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Lead-acid Battery Degradation Mechanisms in

Photovoltaic Systems PVS
CONFERENCE PAPER OCTOBER 2013

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Lead-acid Battery Degradation Mechanisms

in Photovoltaic Systems PVS
W. Merrouche , N. Achaibou, B. Bouzidi

M. Kasser

Division Energie Solaire Photovoltaque,

Centre de Dveloppement des Energies Renouvelables
CDER
16340 Bouzareah, Algiers, Algeria
w.merrouchew@ cder.dz
n.achaibou@ cder.dz
b.bouzidi@cder.dz

Laboratoire Sciences et Gnie des Matriaux (LSGM)

Ecole Nationale Polytechnique ENP
16200 El Harrach, Algiers, Algeria
kasser_m@yahoo.fr

M. Trari
Laboratoire de Stockage et de Valorisation des Energies
Renouvelables L.S.V.E.R., Facult de Chimie
Universit des Sciences et de la Technologie Houari
Boumediene U.S.T.H.B
16111 Bab Ezzouar, Algiers, Algeria
solarchemistry@gmail.com

Abstract Considered a mature and initial low cost

technology, lead-acid battery technology is well understood
and found in a wide range of photovoltaic (PV) energy storage
applications. For this reason, the researchers are very
concerned by the study of degradation mechanisms affecting
the battery lifetime. This paper is an up-date, summarizing the
present understanding. The new aspect is: interpretation of
three degradation mechanisms in relation to the regulation
charge mode adopted in a Photovoltaic system.
Keywords- lead-acid battery; photovoltaic; energy storage;
degradation mechanisms.

I.

INTRODUCTION

Lead-acid batteries are often selected for photovoltaic

systems PVS due to their mature technology and initial low
cost. However, they constitute the weakest point and the
most expensive component over the lifetime of these
systems. For this reason, researchers are very concerned by
the identification and the study of mechanisms which are
the origin of battery degradation. This document studies
three degradation mechanisms emphasized by a deep
cycling test procedure for batteries used in stand-alone
PVS: the irreversible sulphation, the stratification and the
softening. [1, 2]
Several
ageing
mechanisms
may
contribute

Fig. 1 SEB microphotography of +ve plates:

Big PbSO4 crystals

simultaneously to loss of battery performance.

Nevertheless, for each battery design and type of use, there
is generally one dominant ageing mechanism determining
the achievable service life. [3]
II.

IRREVERSIBLE SULPHATION

Considered a principal reaction which manages the

energy conversion mechanisms in the electrochemical
process, sulphation is the result of lead sulphate crystals
PbSO4 formation at +ve and ve plates during the discharge
phase. Whereas, during the charge phase, these crystals are
reversibly transformed to lead dioxide PbO2 in the +ve
plates and to lead Pb in the ve plates.
However, when the battery remains at inappropriate
conditions, particularly in a discharged condition for
prolonged time, the so-called irreversible sulphation
phenomenon is induced. In this case, PbSO4 crystals
become bigger (see figure 1) and cannot, or only partially,
be converted back to an electrochemically active form. This
leads to a significant loss of capacity. [3]

Fig. 2 Irreversible lead sulphate crystals due to stratification

Fig. 3 Change in the mechanical structure of the electrode:

softening

III.

STRATIFICATION

The batteries with liquid electrolyte, (such case of our

study) have, during their operations, a non-homogeneous
acid concentration: the electrolyte is found denser in bottom
of the battery than in top. This phenomenon is often due to
the forces of gravity which intervene on the nature of the
components [04]. The stratification is thus defined as a
vertical gradient of concentration of the sulphuric acid.
Indeed, the pure acid formed during the charge phase has a
higher density than the bulk electrolyte and tends to fall
down at the bottom of the battery. This phenomenon is
favoured by deep discharges, but it may be avoided during
overcharge as the gas particles mix the electrolyte [05].
Initially, the stratification induces heterogeneity in the
electrodes discharge which are less discharged in the bottom
part of the battery. Also, it decreases the capacity and leads
to forming of irreversible lead sulphate crystals (see figure
2) [4].
IV.

SOFTENING

The softening phenomenon is primarily a change in

active mass and electrodes morphology (see figure 3). The
change in the mechanical structure of the electrodes
decrease the porosity of the ve electrode and reduces the
surface area of electrochemical reaction. The consequence is
a loss of capacity by concentrating the chemical reactions

Fig. 5 Hydra Data logger

into restricted space [5, 6]. Deep discharges, overcharge,

increasing the cycle count and operating at high temperature
are the principal causes of softening [7].
V.

TEST SYSTEMS AND RESULTS

A. Test Equipment Presentation

1) Reversible converter
The reversible converter BENNING model DNF 2-72/5
tu spez operates in two modes: charge and discharge. It is
equipped by voltage/current digital display and indicators.
We can regulate the voltage between 2 and 72V, the current
between 5 and 150A. A battery charge is controlled via an
electronic circuit based on a set of charge/discharge voltage
thresholds (setpoints). (See figure 4)

2) Thermocouple
The thermocouple is a temperature sensor, it consists of
two dissimilar metals connected which produce a voltage
when heated. A difference in temperature between two
dissimilar materials generates a potential difference:
Seebeck effect. This potential difference can be transcribed
in temperature. (See figure 6)

3) Data logger
The 2625A Hydra Data Bucket is a 21-channel data
logging instrument that measures the following electrical
and physical parameters: dc volts, ac volts, resistance,
frequency, and temperature. Temperature measurements are
via thermocouples or resistance-temperature detectors
(RTDs). Other parameters can be measured with an
appropriate transducer, such as DC current using shunt
resistor. When the 2625A scans channels configured for
measurement, readings can be displayed, printed out. The
user can choose communications with a host computer over
an RS-232 interface. (See figure 5)
B. Solar batteries tests
1) Batteries presented for test
Two flooded lead-acid batteries are used (See figures 7-

Fig. 4 Reversible converter BENNING

Fig. 6 Nickel-Chromium/Nickel-Aluminium thermocouple

Fig. 7 Fresh flooded lead-acid Battery N01

The obtained discharge curve is illustrated in figure9.

This curve shows that the voltage decreases until reaching
the minimum threshold 11V. This is due to the cohesion of
the active mass in the electrolyte to the lead and transforms
it into lead sulphate; this transformation produces water,
which cause a drop in the density of the electrolyte.
We note an abrupt voltage drop at the beginning of the
discharge, i.e. when the reversible converter is started, and
then the tension continue to decrease. At the end of the
discharge, the tension falls abruptly. Indeed, when the
battery is deep discharged, the active material, strongly
inflated, blocks the pores which prevents the electrolyte
from reaching in-depth the active mass.
- Charge test

Fig. 8 Battery N02 submitted to 30 charge/discharge cycles

8): BERGAN-SUN (Tudor technology). Each battery has:

12V nominal voltage (six 2V cells) and 100Ah capacity
(semi-stationary).
2) Charge/discharge Cycles
30 charge/discharge cycles are carried out on the battery
N02, to have a sufficient state of ageing.
- Discharge test
The discharge test schedule is described below:
The discharge current is fixed to
.
The minimum voltage set-point is regulated to 11v.
The battery voltage is measured using the data
logger.
The temperature is supposed constant 20C.

Fig. 9 Voltage curve during the discharge test

The reversible converter functions as generator in two

stages:
Stage 1- constant current charge: the charging
current is fixed to 20A (limited to 1/5 rated
capacity). The maximum voltage set-point is
regulated to 16V.
Stage 2 - Constant voltage Charge: the charging
voltage is fixed to 16V while the current decreases.
The end of the stage is fixed at the minimum current
threshold 4A.
Figure 10 illustrates the voltage-current curves obtained.
The voltage increases because, during the charge, the power
injected in the battery by the anode produces the acid
formation and thus increases the density of the electrolyte.
At the end of the charge, the density of the active material
drops and part of the current is not absorbed any more. This
current then tends to electrolyze water, producing oxygen
and hydrogen gasses. This phenomenon, called gasification,
has disadvantages of water loss and the positive plate
softening.
C. State of degradation after ageing
The state of degradation of the battery 2 after 30
charge/discharge cycles (see figure 11) could be observed
after comparison with the fresh battery 1. The different
degradations observed on the plates are:

Fig. 10 Voltage/current curve during the charge test

1) The stratification: contrary to the negative plates of the

fresh battery, the white colour of sulphate is concentrated in
the lower part of the negative plates in the used battery.
(See figures 12-13)
2) The sulphation: Big crystals are observed on the used
battery positive plate. (See figure 14)
3) The softening: The electrode deformation accompanied
by loss of the matter as observed as result of mechanical
properties change. (See figure 15)
REFERENCES

Fig. 11 Battery N2 after 30 charge/discharge cycles

[1]
[2]

[3]

[4]

Fig. 12 Fresh Negative plat (battery 1)

[5]

[6]
[7]

Fig. 13 Stratification on negative plat (battery 2) after 30

charge/discharge cycles

Fig. 14 Big sulphate crystals observed on positive plat

(battery 2)

Fig. 15 Positive plat softening (battery 2)

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