or, being
daubed with combustible stuff, were burned by way of light, in the darkness, after the close
of day. Nero opened his own gardens for the show, and mingled with the lowest part of the
throng, on the occasion.” (The description of the cruel manner in which they were burned,
may serve as a forcible illustration of the meaning of “the fiery trial,” to which Peter alludes,
iv. 12.) By Suetonius, also, they are briefly mentioned. (Nero, chapter 15.) “Afflicti suppliciis
Christiani, genus hominum superstitionis novae et maleficae.”――“The Christians, a sort of
men of a new and pernicious (evil doing) superstition, were visited with punishments.”
That this Neronian persecution was as extensive as is here made to appear, is proved
by Lardner and Hug. The former in particular, gives several very interesting evidences, in
his “Heathen testimonies,” especially the remarkable inscription referring to this persecution,
found in Portugal. (Collection of Ancient Jewish and Heathen Testimonies, chapter iii.)
From the uniform tone in which the apostle alludes to the danger
as threatening only his readers, without the slightest allusion to the
circumstance of his being involved in the difficulty, is drawn another
important confirmation of the locality of the epistle. He uniformly uses
the second person when referring to trials, but if he himself had then
been so situated as to share in the calamity for which he strove to
prepare them, he would have been very apt to have expressed his
own feelings in view of the common evil. Paul, in those epistles
which were written under circumstances of personal distress, is very
full of warm expressions of the state of mind in which he met his
trials; nor was there in Peter any lack of the fervid energy that would
burst forth in similarly eloquent sympathy, on the like occasions. But
from Babylon, beyond the bounds of Roman sway, he looked on
their sufferings only with that pure sympathy which his regard for his
brethren would excite; and it is not to be wondered, then, that he
uses the second person merely, in speaking of their distresses. The
bearer of this epistle to the distressed Christians of Asia Minor, is
named Silvanus, generally supposed to be the same with Silvanus or
Silas, mentioned in Paul’s epistles, and in the Acts, as the
companion of Paul in his journeys through some of those provinces
to which Peter now wrote. There is great probability in this
conjecture, nor is there anything that contradicts it in the slightest
degree; and it may therefore be considered as true. Some other
great object may at this time have required his presence among
them, or he may have been then passing on his journey to rejoin
Paul, thus executing this commission incidentally.
This view of the scope and contents of this epistle is taken from Hug, who seems to
have originated it. At least I can find nothing of it in any other author whom I have consulted.
Michaelis, for instance, though evidently apprehending the general tendency of the epistle,
and its design to prepare its readers for the coming of some dreadful calamity, was not led
thereby to the just apprehension of the historical circumstances therewith connected. (Hug,
II. §§ 162‒165.――Michaelis Vol. IV. chapter xxvii. §§ 1‒7.)
the second epistle.
After writing the former epistle to the Christians of Asia Minor,

Peter probably continued to reside in Babylon, since no occurrence
is mentioned which could draw him away, in his old age, from the
retired but important field of labor to which he had previously
confined himself. Still exercising a paternal watchfulness, however,
over his distant disciples, his solicitude before long again excited him
to address them in reference to their spiritual difficulties and
necessities. The apprehensions expressed in the former epistle,
respecting their maintenance of a pure faith in their complicated
trials, had in the mean time proved well-grounded. During the
distracting calamities of Nero’s persecution, false teachers had
arisen, who had, by degrees, brought in pernicious heresies among
them, affecting the very foundations of the faith, and ending in the
most ruinous consequences to the belief and practice of some. This
second epistle he wrote, therefore, to stir up those who were still
pure in heart, to the remembrance of the true doctrines of
Christianity, as taught by the apostles; and to warn them against the
heretical notions that had so fatally spread among them. Of the
errors complained of, the most important seems to have been the
denial of the judgment, which had been prophesied so long.
Solemnly re-assuring them of the certainty of that awful series of
events, he exhorted them to the steady maintenance of such a holy
conduct and godly life, as would fit them to meet the great change
which he so sublimely pictured, whenever and however it should
occur; and closed with a most solemn charge to beware lest they
also should be led away by the error of the wicked, so as to fall from
their former steadfast adherence to the truth. In the former part of the
epistle he alluded affectingly to the nearness of his own end, as an
especial reason for his urgency with those from whom he was so
soon to be parted. “I think it meet as long as I am in this tabernacle,
to stir you up to the remembrance of these things, knowing as I do
that the putting off of my tabernacle is very near, according to what
our Lord Jesus Christ made known to me.” This is an allusion to the
prophecy of his Master at the meeting on the lake, after the
resurrection, described in the last chapter of John’s gospel.
“Therefore,” writes the aged apostle, “I will be urgent that you, after
my departure, may always hold these things in your memory.” All
which seems to imply an anticipated death, of which he was
reminded by the course of natural decay, and by the remembrance
of the parting prophecy of his Master, and not by anything very
imminently dangerous or threatening in his external circumstances,
at the time of writing. This was the last important work of his
adventurous and devoted life; and his allusions to the solemn scenes
of future judgment were therefore most solemnly appropriate. Those
to whom he wrote could expect to see his face no more, and his
whole epistle is in a strain accordant with these circumstances,
dwelling particularly on the awful realities of a coming day of doom.
The first epistle of Peter has always been received as authentic,

ever since the apostolic writings were first collected, nor has there
ever been a single doubt expressed by any theologian, that it was
what it pretended to be; but in regard to the epistle just mentioned as
his second, and now commonly so received, there has been as
much earnest discussion as concerning any other book in the sacred
canon, excepting, perhaps, the epistle to the Hebrews and John’s
Revelation. The weight of historical testimony is certainly rather
against its authenticity, since all the early Fathers who explicitly
mention it, speak of it as a work of very doubtful character. In the first
list of the sacred writings that is recorded, this is not put among
those generally acknowledged as of divine authority, but among
those whose truth was disputed. Still, quotations from it are found in
the writings of the Fathers, in the first, second and third centuries, by
whom it is mentioned approvingly, although not specified as inspired
or of divine authority. But even as late as the end of the fourth
century there were still many who denied it to be Peter’s, on account
of supposed differences of style observable between this and the
former epistle, which was acknowledged to be his. The Syrian
Christians continued to reject it from their canon for some time after;
for in the old Syriac version, executed before A. D. 100, this alone, of
all books supposed to have been written before that translation that
are now considered a part of the New Testament, is not contained,
though it was regarded by many among them as a good book, and is
quoted in the writings of one of the Syrian Fathers, with respect.
After this period, however, these objections were soon forgotten, and
from the fifth century downwards, it has been universally adopted
into the authentic canon, and regarded with that reverence which its
internal evidences of truth and genuineness so amply justify. Indeed,
it is on its internal evidence, almost entirely, that its great defense
must be founded,――since the historical testimonies, (by common
confession of theologians,) will not afford that satisfaction to the
investigator, which is desirable on subjects of this nature; and though
ancient usage and its long-established possession of a place in the
inspired code may be called up in its support, still there will be
occasion for the aid of internal reasons, to maintain a positive
decision as to its authenticity. And this sort of evidence, an
examination by the rigid standards of modern critical theology proves
abundantly sufficient for the effort to which it is summoned; for
though it has been said, that since the ancients themselves were in
doubt, the moderns cannot expect to arrive at certainty, because it is
impossible to get more historical information on the subject, in the
nineteenth century, than ecclesiastical writers had within reach in the
third and fourth centuries; still, when the question of the authenticity
of the work is to be decided by an examination of its contents, the
means of ascertaining the truth are by no means proportioned to the
antiquity of the criticism. In the early ages of Christianity, the science
of faithfully investigating truth hardly had an existence; and such has
been the progress of improvement in this department of knowledge,
under the labors of modern theologians, that the writers of the
nineteenth century may justly be considered as possessed of far
more extensive and certain means of settling the character of this
epistle by internal evidence, than were within the knowledge of those
Christian fathers who lived fourteen hundred years ago. The great
objection against the epistle in the fourth century, was an alleged
dissimilarity of style between this and the former epistle. Now, there
can be no doubt whatever that modern Biblical scholars have vastly
greater means for judging of a rhetorical question of this kind, than
the Christian fathers of the fourth century, of whom those who were
Grecians were really less scientifically acquainted with their own
language, and no more qualified for a comparison of this kind, than
those who live in an age when the principles of criticism are so much
better understood. With all these superior lights, the results of the
most accurate modern investigations have been decidedly favorable
to the authenticity of the second epistle ascribed to Peter, and the
most rigid comparisons of its style with that of the former, have
brought out proofs triumphantly satisfactory of its identity of origin
with that,――proofs so much the more unquestionable, as they are
borrowed from coincidences which must have been entirely natural
and incidental, and not the result of any deliberate collusion.
This account of the second epistle is also taken from Hug and Michaelis, to whom, with
Lardner, reference may be made for the details of all the arguments for and against its
authenticity.
As to the place and time of writing this epistle, it seems quite

probable that it was written where the former one was, since there is
no account or hint whatever of any change in Peter’s external
circumstances; and that it was written some months after it, is
unquestionable, since its whole tenor requires such a period to have
intervened, as would allow the first to reach them and be read by
them, and also for the apostle to learn in the course of time the
effects ultimately produced by it, and to hear of the rise of new
difficulties, requiring new apostolical interference and counsel. The
first seems to have been directed mainly to those who were
complete Jews, by birth or by proselytism, as appears from the terms
in which he repeatedly addresses them in it; but the sort of errors
complained of in this epistle seem to have been so exclusively
characteristic of Gentile converts, that it must have been written
more particularly with reference to difficulties in that part of the
religious communities of those regions. He condemns and refutes
certain heretics who rejected some of the fundamental truths of the
Mosaic law,――errors which no well-trained Jew could ever be
supposed to make, but which in motley assemblages of different
races, like the Christian churches, might naturally enough arise
among those Gentiles, who felt impatient at the inferiority in which
they seemed implicated by their ignorance of the doctrines of the
Jewish theology, in which their circumcised brethren were so fully
versed. It seems to have been more especially aimed at the rising
sect of the Gnostics, who are known to have been heretical on some
of the very points here alluded to. Its great similarity, in some
passages, to the epistle of Jude, will make it the subject of allusion
again in the life of that apostle.
his death.
Henceforth the writings of the New Testament are entirely silent as

to the chief apostle. Not a hint is given of the few remaining actions
of his life, nor of the mode, place, or time of his death; and all these
concluding points have been left to be settled by conjecture, or by
tradition as baseless. The only passage which has been supposed to
give any hint of the manner of his death, is that in the last chapter of
John’s gospel. “Jesus says to him――‘I most solemnly tell thee,
when thou wast young, thou didst gird thyself and walk whither thou
wouldst; but when thou shalt be old, another shall gird thee, and
carry thee whither thou wouldst not.’ This he said, to make known by
what sort of death he should glorify God.” It has been commonly said
that this is a distinct and unquestionable prophecy that he should in
his old age be crucified,――the expression, “another shall gird thee
and carry thee whither thou wouldst not,” referring to his being bound
to the cross and borne away to execution, since this was the only
sort of death by which an apostle could be said, with much propriety
or force, to glorify God. And the long-established authority of tradition
coinciding with this view, or rather, suggesting it, no very minute
examination into the sense of the passage has ever been made. But
the words themselves are by no means decisive. Take a common
reader, who has never heard that Peter was crucified, and it would
be hard for him to make out such a circumstance from the bare
prophecy as given by John. Indeed, such unbiased impressions of
the sense of the passage will go far to justify the conclusion that the
words imply nothing but that Peter was destined to pass a long life in
the service of his Master,――that he should after having worn out his
bodily and mental energies in his devoted exertions, attain such an
extreme decrepid old age as to lose the power of voluntary motion,
and die thus,――at least without necessarily implying any bloody
martyrdom. Will it be said that by such a quiet death he could not be
considered as glorifying God? The objection surely is founded in a
misapprehension of the nature of those demonstrations of devotion,
by which the glory of God is most effectually secured. There are
other modes of martyrdom than the dungeon, the sword, the axe, the
flame, and the stone; and in all ages since Peter, there have been
thousands of martyrs who have, by lives steadily and quietly devoted
to the cause of truth, no less glorified God, than those who were rapt
to heaven in flame, in blood, and in tortures inflicted by a malignant
persecution. Was not God truly glorified in the deaths of the aged
Xavier, and Eliot, and Swartz, or the bright, early exits of Brainerd,
Mills, Martyn, Parsons, Fisk, and hundreds whom the apostolic spirit
of modern missions has sent forth to labors as devoted, and to
deaths as glorious to God, as those of any who swell the deified lists
of the ancient martyrologies? The whole notion of a bloody
martyrdom as an essential termination to the life of a saint, grew out
of a papistical superstition; nor need the enlightened minds of those
who can better appreciate the manner in which God’s highest glory
is secured by the lives and deaths of his servants, seek any such
superfluous aids to crown the mighty course of the great apostolic
chief, whose solid claims to the name and honors of Martyr rest on
higher grounds than so insignificant an accident as the manner of his
death. All those writers who pretend to particularize the mode of his
departure, connect it also with the utterly impossible fiction of his
residence at Rome, on which enough has been already said. Who
will undertake to say, out of such a mass of matters, what is truth
and what is falsehood? And if the views above given, on the high
authority of the latest writers of even the Romish church, are of any
value for any purpose whatever, they are perfectly decisive against
the notion of Peter’s martyrdom at Rome, in the persecution under
Nero, since Peter was then in Babylon, far beyond the vengeance of
the Caesar; nor was he so foolish as ever after to have trusted
himself in the reach of a perfectly unnecessary danger. The
command of Christ was, “When you are persecuted in one city, flee
into another,”――the necessary and unquestionable inference from
which, was, that when out of the reach of persecution they should
not wilfully go into it. This is a simple principle of Christian action,
with which papist fable-mongers were totally unacquainted, and they
thereby afford the most satisfactory proof of the utter falsity of the
actions and motives which they ascribe to the apostles. One of these
stories thus disproved is connected with another adventure with that
useful character, Simon Magus, who, as the tale runs, after being
first vanquished so thoroughly by Peter in the reign of Claudius,
returned to Rome, in the reign of Nero, and made such progress
again in his magical tricks, as to rise into the highest favor with this
emperor, as he had with the former. This of course required a new
effort from Peter, which ended in the disgrace and death of the
magician, who, attempting to fly through the air in the presence of
the emperor and people in the theater, was by the prayer of Peter
caused to fall from his aspiring course, to the ground, by which he
was so much injured as to die soon after. The emperor being
provoked at the loss of his favorite, turned all his wrath against the
apostle who had been directly instrumental in his ruin, and
imprisoned him with the design of executing him as soon as might be
convenient. While in these circumstances, or as others say, before
he was imprisoned, he was earnestly exhorted by the disciples in
Rome, to make his escape. He accordingly, though very desirous of
being killed, (a most abominably irreligious wish, by the way,) began
to move off, one dark night; but had hardly got beyond the walls of
the city,――indeed he was just passing out of the gate-
way,――when, whom should he meet but Jesus Christ himself,
coming towards Rome. Peter asked, with some reasonable surprise,
“Lord! where are you going?” Christ answered, “I am coming to
Rome, to be crucified again.” Peter at once took this as a hint that he
ought to have stayed, and that Christ meant to be crucified again in
the crucifixion of his apostle. He accordingly turned right about, and
went back into the city, where, having given to the wondering
brethren an account of the reasons of his return, he was immediately
seized, and was crucified, to the glory of God. Now it is a sufficient
answer to this or any similar fable, to judge the blasphemous
inventor out of his own mouth, and out of the instructions given by
Christ himself to his servants, for their conduct, in all cases where
they were threatened with persecution, as above quoted.
Referring to his being bound to the cross.――Tertullian seems to have first suggested
this rather whimsical interpretation:――“Tunc Petrus ab altero cingitur, quum cruci
adstringitur.” (Tertullian, Scorpiace, 15.) There seems to be more rhyme than reason in the
sentence, however.
The rejection of this forced interpretation is by no means a new notion. The critical
Tremellius long ago maintained that the verse had no reference whatever to a prophecy of
Peter’s crucifixion, though he probably had no idea of denying that Peter did actually die by
crucifixion. Among more modern commentators too, the prince of critics, Kuinoel, with
whom are quoted Semler, Gurlitt and Schott, utterly deny that a fair construction of the
original will allow any prophetical idea to be based on it. The critical testimony of these great
commentators on the true and just force of the words, is of the very highest value; because
all received the tale of Peter’s crucifixion as true, having never examined the authority of the
tradition, and not one of them pretended to deny that he really was crucified. But in spite of
this pre-conceived erroneous historical notion, their nice sense of what was grammatically
and critically just, would not allow them to pervert the passage to the support of this long-
established view; and they therefore pronounce it as merely expressive of the helplessness
and imbecility of extreme old age, with which they make every word coincide. But
Bloomfield, entirely carried away with the tide of antique authorities, is “surprised that so
many recent commentators should deny that crucifixion is here alluded to, though they
acknowledge that Peter suffered crucifixion.” Now this last circumstance might well
occasion surprise, as it certainly did in me, when I found what mighty names had so
disinterestedly supported the interpretation which I had with fear and trembling adopted, in
obedience to my own long-established, unaided convictions; but my surprise was of a
decidedly agreeable sort.
The inventors of fables go on to give us the minute particulars of
Peter’s death, and especially note the circumstance that he was
crucified with his head downwards and his feet uppermost, he
himself having desired that it might be done in that manner, because
he thought himself unworthy to be crucified as his Master was. This
was a mode sometimes adopted by the Romans, as an additional
pain and ignominy. But Peter must have been singularly
accommodating to his persecutors, to have suggested this
improvement upon his tortures to his malignant murderers; and must
have manifested a spirit more accordant with that of a savage
defying his enemies to increase his agonies, than with that of the
mild, submissive Jesus. And such has been the evident absurdity of
the story, that many of the most ardent receivers of fables have
rejected this circumstance as improbable, more especially as it is not
found among the earliest stories of his crucifixion, but evidently
seems to have been appended among later improvements.
peter’s martyrdom.
The only authority which can be esteemed worthy of consideration on this point, is that
of Clemens Romanus, who, in the latter part of the first century, (about the year 70, or as
others say, 96,) in his epistle to the Corinthians, uses these words respecting
Peter:――“Peter, on account of unrighteous hatred, underwent not one, or two, but many
labors, and having thus borne his testimony, departed to the place of glory, which was his
due,”――(ὁυτως μαρτυρησας επορευθη εις τον οφειλομενον τοπον δοξης.) Now it is by no means
certain that the prominent word (marturesas) necessarily means “bearing testimony by
death,” or martyrdom in the modern sense. The primary sense of this verb is merely “to
witness,” in which simple meaning alone, it is used in the New Testament; nor can any
passage in the sacred writings be shown, in which this verb means “to bear witness to any
cause, by death.” This was a technical sense, (if I may so name it,) which the word at last
acquired among the Fathers, when they were speaking of those who bore witness to the
truth of the gospel of Christ by their blood; and it was a meaning which at last nearly
excluded all the true original senses of the verb, limiting it mainly to the notion of a death by
persecution for the sake of Christ. Thence our English words, martyr and martyrdom. But
that Clement by this use of the word, in this connection, meant to convey the idea of Peter’s
having been killed for the sake of Christ, is an opinion utterly incapable of proof, and
moreover rendered improbable by the words joined to it in the passage. The sentence is,
“Peter underwent many labors, and having thus borne witness” to the gospel truth, “went to
the place of glory which he deserved.” Now the adverb “thus,” (ὁυτως,) seems to me most
distinctly to show what was the nature of this testimony, and the manner also in which he
bore it. It points out more plainly than any other words could, the fact that his testimony to
the truth of the gospel was borne in the zealous labors of a devoted life, and not by the
agonies of a bloody death. There is not in the whole context, nor in all the writings of
Clement, any hint whatever that Peter was killed for the sake of the gospel; and we are
therefore required by every sound rule of interpretation, to stick to the primary sense of the
verb, in this passage. Lardner most decidedly mis-translates it in the text of his work, so that
any common reader would be grossly deceived as to the expression in the original of
Clement,――“Peter underwent many labors, till at last being martyred, he went,” &c. The
Greek word, ὁυτως, (houtos,) means always, “in this manner,” “thus,” “so,” and is not a mere
expletive, like the English phrase, “and so,” which is a mere form of transition from one part
of the narrative to the other.
In the similar passage of Clemens which refers to Paul, there is something in the
connection which may seem to favor the conclusion that he understood Paul to have been
put to death by the Roman officers. His words are,――“and after having borne his testimony
before governors, he was thus sent out of the world,” &c. Here the word “thus,” coming after
the participle, may perhaps be considered, in view also of its other connections, as implying
his removal from the world by a violent death, in consequence of the testimony borne by
him before the governors. This however, will bear some dispute, and will have a fuller
discussion elsewhere.
But in respect to the passage which refers to Peter, the burden of proof may fairly be
said to lie on those who maintain the old opinion. Here the word is shown to have, in the
New Testament, no such application to death as it has since acquired; and the question is
whether Clemens Romanus, a man himself of the apostolic age, who lived and perhaps
wrote, before the canon was completed, had already learned to give a new meaning to a
verb, before so simple and unlimited in its applications. No person can pretend to trace this
meaning to within a century of the Clementine age, nor does Suicer refer to any one who
knew of such use before Clement of Alexandria (See his Thesaurus; Μαρτυρ.) Clement
himself uses it in the same epistle (§ xvii.) in its unquestionable primary sense, speaking of
Abraham as having received an honorable testimony,――(εμαρτυρηθη;) for who will say that
Abraham was martyred, in the modern sense? The fact too that Clement nowhere else
gives the least glimmer of a hint that Peter died any where but in his bed, fixes the position
here taken, beyond all possibility of attack, except by its being shown that he uses this verb
somewhere else, with the sense of death unquestionably attached to it.
There is no other early writer who can be said to speak of the manner of Peter’s death,
before Dionysius of Corinth, who says that “Peter and Paul having taught in Italy together,
bore their testimony” (by death, if you please,) “about the same time.” An argument might
here also be sustained on the word εμαρτυρησαν, (emarturesan,) but the evidence of
Dionysius, mixed as it is with a demonstrated fable, is not worth a verbal criticism. The
same may be said of Tertullian and the rest of the later Fathers, as given in the note on
pages 228‒233.
An examination of the word Μαρτυρ, in Suicer’s Thesaurus Ecclesiasticus, will show the
critical, that even in later times, this word did not necessarily imply “one who bore his
testimony to the truth at the sacrifice of life.” Even Chrysostom, in whose time the peculiar
limitation of the term might be supposed to be very well established, uses the word in such
applications as to show that its original force was not wholly lost. By Athanasius too,
Shadrach, Meshach and Abed-nego are styled martyrs. Gregory Nazianzen also speaks of
“living martyrs.” (ζωντες μαρτυρες.) Theophylact calls the apostle John a martyr, though he
declares him to have passed through the hands of his persecutors unhurt, and to have died
by the course of nature. Clemens Alexandrinus has similar uses of the term; and the
Apostolical Constitutions, of doubtful date, but much later than the first century, also give it
in such applications. Suicer distinctly specifies several classes of persons, not martyrs in
the modern sense, to whom the Greek word is nevertheless applied in the writings of even
the later Fathers; as “those who testified the truth of the gospel of Christ, at the peril of life
merely, without the loss of it,”――“those who obeyed the requirements of the gospel, by
restraining passion,” &c. In some of these instances however, it is palpable that the
application of the word to such persons is secondary, and made in rather a poetical way,
with a reference to the more common meaning of loss of life for the sake of Christ, since
there is always implied a testimony at the risk or loss of something; still the power of these
instances to render doubtful the meaning of the term, is unquestionable. (See Suicer’s
Thesaurus Ecclesiasticus, Μαρτυρ, III. 2, 5, 6.)
Perhaps it is hardly worth while to dismiss these fables altogether, without first alluding
to the rather ancient one, first given by Clemens Alexandrinus. (Stromata, 7. p. 736.) and
copied verbatim by Eusebius, (Church History, III. 30.) Both the reverend Fathers however,
introduce the story as a tradition, a mere on dit, prefacing it with the expressive phrase,
“They say,” &c. (Φασι.) “The blessed Peter seeing his wife led to death, was pleased with
the honor of her being thus called by God to return home, and thus addressed her in words
of exhortation and consolation, calling her by name,――‘O woman! remember the Lord.’”
The story comes up from the hands of tradition rather too late however, to be entitled to any
credit whatever, being recorded by Clemens Alexandrinus, full 200 years after Christ. It was
probably invented in the times when it was thought worth while to cherish the spirit of
voluntary martyrdom, among even the female sex; for which purpose instances were sought
out or invented respecting those of the apostolic days. That Peter had a wife is perfectly
true; and it is also probable that she accompanied him about on his travels, as would
appear from a passage in Paul’s writings; (1 Corinthians ix. 5;) but beyond this, nothing is
known of her life or death. Similar fables might be endlessly multiplied from papistical
sources; more especially from the Clementine novels, and the apostolical romances of
Abdias Babylonius; but the object of the present work is true history, and it would require a
whole volume like this to give all the details of Christian mythology.
In justification of the certainty with which sentence is pronounced against the whole story
of Peter’s ever having gone to Rome, it is only necessary to refer to the decisive argument
on pages 228‒233, in which the whole array of ancient evidence on the point, is given by
Dr. Murdock. If the support of great names is needed, those of Scaliger, Salmasius,
Spanheim, and Bower, all mighty minds in criticism, are enough to justify the boldness of
the opinion, that Peter never went west of the Hellespont, and probably never embarked on
the Mediterranean. In conclusion of the whole refutation of this long-established error, the
matter cannot be more fairly presented, than in the words with which the critical and learned
Bower opens his Lives of the Popes:
“To avoid being imposed upon, we ought to treat tradition as we do a notorious and
known liar, to whom we give no credit unless what he says is confirmed to us by some
person of undoubted veracity. If it is affirmed by him alone, we can at most but suspend our
belief, not rejecting it as false, because a liar may sometimes speak truth; but we cannot,
upon his bare authority, admit it as true. Now that St. Peter was at Rome, that he was
bishop of Rome, we are told by tradition alone, which, at the same time tells us of so many
strange circumstances attending his coming to that metropolis, his staying in it, his
withdrawing from it, &c., that in the opinion of every unprejudiced man, the whole must
savor strongly of romance. Thus we are told that St. Peter went to Rome chiefly to oppose
Simon, the celebrated magician; that at their first interview, at which Nero himself was
present, he flew up into the air, in the sight of the emperor and the whole city; but that the
devil, who had thus raised him, struck with dread and terror at the name of Jesus, whom the
apostle invoked, let him fall to the ground, by which fall he broke his legs. Should you
question the truth of this tradition at Rome, they would show you the prints of St. Peter’s
knees in the stone, on which he kneeled on this occasion, and another stone still dyed with
the blood of the magician. (This account seems to have been borrowed from Suetonius,
who speaks of a person that, in the public sports, undertook to fly, in the presence of the
emperor Nero; but on his first attempt, fell to the ground; by which fall his blood sprung out
with such violence that it reached the emperor’s canopy.)
“The Romans, as we are told, highly incensed against him for thus maiming and bringing
to disgrace one to whom they paid divine honors, vowed his destruction; whereupon the
apostle thought it advisable to retire for a while from the city, and had already reached the
gate, when to his great surprise, he met our Savior coming in, as he went out, who, upon St.
Peter’s asking him where he was going, returned this answer: ‘I am going to Rome, to be
crucified anew;’ which, as St. Peter understood it, was upbraiding him with his flight;
whereupon he turned back, and was soon after seized by the provoked Romans, and, by an
order from the emperor, crucified.”
Nor do the fables about Peter, by the inveterate papists, cease

with his death. In regard to the place of his tomb, a new story was
needed, and it is accordingly given with the usual particularity. It is
said that he was buried at Rome in the Vatican plain, in the district
beyond the Tiber, in which he was said to have first preached among
the Jews, and where stood the great circus of Nero, in which the
apostle is said to have been crucified. Over this bloody spot, a
church was afterwards raised, by Constantine the Great, who chose
for its site part of the ground that had been occupied by the circus,
and the spaces where the temples of Mars and Apollo had stood.
The church, though of no great architectural beauty, was a building
of great magnitude, being three hundred feet long, and more than
one hundred and fifty feet wide. This building stood nearly twelve
hundred years, when becoming ruinous in spite of all repairs, it was
removed to give place to the present cathedral church of St. Peter,
now the most immense and magnificent building in the world,――not
too much praised in the graphic verse in which the pilgrim-poet sets
it beyond all comparison with the greatest piles of ancient or modern
art:
“But lo! the dome! the vast and wondrous dome,
To which Diana’s marvel was a cell;――
Christ’s mighty shrine above his martyr’s tomb.――
I have beheld the Ephesians’ miracle,
Its columns strew the wilderness, and dwell
The hyena and the jackall in their shade.
I have beheld Sophia’s bright roofs swell
Their glittering mass in the sun, and have surveyed
Its sanctuary, while the usurping Moslem prayed.
“But thou, of temples old, or altars new,
Standest alone, with nothing like to thee.
Worthiest of God, the holy and the true!
Since Zion’s desolation, when that He
Forsook his former city, what could be
Of earthly structures in his honor piled,
Of a sublimer aspect?”――
Within the most holy place of this vast sanctuary,――beneath the

very center of that wonderful dome, which rises in such unequaled
vastness above it, redounding far more to the glory of the man who
reared it, than of the God whose altar it covers,――in the vaulted
crypt which lies below the pavement, is a shrine, before which a
hundred lamps are constantly burning, and over which the prayers of
thousands are daily rising. This is called the tomb of the saint to
whom the whole pile is dedicated, and from whom the great high
priest of that temple draws his claim to the keys of the kingdom of
heaven, with the power to bind and loose, and the assurance of
heaven’s sanction on his decrees. But what a contrast is all this
“pride, pomp and circumstance,” to the bare purity of the faith and
character of the simple man whose life and conduct are recorded on
these pages! If any thing whatever may be drawn as a well-
authorized conclusion from the details that have been given of his
actions and motives, it is that Simon Peter was a “plain, blunt” man,
laboring devotedly for the object to which he had been called by
Jesus, and with no other view whatever, than the advancement of
the kingdom of his Master,――the inculcation of a pure spiritual faith,
which should seek no support, nor the slightest aid, from the
circumstances which charm the eye and ear, and win the soul
through the mere delight impressed upon the senses, as the
idolatrous priests who now claim his name and ashes, maintain their
dominion in the hearts of millions of worse than pagan worshipers.
His whole life and labors were pointed at the very extirpation of
forms and ceremonies,――the erection of a pure, rational, spiritual
dominion in the hearts of mankind, so that the blessings of a glorious
faith, which for two thousand years before had been confined to the
limits of a ceremonial system, might now, disenthralled from all the
bonds of sense, and exalted above the details of tedious forms, of
natural distinctions, and of antique rituals,――spread over a field as
wide as humanity. For this he lived and toiled, and in the clear hope
of a triumphant fulfilment of that plan, he died. And if, from his
forgotten, unknown grave, among the ashes of the Chaldean
Babylon, and from the holy rest which is for the blessed, the now
glorified apostle could be called to the renewal of breathing, earthly
life, and see the results of his energetic, simple-minded
devotion,――what wonder, what joy, what grief, what glory, what
shame, would not the revelation of these mighty changes move
within him! The simple, pure gospel which he had preached in
humble, faithful obedience to the divine command, without a thought
of glory or reward, now exalted in the idolatrous reverence of
hundreds of millions,――but where appreciated in its simplicity and
truth? The cross on which his Master was doomed to ignominy, now
exalted as the sign of salvation, and the seal of God’s love to the
world!――(a spectacle as strange to a Roman or Jewish eye, as to a

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Conducting Polymers-Based Energy

Storage Materials 1st Edition Dr

Polymers Coatings: Technology and Applications 1st

Mesoporous materials for advanced energy storage and

Inorganic Nanomaterials for Supercapacitor Design 1st

Mesoporous Materials for Advanced Energy Storage and

Nanostructured, Functional, and Flexible Materials for

Nanophotocatalysis and Environmental Applications

Applications of Ion Exchange Materials in Biomedical

Energy Storage: Systems and Components 1st Edition

Visit the Taylor & Francis Web site at

Chapter 1 Polythiophene-Based Battery Applications.................................................................................................. 1

Chapter 3 Conducting Polymer Derived Materials for Batteries .................................................................................65

Chapter 4 An Overview on Conducting Polymer-Based Materials for Battery Application ........................................79

Chapter 5 Polymer-Based Binary Nanocomposites.....................................................................................................93

Chapter 6 Polyaniline-Based Supercapacitor Applications........................................................................................109

Chapter 7 Conductive Polymer-derived Materials for Supercapacitor ......................................................................123

Chapter 8 Conducting Polymer-Metal Based Binary Composites for Battery Applications......................................135

Chapter 9 Novel Conducting Polymer-Based Battery Application............................................................................145

Chapter 10 Conducting Polymer–Carbon-Based Binary Composites for Battery Applications ..................................155

Chapter 11 Polyethylenedioxythiophene-Based Battery Applications .........................................................................161

Chapter 12 Polythiophene-Based Supercapacitor Applications ..................................................................................177

Chapter 13 Conducting Fibers for Energy Applications .............................................................................................193

Chapter 14 Conducting Polymer-Metal-Based Binary Composites for Supercapacitor Applications .........................209

Chapter 15 Polyethylenedioxythiophene (PEDOT)-Based Supercapacitor Applications.............................................235

Chapter 16 Electrospun Composite Separator for Li-Ion Batteries: A Short Review..................................................255

Chapter 18 Applications of Polyethylenedioxythiophene in Photovoltaics..................................................................287

Chapter 19 Conducting Polymer-Based Ternary Composites for Supercapacitor Applications ..................................301

Jazib Ali Muhammad Bilal

Faiza Altaf Swati Chaudhary

Muhammad Zeeshan Ashfaq U. S. Chavan

Sadia Zafar Bajwa Anirban Dandapat

Fawzi Banat Chittaranjan Das

Prasun Banerjee Navaneethan Duraisamy

D. Baba Basha Kalyan Gayen

Nuzhat Jamila R. Jeevan Kumar

Joon Ching Juan A.B.V. Kiran Kumar

Dilip Kumar Mishra Roshan Paul

Sandeep Pandey Samina Saleem

Devalina Sarmah K. Srinivas

A. Dennyson Savariraj J. Swanson

FIGURE 1.1 Chemical structure of PT and its derivatives.

FIGURE 1.2 Chemical structure of PEDOT and PEDOT:PSS.

1.2 SYNTHESIS potential required for the oxidation of monomer depends on

SCE: Standard calomel electrode.

1 Mg/THF/Ni(biyp)Cl2 Yamamoto et al.

2 Lin and Dudek Mg/THF/M(acac)n Lin and Dudek

3 Sugimoto route FeCl3/CHCl3 Sugimoto et al.

4 Demercuration Cu/PdCl2/pyridine/Δ Yamamoto et al.

5 Souto Maior FeCl3 or R. M. Souto Maior

6 Souto Maior FeCl3 or R. M. Souto Maior

7 Ullmann 1. Br2/AcOH Pomerantz et al.

HH−TT PATs: head−head tail−tail polyalkylthiophenes.

phene-2,5-diyl; P3OT), poly(3-

From all these particulars the conclusion is inevitable, that there

Another series of passages in this epistle refers to the remarkable

A third characteristic of the circumstances of those to whom this

the second epistle.

After writing the former epistle to the Christians of Asia Minor,

The first epistle of Peter has always been received as authentic,

As to the place and time of writing this epistle, it seems quite

Henceforth the writings of the New Testament are entirely silent as

Nor do the fables about Peter, by the inveterate papists, cease