Graphene Supercapacitors

Avila, Roy Jonathan A., 2014-2-0008

College of Engineering
Ateneo de Naga University

AbstractGraphene supercapacitors serve as the

scientists answer to the rapid electronic component
evolution. Supercapacitor makes up to the current IC
technological advancement as its miniaturization
progresses. The graphene as used as a supercapacitor
material aids in lowering the cost of the material and
production because of its abundance. These paper is
meant to discuss all about the graphene supercapacitor.

I. INTRODUCTION

Scientists have been struggling to

develop energy storage solutions such as
batteries and capacitors that can keep up
with the current rate of electronic
component evolution for a number of
years. Unfortunately, the situation we are
in now is that while we are able to store a
large amount of energy in certain types of
batteries, those batteries are very large,
very heavy, and charge and release their
energy relatively slowly. Capacitors, on
the other hand, are able to be charged and
release energy very quickly, but can hold
much less energy than a battery. Graphene
application developments though have led
to new possibilities for energy storage,
with high charge and discharge rates,
which can be made very cheaply. But
before we go into specific details, it would
be sensible to first outline the basics of
energy storage and the potential goals of
developing graphene as a supercapacitor.

II. CAPACITORS AND SUPERCAPACITORS

Capacitors are components that are used
to store charges. Capacitors are also
known as condensers. Commercially used
capacitors are made of two metal foils
rolled into a cylinder with a dielectric
medium in between them. The
capacitance is the main property of a
capacitor. The capacitance of an object is
a measurement of the amount of charges
that object can hold without discharging.
Capacitance is a very important property
in both electronics and electromagnetism.
Capacitance is also defined as the ability
to store energy in an electric field. For a
capacitor, which has V voltage difference
across the nodes and the maximum
amount of charges that can be stored in
that system is Q, the capacitance is Q/V,
when all are measured in SI units. The unit
of the capacitance is farad (F). However,
it is inconvenient to use such a large unit.
Therefore, most of the capacitance values
are measured in nF, pF, F and mF
ranges. The energy stored in the capacitor
is equal to (QV2)/2. This energy is equal
to the work done on each and every charge
by the system summed up. The
capacitance of a system depends on the
area of the capacitor plates, the distance
between the capacitor plates, and the
medium between the capacitor plates. The
capacitance of a system can be increased
by increasing the area, decreasing the gap
or having a medium with higher dielectric
permittivity.

Figure I. Example of a typical capacitor

Also, capacitors are energy storage

mediums similar to an electrochemical
battery. Most batteries, while able to store
a large amount of energy are relatively
inefficient in comparison to other energy
solutions such as fossil fuels. It is often
said that a 1kg electrochemical battery is
able to produce much less energy than 1
liter of gasoline; but this kind of
comparison
is
extremely
vague,
mathematically illogical, and should be
ignored. In fact, some electrochemical
batteries can be relatively efficient, but
that doesnt get around the primary
limiting factor in batteries replacing fossil
fuels in commercial and industrial
applications (for example, transportation);
charge time.
High capacity batteries take a long time
to charge. This is why electrically
powered vehicles have not taken-off as
well as we expected twenty or thirty years
ago. While you are now able to travel 250
miles or more on one single charge in a
car such as the Tesla Model S, it could
take you over 43 hours to charge the
vehicle using a standard 120v wall socket
in order to drive back home. This is not
acceptable for many car users. Capacitors,
on the other hand, are able to be charged
at a much higher rate, but store (as already
mentioned) somewhat less energy.
Supercapacitors, also known as
ultracapacitors, are able to hold hundreds
of times the amount of electrical charge as
standard capacitors, and are therefore
suitable
as
a
replacement
for
electrochemical batteries in many
industrial and commercial applications.

Supercapacitors also work in very low

temperatures; a situation that can prevent
many types of electrochemical batteries
from working. For these reasons,
supercapacitors are already being used in
emergency radios and flashlights, where
energy can be produced kinetically (by
winding a handle, for example) and then
stored in a supercapacitor for the device to
use.
A conventional capacitor is made up of
two layers of conductive materials
(eventually becoming positively and
negatively charged) separated by an
insulator. What dictates the amount of
charge a capacitor can hold is the surface
area of the conductors, the distance
between the two conductors and also the
dielectric constant of the insulator.
Supercapacitors are slightly different in
the fact that they do not contain a solid
insulator.
Instead the two conductive plates in a
cell are coated with a porous material,
most commonly activated carbon, and the
cells are immersed in an electrolyte
solution. The porous material ideally will
have an extremely high surface area (1
gram of activated carbon can have an
estimated surface area equal to that of a
tennis court), and because the capacitance
of a supercapacitor is dictated by the
distance between the two layers and the
surface area of the porous material, very
high levels of charge can be achieved.
While supercapacitors are able to store
much more energy than standard
capacitors, they are limited in their ability
to withstand high voltage. Electrolytic
capacitors are able to run at hundreds of
volts, but supercapacitors are generally
limited to around 5 volts. However, it is
possible to engineer a chain of
supercapacitors to run at high voltages as
long as the series is properly designed and
controlled.

Figure VI. Graphene is an atomic-scale

honeycomb lattice made of carbon atoms.

Figure II. Example of supercapacitors

(Maxwell supercapacitors)

Even though the two can be classified as

both capacitors, the capacitor and the
supercapacitor (ultracapacitor) have
differences such as: supercapacitors have
higher energy density than normal
capacitors. Supercapacitors use two layers
of the dielectric material separated by a
very thin insulator surface as the dielectric
medium, whereas normal capacitors use
only a single layer of dielectric material.
Also, normal capacitors are much cheaper
than the supercapacitors in terms of
production and material.
III. GRAPHENE

In order to understand graphene

supercapacitors. We need to understand
first what a graphene is. Graphene is a thin
layer of pure carbon; it is a single, tightly
packed layer of carbon atoms that are
bonded together in a hexagonal
honeycomb lattice.

Graphene is also the thinnest compound

known to man at one atom thick, the
lightest material known (with 1 square
meter coming in at around 0.77
milligrams), the strongest compound
discovered (between 100-300 times
stronger than steel and with a tensile
stiffness of 150,000,000 psi), the best
conductor of heat at room temperature (at
(4.840.44) 103 to (5.300.48) 103
Wm1K1) and also the best conductor
of electricity known (studies have shown
electron mobility at values of more than
15,000 cm2V1s1). Other notable
properties of graphene are its unique
levels of light absorption at 2.3% of
white light, and its potential suitability for
use in spin transport.
Bearing this in mind, you might be
surprised to know that carbon is the
second most abundant mass within the
human body and the fourth most abundant
element in the universe (by mass), after
hydrogen, helium and oxygen. This
makes carbon the chemical basis for all
known life on earth, so therefore graphene
could well be an ecologically friendly,
sustainable solution for an almost
limitless number of applications. Since
the discovery (or more accurately, the
mechanical obtainment) of graphene,
advancements within different scientific
disciplines have exploded, with huge
gains being made particularly in
electronics and biotechnology already.
The problem that prevented graphene
from initially being available for

developmental research in commercial

uses was that the creation of high quality
graphene was a very expensive
and complex process (of chemical vapor
disposition) that involved the use of toxic
chemicals to grow graphene as a
monolayer by exposing Platinum, Nickel
or Titanium Carbide to ethylene or
benzene at high temperatures. Also, it was
previously impossible to grow graphene
layers on a large scale using crystalline
epitaxy on anything other than a metallic
substrate. This severely limited its use in
electronics as it was difficult, at that time,
to separate graphene layers from its
metallic substrate without damaging the
graphene.
However, studies in 2012 found that by
analyzing graphenes interfacial adhesive
energy, it is possible to effectually
separate graphene from the metallic board
on which it is grown, whilst also being
able to reuse the board for future
applications theoretically an infinite
number of times, therefore reducing the
toxic waste previously created by this
process. Furthermore, the quality of the
graphene that was separated by using this
method was sufficiently high enough to
create molecular electronic devices
successfully.
While this research is very highly
regarded, the quality of the graphene
produced will still be the limiting factor in
technological
applications.
Once
graphene can be produced on very thin
pieces of metal or other arbitrary surfaces
(of tens of nanometers thick) using
chemical vapor disposition at low
temperatures and then separated in a way
that can control such impurities as ripples,
doping levels and domain size whilst also
controlling the number and relative
crystallographic orientation of the
graphene layers, then we will start to see
graphene become more widely utilized as
production techniques become more
simplified and cost-effective.

Being able to create supercapacitors out

of graphene will possibly be the largest
step in electronic engineering in a very
long time. While the development of
electronic
components
has
been
progressing at a very high rate over the
last 20 years, power storage solutions such
as batteries and capacitors have been the
primary limiting factor due to size, power
capacity and efficiency (most types of
batteries are very inefficient, and
capacitors are even less so). For example,
with the development of currently
available lithium-ion batteries, it is
difficult to create a balance between
energy density and power density; in this
situation, it is essentially about
compromising one for the other.
In initial tests carried out, laser-scribed
graphene (LSG) supercapacitors (with
graphene being the most electronically
conductive material known, at 1738
Siemens per meter (compared to 100 SI/m
for activated carbon)), were shown to
offer power density comparable to that of
high-power lithium-ion batteries that are
in use today. Not only that, but also LSG
supercapacitors are highly flexible, light,
quick to charge, thin and as previously
mentioned, comparably very inexpensive
to produce.
Graphene is also being used to boost not
only the capacity and charge rate of
batteries but also the longevity. Currently,
while such materials as silicone are able to
store large amounts of energy, that
potential amount diminishes drastically
on every charge or recharge. With
graphene tin oxide being used as an anode
in lithium ion batteries for example,
batteries can be made to last much longer
between charges (potential capacity has
increased by a factor of 10), and with
almost no reduction in storage capacity
between charges, effectively making
technology such as electronically
powered vehicles a much more viable

transport solution in the future. This

means that batteries (or capacitors) can be
developed to last much longer and at
higher capacities than previously realized.
Also, it means that electronic devices may
be able to be charged within seconds,
rather than minute or hours and have
hugely improved longevity.
Consumers can already purchase
graphene-enhanced products to use at
home. One company already produces
and offers on the market conductive ink
(first developed by researchers at the
University of Cambridge in 2011). This is
made by effectively mixing tiny graphene
flakes with ink, enabling you to print
electrodes directly onto paper. While this
was previously possible by using organic
semi conductive ink, the use of graphene
flakes makes the printed material vastly
more conductive and therefore more
efficient.
IV. SUPERCAPACITORS
Supercapacitors have two conductive
materials (usually metal plates) that are
coated with activated carbon and
are immersed in an electrolyte. One of
these plates has positive ions, while the
other contains negative ions. While
charging, these ions accumulate on the
surface of each carbon-coated plate.

like having two capacitors for the price of

one. This is why supercapacitors are
sometimes referred to as ultracapacitors,
as well as electric double-layer capacitors.
A capacitor generally differs from a
battery in that it can store a higher amount
of energy, but for a shorter period of time.
This allows a supercapacitor to be used in
applications that require larger amount of
energy in repeated bursts (for example, a
camera flash). Batteries, however, supply
the bulk of energy in most devices since
they can store and deliver energy over a
slower period of time.
Even though, the supercapacitors pose a
much greater advantage than the standard
batteries. Supercapacitors have too many
limitations at the present time.

Figure IV. Diagram showing energy density

vs. power density for batteries, capacitors and
supercapacitors.

Like a battery, a standard capacitor

stores electrical energy. Whereas a battery
can both produce and store electrons, a
capacitor can only store them. And
although a battery can dump its charge
slowly through the course of hours, a
capacitor dumps its charge in mere
seconds.
Figure III. Comparison of a battery and
supercapacitor

In order to store energy, each carbon

electrode ends up having two layers of
charge coating its surface. So, for all
intents and purposes, a supercapacitor is

Supercapacitors also have a low energy

density and can only hold 1/5th to 1/10th
the energy of a standard battery. Because
of the organic electrolyte used in
supercapacitors, the fast energy discharge
of a supercapacitor is much higher than

that of a battery. Supercapacitors are low

voltage devices: in order to achieve a
practical working voltage, several need to
be strung together. And at present, mass
production of supercapacitors has not
been something that is cost effective. For
example, if you wanted to use a
supercapacitor to charge your laptop now,
you might have to spend hundreds of
dollars on dozens of supercapacitors.
When connected together, these series of
supercapacitors would create a laptop that
would no longer be very mobile.
Because of these limitations, using
supercapacitors in our home electronics
and mobile devices is not yet feasible.
However, thanks to strides in scientific
research, we are very close to making
breakthroughs that could change this.
V. GRAPHENE SUPERCAPACITORS: WHAT
AND HOW THEY ARE MADE.

Figure V. UCLA researchers develop new

technique to scale up production of graphene
micro-supercapacitors.

Recently, a team of researchers at

UCLA, led by Richard Kaner, uncovered
a way to create graphene-based
supercapacitors that charge and discharge
three times faster than current lithium
batteries. Graphene is the most conductive
material known to man, but it can be
tricky to produce and work with. The best
part of this new discovery is that these
graphene supercapacitors were created

with a simple inexpensive DVD writer.

The researchers learned that after putting
a graphic oxide film on a blank DVD and
then using the DVDs laser to burn the
CD, the graphic oxide is then turned into
graphene. Once they had a few slices of
graphene, an electrolyte was placed
between the slices and a new kind of
supercapacitor was born.
The technique that Kaner developed in
his lab in UCLA is able to produce more
than 100 micro-supercapacitors on a
single disc in less than 30 minutes, using
inexpensive materials.
The process of miniaturization often
relies on flattening technology, making
devices thinner and more like a geometric
plane that has only two dimensions. In
developing the graphene supercapacitor,
Kaner used a two-dimensional sheet of
carbon, known as graphene, which only
has the thickness of a single atom in the
third dimension.
Kaner took advantage of a new
structural design during the fabrication.
For any supercapacitor to be effective,
two separated electrodes have to be
positioned so that the available surface
area between them is maximized. This
allows the supercapacitor to store a
greater charge. A previous design stacked
the layers of graphene serving as
electrodes, like the slices of bread on a
sandwich. While this design was
functional, however, it was not
compatible with integrated circuits.
In their new design, the researchers led
by Richard Kaner placed the electrodes
side by side using an interdigitated
pattern, akin to interwoven fingers. This
helped to maximize the accessible surface
area available for each of the two
electrodes while also reducing the path
over which ions in the electrolyte would
need to diffuse. As a result, the new
supercapacitors have more charge

capacity and rate capability than their

stacked counterparts.
Interestingly, they found out that by
placing more electrodes per unit area, they
boosted the micro supercapacitors ability
to store even more charge.
Kaner and his team were able to
fabricate these intricate supercapacitors
using an affordable and scalable technique
that they had developed earlier. They
glued a layer of plastic onto the surface of
a DVD and then coated the plastic with a
layer of graphite oxide. Then, they simply
inserted the coated disc into a
commercially available LightScribe
optical drive traditionally used to label
DVDs and took advantage of the
drive's own laser to create the
interdigitated pattern. The laser scribing is
so precise that none of the "interwoven
fingers" touch each other, which would
short-circuit the supercapacitor.
The researchers didn't stop there,
though. They began to play around with
electrodes. Kaner said, "We placed them
side by side using an interdigitated
pattern, akin to interwoven fingers. This
helped to maximize the accessible surface
area available for each of the two
electrodes while also reducing the path
over which ions in the electrolyte would
need to diffuse. As a result, the new
supercapacitors have more charge
capacity and rate capability than their
stacked counterparts."

similar fashion to the commercial

LightScribe process. With the precision of
the laser, the drive renders the computerdesigned pattern onto the graphite oxide
film to produce the desired graphene
circuits."
The graphene micro-supercapacitor
made by Kaners team is also highly
bendable and twistable, making it
potentially useful as energy-storage
devices in flexible electronics like roll-up
displays and TVs, e-paper, and even
wearable electronics.
Kaner and his team also showed the
utility of their new laser-scribed graphene
micro-supercapacitor in an all-solid form,
which would enable any new device
incorporating them to be more easily
shaped and flexible. The microsupercapacitors can also be fabricated
directly on a chip using the same
technique, making them highly useful for
integration into micro-electromechanical
systems (MEMS) or complementary
metal-oxide-semiconductors (CMOS).

Figure VI. Production of graphene supercapacitor

In order to label the disk using the DVD

writer, the surface of the disc is coated
with a reactive dye that changes color on
exposure to the laser light. Instead of
printing on this specialized coating, our
approach is to coat the disc with a film of
graphite oxide, which then can be directly
printed on," Kaner said. "We previously
found an unusual photo-thermal effect in
which graphite oxide absorbs the laser
light and is converted into graphene in a

These graphene micro-supercapacitors

show excellent cycling stability, an
important advantage over micro-batteries,
which have shorter lifespans and which
could pose a major problem when
embedded in permanent structures
such as biomedical implants, active radiofrequency identification tags and
embedded micro-sensors for which no
maintenance or replacement is possible.

As they can be directly integrated onchip, these micro-supercapacitors may

help to better extract energy from solar,
mechanical and thermal sources and thus
make more efficient self-powered
systems. They could also be fabricated on
the backside of solar cells in both portable
devices and rooftop installations to store
power generated during the day for use
after sundown, helping to provide
electricity around the clock when
connection to the grid is not possible.
Kaner's micro-scale graphene-based
supercapacitor research is supported
by Maxwell Technologies Inc., a global
leader in manufacturing carbon-based
supercapacitors and other energy storage
devices.
VI. GRAPHENE SUPERCAPACITORS
APPLICATION IN THE NEAR FUTURE
Due to the lightweight dimensions of
graphene based supercapacitors and the
minimal cost of production coupled with
graphenes elastic properties and inherit
mechanical strength, we will almost
certainly see technology within the next
five to ten years incorporating these
supercapacitors. Also, with increased
development in terms of energy storage
limits for supercapacitors in general,
graphene-based or hybrid supercapacitors
will eventually be utilized in a number of
different applications.
Vehicles that utilize supercapacitors are
already prevalent in our society. One
Chinese
company
is
currently
manufacturing buses that incorporate
supercapacitor energy recovery systems,
such as those used on Formula 1 cars, to
store energy when braking and then
converting that energy to power the
vehicle until the next stop. According to
some Korean engineers, graphene
supercapacitors are ready for electric
vehicle in the present time.

Additionally, we will at some point in

the next few years begin to see mobile
telephones and other mobile electronic
devices being powered by supercapacitors
as not only can they be charged at a much
higher rate than current lithium-ion
batteries, but they also have the potential
to last for a vastly greater length of time.
Other current and potential uses for
supercapacitors are as power backup
supplies for industry or even our own
homes. Businesses can invest in power
backup solutions that are able to store high
levels of energy at high voltages,
effectively offering full power available to
them, to reduce the risk of having to limit
production due to inadequate amounts of
power. Alternatively, if you have a fuel
cell vehicle that is able to store a large
amount of electrical energy, then why not
use it to help power your home in the
event of a power outage?
We can expect that this scenario of
using advanced energy storage and
recovery solutions will become much
more widely used in the coming years as
the efficiency and energy density of
supercapacitors increases, and the
manufacturing costs decrease. While
graphene-based supercapacitors are
currently a viable solution in the future,
technology needs to be developed to make
this into a reality. But rest assured, many
companies around the world are already
trialing products using this technology
and creating new ways to help subsidize
the use of fossil-fuels and toxic chemicals
in our ever-demanding strive for energy.

Like any other supercapacitor or ultra-capacitor, graphene supercapacitors work at:

Harvest power from regenerative braking systems and release power to help
hybrid buses accelerate.
Reliably crank semi-trucks in cold weather or when batteries are drained from
repetitive starting or in-cab electric loads.
Provide cranking power and voltage stabilization in start/stop systems,
backup and peak power for key automotive applications and serve as energy
storage in regenerative braking systems.
Capture energy from regenerative braking systems and release power to assist
in train acceleration, and used for vehicle power where overhead wiring
systems are not available.
Open aircraft doors in the event of power failures.
Used in blade pitch systems and to help increase reliability and stability to the
energy grid.
Capture energy and provide burst power to assist in lifting operations.
Provide energy to data centers between power failures and initiation of backup
power systems, such as diesel generators or fuel cells.
Provide energy storage for firming the output of renewable installations and
increasing grid stability.

Figure VII. Uses of Graphene in the present and future

VII. REFERENCES

http://mccreavy.com/wp-content/uploads/2012/03/450V-Capacitor.jpg
http://www.differencebetween.com/difference-between-capacitors-and-vssupercapacitors/
http://www.dvice.com/sites/dvice/files/styles/blog_post_embedded/public/pho
to1-battery-supercapacitor.jpg?itok=XOw8e48http://commons.wikimedia.org/
http://www.thecapitalwide.com/wp-content/uploads/2014/11/graphenemetal.jpg
http://newsroom.ucla.edu/releases/ucla-researchers-develop-new-technique243553
http://www.kurzweilai.net/images/Micro-supercapacitor.production.png
http://www.nanowerk.com/spotlight/id25744_1l.jpg
http://en.wikipedia.org/wiki/Supercapacitor
http://www.graphenea.com/pages/graphene-properties
http://www.graphenea.com/pages/graphene
http://www.graphenea.com/pages/graphene-supercapacitors
http://www.technologyreview.com/view/521651/graphene-supercapacitorsready-for-electric-vehicle-energy-storage-say-korean-engineers/
http://www.eetimes.com/document.asp?doc_id=1322050
http://www.dailymail.co.uk/sciencetech/article-2637723/Super-chargingBreakthrough-battery-technology-fully-charge-cellphone-minutes.html