Electrochimica Acta 45 (2000) 2483 – 2498

www.elsevier.nl/locate/electacta

Principles and applications of electrochemical capacitors

R. Kötz a,*, M. Carlen b
a
Paul Scherrer Institut, General Energy Research Department, CH-5232 Villigen, Switzerland
b
ABB Corporate Research, CH-5405 Baden/Dättwil, Switzerland

Papers received in Newcastle, 20 December 1999

Abstract

Electrochemical capacitors (EC) also called ‘supercapacitors’ or ‘ultracapacitors’ store the energy in the electric field
of the electrochemical double-layer. Use of high surface-area electrodes result in extremely large capacitance. Single
cell voltage of ECs is typically limited to 1–3 V depending on the electrolyte used. Small electrochemical capacitors
for low-voltage electronic applications have been commercially available for many years. Different applications
demanding large ECs with high voltage and improved energy and power density are under discussion. Fundamental
principles, performance, characteristics, present and future applications of electrochemical capacitors are presented in
this communication. © 2000 Elsevier Science Ltd. All rights reserved.

Keywords: Electrochemical capacitors; Electronic applications; Voltage; Supercapacitor; Ultracapacitor; Double layer

1. Introduction market such devices were undertaken by SOHIO [2].

However, only in the nineties electrochemical capaci-
Capacitors which store the energy within the electro- tors became famous in the context of hybrid electric
chemical double-layer at the electrode/electrolyte inter- vehicles. A DOE ultracapacitor development program
face are known under various names which are trade was initiated in 1989, and short term as well as long
marks or established colloquial names such as ‘double- term goals were defined for 1998 – 2003 and after 2003,
layer capacitors’, ‘supercapacitors’, ‘ultracapacitors’, respectively [3]. The EC was supposed to boost the
‘power capacitors’, ‘gold capacitors’ or ‘power cache’.
battery or the fuel cell in the hybrid electric vehicle to
‘Electrochemical double-layer capacitor’ is the name
provide the necessary power for acceleration, and addi-
that describes the fundamental charge storage principle
tionally allow for recuperation of brake energy. Today
of such capacitors. However, due to the fact that there
several companies such as Maxwell Technologies,
are in general additional contributions to the capaci-
Siemens Matsushita (now EPCOS), NEC, Panasonic,
tance other than double layer effects, we will call these
capacitors electrochemical capacitors (EC) throughout ELNA, TOKIN, and several others invest in electro-
this paper. chemical capacitor development. The applications en-
Electrochemical capacitors have been known since visaged are principally boost components supporting
many years. First patents date back to 1957 where a batteries or replacing batteries primarily in electric vehi-
capacitor based on high surface area carbon was de- cles. In addition alternative applications of EC not
scribed by Becker [1]. Later in 1969 first attempts to competing with batteries but with conventional capaci-
tors are coming up and show considerable market
potential. Such applications will also be discussed in
* Corresponding author. Tel.: + 41-056-3102057; fax: +41- detail in the second part of the paper.
056-3104415. The reason why electrochemical capacitors were able
E-mail address: [email protected] (R. Kötz) to raise considerable attention are visualized in Fig. 1

0013-4686/00/$ - see front matter © 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 3 - 4 6 8 6 ( 0 0 ) 0 0 3 5 4 - 6
2484 R. Kötz, M. Carlen / Electrochimica Acta 45 (2000) 2483–2498

where typical energy storage and conversion devices are at the surface of the solid electrode and compensate for
presented in the so called ‘Ragone plot’ in terms of the electronic charge at the electrode surface. The thick-
their specific energy and specific power. Electrochemical ness of the double layer depends on the concentration
capacitors fill in the gap between batteries and conven- of the electrolyte and on the size of the ions and is in
tional capacitors such as electrolytic capacitors or the order of 5 – 10 A, for concentrated electrolytes. The
metallized film capacitors. In terms of specific energy as double layer capacitance is about 10 – 20 mF/cm2 for a
well as in terms of specific power this gap covers several smooth electrode in concentrated electrolyte solution
orders of magnitude. and can be estimated according to equation Eq. (1)
Batteries and low temperature fuel cells are typical
low power devices whereas conventional capacitors
C/A= o*o
0 r/d (1)
may have a power density of \106 watts per dm3 at
very low energy density. Thus, electrochemical capaci-
tors may improve battery performance in terms of assuming a relative dielectric constant or of 10 for water
power density or may improve capacitor performance in the double layer [5]. d being the thickness of the
in terms of energy density when combined with the double-layer with surface area A. The corresponding
respective device. In addition, electrochemical capaci- electric field in the electrochemical double layer is very
tors are expected to have a much longer cycle life than high and assumes values of up to 106 V/cm easily.
batteries because no or negligibly small chemical charge Compared to conventional capacitors where a total
transfer reactions are involved. A monograph volume capacitance of pF and mF is typical, the capacitance of
on electrochemical capacitors was recently published by and the energy density stored in the electrochemical
Conway [4]. double layer is rather high per se and the idea to build
In the following the basic principal of electrochemical a capacitor based on this effect is tempting.
capacitors, the different types of ECs, some theoretical In order to achieve a higher capacitance the electrode
considerations as to the performance of ECs, and some surface area is additionally increased by using porous
applications will be discussed. electrodes with an extremely large internal effective
surface. Combination of two such electrodes gives an
electrochemical capacitor of rather high capacitance.
Fig. 2 shows a schematic diagram of an electrochem-
2. Principle of energy storage ical double-layer capacitor consisting of a single cell
with a high surface-area electrode material, which is
Electrochemical capacitors store the electric energy in loaded with electrolyte. The electrodes are separated by
an electrochemical double layer (Helmholtz Layer) a porous separator, containing the same electrolyte as
formed at a solid/electrolyte interface. Positive and the active material. The potential drop across the cell is
negative ionic charges within the electrolyte accumulate also shown in Fig. 2.

Fig. 1. Sketch of Ragone plot for various energy storage and conversion devices. The indicated areas are rough guide lines.
 R. Kötz, M. Carlen / Electrochimica Acta 45 (2000) 2483–2498 2485

those obtained for available batteries but much higher

than for conventional capacitors. It should be men-
tioned that the above values depend on the double layer
capacitance, the specific surface area of the respective
electrode material, the wetting behavior of the pores,
and on the nominal cell voltage.

3. Classification of electrochemical capacitors

Electrochemical capacitors may be distinguished by

several criteria such as the electrode material utilized,
the electrolyte, or the cell design. With respect to
electrode materials there are three main categories:
carbon based, metal oxides and polymeric materials. A
comprehensive review of possible electrode materials
suitable for ECs is given by Sarangapani [6].

3.1. Electrode material

3.1.1. Carbon
Carbon in various modifications is the electrode ma-
terial used most frequently for electrodes of electro-
chemical capacitors. Reasons for using carbon are
manifold such as (i) low cost, (ii) high surface area, (iii)
availability, and last but not least (iv) established elec-
trode production technologies. Carbons are available
Fig. 2. Principle of a single-cell double-layer capacitor and with a specific surface area of up to 2500 m2/g as
illustration of the potential drop at the electrode/electrolyte powders, woven cloths, felts, or fibers.
interface
Charge storage on carbon electrodes is predomi-
nantly capacitive in the electrochemical double layer.
The capacitance of a single electrode can be esti- Carbon based electrochemical capacitors come close to
mated by assuming a high surface area carbon with what one would call an electrochemical double layer
1000 m2/g and a double layer capacitance of 10 mF/cm2. capacitor. There are however contributions from sur-
This leads to a specific capacitance of 100 F/g for one face functional groups which are in general present on
electrode. activated carbons and which can be charged and dis-
For a capacitor two electrodes are needed with dou- charged giving rise to pseudocapacitance.
bled weight and half the total capacitance (1/C=1/ A typical cyclic voltammogram (CV) for an activated
C1 + 1/C2) resulting in 25 F/g of active capacitor mass glassy carbon electrode is reproduced in Fig. 3 for
for this example. electrochemically activated glassy carbon in aqueous
The difference between single electrode values and and non-aqueous electrolyte [7,8]. The rectangular
specifications given for the complete capacitor is of shape expected for an ideal capacitor is best ap-
significant importance. Whenever specifications of an proached in organic electrolyte, while the redox peak
EC are given, one should indicate whether the values around 0.4 Vsce in aqueous electrolyte illustrates the
correspond to single electrode measurement or are cal- contribution from surface functional groups. This cor-
culated for a complete capacitor. The difference be- responding pseudocapacitance is significantly reduced
tween these two situations is a factor of four and in organic electrolyte because protons are not available.
therefore of significant importance. The effect of surface functional groups containing oxy-
The maximum energy stored in such a capacitor is gen on the stability of carbon electrodes in EC using
given by organic electrolyte was investigated by Nakamura et al.
W=1/2 C U 20 (2) [9]. These authors found that the stability of the acti-
vated carbon increases with the oxygen content when
With a cell voltage U0 of 1 V (aqueous electrolyte) the carbon is used for the anode and decreases when
one obtains a specific energy of about 3.5 Wh/kg of used for the cathode. In general one can observe that
active mass. Using an organic electrolyte with a typical both the stability and conductivity of the activated high
cell voltage of 2.3 V one obtains about 18 Wh/kg of surface area carbon decrease with increasing surface
active mass. These values are considerably lower than area [10].
2486 R. Kötz, M. Carlen / Electrochimica Acta 45 (2000) 2483–2498

have been suggested by several authors [17 – 19] as

electrodes for electrochemical capacitors. The typical
cyclic voltammogram of a polymer however is in gen-
eral not of rectangular shape, as is expected for a
typical capacitor, but exhibits a current peak at the
respective redox potential of the polymer. In order to
be able to use one and the same electrode material on
both capacitor electrodes polymers with a cathodic and
an anodic redox process were utilized recently [19].
Using a polymeric material for electrochemical ca-
pacitor electrodes gives rise to a debate as to whether
such devices should still be called capacitors or whether
they are better described as batteries. In terms of the
voltage transient during charge and discharge and with
respect to the CV they are batteries. Compared to
Fig. 3. Cyclic voltammograms of activated glassy carbon metallic oxides, however, the term capacitor is justified.
electrodes at 100 mV/s in 3M H2SO4 (aq.) and in 1 M The difference being only that the metallic oxides ex-
TEABF4 in acetonitrile. Both electrodes received the same hibit a series of redox potentials giving rise to an almost
electrochemical activation. rectangular CV while the polymer typically has only
one redox peak.
3.1.2. Metal oxides For such capacitors rather high energy density and
The cyclic voltammogram of RuO2 (and also IrO2) power density have been reported [19]. The long-term
electrodes have an almost rectangular shape and exhibit stability during cycling, however, may be a problem.
good capacitor behavior [11,12]. However, the shape of Swelling and shrinking of electroactive polymers is well
the CV is not a consequence of pure double layer known and may lead to degradation during cycling.
charging, but of a sequence of redox reactions occur-
ring in the metallic oxide. The valence state of Ru may 3.2. Electrolyte
change from III to VI within a potential window of
slightly \1 V. The ratio of surface charging to bulk Another criteria to classify different electrochemical
processes was nicely separated by Trasatti [11]. In capacitors is the electrolyte used. Most of the presently
aqueous acid electrolytes the fundamental charge stor- available capacitors use an organic electrolyte.
age process is proton insertion into the bulk material. 3.2.1. Organic
Very high specific capacitance of up to 750 F/g was The advantage of an organic electrolyte is the higher
reported for RuO2 prepared at relatively low tempera- achievable voltage. According to Eq. (2) the square of
tures [13]. Conducting metal oxides like RuO2 or IrO2 the unit-cell voltage determines the maximum stored
were the favored electrode materials in early EC s used energy. Organic electrolytes allow for a unit cell voltage
for space or military applications [14]. The high specific above 2 V. Typically the cell float voltage is 2.3 V with
capacitance in combination with low resistance resulted the possibility to increase the voltage for a short time to
in very high specific powers. These capacitors, however, 2.7 V. The cell voltage is most probably limited by the
turned out to be too expensive. A rough calculation of water content of the electrolyte. In order to achieve
the capacitor cost showed that 90% of the cost resides higher voltage, some companies plan to go up to a float
in the electrode material. In addition, these capacitor voltage of 3.2 V, extreme purification procedures of
materials are only suitable for aqueous electrolytes, special electrolyte have to be applied and the corrosion
thus limiting the nominal cell voltage to 1 V. of the carbon electrodes has to be reduced by special
Several attempts were undertaken to keep the advan- protective coatings [20]. However, similar problems
tage of the material properties of such metal oxides at concerning the potential window of organic electrolyte
reduced cost. The dilution of the costly noble metal by are known from Li-ion battery production and can be
forming perovskites was investigated by Guther et al. overcome.
[15]. Other forms of metal compounds such as nitrides On the other hand organic electrolytes have a signifi-
were investigated by Liu et al. [16]. However, these cantly higher specific resistance. Compared to a concen-
materials are far from being commercially used in ECs. trated aqueous electrolyte the resistance increases by a
factor of at least 20, typically by a factor of 50. The
3.1.3. Polymers higher electrolyte resistance also affects the equivalent
Polymeric materials, such as p- and n-dopable distributed resistance of the porous layer and conse-
poly(3-arylthiopene), p-doped poly(pyrrole), poly(3- quently reduces the maximum usable power, which is
methylthiophene), or poly(1,5-diaminoanthraquinone) calculated according to
 R. Kötz, M. Carlen / Electrochimica Acta 45 (2000) 2483–2498 2487

developed for one or the other electrolyte, not only

because of material aspects but also the porous struc-
ture of the electrode has to be tailored for the size and
the properties of the respective electrolyte.
In order to avoid electrolyte depletion problems dur-
ing charging of the EC, the electrolyte concentration
has to be high. If the electrolyte reservoir is too small
compared to the huge surface area of the electrodes,
performance of the capacitor is reduced. This problem
is particularly important for organic electrolytes where
the solubility of the salts may be low. Zheng and Jow
found, however, that concentrations higher than 0.2
molar are sufficient [24].

4. Electrochemical capacitor performance

The performance characteristics of electrochemical

capacitors differ somewhat from those of conventional
capacitors. In Fig. 4 the impedance plane representa-
tion (Nyquist plot) of an ideal capacitor and a sim-
plified electrochemical capacitor, both having the same
ESR (equivalent series resistance at 1 kHz), are com-
pared. While the ideal capacitor exhibits a vertical line,
the electrochemical capacitor starts with a 45°
impedance line and approaching an almost vertical line
only at low frequencies.
The non-vertical slope of the low frequency
impedance of any real electrochemical capacitor can be
Fig. 4. Schematic representation of the Nyquist impedance easily reproduced in any model equation by replacing
plot of an ideal capacitor (vertical thin line) and an electro- the capacitance expression with a constant phase ele-
chemical capacitor with porous electrodes (thick line). ment (CPE) expression. This amounts to replacing ev-
ery jv expression with ( jv)p, where 0 B pB1, and
P =U 2/4R (3) where p=1 represents an ideal capacitor with no fre-
quency dependence. This non-ideality is a typical fea-
where R represents the total effective series resistance ture of electrochemical charging processes, and may be
(ESR). However, part of the reduction in power is interpreted as resulting from a distribution in macro-
compensated by the higher cell voltage achievable with scopic path lengths (non-uniform active layer thickness)
an organic electrolyte. A listing of potential organic [25] or a distribution in microscopic charge transfer
electrolytes for electrochemical capacitors is provided in rates [26], adsorption processes, or surface roughness.
[21]. The 45° region (Warburg region) is a consequence of
the distributed resistance/capacitance in a porous elec-
3.2.2. Aqueous trode. At higher frequencies the resistance as well as the
Aqueous electrolytes limit the unit cell voltage of the capacitance of a porous electrode decreases, because
EC to typically 1 V, thus reducing the available energy only part of the active porous layer is accessible at high
significantly compared to organic electrolytes. Advan- frequencies. The electrochemical capacitor may thus be
tages of the aqueous electrolyte are the higher conduc- represented by an ideal capacitor with an ESR in-
tance (0.8 S/cm for H2SO4) and the fact that creased by the ‘equivalent distributed resistance’ EDR.
purification and drying processes during production are
less stringent. In addition cost of aqueous electrolytes 4.1. Porous electrode
are usually much lower than for suitable organic elec-
trolytes. Capacitors build by NEC [22] and ECOND The porous electrode is often described by a trun-
use aqueous electrolyte. Aiming at high power density, cated RC-transmission line according to Fig. 5. The
the glassy carbon based capacitor developed in our equivalent circuit of the pore of a porous electrode is
laboratories also uses an aqueous electrolyte [23]. It approximated by a line of R and C elements represent-
should be pointed out that the capacitor has to be ing the elemental double layer capacitance and the
2488 R. Kötz, M. Carlen / Electrochimica Acta 45 (2000) 2483–2498

1
Low frequency Z(0) =

'
jvC
Rw
High frequency Z(v “ )=
jvC
where RW represents the low frequency resistance span-
ning the 45o Warburg region and C represents the low
frequency capacitance, which is determined by the dou-
ble layer capacitance times the total pore surface area.
The total impedance of a capacitor would also include
the ionic resistance of the bulk electrolyte and separator
as well as any contact resistance in the system. The
total impedance would then be Rcontacts + Rsol + Z(v).
For a porous, highly conducting layer with a liquid
Fig. 5. Equivalent circuit representation of the distributed electrolyte filling the pores, the low frequency resistance
resistance and capacitance within a pore. Five-element trans-
RW depends only on the porosity and on the apparent
mission line.
conductivity k of the electrolyte. k may appear to be
somewhat smaller than the bulk electrolyte conductivity
respective electrolyte resistance at a particular depth of if the pores are tortuous instead of straight [29].
the pore. The resistance of the bulk material is assumed
to be much smaller than the electrolyte resistance. At L
Rw = (5)
high frequencies the capacitors behave like small 3pr 2nk
impedance elements (Z=1/jvC) and the current flows
Where L is the active layer thickness (the length of the
predominantly along R1 and C1 into the bulk material
pores for straight, cylindrical pores), r is the pore
and almost no current flows deep down the pore.
radius, and n the number of pores. The porosity, the
Consequently, resistance and double layer capacitance
volume fraction of pores, would be pr 2n/A, where A is
are reduced at high frequencies [27].
the geometric electrode area and n the number of pores
A more complete description of the porous electrode
per volume.
behavior was given by De Levie [28]. Assuming straight
For a theoretical estimation of the contribution of
cylindrical pores with a radius r and length l, a double
the active porous layer to the series resistance we apply
layer capacitance and an electrolyte conductivity k one
the DeLevie transmission line model of a porous elec-

'
can calculate the impedance according to
trode with straight pores considered as cylindrical capil-
Rw laries [28]. The electrolyte conductivity is 0.8 S/cm (3M
Z(v) = coth
jvRwC (4)
jvC H2SO4) and the double layer capacitance at the walls of
the pores is assumed to be 10 mF/cm2. The pores have
a diameter of 3 nm and are arranged in a rectangular
closed packed manner. The resulting porosity of the
layer is 78% with a pore density of 1013/cm2. Such a
layer has a volumetric capacitance of 105 F/cm3 and a
specific resistance of 0.53 Vcm (1.9 S/cm).
The impedance plots and the capacitance versus fre-
quency plots are shown for such a layer in Figs. 6 and
7 for three different thicknesses. The capacitance is
calculated from the imaginary part of the complex
impedance according to
C= − 1/[v Im(Z)] (6)
The impedance plot is equivalent to that sketched in
Fig. 4 and the typical 45° Warburg region is visible for
the three thicknesses. In this high frequency domain the
porous character of the active layer dominates. In the
Fig. 6. Calculated impedance plots for porous electrodes with capacitance versus frequency plot, the capacitance
different thickness. Assumptions: Double layer capacitance: 10 starts to decrease noticeably at high frequency. The
mF/cm2; pore diameter: 3 nm; electrolyte conductivity 0.8 cut-off frequency is roughly related to the RC time
S/cm; rectangular closed packed arrangement of pores 1013/ constant of the single electrode capacitor. At lower
cm2; constant phase element exponent 0.98. frequencies the impedance plot (Fig. 6) approaches a
 R. Kötz, M. Carlen / Electrochimica Acta 45 (2000) 2483–2498 2489

vertical line. A CPE of 0.98 was assumed for the

calculation. In the corresponding capacitance versus
frequency plot the capacitance levels off at lower
frequencies.
Assuming an organic electrolyte with a specific con-
ductance of 0.04 S/cm the very same electrode has a
specific resistance of 10.6 Vcm (0.09 S/cm).
The effect of active layer thickness is demonstrated in
Figs. 6 and 7 where the capacitance versus frequency
plots are shown for electrodes with active layer thick-
nesses of 25, 50, and 100 mm. The increased film
thickness leads to a higher capacitance at low frequen-
cies and of course to an increased distributed resistance
of the film. These two factors cause a higher time Fig. 7. Capacitance versus frequency plot for the electrodes of
constant RC that is reflected by the lower cut-off Fig. 6.
frequency for thicker electrodes. The effect of the pore
number and the pore diameter is simply understood in
the simple porous layer model. The equivalent resis-
be reached for the organic electrolyte. From this plot it
tance of the porous layer is directly proportional to the
is evident that very thin films ( B 10 mm) result in a
porosity of the layer, i.e. to the volume of the elec-
decreased energy density at almost constant power den-
trolyte within the porous structure. Thus, an increase of
sity because the internal resistance is totally determined
the pore number with constant radius or an increase of
by the electrolyte. The same is true on the other end of
the pore diameter at constant pore number results in
the plot where thick films (\100 mm) result in reduced
increased capacitance and reduced resistance. An exam-
power at constant energy density, because now the
ple is given for an increase of the pore diameter from 2
internal resistance is determined by the porous layer.
to 20 nm at constant pore number of 2.5 1011/cm2. The
In order to increase EC performance, the material
respective porosity increases from 0.8 to 78%. The
properties have to be investigated and improved. The
capacitance versus frequency plot in Fig. 8 shows the
resistance of the electrolyte and, particularly, the con-
increased capacitance and the increasing cut-off
tact resistance have to be controlled. An optimized
frequency.
electrolyte and electrode material may allow for poten-
tial windows wider than 3 V. The effect of the nominal
4.2. Maximum achie6able energy density and power voltage of the capacitor cell in case of an organic
density electrolyte is plotted in Fig. 10 for potentials of 2, 3, 4
V. With an organic electrolyte and a 4 V cell voltage
The maximum achievable power and energy densities the capacitor comes close to the power performance of
of an EC can be calculated from Eqs. (2) and (3) the capacitor using aqueous electrolyte.
assuming reasonable values for electrode and electrolyte
layer thickness and conductance. Such a plot is shown
in Fig. 9, where the active layer thickness is the parame-
ter along the curve with a thickness of 1 mm at the left
end and 1000 mm at the right end of the curves. We
assumed for the parameters a volumetric capacitance of
100 F/cm3 for the single electrode, a current collector
thickness of 25 mm and an electrolyte/separator thick-
ness of 25 mm. The separator has a porosity of 50%. As
already mentioned, the active layer thickness is varied
from 1 to 1000 mm. The two curves in Fig. 9 represent
a capacitor with aqueous electrolyte and a 1 V potential
window and a capacitor with organic electrolyte and a
potential window of 2.3 V. The conductance of the
aqueous electrolyte is 0.8 S/cm while for the organic
electrolyte a conductance of 0.02 S/cm was assumed.
As is evident from Fig. 9 on the basis of these Fig. 8. Effect of pore diameter on the capacitance versus
theoretical considerations a power density of up to frequency performance of a single porous electrode. Thickness
2*106 W/l can be achieved for the aqueous electrolyte of porous layer: 100 mm, CPE: 0.98, double layer capacitance
and a maximum energy density of about 20 Wh/l can 20 mF, number of pores 2.5*1011/cm2
2490 R. Kötz, M. Carlen / Electrochimica Acta 45 (2000) 2483–2498

Fig. 9. Calculated maximum achievable power density and maximum achievable energy density for two capacitors with aqueous (1
V) and organic electrolyte (2.3 V). The parameter on the curves is the active porous layer thickness. Assumptions: separator
thickness: 25 mm, separator porosity: 50%, volumetric capacitance of porous layer: 100 F/cm3.

4.3. Ragone plots dc = tan (d) = tan (900 − 8) (7)

Although similar, the above plots do not correspond which is a measure for the quality of the capacitor. The
to Ragone plots. The Ragone plot relates power and power dissipated as heat in the internal resistance is
energy density for one single device: they provide the determined by the cosine of 8. A loss factor of 0.5
energy available for a constant power load. The maxi- (8 =60°) is achieved at a frequency of 12 Hz for the
mum values discussed in Figs. 9 and 10 are only end PSI and of 0.25 Hz for the Panasonic capacitor. At a
points of Ragone plots where the maximum energy
density is related with a vanishing power density and
vice versa. Electrochemical impedance data, the phase
angle 8, and the corresponding Ragone plots for a
Panasonic GoldCap (10 F and 2.5 V) and an aqueous
capacitor developed in our lab [23,30] with 5 V and 0.8
F are shown in Figs. 11a, b and 12. Calculation of
Ragone plots for a constant power discharge of a
capacitor is analytically not possible for a general fre-
quency dependent impedance [31,32]. There is, how-
ever, a simple linear approach [32] to present energy
and power in a Ragone plot, which was used for the
plots in Fig. 12.
The two devices cannot be compared directly because
the Panasonic device is commercially available, while
the PSI capacitor is a laboratory type device only,
without a professional housing. From both plots it is
evident that the maximum power is available only with
very low energy, i.e. for very short time. The phase
angle 8 of the impedance plot (see also Fig. 4) for both Fig. 10. Effect of nominal cell voltage on the maximium
capacitors is shown in Fig. 11b. The efficiency of a achievable power and energy density of Fig. 9 for the capaci-
capacitor is related to the loss factor dc, tor with organic electrolyte.
 R. Kötz, M. Carlen / Electrochimica Acta 45 (2000) 2483–2498 2491

Fig. 11. (a) Measured electrochemical impedance plots for a commercial Panasonic capacitor (10 F, 2.5 V, open squares) and a
laboratory type capacitor (0.8 F, 5 V, filled squares) based on glassy carbon electrodes built at the PSI. (b) Phase angle for the same
two capacitors. (Open symbols Panasonic ‘GoldCap’, closed symbols PSI-cap)

phase angle of 45° about 70% of the power corresponds In a recent comparison of ECs and batteries in EV
to heat production at the internal resistance. applications, Burke and Miller [33] found that there is
a slight advantage of a good capacitor over a good
battery in terms of round trip efficiency, the efficiency
5. Cell design of the capacitor being 92% and that of a NiMH battery
about 85%. Therefore, ESR reduction of electrochemi-
Efficiency is a very important issue for EC in electric cal capacitors is very important in order to compete
vehicle (EV) applications. Part of the available energy is with other storage devices. There are at least four
dissipated at the internal resistance ESR. At high different contributions to the ESR originating from the
power, i.e. high current, this loss can become dominant. (i) electrolyte including separator, (ii) current collector,

Fig. 12. Ragone plots calculated from the measured impedance for the two capacitors of Fig. 11. (Open symbols Panasonic
‘GoldCap’, closed symbols PSI-cap)
2492 R. Kötz, M. Carlen / Electrochimica Acta 45 (2000) 2483–2498

(iii) porous layer including contact to current collector, means a more complex system than a storage system,
and (iv) other contact resistances. but it is most adequate if a large amount of energy is
In order to prevent short circuits between neighbor- needed for a long time. Storage of electric energy can
ing capacitor electrodes, a porous separator has to be be done in electric fields (capacitors), by means of
used as a spacer. Independent of the choice of elec- chemical reactions (batteries), in magnetic fields
trolyte the spacer has to be thin and highly porous in (SMES: superconducting magnetic energy storage) or
order to keep the resulting resistance low. The conduc- by transferring the electric energy to mechanical
tance s of an electrolyte in a porous non-conducting (flywheel) or potential (pumped hydro) energy or to
separator is a function of the porosity p and the specific pressure. The choice of the energy storage device
conductance of the electrolyte so according to [34] should be adequate for the application. Similarities and
differences between batteries and electrochemical ca-
s =sop a with 1.5B aB2 (8) pacitors were discussed by Conway et al. [35,36].
Consequently, the choice of electrolyte, separator The ideal applications for ECs are all those demand-
thickness, and porosity is a complex issue, keeping ing energy for a duration in the time range 10 − 2 s5 t
mechanical stability, volume, and resistance in mind. 5 102 s. For those applications, as well for batteries as
For a monopolar cell arrangement, current flow for conventional capacitors, the ratio of stored energy
along a thin current collector at high currents, which to available power is unfavorable and the devices have
can be expected for fast discharge applications, may to be over-dimensioned due to either the power or
well contribute to ohmic losses. Homogeneous current energy demands. The needs for long lifetime, for many
distribution in monopolar electrochemical cells, espe- charge-discharge cycles (e.g., in combination with pho-
tovoltaics) or for fast recharging rates may increase the
cially at high currents, is an important issue.
time range to days and weeks. The poor energy density
In case of a bipolar EC, where the current flows
of low voltage capacitors makes ECs also attractive for
normal to the current collector (bipolar plate) from one
pulse power applications in the ms range.
to the next cell, the contribution from the current
The basic technology of ECs with carbon electrodes
collectors to resistance is negligible.
is independent of polarity. Nevertheless, present ECs
Compared to conventional capacitors, ECs have the
are not suitable for AC applications and for applica-
disadvantage of a rather low cell voltage. In order to
tions involving a high ripple current. Their internal
achieve several hundred volt capacitor voltage, which is
resistance is higher than the one of conventional capac-
typical for EV and other applications, many single cells
itors and thermal degradation may occur. In addition,
have to be connected in series. The bipolar cell design is
some manufacturers use asymmetric electrode systems
an elegant way to connect many cells in series without
or have special treatments of one of the two electrodes
introducing extra wiring and contact resistance. How-
causing a polarity of the devices.
ever, a bipolar cell stack requires a sophisticated sealing Most ECs are short circuit proven. On one hand, the
concept for each cell. larger internal resistance in comparison to conventional
In order to have a good voltage balance over all capacitors limits the peak power. On the other hand,
units, these have to have equal performance. Otherwise the smaller amount of energy stored in comparison to
different cells will experience different voltage, which batteries allows only a limited heating of the ECs, so
may be higher than the nominal voltage. Such problems that self-ignition does not occur. Another important
have to be overcome by very narrow manufacturing advantage of ECs is that in general, they do not contain
tolerance or by extra electronic controls providing over- hazardous or toxic materials and that they are easy to
voltage protection. These electronic control circuits can dispose. They do not need any servicing during their
be easily added to the single monopolar cells of a life and can withstand a huge number of charge-dis-
capacitor stack, but it will be difficult to add these extra charge cycles [37,38]. In a properly designed system,
protections to the single cells of a bipolar capacitor cycling efficiency is 95% and higher. They are applica-
stack. ble in a large temperature range. Particularly at low
temperature, they substantially outperform conven-
tional batteries. Short-term (ms – s) over-voltage is in
6. Applications general not critical to the devices. If the applied voltage
exceeds the nominal voltage for longer duration, the
Many applications are demanding local storage or lifetime of the EC will be shorted. Gas may be pro-
local generation of electric energy. This may be re- duced which can cause leakage or rupture of the device.
quired since they are in portable or remote equipment, The characteristic time for self-discharge is in the order
since the supply of power may be interrupted or since of days to months. The low voltage of the unit cells
the main power supply is not able to deliver the peak allows an easy adoption to the desired voltage level by
power. Local generation of energy (Diesel generator, connecting cells into series and a modular construction
fuel cell, gas turbine, photovoltaics, etc.) normally of large banks.
 R. Kötz, M. Carlen / Electrochimica Acta 45 (2000) 2483–2498 2493

Fig. 13. Commercial electrochemical capacitors and toy equipped with an Electrochemical Capacitor.

6.1. O6er6iew of commercially a6ailable ECs of 1 F to several hundred Farads. The RC time con-
stant is about 0.3 s. The capacitors are most suitable
The first ECs appeared on the market in 1978 for starter and actuator applications.
(Gold Capacitors from Panasonic/Matsushita) and in Panasonic sells for several years cylindrical single
1980 (Supercap from NEC/Tokin). Two other cell capacitors with capacitance up to 1500 F (Power
Japanese companies entered into the markets with Capacitor, 2.3 V). Maxwell has prismatic shaped
products of comparable ratings end of the eighties ECs (PowerCache Ultracapacitors, 2.3 V) with
(Dynacap from ELNA, Polyacene Capacitor/Battery capacitance values between 8 and 2700 F.
from Seiko Instruments). All those manufacturers Recently Siemens Matsushita (now EPCOS) started to
have products with nominal voltage in the range 2.3– offer identical products. Those capacitors have RC-
6 V and capacitance values of 10 − 2 F to several times in the range 0.6 – 3 s. The manufacturing capa-
Farads. Tokin also offers capacitors at 11 V. The bilities of those types of ECs are presently strongly
costs of those ECs are in the order of a few to a few increased.
ten cents per Joule. The RC-time constant (defined as A selection of ECs is shown in Fig. 13. They are
the low frequency capacitance times the 1 kHz resis- all based on carbon electrodes. Various other compa-
tance) is several s. They are most suitable for con- nies are developing ECs and may soon appear on the
sumer electronic applications. Several hundred million market. At present, the ECs take up B 1% of the
ECs are manufactured and shipped per year. world market for electric energy storage (batteries, ca-
Since the beginning of the nineties, two Russian pacitors) [39]. They show nicely growing market num-
companies are selling ECs (PSCap from Econd, SC bers. The improving performance, the drop of prices,
from ELIT). They offer capacitors with nominal and new applications lead to the prediction of an
voltage in the range 12–350 V and capacitance values exciting future for ECs.
2494 R. Kötz, M. Carlen / Electrochimica Acta 45 (2000) 2483–2498

In another series of applications the EC is used as the

main power source. The EC delivers one or several
large current pulses of several ms to several s duration.
Afterwards the EC is recharged by a power supply of
low power rating. Typical applications are:
“ Toys: for example cars with ‘rechargeable motors’
[42] contain an EC which can be recharged from a
battery- or mains-powered charger. The charging
takes about 10 s and power is supplied to the car for
several 10 s. Due to compactness and low weight the
cars can accelerate very fast.
“ Fail-safe positioning: the EC provides the power for
Fig. 14. Use of ECs in electronic circuits. (a) shows a battery open or close positioning in case of power failures.
powered device where the EC provides power backup of the In the past, mostly spring systems have been used.
load in case of disconnection of the battery. (b) shows an The use of electric actuators with ECs allows to
AC-voltage powered device involving heavy switching cur- make smaller, cheaper and faster systems.
rents. The EC protects the critical load (e.g. memory) from “ Starter applications: the EC provides the main part
large voltage drops. of the pulse power for starting of, e.g. Diesel loco-
motives [43]. It is charged within B 1 min from
6.2. Present applications lead-acid batteries. It allows to start the Diesel en-
gine at very low temperature (Siberia). The size of
The largest part of the ECs sold nowadays is used in the battery system may be reduced by up to 50%.
consumer electronic products, where they mainly serve Since the pulse currents drawn from the batteries are
as backup sources for memories, microcomputers, sys- much smaller, the life of the batteries doubles.
tem boards, and clocks. In these applications there is a In a third type of applications the ECs are used as
primary power source which normally supplies the alternating power sources, e.g. on a day-night basis.
load. The basic setup is shown in Fig. 14. In case of During the day the electric load is supplied by, e.g.
power outages due to disconnection or turn-off of the solar cells, which also recharge the EC. During the
primary source, contact problems due to vibration or night the power is delivered by the EC. Typical applica-
shocks, or a drop of the system voltage due to switch- tions are:
ing-in of other heavy loads, the EC can supply the “ Solar watch: After being completely charged the EC
critical consumers. The EC should be mounted as close may feed the watch for several days. The watch does
to the critical load as possible. Some typical applica- not need any battery replacement during its lifetime.
tions are [40,41]: “ Solar lanterns, road marking lanterns, lighting of
“ Video recorders, TV satellite receivers: backup of time-tables at bus stop, illumination of parking me-
TV-channel setting, recording times, and clock time. ters, traffic warning signals: the combination of solar
The backup is provided for a duration of h to weeks. panels, LEDs instead of incandescent bulbs and ECs
“ Car audio system, taxi meter: backup of radio sta- makes a reliable system with a long lifetime and no
tion memory, taxi fare programs and accumulated needs for maintenance.
fare data while the car-radio or the taxi meter is The possibility for a huge number of charge-dis-
taken out of the car or the car battery is discon- charge cycles, the long lifetime, the large temperature
nected. Backup for a few h to a few days. range, the high cycling efficiency and the low self-dis-
“ Alarm clock radios, process controllers, home bak- charge makes ECs very suitable for this type of
ery, coffee machines: protects clocks and pro- applications.
grammed functions from getting lost in case of
temporary power outage. Backup for min to h. 6.3. Upcoming applications
“ Photo and video cameras, programmable pocket cal-
culators, electronic agendas and organizers, mobile The recent market introduction of low cost ECs with
phones, and pagers. The backup is provided during large capacitance and the capability of using them at
the replacement of the batteries for s to min. high voltage allows a large number of new applications.
In many of those applications, the cost of an EC is Under the most considered ones are electric vehicles
lower or comparable to the costs of a rechargeable (EV), hybrid electric vehicles (HEV) [44], and fuel cell
battery. The most important benefits of ECs are the vehicles. In all three cases the EC will serve as a
longer lifetime, the larger cycling capability, the possi- short-time energy storage device with high power capa-
bility of fast recharging, and the environmental bility and allow to store the energy obtained from
compatibility. regenerative braking. This energy will be reused in the
 R. Kötz, M. Carlen / Electrochimica Acta 45 (2000) 2483–2498 2495

next acceleration phase and boost the acceleration. It Transportation vehicles like people movers on fairs,
allows to reduce the size of the primary power source carriers in hospitals, warehouses or factories, airport
(batteries (EV), internal combustion engine (HEV), fuel buses, wheelchairs, and child and amusement minicars
cell) and keep them running at an optimized operation can be operated in a similar way to the toy described
point. Buses, delivery vans and cars in city areas where above. The ECs will rapidly be recharged at the stops
many go-stop intervals exist are most beneficial. For where people or goods get on and off board. The
example, for an 18t-bus the minimum energy content of braking energy can be reused. The vehicles are not
the EC should be about 2 MJ. Energy savings of bound to any fixed tracks and free of emissions. Due to
20–30% can easily be obtained on an intra-urban line, their small mass they can accelerate very fast. Perma-
what corresponds to many thousand litres of fuel per nent operation without change of batteries is possible.
year. With nowadays ECs such a capacitor bank can be A disadvantage is the limited range.
realized with a mass of about 300 kg. Most vehicles A major part of the operation costs of electric rail-
with electric drives use an operating voltage in the way systems is due to the electricity costs. Very often,
range 300–500 V. A possible setup of a drive system is the braking energy is only partly recuperated due to
various reasons [45]. An energy storage device at the
shown in Fig. 15. Since the voltage of the EC decreases
supply substations, along the railway track, or onboard
during discharge, it has to be adapted to the DC-link
the train may considerably improve the situation. The
voltage by means of a DC-DC converter. Discharge to
benefits are load leveling and support of the mains
half of the nominal voltage allows the use of 75% of the
voltage, lower energy costs, reduction of investment
EC’s total energy content. If the capacitor is further
costs since less substations are needed, and emergency
discharged at high power most of the energy gets lost in
supply in case of power failures. For a tramway with
the internal resistance. The characteristic time for the
780 V supply, the stationary energy storage should
acceleration/braking phases is 10–30 s. With a RC-time contain about 10 kWh and have a power of 1 MW.
constant of the EC of about 1 s or less and including Flywheel and SMES installations are also considered
the efficiency of the DC-DC converter, a round-trip for this application. The requirements for the energy
efficiency of 90% can be obtained. storage device are: large cycling capability, high effi-
The automotive market and transportation business ciency, absolute safety, low investment and operating
offers additional opportunities for ECs. A combination costs, easy control.
of a battery and an EC can provide a more powerful Electric actuators cause the tilting of the coaches of a
and reliable system for engine starting, may deliver high tilting train. Large peak power is needed in irregular
current for fast preheating of catalysts, may assist the intervals, depending on the actual railway track and
electric power steering, and provide local power for curves. Simulations have shown that the average power
actuators and distributed power systems. Aircraft and needed on a winding track is only about 15% of the
ships have similar needs as land-based vehicles. For peak power as shown in Fig. 16 [46]. If ECs are used as
market penetration a system consisting of a battery of energy storage devices they can deliver part of the peak
reduced size and an EC has to be commercially compet- power and the rating of the supply converter can be
itive with the battery-only system. reduced. In addition, after a turn, when the railway

Fig. 15. Schematic of the driveline of a hybrid electric bus using Electrochemical Capacitors as storage device for regenerative
braking. The arrows indicate the flow of energy.
2496 R. Kötz, M. Carlen / Electrochimica Acta 45 (2000) 2483–2498

100 kW to several MW. A 100 kW, 650 V ride-through

system, providing power for 5 s has recently been
presented [50]. In cases where a Diesel generator is
available for backup power, the UPS device has to feed
the load for a maximum of 10 – 20 s until the Diesel
engine is running.
Many actuator applications need high power for a
duration suitable for ECs. Magnetic medium or high
voltage switchgear-systems need current pulses of 50 –
70 ms for switching [46]. Pace makers, defibrillators and
X-ray generators are applications in the medical area.
Various military and space applications exist, e.g. actu-
ators for flood-control of submarine systems, launching
of aircraft on NAVY aircraft carriers, starting of tanks
Fig. 16. Power needs of a tilting actuator of a high-speed and trucks in very cold or hot climate, thrust vector
tilting train. The dotted line indicates the maximum power
control actuators on launch vehicles, bridge power for
demand from the supply converter if ECs are used. The
recuperated energy is not included in the simulation.
submarine computer systems, detonators, pulse lasers.
Load leveling in combination with wind turbines, pho-
tovoltaic generators or wave energy devices may also
coach is moving back to its center position, the tilting
become important for ECs. Powering of remote
mechanism releases energy, which can be fed back and
weather stations, monitoring systems, buoys, vending
taken up by the EC. Substantial energy savings are
machines, emergency lights, etc. in combination with
possible. In case of a power failure the energy stored in
e.g. photovoltaic modules are other future applications.
the ECs allows to move the coach back to its central
The dynamic response of fuel cells can be improved by
position. The EC for this application should have a
using ECs for short-term energy storage. If only little
capacitance of about 60 F at 48 V and, due to the high
power is needed from a fuel cell (e.g. during the night),
current, a low internal resistance. the ECs can supply the base load and the auxiliary
Important applications also appear in telecommuni- system (pump, compressor, reformer) of the fuel cell
cations, particularly associated with cellular phones. can be shut down. This results in an improved effi-
The miniaturization of the phones is also demanding ciency. For elevators, cranes, etc., ECs can provide
for a reduction of the size of the batteries. In the global emergency power in case of power failures. In addition
system for mobile communication (GSM) format, cur- they can be used for load leveling and recuperate
rent pulses of about 0.5 ms duration are needed every 5 energy when the cage is moving down, enabling energy
ms. The pulse power is about ten times larger than the savings.
average power. A combination of a battery with an EC As shown above, ECs are in many cases used in
may substantially improve the power output and in- combination with batteries in so-called hybrid systems.
crease the life of the battery [47,48]. The EC delivers the The battery provides the base load power or recharges
largest part of the pulse power. Between the pulses the the EC at low power rating. In the same way a combi-
battery recharges the EC. The nominal voltage of the nation of conventional capacitors and ECs is also possi-
EC has to correspond to the voltage of Li-ion batteries. ble if energy is needed on a shorter time scale. In this
The EC must have high cycle-life, small size, low cost, case the capacitor delivers the peak power. We have
and should have a typical RC- time well below 1 s. realized in our lab a hybrid capacitor bank consisting
Some industrial processes (e.g. semiconductor, chem- of polymeric film capacitors (3 mF) and ECs (0.8 F).
ical, pharmaceutical, paper, textile industry) are very The bank is used for testing of high-temperature super-
sensitive to short interruptions and disturbances of the conducting material. The bank voltage is 1200 V. The
mains voltage and may result in expensive loss of film capacitor delivers a peak current of 6 kA for
production. Power Quality (for ms to s) [49] and UPS several 100 ms, which is quenching the superconductor.
devices (‘Uninterruptable Power Supply’, for s to min) A steady current of about 2 kA is delivered by the ECs
may protect the sensitive loads. A statistical analysis of for about 100 ms, allowing to study the thermal behav-
power failures shows that most of them have a duration ior of the superconductor. A discharge of the bank on
of B 1 s. Nowadays either capacitors or batteries are a 160 mV load is shown in Fig. 17. If the steady current
used for providing the energy. ECs offer a much better is interrupted, the film capacitor is recharged from the
ratio of energy to power for those applications and will ECs and is then able to supply another current pulse.
allow to reduce size and costs of the systems and to Many more applications can be imagined, but we
make them more reliable. The power needs for the emphasize that an EC is not ‘the’ universal energy
industrial processes mentioned above are in the order of storage device. Its strength is in the area shown on the
 R. Kötz, M. Carlen / Electrochimica Acta 45 (2000) 2483–2498 2497

In comparison to flywheel, SMES, and battery sys-

tems, which also have high specific energy and power,
ECs offer distinct advantages. ECs have no rotating
parts, are very safe devices, do not require cooling and
other auxiliary installations, have a large modularity
with respect to voltage and capacitance, low self-dis-
charge, high cycle-life, can be produced at low costs, do
not need any servicing, and do not contain any environ-
mentally dangerous materials or heavy metals.

Acknowledgements

Financial support by the Board of the Swiss Federal

Institutes of Technology BSIT (Swiss Priority Program
Fig. 17. Discharge current of 1200 V hybrid-capacitor bank on Materials Research) and the Commission for Tech-
consisting of a combination of 0.7 F Electrochemical capaci- nology and Innovation (CTI) is gratefully acknowl-
tors and 3 mF polymeric film capacitors. edged. The authors would like to thank Leclanché SA,
Yverdons-les Bains, Switzerland, Th. Christen (ABB),
Ragone plot of Fig. 1, corresponding to a ratio of CH. Ohler (ABB), and M. Bärtsch (PSI) for providing
energy (in J) to power of about 1. For much larger and data and other information.
much smaller ratios, conventional capacitors and bat-
teries, respectively, are more adequate, unless other
criteria like cycling performance or environmental re- References
quirements become important.
[1] H.E. Becker, U.S. Patent 2 800 616 (to General Electric)
(1957).
[2] D.I. Boos, U.S. Patent 3 536 963 (to Standard Oil, SO-
7. The challenge for electrochemical capacitors HIO) (1970).
[3] T.C. Murphy, R.B. Wright, R.A. Sutula, in: F.M. Del-
nick, D. Ingersoll, X. Andrieu, K. Naoi (Eds.), Electro-
For most of the applications described above, solu-
chemical Capacitors II, Proceedings, vols. 96 – 25, The
tions with conventional devices, i.e. either batteries or Electrochemical Society, Pennington, NJ, 1997, p. 258.
capacitors exist. Those devices are available on the [4] B.E. Conway, Electrochemical Supercapacitors, Plenum
market for \100 years, have technically been opti- Publishing, New York, 1999.
mized, and use elaborated manufacturing methods. Al- [5] B.E. Conway, J. O’M. Bockris, I.A. Ammar, Trans. Fara-
though the energy to power ratio of ECs is often more day Soc. 47 (1951) 756.
adequate, batteries or capacitors are chosen for com- [6] S. Sarangapani, B.V. Tilak, C.P. Chen, J. Electrochem.
mercial reasons. Therefore ECs have to be cost compet- Soc. 143 (1996) 3791.
itive. For electronic applications, it has been shown [7] M. Sullivan, R. Kötz, O. Haas, in: F.M. Delnick, M.
that it is possible to produce ECs at high volume, low Tomkiewicz (Eds.), Electrochemical Capacitors, Proceed-
ings, vols. 95 – 29, The Electrochemical Society, Penning-
cost, and having high reliability. We are convinced that
ton, NJ, 1996, pp. 198 – 209.
this will be soon also the case for ECs with large [8] M.G. Sullivan, M. Bärtsch, R. Kötz, O. Haas, in: F.M.
capacitance. Delnick, D. Ingersoll, X. Andrieu, K. Naoi (Eds.), Elec-
Another challenge is the high voltage demanded for trochemical Capacitors II, Proceedings Volume, vols. 96 –
many applications. Due to the restriction of single cells 25, The Electrochemical Society, Pennington, NJ, 1997,
to a low voltage, several dozens or even many hundreds pp. 192 – 201.
of cells have to be connected in series. Capacitance as [9] M. Nakamura, M. Nakanishi, K. Yamamoto, J. Power
well as leakage resistance of the individual cells have to Sources 60 (1996) 225.
be very uniform during the whole life of the EC. [10] A.G. Pandolfo, A.M. Vasallo, G.L. Paul, Proceedings of
Otherwise, in a series connected string some cells may The 7th International Seminar on Double Layer Capaci-
tors and Similar Energy Storage Devices, Florida Educa-
see an overvoltage and get damaged. One single dam-
tional Seminar, December 1997.
aged cell may deteriorate the performance of the whole [11] S. Ardizzone, G. Fregonara, S. Trasatti, Electrochim.
capacitor system. Precautions are therefore necessary to Acta 35 (1990) 263.
guarantee the balancing of cell-voltages. The balancing [12] R. Kötz, S. Stucki, Electrochim. Acta 31 (1986) 1311.
system should be very reliable, have low cost, and if [13] J.P. Zheng, P.J. Cygan, T.R. Jow, J. Electrochem. Soc.
ever possible, be integrated into the EC. 142 (1995) 2699.
2498 R. Kötz, M. Carlen / Electrochimica Acta 45 (2000) 2483–2498

[14] S. Trasatti, P. Kurzweil, Platinum Met. Rev. 38 (1994) 46. Energy Storage Devices, Florida Educational Seminar,
[15] T.J. Guther, R. Oesten, J. Garche, in: F.M. Delnick, D. December 1998.
Ingersoll, X. Andrieu, K. Naoi (Eds.), Electrochemical [34] D. Fan, R.E. White, J. Electrochem. Soc. 138 (1991) 17.
Capacitors II, Proceedings, vols. 96–25, The Electro- [35] B.E. Conway, J. Electrochem. Soc. 138 (1991) 1539.
chemical Society, Pennington, NJ, 1997, p. 16. [36] B.E. Conway, Power Sources 15, 19th International
[16] T.-C. Liu, W.G. Pell, B.E. Conway, S.L. Roberson, J. Power Sources Symposium, Brighton, England, 1995, pp.
Electrochem. Soc. 145 (1998) 1882. 65.
[17] X. Ren, S. Gottesfeld, J.P. Ferraris, in: F.M. Delnick, M. [37] T.C. Murphy, W.E. Kramer, in: Proceedings of The 4th
Tomkiewicz (Eds.), Electrochemical Capacitors, Proceed- International Seminar on Double Layer Capacitors and
ings, vols. 95 – 29, The Electrochemical Society, Penning- Similar Energy Storage Devices, Florida Educational
ton, NJ, 1996, p. 138. Seminar, December 1994.
[18] C. Arbizzani, M. Mastragostino, L. Meneghello, Elec- [38] M. Bärtsch, A. Braun, B. Schnyder, R. Kötz, O. Haas, J.
trochim. Acta 41 (1996) 21. New Mater. Electrochem. Syst. 2 (1999) 273.
[19] K. Naoi, Extended Abstracts, 49th Annual Meeting of [39] D.M. Zogbi, Proceedings of the 6th International Semi-
the International Society of Electrochemistry, Ki- nar on Double Layer Capacitors and Similar Energy
takyushu, Japan, September, pp. 647, 1998 Storage Devices, Florida Educational Seminar, December
[20] A. Yoshida, K. Nishida, S. Nonaka, S. Nomoto, M. 1996.
Ikeda, S. Ikuta, Japanese Patent 9-266143, (to Matsushita [40] D.M. Zogbi, Proceedings of the 6th International Semi-
Electric), 1997. nar on Double Layer Capacitors and Similar Energy
[21] M. Ue, K. Ida, S. Mori, J. Electrochem. Soc. 141 (1994)
Storage Devices, Florida Educational Seminars, Decem-
2989.
ber 1996.
[22] Y. Kibi, T. Saito, M. Kurata, J. Tabuchi, A. Ochi, J.
[41] Tokin Supercap Application Note.
Power Sources 60 (1996) 219.
[42] Hot Wheels X-V Racers from Mattel.
[23] R. Kötz, M. Bärtsch, A. Braun, O. Haas, Proceedings of
[43] A. Ivanov, L. Poliashov, A. Gerasimov, F. Lev, in:
The 7th International Seminar on Double Layer Capaci-
Proceedings of the 5th International Seminar on Double
tors and Similar Energy Storage Devices, Florida Educa-
Layer Capacitors and Similar Energy Storage Devices,
tional Seminar, December 1997.
Florida Educational Seminars, December 1995.
[24] J.P. Zheng, T.R. Jow, J. Electrochem. Soc. 144 (1997)
[44] V. Wouk, Sci. Am., October 1997, 45.
2417.
[45] F. Moninger, Elektrische Bahnen 96 (1998) 257.
[25] M.F. Mathias, O. Haas, J. Phys. Chem. 97 (1993) 9217.
[26] H. Scher, M. Lax, Phys. Rev. B 7 (1973) 4491. [46] M.W. Carlen, T. Christen, Proceedings of the 7th Interna-
[27] B.E. Conway, W.G. Pell, Proceedings of the 8th Interna- tional Seminar on Double Layer Capacitors and Similar
tional Seminar on Double Layer Capacitors and Similar Energy Storage Devices, Florida Educational Seminars,
Energy Storage Devices, Florida Educational Seminar, December 1997.
December, 1998. [47] X. Andrieu, C. Rouverand, Proceedings of the 5th Inter-
[28] R. De Levie, in: P. Delahay (ed.), Advances in Electro- national Seminar on Double Layer Capacitors and Simi-
chemistry and Electrochemical Engineering, vol. 6, 1967, lar Energy Storage Devices, Florida Educational
pp. 329, Interscience Publishers, New York. Seminars, December 1995.
[29] R.E. DeLaRue, C.W. Tobias, J. Electrochem. Soc. 106 [48] M.F. Rose, S.A. Merryman, Z. Chen, Proceedings of the
(1959) 827. 8th International Seminar on Double Layer Capacitors
[30] M. Bärtsch, M.G. Sullivan, R. Kötz, O. Haas, J. Power and Similar Energy Storage Devices, Florida Educational
Sources 65 (1997) 276. Seminars, December 1998.
[31] W.G. Pell, B.E. Conway, J. Power Sources 63 (1996) 255. [49] K. Chan, A. Kara, Proceedings of the 8th International
[32] T. Christen, M. Carten, C. Ohler, Proceedings of the 9th Conference on Harmonics and Quality of Power, Athens,
International Seminar on Double Layer Capacitors and October 1998.
similar Energy Storage Devices, Florida Educational [50] C.J. Farahmandi, R. Spee, Proceedings of the 8th Inter-
Seminars, December 1999. national Seminar on Double Layer Capacitors and Simi-
[33] A.F. Burke, M. Miller, in: Proceedings of the 8th Interna- lar Energy Storage Devices, Florida Educational
tional Seminar on Double Layer Capacitors and Similar Seminars, December 1998.

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