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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-
lish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the
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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
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seized him. Taking the helmet from the head of his ancient kin, he
placed it on his own head. Likewise did he drape the rotten mantle
about his form, and equip himself with the great sword and the
great floppy boots that almost fell to pieces as he pulled them on.
Next, half tenderly, he deposited the nude mummy on its back in the
dark shadows behind the other mummies. And, finally, in the same
spot at the end of the line, his hand resting on the sword-hilt, he
assumed the same posture he had observed of the mummy.
Only his eyes moved as he observed the peon venturing slowly and
fearfully along the avenue of upright corpses. At sight of Torres he
came to an abrupt stop and with wide eyes of dread muttered a
succession of Maya prayers. Torres, so confronted, could only listen
with closed eyes and conjecture. When he heard the peon move on
he stole a look and saw him pause with apprehension at the narrow
elbow-turn of the passage which he must venture next. Torres saw
his chance and swung the sword aloft for the blow that would split
the peon’s head in twain.
Though this was the day and the very hour for the peon, the last
second had not yet ticked. Not there, in the thoroughfare of the
dead, was he destined to die under the hand of Torres. For Torres
held his hand and slowly lowered the point of the sword to the floor,
while the peon passed on into the elbow.
The latter met up with his father, Leoncia, and Francis, just as
Francis was demanding the priest to run the knots again for fuller
information of the how and what that would open the ear of Hzatzl.
“Put your hand into the mouth of Chia and draw forth the key,” the
old man commanded his reluctant son, who went about obeying him
most gingerly.
“She won’t bite you——she’s stone,” Francis laughed at him in
Spanish.
“The Maya gods are never stone,” the old man reproved him. “They
seem to be stone, but they are alive, and ever alive, and under the
stone, and through the stone, and by the stone, as always, work
their everlasting will.”
Leoncia shuddered away from him and clung against Francis, her
hand on his arm, as if for protection.
“I know that something terrible is going to happen,” she gasped. “I
don’t like this place in the heart of a mountain among all these dead
old things. I like the blue of the sky and the balm of the sunshine,
and the widespreading sea. Something terrible is going to happen. I
know that something terrible is going to happen.”
While Francis reassured her, the last seconds of the last minute for
the peon were ticking off. And when, summoning all his courage, he
thrust his hand into the mouth of the goddess, the last second ticked
and the clock struck. With a scream of terror he pulled back his hand
and gazed at the wrist where a tiny drop of blood exuded directly
above an artery. The mottled head of a snake thrust forth like a
mocking, derisive tongue and drew back and disappeared in the
darkness of the mouth of the goddess.
“A viperine!” screamed Leoncia, recognising the reptile.
And the peon, likewise recognising the viperine and knowing his
certain death by it, recoiled backward in horror, stepped into the
hole, and vanished down the nothingness which Chia had guarded
with her feet for so many centuries.
For a full minute nobody spoke, then the old priest said: “I have
angered Chia, and she has slain my son.”
“Nonsense,” Francis was comforting Leoncia. “The whole thing is
natural and explainable. What more natural than that a viperine
should choose a hole in a rock for a lair? It is the way of snakes.
What more natural than that a man, bitten by a viperine, should step
backward? And what more natural, with a hole behind him, than that
he should fall into it——”
“That is then just natural!” she cried, pointing to a stream of crystal
water which boiled up over the lips of the hole and fountained up in
the air like a geyser. “He is right. Through stone itself the gods work
their everlasting will. He warned us. He knew from reading the knots
of the sacred tassel.”
“Piffle!” Francis snorted. “Not the will of the gods, but of the ancient
Maya priests who invented their gods as well as this particular
device. Somewhere down that hole the peon’s body struck the lever
that opened stone flood-gates. And thus was released some
subterranean body of water in the mountain. This is that water. No
goddess with a monstrous mouth like that could ever have existed
save in the monstrous imaginations of men. Beauty and divinity are
one. A real and true goddess is always beautiful. Only man creates
devils in all their ugliness.”
So large was the stream that already the water was about their
ankles.
“It’s all right,” Francis said. “I noticed, all the way from the entrance,
the steady inclined plane of the floors of the rooms and passages.
Those old Mayas were engineers, and they built with an eye on
drainage. See how the water rushes away out through the passage.
—Well, old man, read your knots, where is the treasure?”
“Where is my son?” the old man counter-demanded in dull and
hopeless tones. “Chia has slain my only born. For his mother I broke
the Maya law and stained the pure Maya blood with the mongrel
blood of a woman of the tierra caliente. Because I sinned for him
that he might be, is he thrice precious to me. What care I for
treasure? My son is gone. The wrath of the Maya gods is upon me.”
With gurglings and burblings and explosive air-bubblings that
advertised the pressure behind, the water fountained high as ever
into the air. Leoncia was the first to notice the rising depth of the
water on the chamber floor.
“It is half way to my knees,” she drew Francis’ attention.
“And time to get out,” he agreed, grasping the situation. “The
drainage was excellently planned, perhaps. But that slide of rocks at
the cliff entrance has evidently blocked the planned way of the
water. In the other passages, being lower, the water is deeper, of
course, than here. Yet is it already rising here on the general level.
And that way lies the only way out. Come!”
Thrusting Leoncia to lead in the place of safety, he caught the
apathetic priest by the hand and dragged him after. At the entrance
of the elbow turn the water was boiling above their knees. It was to
their waists as they emerged into the chamber of mummies.
And out of the water, confronting Leoncia’s astounded gaze, arose
the helmeted head and ancient-mantled body of a mummy. Not this
alone would have astounded her, for other mummies were over-
toppling, falling and being washed about in the swirling waters. But
this mummy moved and made gasping noises for breath, and with
eyes of life stared into her eyes.
It was too much for ordinary human nature to bear——a four-
centuries old corpse dying the second death by drowning. Leoncia
screamed, sprang forward, and fled the way she had come, while
Francis, in his own way equally startled, let her go past as he drew
his automatic pistol. But the mummy, finding footing in the swift
rush of the current, cried out:
“Don’t shoot! It is I—Torres! I have just come back from the
entrance. Something has happened. The way is blocked. The water
is over one’s head and higher than the entrance, and rocks are
falling.”
“And your way is blocked in this direction,” Francis said, aiming the
revolver at him.
“This is no time for quarreling,” Torres replied. “We must save all our
lives, and, afterwards, if quarrel we must, then quarrel we will.”
Francis hesitated.
“What is happening to Leoncia?” Torres demanded slyly. “I saw her
run back. May she not be in danger by herself?”
Letting Torres live and dragging the old man by the arm, Francis
waded back to the chamber of the idols, followed by Torres. Here, at
sight of him, Leoncia screamed her horror again.
“It’s only Torres,” Francis reassured her. “He gave me a devil of a
fright myself when I first saw him. But he’s real flesh. He’ll bleed if a
knife is stuck into him.—Come, old man! We don’t want to drown
here like rats in a trap. This is not all of the Maya mysteries. Read
the tale of the knots and get us out of this!”
“The way is not out but in,” the priest quavered.
“And we’re not particular so long as we get away. But how can we
get in?”
“From the mouth of Chia to the ear of Hzatzl,” was the answer.
Francis was struck by a sudden grotesque and terrible thought.
“Torres,” he said, “there is a key or something inside that stone
lady’s mouth there. You’re the nearest. Stick your hand in and get
it.”
Leoncia gasped with horror as she divined Francis’ vengeance. Of
this Torres took no notice, and gaily waded toward the goddess,
saying: “Only too glad to be of service.”
And then Francis’ sense of fair play betrayed him.
“Stop!” he commanded harshly, himself wading to the idol’s side.
And Torres, at first looking on in puzzlement, saw what he had
escaped. Several times Francis fired his pistol into the stone mouth,
while the old priest moaned “Sacrilege!” Next, wrapping his coat
around his arm and hand, he groped into the mouth and pulled out
the wounded viper by the tail. With quick swings in the air he beat
its head to a jelly against the goddess’ side.
Wrapping his hand and arm against the possibility of a second
snake, Francis thrust his hand into the mouth and drew forth a piece
of worked gold of the shape and size of the hole in Hzatzl’s ear. The
old man pointed to the ear, and Francis inserted the key.
“Like a nickle-in-the-slot machine,” he remarked, as the key
disappeared from sight. “Now what’s going to happen? Let’s watch
for the water to drain suddenly away.”
But the great stream continued to spout unabated out of the hole.
With an exclamation, Torres pointed to the wall, an apparently solid
portion of which was slowly rising.
“The way out,” said Torres.
“In, as the old man said,” Francis corrected. “Well, anyway, let’s
start.”
All were through and well along the narrow passage beyond, when
the old Maya, crying, “My son!” turned and ran back.
The section of wall was already descending into its original place,
and the priest had to crouch low in order to pass it. A moment later,
it stopped in its old position. So accurately was it contrived and fitted
that it immediately shut off the stream of water which had been
flowing out of the idol room.

Outside, save for a small river of water that flowed out of the base
of the cliff, there were no signs of what was vexing the interior of
the mountain. Henry and Ricardo, arriving, noted the stream, and
Henry observed:
“That’s something new. There wasn’t any stream of water here when
I left.”
A minute later he was saying, as he looked at a fresh slide of rock:
“This was the entrance to the cave. Now there is no entrance. I
wonder where the others are.”
As if in answer, out of the mountain, borne by the spouting stream,
shot the body of a man. Henry and Ricardo pounced upon it and
dragged it clear. Recognizing it for the priest, Henry laid him face
downward, squatted astride of him, and proceeded to give him the
first aid for the drowned.
Not for ten minutes did the old man betray signs of life, and not until
after another ten minutes did he open his eyes and look wildly
about.
“Where are they?” Henry asked.
The old priest muttered in Maya, until Henry shook more thorough
consciousness into him.
“Gone——all gone,” he gasped in Spanish.
“Who?” Henry demanded, shook memory into the resuscitated one,
and demanded again.
“My son; Chia slew him. Chia slew my son, as she slew them all.”
“Who are the rest?”
Followed more shakings and repetitions of the question.
“The rich young Gringo who befriended my son, the enemy of the
rich young Gringo whom men call Torres, and the young woman of
the Solanos who was the cause of all that happened. I warned you.
She should not have come. Women are always a curse in the affairs
of men. By her presence, Chia, who is likewise a woman, was made
angry. The tongue of Chia is a viperine. By her tongue Chia struck
and slew my son, and the mountain vomited the ocean upon us
there in the heart of the mountain, and all are dead, slain by Chia.
Woe is me! I have angered the gods. Woe is me! Woe is me! And
woe upon all who would seek the sacred treasure to filch it from the
gods of Maya!”
 CHAPTER XVI

Midway between the out-bursting stream of water and the rock-

slide, Henry and Ricardo stood in hurried debate. Beside them,
crouched on the ground, moaned and prayed the last priest of the
Mayas. From him, by numerous shakings that served to clear his
addled old head, Henry had managed to extract a rather vague
account of what had occurred inside the mountain.
“Only his son was bitten and fell into that hole,” Henry reasoned
hopefully.
“That’s right,” Ricardo concurred. “He never saw any damage,
beyond a wetting, happen to the rest of them.”
“And they may be, right now, high up above the floor in some
chamber,” Henry went on. “Now, if we could attack the slide, we
might open up the cave and drain the water off. If they’re alive they
can last for many days, for lack of water is what kills quickly, and
they’ve certainly more water than they know what to do with. They
can get along without food for a long time. But what gets me is how
Torres got inside with them.”
“Wonder if he wasn’t responsible for that attack of the Caroos upon
us,” Ricardo suggested.
But Henry scouted the idea.
“Anyway,” he said, “that isn’t the present proposition——which
proposition is: how to get inside that mountain on the chance that
they are still alive. You and I couldn’t go through that slide in a
month. If we could get fifty men to help, night and day shifts, we
might open her up in forty-eight hours. So, the primary thing is to
get the men. Here’s what we must do. I’ll take a mule and beat it
back to that Caroo community and promise them the contents of
one of Francis’ check-books if they will come and help. Failing that, I
can get up a crowd in San Antonio. So here’s where I pull out on the
run. In the meantime, you can work out trails and bring up all the
mules, peons, grub and camp equipment. Also, keep your ears to
the cliff——they might start signalling through it with tappings.”

Into the village of the Caroos Henry forced his mule——much to the
reluctance of the mule, and equally as much to the astonishment of
the Caroos, who thus saw their stronghold invaded single-handed by
one of the party they had attempted to annihilate. They squatted
about their doors and loafed in the sunshine, under a show of
lethargy hiding the astonishment that tingled through them and
almost put them on their toes. As has been ever the way, the very
daring of the white man, over savage and mongrel breeds, in this
instance stunned the Caroos to inaction. Only a man, they could not
help but reason in their slow way, a superior man, a noble or over-
riding man, equipped with potencies beyond their dreaming, could
dare to ride into their strength of numbers on a fagged and
mutinous mule.
They spoke a mongrel Spanish which he could understand, and, in
turn, they understood his Spanish; but what he told them
concerning the disaster in the sacred mountain had no effect of
rousing them. With impassive faces, shrugging shoulders of utmost
indifference, they listened to his proposition of a rescue and promise
of high pay for their time.
“If a mountain has swallowed up the Gringos, then is it the will of
God, and who are we to interfere between God and His will?” they
replied. “We are poor men, but we care not to work for any man,
nor do we care to make war upon God. Also, it was the Gringos’
fault. This is not their country. They have no right here playing
pranks on our mountains. Their troubles are between them and God.
We have troubles enough of our own, and our wives are unruly.”
Long after the siesta hour, on his third and most reluctant mule,
Henry rode into sleepy San Antonio. In the main street, midway
between the court and the jail, he pulled up at sight of the Jefe
Politico and the little fat old judge, with, at their heels, a dozen
gendarmes and a couple of wretched prisoners——runaway peons
from the henequen plantations at Santos. While the judge and the
Jefe listened to Henry’s tale and appeal for help, the Jefe gave one
slow wink to the judge, who was his judge, his creature, body and
soul of him.
“Yes, certainly we will help you,” the Jefe said at the end, stretching
his arms and yawning.
“How soon can we get the men together and start?” Henry
demanded eagerly.
“As for that, we are very busy——are we not, honorable judge?” the
Jefe replied with lazy insolence.
“We are very busy,” the judge yawned into Henry’s face.
“Too busy for a time,” the Jefe went on. “We regret that not to-
morrow nor next day shall we be able to try and rescue your
Gringos. Now, a little later——”
“Say next Christmas,” the judge suggested.
“Yes,” concurred the Jefe with a grateful bow. “About next Christmas
come around and see us, and, if the pressure of our affairs has
somewhat eased, then, maybe possibly, we shall find it convenient
to go about beginning to attempt to raise the expedition you have
requested. In the meantime, good day to you, Senor Morgan.”
“You mean that?” Henry demanded with wrathful face.
“The very face he must have worn when he slew Senor Alfaro
Solano treacherously from the back,” the Jefe soliloquized ominously.
But Henry ignored the later insult.
“I’ll tell you what you are,” he flamed in righteous wrath.
“Beware!” the judge cautioned him.
“I snap my fingers at you,” Henry retorted. “You have no power over
me. I am a full-pardoned man by the President of Panama himself.
And this is what you are. You are half-breeds. You are mongrel pigs.”
“Pray proceed, Senor,” said the Jefe, with the suave politeness of
deathly rage.
“You’ve neither the virtues of the Spaniard nor of the Carib, but the
vices of both thrice compounded. Mongrel pigs, that’s what you are
and all you are, the pair of you.”
“Are you through Senor?—quite through?” the Jefe queried softly.
At the same moment he gave a signal to the gendarmes, who
sprang upon Henry from behind and disarmed him.
“Even the President of the Republic of Panama cannot pardon in
anticipation of a crime not yet committed——am I right, judge?” said
the Jefe.
“This is a fresh offense,” the judge took the cue promptly. “This
Gringo dog has blasphemed against the law.”
“Then shall he be tried, and tried now, right here, immediately. We
will not bother to go back and reopen court. We shall try him, and
when we have disposed of him, we shall proceed. I have a very
good bottle of wine——”
“I care not for wine,” the judge disclaimed hastily. “Mine shall be
mescal. And in the meantime, and now, having been both witness
and victim of the offense and there being no need of evidence
further than what I already possess, I find the prisoner guilty. Is
there anything you would suggest, Senor Mariano Vercara é Hijos?”
“Twenty-four hours in the stocks to cool his heated Gringo head,” the
Jefe answered.
“Such is the sentence,” the judge affirmed, “to begin at once. Take
the prisoner away, gendarmes, and put him in the stocks.”
Daybreak found Henry in the stocks, with a dozen hours of such
imprisonment already behind him, lying on his back asleep. But the
sleep was restless, being vexed subjectively by nightmare dreams of
his mountain-imprisoned companions, and, objectively, by the stings
of countless mosquitoes. So it was, twisting and squirming and
striking at the winged pests, he awoke to full consciousness of his
predicament. And this awoke the full expression of his profanity.
Irritated beyond endurance by the poison from a thousand
mosquito-bites, he filled the dawn so largely with his curses as to
attract the attention of a man carrying a bag of tools. This was a
trim-figured, eagle-faced young man, clad in the military garb of an
aviator of the United States Army. He deflected his course so as to
come by the stocks, and paused, and listened, and stared with
quizzical admiration.
“Friend,” he said, when Henry ceased to catch breath. “Last night,
when I found myself marooned here with half my outfit left on
board, I did a bit of swearing myself. But it was only a trifle
compared with yours. I salute you, sir. You’ve an army teamster
skinned a mile. Now if you don’t mind running over the string again,
I shall be better equipped the next time I want to do any cussing.”
“And who in hell are you?” Henry demanded. “And what in hell are
you doing here?”
“I don’t blame you,” the aviator grinned. “With a face swollen like
that you’ve got a right to be rude. And who beat you up? In hell, I
haven’t ascertained my status yet. But here on earth I am known as
Parsons, Lieutenant Parsons. I am not doing anything in hell as yet;
but here in Panama I am scheduled to fly across this day from the
Atlantic to the Pacific. Is there any way I may serve you before I
start?”
“Sure,” Henry nodded. “Take a tool out of that bag of yours and
smash this padlock. I’ll get rheumatism if I have to stick here much
longer. My name’s Morgan, and no man has beaten me up. Those
are mosquito-bites.”
With several blows of a wrench, Lieutenant Parsons smashed the
ancient padlock and helped Henry to his feet. Even while rubbing the
circulation back into his feet and ankles, Henry, in a rush, was telling
the army aviator of the predicament and possibly tragic disaster to
Leoncia and Francis.
“I love that Francis,” he concluded. “He is the dead spit of myself.
We’re more like twins, and we must be distantly related. As for the
senorita, not only do I love her but I am engaged to marry her. Now
will you help? Where’s the machine? It takes a long time to get to
the Maya Mountain on foot or mule-back; but if you give me a lift in
your machine I’d be there in no time, along with a hundred sticks of
dynamite, which you could procure for me and with which I could
blow the side out of that mountain and drain off the water.”
Lieutenant Parsons hesitated.
“Say yes, say yes,” Henry pleaded.

Back in the heart of the sacred mountain, the three imprisoned ones
found themselves in total darkness the instant the stone that
blocked the exit from the idol chamber had settled into place.
Francis and Leoncia groped for each other and touched hands. In
another moment his arm was around her, and the deliciousness of
the contact robbed the situation of half its terror. Near them they
could hear Torres breathing heavily. At last he muttered:
“Mother of God, but that was a close shave! What next, I wonder?”
“There’ll be many nexts before we get out of this neck of the
woods,” Francis assured him. “And we might as well start getting
out.”
The method of procedure was quickly arranged. Placing Leoncia
behind him, her hand clutching the hem of his jacket so as to be
guided by him, he moved ahead with his left hand in contact with
the wall. Abreast of him, Torres felt his way along the right-hand
wall. By their voices they could thus keep track of each other,
measure the width of the passage, and guard against being
separated into forked passages. Fortunately, the tunnel, for tunnel it
truly was, had a smooth floor, so that, while they groped their way,
they did not stumble. Francis refused to use his matches unless
extremity arose, and took precaution against falling into a possible
pit by cautiously advancing one foot at a time and ascertaining solid
stone under it ere putting on his weight. As a result, their progress
was slow. At no greater speed than half a mile an hour did they
proceed.
Once only did they encounter branching passages. Here he lighted a
precious match from his waterproof case, and found that between
the two passages there was nothing to choose. They were as like as
two peas.
“The only way is to try one,” he concluded, “and, if it gets us
nowhere, to retrace and try the other. There’s one thing certain:
these passages lead somewhere, or the Mayas wouldn’t have gone
to all the trouble of making them.”
Ten minutes later he halted suddenly and cried warning. The foot he
had advanced was suspended in emptiness where the floor should
have been. Another match was struck, and they found themselves
on the edge of a natural cavern of such proportions that neither to
right nor left, nor up nor down, nor across, could the tiny flame
expose any limits to it. But they did manage to make out a rough
sort of stairway, half-natural, half-improved by man, which fell away
beneath them into the pit of black.
In another hour, having followed the path down the length of the
floor of the cavern, they were rewarded by a feeble glimmer of
daylight, which grew stronger as they advanced. Before they knew
it, they had come to the source of it——being much nearer than they
had judged; and Francis, tearing away vines and shrubbery, crawled
out into the blaze of the afternoon sun. In a moment Leoncia and
Torres were beside him, gazing down into a valley from an eyrie on a
cliff. Nearly circular was the valley, a full league in diameter, and it
appeared to be mountain-walled and cliff-walled for its entire
circumference.
“It is the Valley of Lost Souls,” Torres utterly solemnly. “I have heard
of it, but never did I believe.”
“So have I heard of it and never believed,” Leoncia gasped.
“And what of it?” demanded Francis. “We’re not lost souls, but good
flesh-and-blood persons. We should worry.”
“But Francis, listen,” Leoncia said. “The tales I have heard of it, ever
since I was a little girl, all agreed that no person who ever got into it
ever got out again.”
“Granting that that is so,” Francis could not help smiling, “then how
did the tales come out? If nobody ever came out again to tell about
it, how does it happen that everybody outside knows about it?”
“I don’t know,” Leoncia admitted. “I only tell you what I have heard.
Besides, I never believed. But this answers all the descriptions of the
tales.”
“Nobody ever got out,” Torres affirmed with the same solemn
utterance.
“Then how do you know that anybody got in?” Francis persisted.
“All the lost souls live here,” was the reply. “That is why we’ve never
seen them, because they never got out. I tell you, Mr. Francis
Morgan, that I am no creature without reason. I have been
educated. I have studied in Europe, and I have done business in
your own New York. I know science and philosophy; and yet do I
know that this is the valley, once in, from which no one emerges.”
“Well, we’re not in yet, are we?” retorted Francis with a slight
manifestation of impatience. “And we don’t have to go in, do we?”
He crawled forward to the verge of the shelf of loose soil and
crumbling stone in order to get a better view of the distant object
his eye had just picked out. “If that isn’t a grass-thatched roof——”
At that moment the soil broke away under his hands. In a flash, the
whole soft slope on which they rested broke away, and all three
were sliding and rolling down the steep slope in the midst of a
miniature avalanche of soil, gravel, and grass-tufts.
The two men picked themselves up first, in the thicket of bushes
which had arrested them; but, before they could get to Leoncia, she,
too, was up and laughing.
“Just as you were saying we didn’t have to go into the valley!” she
gurgled at Francis. “Now will you believe?”
But Francis was busy. Reaching out his hand, he caught and stopped
a familiar object bounding down the steep slope after them. It was
Torres’ helmet purloined from the chamber of mummies, and to
Torres he tossed it.
“Throw it away,” Leoncia said.
“It’s the only protection against the sun I possess,” was his reply, as,
turning it over in his hands, his eyes lighted upon an inscription on
the inside. He showed it to his companions, reading it aloud:
“DA VASCO.”
“I have heard,” Leoncia breathed.
“And you heard right,” Torres nodded. “Da Vasco was my direct
ancestor. My mother was a Da Vasco. He came over the Spanish
Main with Cortez.”
“He mutinied,” Leoncia took up the tale. “I remember it well from my
father and from my Uncle Alfaro. With a dozen comrades he sought
the Maya treasure. They led a sea-tribe of Caribs, a hundred strong
including their women, as auxiliaries. Mendoza, under Cortez’s
instructions, pursued; and his report, in the archives, so Uncle Alfaro
told me, says that they were driven into the Valley of the Lost Souls
where they were left to perish miserably.”
“And he evidently tried to get out by the way we’ve just come in,”
Torres continued, “and the Mayas caught him and made a mummy
of him.”
He jammed the ancient helmet down on his head, saying:
“Low as the sun is in the afternoon sky, it bites my crown like acid.”
“And famine bites at me like acid,” Francis confessed. “Is the valley
inhabited?”
“I should know, Senor,” Torres replied. “There is the narrative of
Mendoza, in which he reported that Da Vasco and his party were left
there ‘to perish miserably.’ This I do know: they were never seen
again of men.”
“Looks as though plenty of food could be grown in a place like this
——” Francis began, but broke off at sight of Leoncia picking berries
from a bush. “Here! Stop that, Leoncia! We’ve got enough troubles
without having a very charming but very much poisoned young
woman on our hands.”
“They’re all right,” she said, calmly eating. “You can see where the
birds have been pecking and eating them.”
“In which case I apologize and join you,” Francis cried, filling his
mouth with the luscious fruit. “And if I could catch the birds that did
the pecking, I’d eat them too.”
By the time they had eased the sharpest of their hunger-pangs, the
sun was so low that Torres removed the helmet of Da Vasco.
“We might as well stop here for the night,” he said. “I left my shoes
in the cave with the mummies, and lost Da Vasco’s old boots during
the swimming. My feet are cut to ribbons, and there’s plenty of
seasoned grass here out of which I can plait a pair of sandals.”
While occupied with this task, Francis built a fire and gathered a
supply of wood, for, despite the low latitude, the high altitude made
fire a necessity for a night’s lodging. Ere he had completed the
supply, Leoncia, curled up on her side, her head in the hollow of her
arm, was sound asleep. Against the side of her away from the fire,
Francis thoughtfully packed a mound of dry leaves and dry forest
mould.
 CHAPTER XVII

Daybreak in the Valley of the Lost Souls, and the Long House in the
village of the Tribe of the Lost Souls. Fully eighty feet in length was
the Long House, with half as much in width, built of adobe bricks,
and rising thirty feet to a gable roof thatched with straw. Out of the
house feebly walked the Priest of the Sun——an old man, tottery on
his legs, sandal-footed, clad in a long robe of rude home-spun cloth,
in whose withered Indian face were haunting reminiscences of the
racial lineaments of the ancient conquistadores. On his head was a
curious cap of gold, arched over by a semi-circle of polished golden
spikes. The effect was obvious, namely, the rising sun and the rays
of the rising sun.
He tottered across the open space to where a great hollow log
swung suspended between two posts carved with totemic and
heraldic devices. He glanced at the eastern horizon, already red with
the dawning, to reassure himself that he was on time, lifted a stick,
the end of which was fiber-woven into a ball, and struck the hollow
log. Feeble as he was, and light as was the blow, the hollow log
boomed and reverberated like distant thunder.
Almost immediately, while he continued slowly to beat, from the
grass-thatched dwellings that formed the square about the Long
House, emerged the Lost Souls. Men and women, old and young,
and children and babes in arms, they all came out and converged
upon the Sun Priest. No more archaic spectacle could be witnessed
in the twentieth-century world. Indians, indubitably they were, yet in
many of their faces were the racial reminiscences of the Spaniard.
Some faces, to all appearance, were all Spanish. Others, by the
same token, were all Indian. But betwixt and between, the majority
of them betrayed the inbred blend of both races. But more bizarre
was their costume——unremarkable in the women, who were
garbed in long, discreet robes of home-spun cloth, but most
remarkable in the men, whose home-spun was grotesquely
fashioned after the style of Spanish dress that obtained in Spain at
the time of Columbus’ first voyage. Homely and sad-looking were the
men and women—as of a breed too closely interbred to retain joy of
life. This was true of the youths and maidens, of the children, and of
the very babes against breasts——true, with the exception of two,
one, a child-girl of ten, in whose face was fire, and spirit, and
intelligence. Amongst the sodden faces of the sodden and stupid
Lost Souls, her face stood out like a flaming flower. Only like hers
was the face of the old Sun Priest, cunning, crafty, intelligent.
While the priest continued to beat the resounding log, the entire
tribe formed about him in a semi-circle, facing the east. As the sun
showed the edge of its upper rim, the priest greeted it and hailed it
with a quaint and medieval Spanish, himself making low obeisance
thrice repeated, while the tribe prostrated itself. And, when the full
sun shone clear of the horizon, all the tribe, under the direction of
the priest, arose and uttered a joyful chant. Just as he had dismissed
his people, a thin pillar of smoke, rising in the quiet air across the
valley, caught the priest’s eye. He pointed it out, and commanded
several of the young men.
“It rises in the Forbidden Place of Fear where no member of the
tribe may wander. It is some devil of a pursuer sent out by our
enemies who have vainly sought our hiding-place through the
centuries. He must not escape to make report, for our enemies are
powerful, and we shall be destroyed. Go. Kill him that we may not
be killed.”

About the fire, which had been replenished at intervals throughout

the night, Leoncia, Francis, and Torres lay asleep, the latter with his
new-made sandals on his feet and with the helmet of Da Vasco
pulled tightly down on his head to keep off the dew. Leoncia was the
first to awaken, and so curious was the scene that confronted her,
that she watched quietly through her down-dropped lashes. Three of
the strange Lost Tribe men, bows still stretched and arrows drawn in
what was evident to her as the interrupted act of slaying her and her
companions, were staring with amazement at the face of the
unconscious Torres. They looked at each other in doubt, let their
bows straighten, and shook their heads in patent advertisement that
they were not going to kill. Closer they crept upon Torres, squatting
on their hams the better to scrutinize his face and the helmet, which
latter seemed to arouse their keenest interest.
From where she lay, Leoncia was able privily to nudge Francis’
shoulder with her foot. He awoke quietly, and quietly sat up,
attracting the attention of the strangers. Immediately they made the
universal peace sign, laying down their bows and extending their
palms outward in token of being weaponless.
“Good morning, merry strangers,” Francis addressed them in English,
which made them shake their heads while it aroused Torres.
“They must be Lost Souls,” Leoncia whispered to Francis.
“Or real estate agents,” he smiled back. “At least the valley is
inhabited.—Torres, who’re your friends? From the way they regard
you, one would think they were relatives of yours.”
Quite ignoring them, the three Lost Souls drew apart a slight
distance and debated in low sibilant tones.
“Sounds like a queer sort of Spanish,” Francis observed.
“It’s medieval, to say the least,” Leoncia confirmed.
“It’s the Spanish of the conquistadores pretty badly gone to seed,”
Torres contributed. “You see I was right. The Lost Souls never get
away.”
“At any rate they must give and be given in marriage,” Francis
quipped, “else how explain these three young huskies?”
But by this time the three huskies, having reached agreement, were
beckoning them with encouraging gestures to follow across the
valley.
“They’re good-natured and friendly cusses, to say the least, despite
their sorrowful mug,” said Francis, as they prepared to follow. “But
did you ever see a sadder-faced aggregation in your life? They must
have been born in the dark of the moon, or had all their sweet
gazelles die, or something or other worse.”
“It’s just the kind of faces one would expect of lost souls,” Leoncia
answered.
“And if we never get out of here, I suppose we’ll get to looking a
whole lot sadder than they do,” he came back. “Anyway, I hope
they’re leading us to breakfast. Those berries were better than
nothing, but that is not saying much.”
An hour or more afterward, still obediently following their guides,
they emerged upon the clearings, the dwelling places, and the Long
House of the tribe.
“These are descendants of Da Vasco’s party and the Caribs,” Torres
affirmed, as he glanced over the assembled faces. “That is
incontrovertible on the face of it.”
“And they’ve relapsed from the Christian religion of Da Vasco to old
heathen worship,” added Francis. “Look at that altar——there. It’s a
stone altar, and, from the smell of it, that is no breakfast, but a
sacrifice that is cooking, in spite of the fact that it smells like
mutton.”
“Thank heaven it’s only a lamb,” Leoncia breathed. “The old Sun
Worship included human sacrifice. And this is Sun Worship. See that
old man there in the long shroud with the golden-rayed cap of gold.
He’s a sun priest. Uncle Alfaro has told me all about the sun-
worshipers.”
Behind and above the altar, was a great metal image of the sun.
“Gold, all gold,” Francis whispered, “and without alloy. Look at those
spikes, the size of them, yet so pure is the metal that I wager a child
could bend them any way it wished and even tie knots in them.”
“Merciful God!—look at that!” Leoncia gasped, indicating with her
eyes a crude stone bust that stood to one side of the altar and
slightly lower. “It is the face of Torres. It is the face of the mummy in
the Maya cave.”
“And there is an inscription——” Francis stepped closer to see and
was peremptorily waved back by the priest. “It says, ‘Da Vasco.’
Notice that it has the same sort of helmet that Torres is wearing.—
And, say! Glance at the priest! If he doesn’t look like Torres’ full
brother, I’ve never fancied a resemblance in my life!”
The priest, with angry face and imperative gesture, motioned Francis
to silence, and made obeisance to the cooking sacrifice. As if in
response, a flaw of wind put out the flame of the cooking.
“The Sun God is angry,” the priest announced with great solemnity,
his queer Spanish nevertheless being intelligible to the newcomers.
“Strangers have come among us and remain unslain. That is why the
Sun God is angry. Speak, you young men who have brought the
strangers alive to our altar. Was not my bidding, which is ever and
always the bidding of the Sun God, that you should slay them?”
One of the three young men stepped tremblingly forth, and with
trembling forefingers pointed at the face of Torres and at the face of
the stone bust.
“We recognised him,” he quavered, “and we could not slay him for
we remembered prophecy and that our great ancestor would some
day return. Is this stranger he? We do not know. We dare not know
nor judge. Yours, O priest, is the knowledge, and yours be the
judgment. Is this he?”
The priest looked closely at Torres and exclaimed incoherently.
Turning his back abruptly, he rekindled the sacred cooking fire from
a pot of fire at the base of an altar. But the fire flamed up, flickered
down, and died.
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