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Lead-Acid Batteries: Science
and Technology
 LeadeAcid Batteries: Science
and Technology
A Handbook of LeadeAcid Battery Technology
and its Influence on the Product
Detchko Pavlov

AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD

PARIS • SAN DIEGO • SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO
Elsevier
Radarweg 29, PO Box 211, 1000 AE Amsterdam, The Netherlands
The Boulevard, Langford lane, Kidlington, Oxford, OX5 1GB, UK
First edition 2011
Copyright Ó 2011 Elsevier B.V. All rights reserved
No part of this publication may be reproduced, stored in a retrieval system or transmitted in any
form or by any means electronic, mechanical, photocopying, recording or otherwise without the prior
written permission of the publisher
Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in
Oxford, UK: phone (+44)(0) 1865 843830; fax (+44)(0) 1865 853333; email: permissions@elsevier.
com. Alternatively you can submit your request online by visiting the Elsevier web site at http://elsevier.
com/locate/permissions and selecting Obtaining permission to use Elsevier material
Notice
No responsibility is assumed by the publisher for any injury and/or damage to persons or property as
a matter of products liability, negligence or otherwise, or from any use or operation of any methods,
products, intructions or ideas contained in the material herein.
Library of Congress Cataloging in Publication Data
A catalog record for this book is available from the Library of Congress
British Library Cataloguing in Publication Data
A catalogue record for this book is available from the British Library
ISBN: 978-0-444-52882-7

For information on all Elsevier publications

visit our website at www.elsevierdirect.com

Printed and bound in the Great Britain

11 12 13 11 10 9 8 7 6 5 4 3 2 1
Dedicated to my mother Ekaterina,
my father Pavel and my wife Svetla
This page intentionally left blank
 Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
Acknowledgements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi

Part 1: Fundamentals of Lead-Acid Batteries. . . . . . . . . . . . . . . . . . . . . . . . . . . 1

Chapter 1: Invention and Development of the LeadeAcid Battery. . . . . . . . . . . . . 3
Chapter 2: Fundamentals of LeadeAcid Batteries . . . . . . . . . . . . . . . . . . . . . . 29

Part 2: Materials Used for Lead-Acid Battery Manufacture . . . . . . . . . . . . . . . .115

Chapter 3: H2SO4 Electrolyte e An Active Material in the LeadeAcid Cell. . . . .117
Chapter 4: Lead Alloys and Grids. Grid Design Principles . . . . . . . . . . . . . . . . .149
Chapter 5: Leady Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .223

Part 3: Processes During Paste Preparation and Curing of the Plates . . . . . . . . .251
Chapter 6: Pastes and Grid Pasting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .253
Chapter 7: Additives to the Pastes for Positive and Negative
Battery Plates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .311
Chapter 8: Curing of Battery Plates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .363

Part 4: Plate Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .405

Chapter 9: Soaking of Cured Plates Before Formation . . . . . . . . . . . . . . . . . . .407
Chapter 10: Formation of Positive LeadeAcid Battery Plates . . . . . . . . . . . . . .443
Chapter 11: Processes During Formation of Negative Battery Plates. . . . . . . . . .481
Chapter 12: Technology of Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .501

Part 5: Battery Storage and VRLA Batteries. . . . . . . . . . . . . . . . . . . . . . . . . .533

Chapter 13: Processes After Formation of the Plates and During Battery
Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .535
Chapter 14: Methods to Restore the Water Decomposed During Charge and
Overcharge of LeadeAcid Batteries: VRLA Batteries . . . . . . . . . . .567
viii Contents

Part 6: Calculation of the Active Materials in a Lead–Acid Cell . . . . . . . . . . . . .605

Chapter 15: Calculation of the Active Materials for Lead–Acid Cells . . . . . . . . .607

Epilogue . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .623
Appendices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .625
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .633
 Preface
The leadeacid battery was invented at the advent of electricity. The discovery of electricity as
a form of energy is the greatest achievement of mankind, which has changed human life
dramatically. For over 150 years, the leadeacid battery technology has developed driven by the
accumulation of new knowledge and the invention of new materials. The leadeacid battery has
become one of the main portable sources of electric power with wide application in man’s
everyday life (transport vehicles, telecommunications, information technologies, etc.). It has
won a dominating position in energy storage and load-levelling applications (reserve electric
power supply and remote area energy systems). Leadeacid batteries are cheap, easy to produce
and easy to recycle, and the resources for their manufacture are practically unlimited. This is
why the leadeacid battery industry has reached annual turnovers of tens of billions of US
dollars on a worldwide basis.
The leadeacid battery is a complex dynamic system, or shall I call it ‘a complex dynamic
world’, in which various processes proceed continuously, at different rates, no matter whether
the battery is on charge, discharge or open circuit. This ‘living’ organism exists due to the
simultaneous operation of two electrochemical systems: the lead system (Pb/PbSO4 and PbO2/
PbSO4) and the water system (H2O/H2 and H2O/O2). The latter is thermodynamically
supported, but kinetically suppressed. These two systems are in continuous competition with
each other, the lead system playing the dominating role, which makes the leadeacid battery
functional and useful to mankind.
This dynamic world is governed by the laws of chemistry and electrochemistry, physics and
physical chemistry, metallurgy and corrosion science. This ‘world’ is a meeting point for the
kinetics and thermodynamics of chemical and electrochemical reactions, crystal nucleation
and growth with diffusion and migration processes, mechanical and corrosion processes in lead
alloys, as well as a number of phenomena of efficient transformation of chemical energy into
electrical energy and vice versa.
My collaborators and I have been studying this ‘world’ for many years now. We have advanced
step by step, overcoming numerous barriers, towards identifying the processes and
phenomena that proceed during leadeacid battery manufacture and operation, disclosing the
mechanisms of these processes and elucidating the structures of the obtained intermediate and
end products. It is really rewarding when you gain all this knowledge.
x Preface

Sooner or later, every man comes to the end of his active professional carrier. Having reached
this point in my life, with this book I want to share the knowledge and experience accumulated
for over 44 years of research with my fellow scientists, battery designers, engineers and
technologists in the battery industry. There are chapters in this book devoted to the funda-
mental theoretical background of leadeacid battery manufacture and operation, and others
discussing more technological issues, thus allowing the reader to find more easily his/her
specific topics of interest.
When writing this book, I rejoiced immensely at ‘the complex dynamic world’ that I was trying
to describe. If it stirs up a similar feeling in you, too, dear reader, then I would believe that the
book has accomplished its mission.
 Acknowledgements

I would like to express my thanks to Mrs. Mariana Gerganska for her valuable help with the
translation of this book and for her amicable criticism and useful remarks.
I also thank Ms. Dina Ivanova for her technical assistance with the graphical illustrations and
all my collaborators from the Lead-Acid Batteries Department of IEES for their most generous
support.
I am grateful to Mr. P. Kirubhagaran and Mr. B. Mageswaran and their team from Elsevier’s
book publishing division, Chennai, for their excellent work in converting my manuscript
into a book. And last, but not the least, I sincerely thank Ms. Anita Koch, Associate Acquisition
Editor at Elsevier, for her patience and understanding throughout the time of preparation and
submission of my manuscript.
I would also like to express my sincere gratitude to the following organizations for their
kindness to grant me permissions to reproduce copyright materials:
• Elsevier B.V.
• The Electrochemical Society, Inc.
• Springer Science and Business Media B.V.
• John Wiley & Sons, Ltd.
While every effort has been made to contact copyright holders or their agents, a few have
remained untraceable. I would be interested to hear from any copyright holders who have not
been acknowledged. I would be grateful if notified of any corrections that should be
incorporated in future reprints or editions of this book.
This page intentionally left blank
 PART 1

Fundamentals of Lead-Acid
Batteries
This page intentionally left blank
 CHAPTER 1

Invention and Development of the

LeadeAcid Battery
1.1. A Prelude
A scientific product is never born spontaneously in a researcher’s mind. Normally, it is a result
of the efforts of many scientists whose work and achievements have provided the background
for and ‘paved the way’ to the invention of this new product. The person recognised as the
inventor of the product is actually the one who has best understood its essence (fundamental
principles) and has produced and convincingly demonstrated this product to the public. Such is
the case with the invention of the leadeacid battery, too.
The discovery of electricity as a form of energy is, if not the greatest, definitely one of the
greatest achievements of mankind. Electricity has changed human life dramatically, making it
easier, more modern and sophisticated. It opened the door for rapid development of industry,
transport, communications and other spheres of activity. In the initial period following the
advent of electricity as a form of energy, electrochemical power sources played a major role.
They were used to produce electric power or served as ‘stores’ of electric energy. So at the
beginning of nineteenth century many chemists and physicists devoted their lives to the
invention and enhancement of various chemical power sources. Some of these will be
discussed in brief subsequently.
In 1801, the French physicist N. Gautherot connected the two electrodes of a Volta cell to two
platinum wires immersed in saline solution and passed electric current through them [1]. Water
decomposed to hydrogen and oxygen, and when the circuit was cut off and the platinum wires
were connected to each other, electric current flowed in the opposite direction for a short time.
A year later in Germany, Johann Ritter (Fig. 1.1) connected a Volta cell to layered discs of
copper and cardboard moistened with NaCl solution [2]. The charging voltage was 1.3 V. After
the circuit was disconnected, a voltage of 0.3 V was measured between the two copper discs.
Ritter conducted similar experiments with lead, tin and zinc plates. Different voltages were
measured for the different types of plates. He called this voltage polarisation.
When electric current flows through lead electrodes immersed in H2SO4 solution, lead dioxide
is formed on one of the electrodes. Such experiments were performed by Kästner in 1810,
Nobili in 1828, Schönbein in 1838 and Wheatstone in 1843 [2].

Lead-Acid Batteries: Science and Technology. DOI: 10.1016/B978-0-444-52882-7.10001-1

Ó 2011 Elsevier B.V. All rights reserved.
4 Chapter 1

Figure 1.1:
Portrait of Johann Wilhelm Ritter [2].

In 1854, the German medical officer Wilhelm Sinsteden (Fig. 1.2), while studying the elec-
trical phenomena, observed that when electric current flowed through lead electrodes
immersed in diluted H2SO4 solution the obtained cell delivered electric current and had
a specific energy output of 0.1 Wh kg
1 for 15 min of discharge [2,3].

1.2. Gaston Planté e The Inventor of the LeadeAcid Battery

In 1859, the French physicist Gaston Planté studied the polarisation between two identical
electrodes immersed in diluted aqueous solution of sulfuric acid. He investigated different
electrodes including silver, lead, tin, copper, gold, platinum and aluminium electrodes. He
established that, depending on the type of electrodes used, the cells were polarised to different
levels when electric current flowed through the electrodes and the cells became generators of
reverse current. He summarised the results of all these experiments in his paper entitled
‘Recherches sur la polarisation voltaique’, which was published in Comptes Rendus of the
French Academy of Sciences in 1859 [4].
Gaston Planté established that the secondary current (as was then called) that flowed through
a cell with lead plates separated by rubber strips and immersed in 10% sulfuric acid solution
 Invention and Development of the LeadeAcid Battery 5

Figure 1.2:
Portrait of Wilhelm Joseph Sinsteden [2].

was the highest and flowed for the longest period of time as compared to all other cells under
test. This cell had the highest voltage, too.
On 26 March 1860, Gaston Planté demonstrated before the French Academy of Sciences the
first rechargeable leadeacid battery comprising nine cells connected in parallel and presented
a lecture entitled ‘Nouvelle pile secondaire d’une grande puissance’ (Fig. 1.3) [5]. This was
practically the birth certificate of the leadeacid battery.

1.2.1. Gaston Planté e The Scientist

Raymond-Louis Gaston Planté was born on 22 April 1834 in the town of Orthez, Basses-
Pyrénées province in France.
The Planté family seems to have been born under a lucky star. All three brothers, Leopold (born
1832), Gaston (born 1834) and Francis (born 1839), gained national, and even international,
fame. Leopold Planté was one of the leaders of lawyers in Paris; Francis Planté was a brilliant
piano player who amazed the cultural world of his time with his talent. He was called ‘God of
the piano’ and gave concerts until the age of 91. The Planté family was an old and highly
respected family from Orthez [6]. The father of the three brothers, Pierre (Pedro), and their
6 Chapter 1

Figure 1.3:
(a) Portrait of Gaston Planté; (b) the first rechargeable lead-acid battery comprising a series of nine
cells connected in parallel.
 Invention and Development of the LeadeAcid Battery 7

uncle Raymond had occupied high posts in the local administration of Orthez and of the
Basses-Pyrénées district. In 1841, Pierre Planté and his family left Orthez and moved to Paris
in order to assure better education for his sons.
Gaston Planté started his education at a private school and then went to the Lycée Charlemagne.
At the age of 16, he became Bachelor of Letters and at 19, Bachelor of Science. Then he
attended the most renowned university in Paris, La Sorbonne, and in 1855 he obtained the
degree Master of Science.
During his university years Gaston impressed his professors with his analytic mind, practical
skills and extraordinary dexterity in doing experimental work. Because of these qualities of the
young student, Prof. Edmond Becquerel chose Gaston Planté as assistant in his laboratory at
the Conservatory of Arts and Crafts.
Under Prof. Becquerel’s tutorship, Gaston mastered the scientific approach to studying natural
processes and demonstrated a lively interest in disclosing natural phenomena. As a result of
this inborn curiosity of his, in 1855, Gaston discovered an unknown fossil bird in a quarry near
Paris. The French Academy of Sciences, in agreement with the British Museum, gave this bird
the name Gastornis parisiensis.
In the middle of the nineteenth century, laboratory experiments demonstrated ever more
clearly the great potential of electricity to be of help to people and to change funda-
mentally their everyday life. Gaston Planté was among the first to realise this and started
investigations of various electrical phenomena. His experiments were very impressive. On
28 March 1858, he was chosen to demonstrate before Emperor Napoleon the Third and the
Empress, in Palais de Tuileries, the principal electrical experiments that were known at
that time [7].
Gaston Planté was very active in the field of electrochemistry. He replaced the then used
platinum electrode with lead electrode in the process of reproduction of full-relief figures in
galvanoplastics. This method was employed for the fabrication of the sculptures decorating the
front of the Opera house in Paris. In 1866, Gaston Planté explored the electrolytic production of
ozone. He came to the conclusion that production of ozone should be performed using lead
electrodes instead of platinum.
Despite his significant achievements in the field of electrochemistry, Gaston Planté remains
essentially a physicist. Since 1873, he studied the difference between static and dynamic
electricity as well as high-voltage phenomena.
In 1877, he constructed a machine (called the Rheostatic Machine) in which he used multi-cell
battery and a bank of capacitors and, with the help of a series of commutators and contacts,
alternately charged the capacitors connected in parallel and then discharged them connected in
series (Fig. 1.4). The large-scale model of this machine comprised 80 capacitors and a series of
8 Chapter 1

Figure 1.4:
G. Planté constructed a ‘Rheostatic Machine’ comprising multiple leadeacid Cells, a bank of
capacitors and a series of commutators and contacts.

leadeacid batteries with 800 cells (1600 V). This machine was able to deliver voltages of up to
200,000 V. Planté used this machine to explore high-voltage electrical sparks. Based on the
results of these experiments, he proposed hypotheses about the origin of spiral nebulae, globe
lightnings and solar spots and even about the origin of the sun.
He performed systematic studies of electrical phenomena and summarised the results of these
studies in the book Recherches sur l’e´lectricite´ (Research on Electricity), which was published
in 1879 but the information in it is still relevant today [8]. In this book Gaston Planté considers
electricity as a very fast flow of electrically charged material, which may in some cases cause
an electric spark or a voltaic arc and in others charge or discharge a battery. Atomic structure
was not known to scientists at that time, but, based on scientific generalisations, Planté
envisaged the involvement of electric charges in the structure of materials. Such was the
scientist Gaston Planté e always ahead of time.

1.2.2. Gaston Planté e The Person

His contemporaries describe Gaston Planté as a very kind-hearted, modest and unselfish man,
fully dedicated to his work e a real workaholic (Fig. 1.5).
Besides his deep interest in science, he loved music and was a virtuoso piano player.
He wrote and spoke fluently English, German, Spanish and Italian. He was deeply
religious and profoundly moral, which gained him sympathy, love and respect from all
who knew him.
Gaston Planté never protected his inventions by patents and showed no interest in obtaining
material benefits from them. He refused all kinds of privileges. Being a widely recognized
scientist, when invited to run for Member of the French Academy of Sciences, he declined the
offer saying that he would lose much time in preparation for the election and would rather
prefer to spend this time working in his laboratory.
 Invention and Development of the LeadeAcid Battery 9

Figure 1.5:
Portrait of Gaston Planté.

He never accepted appointment at official remunerated positions, but did not decline invita-
tions to perform honourable functions. He was:

• Professor of physics at the Polytechnic Association;

• Member of the Emperial Jury at the International Exhibitions held in London in 1863 and
in Paris in 1867.

He received many distinctions and awards, including:

• Knight of the Order of the Rose e Brazil;

• Cavalier of the Legion of Honour of France, Italy and Austria;
• Lacaze Prize of the French Academy of Sciences;
• Golden Medal in Arts Economique;
• Golden Ampere Medal of the Society for Encouragement of National Industry.

When the President of the Society for Encouragement of National Industry, the renowned
chemist Dumas, presented the Ampere Medal to Gaston Planté he said: ‘I am happy to give you
this medal bearing the effigy of Ampere and am sure that in the future our successors will give
a medal with your effigy.’ [6].
10 Chapter 1

Gaston Planté donated the sum of 10,000 Francs, which he received with the Lacaze Prize, to
the Friends of Science Society to help scientists in need, and he sold the two golden medals and
gave the money to the poor.
In 1889, Gaston Planté’s health deteriorated. He began to gradually lose his sight and on 22
May 1889 he died at the age of 55.
In his will, Gaston Planté donated three real estate properties to Friends of Science Society. The
French Academy of Sciences received all his savings under the obligation to award a biannual
monetary prize to scientists or inventors with an important contribution in the field of elec-
tricity. Pierre Curie was the second recipient of this award, which was presented to 21 scientists
between 1893 and 1933.
Such a moral and highly ethical person was Gaston Planté.
In 1989, on the eve of the 130th anniversary of the invention of the leadeacid battery and in
connection with the first LABAT international conference on leadeacid batteries, the Bulgarian
Academy of Sciences, with the approval of the French Academy of Sciences, established an
award, a medal, named after the great French scientist Gaston Planté (Fig. 1.6) [9].

Figure 1.6:
The Gaston Planté Medal.
 Invention and Development of the LeadeAcid Battery 11

The Gaston Planté Medal is presented every 3 years to prominent scientists who have
made significant contributions to the development of leadeacid battery science and
technology. The recipients of the award are elected by an international committee
comprising 15 scientists from all over the world. Up to now the Gaston Planté Medal has
been awarded to 11 scientists from 7 countries as well as to the Advanced LeadeAcid
Battery Consortium for promoting research and development in the field of leadeacid
batteries.

1.3. What Pains Had the LeadeAcid Battery to Go Through

1.3.1. In the Beginning Was the Planté Technology

The leadeacid battery was born some 10 years before the invention of the mechanical
generators of electricity. Being a secondary power source, the leadeacid battery needed
a cheap and easy-to-use charging device. At that time, the battery was charged by Daniell cells
or Bunsen cells, which was not an easy procedure at all.
In 1869, Zénobe Gramme constructed the first direct current dynamo machine, which made
battery charging easy. Mechanical energy was converted into electric energy, which was then
stored in a leadeacid battery in the form of chemical energy.
In 1873, the Bréquet Company was the first to produce Planté leadeacid batteries and Gramme
dynamo machines. Thus, a technical possibility was created to easily generate and store
electric energy. At that time, the system dynamo and leadeacid storage battery was still only
a curious scientific achievement. Electric energy had not yet found practical application in
human life.
In 1879, Thomas Edison in the United States and Joseph Swan in England invented the
incandescent lamp, thus making it possible to convert electric energy into light. The
invention of the light bulb promoted the use of electricity in people’s everyday life.
Electricity entered human lives. Leadeacid battery demand increased. However, large-
scale production of leadeacid batteries was constrained by the technology of their
manufacture.
Immediately after its invention, the leadeacid storage battery attracted the interest of many
researchers who looked for variants of Planté’s cell.
In 1861, Charles Kirchoff in the United States proposed a cell comprising platinum electrodes
immersed in a solution of Pb(NO3)2 and Pb(CH3COO)2 [10]. At the same time, Wilhelm
Siemens in Germany devised a secondary cell with carbon electrodes impregnated with lead
salts and immersed in acid solution [11]. These, however, were rather curious attempts to
create a novel secondary cell.
12 Chapter 1

1.3.2. Development of New Technology for LeadeAcid Battery Manufacture

Application of leadeacid batteries was limited because of the slow process of manufacture of
the electrodes and their low capacity. In the late 1870s there was an acute need of new tech-
nology for leadeacid manufacture.
In 1881, Camille Fauré coated the lead plates with a paste of red lead oxide, sulfuric acid and
water, and then charged them to form Pb and PbO2 active masses. The specific energy of the
battery increased to 8 Wh kg
1 at 10 hours discharge rate [12].
The same year, Ernest Volckmar replaced the lead sheet with lead grid [13] and Scudamore
Sellon [7] used leadeantimony grids instead of pure lead grids. S.C. Curie devised tubular
positive plates for leadeacid batteries.
In 1882, Gladstone and Tribe disclosed the reactions that proceeded at the two electrodes
during battery operation and proposed the double-sulfate theory [14].
In 1883, Hermann Aron studied in detail the processes on charge and discharge of a leadeacid
battery [15]. He established a correlation between the specific density of H2SO4 electrolyte and
discharge time, and first described the processes of battery sulfation.

1.3.3. First Applications of LeadeAcid Batteries in Human Life

Thus, in the early 1880s, a leadeacid battery of high capacity and relatively simple tech-
nology of manufacture was created. This battery rapidly found various practical applications.
In 1881, Gustave Trouvé first used a leadeacid battery in his three-wheeled electric auto-
mobile, which reached a speed of 12 km h
1. In 1886, the first submarine propelled by
leadeacid batteries was launched in France. A leadeacid battery was mounted in a small
dirigible balloon which was propelled at a speed of 4 m s
1. In 1899, Camille Jenatzy reached
a speed record of 109 km h
1 with his cigar-shaped electric car powered with leadeacid
batteries.
The leadeacid battery was quickly adopted in the emerging telecommunications technologies:
first, in Morse electric telegraph and later by the telephone companies in the United States, too.
In 1882, the city of Paris installed a system for the distribution of electricity for lighting
comprising a combination of dynamos and leadeacid batteries. The first electrically lit street
was Grands Magasins du Louvre in Paris (‘the city of lights’). In 1883, Planté supplied the
Imperial Palace of Franz Josef in Vienna with stationary and portable equipment for lighting.
The leadeacid battery was gradually deployed in various sectors of the industry and became an
important means of electric energy production and storage. Thus, the first stage in the
development of the leadeacid battery system and the technology for its manufacture was
completed.
 Invention and Development of the LeadeAcid Battery 13

1.4. The LeadeAcid Battery in the Twentieth Century e Second Stage

in its Development
1.4.1. Leady Oxide Production Processes

In 1881, Camille Fauré developed a process for coating both sides of lead plates, and later lead
grids, with a paste of lead oxide (litharge), red lead, sulfuric acid and water and then charging
the plates to form Pb and PbO2 active masses. This was a revolutionary breakthrough in battery
technology, which opened the way for industrial production of leadeacid batteries. The lead
oxide was produced by melting lead in a reverberatory furnace and then the molten lead was
oxidised by a flow of air and water steam. The process was slow (about 30 hours per batch) and
cumbersome, and the obtained oxide was coarse-grained and had to be mill ground to yield
a product suitable for use in the battery industry.
Methods have been looked for to accelerate the process of lead oxide manufacture. Various
technological processes have been proposed for the production of lead oxide from lead
carbonate, lead acetate, etc., but they all proved to be too complicated and expensive.
In 1898, George Barton patented a new process where molten lead was rapidly stirred and
atomised into small droplets, which were then carried away and oxidised by a humidified air
stream drawn through the pot. The resulting oxide was passed through a series of cyclone
classifiers where the larger particles were separated and returned back to the reaction pot for
further processing, while the fine powder was collected in silos (drums or hoppers).
In a patent of 1926, G. Shimadzu described an adaptation of the ball-mill process used for
grinding ores, pigments, etc., by using lead balls tumbling against one another in a mill.
The friction created sufficient heat to oxidise the outside surface of the lead balls and the
obtained oxide layer fell off continuously in the form of dust. An air flow of a definite
speed and humidity carries away the oxide dust through inbuilt screens to separate the
coarser fractions and return them to the mill. The fine lead oxide particles were collected
in storage silos.
Both the methods (Barton pot and ball-mill) produced partially oxidised lead oxide containing
between 20% and 40% free lead. Hence, this oxide was called ‘leady oxide’. The production
time of this oxide was reduced substantially, which gave a strong impetus to the development
of the leadeacid battery industry after 1926. Nowadays, these two processes are still the
dominating methods for leady oxide production.

1.4.2. New Materials and New Technological Processes Are Adopted

in the Production of LeadeAcid Batteries

The twentieth century was the time of invention and rapid development of many new materials
and novel technological processes, which soon found practical application in the construction
14 Chapter 1

and manufacturing technologies of leadeacid batteries. Let us mention some of these inno-
vative developments.
The ebonite battery case was replaced by polypropylene and polyethylene copolymer or by
acrylonitrile butadiene styrene.
The original wooden sheet separators evolved through sintered PVC to polyethylene or
polypropylene and, in some battery types, to absorptive glass mat (AGM).
The first grid alloys used were lead alloys with 11% antimony content called ‘hard lead’. These
alloys were replaced with low-antimony lead alloys with additions of Sn, As and Ag. Later,
battery grid manufacturers switched to leadecalcium and leadecalciumetin alloys.
At the end of the century, new methods of plate grid manufacture were introduced, parallel to
casting. These include the expanding metal grid process and, more recently, the die-cut
technology.

1.4.3. Solution to the Water Loss and Battery Maintenance Problem

The first and most important problem that battery researchers and engineers had to resolve was
to eliminate or reduce substantially the maintenance of the battery during its exploitation.
In the first half of the twentieth century, lead alloys with high antimony content were used for
the manufacture of the plate grids for leadeacid batteries. These batteries lost water during
operation and hence they needed maintenance. Significant efforts of battery scientists and
technologists in the twentieth century were focused on resolving the water loss problem.
During corrosion of the positive grids, antimony diffuses to the electrolyte and is deposited on
the negative plates. Hydrogen evolution on antimony proceeds at low overpotentials. Hence,
decomposition of water from the electrolyte is accelerated. The battery has to be topped up
with water periodically.
In 1935, Haring and Thomas from Bell Laboratory replaced the leadeantimony grids with
leadecalcium for their stationary batteries. The need for battery maintenance was reduced
substantially [16,17].
In 1957, Otto Jache from Sonnenschein introduced the gel electrolyte and patented the sealed
leadeacid battery [18]. In this battery construction, the oxygen evolved at the positive plates
passes through cracks in the gel and reaches the negative plates, where it is reduced and thus
restores the lost water and suppresses hydrogen evolution. The German company Sonnen-
schein started mass production of gel-sealed leadeacid stationary batteries.
In 1967, Donald McClelland and John Devitt of Gates Corporation in the United States used
AGM separator which facilitated the transport of oxygen to the negative plates and also
 Invention and Development of the LeadeAcid Battery 15

absorbed the electrolyte [19]. Thus, the maintenance-free valve-regulated leadeacid battery
(VRLAB) was invented. Leadetinecalcium grids were used for VRLABs.

1.4.4. Premature Capacity Loss Problem and its Resolution

With the introduction of leadecalcium alloys for the plate grids, however, the life of the battery
on deep discharge cycling declined dramatically to 20e25 cycles. This phenomenon was first
called ‘Sb-free effect’ and later ‘premature capacity loss’ (PCL effect) [20]. It was established
that the PCL effect was a result of certain processes that proceed at the positive battery plate,
more precisely at the interface grid/positive active mass (PCL-1 effect) [21] and/or in the
positive active mass volume (PCL-2 effect) [22].
The capacity-limiting effect of the interface was found to be due to the following reasons.
During battery charge and over-charge, the oxygen evolved at the positive plate surface
penetrates through the corrosion layer to the lead grid and oxidises its surface to PbO. The
obtained PbO layer has high ohmic resistance. It is oxidised by the evolved oxygen to PbOn
(1 < n < 2) and the latter is further oxidised to PbO2. If the rate of PbO formation is higher
than the rate of its oxidation to PbO2, a thick layer of PbO with high ohmic resistance forms on
the grid surface which leads to high polarisation of the plate on discharge and eventually to
capacity loss [23]. Tin and antimony additions to the grid alloy proved to increase the rate of
PbO oxidation to PbO2 and thus the PCL-1 effect was suppressed [24]. The PCL-2 effect is due
to impaired electroconductivity of the contact between the PbO2 particles (neck zones) of the
positive active mass (Kugelhaufen theory) [22]. Tin and antimony added to the grid alloy
improve this contact. So, it is imperative to introduce Sn >1.2% to the leadecalcium positive
grids of batteries for cycling duties in order to reduce or even avoid the PCL effect.

1.4.5. Basic Lead Sulfate Pastes

Another challenge that battery researchers had to face was to disclose the mechanism of the
processes that take place during the manufacture of the plates and to find technological
methods to control these processes.
During the second half of the twentieth century, intense research began into the processes
during manufacture of leadeacid battery plates. J.J. Lander established the formation of
tribasic lead sulfate (3BS) when the battery pastes were prepared at temperatures up to 60  C
(Fig. 1.7a) [25]. At higher temperatures the paste microstructure comprised big crystals of
tetrabasic lead sulfate (4BS), as observed by H. Bode and E. Voss (Fig. 1.7b) [26]. John Pierson
studied the formation of 4BS during high-temperature (83  C) curing of positive battery plates
[27]. The active mass obtained from 4BS paste proved to have longer cycle life than that
produced from 3BS paste [28,29]. It was established that 4BS paste could be obtained only
from an initial three-component mix of 3BS þ orthorhomb-PbO þ tet-PbO without organic
16 Chapter 1

Figure 1.7:
SEM Images of (a) 3BS particles and (b) 4BS particles. Magnification: 10,000.

capillary active substances, for example, the expander lignosulfonate [30,31]. The correlations
between 3BS content and H2SO4/leady oxide ratio [32], and 4BS content and leady oxide/red
lead ratio [33] during paste preparation were determined.

1.4.6. Skeleton and Energetic Structure of Battery Active Masses

The capacity and cycle life of the battery depend greatly on the structure of the active materials.
Hence, it was important to examine the structure of the two types of active masses and to
elucidate how it was formed during the technological process of plate manufacture.
It was established that, during the formation of the positive active mass, both b-PbO2, and
a-PbO2 were formed [34,35]. Investigation of the formation processes proved that it proceeded
in two stages [36,37]. During the first formation stage, 3BS (4BS) and PbO are oxidised
yielding mostly a-PbO2 because the solution in the pores of the cured paste is neutral to
slightly alkaline. Then, in the second stage of formation, the PbSO4 formed during soaking
prior to formation and during the first formation stage is oxidised to b-PbO2 as the solution in
the pores is acidic [37]. The a-PbO2 crystals form the active mass ‘skeleton’ which is less
involved in the chargeedischarge processes but conducts the current throughout the positive
 Invention and Development of the LeadeAcid Battery 17

active mass volume and is connected to the grid providing mechanical support to the active
mass. The b-PbO2 modification is electrochemically active and forms the ‘energetic structure
of the positive active mass’, which determines the capacity of the positive plates [37,38].
Formation of the negative active mass (NAM), too, proceeds in two stages [39]. During the first
stage, 3BS and PbO are reduced forming the ‘lead skeleton of NAM’ which is connected to the
grid, and during the second stage of formation, reduction of PbSO4 proceeds yielding small Pb
crystals of large surface [40,41]. These crystals form the ‘energetic structure of NAM’ and
determine its capacity.
A technological process of formation with circulating electrolyte was developed which
shortened the duration of the formation procedure to 8e10 hours, sustaining optimum
temperature and H2SO4 concentration and minimising air pollution [42,43].

1.4.7. GeleCrystal Structure of the Lead Dioxide Active Mass

When the positive plates for leadeacid batteries are produced using chemically obtained lead
dioxide, their capacity is improperly low. In contrast, when the lead dioxide plates are
produced employing electrochemical methods, they have a high capacity. What is this
correlation between the electrochemical activity of battery positive plates and the method of
lead dioxide production due to?
When VRLABs were adopted for mass production, the volume of H2SO4 electrolyte in the
battery was confined to the amount that the AGM separator could absorb. In order to preserve
the quantity of H2SO4 as active material, its density was increased to 1.31 g cm
3 and even to
1.34 g cm
3. This led to a dramatic drop in capacity of the positive plates.
But why does the electrochemical activity of electrochemically obtained lead dioxide depend
on the acid concentration, whereby the plate capacity declines abruptly at higher H2SO4
concentrations? Researchers argued over the source of the electrochemical activity of lead
dioxide. First, it was related to the formation of oxygen vacancies or of hydrogen ions in the
lead dioxide crystal lattice [44e48]. No direct relation was established, however, between the
electrochemical activity and these components [49e52]. Other researchers explained the
electrochemical activity with the formation of coral-shaped structures of PbO2 [53,54]. It was
also suggested that the impeded contact between the PbO2 crystals determined the electro-
chemical activity of PbO2 [22,55].
Our team, too, carried out research aimed to find the answer to the question. Samples of
chemically and electrochemically obtained lead dioxide were examined with a scanning
electron microscope (SEM) and a transmission electron microscope (TEM). Figure 1.8
shows the SEM images obtained, and the TEM images are presented in Chapters 2 and 10 of
this book.
18 Chapter 1

Figure 1.8:
SEM images of (a) chemically obtained lead dioxide and (b) electrochemically obtained lead dioxide.

As evident from the SEM and TEM pictures, the electrochemically obtained lead dioxide
particles comprise crystal (PbO2) zones and hydrated (amorphous) zones [PbO(OH)2]. The two
types of zones are in equilibrium [56e58].
PbO2 þ H2 O$PbOðOHÞ2 $H2 PbO3
(1.1)
crystal zones gel zones
When this lead dioxide was heated and dehydrated, its capacity declined abruptly. These
results indicate that the electrochemical reaction of PbO2 reduction proceeds in the hydrated
(gel) zones of the particles and it is these gel zones that determine the electrochemical activity
of the lead dioxide [59]. The gel zones of PbO2 particles have both electron and proton
conductivity due to the polymer chains of the lead dioxide structure [59].
For the electrochemical reaction of discharge to proceed:

PbOðOHÞ2 þ 2Hþ þ 2e
/PbðOHÞ2 þ H2 O (1.2)

equivalent amounts of electrons from the crystal zones and Hþ ions from the solution have to
enter the gel zones so as to avoid charging of the gel zones and blocking of the electrochemical
process. It has been established experimentally that gel zones exchange ions with the solution
 Invention and Development of the LeadeAcid Battery 19

and SO2
4 ions are absorbed in the gel zones affecting the gelecrystal zones equilibrium [60].
SO2
4 absorption in the gel zones of PbO2 particles increases with increase of acid electrolyte
concentration. At H2SO4 solution densities higher than 1.29 g cm
3, a great number of SO2
4
ions are absorbed in the gel zones, reducing both the electron and proton conductivity of these
zones. During plate discharge, sulfate ions form immediately PbSO4 in the gel zones, which
leads to rapid electrode passivation. To keep up the capacity of the positive plates, the number
of sulfate ions absorbed in the gel zones of the PbO2 particles should be relatively small. Then,
the reaction of PbO2 reduction will pass through several stages, including first formation of Pb
(OH)2 and water, and then the lead hydroxide will react with H2SO4 forming PbSO4 [59]. In
this way large amounts of PbO2 will be involved in the reduction process, yielding high
electrode capacity. It has been established that the H2SO4 electrolyte concentration should not
exceed 1.28 g cm
3. At these acid concentrations, 20e50% of the positive active mass
(depending on the discharge current) may be involved in the capacity formation processes.
As to the electrochemical activity of chemically obtained lead dioxide, either it is composed of
crystal zones only or, if hydrated, the gel zones in its structure are very small, which is the
reason for the low specific capacity of such an electrode.

1.4.8. The PbjPbOjPbSO4jH2SO4 Electrode

Lander [61] and Burbank [62] applied the XRD method to analyse the substances formed
during polarisation of a lead electrode in H2SO4 solution. Some unexpected results were
obtained. Beside the diffraction peaks for PbSO4 and PbO2, the XRD pattern featured other
peaks, too, which were related to the formation of tetragonal PbO. This was a bit surprising and
posed the question whether PbO formed electrochemically in H2SO4 solution? A counter-
interpretation of the XRD data was immediately proposed, namely that those were diffraction
peaks for a-PbO2 [63]. Many of the diffraction peaks for these two oxides do coincide. The
formation of tet-PbO was refuted based on thermodynamic grounds as well [64].
This dispute in the international literature aroused our curiosity and we conducted combined
XRD and chemical analysis of the products formed on polarisation of a lead electrode in
H2SO4 solution. It was established that on polarisation between
0.400 and þ0.950 V (vs
HgjHg2SO4 electrode) in 0.5 M H2SO4 solution, a PbjPbOjPbSO4jH2SO4 electrode system was
formed [65e67]. It was interesting to disclose the mechanism of formation of PbO in H2SO4
solution. Based on experimental investigations we have proposed the following mechanism for
the formation of lead monoxide. First, a lead sulfate layer forms on the electrode surface
comprising PbSO4 crystals with pores of membrane sizes between them. The lead sulfate
membrane is permeable for water and hydrogen ions, but does not let the larger SO2
4 ions to
get through. The diffusion potential of the PbSO4 membrane was determined [68]. When
electric current flows through the electrode, Pb2þ ions are formed at the interface PbjPbSO4
membrane. These ions react with water at this interface producing Pb(OH)2 and Hþ ions. In
20 Chapter 1

order to preserve the electroneutrality of the anodic layer, the hydrogen ions migrate through
the pores of the PbSO4 membrane to the solution. Pb(OH)2 is dehydrated, as a result of which
tet-PbO forms between the Pb and PbSO4 layers. A mechanism of the growth processes of the
tet-PbO layer on polarisation of the PbjPbOjPbSO4 membrane has also been proposed
[69e71]. These membrane processes proceed sometimes in the leadeacid battery on deep
discharge and sulfation of the negative plates.

1.4.9. Three-Component Expander Added to the NAM

What development did the utilization coefficient of the NAM go through?

The specific surface of NAM is between 0.6 and 1.0 m2 g
1. The PbSO4 formed as a result of
lead oxidation during discharge would rapidly cover this surface and thus reduce substantially
the capacity of NAM. In order to achieve high capacity of the negative plates, the discharge
processes should involve not only the surface of the NAM but also layers from its volume. The
passivating effect of the PbSO4 layer became clearly obvious after the Second World War,
when the wooden separators were replaced with polymers. The cold cranking ability and the
capacity of the battery declined drastically. The negative plates were found to be responsible
for this decline. It was established that lignosulfonate leached from the wooden separator to the
H2SO4 solution and adsorbed onto the lead surface, thus retarding the formation of a passiv-
ating PbSO4 layer, which eventually reduced battery capacity, especially at low temperatures.
As a remedy for this phenomenon, various additives (collectively called ‘expander’) are
introduced in the NAM so as to prevent the formation of a passivating PbSO4 layer and allow
20e50% of the lead (NAM) volume (depending on the current density) to participate in the
oxidation reaction. The organic expander component (lignosulfonate), being a surface active
polymer, is adsorbed on the Pb surface and prevents the formation of a continuous PbSO4 layer
on the electrode surface [72,73]. The other expander component, barium sulfate, provides
nuclei for the growth of numerous small PbSO4 crystals, forming a porous layer instead of the
continuous PbSO4 film [74]. Thus, the lead active mass volume, and not only its surface, can
participate in the discharge reaction. Active carbon additives (the third expander component)
increase the electrochemically active surface of the NAM on which the charge reaction Pb2þ þ
2e
/ Pb proceeds, thus increasing further the NAM volume which is involved in the charge
processes [75]. Moreover, carbon conducts the electric current when a great part of the lead
phase has been oxidized to PbSO4 [76]. That is why the three expander components (ligno-
sulfonates, BaSO4 and carbon) are indispensable attributes to NAM. However, their proportion
in NAM should vary depending on the intended battery duty.

1.4.10. Conclusions
So the utilization of the active materials can be improved by involving greater volume of these
materials, and not only their surface layers, in the chargeedischarge processes. The proportion
 Invention and Development of the LeadeAcid Battery 21

between the skeleton and energetic microstructures of the positive and negative active masses
exerts a strong influence on the capacity and cycle life performance of the battery. Therefore, it
was essential to modify the technology of battery manufacture so as to guarantee formation of
appropriate active mass structures with adequate utilization coefficients.
Any change in materials or technological processes used for leadeacid battery manufacture was
associated with certain problems in battery operation. The research efforts aimed at resolving
these problems resulted in disclosing new structures, processes and properties of leadeacid
batteries. This comes to demonstrate that the leadeacid battery is a fairly complex system whose
proper and effective functioning cannot be reduced to electrochemical reactions only.
Research into the processes that take place during the different technological procedures
involved in the manufacture of positive and negative battery plates gave rise to the science of
battery manufacturing technology.

1.5. Applications of LeadeAcid Batteries

1.5.1. Types of LeadeAcid Batteries

After World War II, production of leadeacid batteries increased immensely, stimulated by the
rapid development of the automobile, transport and telecommunications industries, as well as
by the increased demand for reserve (stand-by) energy, and most recently by the boom of
information technology.
According to their application, leadeacid batteries can be classified into the following main
types:
• SLI (starting, lighting, ignition) batteries used in automobiles.
• Stationary batteries are commonly used for backup power supply, i.e., to generate and
store electric energy for use, on request, by telecommunication systems, electric utility
centres, computer systems, etc.
• Motive power (traction) batteries are industrial batteries used to power in-house transport
vehicles: fork-lift trucks, electric cars, mining equipment, etc.
• Special purpose batteries intended for use in aircraft, submarines, special military
equipment.
• Currently, major scientific and engineering work is focused on the development of
batteries for hybrid or full electric vehicles.
In terms of maintenance, batteries are classified as:
• Flooded batteries (with high-Sb grid alloys) e they require regular maintenance.
• Maintenance-free batteries (with PbCaSn or low Sb, As and Sn for the positive plates and
PbCa grids for the negative plates).
• VRLABs (with PbSnCa grids and AGM separators).
22 Chapter 1

1.5.2. Position of the LeadeAcid Battery Among the Secondary Electrochemical

Power Sources

The leadeacid battery could be adequately evaluated only if compared to the other types of
secondary power sources. A theoretical assessment can be made by comparing the electrical,
energetic, power and economic parameters of the different sources of electricity, but the
relative share of each battery chemistry in practical applications is the most objective evalu-
ation criterion. Table 1.1 summarises the basic energy and power characteristics of six types of
secondary power sources which are currently used most widely. Data from the studies of
Wentzl [78] and Köhler [79] have been used. It can be seen that the leadeacid battery has
inferior specific energy and power characteristics as compared to the other types of batteries.
Table 1.2 presents the unit cost (in Watt-hour per dollar) of the electric energy produced, as
well as the advantages and disadvantages of the different power sources [77]. The leadeacid
battery generates two to three times cheaper energy than all other battery types. Its only
disadvantage is its low specific energy (Wh.kg
1), due to the high atomic weight of lead.
But why, despite their unfavourably high atomic weight, have leadeacid batteries found such
a wide application and occupy leading market positions?
It is because of their advantages, both with regard to performance and economic parameters,
and technology of manufacture. It is not only the technical characteristics that matter for the
mass adoption of a given product in practise. Very often, economic issues are more relevant.
Leadeacid batteries are capable to deliver very high power; they are reliable and easy to
produce. The resources for their manufacture are practically unlimited. Almost 95% of the
materials used in a leadeacid battery are recyclable. A leadeacid battery can store its energy
for a very long time.

Table 1.1: Main characteristics of various batteries.

Specific Specific Energy

Specific Energy Power Energy of Battery*
Voltage Energy Density Density of Cell* (100% SOC)
System (V) (Wh kgL1) (Wh LL1) (W kgL1) (Wh kgL1) (Wh kgL1)
Sealed leadeacid 2.1 30e40 60e75 180 20e35 20e35
(LA)
Nickelecadmium 1.2 40e60 50e150 150 40e60 40e60
(NieCd)
Nickel-metal hydride 1.2 30e80 140e300 250e1000 50e70 40e70
(NieMH)
Lithium-ion LiCoO2 3.6 160 270 1800
Lithium polymer 3.7 130e200 300 3000
Lithium-ion LiFePO4 3.25 80e120 170 1400
*Data from references [78] and [79] are used.
 Invention and Development of the LeadeAcid Battery 23

Table 1.2: Energy cost, advantages and disadvantages of various batteries [77].

Voltage Energy Cost

System (V) (Wh $L1) Advantages Disadvantages
Sealed leadeacid (LA) 2.1 5e8 Cheap Heavy
Nickelecadmium 1.2 2e4 Reliable, inexpensive, high Heavy, toxic material,
(NieCd) discharge rate, good low memory effect
temperature behaviour
Nickel-metal hydride 1.2 1.4e2.8 High energy density, Higher internal resistance,
(NieMH) environment friendly gas formation, self-
discharge
Lithium-ion LiCoO2 3.6 3e5 High specific energy, low Expensive, requires safety
self-discharge electronics
Lithium-polymer 3.7 3e5 High specific energy, low Expensive, requires safety
self-discharge electronics
Lithium-ion LiFePO4 3.25 0.7e1.6 Safe Technology in development

The major disadvantage of the leadeacid battery is that Pb has very high atomic weight, which
reduces the specific energy and power of the battery.
Nowadays, hundreds of millions of leadeacid batteries are produced worldwide, which makes
the leadeacid battery the most successful power source of all times.

1.6. Challenges Calling for a New Stage in the Development

of the LeadeAcid Battery
1.6.1. Hybrid Electric Vehicles

At the end of the twentieth century, consumption of petroleum fuels increased significantly on
a worldwide basis and the first symptoms of a petrol crisis appeared. Automobile manufac-
turers decided to reduce petrol consumption by combining an electrical engine with an internal
combustion engine to propel the vehicle. Thus, the hybrid electric vehicle (HEV) was devised.
Depending on the involvement of the electric motor (battery) in the propulsion of the vehicle,
several types of HEVs have been developed.
a. Full HEVs. An automobile driven by an electric motor alone can pass only a short distance.
The electric battery system is used mainly when the internal combustion engine functions
with low efficiency and when high power is demanded. The battery is partially discharged
during operation of the electric motor and is recharged by the internal combustion engine.
Regenerative braking, too, plays an important role in charging the battery. The electric
system operates at over 200 V. Fuel consumption is reduced by 40%.
b. Mild HEVs. The electric system is called upon mainly during the accelerating phase and for
starting the vehicle. Regenerative charging of the battery when the vehicle decelerates or
24 Chapter 1

stops is essential for reducing the fuel consumption. The electric system in mild HEVs
operates between 100 and 200 V and the fuel consumption savings range from 15% to
20% depending on the driving mode.
c. Micro HEVs. These use the startestop system which turns off the engine when the car stops
and the battery takes over the electric supply needed for all accessories. In urban driving
mode, the fuel consumption is reduced by about 8%.
d. Plug-in HEVs. This hybrid vehicle version uses the mains power supply to charge the
battery. It has the characteristics of both a full electric vehicle and a conventional automo-
bile powered by an internal combustion engine. When the battery is exhausted, the
combustion engine works as a backup power source.
Full electric vehicles are driven by electric motors only, powered by a battery pack that can be
recharged from an external electric power source.
Figure 1.9 summarizes the energy and power demands of micro, mild and full HEVs, as well as
of plug-in HEVs [79]. With the increase of the contribution of the electric motor to car
propulsion, the power and energy demands to the battery increase abruptly. They are the
highest for full and plug-in HEVs.
For the time being, only nickel-metal hydride batteries can perform the tasks and meet the
energy and power demands for application in full HEVs. Intense research and development
work has been carried out aimed to make lithium-ion batteries suitable for the HEV market.
Full HEVs are currently produced by Toyota (the Prius model and the Hybrid Synergy Drive
series), Ford (Ford Escape and Ford Fusion models) and recently General Motors, too.
Mild HEVs also use NiMH batteries. Examples of this type of HEVs are Honda’s Civic and
Insight, Chevrolet’s Silverado, General Motors’ Saturn and Malibu series, BMW’s Concept
7 series, etc.

Figure 1.9:
Energy and power demands on batteries for various types of HEVs [79].
 Invention and Development of the LeadeAcid Battery 25

Leadeacid batteries are generally used in micro HEV applications. Models of these HEV types
are produced mostly in Europe by BMW, Daimler and Citroen.

1.6.2. The Major Problem of LeadeAcid Batteries in HEV Applications

The problems faced by leadeacid batteries in HEV duties are mostly related to the negative plates:
a. The negative plates cannot accept the high charging currents generated on regenerative
breaking.
b. Batteries operate at partial state-of-charge (SOC), which leads to rapid sulfation of the
negative plates.
Figure 1.10 shows the SOC regions of operation of HEV batteries, as summarised by Furukawa
Corporation.
Batteries in conventional cars and micro HEVs operate at over 90% SOC with up to 5% depth
of discharge. At these high SOC levels, the negative plates do not suffer from sulfation.
Batteries in mild HEV duties operate from between 70% and 90% SOC. Under these condi-
tions, the negative plates undergo slow sulfation and special treatment is needed to reverse this
process. The heaviest duty is that of full HEV batteries. Batteries in these applications operate
within the 30e80% SOC region, which facilitates rapid sulfation of the negative plates. These
processes make leadeacid batteries unfit for these two HEV modes.
What approaches have been adopted to resolve these problems and make leadeacid batteries
suitable for HEV applications?
The most logical approach is to look for alternatives to the conventional Pb negative plates or to
reduce their contribution to battery operation. Carbon super-capacitors have been chosen for
this purpose. Probably, there are other methods, too.

Figure 1.10:
SOC regions of battery operation in various HEV duties. Source: Furukawa Battery Corp.
26 Chapter 1

Axion Power International (USA) has replaced entirely the negative plates of VRLABs with
carbon super-capacitor plates [80]. CSIRO and Furukawa Battery have developed and tested
a battery (called the Ultra Battery) with negative plates comprising half regular lead plate and
half carbon super-capacitor plate [81].
Firefly Energy (USA) used carbon foam instead of a lead grid to hold the negative active
material and to maintain a stable 3D structure of NAM with widely open pores [82]
Since 2004, the Advanced LeadeAcid Battery Consortium has been sponsoring research on
addition of electrochemically active carbons to the NAM, thus increasing the reaction surface
on which the charge processes proceed and hence accelerating these processes [83].
These innovations in battery design and technology are still in the process of development and
testing. They are not yet commercially available. But it can be expected that they will mark the
beginning of the third phase in the development of the leadeacid battery technology.

References
[1] Mémoire des Sociétés savantes et littéraires de la Republique Française 1801, J. Phys. 56 (1802) 429.
[2] J. Garche, J. Power Sources 31 (1990) 401.
[3] W.J. Sinsteden, Pogg. Ann. d. Physik u. Chemie 92 (1854) 199, 1.
[4] G. Planté, C.R. Acad. Sci. XLIX (1859) 402.
[5] G. Planté, C.R. Acad. Sci. L (1860) 640.
[6] An Conservatoire National des Arts & Métiers, ‘Gaston Planté et les accumulateurs électriques’, Conférence
de M.L. Juman, 13 June 1934.
[7] J.M. Schmidt, Gaston Planté: A Portrait of the Man, Planté Centennial Commemorative Issues, The
Electrochemical Society Inc., Houston, Texas, October 1960.
[8] G. Planté, Recherche sur l’Électricité, Gauthier-Villars, Paris, 1883.
[9] D. Pavlov, J. Power Sources 30 (1990) 3.
[10] E. Hoppe, Die Akkumulatoren für Elektricität, second ed., Springer, Berlin, 1892, p. 162.
[11] H. Samter (Ed.), Das Reich der Erfindungen, Urania, Berlin, 1896, p. 201.
[12] S.A. Fauré, French Patent 141057, 1881.
[13] E. Volckmar, German Patent 19928, 1881.
[14] J.H. Gladstone, A. Tribe, Nature 25 (1882) 221.
[15] H. Aron, Elekt.-tech. Z. (1883) 58.
[16] H.F. Haring, U.B. Thomas, Trans. Electrochem. Soc. 68 (1935) 293.
[17] E.E. Schumacher, G.M. Bouton, Metals Alloys 14 (1941) 865.
[18] O. Jache, German Patent 1194015, 1958.
[19] O.H. McClelland, J.L. Devitt, US Patent 3,862,861, 1975.
[20] A.F. Hollenkamp, J. Power Sources 36 (1991) 567.
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[25] J.J. Lander, NRL Report No. C-3262, 22 March 1948.
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[28] J. Burbank, J. Electrochem. Soc. 113 (1966) 10.
 Invention and Development of the LeadeAcid Battery 27

[29] R.V. Biagetti, M.C. Weeks, Bell Syst. Tech. J. 49 (1970) 1305.
[30] V. Iliev, D. Pavlov, J. Appl. Electrochem. 9 (1979) 595.
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[42] OMI Acid Recirculation Process, www.OMI-NBE.com
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[49] A.C. Simon, S.M. Caulder, J.T. Stemmle, J. Electrochem. Soc. 122 (1975) 461.
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28 Chapter 1

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 CHAPTER 2

Fundamentals of LeadeAcid Batteries

2.1. Thermodynamics of the LeadeAcid Battery
2.1.1. General Notes
An electrochemical power source comprises two electrodes of different materials immersed in
electrolyte, whereby electrode systems with different potentials are formed at the two electrodes.
Electrochemical reactions proceed at the two interfaces which involve transfer of electrons
between the electrode surface and ions from the solution. The difference between the potentials
of the two electrodes generates the electromotive force of the electrochemical power source.
When the two electrodes (anode and cathode) are connected to a conductor with a load, electric
current which can do work flows between them, i.e., the chemical energy can be converted into
an electrical one. Electric current flows due to changes of the valences of the materials at the two
electrodes. Michael Faraday established that, when one gram equivalent of any substance takes
part in an electrochemical reaction, the quantity of electricity that flows is always equal to 96,487
coulombs (C). This value is called Faraday constant, after the name of M. Faraday, and is denoted
by the symbol F. The value of the constant is generally rounded to 96,500 C.
The electric energy, Q, that an electrochemical power source can deliver when one gram mole
(atom) of material takes part in the electrochemical reactions at the two electrodes is equal to:
Q ¼ nFðE1  E2 Þ (2.E1)
where n is the number of valence electrons that take part in the electrochemical reactions,
and E1 and E2 are the potentials of the two electrodes. F and n are numbers that determine
the quantity of electricity. The electric energy depends on the difference between the
potentials of the two electrodes made of different substances. Hence, the electric energy
will depend on the selection of the materials for the two electrodes and for the electrolyte in
which they are immersed.
Gaston Planté combined a Pb/PbSO4 with a PbO2/PbSO4 electrode in sulfuric acid solution and
obtained an electrochemical power source with high electromotive force. In 1860, he
announced the invention of this power source as an electrochemical leadeacid cell of high
power at a meeting of the French Academy of Sciences.
The leadeacid cell utilises the reactions of lead oxidation (Pb / Pb2þ þ 2e) and of lead
dioxide reduction (Pb4þ þ 2e / Pb2þ). When the Pb and PbO2 electrodes are immersed in

Lead-Acid Batteries: Science and Technology. DOI: 10.1016/B978-0-444-52882-7.10002-3

Ó 2011 Elsevier B.V. All rights reserved.
30 Chapter 2

H2SO4 solution, PbSO4 forms on both electrodes. The Pb/PbSO4 electrode has a highly
negative equilibrium potential as referred to the equilibrium potential of the hydrogen
electrode, while the PbO2/PbSO4 electrode has a highly positive equilibrium potential. This
potential difference generates one of the highest electromotive forces of all electrochemical
power sources based on aqueous solutions.
The second factor that makes operation of the leadeacid cell possible is the high electron
conductivity of PbO2, which ensures involvement of the major part of the PbO2 active material in
the current generation process. The third beneficial factor is the reversibility of the
electrochemical processes and of the structures formed in the leadeacid cell. PbO2 and PbSO4
are slightly soluble in H2SO4 solutions (of 1.10e1.28 relative density), which keeps them on the
electrode surface where the electrochemical reactions proceed. In this way, the electrode
structure remains intact during discharge and re-charge of the battery, and the latter has long
cycle life as a re-chargeable power source. The electrode potentials E1 and E2 depend on the
concentrations of the compounds that take part in the reactions and on the temperature in the cell.
To quantitatively determine these dependences is an issue of electrochemical thermodynamics.
The electrode potentials will be calculated, using thermodynamic data, further in this chapter.

2.1.2. Lead Sulfate Electrode (Pb/PbSO4) Potential

The following electrochemical reaction proceeds at this electrode during discharge and charge:
Pb þ SO2
4 $ PbSO4 þ 2e

(2.1)
The equilibrium potential of this electrode can be calculated using Nernst equation:
0
EPb=PbSO4 ¼ EPb=PbSO4
þ ðRT=nFÞln k (2.E2)*
where k is the equilibrium constant for the electrochemical reaction. According to the law of
mass action, the equilibrium constant is equal to the ratio between the concentrations, or more
precisely the activities, a, of the oxidized and reduced products of the reaction:
k ¼ aPbSO4 =aPb $aSO2 (2.E3)
4

The activity of the solid phases ðaPbSO4 ; aPb Þ is equal to 1.

T is the temperature in K. For 25  C, T ¼ 298K.
R is the universal (or ideal) gas constant; R ¼ 8.314 Joules per kelvin per mole (J K1 mol1)
To convert the natural logarithm into decimal logarithm, RT/nF should be multiplied by 2.303.
Let us assume that n ¼ 1.
2:303RT=nF ¼ 8:314  298  2:303=96500 ¼ 0:059 (2.E4)

*
The E in equation numbers stands for mathematical equations to differentiate them from reactions (chemical or
electrochemical), which are labelled only with a number, e.g. (2.2).
 Fundamentals of LeadeAcid Batteries 31
0
EPb=PbSO is the standard potential of the Pb/PbSO4 electrode. It is equal to the electrode
4
potential at aSO2 ¼ 1. According to the principles of electrochemical thermodynamics, the
4
standard electrode potential corresponds to the increase in Gibbs free energy (DG0 cal),
according to Eqn (2.1).
0
EPb=PbSO4
¼ DG0 =nF (2.E5)
The sign of DG0 is determined by convention. It is negative when a reduction process takes
place at the electrode.
If we substitute the free energy values for the reactants and the final products of reaction (2.1)
in Eqn (2.E5), we obtain:
h  i.
0
EPb=PbSO ¼  DG0PbSO4  DG0SO2 þ DG0Pb nF (2.E6)
4 4

Table 2.1 summarises the thermodynamic characteristics of the substances involved in the
system PbeH2OeH2SO4. By substituting the values for DG0PbSO4 ;DG0SO2 and DG0Pb from
4
Table 2.1 in Eqn (2.E6), we obtain:
0
EPb=PbSO ¼ 4:185$ð193:89 þ 177:34Þ$1000=2:96500 ¼ 0:358 V (2.E7)
4

4.185 is a coefficient of conversion of calories to Joules, multiplied by 1000 for kiloJoules.

Table 2.1: Thermodynamic characteristics of compounds in the system PbeH2SO4eH2O [1].

DG0 DH0 DS0

Compound kcal molL1 kJ molL1 kcal molL1 kJ molL1 kcal molL1 kJ molL1
Pb (crystal) 0.0 0.0 0.0 0.0 15.51 64.91
Pb2þ (aq.) 5.73 23.98 0.3 1.26 4.587 19.20
Pb4þ (aq.) 72.3 302.57 e e e e
PbO (red) 45.25 189.37 52.4 219.29 16.2 67.80
PbO (yellow) 45.05 188.53 52.07 217.91 16.6 69.47
HPbO 2 (aq.) 81.0 338.98 e e e e
Pb(OH)2 100.6 421.01 123 514.76 21 87.89
a-PbO2 51.94 217.37 63.32 264.99 e e
b-PbO2 52.34 219.04 66.12 276.71 18.3 76.58
Pb3O4 147.6 617.71 175.6 734.89 50.5 211.34
PbSO4 193.89 811.43 219.5 918.61 35.2 147.31
PbSO4$PbO 243.20 1017.79 e e e e
3PbO$PbSO4$H2O 397.30 1662.7 e e e e
5PbO$2H2O 336.35 1407.62 e e e e
Pb2O3 98.42 411.89 e e e e
SO2
4 (aq.) 177.34 742.17 216.9 907.73 4.1 17.16
HSO 4 (aq.) 179.94 753.05 211.7 885.96 30.32 126.89
H2SO4 177.34 742.17 216.9 907.73 4.1 17.16
H2 O 56.69 237.25 68.317 285.91 16.72 69.97
Hþ (aq.) 0.0 0.0 0.0 0.0 0.0 0.0
H2 (gas) 0.0 0.0 0.0 0.0 31.21 130.61
32 Chapter 2

Two electrons participate in the reactions at each of the two electrodes, i.e., n ¼ 2.
By substituting the values for k (Eqn 2.E3), RT/nF (Eqn 2E4) and E0 (Eqn 2.E7) in Eqn
(2.E2), we obtain the following equation for the equilibrium potential of the Pb/PbSO4
electrode:
EPb=PbSO4 ¼ 0:358  0:029 lg aSO2 V (2.E8)
4

The increased activity (concentration) of SO2

4 ions in the H2SO4 solution leads to an increase
in the equilibrium potential of the Pb/PbSO4 electrode in the negative direction (i.e., to higher
negative values). At constant SO24 ion concentration, the potential of the Pb/PbSO4 electrode
does not depend on the pH of the solution, but only on the temperature.

2.1.3. Lead Dioxide Electrode (PbO2/PbSO4) Potential

The following electrochemical reaction takes place at the positive electrode during charge and
discharge:

PbSO4 þ 2H2 O $ PbO2 þ SO2 þ

4 þ 4H þ 2e

(2.2)
The equilibrium potential of this electrode can be calculated by the following equation:
0
EPbO2 =PbSO4 ¼ EPbO2 =PbSO4
þ ðRT=2FÞln aPbO2 $aSO2 $a4H þ =aPbSO4 $a2H2 O (2.E9)
4

The activities of the solid phases ðaPbO2 ; aPbSO4 Þ are equal to 1. aHþ can be expressed in pH
0
units. EPbO 0
can be determined in a similar way as EPb=PbSO :
2 =PbSO4 4
 .
0 0 0 0 0 0
EPbO 2 =PbSO
¼  DG PbO2  DG SO2
 4DG Hþ þ DG PbSO4 þ 2DG H2 O 2:96500 (2.E10)
4 4

By substituting the DG0 values for the different reactants and products from Table 2.1, we
0
obtain EPbO ¼ 1:683 V:
2 =PbSO
4

Then Eqn (2.E9) for the dependence of the equilibrium potential of the PbO2/PbSO4 electrode
on the concentration of the reactants in the electrochemical reaction becomes:
EPbO2 =PbSO4 ¼ 1:683  0:118 pH  0:059 lg aH2 O þ 0:029 lg aSO2 (2.E11)
4

If we review the literature sources on leadeacid batteries, we will see that reported data about
the value of the equilibrium potential of the PbO2/PbSO4 electrode differ by 5e6 mV from
the value in Eqn (2.E11). This difference comes from the different DG0 values reported by the
authors for the reactants and products of the electrochemical reaction, as well as whether
a value of F ¼ 96500 C is used or the more precise value of 96487 C.
The values of E0 depend on the crystal modification of PbO2 formed in the active material.
PbO2 exists in two crystal modifications: tetragonal (b-PbO2) and orthorhombic (a-PbO2). For
 Fundamentals of LeadeAcid Batteries 33

b-PbO2 a value of E0 ¼ 1.687 V has been determined [2], whereas the equilibrium potential for
the a-PbO2 modification is E0 ¼ 1.697 V [3].
Equation (2.E11) indicates that the equilibrium potential of the PbO2/PbSO4 electrode
depends strongly on the pH of the solution. With increase in solution pH, the equilibrium
potential of the PbO2/PbSO4 electrode changes by 0.118 V/pH. The value of EPbO2 =PbSO4 is less
affected by the concentration of SO2
4 ions.

2.1.4. Electromotive Force of the LeadeAcid Cell, DE

The electromotive force (EMF) is determined by the potential difference between the two
electrodes: PbO2/PbSO4 and Pb/PbSO4.

DE ¼ EPbO2 =PbSO4  EPb=PbSO4 (2.E12)

By substituting the expressions for the two electrode potentials, EPbO2 =PbSO4 and EPb=PbSO4 ;
from Eqns (2.E8) and (2.E11) in Eqn (2.E12), we obtain the following equation for the
electromotive force DE:
DE ¼ 2:041  0:118 pH  0:059 lg aSO2  0:059 lg aH2 O (2.E13)
4

It can be seen from the above equation that DE depends on the activity of the SO2 4 ions and
water. During battery discharge, H2SO4 is consumed and its concentration in the solution
decreases. This leads to increase of the solution pH and, consequently, to decline in cell
voltage. The slope of the curve DE vs discharge time depends on the changes in H2SO4
concentration in the solution filling the pores of the active materials of the two electrodes. This
feature of the leadeacid battery is unfavourable as every battery user wants to rely on constant
voltage during operation of the battery. When the cell voltage during discharge reaches a value
of 1.70e1.80 V, the battery is considered to be fully discharged and should be subjected to
re-charge.
The reactions that proceed at the two electrodes can be expressed by the following overall
equation:
Pb þ PbO2 þ 2H2 SO4 $2PbSO4 þ 2H2 O (2.3)
So the electromotive force for the leadeacid cell can be expressed by:
DE ¼ 2:041 þ 0:059 lg ðaH2 SO4 =aH2 O Þ (2.E14)
We can calculate the EMF for the different H2SO4 concentrations provided we know the
activities of H2SO4 and H2O at the respective concentrations.
What does activity of ions and molecules actually mean and how does the activity correlate to
the concentration of given ions or molecules?
34 Chapter 2

The law of mass action was first expressed in terms of concentration of ions and molecules that
participate in the reactions. It was assumed that ions and molecules do not interact with each
other, i.e., the solutions were assumed to be ideal. In actual solutions, however, ions and
molecules do interact. In 1908, T. Lewis accounted for this interaction and introduced the term
effective concentration or activity. The activity is a measure of how different molecules in
a non-ideal gas or solution interact with each other. By substituting solution concentrations
for activities it is possible to apply the law of mass action for ideal solutions to real solutions.
The correlation between the activities of ions or molecules in a given solution and their
concentrations is expressed by the following equation:
ai ¼ gi Ci (2.E15)
where gi is the activity coefficient of a given ion (i) and Ci is its concentration in the solution.
It is not possible to measure the activity coefficient of the individual ions in a solution, so
a mean ionic activity coefficient is assumed, g, which gives the activities of all ions of a given
species in the solution.
Table 2.2 presents the mean activity coefficients for H2SO4 ions, the activities of water, aH2 O ;
and H2SO4, aH2 SO4 ; for solutions of different molalities (i.e., H2SO4 concentration in mol
kg1), as reported by Robinson and Stokes [4] and Bullock [5].
Several sets of values have been reported in the literature for the above activities and activity
coefficients, which differ by maximum 3e4%.

Table 2.2: Activity coefficients for H2SO4 ions and activities of H2SO4 and H2O, as reported by
Robinson and Stokes [4] and Bullock [5].

Concentration
mol kgL1 mol LL1 g aH2 O (against molality) aH2 SO4 (against molality) EMF (DE), V
0.5 0.49 0.144 0.9819 0.00148 1.881
0.7 0.68 0.131 0.9743 0.00307 1.900
1 0.96 0.121 0.9618 0.00716 1.922
1.5 1.42 0.117 0.9387 0.0214 1.951
2 1.86 0.118 0.9126 0.0522 1.975
2.5 2.28 0.123 0.8836 0.1158 1.996
3 2.69 0.131 0.8516 0.2440 2.016
3.5 3.08 0.143 0.8166 0.4989 2.035
4 3.46 0.157 0.7799 0.9883 2.054
4.5 3.82 0.173 0.7422 1.888 2.072
5 4.17 0.192 0.7032 3.541 2.090
5.5 4.50 0.213 0.6643 6.463 2.106
6 4.83 0.237 0.6259 11.48 2.123
6.5 5.14 0.263 0.5879 20.02 2.139
7 5.44 0.292 0.5509 34.21 2.154
 Fundamentals of LeadeAcid Batteries 35

According to the electrochemical reaction (2.1), during battery discharge, a flow of electrons is
generated at the negative electrode, which flows through the conductor towards the positive
electrode. This leads to loss of electric energy out of the cell towards an external consumer. The
reverse process occurs during charge, when under the action of an external power source,
electrons produced by the electrochemical reaction (2.2) at the positive electrode flow through
the conductor to the negative electrode and participate in the electrochemical reaction (2.1) in
the reverse direction, whereby lead sulfate is reduced to lead. In this way, the leadeacid cell
is re-charged with electric energy. The loss of electric energy per unit electric charge is the
cell voltage. It is conventionally assumed that the electric current flows in the opposite
direction to that of the electron flow. The product of cell voltage by current flowing through the
electrical circuit gives the electrical power, Pe ¼ DE$I, delivered by the cell for the particular
consumer needs.
The leadeacid cell operates with H2SO4 solutions of concentrations up to 1.28 g cm3
(at 25  C). At higher acid concentrations, the cycle life of the leadeacid cell is shortened.
As evident from the electrochemical reaction (2.3), during discharge, H2SO4 is consumed and
water is produced. Hence, the acid concentration decreases from 1.28 to 1.11 g cm3 on
deep discharge. This leads to a decrease in cell voltage on open circuit from 2.15 to 1.95 V.
The effect of cell voltage change with changes in acid concentration can be determined from
Eqn (2.E14).
Depending on the quantity and physical state of the electrolyte, leadeacid batteries are
classified into four types:

a. batteries with flooded electrolyte (flooded batteries);

b. low-maintenance batteries with large excess of electrolyte;
c. batteries with electrolyte immobilised in absorptive glass mat (AGM) separators and
equipped with a pressure valve (valve-regulated leadeacid batteries, VRLAB);
d. batteries with gel electrolyte.

To improve the power output and the energy delivered by the battery, its electrodes are made of
highly porous materials. Thus, greater amount of the plate mass is involved in the redox
reactions. Highly porous plates are produced employing a complex technology based on
a number of lead compounds and chemical and electrochemical reactions. This technology will
be discussed in more detail in the following chapters of this book.
Having made an overview of the changes in H2SO4 consumption within one chargeedischarge
cycle, let us now see how does the volume of the solid phases at the two electrodes (plates)
change during charge and discharge.
During discharge, part of the lead dioxide is reduced to lead sulfate at the positive plate.
The molar volume of the new solid product (PbSO4) is larger by 92% than the molar volume of
36 Chapter 2

the initial PbO2 phase involved in the reaction. At the negative plate, the process of discharge
(Pb / PbSO4) leads to a 164% increase in volume of the newly formed solid phase as
compared to the volume of the reacted Pb. During charge, the reserve process occurs, namely
the plate volumes diminish by the above mentioned volume percents.
Thus, the plates in the leadeacid cell ‘pulsate’ during cycling, expanding in thickness during
discharge (because of the increased volume of the solid phases in the active masses, which
reduces the pore volume at the same time), and then during re-charge, the plate thickness
decreases and the active mass pore volume increases at that.

2.1.5. Brief Summary of the Lead Compounds Involved in the Manufacture

and Operation of the LeadeAcid Cell

Prior to discussing the electrochemical reactions and the electrode potentials of the Pb/H2O
and Pb/H2SO4/H2O systems, we will make a brief overview of the lead compounds involved in
these systems.

Lead oxide (PbO)

This lead compound exists in two polymorphic forms: tetragonal (b-PbO) and orthorhombic
(a-PbO). The solubility of the two forms in water at 25  C is 0.0504 g L1 for a-PbO and
0.1065 g L1 for b-PbO [6]. Lead oxide forms lead hydroxides, 3PbO$H2O and 5PbO H2O
[7,8]. Lead oxide is hydrated forming Pb(OH)2, a compound of amphoteric nature. It

dissociates to HPbO 2 and Pb(OH) ions. In the battery industry, lead oxide is obtained by
partial thermal oxidation of lead and is called ‘leady oxide’, as it contains between 73% and
85% PbO, the remaining part being non-oxidized lead. The basic constituent of leady oxide is
tet-PbO, but orthorhombic PbO is also present, up to 5e6%. Leady oxide is used for the
preparation of the pastes for leadeacid battery plate production.

Lead sulfate (PbSO4)

At room temperature, this lead compound is usually orthorhombic, but at high temperatures
(>800  C), it acquires a cubic crystal form. Lead sulfate is isomorphic to BaSO4 and SrSO4.
It is poorly soluble in water: 0.0425 g L1 at 25  C and 0.056 g L1 at 40  C. Its solubility
in sulfuric acid solution depends on the concentration of H2SO4. Lead sulfate is formed during
discharge and self-discharge of the positive and negative battery plates. It reacts with PbO
to form basic lead sulfates.

Monobasic lead sulfate, PbO$PbSO4 (1BS)

It is a monoclinic crystalline substance built of long thin crystals. It is formed when PbO is
mixed with H2SO4 solution during paste preparation, within a very narrow pH interval: 8e15
wt% H2SO4/leady oxide. Monobasic lead sulfate is obtained also during soaking of the cured
 Fundamentals of LeadeAcid Batteries 37

plates in sulfuric acid solution prior to formation. 1BS is weakly soluble in water, 0.044 g L1
at 0  C, but is more soluble in weak H2SO4 solutions.
Tribasic lead sulfate, 3PbO$PbSO4$H2O (3BS)
This lead compound forms prismatic crystals with a length of 1e4 mm and 0.2e08 mm in
cross section. Its density is 6.5 g cm3. It is poorly soluble in water, 0.0262 g L1. 3BS is
obtained when leady oxide is mixed with sulfuric acid solution (up to 8 wt % H2SO4/PbO) and
constitutes the basic component of the battery paste when the latter is prepared at temperatures
below 70  C. Tribasic lead sulfate exerts an influence on the structure of the lead dioxide
active mass and thus on some of the performance characteristics of the battery.
Tetrabasic lead sulfate, 4PbO$PbSO4 (4BS)
It comprises prismatic crystals with a length from 10 to 100 mm and diameter from 3 to 15 mm.
4BS is formed when leady oxide is mixed with sulfuric acid solution, H2SO4/PbO < 6 wt%, at
temperature higher than 75  C, as well as during curing of the paste at high temperatures
(>85  C) in the presence of water steam. The structure of the active mass formed from 4BS
ensures long battery cycle life.
Lead dioxide (PbO2)
It exists in two polymorphic structural forms: orthorhombic (a-PbO2) and tetragonal (b-PbO2).
Lead dioxide is non-stoichiometric in composition, PbO2-x, and contains oxygen vacancies.
PbO2 is an n-type degenerated semiconductor with a conductivity of 11,000 ohm1 cm1 [9].
With increase of temperature from 22 to 84  C, the conductivity of PbO2 decreases by about
0.06% with each 1  C step. Lead dioxide is practically insoluble in water, while in sulfuric acid
solution it has a solubility of 0.01 M L1 at 22  C. PbO2 is a strong oxidizer and is readily
reduced to Pb3O4 and Pb2O3, as well as to non-stoichiometric compounds of the general
formula PbOn (1 < n < 2). The surface layers of PbO2 particles, when electrochemically
obtained, are hydrated forming PbO(OH)2.
Red lead (in USA) or minium (in Europe), Pb3O4
This lead compound has spinel structure, similar to that of Fe3O4. Its density is 9.1 g cm3.
It is composed of 2PbO and 1PbO2 and decomposes easily in acids. Red lead is virtually
insoluble in warm and cold water (107 mol L1). It reacts with H2SO4 to form 2PbSO4 and
PbO2. Red lead is used mostly (70e75% of the world production of Pb3O4) in the battery
industry.

2.1.6. The Pb/H2SO4/H2O System

In acidic solutions, Pb2þ and Pb4þ ions are formed (though in low concentrations), whereas in
neutral and weakly alkaline solutions, HPbO 2
2 or PbO3 ions form. The chemical and
Exploring the Variety of Random
Documents with Different Content
 Capt. D. M. Methven
(21st Lancers)

Lieut. A. C. J. Elkan Lieut. J. Hampson

“The following day we were again visited by enemy airmen, but our
batteries and Hotchkiss guns opened such a rapid and effective fire
that after vainly trying to bomb us for some time they finally flew off
in disgust, amidst the frantic cheers of the boys who were interested
spectators.

“Soon after this we commenced our sports, in which every event

was most keenly contested, and at the conclusion of the two days
the results were as follows: Individual Tent-Pegging was won by our
R.S.M., Mr Seekins; Skill at Arms by S.Q.M.S. Higgs; the best troop-
horse was C98, ridden by Pte. Shaw; Officers Jumping went to Mr
Macdonald; the Section Tent-Pegging to ‘B’ Squadron. In the
dismounted events, the 100 yards was won by L.-Cpl. Carter in very
good time, while the 1½ mile relay race was won rather easily by
the team of ‘C’ Squadron, which included Sgt. Burgess, Sgt. Moss,
L.-Cpl. Carter, L.-Cpl. Smithers, L.-Cpl. Bush, and Pte. Bowie. The
tug-of-war was won by the ‘D’ Squadron team after an exceptionally
fine pull, which concluded the programme. At about 8 P.M. the same
evening our party gave another concert, this time to the whole
Division, being assisted in their efforts by some of the crew of the
monitor. This show proved a great success, every one thoroughly
enjoying a good evening’s entertainment. On January 26th some
Divisional races were held on a course we had made some 2 miles
west of our camp, the ground here being splendidly suited for our
purpose, being as flat as a billiard-table for many miles.

“On January 27th General Dunsterville’s force left Baghdad, the

following officers and N.C.O.’s from our Regiment accompanying the
force: Captain Annett, Lt. Cochrane, Sgt. Vernon, Sgt. Taylor, and
Sgt. Saunders.

“Commencing on February 22nd, a 3-days’ race meeting was held at

Akab by the 17th Infantry Division. The Regiment entered several
horses, only one of which was successful—namely, Captain Blythe’s
Army Pattern; while our Concert Party gave a show there on the
nights of the 22nd and 23rd, which were greatly admired by all who
witnessed them, the G.O.C. of that Division sending a letter of
congratulation to our Colonel in having such a talented party. Shortly
after this, on the 28th inst., the Cavalry Division held some athletic
sports, in which several of the events were open to all comers. In
this the Regiment secured several prizes—namely, 1st in the 100
yards for officers, Mr Osmond; the team of ‘C’ Squadron, L.-Cpl.
Carter, L.-Cpl. Bush, Pte. Jones, and Pte. Bowie gaining 2nd prize in
the Relay Race. L.-Cpl. Bush also 2nd in the Obstacle Race, while
another 2nd prize was won by Pte. Bowie in the Open Mile, our tug-
of-war team of ‘C’ Squadron being knocked out in the semi-final
after a very game struggle. On March 4th we turned out a Rugby 15
to play the Australian Wireless Section’s 15, who had played so far
an unbeaten record, and after a most exciting game the match
ending in a draw, neither side being able to score.

“The following day being the anniversary of our charge at Lajj, the
Regiment held a singing competition in the evening. This proved to
be highly amusing, judging by the vociferous cheering which greeted
the competitors’ efforts, the first prize for sentimental songs being
won by Sgt. Burgess, and the first for comic by Pte. Bowie. At the
conclusion of this, our Colonel made a speech in honour of our
comrades who fell in the ‘Charge.’ On reading the names out the
Colonel was almost overcome with emotion, and it was only with
difficulty that he was able to complete.

“About this time we received the news that our forces operating on
the Euphrates river had captured Hit on the 7th inst., and on the
night of the 9th the enemy had evacuated Sahilijah, abandoning 2
mountain guns and much ammunition.

“On the 14th the 2nd Baghdad Race Meeting was held, also the
semi-finals and finals of football, hockey, polo, golf, and boxing
tournaments were contested during the week. Our football team was
knocked out in the third round by the 25th Machine-gun Squadron,
by one goal to nil, after a hard-fought game. The outstanding
feature of this tournament was the match between the Worcesters
and the Buffs, the first game they played being of 60 minutes’
duration; but as neither side was able to score extra time was
allowed, and they played on for three periods of 20 minutes each,
and again neither side was able to gain the advantage. The match
was then postponed until the following day. On the replay, which
lasted with extra time, some 2 hours and 40 minutes with still no
score being registered, both teams withdrew from the tournament.
The Regiment ran several horses in the racing, Lt. Ormrod’s ‘Venus’
again winning the Baghdad Cup. This time she was ridden by Frank
Wootten, the famous jockey, who happened to be in Baghdad at the
time.
“Some little time after this we received the news that our Column,
commanded by Major-General Brooking, operating on the Euphrates
river, had, on the 26th inst., attacked the 50th Turkish Division at
Khan Baghdadi. The Cavalry cutting off the enemy’s retreat along
the Aleppo Road, they surrendered with their Commander, the total
captures being 18 Germans, including 2 officers, 212 Turkish
officers, and 5236 Turkish other ranks, 12 guns, 57 machine-guns, 2
German wireless stations. During the six days’ fighting they pursued
the fugitives of this force to a point some 73 miles north of Awah,
destroying in this village some 300,000 rounds of gun ammunition
and some 3¼ million rounds of rifle ammunition.

“On April 9th some Divisional Races were held on the racecourse
near our camp, and in these several of our horses proved successful,
Lt. Ormrod’s ‘Venus’ winning the ½-mile steeple-chase, and
‘Whiskers’ by the same owner was first past the post in the 6
furlongs, but on an objection being raised was disqualified later. Mr
Welstead’s ‘Nightshade’ with its owner up won the sixth race, while
Mr Jones’ ‘B3,’ ridden by Sgt. Holloway, won the Novices’ Flat Race.

“On the following day we received the welcome news that leave to
India was granted, and a party consisting of 2 officers and 12 men
left the same day en route for India to enjoy a well-earned 28 days’
furlough.

“A few days later, on April 14th, we commenced an Inter-Football

Tournament. The first game was between ‘B’ and ‘D’ Squadrons; this
resulted in a win for ‘B’ by 2 goals to nil. The next match was
between ‘A’ and ‘C’ Squadrons, and this was a win for ‘A’ by 2 goals
to 1, while the following day ‘B’ played ‘A.’ This match was very
keenly contested and aroused great excitement, the result, after
extra time had been allowed, being a draw of 1 goal each. Replaying
again the following day, the result this time was a draw of 2 goals,
and this also after extra time.”
 CHAPTER XX.
THE SUMMER OF 1918—KULAWAND AND TUZ
KERMATLI.

The season of military operations in the country to the north-east of

Baghdad, where the British and Turks now faced each other, may be
said to begin with the month of April, and in that month General
Marshall’s troops were ready to move again.

Before any movements on a large scale began, however, General

Marshall had to deal with two troublesome complications, one on his
left and one on his right.

To the left, in the Mahomedan holy cities of Nejef and Kerbela,

beyond the Euphrates, the British invasion of Mesopotamia had
naturally caused some excitement, and this had been fostered by
German intrigues and gold. The holy cities do not belong to the
same branch of Islam as the Turks, being “Shia,” not “Sunni,” or, as
one might say, Protestant, not Catholic; and having been very
carefully treated by the British they had shown a friendly spirit
enough. Still they were Mahomedan, and contained some fanatical
elements. In the month of January British troops had been attacked
near Nejef, and a few weeks later the British political officer was
murdered. Some punishment had to be inflicted for these offences,
and though General Marshall would not attack the sacred town, it
was blockaded and called upon to deliver up the murderers. Happily
the well-behaved inhabitants, under the guidance of their religious
leaders, decided to accept the British terms, and the whole affair
was satisfactorily settled.
S.Q.-M.S. S. B. Haines, R.S.-M. (late Lieutenant)
D.C.M. M. Churchhouse

Sgt. S. G. Strawbridge,
D.C.M.
 Lieut. W. J. L. Norwood 2nd Lieut. J. H. Lucas

At the same time as this trouble arose to the westward, some

Persian tribes on the east began to respond to the incitement and
gold of German emissaries, and it was found necessary, as General
Marshall says, to “give them a lesson.” But this trouble also proved
to be short-lived. Friendly tribesmen took action against the
malcontents, and with the aid of a small British column completely
defeated them. They lost heavily, “and our aeroplanes turned their
defeat into a rout.”

In the meantime, while these complications were being put straight,

General Marshall had worked out his scheme of action against the
Turks, and had decided that they should again be attacked to the
north-east of Baghdad, so as to drive them farther away and make
the Persian line of communication more secure. His intention was to
expel them from the area about Kara Tepe, Kifri, and Tuz Kermatli,
which will be found marked on the sketch-map, p. 201, and to
occupy those points, thus turning and subjugating the troublesome
range of Jebel Hamrin.

It was a difficult operation if the Turks fought well, and General

Marshall’s scheme of action was carefully worked out. Several
columns were to move from different points, and it is not easy to
follow in detail the movements of each. It will suffice to say that
during the latter part of April and the earlier part of May 1918, in
spite of mountainous ground and torrents of rain, which caused
heavy floods in the rivers and washed away temporary bridges—in
spite too of some stubborn fighting on the part of the enemy—the
whole area was completely cleared and the country was occupied as
far north as Kirkuk, one hundred and thirty miles from the railhead
and considerably more than that distance from Baghdad. The British
losses were very small—only twenty-six killed and two hundred and
ten wounded—while the Turks lost heavily, over three thousand in
prisoners alone.

General Marshall had good reason to be satisfied with this result.

“Owing,” he says, “to the distance covered by these operations, and
to the bad weather which prevailed throughout, the work of the
troops was very arduous, and I have nothing but admiration for the
good work put in by all arms and the excellent co-operation which
was maintained between them.” This co-operation included much
continuous work done by the Cavalry, and on at least two occasions
they had the chance of attacking the enemy as Cavalry, mounted
and sword in hand.

On both these occasions the Thirteenth were well to the fore. They
were no longer with their own Brigade, but had temporarily taken
the place of their old comrades of the Fourteenth Hussars in the 6th
Brigade, then commanded by Brigadier-General Holland Pryor.
General Marshall describes the first action in the following words:
“The 6th Cavalry Brigade ... after an arduous night march overtook
the Turks who had ... taken up a defensive position at Kulawand....
Feigning a frontal attack, whilst gradually working round the enemy’s
right flank, our Cavalry cut the enemy’s lines of retreat and then
charged right through his Infantry, killing some two hundred,
including two battalion commanders, and capturing 565 prisoners, a
mountain-gun, and considerable booty.” This was a fine
performance, and brought the Regiment much credit. It was
followed up by some skilful manœuvring which induced the Turks to
hold a position at Tuz Kermatli, where a day or two later there was
another considerable action. Here again the Cavalry did well, and the
Thirteenth got another chance. This time the actual charge was a
smaller affair, confined to a couple of troops under Lieutenant
Macdonald, but it was spirited and successful, the two troops
galloping a nest of machine-guns, and taking a considerable number
of prisoners with little loss to themselves.

On the 7th of May Kirkuk was taken, and the short campaign came
to an end. “Difficulties of supply,” says General Marshall, “due to
distance and state of ground, now made it imperative to stop further
pursuit,” and a few days later most of the British troops were
withdrawn to their summer camps. The Thirteenth returned to their
old camp at Chaldari, near Baghdad, arriving on the 22nd of May,
and there they remained throughout the summer months.

It proved to be an important and anxious time for the Commander

of the Army, as a force under Major-General Dunsterville was sent
into Persia, and eventually crossed the Caspian to Baku, where there
was some severe fighting. There was much work to be done also in
Mesopotamia itself, and so far as the climate permitted, military
training went on steadily, a special feature being the development of
schools of instruction. But owing to the extreme heat the summer
was for the bulk of the troops a period of inactivity, and it was found
possible to send a large number of officers and men on leave to
India. They wanted all the rest they could get, for they still had
some hard marching and fighting before them, and the Thirteenth,
in their pleasant camp at Chaldari, thoroughly enjoyed the respite.
 AFTER THE CHARGE AT KULAWAND

PRISONERS TAKEN AT KULAWAND

The following extracts refer chiefly to their doings at Kulawand and

Tuz.
 Extracts from narratives by Captain Gowan, enclosed in a letter
from Colonel Richardson, dated 27th July 1918.

“April 26-27, 1918.—The column moved at midnight and marched till

4.45 A.M., arriving at Tel Sharif at that time. The road was difficult to
find in many places, and in the numerous nullahs which were
crossed the going was deep. When the position had been fixed at
dawn, the column moved forward for 2 miles, and then fed at 6 a.m.
After ½ an hour halt the Regiment with advance-guard of C. and C.
moved to M. 27 Central, and halted till 9 A.M. At that time the
Regiment was ordered to move on the Kulawund position, and with
L.A.M. cars and Lewis guns and Ford vans turn it from the W. end by
enfilade fire. Some difficulty was found in locating the position, and
it was not till 11.30 that it was reached and found unoccupied. The
L.A.M. cars and Fords had been unable to get forward owing to
water-logged country and nullahs. A number of Turks with some
tents were seen to be in position on the Tuz-Kifri road, close to the
hills, and their numbers were estimated by an aeroplane at 250. By
12 noon the G.O.C. Brigade had moved forward, and arrangements
were made for a simultaneous attack by the 3 Regiments. At about
12.20 a move forward was made, the Brigade advancing in line of
column of wings, in the order 22nd, 21st, 13th from the right. I
understand that both Indian Cavalry Regiments advanced in line
whilst we were in column of wings: I am not sure whether the 22nd
had all four squadrons or only two. The Regiment had ‘C’ and ‘D’
Squadrons in front line under Captain Godfree, ‘B’ and half ‘A’ in the
second, at about 200 yards’ distance, the remaining troop of ‘A’
being left as guard to our left flank, dressing station, &c., and the
H.G. guns being sent to the flanks. The leading wing on nearing the
road shouldered to the right and were in a position to co-operate
with the 21st Cav. when Captain Godfree received orders from the
Brigade to take no further part in the attack, but to join the
Headquarters near Kulawund village. While he did this the 2nd Wing,
leaving a troop of ‘A’ as escort to the Regimental Aid Post, moved to
the Kifri-Tuz road and scattered along it to the left or Tuz direction,
and succeeded in collecting about 50 prisoners. Two or three
machine-guns were in action against us until we were within 300
yards of the road, and were replied to by the H.G. troop of ‘D’
Squadron from our left flank. A number of the enemy succeeded in
getting away into the ridge of hills E. of the road where Cavalry
could not pursue, and after despatching the prisoners to Brigade
H.Q. the wing rallied and moved to a mound at the edge of the
Kulawund position. From captured officers’ statements it was clear
that this Cavalry attack took the enemy entirely by surprise. The
enemy troops engaged consisted of the 5th Regiment, which had
received orders on the evening of the 26th to withdraw from Tuz.
Expecting only an Infantry attack, on the following morning they
evacuated their positions without undue haste, and after halting
several hours ... were on their way to Tuz on the 27th, when they
were overtaken.

“April 29.—We drew back and circled to the W. behind the battery,
and were ordered to get touch with the 21st and 22nd Cav. and then
attempt to get across the Tuz-Tan road to stop the enemy’s retreat.
Moving W., it was found that the 22nd and 21st were held up by a
nest of M. guns on a small knoll. At the time of our arrival these
were not directed on us, and appeared to have left their position.
Two troops of ‘B’ were accordingly pushed forward, and led off so as
to leave this knoll on their right. After a short distance they came
under M.G. fire, and 2nd Lt. MacDonald wheeled the two troops to
the right, thus putting his own troop in front and that of Sgt.
Brencher in rear. He galloped the hill and took it—the enemy, except
two, escaping being sabred by putting their hands up when the men
were on them. This action opened the way across the plain, and the
three Regiments, 21st, 13th, 22nd from the right, moved across,
meeting small bodies of the enemy, and killing or taking them
prisoners.”

Letter from Colonel Richardson to Sir R. S. Baden-Powell.

 “7th Cavalry Brigade, M.E.F.,
In the Field, 1st May 1918.

“My dear General,—Your note with enclosures regarding Regimental

Monuments and Gravestones reached me only a few days ago, when
we were already on the trek of our present stunt....

“I am sorry to say I quite forget the contents of my letter to Symons

to which you refer, but I imagine it dealt with our part in the battle
of Tekrit; since that time we have been almost continuously in one
camp, on the Tigris, about 40 miles above Baghdad, and although
for more than four months we did not have a shot fired in anger we
were far from idle—i.e., when the wet weather made it possible to
be otherwise. Not only were we able to put in a lot of much-needed
—on account of the numerous officers and other reinforcements
during the past six months—instruction in equitation and elementary
and secondary drill and training, but we were able to have games
and sports—both mounted and dismounted—for the men, and polo
for the officers; we also had the opportunity of getting fitter than at
any time since we have been in this country, and I doubt very much
whether men or horses have ever been fitter physically than when
we started out, ten days ago, for this stunt. Only one Brigade of
Cavalry is being utilised, and it is not the one to which we properly
belong, but we are taking the place of the 14th, who are scattered
about on an independent mission. Our march to the rendezvous was
not propitious, as we were dogged by heavy rain and thunder, which
made life on operation scale, without tents, a delusion and a snare
for four days, but we got through with only one case of pneumonia.
Once we got started on this stunt—the object of which has been to
clear the whole of our northeasterly front of the enemy—we began
to get into a country of magnificent crops and glorious grazing, in
which the horses have been revelling, and growing visibly bigger.
The operations themselves have partaken more of the nature of
South African drives, and Johnny Turk was, I think, caught napping
by the largeness of the scale of the operations, and he has been so
badly fed lately that he could not travel sufficiently quickly to escape
us; however, he put up, as he always does, a jolly good fight when
cornered, and as we were unable to close the fourth side to the
square—i.e., on the north, where a steep ledge of rock, backed by
hilly country, discounted our mobility—a good few got away.
However, we have accounted for nearly 2000 prisoners, ten large
and very many machine guns, and our casualties have been less
than 250 (in the whole force), so I suppose we may reckon the
operations as having been fairly successful. Of course, from the
nature of things, the principal rôle fell to the Cavalry, and even the
Pan-Infantry men were fain to admit that we have done it well. On
the first day we came into touch with the enemy—mostly troops
retiring from outside positions, from which they had been driven by
the Infantry; but, covered by the garrison and guns of the aforesaid
rocky ledge, the three Regiments of the Brigade galloped in two
lines of wings over about 1½ miles of country towards the ledge,
and swung right-handed along the foot of it, the net result being
about 600 prisoners and several machine-guns. The next day there
was a pause, as the main position, which was pretty well served by
big guns, still remained, and we could not hope to take it without
the help of the Infantry; but next morning the latter came through
our outposts, and we concentrated on the left flank and began the
advance, which I may fairly claim the Regiment initiated, which put
the finishing touch to the operations. A good few of the enemy no
doubt escaped through the hill country, and perhaps he got a gun or
two away, but certainly a thousand prisoners and ten guns fell into
our hands.
 Lieut. H. Macdonald, M.C.
Lieut. C. A. G. McLagan
Capt. D. W. Godfree, M.C. (Murdered 14th July 1919
(Wounded at Tus
(21st Lancers) at Amadia by Kurdish
Kermatli, 21st April 1918)
gendarmes)

Sergt. W. Matthews, M.M.

Capt. B. W. D. Cochrane (Killed at Tus Kermatli, Lieut. L. Osmond
28th April 1918)

“When I claim that the Regiment initiated the final advance, I must
explain the situation in more detail: over night 2 squadrons were on
outpost duty on the left bank of the river, and two troops of a third
squadron were away with the first batch of 500 prisoners; the
balance of the Regiment with which I was, was on the right of the
Cavalry Brigade, advancing up the right bank of the river; we were
held up at dusk by the enemy in an entrenched position, and
remained where we stood all night; soon after daybreak the Infantry
took over our line, and the Brigadier sent me off to the left flank to
try and get across the path of the retiring enemy. I found that the
two Regiments of Indian Cavalry had been trying to advance with
the same object for a couple of hours, but were held up by small
parties of enemy entrenched on knolls and well supplied with
machine-guns. I determined to advance, and put one of my few
remaining sabre troops into the scouting line under MacDonald, a lad
who only joined us 6 or 8 months ago. When we got about 800
yards from the nearest knoll he met very heavy machine-gun fire,
but as it was apparently directed against his left flank, he at once
gathered his troops to the right, and following a circular path he
galloped the hill, taking the gunners in flank and reverse, and in less
than five minutes had the whole party of Turks killed or marching as
prisoners to the rear, and 4 machine-guns captured. He had only one
man badly wounded. It was, I think, without exception the quickest
and prettiest—not to say the most successful—small piece of work it
has been my fortune to witness. This little episode put great heart
into the Indians, and thereafter it was almost a race for the foot-
hills; all opposition went like a house of cards, and it was only a
question of mopping up. I, on behalf of the Regiment and
MacDonald, have received congratulations on all sides, and the
Brigade and Divisional Commanders have promised to support my
recommendation for immediate rewards, so I hope MacDonald and
his troop may get the honours they have earned so well.

“With the exception of Twist and of my Adjutant Gowan, I have no

other officers with pre-war training and experience, but we have
been most exceptionally lucky in our temporary officers; for this, I
think, I have to thank Ronnie Brook chiefly, and he would, I am sure,
be interested to see the account of the operations, should you have
it copied.—With all good wishes, yours sincerely,

(Signed) J. J. Richardson.
“P.S.—The following coincidence of special interest has come to light.
Among material captured by MacDonald on the knoll was a
signaller’s telescope, which he gave to his signaller, Sgt. Burgess.
The latter at once recognised it as the one he himself lost at Lajj on
March 5th last year, when his horse was shot and he had to abandon
his gun.”

Letter from Colonel Richardson, dated 7th Cavalry Brigade, M.E.F.,

3rd May 1918.

“For the last fortnight we have been operating with the other
Brigade in place of Col. Bridge’s Regiment, which is engaged on an
independent mission....

“The Regiment has seen some smart fighting, including two charges,
in the past week, and the outstanding feature of the operations,
which has been very successful, and of which I am sending an
account to B.P. [Sir Robert Baden-Powell], has been a gallant and
brilliant charge by a troop of the 13th under MacDonald, a Scotch
lad who joined us about 6 months ago.

“It is a matter of greatest pride, mingled with pleasant surprise to

me, how they continue to roll up with these first-rate performances,
once the opportunity presents itself, and I only hope I may never let
them down.”

Extract from letter from Colonel Richardson, dated 7th Cavalry

Brigade, M.E.F., 25th May 1918.

“After writing to you on the third of this month we continued our

drive northwards for a matter of about 60 miles, the Turks pursuing
their usual tactics—i.e., holding us up at strong positions with their
big guns until dark enabled them to get away their valuable papers
and other important stuff. In this way we made them evacuate the
country as far north as Altum Kupri.

“I do not hesitate to give names now, as I see Reuter has published

the message from Candler, the correspondent, in almost the identical
words that I gave him—he was messing with us during that period—
which is within striking distance, not more than 70 miles, of Mosul,
the big Turkish base.

“Owing to the difficulties of transport we had been on half rations,

but we got most glorious grazing for the horses in most places, so
they did not suffer much until we struck the Jebel Hamrin with its
brackish water and no grazing. Right up there the climate was really
good, and we could work all day, though, of course, it was hottish,
and on one or two nights we got wet through, for, of course, we had
no tents. But in this case also, as soon as we struck the Jebel
Hamrin on our return, the sun became very powerful and the sand-
flies very bad.
 TUZ KHARMATLI, 29TH APRIL 1918

“However, the operations were very interesting, although the

Regiment had no opportunity of doing more than ordinary work,
because Johnny Turk declined to come to grips; but as the Brigade
put it: ‘You did just what I wanted you to, I could not ask you to do
more,’ I don’t think we had any cause to grumble....

“When I wrote you from Mendali, in October, that we were short of

food, I referred only to mess stores and extras; rations have always
been good, especially when we were within measurable distance of
the railway, when we got most excellent frozen beef. Indeed, I
expect we are being much better fed than you poor people.”

Extract from Lance-Corporal Bowie’s Diary.

LT.-COL. J. J. RICHARDSON, D.S.O., AFTER A HARD DAY AT TUZ
 MACHINE GUNS CAPTURED BY THE REGIMENT AT TUZ

“Fate decreed that we were not to finish this tournament, as on the

following morning we were ordered out to take part in operations
again. This was the 18th of April, and we had to leave camp some
few hours later than ordered; owing to the extremely bad weather
and the high floods having broken the pontoon bridge over the river,
it was impossible to cross the Tigris till midday. Heavy rain continued
to fall throughout the day, which made the going very difficult, and
we finally arrived at Baqubah at about 8 P.M., where we picketed
down for the night. Our transport arrived in at 9.15 P.M. Every one
being so thoroughly wet through, and the weather being so bitterly
cold, a rum issue was ordered, after which we were fortunately able
to obtain shelter for the night in a rest-camp near by. Owing to the
heavy rains which had fallen the column did not march for Abu-
Jisrah until 10.30 A.M. the following morning, and after some very
heavy going we made that place at about 3.30 P.M. Our transport
experienced great difficulty in getting along, and did not arrive until
some two hours later. The heavy rains continued throughout the
night. The following morning, April 20th, it was found impossible to
move in consequence of the exceedingly heavy rains, which
continued till 2 P.M., and made the ground a perfect quagmire, and
absolutely impossible for wheels, the men during these two days
having a most uncomfortable time owing to the impossibility of
erecting any sort of shelter. An incident worthy of note here was an
impromptu football match, played amid a perfect sea of mud, in
which the ball not infrequently became imbedded, whilst the rain
poured down in torrents. All this, however, did not deter the players,
who, after a most strenuous game, did obtain some little warmth
from this exercise. At 11.30 A.M. on the morning of the 21st instant
we continued our march to Sharaban, where we arrived about 4 P.M.
Here we joined up with the 6th Cavalry Brigade, who were in
bivouac there. During the next two days we remained in bivouac,
whilst we endeavoured to free ourselves of some of the mud with
which every one was plastered, grazing our horses meanwhile. Here
also our squadrons were arranged to conform with the formation of
the 6th Brigade; each squadron was to consist of three sabre troops
and one Hotchkiss-gun troop. On the morning of April 24th the
Regiment paraded at 9.30 A.M., but owing to heavy rain falling again
we did not move off until 11 A.M., when we marched at the head of
the Brigade crossing the Cutthroat and Auction Bridges; we halted at
Ruz for a short time, and marching on again we crossed the Table
Mountain Bridge over the Diala river at 1.30 P.M. Here we watered
and fed our horses, afterwards moving off again with the 22nd
Native Cavalry, commanded by Lieut.-Colonel Young. We marched on
to Abu-Haiar, arriving there about 5.30 P.M., and bivouacking for the
night. The following morning at 11 A.M. we marched to Ain-Lailah,
which we reached at 3.30 P.M. We bivouacked that night about 1½
miles south of the Pass. The Column commenced marching through
the Pass at 3 A.M. the following morning, but the Regiment being
Rear Guard did not march through till 7.30 A.M., and then proceeding
on to the Nahrin river, where we watered and fed our horses.
Resuming our march till 11 A.M., we joined the remainder of the
Column, who were in bivouac at 12.15 P.M. Here one troop
proceeded to reconnoitre the road over which we were to make a
night march the same night, after which they returned to bivouac at
dusk. Marching again at midnight, the Column proceeded to Tel-
Sharia, arriving at about 4.45 A.M. The road was very difficult to find
in many places, and the nullahs which we had to cross were very
deep, many being almost full of water, owing to the recent heavy
rains. After our patrols had located the enemy at dawn the Column
moved forward some 2 miles and halted till 6.30 A.M., when the
Regiment was ordered to advance another mile and halt. At 9 A.M.
we received the order to advance on to the Kulawand position:
accompanied by our armoured cars and some Lewis guns mounted
on Ford cars, we proceeded to attack it at the west end. We
experienced great difficulty in gaining the position, not through an
enemy resistance, which strangely enough was not offered, but
through the water-logged condition of the country and the very deep
nullahs, and owing to this our armoured cars and Ford cars were
unable to continue the advance. On us eventually gaining the
position we found it to be unoccupied. The enemy, having retired
during the night, were located by our airmen a little later, who
reported them to be holding a position on the Tuz-Kifri road, close
up to the foot of the hills. Although we had no support within 20
miles of us, it was decided to attack them at once. Having worked
our way up to some large Moards [? mounds] some 1¾ miles from
their main position, we took cover here to give [? save] our horses.
Some few minutes later we drew our swords and trotted into the
plain where the 10 squadrons were formed into an extended line in
the formation of a scythe. As we rode on at this pace parties of the
Turks started running down the road, while other groups took up
positions in the rough ground and water-cuts, or kneeling in the high
corn opened fire on us. Here the Turks showed some of their old
spirit in the stand they made, but the sudden flash of our swords in
the sun which made a wide arc of light seemed to take the heart out
of them, and their fire was wild and high, and our casualties few.
Our artillery kept up a creeping barrage on the village as we
attacked, and our line maintaining this pace until within some 500
yards of the enemy, when we lowered our swords and charged into
them. Our aeroplanes which took part in the action flew very low
and increased the enemy’s confusion with bombs and machine-gun
fire. Over 150 Turks were killed and 538 prisoners were taken, also 2
mountain-guns, very few of them escaping in the hills. Meanwhile
Kifri-ain-Faris and Chanan-Keurri had been occupied by our other
columns without opposition, and our movements were so rapid that
2 battalions of the enemy had to take to the hills in order to escape
the net we were spreading for them. We afterwards heard that this
force had been robbed and disarmed by the Kurds, who never lose
an opportunity of revenging themselves on the Turk, and even those
who escaped us in the Kulawand charge returned and surrendered
to us rather than face these tribesmen. After sending back our
prisoners we moved forward to reconnoitre Tuz, and we soon came
under some very heavy accurate gun-fire until about 4 P.M., when
orders were received to withdraw. We then moved back some ten
miles and bivouacked behind our line of outposts for the night. At 6
A.M. the following morning ‘A’ and ‘D’ Squadrons were sent to
reconnoitre Tuz, the Brigade following some half an hour later, while
the 21st Cavalry were despatched to find a ford over the river Aqsu
at Khasradalah. ‘A’ and ‘D’ Squadrons soon came under fire from Tuz
and suffered some casualties. Meanwhile the remainder moved on to
Khasradalah in an endeavour to surround Tuz, but were held up by
enemy machine-guns in position on the banks of the Aqsu river; and
the armoured cars being unable to advance along the Kifri-Tuz road,
no farther advance was possible. We halted here for the night after
having crossed the river, while ‘C’ Squadron and a section of the
Machine-Gun Squadron were thrown forward on each side of the
track; ‘B’ Squadron, having all the horses, were some 1500 yards in
rear down by the river. Intermittent firing was carried on throughout
the night. At 4.30 A.M. we stood to arms and saddled up, receiving
word that our 2 Infantry columns would advance at dawn, one
column advancing up the right bank of the river, and the other up
the left bank, the latter with the object of taking the Heights of the
Naffdach, east of Tuz. The enemy had been reinforced during the
night by a battalion from Tauq, and was holding a front of 7 miles,
stretching from Yanhah-Buyuk to Tuz-Khurmatli, and at Tuz they
held a position covering the road and extending over the hills. At
daybreak the Hotchkiss-gun troop of ‘C’ Squadron opened fire from
the trenches on the right bank of the river, and soon came under
some pretty accurate shell-fire. Shortly after this B Battery, of the
66th Brigade R.F.A., galloped up beside them and opened up a
heavy fire on the enemy’s position at about 6 A.M., the Infantry
having deployed for the 2 main attacks on Tanijah from the south-
west, and on Tuz from the south. We were ordered to withdraw and
make a detour to the west. We circled behind the battery to join up
with the 21st and 22nd Cavalry and get across the Tuz-Tauq road to
cut off the Turks, who were already falling back before our Infantry,
who were advancing with steadiness under machine-gun and
artillery fire, right up to the guns which were in action until they
were within two hundred yards of them. Meanwhile we were held up
for a time by a nest of machine-guns some 1200 yards away on a
small knoll. Two troops of the ‘B’ Squadron, under Lt. MacDonald,
were ordered out as a scout line. They led off to the left of the knoll,
and having got in line with it, wheeled sharply to the right and
charged the position in the rear and the flank, all the enemy except
two throwing up their hands to escape being cut down. The taking
of this knoll opened the way across the plain, and we continued to
advance, charging bodies of Turks here and there, either killing them
or taking them prisoners. The largest body we found was between
the Tauq road and the hills, and these put up some resistance for a
time until charged from two sides by us and the 22nd Cavalry, the
21st Cavalry having wheeled towards Tuz to deal with other bodies,
who at that time were shelling ‘A’ and ‘D’ Squadrons, commanded by
Captain Godfree. A number of the enemy made their way over the
hills and were harassed by our fire. Soon after this the fire of the
enemy died away, and by 9.30 A.M. all opposition had collapsed, the
whole position having fallen to us inside 4 hours with a very slight
loss. 1200 prisoners were taken, 25 machine-guns, and 12 field-guns
that were in the position. The action having passed, we rested for
some time where we were, and on ‘A’ and ‘D’ Squadrons rejoining us
in the afternoon we went into bivouac opposite Tuz at about 3 P.M.
We remained in bivouac here for five days, during which we rested
and grazed our horses. Whilst here, our Brigade Commander
received the following wire from General Egerton: ‘Many
congratulations to troops. Please convey my thanks to General Caley
and General Hollen-Prior for their good work, and that of their
officers and men. Cavalry charge must have been magnificent.
Please accept my repeated appreciation of the performances of all
ranks under your command.’ On the 5th May we moved off at the
head of the Brigade at 8 A.M., and after crossing the bridge of the
Tauq-Chai at about 5 P.M., we bivouacked for the night some 2 miles
north-west of it. We moved off again at 8.30 A.M. the following
morning in the direction of Taza, when shortly after our aeroplanes
reported that the enemy had evacuated their position there. On
receiving this information we were ordered to advance to catch the
retreating enemy at the village of Taza-Kharatli. On arriving here at
11.30 A.M., after crossing the Oazah Chia on the Kirkuk road, we
found the village unoccupied. Making a short halt here we moved off
again at 1.45 P.M., marching on to Kirkuk. The armoured cars, after
having been towed through the river, had preceded us along the
Kirkuk road. At about 3.39 P.M., nearing Balban, we came under
some shell-fire at long range, this we avoided by making a detour to
the east. After sending out patrols, who were met by a very heavy
fire, we galloped forward and dismounted for action against the
enemy holding the trenches just outside Kirkuk. Finding the enemy
so strongly entrenched, we were unable to advance, but hotly
engaged them until dusk, when we were ordered to withdraw and
form an outpost line about 3 miles from the town. This we did about
7 P.M., when a heavy storm broke out and very heavy rains
continued to fall throughout the night, which, combined with the
intense cold, made rest for us that night an impossibility. (The
following names appeared on the Order for the day for gallantry in
action: Capt. J. A. Jeffrey, Capt. A. M. Sassoon, Lt. J. J. Crystall, and
R.S.M. Seekins, all being awarded the M.C.) Our outpost line was
formed near Balban, on a track running east and west. The night
was fairly quiet, except for several loud explosions which occurred in
and near Kirkuk. The morning found the ground more or less a
quagmire, and at 6.30 A.M. we received orders to advance on the
town. ‘A’ Squadron moved off at 8 A.M., followed by the Regiment
and the 21st Cavalry some half an hour later. No resistance was
encountered, and at 10.30 A.M. the Regiment entered the town, ‘C’
and ‘D’ Squadrons, under Capt. Godfree, moving on to the high
ground covering the north of the town. Several large hospitals were
found here, one containing 358 patients, the population being in a
starved condition. There were also several corpses of Turkish
soldiers horribly mutilated. This was said to have been done by
Arabs to avenge the raping of their women-folk. The whole place
was in a filthy condition. At 3 P.M. the Column moved out of Kirkuk
and bivouacked near Taziyan, some 3 miles down the Taza road, a
heavy storm breaking over us just as we were pegging down our
horses. Meanwhile ‘C’ and ‘D’ Squadrons were sent forward to some
hills some 4 miles north of the town to harass the retreating enemy,
and to protect our own main body from attack. These two
squadrons, after successfully hastening the enemy’s retreat,
reconnoitred the road to Yarvali, rejoining the Column in bivouac
about 5 P.M., bringing with them 2 prisoners. The Column remained
in bivouac the following day, and at 12.30 A.M. we received orders to
send 2 squadrons to reconnoitre the northern road to Alton-Kupri as
far as Sakizli, ‘B’ and ‘D’ Squadrons doing this commanded by Capt.
Godfree. They were also accompanied by a Company of the R.E.’s
for the purpose of destroying enemy shell-dumps which were known
to be in the vicinity. Two such dumps were located and destroyed
near the village of Daraman, and at Sakizli 7 large motor-lorries with
engines destroyed were found. These contained 2 mountain-guns, 2
machine-guns, and a large quantity of shell ammunition of various
sizes. At 5 P.M. orders were received by heliograph to proceed to
Yarvali and search it for any documents the enemy may have left.
Arriving there about 8 P.M., we discovered a number of documents,
and also several aeroplane engines and drums of petrol, and a
quantity of shell ammunition. It being necessary to destroy this
material, the wing returned and bivouacked at 11 P.M. The Column
rested, and we grazed our horses all the following day, and at 6 A.M.
on the 10th May we marched on Alton-Kupri with the intention of
driving the enemy over the Lesser Zab river and destroying the
bridge there. We were preceded by 2 of our armoured cars, who at
about 11.15 A.M. were held up by the enemy, who were in position
on Guk-Tappah Hill, while the road was shelled by the enemy’s
batteries in Alton-Kupri. The armoured cars succeeded in driving the
enemy from Guk-Tappah, but were quite unable to advance farther
owing to a deep canal which cut the road at this point. After
observations had been made from Guk-Tappah, the Regiment
received orders to make an encircling movement to the right, whilst
the 21st Cavalry did the same to the left. The 22nd Cavalry
advancing in the centre succeeded, by covered approaches, in
getting within 2 miles of the village which was on the farther side of
the river. The Regiment experienced considerable difficulty in
advancing, owing to a considerable number of very deep nullahs,
which were full of water at the time. The village was hidden from
view by the high ground on this side of the river. We advanced by
wings ‘A’ and ‘B’ leading in extended order. After advancing about 1
mile we were heavily shelled by mountain-guns, 14 pounders and
4.53, and considerable rifle and machine-gun fire was opened on us
by enemy Infantry who were holding a series of trenches and rifle-
pits on this side of the river. The Regiment immediately dismounted
for action. The Hotchkiss-gun troop of ‘A’ Squadron moving forward
opened a very effective fire which was well supported by our
batteries. This proved too much for the enemy, who retired to their
second line of defence. On this side the Hotchkiss-gun troop of ‘D’
Squadron advanced about 1000 yards with ‘C’ Hotchkiss-gun troop in
support. Meanwhile ‘B’ Squadron were endeavouring to get down to
the river bank, but were unsuccessful owing to the heavy rains and
accurate firing of the enemy’s batteries who were dug in on the
opposite bank. We continued to engage the enemy until about 6
P.M., when orders were received to withdraw to Daraman. During our
retirement the enemy shelled us with increased violence, and we
sustained several casualties, but luckily the number was small in
comparison with the terrific fire we were subjected to. One troop of
‘A’ Squadron was left near Guk-Tappah as escort to our casualties,
whilst we continued our march back till 10.45 P.M., when we
bivouacked for the night. Orders were received the next morning to
return to Kirkuk. We did not move off until 2 P.M., and arrived at our
previous bivouac near Kirkuk at about 6 P.M. The following morning a
strong patrol left bivouac at 7 A.M. to reconnoitre a vast stretch of
unexplored country between Taza and Telabw-Shahanah, whilst the
remainder of the Regiment, moving off some half an hour later
marched to Taza, some 9 miles distant, where they went into
bivouac. It was whilst here that a small, but nevertheless fierce,
caste riot broke out among the Indians who had the handling of our
transport. This necessitated the whole of the Regiment having to
turn out fully armed before it could be quelled. At 5.30 A.M. the
following morning, 13th May, the Regiment commenced to march to
Cemetery, where we were to join the 7th Cavalry Brigade again. To
reach the above place we now had to cross some hitherto
unexplored country, and so far not having received any reports from
our patrol which had left us the previous day to reconnoitre this part
of the country, we had to proceed with caution. Halting at about 10
A.M. to water and feed our horses, we moved off again at 11.30 A.M.
Meanwhile our patrols had completed their reconnaissance, and got
into communication with us by helio, sending us a message to the
effect that an enemy column were rapidly disappearing into the hills.
The Regiment not being strong enough to intercept them, the patrol
was recalled and we continued our march, arriving at Cemetery, and
joined the 7th Cavalry Brigade at 8 P.M., after marching some 50
miles. Resting till 4 P.M. the following afternoon, we moved through
the Pass to Ain Nakhailah, some 4 miles distant, bivouacking about 1
mile south of the salt springs there. The following morning we
continued our march on to Daur, which was some 20 miles over a
waterless desert. This proved a very trying time for us, the little
water which we were able to obtain before leaving the springs being
very brackish and salty, which, combined with the intense [heat?],
produced a thirst which was well-nigh unendurable. These arduous
marches, coming on the top of our very recent hard fighting, tested
our endurance to the utmost, several of our men falling out of their
saddles from sheer weakness from want of food and rest. The sight
of the river Tigris had a noticeable and stimulating effect on both
man and horse, and on reaching the river both were jostling each
other in their frantic efforts to quench their burning thirst. On
bivouacking here many of us took the opportunity of having a much-
needed dip in the river. Our way now lay alongside the river, and
owing to the condition of both men and horses, it was decided to
finish our march by easy stages. Accordingly, at 4.30 A.M. the
following morning we trekked to Samarah, a distance of 12 miles,
and bivouacked some 2 miles north of the town. Moving off at the
same time the following morning to avoid the intense noonday heat,
we marched a farther 13 miles and bivouacked at Khan Mifraji at
10.30 A.M. We trekked on to Akab, a distance of 15 miles, the
following morning, crossing the pontoon bridge over the river
Adhaim, and bivouacked about a mile distant on the other side. The
morning after this, commencing at 5 A.M., we did another 17 miles
on to Ktuwair, and went into bivouac there at about 12 noon. From
here we moved off at 4.30 A.M. and marched to Baqubah, another 16
miles distant, where we arrived at about 11.30 A.M. Trekking a
farther 12 miles the following day, we bivouacked at Conningham’s
Post at 10.30 A.M.; the following day, the 22nd May, we again moved
off at 4.30 A.M., and covered the remaining 16 miles to our summer
camp at Chaldari, where we arrived at about 11 A.M., our strength on
marching in being 19 officers, 315 other ranks, and 445 horses. On
the morrow the following was published in Regimental Orders: ‘The
Commanding Officer wishes to take the opportunity of expressing his
keen appreciation of the conduct of all ranks during the recent
operations on the north-eastern front which have so successfully
attained their object. During the course of these operations the
Regiment has encountered, apart from the enemy, many hardships
and difficulties, and it is the cheery spirit in which these hardships
have been met, and the constant courage with which these
difficulties have been overcome, that have elicited once more the
Commanding Officer’s admiration and pride.’

GUNS CAPTURED AT TUZ