Secondary Batteries-Lead-Acid Systems: March 2018

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SECONDARY BATTERIES-LEAD-ACID SYSTEMS
Article · March 2018
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SECONDARY BATTERIES – LEAD–ACID SYSTEMS
Contents
Overview
Negative Electrode
Positive Electrode
Electrode Design
Electrolyte
Separators
Phosphoric Acid Influence
Carbon Additives
Lead Alloys
Grid Production
Curing and Formation
Flooded Batteries
Performance
Valve-Regulated Batteries: Oxygen Cycle
Valve-Regulated Batteries: Absorptive Glass Mat
Valve-Regulated Batteries: Gel
Catalytic Valves
Flow Batteries
Bipolar Batteries
Supercap Hybrid (UltraBatteryTM)
Charging
Coup de Fouet
State-of-Charge/Health
Lifetime Determining Processes
Modeling
Automotive Batteries: Conventional
Automotive Batteries: New Developments
Stationary Batteries
Overview
DAJ Rand, CSIRO Energy Technology, Clayton, VIC, Australia
PT Moseley, International Lead Zinc Research Organization Inc., Durham, NC, USA
& 2009 Elsevier B.V. All rights reserved.
Introduction seldom be called upon to discharge. ‘Traction’ batteries

used to power electric vehicles (EVs), on the other hand,
Leadacid batteries are employed in a wide variety are repeatedly required to undergo deep discharges and
of tasks, each with its own distinctive duty cycle. In recharges over periods of a few hours (the so-called
internal-combustion-engined vehicles (ICEVs), the ‘deep-discharge duty’). In between the extreme cases of
‘automotive’ battery provides a quick pulse of high cur- float duty and deep discharge, batteries employed in
rent for starting and a lower, sustained current for other hybrid electric vehicles (HEVs) and in remote-area
purposes; the battery remains at a high state of charge for power supply (RAPS) systems spend most of the time
most of the time. The same is true of ‘stationary’ batteries cycling about an intermediate state of charge, often near
used for backup power in telecommunications and in 50% (so-called ‘partial state-of-discharge (PSoC) duty’).
other uninterruptible power supplies, although in such In all applications, the battery must be able to provide
service (the so-called ‘float duty’) the battery should adequate power for the task in hand. This may be a more
550
Secondary Batteries – Lead–Acid Systems | Overview 551
severe requirement for batteries in EVs and HEVs than dioxide (PbO2) serves as the positive active-material, lead
for those in solar-based RAPS systems. For traction duty, as the negative active-material, and sulfuric acid as the
the energy storage capability should be provided with a electrolyte. The lead dioxide is present in two crystalline
minimum weight penalty. In essence, the battery should forms, namely, a-PbO2 (orthorhombic) and b-PbO2
have a high ‘specific energy’, i.e., a high energy output (tetragonal); the latter is the predominant phase but there
per unit weight (Wh kg1). Generally, a high coulombic is some evidence to suggest that the relative abundances
efficiency (charge out: charge in) is an asset as this pre- of the two polymorphs influence battery performance.
serves primary energy. Obviously, good operational life is The electrode reactions of the cell are unusual in that
also a prerequisite. This parameter may be defined the electrolyte (sulfuric acid) is also one of the reactants,
chronologically (years of use; the so-called ‘calendar life’) as seen in the following equations for discharge and
or in terms of the number of charge–discharge cycles that charge:
the battery will sustain before the capacity falls to a set At the positive electrode (plate):
percentage of its initial value (the so-called ‘cycle life’).
Discharge
Finally, a sine qua non is acceptable cost. The factors to
be considered are the initial price of the battery, the PbO2 þ 3Hþ þ HSO
4 þ 2e

PbSO4 þ 2H2 O
operational life of the battery, and the associated main- Charge
tenance costs. Lead–acid batteries are eminently suitable ðE1 ¼ þ1:690 VÞ ½I
for medium- and large-scale energy storage operations
At the negative electrode (plate):
because they offer an acceptable combination of per-
formance parameters at a cost that is substantially below Discharge
that of alternative systems. Pb þ HSO4 PbSO4 þ Hþ þ 2e
Charge
A Brief History of Development ðE1 ¼ 0:358 VÞ ½II
The fundamental elements of the lead–acid battery were where E1 is the standard electrode potential for each
set in place 150 years ago. reaction, i.e., the electrode is in a standard state.
In 1859, Gaston Planté was the first to report that a The overall cell reaction is:
useful discharge current could be drawn from a pair of
Discharge
lead plates that had been immersed in sulfuric acid and
PbO2 þ Pb þ 2H2 SO4 2PbSO4 þ 2H2 O
subjected to a charging current. Later, Camille Fauré
Charge
proposed the concept of the pasted plate. The most
commonly employed design is built with ‘flat plates’. ðV 1 ¼ þ2:048 VÞ ½III
These are prepared by coating pastes of lead oxides and
where V1 is the standard cell voltage. It is noteworthy
sulfuric acid on to conductive lead or lead alloy ‘grids’,
that this voltage is the highest for any type of commercial
which act as current-collectors. The plates are then
battery that employs an aqueous electrolyte solution. The
‘formed’ electrolytically into ‘active’ materials. One al-
processes taking place during the discharging of a lead–
ternative cell design uses positive plates in which the
acid cell are shown schematically in Figure 2(a). It
active material is contained in tubes, each fitted with a
can be seen that the HSO4 ions migrate to the negative
coaxial current-collector. Such ‘tubular plates’ serve to
electrode and react with the lead to produce Hþ ions and
prevent shedding of the material during battery service
lead(II) sulfate (PbSO4), which (remarkably) is non-
(v.i.). A more recent cell design, aimed at high-power
conductive. This reaction releases two electrons and,
applications, has a single pair of positive and negative
thereby, gives rise to an excess of negative charge on the
plates, which are interleaved with glass mat separators
electrode that is relieved by a flow of electrons through
and wound together in a cylindrical can (the ‘spirally
the external circuit to the positive electrode. At the latter,
wound’ or ‘jellyroll’ design). Ironically, this arrangement
the lead of the lead dioxide is also converted to lead(II)
mimics that originally used by Planté. Schematics of the
sulfate and, at the same time, water is formed. Thus,
various plate types are given in Figure 1.
lead(II) sulfate progressively develops in equal quantities
at both the positive and negative electrodes, with a
Principles of Operation concomitant weakening of the electrolyte. The decrease
in electrolyte concentration (or relative density) provides
As discussed above, the lead–acid battery has undergone a convenient means for determining the degree of dis-
many developments since its invention, most of which charge that has taken place or, conversely, checking the
have involved modifications to the materials or design, state of charge of the cell. The lead–acid battery is
rather than to the underlying chemistry. In all cases, lead unique in this regard.
552 Secondary Batteries – Lead–Acid Systems | Overview
(a)
Fin
Lead alloy spine
Positive
active material
Lattice grid Braided tube
Expanded grid
(b) (c)
Terminals
Inner cap
Posts
Grid
Absorbent
separator
Spirally wound
cell
Metal
Plastic liner can
(d)
Figure 1 (a) Gaston Planté’s cell and battery; (b) flat plate; (c) tubular positive plate; and (d) spiral-wound cell.
The above processes are reversed on charging. As The gases are released in stoichiometric propor-
the cell approaches full charge, the majority of the tions and, with traditional cell designs (the so-called
lead(II) sulfate will have been converted back to lead or ‘flooded-electrolyte’ batteries), result in a loss of water
lead dioxide and further passage of current will give rise from the cell electrolyte. In contrast to the discharge
to the evolution of hydrogen at the negative electrode process, the specific gravity cannot be correlated
and oxygen at the positive, as shown in Figure 2(b). with the state of charge of the cell until near the end of
Negative electrode Positive electrode

2e− 2e-
Pb PbO2
HSO4− HSO4−
PbSO4 PbSO4
H+ 3H+
2H2O
Pb + HSO4− PbSO4 + H+ + 2e− PbO2 + 3H+ + HSO4− + 2e− PbSO4 + 2H2O
Discharge
Overall: PbO2 + Pb + 2H+ + 2HSO4− 2PbSO4 + 2H2O
Charge
(a)
Current
Pb PbSO4
+I PbSO4 PbO2
Charge Discharge Discharge Charge H2O O2

Potential
Vr
H+ H2
PbSO4 Pb −I PbO2 PbSO4
Overcharge reactions:
H+ H2 H2O 1
2 O2 + 2H+ + 2e−
1
Overall: H2O H2 + 2
O2
(b)
Figure 2 Schematic representation of (a) electrochemical processes during discharge of a lead–acid cell and (b) current–potential
characteristic of each electrode.
the charge when gassing provides good mixing of the sufficient to promote the electrode dissolution–precipi-
electrolyte. tation reactions, the value is so low that there is little
The basic discharge–charge reactions of the lead–acid migration of the material during charge–discharge cyc-
cell involve dissolution–precipitation mechanisms that, ling and, hence, a high degree of reversibility is
collectively, are known as the ‘double sulfate theory’ as maintained.
first suggested by Gladstone and Tribe in 1882. For ex- The capacity (Ah) exhibited by a lead–acid battery
ample, discharge and charge of the electrodes may be when discharged at a constant rate depends on a number
considered as dissolution into, and electroplating out of, of factors, among which are the design and construction
dilute lead-ion solutions. It should be noted that the of the cell, the cycling regime (history) to which it has
lead–acid cell is able to operate effectively as an energy been subjected, its age and maintenance, and the pre-
storage device by virtue of three critical factors. First, vailing temperature. Typical discharge curves for lead–
contrary to thermodynamic expectations, the liberation acid traction batteries at varying rates are shown in
of hydrogen from acids by lead takes place at only a Figure 3. It is immediately apparent that the realizable
negligible rate, i.e., there is a high hydrogen overpotential capacity is strongly dependent on the rate of discharge,
(see Figure 2(b)). Second, the high oxygen overpotential e.g., the capacity obtained from a 30 min discharge is only
at the positive electrode allows lead(II) sulfate to be a fraction of that from a 10 h discharge. Moreover, the cell
converted to lead dioxide before appreciable evolution of voltage is much reduced and, thereby, results in an even
oxygen commences (see Figure 2(b)). Third, although greater reduction in available energy (Wh). In addition,
the solubility of lead(II) sulfate in the electrolyte is as cycling (or life) proceeds, a number of processes
2.2
2.0
Cell voltage (V) 1.8 20 11.3

30
40
65 10 h
5h
3h
1.6 Amperes 104 2h
1h
Discharge time 30 min
1.4
20 40 60 80 100 120
Capacity (Ah)
Figure 3 Typical discharge curves for lead–acid traction batteries.
(‘failure mechanisms’) can degrade this limited per- customary to employ thick grids to ensure adequate
formance further. These are reviewed below. battery life. Better voltage control restricts the extent of
In brief, the key technical challenge to be met in corrosion and, together with the improved defect-free
maximizing battery performance involves facilitating the castings now available, thinner grids are practicable.
delivery, contact and interaction of reactants. In principle, Other methods are employed for the gravity casting of
this requires an adequate supply of acid, solid reactants of grids. A continuous casting process has been developed
high surface area, maintenance of good contact between and employs a rotating, water-cooled drum on which is
the particles of the active material (particularly in posi- engraved a continuous, multiple impression of the grid.
tive plates, which show a tendency to expand during The liquid alloy is introduced to the drum via a ‘casting
chargedischarge service, v.i.), and minimization of the shoe’ located directly over the surface of the drum. An-
insulating effects of lead(II) sulfate. other procedure is to start with a reel of alloy foil that is
then slit and expanded to form a diamond mesh struc-
ture, which is amenable to pasting. Expanded metal
technology is particularly suitable for the lead–calcium
Principles of Manufacture
alloys used in valve-regulated lead–acid (VRLA) bat-
Grids teries, as discussed later. As an alternative to gravity
Traditionally, grids for flat plates are cast from molten casting, some manufacturers punch out grids from lead,
alloy, either singly or in pairs joined by their lugs, and are or lead alloy, sheet and recycle the off-cuts.
quench cooled. Automated casting machinery is quite
Plate Design and Manufacture
sophisticated and much development work has gone into
optimizing the casting process, to produce defect-free Pasted plates
grids of different alloy compositions. Liquid lead alloy is The active material for pasted plates is made by first
gravity-fed into the mold where it cools rapidly and then reacting lead ingots with air in a ball mill, or molten lead
is ejected as a solid grid. With modern casting machinery, with air in a furnace (the ‘Barton pot’ method). The re-
the overall process takes only 3–4 s, and 15–20 pairs of sulting powder – known as ‘leady oxide’ – is composed of
grids are produced each minute. lead monoxide (PbO) and unreacted lead particles (‘free
Over the years, there has been a substantial reduction lead’). In the next stage of plate manufacture, the leady
in the thickness of grids, from more than 2 mm in the oxide is made into a paste with sulfuric acid solution.
1960s to about 0.8 mm today. Several factors have com- During paste-making, a significant proportion of the
bined to make this reduction both possible and accept- leady oxide converts to various basic lead sulfates. These
able, notably, improved casting technology and improved compounds serve to consolidate and strengthen the paste,
charge control systems for batteries. Overcharge can a process that may be likened to the setting of cement.
cause severe corrosion of the positive grid (see the Certain minor additives are included in the mix for the
section entitled ‘FM5 Corrosion’) that results in struc- negative lead plate, i.e., barium sulfate, lignosulfonates,
tural weakness and ultimate failure. Therefore, it was and carbon black. These additives, collectively known as
‘expanders’, serve to improve the low-temperature paste is required. Over the years, the design has moved
performance and extend the cycle life of the battery. toward the use of a thinner plate, which has regular
The expanders prevent individual crystals of lead vertical fins perpendicular to its plane. The purpose of
from growing and combining into a dense structure with these fins is to increase substantially the effective surface
low surface area and, therefore, low electrical capacity. area of the plate and thus improve the stored capacity per
Sometimes fibers and/or binders are added to the paste unit mass and unit volume. Even so, the capacity of the
of the positive plate to give it strength. The pasting op- Planté cell is poor compared with other types of lead–
eration consists of feeding paste from an overhead hopper acid battery. The virtues of the cell are its reliability and
onto cast grids, or onto continuous expanded metal grids, long life on float duties.
that pass horizontally underneath. The negative plates of Planté cells are conventional
After pasting, the plates are flash dried and then pasted types, which use low-antimony lead alloy grids.
‘cured’. Curing consists of putting the stacked plates in an These plates offer a service life similar to that of the
enclosure of controlled temperature and humidity for a positives. During service, active material is gradually lost
given period. This treatment allows the development of from the positive plate and falls to the bottom of the cell
basic lead sulfates and the oxidation of free lead in the as sediment. Nevertheless, the cell retains a constant
active mass to proceed to completion. These processes performance because active material is continuously re-
serve to harden and strengthen the active mass. Finally, formed at the surface of the plate. The space beneath the
the plates are mounted in the battery together with the plates is adequate to accommodate the sediment ex-
separators, welded into groups of like polarity, and pected over 25 years of duty. The cell is housed in a
‘formed’ by charging electrochemically to produce lead transparent plastic container so that it is possible to ob-
dioxide at the positives and spongy lead metal at the serve the accumulation of sediment directly and estimate
negatives. whether end of life is imminent.
Tubular plates
In a tubular cell, the positive plate is constructed from a
‘Traditional’ Failure Mechanisms
series of vertical lead alloy spines or ‘fingers’ that es-
sentially resemble a comb (see Figure 1(c)). These act
The factors that limit the life of a lead–acid battery and
as current-collectors and are inserted into tubes made
result in ultimate failure are several and complex. The
from woven, braided or felted fibers of glass or polyester.
dominance of one over another is bound up with the
The tubes may be either mounted individually or joined
design of the battery, its materials of construction, the
together in a row (the ‘gauntlet’ design) with spacing
quality of the build, and the conditions of use. To identify
equal to that between the spines. The tubes are sealed at
the prime determinants of battery life, it is first necessary
the base with plastic caps, which are mounted on a
to distinguish between ‘catastrophic’ battery failure, as
common bar. The active material is packed into the
indicated by a sudden inability of the battery to function,
annulus between the spine and the tube wall. A mixture
and ‘progressive’ failure, as demonstrated by a gradual
of leady oxide and red lead (Pb3O4) is commonly used
decline in capacity during service.
in the preparation of the positive plates, and con-
Catastrophic failure is usually easy to diagnose and
ventional pastes for the negatives. After filling with
characterize. The following problems are commonly
oxide, the positive plates are soaked in sulfuric acid
encountered.
(the so-called ‘pickling’ process) to convert the majority
of the lead oxides to lead sulfate. This extensive sulfa-
tion (facilitated by the use of red lead) assists the sub-
• short-circuits
Incorrect cell design and component selection, e.g.,
due to plate and separator faults.
sequent formation stage. With the tubular design, it is
not possible to shed active material, except in cases of
• open-circuits arisingduring
Poor quality control battery manufacture, e.g.,
from loose plates/terminals,
severe battery misuse where splitting of the tubes may and/or from the fracture of weak plate-to-strap, strap-
occur. to-terminal, or cell-to-cell connections; attack from
contaminants.
Planté plates
The Planté design was an early form of lead–acid for
• Incorrect operation of batteries (‘abuse’), e.g., under-
charging, overcharging, low electrolyte level (flooded
standby power battery that still finds limited application systems), vibration, high ambient temperature, entry
today. The fundamental difference between Planté cells of harmful foreign species, and prolonged storage with
and all other lead–acid cells lies in the use of a single insufficient recharging.
solid casting of pure lead for the positive plate. The ac-
tive material is formed electrochemically on the positive
• External and/or internal damage, e.g., broken con-
tainers and covers, damaged terminals, and electrolyte
plate, so no mechanical bonding of separately prepared leakage.
Clearly, there is a certain degree of overlap between PbSO4 β-PbO2

some of these categories, and battery failure may have
indeed resulted from some combination of effects.
‘Progressive’ failure is more difficult to predict and
explain. Often, it represents a subtle deviation from op-
timum performance that originates from microscale
changes in plate characteristics brought about by the
influence of manufacturing variables and service con-
ditions. Parameters that depend upon the materials,
processing and design of the battery are known as ‘inner
parameters’, while those determined by the conditions of Figure 4 Projections of crystal structures of PbSO4 and b-
battery use are referred to as ‘outer parameters’. The PbO2. Each contains the same number of lead atoms and thus a
comparison illustrates the volume change that accompanies the
classification is as follows. interconversion of the two compounds.
Inner parameters
• oftheleady
chemical composition and physical properties
oxide;
increase for the transformation of lead dioxide to lead(II)
sulfate (shown in Figure 4) is 92%, whereas that for lead
• method of application,
the composition (including additives), density,
loading and pellet size of
to lead(II) sulfate is 164%. Expansion can occur both in
the plane of the plate (if the grid is stretched by a growing
the paste (for flat plates); corrosion layer) and in the direction normal to the plate
• chemical composition and structure of cured plates
(flat type) or pickled plates (tubular type);
(through expansion of the active material itself). Recharge
of the cell restores most of the lead dioxide, but not within
• chemical composition and structure of formed
plates;
the original volume. By contrast, the negative plate does
not show the same tendency to expand, perhaps because
• plate thickness; lead is softer than lead dioxide and therefore the active
• composition and processing conditions of grids; material is more easily compressed as the conversion to
• composition (including additives) of electrolyte; the more voluminous lead sulfate proceeds. Progressive
• choice of separator; and expansion of the positive plate with cycling service causes
• cell design. an increasing fraction of the active material to become
disconnected from the current-collection process and this,
Outer parameters in turn, lowers the electrical performance of the battery.
• storage time before use; Specifically, the mechanical integrity of the plate is de-
• frequency and current density of discharge; graded by a gradual breaking down of the agglomerate
• depth of discharge; structure of the active material into individual crystallites.
• discharge;
stand time in a state of partial or complete Eventually, shedding of material may occur and promote
the secondary problems of ‘mossing’ and ‘leading through’.
• current and voltage of recharge; These problems refer to the transport of particles of
• temperature;overcharge;
degree of positive active-material to the negative plate and their
• uniformity ofandconcentration and maintenance of subsequent reduction to lead during charging to build up
• electrolyte. voluminous deposits (‘mossing’) and/or dendrites (‘lead-
ing-through’) that can, respectively, bridge plates and
puncture separators to produce short-circuits.
Both sets of parameters will act (to varying degrees) to
cause the eventual failure of the battery.
Conventional batteries (i.e., those with free electrolyte FM2. Water Loss
solution, the so-called ‘flooded’ designs) most commonly
suffer from one or more of the following five failure Production of hydrogen and oxygen during overcharge
mechanisms. can reduce the volume of electrolyte to a degree that
some of the active material loses contact with the liquid
phase. This process can be auto-accelerating in that dry-
FM1. Positive Plate Expansion
out increases the internal resistance of the battery which,
Repetitive discharge and recharge causes expansion in turn, can cause excessive heating during charging and
of the positive active material because, as shown in Fig- consequently an increased rate of water loss through
ure 4, the solid product of the discharge reaction (lead(II) evaporation. It should also be noted that the propensity of
sulfate) occupies a substantially greater formula volume a battery to gas can be strongly influenced by the pres-
than the reactant material (lead dioxide). The volume ence of impurities.
+ − + −
Separator Separator
‘Lighter’
‘Heavier’ acid
acid
Water ‘Lighter’ ‘Heavier’ ‘Heavier’

acid acid acid
Pb + PbO2 + 2H2SO4 2PbSO4 + 2H2O 2PbSO4 + 2H2O Pb + PbO2 + 2H2SO4

(a) (b)
Figure 5 Schematic representation of processes and electrolyte flow that contribute to acid stratification during (a) discharge and (b)
charge.
FM3. Acid Stratification FM1. Positive Plate Expansion

On recharge, sulfuric acid is produced in and between The use of leadantimony alloy enhances the creep
the plates and there is a tendency for acid of higher strength of the positive grid and thus retards growth in
concentration, which has a greater relative density, to the plane of the plate. For the flat design of positive plate,
collect at the bottom of the cell (see Figure 5). The expansion normal to the plate can be moderated by ap-
development of a vertical concentration gradient of acid plying a compressive force to the plate group. Tubular
(the so-called ‘stratification’) can give rise to nonuniform positive plates have gauntlets, which constrain the active
utilization of active material and, consequently, short- material and reduce its tendency to expand, disconnect,
ened service life through the irreversible formation of and shed.
lead(II) sulfate. Acid stratification may also lead to ir-
regular corrosion and growth of the positive grid. FM2. Water Loss
FM4. Incomplete Charging Water loss can be made good by the process of ‘topping
up’.
If either of the electrodes is persistently undercharged,
either because of a defective charge regime or as a result
of physical changes that prevent the electrode from FM3. Acid Stratification
reaching an adequate potential, then a rapid decline in Acid concentration gradients can be removed through
available battery capacity may occur. agitation of the acid by setting the battery to deliberate
gassing during extended overcharge.
FM5. Corrosion
The positive grid is subject to corrosion. The rate of this FM4. Incomplete Charging
debilitating process is influenced by grid composition and
microstructure, plate potential, electrolyte composition, Battery packs operated under PSoC duty (as experienced
and temperature. The corrosion product is generally in RAPS and in EVs) are supported by a management
more electrically resistive than the grid and thus di- system that periodically calls for full charge in order to
minishes the output of the battery. In extreme cases, maintain capacity (a so-called cell equalizing charge).
corrosion results in disintegration of the grid and collapse With the aid of the above four measures, substantial
of the plate. service lives can be obtained from flooded batteries in
their various applications. The drive toward increased
convenience through eliminating the need for water
Traditional Remedies for Failure maintenance and avoiding the release of acid-carrying
gases has led, however, to the widespread adoption of the
Most of the above modes of failure can be suppressed to ‘valve-regulated’ form of the lead–acid battery. This
an acceptable level in conventional lead–acid batteries, as major shift in battery design has brought about a new set
follows. of scientific and technological challenges.
The Valve-Regulated Battery hydrogen at the negative plate:
Toward the end of the twentieth century, the lead–acid 2Hþ þ 2e -H2 ½VI
battery underwent a significant functional revision. For
most of its long history, the battery had operated with its and the corrosion of the positive grid:
plates immersed in a mobile electrolyte and provision
had been made for the hydrogen and the oxygen pro- Pb þ 2H2 O-PbO2 þ 4Hþ þ 4e ½VII
duced during overcharge to be released freely into the Thus, the charging of a VRLA cell is potentially more
atmosphere. The dissipated gases represented a loss of complex than the charging of its flooded counterpart. For
water from the electrolyte but, as mentioned above, this a VRLA cell, thermodynamic/kinetic conditions allow
could be replaced in a regular maintenance operation. the progress of six separate reactions at significant rates:
For many years, scientists and technologists attempted two charge reactions (the reverse of reactions [I] and [II])
to develop ‘sealed’ batteries. At first, efforts focused on and four secondary reactions, i.e., reactions [IV]–[VII].
the catalytic recombination of the gases within the bat- The oxygen cycle, defined by reactions [IV]–[V],
tery; this approach proved to be impractical. Success shifts the potential of the negative electrode to a less
came, however, with the invention of the VRLA battery. negative value and thus decreases the rate of hydrogen
Two versions of the battery entered the market, namely, evolution to a much lower level (i.e., much less than
the ‘gel’ and the ‘absorptive glass- mat (AGM)’ technol- in the older, flooded design of battery). A one-way,
ogies (v.i.). pressure-relief valve is provided to ensure that even the
The VRLA battery is designed to operate by means of small amounts of hydrogen produced do not generate a
an ‘internal oxygen cycle’ (or ‘oxygen recombination high pressure within the battery – hence, the term: ‘valve
cycle’), as illustrated in Figure 6. Oxygen evolved during regulated’. Since the plate is simultaneously on charge,
the latter stages of charging, and during overcharging, of the lead sulfate produced by reaction [V] is immediately
the positive electrode, i.e., reduced to lead via the reverse of reaction [II]. This
restores the chemical balance of the cell, i.e., in stoi-
H2 O-12 O2 þ 2Hþ þ 2e ½IV chiometric terms, the net sum of reactions [IV] and [V]
and the reverse of reaction [II] is zero. Thus, part of the
transfers through a gas space to the negative electrode electrical energy delivered to the cell is consumed by the
where it is reduced (‘recombined’) to water: oxygen recombination cycle and is converted into heat
rather than into chemical energy.
As long as the overcharge current remains moderate,
Pb þ 12 O2 þ H2 SO4 -PbSO4 þ H2 O þ Heat ½V the charge and recombination reactions can remain in
equilibrium and little net gas is generated. For example,
Two other reactions must be taken into account during consider a flooded cell charged at constant voltage, e.g.,
the charging of a VRLA cell. These are, the evolution of 2.45 V, as shown schematically in Figure 7. The current
Electrolyte film Separator Electrolyte film

~0.01 μm ~1 mm ~0.1 μm
DO = 9 x 10−6 cm2 s−1 DO = 0.18 cm2 s−1 DO = 9 x 10−6 cm2 s−1
2 2
2
Positive electrode Negative electrode
Overcharge reaction Recombination reaction

1
H2O 1
O + 2H+ + 2e−
2 2 2
O2 + Pb + H2SO4 PbSO4+ H2O + Heat
Figure 6 Conceptual view of internal oxygen cycle in a valve-regulated leadacid cell. Reproduced from Nelson (1999).
O2
H2
⏐Current⏐
ΔV
Valve-regulated cell
(2.45 V)
IO Ic
2-red
Flooded electrolyte cell
(2.45 V) Ic IO
2
IH IH IO
2 2 2
–1.4 –1.2 –0.8 –0.4 0 0.4 0.8 1.2 1.6
E°Pb/PbSO E°PbO
4 2 /PbSO4
Electrode potential (V) vs Hg/Hg2SO4 electrode
Figure 7 Current distribution in flooded and valve-regulated cells during constant-voltage charging at 2.45 V. (Note that the anodic and
cathodic currents are opposite in sign but, for convenience, both are presented on the same side of the potential axis.)
at the positive electrode is consumed principally by preferred by manufacturers of VRLA batteries for float
oxygen evolution ðIO2 Þ and by grid corrosion (Ic), and is duties, and leadtin alloys for cycling applications.
balanced by that consumed by hydrogen evolution at the If the cell is overfilled with acid initially, the oxygen
negative electrode ðIH2 Þ. With a valve-regulated cell, cycle cannot function because oxygen diffuses through
however, oxygen reduction ðIO2 -red Þ shifts the potential of the aqueous phase at a rate that is approximately four
the negative electrode (DV) and the rate of hydrogen orders of magnitude more slow than through the gas
evolution ðIH2 Þ becomes much reduced, but is not space (see Figure 6). The cell then behaves as if it were
eliminated completely, compared with that experienced of a conventional, flooded design. Toward top of charge,
in the flooded system. With a high recombination effi- first oxygen (from the positive), and then oxygen (from
ciency and with no loss of oxygen from the cell, the rate the positive) and hydrogen (from the negative), are
of hydrogen evolution is balanced by the rate of positive evolved and may be released through the valve. This loss
grid corrosion. In general, the rate at which oxygen re- of water eventually opens gas spaces (due to drying out
combines at the negative plate is a complex function of of the gel or a decrease in the volume of electrolyte held
the cell design, the operating conditions, and the over- by the AGM) and allows the transfer of oxygen to pro-
charge regime. By contrast, the recharge of a battery, ceed. Gas release from the cell then falls to a very low
which performs deep-discharge cycling service is more level.
complicated due to changes in the relative kinetics of the If the oxygen cycle is worked too hard then substantial
several competing reactions as the battery approaches top heat is generated and charging of the negative plate be-
of charge. If recharging is not managed correctly, current comes difficult so that progressive sulfation begins from
may be continually consumed by the internal oxygen the bottom of the plate where the acid concentration
cycle such that the negative plate never reaches a full tends to be highest. The function of the oxygen cycle is
state of charge. subtly linked to the microstructure of the separator
As mentioned above, there are two alternative designs material (for AGM designs) and to the nature of the
that provide the gas space in VRLA cells. One design has charge algorithm applied, especially near top of charge.
the electrolyte immobilized as a gel, whereas the other As a result of the move from the flooded to the valve-
has the electrolyte held in an AGM separator. Gas passes regulated design it is possible that several of the failure
through fissures in the gel, or through channels in the mechanisms discussed above may reappear.
AGM (refer Figure 6).
Antimony is no longer included in the grid alloys for FM1. Replacement of leadantimony alloys with
VRLA cells because this element lowers the hydrogen leadcalcium alternatives, as a means to dis-
overpotential and therefore encourages gassing at the courage hydrogen evolution, reduces the creep
negative electrode. Care needs to be taken against the strength of grids so that expansion in the plane of
introduction of other elements that might act similarly. the plate may again become a concern. Use of a
Excessive gassing at either the negative or the positive separator with insufficient rigidity (i.e., too much
electrode can result in selective discharge of the re- ‘compressibility’) may allow expansion normal to
spective electrode. Leadcalciumtin alloys are the plane of the plate.
FM2. Water loss is reduced to the extent that periodic and Cb is the heat capacity of the materials that comprise
replenishment, as required by flooded cells, is no the battery (J K1). The heat capacity is defined by:
longer necessary. Nevertheless, both hydrogen
X
evolution at the negative electrode and grid cor- Cb ¼ mi Cp ðiÞ ½2
rosion at the positive electrode do cause some
water loss. where mi is the mass of component i (g) and Cp(i) is the
FM3. Any acid stratification that occurs cannot be specific heat of component i (J g1 K1). The specific heat
removed by overcharging because there is little free Cp of VRLA batteries is in the range 0.7–0.9 J K1 g1,
electrolyte and, hence, ineffective mixing. More- while the corresponding value for flooded batteries is
over, water lost cannot be replaced because the slightly above 1 J g1 K1. The difference is mainly due
battery is expected to remain sealed for life. to the additional electrolyte in flooded designs.
FM4. The operation of the oxygen cycle may cause A battery reaches a stable temperature when heat
incomplete charging of either the negative or the generation balances heat dissipation, i.e., when dQ g/
positive plate. dt ¼ dQ d/dt. When heat generation exceeds heat dissi-
pation, ‘thermal runaway’ may result.
Heat Management in Lead–Acid Batteries Heat Dissipation

Heat Generation The dissipation of heat from a battery to its surroundings
Batteries generate heat during chargedischarge cycling normally proceeds via three mechanisms: (1) heat flow
and this must be dissipated to the environment to prevent through the components of the battery and the container
the battery temperature from rising continuously. The walls, (2) heat radiation, and (3) air convection. In prac-
heat effects originate from the change in entropy of the tice, the cooling of a battery takes place mainly through
cell reaction (‘reversible heat effect’), and from energy the side walls of the container. The bottom surface is
losses caused by overpotential factors and ohmic resis- usually in contact with a solid surface, which attains the
tance (‘joule heating’). The former effect is small and same temperature as the battery and then ceases to be an
gives rise to heat generation during charging and cor- effective heat sink. The upper surface plays little part in
responding cooling on discharging. By contrast, joule heat exchange; the lid has no direct contact with the
heating occurs during both charging and discharging. electrolyte, and the intermediate layer of gas, which has
Proper heat management will ensure that the battery low thermal conductivity, hinders heat exchange.
temperature does not exceed a safe level and will The quantity of heat per unit area (W m2) that can
maintain all the cells within as small a range of tem- be conducted through the battery wall per unit time is
peratures as possible. The penalty for allowing the de- given by:
velopment of temperature gradients is nonuniform
states-of-charge and states-of-health between cells, either dQ DT
¼l ½3
of which can result in premature failure. dt x
Overcharging causes greater temperature increases in
VRLA batteries than in flooded types; in the latter de- where l is the thermal conductivity (W m1 K1), x is
signs, much of the heat generated escapes with the gases the thickness of the medium, e.g., the container wall (m),
evolved during charging. Moreover, the heat that arises and DT is the temperature difference across the battery
from the internal oxygen cycle in VRLA batteries wall (K). For plastic materials, l is of the order of
(reaction [V]) can be substantial, especially in aged bat- 0.2 W m1 K1. Thus, for example, the heat conduction
teries where separator dry-out allows oxygen recombin- through a container wall of thickness 3 mm is
ation to proceed at a high rate. Thus, closer attention has 67 W m2 K1.
to be paid to the generation and management of heat in The thermal conductivity of the battery electrolyte
VRLA batteries than in flooded counterparts. solution is higher than that of plastic, and that of lead is
The rate of change in temperature, dT/dt (K s1), of a higher again. Accordingly, the internal heat flux is fast
battery during charging or discharging is given by: compared with that through the container wall, mainly
due to the thermal conductivity of the electrodes, and the
temperature measured at the side wall usually represents
dQ g dQ d
a good approximation of the average cell temperature.
dT dt dt
¼ ½1 This approximation does not hold, however, at high rates
dt Cb
of charge.
where dQg/dt is the heat generated per unit time (J s1 or The quantity of the heat lost per unit area (W m2)
W), dQd/dt the heat dissipated per unit time (J s1 or W), per unit time by the radiation process is governed by the
Stefan–Boltzmann law: and [6], i.e.,
dQ dQd
¼ e s T4 ½4 ¼ 7210 W m2 K1 ½8
dt dt
where e is the Stefan–Boltzmann constant
(5.67 108 W m2 K4), s is the emissivity of the ma- Clearly, the combined processes of radiation and free
terial with respect to an ideal emitter (B0.95 for plastic convection are inadequate to remove all of the heat that
materials is normally used for battery containers), and T is conducted through the battery container (e.g.,
is the absolute temperature (K). For comparatively small 67 W m2 K1 for the example given above). Far greater
differences in temperature between the battery and the rates of heat removal can be achieved by means of forced
environment, the heat dissipated for each unit tempera- flow of liquid coolants over the outer surface of the
ture difference (K) is: battery.
dQ
¼ 526 W m2 K1 ½5
dt The Challenges Ahead
The changes made to the construction of the battery in

For small differences in temperature between the
the move to the valve-regulated design (summarized in
battery and the environment, and a minimum spacing of
Figure 8) have brought new challenges for battery sci-
about 1 cm between facing walls, the rate of removal of
entists and technologists in terms of overcoming the
heat from the battery wall by free convection in air for
various life-limiting mechanisms of the lead–acid battery.
each unit temperature difference (K) is:
The reward for a complete resolution of these issues will
dQ be a battery that requires no maintenance, presents no
¼ 224 W m2 K1 ½6 threat of acid spill, can be deployed with a minimal
dt
footprint, and can deliver high-rate performance com-
For a free-standing battery, the total dissipation of heat is bined with higher specific energy.
given by: There are clear signs that the demands placed on
leadacid batteries, in all existing and prospective ap-
dQd dQ dQ
¼ ðradiationÞ þ ðconductionÞ ½7 plications, are about to undergo a dramatic change. The
dt dt dt
rapidly expanding use of electronics within automobiles,
with the second factor limited by the rate of removal for example, will require batteries with higher power,
by air convection. Thus, the total heat dissipation for good ability to withstand extensive periods of operation
each unit temperature difference is the sum of eqns [5] at a PSoC, and long service life. The same qualities will
+ − One-way valve*
Plate-group pressure Plate-group pressure

(‘compression’) (‘compression’)
Pb–Ca–Sn grid* Pb–Ca grid*
Electrolyte immobilized
in gel or AGM separator*
Figure 8 Schematic of section through a valve-regulated lead–acid (VRLA) cell. Components modified in the change from the flooded
design are denoted by asterisks AGM, absorptive glass mat..
Table 1 New demands imposed on valve-regulated lead– Table 2 Possible configurations of electrical systems for
acid (VRLA) battery performance by present and future markets new-generation vehicles
Application Battery requirements 1. 12 V for stop start (and regenerative braking)
2. High-voltage power-assist hybrid
Automobiles PSoC duty, 1–2 kWh, 20 kW
3. Hybrid with electric range at full power (‘plug-in’ hybrid)
5000 kWh throughput/life
Hybrid electric PSoC duty, 13 kWh, 30 kW
vehicles 600 W kg1
5000 kWh throughput per kWh of view that is likely to prompt a further wave of develop-
capacity
ment of the system.
Electric vehicles 40 Wh kg1 It is now expected that the familiar 12 V battery/14 V
Fast charge alternator system in automobiles will, progressively, be
1000 deep-discharge cycles supplanted by alternative electrical configurations. The
Telecommunications Reliable float life of 10 years at all motivation for this change springs from the pressure for
systems foreseeable operating temperatures reduced vehicle emissions – which relates directly to an
Remote-area power PSoC duty increase in fuel economy. In California, for example, well
supplies Reliable life of 10 years over half of the atmospheric pollution emanates from the
PSOC, partial state-of-charge. road transportation sector, and the need to find practical
ways to abate such pollution is mirrored in many other
regions of the world.
be expected from batteries used to power HEVs. Partial There is much debate over which of the possible
state-of-charge duty brings both an advantage and a electrical configurations for new-generation road vehicles
disadvantage compared with float and cycling duties. On will predominate. Three distinct options have been
the credit side, it has been found that VRLA batteries proposed, as listed in Table 2. Configurations 2 and 3
operated under PSoC regimes at modest rates of charge make use of both electric and internal combustion engine
and discharge enjoy a significant increase in lifetime (ICE) propulsion; these vehicles are generically termed
storage capability (i.e., an increase in the total amount of ‘hybrid electric vehicles’, or more briefly ‘HEVs’.
energy that can be stored and delivered during the life of At present, it would appear that there is no un-
the battery) compared with regular cycling. On the debit equivocal classification of each of the various types of
side, at the higher chargedischarge rates required for new-generation vehicle. The options given in Table 2
HEV duties, VRLA batteries (still in a PSoC mode) range from the dual 12 V battery systems to a plug-in
suffer from rapid and irreversible formation of lead sul- hybrid, which would provide the vehicle with a sub-
fate on the negative plates that curtails operating life. stantial range of electric-only drive. The intermediate
Thus, significant modifications in VRLA design will be sector appears to be already established, namely, high-
required for new-generation transportation applications voltage power-assist vehicles. Following the tentative
(see the section entitled ‘Controlling Secondary Re- introduction of such HEVs to the marketplace in late
actions during High-Rate Charge’, v.i.). Likewise, con- 1999, cumulative worldwide sales are now approaching
sumers are insisting on improvements in VRLA batteries the two million mark. All of these vehicles employ
employed for stationary energy storage in tele- nickelmetal-hydride batteries because, when the ve-
communications and RAPS systems. hicles were designed, it was thought that lead–acid
A summary of the new demands that are being placed products were unable to cope with the required duty
on medium- and large-scale VRLA batteries in all their cycle for an adequate life.
applications is given in Table 1. The necessary transition Vehicles that do not fall within the hybrid classifi-
from the flooded to the valve-regulated version must also cation will retain a conventional ICE architecture, but
be accompanied by a step-function advance in performance. will require batteries (12 V or higher voltage) that are
capable of accepting and delivering much greater power
Future Automotive Electrical Systems than is possible with standard automotive batteries in
order to meet the demands of vehicle design engineers.
The development of the VRLA battery from its flooded The time required for this change to be completed is
electrolyte precursor has involved considerable research unclear.
and technological effort – in managing the oxygen cycle,
in grid alloy and separator designs, and in optimization of
The Challenge of High-Rate Partial
charge strategies. As a result of this work, VRLA batteries
State-of-Charge Duty
are now well-established, reliable devices for the storage
of electrical energy in stationary applications. At the start Obviously, a battery can only be acceptable in any given
of the twenty-first century, however, a new challenge is in application if it is capable of delivering an adequate
Table 3 Typical duty and performance characteristics for valve-regulated leadacid (VRLA) batteries in different categories of
present and new-generation vehicles
Parameter Application
SLI, 12 V Electric vehicle Hybrid electric vehicle
Duty High-rate start Deep cycle High-rate PSoC
State of charge 85–90% 20–100% 6070%a
Maximum normal dischargeb 10C1 4C1 15C1
Maximum normal chargeb 0.5C1 0.5C1 8C1
Failure modes Corrosion, shedding Premature capacity loss Undercharge and sulfation of
negative plates
a
This is the normal operating range for the Honda Insight hybrid electric vechicle (HEV), but the battery management system of this vehicle will allow
a wider range of operation between 30% and 80% state of charge if so required by the driving pattern.
b
In multiples of 1 h rate.
SLI, starting, lighting, and ignition.
service life. As indicated in Table 3, the life-limiting Operation over a reduced range of depth of discharge, as
processes (failure modes) for the conventional starting, required by the new automobile protocols, might be ex-
lighting, and ignition (SLI ) battery (first a 6 V unit, then pected to lead to a longer cycle life than in the case of the
a 12 V unit) are well known, and the reliability of the deep-discharge duty employed for EVs (see Figure 10).
battery has been progressively improved to keep pace This advantage is more than offset, however, by a chal-
with advancements in automobile design over the better lenge to the charge efficiency of the negative plate.
part of a century. Normally, this charge efficiency is high until charging is
When attention focused on pure EVs at the beginning almost complete, so that operation in a PSoC mode
of the 1990s, it was clear that the VRLA battery could not ought to be favorable. It appears, however, that at the
deliver the desired service life. Within a decade, however, very high rates of charge experienced in HEVs (see
the industry, supported by the extensive research pro- Table 3), the charge efficiency is diminished, even when
gram mounted by the Advanced Lead–Acid Battery the plate is not at a full state of charge.
Consortium (ALABC), had made the necessary invest- Lacking a construction that is purpose designed for
ment in research and development to achieve a 10-fold HRPSoC duty, VRLA batteries typically lose at least
increase in deep-cycle life. The VRLA battery was then 50% of their initial capacity after operating in a simu-
able to compete with alternative chemistries (e.g., nickel– lated HEV mode for an equivalent service life of around
cadmium, nickel–metal-hydride, and lithium-ion) as an 32 000 km, as demonstrated by the example given in
acceptable power source for EVs. Figure 11. This loss of capacity has been attributed to a
In all three of the electrical systems that have been progressive buildup of lead sulfate on the negative plate,
proposed for new-generation vehicles (Table 2), the especially at the bottom. Since the battery is not brought
batteries will be required to operate in a manner that is to a full state of charge in PSoC duty (see, e.g.,
quite unlike the duty experienced by present 12 V Figure 9(b)), there is no routine method available to
automotive types (i.e., ‘SLI’ types). In general, the battery remove this lead sulfate.
will have to supply significant amounts of electrical en-
ergy for onboard electrical functions and, in several of
Mechanism of Lead Sulfate Accumulation
the systems, will have to accommodate charge returned
during High-Rate Partial-State-of-Charge Duty
via ‘regenerative braking’ as part of the scheme to save
fuel. Under such duty, the battery will have to operate Recent investigations conducted by the Commonwealth
continuously at a PSoC and accept charge at extremely Scientific and Industrial Research Organisation (CSIRO)
high rates. In addition, high-rate discharge is necessary in Australia have provided the following explanation for
for engine cranking and power assist. Overall, the battery the mechanism of lead sulfate accumulation in negative
is said to undergo high-rate PSoC duty, or more briefly plates during HRPSoC duty.
‘HRPSoC duty’. An example of such duty is shown in The discharge and charge processes at the negative
Figure 9. The anticipated marked shift in the function of plate can be expressed by the reactions [VIII]–[XI]
the battery in new-generation vehicles, together with the shown in Figure 12. During discharge, the conversion of
limitations to its life performance, is summarized in sponge lead to lead sulfate proceeds via two steps. First,
Table 3. the sponge lead at the negative plate reacts with HSO4
Clearly, the lead–acid community now faces a change to form Pb2þ, SO4 2 , and Hþ, i.e., the so-called
in the market that promises to be more far reaching than ‘dissolution process’ (reaction [VIII]). Then, the Pb2þ
was the case with the introduction of modern EVs. combines with SO4 2 to form lead(II) sulfate, i.e., the
100
80
60
40
20
Current (A) 0
0
0 500 1000 1500 2000
−20
−40
−60
−80
−100
(a) Time (s)
80
Equivalent state of charge (%)
70
60
50
40
30
0 500 1000 1500 2000

(b) Time (s)
Figure 9 (a) Composite test cycle compiled from current measurements on the battery in a Honda Insight hybrid electric vehicle (HEV)
running round the Millbrook test track in the United Kingdom. Arduous driving for 1500 s followed by sequence of regenerative braking
events; discharges reach around 15C1 and charges 8C1. (b) Capacity removed and restored during test cycle in (a). Short-term changes
in state of charge involve B4% of total capacity; overall range covered is near 50% of total capacity (removed in 25 min, i.e., at a rate of
1.2C1, and restored in 12.5 min, i.e., at a rate of 2.4C1).
so-called ‘deposition process’ or ‘precipitation process’ value at 10 wt% sulfuric acid (1.07 rel. dens. (relative
(reaction [IX]). The first step is an electrochemical re- density)), and then decreases rapidly with further increase
action and thus involves electron transfer. Such transfer of in concentration (Figure 13). Thus, the Pb2þ will pre-
electrons takes place only on the conductive sites, i.e., on cipitate as lead sulfate at concentrations above the solu-
fresh lead. The rate of the electrochemical reaction is bility curve. Clearly, for a given concentration of Pb2þ
therefore dependent not only on the diffusion of HSO4 above B1 mg L1, the deposition (or precipitation) of
species, but also on the effective surface area of the sponge Pb2þ to lead sulfate will be faster at plate locations that
lead. On the other hand, the second step is a chemical experience high concentrations of acid.
reaction and proceeds at a rate that is acid dependent. The During the initial stages of the discharge of a fully-
solubility of lead sulfate does not increase with increase in charged negative plate, electron transfer can take place at
sulfuric acid concentration. Rather, it reaches a maximum any location because the entire plate is conductive.
1 000 000
100 000
Number of cycles
10 000
1000
100
0 10 20 30 40 50 60 70 80 90
Depth of discharge (%)
Figure 10 Variation of cycle life with depth of discharge of a spiral-wound valve-regulated lead–acid (VRLA) battery. Courtesy of Exide
Technologies.
18
16
14
12
Capacity (Ah)
10
0
0 8000 16 000 24 000 32 000 40 000 48 000
Equivalent km of vehicle travel
Figure 11 Change in capacity of standard valve-regulated lead–acid (VRLA) battery under simulated hybrid electric vehicle (HEV)
duty. Charge and discharge limited to 2C1.
Accordingly, the discharge process (both dissolution and Under low-rate discharge (i.e., o0.4C1), the dis-
deposition steps) occurs both on the surfaces and in the solution rate of Pb2þ from each lead crystal is slow and,
interior of the plate. Nevertheless, the reaction in the therefore, the accompanying consumption of HSO4 in
interior of the plate will soon slow down and/or stop, the interior of the plate is likely to be counterbalanced by
while that at the surfaces of the plate will continue. This the diffusion of HSO4 from the bulk of the electrolyte.
is because less acid is now available in the interior. Furthermore, the subsequent deposition of Pb2þ to lea-
The depth to which lead sulfate penetrates is d(II) sulfate (reaction [IX]) also occurs slowly due to the
dependent on the rate of discharge, as well as on the low supersaturation of Pb2þ in the vicinity of each parent
density and surface area of the plate. Paste density is the lead crystal. (Note that the deposition rate of lead(II)
key factor in providing the macropores that are necessary sulfate is proportional to the degree of supersaturation of
for the transport of solution and ionic species to and from Pb2þ in the sulfuric acid solution, i.e., the higher the
the reaction sites within the interior of the plate, whereas supersaturation, the faster is the deposition rate.) Since
surface area provides sites for the current-generating the rate of deposition is slow, newly formed lead(II)
electrochemical reaction. For the same paste density and sulfate tends to precipitate preferentially on the already-
surface area, the extent to which lead sulfate can pene- deposited lead(II) sulfate crystals, i.e., growth rate >
trate is determined by the discharge rate. nucleation rate. Consequently, the deposited lead sulfate
• Discharge process
Dissolution
Pb + HSO4− − 2e − Pb2+ + SO42− + H+ [VIII]
Deposition
PbSO4 [IX]
• Charge process
Dissolution
PbSO4 Pb2+ + SO42− + 2e− + H+ [X]
Pb + HSO4− [XI]
Deposition
Figure 12 Discharge and charge reactions at the negative plate of a lead–acid cell.
compact layer of tiny lead sulfate crystals will develop on

7
the surface of the plate. This will reduce the effective
surface area for electron transfer and will also hinder the
6 diffusion of HSO4 into the interior of the plate
Solubility of PbSO4 (mg L−1)
(Figure 14(b)). Under such conditions, the discharge

5 reaction cannot proceed into the interior of the plate, but
Temperature 25 °C
stops at the surface and at the walls of the pores.
4
During charging, the conversion of lead sulfate to
3 sponge lead also proceeds via two reactions, namely,
dissolution and deposition. Nevertheless, the nature of
2 each of these reactions differs from that of the corre-
Temperature 0 °C sponding discharge reactions. Dissolution is now the
1
chemical reaction, whereas the subsequent deposition is
0
the electrochemical reaction. The lead sulfate first dis-
1.00 1.05 1.10 1.15 1.20 1.25 1.30 sociates to Pb2þ and SO4 2 ions, i.e., reaction [X], Fig-
Electrolyte density (g cm−3) ure 12. The Pb2þ then receives two electrons and
reduces to lead. i.e., reaction [XI], Figure 12. Simul-
Figure 13 Solubility of lead sulfate in sulfuric acid as function of
acid concentration.
taneously, SO4 2 combines with Hþ to form HSO4 . The
electrons flow to the active sites in the negative plate
material via the grid members because the electrical
will continue to grow to various sizes of discontinuous resistance of the grid metal is much smaller than that of
crystals, both on the surface and in the interior of the the discharged material. In addition to the reduction of
negative plate. This form of lead sulfate is particularly Pb2þ to lead, there is the competing reaction of hydrogen
desirable on the surface of the plate, as it provides an evolution. Usually, hydrogen evolution only takes place
open structure that facilitates the ingress of HSO4 ions. near the end of charging for the following reasons: (1)
Therefore, the discharge process can proceed deep into most of the lead(II) sulfate has been converted to lead
the interior of the plate. Accordingly, the lead sulfate and, correspondingly, the sulfuric acid concentration, i.e.,
develops evenly throughout the cross-section of the the Hþ concentration, has increased and (2) further
negative plate, as shown schematically in Figure 14(a). dissolution of lead(II) sulfate to Pb2þ and SO4 2 is slow.
The formation of lead sulfate on the negative plate is Nevertheless, hydrogen can also be involved during the
quite different under high-rate discharge, e.g., under early stages of the charging process, if the dissolution of
cranking current (B18C1) conditions. The electro- lead(II) sulfate is hindered (v.i.).
chemical reaction, i.e., reaction [VIII], Figure 12, now Having described the basic chemistry of the dis-
proceeds so rapidly that the diffusion rate of HSO4 charge–charge process, it is now appropriate to consider
cannot catch up with the consumption rate. Con- charging of the negative plate after it has been deeply
sequently, lead sulfate forms mainly on the surface of the discharged at a low rate. As discussed above, lead sulfate
plate. Moreover, high-rate discharge generates a very is formed throughout the entire cross-section of the plate
high supersaturation of Pb2þ in the vicinity of each and the relative density of the acid after discharge is low
parent lead crystal. The lead sulfate will therefore pre- because of the high utilization of the active material. The
cipitate rapidly on any available surface, irrespective of dissolution of lead(II) sulfate to form Pb2þ and SO4 2
whether this be sponge lead or already-deposited lead increases at low acid concentrations (see Figure 13).
sulfate, i.e., nucleation rate > growth rate. Thus, a Thus, the subsequent reduction of Pb2þ to sponge lead
Lead sulfate
Grid Grid
HSO4− HSO4− HSO4−
Grid Grid
Sponge lead
(a) (b)
Figure 14 Schematic representation of the distribution of lead sulfate in a negative plate subjected to (a) low-rate discharge or
(b) high-rate discharge.
can take place smoothly before the evolution of hydro- Grid

gen. With an overcharge of B10%, the plate can be
H2 H2
brought to a fully-charged state without any difficulty.
This is also true when the plate is subjected to low-rate
PSoC cycling with equal amounts of charge input and 2e −
charge output. In such duty, the state of charge of the Lead sulfate
negative plate decreases with cycling, but can be brought
to 100% after the application of an equalization charge. H2 H2
By contrast, charging of the negative plate after deep
discharge at a high rate is difficult. Since high-rate dis-
2e −
charge cannot proceed into the interior of the plate, but
stops at the surface, the utilization of the active material
is low. Consequently, the relative density of the acid after
discharge is still at a high level and this decreases the
dissolution of lead(II) sulfate (see Figure 13). The lower
concentration of Pb2þ will then impede the subsequent Negative active-material
electrochemical reaction and, during the early stages of Figure 15 Schematic representation of the charging process of
charging, will cause the negative-plate potential to be- a negative plate after high-rate discharge.
come more negative to such an extent that hydrogen can
start to evolve. Furthermore, as mentioned above, the
electrons flow from the grid members toward the surfaces simulated HRPSoC (HEV) duty is presented in
of the plate. These electrons will reduce some hydrogen Figure 16. The data also confirm that, at this stage, the
ions to hydrogen gas before reaching the lead sulfate top-of-charge potential for the plate exceeds that at
layer, as shown schematically in Figure 15. Thus, com- which hydrogen is evolved. It should be noted that in this
plete conversion of lead sulfate at the plate surface test both charge and discharge are conducted at the 2C1
cannot be achieved, even with an overcharge of 10%, rate. In actual HEV duty, however, the rates will be much
because of the combined effects of the early evolution of higher and the resulting effect on battery performance
hydrogen and the oxygen recombination reaction [V]. In may be more serious.
addition, the overcharge factor will increase with cycling In summary, the lead–acid battery developed over
because progressive water loss will dry out the separator decades for SLI duty must be modified significantly in
and thereby increase the amount of oxygen reaching order to provide the power capability demanded by new-
plate that, in turn, will enhance of the level of oxygen generation vehicles, and to be able to sustain this function
recombination. Thus, lead sulfate will accumulate on the for an adequate service life. The key objective is to
surface of the negative plate and, eventually, the battery overcome the processes that give rise to the accumulation
will be unable to provide sufficient power to meet the of sulfate on the negative plate during HRPSoC duty. In
greater demands of new-generation vehicles. effect, this requires controlling the secondary reactions of
Experimental verification of the concentration of lead hydrogen evolution and oxygen recombination through
sulfate near the surfaces of a negative plate under modifications to the design of the negative plate, as well
Lead sulfate
1500 μm
Cross-section of
negative plate Grid
0
Lead sulfate
0 3400 μm
1735 cycles Electron probe microanalysis showing
buildup of lead sulfate (white regions)
on surfaces of negative plate
–1.6
Negative plate potential (V)
(vs Hg|Hg2SO4)
–1.4
–1.2
Charge
H2 evolution
–1.0
–0.8
0 2000 4000 6000 8000
HEV cycles
Figure 16 Buildup of lead sulfate and concomitant evolution of hydrogen in negative plates after 1735 cycles of simulated high-rate
partial-state-of-charge (HRPSoC) duty (battery initially discharged at C1 rate to 50% state of charge; duty cycle: charge and discharge at
2C1 ¼ 3% state of charge). HEV, hybrid electric vehicle.
as to the morphology and composition of its active ma- stoichiometry of the cell reaction can influence gas
terial. The establishment of a mathematical model for the evolution – either individually or in combination when
VRLA battery operating in HRPSoC regimes would be a subtle synergistic effects can occur. For example, early
valuable asset in predicting performance characteristics indications show that zinc has a strong ability to suppress
and in helping with detailed design adjustments. In for- hydrogen gassing at the negative plate, and that a com-
mulating a sound model of the processes taking place in bination of antimony and iron can suppress the oxygen-
HRPSoC duty, it will be important to establish experi- gassing effect of some transition metals at the positive
mentally how the current at high-rate charging splits plate.
between the main charging reaction and the secondary
(parasitic) reactions. Separator design
The separator plays a crucial role in VRLA cells. Pro-
Controlling Secondary Reactions during vision of a separator with the appropriate microstructure
High-Rate Charge can constrain the rate of oxygen arrival at the negative
The following lines of ongoing research show consider- plate and thus restrict the suppression of the plate po-
able promise for extending the life of VRLA batteries in tential caused by the oxygen recombination reaction.
HRPSoC service.
Carbon inventory
Trace element control The active material on the positive plate generally pres-
Small amounts of trace elements can cause major changes ents a surface area that is significantly greater than that of
in the overpotentials at positive and negative plates, and the negative plate. This manifests itself as a difference in
thus can alter the rates at which the gassing reactions the flux of electrons to the reaction sites on the two
proceed. A thorough study undertaken by CSIRO has plates. If the surface available at the negative plate can be
found that elements not required by the fundamental extended, then the influence of the unequal dependence
on diffusion in negative and positive plates can be increases the heat generated in the cell. Nonuniform
reduced. distribution of current can be ameliorated by increasing
Interestingly, an increase in the quantity of carbon in the electrical conductivity of the grid.
the negative active material can extend battery life under Research conducted at CSIRO has demonstrated that
HEV duty to a significant extent. Moreover, early results the addition of a second current take-off tab, sym-
(again from CSIRO) indicated that the form of the se- metrically placed opposite the first, will bring consider-
lected carbon is of critical importance. Graphite particles, able benefit in terms of improved performance from
evidently with a plate-like form well suited to inter- VRLA cells subjected to HRPSoC duty. The current
particle contact, produce far better results than carbon passing through each tab is half of that which would pass
black when employed in the same weight fraction. Else- through a single take-off and the extra connection also
where, it has been found that acicular conducting par- acts as an additional heat sink. Both these features safe-
ticles are far more effective in increasing the conductivity guard against the development of high operating tem-
of a resistive medium than equi-axed powders, by a factor peratures within cells and result in more uniform
of up to 1000, as dictated by the aspect ratio of the utilization of the plate active-materials. These benefits, in
particles. The influence of plate-shaped particles was not turn, translate to improved power capability and longer
reported but, by analogy with the case of acicular ma- cycle life. For example, in an initial demonstration under
terials, it would seem that any departure from the simulated HEV duty at ambient temperature (24 1C), a
spherical shape would be beneficial. ‘dual-tab’ battery provided 8800 cycles and remained at a
steady temperature of 3872 1C, whereas a commercial
(single-tab) battery sustained only 6900 cycles and
Grid design for high-rate partial-state-of-charge reached a temperature of 65 1C (see Figure 17).
duty The patented dual-tab concept has been applied
At the extraordinarily high power levels demanded in effectively to the spiral-wound design of VRLA (see
HRPSoC duty (see Table 3), consideration must also be Figure 1(d)) in a project funded jointly by the UK
given to optimizing the current collection function of the government and the ALABC to develop HEV batteries.
grid. It is well established that the performance of lead– The design of the cell used in this demonstration is
acid batteries can be adversely affected by a nonuniform shown in Figure 18(a), where the positive and negative
distribution of current over the plates as a result of ohmic connections can be seen projecting from each end of the
losses. This effect becomes more pronounced with in- unit. The performance of this cell was compared with
crease in the rate of charge or discharge and with in- that of the conventional, single-tab cell from which it was
crease in the size of the plate. At the highest rates, the derived. Each cell design was deployed in an 18 cell, 36 V
voltage drop down the grid causes an inhomogeneous battery (Figure 18(b) shows the dual-tab version), and
utilization of the active material (that near the current the resulting batteries were subjected to the simulated
take-off ‘tab’ is worked harder than that further away) and HEV cycle shown in Figure 9(a). During this test, the
Dual-tab battery
Commercial (single-tab) battery
End-of-discharge voltage (EoDV) (V)
14 100
External temperature (°C)
12 EoDV
80
10 EoDV
8
60
6 Temperature
4 40
2 Temperature
0 20
0 2000 4000 6000 8000 10 000
HEV cycles
Figure 17 Performance of dual-tab and commercial (single-tab) batteries under simulated hybrid electric vehicle (HEV) cycling
(charge and discharge at 2C1).
CS
I
RO
(b)
(a)
(c)
36 V battery
Figure 18 (a) Spiral-wound cell with dual tabs. (b) 36 V battery of dual-tab cells under test. (c) Dual-tab battery system installed in
Honda Insight.
battery state of charge was run down to 30% from an In early 2004, a Honda Insight retrofitted with a pack
initial value of 80%, and then returned to 80%. (Note, of these batteries and a purpose-built management sys-
this is an accelerated schedule and is more demanding tem (Figure 18(c)) underwent successful road trials in
than that expected in HEV duty, i.e., 40–60% state of the UK.
charge (see Table 2).) A battery of conventional cells was The above remarkable demonstrations result from the
unable to complete even one pass through the cycle fact that the plate has been designed to avoid hetero-
(Figure 19(a)). By contrast, the dual-tab counterpart geneous current distribution. Such research has provided
completed the cycle with less voltage fluctuation strong evidence that a radical redesign of VRLA batteries
(Figure 19(b)) and, moreover, went on to sustain 65 is necessary for the technology to make a significant
consecutive cycles before failure (Figure 19(c)). When a contribution to the growing HEV share of the transpor-
36 V dual-tab battery was subjected to the same de- tation sector. Provided that the remarkable benefits as-
manding procedure, but with conditioning charging after sociated with the dual-tab design in HRPSoC duty can
every 10 cycles, 291 of these very tough cycles were be attributed to a reduction in ohmic losses, it can then
completed before the battery failed to deliver full power. be anticipated that a similar performance improvement
50
40
30
20 Single tab
Voltage (V)
(a)
50
40
30
Dual tab
20
500 1000 1500 2000
(b) Time (s)
55.0
50.0
45.0
40.0
Voltage (V)
35.0
30.0
25.0
20.0
15.0
0 40 000 80 000 120 000 160 000

(c) Time (s)
Figure 19 Tests based on hybrid electric vehicle (HEV) battery protocol shown in Figure 9(a). Test starts with battery at 80% state of
charge and 40 1C. (a) Conventional (single-tab) battery fails to complete one test. (b) Dual-tab battery completes the test and exhibits a
more stable voltage. (c) Voltage vs time for dual-tab battery through 65 simulated HEV cycles – equivalent to continuous driving for 44 h
without rest or conditioning.
could be achieved by a number of other approaches to capacity can be supplied by using only the acid from
grid design. These include: (1) altering the aspect ratio of within the plate (in pores, and perhaps supported by inert
the grid so as to minimize the distance of the tab from the porous media, which act as local reservoirs). High rates
remote corners of the plate (i.e., avoid tall, narrow plates), can be sustained for small ranges of state of charge be-
(2) increasing the thickness of the appropriate grid wires cause the necessary diffusion path lengths are short.
to reduce the maximum resistance down (across) the Evidence has recently emerged to suggest that such high-
grid, and (3) using copper-cored wires of greater elec- rate capacity could be supplied more readily by thick
trical conductivity (feasible in the negative plate). plates than by thin ones. This new study has shown that,
at discharge rates between approximately C5 and 6C1, the
The role of plate thickness capacities available from batteries with thick plates are
In the past, high power has usually been required over a greater than those available from batteries with thin
wide range of depth of discharge so that very thin plates plates (Figure 20). Evidently, thicker plates, which con-
(high overall surface area) have been used. In HEV duty, tain more acid, are able to support high-rate discharges
however, those charges and discharges that are demanded by using only acid within the pores of the active material.
at the highest rates only draw upon a small fraction of By avoiding the need to draw on acid diffusing from
the battery’s capacity (see Figures 9(a) and 9(b)). This outside, the plate appears to favor high-rate discharge.
2.0
1.9
Log (capacity (Ah))

1.8
1.7
Thin plates
1.6
Thick plates
1.5
1.4
0.5 1.0 1.5 2.0 2.5 3.0
Log (current (A))
Figure 20 Double logarithmic (Peukert) plot of capacities of battery with thin plates (positive 1.7 mm, negative 1.35 mm, 30% of
available acid contained within plates) and battery with thick plates (positive 4.0 mm, negative 2.2 mm, 50% of available acid contained
within plates) over a range of discharge currents. Both batteries have a nominal capacity of 70 Ah.
As the lead–acid battery industry comes to grips with electrode material with a large specific surface area (i.e.,
the novel circumstances of HRPSoC duty, there appears carbon) is combined with a ‘battery-like’ (Faradaic) ma-
to be scope for a fresh approach to plate design, perhaps terial that can be reversibly oxidized and reduced over a
supported by the provision of more porosity within the wide potential range. The energy is stored both by ionic
plates to accommodate more ‘local’ acid. capacitance and by surface (and near-surface) redox
processes that occur during charge and discharge. The
Incorporation of a capacitive function latter are electrochemical reactions (i.e., Faradaic pro-
A quite different approach to overcoming the problems cesses) in which surface ions are reduced and oxidized.
of HRPSoC duty has been taken by CSIRO through the This enhances the amount of stored energy; the capaci-
invention and further development of a radical new de- tance is twice that of the symmetric counterpart (see
sign of VRLA battery in which the negative plate is Figures 21(a) and 21(b)). Moreover, because the ions are
protected from the deleterious effects of high-rate charge confined to surface layers, the redox reactions are rapid
and discharge by sharing the current with an integrated and are fully reversible many thousands of times and this
supercapacitor. makes for a long cycle life.
Supercapacitors differ from conventional electrostatic The CSIRO valve-regulated UltraBatteryTM combines
and electrolytic capacitors in that they store electrostatic a VRLA battery with an asymmetric supercapacitor into a
charge in the form of ions, rather than electrons, on the single unit without the need for extra electronic control.
surfaces of materials with high specific areas (m2 g1) (see The hybrid structure is shown schematically in
Figure 21(a)). In the ‘symmetric’ design, the electrodes Figure 21(c). A VRLA cell, which has one lead dioxide
are usually prepared as compacts of finely divided, por- positive plate and one sponge lead negative plate, is
ous carbon, which provide a much greater charge density combined with an asymmetric supercapacitor, which is
than is possible with nonporous, planar electrodes. composed of one lead dioxide positive plate and one
Supercapacitors can store vastly more energy than con- carbon-based negative plate (i.e., a capacitor electrode).
ventional capacitors and much of the storage capacity is Since the positive plates in the VRLA cell and the
due to the charging and discharging of the electrical asymmetric supercapacitor have the same composition,
double-layers that are formed at the electrode|electro- they can be integrated into one unit by connecting in-
lyte interfaces. The voltage is lower for a conventional ternally the capacitor electrode and the VRLA negative-
capacitor, whereas the time for charge, as well as that for plate in parallel. Both these electrodes now share the same
discharge, is longer because ions move and reorientate positive plate. With this design, the total discharge or
more slowly than electrons. In these respects, the charge current of the combined negative plate is com-
supercapacitor begins to take on some of the character- posed of two components, namely, the capacitor current
istics of a battery, although no electrochemical reactions and the VRLA negative plate current. Accordingly, the
are involved in the charge and the discharge processes. capacitor electrode can now act as a buffer to share cur-
The ‘asymmetric’ design of supercapacitor moves one rent with the negative plate and thus prevent it from being
step closer to a battery (see Figure 21(b)). Here, an discharged and charged at high rates. Prototype batteries,
Symmetric Asymmetric
Charge/discharge by
P Charge/discharge by reversible
P
o o reversible reduction/oxidation P adsorption/desorption
r r o of ions
+ o o − + r −
u u o 1/C T = 1/C1 + 1/C2
s s u Since C1 >> C2
Battery electrode s C T = C2
Both electrodes charged/discharged
by reversible adsorption/desorption of
ions
1/C T = 1/C1 + 1/C2 Asymmetric design has twice the capacitance
C1 C2 of symmetric design
(a) (b)
Structure of UltraBatteryTM
+ − Separator + −
PbO2
Carbon
PbO2 Pb electrode
Lead−acid cell Hybrid supercapacitor

+ i −
i1 Pb
i i2
UltraBattery™ Carbon electrode
PbO2
(c) (d)
Figure 21 Schematic representation of (a) symmetric supercapacitor, (b) asymmetric supercapacitor, (c) UltraBatteryTM, and
(d) prototype UltraBatteryTM.
constructed by the Furukawa Battery Company in Japan, It remains to be seen whether the benefits that can be
were fitted to a Honda Insight and successfully completed a gleaned from these design adjustments, when employed
160 000 km test at the Milbrook Proving Ground in the together, will prove to be sufficient to provide a satis-
United Kingdom. The battery pack demonstrated very factory life for VRLA batteries in new-generation road
good acceptance of the charge from regenerative braking vehicles. If this is indeed achieved, then the rewards,
and remained in an excellent condition throughout. Pilot- particularly in terms of reduced battery costs for such
scale production of the UltraBatteryTM is now in progress vehicles, will be enormous.
in Japan, the USA, and Europe.
Concluding Remarks
Summary
In batteries for HEVs, the cells in the strings will have to For over a hundred years from its conception, the lead–
be matched better than in the past, and also assembled acid cell was normally operated with unrestricted access
and managed in such a way that they will not tend to between the surface of its electrolyte and the external
become unbalanced. atmosphere so that, during periods of overcharge,
All of the future vehicle concepts listed in Table 2 call hydrogen and oxygen were lost from the cell via elec-
upon increased electrical capacity and power compared trolysis. As a result, periodic additions of distilled water
with today’s conventional automobiles. The battery re- were necessary. Since about 1970, an alternative to the
quirements of these future vehicles will not be met by traditional ‘flooded’ cell has been available – one that
present lead–acid products. Adjustments to the grid design avoids the need for water maintenance. Moreover, acid is
and to the surface area and conductivity of the negative- immobilized in the new design and this endows the cell
plate material, as well as the deployment of elements with the additional advantages of being ‘spill-proof ’ and
capable of reducing the proclivity of the cell to evolve gas able to operate in any orientation (upright, on its side, or
(especially hydrogen) during charging, all show promise in even upside down).
advancing the capability of the VRLA battery to cope with The change to the so-called VRLA technology has
the rigorous duties that are envisaged. not, however, been accomplished without some difficulty.
Experience has demonstrated forcibly the fundamental e Stefan–Boltzmann constant

differences between the two systems, and the leadacid (5.67 10 8 Wm 2 K 4)
battery manufacturing industry has faced major chal- k thermal conductivity (Wm 1 K 1)
lenges in investing the VRLA version with a performance r emissivity
to match that of its flooded predecessor. Nevertheless, Abbreviations and Acronyms
research into understanding the electrochemistry, pro- AGM absorptive glass mat
ducing improved cell components and optimizing charge ALABC Advanced Lead–Acid Battery
strategies has resulted in VRLA batteries becoming well- Consortium
established and reliable devices. Operators now take CSIRO Commonwealth Scientific and
advantage of the particular properties of these batteries Industrial Research Organization
for the storage of electrical energy in a wide variety of EoDV end-of-discharge voltage
stationary applications. EV electric vehicle
Much of the recent advancement of VRLA technol- HEV hybrid electric vehicle
ogy has been achieved through a cooperative research HRPSoC high-rate partial-state-of-charge
effort under the auspices of the ALABC. The main effort ICE internal combustion engine
has been directed toward the development of VRLA ICEV internal-combustion-engined vehicle
battery systems for new-generation road transportation – PSoC partial state-of-charge
EVs and HEVs – that will reduce fuel consumption and RAPS remote-area power supply
lower emissions. The progress gained in this endeavor SLI starting, lighting, and ignition
will ultimately also benefit extremely important markets VRLA valve-regulated lead–acid
in telecommunications and RAPS.
Nomenclature
Symbols and Units See Also: Secondary Batteries – Lead–Acid Systems:
C heat capacity (J K 1); also used for Automotive Batteries: New Developments; Carbon
cell/battery capacity (Ah) Additives; Charging; Lead Alloys.
Cb heat capacity of the materials that
comprise the battery
Cp(i) specific heat of component i Further Reading
(J K 1 g 1)
Cx discharge rate (current) of a cell/ (2001) Key World Energy Statistics from the IEA. Paris: International
battery where C is the rated capacity Energy Agency.
Anderman M (2003) Proceedings of Third International Advanced
(Ah) and x is the hour rate Automotive Battery Conference, Section 1, Paper 1. Nice, France,
DO2 diffusion coefficient of oxygen 10–13 June.
Eo standard electrode potential (V) Bode H (1997) LeadAcid Batteries, p. 27. New York: John Wiley &
Sons, Inc.
I current (A) Cooper A (1998) ALABC Project ‘Rholab’, Reliable, Highly Optimized
Ic current at the positive electrode Lead–Acid Battery, Quarterly Reports 1 September 2000 to
consumed by grid corrosion December 2002. Research Triangle Park, NC. Advanced Lead–Acid
Battery Consortium.
I H2 current at the positive electrode Dell RM and Rand DAJ (2001) Understanding Batteries. Cambridge:
consumed by hydrogen evolution at The Royal Society of Chemistry.
the negative electrode Fauré CA (1881) Comptes rendus de l’Académie des sciences Paris
92: 951–953.
I O2 current at the positive electrode Hollenkamp AF, Baldsing WGA, Lau S, et al. (2002) ALABC Project
consumed by oxygen evolution N1.2, Overcoming Negative-Plate Capacity Loss in VRLA Batteries
mi mass of component i (g) Cycled Under Partial-State-of-Charge Duty, Final Report, July 2000
to June 2002. Research Triangle Park, NC: Advanced Lead–Acid
Q heat (J s 1 or W) Battery Consortium.
Qd heat dissipated Lam LT, Ceylan H, Haigh NP, et al. (2002) ALABC Project N3.1,
Qg heat generated Influence of Residual Elements on the Oxygen- and/or Hydrogen-
Gassing Rates of Lead–Acid Batteries, Final Report, July 2000 to
I O22red current at the negative electrode that June 2002. Research Triangle Park, NC: Advanced Lead–Acid
is consumed by oxygen reduction Battery Consortium.
t time Lam LT, Haigh NP, Phyland CG, and Rand DAJ (2005) High
Performance Energy Storage Devices. International Patent WO/
T temperature (K) 2005/027255.
Vo standard cell voltage Lam LT, Haigh NP, Phyland CG, et al. (1998) Proceedings of the
x thickness of wall of battery INTELEC ’98, pp. 452–460. San Francisco, CA.
Meissner E (1998) Brite/Euram Project BE7297, Task 1, Effect of
container (m) Electronically Conducting Additives to the Positive Active Material on
High-Rate Performance of Lead–Acid Batteries, Final Report, 1 Newnham RH, Baldsing WGA, Hollenkamp AF, et al. (2002) ALABC
January 1994 to 31 December 1997. Research Triangle Park, NC: Project C/N1.1, Advancement of Valve-Regulated Lead–Acid
Advanced Lead–Acid Battery Consortium. Battery Technology for Hybrid-Electric and Electric Vehicles, Final
Nann E, Wagner B, Toniazzo V, Lambert U, and Nelson RF (2002) Report, July 2000 to June 2002. Research Triangle Park, NC:
ALABC Project S1.2, Engineered Separators for Optimization of Advanced Lead–Acid Battery Consortium.
Processing and Performance in VRLA Batteries, Final Report, 1 June Planté G (1860) Comptes Rendus de l’Académie des Sciences Paris
2000 to 31 December 2002. Research Triangle Park, NC: Advanced 50: 640–642.
Lead–Acid Battery Consortium. Rand DAJ, Moseley PT, Garche J, and Parker CD (eds.) (2004) Valve-
Nelson RF (1990) Proceedings of the 4th International Lead–Acid Regulated Lead–Acid Batteries. Amsterdam: Elsevier.
Battery Seminar, pp. 3160. San Francisco, CA, USA, 25–27 April. Rand DAJ, Woods R, and Dell RM (1998) Batteries for Electric Vehicles,
Research Triangle Park, NC: ILZRO. p. 203. Taunton: Research Studies Press Ltd.
Nelson RF (1999) Proceedings of the 4th International Lead–Acid
Battery Seminar, pp. 31–60. San Francisco, USA: International Lead
Zinc Research Organization, Inc., 25–27 April.
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SECONDARY BATTERIES-LEAD-ACID SYSTEMS

Article · March 2018

Lead-acid battery development View project

Fuel cell development View project

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Introduction seldom be called upon to discharge. ‘Traction’ batteries

Lead alloy spine

Lattice grid Braided tube

Negative electrode Positive electrode

Pb + HSO4− PbSO4 + H+ + 2e− PbO2 + 3H+ + HSO4− + 2e− PbSO4 + 2H2O

Charge Discharge Discharge Charge H2O O2

PbSO4 Pb −I PbO2 PbSO4

Cell voltage (V) 1.8 20 11.3

Discharge time 30 min

Figure 3 Typical discharge curves for lead–acid traction batteries.

Clearly, there is a certain degree of overlap between PbSO4 β-PbO2

Water ‘Lighter’ ‘Heavier’ ‘Heavier’

Pb + PbO2 + 2H2SO4 2PbSO4 + 2H2O 2PbSO4 + 2H2O Pb + PbO2 + 2H2SO4

FM3. Acid Stratification FM1. Positive Plate Expansion

The Valve-Regulated Battery hydrogen at the negative plate:

Electrolyte film Separator Electrolyte film

Positive electrode Negative electrode

Overcharge reaction Recombination reaction

–1.4 –1.2 –0.8 –0.4 0 0.4 0.8 1.2 1.6

Electrode potential (V) vs Hg/Hg2SO4 electrode

Heat Management in Lead–Acid Batteries Heat Dissipation

Stefan–Boltzmann law: and [6], i.e.,

The changes made to the construction of the battery in

Plate-group pressure Plate-group pressure

Pb–Ca–Sn grid* Pb–Ca grid*

0 500 1000 1500 2000

compact layer of tiny lead sulfate crystals will develop on

(Figure 14(b)). Under such conditions, the discharge

HSO4− HSO4− HSO4−

can take place smoothly before the evolution of hydro- Grid

0 40 000 80 000 120 000 160 000

Log (capacity (Ah))

Lead−acid cell Hybrid supercapacitor

UltraBattery™ Carbon electrode

Experience has demonstrated forcibly the fundamental e Stefan–Boltzmann constant

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