I

Transient Analysis of Pulsed Charging in Supercapacitors

N. Khan', N. Mariun', M. Zaki' and L. Dinesh'
1- Department of Electrical and Electronic Engineering
Faculty of Engineering, University Putra Malaysia
(Fax: +603 9488939, Email: norman@eng.upm.edu.my).
2- Department of Chemistry, Faculty of Science
(Email: mzaki@,fsas.upm.edu.my).
43400 UPM Serdang, D m 1 Ehsan Selangor, Malaysia
Abstract: Transient voltagelcurrent pulses can not
be stored into normal DC batteries. This work
reviews possibility of storing these surges using
supercapacitor. Laser induced plasma may be caused
by firing laser pulses into the clouds charge clusters.
The charge pulses flow down along the laser induced
air wire (LIAW) and passes through a supercapacitor
to charge it. Objective of this study'is to test the
of storing these charges using
possibility
supercapacitors. Energy storage in solid state
electrochemical capacitors (supercapacitors) or ultra
supercapacitors occurs through reversible oxidationreduction (redox) reactions. Contribution of double
layer is less significant, however, a major percentage
of total energy stored is attributed to reversible
surface redox reactions. Different types of
supercapacitors have been analyzed regarding their
charge and discharge performance under repetitively
charging pulses. Our initial analysis based on
existing mathematical techniques, shows that a real
superconductor may charge under transient
conditions at a much higher rate but subsequent
considerations based on mathematical analysis and
available data on supercapacitors technology, lead us
to new recommendations to improve the design of
supercapacitor to perform as an ultrasupercapacitors.

ions in the electrolyte, while the potential on the

negative plates attracts the positive ions. This
effectively creates two layers of capacity storage, one
where the charges are separated at the positive plate,
and another at the negative plate [2].
The history of electrochemical energy storage
devices, especially capacitors and batteries, has
involved attempt to reduce size, including both
weight and volume, and to increase the electrical
energy storage capacity while at the same time
increasing the voltage required for dielectric
breakdown. Recent advances in battery design have
included improvements in life, efficiency and energy
density by making improved lead-acid, nickelcadmium, nickel-zinc and various primary cells.
However, although many of the devices
implementation the recent technological advances
have filled a need, there continues to be a
requirement for efficient high power density devices,
which withstand the rigors of continuous use and
virtually unlimited cycling in electrical circuits.
The occurrence, under certain conditions, of large
electrochemical
capacitance,
including
pseudocapacitance is well established. Recent
technological advances in capacitors have included
aluminum
electrolytic
capacitors,
tantalum
capacitors, ceramic capacitors and supercapacitors.
The supercapacitor is an electrochemical cell or
combination of cells consisting of two electrodes, an
electrolyte and a container. The electrodes are
composed of one or more oxides of ruthenium,
tantalum, rhodium,
iridium, cobalt, nickel,
molybdenum, tungsten or vanadium deposited on a
metal foil. The electrolyte may be acidic, basic or
neutral, such as sulfuric acid, potassium hydroxide or
sodium sulfate. The supercapacitor is made by
laminating
electrodes
onto
the
separator.
Supercapacitors typically employ stacks of
laminated electrodes consisting of a separator
between the electrodes. Ion permeable membranes
have been used as separators, the particular
configuration depending upon the application of the
battery. Current-collector grids or meshes are also
employed in the electrode assembly, if desired.

Keywords: Supercapacitors, transient discharging,

pulsed charging and electrochemical capacitors.

1. Super-capacitor Technology
Electrochemical capacitors (so called supercapacitors
or ultrasupercapacitors) are attractive for their
potential high power and long cycle life [I]. Energy
storage in an electrochemical capacitor is based on,
double layer capacitance at the interface between an
electrolyte solution and a high surface area porous
electrode material such as activated carbon and
pseudocapacitance associated with a reversible redox
process. Supercapacitors store energy electro
statically by polarizing an electrolytic solution.
Though it is an electrochemical device (also known
as an electrochemical double-layer capacitor) there is
no chemical reactions involve in its energy storage
mechanism. This mechanism is highly reversible,
allowing the super capacitors to be charged and
discharged hundreds of thousands of times.

A earlier art electrode as taught by Craig in Canadian

Patent 1,196,683 is made by dipping a sheet of a
conductive metal such as titanium into a solution of
the metal oxide in order to deposit the metal oxide
onto the surface of the metal sheet. The coated metal

Super capacitors can be viewed as two non-reactive

porous plates suspended within an electrolyte, with a
voltage applied across the plates. The applied
potential on the positive plate attracts the negative

0-7803-6355-81001$10.0002000 IEEE

111- 193

sheet is then dried and the dipping and drying

process is repeated to build another thin oxide layer.
This process continued until the oxide layer is of
sufficient thickness to function as an electrode.
Fabricating a supercapacitor electrode by depositing
oxide layers onto a metal substrate as described in
the prior art is costly and very lengthy, requiring
repeated dipping of the electrode in order to build up
an coating of sufficient thickness. Clearly, the
present method of forming an active electrode for
supercapacitors is slow and difficult, requiring much
time, and is not a method that can be relied upon to
achieve high quality, due to the need for repeated
dipping of the electrode. A need exists for an
improved electrode composition that is easier and
faster to fabricate.

2
about 125OC may also be employed. The sheets are
then laminated onto a suitable separator such as
absorbent polypropylene, microporous glass, paper,
felt or cellulose. If desired, a second sheet of active
electrode is laminated onto the remaining side of the
separator.

I
Add salts to Water

c
Add activated carhnn

Ahsnrh salts onto Carhnn

2- Supercapacotor Construction
Another method of manufacturing the electrode of
the invention, fabricates a super capacitor electrode
by absorbing metal oxides onto a high surface area
material such as graphite, activated carbon, or a
sponge metal matrix such as nickel, titanium or other
conductive material [3]. Process flow diagram of
above .technique is quite common and shown here in
Figure 1. Soluble metal salts are mixed into an
aqueous solution in concentrations up to their
solubility product. Suitable compounds are materials
such as the chlorides, bromides, sulfates, nitrates,
sulfides, hydrides, nitrides, phosphides, or selenides
of metals such as ruthenium, tantalum, rhodium,
iridium, cobalt, nickel, molybdenum, tungsten and
vanadium. The porous carbon particles (in the form
of high surface area activated carbon) or other porous
metals are added and mixed into solution to form
thick slurry having an extremely high surface area.

React to form hvdroxides

ir'
Decant

Add fluorncarhon emulsion

+
'
i
b
Knead

Form into sheets

During the mixing, the metal salts are absorbed onto

the surface and absorbed into the pores of the
conductive matrix. Once this is complete, the salts
are chemically converted to the oxides by adding an
appropriate amount of potassium or sodium
hydroxides. The reaction products are left in solution
to serve as the electrolyte for the supercapacitor. The
slurry is partially dewatered by a decanting step. The
residual cake is then transferred to a cokneader
where a 1% solution of a fluorocarbon emulsion such
as Teflon @ TFE Fluorocarbon Resin Dispersion
Product Type 30 (61% solids) from the DuPont
Company of Wilmington Del. Is added to the m'ix.
Concentrations as low as 0.1% and as high as 5%
may also be used depending on the electrode activity.
The resulting slurry is kneaded until the fluorocarbon
resin has been totally fibrillated. The resulting dough
consisting of coated carbon particles entrapped in a
matrix of fluorocarbon resin is now converted into
sheet form to comprise an active electrode by
extruding or rolling into sheets of suitable thickness.
The thickness of the sheets is dependent on the
desired final capacitance of the supercapacitor. The
sheets are dried by passing throfgh an in-line or
batch convection oven at about 110 C.

Onen drv

1.aminate onto senarator

Magnitude cross-sectional view of electrode

Cross-sectional view of electrode

Depending on the type of Ooven employed,

temperatures as low as about 80 C, or as high as

Figure 1 Process flow diagram to manufacture

supercapacitors.

111-194

3
Methods of laminating the active electrodes to the
separator are common, and should be obvious to
those skilled in the art 131.
In order to better understanding the composition of
the active electrode sheet, referred to Figure 1, the
carbon particles are coated with metal oxides. In
practice the coating on the activated carbon particles
is very thin, and penetrates a distance into the pores
of the activated carbon. After the fluorocarbon resin
emulsion is fibrillated into the slurry and formed into
a sheet, the fluorocarbon resin surrounds the coated
carbon particles to entrap and bind them to form a
solid sheet. The sheet of active electrode is laminated
to the separator. If desired, an additional sheet of
active electrode can be laminated to the opposite side
of the separator to form a sandwich. The laminated
sheets of electrodes are then cut into the desired size
and assemble to form a supercapacitor by creating a
stack comprising a laminated electrode, an additional
separator (not shown), another laminated electrode,
and so on, until the desired capacitance is achieved.
The stack is then suitably connected to leads or
terminals and placed into a suitable container. The
supercapacitor is then activated by adding a liquid
electrolyte, such as water, dilute acids (sulfuric or
sulfamic acid), or dilute bases (potassium
hydroxide). The concentrations of the acids or bases
may range from about 0.1 molar to about 5 molar. A
cover is then sealed on the container to complete the
supercapacitor. It can be seen that fabricating an
electrode as described in the invention results in an
electrode that can be made in large quantities, and in
a continuous process if desired. The elimination of
the stepwise method used in the prior art results in an
electrode that is more uniform and has the ability to
be more efficient 13-81.

trostatic or kinetic or gravitational energy to all the

other forms 18-141.
4. Transient Operation Analysis
A super capacitor can be represented by a series RC
element shown in Figure 2. Let us consider its
charging and discharging characteristics under a
small potential say AV applied to it.

-+I--

Figure 2 Supercapacitor equivalent circuit

An initial current surge flows into RC until voltage
on capacitor is AV. Writing the potential difference
equation for above RC circuit:

Differentiating (2)

d(AV.C)
dt

dI
dt

- - -

3. Energy Storage Capability

Energy storage is an equilibrium situation and
involves complementary modes. For example, the
complementary bonding force between the molecules
in the pressure vessel wall contains the kinetic energy
mode of the molecules in a gas confined in a pressure
vessel. This force is macroscopically referred to as an
elastic force but it is really electrostatic in nature.
Similarly, a charged capacitor. stores electrostatic
energy so long as we keep the plates separated. The
force that holds the plates apart and prevents the
dielectric from collapsing is kinetic in nature. It is the
Heisenberg-uncertainty-principle force, which causes
the electrons to attain higher kinetic energy upon
compression, thus preventing them from collapsing
into the nucleus.

RC

dI
.-+
dt

I = 0

I
RC

(3)

(4)

So that it can be simplified to

At t = 0, AV appears across R, therefore the current I

= AViR. It is therefore (6) simplifies to
-

In

(5)
=

(7)

The time dependence of I upon charging of C

through R may be given by

The energy in the complementary mode within one

system is sometimes additive and sometime
subtractive, and sometimes more than two modes of
energy are involved [7]. These complementarities in
energy modes are also the key to energy
compression. We can convert magnetic energy to
electrostatic
or kinetic or gravitational
or
electromagnetic energy with 100% theoretical
efficiency. This is likewise true for converting elec-

AS AVR = I

111-195

e)
4

4P m a
P = ( 1 + r ) 2 .exp

(-

Altematively one may express (9) by

I
I(t = 0 )

exp(

Where T =VRC and r is ration of R L R When R = RL

it is considered to be a matched load condition.

- t I RC

We know, normally, R<<RL it is therefore the

voltage abruptly falls to Vi/2. This defines a pulsed
discharging characteristic of the initially charged
capacitors. A normalized power (PPma) plotted
against time constant T- = t/RC for different values of
ratio r is shown in Figure 3.

Or simply

I = I o exp( - t / RC )
Thus charging and therefore discharging time
constant depends upon the time constant RC (= TC =

5. Transient voltages and Currents

Dynamics of RC networks are determined by their
time constants to estimate power capabilities on
charge, discharge and recharging in commercial
applications. At any time t boundary condition that
can apply may be expressed by

Td).

Considering discharge of current from initial

potential Vi to V can derive condition for maximum power delivery in above RC circuit

AVR + AVC

Ivi

(19)

AVc = V. Almost
At t = 0, AVR = V and at t =
similar argument is true for current. Therefore

Multiplying both sides by I (For P = VI)

P

I~R

(13)

For P = Pma

dP
dI

-=

0 = V i - 21R

= A V , = RC

d ( AV ,
dt

But AVC = V - AVR, therefore

Integration of (21) yields

t

+k

-RC~I(~VR)

(22)

At t = 0, AVR = V, therefore k = -RC InV such that

In
h

2e

(A;,)

RC

Or simply in more recognized form

00

-A VR
V

exp

(- E )
t

The time dependent current I(t) is given by

_______9
T- (= t/RC)
Figure 3 Power versus time constant plot

Power delivered to load from a charged capacitor is

generally given by

111- 196

However, supercapacitors can charge and discharge

within 1 ms - 1 sec time range.

- p w t
Avc
Substituting value of 'VR in (22) gives

V
I ( t ) == -exp(
R

t
RC

--)

To determine a similar relation for discharge current

let us rewrite

It is therefore supercapacitors are considered ideal

for electric power quality apoplications. The
published data further shows that regarding
sumillisecond pulsed operations electronic capacitors
are still better than both of above. Typical parameters
of electronic capacitors and the superconductors as
compared to the batteries are shown in Table 1.
Table 1 Comparision of electronic and super
capacitors with typical Batteries
Function

Electronic
caDacitor

Super
capacitor

Battery

Charge time

ps - ms

ms-min

Hours

Discharge time

ps - ms

ms-days

1-900 min

Energy density

<.01 wh/L

Power density

>io4WIL

0.5-5
Wh/L
103-3x1O3

50-300
Wh/L
G O O W/L

Cycle life

106-108

106-108

200- 1,000

So as

1 - -d V c
---=

Vc

1
RC

dt

Integrating

LogV

-(

&)t

+k

Supercapacitors come with different manufacturer

specifications for CW or pulsed operation. CW type
supercapacitors may be suitable for backup of
CEMOS microcomputers, back up during battery
change, static RAMS, DTCs measuring instruments,
automatic control, electronic typewriters, VCR,
Video disk, phones (memory, auto dialing),
electronic cash registers and engin back up ignition.
However, pulsed type supercapacitors are often
recommended for hybrid batteries for burst power
delivery, actuators, batteries, relays, solenoids,
starters, igniters, display, alarm and transient
charging. Typical characteristics of commercial
spercapacitors are shown in Table 2.
~~

When t = 0, V = Vi, therefore (29) reduces to

LogVi

From one can write

- t / RC )
During discharge of current, through parallel load RL
the time dependent current I(t) is given by

I(t)= yexp( -t/RC )

R

Table 2 Characteristics of
Features

(32)

From above goregoing discussions and derivations

we conclude that for
t = 0, I(t) = Vi/R ;No charge released.
t = 03, I(f) = 0; All charge depleted.
Where RC e t
l/f. So to charge a capacitor with
high Erequency surges RC must be extremely small.

Voltage level (V)

50- IOOV

Current (I)

100 - 300 A

Pulse duration ('t)

6. Characteristicsof Supercapacitors
Commercial supercapacitors may be classified as
high power (ms-several sec), high voltage (>lo0 V)
and high energy density (5-10 times the normal
capacitors) supercapacitors. Electrical energy may be
stored either in batteries or in capacitors. Batteries
can store ener4gy much more than capacitors but its
charge or discharge time is much higher than
capacitors. It is not suitable for pulsed operation.

111- 197

percapacitors
Ranges

1.0 ms-sec

Capacitance 0

1-10F

Power density (KW/L)

5 - 180

Energy Density (KJ/L)

0.5 - 0.6

ESR 8

20 - 30

Temperature cycle

-2OOC to +6OoC

Performance of superconductors regarding charging

and discharging characteristics is graphically shown
in Figure 4.

- sc

............. eC

Discharging

Time(ms)

Figure 4 Capacitor Charging and discharging

characteristics (approximate scale)
Supercapacitors are normally designed for optimum
characteristics in dedicated applications. The
charging and discharging times are decided
accordingly. Commercial capacitors are designed for
specific purpose such as switchgear, power quality,
high speed photography and repetitive applications as
shown in Table 3.

6
Comparision of super capacitors, batteries and
conventional capacitors regarding energy density
versus power density characteristics is shown in
Figure 5 .
If the primary objective is to use supercapacitors for
storing lightning impulses (40 - 100 Ps) then
supercapacitors, if not especially designed for
transients, prove less efficient than electronic
capacitors. The problem with electronic capacitors is
their potential inability to charge and discharge huge
level currents that is otherwise possible using
supercapacitors. Regarding above, either a new
design be awaited or go for some kind of trade-off
between energy densities and charging times.

61

3
r

Table 3 Application oriented charge and discharge

times of supercapacitors.

Log (times (h))

Figure 6 Self-discharge characteristics of
supercapacitors.

Charging
time

Discharging
time

Switchgears

60 - 120 s

20-50s

Power Quality

50 - 100 s

10ms-10s

Flashlamps

10-20s

1 - 100 ms

Pulsed

<1 .O ms

> 1.0 ms

Applications

Supercapacitors are preferred over conventional

capacitors and batteries due to their potential high
energy density and huge power releasing capability
in shorter times.

lo6

1Batteries

///

on

9
IO'

1o3

1o6

Power density (WKg)

Figure 5 Energy density versus power density.

Supercapacitors further suffer from self-discharge

phenomenon due to charged layer and redox
capacitors. The Faradaic leakage current passes
across the double layer by means of electron transfer.
This process coctinues until there is no Gibbs energy
(potential) to derive it. Self-discharge rate of a
typical commercial Panasonic double layer
capacitors is shown in Figure 6. The self-discharge
mechanism is even further accelerated on higher
temperatures as illustrated above.
7. Conclusions
Based on above theoretical analysis and published
data, I am confident to declare, the supercapacitors
have relatively longer charge and discharge times; at
least > 1.0 ms so they are not good for storing
microsecond lightning pulses. However, normal
capacitors may be considered as an alternative. The
DC batteries, whatsoever, are absolutely unable to
store lightning surges.

Performance and suitability priorities regarding

transient storage applications, so far as I can see, the
electronic capacitors are best. Supercapacitors,
however, are much more suitable for leveling
voltage/current plumes created by short circuit faults
on power system. Thus the primary applications of
supercapacitors are more attractive for, vehicles and
power quality area.

7
8. Acknowledgements

This study was supported by an IRPA Project No.

02-02-04-00 15, dated January 1, 2000; being
conducted by Power Group in, Faculty of
Engineering, University Putra Malaysia.

8. References
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Burke

and

T.C.

Mater.Res.Soc.Symp.Proc. PP.

Murphy,
393,375,

1995.
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3.

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5.
6.

7.

8.

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cz.,TheElectrochemical
Society,Inc.,
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P.Malaspina;Fort
Pierce,Fla.;
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Uniquely Advanced Power Technology
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S.A.Boctor,Electric
Circuit
Analysis;
PP.286-301, 1992.
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Trans.Nucl.Sci.NS-l8(4), PP. 235-137,
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111- 199