Contents
PrefaceAcknowledgements
1 1ntroduc:tion to battery technology
Electromotive force . Reversible cells . Reversible
electrodes . Relationship between electrical energy and
energy content of a cell . Free energy changes and electromotive
forces in cells . Relationship between the
energy changes accompanying a cell reaction and concentration
of the reactants . Single electrode potentials
. Activities of electrolyte solutions . Influence of ionic
concentration1 in the electrolyte on electrode potential
. Effect of sulphuric acid concentration on e.m.f.
in the lead-acid battery . End-of-charge and end-ofdischarge
e.m.f. values . Effect of cell temperature on
e.m.f. in the lead-acid battery . Effect of temperature
and temperature coefficient of voltage dEldT on
heat content change of cell reaction . Derivation of
the number of electrons involved in a cell reaction .
Thermodynamic calculation of the capacity of a battery
. Calculation of initial volume of sulphuric acid
. Calculation of operating parameters for a lead-acid
battery from calorimetric measurements . Calculation
of optimum acid volume for a cell Effect of cell layout
in batteries on battery characteristics . Calculation
of energy density of cells . Effect of discharge rate on
performance characteristics . Heating effects in batteries
. Spontaneous reaction in electrochemical cells .
Pressure development in sealed batteries
4 Nickel batteries
Nickel-cadmium secondary batteries . Nickel-iron
secondary batteries . Nickel-zinc secondary batteries
. Nickel-hydrogen secondary batteries . Nickel-metal
hydride secondary batteries . Sodium-nickel chloride
secondary batteries
2 Guidelines to battery selection
Primary batteries . Secondary batteries . Conclusion
Pat3 1 Battery Characteristics
3 Lead-acid secondary batteries
Open-type lead-acid batteries . Non-spill lead-acid
batteries . Recombining sealed lead-acid batteries
5 Silver batteries
Silver oxide-zinc primary batteries . Silver-zinc secondary
batteries . Silver-cadmium secondary batteries
. Silver-hydrogen secondary batteries
6 Alkaline manganese batteries
Alkaline manganese primary batteries . Alkaline manganese
secondary batteries
7 Carbon-zinc and carbon-zinc chloride
primary batteries
Carbon-zinc batteries . Carbon-zinc chloride batteries
8 Mercury batteries
Mercury-zinc primary batteries . Mercury-indiumbismuth
and mercury -cadmium primary batteries
9 Lithium batteries
Introduction . Lithium- sulphur dioxide primary
batteries . Lithium-thionyl chloride primary batteries
. Lithium-vanadium pentoxide primary batteries
. Lithium-manganese dioxide primary batteries .
Lithium-copper oxide primary batteries . Lithiumsilver
chromate primary batteries . Lithium-lead
bismuthate primary cells . Lithium-polycarbon
monofluoride primary batteries . Lithium solid
electrolyte primary batteries . Lithium-iodine primary
batteries . Lithium-molybdenum disulphide secondary
batteries . Lithium (aluminium) iron monosulphide
secondary batteries . Lithium-iron disulphide primary
cells . Lithium- silver-vanadium pentoxide batteries
10 Manganese dioxide-magnesium
perchlorate primary batteries
Reserve type
11 Magnesium-organic electrolyte
primary batteries
12 Metal-air cells
Zinc-air primary batteries . Zinc-air secondary batteries
. Cadmium-air secondary batteries . Aluminium-
air secondary batteries . Iron-air secondary
batteries
13 High-temperature thermally activated
primary reserve batteries
Performance characteristics of calcium anode thermal
batteries . Performance characteristics of lithium anode
thermal batteries
14 Zinc-halogen secondary batteries
Zinc-chlorine secondary batteries . Zinc-bromine
secondary batteries
15 Sodium-sulphur secondary batteries
16 Other fast-ion conducting solid
systems
17 Water-activated primary batteries
Magnesium-silver chloride batteries . Zinc- silver
chloride batteries . Magnesium-cuprous chloride batteries
Part 2 Battery theory and design
18 Lead-acid secondary batteries
Chemical reactions during battery cycling . Maintenance-
free lead-acid batteries . Important physical
characteristics of antimonial lead battery grid alloys
. Lead alloy development in standby (stationary)
batteries . Separators for lead-acid automotive
batteries Further reading
19 Nickel batteries
Nickel-cadmium secondary batteries . Nickel-hydrogen
and silver-hydrogen secondary batteries .
Nickel-zinc secondary batteries . Nickel-metal
hydride secondary batteries . Nickel-iron secondary
batteries . Sodium-nickel chloride secondary batteries
20 Silver batteries
Silver oxide-zinc primary batteries . Silver-zinc secondary
batteries . Silver-cadmium secondary batteries
21 Alkaline manganese batteries
Alkaline manganese primary batteries . Alkaline manganese
secondary batteries
22 Carbon-zinc and carbon-zinc chloride
batteries
Carbon-zinc primary batteries . Carbon-zinc chloride
primary batteries
23 Mercury-zinc batteries
Mercury-zinc primary batteries . Mercury-zinc cardiac
pacemaker batteries
24 Lithium batteries
Lithium-sulphur dioxide primary batteries . Lithiumthionyl
chloride primary batteries . Lithium-vanadium
pentoxide primary batteries . Lithium solid electrolyte
primary batteries . Lithium-iodine primary
batteries . Lithium-manganese dioxide primary
batteries . Lithium-copper oxide primary batteries
. Lithium-carbon monofluoride primary batteries .
Lithium-molybdenum disulphide secondary batteries
. Lithium (aluminium) iron sulphide secondary cells .
Lithium-iron disulphide primary batteries
25 Manganese dioxide-magnesium
perchlorate primary batteries
26 Metal-air batteries
Zinc-air primary batteries . Metal-air secondary batteries
. Aluminium-air secondary reserve batteries
27 High-temperature thermally activated
primary batteries
Calcium anode-based thermal batteries . Lithium anode
thermal batteries . Lithium alloy thermal batteries
28 Zinc- halogen secondary batteries
Zinc-chlorine batteries . Zinc-bromine batteries
29 Sodium-sulphur secondary batteries
References on sodium-sulphur batteries
Pard: 3 Battery performance evaluation
30 Primary batteries
Service time--voltage data . Service life-ohmic load
curves . Effect of operating temperature on service
life Voltage-capacity curves . Shelf life-percentage
capacity retained . Other characteristic curves
31 Secondary batteries
Discharge curves . Terminal voltage-discharge time
curves . Plateau voltage-battery temperature curves
I Capacity returned (discharged capacity)-discharge
rate curves . Capacity returned (discharged capacity)-
discharge temperature curves and percentage
withdrawable capacity returned-temperature curves
. Capacity returned (discharged capacity)-terminal
voltage curves . Withdrawable capacity-terminal
voltage cunies . Capacity returned (discharged
capacity) -discharge current curves . Discharge
rate-capacity returned (discharged capacity) curves .
Discharge rate-terminal voltage curves . Discharge
rate-mid-point voltage curves . Discharge rate-energy
density curves . Self-discharge characteristics and shelf
life . Float life characteristics
Part 4 Battery Applications
32 Lead-acid secondary batteries
Stationary type or standby power batteries . Traction
or motive power type . Starting, lighting and ignition
(SLI) or automotive batteries . Partially recombining
sealed lead-acid batteries . Load levelling batteries .
Electric vehicle batteries
33 Nickel lbatteries
Nickel-cadmium secondary batteries . Nickel-zinc
secondary batteries . Nickel-hydrogen secondary
batteries . Nickel-metal hydride secondary batteries
. Nickel-iron secondary batteries . Sodium-nickel
chloride secondary batteries
34 Silver batteries
Silver-zinc primary batteries . Silver-zinc secondary
batteries . Silver-cadmium batteries
35 Alkaline manganese primary batteries
36 Carbon-zinc primary batteries
Comparison of alkaline manganese and carbon-zinc
cell drain rates . Drain characteristics of major consumer
applications
37 Mercury batteries
Mercury -zinc primary batteries . Mercury-cadmium
primary batteries . Mercury-indium-bismuth primary
batteries
38 Lithium primary batteries
Lithium- sulphur dioxide . Lithium-vanadium pentoxide
. Lithium-thionyl chloride . Lithium-manganese
dioxide . Lithium-copper oxide Lithium- silver chromate
. Lithium-lead bismuthate . Lithium-polycarbon
monofluoride . Lithium solid electrolyte . Lithiumiodine
. Comparison of lithium-iodine and nickelcadmium
cells in CMOS-RAM applications .
Lithium-iron disulphide primary cells . Lithiummolybdenum
disulphide secondary cells . Lithium
(aluminium) iron sulphide secondary cells
39 Manganese dioxide-magnesium
perchlorate primary batteries
Reserve batteries . Non-reserve batteries
40 Metal-air batteries
Zinc-air Primary batteries . Zinc-air secondary batteries
. Aluminium-air secondary batteries
41 High-temperature thermally activated
primary batteries
42 Seawater-activated primary batteries
43 Electric vehicle secondary batteries
Lead-acid batteries . Other power sources for vehicle
propulsion
Part 5 Battery charging
44 Introduction
45 Constant-potential charging
Standard CP charging . Shallow cycle CP charging
of lead-acid batteries . Deep cycle CP charging of
lead-acid batteries . Float CP charging of lead-acid
batteries . Two-step cyclic voltage-float voltage CP
charging
46 Voltage-limited taper current charging
of alkaline manganese dioxide batteries
47 Constant-current charging
Charge control and charge monitoring of sealed
nickel-cadmium batteries . The Eveready fast-charge
cell (nickel-cadmium batteries) . Types of constantcurrent
charging . Two-step constant-current charging
. Constant-current charger designs for normal-rate
charging . Controlled rapid charger design for
nickel-cadmium batteries . Transformer-type charger
design (Union Carbide) for nickel-cadmium batteries
. Transformerless charge circuits for nickel-cadmium
batteries
48 Taper charging of lead-acid motive
power batteries
Types of charger . Equalizing charge . How to choose
the right charger . Opportunity charging
49 Methods of charging large
nickel-cadmium batteries
Trickle charge/float charge . Chargeldischarge operations
on large vented nickel-cadmium batteries .
Standby operation . Ventilation
Part 6 Battery suppliers
50 Lead-acid (secondary) batteries
Motive power batteries . Standby power batteries
Automotive batteries . Sealed lead-acid batteries
Spillproof lead-acid batteries
51 Nickel batteries
Nickel-cadmium secondary batteries . Nickel-hydrogen
batteries . Nickel-zinc batteries . Nickel-metal
hydride secondary batteries . Nickel-iron secondary
batteries . Sodium-nickel chloride secondary batteries
52 Silver batteries
Silver-zinc batteries . Silver-cadmium (secondary)
batteries . Silver-hydrogen secondary batteries . Silver-
iron secondary batteries
53 Alkaline manganese dioxide batteries
Primary batteries . Secondary batteries
54 Carbon-zinc batteries (primary) and
carbon-zinc chloride batteries
55 Mercury batteries
Mercury-zinc (primary) batteries . Mercury-zinc cardiac
pacemaker batteries . Other types of mercury
battery
Lithium-thionyl chloride batteries . Lithium-manganese
dioxide batteries . Lithium-silver chromate batteries
. Lithium-copper oxide batteries . Lithium-lead
bismuthate batteries . Lithium-copper oxyphosphate
cells . Lithium- polycarbon monofluoride batteries .
Lithium solid electrolyte batteries . Lithium-iodine
batteries . Lithium-molybdenum disulphide secondary
batteries . Lithium-iron disulphide primary batteries .
Lithium alloy -iron sulphide secondary batteries
57 Manganese dioxide-magnesium
perchlorate (primary) batteries
Reserve-type batteries . Non-reserve batteries
58 Magnesium-organic electrolyte
batteries
59 Metal-air cells
Zinc-air primary batteries . Zinc-air secondary batteries
. Aluminium-air secondary batteries . Iron-air
secondary batteries
60 Thermally activated batteries
61 Zinc- halogen batteries
Zinc-bromine secondary batteries
62 Sodium-sulphur batteries
63 Water-activated batteries
McMurdo Instruments magnesium-silver chloride
seawater batteries . SAFT magnesium-silver chloride
batteries . SAFT zinc-silver chloride batteries . SAFT
magnesium-copper iodide seawater-energized primary
batteries . Eagle Picher water activated primary
batteries
Suppliers of primary and secondary
batteries
Glossary
Battery standards
Battery journals, trade organizations and
conferences
Bibliography
Index
56 Lithium batteries
Lithium-vanadium pentoxide (primary) batteries
. Lithium-sulphur dioxide (primary) batteries .
Preface
Primary (non-rechargeable) and secondary (rechargeable)
batteries are an area of manufacturing industry
that has undlergone a tremendous growth in the past
two or three decades, both in sales volume and in
variety of products designed to meet new applications.
Not so long ago, mention of a battery to many
people brought to mind the image of an automotive
battery or a torch battery and, indeed, these
accounted for the majority of batteries being produced.
There were of course other battery applications such
as submarine and aircraft batteries, but these were
of either the lead-acid or alkaline type. Lead-acid,
nickel-cadmium, nickel-iron and carbon-zinc represented
the only electrochemical couples in use at that
time.
There now exist a wide range of types of batteries,
both primary and secondary, utilizing couples
that were not dreamt of a few years ago. Many of
these couples have been developed and utilized to produce
batteries to meet specific applications ranging
from electric vehicle propulsion, through minute batteries
for incorporation as memory protection devices
in printed circuits in computers, to pacemaker batteries
used in h.eart surgery. This book attempts to draw
together in one place the available information on all
types of battery now being commercially produced.
It starts with a chapter dealing with the basic theory
behind t!he operation of batteries. This deals with
the effects omf such factors as couple materials, electrolyte
composition, concentration and temperature on
battery performance, and also discusses in some detail
such factors as the effect of discharge rate on battery
capacity. The basic thermodynamics involved in
battery operation are also discussed. The theoretical
treatment concentrates OK the older types of battery,
such as lead--acid, where much work has been carried
out over the years. The ideas are, however, in many
cases equally applicable to the newer types of battery
and one of the objectives of this chapter is to assist
the reader in carrying out such calculations.
The following chapters ,discuss various aspects
of primary and secondary batteries including those
batteries such as silver-zinc and alkaline manganese
which are available in both forms.
Chapter 2 is designed to present the reader with
information on the types of batteries available and to
assist him or her in choosing a type of battery which
is suitable for any particular application, whether this
be a digital watch or a lunar landing module.
Part 1 (Chapters 3-17) presents all available
information on the performance characteristics of
various types of battery and it highlights the parameters
that it is important to be aware of when considering
batteries. Such information is vital when discussing
with battery suppliers the types and characteristics of
batteries they can supply or that you may wish them
to develop.
Part 2 (Chapters 18-29) is a presentation of the theory,
as far as it is known, behind the working of all the
types of battery now commercially available and of the
limitations that battery electrochemistry might place
on performance. It also discusses the ways in which
the basic electrochemistry influences battery design.
Whilst battery design has always been an important
factor influencing performance and other factors such
as battery weight it is assuming an even greater
importance in more recently developed batteries.
Part 3 (Chapters 30 and 3 1) is a comprehensive discussion
of practical methods for determining the performance
characteristics of all types of battery. This is
important to both the battery producer and the battery
user. Important factors such as the measurement of the
effect of discharge rate and temperature on available
capacity and life are discussed.
Part 4 (Chapters 32-43) is a wide ranging look at
the current applications of various types of battery
and indicates areas of special interest such as vehicle
propulsion, utilities loading and microelectronic and
computer applications.
Part 5 (Chapters 44-49) deals with all aspects of
the theory and practice of battery charging and will be
of great interest to the battery user.
Finally, Part 6 (Chapters 50-63) discusses the massive
amount of information available from battery