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Voltage and Temperature Impacts on Leakage

Current in Calendar Ageing of Supercapacitors

Mohamed Ayadi*, Akram Eddahech, Olivier Briat, Jean-Michel Vinassa
Univ. Bordeaux, IMS, UMR 5218 CNRS, F-33400 Talence, France
Laboratoire IMS, 351 cours de la libération, Bat A31, 33400 Talence, Bordeaux, France
Tel: (+33) 5 40 00 26 13, Fax: (+33) 5 56 37 15 45
*e-mail: mohamed.ayadi@ims-bordeaux.fr


Abstract—In this paper, we investigate the monitoring of the
leakage current of supercapacitors during calendar ageing. First,
results of periodic characterization tests during calendar ageing
up to 5000 hours are presented. Then, a model of leakage current
is proposed and validated. Finally, the impact of both the
temperature and voltage is highlighted and quantified.
Keywords-Supercapacitor; calendar ageing; leakage current;
self-discharge.
I. INTRODUCTION
Electric Double-Layer Capacitors (EDLC), or
supercapacitors (SC), are based on the electrostatic storage of
the energy at the interface between an electrolyte and a porous
carbon electrode [1], [2].
SCs are interesting storage components thanks to their high
specific power and efficiency, low-cost and relatively good
lifetime. Thus, they are well suitable for use as peak power
sources, for instance in Hybrid Electric Vehicles (HEV) or for
the pitch control of wind turbines.
However, one of the main challenges still remains in the
understanding of their ageing mechanisms and the
development of new characterization methods [3]. Moreover
than the power cycling ageing mode, the SC performances in
terms of energy and power capabilities decreases also during
rest time (calendar mode). The decay of the performances
depends on both the temperature and the voltage as highlighted
in this paper.
In this work, we propose a method for investigating
calendar ageing of supercapacitor based on the continuous
measurement of the leakage current. In the first part, calendar
ageing experiments and characterization methods are
presented. Then, a model simulating the leakage current during
calendar ageing is developed and presented. Furthermore, we
investigate temperature and voltage impacts on the leakage
current during ageing.


II. CALENDAR AGEING AND CHARACTERIZATION RESULTS
A. Experimental Setup
Supercapacitors are aged at constant voltage and
temperature. During calendar ageing, SCs are placed inside a
climatic chamber in order to control the ambient temperature.
In this study, SCs have been tested with three different
temperatures (40, 50 and 60°C) and three voltage values (2.5V,
2.7V and 2.8 V). The temperature and voltage values have
been selected in order to accelerate the ageing [4]. The
dynamic behavior of a SC is strongly related to the mobility of
ions the electrolyte used and the porosity effects of the porous
electrodes [5]. The operating voltage of the SC is limited by the
stability range of the electrolyte. In our case, the tested cells
have a rated operating voltage of 2.7V.
In this test, the stored energy of the SC is sustained by
maintaining the voltage at a constant value. During the whole
experiment, a dedicated floating test bench is able to accurately
measure the resulting leakage current, which is supposed to be
strongly linked to the SC ageing [6].
B. Characterization Method
In order to quantify the evolution of the SC performances in
terms of internal resistance and capacitance, characterization
tests are made periodically both in frequency (AC) and time-
domains (DC). In the case of AC characterization, an
electrochemical workstation is used for Electrochemical
Impedance Spectroscopy (EIS) tests in a wide frequency range,
from 10 mHz to 10kHz. For DC characterization, a method
based on the SC charging and discharging at constant current
according to the IEC62576 standard is used to determine the
Equivalent Series Resistance (ESR) and capacitance [7].
C. First Results of Calendar Ageing Tests
In this part, we focused only on the evolution of the
capacitance with ageing calculated from the imaginary part of
the cell impedance at 10 mHz. The impact of the voltage and of
the temperature on the capacitance during calendar ageing up
to about 5000h is presented in Fig. 1a and Fig. 1b respectively.
Fig.1. (a) shows that at fixed temperature, respectively 50°C,
the voltage does not affect the ageing beginning (before 1500
h).
978-1-4673-6392-1/13/$31.00 ©2013 IEEE
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POWERENG 2013
However, after 1800 hours the voltage influence becomes
more visible. Fig.1. (b) illustrates the high impact of the
temperature on ageing at a constant voltage of 2.7V. Thus, a
10°C temperature rise affects significantly the capacitance loss.
0 1000 2000 3000 4000
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Ageing time (h)
N
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c
a
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a
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(
%
)


2.5V
2.7V
2.8V

(a)
0 1000 2000 3000 4000
82
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100
Ageing time (h)
N
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40°C
50°C
60°C

(b)
Figure 1. Temperature and voltage impact on calendar ageing of
supercapacitor.
III. INVESTIGATION OF LEAKAGE CURRENT DURING
AGEING
In order to study SCs calendar ageing, rather than
capacitance decline and resistance increase investigation from
characterization [8], the leakage current revealed to be an
important parameter for the study of ageing electrochemical
cells. In fact, this current is measured during all ageing test and
will indicate devices deficiency once its performances
degrades.
In our work, we focused on the floating current which
corresponds to the current absorbed by the SC in order to
maintain a constant voltage during ageing. This current is very
representative of the leakage current. In effect, the
quantification of measured current is very sensitive at the
beginning due to the coincidence of a leakage current evolving
rapidly with ageing and a compensation current of the
relaxation phenomenon. Therefore, experiments on self-
discharge and impacts of temperature and voltage on this
parameter are given below.
A. Ageing Voltage Effect on Leakage Current
The quantification of the leakage current is very sensitive at
the beginning. In effects, it is evolving rapidly to compensate
the relaxation phenomenon [9]. Nevertheless, at a more
advanced stage of ageing, leakage current becomes more
stable. This behavior is dependent on the device voltage
ageing. For example, we see in Fig. 2 that the leakage current is
less than 1mA for 2.5V and 2mA for 2.7V after 1800 hours of
ageing.
500 1000 1500 2000 2500 3000 3500 4000 4500 5000
0
10
20
30
40
50
Time (h)
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a
c
k
a
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e

c
u
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(
m
A
)


2.5V
2.7V
2.8V

Figure 2. Ageing voltage effect on leakage current at 50°C.
B. Leakage Current Proposed Model
In this section, we developed a model for Leakage current
simulation during ageing. The model is represented by
equation (1),
(1)
Physically, the use of square root of the time is related to
diffusion phenomenon [10]. However, the exponential function
is employed to follow the rapid drop of the current. Fig. 3.
Shows a comparison between the model simulation and
experimental results from SC ageing at 2.7 V and 50°C.
500 1000 1500 2000 2500 3000 3500 4000 4500 5000
0
5
10
15
20
25
Time (h)
l
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a
c
k
a
g
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c
u
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(
m
A
)


simulated
measured

Figure 3. Comparison between simulated and measured leakage current
during ageing at 2.7V and 50°C.
1000 2000 3000 4000 5000
0
1
2
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8


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The model has been validated on the three test voltage.
Table. 1 represents model identified parameters from these
different ageing voltages at 50°C.
TABLE I. MODEL ESTIMATED-PARAMETERS FOR DIFFERENT
VOLTAGES.
Parameters/Voltage A B C D
2.5V 7.922 -0.011 -0.028 2.279
2.7V 18.391 -0.009 -0.036 3.277
2.8V 59.950 -0.018 -0.062 5.072

Parameters A and D confirmed the logic of the dependency
of the ageing on the device voltage. Actually, these parameters
increased with voltage increase.
C. Self-Discharge and Temperature Effects on Leakage
Current
In order to study thermal behavior of the leakage current
during ageing, we begin this part with a short focus on
temperature effect on self-discharge. In fact, self-discharge of
SCs is a very slow process which cannot be well determined by
impedance measurements [11].
The progression of the open circuit voltage (OCV) after a
full charge of the SC is analyzed for 48 hours, results show a
quasi-exponential decrease with time and time constant
depends on several parameters, essentially temperature and
charging current [12]. Actually, to neglect current effect and in
order to process similarly as in floating conditions during
ageing, we chose a low charging current namely, 2A. The SC
OCV is presented in Fig. 4 at two temperatures. OCV plots
revealed that device voltage changes significantly during the
first hours and self-discharge is accelerated with increase in
temperature. Basically, we obtained a lower OCV with higher
temperature after 48 hours of self-discharge test.
We observed a similar behavior when plotting the leakage
current from calendar ageing of a SC aged at 2.7V (see Fig.5).
In fact, SC aged at 50°C required a leakage current more than
the SC aged at 40°C.
0 10 20 30 40 50
1.8
2
2.2
2.4
2.6
2.8
Time (h)
V
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t
a
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(
V
)


40°C
50°C

Figure 4. Self-discharge for SC at 2.7V and different temperatures.
0 1000 2000 3000 4000
0
5
10
15
Time (h)
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a
k
a
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c
u
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(
m
A
)


50°C
40°C

Figure 5. Temperature effect on leakage current for SC aged at 2.7V.
In order to study this similar behavior, we used the same
model form described with (1) to simulate the self-discharge
phenomenon. Results are presented in Fig. 6 and showed that
this model matched very well self-discharge behavior. From
the identified parameters, we see that the time constant of the
exponential term is twice higher (-0.0185) than this of the
leakage current.
0 10 20 30 40 50
2
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
Time (h)
V
o
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t
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(
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simulated
measured

Figure 6. Comparison between simulated and measured voltage during self-
discharge at 2.7V and 50°C.
From this study, we will simulates an equivalent circuit
model represented in Fig. 7 and developed here to model self-
discharge taking into account diffusion phenomenon [13]. Next
equations illustrate model relationships,

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POWERENG 2013

Figure 7. Equivalent circuit model for SC at self-discharge.
The first branch which includes R
1
and C
1
is the main
branch. The differential capacitance C
1
is the sum of a constant
capacitance C
0
and a voltage dependent capacitance k u,
(2)
The relation of three branch current can be described by:
(3)
(4)
The relation between current and voltage for the delayed
branch is:
(5)
(6)
This model has been validated on a SC charged until 2.7V.
Results are presented in Fig. 8 and parameters have been
identified for the test running under 50°C.
0 10 20 30 40 50
2.2
2.3
2.4
2.5
2.6
2.7
Time(h)
V
o
l
t
a
g
e

(
V
)

measured
simulated

Figure 8. Model validation.
Temperature impact on SC leakage current
Fig.9 illustrates that a temperature increase on SC under
ageing test, conducted to a rise on leakage current. This
justifies the acceleration of self-discharge at high temperature.
From this we confirm the significance of leakage current in SC
behavior monitoring. Similarly, if the temperature decreases
the leakage current decreased also.
0 5 10 15
35
40
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Time (h)
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Figure 9. Variation of leakage current after a slow variation of temperature.
When supercapacitor reaches end of life, ESR resistance
will increase rapidly and so there is probably a drop on the
device voltage. Hence, leakage current will behaves differently.
Therefore, leakage current could represent a real-time
indication on device health.
IV. CONCLUSIONS
In this work, we studied SCs calendar ageing. Experimental
results have been highlighted. We were interested in the study
of leakage current as a source for calendar ageing monitoring.
Basically, a focus on the factors influencing the leakage current
during ageing have been represented, mainly voltage and
temperature impact. Moreover, a model simulating its behavior
through ageing has been developed.
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