ULTRA CAPACITOR SEMINAR REPORT 2011

INTRODUCTION
General Electric engineers experimenting with devices using porous carbon
electrodes first observed the EDLC effect in 1957. [5] They believed that the energy
was stored in the carbon pores and the device exhibited "exceptionally high
capacitance", although the mechanism was unknown at that time. General Electric
did not immediately follow up on this work. In 1966 researchers at Standard Oil of
Ohio developed the modern version of the devices, after they accidentally re-
discovered the effect while working on experimental fuel cell designs.[6] Their cell
design used two layers of activated charcoal separated by a thin porous insulator,
and this basic mechanical design remains the basis of most electric double-layer
capacitors. Standard Oil also failed to commercialize their invention, licensing the
technology to NEC, who finally marketed the results as “supercapacitors” in 1978,
to provide backup power for maintaining computer memory. [6] The market
expanded slowly for a time, but starting around the mid-1990s various advances in
materials science and refinement of the existing systems led to rapidly improving
performance and an equally rapid reduction in cost. The first trials of
supercapacitors in industrial applications were carried out for supporting the
energy supply to robots.[7] In 2005 aerospace systems and controls company Diehl
Luftfahrt Elektronik GmbH chose supercapacitors to power emergency actuation
systems for doors and evacuation slides in airliners, including the new Airbus 380
jumbo jet.[8] In 2005, the ultracapacitor market was between US $272 million and
$400 million, depending on the source. As of 2007 all solid state micrometer-scale
electric double-layer capacitors based on advanced superionic conductors had been
for low-voltage electronics such as deep-sub-voltage nanoelectronics and related
technologies (the 22 nm technological node of CMOS and beyond).

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The electrochemical ultracapacitor is an emerging technology that promises to play

an important role in meeting the demands of electronic devices and systems both
now and in the future. This newly available technology of ultracapacitors is
making it easier for engineers to balance their use of both energy and power.
Energy storage devices like ultracapacitors are normally used along with batteries
to compensate for the limited battery power capability. Evidently, the proper
control of the energy storage systems presents both a challenge and opportunity for
the power and energy management system. This paper traces the history of the
development of the technology and explores the principles and theory of operation
of the ultracapacitors. The use of ultracapacitors in various applications are
discussed and their advantages over alternative technologies are considered. To
provide examples with which to outline practical implementation issues, systems
incorporating ultracapacitors as vital components are also explored. This paper has
aimed to provide a brief overview of ultracapacitor technology as it stands today.
Previous development efforts have been described to place the current state of the
technology within an historical context. Scientific background has also been
covered in order to better understand performance characteristics.
Possible applications of ultracapacitor technology have also been described to
illustrate the wide range of possibilities that exist. Because of the advantages of
charging efficiency, long lifetime, fast response, and wide operating temperature
range, it is tempting to try and apply ultracapacitors to any application that requires
energy storage. The limitations of the current technology must be fully appreciated,
however, and it is important to realize that ultracapacitors are only useful within a
finite range of energy and power requirements. Outside of these boundaries other
alternatives are likely to be the better solution. The most important thing to
remember about ultracapacitors technology is that it is a new and different
technology in its own right.

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Concept

Comparison of construction diagrams of three capacitors. Left: "normal" capacitor,

middle: electrolytic, right: electric double-layer capacitor In a conventional
capacitor, energy is stored by the removal of charge carriers, typically electrons,
from one metal plate and depositing them on another. This charge separation
creates a potential between the two plates, which can be harnessed in an external
circuit. The total energy stored in this fashion is proportional to both the amount of
charge stored and the potential between the plates. The amount of charge stored
per unit voltage is essentially a function of the size, the distance, and the material
properties of the plates and the material in between the plates (the dielectric), while
the potential between the plates is limited by breakdown of the dielectric. The
dielectric controls the capacitor's voltage.

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Optimizing the material leads to higher energy density for a given size of
capacitor. EDLCs do not have a conventional dielectric. Rather than two separate
plates separated by an intervening substance, these capacitors use "plates" that are
in fact two layers of the same substrate, and their electrical properties, the so-called
"electrical double layer", result in the effective separation of charge despite the
vanishingly thin (on the order of nanometers) physical separation of the layers. The
lack of need for a bulky layer of dielectric permits the packing of plates with much
larger surface area into a given size, resulting in high capacitances in practical-
sized packages. In an electrical double layer, each layer by itself is quite
conductive, but the physics at the interface where the layers are effectively in
contact means that no significant current can flow between the layers. However,
the double layer can withstand only a low voltage, which means that electric
double-layer capacitors rated for higher voltages must be made of matched series-
connected individual EDLCs, much like series-connected cells in higher-voltage
batteries. EDLCs have much higher power density than batteries. Power density
combines the energy density with the speed that the energy can be delivered to the
load. Batteries, which are based on the movement of charge carriers in a liquid
electrolyte, have relatively slow charge and discharge times. Capacitors, on the
other hand, can be charged or discharged at a rate that is typically limited by
current heating of the electrodes. So while existing EDLCs have energy densities
that are perhaps 1/10 that of a conventional battery, their power density is
generally 10 to 100 times as great (see diagram, right).

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The capacitor then evolved into an electrostatic capacitor where the electrodes
were made up of foils and separated by paper that served as the dielectric. These
capacitors are used in the electronic circuit boards of a number of consumer
applications. Here the surface area of one electrode was increased by etching the
electrode to roughen it, reducing the thickness of the dielectric and using a paste-
like electrolyte to form the second electrode.

An ultracapacitor however has a significantly larger storage area. Ultracapacitors

are made with highly porous carbon materials. These materials have the capability
of increased surface areas ranging greater than 21,500 square feet per gram. The
separation distance between the charged plates is reduced significantly to
nanometers (10(-9) cm) in the ultracapacitors by using electrolytes to conduct the
charged ions .

Although they are compared to batteries from the application perspective,

ultracapacitors are unique because there are no chemical reactions involved. They
are considered efficient as they can quickly store and release electrical energy in
the ‘physical’ form.

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Operating principles of the ultracapacitor

The charge-storage mechanism and the design of the ultracapacitor are described.

Based on a ceramic with an extremely high specific surface area and a metallic
substrate, the ultracapacitor provides extremely high energy density and exhibits
low ESR (equivalent series resistance). The combination of low ESR and
extremely low inductance provides the ultracapacitor with a very high power
density and fast risetime as well. As a double-layer capacitor, the ultracapacitoris
not constrained by the same limitations as dielectric capacitors. Thus, although its
discharge characteristics and equivalent circuit are similar to those of dielectric
capacitors, the capacitance of the ultracapacitor increases with the ceramic loading
on the substrate and its ESR is inversely proportional to the cross-sectional area of
the device. Theultracapacitor is composed of an inline stack of electrodes, which
leads to an extremely low inductance device, and it exhibits interesting frequency
dependence. The ultracapacitor principle has been extended to nonaqueous
electrolytes and to a wide temperature range.

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History
General Electric engineers experimenting with devices using porous carbon
electrodes first observed the EDLC effect in 1957.[5] They believed that the energy
was stored in the carbon pores and the device exhibited "exceptionally high
capacitance", although the mechanism was unknown at that time.

General Electric did not immediately follow up on this work. In 1966 researchers
at Standard Oil of Ohio developed the modern version of the devices, after they
accidentally re-discovered the effect while working on experimental fuel
cell designs.[6] Their cell design used two layers of activated charcoal separated by
a thin porous insulator, and this basic mechanical design remains the basis of most
electric double-layer capacitors.

Standard Oil did not commercialize their invention, licensing the technology
to NEC, who finally marketed the results as “supercapacitors” in 1978, to provide
backup power for maintaining computer memory.[6] The market expanded slowly
for a time, but starting around the mid-1990s various advances in materials
science and refinement of the existing systems led to rapidly improving
performance and an equally rapid reduction in cost.

The first trials of supercapacitors in industrial applications were carried out for
supporting the energy supply to robots.[7]

In 2005 aerospace systems and controls company Diehl Luftfahrt

Elektronik GmbH chose supercapacitors to power emergency actuation systems for
doors and evacuation slides inairliners, including the new Airbus 380 jumbo jet.
[8]
 In 2005, the ultracapacitor market was between US $272 million and $400
million, depending on the source.

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Materials
In general, EDLCs improve storage density through the use of a nanoporous
material, typically activated charcoal, in place of the conventional insulating
barrier. Activated charcoal is a powder made up of extremely small and very
"rough" particles, which, in bulk, form a low-density heap with many holes that
resembles a sponge. The overall surface area of even a thin layer of such a material
is many times greater than a traditional material like aluminum, allowing many
more charge carriers (ions or radicals from the electrolyte) to be stored in any
given volume. The charcoal, which is not a good insulator, replaces the excellent
insulators used in conventional devices, so in general EDLCs can only use low
potentials on the order of 2 to 3 V.

Activated charcoal is not the "perfect" material for this application. The charge
carriers are actually (in effect) quite large—especially when surrounded by
solventmolecules—and are often larger than the holes left in the charcoal, which
are too small to accept them, limiting the storage.

As of 2010 virtually all commercial supercapacitors use powdered activated carbon

made from coconut shells.[citation needed][11] Higher performance devices are available,
at a significant cost increase, based on synthetic carbon precursors that are
activated with potassium hydroxide (KOH).[11]

Research in EDLCs focuses on improved materials that offer higher usable surface
areas.

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 Graphene has excellent surface area per unit of gravimetric or volumetric

densities, is highly conductive and can now be produced in various labs, but
is not available in production quantities. Specific energy density of 85.6
Wh/kg at room temperature and 136 Wh/kg at 80 °C (all based on the total
electrode weight), measured at a current density of 1 A/g have been
observed. These energy density values are comparable to that of the Nickel
metal hydride battery.

 The device makes full utilization of the highest intrinsic surface capacitance
and specific surface area of single-layer graphene by preparing curved
graphene sheets that do not restack face-to-face. The curved shape enables
the formation of mesopores accessible to and wettable by environmentally
benign ionic liquids capable of operating at a voltage >4 V.[12]

 Carbon nanotubes have excellent nanoporosity properties, allowing tiny

spaces for the polymer to sit in the tube and act as a dielectric. [13] Carbon
nanotubes can store about the same charge as charcoal (which is almost pure
carbon) per unit surface area but nanotubes can be arranged in a more
regular pattern that exposes greater suitable surface area.[14]

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Ragone chart showing energy density vs.power density for various energy-storage
devices

 Some polymers (e.g. polyacenes and conducting polymers) have a redox

(reduction-oxidation) storage mechanism along with a high surface area.

 Carbon aerogel provides extremely high surface area gravimetric densities of

about 400–1000 m²/g.

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 The electrodes of aerogel supercapacitors are a composite material usually

made of non-woven paper made from carbon fibers and coated with organic
aerogel, which then undergoes pyrolysis. The carbon fibers provide
structural integrity and the aerogel provides the required large surface area.
Small aerogel supercapacitors are being used as backup electricity storage in
microelectronics.
 Aerogel capacitors can only work at a few volts; higher voltages ionize the
carbon and damage the capacitor. Carbon aerogel capacitors have achieved
325 J/g (90 W·h/kg) energy density and 20 W/g power density.[15]

 Solid activated carbon, also termed consolidated amorphous carbon (CAC).

It can have a surface area exceeding 2800 m2/g and may be cheaper to
produce than aerogel carbon.[16]

 Tunable nanoporous carbon exhibits systematic pore size control. H2

adsorption treatment can be used to increase the energy density by as much
as 75% over what was commercially available as of 2005.[17][18]

 Mineral-based carbon is a nonactivated carbon, synthesised from metal or

metalloid carbides, e.g. SiC, TiC, Al4C3.[19] The synthesised nanostructured
porous carbon, often called Carbide Derived Carbon (CDC), has a surface
area of about 400 m²/g to 2000 m²/g with a specific capacitance of up to 100
F/mL (in organic electrolyte).

 As of 2006 this material was used in a supercapacitor with a volume of 135

mL and 200 g weight having 1.6 kF capacitance. The energy density is more
than 47 kJ/L at 2.85 V and power density of over 20 W/g.[20]

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 In August 2007 researchers combined a biodegradable paper battery with

aligned carbon nanotubes, designed to function as both a lithium-ion battery
and a supercapacitor (called bacitor). The device employed an ionic liquid,
essentially a liquid salt, as the electrolyte. The paper sheets can be rolled,
twisted, folded, or cut with no loss of integrity or efficiency, or stacked, like
ordinary paper (or a voltaic pile), to boost total output.

 They can be made in a variety of sizes, from postage stamp to broadsheet.

Their light weight and low cost make them attractive for portable
electronics, aircraft, automobiles, and toys (such as model aircraft), while
their ability to use electrolytes in blood make them potentially useful for
medical devices such as pacemakers.[21]

 Other teams are experimenting with custom materials made of activated

polypyrrole, and nanotube-impregnated papers.

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Density

The energy density of existing commercial EDLCs ranges from around 0.5 to 30
W·h/kg[22][23] including lithium ion capacitors, known also as a "hybrid capacitor".
Experimental electric double-layer capacitors have demonstrated densities of 30
W·h/kg and have been shown to be scalable to at least 136 W·h/kg, [24][25] while
others expect to offer energy densities of about 400 W·h/kg.[26] For comparison, a
conventional lead-acid battery stores typically 30 to 40 W·h/kg and modern
lithium-ion batteries about 160 W·h/kg. Gasoline has a net calorific value (NCV)
of around 12,000 W·h/kg; automobile applications operate at about 20% tank-to-
wheel efficiency, giving an effective energy density of 2,400 W·h/kg.

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ENERGY STORAGE:
• In the past 2 classes we have discussed battery technologies and how their
characteristics may or may not be suitable for microgrids.
• Batteries are suitable for applications where we need an energy delivery profile.
For example, to feed a load during the night when the only source is PV modules.
• However, batteries are not suitable for applications with power delivery profiles.
For example, to assist a slow load-following fuel cell in delivering power to a
constantly and fast changing load.
• For this last application, two technologies seem to be more appropriate:
• Ultracapacitors (electric energy)
• Flywheels (mechanical energy)
• Other energy storage technologies not discussed in here are superconducting
magnetic energy storage (SMES – magnetic energy) and compressed air (or some
other gas - mechanical energy)

FLYWHEEL:
• Kinetic energy:
where I is the moment of inertia and ω is the angular velocity of a rotating disc.
• For a cylinder the moment of inertia is
• So the energy is increased if ω increases or if I increases.

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• I can be increased by locating as much mass on the outside of the disc as

possible.
• But as the speed increases and more mass is located outside of the disc,
mechanical limitations are more important.
• However, high speed is not the only mechanical constraint
• If instead of holding output voltage constant, output power is held constant, then
the torque needs to increase (because P = Tω) as the speed decreases. Hence, there
is also a minimum speed at which no more power can be extracted
• If and if an useful energy (Eu) proportional to the difference between the disk
energy at its maximum and minimum allowed speed is compared with the
maximum allowed energy.

CHARECTERSTIC:

The significant characteristics of ultracapacitors are:

 Low internal resistance in comparison with batteries

 High power density due to high discharge currents

 Ability to operate at temperatures as low as -40°C

 Effective capacitance for specific pulse widths

 Low equivalent series resistance (ESR)

 Higher cycle life, making them suitable for automotive applications

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Advantages
 Long life, with little degradation over hundreds of thousands of charge
cycles. Due to the capacitor's high number of charge-discharge cycles
(millions or more compared to 200 to 1000 for most commercially available
rechargeable batteries) it will last for the entire lifetime of most devices,
which makes the device environmentally friendly. Rechargeable batteries
wear out typically over a few years, and their highly reactive chemical
electrolytes present a disposal and safety hazard. Battery lifetime can be
optimised by charging only under favorable conditions, at an ideal rate and,
for some chemistries, as infrequently as possible. EDLCs can help in
conjunction with batteries by acting as a charge conditioner, storing energy
from other sources for load balancing purposes and then using any excess
energy to charge the batteries at a suitable time.
 Low cost per cycle
 Good reversibility
 Very high rates of charge and discharge.
 Extremely low internal resistance (ESR) and consequent high cycle
efficiency (95% or more) and extremely low heating levels
 High output power
 High specific power. According to ITS (Institute of Transportation Studies,
Davis, California) test results, the specific power of electric double-layer
capacitors can exceed 6 kW/kg at 95% efficiency[10]
 Improved safety, no corrosive electrolyte and low toxicity of materials.

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 .

Disadvantages

 The amount of energy stored per unit weight is generally lower than that of
an electrochemical battery (3–5 W·h/kg for an standard ultracapacitor,
although 85 W.h/kg has been achieved in the lab[3] as of 2010 compared to
30-40 W·h/kg for a lead acid battery), and about 1/1,000th the volumetric
energy density of gasoline.
 Typical of any capacitor, the voltage varies with the energy stored. Effective
storage and recovery of energy requires complex electronic control and
switching equipment, with consequent energy loss
 Has the highest dielectric absorption of any type of capacitor.
 High self-discharge - the rate is considerably higher than that of an
electrochemical battery.
 Cells hold low voltages - serial connections are needed to obtain higher
voltages. Voltage balancing is required if more than three capacitors are
connected in series.
 Linear discharge voltage prevents use of the full energy spectrum.
 Due to rapid and large release of energy (albeit over short times), EDLC's
have the potential to be deadly to humans.

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Applications

Some of the earliest uses were motor startup capacitors for large engines in tanks
and submarines, and as the cost has fallen they have started to appear on diesel
trucks and railroad locomotives.[27][28] In the 00's they attracted attention in the
green energy world, where their ability to charge much faster than batteries makes
them particularly suitable for regenerative braking applications. New technology in
development could potentially make EDLCs with high enough energy density to be
an attractive replacement for batteries in all-electric cars and plug-in hybrids, as
EDLCs charge quickly and are stable with respect to temperature.

China is experimenting with a new form of electric bus (capabus) that runs without
powerlines using large onboard EDLCs, which quickly recharge whenever the bus
is at any bus stop (under so-called electric umbrellas), and fully charge in the
terminus. A few prototypes were being tested in Shanghai in early 2005. In 2006,
two commercial bus routes began to use electric double-layer capacitor buses; one
of them is route 11 in Shanghai.[29]

In 2001 and 2002 VAG, the public transport operator in Nuremberg, Germany
tested an hybrid bus that uses a diesel-electric battery drive system with electric
double-layer capacitors.[30] Since 2003 Mannheim Stadtbahn in Mannheim,
Germany has operated a light-rail vehicle (LRV) that uses EDLCs to store braking
energy.[31][32]

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Other public transport manufacturers are developing EDLC technology, including

mobile storage[33] and a stationary trackside power supply.[34][35]

A triple hybrid forklift truck uses fuel cells and batteries as primary energy storage

Automotive

Ultracapacitors are used in some concept prototype vehicles, in order to keep

batteries within resistive heating limits and extend battery life. [37][38] The
ultrabattery combines a supercapacitor and a battery in one unit, creating an
electric vehicle battery that lasts longer, costs less and is more powerful than
current plug-in hybrid electric vehicles (PHEVs).[39][40]

Motor racing

The FIA, the governing body for many motor racing events, proposed in the
Power-Train Regulation Framework for Formula 1 version 1.3 of 23 May 2007
that a new set of power train regulations be issued that includes a hybrid drive of
up to 200 kW input and output power using "superbatteries" made with both
batteries and supercapacitors.[41]

Consumer electronics

EDLCs can be used in PC Cards, flash photography devices in digital cameras,

flashlights, portable media players, and in automated meter reading,[42] particularly
where extremely fast charging is desirable.

In 2007, a cordless electric screwdriver that uses an EDLC for energy storage was
produced.[43] It charges in 90 seconds, retains 85% of the charge after 3 months,

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and holds enough charge for about half the screws (22) a comparable screwdriver
with a rechargeable battery will handle (37). Two LED flashlights using EDLCs
were released in 2009. They charge in 90 seconds.[44]

Alternative energy

The idea of replacing batteries with capacitors in conjunction with novel energy
sources became a conceptual umbrella of the Green Electricity (GEL) Initiative,
introduced by Dr. Alexander Bell.[45] One successful GEL Initiative concept was a
muscle-driven autonomous solution that employs a multi-farad EDLC as energy
storage to power a variety of portable electrical and electronic devices such as MP3
players, AM/FM radios, flashlights, cell phones, and emergency kits.[46]

Price

Costs have fallen quickly, with cost per kilojoule dropping faster than cost per
farad. As of 2006 the cost of supercapacitors was 1 cent per farad and $2.85 per
kilojoule, and was expected to drop further.[47]

Market

According to Innovative Research and Products (iRAP), ultracapacitor market

growth will continue during 2009 to 2014. Worldwide business, over US$275
million in 2009, will continue to grow at an AAGR of 21.4% through 2014.[48]

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Challenges:
1. The foremost challenge is from traditional batteries such as the lead acid, lithium
ion, nickel cadmium (NiCD), nickel metal hydride (NiMH) and others which
existed in the market for more than hundred years

2. Equivalent Series Resistance values can be optimized only with efficient

packaging of the ultracapacitor

3. Cost of raw materials are significantly high and plays an important role in the
pricing of ultracapacitors

4. Adoption rates are only gradually increasing as end-users realize the benefits of
ultracapacitors

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CONCLUSION
Ultra capacitors have many advantages over traditional electrochemical batteries.
Unlike batteries, "ultra caps" can completely absorb and release a charge at high
rates and in a virtually endless cycle with little degradation. Where they're weak,
however, is with energy storage. Compared with lithium-ion batteries, high-end
ultracapacitors on the market today store 25 times less energy per pound. This is
why ultra capacitors, with their ability to release quick jolts of electricity and to
absorb this energy just as fast, are ideal today as a complement to batteries or fuel
cells in electric-drive vehicles. The power burst that ultra caps provide can assist
with stop-start acceleration, and the energy is more efficiently recaptured through
regenerative braking--an area in which ultracap maker Maxwell Technologies has
seen significant results. In future it will replace the batteries.

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REFERENCE
 Super Capacitor Seminar

 Article on ultracapacitors at electronicdesign.com

 Article on ultracapacitors at batteryuniversity.com

 A new version of an old idea is threatening the battery industry (The

Economist).

 An Encyclopedia Article From the Yeager center at CWRU.

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