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Failures analysis and improvement lifetime of lead acid battery in different

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3rd International Conference on Automation, Control, Engineering and Computer Science (ACECS'16)
Proceedings of Engineering & Technology (PET)
pp. 148-154
Copyright IPCO-2016

Failures analysis and improvement lifetime of lead

acid battery in different applications
Raja Yahmadi#1, Kais Brik#,*2, Faouzi ben Ammar#3
#
Research Laboratory Materials, Measurements and Applications,
National Institute of Applied Science and Technology (INSAT),
Centre Urbain Nord BP 676-1080 Tunis Cedex. phone:
(+216) 703 746, Fax (+216)71 704 329.Tunis
1
[email protected]
3
[email protected]
*
Higher Institute of Multimedia Arts of Manouba (ISAMM), Tunis
2
[email protected]

Abstract—This paper reviews the failures analysis and improves their lifetime in different applications. In this
improvement lifetime of flooded lead acid battery in different context, the different applications of flooded lead acid battery
applications among them uninterruptible power supplies, are firstly studied. Then, the critical failure modes of the lead
renewable energy and traction applications. In fact, the acid battery for different applications are discussed. In the
performances and lifetime of battery are important parts in these
third part, the author proposes corrective actions during the
energy systems. Over time, the performances of lead acid battery
are deteriorated and caused the limit of the service life. In this manufacturing process and during lead acid battery operation
context, the authors propose an approach to identify the critical to reduce their degradation and extend service life according
failure modes of lead acid battery according to the application to the duty cycle. In this context, an appropriate charge cycle
duty cycle. The knowledge acquired on these battery degradation is developed that ensures the full state of charge and protects
modes allow properly propose some recommendations as ways against the overcharging risks.
for eliminating or reducing the identified failure modes for each
application. These recommendations based on the improvement II. DIFFERENT APPLICATIONS OF FLOODED LEAD ACID
of manufacturing process and incorporation an appropriate BATTERIES
charge cycle. The appropriate charge cycle is based on the
multistep current profile that reduces the degradation of battery
The flooded lead acid batteries can be classified according
by ensuring the full state of charge and avoiding the overcharge to the application types in the following main categories:
risks. stationary battery, renewable energy storage battery and
traction battery. Each of these applications of lead acid battery
Keywords—lead acid battery; failure mode; lifetime; charge has its own distinctive duty cycle that presents in this section.
cycle; manufacturing; The stationary battery used in uninterruptible power
supplies (UPS) systems ensures the supply electrical of
I. INTRODUCTION sensitive loads in case of power supply failure such as: power
Lead acid battery is the main source of electrical energy cuts, short interruptions voltage and voltage drop, micro
storage with a wide range of applications such as power cuts, overvoltage, etc. In this case, the battery provides
uninterruptible power supplies, renewable energy and traction power from a few seconds to one hour through a DC/AC
applications. In renewable energy applications, lead acid converter. In normal operation, the battery is continuously
batteries are used to address the problems of the electric charged from the grid through an AC/DC converter until the
power in terms of stability, quality and dependability [1]. full state of charge in order to immediately intervene in case
Similarly, the quality and stability problems of a grid in of grid failure. The classic way of maintaining the full state of
uninterruptible power supplies can be processed by the charge is the "floating": by imposing on the battery a higher
connection of lead acid batteries [2]. Concerning the traction voltage than the open circuit voltage [2].
applications, the advent of vehicle "more electric" or hybrid In the renewable energy applications, the fluctuating energy
contributes to the uses of lead acid batteries for provide all or problems can be solved by connecting lead acid batteries that
part of the energy requirements depending on the rate of provide or absorb a power. In case of high output power of
hybridization and mission of the vehicle [3]. source, the renewable energy is transferred through a DC/DC
The use of lead acid battery in different applications poses converter controlled by MPPT to supply the load and charge
a problem related to the degradation of their performances and the battery. When the output power of the source is
the limit of the service life [4,5]. These reasons make the lead insufficient, the battery supplied the power to the load until
acid battery as the weak link and the most expensive the maximum discharge capacity is reached [6].
component of the system. The main objective of this paper is Among the traction applications, lead acid batteries are
to analysis the failure modes of the lead acid battery and widely used in hybrid electric vehicle. A hybrid electric

ISSN: 2356-5608
vehicle comprises two propulsion members; an electric engine Some of the factors associated with these failure modes are
and an internal combustion engine. The energy storage related to fabrication process and operating conditions. The
devices associates to these two engines are: electrical energy deficiency of battery capacity in the manufacturing process is
storage (battery) and fossil energy storage (fuel tank). The accompanied by the low quality of paste, grid, and electrolyte,
development of hybrid vehicle provides the functions such as pasting, curing and drying process, formation, finishing [10].
stop-start, Zero Emission, boosting and regenerative braking. The non cohesion of active mass can be refers to low quality
The regeneration of braking is a means for recovering part of of paste, pasting, curing and drying process. In addition, the
the kinetic energy of the vehicle through the alternator mode low quality of the plate formation and the low quality of paste
of the electric machine in order to charging the lead acid can contribute to the sulphating phenomenon. The low quality
battery. This energy can also be used for other functions such of grid and the low quality of the plate formation promotes the
as boost mode. In this application, the battery operates under corrosion of the electrode and the low quality of the
high rate partial state of charge (HRPSOC) rather than from a electrolyte facilitates the stratification phenomena during lead
fully charged condition. In fact, the battery cannot supply the acid battery operation. However, the loss of electrical
required starting current when the state of charge (SOC) is connection is due to improper selection of materials during
low and it cannot accept charge efficiently either for high finishing process.
SOC [7]. In stop-and-go function, the engine is stopped each The plates are formed by the application of the paste on the
time the vehicle is stopped, and is restarted when the grids lead alloy in the pasting process. The paste of the plates
accelerator is pressed again. The "Zero Emission" mode is is formed by mixing the lead oxide with water, sulphuric acid
used in the start-up phases of the vehicle, the electric engine and additives. During the curing and drying process, the plates
can completely replace the internal combustion engine for are transported to curing chamber in order to allow the
propelling the vehicle at low speed by using the battery [1]. suitable adhesion of the paste on the grid under controlled
conditions of temperature, humidity and time. Then, the
III. RESEARCH OF CRITICAL CAUSES OF FLOODED LEAD ACID positive and negative plates with separators between them are
BATTERY DEGRADATION BY CAUSAL TREE assembled and placed in the battery case. The cells are
connected with a metal that conducts electricity. The lead
The use of the flooded lead acid battery in uninterruptible terminals or posts are then welded on. During the formation
power supplies, renewable energy and traction applications is process, the battery case is filled with the electrolyte and
in fact the weak point of the system because of the gradual connected to the power source in order to convert the cured
degradation of performance and the limit of their lifetime. The paste of the plate into active mass. After the formation process,
main degradation modes of flooded lead acid battery are the batteries reach the finishing process where the electrolyte
stratification of electrolyte, sulphating of electrodes, corrosion concentration is adjusted and the cover is attached [11,12].
phenomena, non cohesion of active mass and loss of electrical All the types of flooded lead acid batteries suffer from the
connection [4,8]. same damage mechanisms but with different degree
The sulphating of the electrode indicates the growth of lead depending on the particular conditions for each application. In
sulphate crystals (PbSO4) in size. This creation of large this section, the critical failure modes for each application
crystals reduces the amount of active mass available and thus with their causes are identified.
the available capacity. In other hand, the non uniform In the uninterruptible power supply, the main requirement
distribution of electrolyte concentration creates a stratification for the battery is to provide a high current for a short time
of electrolyte wherein the acid is frequently more collected at because the emergency time for UPS systems is usually short.
the bottom of the battery. The stratification of electrolyte leads Therefore, a deep discharge of the battery is produced which
to reduce the battery capacity by concentrating the chemical causes the sulphating phenomenon. The ripples of the DC and
reaction to specific parts of the electrodes [4]. AC voltage at the battery terminals also impose negative
The corrosion is the destruction of the metal under the effects on their performance. The AC ripples are composed
action of the environment that caused by the dehydration two types: discharge and non-discharge. They are of type '' no
phenomenon. This phenomenon appears when the level of discharge '' when their amplitude is small compared to the
electrolyte is too low that makes the electrodes in contact with amplitude of the DC component, otherwise they are of type ''
the air and oxidizes [8]. discharge '', and the ripples current becomes positive and
The degradation of active mass and shedding create the non negative. The ripples of DC and non discharge AC increase
cohesion of active mass. The degradation of active mass is a the internal temperature of the battery. Since, the discharge
process where the loosening of the active mass particles AC ripples leads to the battery charge-discharge cycles with a
resulting in a loss of electronic conductivity. However, the rate determined by the frequency of the AC signal, low
shedding is a mechanical loosening of the active mass and the frequency of AC ripples is particularly harmful to the battery
rest of the electrode. and causes premature ageing [3]. However, the stationary
The loss of electrical connection is caused by the vibration battery undergoes continuous electrochemical reactions even
which produces fatigue failure, particularly between the cast after it is fully charged due to the float voltage that gives a
on strap and pillar post. This failure is due to insufficient relatively small charge current and causes mainly grid
penetration of molten metal at the joint [9]. corrosion. Therefore, the most common failures of stationary
lead acid battery are the positive plate corrosion by the TABLE I
CRITICAL FAILURE MODES OF FLOODED LEAD ACID BATTERY FOR
overcharge, sulphating of the electrode by the deep discharge
DIFFERENT APPLICATION
and the stratification of electrolyte.
In renewable energy applications, the intermittent nature of Traction Stationary Renewable
energy and non suitable charging cycle create extreme battery battery energy storage
battery
conditions for the state of charge of the battery which causes
Stratification of - + +
their failure. The sulphating is occurred when the battery is electrolyte
left in a low state of charge for a long period of time. The low Non cohesion of + - -
state of charge may be accentuated by high battery usage active mass
because of too many amenities, deep and prolonged discharge. Corrosion of the - + +
The corrosion of the electrode can result from a high ambient electrode
temperature and cycles of the order of seconds, minutes or Sulphating of the + + -
hours depending on the source and used profile. Hence, the electrode by deep
reliability problem of lead acid battery in renewable energy discharge
Sulphating of the + - +
systems is the appearance of their overcharging and deep electrode by
discharge which generates sulphating phenomena, corrosion incomplete charge
of electrode and stratification of electrolyte [12]. Loss of electrical + - -
In the traction applications, the lead acid battery connection
encountered problems related to the negative plates. Under
HRPSOC regime, the lead acid battery is infrequent at full A. Improvement Of Battery Lifetime During The
charging in regenerative braking during the decelerating or Manufacturing Process
stopping and provides a high rate of discharge in "Zero The capacity and lifetime of the battery depend greatly on
Emission" mode during starting and acceleration that the structure of the active mass. Hence, improvement the lead
accumulates a lead sulphate on the negative plate and fails acid battery quality requires applying corrective actions
quickly [1,7]. Therefore, the battery fails prematurely due to during the various manufacturing processes.
the sulphating of the negative plates. It was also reported that The stationary battery should have thick plates with high
the negative lugs were corroded severely in these conditions paste density where high energy and power are not requested,
[7]. On the other hand, the traction battery undergoes a lot of but the capability of long living on float or moderate
charge-discharge cycle that cause the non cohesion of active overcharge is an important. In fact, the main failure mode of
masse. The particular condition of traction applications stationary battery is the corrosion of electrode due to the high
generates also the vibration mode of failure due to wear and self-discharge rate. Therefore, several studies have been done
tear of the road. These vibration causes fatigue failure, to reduce the high self-discharge rate of the negative electrode
particularly between the cast on strap and pillar post leading to in batteries with antimony in the positive grid alloys. Since the
loss of electrical connection [9]. Hence, the use of the lead other metals like tin, antimony, calcium, silver are inserted
acid battery in traction applications shows the non cohesion of into the grid composition in order to improve the toughness as
the active mass and the loss of electrical connection; and well as the resistance against corrosion. Low antimony 0.5-
generates new failure modes like the negative plate sulphating 3.5%Sb with Se, Te, S, Cu, As, Sn (Al) are used to decrease
due to HRPSOC. of Sb contamination at negative electrode in UPS applications.
This qualitative analysis of battery degradation in the The use of standard calcium 0.06-0.12%Ca 0-3% Sn, (Al)
different applications allows identifying the critical failure avoids also the Sb contamination at negative electrode [13].
modes according the application. These critical failure modes On the other hand, the low quality of electrolyte facilitates
for each application are summarized in Table I and their the stratification of the stationary and renewable energy
causes are described by a causal tree in Fig.1. storage battery. In this context, the improvement of the
electrolyte quality can be provided by adding boric acid
IV. IMPROVEMENT OF BATTERY LIFETIME H3BO3 (<0.4wt%) in the electrolyte solution prevents hard
The previous section illustrates the causes of lead acid PbSO4 formation and reduces self-discharge of the positive
battery degradation for different applications by causal tree. electrode [5]. The addition of phosphoric acid in combination
Each of the above causes exerts an influence on the with 2.2wt% or 4wt% of colloidal silica in the electrolyte
performance of the lead acid battery and their lifetime. In this decreases the acid stratification on cycling at high discharge
section, the authors propose corrective actions in order to rates and prevents softening of the positive active mass. The
reduce the degradation phenomenon and extend the battery sulphating of negative electrode can be decreased by
lifetime. improvement the quality of paste where the addition of barium
sulphate (0.8-1wt%) and polyaspartate (<0.05wt%) facilitates
the formation of small crystals of lead sulphate (PbSO4).
 Battery degradation

Loss of battery capacity: Loss of battery capacity: Loss of battery capacity:

Renewable energy Stationary application Traction application
application

Hard sulphating by Hard sulphating Stratification Corrosion Non cohesion of Loss of electrical
incomplete charge by deep discharge the active mass connection

Shedding Degradation of
the active mass

Water loss by its

SOC< 50% SOC< 20%
transformation into gas
by electrolysis

Overcharge Overheat

Cycling with Low quality Low quality Deep discharge Low quality of Low quality Presence of air Bad operation Bad choice of Intensive use: High external Low quality Low quality of Cycling: repetitive Vibration Low quality of
incomplete of paste of formation the electrolyte of grid of the charger the charger charge and temperature of pasting curing and chemical transformation finishing
charging cycle discharge fast of the active mass
drying

Fig. 1. Causal tree of the critical failure modes of lead acid battery

The lead acid battery used in electrical vehicle must be able the negative active mass is increased by the lignosulfonate
to withstand long cycling, while featuring high energy density. additive (0.2-0.3wt%) [14,15].
They must be constructed with thick plates supporting high- In addition, standard antimony 4-11%Sb As, Sn, Cu(Ag) in
density pastes, electrochemically formed in low-density acid the grid alloy provides strong grids, stability for active
solutions. The main failure mode of traction battery is the non material in positive electrode, improvement of cycle
cohesion of the active mass. It must have a good quality of the performance [5]. The vibration failure can be avoided by
pasting, curing and drying processes in order to eliminate or addition of more than 2%wt tin content that increase the
reduces the non cohesion of the active mass by controlling the amount of eutectic liquid and improves the fluidity of the
climatic conditions (controlled temperature, etc) that improve alloy. The battery degradation by sulphating of the electrode
the quality of the plate texture. In addition, the battery may be reduced by the implementation of corrective action as
performances are strongly predetermined by the paste type shown previously for stationary and renewable energy
used for the manufacture of the plate. The better active mass is applications.
generally obtained from a cured positive paste 4BS that has a
high output power performance with a longer lifetime than B. Improvement Of Battery Lifetime During The Operational
that of the plates with a cured positive paste 3BS [12]. Phase
The reduction of the non cohesion of the active mass can be In this section, the authors propose corrective actions
take place also by the addition of additives during the mixing during the lead acid battery operation in order to reduce the
process in order to improve the paste quality such as porosity degradation phenomenon and ensure maximum battery
and conductivity. The addition of diatomite (3-5wt%) and reliability. The stratification of electrolyte in UPS and
glass microspheres (1.1-6.6wt%) ensures the increasing and renewable energy applications can be reduces by a proper
the maintaining of the porosity during the restructuring of the maintenance and a suitable energy management system of
active materials while the additive acetylene black (0.2-2wt%) battery. Proper maintenance can extend the battery cycle life
backs the conduction system of the active mass. Some by checking periodically the specific gravity of the electrolyte
manufacturer adds the glass microfibers (0.5-1.5wt%) in the and adjusted to a correct value. The energy management
positive paste in order to increase the specific surface of the system of battery should prevent the deep discharge that
active mass. Otherwise, the conductivity of the negative active causes the stratification of electrolyte and the sulphating of
mass is improved by the addition of black carbon (0.1-0.3wt%) electrode by fixing the maximum state of discharging of the
and expanded graphite (<1.5wt%), while the surface area of battery to 50%. The sulphating of the electrode by the
incomplete charging can be avoided by charging the battery
until the full state of charge 100%.
 In the same way, the energy management system of battery I step _ n+1 = I step _ n − ∆I bat − steps (5)
should prevent the overcharge that generates the corrosion of
the electrode. The overcharge is observed when battery With:
voltage above the maximum charge voltage that I step _ 0 = I C /10
(6)
recommended 2.35V per cell [16]. The maximum charge
The lead acid battery used in this paper has a nominal voltage
voltage of a battery is determined by the following equation.
of 24V and a nominal capacity of 100Ah with initial state of
Vbat-max= Number of cell×2.35V (1)
charge 60%.
Therefore, the authors propose a charging cycle of battery
According to Eqs, (3)- (6), for n=4, there are 4 steps with
based on multistep current in order to reduce the degradation
of battery by sulphating and corrosion of electrode. During the ∆I bat − steps = 2 A and ∆Vbat − steps = 0.3V .
charging cycle, the battery is charged until the voltage reached The used charging current and the corresponding voltages
the floating voltage Vfloating, and then the current decreases range at 25°C are indicated in Table II. The proposed control
over time, until the battery ultimately reaches 100% SOC with strategy that reduces the degradation phenomena and ensures
the charging rate C/50. The floating voltage of a battery is maximum battery reliability is described by Fig. 2. In this
determined by the following equation: control strategy, the battery is charged from an AC source in
Vfloating= Number of cell×2.25V (2) case of UPS applications or wind applications, otherwise, the
The multistep current profile is based on the calculation of battery is charged from a DC source such as PV applications
the voltage variation and the current variation. The voltage and hybrid electric vehicle applications.
variation is determined as follows:
TABLE II
Vbat −max − V floating VOLTAGES RANGE AT THE VARIOUS CHARGING CURRENT
∆Vbat − steps = (3)
n Steps Voltage range Charging current
With: n is the number of steps; (V) (A)
The current variation can be defined as: Step 1 27→27.3 8
I C /10 − I C /50 Step 2 27.3→27.6 6
∆I bat − steps = (4) Step 3 27.6→27.9 4
n
Step 4 27.9→28.2 2
The current steps can be estimated by the following
equation:

T1 Lf

T2
D1
D2 Vbat

I step _ 0
V b a t ≤ V flo a tin g +−

I step _ 1
I bat
V floating < V bat ≤ V bat-1

I step _ 2
V bat-1 < V bat ≤ V b at-2
I step _ 3
Vbat V b a t-2 < V b a t ≤ V b a t-3

I step _ 4
SOC ≤ 100 T1
0
α
Pbat > 0 T2
Idisch arge I ref
V b a t ≥ V b a t-m in +−

0 I bat
Fig. 2 Proposed control strategy of battery.
 The characteristics by Matlab Simulink of current, voltage, by the deep discharge, corrosion of electrode and stratification
state of charge and power of lead acid battery based on of electrolyte, while the renewable energy application shows
multistep current control illustrate in Fig. 3. the failure of battery by the sulfating due to the incomplete
10 charge cycle, the corrosion and stratification phenomenon.
Current (A)

Finally, the authors propose corrective actions during the

5
manufacture process and during lead acid battery operation to
0
0 0.5 1 1.5 2 2.5 3
reduce their degradation and extend their lifetime. In this
Time (s)
x 10
4
context, a charging cycle based on multistep current is
Vbat-max 28 developed in order to take the best care of the battery to be
Voltage (V)

27

26
overcharge and reduce the risk of failure by the incomplete
25 charging.
24
0 0.5 1 1.5 2 2.5 3
Time (s)
x 10
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