WP Report

THEMATIC NETWORK
CONTRACT N
ENK5-CT-2000-20336

Investigation on Storage Technologies

for Intermittent Renewable Energies:
Evaluation and recommended R&D strategy

INVESTIRE-NETWORK

Supercaps Report

DATE OF ISSUE OF THIS REPORT : 2003-06-17

Project funded by the European Community under the 5th Framework Programme
(1998 - 2002)

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WP ST 3_Supercaps

Deliverable_5_ST3_081002_ISET

Written by:

Bernd Willer
Institut fr Solare Energieversorgungstechnik (ISET) e. V.
Knigstor 59, D-34119 Kassel
Tel. ++49-561-7294-0; Fax ++49-561-7294-100
e-mail: bwiller@iset.uni-kassel.de
With the participation of :
Saft, C. Jehoulet
Batscap, E. Planchais
ZSW, A.Jossen

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TABLE OF CONTENTS
1

Overview of the Storage Technology

2
Technical characteristics and applications of the storage technology
2.1
Components and materials of the technology
2.2
Data and performance characteristics
2.2.1
Range of capacities
2.2.2
System voltage
2.2.3
Energy and power density
2.2.4
Cycling service and lifetime
2.2.5
Faradic and energy efficiency
2.2.6
Self-discharge.
2.2.7
2.2.8
2.2.9
2.3
2.3.1
2.3.2
2.3.3
2.3.4

Temperature
Possible degradations during operation
Recommended practices
Present situation of the storage technology
Technology developers and manufacturers
Constructional features and manufacturing methods
Main conventional applications
Present R&D actions

3.
3.1
3.2

Economical Issues
Cost of the storage technology
Installation, operating and maintenance cost

4
4.1
4.2

Environmental Issues
Current knowledge on environmental issues of the storage technology
Improvement options

5.
5.1
5.2
5.3
5.4

Application of the storage technology for Renewable Energy Systems

Existing applications
Operating characteristics
Assessment of the storage technology in these applications
Potential future applications

Needs for R&D on the storage technology for an extended use in

Renewable Energy Systems

Conclusion and Recommendations

References

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1 Overview of the Storage Technology

A new type of electrochemical energy storage system accumulated energy in the
electric field of an electochemical double-layer. It is called:
Double-layer capacitor,
Supercapacitor,
Ultracapacitor,
Electrochemical capacitor or
Pseudocapacitor.
Various commercial bandnames are Goldcap, Powercap or Boostcap.
Double-layer capacitors (DLCs), contain in comparison to conventional capacitors a
significantly enlarged electrode surface and a liquid electrolyte. As electrode material
often active carbon is being used. These materials are mainly characterized by a
large specific surface. At the interface between electrode and electrolyte the
electrochemical double-layer is characterized by a concentration of ions and has a
thickness of only a few molecular diameters.

Figure 1:

Principle of a double-layer capacitor

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The storage of charge mechanism occurs via a separation of charge and alignment
of dipoles in the electrical double-layer as shown fundamentally in figure 1. The
extremely low thickness of this layer coupled with large electrode active area, causes
the relative large capacity of the DLCs compared to conventional capacitors (C
A/d). In DLCs, devices using primarily carbons as active materials, it does not come
to any charge penetration through the double-layer and in normal operation no
electrochemical reactions occur. The double-layer capacitors therefore display in
comparison to electrochemical storage systems a high cycle lifetime and a high
power density. These devices show a high efficiency and they are insensitive with
respect to deep discharge. Prices are still high, but should drastical reduced with
process improvement. The liquid electrolyte limits the voltage-stability of the
capacitors to (13 V), depending on the nature of the electrolyte.
DLCs have been known for more than 50 years.
1962

Standard oil Company operated first DLCs.

1976

NEC achieved a capacity about 0,5 F.

1990

Dornier started the development of electrochemical capacitors for

aerospace.

1992

Capacitors with 500F and 2,3V were developed.

2000

Capacitors with 5000F were developed.

2002

Cost objectives for mass production of 0,01 to 0,02 per Farad were
announced.

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2 Technical characteristics and applications of the storage

technology
2.1 Components and materials of the technology
The mechanical design of real components are
round, spiral cells or
prismatic cells.
The following figure 2 shows the design of real units, tested at ISET.

Figure 2:

Comparison in Size of Selected Double-Layer Capacitors

Electrolyte
There are two types of electrolytes : aqueous and organic.

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Aqueous electrolytes
Acids or bases (H2SO4, KOH) can be both used either with carbon or metal exides
materials. The potential windows is limited to 1 volt, which imposes complex stacking
of several units of supercapacitors to reach a " traditional " voltage (12 volts e.g.).
Ionic conductivity is excellent, and the coefficients of diffusion of the ions often about
10-5 cm2/s. The relative size of the ions (sphere of solvation) varied from 10 to 20 ,
so that they can reach the microporosity. Besides the good wettability of the porous
materials a better impregnation of the materials microporosity in aqueous electrolytes
is possible.
One of the interest of the aqueous electrolytes compared to the organic ones is to
enable, especially on carbons materials, the existence of an additional capacitance
called pseudo-capacitance based on the redox reaction of the hydrated functional
groups at the surface of the materials. This can, for example, double the value of the
capacitance on a carbon material in aqueous electrolyte compared to the same
material in organic electrolyte.
Organic Electrolytes
One will use mainly stable electrolytes under voltage that can going up to 3 Volts (or
electrode potential going up to 4.5 V - 5 V versus Li+/Li). Moreover, in order to
minimize internal resistance, conductivity must be as large as possible especially to
guarantee the low temperature behaviour. In organic carbonates electrolytes, also
used in lithium-ion accumulators, it exceeds with difficulty 15 mS/cm at room
temperature Acetonitrile is, at this point, the only solvent that displays a sufficient
conductivity to enable an almost unchanged cell performance at 30C. One of the
drawback of this electrolyte is toxicity. However, it is today used in 90% of the large
size organic electrolyte supercapacitor. The salt mainly used in this type of device is
Et4NBF4 because of its stability in the potential window and its lower reactivity
towards water pollution.
Electrodes
The electrodes are using, as active materials, carbon metal oxide or polymeric
materials. In a surface area that could reach up to 3000m2/g in the case of carbons.
Additional materials such as binders and conductive carbons are also used in the
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electrodes composition and are very dependent on electrode manufacturing

processes. There are various types of carbon materials used as material of
polarizable electrodes. In particular, the activated carbon powders and the activated
fibres, have a very high active surfaces (typically > 1000 m2/g to 2000 m2/g),
therefore allowing to reach specific capacitances as high as 150 F/g. There are in
general two sources of raw materials to produce activated carbons (powder or
fibers/fabrics). These can be produced either from precursors such as polymers (for
example phenolic resins ) or natural materials such as coconut shells or wood. In
both cases, materials go through a calcination process to give pure carbon and an
activation process to develop a high specific area. For all these materials, it is
possible to tune the activation process to select the specific area for the application.
The choice of raw materials (polymer or natural) has mainly an influence on the cost
of the final product and sometimes on the self-discharge if the process is not well
mastered.

The

carbon materials present the advantage of a low final price

compared to polymer but usually exhibits a higher self-discharge.

In terms of intrinsic capacitance (F/g), the form of the final product (fibers/fabric or
powder) has little influence. The choice is mainly linked to the manufacturing
process. Powder materials need to be processed in order to make an electrode
through a coating or extrusion process. These processes require a dedicated
equipment. The final electrode form is a coating on an aluminium current collector.
These processes are usually used together with a winding process in order to
manufacture spiral cells. Fibres are used in a fabric shape, bought in the activated
form, and are used in prismatic cells. Industrially, spiral cells are often preferred
because of the possibility to get high speed, fully automatic and low cost process.
Some manufacturers have developed and commercialised solutions based on
aqueous electrolytes/metal oxides such as ruthenium oxide (RuO2), iridium oxide
(IrO2) or nickel oxide (NiO2) mainly for military applications. Metal oxide
supercapacitors

are

based

on

high

kinetics

charge

transfer

at

the

electrode/electrolyte interface transforming RuO2 into ruthenium hydroxide Ru(OH)2

leading to pseudo-capacitive behaviour. As explained above. This type of
supercapacitor is interesting for its high specific power linked to the high conductivity
of aqueous electrolytes.
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Separators
The nature of the separator is also linked to the nature of the electrolytes. Aqueous
electrolyte supercapacitors can use the separator commonly used in alkaline
batteries such as polyolefin felts. In organic electrolyte, separators are made either a
microporous membrane or a cellulosic felt. There exists few solutions. More used is a
separator undoubtedly the celgard microporous membrane, but there are also
cellulose separators: cellulose paper with polymeric fibres.
Electrical architecture of systems
Depending on voltage and energy requirements, due to the limited cell voltage,
systems are built up by an association of single cells in series/parallel mode. In the
case of high voltage systems, cells are usually set up in a sub-unit called module.
These modules integrate passive of active device for voltage balancing between the
cells. These cell balancing system can be of the following nature :
passive device with resistance,
passive device with diodes or
active device.
Depending on application profiles, a cooling system might be required.
2.2 Data and performance characteristics
2.2.1 Range of capacities
The range of capacitances is going from 0.05 F to 5000 F. The size of the
supercapacitors can be divided into two families : below 100 F and above 100 F.
Below 100 F they were used mainly in the consumer electronics.

These

supercapacitors have been known for more than 20 years. Some examples of cells
are shown below.

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Figure 3:

Supercapacitor cells with 1 F, left and

0.05 F, right

Above 100 F it is the new field of development for supercapacitors with products from
various manufacturers as shown below.

E
Figure 4:

Some examples of supercapacitor cells

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2.2.2 System voltage

Cell voltages
In operation cell voltages are possible between
(0 V - 2,3 V) / cell ( 2.5 V / cell ) with organic electrolyte
(depending on manufacturer and 2.5-2.7 V allowed for peaks ) and between
(0 V - 1 V) / cell with aqueous electrolyte.
Discharge down to 0V is possible, but up to 0,5 Umax is used in real applications. In
this case, 75% of the energy delivered.
System voltage
There is no standard voltage for systems. Available on the market are systems with
the following voltages.
1 or 2,3 V (one cell),
12V, 24 V or
14 V, 42 V, 56 V, 75 V.
Higher voltage for stand-by or public transportation are often usually built up using
12-14 V basic units.

Figure 5:

15 V system

2.2.3 Energy and power density

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The maximum energy stored in DLCs is given by

E = 1/2 CU2.
The range of energy amount to information of manufacturers is going from
(0,1 - 5) Wh / kg.
The range of power is given from
(100 - 10 000) W / kg.
A realistic final discharge voltage is 0,5 Umax. In this case 75% of the energy is
available. Adapted energy converter are necessary.
2.2.4 Cycling service and lifetime
The cycling lifetime amount according to the information of the manufacturers to
(100 000 - 500 000) cycles.
2.2.5 Faradic and energy efficiency
The faradic efficiency amount to nearly 100%.
The energy efficiency is independent of the current, nearly 85 %- 98 %.
2.2.6 Self-discharge.
The self discharge is very different.
Tested by ISET:

(4 - 100) % energy loss

after 48 hours

Important is in addition the current through a cell balancing system in storage

systems with higher voltage.
2.2.7

Temperature

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The operating range is given for:

(-40 - 60) C (70C).
2.2.8 Possible degradations during operation
Deep discharge:

There is no degradation in consequence of deep discharge.

Slight impact on performances upon repetitive reversals.

Overcharge:

There is a degradation during operation in consequence of

overcharging, if the cell voltages are not limited. Usually in
module, cells are equipped with a safety device. Venting occurs
above 4V with some smokes, no flame, no explosion,
temperature increase about 200C and the weight loss is about
30%.

Cycling:

Cycling is, with floating , the normal mode of degradation as for

accumulators. The ageing process can be linked either to the
ageing of the electrode structure or parasitic electrochemical
reactions such as electrolyte oxidation. In this case, the
maximum voltage has a strong influence on the degradation as
shown in the figure below. This is a continuous process that
results in a loss of capacitance and increase of internal
resistance. Capacitance losses during cycling are often observed
below 10 % even for
cycle number around 1 million.

2.2.9

Recommended practices

Transport and mounting must be realized in fully discharged state. The optimum
charging conditions for energy content should be constant current followed by
constant voltage.
2.3 Present situation of the storage technology

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2.3.1 Technology developers and manufacturers

Figure 15:

The main actors are coming from US, Europe. Japan, Asia and
Australia.

2.3.2 Constructional features and manufacturing methods

Three electrode manufacturing technologies co-exists for supercapacitors.
Coating
Coating is based on the use of carbon powder as raw materials. Depending on the
size of the supercapacitor, different mode of coating can be used. In small
supercapacitors, the activated carbon is impregnated of a binder (typically Teflon or a
cellulose), then pressed to obtain pellets, or a paste. This pasting technology is very
simple and does require sophisticated tooling. However, the main drawback is the
final thickness of the electrode that leads to a high internal resistance especially for
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organic electrolytes. A supercapacitor is then obtained by addition of units assembled

in parallel, with organic or aqueous electrolyte. The interest of this system lies in the
ability of obtaining high capacities, the quantity of active matter used being
significant.
For large supercapacitors, usually in the spiral format, this technology can not be
used. In this case, manufacturers are using technology that is very well known to the
lithium-ion accumulator makers. The carbon is dispersed in solvent with binder and
the solution is then coated on the current collector by a classical printing type
technique. In this way, electrode thickness below 100 m can be reached to
guarantee the low resistance of the device.
Extrusion
The activated carbon is put in the form of a film after addition of a thermoplastic-type
polymer used as binder. The extrusion of the mixture makes possible to obtain highlength homogeneous films, with low thickness (a few tens to hundreds of microns)
being able to be rolled up in a spiral cell.
Fabrics
It is also possible to use carbon fabrics or felts. These fabrics are made from carbon
fibres that have been treated to obtain the right porosity. Typically, one can use
various precursors such as polyacrylonitrile or phenolic resins. These materials are
physically activated or chemically activated to obtain the right microporosity. The
main drawback of the fabric is its high cost due to the price of the raw carbon fibres.
Moreover, their use is limited to prismatic cell design with well-known swelling
phenomena that impacts the ageing performances.
2.3.3 Main conventional applications
The main conventional applications are
for small supercapacitors
power back-up consumer electronic devices and products like

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computer memories,
video recorder and TV satellite receivers,
car audio systems and taxi meter,
alarm clock radios or
photo and video cameras and
for large supercapacitors
transport applications like
storage for rechargeable motors, regenerative braking,
starter applications (diesel locomotives, cars, trucks, military engines)
and
power quality devices (UPS, coupling).
2.3.4 Present R&D actions
Several issues need to be addressed for the future of the technology. One of the
main parameters for acceptance in the possible markets is the cost compared to
well-established accumulator technologies such as lead-acid. In this view, drastic
cost reduction must be made especially in the carbon, electrolyte and separator fields
where target as low as 10 /kg or 1 /m2 have to be reached. This is today the
number one R&D topic world-wide.
The recycleability has to be proven at the same level than other types of
rechargeable systems. The non-toxicity of the cell components especially for the use
in transports need to be assessed.
As these devices are foreseen for use in the field of public transportation and power
quality, life guaranty of more than 10 years has to be proven. This implies R&D work
on the study of the degradation phenomena and improvement of ageing
performances during cycling or floating.

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One of the main drawback of the technology in the field of rechargeable energy
source is linked to the small amount of energy stored compared to accumulators.
Often, the technical requirements of an application lead to the choice of accumulator
in order to not oversize the system due to energy constraint. Therefore, work is also
conducted world-wide, in private or public research, on the increase of the specific
energy of the device while keeping the specific power at a similar level. Goal in the
range of 8 Wh / kg have been announced. This issue can be tackled by investigating
in various directions such as a better use of the volume of the carbon material, higher
cell voltage and thus higher electrolyte stability, novel definition of the electrode
structure.
In all the applications foreseen for supercapacitors, the single cell will be integrated
in series with voltages that could go as high as 800 V. The development of an
intermediate modular structure as well as reliable cell-balancing systems and battery
management systems have also to be implemented.

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Economical issues

3.3 Cost of the storage technology

From world-wide investigations the following cost are result (discharge to Umax/2).
1997:

150 - 500 / Wh ( for single cells ).

2002:

50 - 150 / Wh

( for single cells, 12V units and 42 units )

or 0,03 - 0,08 / F.

2005

aim for 2005 and mass production

0,01 / F.

Typical discharge times are up to 5 s and typical charge time 1 min up to 5 s.

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Environmental Issues

Supercapacitors can be classified in 2 groups with regard to the electrolyte. One

group uses aqueous electrolyte ( sulphuric acid or caustic potash) and the other
group an organic electrolyte. Electrodes are built out of activated carbons. Several
binders can be used in these systems (for example, PTFE, PVdF, cellulosic binders).
Two families of solvents are used today. The majority of the manufacturers worldwide are using acetonitrile (CH3CN), Japanese manufacturers are using solvent
mixture based on organic carbonates such as propylene carbonate. The conductive
salts are dependent on the solvent. For organic systems Tetraethylammonium
tetrafluoroborate salts is a world-wide standard in organic supercapacitors.

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Application of the storage technology for Renewable Energy

Systems

5.1 Existing applications

Existing applications are:
solar watch,
solar lanterns and
road marking lanterns.
5.2 Operating characteristics
Well operating characteristics are:
high cycles per day and high power.
5.3 Assessment of the storage technology in these applications
Important assessment of the storage technology for PV application are:
cost reduction,
recyclability,
self discharge under 10% per week,
an efficiency over 90%,
a range of temperature between (-30 and- 60) C and
a lifetime about (10-15) years.
5.4 Potential future applications
Potential future PV applications are:
solar water pumps,
solar supply for black out windows,
power quality and
power supply for high power loads.

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6 Needs for R&D on the storage technology for an extended use in

Renewable Energy Systems
Needs for R&D on the storage technology for an extended use in Renewable Energy
Systems can be selected into the areas technology, system technology and system
integration.
Aims of technology development are:
cost reduction

factor 10-100 compared to 1997,

high specific energy

over

5 Wh / kg,

recycle ability,
low self discharge

under 10% per week,

high efficiency

>90%,

wide range of temperature

-30 - 60 C and

long lifetime

10-15 years.

Aims of system technology development are:

higher system voltage,
adapted energy converter,
complete systems with electrical and thermal management and
multi storage systems ( battery with supercap e.g.).
Aims of system integration development are:
energy management system,
standard test procedures,
modelling and simulation and
specification of the demands on DLCs system management.

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7 Conclusion and Recommendations

The special properties of Double-Layer-Capacitors open up new areas of application
for this technology. They can be used as energy storage devices in systems, in which
long life-time, high cycle stability, short charging times, short circuit stability and
maintenance-free operation are being demanded and which are exposed to extreme
climatic conditions. Especially areas of application with high short-termed power
performance can be made better accessible. The use in PV-plants makes yet
different demands on the energy storage device. They decide about the choice of the
respective capacitor type and give the producer important information for further
directions in development. Different demands are being made regarding energy and
power, energy and power density, life time, cycle stability, system voltage,
temperature area, moisture area, expense of maintenance, economic tolerance and
costs.
The integration of an inexpensive short-time-storage-system with high cycle lifetime,
maintenance-free operation and a high power density will improve the supply
situation and the economy of numerous photovoltaic applications.

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References
/1/ W. Schmickler
Ladungsspeicherung in der Doppelschicht
2. Ulmer Elektrochemische Tage, Ulm, 1995.
/2/ B. Willer
Doppelschichtkondensatoren als Speicher fr PV-Anlagen
13. Symposium Photovoltaische Solarenergie, Staffelstein 1998.
/3/ R.Ktz, M.Corlem
Principles and applications of electrochemical capacitors.
Electrochimica Acta 45. 2000, 2483-2498.
/4/ A. Schneuwly, M. Brtchi, V. Hermann, G. Sartorelli, R. Gallay, R. Koetz
Boostcap Double-Layer Capacitors for Peak Power Automotive Applications
Procedings of the 2nd AABC Conference, Las Vegas (USA), 2002.
/5/ H. Michel, A. Schwake, B. Staib
Recent Progress in Ultracaps for Automotive Applications
Procedings of the 2nd AABC Conference, Las Vegas (USA), 2002.
/6/ C. Jehoulet, L. Moreau, B. Pichon, D. Rochard, D. Cesbron, A. Chaillet
Ultracapacitors : Power Buffer for Automotive Applications
Proceedings of EVS 17, Montreal, (2000).

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