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Carbon Nanomaterials for
Electrochemical Energy
Technologies
Fundamentals and Applications
ELECTROCHEMICAL ENERGY STORAGE AND CONVERSION

Series Editor
Jiujun Zhang
National Research Council Institute for Fuel Cell InnovationVancouver, British Columbia, Canada

Published Titles
Carbon Nanomaterials for Electrochemical Energy Technologies: Fundamentals and Applications
Shuhui Sun, Xueliang Sun, Zhongwei Chen, Yuyu Liu, David P. Wilkinson, and Jiujun Zhang
Redox Flow Batteries: Fundamentals and Applications
Huamin Zhang, Xianfeng Li, and Jiujun Zhang
Electrochemical Energy: Advanced Materials and Technologies
Pei Kang Shen, Chao-Yang Wang, San Ping Jiang, Xueliang Sun, and Jiujun Zhang
Electrochemical Polymer Electrolyte Membranes
Jianhua Fang, Jinli Qiao, David P. Wilkinson, and Jiujun Zhang
Electrochemical Supercapacitors for Energy Storage and Delivery: Fundamentals and Applications
Aiping Yu, Victor Chabot, and Jiujun Zhang
Photochemical Water Splitting: Materials and Applications
Neelu Chouhan, Ru-Shi Liu, and Jiujun Zhang
Metal–Air and Metal–Sulfur Batteries: Fundamentals and Applications
Vladimir Neburchilov and Jiujun Zhang
Electrochemical Reduction of Carbon Dioxide: Fundamentals and Technologies
Jinli Qiao, Yuyu Liu, and Jiujun Zhang
Electrolytes for Electrochemical Supercapacitors
Cheng Zhong, Yida Deng, Wenbin Hu, Daoming Sun, Xiaopeng Han, Jinli Qiao, and Jiujun Zhang
Solar Energy Conversion and Storage: Photochemical Modes
Suresh C. Ameta and Rakshit Ameta
Lead-Acid Battery Technologies: Fundamentals, Materials, and Applications
Joey Jung, Lei Zhang, and Jiujun Zhang
Lithium-Ion Batteries: Fundamentals and Applications
Yuping Wu
Graphene: Energy Storage and Conversion Applications
Zhaoping Liu and Xufeng Zhou
Proton Exchange Membrane Fuel Cells
Zhigang Qi
Carbon Nanomaterials for
Electrochemical Energy
Technologies
Fundamentals and Applications

Edited by
Shuhui Sun
Xueliang Sun
Zhongwei Chen
Yuyu Liu
David P. Wilkinson
Jiujun Zhang
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742

© 2018 by Taylor & Francis Group, LLC

CRC Press is an imprint of Taylor & Francis Group, an Informa business

No claim to original U.S. Government works

Printed on acid-free paper

International Standard Book Number-13: 978-1-4987-4602-1 (Hardback)

This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to pub-
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Contents
Preface..............................................................................................................................................vii
About the Editors...............................................................................................................................ix
Contributors.................................................................................................................................... xiii

Chapter 1 Carbon Nanomaterials for Li-Ion Batteries..................................................................1

Tongwen Yu, Rui Cai, and Zhongwei Chen

Chapter 2 Carbon Nanomaterials for Li–Sulfur Batteries........................................................... 15

Tongwen Yu, Rui Cai, and Zhongwei Chen

Chapter 3 Carbon Nanomaterials for Na-Ion Batteries............................................................... 27

Tongwen Yu, Rui Cai, and Zhongwei Chen

Chapter 4 Carbon Nanomaterials for Metal—Air Batteries........................................................ 39

Tongwen Yu, Rui Cai, and Zhongwei Chen

Chapter 5 The New Graphene Family Materials: Material Synthesis and Applications in
Lithium-Ion Batteries.................................................................................................. 59
Xin Tong and Shuhui Sun

Chapter 6 Carbon Nanomaterials for Supercapacitors................................................................97

Tongwen Yu, Rui Cai, and Zhongwei Chen

Chapter 7 Carbon Nanomaterials for Li–O2 Batteries............................................................... 111

Xiaoting Lin, Keegan Adair, and Xueliang Sun

Chapter 8 Carbon Nanomaterials for Na–O2 Batteries.............................................................. 137

Xiaoting Lin, Keegan Adair, and Xueliang Sun

Chapter 9 Nitrogen-Doped Carbon Materials for Oxygen Reduction in PEM Fuel Cells........ 153
Qiliang Wei, Xin Tong, Gaixia Zhang, and Shuhui Sun

Chapter 10 New Class of Graphene Materials for Fuel Cells...................................................... 181

Xin Tong, Qiliang Wei, Gaixia Zhang, and Shuhui Sun

Chapter 11 Applications of Carbon Materials in Membranes for Fuel Cells.............................. 217

Chenxi Xu and Mingming Fei

v
vi Contents

Chapter 12 Carbon Nanomaterials in Electrolysis and Hydrogen......................................... 227

Yuyu Liu, Hongbing Zhao, Rongzhi Chen, Jinli Qiao, David P. Wilkinson,
and Jiujun Zhang

Chapter 13 Graphene-Based Sensors........................................................................................... 275

Mahdi Bagheripoor and Robert Klassen
Index...............................................................................................................................................307
Preface
With increasing demand on global energy production and the highly negative impact of fossil fuel
combustion on the environment, exploring clean and sustainable energy sources and developing
associated technologies have become necessary for modern society’s sustainability. To address
this, advanced technologies for both energy conversion and storage are being extensively studied
around the world and are becoming the most critical elements in overcoming fossil fuel exhaustion
and global pollution. Among these, electrochemical energy technologies are considered the most
feasible, environmentally friendly, and sustainable. However, in both the aspects of materials and
technologies, there are still challenges in terms of the performance, cost, and applications of the
energy systems.
Nanotechnology has opened up new frontiers in materials science and engineering to meet these
challenges by creating new materials, particularly carbon nanomaterials, for efficient electrochemi-
cal energy conversion and storage. Compared with conventional energy materials, carbon nanoma-
terials possess unique size-/surface-dependent properties (e.g., morphological, electrical, optical,
and mechanical) that are useful for enhancing the energy-conversion and storage performance.
Over the past few decades, considerable efforts have been made to utilize the unique properties
of carbon nanomaterials. These energy materials include fullerenes, carbon nanotubes, graphene,
and so on, through which tremendous progress has been achieved in developing high-performance
electrochemical energy conversion and storage devices. To accelerate further development, a book
covering all important areas of carbon materials and technologies of electrochemical energy storage
and conversion should be highly desired.
This book gives a comprehensive description of carbon-based nanomaterials (CNTs, graphene,
and other carbon materials) and their associated electrochemical energy conversion and storage
technologies, such as batteries, fuel cells, supercapacitors, and hydrogen generation and storage, as
well as the latest material and modern technology development. It addresses a variety of topics, such
as electrochemical processes, materials, components, assembly and manufacturing, and degrada-
tion mechanisms, as well as challenges and perspectives. This book includes in-depth discussions,
ranging from comprehensive understanding to engineering of components and applied devices. We
believe that a broader view of various carbon nanomaterials and technologies for electrochemical
energy conversion and storage devices makes this book unique and an essential read for scientists
and engineers working in related fields.
This book consists of 13 chapters: Chapters 1–5 are devoted to carbon materials for various bat-
teries (Li-ion, Li–S, Na-ion, metal–air), Chapter 6 describes carbon materials for supercapacitors,
Chapters 7 and 8 discuss carbon materials for Li–O2 and Na–O2 batteries, Chapters 9–11 introduce
carbon materials for fuel cells (catalyst, support, membrane), Chapter 12 focuses on carbon materi-
als in electrolysis and hydrogen, and Chapter 13 is about graphene-based sensors.
We would like to thank all those who have been helpful in the writing of this book, including our
colleagues who kindly devoted their time to contribute chapters, and the staff at Taylor & Francis
for giving us this opportunity.
Shuhui Sun, PhD,
Professor at Institut National de la Recherche Scientifique,
Montréal, Canada
Xueliang Sun, PhD,
Professor at University of Western Ontario,
London, Canada
Zhongwei Chen, PhD,
Professor at University of Waterloo,
Waterloo, Canada

vii
viii Preface

Yuyu Liu, PhD,

Professor at Shanghai University,
Shanghai, China
David P. Wilkinson, PhD,
Professor at University of British Columbia,
Vancouver, Canada
Jiujun Zhang, PhD,
Professor at Shanghai University,
Shanghai, China
About the Editors
Shuhui Sun is a Professor at the National Institut de la Recherche
Scientifique, Center for Energy, Materials, and Telecommunications
(INRS–EMT) in Montreal, Canada, where he directs the laboratory
of sustainable nanotechnology. His current research interests focus
on the development of multifunctional nanomaterials (graphene,
CNTs, MOF, metal, and metal oxides) for energy and the environ-
ment, including PEM fuel cells (low-Pt and Pt-free catalysts), Li-ion
and Na-ion batteries, metal–air batteries, as well as wastewater treat-
ment. He received his PhD in materials engineering from the
University of Western Ontario, Canada, and MSc/PhD in physics
from the Chinese Academy of Sciences. He has published 10 book
chapters, one book, and over 100 peer-reviewed articles in journals including Advanced
Materials, Angewandte Chemie, Advanced Energy Materials, Advanced Functional Materials,
and Nano Energy, and also holds two U.S. patents. He has been invited to present his research
findings at over 100 conferences, workshops, seminars, and institutions worldwide. He is the
recipient of various prestigious fellowships and awards, such as the ECS Toyota Young
Investigator Fellow (2017), Fellow of the Global Young Academy (2017), the Canada Governor
General’s Academic Gold Medal (2012), NSERC-Alexander Graham Bell Canada Fellowship
(2009), the 1st Prize of Natural Science Award of Anhui Province (2014), and the Quebec
Merits Fellowship (2007). He is the Vice President of the International Academy of
Electrochemical Energy Science (IAOEES). He serves as Executive Editor-in-Chief of
Electrochemical Energy Reviews (EER) (Springer–Nature), and an editorial board member for
another five journals related to nanomaterials and energy.

Xueliang Sun is a Professor and Canada Research Chair (Tier I) for

the development of nanomaterials for clean energy at the University
of Western Ontario, Canada. He was elected as a Fellow of the
Canadian Academy of Engineering and a Fellow of the Royal Society
of Canada in 2016. His current research interests are associated with
electrochemical energy storage and conversion. Dr. Sun received his
PhD in materials chemistry at the University of Manchester, United
Kingdom, in 1999. After his PhD, he worked as a Postdoctoral Fellow
in the University of British Columbia, Canada, from 1999 to 2001.
He was a research associate at the National Institut de la Recherche
Scientifique (INRS), Quebec, Canada, from 2001 to 2004 before join-
ing the University of Western Ontario in 2004. Dr. Sun is an author and co-author of over
280 refereed journals, two books, and 15 book chapters, including Nature Communications,
Advanced Materials, Angewandte Chemie International Edition, Journal of the American
Chemical Society (JACS), Nano Letters, and Energy and Environmental Science. His work
has been cited over 13,000 times with an h-index of 60. He holds 10 U.S. patents. Dr. Sun is
actively collaborating with industries and government labs such as Ballard Power Systems,
General Motors, Lithium Phostech Inc., 3M, and China Automotive Battery Institute Inc.
Dr. Sun received various awards such as Early Researcher Award (2006), University Faculty
Scholar Award (2010), and the Western Engineering Prize for Achievement in Research (2013).

ix
x About the Editors

He also serves as Editor-in-Chief for Electrochemical Energy Reviews (Springer–Nature) and

an Associate Editor for Frontiers of Energy Storage (2013–present). Dr. Sun is a Vice Chairman
of the International Academy of Electrochemical Energy (IAOEES).

Zhongwei Chen is a Professor and Canada Research Chair in advanced

materials for clean energy, Director of the collaborative graduate program
in nanotechnology, and Director of the applied nanomaterials and clean
energy laboratory at University of Waterloo, Ontario, Canada. His cur-
rent research interests are the development of advanced energy materials
for metal–air batteries, lithium-ion batteries, and fuel cells. He received
his PhD in chemical and environmental engineering from the University
of California–Riverside. Prior to joining the faculty at Waterloo in
2008, he focused on the advanced catalysts research by the Chancellor’s
Dissertation Fellowship in the Los Alamos National Laboratory (LANL)
in New Mexico. His current research is on advanced materials for fuel
cells, batteries, and sensors. He has published one book, six book chapters,
and more than 170 peer-reviewed journal articles in publications including Nature Nanotechnology,
Nature Communications, JACS, Angewandte Chemie, Advanced Materials, Advanced Energy
Materials, Energy & Environmental Science, Nano Letters, and ACS Nano. To date, these publi-
cations have earned him over 10,000 citations with an h-index of 50 (Google Scholar). He is also
listed as inventor on 18 U.S./international patents, with three start-up companies in the United
States and Canada. Dr. Chen also serves as an editorial board member for peer-reviewed journals
including Scientific Reports (Nature Publishing) and is Vice President of the International Academy
of Electrochemical Energy Science (IAOEES). In 2107, he was elected a Fellow of the Canadian
Academy of Engineering, in recognition of his outstanding abilities. He was also recipient of the
2016 E.W.R. Steacie Memorial Fellowship and member of the Royal Society of Canada’s College
of New Scholars, Artists and Scientists in 2016, which followed several other prestigious honors,
including the Ontario Early Researcher Award, an NSERC Discovery Supplement Award, and the
Distinguished Performance and Research Excellence Awards from the University of Waterloo.

Yuyu Liu is a Vice-Dean and Professor at the Institute of Sustainable

Energy, Shanghai University, China. He received his PhD in environmen-
tal engineering from Yamaguchi University, Japan, in 2003. Then, he
worked at Kyushu Environmental Evaluation Association, Osaka Institute
of Technology, Tokyo University of Agriculture and Technology,
Yokohama National University as Postdoctoral and Research Fellow.
From 2010 to 2016, he was Assistant Professor and Associate Professor of
the Graduate School of Environmental Studies, Tohoku University, Japan.
Dr. Liu has more than 20 years of experience in environmental/electro-
chemical science and technology, particularly in the areas of air quality
monitoring, water and soil research, and their associated instrument
development. Recently, his research interest has moved to the electrochemical reduction of CO2 to
low-carbon fuels. As the first author and corresponding author, he has published over 60 research
papers in peer-reviewed journals, 20 conferences, and keynote/invited/oral presentations, as well as
three co-authored/edited books and seven book chapters (including Electrochemical Reduction of
Carbon Dioxide: Fundamentals and Technology by CRC Press and Environmental Bioengineering:
Volume 11 [Handbook of Environmental Engineering] by Humana Press). He is also a member of
the Japan Society on Water Environment, Japan Society of Material Cycles and Waste Management,
and a Board Committee Member of the International Academy of Electrochemical Energy Science.
About the Editors xi

David P. Wilkinson is a Professor and Canada Research

Chair (Tier 1) in clean energy and fuel cells in the Department
of Chemical and Biological Engineering at the University of
British Columbia (UBC), Canada. He has received a number
of awards and is a fellow of several organizations, including
the Engineering Institute of Canada, the Canadian Academy
of Engineering, the Chemical Institute of Canada, and the
Royal Society of Canada. Dr. Wilkinson’s main research
interests are in electrochemical and photochemical devices,
energy conversion and storage materials, and processes to cre-
ate clean and sustainable energy and water. He has more than
80 issued patents and 160 refereed journal articles covering
innovative research in these fields. Dr. Wilkinson received his
BASc in chemical engineering from the University of British
Columbia (UBC) in 1978 and his PhD in physical chemistry from the University of Ottawa in 1987,
where his graduate work was done with Professor Brian Conway in electrochemistry. Prior to joining
the university in 2004, Dr. Wilkinson had more than 20 years of industrial experience in the areas of
fuel cells and advanced lithium batteries. He has held a variety of leadership positions, including
being Associate Department Head, Executive Director of the UBC Clean Energy Research Center,
Principal Research Officer and Senior Adviser with the National Research Council of Canada
Institute for Fuel Cell Innovation, Director and Vice President of Research and Development at
Ballard Power Systems, and Section Leader for Chemistry at Moli Energy (now E-One Moli Energy).
Dr. Wilkinson is a Board Member of the International Academy of Electrochemical Energy Science
(IAOEES), a Board Member of the Canadian Hydrogen and Fuel Cells Association, and a Board
Member of Mangrove Water Technologies Ltd, a company he recently cofounded.

Jiujun Zhang is a Professor and Dean in the College of Sciences/

Institute for Sustainable Energy at Shanghai University and a
Principal Research Officer (Emeritus) at the National Research
Council of Canada (NRC). Dr. Zhang is a Fellow of the Canadian
Academy of Engineering (CAE), Fellow of The Academy of
Science of The Royal Society of Canada (FRSC), Fellow of The
Engineering Institute of Canada (EIC), Fellow of International
Society of Electrochemistry (ISE), and Fellow of the Royal
Society of Chemistry (RSC), and Chairman/President of
International Academy of Electrochemical Energy Science
(IAOEES). Dr. Zhang received his BS and MSc in electrochem-
istry from Peking University in 1982 and 1985, respectively, and
his PhD in electrochemistry from Wuhan University in 1988.
After completing his PhD, he took a position as an Associate
Professor at the Huazhong Normal University for two years. Starting in 1990, he carried out three
terms of postdoctoral research at the California Institute of Technology, York University, and the
University of British Columbia. Dr. Zhang has over 35 years of research and development (R&D)
experience in theoretical and applied electrochemistry, including over 18 years of fuel cell R&D
(including six years at Ballard Power Systems, 14 years at NRC, and three years of electrochemical
sensor experience, respectively). Dr. Zhang holds more than 15 adjunct/honorable professorships,
including one at the University of Waterloo, one at the University of British Columbia, and one at
Peking University. Up to now, Dr. Zhang has co-authored more than 450 publications, including
250 refereed journal papers with approximately 23,000 citations, 19 edited /co-authored books,
xii About the Editors

11 conference proceeding papers, and 43 book chapters, as well as 140 conference and invited oral
presentations. He also holds over 16 US/EU/WO/JP/CA patents, 11 U.S. patent publications, and has
produced more than 90 industrial technical reports. Dr. Zhang serves as Editor-in-Chief of
Electrochemical Energy Reviews (Springer–Nature), Associate Editor of Green Energy &
Environment (KeAi), Editor of International Journal of Electrochemistry (Hindawi), and editorial
board member for several international journals, as well as Editor for the book series of
Electrochemical Energy Storage and Conversion (CRC Press). Dr. Zhang is an active member of
The Electrochemical Society (ECS), the International Society of Electrochemistry (ISE, Fellow
Member), the American Chemical Society (ACS), and the Canadian Institute of Chemistry (CIC),
as well as the International Academy of Electrochemical Energy Science (IAOEES, Board
Committee Member).
Contributors
Keegan Adair Jinli Qiao
Department of Mechanical and Materials College of Environmental Science and
Engineering Engineering
The University of Western Ontario Donghua University
Ontario, Canada Shanghai, China

Mahdi Bagheripoor Xin Tong

Department of Mechanical and Materials National Institut de la Recherche
Engineering Scientifique (INRS)
The University of Western Ontario Centre Énergie
Ontario, Canada Matériaux et Télécommunications
Quebec, Canada
Rui Cai
Qiliang Wei
State Key Laboratory of Catalysis
Dalian Institute of Chemical Physics National Institut de la Recherche
Chinese Academy of Sciences Scientifique (INRS)
Dalian, China Centre Énergie
Matériaux et Télécommunications
Rongzhi Chen Quebec, Canada
College of Resources and Environment Chenxi Xu
University of Chinese Academy of Sciences School of Materials Science and Engineering
(UCAS) Hefei University of Technology
Beijing, China Hefei City, China
Mingming Fei Tongwen Yu
School of Materials Science and Engineering Department of Chemical Engineering
Hefei University of Technology University of Waterloo
Hefei City, China Ontario, Canada

Robert Klassen Gaixia Zhang

Department of Mechanical and Materials National Institut de la Recherche
Engineering Scientifique (INRS)
The University of Western Ontario Centre Énergie
Ontario, Canada Matériaux et Télécommunications
Quebec, Canada
Xiaoting Lin
Department of Mechanical and Materials Hongbing Zhao
Engineering College of Science
The University of Western Ontario Shanghai University
Ontario, Canada Shanghai, China

xiii
 1 Carbon Nanomaterials
for Li-Ion Batteries
Tongwen Yu, Rui Cai, and Zhongwei Chen

CONTENTS
1.1 Overview of Li-Ion Batteries.....................................................................................................1
1.2 Carbon Nanomaterials for LIBs................................................................................................2
1.2.1 Traditional Carbon.........................................................................................................2
1.2.2 Carbon Nanotubes.........................................................................................................3
1.2.3 Graphene........................................................................................................................7
1.3 Summary and Outlook............................................................................................................ 10
References......................................................................................................................................... 11

1.1 OVERVIEW OF LI-ION BATTERIES

The Li-ion batteries (LIBs) technology commercialized by Sony in 1991 is based on a low-voltage
Li intercalation-deintercalation process in carbonaceous material.1 In detail, LiCoO2 and graphite
were used as the cathode (positive electrode) and anode (negative electrode) material, respectively.
A nonaqueous Li ion-conducting medium acted as the electrolyte. This can be LiPF6 dissolved in a
mixture of ethylene carbonate (EC) and diethyl carbonate, dimethyl carbonate, or an immobilized
gel polymer that contains a mixture of the copolymer poly(vinylidene fluoride-co-hexafluoropro-
pylene). The principle of operation involves the migration of Li ions across the electrolyte located
between the positive and negative electrodes to store or deliver direct current (DC) electrical energy
during the charge/discharge process. During charging, Li ions are removed or deintercalated from
the layered oxide compounds and intercalated into the graphite layers. The process is reversed when
discharging.1 The reactions are as follows:

LiCoO2 + 6C ↔ Li1– x Co O2 + Li x C6 (0 < x ≤ 1)

The charge neutrality for x ≠ 0 can be maintained by the oxidation of Co3+ to Co4+ ion in the cath-
ode. Furthermore, for 0 < x ≤ 0.5 in Li1–xCoO2 and for 0 < x ≤ 1.0 in Li xC6, the reaction is completely
reversible for a large number of cycles.2
LIBs have displaced nickel metal hydride (NiMH) batteries in the electronics market and have
begun to displace NiMH or nickel–cadmium batteries in the power tool market.3 Their excellent
properties, such as light weight, a high operating voltage of ~3.6 V, and a deliverable capacity rang-
ing from 700 to 2400 mA h for a single cell, coupled with the long cycle life and rate capability,
enable LIBs to be extensively used in emerging diverse applications from portable power tools to
hybrid electric vehicles and electric vehicles.4 However, for the above applications, only 50% of
the theoretical capacity of the LiCoO2 cathode is used (140 mA h g−1 vs. theoretical 274 mA h g−1).
Therefore, it is extremely urgent to investigate the electrode materials to improve their capacities.
Herein, we mainly talk about the use of carbon nanomaterials in LIBs.

1
2 Carbon Nanomaterials for Electrochemical Energy Technologies

1.2 CARBON NANOMATERIALS FOR LIBs

1.2.1 Traditional Carbon
Graphite has been used as the anode material in LIBs due to its high capacity, good cyclability,
and low redox potential of 0.15–0.25 V versus Li metal. It can intercalate/deintercalate Li up to the
composition LiC6, indicating that a Li atom can be present between all layers of the host graphite
lattice.5 It leads to a theoretical capacity of 372 mA h g−1. Thus, its reversible capacity is limited.
Efforts to increase the Li content in LiC6 and reversibly cycle have so far not been successful,2 and
the irreversible capacity is strongly associated with the formation of a passivating layer, called the
solid electrolyte interphase (SEI), at the graphite surface. It was found that SEI forms on the exter-
nal surfaces of the graphite particles during the first few cycles of discharge/charge reactions in
EC-based solvents.6 In addition, the graphite anode limits the recharge rates of LIBs.
Porous carbons are one kind of promising anode material for LIBs due to their high surface area and
open pore structure. Furthermore, the well-interconnected carbon walls are usually beneficial for form-
ing percolation networks, reasonable electrical conductivity, a large number of active sites for Li storage,
and minimized mechanical stress for volume expansion/contraction during Li intercalation/deintercala-
tion. Due to these unique properties, porous carbons often show higher capacities in comparison with
traditional graphitic carbons.7 Maier et al. prepared hierarchically porous carbon monoliths of mac-
roscopic dimensions (Figure 1.1) and different shapes using meso-/macroporous silica as a template.
These showed superior high-rate performance when used as anode material in an LIB.8
In addition, microporous carbons have always shown larger capacities than traditional graphitic
carbons, although these are often accompanied by high irreversibilities.7 Furthermore, the effect of
the microporous structure was investigated. For example, the relationship between charge capacity
and crystal thickness (Lc002) in various carbon fibers and polyparaphenylene-based carbon elec-
trodes shows that low crystalline materials (Lc002 < 3 nm) have a larger capacity.9
Partially graphitized porous carbons are a class of attractive materials with promising chemical
properties for LIBs due to their high conductivity and porous structure. Zhang et al. simply prepared
interconnected hollow carbon nanospheres (HCNS) via pressure-assisted reduction and graphitiza-
tion of sucrose. As the anode material, they show a large reversible capacity of 630 mAh g−1 after 50
cycles, with excellent cyclic performance and rate performance, as shown in Figure 1.2.10

2 mm 2 mm

(a) (b)

50 nm 1 mm

(d) (c)

FIGURE 1.1 (a) SEM image of silica template at a lower magnification, (b) SEM images of nanocasting
­carbon (carbonized at 700°C) replica at a lower magnification, (c) at a higher magnification, and (d) TEM
image of nanocasting carbon replica. SEM: scanning electron microscopy; TEM: transmission electron
microscopy. (Copyright 2007, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. From Hu, Y. S. et al.,
Advanced Functional Materials, 17, 1873–1878, 2007.)
Carbon Nanomaterials for Li-Ion Batteries 3

3.0 432.1 500 0.1

dQ/dV (mAhg1V)
400

2.5 300 0.0 3rd cycle

Current (mA)
200
Voltage (V) 2.0 100
–0.1
0
1.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Voltage (V)
–0.2 1st cycle
1.0
0.5 –0.3

0.0 –0.4
0 300 600 900 1200 1500 1800 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Capacity (mAh g–1) Voltage (V)
(a) (b)

2000 100 1600

Specific capacity (mAh g–1)

Specific capacity (mAh g–1)

Coulombic efficiency (%)
Discharge
Charge
1600 Coulombic efficiency 80 1200
Discharge capacity
Charge capacity 0.1C
1200 60
800 0.5C
1.0C
800 40 2.0C
5.0C
400 10.0C
400 20

0 0
0 0 20 40 60 80 100 120
0 10 20 30 40 50
Cycle number Cycle number
(c) (d)

FIGURE 1.2 Electrochemical characteristics of the HCNS electrode. (a) Galvanostatic charge/discharge
curves at a rate of C/10, (b) CV at a scan rate of 0.1 mV s−1, (c) cycling performance at a rate of C/10, and
(d) rate performance at different rates. The inset in (a) shows the differential capacity versus cell voltage plots
during charging of the electrode. (Copyright 2011, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. From
Han, F. D. et al., Advanced Energy Materials, 1, 798–801, 2011.)

Carbon fibers also can be used as the electrode in LIBs. They are roughly classified into two types:
milled mesophase pitch-based carbon fibers and gas phase–grown carbon fibers. The former may act
as a practical anode material with high density of electrode, larger discharge capacity, and better output
current performances, while the latter can serve as a conductive filler in anode and cathode electrodes.11
Carbon coating for cathode materials is one of the most widely used surface modification tech-
niques to improve rate performance.12 Guo et al. found that carbon coating layers could also lead to
stabilized SEI films. Furthermore, the as-prepared carbon-coated Fe3O4 nanospindles (Figure 1.3)
exhibit very high specific capacity (749 mAh g−1 at C/5 and 600 mAh g−1 at C/2).13
As well as these carbon materials, carbon modified by heteroatoms, such as boron,14 sulfur,15
phosphorus,16 and nitrogen,17 has also been suggested as an anode material in LIBs.11 For example,
B-doped carbon materials, which were formed from a mixture of pristine material and boron car-
bide by heat treatment at 2800°C in an Ar atmosphere, show almost the same performance as that of
other highly graphitized electrodes.18 Chen et al. reported the synthesis of N-doped porous carbon
particles with a nitrogen content of up to 17.72 wt% by the pyrolysis of a nitrogen-containing zeo-
litic imidazolate framework at 800°C under a nitrogen atmosphere. Electrochemical tests show that
these particles retain a capacity of 2132 mAh g−1 after 50 cycles at a current density of 100 mA g−1,
and 785 mAh g−1 after 1000 cycles at 5 A g−1 (Figure 1.4).19

1.2.2 Carbon Nanotubes

Carbon nanotubes (CNTs) have been employed as the conductive additives to form conductive net-
works within the cathode materials to increase the increase the capacity, charge/discharge rate, and
the lifetime. The most effective additives include multiwall CNTs (MWCNTs), carbon black, and
carbon fibers.20 MWCNTs can hinder the agglomeration and enhance the electronic conductivity of
4 Carbon Nanomaterials for Electrochemical Energy Technologies

200 nm 200 nm

(a) (b)

0.25 nm

Fe3O4
c
200 nm 2 nm

(c) (d)

FIGURE 1.3 (a) SEM image of the as-synthesized hematite spindles. (b) SEM image of the carbon
precursor–coated hematite spindles. (c) SEM image of the carbon-coated Fe3O4 spindles (Fe3O4-C composites).
(d) High-resolution transmission electron microscopy (TEM) image of the Fe3O4-C composites. The insets
are close views of corresponding samples. All unmarked scale bars are 50 nm. (Copyright 2008, Wiley-VCH
Verlag GmbH & Co. KGaA, Weinheim. From Lee, J. S. et al., Advanced Energy Materials, 1, 34–50, 2011.)

Direct
carbonization
er

(a) (b) (c)

ay
el

Pyrrolic N
On

Pyridinic N
Quaternary N

(d)

FIGURE 1.4 Schematic illustration of the synthesis procedure of N-doped graphene analogous particles and
model of N-doping. (a) ZIF-8. (b) N-rich carbon polyhedron containing large amounts of graphene analogous
particles. (c) Enlargement of one graphene particle analogue; these contain several graphene layers and can
provide abundant active sites at their edges for grafting nitrogen heteroatoms. (d) The schematic of three types
of bonding configurations of N atoms within the hexagonal lattice and edges of a graphene layer. (Copyright
2014, Macmillan Publishers Limited. From Zheng, F. et al., Nature Communications, 5, 5261–5270, 2014.)

the active materials, thus enhancing the cyclic performance. Table 1.1 summarizes the electrochemi-
cal parameters, such as initial charge and discharge capacities and residual reversible capacities, of
various anode materials with and without CNT additives, confirming greatly enhanced cycle perfor-
mance of the nanocomposites containing MWCNTs as compared with the neat anode materials.21
Further studies proved that MWCNTs acted as conductive networks between LiNi0.7Co0.3O2 par-
ticles, and the discharge capacity of the composite cathode containing MWCNTs was 223 mA hg−1
with an 89.9% efficiency at C/10 rate and 214 mA hg−1 at 1C rate in the initial cycle.22,23 Shen et al.
TABLE 1.1  
Electrochemical Parameters of Anode Materials Consisting of Various Types of MWCNT-Based Nanocomposite

Initial Charge Initial Discharge Cycle Residual Reversible Capacity Charge Transfer
Electrode Type Current Rate Capacity (mA Hg−1 ) Capacity (mA Hg−1 ) Number (mA Hg−1 ) Resistance (Ω )
Sn/MWCNT 0.1 C 643 1590 40 627
Sn-MWCNT 50 mA g−1 570 30 442 16.4
SnNi-MWCNT 50 mA g−1 512 30 431 17.3
Bi/MWCNT 25 mA g−1 308 570 50 315
Sb 50 mA g−1 648 1023 30 115
SnSb0.5 50 mA g−1 726 951 30 171
Sb/MWCNT 50 mA g−1 462 1266 30 287
SnSb0.5 /MWCNT 50 mA g−1 518 1092 30 348
Carbon Nanomaterials for Li-Ion Batteries

CoSb3 /MWCNT 312 915 30 265 7.2

Ag/Fe/Sn/MWCNT 0.2 mA g−2 530 300 420
TiO2 50 mA g−1 52 287 75 21 123
TiO2 /MWCNT 50 mA g−1 168 830 75 165 75
SnSb/MWCNT 50 mA g−1 680 1408 50 480
Ag- 0.2 mA cm−2 500 250 30 172 15.8
TiO2 /MWCNT 0.2 mA cm−2 30 > 400
SnO2 /MWCNT 37.2 mA cm−2   728.3 40 126.4
SnO2 37.2 mA cm−2   665.1 40 505.9
SnO2 /MWCNT 850 mA g−1 100 100 60
Li4 Ti5 O12 850 mA g−1 145 145 500 142 38
Li4 Ti5 O12 /MWCNT 50 mA g−1 819 50 279
Si/MWCNT (7:3) 50 mA g−1 1770 50 1250
Si/MWCNT (5:5) 50 mA g−1 1182 50 889
Si/MWCNT (3:7) 0.25 mA cm−2 960 1882 30 1066

Source: W. Guoping et al., Solid State Ionics, 179, 263– 268, 2008.
Note: C is the theoretical capacity of Sn.
5
6 Carbon Nanomaterials for Electrochemical Energy Technologies

found that a novel network composite cathode, which was made by mixing MWCNT with LiFeO4
particles (Figure 1.5), can effectively improve the electron transfer between the active material and
the current collector (Al foil), as well as the electrochemical performance.24 Furthermore, a large
amount of Li+ may be stored in the central core, the interlayer space for MWCNTs, or the empty
space between the nanotubes when they are assembled in bundles.3 Single-walled CNTs (SWCNTs)
are also being investigated in a variety of ways, including conductive additives, current collectors,
and active materials. When they are used as an additive, the high aspect ratio of the SWCNTs can
form an electrical percolation network at much lower weight loading than conventional carbons, such
as carbon black and graphite.25 Theoretical calculations show that SWCNT in LiC2 stoichiometry
has the maximum theoretical reversible capacity value of about 1116 mAh g−1.26 Thus, many effects
have been attempted to achieve the theoretical reversible capacity. Shimoda et al. reported a revers-
ible capacity of about 700 mAh g−1 for SWCNTs that were etched with strong acids to open the tubes
and reduce their length.27 Gao et al. reached a reversible capacity of 1000 mAh g−1 for SWCNTs
that were treated by ball milling.28 Di Leo et al. reported that a measured capacity of 1050 mAh g−1
can be achieved by purified SWCNT electrodes with titanium contacts,29 representing a dramatic
improvement over the conventional graphite LiC6 limit of 372 mAh g−1 for lithium intercalation.30
Another approach to improving the capability involves aligned CNTs, due to their ability to make
better contact with the current collector. For example, Durstock et al. used vertically aligned MWCNTs
that were intimately contacted with a thin nickel metal film (Figure 1.6) as the active electrode mate-
rial, and they have shown high reversible specific capacities of 782 mAh g−1 at 57 mA g−1 in LIBs.31
Laik et al. reported the direct growth of silicon-decorated vertically aligned carbon nanotubes with a
thickness of 5 nm onto metal foil via a two-step CVD process. It exhibits a high reversible Li storage
capacity of 3000 mAh g−1 at 1.3 C, and an impressive rate capability of 1900 mAh g−1 is achieved at 5
C and 760 mAh g−1 at 15 C.32 Bradford et al. used horizontal super-aligned CNT sheets–based silicon
films to design binder-free, thin sheet anodes for flexible LIBs, as shown in Figure 1.7.33
As well as these strategies, CNTs have also been conjugated with nanostructured metal oxides
(MxOy, M=Fe, Mn, Ni, Mo, Cu, Cr) or metal (Si, Ge, Sn, Sn-Sb) to improve the lithium stor-
age capacity and the cycling life in batteries.34,35 Wang et al. proposed and synthesized a new
Sn-Co-CNT@CNT tube-in-tube nanostructure as an anode material for secondary LIBs. They
found that a large number of small CNTs were filled inside a large CNT by the catalytic action of
the filled Sn-Co particles. Furthermore, it showed an unprecedented highly reversible capacity at
both low and high current rates for 200 cycles.36
Although an enormous range of strategies for the use of CNTs have been proposed for improv-
ing the battery performance, from the battery industry point of view, the CNT technology is not yet
considered mature enough. Open issues regarding CNT mass production and cost presently hinder
their use in LIB applications.37

MWCNTs

LiPFeO4
Al foil

1 µm 4 µm

(a) (b)

FIGURE 1.5 SEM images of LiFePO4/MWCNTs composite cathode: (a) plane section and (b) cross section.
(Copyright 2006, Elsevier. From Li, X. et al., Electrochemistry Communications, 9, 663–666, 2007.)
Carbon Nanomaterials for Li-Ion Batteries 7

10 µm 200 nm 100 nm

(a) (b) (c)

20 nm

(e)

50 nm

20 nm
(d)
(f )

FIGURE 1.6 (a–c) SEM images of VA-CNTs/Si structure. (d) Low-magnification and (e) high-magnification
TEM picture of VA-CNTs/Si structure. (f) Carbon (red) and silicon (blue) map of an Si-decorated CNT using
energy spatially resolved energy-filtered TEM. (Copyright 2012, Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim. From Welna, D. T. et al., Journal of Power Sources, 196, 1455–1460, 2011.)

(a) (b)

(c) (d) (e)

FIGURE 1.7 Procedures for synthesizing CNT-Si and CNT-Si-C sheets. (a) A wide, continuous aligned
CNT sheet was drawn from CNT forests and rolled on a cylinder. (b) Photo image of the CNT sheet. The
CNT sheet was placed onto a quartz plate for CVD silicon coating. (c) Photo image of CNT-Si sheet. The
color changed from black to brown, indicating successful Si coating. (d) Photo image of the CNT-Si sheet.
The self-sustained CNT-based structure shows good flexibility. (e) A free-standing and binder-free electrode
for lithium-ion cell testing. (Copyright 2013, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. From Fu, K.
et al., Advanced Materials, 25, 5109–5114, 2013.)

1.2.3 Graphene
Graphene is an allotrope of carbon in the form of a two-dimensional, atomic-scale, hexagonal
lattice in which one atom forms each vertex. It has also attracted much attention for use as an
anode material in rechargeable LIBs because of its ultrahigh surface area, intriguing electronic
and thermal conductivities, structural flexibility, unique porous structure, and broad electrochemi-
cal window.38 For instance, Zhao et al. reported that disordered graphene exhibited high reversible
capacities of 794–1054 mAh g−1 and good cyclic stability. It is suggested that this is mainly ascribed
to additional reversible storage sites such as edges and other defects.39 Zhao et al. synthesized an
unprecedented type of two-dimensional ordered mesoporous graphene nanosheets via a controlled
low-concentration monomicelle close-packing assembly approach, as shown in Figure 1.8. The
graphene nanosheets were used as the anode materials, and the anode shows an ultrahigh initial
 8

Step 1 ste
Step 2 Step 3

Close packing
assembly Micelles aggregation
and crosslinking

Monomicelles lay on the surface

Step 4
Resol precursor PEO-PPO-PEO

Calcination

Surface of the
Monomicelles substrate

FIGURE 1.8 Scheme of the formation process for ordered mesoporous graphene nanosheets. (Copyright 2013, American Chemical Society. From Fang, Y. et al.,
Journal of the American Chemical Society, 135, 1524–1530, 2013.)
Carbon Nanomaterials for Electrochemical Energy Technologies
Carbon Nanomaterials for Li-Ion Batteries 9

discharge capacity of 3535 mAh g−1 at 100 mA g−1, stabilized at 770 mAh g−1 in the following cycles.
Furthermore, even at an ultrahigh current density of 5 Ag−1, a reversible capacity of 255 mAh g−1 is
maintained with excellent cycling stability.40
Almost all of the reported performance of graphene anode materials is significantly higher than
that of graphite. However, the pure graphene electrode exhibits some major disadvantages that hin-
der its application in LIBs.41 To improve the capacity and cycle performance, graphene-based hybrid
nanostructured electrodes with another component, such as oxide, metal, or carbon, are mainly
investigated. This main purpose of this strategy is to use the advantages of both graphene and metal
oxide. Typical examples include graphene/TiO2,42 graphene/SnO2,43,44 graphene/CNTs,45 graphene/
Co3O4,46 graphene/Co(OH)2,47 graphene/Sn,48 graphene/Si,49,50 and graphene/ceramic hybrid elec-
trode materials.51 For instance, Cheng et al. reported the direct growth of vertically aligned CNT
on a free-standing graphene paper, and this was used as the anode material of LIBs.52 Zhang et al.
proposed a solution-based method for the synthesis of three-dimensional TiO2-graphene-carbon
nanotube nanocomposite (Figure 1.9), which acted as the advanced anode material in LIB, and
exhibited ultrahigh-rate capability and good cycling properties at high rates.45 Aksay et al. dem-
onstrated a ternary self-assembly approach using graphene as a fundamental building block to
construct ordered SnO2-graphene nanocomposites, and it was shown that the nanocomposites can
achieve near theoretical specific energy density without significant charge/discharge degradation,
as shown in Figure 1.10.53
The modification of graphene with heteroatom dopants such as boron,54 phosphorus,55,56 and
nitrogen57 has also been investigated to improve the specific capacity. For example, Zhai et al. fab-
ricated an N-doped graphene-SnO2 sandwich paper with 7,7,8,8-tetracyanoquinodimethane anion
as N source. It exhibits large capacity, high-rate capability, and excellent cycling stability, which
are ascribed to the special sandwich structure, short transportation length, and elastomeric space to
accommodate volume changes on Li insertion/extraction.57

Ultrasonication
CNT

GO/CNT

TBOT GO

e– Reduction
e–
Li+
Li+ GNS

TiO2/GNS/CNT TiO2/GO/CNT TiO2

FIGURE 1.9 Schematic illustration for the synthesis of 3D TiO2-GNS-CNT nanocomposites. (Copyright
2011, American Chemical Society. From Shen, L. et al., The Journal of Physical Chemistry Letters, 2, 3096–
3101, 2011.)
10 Carbon Nanomaterials for Electrochemical Energy Technologies

20 µm 1 µm 20 nm 5 nm

(a) (b) (c)

1600
1.4

Specific capacity (mAh/g)

1000
0.01A/g
1.2 0.08A/g
600
Voltage V(vs. LI)
1.0 0.02A/g
Nanocomposite 0
0.8 0 20 40 60 80 100
electrode 0.008A/g
1000
0.6 0.008A/g 0.01A/g
800
0.4 600
400 0.02A/g 0.02A/g 0.02A/g
Membrance 0.2
200
LI foll 0.0 0
0 100 200 300 400 500 600 700 800 0 20 40 60 80 100 120 140 160 180

Specific capacity (mAh/g) Cycle number

(d) (e) (f )

FIGURE 1.10 (a) Side-view SEM image of a self-assembled free-standing SnO2 graphene nanocomposite
(40 wt% graphene) electrode 15 nm thick. Photographs in the inset show a disklike 3 cm diameter SnO2 gra-
phene nanocomposite electrode on the left and a folded electrode on the right. (b) High-magnification cross-
sectional SEM image of the free-standing SnO2 graphene nanocomposite electrode. The electrode is composed
of well-packed wavy layers interspaced by the loosely packed layers through almost the entire cross section.
(c) Cross-sectional TEM images of an SnO2 graphene nanocomposite film. Inset shows high-resolution TEM
image in the nanocomposite film with alternating layers of nanocrystalline SnO2 and graphene materials.
(d) A Li-ion battery configuration directly using a free-standing metal oxide graphene nanocomposite film
as an electrode. The graphene materials in the layered nanostructures function as both current collector and
conductive additives in the anode. (e) Charge/discharge profiles of an SnO2 graphene nanocomposite electrode
(40 wt% graphene) between 0.02 and 1.5 V at a current density of 0.008, 0.02, and 0.08 A g−1, respectively.
(f) (Top) Specific capacity of SnO2 as a function of charge/discharge cycles in the SnO2 graphene nanocom-
posite electrode at a current density of 0.01 A g−1. (Bottom) Specific capacity of SnO2 as a function of charge/
discharge cycles in the SnO2 graphene nanocomposite at different charge/discharge current densities of 0.008,
0.08, and 0.02 A g−1, respectively. Note that the nanocomposite electrode is precycled for 20 cycles at 0.08 A
g−1 to improve the electrolyte wetting and then cycled at 0.008 A g−1 to obtain theoretical capacity. The initial
lower capacity for the first 20 cycles is attributed to insufficient wetting. (Copyright 2010, American Chemical
Society. From Wang, D. et al., ACS Nano, 4, 1587–1595, 2010.)

1.3 SUMMARY AND OUTLOOK

LIBs are dominantly powering most of the portable electronics in our daily life. However, their
relatively low energy and power densities, poor durability, and high cost hinder their common use
in powering advanced hybrid electric vehicles and plug-in electric vehicles. Advances in carbon
nanomaterials have provided the opportunity to design and form novel energy storage materials for
the next-generation high-performance LIBs with higher capacity and longer cycle life.
In this section, three kinds of carbon materials, traditional carbon, carbon nanotubes, and gra-
phene, were briefly introduced as the anode materials in LIBs. The incorporation of carbon nano-
materials into active materials, such as metals and metal oxides, is a generally efficient avenue for
broadening and enhancing the performance of LIBs.
The future directions of carbon nanostructured anode materials for rechargeable LIBs should
focus on designing novel microstructures and morphology to further increase battery energy/power
Carbon Nanomaterials for Li-Ion Batteries 11

densities and enhance the battery performance.38 There is still a great deal of work to do for devel-
oping more sustainable and greener strategies to limit environment pollution.58
A number of advances have been made in cathode materials for future generations, including
Li-containing mixed oxides, Li(Ni1/3Co1/3Al1/3)-O259,60 and Li(Ni1/3Co1/3Mn1/3)-O2,61,62 which have a
lower Co content than LiCoO2 and LiMn2O4. Compared with 3 V cathode LiFeO4, the two materials
act as 4 V cathodes.2 There are also the vanadium-containing phosphates, LiVPO4F63,64 (4.2 V vs. Li)
and Li3V2P3O12,65,66 which show good stability in the charged state.
Besides experimental research, theoretical investigation of carbon nanomaterials involving the
electronic structure, interaction between carbon materials and the active materials, and doping
effects is essential for the design and synthesis of more active electrode materials in LIBs.

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Exploring the Variety of Random
Documents with Different Content
 36 THE AMERICAN vIGNOLA But here, as in the Greek
Doric, there is a great variety in the details of different buildings.
The four faces of the Capital are sometimes made alike, with double
Scrolls on each corner, as in Scamozzi's Ionic, and these Scrolls are
sometimes connected under the Abacus by a continuous curve,
convex up, instead of by a horizontal line. Fig. 125. Sornetimes a
corner column shows Scrolls on the two outer faces and Balusters on
the two inner ones, the double scroll on the corner projecting at 45
degrees, Fig. 12G. Some examples have a wide Necking, adorned
with the honeysuckle ornament, below the Echinus, Fig. 127. A few
Corinthian Capitals are to be found in Greece, but the buildings in
which they occur are in other respects Ionic, or even Doric, Fig. 128.
In the later Greek colonies in Southern Italy are found interesting
varieties of all the Orders. Their most marked peculiarity is the
treatment of the details, Fig. 130. The Trighphs and Dentils are long
and slender, and the moldings refined in outline and sometimes
separated by deep grooves, rectangular or circular, which are not to
be mistaken for moldings. The Architraves lose their importance, the
Ionic Scrolls are often diminished in size, and the egg-and-dart
molding is changed into what are sometimes called Filberts, Fig.
131. The Corinthian Capitals receive a local development quite unlike
that which was finally adopted in Rome itself, as may be witnessed
at Tivoli, Fig. 129, Pompeii, and Herculaneum, Fig. 132. Since the
revival of classical architecture other variations have appeared in
France, Germany, and Italy. mnnnni Fig. 131 Fig. 132
 PILASTERS-PLATE XVI 37 PILASTERS— PLATE XVI The
Romans made their Pilaster Capitals resemble those of the Columns.
This works well, except with the Ionic Capital, in which the
projecting Echinus presents an almost insuperable difficulty. Fig. 133.
As Pilasters do not generally diminish in width at thfe top, their
Capitals are one-fifth broader than those of the Columns. If, in this
case, the Architrave comes in line with the upper face of the column,
the face of the Pilaster projects one-twelfth of a Diameter beyond it,
as appears in the perspectives given in Plates III, IV, VIII, X, and
XII. But Pilasters are often made half a sixth narrower than the
Columns at the bottom, and half a sixth wider at the top, having
thus a uniform Diameter of five-sixths and a half. In this case the
base moldings are spread so as to make the plinth of the usual size,
and in the Corinthian Pilaster Capital, the upper row of leaves, the
volutes, and the abacus have the same dimensions as those of the
columns, while the leaves of the two lower rows are made broader.
Fig. 134. Pilasters generally project from the wall a quarter of their
diameter, but sometimes have to be made thicker in order to receive
string-courses or other horizontal moldings that they cut across. If
made much thicker than this, they are apt to look thicker than the
columns alongside them, and piers always do, noticeably enhancing
the slendemess of the columns near them. Pilasters are generally
plain, but if Ionic and Corinthian Pilasters do not diminish at the top
they are often fluted. Since the columns have twenty-four channels
and twenty-four fillets, and the diameter is nearly a third of the
circumference, there is space on the Pilaster for eight channels and
eight fillets, very- nearly. But as the number of channels must be
one less than the number of fillets, only seven are employed, with
eight fillets. This has the advantage of putting a channel on the axis,
and of making the two outer fillets wider than the others. It is
common to omit the fluting on the sides. But a projection of a
quarter of a Diameter gives room for one channel, and half a
Diameter for three. The Greeks gave their Pilasters Bases like those
of the Columns, but Capitals of their own, composed of a series of
moldings, Fig. 135. Pilasters are preferable -to half columns, which
always look smaller than they are, and have a mean appearance.
Moreover, any moldings that they interrupt seem to cut them in two.
Fig. 136. In these respects, three-quarter columns are better, though
they are apt to look clumsy, and they inevitably make an awkward
junction with the wall behind them, especially if they are fluted.
They also make it uncertain which is the principal supporting
member, the wall or the column. Pig. 133 L Pio. 134 From the
Farnese Palace Fig. 136 *MAi^ JJJ'l ^^ iDnnoi Fig. 13.^1
 38 THE AMERICAN VIGNOLA PEDESTALS— PLATE XVI
C/pper Rait 11 Half Baluslir Fig. 139 As has already been said, a
short Pier is called a Post, and, if it supports something, a Pedestal,
and the Pedestals that support Columns are generally made one-
third the height of the Column. The Cap is one-ninth the height of
the Pedestal, and generally consists of a Bed Mold and Corona.
There is no Cvmatium, a gutter being obviously out of place, but the
Corona is often crowned by a fillet and small Cyma Reversa. The
Base, which is two-ninths of the height of the Pedestal, or, according
to Vignola, only one-ninth, like the Cap, consists of a Plinth and Base
Moldings, among which a Cyma Recta is generally conspicuous, with
a Torus below it. The moldings, in both Cap and Base, are fewer and
consequently larger and simpler in the Tuscan and Doric Orders than
in the Ionic and Corinthian, the Tuscan, according to Vignola, having
no Corona, and the Corinthian a Necking and Astragal. The Cap
projects less than its own height, in many examples, and the Plinth
just as much as the Corona. But Pedestals vary greatly both in their
proportions and in their moldings. PARAPETS A wall low enough to
lean upon is called a Parapet, and whether low or high is often
strengthened by occasional Posts or Pedestals, sometimes of the
same height, sometimes higher. In either case the wall or parapet
has a Cap and Base, which may or may not be like those of the
Pedestals or Posts. A similar strip of wall, with the wall continued
above the Cap, is called a Continuous Pedestal, Fig. 143. This often
occurs between the Pedestals that support Pilasters. BALUSTRADES
In antiquity. Parapets were often pierced by triangular penetrations,
apparently in imitation of wooden fences, Fig. 137. But in modern
times the openings in Parapets are generally filled with a sort of
colonnade of dwarfed columns called Balusters. These frequently
occupy the whole space between one Post or Pedestal and the next,
forming a Balustrade, Fig. 138. If the distance is great, so that the
Cap has to be made of several lengths of stone, a block called an
Uncut Baluster is placed under the joint. Not more than a dozen
Balusters should occur together without such interruption. Against
the Pedestal is often set a Half -Baluster, or, which is better, half of
an Uncut Baluster, to support the end of the Upper Rail, Fig, 139.
 PEDESTALS— PLATE XVI 39 The Cap and Base of the
Pedestals, or of the Parapet or Continuous Pedestal, are called in a
Balustrade the Upper and Lower Rails. The Baluster supports tlie
Upper Rail as a Column supports an Entablature, and stands upon
the Lower Rail as upon a Stylobate, Fig. 139. It has its own Cap, the
height of which, including the Astragal, is onequarter the height of
the Baluster, and consists of a plain Abacus, Echinus and Fillet, and
Necking. These three members are of about equal height, as in the
Tuscan and Doric Capitals The Base of the Baluster is also one-
quarter its total height and resembles the Attic Base. The Scotia, as
in the Greek Attic Base, is generally made the principal member.
Between the Cap and Base is the Shaft, or Sleeve, which has the
outline of a Quirked Cyma Reversa, the greatest diameter, or Belly,
coming at about one-fourth of its height, or onethird the height of
the Baluster, Fig. 140. Its width at this point is also one-third the
height of the Baluster, as is also that of the Plinth of the Base,
exactly, and the width of the Abacus, almost. The Necking is less
than half as wide. The point of contrary flexure in the Cyma Reversa
is half way between Cap and Base, or between the Upper and Lower
Rails. But these proportions are made somewhat lighter for use with
the Ionic and Corinthian Orders. The Rails are sometimes, in height,
one-sixth and twosixths of the space between them, like the Cap
and Base of a Continuous Pedestal; but they are often made much
heavier, even one-third and one-half. Instead of the Cyma Reversa, a
Beak Molding is often used, Fig. 141, and other variations are
frequent. Of these, the most important is the so-called Double
Baluster, which consists of two small Balusters, set together base to
base just like the Baluster on the side of an Ionic Capital, Fig. 142.
Vignola also used a high block under the Plinth. Balusters are often
made square in section, like piers, instead of round, like columns.
Balusters are set about half their height apart, on centers. A
Balustrade, like a Parapet, is intended to lean upon, and should not
be more than 3 or 4 feet high. While, therefore, Columns and
Entablatures are proportioned to the size of the buildings in which
they occur, varying in height from 10 or 12 feet to 50 or 60,
Balustrades, like steps, are proportioned to the size of the human
figure, and in large buildings are relatively much smaller than in
small ones. They thus serve, as do steps, and as does the human
figure when introduced into a drawing, to indicate the scale of a
building. But in very large buildings Balustrades have sometimes
been made of colossal dimensions, that on the top of the front of St.
Peter's, for example, being about 8 feet high.
 4U THE AMERICAN VIGNOLA ATTICS When a Parapet is
placed on top of an Entablature it is called an Attic, that is to say, an
"Athenian" story, Fig. 143. Like Pedestals, Attics va:y much in size
and in architectural treatment. They are generally made about a
quarter as high as the Order below, and should not be more than a
third, and they should have a high Plinth, or even a double Plinth,
Figs. 144 and 153, so as not to be too much hidden by the
projection of the Cornices on which they stand. The place of an Attic
is often taken by Balustrades, Fig. 145. which also should have high
Plinths, below the lower rail. Fig, 143
 PEDIMENTS— PLATE XV 11 41 PEDIMENTS— PLATE XVII
The Gable upon a Classical building is called a Pediment, Fig. 146. It
consists of a Triangular piece of wall, called the Tympanum, which is
in the same plane as the Frieze below; of a Horizontal Cornice,
which divides the Tympanum from the Frieze; and of two pieces of
inclined cornice that surmount the T)-mpanum. The inclined, or
Raking, Cornice is like the cornice that crowns the wall on the sides
of the building, but the Cymatium is a little wider. The Horizontal
Cornice has no Cymatium, and generally terminates in a Fillet, called
the Split Fillet, which divides at the angle where the two Cornices
come- together. If the Cymatium is a Cavetto, the under side of the
Fillet beneath it is beveled, either on the rake or along the wall; if it
is an Ovolo, the same thing happens to the Fillet above it. Fig. 147.
With the Cyma Reversa both occur, with the Cyma Recta, neither,
the fillets having no soffit. This is one of the reasons for employing
this molding in this place. When a Cyma Recta is used in the
Cymatium, it occurs in four different forms. Fig. 14S ; viz. : (1) the
profile of the molding along the wall; (2) the profile of the raking
molding ; (3) the line of intersection of these two moldings — this
lies in a vertical plane, set at 45 degrees; (4) the line of intersection
of the two raking moldings at the top. (1), (2), and (4) have the
same projection but different heights; (1) and (3) have the same
height but not the same projection. According to Vignola, the obtuse
angle at the top of the Pediment is included within an arc of 90
degrees. It accordingly has a slope of 22^ degrees. This is a good
rule for most cases. But if a building is high and narrow, the slope
needs to be steeper, and if it is low and wide, flatter. Inasmuch,
however, as, for a building of a given width, the higher it is, the
larger is the scale of thS Order employed and of all the details of the
Order, it follows that, for a given width of front, the larger the
moldings are, the steeper must be the slope. Fig. 147 Fig. 148
 42 THE AMERICAN VIGNOLA Upon this is founded the
following rule for the slope of Pediments, devised by Stanislas
L'Eveilld, Fig. 149; Taking the upper line of the Horizontal Cornice as
one side, construct below it an equilateral triangle, and taking the
vertex of this triangle as a center, and its side as a radius, describe
an arc of 60 degrees. Taking, then, the summit of this arc as a
center, describe a circle, the radius of which is equal to the width of
the horizontal cornice. Lines drawn from the extremities of the
Corona tangent to this circle will give the upper line of the Raking
Corona. It is obvious that the larger the cornice, relatively to the
length of the front, the steeper will be the slope. It is also plain that
this rule gives steeper Pediments for the Corinthian and Ionic Orders
than for the Doric and Tuscan, and for the Roman Orders than for
the Greek, the cornices being wider. Circular, or Curved, Pediments
have a sweep of 90 degrees, Fig. 150, starting at an angle of 45
degrees. When Pediments are used merely for ornament the upper
part is sometimes omitted, giving a Broken Pediment, Fig. 152. If the
molding that crowns the Corona is omitted, the faces of the three
Coronas are continuous, Fig. 151. This was exemplified in Antiquity
by the recentl}' discovered Treasury of the Cnidians at Delphi. Fig.
150 Fio. 151 Fig. 163 In a Raking Cornice the modillions, dentils and
egg-and-darts have their axes vertical and in line with those in the
Horizontal Cornice beneatli. But in the Maison Carree at Nimes they
are set at right anoles with the Corona, and this is regularly done
with the Eggs-and-Darts where an ovolo occurs alone, without
dentils or modillions. If a modillion occurs at the apex of the
pediment it is broken. This occurs when the center intercolumniation
is Diast3'le, with the columns four Diameters, or twelve thirds, on
centers, giving five modillions over the opening between them, or
with any other spacing which makes their distance on centers a
multiple of four-thirds of a Diameter.
 INTERCOLUMNIATION— PLATE XVIII 43
INTERCOLUMNIATION, OR THE SPACING OF COLUMNS— PLATE
xvill The space between two columns, measured just above their
bases, is called an Inter columniation. It is one Diameter less than
their distance apart on centers, or on edges. Columns are said to be
Coupled, or to have a Pycnostyle, Systyle, Diastyle, or Areostyle
Intercolumniation, according as they are set close together, or are
one, two, three, or four Diameters apart, as nearly as ma}- be; i. e.,
about one, two, three, four, or five Diameters on centers. The
Systyle and Diastyle are the most usual, with an Intercolumniation of
two or of three Diameters. But Coupled Columns cannot be nearer
than one and one-third Diameters, on centers, instead of one
Diameter, on account of the projection of their bases, and in the
Ionic, Corinthian, and Composite Orders, not nearer than one and
one-half Diameters, on account of the projection of their Capitals.
The Intercolumniation of Coupled Columns is accordingly one-third
or one-half of a Diameter, or even a little more, to prevent the Bases
or Caps from actually touching. As this brings them eight-sixths
Diameters, or nine-sixths Diameters, on centers, the Ionic and
Corinthian dentils, which are onesixth Diameter on centers, come
exactly on the axis of the columns. This occurs also with the dentils
of Vignola's Composite Order, which are one-fourth Diameter on
centers, since nine-sixths Diameters equals six-fourths Diameters,
and there is just room for five dentils over the Intercolumniation. But
since the Corinthian ModiUions are four-sixths of a Diameter on
centers, and the shafts of Coupled Columns are nine-sixths
Diameters on centers, it is necessary to TOden each of the two
caissons between the Modillions by one-twelfth Diameter, and
increase the width of the Dentils and Interdentils by one-eighth,
making the Dentils one- eighth of a Diameter in width instead of
one-ninth, and the Interdentils one-sixteenth of a Diameter instead
of one-eighteenth. \'9 X 1^ ^^ F i "i~M X 1 8 ^^ 1 G-J So also the
Pycnost}'le Intercolumniation is made one and one-fourth Diameters
instead of one Diameter (i. e., two and one-fourth Diameters on
centers, instead of two) to avoid crowding. The ancients thought
that even the Systyle columns, with an Intercolumniation of two
Diameters, came too near together, and preferred what they called
the Eusiyle Intercolumniation, of two and one-half Diameters (or
three and onehalf Diameters on centers, in place of three
Diameters). But the moderns prefer to make the Eust5de
Intercolumniation two and one-third Diameters (setting the columns
three and onethird Diameters, on centers), as this brings ever}'
Column in Ionic and Corinthian colonnades exactly under a Dentil,
and every alternate one just under a Modillion, the Dentils being
one-sixth of a Diameter on centers, and the ModiUions two-thirds of
a Diameter. The wider Intercolumniations are preferable, obviously,
when the columns are small, since otherwise it might be difficult to
get between them, and the S}'style, or even the Pycnostyle, when
the columns are ver}^ large, since otherwise it might be difficult to
find stone architraves long enough to span the interval. But the
ancients used Tuscan Columns chiefly with wooden architraves,
setting them as much as seven Diameters
 44 THE AMERICAN VIGNOLA apart, which is called the
Tuscan Intercolunmiation, and which makes the space between the
columns about square. In modern times, also, an arrangement of
coupled columns has been employed, called Areosysiyle, the
columns being set half a Diameter apart, and the space between the
pairs of columns made three and onehalf Diameters. This is greater
than the Diastyle Intercolumniation and less than the Areostyle by
half a Diameter. From the axis of one pair of columns to that of the
next pair the distance is six Diameters. If in a Systyle Colonnade,
with the columns three Diameters on centers, the alternate columns
are moved along until they nearly touch the intervening ones, the
result is an Areostyle Colonnade. This was first used by Perrault in
the Eastern Colonnade of the Louvre, Fig. 153. In actual practice
these rules for Intercolumniation are seldom exactly followed.
DORIC INTERCOLUMNIATIONS— PLATE xvill In the Doric Order,
since the Columns come exactly under the Triglyphs and the
Triglyphs are one and one-fourth Diameters on centers, as on edges
(the width of the Triglyph being one-half of a Diameter and that of
the Metopes three-fourths of a Diameter), the distance of the
Columns on centers must needs be a multiple of one and one-fourth
Diameters. This makes the coupling of Doric Columns difficult, since,
even if the Bases touch, the distance between axes is still one and
one-third Diameters, which is more than that of the Triglyphs by
one-twelfth of a Diameter. This slight discrepancy "can, however, be
got over by making each Base a trifle narrower, or the Triglyphs and
Metopes a trifle wider, or by putting the Columns not exactly under
the Triglyphs, or by employing all these devices at once. If the
Columns are set under alternate Triglyphs so that there is one
Triglyph over the intervening space, their distance apart on centers
is two and one-half Diameters. The Intercolumniation is then one
and onehalf Diameters, and is said to be Monotriglyph. This is the
most common arrangement. But if the scale is small, it is usual, at
least at the principal entrance of a building, to have two Triglyphs
over the opening, the Columns being three and three-fourths
Diameters on centers. The Intercolumniation is then two and
threefourths Diameters, and is called Ditriglyph. Still wider spacing is
employed when the Architraves are of wood. When two, four, six,
eight, ten, or twelve Columns are used in a Colonnade or Portico, it
is said to be Distyle, Tetrastyle, Hexastyle, Ociasiyle, Decastyle, or
Dadecastyle, according to the Greek numerals. Examples are found
at Argos, Assos, Thoricus, and Psestum of facades with an odd
number of columns, three, five, seven, and nine, a column instead of
an intercolumniation coming on the axis, giving tristyle, pentastyle,
heptastyle, and enneastyle porticos. But in all these cases the
entrances were apparently on the sides of the buildings, where there
was an even number of columns.
 SUPERPOSITION— PLATE XVIII 45 SUPERPOSITION—
PLATE XVIII Superposition is the placing of one Order above another,
as in the Roman Amphitheaters and in many modern buildings of
several stories. The more solid forms of the Tuscan and Doric are
naturally placed below, and the Ionic and Corinthian above. The
Composite is sometimes placed below the Corinthian, as being more
vigorous. But in high buildings it is generally placed on the top story,
its large details being better seen at a distance than are those of the
more delicate Order. Even when the same Order is employed in the
different stories it is advisable to have the upper Columns of smaller
diameter than those below, and all the dimensions diminished
accordingly, for the sake of lightness. But it is still more so when
different Orders are superposed, for otherwise the Doric and
Corinthian stories would overpower the Tuscan and Ionic ones
beneath (Plate XVIII, A). It is usual, accordingly, to make the lower
diameter of each Shaft equal to the upper diameter of the Shaft
below it, as if they were all cut from a single piece of tapering stone
(Plate XVIII, B). This makes the scale employed in the second story
five-sixths of that used in the first; in the third, twenty-five
thirtysixths, or about two-thirds; in the fourth, about three-fifths,
and in the fifth, about one-half, if the Five Orders are employed in
regular sequence; this makes the relative height of the Orders in the
successive stories to be as 7, 6f , 61, 5t, and 5, very nearly. The
actual height of the stories themselves may be somewhat modified
by the use of plinths and pedestals. This system of Superposition
makes the distance apart of the Columns in each story, when
expressed in terms, of their own Diameter, six-fifths of that in the
story below. A Eustyle Intercolumniation in one story thus exactly
produces a Diastyle Intercolumniation in the story above, and a
Doric Monotriglyph Intercolumniation, a Systyle (Plate XVIII, F). (f X
3i = 4; f X 2i = 3) Coupled Columns set one and one-third Diameters
apart, on centers, in one story, are, in the story above, one and
three-fifths Diameters o. c, and in the third story nearly two
Diameters o. c. This does very well for fflf Fig. 131 Fig, 155 From the
Pantheon, Rom Fig. 157
 46 THE AMERICAN VIGNOLA From the Fourth Order of the
CoUosseum Fig. 158 From the Villa Caprarola. By Vignola Fic. 159
MMJUll J r Fig. 160 Fig. 161 From the Farnese Palace By San Gallo
Fit;. 162. String-Course From the Strozzi Palace y" ^ Fig. 163.
String-Course From the Palazzo Giraud. By Bramante Fig. 164.
String-Course From the Sachetti Palace. By San Gallo a sequence of
Doric, Ionic, and Corinthian, Fig. 154. But if the lower Columns are
Ionic or Corinthian those above had better be set nearer together,
the axis of the Intercolumniation only being preserved, Fig. 155.
With this exception, Superposed Columns are set so that their axes
are in the same vertical Une, when seen in elevation. But in profile,
as seen in section, the upper ones are set back, the wall against
which they stand generally growing thinner as it goes up, Fig. 156.
Since the Columns themselves also grow smaller, it would not do to
leave too much space behind them. The slightly pyramidal effect
that this gives to a building of several stories is of value, preventing
it from looking top-heavy and high-shouldered (Plate XVIII, C).
OTHER CORNICES AND STRING-COURSES The Five Orders worked
out by Vignola are generally accepted as a standard, though they
are seldom exactly followed in practice, modern as well as ancient
examples exhibiting a great variety in the forms and proportions of
the parts. But familiarity with them is of great service in designing,
since they can safely be employed on all ordinary, occasions, and in
the earlier stages of architectural composition. Other types of nearly
equal merit have been published by Alberti, Palladio, Serlio,
Scamozzi, Sir William Chambers, and others, and a great variety of
cornices, both with and without friezes and architraves, have been
employed in ancient and modern times to crown and protect walls
that were not decorated with columns or pilasters. Many of these
show Blocks or Modillions without any Dentil Course below, as on
Palladio's Composite Cornice, and in many of them the Dentil Course
is plain, forming what is called an Uncut Dentil Course, Fig. 157. In
others, the brackets that support the Corona are brought down so as
to occupy the Frieze, Fig. 158. The most important of these is
Vignola's so-called Cantilever Cornice used by him at Caprarola, Fig.
159. It seems to have been suggested by the Mutules and Trighphs
of his Mutulary Doric. Cornices, and indeed full Entablatures, are
often iised as String-Courses to separate stories, as in the Roman
Amphitheaters. But it is customary to use, instead, a lighter form, of
small projection, somewhat hke the cap of a pedestal, in which the
Cymatium and Bed Mold are often omitted, and the Corona itself
sometimes diminished to a mere fillet. Figs. 160 to 164.
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