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On the Technology of Present-Day

Manufactured Supercapacitors

Conference Paper · October 2006

DOI: 10.1109/ESTC.2006.280016 · Source: IEEE Xplore

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 On the Technology of Present-Day Manufactured Supercapacitors

V.V.N. Obreja1), I. Iordache2), D. Petroi2), C. Ionescu3), V. Golumbeanu3), P. Svasta3)

1)
National R&D Institute for Microtechnology (IMT), Bucharest, Romania
Tel: +4021-490 8212, E-mail: vasileo@imt.ro
2)
National R&D Institute for Electrical Engineering (ICPE-CA), Bucharest , Romania
3)
“Politehnica” University Bucharest (PUB) - Centre for Technological Electronics and Interconnecting Technique,
Str. Splaiul Independentei 313, Bucharest, 060042, Bucharest, Romania

Abstract
Commercial supercapacitors cells available at this time on the market reach a capacitance value as high as
5000 F at a rated voltage of 2.5 V, with specific power of about 2kW/kg(l) and specific energy of about
4Wh/kg(l). Advance in the supercapacitor manufacturing is needed for lower product price and further
performance improvement. Short description of the manufacturing technology of supercapacitors based on
carbon electrodes used at this time, and of recent research results and tendencies existing in the literature
are presented. Initial results from research and development work on supercapacitors started in the country
have been included in the paper.

Introduction
(+)
High performance supercapacitors with a 1 5
capacitance value of thousand of Farads at the
needed working voltage cannot be produced without
advance in the packaging technology. Cheaper
supercapacitor modules based on passive capacitor
cells and semiconductor components assembled in a 6
suitable compact package are required in power 4
electronics applications. Due to their huge electrical
capacitance, the supercapacitors become attractive 3
devices for the electrical energy storage.
Supercapacitor manufacturing technology is a field 8
where still there is place for better understanding of
the involved processes and contribution to the 2
existing knowledge. Supercapacitor, ultracapacitor (-) 7
or electrochemical double layer capacitor are terms Figure 1: Schematics for a charged conventional
used for the same product type. electrolytic capacitor; 1 – electrode 1, 2- electrode 2, 3-
The purpose of this paper is to provide a short separator, 4 –electrolyte, 5 – positive charge layer, 6-
description of the developed manufacturing ionic negative charge layer, 7- negative electronic charge
technology applied to commercial devices, with layer, 8- ionic positive charge layer
emphasis on the limiting factors on device
performance. Results of preliminary experiments the electrical contact between the metallic
performed in our laboratories are presented. electrodes is avoided. The separator is a porous
Commercial Supercapacitors Manufacturing material which allows penetration for ions but not
Technology for electrons. An electrolyte impregnates the porous
separator and the exposed rough surface of the
The electrochemical double electric layer effect
aluminum electrodes. When a voltage is applied
has been used long time ago to reach high
between the two electrodes, a double electric layer is
capacitance values in the manufacture of
formed at the interface between the aluminum
conventional capacitors. In the aluminum
electrode and the electrolyte. The negative and the
electrolytic capacitors, aluminum foil with a
positive charges from the double electric layer are
thickness of the order of ten micrometers is used for
separated by a small distance given by the size of a
the two electrodes. A sketch is shown in Fig.1.
molecule. Therefore a large value of the capacitance
Between the two capacitor electrodes, a layer of
is obtained in comparison with the dielectric
electric isolating material usually called separator is
capacitors. Nonetheless conventional commercial
placed, so that,
electrolytic capacitors exhibit a capacitance value
 1 (+)
3
well below 1 F. Higher capacitance value is possible
only if the area of the double electric layer is in
someway increased to a large degree.
For reasonable size of the capacitor, significantly 7
larger area of the double electric layer is possible if 8
the electrode has a porous structure. In Fig. 2
schematics is shown for a charged supercapacitor 9
with porous electrodes. The presence of a huge
number of pores in the capacitor electrode filled
6
with electrolyte makes possible, big exposed area for
the electrode-electrolyte interface in comparison 5
with an electrolyte capacitor (Fig.1). In such a way
capacitance values significantly higher than 1 F can
be reached. The key element for high capacitance 11
value is the porous material electrode with many
pores of suitable size, so that a high specific exposed 7
surface area is reached (Fig.3). 10
The electrodes for commercial supercapacitors
available at this time are mainly based on activated
carbon material. The use of carbon electrodes in
electrochemical capacitors represents a significant 2 4
(-)
advantage in this technology because carbon has a
low density, and carbon electrodes can be fabricated
with very high exposed surface areas. Although
several companies are already involved in the
fabrication and commercialization of Figure 2: Schematics for a charged supercapacitor; 1
supercapacitors, further improvement of the and 2 - current collectors , 3 and 4 - electrodes , 5 -
manufacturing technology is still required. separator, 6- electrolyte, 7 - pores in the electrode
In the following, a short description is given for material, 8- positive charge , 9- negative ion, 10 -
the electrode realization based on carbon material. negative charge (electron), 11- positive ion
The aluminium foil with a thickness in a range of 20
– 80 micrometers is a material largely used for
current collectors or electrode substrate. The
aluminium foil is etched so that a large number of
irregularities is manifested at the treated surface.
Usually, the electrode layer is not in direct contact
with the aluminium foil as shown in Fig.3. An
intermediate layer there exists which improves the
adhesion of the electrode layer material to the
metallic substrate. This intermediate layer is formed
of electrical conducting particles and a binder 1 2 3
material, able to adhere to the particles and to the
substrate. For conducting particles, carbon powder is Figure 3: Sketch of the electrode plate; 1– metallic
used for example, and fluorine-containing polymer foil substrate, 2- electrode material layer, 3-pores
as the main component for the binder. A slurry is
obtained by mixing the carbon powder and the layer is of the order of 1 micron. On the
binder by means of a solvent. This slurry is intermediate layer, the electrode layer is deposited
preferably subjected to a dispersing treatment in a by using a well dispersed slurry formed of activated
ball mill, so that, an uniformly coating material is carbon particles with an average diameter of 3 – 20
obtained. The prepared coating material for the microns and with specific area of at least 1500 m2/g.
intermediate layer is applied onto the aluminum foil This slurry containsa solvent and binding material as
(the current collector) and then is dried. The drying described for the intermediate layer. The drying
process takes place at a temperature in a range of 70 temperature for the electrode coating layer is in a
–150 oC. The thickness of the intermediate range of 100 –200 oC in order that the solvent to
evaporate. The thickness of the electrode layer is in
a range of 50–200 µm, taking into account the size
and the weight of the fabricated supercapacitor and
its capacitance. The thickness of the electrode layer
can be adjusted by applying pressure by means of a
roll press machine. In such a way an electrode layer
with a thickness of 175 µm can reach a final
thickness of 120 µm. The resultant electrode is cut in
pieces of rectangular shape or other desired shape.
Further drying is then performed in vacuum for the
electrodes at a temperature around of 180 oC, to
remove water content and the remaining solvent.
After their fabrication, an internal resistance and a
peel test are performed for electrodes. For such tests,
usually, a capacitor is assembled by placing a
separator layer between the two electrodes. An
example of separator material known as TF4050
after its trade name is supplied by Nippon Kodoshi
Corp., and is made of regenerated cellulose
nonwoven fabric. Leads are then attached to the
metallic collectors of the two electrodes. Then the
above rectangular assembly is suitably wrapped in a
flexible dielectric film, so that to have two open
sides where the leads to the anode and the cathode
electrode are directed outside. Subsequently, organic
electrolyte solution is poured inside under reduced
pressure and then the open sides of the wrapping are
sealed. As electrolyte, a solution of
trethylmethylammonium boronfluoride in propylene
carbonate can be used.
For the peeling test a charging/discharging
equipment is used and 2.5 V voltage is applied to the
capacitor at 60 oC with constant current at a current
density of about 5 mA/F. Then the capacitor is
discharged at the same current density until 0 V is
obtained. Thereafter, the capacitor is disassembled
to verify whether or not the peeling of the electrodes
has occurred.
For the internal resistance test, continuous
charging–discharging for the 24 hours of the
capacitor in the same conditions as for the above
peeling test is carried out. Then after the voltage on
the capacitor is at 0V, a suitable equipment is used
to measure the internal resistance at 1 kHz. An
internal resistance higher than 30–50 mohm is
considered poor performance for an electrode.
Intensive research is carried out at this time for
electrode and capacitor improving performance.
Innovative concepts are introduced to increase the
density of material pores and the wettability of pores
in the electrolyte solution. New carbon materials and
procedures are used for electrode fabrication, [1-8].
Carbon material cost reduction is a matter of
increased concern, [9-10]. For the improvement of
the supercapacitor internal resistance, a surface
treatment for the aluminum current collector foil by
means of the sol-gel method has been investigated.
An internal resistance of 0.5 ohm/ cm 2 and specific
capacitance of 95F/g has been reported, [11].
Experimental work has been reported on the uniform
poor distribution and their density increase in the
carbon material, [12-14]. Due to the progress
achieved in the pore size and their distribution,
carbon electrodes with a specific surface area as high
as 2000 m2/g are available at this time. Specific
capacitance as high as 100 F/g can be reached by
using such electrodes.
Instead of carbon material for the electrode,
metal oxides can be used, [15 –18] with the
advantage of low internal resistance. Composite
electrodes based on carbon and oxide material have
been experimented, [19]. Conductive polymers are
also of interest as electrode material, [20 – 24].
Redox processes store and release charge in
capacitor electrodes based on conductive polymers
at the contact with an electrolyte. In conducting
polymer electrodes charging takes place throughout
the bulk film and not only at its surface like in the
case of carbon electrode. Nonetheless long term
stability may be a problem in the case of conducting
polymers. For this reason, composite electrodes
based on conductive polymer and carbon have been
investigated, [25 –26]. Hybrid supercapacitors made
of a conductive polymer electrode and a carbon
based electrode, exhibit improved performance in
comparison with carbon-carbon supercapacitors, [27
–31].
High quality electrodes with high specific area
are not enough to fabricate high performance
supercapacitors. Without a suitable electrolyte, the
formation of the double electric layer is not possible.
The electrolyte determine the working voltage of the
supercapacitor and its internal resistance. The size
of the ions has to be fitted to the electrode pores.
Organic and aquaeous electrolytes are usually used
in commercial supercapacitors. The organic
electrolytes provide for a cell capacitor a working
voltage of 2.5 V, whereas the aquaeous electrolytes
a voltage of 1V. The aquaeous electrolyte has higher
conductivity and this improves the internal
resistance. Besides liquid organic or aquaeous
electrolytes, solid state electrolytes have been
experimented, [32 –34].
The separator is another important component of
a supercapacitor. It has to be ion –permeable. Paper
or polymer separators are used with organic
electrolytes and ceramic or glass fiber separators are
used with aquaeous electrolytes.
 The package or the case of capacitor has not to
contribute significantly to the weight or volume of
the final product, and has to provide good sealing of
the supercapacitor components. At this time organic
solid materials and aluminium are used to house the
supercapacitors.
In the supercapacitor manufacturing process,
testing and characterization of materials and of the
final product is very important. Parameters like the
capacitance, equivalent series resistance, specific
energy, specific power have to be measured so that
to meet the specifications from the product data
sheet. As measurement techniques, the cyclic
voltametry, the charging at constant current for
Ragone diagrams, the impedance spectroscopy and
the repetitive application of power are used. The
cyclic voltametry is a means to evaluate the
capacitance. A current – voltage diagram is
obtained by applying voltage variation with the time
(dV/dt =const). The current response is recorded. An
ideal capacitor would indicate a rectangular diagram
but this is not the case in practice. The cyclic
voltametry gives information about the electrode
reversibility for example. The charging or
discharging at constant current is a means to
evaluate the specific energy and the power of the
supercapacitor. With these parameters in
coordinates, a Ragone diagram is obtained. At the
charging and discharging of the cell, a voltage
response is obtained. The time current integral
determines the introduced or extracted electrical
charge, the current-voltage product determines the
power, and the half product of electrical charge-
voltage determines the energy. The internal
resistance of the supercapacitor is determined by the
ratio of the voltage variation and current variation, if
it is supposed that this is in series with the
capacitance. This measurement method is enough
precise at low current level. At high current level
deviation is possible from the supposed behavior.
The impedance spectroscopy requires a special
equipment. A Nyquist diagram is obtained. For an
ideal capacitor the diagram is a straight vertical line
at a distance from the origin given by the internal
resistance. The repetitive constant power application
can give useful information for modelling. The
device is charged at constant power level until a
chosen voltage level is reached. When the voltage
level is reached, the current is reversed and
discharging takes place. A diagram having a
coordinate with the ratio of the electrical charge and
the current, and another coordinate with the voltage
variation and the current is useful to determine the
electrical capacitance and the time constant. Then
the time constant gives the internal resistance.
Good part of commercial supercapacitors
available at this time are cells with an working
voltage of 2.5 V. Several companies are involved in
the fabrication and commercialization of such
products. Supercapacitor cells with a capacitance as
high as 5000 F at a rated voltage of 2.5 V with a
specific power of 2kW/kg (2.3kW/l) and a specific
energy of 4.1 Wh/kg (4.7 Wh/l ) are already
available on the market. The weight of such a
product is about 1 kg and the volume about 1l. The
series resistance is lower than 1 mohm . For cells
with a lower capacitance value at the same working
voltage of 2.5 V, the weight and the volume
decreases but the series resistance is higher.
Supercapacitor modules are available on the market
with working voltage higher than 2.5 V up to 300 V
but at higher weight and volume. The price for
commercial supercapacitor products available at this
time is a major problem for their use in power
electronics applications. Further advance in the
manufacturing process is required to decrease the
costs.
Initial experiments
In the our experiments, fine carbon powder used
in some industrial processes has been used to test
such available material at low cost. The average size
of the carbon granules was of 1 micrometer. The
powder was well mixed. with a binder and layers of
such slurry have been deposited on aluminium foil
with a thickness of 25 and 50 micrometers and width
of 100 mm. The carbon coating material was then
dried at 100 oC on a hot plate. The thickness of the
carbon layer was of 0.1-0.2 mm. Rectangular pieces
with dimensions of 50 and 30 mm have been cut
from the prepared material to be used as capacitor
electrodes in laboratory experiments. Then the
deposited carbon layer was impregnated with a
solution of potassium chloride, used as electrolyte.
Between two such wetted electrodes with
electrolyte, a piece of special paper also impregnated
with the same electrolyte, and used as separator has
been placed. The separator size (60 and 40 mm ) was
higher than that of the electrodes. The assembly was
wrapped in polyester foil with a thickness of 25
micrometers, so that two aluminium foil bands used
as capacitor leads in contact with the aluminium side
of the electrodes. The other end of the aluminum foil
bands is available outside of the assembled
capacitor. The assembly has been placed between
 two solid flat plates so that some pressure to be
applied between electrodes and separator. The
charging of the experimental capacitor has been
carried out by means of a power source at initial
voltage of 0.5 V. The experimental capacitor could
not be charged in a safe mode above 0.8 V. A
capacitance value of about 0.5F has been evaluated
which is significantly higher than the corresponding
one for an equivalent conventional electrolytic
capacitor. It has to be said that this value is a poor
result when compared with commercial
supercapacitor of about the same electrode area..
Nonetheless, such results are encouraging to
proceed to more elaborated experimental work
development.
Conclusions
In the supercapacitor manufacturing technology
,electrodes as the main component have to be
realized with a specific exposed area of the order of
one thousand square meters per gram. Such area is
possible if the electrode material with a thickness of
the order of one tenth of millimeter has a high
degree of porosity. At this time the activated carbon
material is the most used as electrode material. The
carbon electrode material is deposited on a metallic
foil, usually of aluminium. Metallic oxides and
conductive materials may be used as electrode
materials but with some disadvantages. Organic and
aquaeous electrolytes are used for the commercial
supercapacitors. In the our preliminary experiments
with carbon powder, with granule size of the order
of one micrometer, laboratory capacitor cells have
been realized. The exhibited capacitance value was
significantly higher than that of an equivalent
electrolytic capacitor.
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